摘要:

1574 ROWE AND LEVIN STUDIES IN THE CLXXIII .-Xt udics in the Dihydmnaphthalene Se?*ies. Part I. The ar- Dih yd yo-a -nap h t h y lanzines and their Deqivatives . By FREDERICK. MAURICE ROWE and ESTHER LEVIN. THE investigation of the conditions governing the conversion of a-naphthylamine into ar-tetrahydro-a-naphthylamine by the action of sodium and an alcohol carried out by one of us (T. 1918 113, 955; J . SOC. Dyers and Col. 1919 35 128) culminated in the proof that the first stage in the reaction is the formation of 5 8-dihydrea-naphthylamine which undergoes isomeric change to the 5 6- or 7 8-compound and that the latter is then reduced to t'he tetrahydroiderivative ( J . SOC. Chem. I d . 1920 39 2 4 1 ~ ) , thus : H NH, /\/\ I l l \/A/ H H NH, H A / \ I l l \/\/ -+ B NH, \/\/ H Them appears to be little doubt that the reason why ar-tetra-hydro-a-naphthylamine has been obtained in the past only when sodium and amyl alcohol have been employed for the reduction, and not when other alcohols have been used is that the normal conditions of the reaction have been suitable for the isomerisation of the intermediate 5 8-dihydro-a-naphthylamine only in the former case.The isomerisation. which is effected by heating with sodium alkyloxide is influenced by both the factors of temperature and concentration of the alkali. There is an important difference in properties between 5 8- and 7 8-dihydro-a-naphthylamine for only the latter is reduced to ar-tetrahydro-a-naphthylamine by treatment with sodium and ethyl alcohol in the absence of an indifferent solvent of high boil-ing point.The present communication consists of a description of the means employed for the isolation of the pure dihydro-a-naphthylamines, the proof of their constitution and the preparation of certain of their derivatives. Owing to the close relationship betweeii a-naphthylanhe its two dihydro-derivatives and its tetrahydro-derivative the discovery of a suitable derivative of these bases which by possessing a dis-tinctive crystalline form in each case would afford a ready means of purification and characterisat.ion was highly desirable DIHYDRONAPHTHALENE SERIES. PART I. 1575 After a number of trials it was found that the most suitable compound to prepare was the benzylidene derivative which was readily obtained in a pure condition from each of the crude bas-, and moreover by hydrolysis of the benzylidene derivatives the bases were readily obtained in a pure state.The following table shows the difference in melting point and crystalline form exhibited by the four benzylidene derivatives : Benzylidene -a - naphthylamine. Small pearly plates. m. p. 70-71O Benzylidene - 5 8 -dihydro - a - Massive rhombic pyra-naphthylamine. mi& with brachy-domes and brachv-m. p. 69'. pinalioids. naphthyl amine. are a combination of a rhombic prism and pyramid with brachypinakoicis. thylamine. with brachypinakoids. Benzylidene - 7 8 - dihydro - a- Long crystals which m. p. 64'. Benzylidenetetrahydro-a - naph- Flat rhombic prisms m. p. 61.6'.The melting point of each of these compounds was depressed by admixture with any other. It should be noted that although ar-tetrahydro-a-naphthylamine has been frequently compared with o-2-xylidine in the past as far as the formation of a crystalline benzylidene derivative is concerned it is more strictly comparable with p-xylidine as the isomeric xylidines form non-crystalline benzylidene derivatives. The benzylidene derivatives of the three hydrogenated bases readily form large crystals and it is a simple matter to obtain well-formed crystals of these compounds weighing upwards of 1 gram each. Both 5 8- and 7 8-dihydro-a-naphthylamine condense with diazonium salts with the direct formation of aminoazo-compounds, and they may also be diazotised and combined with amines or phenols forming azo-dyes which differ in shade from similar azo-dyes derived from a-naphthylamine or ar-tetrahydro-a-naphthyl-amine.The relation of the shades of similar azo-dyes produced from the four amines by the two different methods is shown in the following table : Naphthaleneazo-p-naphthol ........................ 5 8-Dihydronaphthaleneazo-~-naphthol ......... 7 8-Dihydronaphthaleneazo-p-naphthol ......... Tetrahydronaphthaleneazo-p-naphthol.. .......... p-8ulphobenzeneazo-a-naphtlhylamine ......... p-Sulphohenzeneazo-5 8 - dihydro -a - naphthyl-p-Sulphobenzeneazo - 7 8 - dihydro -a - napht.hy1-p - Sulphobenzeneazotetrahydro -a -naph thylamine amine. amine. Clarot. Red rather bluer than Para-Red. Orange-red. Orange.Reddish-brown. Brownish-yellow Dull orange. Vivid orange 1576 ROWE AND LEVIN STUDIES IN THE As the four acid dyes are velry sensitive to acids the shades are those produced after the dyed material had been soaped. The shade produced by an azo-derivative of 5 8-dihydro-a-naphthylamine is more nearly related to that produced by a similar azo-derivative of a-naphthylamine whilst the shade produced by a 7 8-dihydro-a-naphthylamine derivative is more nearly related to that produced by a similar tetrahydro-a-naphthylamine derivative. The crude base was prepared from a-naphthylamine by the action of sodium and ethyl alcohol in the presence of an indifferent solvent of high boiling point (Farbenfabriken vorni. F. Bayer & Co., D.R.-P. 305347). A mixture of 400 C.C.of dry solvent naphtha (b. p. 139O) and 30 grams of sodium contained in a flask fitted with a reflux condenser was boiled and a solution of 34 grams of a-naphthylamine in rather more dry ethyl alcohol than is necessary to dissdve the sodium added drop by drop through the condenser. Boiling was continued until all the sodium had disappeared; an excess of alcohol is desirable in order to complete the reaction as quickly as possible. The mixture was poured into water the solvent naphtha layer separated acidifield with hydrochloric acid, and the solvent naphtha removed by distillation in a current of steam. The residue was filtered from a little tar and allowed to crystallise. The hydrochloride was basified the base allowed to crystallise and after pressing well it was melted with 10 per cent.of its weight of toluene cooled in a freezing mixture of ice and salt filtered quickly and dried. It was converted into the benzylidene derivative by mixing 31 grains of the base with 15 grams of benzaldehyde and allowing to remain until thel mixture solidified. The product was pressed well and crystallised twice from light petroleum (b. p. 70O). Benzylidene-5 g-dihydro-a-nczpht~~iylami,i e forms massive rhoiiibic pyramids with brachydomes and brachypinakoids inelting at 6 9 O (corr.) (Found C = 87-75 ; H = 6.51. C,;H,,N requires C = 87.55 ; H=6.44 per cent.). The benzylidene derivative was hydrolysesd by warming with hydrochloric acid and the benzaldehyde removed by distillation in a current of steam. The residue after filtration n-as basified and the base distilled DIHYDRONAPHTBALENE SERIES.PART I. 1677 5 8-Dihydro-a naphthylaminp forms large colourless rhombic plates or needles melting at 3'i.So (corr.) and boiling a t 2 4 7 O / 408 mm. and the hydrochloride forms sto'ut colourless needles. Both the base and the hydrochloride turn pink on exposure t o air (Found C = 82.59 ; €I = 7.65. C,,€I,,N requires C = 82.76 ; l-3 =7*58 per cent.). When the amine was diazotised and treated with an alkaline solution of sodium stannite Ag- or 1 4-dihydronaphthalene con-sisting of colourless plates melting at 24.5-25O was obtained, which formed a compound with mercuric acetate crystallising from benzene in colourless needles melting a t 121° and a dibromide, long glistening thin prisms melting at 71.5-72O.5 8-Dihydroaccto-a-?iap~~thalide crystallises from alcohol in colourless silky needles melting at 163O (corr.). It may be1 sub-limed unchanged (Found C = 77.15 ; H = 7.01. C,,HI30N requires C = 77.01 ; H = 6.95 per cent .). 2 4 -D ini trop h en y l-5 8-di hy d r o-a-72 np h t h ylamine was obtained by heating under reflux a mixture of 5 grams of the base 6.9 grams of 4-chloro-m-dinitrobenzene dissolved in 100 C.C. of alcohol and a solution of 4.6 grams of crystallised sodium acetate in a little water. The product crystallises from acetic acid or toluene in reddish-brown rhombic plates melting at 144O' (corr.) (Found : C=61*89; €€=4*27. C,,fI,,0,N3 requires C=61*74; H=4.18 per cent .). The sodium salt of p-sulphobenzeneazo-5 8-dihydro-a-naphthyl-mnine was obtained by the addition of diazotised sulphanilic acid to an aqueous solution of the hydrochloride of the base.The product which separated as a crystalline precipitate was dissolved in the minimum quantity of boiling dilute aqueous sodium carbonate and on cooling the salt separated in glistening brown plates. 6 S(0r 7 g ) - D ~ ~ . y d r o - a - n a p k t h y l ~ ~ ~ n e , a-Naphthylamine was reduced to 5 8-dihydro-a-naphthylamine, as already described. When all the sodium had disappeared the mixture was distilled until the internal temperature rose to 140°, and heating was continued a t that temperature for one hour, during which period ammonia was evolved o'wing to some decom-position of the amine. The mixture was poured into water the 3 M 1578 STUDIES IN THE DIHYDRONAPHTHALENE SERIES.PART I. oily layer separated acidified with hydrochloric acid and the remainder of the solvent naphtha removed by distillation in a current of steam. The rwidue was filtered from tar and allowed to crystallise. The hydrochloride separated in straw-coloured, feathery needles quite different in appearance from the less soluble hydrochloride of the isomeric base. The hydrochloride was basified the base extracted with ether and converted into the benzylidene derivative as described for the isomeric compound. Benzylidene-7 8-dihydro-a-naphthylamine separates from light petroleum in long crystals which are a combination of a rhombic prism and pyramid with brachypinakoids melting a t 64O (corr.) (Found C = 87.39 ; H = 6.48.C,,H,,N requires C = 87.55 ; H = 6.44 per cent .) . The benzylidene derivative was hydrolysed by warming with hydrochloric acid the benzaldehyde removed by extraction with ether the solution of the hydrochloride basified extracted with ether and the base distilled. 7 8-Dihydro-a-nuphthylamine is a colourless oil boiling a t 180-182°/30 mm. which rapidly darkens on exposure to air and is less stable than the isomeric base. It did not crystallise when maintained a t - 1 8 O for a considerable time (Found C=82.66; €1=7*71. C,,H,,N requires C=82*76; H=7.58 per cent.). When the amine was diazotised and treated with a solution of alkaline sodium stannite hl- or 1 2-dihydronaphthalene crystal-lising in coloarless plates melting a t -go was obtained which formed a compound with mercuric acetate of high melting point, insoluble in benzene and a dibromide stout prismatic crystals melting a t 70-71'.7 8-Dihyclroaceto-a-nuphthalide forms colourless silky needles melting a t 153O (corr.). The yield was not good olwing to the instability of the amine a t the temperature of acetylation (Found : C = 77-00 ; H = 7.01. C,,HI30N requires C = 77.01 ; H= 6.95 per cent.). 2 4-Dinitropheny 2-7 8-dihydro-a-nupht hylamine was obtained in a similar manner to that used for the isomeric compound. It crystallises from acetic acid or toluene in glistening reddish-brown leaflets or needlw melting at 136O (corr.) (Found C=61*78; H = 4.13. The sodium salt of p-sulpho benzeneazo-7 8-dihydro-a-naphthyl-amine was obtained in a similar manner to that used for the immeric compound. It crystallises in reddish-brown glistening plates. ar-Tetrahydro-a-naphthylamine was readily obtained from 7:8'-dihydro-a-naphthylamine by adding 15 grams of sodium to a C,,H130,N3 requires C = 61-74 ; H = 4.1 8 per cent .) THE FORMATION AND STABILITY OF SPIRO-COMPOUNDS. 1579 boiling solution of 10 grams of the base in 200 C.C. of dry ethyl alcohol. The mixture was worked up in the usual manner. For purposes of comparison benzyliclene-ar-tetrah.ydro-a-nuphth ylumine was prepared from ar-tetrahydro-a-naphthylamine. It crystallises from light petroleum in flat rhornbic prisms with brachypinakoids melting a t 6 1 . 5 O (corr.) (Found C= 86.70 ; H = 7.33. C,,H,,N requires C = 86.81 ; €I = 7-23 per cent.). DYESTUE'FS RESEARCH LABORATOBY, MUHICIPAL COLLEGE OB TECHNOLOGY, MANOHESTEB. [Received November loth 1920.

