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Proceedings of the Chemical Society. March 1961 |
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Proceedings of the Chemical Society ,
Volume 1,
Issue March,
1961,
Page 93-128
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PROCEEDINGS OF THE CHEMICAL SOCIETY MARCH 1961 ANCIENT GLASS AND GLASS-MAKING By Professor W. E. S.TURNER, O.B.E. F.R.S. F.S.A. THEterm ancient as applied to man-made glass can carry us back with reasonable justification to about 2500 B.C. and with certainty to about 2000 B.C. The earliest objects are beads and amulets such as have been found in tombs in Egypt of the VIth (ca. 2500 B.c.) and succeeding dynasties. In Mesopotamia H. R. Hall in 1919 discovered a lump of dark blue glass at Eridu in Chaldea which he ascribed to 2000 B.C. It has recently been analysed and reported on by Sir Harry Garner and is indeed at the moment the oldest specimen of glass of which we know the composition (see Table 1. col. 1). Claims have been made on behalf of both Mesopotamia and Egypt as the country in which glass originated and it is of interest to compare their respective contributions.In quantity and variety the finds in Mesopotamia and Western Asia fall far below those in Egypt. In Western Asia specimens in addition to that from Eridu have been found at Azarbaijan; at Nippur from Babylonian times (ca. 1400 B.c.); at Lachish (1400 B.c.); at Gordion in Phrygia (VII century B.c.); Nippur (ca. 250 B.c.); and along the Syrian coast. Beads are among the earliest objects but as early as 1400 B.C. small statues were carved from solid glass as also were the Sargon vases (722-705 B.c.) of the Assyrian empire found at Nineveh and now in the British Museum. Mallowan’s excavations at Nimrud in 1951 and 1952 brought to light fragments from the VIIIth to VIth century B.C.of nearly colourless trans- parent shallow dishes and three large cakes of opal glass two of them turquoise blue the other sealing-wax red (Table 1 col. 6) of the types em- ployed widely for inlaid work. Apart from the limited number of specimens Asia has provided us with the two earliest literary records (on clay tablets) of ancient glassmaking (1) that tran- scribed by C. J. Gadd and R. C. Thompson and published in 1936 in Iraq pp. 87-88; it is assigned to a date not later than 1700 B.c.; this early Babylonian text contained recipes for glazes of which a prime constituent was a glass of a kind assumed to be known; (2) clay tablets from the Royal library of Assur-bani-pal (668-63 1 B.c.) recording recipes for glasses and some disconnected sections of a description of the construction and operation of the glass- melting furnaces.R. Campbell Thompson pub- lished his translation of them in 1925 in the “Chemistry of the Ancient Assyrians” and after its later revision in “A Dictionary of Ancient Assyrian Chemistry and Geology,” 1936. The Egyptian contribution contains no certain literary reference to glass-making which seems surprising in view of the extensive records by wall paintings in the tombs of the nobles of many 93 phases of daily life including the crafts such as alabaster vase-making gold refining in crucibles gold-beating pottery etc. ; but the practical evidence is abundant.The industry appears to have smouldered for a thousand years from at least 2500 B.C. when its products were beads and amulets melted in small stone moulds and then burst into activity during the XVIIIth dynasty (1580-1320 B.c.) with a specially brilliant period between 1450 and 1350 B.C. The two chief centres were Thebes and Akhetaton (or present day Tell-el-Amarna). No other ancient glass-making site has yielded so much evidence of processes employed as has that at Tell-el-Amarna where a new city was established by Akhetaton in ca. 1370 B.C. Excavations by Flinders Petrie and others have yielded crucibles both new and with glass adhering; glass in various stages of fusion; rods of glass of many colours; beads amulets and sand-core vases and hollow-ware made by a process arising out of Egyptian faience manufac- ture which goes back to at least the fourth mil- lennium B.C.This faience was made from a core of powdered rock crystal or sand with suitable agglutinant and glazed by dipping it into an alkaline slip or slurry containing the desired in- organic pigment and then firing it. When eventually applied to make hollow glass vessels the core was built up round the end of a metal rod by which it could be rotated in or over a furnace. The covering of glass could be built up by successive applications of pigmented slurry ; or by feeding powdered glass on to the surface; or provided glass sufficiently fluid were available by dipping the rod into molten glass.In each case a smoothing tool to distribute the glass might be needed. The object was usually ornamented by festoons of coloured parallel glass threads drawn from the heated and softened end of thin coloured rods as the object was rotated over the furnace. When the vase had been annealed cooled and polished the rod was withdrawn and the core of sand more or less completely scraped out. Hundreds of these sand-core vessels and numerous fragments from this early period still exist in the museums of the world. In the XVIIIth dynasty also statues were made by grinding carving and polishing from a lump, often with a turquoise-opal glass as basis. One such statue is 15 inches high. The discovery and excavation by Lord Carnarvon and Howard Carter in 1923 of Tutankhamun’s tomb brought PROCEEDINGS to light objects of great splendour.Those in glass which must have been in course of prepara- tion in the period 1370-1350 B.c. included a throne with a large panel in moulded glass depict- ing the monarch and his queen in conversation the body of each being of red-brown opaque glass and the head-dress of dark blue; an outer coffin for the king’s burial covered from upper chest downwards with loops of small glass discs gold wire-connected in dark blue (imitating lapis lazuli); turquoise and red brown glasses following each other in orderly sequence whilst long rectangular bars of dark blue glass sup- ported parts of the head of the effigy and the head dress; and a head rest of turquoise opal glass made in two parts each ground and polished from a mass and fitted together so as to constitute the cusp-shaped head-rest proper 19 inches between the tips a combined central pillar and a massive base 25 inches in length.Each part would involve fusion of a mass of glass in a crucible pouring the molten glass into a mould and annealing it at a very slow rate. The glass objects discovered in Tutankhamun’s tomb testify to a very high standard of technical knowledge. But for the organised plundering of royal tombs a practice which the court officials seemed unable to circumvent it is probable that other masterpieces in glass would have remained to illustrate and perhaps to disclose how the technical problems were overcome.Glass-making continued at a high level during the XIXth and XXth dynasties although the remains are scanty. From about lo00 B.C. onwards there is no evidence of glass manufacture in Egypt until the sixth century B.C. when the Persians made them- selves masters of the country. Sand-core vessels were again made in large numbers over several centuries and were probably supplied to Phoenicean traders. When the Greeks conquered Egypt and founded Alexandria that city before and for centuries after the beginning of the Christian era became renowned as a glass-making centre; and later under the Romans and from 642 A.D. under the Arabs Egypt continued until about 1400 A.D. to contribute new tech- niques to glass-making. From Egypt and from Mesopotamia glass- making spread eastwards northwards and west- wards being handed on by connections of which the major ones are indicated in the annexed chart.MARCH1961 95 ~~ ~~ ~~ ~ _______________~ TABLE1. Compositions of some ancient glasses over the period 2000 B.C. to the XIIIth century A.D. 1 2 3 4 5 6 Eridu Thebes Nippur El Amarna Nimrud Nimrud ca. 2000 B.C. ca. 1500 B.C. ca. 1400 B.C. ca. 1370 B.C. ca. XIII/VIth ca. XIII/VIth (Artificial lapis cent. B.C. cent. B.C. (dark blue) (dark blue) lazuli (dark blue) (transparent) (sealing-w ax dark blue) red) Si02 (65.0) 67-82 65.0 62.6 71.5 39.5 A1203 2.5 4-38 2.13 1.52 0.48 4.35 Fe203 2.4 1-08 0-97 0.64 0.9 1 -Ti02 0.09 -tr 0.19 B203 0.15 -__ -_ 0-11 -p205 Sb205 --0.30 4.4 CaO 3.5 4.83 5.65 12.15 4.82 4.4 -MgO 3.4 2.30 2.52 4-88 3.07 PbO -0.19 -22.8 Na,O 17.0 18-71 17-37 17.20 12.70 9.7 1 K2O 4-5 2-30 1-68 tr 0-88 1.91 CUO 0.49 1*96 1-94 0-65 -(Cu20 13.58) Mn203 0-04 1.12 0.65 0.20 0.02 __ -_ I coo 0-15 -0.93 NiO 0.01 I so3 -0.97 1-70 0-43 0.99 7 8 9 10 11 12 China Rome Rome Rome Samarra Dale Abbey 220 ~.~.-206 ca.30 B.C. 1st cent. A.D. IInd cent. A.D. (Mesopotamia) (Derbyshire) A.D. IXth cent. A.D. XIIIth cent. A.D. (opalescent) (dark blue) (dense opal) (transparent) (transparent) (transparent green) SiOz 34.4 65.7 60-0 68.82 68.5 46.9 0.76 2.4 2.8 0.74 0.70 3-02 A1203 0.16 2-3 0.45 tr 0.9 1 1 -46 Fe203 p205 -0.18 0.13 -__ 4.11 I -8.8 -I Sb205 CaO 0-12 9.0 8.3 5.60 5.7 1 19-01 MgO 0.34 0.6 1.1 1 -04 5.28 5.00 -PbO 43.2 -1.86 0.95 BaO 12.6 --Na20 4.32 16.2 15.8 18.24 14.95 0.12 K2O 1 -02 1-0 0.7 1.17 2.83 16-96 CUO -0.5 Mn20 -1.6 -_ 1.37 coo -0.12 -I -NiO -so3 0-48 -1.2 2-34 0.54 ? References (1) Sir Henry Garner Zruq 1956 18 Part 2 p.147. (2 3 10 and 11) Neumann and Kotyga Z. angew. Chew. 1925 38 776. (4) Turner J. SOC.Glass Technol. Trans. 1954 38 436. (5 6) Turner Iraq 1955 17 57. (7) Seligman and Beck Bull. No. 10 Museum of Far Eastern Antiquities Stockholm 1938. (8 9) Turner J. SOC.Ghs Technol. Trans. 1959,43,262. (12) Heaton J. SOC.Arts 1907 55,468. In every new region where glass-making was introduced some new features were developed to which in this brief article I cannot refer.It may be stated however that a major change in method and products took place in the industry on the threshold of the Christian era in that someone discovered how to gather molten glass at the end of a metal pipe to blow it into a bubble and by further dexterous manipulation and tools to shape it either entirely freehand or by blowing it up to the required shape and size in a mould. Hitherto the production of glass objects had been a slow and often multi-staged process so that only the wealthy could possess them. Glass indeed was a semi-precious material made to substitute lapis lazuli tur- quoise jasper carnelian etc. The new process of blowing it from molten glass was speedy and could be adopted to produce containers domestic and medical ware and handsome urns for cremated remains.The museum at Pompeii contains many such examples excavated from that city which was overwhelmed by volcanic action in 79 A.D. This date in fact provides a landmark by which progress in glass-making can be assessed. The essential principle underlying the making of glass remained unchanged from the earliest times until the XVIIth and XVIIIth centuries A.D. It consisted in fusing together powdered rock crystal or sand with alkali salts widely obtained by burning plants or wood. The glass so obtained was subsequently remelted with added minerals or calcined metals to produce colours in many different shades; minerals con- taining copper cobalt iron and manganese were commonly used.It is very interesting to note from Table 1 the general similarity of composi- tion of the dark blue glasses from 2000 B.C. down to the period of the Portland vase in Roman times. A whole range of blue glasses was ob-tained from copper and cobalt alone or in con- junction or with iron and manganese; greens were yielded by iron and by copper; purples by manganese; opal (white) by antimony and opaque yellow by antimony in conjunction with lead; sealing-wax red (opaque) by cuprous oxide. Tin oxide for long regarded as the prime opalising agent in ancient times has been shown by recent thorough-going investigations by Turner and Rooksby not to have come into use PROCEEDINGS until after the lapse of several centuries of the Christian era.The ancient glasses fall into two general types the alkali-lime-magnesia-silica and the alkali- lead oxide-silica type the former being pre- dominant. Egyptian glasses are known which contain small or modest amounts of lead oxide but in the main they are based on alkali-lime- magnesia-silica with alumina and the colouring oxides referred to above. The alkali usually was a mixture of soda and potash with one or the other greatly predominant according to the source of the ash that from the maritime plants of the Egyptian Syrian and Spanish coasts yielding mainly soda. In the factories in Central and Western Europe from the Xth to the XVIth centuries A.D. the ash was derived mainly from forest growth (and particularly beechwood and oak) and contained a high proportion of potash to soda as well as a very high content of lime magnesia and phosphate.The marked effect of using such ash on the composition of window glass of the period is shown by the analysis quoted in Table 1 (col. 12). TABLE 2. Compositionof some sands-fiontancient sites. Egyptian Syrian coast Karnak Pyramids El Mouth of Giza Amarna Belus Haifa SO 83-61 82-3 60.46 80-8 2-25 3.9 )1.32 ,)1-45 1 -73 0.12 1 -0.44 --0.08 -12-01 8.4 18.86 8.8 1-23 trace 0-83 -I (NaCI 0.19) 0-30 --0-74 --0-02 --0.22 0.05 -The complexity of the ancient glasses as revealed by complete and precise analysis so far from being a demonstration of great knowledge by the glass-makers is evidence of a certain degree of helplessness in controlling the raw materials with which they worked.The many constituents found could only have been derived from the sand or the alkaline ash or from cor- rosion of the crucible. Tables 2 and 3 show how the raw materials could affect the composition. The sands probably used in ancient times were MARCH1961 -I x a -4 z" cd .M 0 .M h +% 4c 0 c pc 6 9s PROCEEDINGS TABLE 3. Content and composition (%) of nshfrom various air-dried vegetable materials. (Calculated from data in Thorpe’s “Dictionary of Applied Chemistry,” 1937 Vol. I pp. 508-509.) Substance Totalash SiO CaO hlgO Na,O K,O P,O SO S c1 Wheat straw 4.26 66.2 6.1 2.5 2.8 11.5 5.4 2.8 3.8 -Fern 5-89 6.1 14.1 7.6 4.6 42.8 9-7 5-1 -10.2 Wheat (grain) 1-77 1.7 3.3 12.4 3.3 31.1 46.3 2.2 -8.4 Beech (leaves) 3.05 33.8 44.9 5.9 0.7 5.2 4.7 3.6 -0.3 I Beechwoad trunk 0.55 5.4 56.4 10.9 3.6 16-4 5.4 1.8 -Beech brushwood 1.23 9-8 48.0 10.6 Oak 0.51 2.0 72.5 3.9 all likely to have contained substantial amounts of lime magnesia alumina and iron oxide as impurities; and even if a pure sand or rock crystal were employed the alkaline ash would supply them as well as chlorides sulphates and phosphates.We have no knowledge of the eoni- position of samples of ancient ash but the data in Table 3 indicate its probable complexity. The ancient glass-makers did not know they were using lime in the composition of their glasses.They did know that some types contained lead because from the earliest times the starting point for such glasses was to calcine metallic lead. 2.4 13.8 12.2 0.8 - 3.9 9.5 5.8 2.0 - I They learned the importance of the part played by lime only when as the result of progressive purification of the ash the glass became unstable and easily affected by atmospheric moisture. Recognition of this defect in the XVIth century led glass-makers cautiously and with conflicting results to investigate the effects of lime on glass stability; but it was not until the end of the XVJIIth century that proofs of its value were accepted. Another half-century of steadily de- veloping chemical knowledge elapsed before the need for lime and other stabilisers was widely understood and acted on.CENTENARY LECTURE* Some Naturally Occurring Acetylenic Compounds By N. A. SORENSEN (INSTITUTTFOR ORGANISK KJEMI NORGES HOGSKOLE, TEKNISKE TRONDHEIM NORWAY) THEoccurrence of acetylenic compounds in Nature was realised independently about 1890 by the French chemist A. Arnaudl and the German chemist F. W. Semmler,2 the latter well-known for his contribu-tions to terpene chemistry. From the seed oil of some Picramnia species Arnaud isolated an acid “tariric” acid which he proved to be octadec-6-ynoic acid. Table 1 lists the acetylenic fatty acids so far found in Nature all of them are C, acids and they have been found in a few closely related families. Semmler’s work concerned a different corner the essential oil of the tiny carline thistle (Carlina acaufis).The main component he named carlina oxide and his own experiments restricted the possible formula to three (1-III). Semmler apparently over- looked Arnaud’s work and selected the allenic formula (III) on the hypothesis that acetylenic com- pounds ought not to occur in Nature and it was not until 1933-35 that the correct structure for carlina oxide was e~tablished.