摘要:

J O U R N A L E. 0. C. BALY. HORACE T. BROWN LL.D. P.R.S. A. W. CROSSLEY D.Sc. Ph.D. F.R.S. WYNDHAM R. DUNSTAK &I. A F. R.S. &I. 0. FORSTER. D.Sc. Ph.D. F.R.S. J. T. HEWITT RLA. D.Sc. P1i.D. OF R. MELDOLA F.R.S. G. T. XORGAN D.Sc. SirW.Ra&fsAY K.C.B. LL.D.,F.R.S. A. SCOTT 11. A. D.Sc. F.R.S. T. E. THORPE C.B. LL.D. F.R.S. JOHS WADE D.Sc. THE CHEMICAL SOCIETY. ABSTRACTS O F PAPERS ORGANIC CHEMISTRY. ON E. C. G. F. ARMSTRONG Ph.D. D.Sc. F. BAKER Ph.D. B.Sc. BARGER M.A. D.Sc. R. J. CALDWELL D.Sc. W. A. DAVIS B.Sc. H. M. DAWSON Ph.D. D.Sc. T. EWAN B.Sc. Ph.D. J. V. EYRE Ph.D. W. H. GLOVER Ph.D. E. GOULDISG D.Sc. P. HAAS B.Sc. P1i.D. W. D. HALLIBUXTON M.D. F.R.S. T. A. HENRY D.Sc. E. HOPTOX B.Sc. 2. KAHAN B.Sc. L. DE ICONINOH. A. MCKESZIE M.A. D.Sc. N. H. J. MILLER Ph.D. ' G. T. J~ORGAN D.Sc. ' J. C. PHILIP M.A. P1i.D. T. H. POPE B.Sc. ' W. ROBERTSON. E. J. RUSSEL D.Sc. P. B. SCHRYVER D Sc. Ph.D. G. SENTER Ph.D. B.Sc. 1 W. P. SKERTCISLY. C. SXITH D.Sc. 1 L. J. SPENCER h1.A. J. J. SUDBOPOUGH Ph.D. D.Sc. ' A. JAMIESON WALKER Ph.D. B.A. G. YOUXG Ph.D. I RI. A. WHITELET D.s~. 1 w. 0. WOOTTON B.SC. 1908. Vol. XCIV. Part I. LONDON GURNEY JACKSON 10 PATERNOSTER ROW. 1908.RICHARD CLAY & SOSS I ISIITED BREAD STREET HILL E.C. AXD BVNQAY. SUFFOLK.

ISSN:0368-1769    

DOI:10.1039/CA90894FP001

出版商:RSC    

年代:1908

数据来源: RSC

摘要:

J O U R N A L E. C. C. BALY. HORACE T. BROWN LL.D. F.R.S. A. W. CROSSLEY D.Sc. Ph.D. F.R.S. WYNDHAMR.DUNSTAN,M.A. F.R.S. &I 0. FORSTER D.Sc. Ph.D. F.R.S. J. T. HEWITT M.A. D.Sc. Ph.D. OF R. MELDOLA F.R.S. G. T. MORGAN D.Sc. Sir W. RAMSAY E.C.B. LL.D. ,F. R.S. A. SCOTT M.A. I?.Sc. F.R.S. T. E. THORPE C.B. LL.D. F.R.S. JOHN WADE D.Sc. THE CHEMICAL SOCIETY. T. EWAN B.Sc. Ph.D. W. H. GLOVER Ph.D. E. GOULDING D.Sc. P. HAAB B.Sc. Ph.D. W. D. HALLIBURTOK M.D. F.R.S. T. A. HENRY DSc. E. HORTON B.Sc. Z. KAHAN B.Sc. J. V. EYRE Ph.D. S. B. SCHRYVER D.Sc. Ph.D. W. P. SKERTCHLY. C. SMITH D.Sc. L. J. SPENCER M.A. J. J. SUDBOROUGH Ph.D. D.Sc. A. JAMIESON WALKER Ph.D. B.A. M. A. WHITELEY D.Sc. W. 0. WOOTTON B.Sc. G. SENTER Ph.D. B.SC. 1908. Vol. XCIV. Part 11. LONDON GURNEY & JACKSON 10 PATERNOSTER R O W 1908.RICHARD CLAY & SONS LIMITED BREAD STREET HILL E.C. AND BUNGAY SUFFOLK.

ISSN:0368-1769    

DOI:10.1039/CA90894FP003

出版商:RSC    

年代:1908

数据来源: RSC

摘要:

ERRATA. 259 33 477 477 477 477 47 7 667 1001 1257 336 337 755 640 641 547 973 973 COLLECTIVE INDEX 1873-1882 (AUTHORS). Page Line 11 col. i for “773 ” read (‘ 173.” VOL. LXX (ABSTR. 1896). PART I. 9 for ‘( COOEt~C(OH)(CO~NHPh)~C(OH)(CO~NHPh)~COOEt ” read (‘ COOEt~CH(O~CO~NHPh)~CH(O~CO~NHPh)~COOEt. ” VOL. LXXIV (ABSTR. 1898). PART I. for ‘; Methoxytolualdehyde ” read ( ( Ethoxytolualdehyde.” delete “ whilst the isonieride.” for (‘ :OEt ” ~ y d “ :OMe.” f o r ‘( OEt ” read ‘I OMe.” 1 2 3 3 delete “third. 4 COLLECTIVE INDEX 1893-1902. PART I1 (Subjects). 17 col. ii i7ise~t ( ( Ethoxytolualdehyde (GATTERM ASS AND FBENZEL) 24 i de2ete (‘See also Methyldiphenylamine.” 1898 i 427.” 5 ii for (‘ phenyltoluidine read “ phenyltolylamine.” VOL. LXXXVIII (ABSTR. 1905). PART I. ii} for ‘( arylsulphonates ” read ( ( arylsulphinates.” PART I1 5* 7” 9* 11* 19” for ( ( rice” read “ rye.” VOL.XC (AESTH. 1906). PART I. for ( ( Georg ” read (‘ Wilhelm.” PART 11. 12” fw ‘( the sulphide ” read “iron.” ii ‘::* i} for “ Georg” yead (‘ Wilhelm.” * From bottom.ERRATA (contimed). VOL. XCII (Asa~n. 1907). PART I. Line 1 16 9 for “ 2-Nitroisophthalic acid ” read ‘‘ 2-Nitroisophthalic acid.” “ phenylrhodanic ” rend “ anilinorhodanic.” “ hexahydro-m-toluic acid ” read ‘ l-methylcycEohexane-t2-carboxylic acid. ” Page 137 233 509 1009 1059 1068 1071 1076 44 249 266 275 288 845 406 408 457 474 49 4 590 591 591 652 687 692 765 773 809 810 810 810 811 810 810 810 811 810 PART I1 (INDEX). 19“ col. ii for “ 662 ” read “622.” 10 y y i “Koffler” read “Loffler.” 10“ ) i insert “an attempt to synthfgise collidine A.i 440.” 2 y y ii for “ Maper” rend “Meyer. 10 ,) ii insert “ reversible reactions of tho first order A ii 753.” VOL. XCIV (ABSTR. 1908). 5% 5 19” 8“ ‘‘ 2-Phenylpyrrolidine read “ 2-Yhenylpyrroline.” for “ C,,H,,N,,MeI,HI,H,O ” mad “ C,,H NoMcI,€~I,H~O.” “ C&le2.C0.CMe:CH,” read G g CHMe,*?O%Me:CH,. (‘ diethylaminoethyl )’ ;fad ‘‘ diethylaminopropyl.” 13 14 ‘( 8-~~nyl-l-metltyl-2-quinol~~ie read ‘ ‘ 3 -phen y 2-1 -methy 1-2 -qwino Zone.” 16“ 11“ 21 20” 4 6” 5“ ‘ ‘ KUHN ” read “ KAHN. ,) “GIALDINO ” read “ GIALDINI.” y ‘ 1-isopropylhexane-2-o.lze ’’ reEd (‘ 1-isopropyEcyclohexane-2-o~~e.” “ ROELKEE ” read “ ROLKEH. “ 4-)2itro-4-hyclroxyd~phenyla~~ine” read “ aniinophenylthiocarbamide ” read “ aminophenylcarbamide. ” ,) “ NMe;C6H4*As(OH)*ONa ” rend “ N~~e;C,H?.AsO(OH).ONa.” ‘ ‘ 4 -~iitro-4’-hydroxyd~phenylanLilLe.” lo* y y “HC1,Cl” read “CHClI,.” 20 21 “ crystallising ” read “ t$ sodiiint salt crystallises.” ‘‘ CH,*CO ” “CH;CO g “1899 ” read “ 1889.” 21 I >NH*C,H,(CO&e) read I >NmC,H,(CO,Me) 21” “ TI11 ” read “ XXIX.” 17 delete “ FUNIA.” CH;CO CH,-CO 4 7” for ‘‘ a-BromoisohexyE-8-a~nNzi.nob.utyric acid” read 1s) ‘ ‘ a-Bromoisohexo7JZ-B-amino~z~tyric wid. ” i! } ) “ dE-fenchene ” read “ I)-Z-fenchene.” 1 “ dl-hydroxyfenchenic acid ” read ‘‘ D.E-liydroxyfencheiiic acid.” 6 12” “ dd-fenchene ” read “ Dd-fenchene.” 927 1 2 3 &ouZd read ‘‘ p-Nit~ab~tseneazosaZ~yZ~c acid m. p. 256” ; the constitu- tion is proved by its yielding aminosalicylic acid and p-phenyl- enediamine when reduced by sodium hyposulphite in hot aqueous solution.” 927 13 for “ hydrogen” read ‘‘ hypo-.” * From bottom,ERRATA (co?Ltin?ied) Page Line 927 21 22 j b r ‘( dianiinodiphenyl derivative of csrbamide ” road 927 24 bcjiurt “p-ami~iophenol)~ insert (‘ diazotised.” 927 25 “ aminosalicylic acid ” insert ‘‘ diazotised.” 931 22 for “X” read “XXXIV.” I‘ diaininodiphenglcarbamide derivative.” 1017 19 ,) “not” read “now.” PART 11. 118 19++ “ BATLLIS ” read “ RAYLISS.” 124 21 ‘’ 190 ” rerid “ 1907.’’ 234 12 234 24 9 for ‘‘ GUILLAUME SCHZPFEE ” TcCfd ‘‘ GEORCES SCHiEFFEK.” “ Titration of Formaldehyde ” read ‘‘ Formaldehyde-titration.” 14 15 ) ) “Formaldehyde may be titrated with alkali and phenolphthalein as indicator )’ read (‘ Soreiisen’s so-called ‘ formaldehyde- titration’ (this vol. i 115) may be carried out.” 234 27 “ usual titration ” read ‘‘ formaldehyde-titration.” 393 8” ,) ‘( C. S.” read “G. S.” 421 11* ) ‘‘ J. Lnndw,” read “J cxpcr. Landm.” 422 19” ( ( one inch ” read “nine inches.” 464 16 ,) ‘‘ 517 ” read “ 644.” 719 11“-6” The statement and criticism are irrongly attributed. The state- ment is by Knoop the criticism by Friedmann. 743 2“ for “ 1908 ” read (‘ 1898.” 1058 2” ) “ ALLARET ” ?W6d “ ALLARD.” ” From bottom.

ISSN:0368-1769    

DOI:10.1039/CA908940X007

出版商:RSC    

年代:1908

数据来源: RSC

摘要:

JOURNALS FROM WHICH ABSTRACTS ARE MADE. All references to Journals should give the abbreviated title the year of publication the series the volume 2rntl the page ; thus UCY. 1901 34 2155 ; Bzdl. SOC. chim. 1901 [iii] 25 794; G‘axcttn 1901 31 i 551. ABBREVIATED TITLE. Amcr. Chcnz. J. . . . Anxr. J. Phmm. . . Amer. J. Pliysiol. . . Anier. J. Sci. . . . Ann!. Fis. Quim . Analyst . . . . Annalen . . . Ann. I’hysik . . . Ann. Chin. nnnl. . . Am. Chinz. Phys. . . Ann. Inst. Pasteur . . Ann. sci. U?~iz. J~SS?J . Arch. expt. Patk. Pltnrm. . Arch. Hygiene . . Arch. iV4erland. . . . Arch. Pharnz. . . . Arch. Sci. phys. nut. . Arkiv Kern. Min. Geo7. . Atti R. Accad. Sci. Y’ori?io. Atti E. Accnd. Limci . Bcitr. c h e w . I’l~ysiol. I’nlh. . Ber. . . . . . Bcr. Dmt. hot. Gcs. . . Ber. Deut.pharni. Ges. . BET. Deut. p h p d x 1. Gcs. . * B e d . Zentr. . . . Bio-Chcm J. . . . Biochem Zeitsch. . . 3017. chint. fami. . . Bdl. Acad. roy. Bclg. . Bull. Acad. Sci. CTacozu Bdl. Acad. Sci. St. PCtcn- Bull. Assoc. chim. Sucr. Dist. Bull. Coll. Agr. T6h.1~6 . Wdl. Geol. SOC. Anzer. . Bull. Imp. Imt. . . B.ull. Xoc. chim. . . Bidl. SOC. chim. Bely. . Bull. Xoc. f r m c . Min. . Bull. Xoc. ind. Ndhotsse . Centr. Bakt. Par. . . Centr. Min. . . . bourg. *Chem. Zentr. . . JOURSAL. American Chemical Journal. American Journal of Pharmacy. American Journal of Physiology. American donriial of Science. h a l e s de la Sociedad ISspaT~ola Fisica y Qniniica. The Analyst. Justus Liebig’s Annalen cler Cliemie. Annslen der Pliysik. Azlnales dc Cliiniie anslytique appliqube h l’hdustrie Aniiales tie (‘himie et de Physique.Aniiales de 1’Institut I’nsteur. Annalcs scientitiques de I’Universit6 de Jassy. Archiv fiir esperinientelle Pathologie und Pharmako- Arcliiv fur Hygiene. Arcliir,es Nkerlaudaises des sciences exactes e t natur- Archiv der l’harmazie. Arc1:ivcs cles Sciciicc.s Iihysiqnes et naturellcs. Arkiv fiir Kciiii Mineralogi och Gcologi. Atti dclla Reale Accadeinia delle Scienze d i Torino. Atti della fle:~le Accadeinia dei Lincei. 13eitril.g~ fiir chinisclie Pliysiologie und Pathologie. Berichte der 1)eutschen cheniischen Gesellschaft. Bericlite der I>eutschen botanischen Gesellscliaft. Bericlite der Dcutsclien pliarm~tzeutischen Gesellschaft. Bericlite der Dentsclien physikalischen Gesellschaft. Biedermann’s Zentralblatt fur Agriknltnrehemie und The Eio-Chemical Journal.Biochcniisclie Zeitschrift. Rollettino cliiinico farrnacentico. AcadBniie royale de Belgiquc-Bulletin de la Classe Eiilletin intcriiational de 1’AcadQmie des Sciences de 13111Ietin tle l’dcaclbmie Impbriale des Sciences de St. Bulletin de I’Association des cliiniistes cie Sucrerie e t Bulletin of the College of Agriculture Imperial Uni- Bulletin of the Geological Society of America. Bulletin of the Imperial Institnte. Bulletin de la Socikt6 cliiniique tle France. Bulletin tle la Socidt6 cliimique de Belgique. Bullet.in de la Focikt6 francaise de RliiiBralogie. Bulletin de la 8oci6ti. iiidustrielle dc lliilhouse. Centrdblatt fur Uakteriologie Parasitenkunde und Centralblatt fiir 11 incrnlogie Geologie und Palaeonto- Cliemisches Zentralblatt.h l’ilgiculture i la I’harniacie et j la Biologie. logie. elles. rationellen L:n~d~~iirtsch;tfts-Beti~ieb. des Sciences. Cracovie. 1’Ctersbonrg. de Distillerie. versity T6ky6. Iiifektionslcranklieiten. logie. * Abstracts from the Z c ~ ~ t m l b l a l t are made only i i i the case of papers puldislied in journals other than those iiicluded i l l this 1;sI.JOURNALS FROM WHICH ABSTRACTS ARE MADE. ABBBEVIATED TITLE. JOIJRNAL. Chenz. iVews . . . Chemical News. Ch,em. Rev. Fett-Harz-Id. Chemische Revue uber die Fett- uiid Harz-Industrie. Chein. Weekblacl . . Chemisch Weekblad. Chem. Zeit. . . . Cheniiker Zeitung. Conapt. rend. . . . Comptes rendus hebdomadaires des Skances de Exper. Stat. Record . . Experiment Station Record.Gazzetta . . . . . Gazzetta chimica italiana. Geol. Mag. . . . . Geological Magazine. Jahrb. illin. . . . Neues Jahrbuch fur Minerdogie Geologie und Pal- Jahrb. Min. BeiZ,-Bd. Neues Jahrbuch f i r Minerdogie Geologie und Pal- Jahrb. Radionktiv. Elektro- Jahrbuch der Radioaktivitat und Elektronik. J. Avzer. CJLem. Soc. . . Journal of the American Chemical Society. J. Biol. C‘hem. . . . Journal of Biological Chemistry New York. J. Chinz. phys. . . . Journal de Chimie physique. J. GeoZ. . . . Journal of Geology. J. Zyqiene . . . Journal of 1 l ygiene. J. Inst. Erezvi~zg . . Journal of the Institute of Brewing. J. Landw. . . . . Journal fur Landwirtschaft. J. Ned. Research . . Jouriial of Medical Re5earch. J. Path. Bact. . . . Journal of Pathology and Bacteriology.J. Phnrm. Chinz. . . Journal de Pharmacie et de Chiniie. J. Physical Chenz. . . Jourml of Physical Chemirtrp. J. Physiol. . . Journal of Physiology. J. Physique . . . Journal de Physique. J. pr. Cheaz. . . . Journal fiir praktische Cheniie. J. Roy. Ayric. SOC. . . Journal of the Royal Agricultural Society. J. Roy. Sac. New South Journal of the Royal Society of Xew South Wales. J. Russ. Phys. CJwn. Soe. . Jouriial of the Physics1 and Chemical Society of J. SOC. Chem h i d . . . Journal of the Society of Chemical Industry. J. SOC. D ~ I T S . K. Sveuska Yet- A i d . Eiaizdl. Lawcet. . . . . The Lancet. Land,w. Yerswchs-Xtnt. . Die lniid~~irtscliaftlichen Versuclis-Stxtionen. illem. dccnd. h‘ci. Torino . hlemoiie della Jiealc Accadeiiiia delle Scienze di Torino Mein.Coil. Sci. B t g . KyGt6. Memoirs of the College of Science and Engineering Iiy6t6 Imperial University. Mem. Jlanchestcr Phil SOL Xemoirs and l’roceedings of the Manchester Literary aiid I’hilosophical Society. Metallurgie . . . Metallurgie. Nilch. Zcntr . . . Milchwii tschaftliches Zen tralblatt. Min. Mug. . . . . 3lincralogicnl Magazine and Journal of the Mineral- ogical Society. Mowatsh. . . . . lfonatshefte fur Chemie nnd verwandto Theile anderer Wissenschaften. NZLOVO Cim. . . . I1 Nuovo Cimanto. PJuger’s Archiv . . . Archiv fur die gesammte Physiologie des Menschen ~uid der Thiere. Pharnz. J. . . . . Phariiiacenrical Journal. Pharm. Rev. . . . Pharmaceutical Review. Pharm. Weekblad . . Pharmaceutisch Weekblad. Plbai-rn. Zeit. . . . Pharmazeutische Zeitung.Pharm. Zentr-Jz. . . Pharmazeutische Zentralhalle. Philippine J. Xci. . . Philippine Journal of Science. Phil. Nag. . . . Philosophical Magazine (The London Edinburgh and l’ilcadhmie des Sciences. aeontologie. aeontologie. Beilage-Band. . nik. Wales. Russia. Journal of the Society of Dyers and Colourists. Iioiigl. Svenska Vetenskaps-Alrademieiis Handlingar. Dublin).JOURNALS FROM WHICH ABSTRACTS ARE MADE. ABBREVIATED TITLE. Phil. Truns. . . P?tysikaZ. Zcitsch. . . Proc. Anaer. Physio7. Soc. . Proc. Cuntb. Phil. Soe. . Proc. K. Aknd. Wetcrzsch. Yroc. P l d . SOC. Glasgozu . Proc. PlLysiol. Soc. . . Proc. Hoy. Soc. . . . Proc. Boy. Soc. Edin. . Quart. J. my. P?qsiol. . Qzmrt. J. Geol. Soc. . Rcc. trar. chinz. . . A.msterdanz. Ilend. dccnd. Sci. FIS. drat.Xev. de JI&?aZlurgie . . Xec. intern. Falsif. . . Sci. Proc. 1Zoy. BzLhl. SOC. . Sci. Trans. Loy. Dubl. SOC. Xitzzc?tysbcr. K. ,4 kad. Wiss. Sitzungsber. K. Akacl. Nun- Trans. Amcr. Electrochcm . Tram. Amcr. Inst. iVining l ' m u s . Fat-aday SOC. . . 2'rcLns. Noca Scolia Inst. Trnns. Path. Soe. . . Trans. IZoy. SOC. CaiincEa . Tram. Koy. Sos'oc. Edin. . Trwns. Iloy. I ~ i s h Acad. . Tsch. A h . Mitt. . . U.8. A. Dcpt. Agric. Bull. . U.S.B. Gept. Ayric. Xcp. . Verh. Ges. dcut. iI-alurfo.rscii. IJ-iss. Abltniid. Phys. - Tech. hTnpoli. L'edin. chen. SOC. Eng. sci. Aerztc Rcic?1snnstalt. Z; itsch . Zeitsch. Zeitsch. Zeitsch. Zdsch. Zeitsch. Zcilsch. ze itsch. Zeitseh. Zeitsch. Zeitseh. anal. Chcnz. . . angcw. Chcm. anory. C'hena . . Biol. . . . Chcm. I n d .KolZoidc. Elektrochcnz. . . Farb.-Ind. . . Kryst. illin. . . Nahr. Genussm. . ofentl. Chew. . . p h zis ika 1. Ch em. . JOURNAL. Philosophical Transactions of the Royal Society of Physikalische Zeitschrift. Proceedings of the American Physiological Society. Pruceedings of the Cambridge Philosophical Society. Koninklijke Akademie van Wetenschappen te Amster- Proceedings of the Glasgow Philosophical Society. Proceediiigs of the Physiological Societ,y. Proceedings of the Royal Society. Proceedings of the Royal Society of Edinburgh. Quarterly Journal of experimental Physiology. Quarterly Journal of the Geological Society. Receuil cles travaux chimiques des Pays-Bas e t de la Rendiconto dell' Accademia delle Scienze Fisiche e Revue de M6tallurgie. Revue int crnation ale des Falsifications.Scientific I'roceedings of the Royal Dublin Society. Scientific Transactions of the Royal Dublin Society. Sitzungsberichte cler KoIiiglich Preussischen Akaderiiie Sitzungsberichte der koiiiglich bayerischen Akaclemie Transactions of the American Electrochemical Society. Transactions of the American Institute of hiiniiig Transactions of t.he Fnraday Society. Transactions of the Nova Scotia Institute of Science. London. dam. Proceedings (English version). Belgique. Matematiche-Napoli. der Wissensthaften zii Berlin. der Wissenschaften 211 BIiinclien. Engineers. Transactions of the Pathological Society. Transactions of the Royal Society of Canada. Transactions of the Koyal Society of Edinburgh. Transactions of' the Royal Irish Academy. Tscheimak's hlineralogische blitteilnngen.Bulletins of thc Department of Agriculture U. S. A. Reports of the Deliartnient of Agriculture U.S.A. Verhandluiig der Gesellschaft deutscher Naturforscher und Aerzte. Wissenschaftliche Abhandlungen der Physikalisch- Tecliiiischen Reichsanstalt. Zeitschrift fiii. aiidytisclie Cht*mic. Zeitschrift fiir angewandte Chemie. Zeitschrift fur auorgaiiische Cheinie. Zeitschrift fiir Biologic. Zeitschrift fiir Chemie uiid Iiidustrie der Xolloide. Zeitschrift t'iir Elektrochcniie. Zei tsch rift f iir Farben- I udiis trie. Zeitschrift fiir Krystallographie uncl Nineralogie. Zeitschrift fur Untersucliung der Kalirurigs- und Zeitschrift fur ijfientliche Cliemie. Zeitschrift fiir Dhvsikalische Chcmie Stijchiometrie Geiiussmit tel. . " und Verwanht~chnftslt.hre. Zeitsch. physiol. Chcm. . Iloppe-Seyler's Zeitschrift fiir physiologische Chemie. Zeitsch. prakt. Geol. . . Zeitschrift fur praktischc Geologie. Zeitsch. Vw. deut. Zzdccrind. Zeitschrift des Vereins der deutschen Zucker-Industrie Zeilsch. zc-iss. Photograph. Zeitschrift fiir wissenschaftliche Photographie Photo- Photophysik. Photochem. . Zeitsch. Zuckekd. Bohm. . Zeitschrift fur Zuckerindustrie i n Bohmen. physik und Photocheniie.

ISSN:0368-1769    

DOI:10.1039/CA908940X010

出版商:RSC    

年代:1908

数据来源: RSC

摘要:

