摘要:

THE CATALYTIC ACTION OF IODINE IN SULPHONATION. 1405 CLllI.-The Catalytic Action of Iodine in Sulphonation. Part r. By J~ANEKDRA NATH RAY and MANIK LAL DEY. THE present investigation was undertaken with the view of ascer-taining whether the addition of a trace of iodine to sulphuric acid (D 1.84) facilitates the sulphonation of aromatic compounds (com-pare Heinemann Brit. Pat. 12260 of 1915). It has been found that ordinary sulphuric acid and a trace of iodine can advan-tageonsly be used in place of fuming sulphuric acid with o r witthout the addition of phosphoric olxide et'c. The nature of the product is changed in certain cases, thus making ela,sy the preparation of some of the acids difficult to obtain. The catalytic sulphonation is facilitated by the presence of an amino- hydroxy- or halogen group in the molecule but proceeds with less ease in the case of carboxylic acids and is inhibited in the case of nitro-compounds.This fact probably explains the non-formation of disulphonic acids in the product. It is significant that there is an optimum tempera-ture for each reaction in which maximum transformation takes place. It has also been noticed that there is some liberation of iodine vapour but no trace of sulphur dioxide or hydrogen iodide could be detected in the space above the reaction mixture. The discrepancy between the actual yield and that theoretically possible was accounted for in nearly all cases by the unchanged original material. EXPERIMENTAL. I n the experiments to be described below the general method of work was to heat a mixture of a few grams of the substance and the calculated quantity or an excess of sulphuric acid (D 1-84) together with a trace of iodine for a few hours a t the temperature determined by trial a t which the transformation was greatest.The product was poured into water the free sulphuric acid removed with barium carbonate or hydroxide and the acid liberated from the filtrate by exactly neutralising with sulphuric acid. The solution of the free acid was concentrated whereupon it was obtained in a crystalline condition. I n some cases the product was poured into a saturated solution of potassium chloride when the potassium salt separated in fine crystals (0-nitrophenol etc.). The acid or the potassium salt was converted by the usual method into the sulphonyl chloride 1406 T H ~ CATALYTIC ACTION OF IODINE IN SULPHONATION.from which the amide mercaptan etc. were prepared in order to characterise it. Some of the sulphonic acids described gave colour reactions with ferric chloride and characteristic salts with heavy metals. When the acid could not be satisfactorily identified it was transformed through its amino- or nitro-groups etc. into the corresponding hydroxy- or amido-compounds etc. in order to establish its constitution. I n some cases it was found convenient to extract the sulphonic acid from the sulphonated mass with alcohol (0-toluidine). The results obtained from the fusion of the products with potassium hydroxide were not taken into account unless sub-stantiated by