~g* It is remarkable that since 1935 progress has been so rapid that a single lecture cannot contain all the naturally occurring acetylenes and a few only of the remarkable variations in this class of compound have HC-CH HC-CH I II II HC! C-C..CCH,Ph HC ,t.CHiC=CPh ‘0’ 0 (1) (a HC-CH H& tCH=C=CHPh ‘0’ F.W. Semmler’s alternatives for carlina oxide. to be selected for discussion. It may thus be useful to look again at the two first members of the class for these tariric acid and carlina oxide are-except for the acetylenic bond-seemingly as unrelated as compounds could be. * Delivered before the Chemical Society at The University Glasgow on February 17th 1960; at The University Aberdeen on February 19th; and at the Imperial College of Science and Technology,London on February 26th. Arnaud Compt. rend. 1892 114 79; 1902 134 473. Semmler Chem. Zrg. 1889 13 1158; Ber. 1906,39 726; 1909,42 2355. Gilman van Ess and Burtner J. Amer. Chem. Soc. 1933 55 3461. Pfau Pictet Plattner and Susz Helv. Chim. Acta. 1935 18 935.MARCH1961 TABLE1. Natural acetylenic fatty acids. Constitution CH3. [CH,],,*C-C. [CH,],.CO,H CH,=CH. [CH,],.CrC+CrC. [CH2],.CO,H CH,=CH* [CH,],.CH =CH.C=C*C EC. [CH,],.C02H CH =CH. [CH,],*C C*C C.CH(OH)* [CH,],C02H CH,=CH-[CH,],.CH=CHC=CC=C-CH(OH). [CH,],C02H Name Tariric Genus Picramnia Family Simarubaceae Ref. 1 acid Isanic acid Ongokea Olacawie 5 Bolecic acid Ongokea Olacaceae 5 Isanolic Ongokea Olacaceae 6 acid Goric acid Ongokea Olacaceae 6 Ximenynic Ximenia Olacaceae 7 acid CH,. [CH2],CH =CH.C-C*CH(OH). [CH2],C02H It is not possible to follow the development historically; different threads are more or less distinct though they intermingle; so let us consider first a tiny Compositae plant Lachnophyllum gos-sypinum Bg.,growing in the semi-deserts of Azer- beidschan.Local Russian industries in the thirties It used a crystalline component of the essential oil of this plant for the manufacture of soap perfumes. These perfumes are strangely enough still of un- known constitution but the structure of the crystal- line compound was fully exposed in a remarkable paper of Viljams Smirnov and Goljmov in 1935.1° It received the name cis-lachnophyllum ester. Its TABLE 2. Methyl esters of acetylenic C, CH3CH,CH,C EC-CECCH =CHC0,Me CH3-CH=CH-C =C.C ECCH =CH-C0,Me CH3CH =CHCrCC=CCH,.CH,CO,Me CH3-C=C*C~C-C= CCH =CHC0,Me structure is shown in Table 2. The other esters of Table 2 have been isolated from plants of the same family but I would certainly not claim that my col- laboratorsl' have found all the variations that occur in the Compositae.Among the seven esters of Table 2 Castille Annalen 1939 543 104; Meade cited by Jones Whiting Armitage Cook and Entwhistle Nature 195I 168 900. Kaufmann Baltes and Herminghaus Ber. 1937 70 903; Riley J. 1951 1346. ' Lighthelm and Schwarz J. Amer. Chem. SOC.,1950 72 1868. Hatt Triffett and Wailes Austral. J. Chem. 1959 12 190. Lighthelm Chem. and Znd. 1954 249. lo Viljams Smirnov and Goljmov Zhur. obshchei Khim. 1935 A 5 1195. 11 N. A. Sorensen and Stene Annalen 1941 549 80; Stavholt and N. A. Sorensen Acta Chem. Scand. 1950 4, 1567; Stavholt Holme Nestvold Pliva J. S. Sorensen and N. A. Sorensen ibid. 1952,6 883; J. S. Sorensen Bruun Holme and N.A. Sorensen ibid. 1954 8 26; Holme and N. A. Sorensen ibiC;. p. 280. (San t a1 bic (San talum) (San t alaceae) acid) Exocarpus Santalaceae 8 Ximenia Olacaceae 9 is the first polyacetylenic compound isolated in crystalline form cis-dehydromatricaria ester was observed in 1826 as a crystalline deposit in the essential oil from European mugwort (Artemisiu vulgaris L.). is at once evident that these seven esters represent very simple variations on a single theme namely unsaturated C, acids; yet as in other classes of acetylenic compounds the Compositae family has provided examples of C12,C13 CI4 CJ5 and C, carbon chains so that this monotony with the methyl esters is rather remarkable. Members of these seven acetylenic esters have so far been isolated acids of the Compositae.cis-Lachnophyllum ester trans-Lachnophyllum ester 2-cis-8-cis-Matricaria ester 2-trans-8-cis-Matricariaester 8-cis-a,/3-Dihydromatricariaester cis-Dehydromatricaria ester trans-Dehydromatricaria ester with certainty from only two of the thirteen tribes into which most botanists divide the Compositae family. Moreover we have to go far away botanically to find the closest chemical relatives. Of the fungi the subgroup Basidiomycefes has furnished much the largest number of polyacetylenic compounds known. compound in Table 4) occurs as its methyl ester in Table 3 lists some of the compounds isolated by the sub-tribe Anthemidinae (cf. Table 2). E. R. H. Jones and collaborators12 from a single From the structure of some 50 polyacetylenic species Polyporus anthracophilus; the Table has been compounds isolated from Basidiomycetes E.R. H. compressed in so far as most of the acids occur both Jones has developed the rule that compounds with a TABLE 3. Polyacetylenes from the fungus Polyporus anthracophilus reported by E. R. H. Jones and his collaborators. CH3-CH =CH*C=C-CEEC.CH =CH.CH2.OH trans- trans-Matricarianol CH3CH=CHC=C.C~CCH =CHCO,Me trans- trans- Ma t ricari a ester HO.CH,CH,CH,-C =C.C =CCH =CH-C02Me MeO2C.CH2-CH,.C=C-C=CCH =CHCOpMe MeO,C-CH=CH-CfCC=C CH =CH CO Me free and as methyl esters. Whereas the scentless may- free ethynyl end group have an odd number of weed affords two of the three possible cis-isomers of carbon atoms in the chain whereas bifunctional matricaria ester these fungi synthesise the stable polyacetylenes occurring alongside them have an di-trans-compound.The corresponding alcohol even number. The first four Drosophila compounds trans-trans-matricarianol has been isolated both of Table 5 illustrate the rule; the fifth is the only from fungi and from higher plants (e.g. the Aster exception known from fungal metabolites. sub-tribe of the Compositae). The striking features The compounds that induced E. R. €3. Jones and of Table 3 are first the bifunctional character- his colleagues to study the Basidiomycete acetylenes alcohol or ester groups at both ends-and secondly were the fungal antibiotics. These were recognised the C8compound both features so far unparalleled about 1950 by workers at the New York Botanical in higher plants.Both seem to be typical criteria of Garden including Kavanagh Hervey and Marjorie Basidiomycetes Tables 4 and 5 give further examples Anchel who however did not at first realise their from the remarkable series isolated by Jones’s acetylenic character. The complexity of the series group.12 trans-Dehydromatricaria acid (the third also has increased markedly during the investigations TABLE 4. Further polyacetylenes from Basidiomycetes reported by Jones and his collaborators. HO2C-CH2.CH2-C EC-CEC-C ZEC*C02H Merulius lacrymans t CH3CrC-C ECC =CCH =CHC02H Pleurotus ulmarius CH,. C CCEC. C ECCH =CHCHO Pleurotus panaeolum f CH,.CrC*C ECCEC-CH =CHCH2.0H Pleurotus ulmarius TABLE5.Acetylenes of known structure in the Basidiomycete Drosophila subatrata. C Cll CH C-CH,-C= CC rCCH=CHCH2C02H Drosophilin C c Cll CH2 =C =CHC=C.CECCH=CHCH~.CO~H Drosophilin D C HC- C-C ZE CCH =CHCH2CH2C02H C Drosophilin E Clo t t H0,CCH =CH*C=C.CFC.CH=CH.CO,H Cll HO2C.CH2*CH2-CH,*C C *C EEC-CH=CH-CO,H Bu’Lock Jones and Turner J. 1957 1607; Gardner Jones Leeming and Stephenson J. 1960 691 ; Jones Leeming and Remers J. 1960 2257. MARCH1961 101 at Manchester and Oxford. Table 6 lists some of the Arima and Okamotozl in 1930 described the isola- acetylenic antibiotics.13-20 Three comments should tion of a hydrocarbon “capillen” from this plant; the be made. (1) Nocardia is not a fungus but an Actino- formula was given as C13H14.Still earlier (1922) the mycete; the isolation and the elucidation of the chemists of Schimmel & Co., had steam-distilled structure of mycomycin are due to Celmer and the root of couch-grass (Agropyron repens) their sol om on^^^ at Chas. pfizer Inc. (2) Marasmin was product was not investigated until 1944 and sur- found by Dr. Gerd Bendz15 at Uppsala; marasmin prisingly consisted of more than 90% of a single TABLE 6. Some polyacetylenic antibiotics. Nocardia Agrocybe Clitocybe Clitocybe Clitocybe Coprinus Coprinus CH_C*C-C*CH =C=CHCH =CH.CH =CH.CH,CO,H HO-CHzC~CC~C.C~C-CO.NH H0,CCH =CH*CrCC,C.CO*NH HO2C*CH=CH*C~C*C~C*CN H0,CCH =CH-C-C*CrC.CrC.CH,.OH CH C-C CC CCH =CHCHO CH=C-CrC*CzCCH =CH*CH,*OH Mycomycin14 Agr oc ybid3 Diatretyne PS Diatretyne U17 Diatretyne IW8 (Ref.19) Coprinus Coprinus CHEC-C ECC ~CCH(OH)CH(OH)*CH,-OH HO.CH2.C =C*C ECC -CCH =CH.CH,.OH Poria Poria CH CHZCC~C-CH=C =CH-CHCH,-CH,*CO CCrC-CH=C =CH-CH(OH)CH,CH,CO,H -0-J Nemotinic acid2* Nemotin20 Poria Poria CH,.C=C*C rC.CH =C=CH.CH(OH).CH,.CH2.C0,H CH,*CrC.CrC.CH =C =CH-CH,-CH,CO L-O-J Odyssic acid2* Odyssin20 Marasrnius CHICCEC-CH =C=CH.CHZ.CH,-OH and mycomycin are both remarkably active against hydrocarbon which was named “agropyrene” and tubercle bacilli both in vitro and in vivo. (3) The long for which TreibsB developed the C, formula (IV). series of antibiotics whose constitutions were worked This formula conflicted with the properties of the out by Jones et al. include many compounds of in- trans-isomer synthesised by Cymerman-Craig et a1.2Q credible instability.I thought myself that mycomycin in 1954. In the same year Harada25 re-isolated capil- had put up a boundary fence for what could be len and proposed a C, formula. Harada at first isolated and studied by structural methods; but I am thought capillen was an isomer of agropyren but in now convinced that the Coprinus aldehyde for 1957 he corrected26 the formula to C12H10 and proved example has moved this boundary incredibly further PhCH,CH= CH-CrCMe (IV) out. Old In connexion with the remarkable antibiotic pro- for agropyrene -f perties of these fungal acetylenes it may be mentioned Ph.CH,C_CCrCMe PhCOCrCCsCMe that Semmler’s original carlina oxide is very toxic to Capillen26 0 Capillin (VI) Staphylococcus aureus; like most of the fungal anti- Ag ro py rene } (‘1 biotics it is however too toxic to be of practical use.the structure by synthesis. Simultaneously Lmai and In discussing the antibiotic properties I may perhaps his collaborator^^^ isolated the fungicidal principle of interpose some history. Arternisia capillaris from the A. capillaris which they named “capillin” and Far East has long been known to be fungicidal. proved the structure (VI). l3 Kavanagh Hervey and Robbins Proc. Nat. Acad. Sci. U.S.A. 1950,36 102; Ashworth Jones Mansfield Schlogl Thompson and Whiting J. 1958 951. l4 Celmer and Solomons J. Arner. Chem. SOC.,1952,74 1870,2245,3838; 1953,75 1372,3430. l5 Bendz Arhiv Kemi,1959 14 305,475; 1959 15 131. l6 Anchel J. Arner. Chem. SOC.,1953 75,4621. Anchel Science 1955 121 607; cf.Ashworth et a/.,ref. 13. l8 Anchel Arch. Biochem. Biophys. 1959 85 569. l9 Jones and Stephenson J. 1959 2197. 2o Anchel Polatnick and Kavanagh Arch. Biochem. 1950 25 208; Bu’Lock Jones and Leeming J. 1955 4270; 1957 1097. 21 Arma and Okamoto J. Chem. SOC.Japan 1930 51 781. 22 Schimmel & Co. Ann. Report 1922 p. 55. 23 Treibs Chem. Ber. 1947 80 97. 24 Cymerman-Craig Davis and Lake J. 1954 1874. 25 Harada J. Chem. Soc. Japan 1954,75 727. 26 Harada J. Chem. SOC.Japan 1957 78 415 1031. 27 Tmai Theda Tanaka and Sugawara J. Pharm. SOC. Japan 1956 76 397 400. PROCEEDINGS Cymerman-Craig in collaboration with Treibs28 last year proved the identity of agropyrene and capillen and demonstrated the smooth autoxidation of the hydrocarbon to the ketone.This ketone capil- lin is interesting not only because of the ease of introduction of an oxygen function but also because it is stated to be one of the most potent fungicides known. Agropyren (= capillen) is so far the only acetylenic compound found in grasses. However although a few grasses have been studied properly because of accompanying monoalcohols and ketones are practically non-toxic. Yet another class of biologically active compounds are the insecticides. The Compositae family yields beside the technically important pyrethrum group another interesting type namely the unsaturated isobutylamides. The most active principles seem to be derived from polyolefinic acids but from Crombie’s work31 we know that at least two of the components in Anacyclus pyrethrum are acetylenic (VII and VIII).TABLE 7. Polyacetylenic compounds from umbelliferous plants as reported by Lythgoe and his collaborators. Oenanthe Diol HO-CH,.CH=CH-[C=C 1,-[CH=CH 1,-[CH,],CH(OH). [CH,],-Me Mono-ol HOCH,CH=CH-[CrC],-[CH=CH],. [CH,],.Me Ketone CH,CH =CH-[C%C],-[CH =CH],.