ISSN:0368-1645    

DOI:10.1039/CT9201701574

出版商:RSC    

年代:1920

数据来源: RSC

摘要:

THE FORMATION AND STABILITY OF SPIRO-COMPOUNDS. 1579 CLXXIV.-The Formation and Stability of Compounds. Part 111. spiro- Compounds c y clo Pentane. By OSCAR BECHER and JOCELYN FIELD THORPE. spiro-f+om IN Part I of this series (Beesley Ingold and Thorpe T. 1915, 107 1080) attention was directed to the fact that when the normal angle between two of the valencies of a carbon atom is changed as the result of their inclusioln in a ring groups attached by means of the other two valencies apparently take up an altered relative position. The hypothesis which was suggested in this connexion was that when two of the valenciee a and b of a carbon atom are maintained by their participation in a ring a t some inclination other than the normal the two remaining valencies, c and d will assume directions which enclose an angle differing from the normal in the opposite sense.In particular if 2p be the angle formed by the valencies a and b the angle 20 between the directions taken up by the valencies c and d will be deter-mined by the condition that these directions are equally inclined to each other and to the directions occupied by the valencies u and b . Thus the angles between the lines of action of the follow-ing pairs of valencies namely a and c b and c a and d b and d , are all equal to 28. From this condition it follows that i f 2P is greater than the normal angle (namely the angle 2tan- v S = 109O28/16// subtended a t the centre of a regular tetrahedron by one cf its sides) then 20 will be less than this amount and vice versa.A general equation from which 28 can be calculated when 2/3 is known may very readily be obtained by the following method. 3 H 1680 BECXER AND THORPE THE FORMATION AND Let a small sphere (see figure) be described around the carbon atoni as centre and let the points A R C and D in which tho lines of action of the valencies a b c and d cut the sphere be joined by great circles. Let M and N be the two points of inter-section of the great circle A B with the great circle CD M being nearest A and B and N nearest C and B. This construction involves the description of a number of right-angled spherical triangles and1 a consideration of any of them such as for example, the triangle BC’M shosws that The solution of this equation is C O ~ 28 =COS p . COS (r - e).cos e = j ( J c 0 ~ 2 p + s -COS p) fo’r all real values of the angles. The gelneral character of this solution is exhibited in the following table in which 28 is calcu-lated for a number of values of 2P which the different alicyclic structures may be‘supposed to determine : Ring. cycZoPropane ......... cy cl oBu t ane ......... cycZoPentane ......... cycloHexano ......... cycloHeptano ......... cycZoOc tam ......... No ring ............... 28. 60” 0’ 0” 90 0 0 108 0 0 120 0 0 128 34 17 135 0 0 109 28 16 2P. 116“ 55’ 66” 112 58 44 109 46 13 107 14 58 105 16 3 103 40 38 109 28 16 From this table it will be seen that in one case namely that corresponding with the cyclopentane ring the angle 28 differs from the normal angle by some minutes of arc only.This case, therefore is of particular interest since groups attached to two of the valencies of a carbon atom the remaining t’wo valencies o STABILITY OF SPIRO-COMPOUNDS. PART III. 1581 which are bound in a cyclopeiitane ring should differ but little in their reactions and particularly in their interactions from corresponding groups in a similar structure froni which the cyclopentane ring is absent. The present communication deals with this case the comparison instituted being between 68-dimethylglutaric acid (I) on the one hand and cyclopentane-1 1-diacetic acid ( I T ) on the other and it is shown that the] reactions of desrivatives of the latter acid follow very closely the analogies presented by the corresponding deriv-atives of the former.I n Part I the result of an experimental study of cgdohexaiie-1 1-diacetic acid (111) was described and it was shown that the (111.) behaviour of certain derivatives of this substance differed very notably from that of the corresponding nienibers of the dimethyl-glutaric series. The principle points of contrast presented themselves in coniiexion with : (a) The unstable character which the dibromo-ester of cycTo-hexane-l 1-diacetic acid (IV) possesses owing to the tendency i t has to eliminate ethyl bromide and to pass into the bromoclactone ester (V) whereas the corresponding dibronlo-ester of 60-dimethyl-glutaric acid (VI) is stable. C HBr*CO,Et CH(CO,Et)*? Me CH Br CO,Et C6'310<~~Br*~0,Et pFllo<CHBr--CO Me>C<CHBr*CO,Et ( b ) Ths great stability of aydohexanesyirocyclopropanedicarb-oxylic acid (VII) which for example resists the action of con-centrated hydrochloric acid a t 240° whereas the corresponding dimethylcyclopropanedicarboxylic acid (caronic acid) (VIII) is transformed into terebic acid (IX) by 5 per cent.acid a t 200O. (IV. 1 W e ) (VI.) CH*CO,H Me CH=CO,H O--CMe, C6Hlo<~Irl co,a M e>'<h *CO,R ~ o ~ c H ~ ~ H*CO,II (VII.) (VIII.) PX.) C,H,,:CH*CO,H (X.) (c) The tendency to tho formation of cyclohexylideneacetic acid (X) when the bromo-lactone ester is treated with alkalis 1582 BECKER AND THORPE THE FORMATION AND Clearly the fact that groups can be eliminated from the acetic acid residues more readily in the cyclohexanediacetic series than in the dimethylglutaric series and also the fact that the products formed by the establishment of a bond between the residues are more stable in the cyclohexane series are both in full accord with the idea that the acetic acid residues are closer together in the cyclohexanediacetic series than in the dimethylglutaric series as the calculation of 2P fo'r the cyclohexane ring indicatw.On the other hand the relation which the conversion of the bromo-lactone ester into cyclohexylideneacetic acid large quantities of which are produced under widely varying conditions,+ bears to molecular structure is not very clear although it is doubtless connected with the greater stability which according to the hypothesis here put forward the cyclohexane ring should bestow on the semi-cyclic double bond when comparison is made with the double bond in dimethylacrylic acid CMa2:C€I*C0,H.On the basis of the hypothesis outlined one would therefore expect that in regard to the elimination of the groups from the acetic acid residues and also in regard to the stability of the products in which a bond has been established between the acetic acid residues and as regards the tendency to the formation of an unsaturated monobasic acid the derivatives of cyclopentanediacetic acid would resemble those of dimethylglutaric acid rather than those of cyclohexanediacetic acid in spite of the fact that in mole-cular weight and in cyclic structure cyclopentanediacetic acid comes closer to the latter. Actually the expectation has been realised. I n particular it is shown in the present paper that: (u) As regards the stability of its dibromo-ester cyclopentane-diacetic acid resembles dimethylglutaric acid more closely than i t resembles cyclohexanediacetic acid.Thus on distilling et Ivy! aa'-dibromocyclopentccne-l 1 -diacetnte (XI) under diminished pressure the major portion passes over unchanged some 10 per cent. only being changed into the bromo-ester (XII). In similar circumstances the cyclohexane bromo-ester is completely converted into the bromo-lactone ester and ethyl bromide. Ethyl dibromo-dimethylglutarate in small quantities distils practically without * Under certain conditions however the cyclohexylideneacetic acid itself becomes unstable and passes quantitatively into the isomeride with the double bond in the ring.This is therdore the product actually isolated in the circumstances (Zoc. cit.) STABILITY OF SPIRO-COMPOUNDS. PART ITS. 1583 decomposition although the corresponding bromo-lactone ester can be obtained by repeated slow distillation. ( 6 ) cycZoPentanespirocyclopropane-1 2-dicarboxylic acid (XIII) does not possesses the same general stability as the corresponding cyclohexane derivative. Thus whilst the latter is stable to con-centrated hydrochloric acid at 240° the former is rapidly demm-posed even a t 200° by 5 per cent. acid. Under these conditions, the dimethyl analogue caronic acid is also decomposed. $?H,*CH CH CO,H CA,*CH >c<bH*CO,H (XIII. ) (XIV.) $JH,*CH CH(CO,E)*C C H,*C H >c<CH(OH)--CO (XV.) (c) cycZoPentylideneacetic acid (XIV) can be isoiated from the product obtained by hydrolysing the bromo-lactone ester (XII) with alkalis.It is however apparently formed in very much smaller amount than is the case with the correspo'nding cyclo-hexylidene derivative. I n the dimethylglutaric series this curious reaction has not yet been observed a t all and indeed it may be peculiar to cyclic compounds. I n view of these results the chemistry of cyclopentanediacetic acid and its derivatives may be said to come well into line with the general view which forms the present working hypothesis underlying the experiments recorded in this series of papers. Ethyl ad-dibromocyclopentane-1 1-diacetate (XI) is produced by the action of phosphorus pentabromide and bromine on the anhydride of cyclopentane-1 1-diacetic acid (XIX) and subse-quent treatment with alcohol.From this a considerable quantity of the bromo-lactone ester (XII) can be abtained by repeated dis-tillation. The lactone on hydrolysis with 25 per cent. aqueous potassium hydroxide yields two compounds namely cyclopentyl-ideneacetic acid (XIV) (Wallach Annalen 1902 323 159 ; 1906, 347 324; Harding and Haworth T. 1910 97 493) and the lnctonic acid of aa'-di~ydro~~cyc1a~)entane-l I -&acetic acid (XV). The similarity between the open-chain series and that contain-ing the five-membored ring is also shown in the behaviour of the diacetic acids towards mono-bromination. Thus the mono-bromination of cyclopentanediacetic acid leads to the formation of ethyl a-bromocyclopentane-1 I-diacetic acid (XVI) in the same manner as dimethylglutaric acid yields ethyl a-bromodimethyl-glutarate.It will be noted that the a-brominated ester of cyclo 1584 BECKER AND THORPE THE FORMATION AND hexane-1 1-diacetic acid could not be obtained (T. 1915 107, 1084). I n the cases of both dibromination and monobromination besides the neutral esters obtained one and the same acid (XVII) is pro-QH,-CH CHBr*CO,Et CH,. CH2>C<CH2* Copt (XVI.) (XVII. ) 7 El,* C H C H( C0,H) ? CH,*CH2>c<CH,--- CO (XVIII.) ducecl. The acid product of broniination as well as the neutral ester on treatment with highly concentrated potassium hydroxide solution yields in addition to the lactone of a-hydroxycyclo-pentanediacetic acid (XVIII) both the trans- and cis-modifications of the spiro-acid (XIII) and (XX).trans-cycloPentanespirocyclopropane-1 2-dicar boxylic acid on distillation under atmospheric pressure yields the anhydride (XIX) of its cis-isomeride from which the cia-acid (XX) can be obtained in the usual manner. H* C* CO,H H*C*CO,H I CH,*CH, I (XIII.) (XX. ) FH,*CH CH*CO (XIX.) CH,*CE€[ >C<bH.C(J>O It should be added for the benefit of those who may wish to prepare the substances described in this paper that many difficul-ties were encountered owing to the remarkable lack of tendency to crystallise which they exhibit. At one tinlei it was thought that the research would have to be abandoned for this reason but, owing to its importance in relation to the general scheme of work a t present being undertaken in these laboratories it was necessary that every effort should be made to bring it to a successful con-clusion.As will be seen from the experimental portion this was ultimately accomplished although in some cases the compounds described became crystalline only after keeping for several months. EXPERIMENTAL. Dibromination of cycloPentane-l 1-diacetic Acid. Dibromination was effected by treating 23.2 grams of the acid, prepared by Kon and Thorpe's method (T. 1919 115 700) wit STABILITY OF SPIRO-COMPOUNDS. PART 111. 1585 115 grams of phosphorus pentabromide and after a clear solution had been obtained by gentle heating on the water-bath adding gradually 43 grams of bromine. The interaction was completed by heating until the halogen had disappeared and when cold the dibromo-acid bromide was poured into' 500 C.C.of well-cooled absolute alcohol. The oil which was precipitated by water was extracted by ether and the ethereal extract thoroughly shaken with dilute aqueous sodium carbonate solution to remove acid products. The ether was then evaporated. Ethyl aaf-dibromo-cyclopentane-1 1-diacetate (XI) boils at 211-212°/30 mni. and is a colourless fairly mobile oil (Found Br = 39-39. C,3H,,0,Br, requires Br = 40.0 per cent .). aaf-l)ibronzocyclopcii t a n e - 1 I-clincetic acid, C4H, C( CHBr* CO,H),, is obtained as a white crystalline precipitate when the dibromo-acid bromide obtained in the above experiment is poured into formic acid. It separates from formic acid in small prisms which melt at 177O (Found Br=46*43.C,HI2O4Br requires Br = 46.5 per cent.). Lactone of Ethyl a-Bromo-a-hydroxycyclopentane-1 1-diacetate (XII). The mixed cis- and trans-lactones of this formula are produced by the repeated distillation of the dibromo-ester whereby ethyl bromide is also formed. The mixture boils a t 220-222O/25 mm., and is a colourless viscid oil (Found Br=27.71. Cl1H,,O4Br requires Br= 27.5 per cent.). As the lactones showed no tendency to crystallise we were unable to1 separate the cis- and trans-isomerides. IXydrolysis of the BTomo-lac ton e. (a) cycloPentylicZeneace t ic Acid (XIV).-This acid can be prepared in small yield by hydro-lysing 12 grams of the lactone by means of 60 C.C. of a 25 per cent. aqueous potassium hydroxide a t the boiling point for two holurs.The clear solution is evaporated1 to a small bulk and acidified when the unsaturated acid separates and can be purified by recrystallisation from water. It melts at 52O (Found: C = 66.53 ; B= 7.94. (b) The lactonic acid of aa-dihy~Zrox~cycloerLtane-l 1-diacetic acid (XV) is obtained from the filtrate after the separation of cyclopentylideneacetic acid by extracting it after saturation with ammonium sulphate with ether. Ths product left when the ether is evaporated is a gum which solidified only after being kept f o r some months. It crystallises from benzene in small colourless Calc. C = 66.7 ; H = 7.9 per cent.) 1586 BECKER AND THORPE THE FORMATION AND prisms which melt a t 139-140O (Found C=53.88; H=5.98. C,H,,O requirw C = 54-0 ; H = 6.0 per cent.).The melting point of this compound would suggest that it is the trans-modification corresponding with the trans-modification of the higher homologue (T. 1915 107 I l O O ) which melts at 145O. Mon>obrornination of cycloPentnne-1 1 I-diacetic A cid. Twenty-six grams of cydopentanediacetic anhydride prepared by treating the acid with acetyl chloride (T. 1919 115 700), were mixed with 80 grams of phosphorus pentabromide and 28 grams of bromine added the process of bromination being the same as that already described in the case of dibromination. Ethyl aa'-Bromo-cyclopentane-1 1-diacetate (XVI).-The ester was distilled under diminished pressure and obtained as a nearly colourless oil which, however was shown by analysis to contain a small quantity of unbrominated ethyl ester o r possibly the corresponding lactone ethyl ester.Ultimately i t was found that a comparatively pure product could be obtained by using 9 per cent. excess of bromine (that is 31 grams instead of 28). The ester produced in this way boiled a t 192O/17 mm. (Found Br=25-43. C,3H210,Br requires Br=24*9 per cent.). (2) The Acid Product of Bromination. Ethyl Hydrogen a-Bromocyclopentane-l 1-diacetic A cid (XVII) .-This acid ester is identical with the one produced by acidifying the sodium carbonate extract from the dibromination experiment. I n the present instance it is obtained in the same manner from the mono-brominated product. It cannot be distilled without decomposition, but gave a fairly good analysis in the crude state (Found: Br =26*12.C,,Hl,O,Br requires Br =27.2 per cent.). (a) The Lactone of a-Bydroxycyclo-pentane-1 I-diacetic Acid (XVIII) .-By the action of boiling aqueous sodium carbonate on the above acid product o'f bromin-ation the lactone is obtained as sole product. Eight grams of the crude acid bromo-ester were hydrolysed by boiling for six hours with a solution containing 4.5 grams of anhydrous sodium carbonate in 45 C.C. of water. The clear solution obtained in this way was extracted repeatedly with ether the ethereal solution yielding 5 grams of a viscid gum on evaporation. This material distilled a t 228-230°/15 mm. but several months elapsed before it com-menced to crystallise. It is freely soluble in all the usual organic solvents with the exception of light petroleum in which it is insoluble and can be purified by treatment with the 40-60° (1) The Neutral Product of Brominution.The Action of Alkalis STABILITY OF SFIRO-COMPOUNDS. PART IIT. 1587 fraction of this solvent when it is obtained as a white crystalline powder melting a t 69-70° (Found C = 58.59 ; H = 6.65. C,H,,O, requires C = 58.7 ; H = 6-6 per cent.). The silver salt of the corresponding dibasic acid is precipitated when silver nitrate solution is added to a solution of the ammonium salt which has been prepared by heating a solution of the lactone in excess of dilute ammonia (Found Ag = 51.90. C,R120,Ag, requires Ag = 51.9 per cent.). t rails-cyclo Pentariespirocyclopropn e-1 2 -riicar boxyl ic A cid (XIII) , This spiro-acid is best prepared by the action of very concen-trated aqueous potassium hydroxide on the acid bromo-ester but i t can also be prepared from the neutral bromo-ester if the right conditions are observed.(a) From the Acid Bromo-ester.-A solution containing GO grams of potassium hydroxide in 50 C.C. of water was heated until the temperature reached 150° when 19 grams of the acid product of bromination were cautiously added as rapidly as possible and the vigorous reaction was allowed to subside. When cold the solid mass was dissolved in water and acidified with hydrochloric acid when crystals of the spiro-acid separated on cooling. (b) From the Neutral Bromo-ester.-Fifteen grams of the neutral monobromwster were mixed with an alcoholic potassium hydroxide solution containing 15 grams of the hydroxide in 9 C.C.of water and 60 C.C. of absolute alcohol and heated for ten hours. The solution freed from alcohol yielded the spiro-acid on acidification. The acid crystallises from water in colourless plates melting a t 2 1 1 O (Found C =58-79 ; H = 6.46. C,13,204 requires C=58.7; H = 6 - 6 per cent.). The silver salt is a white. crystalline powder (Found Ag=54.19. C,H,,04Ag2 requires Ag = 54.2 per cent.). The dz’anilide C 4 H 8 C < X ~ ~ 0 0 ~ ~ ~ was prepared by heating the acid with excess of aniline a t 200° for two hours and recrystal-lising the product from dilute alcohol. It forms white silky needles melting a t 289O (Found C = 75.34 ; H = 6-71. C,,H2,O2N, requires C = 75.4 ; H = 6.6 per cent.).cis-cycloPentanespirocyclopropane-1 2-dicar boxylic Acid (XX) . The filtrate from the trans-acid was extracted repeatedly with ether the ethereal solution yielding a gum on evaporation which became part,ly solid on keeping. This was found to be a mixtur 1588 THE FORMATION AND STABILITY OF SPIRO-COMPOUNDS. of the lactone (XVIII) and the cis-acid Irom which the latter could be separated by spreading on a porous plate. The cis-acid is ho'wever best prepared by distilling the trans-acid under diminished pressure and treating the anhydride of the cis-acid which is then formed with water. The cis-syiro-acid crystallises from a small quantity of water in white flatteneld prisms which melt a t 170O. It is much more readily soluble in water than the trans-isomeride (Found C= 59.03 ; H == 6.55.C,H,,O requires C=58*7; H=6.6 per cent.). The anhydride of the cis-acid (XIX) was prepared by the action of acetyl chloride on the cis-acid and also as mentioned above, by distilling the trans-acid under diminished pressure. As it showed no tendency to crystallise it was characterised by con- by treating H*CO*NHPh version into the anilic acid C,B,:C<y CH*CO,H it in benzene solution with the calculated quantity of aniline. It crystallises from dilute alcohol in small needles which melt a t 1 8 7 O (Folund C= 69-40 ; H = 6.62. C,,H,,O,N requires C = 69.5 ; H=6*6 per cent.). The Stability of the trans-Modification.-It was soon seen that the trans-acid was very much less stable towards concentrated hydrochloric acid a t 250° than the corresponding cyclohexane derivative for under these conditions it was found to undergo complete decomposition. The action of 5 per cent. acid was there-fore tried and it was fcund that whereas at 150° the acid remained unchanged even on prolonged heating at 200° it was completely decomposed in the course of an hour. Under the conditions, therefore which transform caronic acid into terebic acid the trans-cyclopentanespiro-acid is broken down into several products, of which free carbon is the chief. The cis-acid behaved in the same way although there was evidence that it was partly trans-formed into the trans-acid prior to decomposition. Otherwise the trans-acid like similar acids of the series is remarkably stable. It can for example be boiled for a short time with acid perman-ganate without change and is stable to alkaline permanganate in the cold. I n conclusion we wish to express our thanks to Mr. C. K. Ingold and to Mr. G . A. R. Kon for much help in this very difficult piece of experimental work during the absence of one of us abroad. THE IMPERIAL COLLEUE OF SCIENCE AND TECHNOLOUY, SOUTH KENSINGTON. [Rrcriued O C ~ O ~ P Y Sfith 1920.