further evidence.Sulphonation of Benzoic Acid. A mixture of 12 grams of benzoic acid 9 C.C. of sulphuric acid, and a small cryst'al of iodine' was heated a t 175-180O for aboutl six hours at the end of which time no free benzoic a,cid separated on diluting a sample,. The1 liquid after cooling was poured into watelr, when a clelar solutioln was obtaineld. T'hs solution was neutrdised with barium carbolnatel the precipitated barium sulphate filtered off, and the1 filtrate exactly iieluttraliseld with dilute sulphuric acid. After filtering the liquid was concentrated to a syrup and on keeping in a desiccator crystals were obtained which were Grained washed with a small quantity of alcohol and dried over sulphuric acid in a vacuum. The anhydrous crystals melted at 134-135O (uncorr.), and were very hygroscopic.A test experiment was conducted side by side with the above in which no iodine was used; almost the whole of the bexizoic acid was recovered unchanged. The crystals in aqueous solution gave .a reddish-brown coloration with ferric chloride but no precipitate and were identified as o-sulphobenzoic acid by the formation of salicylic acid when fused with potassium hydroxide a t a moderately low temperature (Found S=15*0. I n the above experiment about a gram of benzoic acid sublimed away and was thus not sulphonated. The following table gives a resume of the results obtained with other substances : Calc. for acid +lH,O S=14.57 per cent.) THE RESOLUTION OF THE KETO-D~LACTONE ETC. 1407 Products by known met hods. Toluene ..........o- and p-acids Benzoic acid ...... rn- and p-acids Phthalic acid . . . . . . -Catechol .......... 3-acid Quinol . . . . . . . . . . mono- and di-sulphonic acids o-Nitrophenol.. . . . . p-acid p-Nitrophenol . . . . o-acid Nitrobenzene . . . . . . m-Dinitrobenzenc . . -o-Nitrotoluene .... p-acid p-Nitrotoluene . . . . o-acid o-Nitroaniline.. . . . . p-acid p-Nitroaniline .... o-acid 3-Nitroaniline . . . . &acid o-Toluidine . . . . . . &acid p . Tolui dine . . . . . . . . Chlorobenzene .... o- and p-acid Bromobenzene . . . . o- and p-acid Subs t aiicc. --By the present, method. p-acid only o-acid no product 4-acid mono-acid p-acid o-acid no product no product p-acid o-acid p-acid o-acid 6-acid 6-acid no product p-acid p-acid Opti- Time mum of re-Yield. temper- action Per cent. ature. Hours. 90-95 100" 1 Above95 175-190 6 - - -75 60-55 1+ 73 70 4 70 50 -70 5 60 50 10 60- 65 -85 85 120 5 100-105 6 - -150 5 140 4 125 44 140 3 150 4$ 150 3 - -110 13 100 3 Summary and Conclusions. (1) Iodine acts as a positive catalyst in sulphonation. (2) Catalysis takes place smoothly when hydroxy- amin* chloro-, bromo- or carboxy-groups are contained in the molecule but with difficulty or not a t all with nitro- or sulphonic substituents. (3) There is an optimum temperature for each substance when the maximum transformation takes place. We have much pleasure in according our best thanks to Sir COLLEGE OF SCIENCE, P. C. RBy for the interest he has taken in the work. UNIVEXSXTY OF CALCUTTA. [Received January 28th 1920.