I NO RG Ll N I C C H E M IS TRY. 31 Inorganic Chemistry. The Development of Inorganic Chemistry in the last Forty Years. HANS LANDOLT (Ber. 1907 40 4627-4637).-A lecture delivered before the German Chemical Society. Activity of the Halogens Chlorine Bromine and Iodine in Relation to,Mercury. M. C. SCIIUYTEN (Shem. Zeit. 1907 31 1135. Compare Abstr. 1896 ii 524).-Even in the presence of an excess of the salt the halogen in mercuric chloride bromide or iodide may be replaced by either of the other halogens tha only exception being the action of iodine on mercuric bromide; in this case no bromine is displaced by the iodine. New Polymorphous Form of Iodine. W. A. I~URBATOFF (Zeitsch. anorg. Chem. 1907 56 230-232).-When solutions of iodine in various solvents are evaporated to crystsllisation the element separates either as rhombic plates or as dendritic aggregates.The separation of a definite crystalline form does not depend on the colour of the solution but on the temperature the common rhombic crystals being obtained at the higher temperatures. The trimsition temperature could not be determined by the usual thermal method as there was no break i n the cooling curve of iodine from 100-O' but mas established approximately by condensation on a glass surface kept at different temperatures ; below 46-47' the dendritic crystals mere obtained a t Action of Iodine on some Elements in Vacuum. MARCEL GUICHARD (Conapt. rend. 1907 145 807-808).-When a tube con- taining iron wire and iodine separated by an asbestos plug is evacuated sealed and heated in such a manner that the iron is kept a t 500' and the iodine a t 180° ferrous iodide is formed and sublimes in the form of deep red crystals.Uranium and nickel also form iodides under similar conditions the former as dark grey lamellie. In the case of very volatile iodides such as those of aluminium and silicon it is necessary to keep the three portions of the tube (bent so that the middle portion is horizontal and the others pointing slightly down- wards) a t three different temperatures the icdine a t one end at 180° the metal in the middle at 500" and t8he otiicr eud (to receive the W. H. Q. W. H. G. higher temperatures the rhombic modification. (3 s.32 AUSl'ItACTS OF CHEMICAL PAPEILS. iodide) a t 15". the iodine vapour and retards the action.Otherwise the iodide formed remains mixed with E. H. Amorphous Sulphur. V. The System Sulphur-Iodine. ALEXANDER SMITH and CHARLES I\I. CARSON (Zeitsch. physikal. Chena. 1907 61 200-208. Compare Abstr. 1906 ii 157; 1907 ii 20)- The proportion of 8 in the equilibrium mixture of X h and Sy a t a given temperature is raised by the addition of iodine. Thus at 150' and in the absence of iodine the percentage of S in the equilibrium mixture is 6.7 ; when one part of iodine is present per one hundred parts of sulphur the percentage of S is 12.26; when five parts of iodine are present per one hundred parts of sulphur the percentage of 8 is 17-86. The effect of the presence of two parts of iodine per one hundred parts of sulphur at different temperatures is shown in the following table Temperature ..............................150' 165' 220' 310' 448' ...... 6.7 14.0 29.4 32.6 34.1 with iodine ............ 13.8 24.1 47.0 54.2 62.7 insoluble sulphur A study of the freezing points of mixtures of sulphur and iodine shows t h a t neither compounds nor solid solutions are formed (compare Boulouch Abstr. 1903 ii 538). The authors reply to Hoffmann and Rothe (Abstr. 1907 ii 539). J. C. P. Electro-Syntheses. SIMA M. LOSANITSCH (Ber. 1907 40 4656-4666).-An investigation of the behaviour of various substances i n a gaseous form both when alone and mixed together under the influence of a silent electric discharge. The apparatus and method employed have been described (Abstr. 1897 i 179). Sulphur dioxide is converted into sulphur trioxide with liberation of sulphur; in the presence of hydrogen or hydrogen sulphide water is formed and sulphur liberated.Nitric oxide yields nitrogen and nitrogen peroxide; when mixed with hydrogen i t is reduced to nitrogen the latter interacting with the water formed yielding ammonium nitrite. A mixture of nitric oxide and hydrogen sulphide yields an aqueous solution of ammonium polysulphide. Carbon disulphide vapour is converted into a polymeride (CS2)l an almost black substance which decomposes into its components when strongly heated. A mixture of carbon disulphide and hydrogen or hydrogen sulphide yields a brown substance C H2S previously inaccurately described as a polymeride of carbon monosulphide (CS) (Zoc. cit.) and by Berthelot (Abstr. 1899 i 657) as a substance having the composition C2H2S,. Carbon disulphide yields with carbon mon- oxide a brown insoluble substance 3CS2,2C0 ; with ethylene a brownish-yellow insoluble substance 5CS2,2G,H ; with acetylene an almost black insoluble substance 3CS,12C2H2.Acetylene alone is converted into a viscid or solid mass containing (1) a fragrant viscid swbstance soluble in alcohol and ether which rapidly absorbs oxygen from the air forming a s u b s t a ~ ~ c e (3C,H,,C,H,,O) ;INORGANIC CHEMISTRY. 33 (2) an insoluble substccnce C4?H, yellowish-brown by reflected and yellowish-red by transmitted light having an empyreumatic odour ; i t absorbs oxygen forming the substance C,,H,608. These acetylene condensation products decompose a t 100' ; they also evolve an emana- tion which liberates iodine from potassium iodide and produces a reducing action through aluminium or gold leaf on a photographic plate ; the emanation is not a radioactive emanation the action pro- duced being probably due to absorbed oxygen present in a labile state.The same substances are produced together with polymerised acet- aldehyde when water is present with the acetylene. Equal volumes of acetylene and hydrogen or methane give a clear yellow product contain- ing a viscid liquid soluble in ether and an insoluble solid of the formulzle C,Hl9 and C,H respectively. Equal volumes of acetylene and ethyl- ene yield (1) a substance C,H,,C,H obtrtined as a red viscid fragrant liquid ; (2) a solid substance 3C,H2,C,H insoluble in all solvents and decomposing when heated.Equal volumes of acetylene and hydrogen sulphide yield (1) a yellow substance C,H,,S soluble in ether ; (2) a yellow substance Cl,Hi4S insoluble in ether. Acetylene with carbon monoxide yields a yellowish-brown insoluble substance which absorbs oxygen rapidly forming a substance 4C2H,,co,0,. Equal volumes of acetylene and sulphur dioxide condense with the formation of a dark brown insoluble substance O,II,OS. Ethylene is converted into a yellowish-red oily substance soluble in alcohol ; it absorbs oxygen forming a viscid substance (Gl,H,?O)2. Equal volumes of ethylene and methane yield a clear yellow viscid liquid which absorbs oxygen forming a viscid substance C,,H,,O,. Ethylene and hydrogen sulphide yield a substance (C2H4S)6 obtained as a viscid yellowish-red liquid It is probable that ethyl mercaptan is first formed since this compound yields the same substance under the influence of a silent discharge.Ethylene and carbon monoxide yield (1) a substance (2C,H,,CO) obtained as a yellowish-red viscid liquid soluble in ether &c. ; (2) an insoluble szcbstnnce (2C,H,,CO),. W. H. G. Atomic Weight of Tellurium. WILLY MARCKWALD (Bey. 1907 40 4730-4738).-hlthough both Staudenmaier and Bfyliixs had drawn the conclusion from a series of fractional crystallisations that telluric acid is a uniform substance these authors had not sufficiently considered the possibility of their having dealt with an isomorphous mixture which could be separated only by a systematic method of crystallisation. The author accordingly examined about 1500 grams of telluric acid from the latter standpoint and after several hundred crystallisations obtained twenty fractions of about equal weights ; between the first and last fractions there was not however t h e slightest difference.There is no doubt as to the uniformity of tellurium For the determination of the atomic weight of tellurium the author has modified the method of Staudenmaier namely the conversion of telluric acid into tellurium dioxide (Abstr. 1896 ii 97). Crude tellurium obtained from the Selmeczbanya mines was converted into dioxide and separated from copper lead silver Src. VOL. XCIV. ii. 334 ABSTRACTS OF CHEMICAL PAPERS. The dioxide was then oxidised to telluric acid by means of chromic acid and submitted t o a prolonged series of crystallisations from water.The telluric acid used in the doterminations was dried over phosphoric oxide in a vacuum. It is worthy of note that when telluric acid is exposed over phosphoric oxide for two months in a vacuum it remains practically constant in weight. The method is based on the action as represented by the equation H,TsO = TeO + 0 + 3H,O. The heating was conducted in a platinum vessel by means of a n electrical oven the temperature at the bottom of the vessel being measured through a Le Chatelier clement by means of a millivolt meter. The temperature a t the top of tho platinum vessel was maintained lower than that at the bottom in order to guard against volatilimtion of the dioxide The temperature was gradually raised in the course of two to three hours from 100" to 160" and then gradually in the course of three to four hours more to 650° which temperature was maintained for another hour.The residue was always white and quite free from the trioxide. The weight did not alter on further heating for one hour. The various precautions taken are indicated. As R mean of six experiments the value 126*85( +,0*02) was obtained on the basis of 0 = 16 and H = 1.005. This valuo is lower tlian that of iodine (I= 136.97). LEON EEUNEL and PAUL Wooc (Conxpt. s*end. 1907 145 922-924. Compare Woltereck Abstr. 1904 ii 115).-Attempts to effect the synthesis of ammonia by passing a mixture of pure hydrogen (3 vols.) and nitrogen (1 vol.) over a mixture of thorium and cerium oxides pulladinised pumice quicklime soda lime calcium chloride cltlciurn molybdate anhydrous barium or strontium oxide manganese dioxide aluminium phosphate or magnesium phosphate a t 15' to 350° were unsuccessful. The gaseous mixture reacts with nickel sesqiii- oxide at 180" t o 200' to form water and a trace of ammonia but the reaction is fugitive.If however a mixture of air and excess of hydrogen is passed over heated nickel sesquioxide the latter is alternately reduced and reoxidised and the energy liberated by the reactions causes the formation of small quantities of ammonia ; the reaction is continuous provided that the nickel oxide is not allowed to become incandescent owing to the heat of the reaction. Thisis effected by suspending the tube containing the nickel oxide in a bath of petroleum b. p. 200-240".Boiling Point of Liquid Ammonia. EDWARD C. FIXANULIN (Ann. Ply& 1907 [iv] 24 367-369).-R critical review of the determinations made by de Porcrand (AWL Chiin. Phys. 1903 [vii] 28 537) Gibbs (Abstr. 1905 ii 670) Yerman and Davies (Abstr. 1906 ii 743) and Brill (Abstr. 1906 ii 847) leads the author to the conclusion that Gibbs' value ( - 33.46') is probably correct to within 0-1". J. C. 1'. Formation of Nitric Oxide in High Tension Arcs. FRITZ HABEE and ADOLF KOENIG (Zeitsch. EZekti-ocitem. 1907 13 725-743). -An alt ernsting current ~7as passed through mixtures of oxygen and A . McK. Catalytic Synthesis of Ammonia from its Elements. M. A. W.INORGANIC CHEMISTRY. 35 nitrogen under pressures varying from about 40 mm. to 200 mm. Electrodes of platinum oxidised iron and Nernst glowers were used The gas mas passed through water-cooled tubes of hard glass or quartz of 5 to 7 mm.bore along the axis of which the discharge passed. A t the lower pressures the whole mass of gas in the tube glowed with a pink light with the exception of a thin film next to the wall of the tube; at the higher pressures the glowing coIumn of gas tended to contract further from the walls. The best results are obtained when the gas does not flow over the electrodes and when the latter are very hot. Electrodes of iron or Nernst filaments give the best results. The percentage of nitric oxide in the gas increases with the current up to a maximum which is not affected by further increase of current. The greatest concentration of nitric oxide is obtained with gas a t 100 mm.pressure The maximum percentage of nitric oxide obtained with each mixture was (at 100 mm.) Percentage of oxygen in mixture 20.9 48.9 44.4 75.0 81.7 Pencentage of nitric oxide ...... 9.8 14.4 14.3 12.77 12.1 Assuming that the formation of nitric oxide is a purely thermal phenomenon and using Nernst's determinations of the equilibrium concentrations these results indicate that the temperature oE the gas in the path of the arc was between 4300' and 5000O absolute. From the thickness of the non-luminous film of gas between the luminous gas and the walls of the vessel the authors calculate that the temperature of the hot gas could not have exceeded 3000'; further the rate of cooling of the gas was smaII so that nitric oxide formed by very high temperature alone would probably have been decomposed.The authors incline rather to believe that the temperature was low and the high percentage of nitric oxide found was produced by collisions of electrons ; owing to the low temperature the nitric oxide thus formed escaped decomposition which is not the case in the hotter flames produced in gases under atmospheric pressure. Non-existence of a Common Solvent for White and Red Phosphorus. ALBERT COLSON (Compt. rend. 1907 145 11 67-1 168).-Schroetter stated that red phosphorus is soluble in oil of turpentine; this statement has been contested and the author shows that pure red phosphorus does not dissolve in oil of turpentine or in the polymerised products obtained by the action of heat on the solvent even when heated a t 270' in n sealed tube provided that air is excluded.Further red phosphorus is not altered when heated a t 275-285O in a sealed tube containing a solution of phosphorus in turpentine. There exists moreover no common solvent for white and red phos phorus for Lemoine has shown t h a t the two varieties have the same vapour density corresponding with the molecule P ; according to van't Hoff's hypothesis therefore the two varieties mould become identical in a common solvent. Action of Hydrogen Phosphide on Mercuric Chloride or Bromide PHg,CI and P,Hg,Br,. PAUL LEnrouLT (Compt. rend. T. E M. A. w. 1907 145 1175-1177) -H. R O F ~ (YOYY. A I Z ~ ~ . 1837 40 75 87h 3-. 236 ABSTRACTS OF CHEMICAL PAPERS obtained a yellow amorphous compound PHg,CI 1 &€120 by the action of hydrogen phosphide on mercuric chloride and an analogous compound of a bromn colour when mercuric bromide replaced the mercuric chloride.The author finds however that mercuric chloride gives with hydrogen phosphide t,he anhydrous compound PHg,C! whereas mercuric bromide forms the compound P2Hg5Br4 according t o the equations f . PII + SHgCl = 3HC1+ PHg3C13 ; 11. 2PH3 + 5HgBr2 = 6HBr + P,Hg,Br4. The presence of excess of hydrogen phosphide even locally as when the gas is bubbled through a solution of the mercuric halide leads to a reduction of the salt with liberation of mercury and the best results are obtained when an aqueous solution of hydrogen phosphide is carefully poured on to the surface of a concentrated solution of the mercuric halide and the cowesponding potassium salt and the mixture suddenly shaken; the precipitate thus obtained is uniform in colour and of constant composition.M. A. W. Action of Arsine on Solutions of some Metallic Salts. HANS RECKLEBEN GEORG LOCKEMANN and ALFRED ECKARDT (Zeitsch. anal. Chenz. 1907 46 671-709).-Arsine is absorbed rapidly and completely by silver nitrate solution but slowly by mercury copper lead tin and iron salt solutions ; the latter solutions are useless for the quantitative absorption of arsine. The reaction with silver nitrate solution does not take place exactly according to Lassaigne's equation ASH + GAgNO,+ 3H,O = H3As03 + 6Ag + 6HNO but in part ac- cording to the equation ASH + 3AgN0 = Ag,As + 3HN0,. The silver arsenide is not very stable in the presence of the nitric acid and further action takes place Ag3As + 3AgN0 + 3H20 = H,AsO + 6Ag + SHNO,.I n dilute ammoniacal silver nitrate solution three reactions take place consecutively or simultaneously (a) As f3 t- S(AgNK,)NO = Ag3As + 3NH4N03 ( b ) Ag,As + 3(AgNH,)NO + EH,OH + H,O = NH,AsO + 6Ag + SNHI,N03 and (c) NH,AsO + 3(AgNH3)N0 + 8NH40H = (NH,),AsO + 2Ag + 2NH4N0,. Metallic arsenic when warmed with ammoniacal silver nitrate solution is oxidiaed thus As + 5(AgNH,)NO + 3NH40H + II,O = (NH,),AsO + 5Ag + 5NH,NO,. I n ammoniacal solution and in the presence of air srsine is readily oxidised. T t is also mentioned in the paper that finely-divided silver is not attacked by 6.3% nitric acid within four hours at the ordinary temperaturo and N/10 nitric acid is only very slowly reduced a t the ordinary temperature by arsenious acid.w. P. x. Compounds of Arsenic Sulphates with Potassium Calcium and Lead Sulphates. HUGO KUHL (Arch. Pltccrm. 1907 245 377-379).-The crystalline compounds 2K20 As20,,4SO CaO As,0,,3S03 PbO,As,O,,%SO were obtained by dissolving arsenious oxide and potassium calcium or lead sulphate in concentrated sulphuric acid and driving off sulphuric acid by heating ; with strontium and barium sulpbrttes similar compounds could not be obtained. C. F. B.INORGANIC CHEMISTRY 37 Identity of Graphite and ‘ I Temper ” Graphitic Carbon in Cast Irons. GEORGES CHARPY (Compt. rend. 1907,145,1173-1 174). -It was stated by Forquignon and Ledebur that the carbon (graphite) contained in cast iron that has been cooled gradually differs from the carbon (“ temper ” carbon) that separates in rapidly-cooled cast iron in that the latter is volatile and the former non-volatile when a stream of hydrogen or nitrogen is passed over the red-hot cast iron.Wust and Geiger find however (Abstr. 1006 ii SS) that pure hydrogen o r nitrogen is without action on “temper ” carbon or on graphite. The author has therefore examined the chemical behaviour of the free carbon obtained from two portions of cast iron one of which had been gradually the other rapidly cooled and the results show that graphite and the so-called ‘ I temper ” carbon are identical both with regard to the velocity with which they are oxidised to graphiticacid and to the rate at which they are completely eliminated in the gaseous form when a stream of pure hydrogen is passed over the cast iron a t 1000”.151. A. W. Solubility of Potassium Iodide in Water and of Water in Potassium Iodide at Low Temperatures. ROBERT KREMANN and F. KERSCIIBAUM (Zeitsch. nnorg. Chem. 1907 56 218-222).- Meusser (Abstr. 1905 ii 317) has recently determined the complete solubility curves for water with potassium chloride and bromide respectively and found no evidence of the formation of hydrates but in the case of water and potassium iodide there was a break in the observations from 42.7% to 53.5% of the salt the eutectic point being determined by extrapolation. The authors have now determined the complete curve including observations within the limits indicaked and find no evidence of chemical combination ; the eutectic point lies at - 23*1° the mixture containing 52.2% by weight of potassium iodide.G. S. Waterglass. VI. JOHN 81. ORDWAY (Amer. J. Sci. 1907 [iv] 24 473-478).-1n a.n earlier paper (Amer. J. Sci. 1865 40 190) it has been shown that when alcohol is added to solutions of sodium and potassium silicates basic silicates are precipitated. On mixing strong solutions of sodium silicate and lithium chloride precipitates are produced containing varying quantities of lithium and sodium silicates. By re-dissolving these precipitates and adding lithium chloride to the solutions the proportion of lithium in the product can be gradually increased but pure lithium silicate cannot be obtained in this manner. When however freshly-prepared silica is digested with lithium hydroxide solution a t the ordinary temperature a solution of lithium silicate Li,SiO is produced.On heating this solution a precipitate is produced which re-dissolves on cooling. Soluble rubidium silicates can be obtained of composition varying from Rb,O,SiOz to 2Rbz0,9Si0,. I n the case of the lithium silicates the range is not so great. When ammonia is added to a solution of a silicate containing a large proportion of silicic acid a precipitate is usually produced. E. G.38 A13S'rRACTS OF CHEMICAL PAPERS. Ammonium Amalgam. G . MCPIJAIJ SMITH (Bey. 1907 40 4893. Compare Abstr. 1907 ii 615).-A reply to the criticisms of Tra,vers (Abstr. 1907 ii 865). It is argued that ammonium amslgam is completely analogous t o sodium and potassium amalgams which a,re regarded as solutions of NaHg or IiEig in mercury.E. F. A. Amalgams. The Hydrargyrides of the Alkali and Alkaline Earth Metals. G. McPIrArL SMITII (Anzer. Chena. J. 1907 38 671-683).-F~irther evidence in favour of the views expressed regarding the nature of amalgams in previous papers (Abstr. 1905 ii 164 450; 1906 ii 6 7 3 ; 1907 ii 462 463 615) is brought forward and it is shown that unlike the amalgams of the alkaline earth metals those of the common alkali metals do not increase in stability with increase in the atomic weight of the alkali metal used (the order of stability being Li K Na). The amalgams used were liquid and were prepared by electrolysing a solution of the chloride of the appropriate metal in presence of mercury. The relative stabilities of the amalgams were tested (I) by the rate of decomposition on exposure to air (2) by the capacity for decomposing water (3) by the rapidity with which they were decom- posed by ammonia solution and (4) by the composition of the equilibrium amalgam obtained when the amalgam under investigation was acted on by an aqueous solution of sodium chloride and the chloride of its own metal.By all four methods of investigation i t was found that the relative stabilities of the amalgams examined increased in the following order K Rb Cs. The mercury compound of lithium i s the least stable i n the alkali metal group ~vhilst that pf sodium is the most stable. Sodium amalgam also behaves in an exceptional manner ; thus on exposure t o air no sodium peroxide is formed whereas the corresponding peroxide is formed in each case when an amalgam of potassium rubidium or cesium is exposed to air.The metals of the pairs Cs,Na and Rb,Na are like most of the other metals of the alkali and alkaline earth groups reversibly displaceable in aqueous solution in presence of mercury. T. A. H. Artificial Reproduction of Barytes Celestine and Anglesite and Isomorphous Mixtures of these Substances. PAUL GAURERT (Cowipt. rend. 1907 145 877-879).-Behren's micro- chemical reaction for the detection of certain metals (Abstr. 1886 917; 1891 766) gives confused results in the cases of barium and strontium. By a modification of the method the author has obtained crystals of the sulphates of barium strontium lead or calcium similar to those of the natural minerals and of such dimensions that the optic axial angles which are characteristic for each substance could be measured.The method consists in evaporating to dryness 100 C.C. of a saturated sulphuric acid solution of the metallic sulphate a t the boiling point or a t n slightly lower temperature and in the case of barium or strontium sulphate the crystals thus obtained were sufficiently large to admit of gouiometrical measurement. MixedINORGANTC CIIEMISTRY. 39 crystals of barium and strontium sulphate or of either of theso sulphates with that of lead were prepared similarly. Calcium sulphate not being isomorphous with the preceding sulphates does not form with them mixed crystals although the crystal forms of these sulphates are modified by the presence of calcium sulphate in the solution.M. A. W. Colloidal and Gelatinous Calcium and Magnesium Com- pounds. A kad. miss. Bedin 1907 620-822. Compare Neuberg and Neimann Abstr. 1906 ii 753).-Calcium sulphate calcium phosphate and calcium oxalate are precipitated in a gelatinous form when sulphuric acid phosphoric acid and oxalic acid respectively are added t o a methyl- alcoholic solution of calcium oxide. The clear viscous colloidd solution of calcium carbonate obtained by passing a stream of carbon dioxide into a methyl-alcoholic solution of calcium oxide may be evaporated without undergoing decomposition to a thick liquid which sets t o a jelly. If a current of carbon d.ioxide is passed into a suspension of calcium oxide in methyl alcohol the liquid after about five to six hours is transformed into a solid jelly which dissolves slowly in methyl alcohol.The colloidal calcium carbonate is miscible with several organic solvents for example benzene chloroform aud ether. Analogous colloidal magnesium compounds may be similarly prepared from a methyl-alcoholic solution of magnesia. Analysis of the isolated gelatinms salts (sulphate phosphate and oxalate) ofAcalcinm and magnefiium showed that they did not contain combined methyl alcohol. CARL NEUBERG [and in part 13. REJvALD] (Sitxungs6ei.. W. H. G. The Autoreduction of some Metallic Oxides in the Vacuum of the Cathode Light and on the Volatility of the Corrs- sponding Sulphides. . F. DAMM and FRrEDRrCH KRAFFT (BOY. 1907 40 4775-4778).-The behaviour of oxides when heated is sometimes quite otherwise in a vacuum than under ordinary pressure.Thus cadmium oxide a t 1000' decomposes into oxygen and cadmium whereas in air it is completely stable. The experiments were carried out in quartz tubes heated in a Heraeus electric oven At 750° lead oxide gives a metallic mirror and bismuth oxide decomposes slowly at 650". Antimony oxide volatile a t about TOOo is not completely de- composed a t 1050O. It is conjectured that tho autoreduction of the common metals may proceed in stages like that of antimony oon- sisting (1) of simultaneous oxidation and reduction and (2) conversion of a higher oxide into a lower. The sulphides are more volatile than the corresponding oxides cinnabar sublimes at 400" and cadmium sulphide very quickly at 770-780' whereas lead sulphide volatilises at 600' ; the sulphides of bismuth antimony and arsenic sublime a t 740° 530° and 230" in the vacuum of the cathode light T t is possible to separate by distiIIation mixtures of arsenic and 4Sb,06 = 3Sb,08 + 4Sb,,40 ABSTRACTS OF CHEillICAL PAPERS.antimony sulphides or mercury and lead sulphidcs under those con- ditions as well as sulphur selenium and tellurium. The suphides of copper tin and silver are decomposed; the first two lose half their sulphur content and the last is converted into metal and sulphur. W. R. Solubility of Certain Lead Compounds in Water. MAX PLEISSNER (Clzem. Zenir. 1907 ii 1055-1056 ; from Arb. Kais. G'esundh.-Amt F1907 26 384-443).-This investigation was under- taken in connexion with the risk of contamination of water supplies by lead.Lead oxide and hydroxide and the normal and basic carbonates sulphates and chlorides have been studied. When hot solutions of lead salts are treated with alkali hydroxides lead oxide PbO is precipitated whilst from cold solutions hydrated oxides separate. The lead oxide forms greyish-yellow scales with a metallic lustre and gives a greenish-yellow powder. The same oxide is produced by the action of water containing much dissolved oxygen on lead whilst by thb action of water containing but little oxygen the hydrates are formed. A hydrate Pb,02(OH)2 has been identified but higher hydrates probably exist the solubility increasing with the degree of hydration. The oxide and its hydrates appear t o dissociate thus Pb(OH) Pb(0H)' +OH' the degree of dissociation in a solution saturated at 18" amounting to about 25%.The solubility of lead sulphate and chloride in water is diminished by the presence of sulphuric or hydrochloric acid whilst that of the carbonate is increased by the presence of carbonic acid. The following basic lead salts have been obtained and their individuality established by application of the phase rule. &-Basic lead carbonate Pb0,2PbC0,,H20 ; $-basic lead sulphate and chloride PbO,PbSO and P b0,PbC12,H,0 ; $-basic lead sulphate and chloride 3Pb0,PbS0,,H20 and SPbO,PbCI,,H,O. These salts are less soluble in water than the corresponding normal salts. The solubility (millimols. P b per litre) and the specific conductivity of the saturated solutions after deducting the value for the conductivity of the water are as follows a t 1 8 O PbO Pb,O,(OH) PbCO Pb,(CO,),( OH) PbSO Solubility ......0.31 0.45 0'0002 < 0.0002 0-126 Specific conductivity 19.5 27'3 - - 33 *9 Solubility ...... 0.050 0'106 33'6 0.38 0'10 conductivity 8.8 9.3 4512 68 19 Pb,O( SO4) Pb,O,(OH),(SO,) PbCI PbCI,(OH) Pb4C1,02(OH)2 Specific E. G. Aluminium Titanide. WILHELM MANCHOT and P. RICHTER (Artnalem 1907 357 140-144. Compare Manchot and Fischer this vol. ii 46).-Attempts to prepare double aluminium titanides with the object of investigating the capacity of titanium t o form chains have resulted only in the formation of aluminium titanide,INORGANIC CHEMISTllY. JL A1,Ti (Wiihler Annwleit 1860 113 248; 115 10s). The titanide is best prepared by fusing 24 parts of potassium titanofluoride with 45.5 parts of aluminium and gently heating the regulus with dilute sodium hydroxide.The product forms silver-white leaflets D 5.5 is brittle hardly scratches steel glass or fluorspar contains tervdent titanium since i t forms a blue solution in hot dilute sulphuric acid evolving twelve atomic proportions of hydrogen and evolves thirteen atomic proportions of hydrogen when dissolved in aqueous potassium hydroxide. The titanide may have the double formula AI,Ti*TiRl but this cannot be decided. HENRY REYNOLDS (Clmn. News 1907 96 260).-The author considers that manganese which shows only the slightest resemblance t o the halogens should be placed in the eighth group with iron nickel and cobalt. It resembles these metals in physical properties and in the formation of similarly con- stituted and isomorphous simple and double salts M”SO 7H,O and R,S0,1M”S0,,6H,0 alums metallo- and metalli-cyanides. Moreover potassium manganate and permanganete find a parallel in potassium osmite potassium ruthenate and per-ruthenate.I n many cases a regular gradation of properties can be traced from manganese to cobalt and a corresponding gradation from ruthenium G. Y. Manganese and the Periodic Law. to palladium and from osmium to platinum. c. s. [Determination of the] Melting Points of the Iron Group Elements by a New Radiation Method. GEORQE K. BURGESS (Bureau Stand. ITashington 1907 3 (3) 345-355).-The m. p. of minute quantities of difficulty fusible substances have been determined by a method based on the measurement of the intensity of a particular monochromatic radiation from platinum (compare Burec6u Stand.IVasliington 1905 1 189; 1907 3 1). Within a blackened brass cylinder filled with hydrogen is a strip of platinum 60 x 4 x 0.02 mm. which is heated electrically to any desired temperature. On this strip is placed about 0.001 mg. of a metal or its oxide which is matched through a mica window in the cylinder by one observer through a microscope whilst simultaneously a second observer reads the temperature of the platinum strip by means of a Hol born-Kurlbaum optical pyrometer. The indications of the pyrometer are subject to two corrections one for the reflection and absorption of the mica the other for the selective emission of the platinum for the light used red light A = 0 .6 6 ~ . The following metals in a state of maximum obtainable purity have m. p. iron 1505’ ; chromium 1489” ; cobalt 1464” ; nickel 1435’; manganese 1201’. The m. p. of cobalt and nickel are correct t o within 5O those of the other three to within less than 10”. C. €3. Constitution of Roussin’s Salts. LIVIO CAMBI (Atti R. Accad. Lincsi 1907 [v] 16 ii 658-660. Compere Abstr. 1907,ii 960).-The simultaneous action on potassium heptanitrosulphide of mercuric cyanide in amount equivalent t o the sulphur present and potassium cyanide in the quantity necessary for the complete formation of ferro- cyanide yields mercuric sulphide alkali nitrite and ferrocyanide,42 ABSTRACTS OF CHEMICAL PAPERS. as would be expected from the constitution attributed to Roussin's salts by the author (Zoc.cit.). The phenomena observed in tho precipitation of Roussin's salts by silver nitrate have led the author to assume that hyponitrous acid rednces ferric to ferrous salts. Preliminary experiments indicate that this reduction does not take place. The investigation is being continued. T. €1. P. 1 2Dichlorotetramminecobalt Salts ; Ammonia-violeo-Salts. ALFRED WERNER (Be?.. 1907,40 4S17-4825).-Nurnerous examples of stereoisomerism of cobalt salts containing organic amino-residues have been described (JGrgensen Abstr. 1898 ii 226 ; Werner and others 1901 i 510 512 ; 1907 i lSS 290 482 590). Hitherto the simp1 es t tetramm ineco b d t salts for example the dichloro t e t rammine- cobalt salts [Cl,Co(NH,),] X have been obtained in one form only the so-called pmseo-salts ; a stereoisomeric series of salts the uioteo-salts has now been prepared by the action of hydrochloric acid on octamminedioldicobalt salts (Abstr. 1907 ii 965).When concen- trated hydrochloric acid is used a t low temperatures the reaction proceeds according t o the equation [(NHJ,*CO(OH)~CO(NH,),IX + 2HC1= [(NH,),Co(OH),]Cl + [CI,Co(NH,),]Cl a mixture of 1 2-di- aquotetramminocobalt chloride and 1 2-dichlorotetrarnminecobalt chloride being formed; the former is readily soluble in water whereas the latter forms sparingly soluble intensely blue crystals. The violeo- salt contains small amounts of the isomeric praseo-salt from which it may be freed by conversion into the practically insoluble dithionate.The chloride can then be regenerated by rubbing the thionate with ammonium chloride. The following salts have been analysed chloi-ide YCl,iH,O [Y = Cl,Co(NH,),] bromide iodide and nitrate all anhydrous dithionate YzSz06 and sulphccts Y,SO,. The chloride becomes anhydrous a t 60° and all are characterised by an intense violet-blue colour. The aqueous solutions are somewhat less stable that those of the corre- sponding praseo-salts ; even a t 0" the solutions assume a reddish-violet colour owing t o the formation of the chloroaquotetramminecobalt salts. When suspended in concentrated hydrochloric acid the violeo- chloride is converted into the praseo-chloride. The violeo-salt is regarded as a &-compound with the 1 2-constitution. Complex Metal Ammonia Derivatives.VI. Octammine-p- *NH amino-01-dicobalt Salts (NH,),Co "Co(N H,),]X,. ALFRED WERNER (Bey. 1907,40,4605-4615. Compare Abstr. 1907 i 1012 ; ii 965).-When an ammoniacal cobalt nitrate solution is oxidised by a slow current of air and a n excess of sulphuric acid then added Vort- mann's insoluble sulphate separates. The author has shown previously (Abstr. 2898 ii 223) that this product is not homogeneous since two compounds a red and a green can be separated from it both of which belong t o the class of complex cobalt salts. I n the present paper the constitution of the red salt is elucidated. Salts of the types in question are decomposed by a mixture of hydro- chloric and sulphuric acids into pentammino and tetrammine salts from which it folIows that 4 molecules of ammonia are attached J.J. S. [ OH2INORGANIC CHEMISTRY. 43 t o each of the two cobalt atoms. The constitution of the red series of salts is discussed. The formula [(NH,),Co:NH*CooH2 X is not favoured because an imino-group could not be detected; no salt formation took place either with acetic acid or dilute minernl acids; no acetylation took place by the action of acetic anhydride and no nitroso-compound resulted from the action of nitrous acid. Further the compounds in question were neutral in aqueous solution and not acid as would be the case if the formulation just stated were correct. (NH3)4 1 On the other hand the formulation [(NH,),CO.~~,,,CO(NH,) *OH* 1 X accords with the experimental resul&. Since the gobalt atom; are saturated with respect to co-ordination numbers the fact that all the acid groups are inorganic in character is explained.The complex radicle contains no water and the salts do not consequently give an acid reaction when dissolved in water. The amino-group behaves like ammonia in metal ammonia compounds being indifferent towards chemical reagents in the cold. The hydroxyl group also does not have the property of adding on hydrogen ions. For those amino- groups which bind two metal atoms together the author proposes the nomenclature ‘‘ p-amino.” Octammine-p-sulphatoamino-dicobalt nitrate obtained from Vort- mann’s sulphate was shaken with concentrated hydrochloric acid until the reddish-violet tint of the salt had changed to brown. The product was washed with alcohol and hydrochloric acid added t o its aqueous solution when the brownish-violet chloro-chloride separates. The f 011 owing oct ammine-p-amino -01-d icobalt salts were prepared.The &Zooride YCl,,BH,O (Y = (NH,),Co. *NR og C O ( N H ~ ) ~ ~ ) forms [ glistening brownish-red prisms ; by the action of hydrochloric acid it is converted into pentammine and tetrammine cobalt salts. The bromide YBr,,4H20 forms glistening red scales. The nitrute S(NO,) forms dark red needles and scales. The mlpiiate Y(S04),,2R20 forms brownish-red silvery scales. The dithionate Y(S,0,),,2H20 forms silvery raspberry-coloured leaflets. The tlLiocyanate Y (CNS) forms red crystals A. McK. Complex Metal Ammonia Compounds. VII. Hexammine- trioldicobalt Salts. ALFRED WERNER [and in part EMIL RINDSCHEDLER and ADOLF GRSN] (Ber.1907 40 4834-4844. Com- pare Abstr. 1898 ii 223; 1899 ii 658; 1907 i 482 1012; ii 965 and preceding abstract).-~examm~netr~o~d~cobccZt saEts of the r *OH- 7 type (NH,),Co*OH*Co(NH,) X may be prepared by the follow- 1 OH- ing methods. 1. The chloride is obtained by the action of sodium hydroxide solution on dichloroaquotriarnmine cobalt chloride. 2. The sulphate by the action of sodium hydroxide solution on chlorodiaquo- triammine cobalt sulphate. 3. The bromide by warming chlorobromo- aquotriammine cobalt bromide with a little water a t 60’. 4. The44 SBSX'RACTS OF CHEMICAL PAPERS. sulphate by leaving chlorodiaquotriammine cobalt sulphate with potass- ium bromide solution for several days at the ordinary temperature. When decomposed with halogen hydracids the salts give quantita- tive yields of triamminecobal t salts indicating that three ammonia residues are attached to each cobalt atom.The acid residues are readily ionised as each salt can be transformed into the others by double decomposition. Their aqueous solutions are quite neutral t o litmus and hence the salts cannot be aquo-salts. They are isomeric with the black dodecamminehexoltetracobalt salts [Co(OH)6tco(RH3)41 1x6. The following salts have been prepared. C l d o d e [ ~ N H ~ ~ ~ C o ( 0 H ~ 3 c o ( N ~ 3 ~ ~ ~ c 1 ~ ~ H ~ 0 ~ best obtained by rubbing the sulphate with ammonium chloride acd water brownish-red needles and prisms from dilute alcohol decom- pose a t 100". Byonaide anhydrous red prismatic crystals soluble in about thirteen times its weight of water a t the ordinary temperature.Nitrate red prisms containing 2H20 becomes anhydrous when kept over sulphuric acid. Sulphate crystallises with 6H20 pale red prisms loses SH,O over phosphoric oxide and the last molecule a t 77". Bithionate [ (NH,),Co( OH)3Co(NH3j,] 2( S,O,!,,H,O obtained by the &ion of a saturated solution of sodium dithionate on a solution of the bromide at Oo dark red needles and prisms. Thiocpnate anhydrous dark red needles soluble in 3 parts of water at the ordinary temperature. J. J. S. Pentamminecobalt Salts with Several Nuclei. JULIUS SAND and G . B~KMAN (Be?. 1907 40 4497-4504).-Sand and Genssler have described two a black and a red series of pentamminenitroso- cobalt salts (Abstr. 1903 ii 549; 1904 ii 39).These salts especi- ally those of the black series are characterised by their great reac- tivity The present paper contains an account of the compounds obtained by the action of iodine on the black pentamminenitrosocobalt chloride and nitrate in alcoholic solution and of the complex salts derived from these. When boiled with alcoholic iodine the black chloride Co2(N2Oz)(NH,)lOC14~ yields the chloride [Co3C11,(NH3)i,(H,0)2]C16 which after being boiled with hydrochloric acid separates from its ice-cold aqueous solution on addition of hydrochloric acid potassium chloride or alcohol in green crystals ; with v ? ~ ~ has the molecular conductivity p = 731 and gradu- ally decomposes in aqueous solution at 25O the conductivity increasing with the time. The action of potassium iodide on the chloride in ice- cold aqueous solution leads to the formation of the green crystalline iodide [CO,C~I~(NH~),,(H~O)~]I~ whilst the action of nitric acid leads to the formation of the nitrate [Co3C1I,(NH,),,(H20),](NO3),.The solubility of these three salts decreases from the chloride through the nitrate to the iodide which is only very sparingly soluble. When treated with cold nlcoholic iodine the black nitrate Co2(N,O,)(NH,)1,( KO,),,PHYSIOLOGICAL CHEMISTRY. 45 forms a peen substaszce which when boiled with 20% nitric acid yields the green complex scclt [Co,I,(NO,)(NII,),,(H,O),I(NO,),. Equilibrium of the System Nickel-Bismuth. A. PORTEVIN (Compt. rend. 1907 145 1168-1 17O).-The freezing-point curve of mixtures of nickel and bismuth consists of three branches the points of intersection are given by the reactions Ni + Bi 2 NiBi(?) at 654" and Ni+NiBi(?) I n neither case however is the reaction complete.14. A. ?V. ALBERT COLSON (Ann. Cliinz. Phys.. 1907 [viii] 12 433-467).-A rksumt' of work already published (compare Abstr. 1905 ii 94 460 592 639; 1906 ii 74 233 ; 1907 ii 177 267 356 474 780). New Compound of Uranium the Tetraiodide. MARCEL GUICHARD (Compt. Tend. 1907 145 921-922).-When iodine vapour is passed over uranium at 500' in sealed vacuum tubes (this vol. ii 31) the tetraiodide UI is formed as a crystalline sublimate con- sisting of fine black needles in. p. about 500° DI5 5.6. It is reduced when heated in hydrogen decomposed by chlorine yielding the chloride and iodine trichloride readily oxidised by oxygen or air to form the oxide U,O and dissolves in water to form a green acid solution giving the charnc teris tic reactions of uranium salts.G. Y. Nisi a t 462". The Green Chromium Sulphates. AT. A. W. M. A. W. Colloidal Hydroxides of Thorium Zirconium and Uranium. B ~ L A SZILARD (J. China. Phys 1907 56 488-494).-The author considers that there are two distinct classes of colloids those contain- ing a little electrolyte which are very stable and those quite free from electrolytes which are also fairly stable. Colloidal thorium hydroxide free from electrolytes has been prepared by decomposing thorium nitrate with excess of dilute ammonia and mashing the residue until free from ammonia which takes three to six days The product is a fine milky suspension in which the particles cannot be separated either by filtration or decanta- tion ; it is precipitated by electrolytes and by the carbon dioxide of the air.Colloidal zirconium hydroxide was prepared by tho same method and shows similar properties. Colloidal thorium hydroxide containing a little electrolyte has been obtained by adding precipitated thorium hydroxide to thorium tetrachloride so long as the former is dissolved. This solution is much more stable than that free from electrolytes is not affected by light or by boiling and is not precipitated by small quantities of electrolytes or by weak acids (compare Miiller Abstr. 1906 ii 762). Colloidal uranyl hydroxide containing a little electrolyte has been prepared by the gradual addition of uranyl hydroxide to a dilute solu- tion of uranyl nitrate as long as the former is dissolved ; the solution thus obtained is orange-yellow in colour and very stable.The uranyl hydroxide for this purpose was obtained by exposing to light a mixture of uranyl acetate and ether and thoroughly washing the resulting precipitate. G. S.46 ABSTRACTS OF CHEMICAL PAPERS. Spitting of the Acid Vanadates of Univalent Metals WILHELM PRANDTL and HANS MUESCIIHAUSER (Zeitsch. ccrtorg. Clrmm. 1907 56 173-2OS).-In a previous paper (Abstr. 1905 ii 170) it was shown that when certain alkali acid vanadates xMz0,yV205 are allowed to cool from high temperatures a vigorous evolution of oxygen takes place on solidification the mass spitting as solidifying silver does. On again heating in air oxygen is absorbed and the acid vanadates are regenerated.This phenomenon is due t o the reversible change of the acid vanadates xM,O,yV,O to vanadylvanadates xRT20,(y-x) V205,xV204) on solidification. Only the oxides of the univalent elements of the first group in the periodic tlable give acid vanadstes which spit on solidification. The respective oxides were mixed with vanadium pentoxide in varying proportions and the composition of the mixtures which gave the highesl; proportion of oxygen determined ; the results varied with the nature of the oxide and were as follows Ns,0,6V20 ; Ag,O,6V2O5 ; K,0,5V20 ; Rb20,5V,O ; Cs,0,5V2O ; Li,0,2V2C!,. From mixtures of the same alkali oxido wlth varying proportions of vanadium pentoxide the same vanadylvanadate is obtained the composition of the four most important being as follows Na,0,5V2O,,V,O ; Ag20,5V,0,,V20 ; 2 h ' 2 0 9 ~ 2 0 5 ~ 2 ( ~ 1 ; 4Li,o,7~,?,,V20,.The com- position of these compounds was determined approximately by treating the mixtures containing them with boiling dilute ammonia which dissolves unaltered V,O,. The amounts of oxygen evolved from solidifying sodium and silver vanadates correspond fairly closely with those calculated from the composition of the vanadylvanadates as determined above so that the reaction is nearly complete but in the case of the potassium rubidium caesium and lithium vanadates the amounts of evolved oxygen are much less than the calculated values showing that the decomposition on cooling is incomplete. When mixtures of vansdium pentoxide and two alkali oxides are employed the amount of oxygen evolved is approximately the mean of that obtained with the separate oxides.The addition of boron trioxide in moderate amount to the mixtures does not affect the evolution of oxygen but when considerable amounts of phosphates are present the fused mass solidifies without the liberation of oxygen probably owing to the previous formation of vanadyl phosphate. G. 8. Silicon Chains. WILHELM MANCHOT and H. FISCIIER (Anirixden 1907 357 129-139. Compare Manchot and Kieser Abstr. 1905 ii 165 ; 1906 ii 83 ; Vigouroux Abstr. 1906 ii 30).-I. Vcc?2c~diu(tl2 AZuminium SiZicides.-W hen heated together potassium . silicofluoride aluminium and ammonium metavanadate form three vanadiurn aZuminiurn silicicles depending on the proportions of the mixture.I n presence of an excess of vanadium and small amounts of silicon the chief product is tt silicido crystallising in small dark octahedra together with small amounts of a silicide crystallising in large hexagonal prisms. As the proportion of silicon is increased and t h a t of vanadium diminished the octahedra disappear and a silicideINORGANIC CHEMISTRY. 47 crystallising in monoclinic leaflets is formed becoming the chief product when the mixture contains a large excess of silicon. Of these vanadium aluminium silicides only the hexagonal silicide V A12Si13 has been isolated. It crystallises in greyish-white prismatic needles J ) 4.3 hardness slightly above 5 and reacts with hydrofluoric acid with development of heat forming in absence of air a reddish-violet solution containing vanadium dijuoride VP which on exposure to air in presence of excess of hydrofluoric acid evolves hydrogen and forms the green vanadium trifluoride solution.The hexagonal silicide is stable towards boiling concentrated hydro- chloric nitric or sulphuric acid aqum regicc or fused potassium chlorate remains unchanged when heated in a current of oxygen over the bunsen flame and is not attacked by chlorine at the ordinary temperature but at a red heat is converted into volatile chlorides and is dissolved by fused alkalis or alkali carbonates. 11. Constitution of the SiEicides.-When treated with an excess of hydrogen fluoride as was described in the case of the chromium salts (Abstr. 1906 ii 63) the hexagonal vanadium aluminium silicide evolves seventy-four atomic proportions of hydrogen whereas if tlie ailicon mere completely transformed into the fluoride eighty-two atomic proportions including eight from the conversion of the difluoride into the trifluoride should be evolved.It is considered that this points t o linkings between silicon atoms which are not resolved by hydrofluoric acid. It is found impossible to construct a formula for the hexagonal silicide in which not more than eight of the thirteen silicon atoms are linked to form a chain. G. Y. Action of Sodium and Barium Peroxides on Gold. Aurates. FEENAND MEYEB (Compt. rend. 1907 145 805-807).-When pre- cipitated gold is added t o fused sodium peroxide a vivid reaction takes place and sodium aurate is formed.A similar but much less complete reaction occurs with barium peroxide. From the aurate auric hydroxide is prepared by means of sulphuric acid adopting the precautions recommended by Fremy (Ann. Chim. Plqs. 1851 31 [iii] 478). Analyses of the bydroxide dried in a vacuum in the dark agree with the formula Au20,,3H20 ordinarily written Au(OH) but from analyses of the aurates the author proposes the formula AU,O,(OH)~,ZH,~. Iiruss has described the hydroxide Au,O,,H,O which be writes AuO.OH. The aurates of sodium (bright green needles) and potassium are prepared by treating tt solution of the hydrate with the alkali in au atmosphere free from carbon dioxide and evaporating in a vacuum in the dark. They have formulx of the type M2(Au02)2. 'l'he salts of the alkali earth metals aiw obtained by treating solutions of their hydroxides with an alkali aurate solution. They form voluminour light green precipitates which retain much water are sensitive to light and have the forniulrt M(huO,),. The degree of hydration of ths aurates is diiiticult t o determine but it tends towards the limit of 611,O for those of potassium calcium strontium and barium and 2H20 for that of sodium. The aurates are stable towards lie& when dry but iu48 ABSTRACTS OF CHEMICAL PAPERS. solution are decomposed by light or heat giving a violet-black residue of aurous oxide Au,O. Sulphur dioxide and alcohol (slowly) precipitate metallic gold from their solutions which with dilute sulphuric and nitric acids form auric hydroxide and a sulphate or nitrate. Hydrochloric acid dissolves them forming gold chloride and an alkali or alkali earth chloride. With organic-matter they form powders wliich detonate when heated. E. H. Gold Chromate. N. A. ORLOFF (Clmz Zeit. 1907 31 1182).- A solution of auric clwoinate Au,(CrO,) is obtained by treating a large excess of freshly-precipitated silver chromate with a solution of auric chloride On evaporation the solution deposits at first gold but subsequently the chrornude Au,( CrO,),CrO crystallises from the red mother liquor. W. H. G.