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DOI:10.1039/CT9201701579

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年代:1920

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DISODIUM HYDROGEN PHOSPHATE DODECAHTDRATE. 1589 CLXXV.-BisocZium Hyclr.oye7L Dodecahydrlc te. By DALZIEL LLEWELLYN HAMIWICK HECTOR and HENRY Boom. Phosphate KENNETH GOADBY, THE system disodium hydrogen phosphatewater has been investi-gated by Shionii ( i l l e m . Coll. Sci. E n g . Kyoto 1908 i 406) who showed that three hydrates (Na,HPO '1 2 H,O N a,H P 0 ,7 H,O , Na,HP0,,2H20) are capable of existence in contact with saturated aqueous solutions at different temperatures. I n the neighbour-hood of looo anhydrous salt is the stable solid phase. Shiomi records the following invariant points (breaks in a solubility curve) : Solid Phases. Temperature. Na2HP0,,12H,0-Na,HP04,7H,0. ........................ 36-48' Na,HP04 7H20-Na,HP0,,2H,0. ........................48.0 Na,HPO, 2H,O-Na,HP04 ................................. 95.2 The eutectic temperature (ice Na,HP04,12H20-solution) is given as -0.45O by Rudorf A 7 1 n . I'hys. Chern. 1864 [ii] 122, 337) and as -0.9O by Guthrie ("Recueil de Const'. Phys."). Certain peculiarities of the dodecahydrate having led to the suspicion that Shionii's analysis of the system was incomplete the various hydrates were examined by means of heating and cooling curves. Arsenic-f ree dodecahydrate was recrystallised and pre-parations of the other hydrates were made from it. The dihydrate is conveniently prepared by boiling the finely powdered dodeca-hydrate with ethyl alcohol. The heptahydrate was prepared by fusing together the appropriate mixture of dodecahydrate and dihydrate and cooling.The finely powdered hydrates were suspended in xylene and stirred with a thermometer in jacketed tubes immersed in a glycerol bath. Well-defined arrests were obtained on the heating and cooling curves at' the following temperatures : Na,HP04,2H20-Na2HP0 95.20 94.92 95.00 94.90 94.92 (corrected) ; mean 94.97O. Na,HP04,7H20-Na,HP0,,2H,0 48.5 48.0 48.0 47.8 48.0, 48.2; mean 48.09O. Na2HP0,,12H,0-Na2HP0,,7H20 35.0 35.1 35.4 35.0 35.0, 35.05 35.0 35.0 35.6 35.05; mean 35.0°. At the same time sharp breaks in the heating and 'cooling curves for the dodecahydrate were observed a t 29.6O (29.6 29.6 1690 HAMMICK QOADBY AND BOOTH: 29.5 29.55 29'65O). From these results it appeared that Shiomi's points a t 95.2O and 36-45O were probably too high. The transition temperature a t 35*0° found by the authors is in agreement with Tilden's (T.1884 45 409). It seemed moreover likely that tho break in the heating and cooling curves observed at 29.6O indicated a change of phase a t that temperature. In order to test this conclusion crystals separating from a solu-tion od sodium phosphate at 33O were collected and examined. They closely resemble in appearance the ordinary large monoclinic crystals obtained a t the ordinary temperatures; on keeping how-ever in a closed tube a t the ordinary temperatures (15-20°) they become opaque and friable. Analysis of the clear crystals gave the following result 2.3910 grams gave 0.7505 gram of magnesium pyrophosphate whence the number of molecules of water of crystallisation for one molecule of disodium hydrogen phosphate is 11.95.The solid phase in equilibrium with solutioas between 29'6O and 35.0° is therefore a dodecahydrate. Crystals of ordinary dodeca-hydrate kept in a closed tube in a thermostat above 29'6O (at 33') slowly lose their transparency and rigidity whereas crystals formed between 29'6O and 35-0° undergo no change. The conclusion is therefore drawn that disodium hydrogen phosphate dodecahydrate exists in two forms a and /3 the a-form being stable between 29.6O and 35*0° and the ordinary or p-form, below 29.6O. Shiomi's solubility data (Zoc. c i t . ) give no indication of any change in the solid phase in equilibrium between Oo and 36*5O. Solubilities were therefore redetermined from the eutectic tempera-ture to above the transition temperature of the a-dodecahydrate into hep t a hydrate.The temperature of the eutectic was found by stirring solutions of sodium phosphate in freshly dihlled water in jacketed tubes cooled in a brine-bath a t -3.00 to - 4 ~ 0 ~ . Steady temperatures* were obtained a t the following points which remained unchanged for at least half a minute on remosving the tube from the brine-bath -0*42O -0*47O - 0 ' 4 7 O '-0-/7O. In the first two experiments the solid phase separating first was ice. In order to determine the composition of the liquid phase a t the eutectic a solution that had been brought to the eutectic point was stirred in a freezing mixture of ice and sodium phosphate for about half an hour solid matter allowed to settle and about 5 grams of the supernatant liquid were removed with a pipette and analysed.The thermometer W~EI graduated in 1/60" and was standardised before 1lae DISODIUM HYDROGEN PHOSPHATE DODECAHYDRATE. 1591 The result is shown in the table below. The other solubilities there given were determined as follows. Saturated solutions were prepared by stirring the appropriate solid phase with distilled water in an electrically heated and con-trolled thermostat temperature being colnstant to within k0.02O. In order to make certain that' the true solid phase in equilibrium was present during the whole period of stirring an approximately saturated solution was prepared a t a higher temperature than that of the thermostat' and introduced into the solubility apparatus, together with a few crystals of the expected solid phase.Stirring was continued for three to four hours,* a portion of the saturated solution being then siphoned through a glass-wool filter into a 40' 30 20 10 0 %- ' 3 SOLUBII -,-I-L 0 5 10 small weighed bottle. The whole operation was carried o u t in the thermostat. ~~ The composition of the saturated solution was determined by conversion of the dissolved phosphate into magnesium pyre phosphate. The temperature of the thermostat was recorded with standard thermometers graduated in 1 / 20° the mercury thread being totally immersed. Seventeen determinations were com-pleted; two results were discarded owing to suspicion of leakage of water from the thermostat into! the solubility apparatus. The remainder are given below as grams of anhydrous disodium hydrogen phosphate in 100 grams of solution.* It was found that no difference greater than 0.05 per cent. was pro-duced in the value of a solubility by continuing the stirring for eight houru 1592 HUNT THE PREPARATION OF ETHYL IODIDE. Temperature. Solubility. - 0.47' (eut,ectic). 1-46 -t 6.00 * 2.73 19-95 7-26 22.77 8-93 24.15 9.53 25-78 10.90 27.80 14.16 28.65 15.57 29.05 16.04 Temperature. + 29.50" 30.10 3O.YC1 32.50 33.70 34.70 36.50 40.02 Solubility. 17-18 19-45 20.08 22-57 54.63 29.75 31-18 35.56 * Temperature at which a solution containing 2.81 grams in 100 grams of water begins to crystalliae. These results are1 plotted in the figure. The solubility curve shows distinct breaks a t 29-5-29*6O corresponding with the invariant point a-Na,HP0,,12H,0-~-Na.L~IP0,,12H,0-solutioii, and at 35.0° corresponding with a-Na2HP0,,12H,O-Na,HP04,7H,0-solution. Summary. (1) Disodium hydrogen phosphate dodecahydrate exists in two forms a and j3. The transition temperature between the a- and &hydrates is 2 9 . 6 O . The a-hydrate passes into heptahydrate at 35'0° (not 36*45O as given by Shiomi Zoc. cit.). (2) The euteclic point /3-dodecahydrate-ice is found to be at - 0*47O agreeing closely with Riidorf's value - 0 ~ 4 5 ~ (Zoc. cit.). (3) The solubilities of the two dodecahydrates have been deter-mined ; from the solubility curves the transition temperatures are found to agree with those deduced from heating and cooling curves. CHEMICAL LABORATORY, THE COLLEGE, WINCHESTER. [Received November 15th 1920.