[CH,],-CO- [CH,],-Me Cicuta Diol HO~CH,~[C~C],-[CH=CH],~CH(OH)~[CH,],~Me Mono-ol HO-CH,. [CrC],-[CH =CHI2- [CH,],.Me their importance in the essential oil industry most of them have scarcely been studied by chemists at all. Before we remove the formula (IV) which I have named “old agropyren” from the naturally occurring acetylenes we should consider a 1957 paper of Goljmov and Afa~anev.,~ In the Russian mugwort Artemisia scoparia they found two hydrocarbons; one C1,HI0 was identical with capillen; the other C1,HI2 was again stated to have the formula of “old agropyren.” With the capillen group we meet again the phenyl residue present in the old carlina oxide but absent so far from the Basidiomycetes compounds.It was somewhat of a disappointment to my collaborators that in our first hundred Compositae plants in- vestigated we did not meet this classical compound. Carlina acaulis does not occur in Scandinavia but two sub-species of C. vulgaris grow on the dry calcareous soils of the southern part. My wife first investigated the sub-species euvulgaris from Uppsala; CH3CH2CH2CrC.C~CCH2CH2*CH =CH*CH =CHCO.NHBui Anacyclin (VII) CH3CH=CHC~C-C~C*CH2*CH2*CH =CHCH =CH-CO-NHBu’ Dehydroanacyclin (VlII) Another class of physiologically active compounds was elucidated by Lythgoe and his group at Cam- bridge.3O The Umbelliferae family comprises many toxic species; a few contain alkaloids; most of them however contain coumarins and furanocoumarins.Two genera Cicuta and Oenanthe have long been reputed to cause convulsions in and death of cattle. The early chemistry of these poisons was merely con- fusing; the remarkable results of Lythgoe’s work are reproduced in Table 7. The highly toxic principles cicutoxin and oenanthotoxin are the two diols; the she found no carlina oxide but instead trideca- 2,10,12-triene-4,6,8-triynylacetate.32 This straight- chain aliphatic compound is interesting; the free alcohol has the same composition C,,H,,,O as carlina oxide and an alcohol (again occurring as acetate) from several Coreopsis species.More than 10years ago Sir Ian Heilbron and his collaborator^^^ demonstrated the conversion of pentenynol into 2-methylfuran. The scheme given by Sir Ian would lead from the Coreopsis alcohol to isocarlina oxide which through the Semmler formula should finally 2* Cymerman-Craig Lock and Treibs Chem. and Jnd. 1959 952. 29 Goljmov and Afasanev Zhur. obshchei Khim. 1957,27 1698. 30 Anet Lythgoe Silk and Trippett J. 1953 309. 31 Crombie J. 1955 999. 32 J. S. Sorensen and N. A. Sorensen Acta Chem. Scand. 1954 8 1763. 33 Heilbron Jones Smith and Weedon J.1946 54; Heilbron Jones and Sondheimer J. 1947 1586. MARCH1961 103 give carlina oxide. At the other end of the molecule acetylenic alcohols which except for the Coreopsis we have to curl up a dienyne group to a benzene ring. alcohol mentioned above are all aliphatic. Whereas Although the process does not sound unlikely to the the Compositae methyl esters have so far been organic chemist it is rather far from the shikimic restricted to C1, the alcohols have been found in the acid route to the aromatic series generally accepted C, and the C13 series. We recollect that Lythgoe’s by biochemists. Umbelliferae toxins furnished C1 alcohols. From the Before we pursue this problem we should perhaps Compositae family Professor Bohlmann in Germany rapidly mention some other compounds from Com- has obtained alcohols of both the C, and the C, positae.Table 9 shows the acetylenic alcohols found series during his researches on the so-called centaur at my Institute all of them present in the plants as X and Y. acetates.34 We meet mono- di- tri- and tetra-These centaur X compounds were first described TABLE 8. +I + 1 H2C=C* C H= CH *CH,.O’ Ph*CsC*CH=C*CH= CH *CHiO- HC=CH HC=CH II I bH2 H&=C CH M=CCH=C ‘0’ 0 HC-CH II It 0 Me-C /CH HC-CH 0 Ph.-C.CH,.C II ,CHII i HC-$I-! PhCH =C=CH *C /CH0 II 1 HC-CH Ph*CH,*eC-(! b’ Ph.C=CGC*CH=CH .CHi OH Coreopsis HC-CH II Carlina acauirs Ph+CH,.C=CC /&H 0 TABLE 9. Acetylenic alcohols isolated from the Conpositae. 2-trans-8- trans 2-trans-&cis Aster CH3.CH =CH*C =C*C rCCH =CH.CH,.OAc Brachycome CH3-CH =CH.C_C*CH =CHCH=CH-CH,.OAc 4-cis Matricaria CH3.CrC.CrCCH=CHCH=CH-CH=CHCH,-CH,-OAc 54s Coreopsis CH =CHC~CCEC-C~CC~C-CH =CHCH,-OAc trans Carlina CH =CH-CH =CH.C=C*CSC.CZCCH =CH-CH,.OAc 10-cis Coreopsis PhCrCC=CCH =CHCH,.OAc trans 34 Holme and N.A. Sorensen Acta Chem. Scad. 1954 8 34; J. S. Sorensen and N. A. Sorensen ibid. p. 1741; Christensen,Norges Tekniske vitenskapsakademi Ser. 2 1959 No. 7; Sunde Holme and J. S. Sorensen unpublished work. 104 PROCEEDINGS by Lofgren,35 who found that alcoholic extracts of Clearly the latter curve represents a mixture the cornflowers gave spectra with remarkable fine struc- arrows indicating maxima due to dihydrocentaur X.ture. During the isolation of the cis-dehydromatri- The Centaurea compounds have been separated by caria ester from Artemisia vulgaris at my Institute Professor B~hlmann.~~ Bohlmann states that there Miss Stavholtll found two other acetylenic com- are many small unresolved fractions containing yet pounds a ketone to which I shall return later and a other compounds; his pure compounds are reported hydrocarbon whose principal absorption maxima in Table 10. It is a really remarkable series. The X3 were identical with those of the dienetriynes syn- compound was isolated by Bohlmann from several thesised by Jones et al. in Manchester and with those Centaurea species and from Arremisia vulgaris. In TABLE10. Centaurea (cornflower) polyacetylenes reported by Bohlmann and hrs collaborators.( CH,*CH =CH.C_C.C-C.CrC.CrC.CH = CH “391 5” CH3*CH =CHC=C.C=C.CrC.CH=CH*CH = CH C13 CH3. CH =CH C rC*CE C-C rC.CH =CH.CHCI*CH~*OAC CH3*CH =CHC rC*CrC*C=C*CH = CH.CHClCH2*OH CH3CH= CH C rC.CSEC*CrC*CH =CH*CH(OAc).CH,.OAc C, CH,-CrC-C~CC‘~C-CH =CH.CH =CHCH,CH(OAc)CH,CH,~OAc Centaur X ( ?) CH3CH =CH-C-C-CGC.CH =CH.CH =CH.CH,CH(OAc).CH,.CH,.OAc Centaur X, I the C15 series we find 1,3-glycols in the C, series both 1 ,Z-glycols and chlorohydrins. The two hydro- carbons at the top of the Table were known before from other Cornpo~itae.~~~~~ The name “391 5” is 45 derived from the longest-wave maximum. Bohl-mann states that the “3915” hydrocarbon is one of the most widely occurring acetylenes of the genus Centaurea; its few absences are seemingly connected 40 with taxonomic divisions.The same holds for its occurrence in the Compositae family asa whole. So cu far it has not been found in the two tribes where we (r -found the Cl0 esters but it occurs in most of the 35 others. Table 11 lists the acetylenic hydrocarbons is~lated~*-~~ by my group from Compositae. The pentayne at the head of the Table is the first coloured acetylene met in Nature; it is remarkably stable in the plant and in solution but as expected very 30 unstable in the solid state. Whereas the “4100” hydrocarbon has never been found in quantity the cis-trans-isomeric tetraynes (the “3915” hydrocarbons) occur in rather large 2500 3000 3500 amounts in many ordinary garden fiowers; some of them such as Dahlia and Coreopsis are plants which Wavelength have often been studied by chemists.The reason why FIG. 1. Ultraviolet spectrum of dienetriyne from the acetylenes had to wait so long for detection is Artemisia vulgaris. Full line centaur X. simply the very late use of spectrographs in phyto- chemical laboratories Once spectra such as those of of Lofgren’s centaur X. Fig. 1 shows the absorption Fig. 2 are observed it could not take long to track of our Artemisia hydrocarbon and one of Dr. down their origin for they are truly remarkable. Lofgren’s curves redrawn to the same peak height. In Table 11 we met two hydrocarbons with a 35 Lofgren Acta Chem. Scand. 1949 3 82. 38 Bohlmann and Herbst Chem. Ber. 1958 91 1631 ; Bohlmann Postulka and Ruhnke ibid.p. 1642. 37 J. S. Sorensen and N. A. Sorensen Act0 Chem. Scand. 1958 12 756. 38 Cf. Jones Skattebol and Whiting J. 1958 1054. as J. S. Sorensen Holme Borlang Tuxen and N. A. Sorensen Acta Chem. Scand. 1954 8 1769. 40 J. S. Sorensen and N. A. Sorensen Acta Chem. Scand.. 1958 12 765. MARCH1961 phenyl residue. During his efforts to synthesise trideca-l,3,1 I-triene-5,7,9-triyne Dr. Skattebo141 sur- prisingly obtained fractions with the spectrum of a phenylheptenediyne. The synthetic route (IX)-(X) is shown in the annexed scheme; it is only an applica- tion of a standard route from a mono- to a di- acetylenic compound. The side reaction in which no stages were isolated between the dichloride and the aromatic compound seems to be a general one when a butadiene residue appears at one end of the acetylenic linking.In Dr. Skattebol’s synthesis of the tridecatrienetriyne the group R was pentenyl; the reaction was later tested with R = phenyl leading to tolan as the by-product. Bearing in mind the pair of compounds we met in closely related Carlina species and the fact that tri- deca-1,3,1 l-triene-5,7,9-triyne and phenylhepta-l,3- diyn-5-ene occur in the same part of several Coreopsis species I think it likely that these plants synthesise the pheny 1 ring directly from unsaturated aliphatic precursors. The other phenyl compound in Table 11 the phenylheptatriyne would according to this hypo- thesis correspond to the double-bond isomer of the “3915” hydrocarbon CH,=CH.CH=CH.CrC.C=C.C=C.C=CMe Nevertheless this hydrocarbon has neither been isolated from a natural source nor been synthesised.TABLE 11. Acetylenic hydrocarbons in Compositae (except Centaurea). CH3-C~C.C~C.C_C-CE C-C 3CCH =CH “4100” Ref. 39 CH3CH =CH*C~C*CZEC*C~C*C~CCH =CH “3915” Refs. 34 38 1I-cis and 11-trans CH,*CH=CH*CEC.CEEC*C=C.CH=CH.CH-CH 3-cis Ref. 37 CH,CH=CH.CrC*C=CPh Ref. 37 CH,*C=C-C=C-Cr CPh Ref. 40 CH,*CH =CH*CrC*CrC.CH =CI-I-CH=CH*CH =CH2 Ref. 34 F 5-0 4.5 40 3.5 30 2.5 2400 2800 3200 3600 4000 Wave t engt h (i) FIG. 2. Ultraviolet spectra of (A) trideca-1,ll-diene-3,5,7,9-tetrayne (11)from Coreopsis (inhexane) (B) tetradeca-2,12-diene-4,6,8,1l-tetrayne(I) (in ethanol),and (C)purest fraction of compound(11)from Cnicus benedictus L.The phenylheptatriyne itself is an extremely nice compound with a very beautiful ultraviolet absorp- tion spectrum (Fig. 3) and with high crystallising power. In fact the essential oils of some Coreopsis species deposit crystals of this hydrocarbon when stored at -24”. On one occasion my wife when chromatographing such an oil took the usual routine cuts in the eluent and obtained one nice crystalline fraction after the other. Although the R.CH(OH) CXCH (OH).CH =CH.CH=CH (1x1 melting points of the later fractions fell by some degrees I hardly would have paid attention to it as the spectrum of the whole essential oil was dominated by the sharp fingers of the phenylheptatriyne.Fortunately my wife measured the spectra of these last fractions and got curve A of Fig. 4. Curve B is the spectrum of the tetrahydro-compound. Neither of these gave any information. However an infrared I1Skattebol and N. A. Sorensen Acta Chem. Scand. 1959,13 2101. 106 PROCEEDINGS spectrum revealed a monosubstituted phenyl residue and by comparison with the curve given by Birkin- shaw and Chap1ena2 for junipal we thought that we might have a 2,5-disubstituted thiophen. The rest of the work was ea~y.4~ ‘S’ Junipal Hi-CH Ph-C )-C=S CMe MeC=C.@CC=C-CH=CHCC&Me HC-CH MeCEC-8 ,C-CH=CH CO,Me II s. 4-5 4.0 I I I I\ 2600 3000 3400 A Wavelength (A) FIG.3. Ultraviolet spectrum of l-phenylhepta-1,3,5-triyne. 3.5 In the annexed formula are shown the formal con- 4 01 nexion bet ween 2-p hen y1-5-p rop y n y lthiop hen and -phenylheptatriyne the constitution of junipal (one of the odorous principles which Birkinshaw and Chaplen isolated from the Basidiomycete Daedelia 3-0 juniperina) and the first thiophen to be isolated from plants viz.the terthienyl which Zechmeister et a1.44 isolated from Tagetes erecta (Tagetes is another member of the Compositae). Also given is a scheme leading from dehydromatricaria ester to two isomeric thiophens the reason for this inclusion is the work of Erling G~ddal*~ on two crystalline compounds from tansy root (Chrysanthemum vulgare Bernh.) I 1 which he proved to be the cis-trans-isomers of com-2400 2800 3200 3600 pound (XI); the trans-isomer was then synthesised Wavelength (w) by Dr.Skattebol who incidentally prepared junipal FIG.4. Ultraviolet spectra of (A) 2-phenyl-5-prop- as an intermediate. 1‘-ynylthiophen and (B) 2-phenyl-5-propylthiophen(in The forrnal connexion between phenylheptatriyne hexane). 42 Birkinshaw and Chaplen Biochern. J. 1955 60 255. 4s J. S. Sorensen and N. A. Sorensen Acta Chem. Scand. 1958 12 765. 44 Zechmeister and Sease J. Amr. Chem. SOC.,1947 69 273. 45 Guddal and N. A. Sorensen Acra Chern. Scad 1959 13 1185. MARCH1961 and 2-phenyl-5-prop- 1'-ynylthiophen viz. dehydro-matricaria ester and methyl /3-(5-prop-l'-ynyl-2- thienyl)acrylate is very simple and obviously in- dicates a biochemical relation. I should like to draw attention to a 1953 paper by Challenger and Holmes.46 At that time only a few polyacetylenes were known from the Compositae and the only natural thiophen was the terthienyl of Zechmeister and Sease.On this meagre evidence Challenger and Holmes proposed a connexion between natural poly- acetylenes and terthienyl. The pclyacetylene corre- sponding to terthienyl is however hexa-acetylene and the only fact about this hydrocarbon is that all efforts to synthesise free polyacetylenes higher than triacetylene have led to carbonaceous material at temperatures below -80". The elucidation of the structure of these thiophens aroused misgivings in our minds for broad-banded spectra such as are given by these compounds had regularly been left out of consideration by us.The compound we started with luckily turned out not to be acetylenic at all. It was 5-butadienyl-5'-methyl- 2,2'-bithienyl (XU); but this again is formally derived from the asymetric trideca-1,3-diene-5,7,9,11-tetrayne which curls up to phenylheptatriyne so we do think it belongs to our series although it is devoid of an acetylenic bond. It was isolated by Mrs. Synnarve Liaaen-Jensen from some Bidens species. She suggested the structure given and this was sub- sequently confirmed by synthesis by Dr. Skattebol. Last spring Dr. J. H. Uhlenbroek and his col- laborator~~~ in the research laboratory of Philips- Roxane demonstrated that Zechneister's terthienyl was one of the nematocidal principles of extracts from Tagetes roots.More potent however than terthienyl was a liquid with a broad ultraviolet maximum at 3400 A.The Dutch chemists gave this nematocidal principle formula (XITI). Fractions with (XI1) C)-C!CaC-CH =CH2 (XIII) identical ultraviolet and infrared spectra had been isolated in my laboratory from Berkheya macroce- phala and Echinops sphaereocephalus. During our synthetic efforts to clear up these compounds Mr. E. Sunde synthesised the bithienyl derivatives 2-4 whose ultraviolet absorption maxima are shown in Table 12. We find it difficult to reconcile these maxima with the constitution proposed by Uhlen-broek et al. for the natural product and our guess TABLE 12. Ultraviolet absorption maxima (A) of some monosubstituted bithienyls related to the nematocidal principle of Tagetes.No. R ~Kllax. 