ISSN:0368-1769    

DOI:10.1039/CA9089405031

出版商:RSC    

年代:1908

数据来源: RSC

摘要:

48 ABSTRACTS OF CHEMICAL PAPERS. Mineralogical Chemistry. Optical Activity of Mineral Oils in Clonnexion with the Question of their Origin. EOMAN ZALOZIECKI and IT. KLARFELD (Chem. Zeit. 1907 31 1155-1156 1170-1172. Compare Kraemer and Spilker Abstr. 1900 i 73 333 ; Walden Abstr. 1906 ii 368; Marcusson Abstr. 1907 i 466 ; Neuberg Abstr. 1907 i 577).-As a general rule light-coloured Galician mineral oils are optically inactive whereas the heavy dark-coloured oils are optically active. Of the fractions obtained from the latter oils only those boiling above roughly 200°/12-15 mm. are optically active. Since heavy dark- coloured mineral oils contain a high proportion of asphaltic and resinous substances the conclusion is drawn that the optical activity of these oils is almost entirely due to the preseuce of colophonic and terpene- like hydrocarbons. The authors discuss the several theories which have been advanced to explain the origin of mineral oils and come to the conclusion that mineral oils are derived not only from fats of higher anirnals but also from substances of both animal and vegetable origin which do not readily putrefy such as waxes wax-fats resins gums &c.W. H. G Enstatite- Augite in Diabase from Tasmania. ALFRED OSANN (Centr. illin. 1907 705-71 I).-Analysis I by Dittrich is of a pale- coloured pyroxene isolated from a medium-grained fresh rock (anal. 11) ccmposed only of pyroxene and zoned plagioclase SiO,. TiO,. A1203. Fe,OB. FcO. MnO. MgO. CaO. Na,O. K20. H,O. Total. 1. 51.87 0'21 2'02 3.50 8.98 0-1s 16'26 15.70 0.16 0'09 1 2 0 100-17 11. 52.49 0'62 16.44 2.60 5.30 trace 6'18 11'71 8.06 1.09 1-67 100.06" * Also t i w e 01 P,Oj.PHYSIOLOGICAL CHEMISTRY. 49 The grains of pyroxene consist of an intergrowth of two optical varieties differing in birefringence and in optical orientation (the optic axial plane being pal-allel to the plane of symmetry in one and perpendicular to it in the other). An attempt to separate these two portions for analysis was not successful. I n the low content of calcium and iron and in the peculiar optical characters this pyroxene resembles those of the enstatite-augite series of W. Wahl (Tsch. >fin. JIiit. 1907 26 1). The comparatively large amount of water is probably present as basic hydrogen L. J. M.

ISSN:0368-1769    

DOI:10.1039/CA9089405048

出版商:RSC    

年代:1908

数据来源: RSC

摘要:

PHYSIOLOGICAL CHEMISTRY. 49 Physiological Chemistry. Tension of Carbon Dioxide in A1veola;r Air during Exercise. BERTRAM J. COLLINGWOOD and H. L. F. BUSWELL (Proc. Physiol. Xoc. 1907 xxi-xxii ; J. Physiol. 36)-The method adopted for collecting alveolar air was rather different from that used by .Haldane and Prieatley but the results which show much greater variations than those given by the first-quoted authors are stated to confirm their statement that the hyperpnea of muscular work is due t o a rise of carbon dioxide pressure in the respiratory centre. Tension of Carbon Dioxide in Alveolar Air during Chloro- form Narcosis. BERTRAM J. COLLINGWOOD and H. L. F. BUSWELL (Proc. Physiol. Xoc. 1907 xxiv-xxv ; J. Physiol. 36).-As anmthesia advances there is a well-defined rise of carbon dioxide tension in the alveolar air.Increased tension of the gas in the venous blood also occurs which is due either to the slowing of the blood-stream or to deficient lung ventilation. Hypotherrnolysin. W. D. H. The experiments were made on cats. W. D. H. G. OLIVI (Zeitsch. physiol. Chenz. 1907 539 484-495).-Low temperatures (lo to 2') alter the red corpuscles so that their receptors are no longer able to unite with ordinary hzemo- lysin but at the same time there is developed a specific anti-substance for the cooled corpuscles which is called hypothernzo2ysin. The change produced by cooling is not total a :certain number of receptors remaining unchanged and capable of uniting with normal hzmolysin. The bearing of this observation on the hzmolysis of paroxysmal The Chemical Hamolysins.111. ALBERT J. J. VANDEVELDE (Bull. Xoc. chim. Belg. 1907 21 373-380. Compare Abstr. 1907 ii 792).-The paper is partly polemical against I Fuhner (Abstr. 1907 ii 631) and deals with the hzemolyticaction of ethyl alcohol digitalin strophantin saponin difluoroethyl alcohol the three isomerides iso- propyl formate methyl propionate and ethyl acetate the three com- pounds isobutyl acetate ethyl isobutyrate and isopropyl propionate the toluic acids and the nitro- hydroxy- and amino-benzoic acids towards defibrinated ox-blood. The value 15.4888% by weight (Abstr. 1907 ii 632) for the limiting hzemolytic value of ethyl hamoglobinuria and rheumatism is discussed. w. D. IT. VOL. XCIV. ii. 450 ABSTRACTS OF CHEMICAL PAPERS. alcohol is confirmed The critical coefficient (the ratio of isotoxic quan- tities of the substance and of ethyl alcohol multiplied by 100) of digitalin (Nerck) and of digitoxin (Mcrck) in alcoholic solution is 0,0036 in aqueous solution 0.40.Comparison of these two figures gives further evidence that :substances have a greater toxicity in alcoholic solution than when aloDe. The critical coefficient of strophantin or oudbain and of saponin in alcoholic solution is 0.13. Difluoroethyl alcohol has a critical coefficient 9292 showing that substitution of fluorine only slightly alters the toxic properties of ethyl alcobol (of which the critical coefficient is obviously 100). Com- parison of the critical coefficients of isopropyl formate (5 %7) methyl propionate (5.67) and ethyl acetate (11,31) and also of isobutyl acetate (4*34) ethyl isobutyrate (4.85) and isopropyl propionate (5*19) shows that the more symmetrical isomeride has the higher value. The values obtained for the critical coefficients of the sub- stituted benzoic acids have already been described (Abstr.1907 ii 890). E. H. Nature of the Alkalinity of Intestinal Juice. EGIDIO POLLACCX (Boll. Chim. Farm. 1907 46 18'J-791).-The alkalinity of intestinal juice is a t least partially due to the presenceof ammonia or an ammonium compound. The total volatile alkali evolved on heating 1000 grams of the fresh intestines of the bog amounts to 0.0268 gram of ammonia or 0*1513 gram of ammonium carbonate or 0.531 gram of ammonium oleate. T. H. P. Animal Digestion. E. S. LONDON and W.W. POLOWZO~VA (Zeitsclr. physiol. Cltena. 1907 53 429-452).-From experiments on dogs with fistuls the following conclusions are drawn ; about 50% of the digested products are absorbed in the jejunum and from 40-60% of the nitrogen. The concentration of protein cleavage products in the fluid to be absorbed is about 0.4%. By gastric digestion alone the protein material passes into the intestine in an absorbable state. Qlycine is absorbed in the same measure as the higher products of protein cleavage. The addition of the duodenal juices t o the products of gastric digestion does not increase the rate of absorption. About 30% of the duodenal juices is absorbed in the jejunum. Aqueous solutions of monobutyrin and sodium oleate pass through the intestine more slowly than fluids which contain protein cleavage products.Sodium oleate is absorbed more slowly than monobutyrin and protein cleavage products ; it causes increased secretion of intestinal juice. Solutions of sugar and dextrin are rapidly and completely absorbed in the jejunum. Dextrin solutions cause little or no secretion of bile but an abundant secretion of pancreatic juice A.11 these statements are supported by figures and details are added on rate of digestion in 3itr.o with mixtures of juices. Behaviour of Glucosamine and of the First Product of its Transformation in the Animal Body KARL STOLTE (Beitr. chem. Plqsiob. Path. 1907 11 19-34).-Free glucosamine (chitosnmine) dissolved in wator or in methyl alcohol is gradualiy changed as was W. D. H.PHYSIOLOGICAL CHEMISTRY.51. shown by Lobry de Bruyn (Abstr. 1899 i 732) into a substance which can also (and more readily) be obtained by the action of alcoholic ammonia on lawulose. The molecular weight of the acetyl derivative of this substance has now been determined and shows that Lobry de Bruyn’s formula must be doubled so that it becomes Ci2H2008N2. The acetyl derivative C,,H,,O,,N contains eight acetyl groups and not four as supposed by Lobry de Bruyn. When oxidised with hydrogen peroxide the substance is now found to yield pyrazine-2 5-dicarboxylic acid previously described by Stohr (Abstr 1892 507 ; 1893 i 487). The transformation product of glucosamine and of hvulose for which the name fructosazine is suggested is therefore 2 5-clitetra~?/drox?/buty~yraxine c,H,o,-c<~H~$~* c,H,o and its formation from glucosamine mould appear to take place according to the equation ZC,H,,O,N + 0 = C,,H,,O,N + 3H20.By means of intravenous injection into rabbits the maximum dose of glucosamine mas now determined which could be broken down by the organism without any of the substance passing into the urine. This dose was very small 1/25 of the corresponding quantity OF dextrose and of laevulose. A transformation into fructosazine in the organism could not be observed with certainty. Moderate doses of fructosazine up to one gram when given pel. os were completely oxidised. G. I;. Value of Ultimate Protein Cleavage Products in the Organ- ism; Experiments on a Dog with Eck’s Fistula. E ~ L ABDERHALUEN and E S. LONDON (Zeitsch. physiol. Chem.1907 54 80-85. Compare Abstr. 1907 ii 369 892).-A dog with an Eck’s fistula (a connexion between the portal vein and vena cava inferior cutting out the liver from the portal circulation) not only remained in nitrogenous equilibrium but retained nitrogen when fed on the ultimate cleavage products of protein (rnekt) €or eight days. This result does not give support to the view that the liver plays an essential part in protein synthesis but rather that this synthesis takes place in the intestinal wall. Comparative Study of Phenols as Agents in Partheno- genesis. YVES DELAGE and P. DE BEAUCHAXP (Con@. rend. 1907 145 735-738).-Loeb’s hypothesis that parthenogenesis is due to certain agents increasing the velocity of oxygen-transport is not supported by the present experiments j for substances such as catechol quinol and pyrogallol which have this property in a high degree are the least active in promoting parthenogenesis whilst resorcinol and phloroglucinol are very active although they possess little or no power of transporting oxygen How these materials act and how sugar acts as a favouring factor in their action are subjects which are discussed but not decided.W. D. I€. Physical and Chemical Properties of Nerves. I. NATHANIEL H. ALCOCK and a. ROCHE IJYNCII (2 Pl’Lysiol. 1907 36 93-103).- The average percentage of water in mectullatecl nerves varies in differ- G. B. 4-252 ABSTRACTS OF CHEMICAL PAPERS. ent species of animal; €or instance cat 67.3; dog 75.4 and horse 69.3. The percentage in the non-medullated nerves of the horse is 81.2.There are also variations in the same species and in different nerves of the same animal Cats’ nerves remain unchanged in weight in 1 *16% sodium chloride solutions ; in 1.1 7% solutions they lose weight and in 1.46% solutions of potassium chloride they gain weight. The average percentage of chlorine in medullated and non-medullated nerves of the horse is the same (0.23). The medullary sheath contains less water than the axis cylinder but a not dissimilar amount of chlorine W. D. H. Sulphur Compounds of the Nervous System. WALDEMAR KOCH (ZeitscTt,. pTt,ysioZ. Chem. 1907 53 496-507).-The sulphur compounds of nervous tissue are divided into four groups (1) that of lipoids for example protagon; (2) that of extractives soluble in 95% alcohol; (3) that of extractives insoluble in boiling alcohol and ether but soluble in cold water ; (4) that of proteins.The view is advanced that in so-called protagon a sulphur compound acts as a link between lecithin and cerebrin. The sulphur compound under heading (2) consists as to one-tenth of its amount of inorganic sulphates and the remainder of a taurine-like compound. Those under heading (3) con- sist mainly of inorganic sulphates but the presence of protein-like sulphur compounds (gelatin ?) is suggested. The pzotein sulphur (heading 4) is contained in neuro-keratin and nucleo-protein. The amount in albumin and globulin was not estimated. Estimation of these substances in grey and white matter shows that grey matter con- tains nucleo-protein globulin and neutral sulphur and white matter contains the higher proportion of neuro-keratin and lipoid-sulphur. The importance of the sulphur compounds for the oxidation processes in the brain is discussed; the brain has to be provided with excess of oxygen in order to perform its work.I n Dementiaprcecox there is a marked lessening of the neutral sulphur (35% on the average; three cases) and a rise of inorganic sulphates; the lipoid-sulphur is not altered. Interference with oxidation processes will explain some of the symptoms of this disease Glycogen in Frogs during Inanition. EDUARD PFLUGER (Pfliiger’s Archiw 1907 120 253-289).-The author’s previous work has shown that during inanition in dogs glycogen does not entirely disappear from the body ; in one animal for instance after a fast of twenty-eight days the liver and muscles still contained fifty-two grams of glycogen.The present experiments on frogs confirm this. They were kept for months from August onwards in water renewed daily no food was given; flies and other insects being kept out of the trough by a fine net. A t intervals ten frogs were taken and analysed by methods which are described in full. There is no accumulation of glycogen before the winter sets in ; artificial warmth like the summer causes the glycogen to diminish and a slight diminution was noticed in the first month. After this the glycogen steadily increased from 47% to 56%. Indeed the increase was almost as marked as in frogs freshly collected from time to time in which case of course food was available. W.D. H. W. D. H.PHYSIOLOGICAL CHEMISTRY. 53 General Mechanism of the Transformation of Glycogen into Dextrose in the Muscles and Tissues. F. MAIGNON (Compt. rend. 1907 145 730-732).-The muscles possess an amylase which is regarded as the agent which transforms glycogen into sugar. This occurs continuously in the normal state but is exaggerated under certain influences ; crushing accelerates it because by that means the glycogen and the.enzyme are brought more closely &to contact. W. D. H. Creatine and Creatinine in Meat and Meat Extracts. A. D. EMMETT and HARRY S. GRINDLEY (J. Biol. Chem. 1907 3 491-516. Compare Abstr. 1906 ii 242)-With certain modifications the Folin method is as applicable to meat and meat extracts as it is to urine. Creatine and creatinine together are present to the extent of 0.45% in meat and from 1’4% to 6.5% in meat extracts.Hehner gives the latter number as 10-12%; his methods are criticised. Chemical Composition of Hair. THOMAS A. RUTHERFORD and PHILIP B. HAWK (J. Biol. Ckem. 1907 3 459-490).-The chemical composition of human hair is influenced by race sex age colour of hair and other factors. As judged by the numerous tables presented the differences do not appear to be great. In different races the sulphur-nitrogen ratio for instance varies from 1 3.2 to 1 2.9. W. D. H. W. D. H. Tissue Respiration in Perfused Kidneys. HORACE M. VERNON (J. Physiol. 1907 36 81-92. Compare Abstr. 1907 ii lll).- After perfusion of an excised mammalian kidney with Locke’s solution for eleven hours the gaseous metabolism falls to half its initial value.This does not occur if 2% of rabbit’s serum is added; sheep’s serum is less efficient egg-white much less so and milk is of no value at all. Witte’s peptone (0.01% to 1%) is as efficient as serum proteins; diglycyl-glycine glycine and leucine have a slight sustaining influ- ence but urea produces a distinct improvement. Grab Extract. Iv. D. ACKERMANN and FRIEDRICH KUTSCHER (ZeitscA. Nahr. Genussm. 1907 14 6S7-691).-1n addition to the bases recorded previously (Abstr. 1907 ii 283 491) as being present in this extract the following have been isolated crangitine methyl- pyridonium hydroxide neosine and crangonine. W. D. H. Crangitine hydrochloride m. p. 160’. The aurichloride C1,H,,,O,N2,2HAuC1 forms short pale yellow prisms m.p. 162-165’. Crangonine auri- chloride forms groups of short needles m. p. 130-140’ (not sharp). Neither base was obtained in the uncombined state. w. P. s. Spectroscopic and Chemical Behaviour of the Pigment Secretion of Aplysia punctata. RAFFAELE PALADINO (Beitr. chem. Physiol. Path. 1907 11 65-70)-A table is given of the absorption spectra of the pigment in various solvents ; the results differ not incon- siderably from those obtained by previous observers such as MacMunn (Abstr. 1899 ii 313). The chloroform extract of a solution of the54 ABSTRACTS OF CHEMICAL PAPERS pigment in dilute acetic acid left on evaporation a partially crystal- line substance containing nitrogen and iron and perhaps traces of manganese. G B. Excretion of Creatine and Creatinine in Hepatic Disease.E. MELLANBY (Proc. Plhpiol. Soc. 1907 xxiii ; J. Physiol. 30).-1n ascitic fluid due t o liver disease no creatine or creatinine is found. I n this condition creatinine is diminished in the urine; this is attributed to circulatory disturbance and lessened hepatic functions. Creatine in the urine is increased in cancer of the liver (two cases) ; this is attributed to breakdown of muscle failure to convert it into creatinine or a direct production in the turnour. EMIL ABDERHALDEN and BRUNO BLOCH (Zeitsch. plupio2. Chem. 1907 53 464-483).-Administra- tion of large amounts of water to a patient suffering from alcaptonuria caused a great increase in the excretion of nitrogen but the quantity of homogentisic acid remained constant ; the urinary ammonia was increased.The action of water is believed not to be due t o an increase of nitrogenous metabolism but mainly to a washing out of the products readily. No conclusive answer mas obtained t o the question whether the urinary nitrogen comes chiefly from exogenous or endogenous metabolism ; after inanition however the rise in excretion after giving nitrogenous food is very rapid. Some ohserva- tions were also made on the value of gelatin and amino-acids in the diet. About half of the protein-nitrogen was replaceable by gelatin but it is of importance not merely to examine the urine on the day of administration as after effects are seen for some days later. Both gelatin and amino-acids increased the excretion of homogentisic acid. W. D. H. W. D. H.Metabolism in Alcaptonuria. Uroleucic Acid. ARCHIBALD E. GARROD and WILLIAM H. HARTLEY (J. Physiol. 1907 36 136-142).-The existence of a second alcapton acid in cases of alcaptonuria has been mooted by severaliobservers who have named it after Kirk uroleucic acid. The present investigation lends no support to this idea ; uroleucic acid is 5t residue consisting of homogentisic acid mixed with impurities. W. D. H. Xanthine as a Cause of Fever. ARTHUR R. MANDEL (Amer. J. Physiol. 1907 20 439-443).-1n fever there is a distinct relation- ship between rise of temperature and the appearance of purine bases in tbe urine. The administration of xanthine or caffeine will effect a rise of body temperature in monkeys. This may be neutralised by the simultaneous administration of sodium salicylate.It is suggested (1) that in aseptic fever the fall in uric acid is due to lessened circulation through the kidneys owing to vaso-constriction ; (2) that in surgical fever the purine bases are derived from crushed tissues; (3) that in septic fevers the action of toxins is to lessen the power of such tissues as muscle to oxidise xanthine to uric acid and (4) that xanthine forms a combination with salicylic acid similar to diuretin ( = caffeine + salicylic acid) thereby rendering it innocuous. W. D. H.PHYSIOLOGICAL CHEMISTRY. 55 Action of Aconitine on Nerve Fibres. AUGUSTUS D. WALLER (Proc. Physiol. Soc. 1907 xxx-xxxii ; J. Physiol. 36).-If a frog is chloroformed and then killed by aconitine its nerves give no electrical response on excitation.If a normal frog’s nerve is bathed in a solution of aconitine it exhibits a peculiarity also produced by proto- veratrine namely the response is persistent and is not followed by an after effect in the opposite direction ; the normal unfatiguability OF a normal nerve is also abolished. W. D. H. Physiological Action of Adrenaline w. I<RETIJCHhfER (nrch. exp. Path. Pharm. 1907 57 423-437 438-440).-The administra- tion of repeated doses of adrenaline in animals raises the blood- pressure until a maximum is reached and it can be kept up by keeping up the injection. On cessation the blood-pressure returns to normal the rate of return being inversely proportional to the amount in the blood previously and this gradually disappears. The rate of return is decreased by the administration of acids the acid ions inhibiting the destruction of adrenaline in the blood and tissues.W. D. H. Hypnotic Action of the Valeric Acid Group. A. VAN DER EECKHOUT (Arch. exp. Path. Pharm. 1907 57 338-357).-Tho recently-introduced narcotic Brornoural is monobromoisovaleryl- carbamide CHMe,.CHBr*CO*N~*CO*~H~ m. p. 149’. It is a pure narcotic producing no primary excitation and no ill effects even in large doses in frogs rabbits and dogs. It acts rapidly having a selective action on the cerebrum and leaving the bulb and cord intact. A large number of similar sub- stances were investigated and as s rule their activity is propor- tional to their solubility in fats. Chloroisovnlerylcarbamide and a-bromo-a-met hylbutyrylcarbamide are also narcotics ; bromoisovaler- amide is narcotic and toxic ; iodoisovalerylcarbamide bromobutyryl- carbamide and bromobutyramide are toxic and the following corn- pounds are either very feeble narcotics or are inactive bromovaleryl- carbamide isovalerylcarbamide valerylcarbamide bromoisobutyryl- carbsmide and bromoisobutyramide. It has no cumulative action.W. D. H Nitrite Poisoning after the Internal Administration of Bismuth Subnitrate. A. BOHME (Arch. exp. Path. Pharm. 1907 57 441-453).-The administration of large quantities of bismuth subnitrate in men leads to the formation of nitrous acid and the con- sequence is methacmoglobinuria. The same follows in vitro in bacterial cultures and is also produced by mixing fecal matter with the salt. Similar results were obtained in experiments in animals. W. D. H. Cresol Poisoning. FERDINAND BLUNENTHAL and ERNST JACOBY (Biochem. Zeitsch. 1907 7 39-44).-Whilst it is not denied that cresol affects many organs such as the liver injuriously the principal cause of death is held to be the combination of the poison with the lipoids of the brain. Cresol readily forms compounds with fats and56 ABSTRACTS OF CHEMICAL PAPERS. fat-like substmces. The amount found per gram of brain is very constant whatever the dose of cresol given. If however the cresol is administered dissolved in olive oil poisonous symptoms are not readily produced; it is absorbed slowly and excreted by the kidneys rapidly. I n such cases the amount in the brain is much less than when cresol is given in aqueous solution. Full protocols of experi- ments are given. W. D. H.

ISSN:0368-1769    

DOI:10.1039/CA9089405049

出版商:RSC    

年代:1908

数据来源: RSC

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56 ABSTRACTS OF CHEMICAL PAPERS. Chemistry of Vegetable Physiology and Agriculture. Chemistry of the Bacillus Coli Communis. MARY F. LEACH (J. BioZ. Chew,. 1907 3 443-458 Compare Abstr. 1906 ii 568). -By the action of sodium hydroxide and alcohol part of the protein of the bacterial cells goes into solution in alcohol and part remains undissolved. The solution contains the poison of the cell; the insoluble portion includes carbohydrate nucleic acid compounds and an immunising substance. Whether the immunising substance con- tains nucleic acid and depends for its action on this circumstance is uncertain. aW. D. H. Formation of Glycogen by Yeast. FREDERICK W. PAVY and HUBERT W. BYWATERS (J. Fhylsiol. 1907 36 149-163).-Com- tnercial (balloon) yeast contains 5% of glycogen or 25% in the dry material.Incubation with water decreases the amount slightly but with dextrose the amount is increased twice or thrice in as many hours. Beyond a certain point however increase in the concentra- tion of the dextrose inhibits glycogen formation. Tartaric acid nhibits the process and favours the disappearance of the glycogen. fiodium phosphate has no influence but boiled yeast juice promotes glycogen production. The phenomena are due to increased cell growth and not to simple accumulation of glycogen in pre-existing cells. W. D. H. Assimilation of Carbon in Bacteria which Oxidise Hydrogen. A. F. LEBEDEFF (Biochem. Zeitsch. 1907,7 1-lo).-Certain bacteria which can assimilate carbon from carbon dioxide liberate free oxygen and this enables the oxidation of hydrogen to be carried out.The figures given are rather different from those which theory demands an excess of hydrogen being always observed. The con- clusion however is drawn that in all probability the chemistry of carbon assimilation in bacteria is not very different from what occurs in green plants. Fixation of Nitrogen in Soil by Free Bacteria and its Importance for the Nutrition of Plants. ALFRED KOCII J. LITZENDORFF F. KRULL and A. ALVES (J. Lnndw. 1907 55 355-416).-Assimilation of nitrogen in soils is increased by addition W. D. H.VEGEL'ABLE PHYSIOLOGY AND AGRICULTURE. 57 of dextrose sucrose soluble starch and probably cereal straw the amount thus fixed being 8-10 mg. per gram of sugar. Frequent applications of sugar tend to diminish rather than increase the amount of nitrogen fixed.The best results in relation to the amount of sugar were obtained with one application of 2%. Fixation of nitrogen was increased by superphosphnte basic slag and irou sulphate and retarded by lime potassium sulphate and chloride carbon disulphide and perhaps by magnesium sulphate. N. H. J. 1sI. Biological Succession of Mineral Substances in Marine Algae. FRANCESCO SCURTI and s. c:ar,DIERI (Chem Zentr. 1907 ii 1089 ; from 8tccx. sperim. agrar. itaE. 1907 40 225-233).-In continuation of the work of Scurti (Abstr. 1907 ii 122) it has been found that the elements contained in the marine algze can be arranged in two groups. Those of the first group including chlorine calcium magnesium potassium sodium and silicon gradually increase in quantity during the formation of the spores whilst after t h e b appearance these elements gradually decrease.The second group embraces iodine and phosphorus. The behaviour of iodine has already been recorded (Zoc. cit.). Phosphorus is absorbed during the production of the spores but unlike the elements of the first group it still further increases in amount after maturation is a t an end and thus reaches its maximum in winter. E. G. Application of Bio-chemical Methods for the Detection of Sugars and Glucosides in Plants of the Tribe Taxeze. CHARLES LEFEBVRE (Arch. Phawn. 1907 245 493-502. Compare Abstr. 1907 i 864).-Indication of the presence of various sugars and gluco- sides in extracts of plants &c. may be obtained by treating these extracts with enzymes such as invertase and emulsin.The change in the optical rotatory power of an extract of young twigs of Yccxus baccata on treatment with invertase appeared to point to the presence of sucrose but practically the same change is observed on treating rathose with invertase. However by treatment with barium or strontiurn hydroxide and fractional precipitation with alcohol were obtained besides raffinose (compare Abstr. 1907 ii 715) crystals of sucrose and indications of the presence of a lavorotatory sugar which does not reduce Fehling's solution. Investigation of twigs of Taxus baccata gathered a t various times of the year showed that the quantity of sugars present does not vary considerably whilst the quantity of taxicatin present is greatest in the autumn and winter and smallest from April to July.The leaves and twigs of Cephalotaxus drupacea Cephalotaxus pedunculata Podocccrpus Chinensis and Yorreya rnpristica all contain sugars glucosidic substances hydrolysed by emulsin and ferments similar in action to invertase and emulsin. W. H. G. Causes of the Displaceinent of Absorption Bands in the Leaf. D. IWANOWSKI (Ber. deut. hot. Ges. 1907 25 416-424).- In the investigation of the well-known difference between the spectrum58 AUSTRACTS OF CHEMICAL PAPERS. of a living leaf and that of an alcoholic chlorophyll solution the spectro-photometric method is preferable to the spectroscopic. By means of the former method the leaf-spectrum is found to differ from that of the solution in having a much greater absorption at the red end (a-B) and in having both the principal absorption bands some- what displaced towards the red.This difference has generally been attributed to the chlorophyll of the chloroplasts being in the solid state. Solid solutions of chlorophyll in gelatin and in paraffin-wax were however found to have a spectrum differing but slightly from that of an alcoholic solution. By adding'a little neutral salt(for example MgSO,) to a concentrated alcoholic chlorophyll solution greatly diluted with water the author obtained a fine suspension which bad a spectrum very similar to that of the living leaf. This similarity is attributed to the circumstance that in both cases the spectrum is largely due to the reflected light whereas in the case of an alcoholic chlorophyll solution it is wholly formed by transmitted light.G. B. Fruit of Celestrus scandens and Solanum Dulcamara. A. A. WELLS and GRANT S. REEDER (C'Aem. News 1907,96,199-200). -Berries of Gelestrus scandems were found to contain lzlevulose tartaric acid and gallic acid. The seeds contain pslmitic acid and an oil which yields olein and a small amount of palmitin when hydrolysed. Berries of SoZccmm Dulcumara contain tartaric and citric acids and fructose. N. H. J.M. Supposed Toxicity of Hungarian Haricots. LBON GUIGNARD (Compt. rend. 1907 145 11 12-1 11 8).-A reply to Evesque Verdier and Bretin (Abstr. 1907 ii 912). The author has examined a sample of the Hungarian haricots stated by Evesque Verdier and Bretin to contain 0.342 gram of bydrogen cyanide per kilo.and finds that in common with all the specimens of Hungarian haricots that he has examined (Abstr 1906 ii 301) they do not contain a trace of hydrogen cjanide. He also shows that the method of macerating the beans with water containing tartaric acid preliminary to estimating the hydrogen cyanide is untrustworthy as the tartaric acid exercises a paralysing effect on the ferment (emulsin) that causes the hydrolysis of the cyanogenetic glucoside. Chemistry of Mistletoe (Viscum album). M. LEPRINCE (Compt. rend. 1907 145 940-941).-The author has obtained 1.6 grams of a crystalline hydrochloride of a base from 25 kilos. of dry mistletoe plant ; the crystalline platinicldoride (C8H11N),,H,PtCI decomposes a t 250'. M. A. W. M. A. W. Inosites of Mistletoe. GEORGES TANRET (Compt.rend. 1907 145 1196-1 198).-The fresh ripe berries of- mistletoe contain in addition to dextrose lzevulose and -sucrose i-inosite and r-inosite ; 12 grams of the former and 4 grams of the latter being obtained from 1 kilo. of the fresh fruit or four times these quantities from 1 kilo. of dry fruit. Up to the present the leaves of the walnut tree haveVEGETABLE PHYSIOLOGY AND AGRICULTURE. 59 formed the chief source of i-inosite (Tanret and Villiers Abstr. 1877 ii 304 ; lS7S 390; Maquenne and Tanret Abstr. 1890 471) but the yield is only one-sixteenth of that afforded by mistletoe. The isolation of r-inosite from mistletoe is important as affording the first instance of the separation of a racemic sugar from a living organism. The leaves of the mistletoe plant also contain the inosites probably in the form of some compound because the author could only isolate 0.50 gram from 1 kilo.of dry leaves. Lippia scaberrima (Beukess Boss). FREDERICK B. POWER and FEANK TUTIN (Arch. Pharm. 1907 245 337-350; Amev. J. Phcwm. 1907 79 449-462).-Dried stems and leaves of this South African plant were examined. I n addition to resins and other amorphous products the following substances were isolated. (1) An aromatic essential oil (0*25%) b. p. 220-230° Dig 0.950 uD + 7'36' (100 mm. tube). (3) Hentri- acontane C31H6Q m. p. 68'. (4) A paraffin m. p SO" in very small amount. (5) A phytosterol C,7H,,0 m. p. 134'. (6) Unsaturated alcohols probably of the general formula C12H2G-40 and containing one double linking. (7) Formic and butyric acids in the uncom- bined state.(8) Esters of various acids including formic butyric valeric arachic and linoleic. (9) Lippianol C,,H,,O a colourless crystalline substance having the properties of a monohydric alcohol ; m. p. 300-308" (decomp.) [.ID + 65' in 0.5% alcoholic solution. (10) Minute quantities of two yellow crystalline substances m. p. 267' (approx.) and a trace of a colourless crystalline substance m. p. 123". (11) Dextrose (mainly in the inactive form). A glucoside-like substance was also present but mas not isolated; it yielded on hydrolysis dextrose and other products which were not identified. 0. F. B. M. A. W. (2) .Heptacosane C2'7H5G m. p. 59". The Fruit of Styrax Obassia. Y. ASAHINA (Arch. Phawn. 1907 245 325-328).-By extracting the husks with 60% alcohol stymcitol was obtained in yield equal to 10% of the drug.This crystalline substance C,H,,O,,. m. p. 1 5 5 O [u]% - 71*72" is very readily soluble in water sparingly so in strong alcohol; reduces ammoniacal silver nitrate but not Fehling's solution even after boiling with dilute mineral acids although it does so after oxidation with sodium hypobromite or nitric acid; does not form a compound with phenylhydrazine acetate or with benzaldehyde when shaken with the latter and 50% sulphuric acid; yields no crystalline acetyl or benzoyl derivative; forms P-hexyl iodide when distilled with hydriodic acid and yellow phosphorus. The kernels yielded 18% of fatty oil when extracted with ether. The oil expressed from the seeds had DI5 0*974O acid number 9 saponification number 180 iodine number (Hiibl) 127 Hehner's number 91.c. E. B. Physico-chemical Processes in the Production of Soil PAUL ROHLAND (Chem. Zentr. 1907 ii 724 ; from Landw. Jahb. 36 473-483).-The colloids present in soils are derived from feldspar by60 ABSTRACTS OF CHEMICAL PAPERS. the action of water and carbon dioxide. Their coagulation by electro- lytes probably depends on the simultaneous separation of hydroxyl ions from the alkali. Soils containing colloidal hydroxides a t a constant temperature take up or lose water until the vapour tension of the colloid equals the surrounding vapour tension. Alterations in tem- perature continuously alter the amount of water. Adsorption is attributed partly to chemical actions partly to adsorp- tion and is perhaps also due to catalytic influences.N. H. J. M. Protective Action of Colloids on Clay Suspensions. GUSTAV KEPPELER and ALBERT SPANGENBERC (J. Lmdw. 1907,55,299-300). -Kckenberg (ibid. 1906 343) showed that much greater amounts of alkali are required to flocculate suspensions of natural clay soil than in the case of kaolin and attributes his results t o a protective action exercised by the humus. Determinations of the amounts of alkali required for flocculation showed that varying results are obtained with different soils and it is found that the amounts depend on the quantity of humic acid in the soil. N. H. J. IK. Movement of Ammoniacal Nitrogen in Nature. PAUL EREENBERG (Chem. Zentr. 1907 ii 723-724 ; from Mitt. Landw. Imt. K. Umiv. Breslau 1907 4 1-254).-Loss of ammonia by evaporation from soils is only to be expected in the case of sandy soils containing much calcium carbonate and deficient in zeolitic compounds and humus and then only at the highest summer temperatures when the soil is dried up and when there has been a heavy application of nitrogenous manure.Ammonium salts are undoubtedly directly utilised by plants. With the exception however of plants utilizing acids the amount of nitrogen so taken up is insuficient and for satisfactory growth nitri- fication is essential. Even then the loss is extremely small. N. H J. M. Influence of Plant Constituents on the Physical and Chemical Properties of Soils. VIKTOR ZAILER and LEoPoLn WILK (Chem. Zen&. 1907 ii 732-734 ; from Zeitsch. Moorkultur u. Torfverwert.1907 l-l09).-The physical properties of peat especially when only slightly decomposed which vary distinctly when the peat is derived from only very distantly related plants are coherence density capacity for holding water hygroscopicity and absorptive power ; other physical properties seem to depend less on botanical composition. Hygroscopicity decreases as decomposition proceeds notwithstanding the increase of humus substances. Absorp- tion of ammonia depends chiefly on free humic acid and related colloids. The amount of ash in peat is generally higher than would be indicated by the botanical composition. Potassium and sodium salts are almost completely washed out and phosphoric acid to a considerable extent whilst calcium and iron remain almost unchanged in quantity.The amount of nitrogen depends mainly on the amount originally present in the plants and to a less extent on chemical processes and chitinous remains. N. H. J. M.ANALYTICAL CHEMISTRY 61 Fallow. WILHELM KEUGER and BERTHOLD HEINZE (Chent. Zentr. 1907 ii 726 ; from Las~ctw. Jahrb. 36 3S3-423).-During a fallow the amount of soluble forms of nitrogen especially nitrates increases. The number of micro-organisms increases a t first and then gradually diminishes. The total nitrogen seemed to increase but this requires confirmation. N. H. J. M. Manurial Experiments with Different Kinds of Nitrates. JOHN SEBELIEN (Landw. Yersuchs-Xtat. 1907 55 293-297).-Pot experiments with white mustard grown in poor sandy soil showed that the yield when manured with calcium nitrate and with “ sulphate- nitrate ” respectively was about five times as great as with sodium nitrate and that far greater amounts of these manures may be applied without injury as compared with the ordinary inorganic nitrogenous manures.‘‘ Sulphate-nitrate ” [CaSO + 2(NH4),N0,] is prepared by mixing calcium nitrate with ammonium sulphate (equal mols.) the idea being to avoid the difficulty in the use of calcium nitrate due to its deliquescence. Further experiments with oats grown in sandy soil and in loam showed that sodium and calcium nitrates had about equal effects. N. H. J. IT. Is a Favourable Stimulating Effect on the Development of Crops by Small Amounts of Manganese Salts Observable in the Field? HJALMAR TON FEILITZEN (J. Landw. 1907 55 289-292).-The soil on which the experiment was made consisted chiefly of slightly decomposed sphagnum peat and has been under cultivation since 1894 when sand and lime were applied as well as artificial manures which have been applied each year since. An application of 10 kilos. of magnesium sulphate per hectare was found to have no effect on oats. N. H. J. 3%. Leucite and its Application as a Manure. UGO ALVISI and DOMENICO VENDITORI (Gaxzetta 1907 37 ii 379-383).-No action takes place between leucitic materials and superphosphates when these are applied together as manures so that the value of the super- phosphate remains uninjured. T. H. P.