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DOI:10.1039/CT9201701589

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年代:1920

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1592 HUNT THE PREPARATION OF ETHYL IODIDE. CLXXV1.-The Preparation of Ethyl Iodide. By BEATRICE ELIZABETHA HUNT. THE preparation of ethyl iodide has recently been investigated by Adams and Voorhees ( J . Amer. Chent. SOC. 1919 41 789)) who recommend the employme'nt of Walker's method (T. 1892 61, 717) in a slightly modified form. An alternative method how-ever appeared possible in view of the work of Beilstein and Rieth (Annalen 1863 126 250) and this process forms t,he subject of the present communication HUNT THE PREPARATION OF ETHYL IODIDE. 1593 Experiment showed that with the use of 80 per cent alcohol in place of absolute alcohol the vigour of the reaction caused by the addition of iodine was so much reduced that the time required to mix 500 grams of iodine with the requisite amount of alcohol and red phosphorus was not more than twenty minutes.Further the yield was not affected by the omission of the customary period of keeping a t the ordinary temperature but boiling under reflux for two and a-half hours followed by immediate distillation was sufficient to' ensure a good yield. The use of a large excess of alcohol is often suggested but this proved unnecessary and indeed, rendered the process of purification niore difficult and thus reduced the yield. I n most modern text-books the iliain reaction is regarded as taking place according to tlis equation P + 31 + C2H60 = 3C,HjI + P(OH),, but Beilstein (loc. c i t . ) interprets it thus: P + 51 + C,H,O = 5CzI151 + H,PO 3- H20. Estimations of the amount of unused phosphorus remaining after distillation agreed with this interpretation which was further verified by the preparation of ethyl iodide using the amount of phosphorus required by Beilstein's equation when a good yield was obtained.I n practice however it proved better to use an excess of phosphorus to ensure purity of the product. E S I' E R I M E N T A Id. To 500 grains of iodine in a flask of 4 litres capacity cooled by water about 281 grains of 80 per cent. alcohol (by weight) were: added and thereafter during the course of about twenty minutes, 50 grams of red phosphorus with shaliiiig after each addition to ensure complete mixing. The first additions of phosphorus caused evolution of heat and boiling of the1 liquid in tho flask but no loss of vapour occurred.A reflux condenser was then attached to the flask and the latter heated in a water-bath so that the contents boiled gently. After about two and a-half hours iodine vapour was no longer visible although the mixture remained dark in colour. The ethyl iodide was without cooling distilled off through a short two-bulb condensing column by heating first in a watar-bath and aft,erwards an a brine-bath. All the distillate passed over a t 63-43' and was colourless except for a small fraction a t the end which had a yellow tinge. A few drops of sodium carbonate solution were added t o ensure absence of free hydriodic acid and a few drops of a dilute solution of sor7iun1 thiosulpliat 1594 GREENWOOD AND NIERENSTSIN : to remove any free iodine since ethyl iodide purified with sodiuni t$hiosulphate was proved to darken less quickly on keeping than when sodium carbonate alone was used and the purification was accomplished more rapidly. The oil was then washed with water, dried over calcium chloride and redistilled. The yield was 566 grams (92 per cent. of 'the theoretical) and the unused red phosphorus amounted t~ 24.45 grams. UNIVERSITY COLLEGE, SOUTH AMPTON. [Rm-iued October 2tith 1920.

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1594 GREENWOOD AND NIERENSTEIN : CLXXVI1,-Studies in the Chronzan Series. Part I. By ANNIE GREENWOOD and MAXIMILIAN NIERENSTEIN. IN order to obtain confirmatory evidence of the views expressed by one of us wibh regard to the action of metallic sodium and alcohol on catechin tetramethyl ether (this vol. pp. 971 1151) we thought it advisable to study the effect of these reagents on some simple derivatives of the chroman series. Our observations on 1-phenylchroman (I} and 3-phenylchroman (III) which are described in the present communication confirm in every respect the deductions made in the case of catechin tetramethyl ether. Thus we obtained 2-hydroxy-ay-diphenylpropane (11) and 2-hydr-oxy-aa-diphenylpropane (IV} by the action of metallic sodium on I-phenylchroman (I) and 3-phenylchroman (111) respectively.We also found that whereas the ay-derivative (11) is recovered unchanged on oxidation 2-hydroxy-aa-diphenylpropane (IV) yields under the same conditions 2-hydroxydiphenylacetic acid (V). 0 /\/><yHPh /\OH I ICH~-CH,.CH,P~ \/ 1 1 \ / \ P f l 2 CH2 (1). (11. ) (111 1 (1V. 1 w. 1 1-Phenylchroman (I) has been previously prepared by Harries and Busse ( B e r . 1896 29 380) and Feuerstein and Musculu STUDIES IN THE CXROMAN SERIES. PART I. 1695 (ibid. 1901 34 412). We have obtained 3-phenylchroman (111) according to Semmler’s scheme for the synthesis of chroman (Ber., 1906 39 2855). 3-Phenyldihydrocoumarin (VI) was reduced to 2-o-dihydroxy-aa-diphenylpropane (VII) and subsequently con-verted into 3-phmylchroman (111).E x P E R I M E N T A L. 2 -Aydroxy-a y -diphenylpropan.e ( T I ) . To a solution of 11.5 grams of l-phenylchroman prepared accord-ing to Harries and Busse’s method in 150 C.C. of alcohol are added 50 grams of metallic sodium and the solution is heated for eight hours on a water-bath. The alcohol is removed with steam and, at the same time 4.5 grams of unchanged l-phenylchroman are recovered. This unchanged material is again reduced 20 grams of sodium and 100 C.C. of alcohol being used. The combined aqueous solutions are extracted with ether in order to remove any unchanged l-phenylchroman (0- 72 gram of unchanged product was recovered on evaporation of the ether) the solution acidified with dilute sulphuric acid and extracted several times with ether.The dried ethereal extract leaves on evaporation an oil which solidifies on keeping over paraffin in a vacuum. It’ crystallises from light petroleum in slender glistening needles which melt sharply at 21.5O. The alcoholic solution turns violet with alcoholic ferric chloride. The yield is 69 per cent. of the theoretical (Found*: C=85-1; IX=7.6. C,,H,,O f requires C=84*9; H=7*5 per cent.). Diazomethane converts the ethereal solution into the methyl ether the yield being 86 per cent. of the theoretical. It is a viscous colourless oil which boils a t 143-147°/11-12 mm. (Found 1 C = 84.9 ; H =8.2. CI6Hl80 requires C = 85.0 ; H = 7.9 per cent.). * Dried over paraffin in a vacuum. -f Braun and Deut,sch (Bey. 1912 45 2187) have prepared 2-hydroxy ny-diphenylpropane in a different manner.They describe i t as a yellow, viscous odourlees oil which boils at 198-502°,/15 rnm. They calculate, however wrongly for C,,R1,O which requires C = 86.5 ; H = 5.8 and they find C = 86.63 ; H = 6-01 per cent. 5 Dried over-paraffin in zb vacuum 1596 GREENWOOD AND NIERENSTEIN : 3-PhenyZtZ.ihydrocoumarin (VI) . This substance has been prepared by Liebermann and Hartmann (Ber. 1891 24 2582) and Simonis (“Die Cumarine,” 1916, p. 132) but1 neithelr method was used by us. We have prepared it by the action of acetyl chloride on 2-methoxy-PO-diphenyl-propionic acid (compare Stoernier and Friderici Ber. 1908 41, 340). For the synthesis of this acid we used Fosse’s method (Ann. Chim. 1920 [ix] 13 105) which seemed t o us preferable to that employed by Stoernier and Friderici (7oc.c i t . p. 335). TwenLy-six grams of 2-methoxydiphenylcarbinol (prepared according to Stoermer and Friderici’s method Zoc. c i t . p. 332) are heated in an oil-bath for four hours at 120° with 50 grams of ethyl malonate. The excess of the ethyl malonate is distilled off and the solid crystallised from alcohol from which it separates in long, prismatic needles which melt a t 134-135O carbon dioxide being evolved (compare Stoermer and Friderici loc. c i t . who give 131O). The yield is 92 per cent. of the theoretical. 2-Methoxy-PP-diphenylpropionic acid (23 grams) dissolved in glacial acetic acid (100 c.c.) is converted into1 3-phenyldihydro-coumarin with acetyl chloride (15 grams) on keeping for forty-eight hours a t the ordinary temperature!.The precipitate formed on the addition of water contains some unchanged 2-methoxy-PP-diphenylpropionic acid which is remo’ved by dissolving the pro-cipitate in ether and washing the ethereal solution with a 10 per cent. sollution of sodium hydrogen carbonate saturated with carbon dioxide. The solid left’ on evaporation of the dried solution crystallises from alcohol in stout plates which melt at 8 2 O as given by Liebermann and Hartmann (Toc. c i f . ) . 2-o-Dih?/clron.?/-aa-c~i~?~,e?~yl~)~o~)(~ i t e (VII) . To a solution of 22 granis of 3-phenyldihydrocoumarin in 175 C.C. of alcohol 50 grams of metallic sodium are added and the solu-tion is kept a t the boiling point for eight hours when all the sodium disappears. The solution freed from alcohol by steam distillation is acidified extracted with ether and the drield ethereal extract leaves on evaporation an oil yielding a main fraction, which boils at 195-204°/11-12 mm.On redistillation of this fraction a colourless heavy oil is obtained which boils constantly a t 197-199O/11 mm. Jt is soluble in the usual organic solvents, and does not solidify even on prolonged keeping in a freezing mixture. The yield is 68 per cent. of the theoretical (Found % : C=79 1 ; H-7.3. C,,-,H,,O,? requires C-78.9; IT-’7.0 per cent.). * Driccl over parefhi in a vmxnnn STVTDIES I N THE CIIROMAN SERIES. PART I. 1597 3 1’h ciiylchromaii (111). A solution of 16 grams of 2-w-dihydroxy-act-diphenylpropane in 100 C.C. of absolute alcohol is heated on a boiling-water bath dry hydrogen chloride being passed through the solution a t intervals.The solution is reduced to 20 C.C. and diluted with 300 C.C. of water which causes a heavy oil to separate. The oil is extracted with ether and the etherelal extract washed first with dilute alkali and then with water. The dried ethereal extract gives on evapor-ation an oil which is dried in a vacuum over paraffin. The sub-stance obtained in this way is very readily soluble in the usual organic solvents but by dissolving about one part of the oil in about four parts of boiling light petroleum and keeping in a freezing mixture of ice and salt long prismatic needles are obtained which melt sharply a t 38-5O. The yield is 78 per cent. of the theoretical. The addition of ferric chloride to a suspension of 3-phenylchronian in concentrated sulphuric acid produces a reddish-violet coloration even i f the substance has been crystal-lised several times.Chroman prepared according t o Semmler’s method (Zoc. c i t . ) and 1-phenylchronian also1 give a faint violet coloration with ferric chloride and concentrated sulphuric acid. These observations are of great interest in connexion with the chemistry of catechin in view of the importance which has been attached to the fact that both catechin tetramethyl ether and the coumarans give a violet coloration with ferric chloride and con-centrated sulphuric acid (compare Kostanecki and Lamp Ber., 1906 39 4007 ; Freudenberg ibitl. 1920 53 [B] 1423) (Found * : C=86-1; H-6.8. Cl,H140 requires @-85.7; H = 6 * 6 per cent.).2-Hydro x y -aa-d iph c IL y 1 pro pane (IV) . Nine grams of 3-phenylchronian dissolved in 150 C.C. of alcohol, are heated with 40 grams of metallic sodium and the alcohol is removed with steam. From the fact that on steam distillation, no unchanged 3-phenylchroman was recovered as observed in the case of 1-phenylchroman it may bel deduced that the 3-phenyl-chroman nucleus undergoes fission more easily than the 1 -phenyl-chroman nucleus. The ethereal extract oE the acidified solution leaves on evapor-ation an oil which gives a main fraction boiling a t 226-231°/ 13-14 mm. The pure substance is a viscous colourless oil which boils at 214-216O/5-6 mni. and is soluble in all the usual organic solvents. The product does not solidify even on prolonged * Dried over paraffin in 8 vmuum 1598 STUDIESilIN TKE CHROMAN SERIES.PART I. keeping in a vacuum or in ay freezing mixture. The alcoholic solution of 2-hydroxy-aa-diphenylpropane turns violet with alcoholic ferric chloride. The yield is 71 per cent. of the theoretical (Found * C= 85.2 ; H = 7.8. C,,H,,O req,uires C = 84.9 ; H=7.5 per cent.). Diazomethane converts the ethereal solution into the methyl ether the yield being 74 per cent. of the theoretical. It is a viscous colourless oil which boils at 176-179O/4-5 mm. (Found* C=84-7; H=8*1. C,,H,,O requires C=85*0; H=7*9 per cent .). 2-~ydroxydiyhenylacetzc ,4 cid (V) . Five grams of 2-hydroxy-aa-diphenylpropane dissolved in 100 C.C. of a 20 per cent. solution of potassium hydroxide in water, are oxidised on a boiling-water bath for four hours witah 5 grams of potassium permanganate in 100 C.C.of water. The solution is filtered while hot and after cooling acidified with dilute sulphuric acid. The grey-coloured precipitate is not filtered but the solution extracted several times with ether in which the precipitate dis-solves. The dried ethereal extract leaves a solid which crystallises from dilute alcohol with the aid of animal charcoal in prismatic needles melting at 86-87O as given by Bistrzycki and Flatau (Ber. 1895 28 990). The yield is 64 per cent. of the theoretical. On heating 2 grams of the acid with acetic anhydride and anhydrous sodium acetate a quantitative yield of 2-phenyl-mumaran-1-one is obtained (compare this vd. p. 1155). It crystallises from alcohol in prismatic needles which melt a t 113-114O as given by Bistrzycki and Flatau (Eoc.c i t . p. 989). Neither the melting point of 2-hydroxydiphenylacetic acid nor of 2-phenylcoumaran-1 -one was found to be depressed when mixed with the corresponding substances which had been prepared accord-ing to Bistrzycki and Flatau’s method. Addendum. Marschalk (Ber. 1910 43 1700) a t the suggestion of Kostanecki has proposed the names depsan (from 6+0 to tan) for p-benzylcoamaran depsanoll foc leuco-p-beinzoylcounlaran and 3 5 3’ 4/-tetrahydroxydepsanol for catechin. 0 OH 0 Depsan. Catechin (Kostanecki’s formula). * Dried over paraffi in a vacuum DEPENDENCE OF OPTICAL ROTATORY POWER ETC. 1699 This nomenclature has been freely used by Kostanecki’s collaborators (compare for example Bielinki Diss.Bern 1911), which is to be regretted for the following reasons (1) From Emil Fischer’s well-known researches the name clepside which is also derived from 8 l 4 0 has become ciefinitely associated with a series of anhydrides. (2) The name tetrahydroxydepsanol suggested for catechin indicates that catechin possesses tanning properties which is not the case (compare Prcxter “ The Principles of Leather Manufacture,” 1903 ; Perkin and Everest “ The Natural Organic Colouring Matters,” 1918). (3) Most of tha recent researches point towards a chroman formula for catechin as originally suggested by A. G. Perkin (T. 1902 81 1172; 1905 87 404) and the possibility that catechin is a coumaran derivative has become very remote. For these reasons the authors would suggest that the names depsan depsanol etc. should no longer be used in connexion with catechin. The authors wish to express their indebtedness to the Collston Society of the University of Bristol for a grant which has covered the expenses of this research. CHEMICAL DEPARTMENT, BIOCHEMICAL LABORATORY, UNIVERSITY OF BRISTOL. [Recewed Noue&r Qth 1920.