1 C-CCH =CH2 3400? 2 .CZZC-CH,.CH 3350 3 *C=CH*CH2CH3 3390 5 COMe 3425 6 .CZEC-CH,*CH=CH ? points to a pent-4-en-1-yl side chain (the last member in Table 12) but our synthesis of this compound is not complete. When isolating trans-dehydromatricaria ester from some Matricaria species my wife and Miss Holme obtained also small amounts of two crystalline com- pounds at that time characterised only by their melting points and ultraviolet spectra (ses Fig. 5).48 2600 3200 3800 Wavelength (A) FIG.5. Ultraviolet spectra of (A) substance mp. 47-548-5", from Matricaria inodora L. and (B) substance m.p. 4-45" from M.oreades Boiss (in hexane). 48 Challenger and Holmes J.1953 1837. 47 Uhlenbroek and Bijlvo Rec. Trav. chim. 1958 77 1004. *' Sorensen Bruun et af.,ref. 11. When later we obtained infrared data these two compounds were recognised as monosubstituted thiophens. When work was resumed on them seasonal changes in the plant material prevented the original chromatographic separations from being reproduced. The number of pure compounds isolated increased to five. Syntheses of two of them (XIV) and (XV) are reproduced in the attached scheme. A third is the ap-dihydro-ketone. CJC=CH + 1 QcecH *C-CH=CH *CH=CH .CH=CH (XIV) m.p. 48" Certainly there are yet other monothiophen deri- vatives present in the two Matricaria species in- vestigated. But let us consider the compounds revealed so far in some closely related species of the subtribus Anthemidineae.At the top of Table 13 stands Centaur X from mugwort root hydrocarbon fractions with the same spectrum were met in extracts of Matricaria inodora. PROCEEDINGS The next is Miss Stavholt's ketone (see above) that occurs with Centaur X and cis-dehydromatricaria ester in mugwort; its constitution was established partly by the work of Miss Dagny Holme partly by Bohlmann et al. ;49 fractions containing this ketone are troublesome during the isolation of the mono- substituted thiophens. Then follow five esters of C, acids whose striking feature is the correspondence of the unsaturated part. Ph.N Me .CH =CH -CH= CH * CHO =cH a=cH .wo c$C-CCH=CH *CH=CH COEt (XV) m.p.44" According to Jones's hypothesis a natural com- pound ending in an unsubstituted ethynyl group is derived from one with a carbon atom more (some- times occurring with it in the plant). By substituting hydrogen for methyl in the compounds at the top of Table 13 and curling up the first two acetylenic groups to a thiophen ring we get the compounds at the bottom of the Table. The CIS hydrocarbon TABLE13. Related compounds in the tribiis Anthemideae subtribus Anthemidineae. C, CH,-C=CC=C-CCH=CH*CH=CH. [CH,] dCH= CH Artemisia (Matricaria) C, CH~C=C*CsC.C=CCH=CH* [CH,]iCO*CHiCH Artemisia (Matricaria) CH;C=C.C=-C.C=C.CH =CH *C02Me cis in Artemisia trans in Matricaria CH,CH =CH C=C.C=CCH =CH.CO2Me 2-cis-84s 2-trans-84s Matricaria CH,CH =CH .C%C-C=GCH,-CH ** CO ,Me 8-cis Matricaria ~ J C ECCH=CH CH =CH *CO.CH,.CH Matricaria inodora UJLccH =cH a,-cH,co.cH,.cH Ma tricaria inodo ra 49 Bohlmann Mannhardt and Viehe Chern.Ber. 1955 88 361. MARCH1961 has the entire unsaturated chain of Centaur X,. The difference of one carbon atom between the three thiophens corresponds to parallel differing polyacetylenes with a free ethynyl group. This is an 4.5 analogy to the exception found at Oxford for one polyacetylene isolated from Drosophila subatrata (see above). However I do not think this difference need go any deeper than that between the propionic 4-0 acid residue and the vinyl residue in the porphyrin series. w From this point of view I have looked with p suspicion at the right-hand end of Centaur X and wondered if there should have been at the head of Table 13 an ordinary (although rather unsaturated) 3.5 fatty acid.Bu’Lock and Gregory50 and other biochemists have proved that the polyacetylenes are synthesised from glucose through acetate. But that does not tell 3.0 us whether they are built through C,,fatty acids or not. In this connexion I should like to call attention to a peculiar phenomenon observed by Boekenoogensl 23 years ago. The oil from fresh boleka nuts contains 2600 3000 3400 3800 Wavelength (i) very little unsaponifiable matter (0-7-1 *5%). If the FIG. 6. Ultraviolet spectra of (A) lactone of 4-kernels are not dried properly they become red and hydroxydeca-2,4,8-trien-6-ynoicacid (B) cis-cis-later black.The oil from these black kernels has matricaria ester and (C) “Composite cumuZene I” 10-1 5 % of unsaponifiable matter which Castille (ref. 53) (in hexane). CH. -CH.[CHJ~-C~C*C~C.CH{OH)*[CH,I,.CO,H 22 I CHp= CH.[C H,],.C G6.CFEC H OHC*[CH.J,CO2H CH,= CH*[CH&*CH= CH*C,C*CGCH f 2 CH,= CH+[CHJ,.CH= CHC~C*CrC.CH(OH)*[CH,I,.CO,H Splitting of boleka hydroxy-acids proved to be decenediynes. I have sketched this autolysis of the boleka hydroxy-acids in the annexed chart. de Vrie~~~ demonstrated recently that this process could be simulated with alkali and oxygen. It may be that the enzymes arising in the reddening boleka nuts will give a valuable clue as to how Nature makes the short-chained polyacetylenes.When compiling the Anthemidineae acetylenes in Table 13 I omitted for simplicity the thiophen ester from tansy root. Two other compounds with broad indefinite ultraviolet spectra merit consideration. Fig. 6 shows three ultraviolet spectra. Curve C is that of the so-called “Composite c~mulene.”~~ We 50 Bu’Lock and Gregory Biochern. J. 1959 72 322. obtained this material from the green part of scent-less mayweed and supposed it to be both a pure com- pound and a cumulene; in fact it was neither. Curve A is that of the pure substance first isolated by Miss Dagny Holme from a Chrysothamnus species. In collaboration with the Jones group Dr. Per Koch Christensen demonstrated that this Chryso-thamnus compound was the lactone into which the free cis-cis-matricaria acid (cf.curve B) is trans- formed in polar solvents the change being (XVI) -+ (XVII). If my wife and I had searched our mother- liquors when in 1940 we saponified the matricaria ester to the free acid we should have found this 51 Boekenoogen Fette u. Seifen 1937 44 244. j2 de Vries “L‘Huile de Boleko,” Publn. de la Direction de l’Agriculture de Gerets en de I’Elevage Brussels 1956. ,j3 N. A. Sorensen and Stavholt Acta Chem. Scand. 1950 4 1080. compound. However first we had no spectrograph at that time and secondly my view was then that such a free acid would be so unstable that I should have paid no attention to a broad-banded mother- liquor but only classified it as a mixture of decom-position products.HC. CE C*CsC.CH \ HCC FH CH HOCO 1 H/C=CH HC.C=CCH=C ,‘co 0 (XVII) Christensen% has demonstrated that some of the Compositae richest in cis-lachnophyllum ester con- tain the corresponding lactone. Time has not allowed us to check whether mugwort root contains the lactone as well as cis-dehydromatricaria ester ;since dehydromatricaria ester when synthesised at Oxford was found to lactonise very rapidly this would be expected. I 1 I I I 2400 2800 3200 360C Wave length (i) FIG.7. Ultraviolet spectrum of a diacetylenefrom Matricaria matricarioides. PROCEEDINGS We have learned albeit in a rather irrational way that free 2-cis-enynoic acids cannot exist in the cells as water is one of the most powerful catalytic solvents for their lactonisation so it is no wonder that the 2-enynoic acids found by Jones and his colleagues in fungi were all the trans-isomers.The main component of rayless chamomile Matricaria matricarioides has the ultraviolet spec- trum shown in Fig. 7 and from a comparison with umbelliferone was at first labelled “perhaps coumar- ins?” Dr. Christensen% has not been able to obtain this compound crystalline but by oxidative degrada- tion has made formula (XTX) very likely.54 This t HC=CH I1 compound might then originate from cis-dehydro- matricarianol (XVIU) by cyclisation. In contrast with the above mentioned acid-transformation of trans-pentenynol into 2-methylfuran the process leading only to cyclisation has been shown by Jones and his to take place in weak alkali and to occur only with the cis-alcohols.Whereas the corre- sponding acids lactonise in aqueous solution in a few minutes at room temperature and accordingly the plants scarcely need to develop enzymes for this pro- cess cyclisation of the cis-alcohols is very slow in a neutral medium and I suppose that the rayless chamomile has enzymes for this reaction. This I should like to know for certain because clearly it is these enzymes that catalyse the first step from the aliphatic precursor retained in Carlina vulgaris to the classical benzylfuran of Carlina acaulis. And so we are back with the problems disclosed by F. W. Semmler 70 years ago-and still we have much to learn of the ways in which the formally so simple aliphatic poly- acetylenes are transformed into a variety of complex aromatic and heterocyclic products.Cf. Christensen N. A. Sorensen Bell Jones and Whiting “Festschrift Arthur Stoll,” Basle 1957 p. 545. 65 Jones Proc. Chern. Soc. 1960 199. UARCI-I 111 COMMUNICATIONS The Role of Acetate and Malonate in the Biosynthesis of Penicillic Acid By RONALD and JOHN G. KEIL BENTLEY (DEPARTMENT AND NUTRITION SCHOOL HEALTH, OF BIOCHEMISTRY GRADUATE OF PUBLIC UNIVERSITY PITTSBURGH OF PITTSBURGH 13 PA.) BIOSYNTHESIS of penicillic acid (V) in Penicillium cycfopiwm was studied by Eirch et a1.l with [l -14C]acetate. They suggested a head-to-tail con- densation of four acetate units to give orsellinic acid OV) and a subsequent ring cleavage to penicillic acid.Independently we studied formation of penicillic acid from D-[ 1-14C]-or ~-[6-~~C]-gllucose, L-[Me-14C]methionine,H-l4CO,H and [1-14C]- and [2-l'*C]-a~etate.~ C8) was found to be derived from formate or the methyl group of methionine. Values for C(7)obtained by Kuhn-Roth oxidation of peni- cillic acid dibromide to yield C(,)H,C(,)O,H sug-gested that C(7)was not derived from the methyl group of acetate; in this work C(4)was obtained by difference. Direct values for C(4)have now been (1) 'FOJ CH acid synthesised from H02C-14CH,C02H carbons 2 4 and 6 each contained about 33% of the total activity and was not labelled. From H0,14CCH2.14C02H carbons 1 and 3 each con- tained 50% of total activity and C(s) was not labelled.The labelling pattern is strikingly different in penicillic acid derived from acetate or malonate. While C(7) and Co) represent a unit derived from acetate these atoms are not significantly labelled by either carbon or malonate. Malonate is therefore not significantly converted into acetate and apparently represents a precursor beyond the acetate level. Since Mosbach has demonstrated the sequence acetate -+ orsellinic acid -+ penicillic acid in P. barnense a similar situation may be presumed in P. co2 3Ocd OH 8: ** 'CH *"C02H 4 O '$H b m0CO2H OCO-SCoA (m (Iv> OC;carbon derived from malonate carboxyl or CO,. BC; carbon derived from C(l) or C(6)of glucose or from acetate-methyl. @;carbon derived from acetate-carboxyl.RC; carbon derived from C(l) or C(6)of glucose or from acetate-methyl or from malonate-methylene. 4)C; carbon derived from acetate- or malonate-carboxyl. AC; carbon derived from methyl of methionine or from formate. obtained by oxidation of dihydropenicillic acid with chromic acid to isobutyric acid and decarboxylation of the latter by Schmidt degradation. These addi- tional results show unequivocally that carbons 2 4 6 and 7 are derived from C(l)or of glucose and from the methyl-carbon of acetate; carbons 1,3 and 5 are derived from the carboxyl-carbon of acetate. This information is consistent with the conversion of glucose into pyruvate by the Embden-Meyerhof path and the subsequent formation of acetyl-coenzyme A (I).Methylene- and carboxyl-labelled malonate were also converted into penicillic acid in P. cyclopium NRRL 1888 respectively with 35% and 9.5% recovery of added radioactivity. In penicillic Birch Blance and Smith J. 1958 4582. Keil Fed. Proc. 1960 19 242. Mosbach Acta Chem. Scand. 1960,14,457. cyclopiurn. Further we have now identified orsellinic acid in P. cyclopium cultures by paper chromato- graphy. The results with malonate however suggest that a modification of the proposed head-to-tail con- densation of acetate units is necessary. Orsellinic acid is apparently formed by condensation of one mole- cule of acetyl-coenzyme A 0)and three of malonyl-coenzyme A (11) to form an intermediate (111) or a similarly labelled compound as shown in the chart.The early stages in the biosynthesis of orsellinic acid would therefore be analogous to those for fatty acids.4 Three acetyl-coenzyme A units are converted into malonyl-coenzyme A units by fixation of carbon dioxide; the fixed carbon dioxide is released at a later stage in agreement with our finding that added For a review see Stumpf Ann. Rev. Biochem. 1960,29 261. NaH14C0 is not incorporated into penicillic acid. Although the conversion of malonyl-coenzyme A into acetyl-coenzyme A has been described5 as occurring in micro-organisms this reaction is apparently insignificant in P. cyclopium. It seems Hayaishi J. Biol. Chem. 1955 215 125. PROCEEDINGS likely that some other head-to-tail condensations of acetate may also involve malonate as an intermediate.This work has been supported by a grant from the National Science Foundation. (Received December 30th 1960.) The Acid-catalysed Self-condensation of Acetic Anhydride and Analogous Compounds By P. F. G. PRAILLand A. L. WHITEAR ELIZABETH LONDON, (QUEEN COLLEGE W.8) DISSOLVING strong acids in acetic anhydride is known to cause condensation but apart from the complex (I) 3 BF, obtained in the presence of boron trifluoride,l little is known about the products. We have found that a crystalline perchlorate can be obtained from solutions of perchloric acid in acetic anhydride. In spite of reports to the contrary,2 dehydroacetic acid can be acetylated and the product is identical with that obtained from acetic anhydride alone.The initial product appears to be the per- chlorate m.p. 223" (decomp.) of compound (11). This salt has Amax. 221 and 243 mp (infl.) (log E 4.40 4-06) consistent with a y-pyrone structure and the characteristic &lactone absorption at 1720-1 750 cm.