ISSN:0368-1769    

DOI:10.1039/CA9089405056

出版商:RSC    

年代:1908

数据来源: RSC

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ANALYTICAL CHEMISTRY A n a l y t i c a l Chemistry. 61 Improvements in Hemple’s Gas-Analysis Apparatus. GEORGE DE VOLDERE (Chem. Zentr. 1907 ii 11 13-1 114 ; from Zeitsch. chrn. Apparaternkunde 1907,2 344-346).-The levelling tube is replaced by a levelling reservoir fitted with a side tube having the same diameter as the burette. The burette is constructed as recommended by Pfeiff er62 ABSTRACTS OF CHEMICAL PAPERS. (Abstr. 1907 ii 194) but the capillary tube between the first enlargement and the stopcock has been omitted and a four-way cock has been put instead whilst a second tube serves for the purpose of applgifg suction or pressure. The chief advantage of this arrange- ment is that the burette can be fixed firmly by means of a clamp. The U-tube in the pipette has been also replaced by a four-way stop- cock.For further details the illustrations in the original article should be consulted. A convenient apparatus is also described for the combustion of gases by means of palladium asbestos. L. DE K. Use of Chloral Hydrate Chloral Alcoholate and Bromal Hydrate Solutions in Chemical Microscopic and Micro- chemical Investigations. EDUAXD SCHAER (Be?*. deuut. piharm. Oes. 1907 17 407-41 3).-Aqueous and alcoholic solutions of chloral hydrate and bromal hydrate dissolve a large number of inorganic and organic substances which have no other common solvent. Where complete solution of a mixture is necessary or advantageous as a preliminary step to the detection or separation of its components the employment of 60% to 80% aqueous or alcoholic chloral hydrate solutions as the solvent is recommended.The value of chloral hydrate as R clearing agent for microscopic [preparations depends on its penetrating power as also on its action as a solvent for the cell contents which render the preparation opaque. I n many cases the best results are obtained by successive treatment with concentrated aqueous and alcoholic solutions. I n microchemical analysis it has been found possible with the aid of chloral hydrate solutions of the alkaloid reagents to determine the location of alkaloids in plant structures. G. Y. Isolation of Traces of Mineral Substances from Saline Mixtures. Application to Medical Chemistry Toxicology and Hydrology Q. M E I L I ~ E (J. I’l~ccrm. Chim. 1907 {vi] 26 443-460).-A summary of the methods used in analysis for concentrating small quantities of substances which might otherwise escape detection.For instance traces of lead in water are carried down completely by adding a little copper sulphate before passing hydrogen sulphide and phosphoric and arsenic acids are precipitated completely in presence of ferric hydroxide. I n some cases extraction by means of an immiscible solvent in a suitable apperntus gives good results. Strong hydrochloric acid extracts lithia from alkali chlorides &c. L. DE Addition of Indigo in Titrations with Methyl- or Ethyl- orange. ROBERT LUTHER (Chem. Zeit. 1907 31 1172. Compare Kirschnick Abstr. 1907 ii 910).-Solutions of indigo-carmin and methyl-orange are mixed in such proportions that when added to a saturated solution of carbon dioxide in water a neutral grey tint is obtained (compare Kiister Abstr. 1897 ii 74).When such a mixture of methyl-orange and indigo-carmin is used the change of colour during the titration of an alkali wit.11 acid is as follows yellow,ANALYTICAL CBEMISTRY. 63 green colourless (or grey if a large quantity of indicator is taken) violet. The change from green or violet to the neutral grey or colour- less stage is said to be very decided and sharp. The addition of indigo t o solutions which are tinted yellow is also advantageous. Behaviour of Chlorates and Perchlorates during Reduction. DOMENICO VENDITORI (Gaxxetta 1907 37 ii 383-386).-1n presence of sulphuric acid finely-divided aluminium reduces chloric acid completely t o hydrochloric acid but has no reducing action on perchloric acid.Chloric acid may hence be estimated by converting it into hydrochloric acid and then estimating the latter by Trolhard’s method. T. H. P. W H. G. Detection of Fluorine Compounds in Wines. L. VANDAM (Ann. China. anal. 1907 12 466-468; Rev. irztem. Fahi$ 1907 20 147-14S).-Two hundred C.C. of the sample are mixed with a few drops of a 20% solution of sodium sulphate and then with 10 C.C. of a 10% solution of barium acetate. After twelve hours the bulk of the liquid is poured off and the precipitate collected on a filter washed dried and ignited in a platinum crucible. After moistening with a drop of water a little sulphnric acid is added and the crucible is at once fitted with an india-rubber ring supporting a paraffin-coated match-glass the convex part of which carries a n inscription made with a soft point.The watch-glass is kept cold by a current of cold water. After heating the crucible for half an hour on a boiling water-bath the watch-glass is gently heated to melt the paraffin coat- ing and wiped with a soft linen cloth. If the sample is pure no inscription will be visible or at most but very faintly on breathing on the glass but a visible etching is noticed even when there is as Estimation of Sulphur Dioxide in Wines. CARLO MENSIO (Gaxxefh 1907 37 ii 344-355).-The maximum amount of total sulphur dioxide per litre of mine permitted in ItaIy is 0.2 gram of which not more than 0.02 gram should be in the free state. According t o the official method of estimat’ion sulphur dioxide which is evolved from mine on boiling is regarded as existing in the free state i n the wine.The author shows that t h i s view is inaccurate since compounds such as that formed by sodium hydrogen sulphite with acetaldehyde give up from 30% to 75% of their suiphur dioxide when boiled in aqueous solution and from 90% to 95% when boiled with wine. The most accurate method of estimating the total sulphur dioxide in wine consists in acidifying with phosphoric acid and distilling in a current of carbon dioxide the distillate being collected in iodine solution in which the sulphur dioxide may be estimated either by titration of the excess of iodine with sodium thiosulphato or by Haas’s method (Abstr. 1882 773). None of the methods given for estimsting free sulphurous acid in a mine yields accurate results.As the experiments of Franz and Eost (Abstr. 1904 ii 632) indicate that the toxic action of combined sulphur dioxide is not greatly dissimilar from that of the uncombined and as the presence little as 10 mgs. of ammonium fluoride per litre. L. DE K.64 ABSTRACTS OF CHEMICAL PAPERS. of the latter in a wine is detectable by the taste the fixing of a limit to the proportion of free sulphur dioxide should be abolished. T. H. Y. Digestion of Urine in the Estimation of Nitrogen by the Kjeldahl Method. PHILIP B. HAWK (J. Arner. Chenz. Xoc. 1907 29 1634-1 637).-The nitrogen in urine may be estimated equally well by digestion with sulphuric acid and copper sulphate sulphuric acid and metallic mercury or sulphuric acid metallic mercury and potassium sulphate added towards the end.In any case the boiling Alkalimetric Estimation of Phosphoric Acid by Neumann’s Method. J. P. GREGERSEN (Zeitsch. physiol. Clbern. 1907 53 453-463. Compare Abstr. 1903 ii 243; 1905 ii 68).-As the result of numerous series of experiments the conclusion is drawn that Neumann’s method gives excellent results when the following precautions are taken. I n the destruction of the organic material and the formation of ash 20 C.C. of Neumann’s acid mixture should be used and during the process concentrated nitric acid and not the mixed acids should be dropped in. I n the precipitation 250 C.C. of liquid should be used and this should contain 15% of ammonium nitrate only a slight excess of ammonium molybdate being employed; thus for 10-15 mgs.phosphorus 4 grams of molybdate suffice. I n the final titration it is advisable to add a slight excess of standard acid to boil in order to remove carbon dioxide and then to titrate back with 0*5N sodium hydroxide. Estimation of Phosphoric Acid in Basic Slags by Grete’s Method. C. H. KETNER (Chem. TKeekbZud. 1907 4 757-764).- Grete’s method (titration with gelatin-molybdenum solution until no further precipitate is formed) has been applied.successfully in the Dutch agricultural stations but for soluble phosphoric acid only. The author has tried to use it for total phosphoric acid also and after some trials has succeeded by working as follows. Ten grams of the basic slag are powdered moistened with a little water and then heated in a 500 C.C.Jena flask_with 50 C.C. of sulphuric acid for about half an hour and until white fumes are formed. When cold water is added and when again cooled water is added up to the mark and the whole is thoroughly shaken and filtered. Twenty-five C.C. of the filtrate are neutralised with ammonia 20 C.C. of ammonium nitrate solution (1 a) a teaspoonful of powdered potassium nitrate and 15 C.C. of nitric acid D 1.2 are added and the solution is then heated to boiling and titrated. In standardising the gelatin-molybdenum solution as usual with dihydrogen potassium phosphate in presence of the above substances there should also be added 16 C.C. of 10% ammonia previously neutralised with dilute sulphuric acid. should be continued for a t least thirty minutes.L. DE K. J. J. 8. L. DE K. Estimation of Arsenic by the Gutzeit Method. CHARLES R. SANGER and OTIS F. BLACK (J. Xoc. Chem. Incl. 1907 26 1115-1123).-The modification suggested by the authors in order t oANALYTICAL CHEMISTRY. 65 make the Gutzeit method quantitative consists in allowing the arsine to pass over the surface of a strip of paper impregnated with mercuric chloride. The band of colour thus obtained is compared with a series of bands prepared from known amounts of arsenic. The sensitised paper is inserted in the form of a strip in a horizontal delivery tube leading from the evolution flask The exact method of carrying out the estimation is given a t length in the original paper together with remarks on the precautions to be observed and on tho influence of certain interfering substances.w. P. s. Estimation of Arsenic in Urine. CHARLES R. SANGER and OTIS F. BLACK (J. SOC. Chenz. Ind. 1907 26 1123-1127 ; Zeitsch. anorg. Chew. 1907 56 153-157).-The evaporated urine is dis- tilled with hydrochloric acid the distillate is oxidised with nitric acid the latter is removed by heating with sulphuric acid and the remain- ing solution is used for the estimation of the arsenic. About 200 C.C. of the urine are evaporated to a volume of 35 C.C. and then introducedintoa distillation flask. One hundred C.C. of pure hydrochloric acid are added and the mixture is distilled the distillate being collected in a receiver containiug 25 C.C. of concentrated nitric acid. When about 100 C.C. have distilled over the distillate is treated with a further 25 C.C.of nitric acid and evaporated to a small bulk ; 5 C.C. of sulphuric acid are next added and the heating continued until the nitric acid has been expelled. The residue is diluted with water to a definite volume and EL part of it employed for the estimation of the arsenic the Marsh- Berzelius method being used for the latter purpose w. P. s. Estimation of Hydrofluosilicic Acid. SANUEL H i i ~ ~ a (Chenz. Zeit. 1907 31 1207-120S).-The process is based on the fact that 1 mol. of hydrofluosilicic acid is neutralised by 2 mols. of sodium hydroxide when using methyl-orange as indicator whereas 6 mols. aro required if phenolphthalein is the indicator. Twenty-five C.C. of the sample are titrated with N-sodium hydroxide in presence of methyl-orange The result equals hydrofluosilicic acid and any other mineral acid present.The liquid is now heated to boiling and titrated while hot with phenolphthalein as indicator. Four mols. of sodium hydroxide now represent 1 mol. of hydrofluosilicic acid. The method is not strictly accurate owing to the slight dissocia- tion of the sodium silicofluoride formed but this does not interfere with its technical application. L. DE I<. The Carrasco-Planoher Method of Estimating Carbon and Hydrogen in Organic Suhtances. WILHELM LENZ (Zeitsch. ccnal. Chem. 1907 46 557-565).-The results of a number of estimations of carbon and hydrogen in salicylic acid by this method (Abstr. 1906 ii 201) are given. Whilst in some cases the quantities of carbon and hydrogen found agreed with those required by theory in others the carbon was as much as 3.5% too low.The loss was due to the forma- tion of carbon monoxide ; the quantity of the latter produced appeared t o depend on the speed at which the combustion was carried out the VOL. xciv. ii. 566 ABSTRACTS OF CHEMICAL FAPERS. longer the time taken for the estimation the greater the amount of carbon monoxide formed. Estimation of Carbon Monoxide in Atmospheric Air. J. LIVINGSTON K. TVIORGAN and JOHN E. MCWIIORTEH (J. Amer. Chem. Soc. 1907 29 15S9-1592).-The air is passed first through tubes containing sulphuric acid and potassium hydroxide. If it is desired to estimate also the carbon dioxide another tube containing standard barium hydroxide is placed in front of the sulphuric acid tube.The carbon monoxide is then absorbed in a U-tube cor~taining iodine pent- oxide and heated a t 150' in a glycerol-bath The products of the reaction free iodine and carbon dioxide are passed through a tube containing potassium iodide solution and the iodine is af terwards titrated with iV/lOOO thiosulphnte by way of a check. The carbon di- oxide is absorbed in standard barium hydroxide the excess of which is then titrated as usual with standard oxalic acid In estimating carbon monoxide by passing it over iodine pentoxide the ends of the lJ-tube should be sealed off after filling so as t o avoid traces of greasy matter from the lubricant used with glass stoppers. w. P. s. L. DE K Volumetric Estimation of Potassium as the Cobaltinitrite. %V. A. DRUSEIEL (Anzer.J. Sci. 1907 [iv] 433-438 ; Ze&tsc?$. anorg. Chem. 1907,56 223-329).-A moditication of the method proposed by Adie and Wood (Trans 1900 37 1076) The solution is mixed with excess of sodium aobaltinitrite and a little acetic acid and evaporated to a pasty condition on a water-bath. The residue is treated with cold water and the precipitate collected and washed on a n asbestos filter. The filter and contents are then heated with excess of N/10 permanganate for some five minutes when excess of dilute sulphuric acid ( 1 7) is added and the whole heated short of boiling until the manganese precipitate has completely dissolved. The excess of permanganate is estimated as usual by first bleach- ing with N/10 oxalic acid and then titrating with permanganate. Working in this manner 1 c,c.of N/10 permanganate=0*000856 gram of K,O The process is suitrible for the estimation o€ potash in manures not being interfered with by the presence of phosphoric acid. New Volumetric Method of Estimating Sodium Sulphide. E. PODRESCHETNIKOFF (Zeitsclh. 8 w b . Ind. 1907 6 3SS).-The new method permits of the estimation of both sodium hydroxide and sodium sulphide owing to the latter undergoing complete hydrolysis in dilute solution according to the equation Na,S e H,O = NaHS + NaOH. On titrating a very dilute solution of the sulphide with N/10 sulphuric acid in the presence of phenolphthalein as indicator the quantity o€ sodium sulphide plus the free hydroxide is obtained. The amount of sulphide alone is then determined by adding a slight excess of formalde- hyde and titrating by means of the acid the sodium hydroxide liberated according to the equation NaHS + CH,O + H,O = NaOH + OH*CH,-SH.The results obtained by this method are quite accu- rate. W. A. D. L. DE K.ANALYTICAL CHEMISTRY. 67 Biological Method for Estimating Alkali Carbonates in Soils. HARALD R. CHRISTENSEN (Cents.. Bakt. Par. 1907 ii 19 735-736).-1t was shown previously that azotobacter is unable to utilise calcium in the form of sulphate chloride and tribasic phosphate. It is now shown that scme soils deficient in cdcium in conjunction with mannitol and potassium phosphate will develop a growth of azotobacter when supplied with calcium sulphate similar to that obtained when calcium carbonate is added. Such soils show almost invariably an alkaline reaction and the conclusion is drawn that an alkali carbonate is present which interacts with tho calcium salt to form calcium carbonate.It is proposed to utilise the different behaviour of calcium sulphate in different soils for ascertaining the amounts of alkali carbonates present. N. H. J. &I. Volumetric Estimation of Magnesium. LEOPOLD ROSENTHALER (Zeitsch. and. C h m 1907 46 714-716).-The magnesium salt is dissolved and treated with a measured volume (an excess) of potassium hydrogen arsenate KH AsO solution (containing about 9 grams per litre). The mixture is then diluted to a known volume with 10% ammonia and mixed. After three hours the solution is poured through a filter and a portion of the filtrate say 100 c.c is evaporated to dryness on the water-bath.The residue is dissolved in a very little water the solution is transferred t o a stoppered flask the basin is rinsed out with a little concentrated hydrochloric acid which is also added to the flask and the acid solution is then treated with con- centrated potassium iodide solution. If a precipitate forms a little more water is added ; if not hydrochloric acid is added before adding the water. The liberated iodine is then titrated back with thiosulphate solution. The difference between the amount of potassium hydrogen arsenate added and that found in excess represents the quantity precipitated with the magnesium ; 1 C.C. of N/10 thiosulphate solution corresponds with 0*002018 gram of magnesia (MgO). 'cv. P. s. Detection of Small Quantities of Zinc by Electrochemical Means.WALTEH. NEUMANN (Zeitsch. Elektrochem. 1907 13 751-752). -The solution to be tested containing sufficient potassium hydroxide t o render it roughly N / l O is electrolysed using a small platinum bead as anode and a brightly polished thin copper wire as cathode. Should zinc be present the copper becomes coated with a bright white deposit of zinc which may be removed by dipping the wire in 2iV potassium hydroxide solution. It is possible by this method to detect zinc in 0.1 C.C. of a N/40,000 solution of the metal. The solution to be tested must not contain chloride or nitrate. W. H. G. A Method of Estimating very Small Quantities of Zinc. GABRIEL BERTRAND and MAUKICE J AYILLIER (Conzpt. rend. 1907 146 924-926).-The method described previously (Abstr.1907,ii 53) of precipitating small quantities of zinc in the form of hydrated calcium zinc oxide can be employed for the estimation of the metal in solutions containing 0.1 mg of zinc in 3 litres in the presence of tin antimony 5-268 ABSTRACTS OF CHEMICAL PAPERS. arsenic copper cadmium cobalt lead silver iron manganese alumin- ium barium calcium magnesium sodium and potassium as carbonates chlorides sulphates nitrates phosphates silicates and sulphides. For details of the separation the original must be consulted. The final separation of the zinc from the calcium in the hydrated calcium zinc oxide is best effected by dissolving in hydrochloric acid evaporating t o dryness precipitating the zinc as sulphide in the pre- sence of sodium acetate and weighing as the sulphate.Rapid Estimation of Zinc by Electrolysis. FRANCIS C. FRARY (J. Amer. Chem. Xoc. 1907 29 1596-1603).-A solution contain- ing about 8 grams of sodium hydroxide and 0.1 gram of zinc deposits all the metal on a nickel gauze in thirty minutes with electromagnetic rotation (Abstr. 1907 ii 649) and a current of 4.5 amperes. The temperature should be as low as possible. For quantities of zinc up to 0.2 gram the strength of the current should be 4.5 amperes for fifteen minutes and then 1.5 amperes for twenty minutes. It is advis- able always t o test the electrolysed liquid to see whether the precipita- A. R. THORNEWELL (Chem. Zentr. 1907 ii 1269 ; from Chemist and Druggist 1907,71 413).-The solution should be perfectly neutral to methyl-orange and contain about 0.3 mg.of zinc per C.C. Two hundred C.C. are mixed with 25 C.C. (or more) of N-sodium hydroxide previously saturated with hydrogen sulphide and the whole is diluted to 250 C.C. and well shaken. Twenty-five C.C. of the clear supernatant liquid are then mixed with 25 C.C. of N/10 sulphuric acid the hydrogen sulphide is expelled by boiling and when cold the excess of acid is titrated mibh NIlO sodium hydroxide using methyl-orange as indicator. The zinc is then calculated from the amount of alkali Volumetric Estimation of Lead. €1. BOLLENBACH (Zeitsch. ccnab. Chem. 1907 46 582-588).-1n the process described ths lead solution is titrated with permanganate in alkaline solution. Sodium hydroxide is added to the lead solution until the precipitate which at first forms is redissolved and the whole is then diluted to a known volume.Fifty C.C. of this solution are run from a burette into a measured excess of potassium permanganate solution placed previously in a 500 C.C. flask together with 300 C.C. of hot water and 5 C.C. of N/2 sodium hydroxide solution. The addition of the lead solution is accom- panied with constant agitation of the permanganate mixture. After the lead solution has been introduced the solution is cooled diluted to 500 c.c. and the excess of the permanganate estimated either iodo- metrically or by the use of a lead solution of known strength. The per- manganate solution should contain 3 9 grams of the salt per litre and be titrated against the standard lead solution. The reaction takes place according t o the formula 2KMn0 + 6Pb(ONa) = 2Mn0 c 3Pb,0 + K,O + 6Na20.The presence of chlorides bromides and sul- phates has no influence on the results obtained by the method but iodides and substances which reduce permanganate should not be M. A. W. tion has been complete. L. DE K. Estimation of Zinc. absorbed. L. DE K. present. w. P. s.A N A LY T I C A L C H E R l I STRY . 69 Red Leads and their Examination. ALFRED PARTHEIL (Arch. P?tumn. 1907 245 519-528).-According to the Deutsche Arznei- buch IV the purity of red lead may be tested by adding 2.5 grams of the material mixed with 0.5 gram of oxalic acid to 10 C.C. of hot nitric acid and then adding gradually 25 C.C. of hot water ; not more than 0.035 gram should remain undissolved. It is shown that this test is quite useless owing to the formation of insoluble basic lead oxalates lead oxalonitrate C ~ C .The following method is said to give better results 10 C.C. of water 5 C.C. of lactic acid and 10 C.C. of 25% nitric acid are added to 2-5 grams of the red lead ; R violent reaction takes place after which the insoluble residue is weighed. JAROSLAV MILBAUER and VLADIM~R STAN~K (Zeitsc?~ anal. Clmt. 1907 46 644-656).-The well-known blue coloration produced when copper sulphate solution is treated with ammonia has not always the same intensity for equal quantities of the metal. Increasing quantities of ammonia or ammonium chloride diminish the depth of colour whilst ammonium carbonate has the opposite effect the maximum coloration obtained with ammonia and copper sulphate being increased by one-third on the addition of ammonium carbonate.Potassium hydroxide in the presence of amines gives with copper sulphate a coloration varying from 56% to 66% of that obtained with ammonia. Many other instances are given but in each the coloration is less than that yielded by ammonia. An ammoniacal copper solution has a coloration one hun- dred and fifty times more intense than a copper sulphate solution Estimation of Mercury by Reduction with Hydrogen .Per- oxide. A. KOLB and A. FELDHOFEN (Zeitsch. angem. Chenz. 1907 20 1977-1 gSO).-Twenty-five C.C. of mercuric chloride solution con- taining about 0.1 gram of mercury are mixed with 25 C.C. of 2iY hydro- chloric acid and 25 C.C. of 10% tartaric acid solution. The liquid is neutralised with ammonia and again faintly acidified with tartaric acid.The whole is heated on the water-bath and 10 C.C. of hydrogen peroxide are added and then from time t o time another5 c.c. so that 25-30 C.C. are used in the space of forty-five minutes. The precipitated calomel may be collected and weighed or better titrated iodometrically . The process is also useful for the separation of mercury from arsenic Detection of very Small Quantities of Mercuric Chloride. K. KOF and HUGO HAEIIN (Arch. Pharm. 1907 245 529-533).- The vapour arising from a mercuric chloride solution can not only be caught on a photographic plate (compare Abstr. 1907 ii 7321 but also on moist filter paper. A moistened filter paper resting on a thin glass slide and placed for one hundred and sixty-five hours at a distance of about 1 cm.above the surface of a 2% aqueous solution of mercuric chloride turns dark when treated with hydrogen sulphide except where it has been protected by the strip of glass. The photographic effect may be employed W. H. G. Colorimetric Estimation of Copper. containing the same quantity of copper. w. P. s. antimony tin cadmium and bismuth. L. DE K.70 ABSTRACTS OF CHEMICAL PAPERS. for the detection of small quantities of mercuric chloride. A dist,inct white patch is obtained on developing a photographic plate which has been kept at a distance of 2 to 3 mm. from one drop of a 0.01% solution of mercuric chloride for twenty-four hours. The same effect on the plate is produced if instead of the drop of mercuric chloride solution one drop of the distillate obtained by steam-distilling 100 C.C.of a 0.01% mercuric chloride solution until 100 C.C. of distillate are OF- tained is employed. Acidimetric Assay of White Precipitate. ERWIN RUPP and F. LEHMANN (Phccmt. Zeit. 1907 52 1014).-0+2-03 Gram of the powdered sample is dissolved in 50 C.C. of water and 2-3 grams of potassium iodide and the ammonia and potassium hydroxide liberated in the reaction are titrated with N/10 hydrochloric acid with 1-2 drops of 0.2% alcoholic methyl-orange solution as indicator. 0.2 Gram of the commercially pure article requires 1506-16 C.C. of N/IO acid. W. H. G. L. DE K. Complete Analysis of Mercury Cyanides. ERWIN RUPP and F. LEHMANN (Pharrn. Zeit. 1907 52 1020).-One gram of the com- pound is dissolved and the solution made up t o 100 C.C.In order to estimate the mercury 20 C.C. are placed in a flask and after adding 1-2 grams of potassium iodide and 3-6 C.C. of officinal potassium hydroxide the mercury is reduced to the metdlic stato by adding 2-3 C.C. of officinal formaldehyde previously diluted with 20 C.C. of water. After shaking thoroughly for two minutes a slight excess of acetic acid is added and then 25 C.C. of N/lO iodine. When after repeated shaking the mercury has redissolved 10 C.C. of dilute sulphuric acid are added and the excess of iodine is titrated with N/10 thiosulphate. I n order to estimate the cyanogen 10 C.C. of the solution are mixed with a little water and 5-10 C.C. of officinal sodium hydroxide and 25 C.C. of N/10 iodine are added slowly with con- stant agitation.The whole is allowed to remain for two t o three hours or else heated for twenty to thirty minutes in the water-bath. The liquid is diluted to 100 c.c. acidified with about 25 C.C. of hydrochloric acid and titrated with thiosulphate ; 0.1 gram of mercury Borax Bead Test for Praseo- and Neo-dymium Salts. JAROSLAV MILBAUER (Zeitsch. anal. Chem. 1907 46 657-658).-The following colorations are obtained when these s a h are heated in the usual way on a borax bead. Neodymium in oxidising flame no colour; in reducing flame violet if sufficient of the salt is used. Praseodymium oxidising flame yellowish green ; reducing flame green. The colorations are seen only when the bead is cold. Beads consisting of phosphates may be employed in place of borax.cyanide = 15.87 C.C. of N/10 iodine. L. DE K. w. P. s. Detection and Estimation of Small Quantities of Man- ganese. MAURJCE DUYE (Ann. Chim. anal. 1907 12 465-466).- A pink or red coloration is obtained when a trace of manganese salt is heated with moderately alkaline potassium hypochlorite solution (10%)ANALYTICAL CHEMISTRY. 71 to which has been added 1 drop of copper sulphate solution (10%). A precipitate of cupric oxide is produced and the coloration is observed in the Fupernatant liquid. The reaction may be made quantihative by comparing the coloration obtained with that produced by known Modiflcation of Volhard's Method of Estimating Man- ganese. ERWIN W. MAYER (Zeitscl~ angew. Chem. 1907 20 1980-1 981).-Four modifications of the process are described of which the following two are the most suitable for technical purposes. (1) One gram of ferromanganese 4 grams of pig-iron or 8 grams of steel are dissolved in nitric acid (D 1.2)'; thesolution is evaporated to R small bulk diluted with water introduced into a litre-flask and mixed with a sufficiency of zinc oxide emulsion to precipitate the iron.The whole is then diluted to 1 litre and in 250 C.C. of tho filtrdte the manganese is titrated with standard permanganate (2) The sample is dissolved as before in nitric acid but before boiling down cz few Clay Analysis. Residue Left After Volatilisation of the Silica with Hydrofluoric and Sulphuric Acids. W. R. BLOOR (J. Amer. Chem. Soc. 1907 29 1603-1 606).-Experiments showing that the residue obtained on heating the separated silica with hydrofluoric and sulphuric acids does not consist of iron and aluminium oxides only but contains also the other constituents of clay such as calcium and Precipitation of' Iron by Ammonia in Presence of Tartaric Acid.WILHELM STRECRER (Chem. Zeit. 1907 31 1217. Compare Grossmann and Schuck Abstr. 1907 ii 819).-Ferric hydroxide is precipitated completely on addition of ammonia to a soIution con- taining 0.1110 gram of iron in the ferric state and 0.1911 gram of tartaric acid in 53 C.C. If a larger proportion of tartaric acid is present the precipitation is incomplete and is finally inhibited Attempts to isolate a complex compound from the resulting red solu- tion containing excess of tartaric acid have been unsuccessful as the products obtained do not have a constant composition (compare MAhu Colorimetric Comparison of Copper and Nickel Solutions.JAROSLAV MILBAUER (Zeitsch. anal. Chem. 1907 40 656-657).- Nickel salts when treated with ammonia give a similar blue coloration to that obtained with copper salts. The author finds that one part of copper gives a coloration equal t o that yielded by eighteen parts of nickel and this fact renders the test of little use in testing very small quantities of the latter metal. I n fact a N/100 ammoniacal nickel solution is practically colourless whilst a copper solution of equivalent concentration has a marked blue colour. amounts of manganese. w. P. s. drops of hydrochloric acid are added. L. DE K. magnesium oxides also titanium. L. DE K.Jalmesber. Chem. 1873 569). a. Y. w. P. s. Brunck's Dimethylglyoxime Procees for the Estimation of Nickel. HERRMANN GROSSMANN and BERNHARD SCEI~CK (Xeitsch. angew. Chsna 1907 20 1981-1982).-~ reply to Grunck (Pbstr.,72 ABSTRACTS OF CHEMICAL PAPERS. 1907 ii 989) in which the authors uphold the accuracy of their own dicyanodiamidine process. L. DE K. Volumetric Estimation of Bismuth. RICHARD EHRENFELD (Zeitsch. unal. Chern. 1907 46 710-71 l).-The process consists in precipitating the bismuth with excess of sodium phosphate and afterwards titrating back this excess. The bismuth solution is acidified with nitric acid to prevent the formation of basic salt a known excess of sodium phosphate solution is added and the mixture is diluted to a known volume. After filtration or settling the excess of phosphate is titrated in a portion of the clear solution; uranium acetate solution is used for the titration and suflicient sodium acetate is added to the solution to be titrated in order to remove the free nitric acid {compare Abstr. 1906 ii 55 ; 1907 ii 403).w. P. s. Apparatus f o r the Prevention of Acid Fumes in Gold and Silver Assaying. DARD (Ann. Chim. ancd. 1907 12 425-426).- A portable apparatus which may be placed in front of any kind of chimney. The hydrochloric or nitrous vapours are made to traverse a layer of fragments of white marble and the carbon dioxide liberated is carried off by a central chimney-funnel which will act readily owing to the heat given off by the burners. Several assays can be made simultaneously without suffering from irritatiog fumes. L.DE K. Refractometric Analysis of Organic Mixtures. ADOLF BEYTHIEN and R. HENNICKE (Pharm. ZentT.-h. 1907,48,1005-1013). -The composition of a mixture containing any two of the following substances may be ascertained from its refractive index the constants taken being acetone ng 1.3620 nz 2.3590 ; carbon disulphide n:” 1.6315 ; oil of turpentine ng 1-4690 ; carbon tetrachloride nz 1.4630 ; xylene qag 1.49680 ; ethyl bromide n1,5 1.42540 ; chloro- form ng 1.4466. Mixtures containing three of these substances may be analysed in the same way if one of the constituents can be estimated by a separate method. w. P. s. Reaction of Phloroglucinol-Hydrochloric Acid with Essential Oils. KARL KOBERT (Zeitsch. anal. Chem. 1907 46 711-714).- The author finds that only those essential oils which contain an allyl- group give a red coloration when treated with a hydrochloric acid solution of phloroglucinol.A red coloration is obtained with the essential oils of mustard cloves pimento dill orange-blossom jaborandi leaves tarragon basil bay lavender Peru balsam geranium parsley and sassafras. w. P. s. Detection of Methyl Alcohol in Fermented Liquids. JULES WOLFF (APLPZ. Chin2. anccZ. 1907 12 470-471).-Any alcoholic liquid containing sucrose invert-sugar or caramel should be redistilled before testing it for methyl alcohol by means of chromic acid &c. (formation of formaldehyde polymerides). These substances yield formaldehydeANALYTICAL CHEMISTRY. 73 when thus tested and consequently methyl alcohol may be stated to be present in a spirit when such is not the case.w. P. s. Normal Tubes for the Polarimetric Estimation of Sucrose. H. ROUSSET (Ann. Chim. a n d 1907 12 468-470).-The use of tubes 1’79.2 mm. and 358.4 mm. in length is recommended for the estimation of sucrose by means of Laurent and Duboscq’s or Vivien’s polarimeters. The weight of the sample taken is 20 grams in 100 C.C. of water and the percentage of sucrose is obtained without calculation. w. P. 8. Estimation of the Most Important Acids that Occur in Wine in Presence of Alcohol and Glycerol. A. HEIDUSCHKA and GEORGE QUINCKE (Arch. Phccrm. 1907 245 458-461).-The method described was tested with a mixture of acetic lactic tartaric malic and succinic acids with alcohol and glycerol (and water) and found t o give good results.Of such a mixture 50 C.C. are neutralised with aqueous barium hydroxide and evaporated to 15 c.c. care being taken to keep the liquid neutral. The residue is rinsed with a little hot water into a measuring cylinder and mixed with so much alcohol that the mixture contains 80% (by volume) of the latter. The precipitate of barium tartrate malate and succinate is collected on a filter and washed with 80% alcohol. The filtrate which contains barium acetate and lactate and glycerol is freed from alcohol by evaporation and diluted t o a known volume. An aliquot portion is distilled under diminished pressure the distillate is diluted to a known volume an aliquot part of it is oxidised with a large excess of potassium dichromate and dilute sulphuric acid (say 5 C.C.with 50 C.C. N / l O dichromate solution and 50 C.C. 20% sulphuric acid) by heating for one hour in a pressure-bottle in t.he water-bath and the excess of dichromate is estimated by adding potassium iodide and titrating with N/10 sodium thiosulphate solution; in this way the glycerol is determined. An aliquot portion of the filtrate is oxidised in the same way without being distilled first ; in this way the sum of t h e glycerol and the lactic acid is determined (C,H,O requires 20). The precipitated barium salts with the filter are brought into a measuring cylinder stirred with 20 C.C. of water containing some sulphuric acid diluted with alcohol to 100 c.c. and filtered. Of the filtrate 80 C.C. are mixed with 0.5 C.C. of 20% potassium acetate solution 15 grams of powdered potassium chloride and 2 C.C. of acetic acid and allowed t o remain for twelve hours ; the Precipitated potassium hydrogen tartrate is then filtered off and its amount determined by titration.The filtrate is freed from alcohol by evaporation mixed with 50 C.C. of dilute sulphuric acid and titrated with N / l O potassium permanganate solution; in this way the malic acid is determined (C4H605 requires 60). The oxidised liquid is evaporated to dryness with quartz sand the residue is extracted with ether the extract is evaporated and the succinic acid left is weighed. The alcohol is estimat,ed by neutralising another portion of the original mixture distilling off the alcohol and oxidising a portion74 ABSTRACTS OF CHEMICAL PAPERS.of the distillate with dichromate and sulphuric acid as described above (C2'EI,0 requires 20). The acetic acid is estimated by distilling another portion of the original mixture and titrating the distillate. C F. B. Estimation and Colour Reactions of Qlycuronic Acid. K. U. L E F ~ V ~ ~ E and BERNHARU TOLLENS (Ber. 1907 40 4513-4523 ; Zeitsch. Fer. deut. Xucke:e,.irnd. 1907 57 1097-11 10. Compare Neuberg and Neimann Abstr. 1905 ii 436; Tollens ibid. 559).- When boiled with hydrochloric acid glycuronic acid yields fur- furaldehyde and carbon dioxide (Giinther and Tollens Abstr. 1890 1352; Chalmot and Tollens Abstr. 1891 5G8; Mann and Tollens Abstr. 1895 ii 335). On this reaction the authors have based two methods of estimating glycuronic acid ; in the first the furfuraldehyde is converted into andmeighed as its phloroglucide; in the second the carbon dioxide evolved is absorbed and weighed.The weight of the phloroglucide is one-third and that of the carbon dioxide one-quarter of the glycuronic acid Details are given of estimations with gly- curonic acid euxanthic acid magnesium euxanthate and sodium urochloralate in which the error does not exceed 1-1*5%. By tlie first method piuri (Indian-yellow) is found to contain 18% to 19.5% of glycuronic acid equivalent to 43.1% to 46.7% of euxanthic acid ; Graebe Aders arid Heyer (Abstr. 1902 i 39) found piuri to contain 39% to 46% of euxanthic acid. To estimate pentoses and glycuronic acid in presence of each other the amount of glycuronic acid is determined by the carbon dioxide method and one-third of its weight substracted from the phloroglucide the remainder of this being equivalent to the pentosos.Piuri is found to contain 1.39% of nitrogen which is only partly accounted for by the presence of small amounts of hippuric acid and a substance which is probably m-toluic acid; another specimen con- tained benzoic acid. Contrary to Bial's (Abstr. 1902 ii 703) and Sachs's (Abstr. 1907 ii 135) statements glycuronic acid reacts with Bial's orcinol reagent but more slowly than the pentoses and only on continued heating of the reaction mixture. The green coloration can be detected with 0.0025 mg. of xylose 0.005 mg. of arabinose and 0.035 mg. of glycuronic acid. With phloroglucinol in presence of ferric chloride glycuronic acid forms a dirty red turbid solution which gives a spectrum with a band atl the 11-line less marked than the band lying to the right of the' U-line in the pentose-phloroglucinol spectrum. G.T. Detection and Estimation of Benzoic Acids in Ketchups Fruits and Ciders. HAHKY S. REED (J. Amzes-. Ciiem. Xoc. 1907 29 1626-1 629)-The sample is acidified with sulphuric acid the benzoic acid is extracted with chloroform and the latter is evaporated in a current of air in a special apparatus. The residue is then heated at 260" in a current of air and t h e rc)littilised henzoic acid absorbed in aqueous sodium hydroxide. Prom this it is recovered by acidifyingANALYTICAL CHEMISTRY. 45 the solution and shaking with chloroform and the residue left on evaporation is then tested for benzoic acid by converting it first into m-dinitrobenzoic acid and this into ammonium diaminobenzoic acid which has a characteristic appearance.The quantitative estimation is based on the fact that calcium bendoate is fairly soluble in cold water. The chloroform residue of the acid is treated with a definite amount of milk of lime and the benzoic acid is calculated from the amount of calcium found in the solution after allowing for dissolved calcium oxide as found by a blank experiment L. DE K. Estimation of Fat in Skimmed Milk. R. L E Z ~ (Cornpt. rend. 1907 145 817-S18),-Three litres of the skimmed milk are heated to a temperature of 40" and treated with 60 C.C. of a solution prepared by dissolving 80 grams of sodium hydroxide in 180 C.C. of ammonia and diluting to a volume of 250 C.C. The treated milk is then subjected to centrifugal action a small apparatus being used and the cream thus separated is used for the analysis the estimation of the fat being made by Gerber's process.w* P. s. Elstimation of Some Alkaloids by Means of Picrolonic Acid. HERMANN MATTHES and 0. RAMMSTEDT (Zeitsch urrzd. Clwn 1907 46 565-574). -Gotarnine codeine and morphine give insoluble pre- cipitates when treated with picrolonic acid and this reaction may be used for the estimation of these alkaloids in preparations such as tablets powders Stc. A tablet or a quantity of the powder equivalent to about 0.05 gram of alkaloid is dissolved in 10 C.C. of water the solution is filtered and after washing the filter and inaoluble residue the filtrate is treated with 2.0 C.C.of 2c'/lO alcoholic solution of picrolonic acid. The mixture is placed aside for fifteen hours a t the ordinary temperature after which t h e the precipitate is collected on a weighed filter washed with water dried a t l l O o ant1 weighed. The precipitates have the following formuls cotsrnine picrolonate C1,Hl,O,~,C,,H,O,N ; codeine picrolonate and morphine picrolonttte Cl,H,,O,N,CloH,O,N (comp:zre Abstr. ~18%?1O,N ,ClOH*O,N4 1907 ii 592). w. P. 8. Estimation of Cystine in Urine. J. F. GASKELL (J. P?qsioZ. 1907 36 142-149).-The addition of acetone renders the acetic acid method of estimating cystine a trustworthy one. I n five cystine calculi cystine crystallised in hexzgons but i t may crystnllise in other forms. The specific rotation of cystine dissolved in ammonia is - 97*5" and dissolved in hydrochloric acid - 223".Hair-cystine and calculus-cystine are identical. W. D. H. Estimation of Indigotin in Indigo-yielding Plants. CYRIL BERGTHEIL and RICHARD V. BRIGGS (J. SOC. ClLem. Ind. 1907 26 1172-1 174).-The modifications of the persiilphate strid isatin methods suggested by Orchardson Wood and b'loxani (hbstr. 1907 ii 415) are considered by the authors to be useless in ordinary practice both76 ABSTRACTS OF CHEMICAL PAPERS. leading to untrustworthy results unless the exact indican-content of the sample is known previously and the methods adjusted accordingly. w. P. s. Analysis of Indigo (111) and of the Dried Leaves of Indogofera Arrecta and Indigofera Surnatrana. R. GAUNT P.THOMAS and W. POPPLEWELL ELOXAM (J. h’oc. Chem. I d 1907 26 11 74-1 182). -As the result of continued use of the tetrasulphonate method the authors consider that the claims for accuracy made for this process (Abstr. 1906 ii 819) are fully substantiated. For the analysis of the leaf the isatin method is at present the only trustworthy one; the product obtained from it has been proved to be almost chemicallypure indirubia. A s the formation of indirubin can only originate from the indoxyl liberated from the indican on hydrolysis the quantity of indirubin obtained must be a true expression of the amount of this substance which is present. w. P. s. Titration of Tannin by Means of Iodine. FERDINAND JEAN (Ann. China. and. 1907 12 426-427).-9 reply to Cormimbeuf (Abstr. 1907 ii 994). The author states that the iodine process is trustworthy but the titration should take place in a solution contain- ing excess of sodium hydrogen carbonate. 1,. DE K. Vanillin-Hydrochloric Acid as a Test for Albumin and Tryptophan. LEOPOLD ROSENTHALER (Chem. Zentr. 1907 ii 946 ; from Apoth. Zeit. 1907 22 67S).-Winckel has shown (Apoth. Zeit. 1905 22 209) that several fruit juices and substances con- taining ferments give a violet coloration with vanillin and hydro- chloric acid and has concluded that this is a characteristic reaction of ferments. I n the present paper it is pointed out that albumin globulin and casein give a violet coloration with vanillin and hydrochloric acid ; likewise also tryptophan but not phenylalanine tyrosine histidine or pyrrolidine-2-carboxylic acid. W. H. G. Estimation of Pepsin by Mean8 of Edestin. EKNST FULD and LOUIS A. LEVISON (Biochema. Zeitsch. 1907 6 473-501).-The method is based on the principle that edestin (the crystallire protein from hemp seeds) is precipitated by sodium chloride from its solution in 0.3% hydrochloric acid but that the products of its digestion are not so precipitated. Accordingly the minimum quantity of gastric juice is found which when added to a definite volume of the edestin solution prevents the formation of a precipitate when solid sodium chloride is added after half an hour’s incubation. G. B.