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DOI:10.1039/CT9201701594

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年代:1920

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DEPENDENCE OF OPTICAL ROTATORY POWER ETC. 1699 CLXXVII1.-Studies on the Dependence (4 Optical Rotatory Power on Chemical Constitution. Part IIL I ; 4- Naphthylenebisiminoca~p~or. By BAWA KARTAR SINGH and MAHAN SINGH. THE highest recorded molecular rotation is that of p-phenylene-bisiminocamphor which has [MI, 6173O in pyridine (Forster and Thornley T. 1909 95 ,942). In the present communication is recorded the molecular rotatory power of another similarly constituted compound namely, 1 4-naphthylene bisiminocctmpkor which is endowed with a far higher rotatory power than any compound hitherto known. The marked effect of conjugated linkings on the optical rotation of compounds has already been demonstrated by Rupe (Annulen, 1910 369 311) and Hilditch (T. 1909 95 1570).It is furthe 1600 SINGH AKT) SINGR STUDIES ON THE DEPENDENCE OF ernphasised by the rotation-constants of a series of compounds, similar to the one under discussion described by Forster (Zoc. cit.) and Singh (T. 1919 115 19; this vol. p. 980) and their collaborators. One of the necessary conditions for producing compounds of high molecular rotation appears to bel t o have within a relatively narrow molecular compass the optimum association of unsaturated groups. It is brought out very clearly by counting the number of double linkings in the structural formulae of 1 4-naphthylenebis-iminocamphor y -phenylenebisiminocamphor and 4 4'-diphenylene-bisiminocamphor and comparing the molecular rotatory powers in chloroform : \-/ Nine double linkings. Seven double linkings.Ten double 1inl;ing.s. This illustrates the effect of the optimum association of azethenoid groups conjugated linkings and benzene rings within a given molecular compass. The narrower the molecular compass containing a given number of conjugated linkings the higher is the rotation. Ths effect of solvent on the magnitude of rotation of 1 4-naphthylenebisiminocamphor is remarkable. It is shown in t lie following table r m . Chloro- Methyl Ethyl form. alcohol. alcohol. Pyridine. I 4-Naphthylenebisiminocamphor . . 817ij3 9052' 12071' 13416' p-Phenylenebisiminocanlphor . . . . . . . . 6096 * 6009 5289 61 73 * Difference ........................ 2079 4043 6782 7243 * Forster and l'hornloy (Zoc. cit.) OPTICAL ROTATOIZY POWER ON CHEMICAL CONSTIT'UTION.160 1 E X P E R I M E N T A L. 1 ; 4-Naphthylenebisiminocamphor. When camphorquinons (2 mols.) 1 4-naphthylenediamine dihydrochlorids (1 mol.) and excess of sodium acetate are thoroughly mixed a red colour is developed almost immediately. The mixture after being heated for half an hour on the water-bath a t 60-70° is extracted with alcohol and on diluting with water a red substance is deposited which crystallises from alcohol in red rectangular plates melting at' 228-229O (with blackening). It is solirblei in pyridine chloroform ethyl alcohol or methyl alcohol and insoluble in ether or water (Found N=6*33. C,,H,O,N requires N= 6.16 per cent.). The rotatory power deterniinations were made by dissolving the given weight of the substance in the given volume of the solvent, and the following results without any mutarotation were obtained.Ths length of 'the tub0 was O.5-dcm. in the case of pyridine and in the case of the remaining solvents it was 2-dcm. Sub-8 tance. Solvent. Gram. Chloroform ........................... 0.0213 ........................ 0.0186 Methyl alcohol ..................... 0.0181 Ethyl dcohol ........................ 0.0132 ........................ 0.0168 Pyridine ........................... 0.0 122 9 9 9 9 Volume. C.C. 40 100 100 100 100 50 Tem-perature. a,. [MI,. 18.1' 1,914' 8187' 18.8 0.668 8196 18.4 0,732 9052 18.4 0.706 12071 18.4 0.905 12239 30 0.36 13416 All attempts to reduce this compound have failed. For comparison with the foregoing substance the following measurements were made with p-phenylensbisiminocamphor : Sub-stance. Volume. Tem-Sol vent . Gram. C.C. perature. a,. [MI,. Chloroform ........................... 0.0286 20 24.5' 4-31' 6088 Methyl alcohol ..................... 0.0357 20 21.7 4-41 6009 ..................... 0-0254 20 21.7 3.15 5005 Ethyl dcohol. ....................... 0.0264 20 21-7 3.46 6289 9 9 THE CHEMICAL LABORATORY, GOVERNMENT COLLEGE, LAHORE PUNJAB INDIA. [Receiued November 9th 1020.1 VOL. cxm. 3

ISSN:0368-1645    

DOI:10.1039/CT9201701599

出版商:RSC    

年代:1920

数据来源: RSC

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1602 PERMEABILITY 03' GLASS TO IODINE AND BROMINE VAPOURS. CLXXIX.-The Permeability of Glass to Iodine .and Byornine Vapours. By JAMES BRIERLEY FIRTH. IN a previous conilnunication (P. 1913 29 112) the author described experiments which showed that ordinary glass is not permeable to1 the vapours of iodine and bromine a t 360° after fifty days and after two years at the ordinary temperature. In the present paper the results are recorded after the experi-ments have been continued for a further period of seven and a-half years making nine and a-half years in all. After two years the tubes of the second series were again heated for a further period of fifty days at' 360° and then the tubes of both series set aside and examined periodically. After a period of nine and a-half years the silver in the tubes of the first series namely those which had not been heated showed no indication of attack by the halogen but in the case of the tubes which had been heated to 360° (100 days in all) the silver in two of the tubes showed distinct attack in the case of iodine whilst in the case of bromine in this series also there was no indication of any action on the silver.The tubes were then broken up and the thickness of the walls of the bulb; was accurately measured by means of a micrometer gauge. The silver foil in every case was carefully examined and the presence of silver iodide confirmed in the two cases. The measurement of the thinnest part of the bulb is given in each case. I n the first series the thickness of the bulbs varied in the case of bromine from 0.206 to 0.332 mm.and in the ease of iodine from 0.204 to 0.338 mm. I n the second series the thickness varied from 0.207 to 0.364 mm. in the case of bromine and 0.208 to 0.385 mm. in the case of iodine. I n the tubes in which thel silver was attacked by iodine the thicknesses of the bulbs containing the halogen were 0.208 mm. and 0.211 mm. respectively and the conditions (a) vacuum inside and outside ( b ) vacuum outside and atmospheric pressure inside a t the ordinary temperature. It should be noted that in the case of the tubes which had been heated the iodine condensed on the walls of the bulb as a thin film whereas in the case1 of the tubes which had not been heated, the iodine was in small crystals VELOCITY OF DECOMPOSITION OF HIGH EXPLOSIVES ETC.1603 The experiments indicate that it is possible for iodine to pass through a thin glass partition under certain conditions but the rate of diffusion is exceedingly slow the iodine taking about nine years to1 diffuse through a thickness of 0-2 mm. of glass. There is no evidence whatever of the passage of bromine through a similar thickness of glass even after nine and a-half years. The experiments do not in any sense support the explanation of Zengelis for the loss observed in Landolt’s experiments since the time taken in the cases where a positive result has been obtained is considerably greater than the duration of Landolt’s experiments and further the thickness of the glass penetrated woald be much less than the thicknem of the glass used by Landolt. In conclusion therefore it may be stated that iodine and bromine do not diffuse through a glass partition under ordinary experimental conditions but only in extreme cases involving the use of very thin glass over a very long period does the possibility arise. THE CHEMICAL DEPARTMENT, UNIVERSITY COLLEGE, N OTTIN OH AM. [Receiued November 16& 1920.