-l is absent. Attempts to obtain the free base (I1) gave 3-aceto- acetyl-4-hydroxy-6-methyl-2-pyrone (III) m.p. 1 17" and this was readily hydrolysed to dehydroacetic acid. Water rapidly converted the original per- chlorate into an isomeric salt which yielded the base (IV) m.p. 183-184" A,,,. 239 and 298 rnp (log E 4.27,4.00) v,,,. (in Nujol) 1750 cm.-l. The perchlorate of base (IV) is also obtained by dissolving the lactone (111) in a solution of perchloric acid in acetic acid If the acetic acid is replaced by Meerwein and Vossen J.prakt. Chem. 1934 14-1 149. Collie J. 1891 179; Perkin J. 1887 484. Badcock Dean Robertson and Whalley J. 1950 903. Fleischmann J. 1907 250. OH COCH,*COMe 0 CV 1 (Vl) Me (Vl I) (v1II) acetic anhydride the lactone (111) gives the per- &lorate of the isomer (II). Previous efforts3 to synthesise 00-dimethylcitro- lnycinone (v; R = OMe) by way ofthe acetoaWtY1 compound (VI) (R = OMe) were not SUCceSSful owing to inability to C-acetylate 3-acetyl-4-hydroxy- 6,7-dimethoxycoumarin. We have prepared the citro- mycinone ('; = H by the action Of anhydride and perchloric acid on either 4-hydroxy- coumarin or its 3-acetyl derivative; there is some evidence that a compound analogous to (11) is also formed in small amount.Fleischmann* considered that condensation of 4-hydroxy-6-methyl-2-pyrone with ethyl acetoacetate might give compound (11) or (VII) and favoured the latter structure. Re-examination of Fleischrnann's compound has shown that its chemical properties and light absorption are more consistent with those expected for the dilactone (VIII). (Received December 19th 1 960.) MARCH1961 113 The Addition of “Halogen Monofluorides”* to Fluoro-olefins By R. D. CHAMBERS and J. SAVORY W. K. R. MUSGRAVE (THE DURHAM IN THE UNIVERSITY COLLEGES OF DURHAM) IF iodine pentafluoride and iodine or bromine tri- fluoride and bromine are mixed in stoicheiometric proportions so that the mixtures correspond to IF and BrF then these mixtures are effective sources of iodine monofluoride and bromine monofluoride respectively.Only very recently has iodine mono- fluoride been prepared,l although Durie2 earlier observed iodine monofluoride spectroscopically and the conductivity measurements by Quarterman Hyman and Kat~,~ of mixtures of bromine tri- fluoride and bromine suggest the formation of bromine monofluoride. A mixture of iodine penta- fluoride and iodine reacted easily with fluoro-olefins ; tetrafluoroethylene yielded pentafluoroiodoethane; chlorotrifluoroethylene gave l-chloro-l-iodo- (45 %) and 1 -chloro-2-iodo-trifluoroethane (55 %) ; 1 l-di- fluoroethylene gave 1 ,1 ,l-trifluor0-2-iodoethane; and hexafluoropropene gave an excellent yield of a new iodo compound heptafluoro-2-iodopropane.Similar reactions with bromine trifluoride and bromine gave the corresponding bromo-derivatives. Many com- plicated reaction schemes may be devised involving the self-ionisation of the halogen fluoride^,^ but the mode of addition is most easily explained in terms of the formation of halogen monofluorides IF + 21 + 51F 61-6-s+ s-I-F + CFz=CF * CF3 -+ CF3 * CFI * CF It has been well established that nucleophiles become attached preferentially to the difluoromethylene part of a fluoro- or fluorohalogeno-olefin.5 However when bromine or iodine is attached to a carbon atom already carrying a halogen atom steric interference between the large halogen atoms must occur thus reducing both the stability and the extent of forma- tion of the product.This steric factor tends to make addition of “halogen monofluorides” to fluoro-olefins less specific e.g. 6t 6-6+ 6-I-F + CF,=CFCI -+ CF,*CIFCI + CF21*CFzCI Tetrachloroethylene gave exclusively tetrachloro- 1 ,Zdifluoroethane with iodine pentafluoride and was isolated can again be ascribed to the instability of a CCI,I group arising from steric interference between the halogens. Heptafluoro-Z-iodopropane (Found F 44.6; I 42.9. C3F,I requires F 44.9; I 42-8%) b.p. 38-0° was distinguished from the familiar isomer hepta- fluoro-1 -iodopropane by its infrared spectrum which had strong bonds at 7-75 8-00,8-42 8-88 10.40 11.20 13.25 13-95 14.2 p (doublet).Hydro- lysis with potassium hydroxide in acetone yielded 2H-heptafluoropropane which can easily be distin- guished from 1H-heptafluoropropane by its infrared spectrum. Fluorine magnetic resonance spectra con- firmed the structure and supported CF,CFBr-CF as the structure of bromoheptafluoropropane obtained from the reaction between hexafluoropro- pene and bromine trifluoride plus bromine. A Grignard reagent was prepared from hepta- fluoro-2-iodopropane by exchange with pheny Imag- nesium bromide; hydrolysis gave CF,-CFHCF and hexafluoropropene;and reaction with acetone yielded a new fluoro-alcohol 3,4,4,4-tetrafluoro-2-methyl-3-trifluoromethylbutan-2-ol (CF,),CF -CMe * OH lodine-lithium exchange occurred between hepta- fluoro-2-iodopropane and butyl-lithium at -78 O and on warming lithium fluoride was eliminated giving a quantitative yield of hexafluoropropene.Thus heptafluoro-2-iodopropane and the corre- sponding lithium and Grignard reagents have potential synthetic value for the preparation of branched-chain organic and organometallic fluoro- alkyl compounds. Preliminary work indicates that the iodo-compound is a useful starting material to use in a process for the preparation of highly branched-chain fluoro-olefins and fluoro-alkanes,@ which it is hoped will be a step towards fluoro- compounds of high molecular weight with a wide liquid range. We thank Dr. L. H. Sutcliffe of the University of Liverpool for the nuclear magnetic resonance spectra and one of us (J.S.) thanks the D.S.I.R.for a maintenance grant. iodine; that no tetrachloro-1-fluoro-2-iodoethane (Received February 6th 1961 .) * Halogen in the sense used in this paper does not include fluorine. Schmeisser and Scharf Angew. Chem. 1960,72 324. Durie Proc. Roy. SOC.,1951 A 207 388. Quarterman Hyman and Katz J. Phys. Chem. 1957 61 912. See Clark Chem. Rev. 1958 58 869 for a discussion of the self-ionisation of interhalogen compounds. Miller and Fainberg J. Amer. Chem. Soc. 1957 79 4164 and references cited therein. Chambers Musgrave and Savory unpublished results. PROCEEDINGS Measurement of the Vibrational Relaxation Time of Tetradeuteromethane By T. L. COTTRELL and A. J. MATHESON (DEPARTMENT THE UNIVERSITY OF CHEMISTRY EDINBURGH) REPORTED values of Zl0 the number of collisions tetradeuteromethane prepared from heavy water and required for vibrational deactivation and p the aluminium carbide containing 1.6% of air as the vibrational relaxation time in methane seem low on only impurity detectable by gas chromatography.the Lambert-Salter1 plot of log Z, against the The relaxation time is 3.9 x sec. a figure more lowest fundamental vibration frequency of the mole- than double the result for methane. On the other cule. Although published work on methane around hand theory4 as well as Lambert and Salter’s em- 300”~ by Cottrell and Martin2 and by Edmonds and pirical generalisation shows that the relaxation time Lamb3 shows good concordance both these in- of tetradeuteromethane should be less than that of vestigators appear to have used purified natural gas methane.It is very difficult to account for a relaxa- without specifically identifying impurities. There is tion time larger than the correct one and thus the thus the possibility that their results are low because tetradeuteromethane result is unlikely to be too long. of impurities. This therefore suggests that published results for We have used the ultrasonic technique2 between methane are too low. 50 kc sec.-l atm.-l and 500 kc sec.-l atm.-l to One of us (A.J.M.) thanks D.S.I.R. for a main- measure the relaxation time at 298”~ of a sample of tenance grant. (Received January 31st 1961.) Lambert and Salter Proc. Roy Soc. 1959 A 253 277. Cottrell and Martin Trans.Furuduy Soc. 1957 53 1157. a Edmonds and Lamb Proc. Phys. Soc. 1958 A 72,940. Herzfeld and Litovitz “Absorption and Dispersion of Ultrasonic Waves,” Academic Press New York 1959. A New Route to 4-Methyl-3-oxo-d4-steroids By D. N. KIRK and V. PETROW (THE CHEMICAL LABORATORIES LTD. LONDON RESEARCH THE BRJTISH DRUG HOUSES N. 1) THE preparation of 4-methyl-3-0x0-d4-steroids(111; (partially deactivated by refluxing acetone for 30 R = Me or H) by controlled monomethylation of min.) in acetone for 4-5 hr. Overall yields are the corresponding 3-0x0-d4-steroids1 (I; R = Me or generally good and in some cases reach 80%. H) has hitherto formed the most direct route. The Primary and secondary hydroxyl groups are products however are invariably admixed with preferably acylated before treatment with Raney substantial quantities of the corresponding 4,4-di- nickel to prevent their oxidation by the metallic catalyst in presence of acetone.17 a-Hydroxypregn- an-20-ones likewise require acetylation to prevent D-homo-rearrangement during the first stage of the 0m-o@-om Me (m) process. 16a,17 a-Epoxides pregn-l6-en-20-ones, (1) CH,SR‘ (a) and other groups which react with thiols clearly methyl-3-oxo-d5-derivatives thereby limiting the interfere with the process as do such groups as usefulness of the method. We have now discovered alkenyl and alkynyl which are reduced by Raney a more convenient and efficient route to (III) viz. nickel. (i) the condensation of the 3-0x0-d4-steroid (I) with The following products indicate the scope of the formaldehyde (> 1 mol.of 40% aqueous solution new reaction or of paraformaldehyde) and an organic thiol (2-3 4-Methylandrostenedione 2~,4-dimethyltesto-mol. of for example benzene- or toluene-p-thiol or sterone 4-methyl-1 9-nortestosterone 9 a-fluoro- -an alkanethiol) in the presence of a tertiary base 1 1 p,17p-dihydroxy-4,17 a-dimethylandrost-4-en-3 (e.g. triethylamine) in ethanolic solution (30-50 hr. one 4,16 cc-dimethylprogesterone 11a-hydroxy-4-under reflux) or in excess of a hydroxy-tertiary base methylpregn-4-ene-3,20-dione 17a-acetoxy-4-(e.g. 8-12 hr. at 110-120” in aqueous triethanol- methylpregn-4-ene-3,20-dione,1 7 cc-acetoxy-4,6&di- amine) whereupon the corresponding 4-organothio- methylpregn-4-ene-3,20-dione,16u,17 a,isopropyl- methyl-3-0x0-d4-steroid (11; R = Me or H; R = idenedioxy-4-methylpregn-4-ene-3,20-dione ethyl -oate and phenyl p-tolyl or alkyl) is formed and(ii) conversion 4-methyl-3-oxopregna-4,17(20)-dien-21 of this compound into the 4-methyl-3-0x0-d 4-steroid 4-methylcortisone (B.M.D.). 011; R = Me or H)by heating it with Raney nickel (Received January 27th 1961). Atwater J. Amer. Chem. SOC.,1960 82 2847. MARCH1961 115 X-Ray Study of Crystals isolated during the Synthesis of 1,12-o-Phenyleneperylene By W. A. C. BROWN and J. MONTEATH J. TROTTER,* ROBERTSON DEPARTMENT GLASGOW, (CHEMISTRY THEUNIVERSITY W.2) 1,12-O-PHENYLENEPERYLENE (naphtho [1,2,3,4-g,h,i]-perylene) (111) has recently been prepared from the quinone (I) directly and via an intermediate whose spectrum suggested a naphthalene derivative such as the tetrahydro-compound (II),although the analysis corresponded more closely to that of a dihydro-c0mpound.l When chromatographed on alumina the mother-liquor from the first stage gave a trace of perylene (identified spectroscopically) and also large colourless plates which were submitted to X-ray examination.These colourless crystals were monoclinic with a -21.04 b = 6.32 c = 10.17 A,18 = 105.2" d measured = 1.299 g.~rn.-~, space group Cc or C2/c. These measurements required three molecules of either Cz6H1 (the dihydro-compound) or C26HZo (tetrahydro-compound) in the unit cell. As this is extremely improbable it was concluded that the colourless plates must be some other hydrocarbon with formula CZ0Hl4 and four molecules in the cell.This immediately suggested that the crystals were 1 ,l'-binaphthyl which would be the precursor of the perylene obtained in the reaction. The chemical analysis and ultraviolet spectrum of the crystals cor- responded accurately to those of 1,l '-binaphthyl but there were two discrepancies. A powder photo- graph of the crystals was not identical with that of an authentic sample and the melting point (148-149') was rather lower than the values reported for 1,l'-binaphthyl. However the wide range of melting points reported in the literature suggested that 1,l'-binaphthyl might exist in more than one crystal- lographic modification and in addition the crystals probably contained small amounts of impurity.It was decided to establish the identity of the crystals by a complete structure analysis. It seemed likely that the true space group might be C2/c with each molecule situated either on a centre of symmetry or a two-fold rotation axis. Considera- tion of the molecular geometry suggested that the two-fold axis was more likely but in the projection along the 6-axis both possibilities are identical and it was not necessary at this stage to choose between them. By using Fourier transform methods a trial structure was set up and structure factors calculated for all the hOZ reflexions R being 45%. A Fourier series was summed from measured structure ampli- tudes and calculated signs; the resulting map is shown in the Figure the binaphthyl molecule being very well-defined.New centres were chosen and structure factors recalculated; R was 29 %. A further cycle reduced R below 20 % so that there is no doubt that the crystals are 1,l '-binaphthyl. Measurements of projected distances in the Figure indicate either that the molecule is centrosymmetrical and therefore trans-planar or (and this is considered more likely) that it possesses a two-fold symmetry axis and the angle between the planes of the two sets of naphtha-lene rings is about 73";that is the molecular con- figuration is slightly nearer cis than trans. Work is continuing to establish this point with certainty and to obtain an accurate account of the geometry and dimensions of the molecule.0 I2 3A u Electron-density projection along [Ol01. Contours at intervals of I eA-2 starting at 2 eA-2. It appears that the zinc dust melt of the quinone (I) in the preparation of 1,12-0-phenyleneperyleneyields a mixture of substances-binaphthyl perylene o-phenyleneperylene and perhaps dihydro- and * Present address Department of Chemistry University of British Columbia Vancouver 8 Canada. Clar Ironside and Zander Tetrahedron 1959 6 358. f 16 PROCEEDINGS tetrahydro-compounds such as (11). The crystals impurity indicated by the rather low melting point. examined by the X-ray method were obtained from one fraction from the chromatogram and are We are indebted to Dr. E. Clar for crystal samples 1,l'-binaphthyl with perhaps a small amount of and for much helpful discussion.