ISSN:0368-1769    

DOI:10.1039/CA9089405061

出版商:RSC    

年代:1908

数据来源: RSC

摘要:

Organic Chemistry. Viscosity of Ethyl Alcohol. L. GAILLARD (J. P h u ~ z . Chim. 1907 [vi] 26 482-487).-The relative viscosities (compared with that of water taken as unity) of absolute ethyl alcohol and of mixtures con- taining from 1 to 10 molecules of water per molecule of alcohol are 1.45 2.53 2.96 3.10 3.10 2-95 2.84 2-67 2.55 2.43 and 2.23 respectively whilst those of mixtures containing 95% 20% 15% 11% lo% and 5% of alcohol are 1.78 1.96 1.65 1.45 1.35 and 1.21 all the values having been obtained a t 15". Examination of these values shows that the viscosity of ethyl alcohol increases with dilution until a maximum value of 3.1 is reached for the two mixtures of the composition EtOH73H,0 and EtOH,4H,O and then diminishes and that absolute alcohol and a mixture containing 11% of alcohol have the same viscosity.This confirms the existence of the trihydrate the formation of which is accompanied by the maximum contraction and renders probable the existence of the tetrahydrate. Mixtures of the two alcohols EtOH,3H20 and EtOH,4H20 in any proportion what- ever all have the viscosity 3-1 indicating that intermediate hydrates are not formed. E. H. Action of Zinc Ally1 Iodide on the Anhydrides of Mono- basicAcids. ALEXANDER M. SAYTZEFF (J. BUSS. Phys. Chem. Xoc. 1907 39 Chem. 1232-1239).-Whenan anhydride of a monobasic acid reacts with ally1 iodide in the presence of zinc the following reactions most probably occur O(CO-R) + C,H5*ZnI = C,H,*CR(OZnI)*O*COR -+ CR(C,H,),*OH and as a side reaction CR(C,H,),*OZnI -+ C,H,* CR* 0- COR . The yield and purity of the alcohol are much superior to that obtained when the ester is employed instead of the anhydride.The following substances have been obtained. Methyldiallyl- carbinol yield 36.5% of the theoretical having b. p. 157-159" B 0,87747 Bio 0.86314 Bi 0.86258 (Sorokin gives B 0.8640 Bi3 0.8524). Ethyldiallylcarbinol yield 37-39% b. p. 175-1 76"/ 755.6 mm. Di 0.88603 0,86877 D: 0.87002 (Smirensky B 0.8776 0.8637). Propyldiallylcarbinol yield nearly 41% b. p. 192-194O DO 0.87939 L):* 0-86286 Di! 0.86412 (P. arid A. Saytzeff Ug 0.870'7 Bio 0.8564). isoPropyldiallylcarbino1 yield 3774 b. p. 18'7-188" 0; 0.88859 0.87133 0: 0,87259 (Rjabinin and Saytzeff 0 0.8647 B 0.8512). Alkylene Glycol-chlorohydrin E t h e r s and their Changes. JOSEF HOUBEN and KARL FUHRER (Ber.1 9 07,40,49 9 0-5 00 0)-Ethy lene glycol- chlorohydrin ether [a-chloro-/3-ethoxybutane] CH,Cl-CHEt *OEt7 origin- ally obtained by Lieben using zinc ethyl is more conveniently prepared by the interaction of dichloro-ether and magnesium ethyl bromide. It is not converted into methyl ethyl ketone or indeed changed by heating in boiling methyl alcohol with sodium hydroxide. a-Cldoro-P-ethoxyiso- hexicne,CH,Cl*CH(C,H,)*OEt is a colourless liquid b. p. 60-61"/8 mm. Z. K. Y vord. XCIV. i.74 ABSTRACTS OF CHEMICAL PAPERS. iso-a-Cldoro-P-ethoxy-isoheptane CH,Cl*CH(C,H,,)*OEt is a colourless liquid of unpleasant odour b. p. 77-'78"/9 mm. p-ChZoro-a-ethoxyethyl- benzene CH,Cl*CHPh*OEt is a colourless pleasant smelling liquid b. p. 107-108"/9 mm. ; when heated with sodium hydroxide it is converted almost quantitatively in to acetophenone and for the preparation of this from bromobenzene it is not necessary to first purify the hydrin ether.By the action of sodium iodide on the above chlorohydrin ether the chlorine is to a large extent replaced by iodine; the product obtained has b. p. 11O-11lo/9*5 mm. and distils as a dark red oil without much decomposition a t 226O/760 mm. y-Chloro - a - ethoxypropylbenxene CH,Cl*CH(CH,Ph)*OEt is a colourless liquid of agreeable odour b. p. 125-126O/9.5 mm. which like the aliphatic compounds is not altered on boiling with sodium hydroxide. 1-P- Chloro-a-ethoxyethyhaphthalene CH,C1*CH(C,,H7)*OEt has b. p. 178-179°/9 mm. and forms a yellow liquid of faint odour. Heated with sodium hydroxide it forms a-napht hy 1 me thy1 ketone.HENRY D. DAKIN (J. Biol. Chem. 1908 4 77-89).-Ammonium butyrate is readily oxidised by hydrogen peroxide a t 37" but the reaction is accelerated by warming. The products obtained mere acetoacetic acid acetone propaldehyde acetaldehyde acetic and formic acids and carbon dioxide; propionic acid was probably also present. It is probable that a- and P-hydroxybutyric acids are the initial products. All products except acetone are on further treatment converted eventually with carbon dioxide and water. Acetone is very resistant t o hydrogen peroxide. There is no need to assume that acetone is formed as an intermediate substance in the oxidation of all the butyric acid formed in the body. It is probable that P-hydroxybutyric acid may be decomposed so as to give acetic acid and its oxidation products.It is much less probable that the a-acid is an alternative initial product in tissue oxidation; this however may be further oxidised through propionic acid. W. D. H. J. TH. BORNWATER (12ec. trav. chim. 1907 28 413).-When yellow mercuric oxide is shaken with an aqueous solution of m-heptoic acid a t the end of some days the oxide is completely transformed into a white precipitate of mercuric heptoate (CH,Me*[CH,],*CO,),Hg. It crystallises from methyl alcohol in nacreous plates m. p. 106'5O. Solutions of the salt decompose after a time mercuric oxide being deposited ; they are rendered more stable by addition of heptoic acid. Mercuric heptoate does not form a double salt with mercuric chloride.E. F. A. Oxidation of Butyric Acid by Hydrogen Peroxide. Mercuric Heptoate. E H. Derivatives of Undecenoic Acid J. TH. BORNWATER (Rec. trau. chim. 1907 26 409-4 1 2).-Methyl undecenoate (Noerdlinger Abstr. 1890 1237) prepared according to Perkin's method for the ethyl ester (Trans. 1886 49 ZOS) has b. p. 249*5-250°/780 mm. m. p. - 27.5" D15 0.889. As the temperature rises from 11.2' to 2 5 O the ?2D falls from 1.44301 to 1.43727. Ethyl undecenoate has m. p. - 37*5* b. p. 263-263-5"/780 mm. D15 0.881. Undecenornethylamide CH,:CH*[CH-,],.CO.NHMe,ORGANIC CHEMISTRY 75 prepared by the action of an aqueous solution of methylamine on the crude chloride forms fine crystalline plates m. p. 46' (below that of the arnide Franchimont Abstr. 1897 ii 542).Undecenodimethyl- amidr CH,:CII*[CH2],*CO*NMe2 obtained by shaking an ethereal solution of the chloride with an aqueous solution of dimethylamine hydrochloride is a liquid b. p. 186.5'/20 mm. D;' 0.89278 which solidifies when cooled in ice and salt to a solid m. p. - 16.5'. E. H. Action of Ozone on Compounds containing Triple Linkings. CARL D. HARRIES (Bey. 1907 40 4905--4908).-The author disputes Molinari's statement (Abstr. 1907 i 1039) that ozone does not react with substances containing a triple linking or a benzene double linking. Stearolic acid and phenylpropiolic acid yield with ozone unstable gubstances which exhibit the typical reactions of ozonides. c. s. Oxidation of Ammonium Salts of Hydroxy-fatty Acide with Hydrogen Peroxide. HENRY D. DAKIN (J. Biol.Chem. 1908 4 9l-l00).-The ammonium salts of glycollic lactic a- and /3- hydroxybutyric a-hydroxyisobutyric and a-hydroxyisovaleric acids were oxidised with hydrogen peroxide. With the exception of glycollic and P-hydroxybutyric acids the primary products are an aldehyde carbon dioxide and water [R*CH(OH)*CO,H =R*CHO + CO +H,O]. In the Case of a-hydroxyisobutyric acid acetone is formed. More or less of the aldehyde is further oxidised to the corresponding acid and in some cases oxidation goes on still further ; thus lactic acid yields acetaldehyde acetic acid and carbon dioxide Leucic acid undergoes oxidation like other hydroxy-acids. Glycollic acid yields firat glyoxylic acid and formaldehyde then formic acid and finally carbon dioxide and water /3-Hydroxybutyric acid yields numerous products including acetoacetic acid acetone acetaldehyde acetic and formic acids and carbon dioxide.W. D. H. The Reduction of Ethyl Oxalate. WILHELM TRAUBE (Bey. 1907 40 4942-4956. Compare Lowig J. pr. Chem. 1861 [iJ0 83 129 and 84 1 ; Debus this Journ. 1872 25 365 ; Eghis ibid. 1871 24 820)-A solution of ethyl oxalate in absolute alcohol was reduced with sodium amalgam and in order to avoid hydrolysis of the esters tile product was mixed with an excess of alcoholic hydrogen chloride and fractionally distilled. I n the first fraction ethyl alcohol hydrogen chloride and a small amount of ethyl carbonate passed over and then a small amount of ethyl glyoxalnte alcoholate and ethyl glycollate. A fraction distilling between 170' and 220° consisted mainly of ethyl diethylglyoxylate CH(OEt),*CO,Et and ethyl oxomalonate CO(CO,Et) together with a little ethyl oxalate.The residue wheu distilled under reduced pressure gave a fraction 160-200"/20 mm consisting mainly of ethyl deoxalate (Klein Abstr 1880,36) (crystals) and ethyl tartrate (liquid). Tliu diethylglyoxylic ester which is formed in considerable amounts is not a primary reduction product 9 276 ABSTRAOTS OF CHEMICAL PAPERS. but is formed by the action of the alcohol and hydrogen chloride on the ethyl glyoxylate alcoholate. The formation of the acetal can he prevented by using just sufficient hydrogen chloride to neutralixe the alkali formed during the reduction or by using an alcoholic solution of oxalic acid. Under these conditions the chief product is the alcoholate (20-25 grams from 100 of ethyl oxalnte) which appears to be the first product of reduction EtO*CO*CO*OEt -+ EtO*CO-CH(OH)*OEt. Ethyl g2yoxubte alcoholate CO,Et*CH(OH)*OEf may be separated from the mixture of reduction products by fractional distillation and forms a colourless liquid b.p. 136-138O. When heated i t gives rise to an extremely strong odour and when mixed with the theoretical amount of phosphoric oxide decanted and distilled it yields ethyl glyoxalate b. p. 130° which readily polymerises. When warmed with barium hydroxide the alcoholate and also glyoxylic acid yield gaseous hydrogen. The alcoholate condenses with ethyl malonate in the presence of acetic anhydride yielding Perkin and Bishop's ethyl ethylenetricarboxylate (Proc. 1891 7 41) which is hydrolysed with 25% hydrochloric acid to fumaric and malic acids.The ethyl ethylene- tricarboxylate reacts with ethyl malonate and sodium ethoxide forming ethyl propanepentacarboxylate from which tricarballylic acid is produced on hydrolysis. Attention is drawn to the fact that many of the products formed by the reduction of ethyl oxalate occur in plant structures (compare Koenigs Ber. 1S92 25 800). J. J. S. Simple Ester Anhydrides of Saturated Dibasic Organic Acida. D. MOL (Rec. tiwv. cAim. 1907 26 373-408. Compare Abstr. 1906 i 4).-The ester anhydrides of the dibasic acids are obtained by (1) the action of the monoalkyl chloride on the mixed alkali alkyl salt; (2) the interaction of phosphoryl chloride and a slight excess of the alkali alkyl salt (compare Gerhardt Annalen 1853 8'7 237; Geuther ibid.1862 123 113) or (3) the action of acetyl chloride on the alkali alkyl salt (compare Bouveault Abstr. 1900 i Ethyl anhydro-oxalate O(CO*CO,Et) can be prepared by either of the three methods. It is a colourless liquid with a faint odour b. p. 139O/15 mm. 140°/16 mm. which in a freezing mixture solidifies t o crystals m. p. 8O. The liquid has D:"'" 1.2480 m2 1.42762 rt? 1.42592. Its ethereal solution reacts with dry ammonia gas form- ing ethyl oxaninte and ammonium ethyl oxalate. When very rapidly heated at 240° ethyl anhydro-oxalate decomposes evolving carbon dioxide and forming anhydrous ethyl rnesoxalate and a liquid having the same empirical formula as the latter but double its molecular weight.At 150° the ester anhydride forms carbon monoxide and dioxide and ethyl formate. Attempts to prepare ethyl anhydro- malonate by the second and third methods give no definite result pro- bably owing to the reactivity of the hydrogen atoms of the :CH group. The action of potassiiim ethyl malonate on ethyl malonic chloride has not been studied. Ethyl anhydrosuccinnte O(CO*CH,*CH,*CO,Et) is prepared either f;)S the interaction of sodium ethyl succinate (Blaise Abstr. 1899 i 474).ORGANIC CHEMISTRY. 77 793) and ethyl succinic chloride obtained by a modification of Michaelis and Hermens' method (Abstr. 1892 1494) or by the action of phosphoryl chloride on the former salt. It forms colourless crystals m. p. 28O. I n ethereal solution i t is attacked by dry ammonia forming ethyl succinamate C,H,,O,N as colourless needles m.p. 75" and an extremely deliquescent solid identified from its reactions as ammonium ethyl swcinate. When boiled under the ordinary pressure ethyl anhydrosuccinate carbonises and after four distillations a mixture of much succinic anhydride and a little ethyl succinate is obtained. By the action of phosphoryl chloride on sodium ethyl glutarate (obtained by Blaise's method) ethykanhydvoglutarate O(CO*CH,*CH,*CH,~CO,Et) is formed as a colouriess liquid which when strongly cooled solidifies to crystals m. p. 7-8". The liquid has b. p. 150°/15 mm. D:3'5 1.1245 rtg 1.44466 and rtg 1.44275. The author points out that the customary method of preparing acid chlorides by addition of phosphoryl chloride to the salt of the acid is contrary to the original directions of Gerhardt who added the powdered salt to the oxychloride. This would account for the poor yields obtained by some workers.A vacuum distillation apparatus based on Dewar's absorption of gases by charcoal cooled in liquid air is described. E. H. . Synthesis of Methylethylmalic Acid. M. L. SHDANOVITSCH (J. Buss. Php. Chem. SOC. 1907 39 Chem. 1411-1414).-Ethyl a-bromobutyrate reacts with pyruvic acid in the presence of zinc forming ethyl methylethylmalate CO,Et*CHEt*CMe(OH)*CO,Et the yield being 81-S4% of the theoretical ; when hydrolysed crystals are formed which could not be purified. The ammonium salt has m. p. 172.5-174"; at 1 7 9 O it resolidifies and then melts a t 180-18lo (Micha.el m. p. 179O) ; the silver salt has also been obtained.Z . K. Conversion of Methyl Alcohol into Formaldehyde and the Preparation of Formalin. E. I. ORLOFF (J. Buss. Yhys. Chern. Xoc. 1907 39 1414-1439. Compare Abstr. 1907 i S92 1008).-The conversion of methyl alcohol into formaldehyde is not a reversible reaction and is accompanied by secondary reactions such as CH20-+ CO+H and 2H2+O2=2H,O &c. The yield of formaldehyde is a maximum when the following relations are observed. The quantity of oxygen the total quantity of alcohol vapour = 0-4 1 ; oxygen total quantity of the gaseous mixture = 0-1375 1 ; total quantity of alcohol vapour total quantity of gaseous mixture = 0.342 1. When in these circumstances the action proceeds without the application of external energy C2C,/V2= 0*00103 (where C and C = concentration of the methyl alcohol and oxygen respectively and Y= the mean velocity of the gaseous mixture through the catalyst).The function of the catalyst is discussed at length the above rela- tions being true when the catalyst consists of a roll of copper gauze 12 cm. in length 16 mm. transverse section in which there are 15 x 15 threads in each cubic centimetre.’I8 ABSTRACTS OF CHEMICAL PAPERS. The ordinary thermodynamic equation for the energy of a reaction is not applicable here. An equation is deduced by which it is possible to calculate the total quantity of gas which should be obtained in any experiment but it was observed that the quantity actually obtained was always more than that required by this equation this being due to the absorption of the unknown gas (CH,),O by the palladium chloride contained in the palladium employed for the absorption of hydrogen.The mixture of gases in the various experiments contains 2% to 18% of this gas which has an odour resembling slowly oxidising phosphorus and is decomposed at a red-heat. The Ammonia Reaction for Distinguishing between Enolic and Ketonic Derivatives. 11. ARTHUR MICHAEL and HAROLD HIBBERT (Bey. 1907 40 4916-4918. Compare Abstr. 1907 i 1010).-The untrustworthiness of this reaction is further borne out by the behaviour of enolic ethyl diacetosuccinate in solution. From a light petroleum solution the ketone is precipitated ; from ethyl bromide the ammonium salt of the enol and from chloroform a mixture of ketone and enolic salt.Where the enol reacts more readily than the ketone an almost quantitative separation of the tautomeric substances can be effected with aqueous ammonia. Ketonic dibenzoylacetyl- methane and enolic tribenzoylmethane with ammonia in organic Synthesis by Means of Mixed Organo-metallic Compounds of Zinc. Constitution of the P-Acetoxy-ketones. EDMOND E. BLAISE (Compt. rend. 1907 145 1285-1287).-The P-acetoxy- ketones prepared by the condensation of the chlorides of pacetoxy- aliphatic acids with mixed organo-metallic derivatives of zinc (Abstr. 1907 i 749) do not form crystalline derivatives with either phenyl- hydrazine p-nitrophenylhydrazine phenylbeneylhydraeine or semi- carbazide. The only reaction for ketones giving a positive result is obtained with sodium nitro-prusside which in the presence of a trace of potash produces the characteristic yellowish-red coloration stable in acetic acid.Z . K. solvents both give precipitates. w. K. I n order to decide between the alternative formuh I. OAc*CHR*CH,*COR’ and 11. CHR<z;:>CR*OAc for the /3-acetoxy-ketones the author has determined their molecular volumes and those of compounds in which a closed lactonic or oxide- chain is known to exist. Whilst in the latter case there are con- siderable differences between the calculated and observed values due to the closure of the chain in the former only the normal differences characteristic of open-chain compounds are found. The conclusion is drawn that the P-acetoxy-ketones have the ketonic constitution (I). E. H. 0. MILLER (Ber.1907 40 4903-4905. Compare Vieweg Abstr. 1907 i 893). -Gladstone’s formula for mercerised cellulose C,,H,,Olo~NaOH is not substantiated by the experiments of the author who fmds that the percentage of sodium hydroxide in mercerised cotton increases with the concentration of the alkaline solution. Behaviour of Cellulose with Sodium Hydroxide. c. 8. ’79 ORGANIC CHEMISTRY Stereochemistry of Chromium. 111. PAUL PFEIFFER (Zeitsch. anorg. Chern. 1907 56 261-278).-The paper contains a summary of the mutual relationships of the stereoisomeric chromium salts and the methods for determining their constitution Part of the experi- mental material has already been published (Abstr. 1905 i 33; 1906 i 71 ii 614; 1907 i 895) and the remainder will be published in detail later (compare next abstract).The more important methods used in determining the constitution of the compounds have Stereochemistry of Chromium. IV. The Isomeric Dibromo- salts. PAUL PFEIFFER (Zeitsch. anorg. Chem. 1907 56 279-295. Compare previous abstract).-It has been shown in earlier papers that the diacidodiethylenediaminechromium salts [ En,CrX,]X (where En = ethylenediamine and X =acid group) exist in two stereoisomeric already been dealt with (Zoc. cit.). G. s. modifications distinguished as the cis-form (violet L -J salts) and the trans-form [g>Cr<g]X (green salts) respectively. L J I n the present paper the dibromo-salts and certain of their derivatives are described. Their constitution has been established mainly from their relationship to the dioxalato-salts already described.cifi-DibromodiethyZened~aminechromiu~ bromide [En,CrBr,]Br,H,O and the corresponding iodide and dithionate described in a previous paper (Abstr. 1907 i 895) have been more fully investigated. t r a ~ s - ~ ~ b r o m o d i e € ~ ~ y l e n e d ~ a ~ ~ ~ ~ e c ~ ~ ~ o m i u n ~ bromide [En,Cr Br27Br,H20 (microscopic,.green plates) is prepared by evaporating a n aqueous solu- tion of the diaquo-salt [En2Cr(02H,)Br]Br2 with hydrobromic acid in the presence of mercuric bromide. A double salt [En2CrBr2] Br,HgBr separates as a green liistrous crystalline powder; on the removal of the mercury by means of hydrogen sulphide a green solution containing the trans-salt is obtained. The corresponding salts described below are obtained from the green solution by double decomposition with the alkali salt of the correspond- ing acid.All including the bromide itself are soluble in water but the solutions are very unstable the iritraradicle bromine is eliminated and the colour changes simultaneously from green t o yellowish-brown With concentrated hydrobromic acid the compound [En,CrBr,]Br gives a double salt [En2CrBr,]Br,HBr,2H20 which occurs in grass- green transparent plates and is very unstable. trans-Dibromodieti~ylened~a~inechro~i~~ dithionate [Eo,CrBr,]S,O occurs in hstrous flat green needles ; the corresponding iodide nitrate and thiocyanate also form lustrous green needles. The compound [ En,CrI,]T,HgT obtained by the action of hydriodic acid on a solution of the bromobisaquobromide and mercuric iodide occurs in lustrous deep green leaflets almost insoluble in water.tmns-Dichlorodiethylened~a~inechrornizc~ dithionate [ En2CrC1,1S,0 prepared by the general method occurs in lustrous red needles which turn green on rubbing. trans-DiciLlorodiethylenedia~~,nechromiz platinichloride [En2CrC1,]PtC16,12H,0,SO ABSTRACTS OF CfIEMTCRL PAPERS. obtained by the action of chloroplatinic acid on the corresponding chloride forms small yello wish-green needles. Optically Active Trimethyl-a-propiobetaine (a-Homobetaine). EMIL FISCKER (Ber. 1907 40 5000-5008. Compare Abstr. 1907 i 192).-l-Trimet?~yZp~opiobetaine CHMe<i!Fei>O (compare Brii hl this Journ. 1876 i 698) prepared by the interaction of d-bromo- propionic acid with trimethylamine in the cold forms colourless plates decomp.242' (corr,) [a] - 19.7". It forms two dimorphous auri- chlorides (compare the behaviour of betaine Eischer Abstr. 1902 i 428 and Willstatter Zoc. cit. 266) the one crystallising in lustrous gold-colourcd thin crystals m. p. 259' (decomp. corr.) from the acid solution and the other forming a yellow powder consisting of micro- scopic short needles aggregated in crosses or six-armed stars m. p. 226' (corr.) obtained on crystallisation from warm water. They give the unchanged active betaine when decomposed with hydrogen sulphide. An identical trimethylpropiobetaine is obtained by the action of methyl iodide on d-alanine. The action of ammonia and of trimethylamine on d-a-brornopropionic acid takes place accordingly in the same stereochemical sense whilst it has already been shown that no Walden rearrangement takes place in the case of ammonia.By the interaction of trimethylamine and ethyl d-a-bromopropionnte in alcoholic solution a t the room temperature the compound CH,*CH( NR!Ie,Br)-CO,Et is formed quantitatively in large colourless needles m. p. 150-151O (corr.) but is quite optically inactive and is identical with that formed from inactive ethyl a- bromopropionate. Tha aurichloride separates in very thin characteristic yellow plates m. p. 96-97' (corr.). The compound yields inactive trimethyl a-propiobetaine when treated with silver oxide. It is possible by interrupting the reaction a t an early stage to obtain a product having [a]= - S-l' which yields a propiobetaine [a] - 3*2' that is about five-sixths racemised.Excess of trimethylamine rapidly racemises salts of ethyl trimethylaminopro- pionate but is without action on salts of ethyl d-alanine ester. It would appear that the mere presence of a quaternary ammonium group is sufficient greatly to increase the tendency of the betaine to racemise autoracemisation at a low temperature being characteristic of optically active quinquevalent nitrogen derivatives. G. S. E. F. A. Oxidation of Leucine a-Aminoisovaleric Acid and a-Amino- n-valeric Acid with Hydrogen Peroxide. HENRY D. DAKIN (J. Biol. Cheni. 1908 4 63-76).-Leucine on oxidation with hydrogen peroxide yields isovaleraldehyde isovaleric acid ammonia and carbon dioxide. On further oxidation acetone is formed from the isovaleric acid. The reaction closely resembles several biochemical changes in which leucine takes part.Breinl and Baudisch's statement as t o the formation of isobutaldehyde is incorrect and the product Liebig described when lead peroxide is used is not butaldehyde but isovaleraldehyde. a- Aminoisovaleric acid under similar conditions yields imbutaldehyde isobutyric acid ammonia and carbon dioxide.ORGANIC CHEMISTRY 81 Payt of the isobutyric acid is further oxidised with acetone and carbon dioxide. With lead peroxide a-aminoisovaleric acid yields isobut- aldehyde. a-Amino-m-valeric acid on oxidation yields n-butaldehyde butyric acid ammonia and carbon dioxide. On further oxidation the butyric acid is in part decomposed with formation of acetone aldehydes lower fatty acids and carbon dioxide.The first steps in the oxidation of each of the above amino-acids are analogous t o those observed in other amino-acids and may be expressed as follows R*CH(NH,)*CO,H + 0 = R CHO + NH + CO,. R*CH(NN,)*CO,H + 0 = R*CO,H + NH + CO,. W. D. H. Action of Nitrous Acid on Allylamine. LOUIS HENRY (Compt. Tend. 1907 145 1247-1249).-When an aqueous solution of allylamine neutralised by hydrochloric acid is treated with sodium nitrite allyl alcohol is the sole product. This shows that at the moment of formation the allyl alcohol does not undergo the isomeric change CH, CH*CH,*OH -+ CH,:C(OH) CH which occurs in the saturated propyl alcohol since the unsaturated alcohol CH,:C(OH)*GK would be immediately transformed into acetone and this is not formed. Thus allylamine behaves differently from propylamine towards nitrous acid The action of nitrous acid on allylamine niny be compared with t h a t on trimethyleneamine which gives not isoallyl alcohol YH2>CH*OH but allyl alcohol (Kijner J. Russ.Phys. Chem. Xoc. 1901 33 377). The action of sodium nitrite on dibromopropylamino hydrocbloride CH,*Br*CHBr*CH,NH,,HCl (Henry Awn,. Xoc. Sci. BrusseZs 1880 4 317) appears to be more complicated than the reaction with allylamine. VICTOR AUGER (Compt. rend. 1907 145 1287-1 290).-Potassium cyanide in con- centrated aqueous solution acts on (1) methyl sulphate giving 92% of the theoretical yield of acetonitrile ; (2) ethyl sulphate 90% of propionitrile ; (3) sodium methyl sulphate (which contrary to Beilstein is not anhydrous but contains lH,O) 92% of acetonitrile and 0.2-0*8% of methylcarby lamine ; (4) potassium ethyl sulphate ‘15% propionitrile and 0.45% of ethylcarbylamine (using the dry salts only 55% of propionitrile is obtained) ; (5) methyl iodide 95% aceto- nitrile and (6) ethyl iodide in the presence of methyl alcohol 97% of propionitrile in the form of its constant boiling mixture with methjl alcohol.I n the last two cases the carbylamine if formed would be destroyed by the alkyl iodide. Thus whilst Guillemard’s results (Alnstr. 1907 i 300) lead to the conclusion that potassium cyanide has the isocyanide constitution when in the solid state those of the author assign to it a normal structure when in aqueous solution. CH2 E. H. Preparation of Methyl and Ethyl Cyanides. E. H.82 ABSTRACTS OF CHEMICAL PAPERS.Preparation of cycZoPropane. GABRIEL GUSTAVSON (J. pr. Chern. 1907 [ii] 76 512. Compare Willstatter and Bruce Abstr. 1907 i 1018).-In the author's method of preparing cyclopropane (Abstr. 1888 240 ; 1899 i 421) by the action of zinc dust on trimethylene dibromide the reaction is carried out in 75% alcohol and the tempern- ture is raised above 60° only towards the end. The first portions of the product are rejected as the trimethylene dibromide always contains propylene dibromide. G. Y. ALFRED KLIEGL (Be?.. 1907 40 4937-4942. Compare Baeyer and Lahr Abstr. 1900 1 141).-o-Nitrotriphenylmethane cannot be obtained by condensing o -nitrobenzaldehyde with benzene. The product is a colourless resin which is completely soluble in concentrated sulphuric acid. The desired compound may be prepared readily from o-nitrobenzylidene chloride and benzene by Friedel and CrLtfts' synthesis.o-Nitrobenzylidene chloride N02-C6H4* CHCI (70-75%) and a small amount of a-a-dichloro-2 2'-dinitrobenxyl ether (5%) are formed by the action of phosphorus pentachloride on a benzene solution of o-nitrobenzaldehyde. The benzylidene chloride is a lemon-yellow liquid b. p. 143-144'/12 mm. and solidifies in a freezing mixture. It decomposes on exposure t o light or when kept for some time in contact with the atmosphere. When warmed with concentrated sulphuric acid the aldehyde (40%) is regenerated. The benzyl ether is probably identical with the product obtained by Zimmermann and Miiller (Abstr. 1885 771). A better yield (29%) is obtained by the action of phosphorus pentachloride on a well-cooled chloroform solution of the aldehyde.It is very sparingly soluble in all the ordinary solvents but may be crystallised from pure ethyl acetate and decomposes a t about lSOo. When boiled with acetic acid it yields the aldehyde and with alcohol the diethylacetal of the aldehyde NO,*C,H,*CH(OEt) b. p. 154-156O/18 mm. o-Nitrotriphenylmethane CI,Hl,O,N is best obtained when the reaction mixture with an excess of benzene is kept at the ordinary temperature for several days and then decomposed with dilute hydro- chloric acid. It crystallises from alcohol in palo yellow glistening plates or from light petroleum (100-140') in compact prisms m. p. 93-94' and does not give a coloration with alcoholic potassium hydroxide.J. J. 5. Action of Dichloroacetic Acid on Aniline and its Homo- logues. I. IWAN VON OSTROMISSLENSKY (Bey. 1907 40 4972- 4979).-When o-toluidine is treated with dichloroacetic acid the author was unable to detect the formation of di-o-toluidinoacetic acid according to Meyer (Abstr. 1884 47) ; the main product of the action was o-methylaminop~enyl-o-toZ.uidinoacetic acid C,,H,,O,N which separates from alcohol in prismatic needles m. p. 239-240° (decomp.). o-l'olyl-o-methylimesatin C16H140N2 obtained as a by- product separates from alcohol in glistening golden-yellow leaflets m. p. about 225' (decomp.) ; when boiled with acids it forms o-methyl- isatin and the toluidine salt. Synthesis of o-Nitrotriphenylmethane. (NO,*C',H,*CHCl),OORGAXIC CHEMISTRY.83 The mechanism of the interaction of o-toluidine and dichloroacetic acid is discussed and the results obtained by Meyer from the action of p-toluidine on dichloroacetic acid are confirmed. The action of aniline on dichloroacetic acid was also studied. A. McK. Salts and Ethers of Hexanitrodiphenylamine. D. K. ALEX- ANDROFF ( J . Russ. Phys. Chenz. Soc. 1907 39 Chem. 1391-1395).- s-Hexanitrodiphenylamine CI,H,(N0,),*NH*C6H~(NO~)~ is a typica,l example of a pseudo-acid (compare Hantzsch Abstr. 1906 i 576 651 833 856); thus whilst it is itself a slightly-coloured non- electrolyte its salts which are either the qn- or anti-derivatives are all bi ightly coloured. The sodium lithium silver and ammonium salts are red; the potassium and rubidium salts dark violet; they all correspond with the formula C,,H,O,,N,M.The crystalline forms of the two series are different but they all form bright yellow solutions. From the silver salt red solutions of either the syn- or anti-methyl and propyl ethers were formed which could not be isolated. Z. K. Which Substances Contain a Readily Resolvable Single Carbon-Nitrogen Linking ? HEHMANN EMDE (J. pr. Chem. 1907 [ii] 76 509-511. Compare Mohr Abstr. 1907 i 72l).-It was shown previously that on reduction with sodium amalgam cinnamyl- trimethylammonium chloride CHPh:CH*CH,*NMe,U yields tri- methylamine hydrochloride and a-phen ylpropylene (Schmidt and Emde Abstr. 1906 i 945). On the other hand the corresponding chloro- hydrin formed by addition of hypochlorous acid to the ethylene linking when reduced with sodium amalgam yields an amino-alcohol hydrogen being substituted for the chlorine atom.Hence the C-N linking in the cinnamylamine is rendered unstable by the ethylene linking in the grouping C:C*C*N. G. Y. Action of the Chlorides of Phosphorus on Phenolsulphonio Acids. I. RICHARD ANSCHUTZ (AnnuZen 1907 358 92-97)- The action of phosphorus pentachloride on phenol-p-sulphonic acid if analogous to that of the pentachloride on p-hydroxybenzoic acid (Abstr. 