ISSN:0368-1645    

DOI:10.1039/CT9201701602

出版商:RSC    

年代:1920

数据来源: RSC

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VELOCITY OF DECOMPOSlTION OF HIGH EXPLOSIVES ETC. 1603 CLXXX-The Velocity of Decomposition of High Explosives in a Vucuzcm. Part II. Yi*initro-p hen ylmetlzylniti.oc~mine ( Il’etryl). By ROBERT CROSBIE FARMER. TETRYL is widely used for explosive purposes and the control of its stability is of considerable practical importance. On account of the instability of the nitroarninegroup the compound decom-poses much more rapidly than compounds of the triiiitrobenzene type and may undergo detmkration on storage if not completely purified. It was mainly for the control of the manufacture of tetryl that the vacuum stability test described by the author (this vd. p. 1432) was devised and this test has been used as the standard method for a number of years. A temperature of 120° has been found best for the measure-ments.‘Tetryl is solid a t this temperature (m. p. 1 2 9 O ) and gives convenient volumes of gas in aboat two days. The gases consist of carbon dioxide carbon monoxide nitrogen and oxygen and the residue is a complex mixture containing picric acid etc. The 3 ~ 1604 FARMER THE VELOCITY OF DECOMPOSITION OF evolution of gas proceeds with an acceleration and an arbitrary period of forty hours has been taken for the standard test. Samples of well-purified tetryl give evolutions of 1.5 to 3 C.C. from 5 grams of explosive. The reaction is very sensitive to catalytic influences and products containing minute quantities of residual impurities decompose much more rapidly. It appears probable that one of the main causes of instability is the presence of analogues of tetryl containing a nitro-group in the meta-position.Traces of picric acid may also be present; this compound has been found to1 decrease the stability greatly. The temperature-coefficient corresponds with a factor of 1.9 for each 5O that is approximately the same as for moet other explosives which undergo gradual decomposition. The logarithms of the velocities give approximately a straight line when plotted against the temperatures. By extrapolation to ordinary temperature it is found that forty hours a t 120° corresponds with about 1700 years a t 20". Such extrapolations must naturally be taken with reserve as the decomposition is of a complex nature and may include reactions the temperature-coefficients of which vary but the result shows that the purified substance is almost free from any tendency to1 decompose when stored a t ordinary temperatures, unless decomposition is induced by contact with any material of a reactive nature.A point of interest in the study of the stability of tetryl is that, measurements can be made both above and below the melting point. I n the case of most nitro-compounds the velocity of decom-position becomes sol low at the melting point that measurements on tho solid compound are scarcely possible. In view of the behaviour of many substances of melting with simultaneous decomposition it is instructive to make quantitative tests in the solid and the molten condition. When measurements are made on the solid substance at different temperatures a uniform tempera-ture-coeEcient is obtained.A t the melting point, an abrupt change takes place in the velocity of decomposition. The effect of the molten condition is to increase the velocity approximately fifty-fold. Beyond this point the velocity again increases uniformly with the temperature as before. When the logarithms of the velocities are plotted against tho temperature 'the measurements abo've the melting point give a straight line which is approxim-ately parallel to the line representing the velocities below the melting point (Fig. 5). This great increase of velocity on melting is the main cause of the acceleration in the decomposition at 1 2 0 O . When a slight decomposition has occurred the products of the decompositio HIGH EXPLOSIVES IN A VACUUM.PART 11. 1605 form a eutectic mixture with a part of the tetryl and this liquid portion at once decomposes with the higher velocity. It is always observed after testing that the crystals show signs of having been partly melted. This acceleration tends t o accentuate the differ-ence between tetryls of different initial stability. I n the molten condition the acceleration is much less marked and is in this case due to auto-catalysis. Pure and impure samples also show much less difference in their velocity curves in the molten conditim. The rapid decomposition of molten tetryl makes it impossible to obtain accurate measurements of its freezing pointl (" setting point' ") but the melting point can be determined by the capillary method without any appreciable error due to decomposition.The purest samples gave a melting point of 1 2 9 . 1 O . The above behaviour on melting formed an explanation of the results obtained on mixing tetryl with trinitrobenzene trinitro-toluene etc. These mixtures decomposed much more rapidly than tetryl itself a t looo to 1 2 0 O . This appeared a t first to indicate a chemical interaction but was simply due t o the loweiring of the melting point of the tetryl. The rates of decomposition of the mixtures at' temperatures above the melting point of tetryl agreed with those of tetryl whilst at lower temperatures they agreed with the extrapolated velocities from the temperature-velocity curve of molten tetryl (Fig. 5 ) . It may therefore be concluded t h a t ' a t temperatures belo'w the mellting point of the eutectic mixtures the stability of these mixtures will not differ from that of tetryl alone.It was not possible to test this as the rate of decomposition of tetryl can scarcely be measured a t temperatures much bebw 100'. I n the case of s-trinitrocm-xylem however it was possible to obtain measuremynts below the melting pclint of the eutectic mixture and these agreed approximately with those made on tetryl alone. These deductions have been confirmed by prolonged climatic trials of such mixturw att 500. Trinitrophenol caused a great increase in the rate of decomposi-tion of tetryl after making allowance for the loiwering 09 the melting point. As trinitrophenol is a decomposition product of tetryl this probably forms the main explanation of the auto-catalysis.Mixtures of small proportions of nitric and acetic acid did not accelerate the decomposition. Probably the acids were removed by distillation in the vacuum before they were able to exert any decomposing action. Sulphuric acid on the other hand gave rise to' a very rapid evolution of gas. Since the completion of the above work a few measurements have been given by Knowles (J. I n d . Eng. Chem. 1920 12 246) 1606 FARMER THE VELOCITY OF DECOMPOSITION OF using a modification of Obermuller's test. He gives the gas evolu-tion as 20 to 30 mm. per hour for commercial tetryls but the temperature and the volume of the apparatus are not stated. E x P E R I M E N T A L. Method of 7Vorking.-This was essentially the same as that described in Part I (Zoc.cit.). The standard procedure was as follows The tetryl was dried for four hours in a steam-oven and 5 grams were weighed into the heating tube which was then con-nected with the manometer. A mixture of heavy petroleum and ceresine wax was used as lubricant; these ingredients were care-fully examined to ensure that they were inert and the smallest possible quantity of the lubricant was used. After exhaustion, FIG. 1. 3 0- 2 t, 1 Hours 10 20 30 40 Normal decomposition of tetryls as manujactured ( 5 grams at 120"). the tube was heated for a few hours a t 80° to remove any volatile matter and was then again exhausted and flushed out twice with dry air. The exhausted tube was then inserted in the bath a t 120° and packed round the top with asbestos wool.A period of one and a-half hours was allowed for the level of the mercury in th0 manometer to become steady and readings were then taken ov0r a period of forty hours. For special purposes such as the measurement of temperature-coefficients the above conditions were modified as required. Precautions against explosion were taken as described in Part I but no explosion of tetryl occurred in the whole of the experiments. (a) Typical Results of Tetryl as Manufactured and Purified by -4cetone and TT'ater.-A number of these is shown in Fig. 1. Th HIGH EXPLOSIVES IN A VACUUM. PART 11. 1 GO? general character of the evolution is seen from the curves. A marked accelleration occurs due in part to auto-catalysis but in a greater degree to the progressive formation of eutectics.Attempts to determine the order of reaction serve therefore no useful purpose. Analysis of the gases from three experiments gave the following results : (i. 1 (ii.) (iii.) CO ........................... 20.0 21-5 23.3 co ........................... 5.5 7-1 5.8 0 ............................ 6-9 6.1 4.9 N? ........................... 67.6 65.3 66.0 These analyses do not take account of the nitric peroxide present. This was determined spectroscopically as indicated in experiments cited below. FIG. 2. Prolonged decomposition ( 5 grams 01 tc tryl). (b) Dlecomposition in Air and in a Current of Carbon Dioxide. -The velocity of evolution of gas at atmospheric pressure was originally used for the comparison of the stability of samples of tetryl but although this formed some guide in the purification of tetryl during the manufacture it was not so trustworthy as the vacuum method and may therefore be passed over.Two experi-ments may however be quoted in which the decomposition a t atmospheric pressure was continued until the gas-evolution almost ceased. The object of these was to ascertain whether the acceler-ation which occurred a t first would continue until i t culminated in an explosion. The thermostat was surrounded by a niound of earth and the readings were taken with a telescope. No explosion occurred however and it was possible to observe the whole course of the gas-evolution. Fig. 2 shows the gas-evolution from 5 grams of tetryl at 120° and 1250 respectively. In the latter case tb 1608 FARMER THE VELOCITY O F DECOMPOSITION OF gas-evolution ultimately almost ceased and the total volume of gas amounted to 1.27 mols.per mol. of tetryl. The residue was a dark resinous mass which did not yield any results on cry stallisation. Will's method (Zeitsch. angew. Chent. 1901 14 743 774) in which the exploaive is heated in a current of carbon dioxide was also applied t o tetryl. Fig. 3 shows the evolution of nitrogen from 2.5 grams of tetryl a t 125O over a period of thirty-two hours. The proportion of nitric peroxide was also measured spectroscopically by Robertson and Napper's method (T. 1907 91 761). On account of the low rate of evolution a very long observation tube was necessary in order to render the spectrum of the nitric peroxide WiZZ test (2.5 grams of tetry4 at 126").distinctly visible. The proportion of nitric peroxide decreased as the evolution proceeded (Fig. 3): It is of interest tot co'mpare the evolution of nitrogen from tetryl and guncotton respectively under the conditions of Will's test. A g o d guncotton gives approximately 1.5 milligrams of nitrogen i n four hours at 125O in a current of carbon dioxide whereas tetryl when well purified gives only 0.15 to 0.21 milligram in four hours. Its rate of decomposition is therefore only about one-tenth that of guncotton. (c) Purification of TetryZ.-The application of the vacuum test to the control of stability in the purification treatment is illus-trated in the following examples. Fig. 4 shows the effect of fractional precipitation of crude tetryl from acetolne by water afte HIGH EXPLOSIVES IN A VACUUM.PART 11. 1609 removing t4he nitration acids by t*reatment with hot water. The bulk of the tetryl was contained in fraction 2 which showed the greatest stability. Gas-evolution from 5 Grams at 12W. Time required for evolution of 2 C.C. C.C. in 40 Hours. hours. - Undiesolved residue Fig. 4 (c) ......... 4-6 First precipitation Fig. 4 ( e ) ......... 14.5 11.80 Second , Fig. 4 (k) ......... 34.0 2-40 Final ,) Fig. 4 (u) ......... 2.5 -FIG. 4. Purijkation 01 tetryl. This was confirmed by the Will test which gave the follolwing evolutions of nitrogen from 2.5 grams of tetryl in four hours at 125O undissolved residue 3.39; crop 1 0.51; crop 2 0.16; final crop 5-76 milligrams.Re-purification of the tailings by the same method gave the f dowing results : Crop 1 ( 5 grams) Fig. 4 (m) ... 1.90 C.C. in 40 hours. Crop 2 ( 5 grams) Fig. 4 ( h ) ... 2-55 C.C. 99 Residue (5 grams) Fig. 4 (n) ... 1.80 C.C. 9 ) A stable crop of crystals from the acetone-water treatment was 3 N 1610 FARMER THE VELOCITY OF DECOMPOSITION OF further crystallised from alcohol but this did not decrease the rate of decomposition. Before crystallisation from alcohol 2.40 C.C. in 40 hours Fig. 4 (k) After 9 ) ¶ ¶ ). 2-80 C.C. 9 p . ) Fig. 4 ( 9 ) In order to ascertain whether tetryl which had been partly decomposeld could be restored to its original stability by crystal-liaation the residue from a test after forty-four hours a t 120° was recrystallised from alcohol.This gave 6.85 C.C. from 5 grams in forty hours at 120° showing that the harmful impurities had not been removed (Fig. 4 f). Crystallisatio'n from toluene was applied to a very impure sample and to a sample previously purified by acetone and water. Gas-evolution from 5 Grams at 1 2 0 O . Time required for an evolution of 2 C.C. C.C. in 40 HOW& hours. - Unetable sample Fig. 4 (b) . . . 2.5 After crystallisation Fig. 4 ( d ) . . . 10.6 Stable sample Fig. 4 (k) ... 34.0 2.40 After crystallisation Fig. 4 (E) ... 37.0 2.30 -In some cases it was found that. the stability decreased on crystal-lisation especially from solvents in which tetryl was readily soluble. As this could not be due to the introduction of chemical impuri-ties it could only be attributable to the physical condition of the substance.The stability was found to be affected by the size of crystal large crystals decomposing more rapidly than small ones. This was probably due to the retention of volatile decomposition products within the crystals. The slight differences in the size of crystals of the tetryl in ordinary use for explosive purposes did not however affect the stability appreciably. (d) Temperature-coefficient of the Velocity of Becomposition.-As the evolution of gas proceeds with an acceleration it was con-ZnfEuence of Temperature on Rate of Decomposition. Initial velocity. & Tetryl Tem- /->- C.C. per gram Grams. perature. 0.5 C.C. 1.0 C.C. 2.0 C.C. 6.0 C.C. per hour. _Log. 5.0 100.0" 141 - 644 - 0.00071 3-85 0*00061 4.79 6.0 100.0 164 - - -6.0 111.0 - 73 152 255 0.0027 3'43 6.0 111.0 - 69 147 253 0.0029 $46 5.0 120.0 - 26 42 65 0.0077 T89 5.0 120.0 - 23 37 - 0.0087 3-94 0.5 126.8 6.0 7.3 - - 0.10 1.00 0.6 129.9 - 1-36 2.2 4.4 1.5 0.18 0.5 134.6 - 0.56 1.09 2.42 3.6 0.56 0.6 135.3 - 0.42 0.78 1-66 4.8 0.68 0.6 138.6 - 0.27 0.63 1.19 7.4 0.87 Time (hours) for evolution of HIGH EXPLOSIVES IN A VACUUM.PART 11. 161 1 sidered best' to take the initial velocities as the basis for the calcu-lation of the temperature-coefficient. Measurements were made both above and below the melting point,. The lower curve in Fig. 5 shows the logarithms of the velocities in relation to the temperature. It is seen that the solid substance has a regular temperature-coefficient (approximately equal to 1.9 for 5O).A t the melting point' there is a break in the curve and above this point it again proceeds in a straight line. The measure-ment a t 126.8 gave a low velocity a t the start but this increased extremely rapidly as the tetryl melted. The difference in velocity between solid and molten tetryl at 120° is in the ratio of 1 to 50. The following table shows the effect of heating mixtures of tetryl with trinitrotoluene and other nitro- compounds. Mixtures of Te tryl with Nitro-compounds. InflueTzce of Temperature. Initial velocity. YAP Admix- Time (hours) for evolution of C.C. per gram of tetryl Tetryl. ture. Tem- c A - Grams. Grams. perature. 0.5 C.C. 1.0 c.c.. 3.0 C.C. 5-0 C.C. Trinitrotoluene mixtures : 5.0 5.0 100.0" -5.0 5.0 100.0 -5.0 5.0 110.5 -5.0 5.0 110.6 -0.6 0.5 120.0 -0.5 0.5 128.6 -0.5 0.5 129.0 -0.5 0.5 134.6 -Trinitrobenzene mixtures : 5.0 2.5 100.0 -5.0 5.0 110.5 -5.0 5.0 110.6 -0.5 0.5 120.0 -0.5 0.5 135.3 -Trinitroxylene mixtures : 6.0 2.5 100.0 124-0 5.0 2.5 110-0 21.5 5.0 2.5 120.0 1-86 0.5 0.5 140.7 -0.5 0-5 140-8 -Dinitrobenzene mixtures : 6.0 5.0 100.0 -6.0 5.0 100.0 -8.5 8.5 2.6 2.5 4.5; 1-23 1.41 0-51 10.4 2.4 2.5 4-05 0.56 -36.7 -0.24 0.20 11.1 12.0 Fig.5 shows the relationship 14.3 28.7 14.7 30.4 4.4 8.5 4-3 8.3 7.8 14.8 2.23 -2.48 4.85 0.90 -17.4 35.0 3.95 -3.92 -6.40 13.2 1.00 2.18 - -61-5 99.0 - _-0.43 0.99 0.38 0.85 16.8 29.9 18.3 31.8 between the per hour.0.023 0.023 0.077 0.080 0-44 1.63 1.42 3-92 0*019 0-083 0.080 0-49 3.57 0.00081 0-0047 0-054 8.3 10.0 0.018 0.017 Log. -- 2.36 2-36 3.89 1-64 0.21 0.16 0.59 2.90 2.28 3-92 5.90 1-69 0.66 -4-01 $67 2-73 0.92 1.00 2-26 3-23 logarithms of the velocit.ies and the temperature. It is seen that above the melt-3 N* 1612 FARMER THE VELOCITY OF DECOMPOSITION OF ing point of tetryl ( 1 2 9 O ) the velocities for tetryl and the mixtures coincide. Below 1 2 9 O the values for solid tetryl are much lower (curve 1). The values for the mixtures with dinitrobenzene tri-nitrobenzene and trinitrotoluene are shown in curve 3. These admixtures lower the melting point of the tetryl and form liquid mixtures ; the velocities of deco'mposition correspond therefore, with those of molten tetryl and their logarithms lie approxim-ately on a straight line forming an extrapolation of the values for molten tetryl.In the case of trinitroxylene the eutectic is almost completely solid a t looo and here the velocity becomes nearly equal to that of somlid tetryl (curve 2). Measurements on the trinitrotoluene and FIG. 6. Influence of temperature on uelocity. trinitrobenzene mixtures were not taken below the eutectic melt-ing points but prolonged climatic trials a t 50° indicated that very little decomposition occurred) in a year a t this temperature. A noticeable feature of the mixtures of tetryl with trinitro-benzene (and to a less extent with trinitrotoluene) was that on cooling t o the ordinary temperature after melting they remained very persistently supercooled forming viscous dark reddish-brown colloids.The trinitrobenzene mixtures crystallised only after several days. Varioas tetryls were mixed with trinitrotoluene to ascertain whether tests at looo would be of value in discriminating between pure and impure samples. This method was however of relatively little value as compared with the direct test on solid tetryl a t 12QO HIGH EXPLOSIVES IN A VACUUM. PART 11. 1613 I n all cases the acceleration of the decomposition is much greater in the solid condition in consequence of the progressive melting clue to the decomposition. This is shown in the following table. Acceleration in the Decomposition of Tetryl.Tetryl. Grams. Solid ............ 5.0 ............ 6-0 ............ 5.0 Liquid ............... 0.5 , ............... 0.5 ................. 0.5 , ............... 0.5 9 , 9 , Tern -peraturc. l l l . o o 111.0 120.0 129.9 134.6 135.3 138.6 Initi a1 velocity. 0-0027 0-0029 0.0077 1-5 3.6 4.8 7.4 Mean velocity from 2 C.C. to 6 C.C. 0.0058 0.0057 0.026 2.7 4.5 6.8 9.1 Ratio. 2.1 2.0 3.4 1.8 1.3 1.4 1.2 This was confirmed by the Will test in a current of carbon dioxide. Thus the values at 1 2 5 O were as follows: First Second , , 0.53 ) 9 9 I ?# Third , , 2.25 milligrams , 9 P, Fourth , ) 6.28 , 3 9 1 9 Fifth , , 13.39 , 7 9 ? Y , 4 hours 0.21 milligram of N per 2.5 grams of tetryl.(e) Reactions of Tetryl.-Nitric and acetic acids in small pro-po'rtion did not affect the velocity of evolution materially. In general acids accelerate the decomposition but these acids being volatile were probably removed by the vacuum before they had time to exert any catalytic action. Gas-evolution at 120°'. 20 hours. 40 hours. Tetryl 6 grams ............ 0.96 2.70 2-38 Tetryl 6 grams Nitric acid 0.01 gram } **.*.***. 2.33 Tetryl 6 grams Acetic acid 0.01 gram} **""." 0'85 0'83 Sulphuric acid on the other hand being non-volatile accelerated Even at 80° a marked evolution the decomposition very greatly. of gas occurred. Gas-evolution at 80°. 20 40 60 80 100 hours. hours. hodre. hours hourr. 4.16 4.46 Tetryl 6 grams Sulphuric acid 0.01 gram} le60 2.70 3*55 Picric acid also gave rise to a rapid evolution of gas when mixed with tetryl 1614 VELOCITY OF DECOMPOSITION OF HIGH EXPLOSIVES ETC.Tem- f 20 40 60 80 100 perature. hour. hours. hours. hours. hours. hours. Tetryl 6 grams ............... 120" - 0.50 1.25 3.50 8.50 - ......... 100 - 0.15 0.20 0.25 0.30 0.35 1-60 3.90 6-40 9.20 12.35 ** 9 ) ... pic,,ic 0.5 E;ram ... 120 0.85 - - - - - 4.5 grams I Tetryl * 9 9 9 9 9 ... 100 - , , ) , ... 60 - - - - - 0-02 Some allowance must be made for partial melting of the tetryl containing 10 per cent. of picric acid butl apart from this the picric acid certainly affected the stability adversely. Picric acid was found to be a decomposition product of tetryl and this is doubtless one of the causes of the auto-catalysis which is observed.The influence of some other admixtures is shown in ths following table. These all formed liquid mixtures with tetryl a t looo and, on this account the velocities should be compareld with that of a mixture of tetryl and trinitrotoluene rather than tetryl alone. In the case of p-dichlorobenzene the liquefaction was probably i ncom p 1 et e . Gas-evolution at looo. Hour3 required for evolution of Initial velocity. /-A \ C.C. per gram 1 C.C. 2 C.C. 3 C.C. of tetryl per hour. 9.0 17-1 0.036 :grrffns) i: 10.3 18.6 0.029 " } 17.0 25.0 42.0 0.012 Tetryl Nitrobenzene Tetryl p-Dichlorobenzene 6 ,, Tetryl Diphenyl ether 5 )) ' ') } 2.7 6.1 - 0-074 Summary. The velocity of evolution of gas in a. vacuum a t 1200 forms a useful methosd for the control of the stability of tetryl in the manu-facture. The effect of purification and of various admixtures is shown. The temperature-coefficient of the decomposition of solid tetryl is 1.9 fo'r 5 O . At the melting point an abrupt change in the velocity is observed the molten tetryl decomposing about fifty times as rapidly as the solid. The acceleration in the decornposi-tion of tetryl a t 120" is to a great extent due to progressive melt-ing. Admixtures which lower the melting point also give a rapid evolution apart from any chemical action which they may exert. The thanks of the author are due to the Director of Artillery for permission to publish the above results. RESEARCH DEPARTMENT, ROYAL ARSENAL, WOOLWICB. [Received November 13th. 1920.