(Received February loth 1961.) Photoisomerisation of Eucarvone to 1,5,5-Trimethylnorborn-2-en-7-one By J. J. HURSTand G. H. WHITHAM (DEPARTMENT UNIVERSITY OF CHEMISTRY OF BIRMINGHAM) IsoMERIsAnoN of suitably substituted norbornane tively. That these acids were trimethyloxocyclc-derivatives to compounds containing a cycloheptane hexanecarboxylic acids was indicated by infrared and ring is well authenticated and occurs under pyrolytic nuclear magnetic resonance spectra. Furthermore the c0nditions.l We now report the first example acid (X) m.p. 121-122.5" was identified as 1,3,3- of the reverse process induced in this case by trimethyl-5-oxocyclohexanecarboxylicacid by com- photochemical means. parison with an authentic sample obtained on Irradiation of an aqueous acetic acid solution of hydrolysis of the corresponding nitrile in turn pre- eucarvone (I) with sunlight resulted in the formation pared by addition of cyanide to is~phorone.~ of two photoisomers in approximately equal amounts.This conversion of eucarvone into the photo- One of these is 1,4,4-trimethylbicyclo [3,2,0]hept-6- isomer (111) represents a new type of photoisomerisa- en-Zone (II) already obtained and identified by tion of unsaturated ketones and possibly occurs by Buchi and Burgess. The other photoisomer pre- collapse of an excited state as shown schematically viously unreported is shown to be 1,5,5-trimethyl- in (XI) norborn-2-en-7-one (111). h The ketone (III) b.p. 68-70"/12 mm. had v,,,.(in CCl,) 1782 (highly strained cy~lopentanone~) 3050; (in CS,) 792 737 690 crn.-l (cis-disubstituted double bond); A,,,. (in EtOH) 270 mp (E 58). It did not incorporate deuterium when heated under reflux with sodium methoxide in dioxan-deuterium oxide and hydrogenation in ethanol over palladium- 0 0 carbon resulted in the rapid uptake of hydrogen (1 mol.) with formation of a saturated ketone [vmax. (in CS,) 1770 cm.-']. The bridged structure (HI) was assigned on the basis of the following degradation. Reduction with lithium aluminium hydride gave one alcohol (IV).* Epoxidation of the latter with per- benzoic acid followed by reductive cleavage of the epoxide ring with lithium in ethylamine gave a mix- ture of two crystalline glycols (V) and (VI)? separable by chromatography.Oxidation with 6~-chromic acid in acetone gave the corresponding diketones (VIT) and (VIII) each of which had vmax.(in CS,) 1780 We thank Professor M. Stacey F.R.S. for and 1740 cm.-l. Cleavage of the b-diketone system encouragement; one of us (J.J.H.)is indebted to the present in (VII) and (VIII) with potassium hydroxide University of Birmingham for a research scholarship. in methanol gave the keto-acids (IX)and (X) respec-(Received January 23rd 1961.) * Stereochemistry is assigned from studies on the solvolysis4of the methanesulphonate and comparison with that of the epimer obtained in addition to (IV) by reduction of ketone (111) with sodium in ethanol. 7 Configurations based on the known mode of attack of perbenzoic acid on norbornenes.Woods J. Org. Chem. 1958 23 110; Matteson Drysdale and Sharkey J. Amer. Chem. Scc. 1960 82 2853. Buchi and Burgess J. Amer. Chem. SOC.,1960,82,4333. Cookson Hudec and Williams Tefrahedron Letters 1960 No. 22 29. Winstein Shatavsky Norton and Woodward J. Amer. Chem. Soc. 1955,77,4183; Winstein and Stafford J. Amer. Chem. SOC.,1957,79 505. Whitmore and Roberts J. Org. Chent. 1948 13 31. MARCH1961 117 End Groups in the Polymer from the Reaction of Diazomethane with Organoboron Compounds By 3 E. LEFFLER and B. G. RAMSEY STATEUNIVERSITY FLORIDA, (FLORIDA TALLAHASSEE U.S.A.) GOUBEAU suggested a rearrange- molecular weight isolated by chromatography on and ROHWEDDER~ ment mechanism for the formation of polymethylene neutral alumina has infrared bands in carbon tetra- from diazomethane and boron catalysts.Bawn chloride solution at 2920 2850 and 1460 ern.-' Ledwith and Mathies have recently found some (polymethylene) and a band at 699 cm.-l attributable indication of alkoxy- and fluorine end groups in the to a monosubstituted benzene ring. The product from triphenylboron and dipheny 1-diazomethane gave on treatment with hydrogen X,B + CH,N,-X,B-$H -X,B-CH,X peroxide triphenylmethanol and triphenylmethane "-1 I besides phenol and benzophenone azine. Tri-l-naphthylb~ron~~~ also catalyses the decom- X,B.[CH,] X-X,B-CH,CH,X position of diazomethane. The resulting poly- -["x;&,] methylene had infrared bands at 777 and 790 crn.-l characteristic of a naphthalene ring with a single infrared spectrum of the polymer from the reaction substituent in the a-p~sition.~ The ultraviolet of diazoalkanes with boron trifluoride or trialkoxy- absorption spectrum resembled those of 1 -methyl-borons.2 This prompts us to report some of our and 1-ethyl-naphthalene.Assigning the same experiments on the reactions of diazomethane and extinction coefficient to the 1-naphthyl end group triaryl borons. in the polymer as is observed for the 283 mp The polymer formed from the reaction of diazo-band of 1-ethylnaphthalene we compute the average methane in ether with triphenylboron was accom- degree of polymerization to be 30 methylene units in panied by small amounts of toluene isolated after the hexane-soluble polymer fractions. acid-hydrolysis of the reaction mixture.The product after treatment with hydrogen peroxide contained We thank the Office of Naval Research for its benzyl alcohol in 20% yield based on triphenyl- support of this work. boron. A small amount of a waxy polymer of low (Received January 30th 1961.) Goubeau and Rohwedder. Annulen. 1957.604. 168. Bawn Ledwith and Mathies J. Pdymer'Sci.,'1959,34 93. Brown and Sujishi J. Amer. Chem. SOC.,1948 70 2793. * Krause and Nobbe Ber. 1930 63 934. Werner Austral. J. Chem. 1955 8 355. A Cyclopentadienide Anion that is Stable in Water By R. C. COOKSON, J. HUDEC,and B. WHITEAR (THE UNIVERSITY SOUTHAMPTON) obtained an adduct (A) of dimethyl malonate state only-by ultraviolet spectra in solution and DIELS~ with two mol.of dimethyl acetylenedicarboxylate diffuse reflectance spectra of the solids. which on treatment with aqueous potassium acetate The infrared spectrum of A shows no hydroxyl gave the salt of a substance (B) Cl5HI6Ol0.Mainly group and its ultraviolet spectrum (Amax. 211 and because of his preconceptions about the mechanism 281 mp E 8000 and 3300 respectively) is at too short of the reaction Diels formulated A as the hemiketal a wavelength for (I). We suggest structure (111) or its (I) and B as the cyclopentadiene (11; R = H). The conjugated tautomer formed by a double Michael structure of B seemed to be supported by its forma- addition. We have been unabIe to find the isomer,' tion of an unstable adduct with maleic anhydride m.p. 183" of A which Diels believed was the other assumed to be a normal Diels-Alder adduct.The geometrical form required by his formula (11). How-adduct described and the one formed with tetra- ever an analogue m.p. 215" is formed by using cyanoethylene have been shown to be merely charge- ethyl methyl malonate which might perhaps have transfer molecular complexes existing in the solid contaminated his dimethyl malonate if it had been Diels Ber. 1942 75 1452. PROCEEDINGS made from the diethyl ester by incomplete ester cyclisation of anion (IV) cleavage of the ester (V) exchange and might have depressed the m.p. and dehydrogenation of anion (VI) by the hydrogen- The implausible loss of elements of carbon acceptor (111)-Mizox :wx XsX /X X (1) (ID "I) + RO CO,Me X + H,-III X-$$-x x x (VIII) * X = C0,Me in all formula.monoxide and methanol suggested1 to explain the conversion of A into B is now unnecessary the re- action is a base-catalysed disproportionation from which we have isolated the second product a dihydro-derivative of A as a viscous liquid (Amax. 213 mp E 8000). The sequence thus involves identical ultraviolet spectra (Amax. 265 and 295 mp E 50,000 and 15,OOO). The apparent pH values of aqueous solutions of sulphuric acid hydrochloric acid and the cyclopentadiene (11; R = H) were respectively at 0.04~ 1.66 1.54 1-54; at O-O~N,1-4 1-24 1.24; at 0.8~ readings with a glass electrode are at best only semiquantitative but hydrochloric acid had an apparent pH of about 0.2 whereas the cyclo- pentadiene (11; R = H) gave a slightly negative reading.It is therefore considerably stronger than sulphuric acid (as a dibasic acid) and probably stronger than hydrochloric acid. The acid (11; R = H) decomposes diazomethane to form the C-methyl derivative (11; R = Me) m.p. 102-103" (Amax. 223 and 295 mp E 8350 and 6000) easily cleaved by mild base to salts of the anion (VIII) (Amax. 270 and 308 mp E 34,700 and 13,570).7 Ultraviolet spectra reported were measured in methanol. We acknowledge with gratitude an I.C.I. Research Fellowship (to J.H,) and a Perkin Centenary Fellowship (to B.W.). (Received January 23rd 196 1 .) The cyclopentadiene (II;R = H) is an extremely strong acid. In water and alcohols the acid and its potassium and tetrabutylammonium salts have (") t It also reacts with carbonyl compounds with loss of one methoxycarbmyl group ;e.g.,p-dirnethylaminobenzaldehyde yields the corresponding merocyanine dye (A,, 540 mp).A Nuclear Magnetic Resonance Study of Hydrogen Bonding in Liquid Amines By J. FEENEY and L.H. SUTCLIFFE OF INORGANIC CHEMISTRY LIVERPOOL) (DEPARTMENT AND PHYSICAL THE UNIVERSITY OPTICAL spectroscopic techniques have provided much data in the past on hydrogen-bonded systems. More recently nuclear magnetic resonance spectro- scopy has been used for such systems having the advantage that weak hydrogen bonding can be de- tected. Various physical methods have been used to establish the existence of hydrogen bonding in liquid amines but no measurements on its extent have been made.We now report some data we have obtained from nuclear magnetic resonance measure- ments. Since traces of water affected the spectra the amines were left over sodium wire for 24 hours and then distilled in a high vacuum. The most suitable inert solvent for studies of self-association is carbon tetrachloride but unfortunately many amines includ- l Saunders and Hyne J. Chem. Phys. 1958. 29. 1319. ing isobutylamine react quickly with it and no other suitable solvent could be found. Mono-and di- ethylamine are sufficiently inert towards the solvent and have a large enough dilution shift for quantita- tive measurement (the measurements were made with a Varian 4300 B NMR spectrometer operating at 40.00Mc./sec.).Chemical shifts of the hydrogen resonance of the amine groups were measured to a precision of & 1% from some other band in the spectrum usually the central line of the triplet of a methyl group. Between six and twelve recordings of each spectrum were made and the mean shifts taken. Solutions of various concentrations were prepared by weighing and the data obtained were treated by Saunders and Hyne's rneth0d.l When pure mono- ethylamine diethylamine and isobutylamine were MARCH1961 cooled the amine-hydrogen nuclei became progres- sively deshielded until near the melting point the chemical shift of these nuclei became constant. This is taken as the chemical shift of the n-mer and corresponds to hydrogen-bonding of all the species.The accuracy of the values (c./sec.) given in the Table is affected by line broadening at low tempera- tures. Addition of carbon tetrachloride to the ethyl- amines caused the amine-hydrogen nuclei to be more shielded as the number of species that are not hydrogen bonded increased. <O-lM-Solutions gave a constant chemical shift whose value may be regarded as that of the pure monomer. The difference between the chemical shift of the monomer and the n-mer is called the association shift. Association shifts similar to that found in ammonia by Schneider et aL2 were obtained for the amines examined. Monomer n-Mer Associa-shift (room temp.) Monoethylamine 17.7 Diethylamine 22.4 Isobutylamine ? Ammonia2 -shift tion (just above shift the m.p.) -22.1 39.8 -17.2 39.6 -35 35f -42 In order to interpret the data for the progressive dilution of mono- and of di-ethylamine it was news- sary to postulate a monomer-tetramer equilibrium.The resulting association constants were found to be 3 x and 1 x 10-3~-3 respectively. n-Mers greater than tetramers are probably additionauy present at >8M-concentrations. The heat of forma- tion of the tetramer of diethylamine was estimated to be -1-7kcal. per mole of tetramer. (Received February 1Oth 196 1 .) Schneider Bernstein and Pople J. Chem. Phys. 1958 28 601. The Reductive Condensation of 2,5-Dimethylpyrrole :A Novel Isoindoline Synthesis By R. BONNETTand J. D. WHITE (CHEMISTRY UNIVERSITY VANCOUVER DEPARTMENT OF BRITISH COLUMBIA 8 B.C.CANADA) PREVIOUSworkers1 have favoured the partial structure (I) for a base C,,H,,N formed by the pro- longed treatment of 2,5-dimethylpyrrole with metal- acid systems. It has now been found that 2,5-di- methylpyrrole when refluxed with tin and aqueous hydrochloric acid gives a 57 % yield of 1,3,4,7-tetra- Me Me [bMe\2H m N H &:OMe MeMe Me Me (1) methylisoindoline (11) b.p. 85-90"/0-6 mm. obtained as a viscous liquid which reddens on storage and readily forms a solid derivative with aerial carbon dioxide. The structural assignment (11) rests on the satis- factory elemental analyses of the base and its derivatives [hydrochloride m.p. 267-268" (de-camp.) ; nitrate m.p.176-178" ; benzenesulphon-amide m.p. 127-128'1 and on the following evidence. The base yielded an N-nitroso-derivative (m.p. 93"; positive Liebermann test) and the benzenesulphonamide was insoluble in alkali hence the base is a secondary amine. Electrometric titration in 20% aqueous ethanol gave an apparent pKa value of 8-8and an equivalent of 178 (calc. 175). The ultra- violet spectra of the base and its salts were similar (e.g. nitrate in methanol h,,,. 265.5 270.5 274.5 mp; log E 2.52 2.47 2.45 respectively) and moreover resembled the spectrum of 4,7-dimethyl- indane.2 This evidence for a benzenoid chromophore finds further support in the infrared spectrum of the base which had peaks at 331 1 (NH) 1865,1490 and 806 cm.-l the last strong absorption in the absence of strong absorption in the 700-750 cm.-l region being taken as evidence for two adjacent hydrogen atoms on a benzene ring The strength of the base and the lack of marked change in its ultraviolet spectrum on salt formation indicate that the nitrogen atom cannot be adjacent to the benzene ring.Partial oxidation by alkaline permanganate furnished a small yield of 3,6-dimethylphthalic an- hydride (111) ; prolonged oxidation with the same reagent gave a 32% yield of benzene-1,2,3,4-tetra- carboxylic acid providing further chemical support for the isoindoline structure. Confirmation came Plancher and Cuisa Atti R. Acad. Lincei. Rend. Classe Sci. fkmat. nat. 1906 15 447; cf. Beilstein's "Handbuch der organischen Chemie," Julius Springer Berlin Vol.XX p. 299. Entel Analyt. Chern. 