1906 i 500) must lead to the formation in the first place of phosphoryl chloride and phenol-p-sulphonyl chloride and there- after to that of chlorosulphopheuyl dichloro-orthophosphate S0,Cl C,H,* O*POCl whereas Kekulk obtained p-chlorophenylphosphoryl chloride (this Journ. 1873 1239). On re-investigation of the reaction it has been found that Kekulk's compound is formed only if the immediate product is distilled under the ordinary pressure.is obtained if the product of the action of phosphorus pentachloride on potassium phenol-p-sulphonate is extracted with light petroleum ; it crystallises in colourless needles m. p. 87-88" b. p. 203"/13.5 mm. The dichlorophosphate C6H404Cl,SP,84 AUSTBACTS OF CHEMICAL PAPERS. prepared in the same manner from potassium 2 6-dibromophenol-4- sul phonate separates from carbon tetrachloride as a hygroscopic white crystalline crust m. p. 76-78' (compare Zincke and Glahn Abstr. 1907 i 698). G. Y. Oxidation of Thymol by the Oxidising F e r m e n t of Mushrooms. H. CousiN and HENRI HERISSEY ( J . Pharrn. Chim. 1907 [vi] 26 487-491.Compare Bougault Abstr. 1902,i 638).-When an aqueous solution of thymol is treated with the oxidising ferment of mushrooms in the presence of air a white precipitate is formed (Bourquelot Abstr. 1897 ii 66). The authors have prepared this precipitate by means of the ferment obtained from Russula delica and from Lactarius controversus. It contains the dithymol C,,K,~U,,H,O m. p. 100-101' described by Dianine (Abstr. 1882 623) which after the first melting resolidifies and again melts a t 164.5' (corr.) (Dianine gives 165-5') the m. p. of the anhydrous substance. The dithymol so formed is very pure giving colourless solutions in alkalis instead of the orange solutions obtained by Dinnine. The ferment obtained from the second source gives a less pure product.The white precipitate contains other compounds which seem to be of a quinonoid nature and have not yet been obtained crystalline. The oxidation product of thymol has no antiseptic power and the authors conclude that in many circumstances thymol is a bad antiseptic agent. E. H. Sulphoxides and Sulphines. KARL A. HOFMANN and K. OTT (Ber. 1907 40 4930-4936).-A solution of ferric chloride in thionyl chloride reacts with heptane from petroleum yielding a blood- red oil which gradually solidifies to a black crystalline mass of ditolyl- sulphoxide ferrichloride SO( C7H,),,FeC13 m. p. 60.5'. It decomposes when heated with water yielding ditolylsulphoxide and ferric chloride and dissolves readily in chloroform to an intense reddish-violet solution which shows two absorption bands 660-680 pp and 520-618 pp in addition to complete absorption from 440 pp in the violet end.A molecular mixture of benzyl sulphide and benzyl chloride reacts with an ethereal solution of ferric chloride yielding tribenxylsulphine chloride ferrichloyide S( C7H7)3Cl,FeC13 which crystallises from alcohol in pale yellowish-green twinned plates m. p. 98.5'. Bistribenxyl- suZphine chloride ferrichloride 2S(C7H7),C1,FeC1 is formed when excess of benzyl chloride is used or by the action of thionyl chloride and benzyl chloride on ferric chloride at the ordinary temperature. It forms thick glistening crystalline plates m. p. 9'7-107' (decomp.). I'ribenxylsulphine plutinichloride [S( C7H7),1,PtCIG is imoluble in water and has rn. p. 186O. I'ribenxylsulphine iodide forms a pale yellow powder m.p. 75' and the ferrocyccnide s(C7H,),H,FeC,N a white precipitate which decomposes at 180'. Benzyl chloride and benzyl sulphide do not appear to react in the absence of ferric chloride. The following mixed sulphine chlorides have been prepared with the aid of ferric chloride and from the ferri- chlorides the ferrocyanides have been obtained by precipitating with Toluene yields tho same product.ORGANIC CHEMISTRY. 85 ammonia and adding potassium ferrocyanide solution to the filtrate dibenzyl-tert.-butylsulphine chloride dietb y 1-tert.- butylsulphine chloride benzyldiethylsulphine chloride dibenzyl ethylsulphine chloride and triethylsulphine chloride The ferrocyanides form white precipitates all of which with the exception of the last are insoluble in water.The accelerating effect of the ferric chloride appears to be due to the formation of an additive comDound of the chloride with the sulphide. I ' 5. J. S. Transformation of the Tetramethylene Ring into the Trimethylene Ring. NICOLAUS J. DEMJANOFF (Ber. 1907 40 4961-4963).-Perkin (Trans. 1894 65 950) found that when cyclo- butylamine NH,*CH<CH%>CH2 is acted on by nitrous acid an alcohol C,H,O is formed to which he assigned the formula OH*CH<CH2>CH2. The author concludes that in the action in question the tetramethylene ring is converted into the trimethylene ring. It was oxidised by means of a mixture of chromic and sulphuric acids in aqueous solution ; the oxidation product exhibited reactions typical of aldehydes and the semicarbazone prepared from it was by no means uniform since by treatment with ether it was resolved into cyclobutanonesemi- carbazone m.p. 202" and a semicarbazone m. p. 126-127' which has all the properties of cydopropaldehydesemicarbazone. The latter compound is decomposed by dilute acids t o form an aldehyde. It is concluded that the oxidation product of the alcohol obtained from the amine NH,*CH<:E:>CH is a mixture of cgclobuttt- none and cyclopropanealdehyde. A. McK. CycZoButylcarbinol and its Isomerisation to Pentamethylene Derivatives. NICOLAUS J. DEMJANOFF (Bey. 1907,40,4959-4961).- cycZoButylcarbino1 OH*C€12*CH<cH2>CH (compare Perkin Trans 1901,'79,329) may be conveniently prepared by the reduction of ethyl c~clobutanecarboxylate by means of sodium and alcohol according to Bouveault and Blanc's method.It is a transparent thick oil b. p. 142-142*5O/750 mm. Di 0,9199 Di 0.9129 T Z ~ 1.4449. When warmed with concentrated hydrobromic acid it is converted into the bromide C,H,Br a transparent liquid b. p. 137-139' Dii 1.400 ng 1.4875. When reduced a hydrocarbon C5HZ0 is formed with b. p. 49.5-50° ; the propertlies of t h i s hydrocarbon agree with those CH% CH2 The alcohol C,H,O has b. p. 123-121'. CH2 of 'cyclopentane; but differ from those of methylcyclobutane. A. McK. Aromatic Alcohols. New Reactions. ROBERT FOSSE (C071zpt. reidd. 1907 145 1290-1293).-33enzhydrol-p-diinetbylamine similarly to xsnthhydrol and dinaphthapyranol (Abstr. 1906 i 975SG ABSTRACTS OF CHEMICAL PAPERS and benzhydrol-p-p-tetramethyldiamine (Abstr. 1907 i 414) con- denses with methylenic derivatives with elimination of water thus NMe,*C,H,*CHPh*OH + H*CHXY = H,O + NMe,*C,H,*CHPh'CHXY.By this reaction p - d i m e t h y Z a r n i n o b e n ~ ~ ~ d r ~ l ~ e n ~ o y l a ; e NMe,* C,H,* CHPh* CH (COPh) *COMe small faintly sulphur-yellow crystals m. p. 157-1 5 8 O and p-dimethyl- arninobenxhydrylucetylacetone colourless needles ni. p. 13 lo are obtained. I n the same way benzhydrol itself reacts with /I-ketonic esters and P-diketones giving compounds hitherto only obtainable by the action of a halogen derivative of diphenylmethane on the sodium compound of the methylenic derivative. By this new reaction there were prepared ethyl benxhydrylbenxo ylacetnte CHP h,* CH( CO P h) -CO,E t needles rn.p. 135' (on mercury) ; benxhyd~ylbenxoylacetone CHPh,* CH(COPh)*COMe fine white needles in. p. 148-1 50' and benxhydrylacetylucetone CHPh,*CH(COMe) m. p. 116' (on mercury). The hydroxyl of different diary1 secondary alcohols will also combine with methylenic hydrogen forming the compounds ethyl phenyl-a-naphthylmethyl benxoylucetate,aCloH7* CH Ph* CH( COPh) *CO,Et m. p. 160' (varies with duration of heating) ; phenyl-a-n~~hlhylrnethyl- acetylacetone aCl,H7*CHPh*CH(COMe) m. p. 126' (on mercury) ; phenyl- a-Taaphthyl melhylbenzoy Zucetone aC,,H,* CHPh*CH( COPh)*COMe m. p. 185-185.5' ; p-methylbenxhydrylucetyZcccetone CH,*C,H,*CHPh*CH(COMe) m. p. 104-106O and p-methylbeizxhydrylbe~xoylacetone CH,*C,H,*CHPh* CH( COPh)*COMe m. p. 130° (on mercury). By the action of methyl malonate on triphenylcarbinol carbon dioxide methyl alcohol methyl acetate and methy2 triphenylmethyl- malonate m.p. 130-131' (on mercury) are formed thus CPh,*OH + ZCH,(CO,Me) 2 CO + MeOH + C€€,*CO,Me + CPh,-CH(CO,Me),. This reaction with ethyl malonate gives Henderson's ethyl triphenylmethylmalonate aud at the same time triphenylmethane according to the equation CPh,*OH + CH,(CO,Et) = CO + CH,*CHO + CH,*CO,Et + CHPh,. Hitherto it has been possible to replace the oxygen in aldehydes by the group :CXY but not the hydroxyl in alcohols by the group *CHXY. E. H. Catechin. STANISLAUS TON KOSTANECKI and VICTOR LABIPE (Be?.. Compare Abstr. 1902 i 553 637; 1907 i 1907 40 4910-4912. 73).-lodocotechin tetranzebhyt ether m. p. 192-193' decornp. at 205O is obtained after a few hours when alcoholic solutions of catechin tetramethy1 ether and of iodiueORGANIC CHEMISTRY. 87 and iodic acid are mixed ; it separates from alcohol in long white needles forms an acetate C2,H2,071 m.p. 189O and develops a yellow colour with concentrated sulphuric acid which after a time becomes violet. The halogen is readily eliminated by zinc dust and alkali catechin tetramethyl ether being regenerated. Other halogenated pliloroglucinol derivatives in alcoholic solution lose the halogen in a similar manner. Ciamician and Silber's bromo- maclurin pentamethyl ether (bromoveratroylphloroglucinol trimethyl ether) is converted into leucomaclurin pentamethyl ether (2 4 6 3' - 4'-pentamethoxybenzhydrol) whilst phloroglucinol tri- methyl ether is regenerated from ~ibromophloroglzccinot trimethyl ether C,HBr,(OMe) m.p. 132-133' which is obtained by the bromination of the trimethyl ether in glacial acetic acid. c. s. Ethyl Diazoacetate and m-Xylene. EDUARD BUCHNER and KONRAD DELBRUCK (Annalefi 1907 358 1-35).-Buchner and his co-workers in a series of investigations (Abstr. 1896 i 230 ; 1897 i 282; 1898 i 639 ; 1900 i 298 ; 1901 i 385) have shown t h a t the product of the action of ethyl diazoacetate on benzene is ethyl norcardienecarboxylate a derivative of a dicjclic system consisting of a three-atom and a six-atom ring making together a seven-atom ring. Buchner and Feldmann (Abstr. 1904 i 57) have found the action of ethyl diazoacetate on toluene to lead t o the formation of ethyl 3-methylnorcardiene-7-carboxylate or of the products of the conversion of this into derivatives of the methylated seven-atom ring.In the present paper the substances obtained from ethyl diazoacetate and m-xylene are described and their constitutions discussed. The almost colourless oil b. p. 129O/10 mm. obtained on fractionally distilling the product of the action of ethyl diazoacetate on m-xylene yields analytical figures corresponding with ethyl dimethylnor- cardienecarboxylate but is a mixture containing comparatively little of this ester. The oil b. p. 115-125°/10 mm. obtained in the same manner from rnethvl diazoacetate when shaken with aaueous ammonia at Oo yielis 3 5-dimethyZ-A2~4-norcardiene-7-car~oxy~~mide (?H:CMeo~H>CH*CO*NH which crgstallises in colourless needles CMe:CH*CH m.p. 14Z0 and reduces permanganate in sodium carbonate solution. When boiled with 30% sulphuric acid the amide is hydrolysed forming 1 3-dimethylphenyl-4-acetic acid but if boiled with 5% sodium hydroxide it forms 3 5-dimethylcy~lo-A~~~~~-heptutrielze-l -carboxylic F]H:CMe*CH2>C*C02H. This crystallises in leaflets m. p. 151° CMe:CH-CH acid decolorises permanganate in sodium carbonate solution gives with concentrated sulphuric acid a yellow coloration resembling picric acid and when boiled with aqueous sodium hydroxide yields an acid m. p. 1 1 3 O . . The hydr 1 ysis of the crude ethyl dimethylnorcardienecarboxylate with sodium hydroxide leads to the formation of 3 5-dimethyZ-88 ABSTRACTS OF CHEMICAL PAPERS. which crystallises in flat needles m.p. 148O decolorises permangan- ate in sodium carbonate solution but is stable in air and gives a J ellow coloration with concentrated sulphuric acid. The mag- nesium calcium and barium salts are readily but the salts of the heavy metals only sparingly soluble ; the silver salt C,,H,,O,Ag is hygroscopic and when heated evolves the free acid m. p. 148'. The amide C,,H,,ON crystallises in colourless needles m. p. 107' becomes yellow and resinous on exposure to air reduces permanganate in sodium carbonate solution gives the characteristic yellow coloration with concentrated sulphuric acid and on hydrolysis with alkalis yields the acid m. p. 148'. On .treatment with bromine in glacial acetic acid solution under cooling the acid forms a dibromide Cl0HI2O2Br2 which is obtained as a white crystalline powder becomes yellow on exposure to light or at loo" decornp.1 8 5 O and is only partly soluble in aqueous sodium carbonate. The action of hydrogen bromide on the acid m. p. 148" leads to the formation of 1 :. 3-dimethylphenyl-4-acetic acid m. p. 105' ; the amide C,,H,,ON crystallises in colourless needles m. p. 183O. In some cases the formation of an unstable pyoduct intermediate between the dimethyl- cyctoheptatrienecarboxylic acid and the dimethy lphenylacetic acid was observed. 3 5-Dimethylcy~lo-A~~~-heptudielze- 1 -carboxylic acid C7H7Me,*C0,H prepared by reduction of the heptatrienecarboxylic acid m. p. 148" with sodium amalgam in presence of carbon dioxide crystallises in colourless needles m. p. 123" decolorises permanganate in sodium carbonate solution is readily oxidised by air and does not give a coloration with concentrated sulphuric acid.The amide crystallises in colourless leaflets m. p. 101'. The dibromide decornp. 1 7 5 O decolorises permanganate. 3 ~-D~methy~cyclo-A5-?~eptene-~-carboxyl~c acid C7H,Me,*C0,H prepared by reduction of the cycloheptatriene- or cycloheptadiene- carboxylic acid with sodium amalgam in boiling sodium carbonate solution in presence of n current of carbon dioxide separates from dilute alcohol in crystals m. p. 80' decolorises permanganate in sodium carbonate and bromine in glacial acetic acid solution is not further reduced by sodium amalgam and does not undergo trans- formation when boiled with aqueous potassium hydroxide. The amide crystallises in leaflets m.p. 167-168O. The acid is converted by theaction of hydrogen bromide in glacial acetic acid solution at looo or of boiling 50% sulphuric acid into 3 5-dirnethylcycloheptune- y-carbolactone C7H,,Me,<~o which crystallises from light petroleum in stout prisms m p. 76' and when boiled with aqueous sodium hydroxide forms the sodium salt of the corresponding hydroxy-acid which is isolated in the form of its silver salt as a white precipitate. 3 5-Dimethylcyclol~eptanecnrboxylic cbcid C,,H,,O,N prepared by reduction of the three preceding unsaturated acids with sodium in amyl alcoholic solution is obtained as an oil with an odour resembling that of the fatty acids. The amide C,,H,,ON crystallises in whiteORGANIC CHEMISTRY. 89 needles m.p. 157"; the silver salt C,,,H,,O,Ag forms yellow leaflets. G. Y. A Case of the Inhibiting Action of the Carboxyl Group. MAXIMILIANNIERENSTEIN and T. A. WEBSTER (Ber. 1908,41 80-81). -The condensation of various phenols and phenolic acids with formaldehyde in the presence of hydrochloric acid to insoluble diphenyl- methane derivatives (compare Abstr. 1907 ii 192) has been studied. With all phenols the precipitate obtained is completely insoluble in hot water; with hydroxy-acids the amount of precipitate is often less and only a portion is insoluble in boiling water. The soluble portion consists of hydroxyaurincarboxylic acids. With protocate- chuic acid and vanillic acid precipitates were not obtained. J. J. 8. Constitution of Phenylnaphthalenedicarboxylic Acid.A Reply t o Stobbe. ARTHUR MICHAEL and JOHN E. BUCHER (Ber. 1908 41 70-73. Compare Stobbe Abstr. 1907 i 769).-The formation of o-benzoylbenzoic acid by the oxidation of l-phenyl- naphthalene-2 3-dicarboxylic anhydride has been already mentioned by the authors. Most of the differences between Stobbe's results and those obtained previously by the authors (Abstr. 1898 i 256) are due to the fact that Stobbe did not follow the authors' detailed instructions. J . J. S. Condensation Reactions of &Unsaturated Aldehydes ; Formation of Benzene Rings. HANS MEERWEIN (ArznaZen 1907 358 71-91).-The formation of aromatic from aliphatic compounds takes place in some cases with great ease whilst analogously con- stituted substances may not undergo ring condensation. Thus whereas the condensation product of methylethylacraldehyde and acetone is readily transformed into +-cumene (Barbier and Eouveault Abstr.1895 i 643) Dautwitx (Abstr. 1906 i 803) was unable t o obtain p-xylene from the Condensation product of tiglic aldehyde and acetone. The present author who has undertaken a systematic investigation of the factors determining the formation or non-forma- tion of rings in such cases finds that o-hydroxyrnesitylenic acid (I) is Cxmed from the condensation product (11) of methylethylacraldehyde and methyl malonate but that the condensation products of crotonaldehyde (111) and tolualdehy de (IT) with methylmalonate do not form aromatic hydroxy-acids CH,Me CH CH3 /\/ p M e Me / / \-/ "OH EH 70,Me RH flO,Me CIT \/ CH CH (1.1 (11.) (111.) (IV.) The ring formation is bevidently determined by the presence of VOL.XCIV. i k90 ABSTRACTS OF CHEMICAL PAPERS. substituting groups and by their position. Attempts ~ to ppepara aromatic hydrocarbons from the condensation products of croton- aldehyde and o-tolualdehyde with acetone were unsuccessful. Condensation of ap-Unsaturcited Aldehydes with Methyl Malonate Xynthesis of Homologous A~cclicyclic A cids.-Methyl citralidenemalonate CMe,:CH*CH,*CH,*CMe C H*CH :C( CO,Me),. formed in a 6 3% yield by the action of citral on methyl malonate in presence of pipendine at - loo is obtained as a viscid oil b. p. 190-195'/20 mm. DI5 1.043 ng 1.5126 ; the mol refraction observed 76.60 is considerably greater than the calculated 73-73 as has been found by other authors in the case of compounds containing conjugated ethylene linkings.When boiled with sodium hydroxide in alcoholic solution the ester is con- verted into an acid which is either 4-methyl-3-isoanzenyls~Z~cyl~c acid CMe,:CH*CH,*G',H,Me(OH)*CO,H or $-isohexen ylsalic y lie acid CMe, CH*CH CH C,H,( OH) C0,H. This crystallises in needles m. p. 16G-167' sublimes when carefully heated distils with superheated steam gives an intense blue colora- tion with ferric chloride in highly dilute alcoholic or aqueous solution and forms a dibroniide Cl,H,,0,Br2 crystallising in prisms rn. p. 160-161°. Methyl crotonylidenemalorzate C9Hl2O4 obtained in a 39% yield by the action of crotonaldehyde on methyl malonate in presence of piperidine a t - 5 O forms a yellow oil with a faint oclour b.p. 130-135O/15 mm. 1.1105 I Y L ~ 1.48849 The condensation product of a-methyl-P-ethylacraldehyde and methyl malonate C1,HI,O b. p. 139-145'/16 mm. is obtained in a 30% yield When boiled with alcoholic sodium hydroxide it is converted into o-hydroxymesitylenic acid m. p. 180" (Fittig and Hoogewerff Annalem 1869 150 333). Methyl o-tolylidenemalonate C,,H,,O forms white crystals m. p. 69-60' b. p. 165-170°/11 mm. and on hydrolysis yields o-methyl- cinnamic acid. Condensation of Crotonaldehyde with A cetone ; Cyotonylideneacetone. -The action of crot(ona1dehyde on acetone in aqueous sodium hydroxide leads to the formation of crotonylideneacetone CHlKe:CH*CH:CH*COMe in a 23% yield ; it is obtained as a mobile strongly refracting oil with an aromatic odour b.p. 78-80°/16 mm. D15 0,8990 ng 151954 is readily oxidised on exposure to air and forms an additive compound with four atoms of bromine. The oxime C7Hl10N crystallises in white needles m. p. 90-92' b. p. 124-125'/14 mm.; the semicarb- axone C,H,,ON crystallises in nacreous leaflets m. p. 157-158O ; the phenylhydraxone forms yellow leaflets m. p. 70-71O. On oxidn- tion with sodium hypochlorite at 70° the ketone yields chloroform and sorbic acid. o-ToZylidenecccetone C,,H,,O solidifies when cooled with ice and melts about the ordinary temperature forming a colourless strongly refracting oil b. p. 136-138"/10 mm. Constitution of Tannin. 111. MAXIMILIAN NIERENSTEIN (Bey. 1908,41,77-SO. Compare Abstr. 1905 i 914 j 1907 i 331).-The G. Y.ORGANIC CHEMISTRY.91 penta-acetyl tannin M. p. 203' may be reduced to the acetyl derivative m. p. 166O by means of zinc dust and glacial acetic acid. The latter acetyl compound acetyl-Ieucotannin when further acetylated in the presence of pyridine yields a hexa-acetyl-Zeucotannin m. p. 159'. Penta-acetyl-lencotannin is not reduced and penta-acetyl tannin cannot be further acetylated. These observations support the view that tannin is a mixture of digallic acid (tannin) and the corre- sponding reduction product (leucotannin) C,H,(OH),*CO*O*C,H,( OH),* CO,H (tannin) C,H,(OH),-CH(OH)*O*C,H,(OH),*CO,H (leucotannin). which may account for the optical activity of ordinary tannin. rufigallic acid than does triacetylgallic acid. The formula for leucotannin contains an asymmetric carbon atom When oxidised penta-acetyl tannin gives more ellagic acid but less J.J. S. Glycidic Esters and Aldehydes in the Naphthalene Series. GEOHGES DARZENS (Compt. rend. 1907 145 1368-1343. Compare Abstr. 1905 i 1 1 6 ; 1906 i 62 137 430; 1907 i 178 182 627).- Ethyl p- l-naphthyZ-P-methylZ~~~~ate O< . I obtained by 'the CH*CO,Et ' condensatiqn of a-naphthyl methyl ketone with :thy1 chloroacetate in the presence of sodium ethoxide is a colourless viscous liquid b. p. 1 65-170'/4 mm. ; the corresponding acid on distillation decomposes into carbon dioxide and a-1 -naphthylpropaZdehy.le C,,H7*CHMe*CH0 an amber-coloured liquid with an odour similar to t h a t of hydratrop- aldehyde b. p. 131-132'/4 mm. ; the sernicnrbaxone has m. p. Ethy I p-2 -nrq&?~yl-/3-meth ylg Zycidate similar1 y prepared t o the above is an odourless liquid b.p. 175-1SOo/5 mm.; the corre- sponding acid is solid and yields on distillation a-Z-nuphtlzylprop- ddehyde m. p. 53'; the semicarbaxone has m. p. 134-135'. The semicarbaxones of a- and up-naphthyl methyl ketone have m. p. 232-233' and 235-237O respectively. 209-21 0'. M. A . W. Mentbazine. NICOLAI M. KIJNER (J. Rzcss. Phys. Chern. Xoc. 1907 39 Chem. 1246-1250. Compgre Abstr. 1900 i 277).- I-Menthone when treated with hydrazine hydrate a t the ordinary temperature forms chiefly I-menthazine m. p. 51" [a]. - 107.68O; at higher temperatures or when the mixture is distilled it forms d-menthazine m. p. 8 3 * 5 O [a]= + 64-89' t o + 85.27". The latter is also formed when d-menthone is employed. The liquid product formed in the action of hydrazine hydrate on I-menthone consists of a mixture of I- and d-menthazines.The production of the d-men- thazine is due t o the isomerisation of I-menthazine at higher temperatures. Z. K. Ketone Derived from P-Hexahydrocarvacrol. LBON BRUNBL (Compt. vend. 1907 145 1427-1429).-When the P-hexahydro- carvacrol (P-carvacrornenthol) obtained by the direct hydrogenation h.292 ABSTRACTS OF CHEMICAL PAPER& of carvacrol in the presence of reduced nickel (Abstr. 1906 i 81) is oxidised with chromic acid it yields the ketone carvacromenthone b. p. 221-221*5O DO 0.908. The oxime amine and two isomeric semicarbazidea were prepared and were found to bo identical with the corresponding derivatives of tetrahydrocarvone described by Baeyer (Abstr. 1893 i 359) and Wallach (Abstr.1894 i 44; 1896 i 101) ; it follows therefore that P-carvacromenthol (1-methyl-4-iso- propylcyclohexane-2-01) is identical with tetrahydrocarveol. M. A. W. Components of Ethereal Oils. Constitution of Umbellu- lone C,,H,,O. FRIEDRICH W. SEMMLER (Bev. 1907,40,5017-5023). -The physical data for dihydroumbellulone show that it is not a dicyclic derivative belonging to the pinene camphor or dicyclo- octanone series (compare Tutin Trans. 1906 89 1104; 1907 91 271). Umbellulone C,,H,,O has b. p. 93-98'/10 mm. D20 0.958 aD 1.4895 uD -31.5' (100 mm. tube) mol. ref. 45.19. Dihydro- umbellulol C,,H,,O has b. p 91-93'/10 mm. D20 0,931 fiD 1.47348 aD - 27.5' (100 mm. tube). /I-Dihydroumbellulone C,,H,,O has b. p. S3-8'7'/10 rnrn,;Dio 0.928 !uD 1.451168 uD - 30.5' (100 mm.tube). forms oxymethylene and benzylidene com- pounds showing that the keto-group is adjacent t o a CH group. The oxymethylene compound has b. p. 105-107'/10 mm. D" 1.001 TZ 1.49097 ; it yields homotanacetonedicarboxylic acid on oxidation and gives a violet-red coloration with ferric chloride. The benxyl- idene compound has b. p. 185-188'/9 mm. D20 1.03 mD 1.574 and aolidifies to minute needles m. p. 81-82'. The molecular refractions of these compounds are all considerably higher than the calculated values as is also the case in the tanacetone aeries. I-Benzylidene-P-dihydroumbellnlone yields on oxidation d-homotan- acetonedicarboxyEic acid m. p. 146-147' uD + 2.5' (20% solution in 100 mm. tube) which unites with the I-homotauacetonedicarboxylic acid from d-tanacetone (compare Semmler Abstr.1904 i 176) to form i-homotanacetonedicarboxylic acid m. p. 179" and crystallising in short needles. The d-acid forms a neutral ethyl ester b. p. 148-153'/ 10 mm.,and an oily acid ethyl ester. Dihydroumbellulone is regarded as a tanacetone of the methone series CH,< C(CHMe2'*Co>C I whereas umbellulone has a double Dihydroumbellulone CH-CHMe bond adjacent to the keto-group GB,<?(CHMe2)- GO." CH.CM~:CH' E. F. A . Oxygen Derivatives of Camphene. THADDEUS MILOBENDSKI (J. Buss. Phys. Chern. Soc. 1907 39 Chenz. 1395-1403).-'I1he camphene prepared from isoborneol has m. p. 47.5-48*5' b. p. 159.5'/755 mm. and is optically inactive ; that from pinene hydro- bromide has m. p. 44-45' b.p. 159*5"/755 mm. [.ID -41'46'. * Ste also Tntin Proe. 1908 24.ORGANIC CHEMISTRY. 03 The formar when oxidised with permanganate yielded only a very small quantity of neutral products containing a glycol m. p. 197.5-19S*5° and a trace of acid having the odour of acetic acid. The glycol obtained from the other camphene has m. p. 181-185' [a] +21@40'; after subliming a t l l O o m. 'p. 156-177' and when re-sublimed at 96" m. p. 169- 175'. The glycol obtained from diacetyl- camphene has m. p. 160-161'. The first glycol m. p. 197*5-198*5' when dehydrated yields camphenilonealdehyde m. p. 68-5-70" and a white resinous substance distilling above 300°/15 mm. When the glycol is oxidised with potassium permanganate it yields camphenilone m. p. 36-37" a small quantity of volatile acids camphenilic acid m.p. 170-1 71" (sodium salt C,oH,,0,Na,5B,0) and camphenecam- phoric acid m. p. 135-136". With nitric acid the glycol yields two acids CloH1602 m. p. 93*5-94' C,,H,,O m. p. 191*5-192*5O apocamphoric anhydride C,H,,O m. p. 1 77*5-17S0 a ketonic acid m. p. 235O the oxinze of which has m. p. 195-196.5' and some other crystalline products which could not be isolated. With chromic acid the glycol yields camphenilone and cemphenecampboric acid. Camphenecamphoric acid obtained from either of the two camphenes mentioned above is optically inactive and has m. p. 135*5-136' and distils a t 235-237'/10-11 mm. 250-251"/20 mm. but when it is obtained from camphene prepared from borneol chloride it has m. p. 145-1 46'. The chloroanhydride of camphenecamphoric acid has b.p. 153.5-154.5O/13 mm. but in estimating the chlorine in alcoholic solution the results are too low. It was not found possible to obtain the pure ethyl ester by Fischer's method. The chromate is also described. An attempt was made to determine the constitution of the acid by bromination then removing hydrogen bromide by means of potassium hydroxide and finally oxidising t h e unsaturated acids so obtained with potassium permanganate but without success. One crystalline unsaturated acid m. p. 147.5-149" was thus isolat'ed ; it is readily soluble in water alcohol and chloroform. Z. E. Investigations in the Terpene and Camphor Series. LEO A. TSCHUGAEFF (J. Russ. Yhys. Clierrz. Soc. 1907 39 Chem. 1324-1343. Compare Abstr. 1905 i 71 166).-Since pinene is very unstable most of its derivatives have a different constitution from the parent substances ; consequently to obtain true derivatives the xnnthogen reaction has been applied as in this case polymerisation does not occur.Pinocamyheol was prepared from pinene by a modifi- cation of Wallach's method and then converted into the xanthogen derivative C,,H,7*O*C*Y,Me m. p. 60.5-61' ; it forms rhombic cryoltals [a b c = 1.3747 1 0.978751. A t 180-190° it decomposes thus C,oH,7-O*CS,Me -+ C,(,H,6 + MeSH + cso yielding inactive pinene; from this it is evident that pinocamphone and pinocampheol are true derivatives of pinene (compare Wallach and Engelbrecht Abstr. 1906,ii 683). I-Dihydrocarveol was converted into the xanthate CloH,~*O*CS,Me which by the action of ammonia yielded the arnide C,,HI7*O*CSNH m.p. 62-63' [a12 -138+39°,; it forms rhombic crystals [ c c b c == 0.6548 I 0.705SI. The racemic modification of this amide has94 ABSTRACTS OF CHEMICAL PAPERS. m. p. 95*5-96O crystallises in small needles and is much less soluble in organic solvents than the active amides. Methyl dihydrocarveol xanthate decomposes at 180-190' in exactly the same manner as pinocampheol xanthate forming the terpene CloHl6 b. p. 172-1 74O n2g5 1.469'72 D:::; 0.8382 [a] + 131.93'. The Sachgeisa oil or resin which is used as a chewing gum by the natives of South Caucasia when subjected to steam distillation yields an oil consisting almost wholly of inactive pinene together with a small quantity of active terpene. The resin is analogous with that obtained from the bark of the tree Pistacia Zenticus and known as mastic.Z. K. New Method for the Hydration of Pinene. PHILIPPE BARBIER and VICTOR GRIGNARD (Compt. rend. 1907 145 1425-1427)- When pinene in acetic acid solution is treated with a solution of benzenesulphonic acid it is converted to the extent of 52.3% into terpineol. For this purpose freshly-distilled French pineae is dissolved in an equal weight of acetic acid one-tenth of its weight of a 50% aqueous solution of benzenesulphonic acid added and the mixture shaken until it becomes homogeneous. After twelve hours water is added and the insoluble layer washed dried and separated by distilla- tion into two fractions the first boiling below SSo/15 mm. consists of unchanged pinene with a small quantity of a terpadiene b.p. 175-178" and the second fraction boiling above 85"/15 mm. after saponifi- cation with alcoholic potassium hydroxide at 1 10-115° is composed of terpineol b. p. 100-105°/13 mm. m. p. 35" together with a small quantity of borneol fenchyl alcohol and a viscous substance not identified. When lasge quantities of purified pinene are submitted to the above reaction a hydrocarbon having a lower boiling point than the original pinene can be isolated from the product. M. A. W. Santene. OSSIAN ASCHAN (Bey. 1907 40 4918-4923).-1n addi- tion to I-pinene I-camphene phellandrene Miiller's santene has been isolated from Siberian turpentine and identified by conversion into the nitrosochloride nitrosite tribromide (m. p. 77-80°.Miiller gives 62-63"} and hydrochloride as well as by direct comparison with the santeno obtained from sandal wood oil (Abstr. 1900 i 678). It has b. p. 140° D15 0.8698 n2'2 1.4690 and the formula C,H is confirmed. flaantenol acetate C,H,;OAc prepared by using acetic and aulphuric acids is a clear liquid resembling isobornyl acetate in odour b. p. 215-219°/760 mm. and S8-89"/8 mm. D2\ 0.9S71 optically inactive rz 1.45929 thus showing the compound t o be saturated. The santenol obtained on hydrolysis is a solid mixture two- thirds of which bas b. p. 195-196' and the remainder b. p. 196-198" and the conjecture is made that it is similar t o the isoborneol-borneol mixture obtained from camphene. By recrystallisation from light petroleum large transparent plates a.p. 97-98" are obtained. TheORGANIC CHEMISTRY. 95 phenylurethane forms long needles m. p. 61 -62'. Oxidation of snntenol results in the formation in small quantity of a ketone (ssmkarbazone m. p. 225-226'). Santene is also a constituent of oils from Pinzls picea Abies exelsa and a Swedish turpentine. W. R. Rusrsian Turpentine Oil and Russian Pine Tar Oil. IWAN SCHINDELMEISER (Chern. Zeit. 1908 32 8).