ISSN:0368-1645    

DOI:10.1039/CT9201701603

出版商:RSC    

年代:1920

数据来源: RSC

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THE FORMATION OF 2 3 6-TRINITROTOLUENE ETC. 1615 CLXXXI.-The Formation of 2 3 6-Trinitrotohene in the Nitration of Toluene. By ROYSTON BARRY DREW. IN the mixture of trinitrotoluenes obtained by the direct nitration of toluene previous workers have identified only 2 4 6- 2 3 4-, and 3 4 6-trinitrottoluenes of the six possible isomerides. Molinari and Giua (Zeitsch. ges. Schiess. ‘16. Sprengstoffw. 1914 9 239) claimed to have isolated the 2 3 6-compound previously unknown, to which they assigned a nielting point of 79*5O but this com-pound has been synthesised by Korner and Contardi ( A t t i R. Accad. Lincei 1916 [v] 25 ii 339) and by Brady and Taylor (this vol. p. 876) and found to melt at 1 1 1 O ; the latter authors have suggested that Molinari and Giua’s compound was probably a molecular compound of 2 3 4- and 3 4 6-trinitrotoluenes.Will (Ber. 1914 47 704) has studied the nitration of 2:3- and 3 6-dinitrotoluenes and states that the sole products of their nitra-tion are 2 3 4- and 3 4 6-trinitroto1uene.s. More recently how-ever Marqueyrol Koehler and Jovinet (Bull. SOC. chim. 1920, [iv] 27 420) have obtained a third trinitrotoluene in addition to the 2 3 4- and 3 4 6-compounds from the nitration of m-nitro-toluene. Their results are incomplete and they have not identified the compound but as they found it was formed to a small amount in the nitration of 2 3- and 2 5-(or 3 6-)dinitrotoluenes they conclude it must be either the 2 3 6- or the 2 3 5-trinitro-deriv-ative. The present author previous to the publication of Marqueyrol Koehler and Jovinet’s results had investigated the nitration of 2 3- and 3 6-dinitrotoluenes and found that in eaoh case the product contains about 15 per cent.of 2:3:6-trinitro toluene. Other workers have shown that about 4 per cent of m-nitro-tduene is formed in the mono-nitration of toluene under the usual conditions and that on further nitration of this compound about half the product is a mixture of 2 3- and 2 5-dinitrotoluenee. In crude trinitrotoluene obtained by the direct nitration of toluene, there must be therefore about 0.3 per cent. of 2 3 6-trinitro-toluene. Opportunity however has not arisen to isolate this small amount from commercial samples of trinitrotoluene. Further a new method of preparing 2 3 6-trinitrotoluene has been devised which is easier than that described by Korner and Contardi (Zoc.c i t . ) and starts from trinitro-m-crewl ; this is mor 1616 DREW THE FORMATION OF 2 3 6-TRtNITROTOLUENE readily obtainable than the 2 6-dinitrotoluene required in Brady and Taylor's synthesis (Zoc. cit.). The reactions involved are aa follows : Methylpicramic acid obtained by the reduction of trinitro-m-cresol has been oriented only indirectly by Borschc and Heyde (Ber. 1906 39 4092) and the above synthesis fully confirms the view of these authors. E X P E R I Y E N T A L . Nitration of 3 6-Dinitrotoluene.-Forty grams of 3 6-dinitro-toluene were added to 250 C.C. of a mixture of sulphuric and nitric acids (HNO = 17.5 ; E2S0 = 78 ; H,O = 4.5 per cent.).The mix-ture was mechanically stirred and the temperature raised to 80° and kept at that point for an hour when the temperature was raised to looo for a further two hours and finally to 120° for fifteen minutes. The mixture was then cooled and poured into water the solid collected and washed repeatedly under water with the injection of steam until free from acid. The freezing point of the product after drying was found to be 95-4O as against 103O for pure 3:4:6-trinitrotoluene. The mixture was recrystallised from acetic acid to remove most of the 3 4 6-trinitrotoluene and by diluting the filtrate a mixture richer in 2 3 6-trinitrotoluene was obtained. Attempts were made to separate this mixture by crystallisation from various solvents but without success a mixture melting constantly at 7 8 O being obtained.A portion was treated with alcoholic ammonia in the hope that i t would be possible to separate the corresponding dinitrotoluidines but an oily intractable product was obtained. A successful separation was ultimately brought about by the action of hydrazine hydrate. It had been observed by Brady (ppivate rommum'cation) that hydrazine hydrate reacts readily with 2 3 4-and 3 4 6-trinitrdtoluenes giving red crystalline compounds sparingly soluble in alcohol. It has been found that 2:3:6-tri-nitrotoluene behaves in a different manner towards this reagent IN THE NITRATION OF TOLUENE. 1617 which can therefore be used to effect a separation. The mixture of 3 4 6- and 2 3 6-trinitrotduenes was dissolved in methyl alcohol a solution of hydrazine hydrate added and the mixture warmed on the water-bath for some time.On cooling the red precipitate was collected and fractionally crystallised from alcohol, and from the more readily soluble portion a colourless compound was isolated which was identified as 2 3 6-trinitrobluene by the method of mixed melting points with it sample of this compound prepared by Brady and Taylor’s method. Nitration of 2 3-BinitrotoZuene.-This was effected in an exactly similar manner to the nitration of 2 6-dinitrotoluene. The product had a freezing point of looo as compared with 112O in the case of pure 2:3:4-trinitrotoluene. The separation was brought about by means of hydrazine hydrate and the 2 3 6-tri-nitrotoluene isolated and identified.The approximate amount of 2 3 6-trinitrotoluene present in the mixtures obtained by the nitration of 3 6- and 2 3-dinitrotoluenes was determined by making up mixtures of pure 3 4 6- and 2 3 4-trinitrobluenes with 2 3 6-trinitrotoluene and determining their freezing points. It was found that these corresponded with the freezing points of the products of nitration when about 15 per cent. of the 2 3 6-compound was present. 2 6-Dinitro-m-cresoZ.-This was prepared from 2 6-dinitrol-4-amino-mcrewl. The method given for the preparation of this compound by Rellner and Beilstein (Annulen 1863 128 166) did not give good yields so a modified method was adopted. Twenty grams of trinitro-m-cresol were dissolved in 50 C.C. of boiling methyl alcohol and 200 C.C.of 15 per cent. ammonium sulphide slowly added. Vigorous action took place and when it subsided, the mixture was cooled diluted and acidified with hydrochloric acid. The sulphur was filtered off and the filtrate evaporated to small bulk. On keeping the 2 6-dinitro-4-amino-m-cresol separated and was crystallised from alcohol with the addition of animal charcoal. It was found that the usual method for the removal of the amino-group by the action of sodium nitrite on a boiling alcoholic solution of the amine containing sulphuric acid did not give good results with this cornpound owing to the stability of the diazo-compound formed ; accordingly the following method was adopted. Ten grams of 2 6-dinitro-4-amino-mcresol were dissolved in 70 C.C.of hot alcohol 20 C.C. bf ciinceiii;rated hydrochloric acid added and then gradually 10 grams of sodium nitrite dissolved in a minimum amount of water. As soon as the reaction ceased, the mixture was cooled and the precipitate collected. There wa 1618 THE FORMATION OF 2 3 6-TRINITROTOLUENE ETC. thus obtained a stable greenish-yellow crystalline material which deflagrated on heating and was probably the diazo-oxide corre-sponding with that obtained from picramic acid. This compound was treated with 30 C.C. of concentrated formic acid and a small quantity of copper polwder added when a violent reaction took place nitrogen and carbon dioxide being evolved. After filtering from the copper and diluting tlie filtrate an oil separated which slowly crystallised; the crystals were pressed on it porous tile and recrystallised from benzene when 2 6-dinitro-m-cresol separated as a whiter crystalline compound melting a t 1 3 3 O (Found N=14.1.C,H,O,N requires N = 14.1 per cent.). 2 6-Binitro-m-tolyl Methyl Ether.-The ammolnium salt of 2 6-dinitro-m-cresol was prepared by dissolving the cresol in alcoholic ammonia and evaporating the solution on the water-bath until crystallisation took place on cooling. The filtered crystals were dissolved in the minimum amount of alcohol and the calculated quantity of alcoholic silver nitrate was added when the silver salt separated in lustrous grey crystals which deflagrate violently on heating. Five grams of the silver salt were added to a solution of 5 C.C. of methyl iodide in alcohol when immediate action took place and after removal of the silver iodide the solu-tion was diluted and the precipitated 2 6-dinitro-m-tolpl methyl ether crystallised from alcohol when it was obtained in white needles melting a t 1 1 5 O (Found N= 13.4.C8H,0,N2 requires N = 13.2 per cent.). 2 6-Dinitro-m-toluidine and 2 3 6-Trinitrotoluene.-Five grams of 2 6-dinitro-m-tolyl methyl ether were heated to 130° with 5 c.a. of ammonia and 20 C.C. of alcohol. On cooling and diluting, 2 6-dinitro-m-toluidine was precipitated and identified by the method of mixed meflting points with a sample of this compound prepared by Cook and Brady (this vol. p. 750). 2 6-Dinitro-m-toluidine can be converted into 2 3 6-trinitrotoluene by Korner and Contardi’s method (Zoc. cit.). The author wishes t a express his thanks to the Director of RESEARCH DEPARTMENT, Artillery for permission to publish this work. ROYAL ARSENAL WOOLWICH. [Received October 26th 1920.