1954 26 612. from the proton magnetic resonance spectrum of the base (neat 40Mc. sec.-l dichloromethane as external standard T scale3) which showed peaks with T values of 3.4 (singlet; aromatic H) 6-0 (quadruplet; H at positions 1 and 3 split by CH at those positions) 8.2 (singlet; CH at positions 4 and 7) and 8.9 (doublet; CH at positions 1 and 3 split by H at those positions). The peak areas were in the respec- tive ratio 1.0:1-0:2.9:2.8,again in agreement with structure (III). The interesting possibility exists that the iso- Tiers J. Phys. Chem. 1958 62 1151. PROCEEDINGS indoline is formed by a reaction of the Diels-Alder type (a reaction infrequently found in pyrrole chem- istry) followed by reduction and aromatisation steps (see scheme).We are investigating this and other possible mechanistic routes as well as the stereo- chemistry of the 1,3-positions of the product. We thank Dr. D. E. McGreer for the proton magnetic resonance spectra and the National Research Council of Canada for their support of this work. (Received January 12th 1961.) Structure of a Sydnone By HARTMUT F. JELLINEK and AAFJEVos B~MGHAUSEN (LABORATORIUM CHEMIE,ANORGANISCHE VOOR ALGEMENE Cmm EN KRBTALCHEMIE RIJKSUNIVERSITEIT THE NETHERLANDS) GRONINGEN ALTHOUGH meso-ionic compounds and in particular the sydblones have aroused considerable interest,' no Wstal structure of a SYdnone has been repofid SO far. we have undertaken an investigation of N-P-bromophenylsydnone (I).The compound crystallises in space group Pi with two molecules per unit cell; the dimensions are a = 1.39 'OVo6 A; = 10*17 Oeo5 A; = 3'92 0*04A; a = 79.2" 0.1";/3 = 94.2" f0.05";y = 103.7" f0.2". A three-dimensional electron-density map com- puted from 984 out of 1017 observed independent reflexions hkl (I = 0,1,2,3) is shown in the Figure. Both the phenyl ring and the sydnone ring are planar but the molecule is twisted around C,-N as an axis; the two ring-planes contain a dihedral angle of 27". Atom 0 lies in the plane of the sydnone ring but the bromine atom is tilted 0-05 A out of the plane of the phenyl group. The bond distances (A) are found to be C-C in phenyl ring 1.365-1 -393 Br-C 1-92 Ol-CS 1.41 Ch-N 1.45 C8-C7 1-38 Ni-N 1.30 C,-Ni 1.33 Nz-0 1.34 c,-0 1.20 Baker and Ollis Quart.Rev. 1957 11 15. The consistency of the distances in the phenyl ring indicates an accuracy of 0.03 A in the bond lengths. Our results are in agreement with the meso-ionic aromatic character of the sydnone system. A detailed The N-p-bromophenylsydnone molecule seen front perpendicular to thephenyl ring. Contours are at arbit- rary intervals and around bromine they are five times as large as around the other atoms. The temperature movement of the bromine atom is seen to be strongly anisotropic. discussion is postponed until the refinement of thij structure and our structure determination of N-phenylsydnone are completed.We thank Professor J. F. Arens for the sample of N-p-bromophenylsydnone and Dr. D. W. Smits Mr. D. Zaagman and Mr. H. Schurer for their assistance. A stipend awarded to one of us (H.B.) from the funds of Professor The0 Goldschmidt is gratefully acknowledged. (Received January 19th 1961.) MARCH1961 ~~ Infrared Detection of Hydrogen Bonding in Gaseous Mixtures The Origin of Broad Bands By J. ARNOLD and D. J. MILLEN J. E. BERTIE (UNIVERSITY GOWER LONDON, COLLEGE STREET W.C. 1) IN an attempt to investigate the origin of the broadening of infrared bands which is frequently associated with hydrogen bonding we have sought the spectra of simple gas-phase complexes. Several gaseous mixtures have been found to show infrared evidence of hydrogen bonding strong bands are observed for the complexes formed in mixtures of hydrogen chloride or fluoride with various ethers and weaker indications are also found in a variety of other mixtures including hydrogen chloride with acetone hydrogen bromide with ethers and hydro- gen fluoride with methyl cyanide.The bands are quite different in character from those1 for mixtures of hydrogen fluoride with compounds which are less basic than those used in the present work e.g. carbon dioxide and sulphur dioxide. Fig. 1 shows the band observed at approximately 2580 cm.-l for a mixture of hydrogen chloride and dimethyl ether. The pressure-dependence of its in- tensity shows that it arises from a 1:1 complex and the shift in frequency to approximately 1880 cm.-l when the deutero-acid is used leads to the assign- ment as v3 (Fig.2) that is essentially the hydrogen- chlorine stretching vibration of the complex. Bands FIG.1. Band in spectrum of'the complex Me,O,HCI. with very similar contours were found for complexes formedby ethyl methyl methyl n-propyls and methyl isopropylethers. The bandsare much less broad than those observed for liquid ether-hydrogen chloride mixtures but still have half-widths which are several times that expected for the normal rotational envelope. It seems important to examine first the possibility of explanation of the band breadth in terms of Ferrni resonance since the breadths and contours of the 0-H stretching bands of gaseous carboxylic acid dimers have been interpreted in this way.2 In the present case this theory would suppose that the con- tour in Fig.1 arises from a superposition of the H-CI stretching frequency and a number of neighbouring overtones or combination bands of the ethereal part of the complex which have become much intensified by stealing of intensity through Fermi resonance. There are in fact combination bands for the di- methyl ether molecule which could plausibly be in- voked in this way. In order to test the possibility of this interpretation the spectrum of the hydrogen- bonded complex of deuterated dimethyl ether was examined. The combination levels available for Fernli resonance in this case are quite different from those of the light ether but the band contour of the-hydrogen-bonded complex was found to be essential- ly unchanged.It appears therefore that Fermi resonance does not play an important part in line- broadening for the compIexes studied here. This view is confirmed by the very close similarity of the band. contour found for complexes formed by hydrogen. chloride with the various methyl ethers mentioned. above. Further confirmatory evidence is obtained from the spectrum of the complex formed by hydrogen chloride and acetone where in spite of the structural change and displacement of the band by 100 cm.-l to higher frequencies compared with di- methyl ether the general features of the contour are preserved. Since the evidence leads to the conclusion that the shape of the band for these complexes is not de- pendent on the internal properties of the organic molecule the problem reduces to seeking a broaden-ing mechanism on the basis of a triatomic model X..-H-Cl.The band contour may then be interpreted in terms of the two expected stretching frequencies v1 and v3 essentially the stretching frequencies of the- hydrogen bond and the H-C1 bond respectively (see Fig. 2). In the assignment shown in Fig. 1 the strong central peak is assigned as v3 14 and the approximately equi-spaced subsidiary bands are assigned as sum. and difference bands of v1 and v3. The breadth of the Burke and Smith J. Mol. Spectroscopy 1959 3 381. Bratoz Hadzi and Sheppard Spectrochim. Acta 1956 8 24. overall band is thus attributed in this interpretation to a progression in v1 accompanying the v3 It0 transition.In Fig. 1 the OtO member of the progres- sion has been assigned to the strongest peak but it may be as Sheppard3 has suggested in a modification of Stepanov’s earlier discussion,* that considerations analogous to the Franck-Condon principle need to be taken into account to understand the intensity distribution; the strongest peak might in this view be assigned to the 14member of the vl progression. There is insufficient evidence to decide with certainty between these possibilities at present but the general conclusion drawn here remain unaffected. The spectra of the complexes formed between ethers and hydrogen fluoride provide additional sup- port for a sum-and-difference-band interpretation.The band structure observed for the complex formed 3700 3500 3300 IIIIII 1 1 11 I cm? FIG.3. Band in spectrum of the coniplex Me,O,HF. PROCEEDINGS with dimethyl ether is shown in Fig. 3 from which it can be seen that the sum band v1 + v3 is in this case clearly resolved from vl. The increase in fre- quency of v1 in passing from hydrogen chloride to hydrogen fluoride (from approximately 100 to 200 cm.-l) is in accord with the smaller mass of the hydrogen fluoride molecule and a stronger hydrogen bond. The hydrogen-bond stretching force constants are found to be approximately 0.11 and 0.30 md/A for the hydrogen chloride and fluoride complexes respectively. The results for the various mixtures examined here suggest that sum-and-difference bands may con-tribute to the broadening observed in the spectra of hydrogen-bonded complexes generally but it is not suggested that it is the only cause of broadening.Even in the present gas-phase spectra the individual bands in the progression have half-widths of about 100 cm.-l. This broadening may arise from predis- sociation although unresolved hot bands associated with the low-frequency stretching and bending vibra- tions of the hydrogen bond must contribute to the width and may be responsible for the whole of it. The band widths indicate that even if predissociation is important the life time of the complex in the excited vibrational state v3exceeds 3 x sec. In addition there is in general the possibility of broadening by the Fermi resonance mechanism to consider.The reason why this effect appears to be important in the carboxylic acid dimers and not in the complexes studied here may be that its operation requires over- tone or combination bands which belong to the acidic part of the complex; anharmonic coupling between bonds separated by a weak hydrogen bond may be too small to be effective. (Received February 8th 1961.) Sheppard “Hydrogen Bonding,” ed. Hadzi Pergamon Press London 1959 p. 85. Stepanov Zhur. fiz. Khim. 1945,19 507; Nature 1946 157 808. The Structure of Crystalline Biphenyl By A. HARGREAVES and S. HASAN RIZVI DEPARTMENT OF SCIENCE MANCHESTER (PHYSICS COLLEGE AND TECHNOLOGY 1) and J.TROTTER (DEPARTMENT UNIVERSITY VANCOUVER OF CHEMISTRY OF BRITISH COLUMBIA 8 CANADA) ELECTRON-DIFFRACTION investigations of biphenyl vapourlJ have indicated that the two rings are not coplanar the angle between their planes being with- in rather wide limits of error 45”. The molecular configuration in the solid was established3 by the observation that the crystals have two molecules in a unit cell of space group P2,/a,this requiring a mole- cular centre of symmetry and hence coplanar rings. Further X-ray study4p5 was not sufficiently detailed to provide more accurate information about the molecular configuration or dimensions. Such a detailed X-ray diffraction investigation of Karle and Brockway J. Amer. Chem. SOC. 1944 66 1974. a Bastiansen Acta Chem.Scand. 1949 3 408. Dhar Indian J. Phys. 1932 7,43. Dhar Pruc. Nat. Inst. Sci. India 1949 15 11. Kitaigorodsky Acta Physicochimica U.R.S.S. 1946 21 575. MARCH1961 crystalline biphenyl is long overdue especially in view of recent example^^^^ of statistically-centred arrangements of non-centred molecules in space group P2Ja. If such an arrangement were present in biphenyl then non-coplanar molecules could be accommodated even in space group P2Ja with z=2. Detailed analyses of the crystal structure of bi- phenyl are now being undertaken independently in Manchester and Vancouver. Careful examination of the photographic records reveals a very weak 030 reflexion (forbidden in P2,/a) but since no other OkO reflexions with k odd are observed it seems that this is possibly a Renninger reflexion.Nevertheless the analyses proceeded without an initial choice between the three possible space groups Pa P2/a and P2,/a. Two plausible trial structures were de- rived one with non-coplanar molecules in space group P2/a and another with centrosymmetrical and hence coplanar molecules in P2,/a. The first of these gave reasonable agreement between measured and calculated structure factors for many reflexions but very poor agreement for some others. The second gave good agreement for all the reflexions and refine- ment has proceeded satisfactorily in space group P2,/a. There has been no indication at any stage of any lowering of symmetry to Pa or of any disordered arrangement of molecules.The hydrogen atoms are reasonably well resolved in (Fo -Fc) maps and there is some indication that the ortho-hydrogen atoms might be displaced from their positions in an ideal planar model with 120" valency angles. It will probably be possible to define these displacements more precisely when refinement is complete. The length of the central C-C bond is 1-50 at the present stage of refinement. (Received December 29th 1960.) Trotter Acta Cryst. 1958 11 355. Robertson Shearer Sim and Watson Nature 1958 182,177. NEWS AND ANNOUNCEMENTS Congresses.-International Congresses. Conference on Corrosion caused by Industrial Water Pollution (JournCes Corrosion dfie aux Eaux Industrielles) is to be held in Likge June 5-7th 1961.Details may be obtained from European Federation of Corrosion Postfach 7 Frankfurt am Main Germany. The Ninth International Conference on Spectro- scopy is to be held in Lyons France on June 5-10th 1961. Details can be obtained from Groupement pour 1'Avencement des Mgthods Spectrographiques 1 rue Gaston-Boissier Paris 15e France. Twenty-first International Congress of the Pharma- ceutical Sciences is to be held in Pisa September 4-8th 1961. Details may be obtained from Inter- nationd Pharmaceutical Federation 1 1 Alexander- straat The Hague NetherIands. Second International Symposium on Chemo-therapy will be held in Naples September 14-17th 1961. Details may be obtained from Dr. P. Rentchnick Secretary-General Case 229 Geneva 4 Switzerland.Colloid Centenary Symposium. An informal dis- cussion meeting sponsored by the Faraday Society will take place on June 27th 1961 in Glasgow to mark the centenary of the paper in which Thomas Graham (First President of the Chemical Society) first applied the colloid in its physicochemical sense (Phil. Trans. 1862 p. 184). Further information may be obtained from Dr. A. J. Hyde The Department of Chemistry The Royal College of Science and Technology Glasgow (2.1. Election of New Fe1lows.