-Russian turpentine and pine tar oils contain sylvestrene dipentene and in the pinene fraction nopinene identified by the formation of the sparingly soluble acid m. p. 1 2 6 O and sparingly soluble sodium salt on oxidation with perman- ganate. The pine tar oil contains also toluene cymene and a quinone- like substance which has a sharp odour is resinified becoming yellow on treatment with sodium hydroxide and metallic sodium and reacts with hydroxylamine and phenylhydrazine together with saturated acyclic hydrocarbons one of which b. p.98-99' is probably a heptane. A sesquiterpene present in Russian pine t a r oil is,. perhaps identical with the sesquiterpene occurring together with cadinene in cade oil. G. Y. Turmeric Oil. HANS RUPE (Bey. 1907,40 4909-4910. Corn- pare Jackson and Menke Abstr. 1883 482).-When turmeric oil is boiled with dilute sodium hydroxide the main product is a substance containing oxygen b. p. 156'/12 mm. which is probably not identical with Jackson and Menke's turmerol and does not exhibit the properties of an alcohol aldehyde acid or ketone. When boiled with stronger alkali it yields an optically active ketone C,,H,,O b. p.11 9-1 20°/S mm. which forms a sernicarbaxone m. p. 11 9.5-1 20.5O an oxime b. p. 159'111 mm. and well-crystallised condensation pro- ducts with aromatic aldehydes. The ketone is oxidised by potassium permanganate to terephthalic acid and p-methylacetophenone and yields by treatment with alkali hypobromite a hydroxy-acid C12Hlc03 m. p. 150° and an acid C12H1602 m. p. 33-34' ; the latter is oxidised by potassium permanganate to a dicarboxylic acid O,,H,,O m. p. 228'. c. 8. Action of Nitrous Acid on Caoutchoucs. OTTO GOTTLOB (Zeitsch. angew. Chew%. 1907 20 2213-2221. Compare Harries Abstr. 1005 i 223 ; this vol. i 39).-The products obtained by the action of nitrous fumes on crude or purified caoutchoucs vary in com- position with the proportion of nitrogen peroxide present in the mixture of nitrogen oxides but all are more or less impure forms of Harries' nitrosite C1,H,,O7N,.The latter substance can only be obtained in a pure state by strictly following the directions given by Harries (Abstr. 1903 i lS9). The existence of the nitrosate C9HlBOON2 described by Alexander (Abstr. 1905 i 223 ; 1907 i 433; Zeitsch. angew. Chem. 1905 18 164) is doubtful. The same author's statement that. carbon dioxide is liberated during the action of nitrous fumes on caoutchouc is correct but the quantity evolved only corresponds with roughly 0.3% of the total carbon present in the caoutchouc treated. W. H. G,96 ABSTRA7TS OF CHEMICAL PAPERS. f * West African Copals especially Angola and Cameroon Copals. ALEXANDER TSCHIRGH and H.RAGKWITZ (Arch. Pharrn. 1907 245 415-426. Compare Abstr. 1897 i 92).-The constants are given of samples of copal from Sierra Leone Accra Benin Loango Congo and Benguela. The Angola copal examined had m. p. 140-170° acid number 135 saponification number 155 and iodine number 66. The copal was extracted with ether. From the ethereal solution 1% aqueous ammonium carbonate did not extract anything but I % aqueous sodium carbonate extracted (1) amorphous angocopalolic acid C23HR6.03 m. p. 8 5 O acid number 157 corresponding with monobasicity (the szlvey salt was analysed) saponification number 155 and iodine number 7 1 corre- sponding with one double bond precipitated in alcoholic solution by lead acetate and (2) st resinous acid not so precipitated.By evaporating the ether and distilling with steam an essential oil b. p. 140-160" D 0.85 3 passed over whilst yellow amorphous a-angocopaloresen C30F540A or C,,H,,O rn. p. 63-65' remained behind. From the residue of the copal insoluble in ether alcohol-ether extracted in addition to traces of angocopalolic acid yellow P-angocopaloresen C25HaS04 m. p. 220-224'. There remained insoluble in alcohol- ether a substance resembling bassorin soluble in aqueous sodium hydroxide and insoluble inorganic silicates. I n 100 parts of the drug are contained angocopalolic and other acids soluble in ether 64 ; essential oil 2 ; a-angocopaloresen 3 ; acid soluble in ether (t) 5 ; P-angocopaloresen 20 ; substance resembling bassorin 0.3 ; ash 5.7. The Cameroon copal examined had m.p. 105-125' acid number 126 saponification number 157 and iodine number 68. After extraction with ether for three rnonthF aqueous ammonium car- bonate did not extract anything from the ethereal solution but 1% aqueous sodium carbonate Extracted (1) amorphous cameroo- copalolic acid C21H3603 m. p. 98-100° acid number 160 corre- sponding with monobascity (the silver salt was analysed also) saponi- fication number 188 and iodine number 76*5 corresponding with one double bond precipitated iu alcoholic solution by lead acetate ; and (2) a resinous acid not so precipitated. By evaporating the ethcr and dietilling with steam a yellow essential oil b. p. 145-155' D 0.830 was driven over whilst viscous a-carneroocopaloreselz remained behind. From the residue of the copal insoluble in ether alcohol-ether extracted p-cameroocopalovesen C25H3S04 m.p. 220-224O. There remained insoluble in alcohol-etlher a substance resembling bassorin soluble in aqueous sodium hydroxide and an insoluble residue largely inorganic in character. I n 100 parts of the drug are contained cameroocopalolic and other acids 70 ; essential oil 2 ; a-cameroo- copaloresen 3 ; /I-cameroocopaloresen 20 ; substance resembling bassorin 3 ; ash 2. C. F. B. Heerabol Myrrh OSCAR VON FRIEDRICHS ( A d . Pharm. 1907 245 427-457. Compare Kohler Abstr. 1890 1317 ; Tucholka Abstr. 1897 i 584; and especially Tschirch and Bergmann Abstr. 19Q6 i 197 ; Lewinsohn Abstr. 1906,i 972).-Commpial samples ofORGANIC CHEMISTRY. 97 Myrrh0 eZecta aere examined and consisted of yellowish-brown to reddish-brown pieces with a waxy translucent fracture.The following substances were isolated from it (1) a volatile essential oil (8*8%) viscid yellow t o yellowish-green DIP 1.0 11 12. 1.5359 [ u] - 73*9' acid number 6.15 and ester number 47.6. From this oil there were separated formic and acetic acids and a crystalline acid m. p. 1 5 9 O which was not volatile with steam m-cresol cuminsldehyde and cinnamaldebyde and the crystalline monobasic myrrholic acid C17H,,05 m. p. 236' (of which t h e amorphous silver lead and coppel. salts were analysed) and the sesquiterpene heerabolene C,,H, b. p. 130-136'/16 mm. D2* 0.943 T, 1.5125 u 14'10' in 100 mm. tube the molecular refraction indicating a tricyclic sesquiterpene; this yielded a crystalline &hydrochloride C,,I-T,,,ZHCt m.p. 98-93'. (2) That part of the resin which was soluble in light petroleum yielded some acetic acid when submitted t o dry distillation. From that part of the drug insoluble in light petroleum but soluble in ether the following constituents were separated a-commiphoric cccid C,,H,,O m. p. 201-203" is monobasic ; p-cornmiphoric acid m. p. 2 0 5 O has the same formula and basicity; y-commiphoric acid C,7H2,0 m. p. 169-172' is monobasic; all three acids are amor- phous yellow to brown cannot be ncetylated and do not contain methoxy-groups. a-Heerabo-myrrhol G18H2605 m p. 248-250° forms a diacetpl derivative of m. p. 228' (decornp.) and is precipitated from an alcoholic solution by lead acetate ; P-heerabo-inyrrihol C20H2,i06 m.p. 1 6B0 forms a diacetpl derivative. Commipphorinic acid C,,H 3608 m. p. 135" is brown amorphous and monobasic ; the barium salt is insoluble in water and alcohol. A yellow alcohol C,,H,,O b. p. 264" which forms a monoacetyl derivative of b. p. 243' and 1s volatile with steam ; and the non-volatile yellow amorphous heeraboresen C,,H,,O m. p. 100-102° which contains one methoxyl group. The part of the drug insoluble both in light petroleurn and in ether was soluble in aqueous sodium carbonate. It was separated into (1) brown amorphous monobasic a-i~eerccbo-nzy.1.r~ololic acid C1,H,,O7 m. p. 320-225' of which the amorphous silver and lead salts were analysed but no acetyl derivative could be prepared ; i t is pre- cipitated in alcoholic solution by lead acetate and ( 2 ) p-myrrhololic acid C,,H,,O rn.p. 187-190° not so precipitated brown amorphous and monobasic of which the silcer salt was annlysed. The gum had [.ID + 2 3 . 8 O in 2% aqueous solution and was mixed with an enzyme of the oxyciase group ; when oxidised with nitric acid it yielded mucic acid and when distilled with hydrochloric acid furfuraldehyde ; hence it probably contained galactose and arabinose. No bitter principle was detected but the volatile oil has a biting unpleasant taste. C. I?. B. Baptisia Glucosides. IV. +-Baptisin. K. GORTER (Arch. Pharm. 1907 245 561-572. Compare Abstr. 1897 i 627; 1898 j 39; 1906 i 973).-The presence of one hydroxyl group in $-baptigenin has been confirmed by the preparation of the benzoate Gl5H9O5B2 crystallising in small white needles m. p.216'.98 ABSTRACTS OF CHEMICAL PAPERS. The substance obtained by heating the sodium derivative of $-baptigenin with ethyl iodide and alcohol (compare Abstr. 1906 i 973) is now shown to have the composition C,,H,,O and is named +!&xptigin; it crysballises in small colourless plates m. p. 172’ (not 1 6 9 O as previously stated). It yields neither an acetyl nor a benzoyl derivative and consequently cannot contain a hydroxyl group. Since the formation of $-baptigin is accompanied by the production of formic acid it follows that $-loaptigenin must have the partially structural formula CIpHsO,:CH*OH. No $-baptigin results on heating sodium t,6-baptgenin with ethyl alcohol alone and in the presence of ethyl iodide only one-half of the $-baptigenin is converted into $-baptigin.What probably happens in the latter case is as follows part of the sodium q-baptigenin is converted into the ethyl ether which is then hydrolysed with the formation of +-baptigin and ethyl formate C,,H,O,:CH*OEt + H,O = C14H1,0 + H*CO,Et. The ethyl formate together with ethyl alcohol reacts with more sodium $-baptigenin forming ethyl ether sodium formate and $-baptigenin C,,H,O,:CH*ONa + H*CO,Et + EtOH = C,,H,O,:CH*OH -t H*CO,Na + OEt,. The substance CJi4,O4 previously described (Abstr. 1898 i 39) is now shown to be rnetlqlbaptigenetin and is formed together with formic acid on hydrolysing $-baptigin with alcoholic potassium hydr- oxide. It yields on acetylation two acetyl derivatives colourless rhomboidal crystals m. p. about 1 as0 and colourless rectangular crystals m.p 148’. These could not be isolated in a pure state but it is probable from an analysis of the mixture that the compounds formed are triucet ylmeth y lbaptigmetin and acety bunhydrometh ylbapti- genetile. From the above facts together with those previously published (Zoc. cit.) it follows that baptigenetin must have the partially structural formula (I) and $-baptigin the formula (11). Since +-baptigenin when heated with potassium hydroxide solution yields baptigenetin formic acid and methyl alcohol it is probable that i t has the formula (111) /OMe ,,/O*CH CH-OH C12H,(OH),<gg {i] C H -O*C‘HO C H -O*CHO l2 “ 0 [l 41 l2 “\0[1 41 (1.1 (11.1 (111.) When heated under pressure with 5% hydrochloric acid a t 200’ for two hours methylbsptigenerlin yields a small quantity of a substance which has the properties of catechol.It is possible therefore that baptigenetin is a derivative of diphenylene oxide W. H. G. Chitin. TIIEODOR n. OFPER (Biochenz. i%itsch 1907 7 11 7-1 27). -Chitin prepared from the carapace of the lobster by successive treatment with dilute hydrochloric acid boiling 10% potassium hydr- oxide potassium permauganate arid sodium hydrogen sulphite was hydrolysed by 70% sulphuric acid at the ordinary temperature and yielded two amorphous substances of the Composition C,,H2,0,,N2. OneORGANIC CHEMISTRY. 99 of these is acetyldiglucosamine m. p. 194' (decomp.) soluble in water and optically inactive. The other is insoluble in water gives a reddish- brown coloration with iodine and is regarded as a polymeride of the former substance.I n acetyldiglucosamine one amino-group is probably acetylated whilst the amino-group of the second glucosamine molecule is condensed with the aldehyde group of the first. Chitin itself is regarded as a highly polymerised acetyldiglucosamine. G. B. Solanin from the Seeds and Flowers of Solanum Tuberosum. AMEDEO COLOMBANO (Atti R. Accad. Lincei 1907,;[v] 18 ii 683-690 ; 755-762. Compare Odd0 and Colonibano hbstr. 1905 i 455).- From a study of the physical and chemical characters of various samples of solanin the author draws the conclusion that the latter exhibits properties varying wiih the source from which i t is obtained. Thus solanin extracted from Solanum tuberosum differs essentially from that isolated from 8.sodomwum the two products yielding different solanidins when treated with boiling dilute hydro- cLloric acid. T. H. P. Phylloxanthin. LEON MARCHLEWSKI (Biochem. Zeitsch. 1907 7 282-285. Compare Abstr. 1907 i 69 71 784 7S7 865 S66 867 948).-Polemical. The identity of certain chlorophyll derivatives described by Tsvett and Willstatter is discussed and the former's spectroscopic results with phylloxanthin are described as incorrect. W. D. H. Rottlerin. FRANZ HEREMANN (Arch. Pharm. 1907 245 572-585. Compare A. G. Perkin Trans. 1893 63 975; 1895 67 230; Telle Abstr. 1906 i 973; 1907 i 435; Thorns Abstr. 1907 i 545).- Perkin's isorottlerin is considered t o be impure rottlerin ; his formula C33H3009 for the latter compound is however confirmed.Rottlerin in alkaline solution yields on oxidation with hydrogen peroxide at 75O cinnamic and benzoic acids. 2 4 6-Trihydroxytoluene results on de- composing rottlerin with concentrated potassium hydroxide solution at 150"; the same compound is also formed together with 2 4 6- trihydroxy-nz-xylene acetic acid and a tarry substance by heating a solution of rottlerin in 15% aqueous sodium hydrexide a short time with zinc dust. The tarry substance is oxidised in alkaline solution by hydrogen peroxide with the formation of a dibasic acid C,7H,,04 crystallising in slender colourless needles m. p. 184"; the silver salt U17H,,0,Ag2 and ethyl ester crystallising in needles m. p. 1 1 5 O were prepared. The acid is converted by cold fuming nitric acid into a dinitro-derivative I I I 1 crystallising in small colourless rhombic plates \/ \/ 284O ; the corresponding ccrnine forms C02H rinEshaped crystals.The dibromo-derivative C17H,,0,Br resiilts on treating the acid with bromine in glacial Bfe Me /\-GH2- /\ C17H1404(N02)2,100 ABSTRACTS OF CHEMICAL PAPERS. acetic acid; it forms stellate crystals m. p. 172-173'. bable that the acid bas the formula given on p. 99. It is pro- W. H. G. Cinchona Alkaloids. VIII. Constitution of Cinchonine PAUL RABE [with OTTO BU~HHOLZ] (Ber. 19OS 41 62-70).-The base C,,H,,ON (Abstr. 1907 i 954) obtained by oxidising cinchonine with chromic acid is termed cinchoninone in order t o indicate its relation to tropinone and codeinone. It is amphoterio in character and exhibits keto-enolic tautomerism since it yields both an oxime and an 0-benzoyl derivative.It is readily reduced and under special conditions can be converted back into cinchonine ; under normal conditions however a rupture of the molecule occurs duriag the reduction. Nitrous acid (arnyl nitrite) decomposes the ketonic base yielding cinchonic acid and a n oxime C,NH,,:N.OH a reaction which is analogous to the formation of diacetylmonoxirne from ethyl methyl- acetoncetate. The presence of the grouping -CO*CH< is t h w established. The oxime when hydrolysed yields meroquinenine and assuming Koenig's formula for this compound the following con- stitutional formul,? are deduced for the oxime C,NH13*NOH and cinchoninone CH,-CH* CH*CH:CH CH,*CH* CH-CH :CIS j I. 1 $%I IJ. 6HZ HO*N:C-N- CH C911,N*CO*CH N-CH,.Cincho?zi?zoneoxinze C1,H,,ON obtained by the action of free bydroxylninine on the ketone in a strongly alkaline solution forms a pale yellow amorphous powder m. p. 105-110'. It yields a methiodide C,,H,,ON,,IIIeI which has no definite m. p. ; it begins t o soften at 135" arid decomposes a t 145-150'. The benzoyl derivative C26H2402N2 of the base crystallises from light petroleum in colourless needles m. p. 131'; i t is readily hydrolysed by alkalis and possesses very feeble basic properties. Cinchoninone methiodide also yields a benzoyl derivative C,6H2,02N2,il!teI which is hydrolysed when boiled with alcohol. A 75% yield of a'-ozimino-~-vinyZ-quinuclid~ns (formula I above) is obtained by the action of amyl nitrite and sodic ethoxide on the ketone; i t crystallises from ethyl acetate or a mixture of ether and light petroleum (b.p. 40') in colourless prisms or needles m p. 146-147" and yields a methiodide C9H,,0N,,MeT xn. p. 224O (decomp.). *J. J. 5. Alkaloids and Bitter Principles of Calumba Root. VIII. KARL FEIST (Arch. Pharm. 1507 245 586-637. Compare Gadamer A.bstr. 1903 i 5 0 ; 1906 i 976)-Three alkaloids have been ob- tained from calumba root namely columbamine jateorrhizine and palmatine. Gunzel's work on columbamine (Abstr. 1906 i 976) has been confirmed ; further investigation has shown t h a t columb-ORGANIC CHEMISTRY. 101 axnine contains a hydroxyl group in addition to the four -OM0 groups ; columbamine iodide consequently has the partly structural formula C,,H,NI( OMe),*OH. Jnteorrhizine iodide which has the empirical formula C,oH,,O,NI is found to contain three -0Me groups and two hydroxyl groups so that the formula may be written C,7.H,NI(OMe),(OH),; in fact columbamine is a monomethyl ether of jateorrhizine since the mono- methyl ether of columbamine is identical with the dimethyl ether of jateorrhizine. Both coluinbamine and jat,eorrhizine also their methyl ethsrs are very similar to berberine yielding colourless tetra- hydro-derivatives Ssc.The methyl ether of columbamine yields on oxidation with potassium permanganate corydaldine (Dobbie and Lauder Trans. 1902 81 145) together with a trimethoxy-o-phthalic acid. The acid which was not obtained in a pure state melted a t almost the same temperature as gallocarboxylic acid trimethyl ether (3 4 5-trimet,hoxy-o-phthalic acid) but crystallised in a different form.Should the two acids on further investigation be proved to be identical then salts of columbamine methyl ether must be represented by formula I. If not the only other trimethoxy-o-phthalic acid po?sible is 3 4 6-trimethoxy-o-phthalic acid and salts of columbamine methyl ether mould then have the formula I1 OMe OMe X X The third alkaloid palmatine only small quantities of which are present in caluniba root closely resembles berberine ; it contains four OMe groups but no hydroxyl group and the iodide has the formula C,7H,o0,NT(OMe) ; the relationship existing between this alkaloid and columbamine is not yet known. The discovery of a second bitter principle in cnlurnba root named provisionally ' $ bitter principle 11," led to an investigation of columbin.The value obtained for the mol. wt. of the latter compound by the boiling- and freezing-point methods varied considerably with the solvent employed; consequently the mol. wt. of this substance is still unknown (compare Ulrich Abstr. 1907 i 331). Owing to the similarity of the two substances it is possible that the columbin hitherto investigated has been contaminated with (' bitter principle 11." Colurrdmmine nitrate C2,H,,0,W,,2&H20 crystallises in lemon-yello w needles m p. 232' ; the platinichloride (C2,H,,05N)2,H2PtCl is a yellow powder m. p. 238' (decomp.) ; the aurzchloride forms slender needles m. p. 220" (decomp.). Concentrated solutions of columbamine sulphate or nitrate yield on treatment with strong aqueous potasaium hydroxide the inner anhydride of columbamine which crystaliises in violet-black prisms commences to melt at 190° and decomposes above this temperature.Tetrahydrocolumbamine is most readily prepared102 ABSTRACTS OF CHEMICAL PAPERS. by the reduction of columbamine nitrate ; the suZphacte crystallises i n white silky needles ; the chloride forms a colourless crystalline powder commences to melt a t 150° and is completely molten a t 215'. All attempts to separate tetrahydrocolumbamine into its optically active components mere unsuccessful. Columbamine chloride reacts with benzoyl chloride yielding a substance obtained as a light yellow crystalline powder m. p. 152'. In pyridine solution however a substance obtained as a light yellow powder m.p. 212-213' is formed. Acetyl chloride reacts with columbamine chloride in pyridine forming a substance (acetyl derivative 2) which crystallises in slender yellow needles Q. p. 220' (decomp.). None of these substances was obtained in a pure state. That columbamine contains a hydroxyl group is shown by the preparation of the methyl ether ; the iodide of columbamine methyl ether results on heating colnmbamine iodide with potassium hydroxide methyl alcohol and methyl iodide in a sealed tube a t 100'; it crystal- lises in prisms m. p. 238-240'; the sulphate results on treating columbamine iodide with methyl sulphate in the presence of alkali; the rzitmte crystallises in slender light yellow prisms m. p. 2 3 P (decomp.). A concentrated solution of the sulphate when treated with 50% aqueous potassium hydroxide yields the $-form of columbamine methyl ether; it crystallises in light yellow prisms m.p. 136'. Columbamine methyl ether yields with chloroform an additive corn- pound C,,H,,O,N,CHCI forming small light grey crystals m. p. 1 8 2 O and with acetone an additive compound obtained as a dirty yellow fine crystalline powder. T'etrahydrocolumbnmine methyl ether is obtained by reducing the nitrate of columbamine methyl ether ; it crystallises in colourless prisms m. p. 148'. Columbamine methyl ether yields on oxidation with aqueous potassium permanganate corydaldine a trimethoxyphthalic acid CY6H(OMe),(C0,H) crystnllising in colourless slender needles m. p. 200° and an acid containing nitrogen crystallising in colourless prisms m.p. 200-202°. The composition of the latter acid is not yet known; its hydrochloride forms colourless needles rn. p. 208' (decomp.) and ccurichloyide crystallises in slender light yellow needles m. p. 188' (decomp.). I n order to compare the above trimethoxy- phthalic acid with gallocarboxylic acid methyl ether (3 4 5-tri- methoxyphthalic acid) this compound was prepared by treating the acid with diazomethane in ethereal solution and hydrolysirig the dimethyl ester so formed with alcoholic potassium hydroxide ; it crystallises in small colourless rhornbic plates m. p. 195'. Gallo- carboxyiic acid yields on treatment with methyl sulphate,in the presence of alkali a substance probably a monomethyl ether C,H,O,(OMe) crystallising in colourless needles m.p. 251 '. Jateorrhixine iodide C20H200,NI,H20 crystallises in reddish-yellow needles m. p. 208-210' ; the corresponding chloride crystallises from water with +H,O in light yellow needles m. p. 2U6' and from alcohol with 1H20 in copper-coloured needles m. p. 206'; the sulphate forms brownish-yellow prisms ; the nitrate crystallises in glistening C,,H,N*(OMe)vORGANIC CHEMISTRY. 103 golden-yellow needles m. p. 225" (decomp.). The latter salt yields on reductioo tetrahydro~ateorrhixine C,,H,,O,N crystallising in colourless needles m. p. 206". Jateorrhizine iodide yields on methylation a dimethyl ether identical with columbamine methyl ether iodide Palmutine iodide C,7Hlo0,NI(OMe) remains undissolved on treating the mixture of iodides of the alkaloids obtained from calumba root with aqueous sodium hydroxide ; it crystallises in slender yellow needles m.p. 238-240' (decomp.). The corre- sponding mitrate C,,H2,0GN*N0,,1 $H,O forms slender lemon-yellow needles m. p. 238-240". Reduction of this salt leads to the formation of tetrahydropaZmatine C,,H,,O,N crystallising in colourless leaflets m. p. 145" ; the cuwrichZorzcZe C,,H,,O,N,HAuCl forms small cinna- mon-brown crystals. An alcoholic extract of calumba root yields on evaporation a mixture of orange-red prisms and nodular aggregates of yellow crystals. The orange-red substance was found on investigation t o be jateorrhizine chloride with 2H,O. The yellow substance was found to be a mixture of columbnmine nitrate with some '' bitter principle 11." The latter substance crystallises in prisms m.p. 246' (decomp.) and is a lactone. I n agreement with the statement of Ulrich (Zoc. cit.) columbic acid was not detected in the alcoholic extract. W. H. G. isosparteine an Isomeride of Sparteine. CHARLES MOUREU and AMAND VALEUR (Compt. read. 1907 145 1343-1345. Compare this vol. i 44).-isoSparteine CI5Hz6N2 obtained by treating the hydriodide (Zoc. cit.) with sodium hydroxide is a colourless almost odourless oil b. p. 177*5-1'77" (corr.)/16.5 mm. [.ID - 25.01O in 10% alcohol SOlUtiOn Di7 1*02793,n~1.53319 ; the dihydrochloride is a deliquescent crystalline solid ; the pkatinichloride Cl,H2,N,,H2PtCI,,l~5H,0 forms silky tufts of crystals blackens at 230° and decomposes at 257-260" ; the sulplmte forms a thick syrup soluble in water or the alcohols and insoluble in acetone o r ether; the hydriodide m.p. 202' (corr.) has al - 33.2" in 5*5%methyl-alcoholic solution ; the dihydriodide Cl,H2,N,,2HI,H,0 is a crystalline salt optically inactive and yields the hydriodide on treat- ment with sodium carbonate ; the picrate C,,H,,N,,ZC,H,07~ crystal- lises in needles and has m. p. 178" (corr,). isoSparteine methiodide (Zoc. c i t . ) cannot be obtained by the action of methyl iodide on the base ; it is a crystalline salt m. p. 232O (corr,) [.ID - 18-39" in 1.25% aqueous solu- tion o r - 1 6 ~ 7 9 ~ in 6.2% methyl-alcoholic solution ; the hydriodide loses its water of crystallisation at 145O decomposes with loss of Me1 at 220-225" and has uD - 11*80° in aqueous solution. isosparteine is a saturated ditertiary base; it does not reduce acid permanganate solution and on treatment with hydrogen iodide does not yield methyl iodide ; the compound therefore contains methyl groups associated with nitrogen (Herzig and Meyer Abstr.1896 i 68). C,,H2,N,,MeI,HI,H,O M. A. W. Synthesis of Pyrrole and Piperazine Derivatives from the Three Nitroanilines. WALTHER BORSCHE and J. CAMPHER TITSINGH (Ber 1907 40 5008-5017).-The three nitroanilines dis-104 ABSTRACTS OF CHEMIQAL PAPERS. solved in acetic acid react with ethyl phenacylacetate to give pyrrole derivatives of +he following constitution C*2Et*F=CMe>N.C,H*.N02 CH:CPh The yield in the case of the metn- and para-compounds is about 70% but is much less from the ortho-derivative. Paat (Habilitations- schrqt Wiirzburg 1690) found that o-nitroaniiine did not react with ethyl phenacylacetate.f oi'ms citron-yellow rhombic plates m. p. 146-147' ; zinc chloride and bydrogen chloride reduce it t o the corresponding base ethyl-5-phenyl- l-m-urninopT~enyl-2-met~~~~~rrole-3-ca~~boxyla~e crystallising in colour- less needles m. p. 1 4 5 O which when diazotised and combined with phenol forms an orange hydroxycmo-compound. The corresponding p-nitrophenyl~yrrole derivative forms yellowish- red thick plates a. p. 116-117' and the p-amiizophenylpyrrole compound colourless matted needles m. p. 16 1-1 62'. The o-nitro- phenylpyrrole compound gives yellow needles m. p. 96-97' and the o-amicnophenyZ derivative m. p. log" decomposes rapidly in the atmosphere becoming red. s-Bis-m-nitrophenylaminoethane C,H,(NH*C,H,*NO,) (compare Gattermann and 'Hager Abstr.1884 1142) prepared by the inter- action of nz-nitroaniline and ethylene dibromide in presence of sodium acetate a t 150° whereby contrary to the experience with aniline no cyclic compound is formed has m. p. 206-208O. The corresponding tetra-ccnline crystallises in colourless glistening plates or flat needles m. p. 107O and forms a tetra-acetate separating in colourless needles m. p. 272". Ethy I- 5 -p7ke?zyZ- 1 - m- nitropJLenyZ-2 -met JL y Zpyrrrole - 3 -car box y lu te prepared by further heating of niiroph~nylarninoethane with ethylene dibromide forms brownish-yellow needles m. p. 220". s-Bis-p-nitro- phenylaminoethane (compare Jedlicka Abstr. 1 S93 i 699) is obtained in small quantity only by this reaction.Still worse is the yield in the case of the o-compound (compare Jedlicka loc. cit.) due to the decrease in basicity and less tendency to form quaternary ammonium compounds. n2-Nitroaniline reacts with chloroacetic acid to form a mixture of m-nitrophenylglycine N0,*C,H,=NH*CH,*C02H a yellow compound m. p. 158-159' and m-nit7.ophenyZgTycine-m-nitroaniZ~~e N0,*C,H4*NH* CH,* CO*NH*C,H,*NO a brown crystalline powder m. p. 201-20Z0. p-Nitroaniline reacts similarly to give y-nitrophenylglycine m. p. 225' and p-nitrophenyl- glycine-p-nitronnilide m. p. 260'. o-Nitroaniline on the other hand gave only traces of o-nitrophenylglycine. E. F. A. Catalytic Action of Finely-divided Metals on Nitrogen Compounds. MAURICE PADOA and C. CHIAVES (Atti R. Accad. Lincei 1907 [v) 16 ii 762-766.Compare Abstr. 1907 i 722).- When carbazole is heated at 200-220' for twelve to eighteen hours inORGANIC CHEMISTRY. 105 hydrogen under 8-10 atmospheres pressure and in presence of reduced nickel the following products are obtained (1) a base which yields a platinichloride m. p. 21 3" (decomp.) ; and (2) 2 3-diethylindole (?) m. p. 9 5 O and forms a dark-red piwate m. p. 172-173O and a picryl chloride compound C12H15N,C6H2Cl(N0,) m. p. 117'. The Melting Point of Phenylhydrazine and of Certain Osazones. Enm FISCHER (Bey. 1908 41 73-77).-Phenylhydrazine was purified by fractional distillation at 15-20 mm. solidification and removal of the liquid portion (repeated four times) crystallisation from anhydrous ether at low temperatures and finally by distillation under 0.5 mm.pressure. The melting point of the product as determined by stirring with a normal thermometer was found to be + 1 9 * 6 O . For ordinary purposes i t is sufficient to crystallise the base once or twice from its own volume of pure ether and then to distil once under a pressure of 10-20 mm. The base should be coloured pale yellow and should dissolve in ten times its vol. of a mixture of 50% acetic acid (1 pzrtj and water (9 parts). I n the preparation of osazones it is an advan- tage to use the old method namely a mixture of 2 parts of phenyl- hydrazine hydrochloride and 3 of sodium acetate as the sodium chloride thus formed facilitates the formation of the osazone. The phenyl- hydrazine hydrochloride must be colourless and if coloured should be crystallised from alcohol. The melting points of osazones depend to a certain extent on the manner in which the substances are heated.The previous melting points are confirmed namely 205' or 208' (corr.) for phenylglucosazone when the osazone is heated fairly rapidly. 'rutin's value of 2 1 7 O (Proe. 1907 23 250) could not be obtained. Certain phenylhydrazones for example pyruvic acid phenylhy drazone which decompose when heated melt differently according t o the rate at which they are heated. Action of Phenylhydrazine on Dibrornopyrotartaric Acid. FRITZ FICHTER and MARKUS GUGGENHEIM [and in part LUDWIG BRASCH] (J. p r . Chem. 1907 [ii] 76 545-551).-The action of phenylhydrazine on di bromopyrotartaric acid in hot aqueous solution leads t o the formation of the phenylhydrazone of P-aldehydopropionyl- phenylhydrszide (Perkin and Sprankling Trans.1899 75 11 ; Ellinger Abstr. 1904 i 639). As Reitter and Bender have found t h i s substance to be formed also by the action of phenylhydrazine on aconic acid (Abstr. 