ISSN:0368-1645    

DOI:10.1039/CT9201701615

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年代:1920

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HENRY HYENANCSHIN AND OTHER CONSTITUENTS ETC. 1619 CLXXXII. -Hyenanchin and other Constituents of Hyenanche globosa. By THOMAS ANDERSON HENRY. Hyenanche glo bosa Lamb (Toxicodendrom cnpense Thun) is the sole member of a genus of the natural order Euphorbiacm and in distribution is confined tot South Africa. The name of the plant is said to have originated from the use olf the seeds in South Africa as a poison for wild animals especially hyenas. I n 1858 Henkel obtained by fractionation of a concentrated alcoholic extract of the fruits a syrupy preparation which proved to be highly toxic (Arch. Pkamz,. 1858 144 16). Engelhardt subsequently prepared the toxic constituent which he named hyenanchin in a crystalline condition but beyond stating that it was neither an alkaloid nor a glucoside made no1 attempt to characterise it (Arb.pharm I n s t . Dorp. 1892 8 5). Shcztly afterwards E. Merck (Merck’s Ann. Report 1895 123) pointed out that if the observation made by Henkel and by Engelhardt, that hyenanchin exerts a strychnine-like action on the brain but is without action on the spinal cord is trustworthy the substance might be of some therapeutic value as a substitute for strychnine in cases where cerebral action alone is required. For a supply of the plant the author is indebted to Mr. I. B. Pole Evans Chief of the Division of Botany Department of Agriculture Pretoria. E X P E R I M E N T A L . The material used included steins (1 kilo.) leaves (2 kilos.) and fruits (4 kilm.). Each of these parts of the plant was extracted separately with chloroform in a continuous hot percolatioa apparatus yielding in the case of the stem and leaves a hard, dark green wax and in that of the fruits a neutral dark yellow oil which was not examined in detail.Extraction was continued with hot 95 per cent. alcohol and the liquid concentrated to a thin syrup which was polurd into five volumes of water causing the separation of sparingly soduble tannin containing a small amount of a yellow colouring matter. The filtrate after purifi-cation with lead acetate in the usual manner was concentrated under reduced pressure to a viscid syrup which was then extracted repeatedly with an equal volume of ethyl acetate until it was free from bitterness and no longer toxic. The brown sticky residue left on distilling off the ethyl acetate was dissolved in three time 1620 HENRY HYENANCHIN AND OTHER its weight of water and set aside when after some weeks a bitter, poisonous crystalline material separated.Mere traces of this were obtained from the leaves and stems and only 6 grams from the fruits (0.15 per cent.) but this does not represent all that is present as the mother liquor was still toxic and intensely bitter, and in the case of the fruits a further 1.7 grams (making a total yield of 0.19 per cent.) were obtained by repeating the treatment with ethyl acetate. This crude material could only be recrystallised by adding it to fifty times its weight of boiling water and' filtering rapidly, when on cooling there separated a crop of slender colourless needles.Slight concentration of the filtrate gave a further crop of the same substance and reduction of the mother liquor from this crop to half its original volume led to the separation of a second substance crystallising in short colourless hexagonal prisms of which more was obtained by further concentration. This second substance forms about two-thirds of the original crystalline material and it is proposed to apply to it Engelhardt's name hyenanchin; as the substance crystallising in needles is an isomeride of this i t may appropriately be called isohyenanchin. Hyenanchin. This substance isolated as described above and purified by repeated recrystallisation from boiling water has no melting point, but when heated becomes yellow a t 200° then darkens and finally decomposes sharply with effervescence at 234O.It dissolves in water to the extent of 1-18 per cent. a t 15O is more soluble in boiling water and sparingly so in alcohol butyl alcohol ethyl acetate or acetone. It has [a] + 14.7" in water (Found C=58.2, 58.3 58.05 57-9; H=6*03 6.01 6.4 6.3. Loss at llOo in a vacuum nil. Hyenanchin contains no nitrogen reduces Fehling's solution on boiling and silver nitrate solution on gently warming or on keep-ing in the cold decolorises permanganate immediately and gives an amorphous yellow precipitate with bromine water. Boiling dilute hydrochloric acid converts it into an amorphous brown sub-stance which gives a characteristic orange-coloured amorphous precipitate with phenylhydrazine in the cold. No sugar is pro-duced.On warming with alkalis hyenanchin furnishes a distil-late containing a minute quantity of a substance which gives the iodoform reaction reduces Fehling's solution and furnishes a semi-carbazone crystallising in short colourless needles and decom-posing at ZOOo which may be acetolsemicarbazone C,H,02N3 (decornp. 195-200O) (Found N=31.12. Calc. N=32*06 per C,,HI8O7 requires C = 58.06 ; €€= 5.8 per cent.) CONSTITUENTS O F HYENANCHE GLOBOSA. 1621 cent.). A specimen of acetdsemicarbazone prepared under similar conditioas and without recrystallisation gave N = 30.8 per cent., and a mixture of the two decomposed a t 198O. No derivatives off hyenanchin with hydrosylamine phenylhydrazine o r semicarb-azide could be obtained. Actiom of Baryta.-Although hyenanchin is not acid to indicators it neutralises alkalis but its titratioa presents difi-culty olwing to the ease with which it becomes coilourad and decom-poses in presence of alkalis.If a solutioln of hyenanchin to which excess of baryta has been added is warmed or kept for several days it becomes brown and turbid the latter due to the gradual separation of barium carbonate. By dissolving it in A7/5-baryta and a t once titrating with N/5-sulphuric acid in the presence of phenolphthalein a fairly satisfactory end-point is obtained (Foand Ba(OH) required for neutralisation 55.2 55.05. Calo. for two C0,H groups 55.3 per cent.). On evaporating in a vacuum the filtrate from the barium sulphate foirmed barium carbonate is gradually deposited and the filtrate from this yields on complete evaporation in a vacuum, a nearly coloarless varnish which appears tor consist chiefly of a barium salt of a monocarboxylic acid since it yields on addition of excess of N/5-sulphuric acid 29.8 per cent.of its weight of barium sulphate (C,,H,,O,,Ba requires BaSO = 31.5 per cent.). The corresponding acid obtained by adding the calculated quantity of N/5-sulphuric acid to an aqueous solution of this salt and evaporating the filtrate to dryness in a vacuum is a colourless varnish which is readily soluble in water and reduces Fehling’s sollution on boiling and ammoniacal silver nitrate in the cold. The acid does not’ regenerate hyenanchin on drying even atl 150° in a These results indicate that hyenanchin is probably a dilactolnne, convertible by the carefully regulated action of weak alkali into the corresponding dihydroxydicarboxylic acid C,,H,,O, which is unstable and readily loses one carboxyl group.Action of Acetic Anhydride.-When hyenanchin is heatedl with acetic anhydride at looo most of it crystallism out unchanged on coolling but if a drop of pyridine be added and the heating con-tinued it is converted into a soft sticky resin from which with great difficulty theire cam be separated by repeated crystallisation from dilute alcolhol a small yield of crystalline material conslisting of a t least three substances (a) cream-coloared needles softening a t 136O and finally melting and decomposing a t 169O; ( b ) colour-less nsedles m. p. 1 2 6 O ; (c) colourless short needles m. p. 104O.Only a few centigrams of each of these substances were obtained, vwuum 1622 HENRY HYENANCHIN AND OTHER so that they could not be satisfactorily purified for examination, but it is probable that only the second is a true acetyl derivative od hyenanchin (Found C = 56.7 57.05 ; H == 5.7. Cl,H1707Ac and C,,H1607Ac require C=57-9; 13=5.6 per cent.). isoHye?tanchin crystallises from boiling water in long slender needles with a silky lustre has no melting point butl becomes brown a t 245O and decomposes sharply with effervescence at 299O. It. dissolves in water to the extent of 0.26 per cent. a t 15O is ' some-what more soluble in boiling water and less so in alcohol or ethyl acetate. [a] -61'3O in water (Found C=58*08 58-25; H=5*97, 6.16. It reduces Fehling's solution on boiling and ammoniacal silver nitrate in the cold.A ction of Baryta .-isoHyenanchin dissolves immediately in excess of N/5-baryta solution forming a solution which only beconies slightly yellolw after remaining several days a t Oo and under these conditions combines with sufficient baryta to neutralise one carboxyl group (Found on immediate titration 29.8; after three days a t Oo 29.2. Calc. for one CO,H group 27.7 per cent.). On again adding excess od A7/5-baryta solutioa and boiling gently for it few minutes and titrating back baryta equivalent to a second carboxyl grotup is folund to have been absorbed (Found: 25.9. Calc. 27.7 per cent. Total for two CO,H groups=55'4. Calc. 55-3 per cent.). A second estimation made by heating isohyenanchin wifh excess of iVI5-baryta solution for one hour a t looo and tit<rating back gave 56.2 per cent.The filtrate from these estimations on concentration behaved like the similar p r s paration from hyenanchin (p. 1621) and gave as a final residue an amorphous barium salt yielding 29.1 per cent. 09 barium sulphate on precipitation with N / 5-sulphuric acid. C,,H1807 requires C = 58.06 ; H = 5-80 per cent.). Physiological A c t i o n of Hyenanchin and isoHyenanchin. The author is greatly indebted to1 Dr. J. Trevan of the Well-come Physiological Research Laboratories who kindly undertook the examination of a series of preparations of Hyenanche and finally of the pure substances isolated. Dr. Trevan reports that hyenanchin has a physiological action almost identical in kind with that o,f picrotoxin but is much weaker.GoI-Iyenanchin on the contrary is not toxic in such doses as can be injected intra-venously C0"ST~TOEN'l'S OF HYENANCHE GLOBOSA. 1623 Relationship of Hyenanchin and isoiyenanchin t o other #on-nitrogenous Convulsant Poisons. The reactions described above and the physiological action of hyenanchin indicate that the latter belongs to the group of con-vulsant non-nitrogenous poisons of which picrotoxinin Cl5Hl6O6 (m. p. 206'5O [a] +4040r in alcohol) coryamirtin C,,H,,O, (m. p. 225O dextrorotatory) and tutin C,&,O7 (m. p. 208-209°, [a] +9*25O in alcohol) are the only well-defined members knolwn. Associated with picrotoxinin in the molecular compound picro-toxin C,H,,O,, is the substance picrotin C,,HI8O7 (m.p. 245-246O [aJD -55.2O in water) which is not toxic. Picrottoxinin and picrotin are both dilactones and are now believed to contain, respectively one and two hydroxyl groups the function of the sixth and seventh oxygen atoms respectively being still unknown (Horrmann Annalen 1916 411 273). Both these substances yield small quantities of acetone on distillation with alkali. Picrotin is isolmeric with hyenanchin and isohyenanchin and in many ways is very similar t o the latter. The1 two have therefore been carefully compared and found not tot be identical the chief differences being that picrotin has a definite melting point and is completely converted into the corresponding dicarboxylic acid by baryta in the cold whilst isohyenanchin has no definite; melt-ing point and is converted into the corresponding dicarboxylic acid by baryta in two well-defined stages.A mixture of both substances begins to sinter a t 2 2 5 O which is well below the melb ing and decomposing points of t,he two components. A number of substances of the formula C1,HJ807 have also been prepared from picrotoxinin and picrotin (compare Horrmann Zoc. cit .), namely picrotin-lactone (33B0 decomp.) picrotoxic acid (m. p. 230-231° [a] + 81.7O crystallises with 2H,O) a-picrotoxink acid (m. p. 209O [a] -48O) and /3-picrotoxinic acid (m. p. 235O, [a] -48O). None of these closely resembles either hyenanchin or isoh yenanchin. Sub s id i ar y C o n s ti t u e n t s of H ye nan c h e g 1 o b o s a. Examination of the Wax. Isolatiom of a New Phtytosterol and a New Wax AZcohol.The dark green wax from the leaves and stems was mixed with an equal weight of animal charcoal and extracted with boiling ethyl acetate yielding a greenish-yellow solution. This on cool-ing deposited a. mixture od two substances which were separated by heating the solution to boiling and adding enough ethyl acetat 1624 HENRY HYENANCHIN AND OTHER to keep both substances dissolved a t 35O. On keieping the liquid then depmited gelatinous granules which filtered with difficulty, and on drying in the air formed a pale brownish-green hoirny mass. This was purified by distillation in a vacuum and recrystal-lisation frmn ethyl acetate when it formed colourless masses od minute needles melting atl 82-83O (corr.). A number of solid alcohols melting near this1 temperature are known but all oif them differ slightly in compolsition and most of them in crystalline form from hyenanche alcohol and of those tried ceryl myricyl and wheat* alcojhols all depressed the melting point.It is readily soluble in chloroform boiling ethyl acetate or alcohol and spar-ingly so in ether does n o t combine with bromine and appears t~ be a new saturated alcohol of the formula C,H,,*OH (Found in substance dried a t GOo in a vacuum C=81*02 81.27 81.19 -f ; H = 13.5 13.55 13.89.1- C,,H,,O requirm C = 81.3 ; H = 14.1 per centl. ) . When boiled f o r several hours with acetic anhydride in presence of pyridine it yields an acetyl derivative which is readily hydro-lysed on recrystallisation from most solvents but separates from acetic anhydride in s o f t masses of colourless needles melting a t 75" (corr.) (Found C = 78.8 ; I3 = 13.0.C,,H,,O requires C=78.7; H=13*1 per cent.). Carnaubyl alcohol which also has this formula crystallises in leaflets (m. p. 68-69O) and is quite distinct from the alcohol od 31. gkobosa. The other known alcoholls of this formula are either liquid o r of much lower melting point than Ilyenanche alcohol. The filtrate from the alcohol1 oln concentration deposited a second substance which after repeated crystallisation from boiling ethyl acetate forms long lustrous needles melting at 265O (corr.) is readily soluble in chlolroform olr boiling ethyl acetate and spar-ingly so in alcohol even on boiling (Found C=83*66 83.95; R=11*35 11-66.CBH,,O requires C=84-4; H=11-55 per cent,). [a]g -22.4O in chloroform. It gives a typical phytosterol reaction with sulphuric acid in the presence of acetic anhydride and furnishes a monoacetyl deriv-ative crystallising from hob ethyl acetate in small spheroidal massw of colourless needles melting a t 244O (corr.) (Foand: G=81.12; H=10*96. C,,H,,O requires C=81*8; H=10*9 per centl.). This substance appears t o be a new phytosterol belonging to the series represented by the general folrmula CnH2n-100 of which a t least eight are now knolwn beginning with alcornol C,H,,O * For a specimen of this alcohol the author is indebted to Mrs. M. T. Ellis (Biochem. J . 1918 12 160). t Regenerated from acetyl derivative CONSTITUENTS O F HYENANCHE GLOBOSA. 1625 (Hartwich and Dunnelnberger A rch.Pharm. 1900 238 348), and terminating with amyrin C,H~,O (Windaus and Welsch, ibid. 1908 246 506). The new phytosterol is exceptional in this series in being lzvorotatory and in giving an acetyl derivative melting at a lower temperature than the parent substance but in all other respects it resembles other members of the series. Isolation of a New Yellow Colouring Matter. The colouring matter was obtained in small amount (total 2.3 grams crude 1.0 gram pure from all three sources) by extracting the sparingly soluble tannin (p. 1619) with boiling dry ether and was recrystallised from alcohol from which it separated on slotw evaporation in microscopic yellow needles which became brown a t 200° and finally melted and decomposed at 270-280O.It is moderately soluble1 in alcohol sparingly so in ether and insoluble in chloroform. The solution in alcohol gives a brownish-black pre-cipitate with ferric chloride (Found C = 62-43 62*1,* 62.1 % ; H=4*4 4*4,* 4-25.* C,,H,,O, requires C = 62.5 ; H = 4-16. C,,H120,,2H20 requires loss 11.1 per cent.). The collouring matter furnished an acetyl derivative crystal-lising from holt alcohol in masses of cream-cololured needles melt-ing a t 234-236O (dwomp.; corr.) (Found C=63*4; H=4.0. Loss a t 60° in a vacuum nil). On regeneration with hydrochloric acid in the presence of hot acetic acid the acetyl derivative yielded 71.3 per cent. of colouring matter identical with the cilriginal sub-stance. Sulphuric acid could not be used for this purpose as i t appeared to convert the colouring matter into a soluble sulphmic acid (compare A. G. Perkin T. 1899 75 448). These results indicate that the acetyl derivative should be represented by the formula C15H,0,Ac3 (requires C = 63.6 ; H = 4.04 ; colouring matter, 72.7 per cent.) which is a triacetyl derivative of the parent sub-stance less one molecule of water. The reactions of the colour-ing matter indicate that it? belongs tot the flavone group in which the loss of a molecule of water o n acetylation does not appear to have been recorded previously except doubtfully in the case of morin (A. G. Perkin loc. cit.). Unfortunately the small amount oS material available precluded further investigation of this and other points. Loss in a vacuum at looo 10.08. WELLCOME CHEMICAL RESEARCH LABORATORIES. [Received November 26th 1920.1 * Regenerated from acetyl derivative

ISSN:0368-1645    

DOI:10.1039/CT9201701619

出版商:RSC    

年代:1920

数据来源: RSC