-129 Candidates whose names were published in Proceedings for January were elected to the Fellowship. Deaths.-We regret to announce the deaths of the following Mr. E. J. Bond (22.12.60) Managing Director Goodlass Wall and Co. Ltd.; Mr.L. G. S. Hebbs (14.5.60) of Cross and Bevan Consulting Chemists; Dr. A. Henley (8.1.61) biochemist to Little Bromwich Hospital; Mr. J. Kearns (26.7.60) of Dublin; Professor S. S. Miholic (12.8.60) of the Faculty of Science Zagreb; Mr. H. E. Stevenson (23.12.60) of Epsom a Fellow since 1903. Personal.-Dr. E. I. Akeroyd has been appointed Deputy Managing Director of the Permutit Com- pany Dr. T. V.Arden has been appointed a Director of the Permutit Company. Dr. S. Basu of the department of chemistry University College of Science and Technology Calcutta is now visiting Associate Professor in chemistry at the University of Indiana. Mr. A. D. Baynes-Cope has been appointed Principal Scientific Officer in the research laboratory of the British Museum.Dr. C. J. L. Booker University of Cambridge has taken a research fellowship at the division of applied 1 24 chemistry National Research Council Ottawa. Dr. D. W.Broad has been seconded for service in the United States for a period of three years as technical representative for the General Chemicals Division of Imperial Chemical Industries Limited and Plant Protection Limited. Dr. R. S. Edmundson is now lecturer in organic chemistry Institute of Technology Bradford. He was formerly a research chemist with Fisons Pest Control Ltd. Dr. J. P. Elder has taken up an appointment as investigator in the electrodeposition department of the British Non-Ferrous Metals Research Associa- tion. Dr. J. Hannah has joined the Merck Sharp and Dohme Research Laboratories Division of Merck and Co.Inc.as a chemist. Mr. A. J. Harrison has been appointed senior assistant analyst Public Analyst’s Department City of Portsmouth. Mr. A. W.Jackson of the U.K.A.E.A. Dounreay Experimental Reactor Establishment has been appointed manufacturing manager Italy of Beecham Overseas Limited Milan. Dr. J. Leicester has been appointed principal of the Northern Polytechnic London,N.7. Dr. J. Lewis has been appointed a Reader in Chemistry at London University in respect of his work at University College. Mr. R. G. Mason a Director of A. Boake Roberts & Co.Ltd. has been appointed to the board of its parent company A. Boake Roberts & Co.(Holdings) Ltd. PROCEEDINGS Dr.T. M. Oza has been appointed principal of the D.K.V. Arts and Science College Jamnagar Sourashtra India. Dr. S. K. Pavanararn after two years in the Banting and Best Department of Medical Research will be working as assistant to Professor Dr. K. Meyer in the Pharmaceutical Department of the University of Basle from March 1961. Mr. W. W. Reid is leaving England to take up the appointment of chief chemist W. D. & H. 0. Wills (Aust.) Limited Sydney. Dr. H. L. Richardson head of the Agricultural Overseas Section Billingham Division Imperial Chemical Industries Limited and President of the Fertiliser Society has been seconded to the Food and Agriculture Organisation of the United Nations in Rome for two years as Project Manager of FAO’s Fertilizer Programme.This is a world-wide scheme financed by the fertilizer industry as a contribution to the Freedom from Hunger Campaign which aims at increasing food production in the under-developed countries. Dr. G. T.Seaburg Honorary Fellow has been appointed chairman of the U.S. Atomic Energy Commission. Dr. W. G. Schmidt has been appointed chief chemist at Scott Bader and Co.Ltd. Professor P. S. Skell of the Pennsylvania State University will be working at the Institut fur Organische Chemie Universitat Munchen Karlstr. 23 Munchen 2 from January 15th to July 15th 1961. Mr. R. L. Stephens recently joined Charles Beds man Limited London manufacturing chemists as a director and chief chemist. FORTHCOMING SCIENTIFIC MEETINGS London Thursday May 4th 1961 at 7.30 p.m.Simonsen Lecture “Some Pathways in Biosyn-thesis,” by Professor A. J. Birch D.Phil. F.A.A. F.R.S.To be given in the Rooms of the Society Burlington House,W. I. Birmingham Friday May 5th 1961 at 4.30 p.m. Lecture “Synthetic Applications of Metal Car-bonyls,” by Professor R. C. Cookson M.A. Ph.D. Joint Meeting with the Birmingham University Chemical Society to be held in the Chemistry Department The University. Cambridge (Meetings will be held in the University Chemical Laboratory Lensfield Road.) Monday April 24th 1961 at 5 p.m. Lecture “Stereochemistry of Some Dissolving Metal Reductions,” by Dr. M. J. T. Robinson. Monday May 8th at 5 p.m. Lecture “Constituents of Acacia Species; Leuco- anthocyanidins and 4-Hydroxypipecolic acid,” by Dr.J. W. Clark-Lewis Ph.D. F.R.I.C. Wednesday May 17th at 5p.m. Lecture “The Total Synthesis of Tetracyclines,” by Dr. J. H. Boothe. MARCH1961 DWhatil Monday May Sth 1961 at 5 p.m. Lecture “Recent Advances in the Chemistry of D Vitamins,” by Professor B. Lythgoe Ph.D. F.R.I.C. F.R.S. Joint Meeting with the Durham Colleges Chemical Society to be held in the Science Labora- tories The University. Hull Thursday April 27th 1961 at 5 p.m. Lecture “The Electron-spin Resonance of Some Inorganic Crystals,” by Professor H. C. Longuet- Higgins M.A. D.Phil. F.R.S. to be given in the Department of Chemistry The University. (NOTE This meeting was originally arranged for May 4th.) Irish Republic Wednesday April 26th 1961 at 5.30 p.m.Official Meeting and Tilden Lecture “Recent Studies on Many-membered Rings,’’ by Professor R. A. Raphael D.Sc. Ph.D. A.R.I.C. to be given in the Department of Chemistry University College Dublin. Newcastle upon Tyne Thursday May 4th 1961 at 5.30 p.m. Bedson Club Lecture “Anatomy of Haemoglobin,” by Dr. M. F. Perutz F.R.S. North Wales Thursday April 27th 1961 at 5.45 p.m. Lecture “Forensic Science,” by Dr. F. G. Tryhom F.R.I.C. Joint Meeting with the University College Chemical Society to be held in the Chemistry Department University College Bangor. St. Andrews and Dundee (Joint Meetings with the University of St. Andrews Chemical Society to be held in the Chemistry Department St.Salvators College St. Andrews.) Thursday April 2&h 1961 at 5.15 p.m. Tilden Lecture “Electron Configuration and Struc- ture of Transition-metal Complexes,” by Professor R. S. Nyholm D.Sc. F.R.I.C. F.R.S. Friday April 28th at 5.15 p.m. Lecture “Chemistry of Photography,” by Mr. J. M. Taylor. Swansea Monday May 8th 1961 at 4.30 p.m. Simonsen Lecture “Biosynthetic Routes to Phenolic compounds,” by Professor A. J. Birch D.Phil. F.A.A. F.R.S. Joint Meeting with the University College Chemical Society to be held in Department of Chemistry University College. APPLICATIONS FOR FELLOWSHIP (Fellows wishing to lodge objxtions to the election of these candidates should communicate with the Honorary Secretaries within ten days of the publication of this issue of Proceedings.Such objections will be treated as confidential. The forms of application are available in the Rooms of the Society for inspection by Fellows.) Abbiss Terence Pemberton B.A. “The Grove,” Duxford Cambs. Alben James Otis M.S. Ph.D. Department of Physio-logical Chemistry The Johns Hopkins University 725 N. Wolfe Street Baltimore 5 Maryland U.S.A. Arthur Neville Langsford B.Sc. Lincoln College 45 Brougham Place North Adelaide South Australia. Attaway David Henry B.S. 569 South University Boukvard Norman Oklahoma U.S.A. Ayscough Peter Brian M.A. Ph.D. 36 Cardigan Road Headingley Leeds 6. Baburao Kotamraju Ph.D. Department of Chemistry, Illinois Institute of Technology Chicago 16 Illinois, U.S.A.Bacon Neville B.Sc. A.R.C.S. 29 Westerdale Grove Hull. Banerjee Kala Chand M.Sc. 66 West Cromwell Road London S.W.5. Barnes John Conquest Ph.D. Department of Chemistry, Massachusetts Institute of Technology Cambridge Massachusetts,U.S.A. Barr Donald Eugene M.S. P-49 Bucknell Village Lewisburg Pennsylvania U.S.A. Basu Nilaj Kumar M.Sc. Research Department I.C.I. Ltd. Pharmaceuticals Division Alderley Park, Macclesfield Cheshire. Beard John Herbert B.Sc. chemistry Department University College of North Staffordshire Keele Staffs. Bedford Alan Frederick M.Sc. “The Whistlers,” Whitley Hill Henley-in-Arden Solihull Warwicks. Bell. Philiu Alan. 51 Park Lane. Tutburv. Burton-on- Trent Siaffs. Best.John Sheridan. 5 Allerton Grange Drive. Leeds 17. Biddle Brian Norman. 412 Burto; Road,* Midway Burton-on-Trent. Bowering William David Samuel M.Sc. Ph.D. 7 Home End Fulbourn Cambs. Brisdon Brian John B.Sc. “Fairview,” Hilldene Way West End Southampton Hants. Brown Michael Peter Ph.D. 21 Hazel Avenue Guild- ford Surrey. 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H.M.S.O. London. 1958. Subject catalogues headings and structure.E. J. Coates. Pp. 186. Library Association. London. 1960. (Presented by the Library Association.) Dizionario Tecnico Italiano-Inglese. L. Aghina. (Con particolare riferimento alla Industria Chimica.) Pp. 431. Vallecchi Editore. Florence. 1961. (Presented by the publisher.) The chemical industry in Europe 1959-1960 a study prepared by the Chemical Products Committee. Pp. 221. O.E.E.C. Paris. 1961. (Presented by the publisher.) Trattato di chimica industriale. Edited by M. Giua. Vol. 2. Pp. 1285. Unione Tipografico-Editride Torinese. Turin. 1960. (Presented by the publisher.) Chemical instrumentation a systematic approach to instrumental analysis. H. A. Strobel. Pp. 653. Addison-Wesley Pub. Co. Reading Massachusetts.1960. Laboratory management and techniques. J. A. Edwards. Pp. 207. Butterworths Scientific Publications. London. 1960. Pulp and paper chemistry and chemical technology. J. P. Casey. Vol. 2. 2nd edn. Pp. 1249. Interscience. New York. 1960. Department of Scientific and Industrial Research. Fuel Research 1917-1958 a review of the work of the Fuel Research Organisation of D.S.I.R. H.M.S.O. London. 1960. (Presented by the publisher,) Landolt-Bornstein Zahlenwerte und Funktionen aus Physik Chemie Astronomie Geophysik und Technik. Edited by A. Eucken et al. Vol. 2. Part 7.6th edn. Pp.959. Springer-Verlag. Berlin. 1960. Biographisch-Literarisches Handworterbuch der exak- ten Naturwissenschaften. J. C. Poggendorff. Vol. 7a; Part 4 S-Z; section 4.Pp. 448. Akademie-Verlag. Berlin. 1961. Handbook of chemistry and physics :a ready-reference book of chemical and physical data. Edited by C. D. Hodgman et al. 42nd edn. Pp. 3481. Chemical Rubber Publishing Co. Cleveland Ohio. 1960. Wave mechanics and valency. J. W. Linnett. (Methuen’s Monographs on Chemical Subjects.) Pp. 184. Methuen. London. 1960. An introduction to transition-metal chemistry :ligand-field theory. L. E. Orgel. Pp. 180. Methuen. London. 1960. The physicochemical constants of binary systems in concentrated solutions. J. Timmermans. Vol. 4. Pp. 1332. Interscience. New York. 1960. Polarographisches Praktikum. J. Heyrovsky. (An- leitungen fur die Chemische Laboratoriumspraxis Vol. 4.) 2nd edn. Pp. 116. Springer-Verlag.Berlin. 1960. The radiochemistry of beryllium. A. W. Fairhall. Issued by the United States National Research Council Subcommittee on Radiochemistry. Sponsored by the United States Atomic Energy Commission. (Nuclear Science Series NAS-NS 3013.) Pp. 58. Subcommittee on Radiochemistry National Academy of Sciences. Wash- ington. 1960. Perehlorates their properties manufacture and uses. Edited by J. C. Schumacher. (American Chemical Society Monograph Series No. 146.) Pp. 256. Reinhold. New York. 1960. Gmelins Handbuch der anorganischen Chemie. Quecksilber. System-nummer 34. Pp. 466. Verlag Chemie GmbH. Weinheim. 1960. Gmelins Handbuch der anorganischen Chemie. Lithium. Erganzungsband. System-nummer 20. Pp. 525. Verlag Chemie GmbH.Weinheim. 1960. Gmelins Handbuch der Anorganischen Chemie. Schwefel. Teil B. System-nummer 9. 8th edn. Pp. 1130. Verlag Chemie GmbH. Weinheim. 1960. Oxide ceramics physical chemistry and technology. E. Ryshkewitch. Pp. 472. Academic Press. New York. 1960. Chemie und Technologie der Silicone. W. Noll. Pp. 460. Verlag Chemie GmbH. Weinheim. 1960. Silicones. Edited by S. Fordham. Pp. 252. George Newnes. London. 1960. Organo-Metallic Compounds. G. E. Coates. 2nd edn. Pp. 366. Methuen. London. 1960. X-ray absorption and emission in analytical chemistry. H. A. Liebhafsky H. G. Pfeiffer E. H. Winslow and P. D. Zemany. Pp. 357. John Wiley & Sons. New York. 1960. Comprehensive analytical chemistry. Vol. 1b. Edited by C. L. Wilson and D.W. Wilson. Pp. 878. Elsevier. Amsterdam. 1960. Spot tests in organic analysis. F. Feigl. 6th edn. Pp. 675. Elsevier. Amsterdam. 1960. Official methods of analysis of the Association of Official Agricultural Chemists. Edited by W. Horwitz. 9th edn. Pp. 832. Association of Official Agricultural Chemists. Washington. 1960. Allgemeine und angewandte Kolloidkunde. E. Mane-gold. Vol. 1. Pp. 925. Vol. 2. Pp. 1697. Strassenbau. Heidelberg. 1956. Technique of organic chemistry. Edited by Arnold Weissberger. Vol. 1. Physical methods of organic chem- istry. 3rd edn. Part 111. Pp. 2634. Part IV. Pp. 3539. Interscience. New York. 1960. Name index of organic reactions J. E. Gowan and T. S. Wheeler. Pp. 293. Longmans. London. 1960. a-Aminoalkylierung Darstellung und Eigenschaften der Kondensationsprodukte H-Acider Stoffe mit Car- bonylverbindungen und Aminen.H. Hellmann and G. Opitz. Pp. 336. Verlag Chemie GmbH. Weinheim. 1960. Radioactive isotopes in biochemistry. E. Broda. Pp. 376. Elsevier. London. 1960. The chemistry of nucleic acids. D. 0.Jordan. Pp. 358. Butterworths Scientific Publications. London. 1960. Metabolic pathways. Edited by D. M. Greenberg. Vol. 1. Pp. 572. Academic Press. New York. 1960. Lipide metabolism. Edited by K. Bloch. Pp. 41 1. John Wiley & Sons. New York. 1960. Toxicology mechanisms and analytical methods. Edited by C. P. Stewart and A. Stolman. Vol. 1. Pp. 774. Academic Press. New York. 1960. A laboratory manual of analytical methods of protein chemistry (including polypeptides).Edited by P. Alexander and R. J. Block. Vol. 2. Pp. 518. Vol. 3. Pp. 286. Pergamon Press. Oxford. 1960. The composition of foods. R. A. McCance and E. M. Widdowson. Pp. 252. (Medical Research Council Special Report Series No. 297.) 3rd edn. H.M.S.O. London. 1960. Chemistry and technology of fertilisers. Edited by V. Sauchelli. American Chemical Society Monograph Series No. 148. Pp. 692. Reinhold. New York. 1960. The surface chemistry of metals and semiconductors a symposium sponsored by the Office of Naval Research and the Electrochemical Society Columbus Ohio 1959, edited by H. C. Gatos. Pp. 526. John Wiley & Sons. New York. 1960.
ISSN:0369-8718
DOI:10.1039/PS9610000093
出版商:RSC
年代:1961
数据来源: RSC
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