1905 i 669) the interaction of phenylhydrazine and dibromopyrotartaric acid takes place probably in two stages the first consisting of the formation of phenylhydrazine hydrobromide and aconic acid. When boiled with mercuric oxide in alcoholic solution the phenylhy drazone-hydrazide is oxidised forming the diphenyldi- hydrotetrazone of P-aldehydopropionylphenylhydrazide N,Ph,(N:CH* CH2*CH2*CO-N,H2Ph)2 which separates in yellowish- or reddish-brown crystals m. p. 1229 gives with concentrated sulphuric acid a brown coloration becoming blue and finally violet and when heated with phenylhydrazine on the c6H,<NH>CEt CEt which crystallises from light petroleum in scales T.H. P. J. J. S. VOL. xciv. i. e'106 ABSTRACTS OF CHEMICAL PAPERS. water-bath is reduced to the phenylhydrazone-hydrazide ; the diphenyldihydrotetrazone is formed also but in smaller yields if a current of air is passed through a hot alcoholic solution of the phenylhydrazone-hydrazide. When treated with concentrated hydro- chloric acid in the cold the diphenyldihydrotetrazone is hydrolysed forming the diphenyldihydrotetrazone of P-aldehydopropionic acid which crystallises in colourless leaflets m. p. 160'. As this substance has not an acid reaction and does not react with barium carbonate but forms a readily soluble yellowish-white satt when boiled with aaueous barvta.it is considered to have the constitution The p-brorno~~enylhy~rccxone of P-aldegydopropionyl-p-bromopheny l- hydrazide C6H4Br*NH*N C H CH,*CH,- CO *N,H C6H4Br prepared by the action of p-bromopheny lhydrazine on dibromopyrotartaric acid crystallises in white needles m. p. 206'. The p - tolylhydraxone of /3 - aldehydopropionyl - p - tolylhydrazide C,,H,,.ON crystallises in glistening leaflets m. p. 2 1 7 O and on oxidation bv means of a current of air in alcoholk solution yields the di-p-tolytdi~~di*otetraxone C,,H,,O,N cry stallising in yello fv needles m. p. 153'. G. Y. Hofmann's Reaction with Amides and Hydrazine Derivatives of Carbonic Acid. AUGUST DARAPSKY (J. pr. Chem.1907 [ii] 76 433-466. Compare Schestakoff Abstr. 1905 i 332).-A detailed account of work previously published (Abstr. 1907 i 729). The following facts are new. Benzoylsemicarbazide is best prepared by the action of potassium cyanate on benzoylhydrazide in glacial acetic acid solution ; it is not oxidised to the azocarbonamide by chromic acid and when treated with sodium hypochlorite yields nitrogen carbon dioxide and benzoic acid. p-Bromophenylazocarbonamide sinters at 160' m. p. 17'7" (m. p. 165O Hantzsch and Glogauer Abstr. 1898 i 78). The action of sodium hypochlorite on p-methyl- p-bromo- and p-nitro-phenylazocarbonamide leads to the formation of the corresponding azoimides together with small amounts of the s-azo-compounds. P-Naphthylazoimide (Culmann and Gasiorowski Abstr.1889,1156) crystallises in white prisms m. p. 31-32'. as-Dibenzyl- and as-diethyl-carbarnides do not yield the as-disubsti- tuted hydrazines when treated with sodium hypochlorite. Benzoylhydrazide is converted by the hypochlorite into benzylidene- benzoylhydrazone or dibenzoylhydrazide and azodibenzoyl depending on the conditions of the reaction. G Y. Conversion of the Azine of 1 -MethylcycZohexone-3-one in to l-MethylcycZohexyl-3-hydr~~ine NICOLAI M. KIJNER ( J . &uss. Phys. Chem. Xoc 1907,39 Chem. 1240-1245. Compare Abstr. 1900 i 277 333)-The mine is prepared by the action of hgdrazine hydrate on methylcyclohexanone b. p. 170-172°/770 mm. aD + 1.52' (100 mrn.) but when the mine is decomposed with hpdruehloric acid itORGANIC CHEMISTRY 109 yields methylcyclohexanone b.p. 169*5'/750 mm. and uD + 12.20'. The alcoholic solution of the azine is reduced readily by sodium forming methylcyclohexylamine b. p. 154-155' aD - 1.70" (100 mm.) and rnethylcyclohexahydrrnzone methylcyclohexanone CHMed:2:eCH*NH*N Cd:2:!>CHMe b. p. 214'/90 mm. a' thick pale greenish-yellow liquid uD - 2 6 ~ 5 4 ~ (100 mm.). When treated with dilute acids it decomposes forming methylcycloliexanone and a salt of methylcyclohexylhydrazine which with alkalis forms the free methylayclohexylhydrazine b. p. 2095-210*5'/760 mm. Di0 0.9274 nz 1.4786 [.ID - 9.66'. It is a colourless liquid becoming thick but not crystallising at - 20'. It combines with hydrochloric and sulphuric acids and also with benzaldehyde and menthone.The com~oulzd,NHPh*CdoNH*NH*C7H13 crystallises in long needles m. p. 135" [a]D - 17.66'. Methylcyclo- hexane has n 1.42128. K. GEORGE FALK and JOHN M. NELSON (J. Amer. Chern. Xoc. 1907 29 1739-1744).-From the consideration of a number of compounds containing a double bond and existing in two stereoisomeric modifications it is inferred that if one of the isomerides is coloured the other will either be colourless or of a different colour from the first. Z . K. Stereochemistry of Indigotin. Indigotin has the constitution C,H,<:g>C:C<gE>C,H the carbonyl groups being in the 'cis-position since the compound yields only a mono-oxime (Thiele and Pickard Abstr. 1898 i 493). There is a Dossibilitv of the existence of a trans-isomeride which would be expected to have a different colour from that of ordinary indigo.Liebermann and Dickhuth (Abstr. 1892 480) have described a red diacetylindigotin. Ilt is suggested that a stereoisomeric change takes place during the formation of this compound and that it has the 8rc-cm-configuration. Similarly the tmns-structure is proposed for other red indigotin derivatives. Liebermann and Dickhuth's work has been repeated and their results confirmed. A general scheme is given of the relations between the acetyl derivatives of indigo and the bast methods of passing from one compound t o another. Liebermann and Dickhuth regarded a-diacetylindigo-white as containing the group *CO*bH*hH*CO* and the @compound as containing the group *C(OH):U*C:C(OH)*. It is considered more likely however that the a-form is internally compensated and that the /?-form is a racemic mixture capable of resolution into its optically active components.I 1 E. G. Electrolytic Reduction of Indigotin. HENRI CHAUMAT (Compt. rend. 1907 145 1419-142l).-lndigotin can be readily reduced by electrolytic hydrogen when it is intimately associated with the cathode of a cell in which sodium carbonate solution is undergoing elwtrolysie i 2108 ABSTRACTS OF CHEMICAL PAPERS. For this purpose the indigotin in a fine state of division mixed with a slightly coarser powder of graphite is piled round a stick of carbon in a linen bag and forms the cathode of an electrolytic cell charged with sodium carbonate solution and provided with a porous diaphragm to separate the two electrodes. The hydrogen liberated a t the cathode during the electrolysis reduces the indigotin to indigo-white which is dissolved by the equivalent of sodium hydroxide simultaneously formed.The introduction of the porous diaphragm to protect the reduced indigotin from the action of electrolytic oxygen liberated at the anode greatly increases the resistance of the cell and can be dispensed with if a solution of alkali or alkaline earth sulphite hydrogen sulphite or sulphide is added to the bath these salts being more readily oxidised than the indigo-white. HEINRICH WIELAND and LEOPOLD SEMPER (Annalert 1‘307 358 36-70. Compare Wieland Abstr. 1903 i 764; 1904 i 54).-The results of the investigation described in this paper have led the authors to suggest CH-YH for the so-called glyoxime peroxide the structural formula MeOaN- which is an oxide of furazan and is termed furoxan.The nomen- clature of the derivatives of glyoxime peroxide is altered accordingly ; thus diphenylglyoxime peroxide I I ,becomes diphenylfuroxan M. A. W. Constitution of the Glgoxime Peroxides. >o C Ph-8 Ph N*O*O*N The furoxans are readily converted into the corresponding furazans when heated with phosphorus pentachloride. In this manner phenyl- furazan ig prepared from phenylfuroxan. Diphenylfuraxan C,,H1,ON obtained from diphenylf uroxan crystallises in colourless prisms m. p. 94* yields an odour of benzonitrile and phenyIcarbimide when heated and remains unchanged on treatment with Caro’s acid. the action of phosphorus pentachloride on anisylmethylfuroxan ; it crystallises in white plates m.p. 79-41’. Phenylfuroxan (Scholl Abstr. 1891 317) cryst allises in colourless plates m. p. about 95O (slight decomp.) is stable in a desiccator yields benzonitrile but contrary to Scholl’s statement not benzaldehyde on prolonged boiling with alcohol dissolves unchanged in concentrated sulphuric acid or boiling concentrated hydrochloric acid and does not give Liebermann’s reaction or a coloration with ferric chloride. When treated with dilute sodium hydroxide phenylfuroxan rapidly dissolves evolving an odour of benzonitrile arid phenylcarbylamine and forming a yellow solution which must contain oxirninobenzoylformhydroxamic acid NOH:CPh*C(NOH)*OH as it gives with ferric chloride an intense brownish-red coloration stable towards mineral acids and with copper acetate a dirty green slimy precipitate which after solution in an acid gives the coloration with ferric chloride. When treated with ice- cold alcoholic potassium hydroxide or aqueous sodium carbonate and' ORGANIC CHEMISTRY.109 ether phenylfuroxan undergoes isomerisation which is explained with CPh*$lH*OH and the aid of the hypothetical intermediate product I I N*O*N*OH fi 'OH ; this K*O*N leads to the formation of hydroxyphenylfurazar crystallises in colourless needles m. p. 110-1 11' (decomp.) dissolves in aqueous alkalis and can for the greater part be regained by immediate acidification but is gradually decomposed by the alkali forming the preceding hydroxamic acid and benzonitrile. The hydroxyfurazan gives a brown coloration with alcoholic ferric chloride forms a crystalline acetate and reacts with phosphorus pentachloride with explosive violence yielding a crystalline product. OxirninobenxoyZamidoxime NOH CPh C(NOH) *NH prepared by treating phenylf uroxan in ethereal solution with ice-cold aqueous ammonia or in small amount by prolonged boiling of oximinobenzoyl cyanide with hydroxylamine crystallises in colourless leaflets m.p. 154O is soluble in alkalis or mineral acids and gives a n olive- brown coloratiou with ferric chloride. The dibenxoyl derivat rve C22H1704N3 forms leaflets m. p. 175-1 76'. Crystalline substituted amidoximes are formed from phenylfuroxan by the action of phenylhydrazine NOH:CPh*C(NO H )*NH*NHPh m. p. 173O (decomp.) or aniline NOH:CPh*C(NOH)*NHPh m. p. about 180' (decomp.).When boiled with water phenylf uroxan yields benzonitrile oxide which polymerises forming diphenylfuroxan formhydroxamic acid and an odour of benzonitrile. The transformation of furoxans into isonitrosoisooxalines has been described by Tonnies (Abstr. 1881 167) and by Angeli (Abstr. 1892 1 198). ifioNitrosoalzisy2iHooxaxoliiae OMe C,H4* CGN C(NuH'*xH2 formed by boiling anisylmethylfuroxan with methyl-alcoholic potassium hydroxide crystallises in colourless needles m. p. 172' (decomp.) is soluble in aqueous sodium carbonate and is decomposed when treated with alkalis. The benzoyl derivative Cl7Hl4O,N2 crystallises in white needles m. p. 143'. The action of methyl sulphate on the solution obtained on heating anisylmethyl- furoxan with methyl-alcoholic potassium hydroxide leads to the formation of a methyl derivative of isonitrosoanisylisooxazoline C1?H1203N2 crystallising in needles m.p. 107-1 08'. The dieubstituted furoxans are less reactive than the mono- substituted and are not attacked by ammonia aniline or phenyl- hydrazine even at high temperatures under pressure. Diphenyl- furoxan remains almost unchanged on prolonged boiling with alcoholic potassium hydroxide With magnesium organic compounds the furoxans form labile additive products from which they separate unchanged on treatment with water. The additive compound of magnesium ethyl iodide and anisylmethylfuroxan is an insoluble yellow substance. The $-nitrosite (N20?)[CH(CBH4*OMe)*CH2*NO,I formed from p-methoxgstyrene is obtained as a white crystalline powder decomp.110 ABSTRACTS OF CHEMICAL PAPERS.1 0 7 O gives the reactions for +-nitrosites and on distillation in a current of steam yields nitroanisylethylene and the nitro-oxime of p-met hoxystyrene OMe*C,H,*C(NOH)*CH,*N02. This crystsllises in colourless needles m. p. 112O decomp. 135O dissolves in aqueous alkalis and is precipitated by acids. This +-nitrosite and nitro-oxime differ from the homologous compounds derived from anethole in that they do not yield the Eorresponding furoxan. G. Y. Reduction of Diethylthiobarbituric Acid ALFRED EINHORN and HEINRICH VON DIESBACH (Ber. 1907 40 4902-4903).-The reduction of diethylthiobarbituric acid by sodium amalgam leads to the formation mainly of diethylmalonamide ; the by-products are 4 6-dihydroxy-5 5-diethyl-2 5-dihydropyrimidine (compare Tafel and Thompson this vol.i 58) which is isolated in the form of the double salt with mercuric chloride C,,HI,02N,,HgC12 m. p. 2 15-2 18O and bisdiethulmalonuZtetl.cl-aminoethane m. p. 340° which separates from dilute alcohol in white prisms containing 2H,O. 0. s. Thiazinee. 11. Derivatives of Tetraethylthionine. ROBERT GNEHM and ALFRED SCHINDLER (J. p r . Chem. 1907 [ii] 76,471-488. Compare Gnehm and Walder this vol. i 63).-Tetraethylthionine (ethylene-blue) is more reactive thaa methylene-blue as whilst the actmion of the theoretical amount of nitric acid in glacial acetic acid solution leads t o the formation of nitroethglene-blue NE t2* C,H,<:> C,H2 (NO,) NEt2X the nitration readily proceeds further to the formation of the nitrate of a dinitronitroso-base OH*N:C,H,< N s>C,H(NO,),*NEt,,HNO ; the position of the nitro-groups i n this base has not been determined.The paper contains an account of these substances and their reduction products. Tetraethylthionine is prepared by the action of sodium thio- sulphate and hydrochloric acid on nitrosodiethylaniline hydrochloride and treatment of the product with diethylaniline hydrochloride zinc chloride and sodium dichromate in boiling aqueous solution. The zincochloride is salted out as a blackish-blue powder and when gently heated with nitric acid in acetic acid solution yields dinitroisonitroso- diethylaminothiazine nitvate C,,H,,0,N5S HN0,,&H20 which separates from alcohol in green crystals ; the hydrobromide prepared by the action of hydrobromic acid and methyl alcohol on the nitrate is obtained in green crystals or as a brown powder forms bluish-red dichroic solutions which wibh the exception of the aqueous solution are fluorescent and with concentrated sulphuric acid gives a malachite-green coloration becoming bliie and finally rose-red on dilution. The free base formed by the action of sodium hydroxide on the hydrobromide is obtained as a brown flocculent precipitate ,H,505N!jS,HBr,$H20,ORGANIC CHEMISTRY.111 detonates when heated on platinum is insoluble in alkalis and again forms the dye on solution in hydrochloric acid. It gives with phenyl- hydrazine in acetic acid solution a brownish-yellow precipitate with ferric chloride a blood-red coloration with potassium ferricyanide a flesh-red solut’ion with phenol and concentrated sulphuric acid a green solution becoming bluish-red when poured into dilute sodium hydr- oxide and with aniline in methyl-alcoholic solution a violet coloration.The hydrochloride is crystalline. I n Formanek’s spectroscope the aqueous solution of the dye shows a line a t X=573 the alcoholic solution shows a line at X=573*4 and an absorption band in the blue; on addition of ammonia the lines disappear but the band persists Reduction of the dye with stannous chloride and hydrochloric acid leads to the formation of the hydrochloride of the leuco-base C,,H2,N,S,3HCI which separates from aqueous hydrogen chloride in crystals containing 5H20 or from methyl-alcoholic hydrogen chloride in white crystals Cl,H2,N,S,3HC1,3CH,0.The light brown base m. p. above 300° is readily oxidised by air. The dye prepared by oxidation of the leuco-base with ferric chloride is isolated as the xincochloride C16Hl,N,S,2HC1,ZnCI fcH40. It forms green to brown solutions in water alcohols or acids; the spectrum of the alcoholic solution has strong absorption in the red or after addition of ammonia a broad band in the green. Ethylene-green (Izitroethylerte-blue nitrotetraethylthionine) is isolated as the xincobrornide C20H240,N,SBr,~ZnBr,,2H20 ; it dissolves in water alcohols or acetic acid forming a bluish-green solution gives with concentrated sulphuric acid a dirty blue coloration becoming reddish- brown violet and finally bluish-green on addition of water and with fuming nitric acid a reddish-violet becoming deep blue on dilution. Addition of sodium hydroxide to the aqueous solution leads to the formation of a reddish-violet coloration and a precipitate which yields the original dye on treatment with hydrochloric acid ; potassium ferrocyanide in aqueous solution gives a light green coloration.The spectrum of the aqueous solution has a broad line at X = 639.7 and that of the alcoholic solution a broad line at A = 672. The hydr- iodide crystallises in green needles. ArninoethyZene-blue prepared by reduction of ethylene-green with stannous chloride and oxidation of the product with ferric chloride is isolated as the xincobromide C20H2eN4SBr,&ZnBr2,1 iH20. It forms deep blue solutions gives with concentrated sulphuric acid a reddish- brown with concentrated hydrochloric acid a yellow or with fuming nitric acid a reddish-violet coloration becoming violet to bluish-violet on dilution and yields a brown precipitate with sodium hydroxide.The spectrum of the alcoholic solution has a line about X = 623.8 and strong absorption in the red. Bvomoethylene-blue is formed by the action of bromine on ethylene- blue nitrate in glacial acetic acid solution ; the xincobromide C20H,6N,SBr,HBr,$ZnBr2,H20 was analysed. The dye forms deep blue solutions and gives with concentrated sulphuric acid an apple- green with concentrated hydrochloric acid a bluish-green and with fuming nitric acid a dark brown coloration becoming blue to violet-11.2 ABSTRACTS OF CHEMICAL PAPERS. blue on dilution On addition of so ium bydroxide the aqueous solution becomes violet and when d t e d turbid ; .on addition of ammonia the solution becomes reddigh-violet and fluorescent but blue when heated.With sodium hydroxide the alcoholic solution gives a cherry-red precipitate. The spectriim of the aqueous solution has a broad line at X=670 and a minor line at X=624; after addition of potassium hydroxide the broad line has X=676 and the minor line A - 614.8. The action of alcoholic ammonia on ethylene-blue nitrate at 145-150' leads t o the formation of as-diethylthionine which on oxidation and treatment with zinc bromide yields the xincobwmide NH,*C6H,<~>C6H,:NEt2Br,ZnBr*OH,H20 ; this loses H,O at 80-90'/35 mm. The dye is readily soluble forming deep blue solutions gives a reddish-brown product with fuming nitric acid and a reddish-violet precipitate with sodium hydroxide becoming blue on addition of hydrochloric acid and is readily reduced to the leuco-base by stannous chloride.Ammonia deepens the shade of the dye but on heating precipitates the base ; potassium ferrocyanide in acetone solution gives a light green precipitate. The aqueous solution gives a spectrum with a line at h=676 the alcoholic solution a line at X = 662 and strong absorption on the right. G. Y. Thiazines. 111. Derivatives of Alkylated Benzylanilines. ROBERT GNEHM and ALBERT SCHijNHOLZEH. (.I. pr. Chem. 1907 [ii] '76 489-508. Compare preceding abstract ; Scholtz Rohde and Bosch Abstr. 1904 i 992).-Attempts to prepare simple thionines from benzylmethyl- and benzylethyl-aniline were unsuccessful but on the other hand thiazines have been prepared from the sulphonic acids of these bases.The thiazines so obtained and a number of derivatives of benzylmethpl- and benzylethyl-aniline are described. The suZphate of as-benzylethyl-p-phen ylenediamine CH,Ph*NEt *C,H,*N H2,H2S04 has m. p. 146-148O (decomp.). BenzyZrnethyZ-p-nitrosoa?tiline NO*C,H,-NMe*CH,Ph separates from benzene in steel-blue crystals m. p. 52-53'; the hydrochloride forms n yellow crystalline precipitate m. p. 138'. The diarnine prepared by reduction of benzylmethyl-p-nitrosoaniline is obtained as a black oil and forms a sulphate crystallising in long white needles. Benz?lZethyZanilines~p~onic acid NEtPh*CH2*C,H,-S0,H,H,0 pre- pared by heating benzylethylaniline with sulphuric acid at 1 10-l2Oo crystallises in prisms sinters at 160-170' m.p. about 1909 The crystalline barium (C1,Hl6O,NS),Ba,4H20 and potassium salts were analysed. The oxidation of the sulphonic acid with chromic @cid leads to the formation of only small amounts of azobenzene and traces of benzoic acid. When heated with potassium hydroxide at 240-300° the potassium sulphonate yields p-~~ydroxybenxybthyk~nzZi.rze NEtPh*CH,*C,H,*OH m. p. 62-63' which does not form a rhodamine with phenol. The nitroso-derivative prepared from the sulphonic acid or its potassium salt is very soluble forms a green or in presence of C,,H160,NSK,ORGANIC CBEMISTR~ 113 mineral acids an orange-red solution and yields a green amorphous pracipitate with lead acetate. On reduction with zinc dust and sulphuric acid ?t forms an amino-sulphonic acid which is formed also by reduction of the dark red amorphous axo-sulphonic acid prepared by coupling diazobenzene chloride and benzylethylanilinesulphonic acid in alkaline solution ; the amino-sulphonic acid cannot be isolated either in the free state or as a salt.Dibenz yldiethylthioninedis~lphonic acid (?3H4'CH2>NEt C,H3<~>C,€€,oNE t * CH,-C,H,* S03H so,-o prepared &from benzylethylnitrosoanilinesulphonic acid by reduction with zinc dust and hydrochloric acid and successive treatment of the product with sodium thiosulphate and dichromate is identical with commercial thiocarmine. It is obtained as a bluish-black amorphous powder is readily soluble in water or alcohol is precipitated by sulphuric acid and gives with concentrated hydrochloric acid a green coloration becoming blue on dilution. Theleuco-compound C,0H3,0,N,S3 formed by reduction of the dye with zinc dust separates as a yellow flocculent precipitate on addition of sulphuric acid.The derivatives of benzylmethylaniline are prepared in the same manner as those of benzylethylaniline. Benx~lmethylanilin~~ulp~~onic acid C,,H,,03NS is obtained as a crystalline powder readily soluble in water ; the barium and potass&n C,,HI,03NSK salts are described. p-Hydroxybenaytmeth~baniline C,,H,,ON is obtained as a crystalline mass m. p. 40-41'. The nitroso-derivative of benzylmethylanilinesulphonic acid prepared by the action of amyl nitrite on the sulphonic acid in glacial acetic acid solution is obtained as a reddish-brown crystalline powder ; the product formed on reduction of this with zinc dust and sulphuric acid is not the p-amino-sulphonic acid Dibenzyldimethylthion~n~d~s~lp~onic acid and its salts are readily soluble and separate only as resins.The Zeuco-compound forms a yellow flocculent precipitate which decomposes becoming black when dried in a vacuum. rn-Nitrobe~xylnaethylsniline C R 402N2 prepared by nitration of benzylmethylaniline by Groll's method (Abstr. 1886 347) crystallises from alcohol in yellow leaflets m. p. 51-52'; the picrote m. p. 112-113O. Oxidation of the nitro-base leads to the formation of m-nitrobenzoic acid whilst reduction with seannous chloride and hydrochloric acid leads to the formation of m-aminobenxylmethyl- annitine which is isolated in the form of its acetyl derivative NMePh*CH2*C,H,*NHAc crystallising in coloiirless leaflets m.p. 88". Reduction of m-nitrobenzylethylaniline and treatment of the product with acetic anhydride leads t o the formation of the acetyl derivative NEtPh*CH2*C,H,*NHAc crystallising in leaflets m. p. 96'. Reduction of Azo-compounds by Means of Sodium Hypo- sulphite. HARTWIU FRANZEN and P. STIELDORF (J. pr. Chenz. 1907 [ii] 76 467-471. (C,,H,,O,NS),Ba,2T-IzO G. Y. Compare Grandmougin Abatr. 1907 i 850).-.114 ABSTRACTS OF CHEMICAL PAPERS. The reduction of an azo-compound such as helianthin to two primary amine molecules by means of sodium hyposulphite might take place according to the equation (I) NMe,*C,H,*N,*C,H,*SO,Na + 2Na2S,0 + 4H20 = NMe2-C,H4*NH2 + NH,*C,H,*SO,Ka + 4NaHS03 or (11) NMe,.C,H,*N,.C,H,*SO,Na + Na,S,O + 3H20 = NMe2*C,H,*NH + NH,*C,H,*SO,Na + NaHSOs + NaHSO,.The authors have employed two methods to determine by which reaction the reduction takes place. As 1 mol. of sodium hyposulphite requires 6 atoms but 1 mol. of sodium sulphite only 2 atoms of iodine when titrated the product of reaction (I) must reduce two-thirds but that of (11) only one-third of the iodine required for the titration of the same amount of the original sodium hyposulphite solution. The results obtained with helianthin and p-sulphobenzeneazo-a-naphthol show that the reaction takes place according to equation (I) The same result is obtained by determining the amount of sulphuric acid in the hyposulphite solution before and after the reduction ; only a very slight increase is found whereas according to equation (11) each mol.of hyposulphite must yield 1 mol. of sulphuric acid. G . Y. Action of Diazobenzene on Blutaconic Acid and Ethyl Glutaconate. FERDINAND HENRICH and W. THOMAS (Ber. 1907 40 4924-4930).-When glutaconic acid is treated with diazobenzene chloride (2 mols.) formccxylacrglic acid NHPh*N:C(N:NPh)*CH:CH*G02H is obtained accompanied by the evolution of carbon dioxide crystal- lising from alcohol in reddish-brown felted needles m. p. 1 9 9 O (decornp.). The sodium and potassium salts are sparingly soluble ; the silver salt is dark coloured. The ethyl ester C,,H,O,N crystallises in long slender dark red needles m. p. 1 2 3 O and is not identical with the formazyl compound previously obtained from ethyl glutaconate and diazobenzene chloride (Abstr.1902 i 422). This is now shown t o be ethyl r-p~enylaxogluta,co7zonate-phe~ylhydraxonQ CO,Et*C(N*NHPh)-CH:C(N:NPh)*CO,Et as it readily loses alcohol on boiling its alcoholic solution forming ethyl l-piLenyld-~enxeneaxo-6-pyridnxone-3-carboxylate Nph<N:C(c02Et )>C CO*C(N,Ph) Hs which crystallises in small brownish-yellow crystals m. p. 163-1 640. The conclusion that the azohydrazone has the constitution ascribed to it is supported by the fact that etbyl a-methylglutaconate does not give a corresponding derivative with diazobenzene chloride. With ethyl glutaconate the diazo-salts From 0- and p-toluidine and chloro- and bromo-anilines give similar derivatives to diazobenzene ; the tolyl compounds are deep dark red in colour and the others are yellow- ish-red.W. R. Action of Nitrous Acid on Proteins. ZACCARIA TREYES and GIOVANNI SALOMONE (Biochem. Zeitsch. 1907 '7 I1 -23).-Nitrous acid acting on proteins a t 0' produces ill-defined substances which the authors regard as diazo-compounds. The group of the proteinORGANIC CHEMISTRY. 115 molecule concerned in diazotisation is not the same as that which is concerned in the fixation of labile sulphur or in the combination with formaldehyde. The diazo-compounds show all the characteristic protein reactions although somewhat slowly and less clearly. After precipitation of the diazo-compounds no proteins remain in solution. On boiling with water and alkali the diazo-compounds form proteinq which give a violet biuret reaction.The biuret reaction can scarcely depend on the presence of the complex CO*NH since this group would be destroyed by the action of nitrous acid. G. 13. Studies on Enzymes. I. Quantitative Measurement of Pro- tein Hydrolysis by “Formaldehyde Titration.” S. P. L. SORENSEN (Biochem. Zeitsch. 1907 7 45-101).-The existing methods for estimating the extent of protein hydrolysis are arbitrary and unsatis- factory. A rational method must at4tempt the measurement of the quantity of carboxyl- and amino-groups formed during the hydrolysis. This is best done by titrating the carboxyl group with alkali after the aminic function has been abolished by formaldehyde according to Schiff’s method (Abstr. 1903 i 232). The reversibility of t h i s reaction and other circumstances render the employment of certain precautions necessary to ensure accuracy.The indicator must show an end point with as high a concentration of hydroxyl ions as possible; hence phenolphthalein or thymolphthalein (preferable in many cases) must be employed. The end point is not indicated by the appearance of a faint pink coloration but the titration must be continued until the solution has the same strong red colour as a test solution which is prepared for comparison by adding a few drops of 1V/6 baryta to a dilute formaldehyde solution. The latter has been neutralised previously so as t o give only a faint pink colour with phenolphthalein and by the addition of the baryta acquires the pronounced red colour which is desired. Under these conditions the amount of amino-acid found (in R pure N/10 solution) amounts on the average to 98% of the actual amount present.This applies to a large number of mono- di- and oxy-amino- acids ; only in the case of phenylalanine and tyrosine is a considerably smaller amount found than that actually present. The ratio between the extents of protein hydrolysis as measured by this method and by precipitation with tannic acid is generally greater than 1 ; at least in the early stages formaldehyde titration indicates a greater degree of hydrolysis than tannic acid precipitation. After the addition of formaldehyde uric acid can be titrated sharply as a monobasic acid. G. B. Hydrolysis of the Globulin from the Almond (Amandin). Hydrolysis of the Proteins of Maize. Hydrolysis of Gliadin from Rye.THOMAS B. OSBORNE and SAMUEL E. CLAPP (Amer. J. Phy~+ioZ. 1908 20 470-476 477-493 493-499)- The following table gives the main results in percentages :116 ABSTRACTS OF CHEMICAL PAPERS Amandin. Gliadin Gliadin Hordein Zein Alkali-soluble (rye). (wheat). (barley). (maize). protein of maize. Glycine ............ 0.51 0.13 0.02 absent absent 0'25 Alanine ... ........ 1.40 1-33 2-00 0'43 2.23 not isolated Veline ............... 0*16 not isolated 0.21 0'13 0.29 not isolated Leucine ............ 4.45 6.30 5-61 5.67 18-60 6 *22 Proline ............... 2'44 9.82 7.06 13.73 6.53 4-99 Phenylalanine ... 2.53 2.70 2.35 5.03 4.87 1'74 Aspartic acid ...... 5.42 0.25 0 5 8 not isolated 1'41 0.65 Glutamic acid ...... 23'14 33*81 37.33 36.33 18-28 12'72 Serine ...............( 2 ) 0.06 0.13 not isolated 0.57 not isolated Tyrosine ............ 1.12 1.19 1.20 1.67 3.55 3.78 Arginine ............ 11.85 2.22 3.16 2.16 1'16 7 -06 Lysine ............... 0.70 absent absent absent absent 2'93 . Histidine ............ 1.58 0'39 0.61 1.28 0.43 3.00 Ammonia ......... 3.70 5'11 5.11 4.87 3.61 2.12 Tryptophan ...... present present present present absent present - Cystine ............ - not deter- 0.45 not deter- not deter- mined mined mined Total ...... 59.00 64.31 65-81 71'32 61.53 45'44 The amino-acids absent in zein are present in the alkali-soluble protein of maize so thab the mixture yields all the amino-acids usually obtained from proteins. The gliadin of wheat and rye are probably identical but the differ- ences between it and hordein and zein are noteworthy. These three proteins are all soluble in alcohol and form a group characterised by their high content of glutamic acid protein and ammonia their low content of arginine and histidine and absence of lysine. Zein also lacks tryptophan and glycine. Fatty Acids of Protein Putrefaction and Optically Active Valerie and Hexoic Acids. CARL NEUBERU and E. ROSENBERU (Bio- chem. Zeitsch. 1907,7,178-190. Compare Abstr. 1906 i 923).-One kilo. of casein yielded on putrefaction 117 grams of fatty acids. More than one-third of these consisted of butyric acid which is considered to be derived from glutamic acid since this acid occurs abundantly among the amino-acids formed in the hydrolysis of casein. Somewhat smaller quantities of formic valeric and hexoic acids were obtained and still smaller yields of acetic propionic and a decoic acid. The valeric acid fraction had a rotation indicating the presence of 18% of d-u-methylbutyric acid and the hexoic acid fraction probably contained 46% of P-methylvaleric acid (derived from isoleucine). Similar results were obtained with putrefied gelatin. Conversion of Optically Inactive Triolein into an Optically Active Glyceride and an Optically Active Acid. CARL NEUBERG and E. ROSEHBERU (Biochem. Zsitsch. 1907 '7 191-198).- The authors have repeated and confirmed Neuberg's work on the diglyceride of dibromostearic acid (Abstr. 19U6 i 923). JULIUS LEWHOWITSCH (Chem. Zeit. 1908 32 54-55) ascribes the optical activity of Neuberg and Rosenberg's products to the intro- duction of optically active ricinus oil with the lipase employed in the hydrolysis of the glyceride. W. D. H. G. B. G. Y.

ISSN:0368-1769    

DOI:10.1039/CA9089400073

出版商:RSC    

年代:1908

数据来源: RSC