ISSN:0368-1645    

DOI:10.1039/CT9201701405

出版商:RSC    

年代:1920

数据来源: RSC

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THE RESOLUTION OF THE KETO-D~LACTONE ETC. 1407 CLIV. -The Resolution of the Keto-dilactone of Benzophenone-2 4 2 4'-tetracarboxyEic A cid. By WILLIAM HOBSON MILLS and CHARLES REYNOLDS NODDER. IT follows from the theory of the tetrahedral distribution of the four valencies of the carbon atom that it spirocyclic compound of the type should exist. in two enantiomorpho,us forms 1408 MILLS AND NODDER RESOLUTION OF KETO-DlLACTONE Previous atteiiipts to oblaiu experimental confirmation of tho inolecular asymmetry of such coiiipounds by resolution into optically active antipodes have however been unsuccessful (Marck-wald Ber. 1906 39 1176; Leuchs and various pupils Ber. 1912, 45 189 2114; 1913 46 2420) although Leuchs and Gieseler were able to obtain bis-6-bromo- y -valerolactone-aa-spirane which contains only two asymmetric carbon atoms in three inactive modifications and they attributed the existence of the third form to the presence of a third centre of asymmetry in the substance, due to its spirocyclic configuration.A spirocyclic compound of the type in question which appeared specially suitable for investigation is the keto-dilactone (I) of benzophenone-2 4 2’ $’-tetracarboxylic acid (11). This compound was prepared by one of us (Proc. Camb. Phil. Soc. 1915 18 149) from di-mxylyl ketone by oxidation to benzo-phenonetetracarboxylic acid and dehydration of the latter by heat-ing with hydrochloric acid. The method of synthesis together with the fact that ths product possesses the correct molecular weight, as we have found by the ebullioscopic method in acetone solution, leaves no doubt that it possesses the structure represented above.After unsuccessful attempts with the commoner alkaloids we have succeeded in resolving this substance into two optically active modifications with specific rotations [aID of approximately k 17O by means of a synthetic optically active base a-phenylethylamine (Hunter and Kipping T. 1903 813 1147; LovBn J . pr. Chem., 1905 [ii] 72 307). Using the d-base the I-acid was obtained, and the d-acid was isolated from the filtrate with the aid of the I-base. The 1-Keto-dilactonic A cid.-The following experiment is described as an example of several which have been carried out with similar results. The keto-dilactonic acid (5.75 grams) was suspended in methyl alcohol (100 c.c.) and a solution of cl-a-phenylethylamine (4.09 grams) having [a]’;;’ 39*64O in methy OF BENZOPHENONE-2 4 2' 4'-TETRACARBOXYLIC ACID.1409 alcohol (12 c.c.) was added drop by drop. The temperature rose from 2 2 O to 2 6 O and a clear solution was obtained after the addi-tion of about two-thirds of the base. After all the base had been introduced dry ether (110 c.c.) was added. The salt rapidly crystallised crystallisation being assisted by rubbing with a glass rod. The crop thus obtained (about 7 grams) was recrystallised from a mixture of methyl alcohol (210 c.c.) and ether (330 c.c.). The recrystallised salt (about 2 grams) was decomposed by treat-ment with hydrochloric acid (D 1-08> and the liberated keto-dilactonic acid carefully washed with water and dried.It was dissolved in niethyl ethyl ketone in which it is more readily soluble than in the other common solvents and polarimetrically examined ; 1.0375 grams in 30 C.C. gave aEo -2.25O (Z=4) whence [a];' - 1 6 . 3 O . Of this product 0.943 gram was combined as before with 0.671 gram of d-base. About 1 gram of salt was obtained which on decomposition gave 0.6127 gram of acid. This was polarimetric-ally examined 0.6127 in 13-1 C.C. gave ug5 - 1-58O ( I = a) whence The I-keto-dilactonic acid was recovered from s o h -tion and analysed (Found C = 59.4 ; H = 2.44. C,,H,O re,quires C=59*99; H=2*37 per cent.). The highest specific rotation which we have observed for the Z-acid in the experiments which we have carried out up to the present is [a];' -17.4O in methyl ethyl ketone solution.The d-Keto-Iactonic d cid.-The filtrate from which as described above the first crop of d-base-Z-acid salt had been deposited gave, on acidification 1.3 grams of an acid which proved to be destro-rotatory; 0.679 gram in 30 C.C. of methyl ethyl ketone gave u$ 0 ~ 7 1 ~ (1=4) whence [a] 7.9'. This acid was then combined with I-a-phenylethylamine having [a] - 38*5O in the following manner. The acid (1.23 grams) was suspended in methyl alcohol (10 c.c.) I-base (0.87 gram) dissolved in methyl alcohol (2 c.c.) was added and the salt precipitated with dry ether (6 c.c.). The acid (0.6585 gram) liberated from this salt was again combined with I-base (0.47 gram). The salt thus obtained gave on decom-position 0.559 gram of acid which was polarimetrically examined ; 0.559 gram in 13.1 C.C.gave a 1.50° (1=2) whence [a] 17'5O. From this acid by repeating the above process 0.426 gram of acid was obtained on which the following observation was made : 0.426 gram in 13.1 C.C. of methyl ethyl ketone gave a 1*1l0, whence [a] 1 7 . 1 O . This acid was then recovered from solution and analysed (Found C = 59.70 ; H = 2.38. C17H,0 requires C = 59.99 ; H = 2.37 per cent.). The optically active forms of the keto-dilactonic acid are con-- 16.9O 1410 ATKINSON HEYCOCK AND POPE THE PREPARATION AND siderably more readily soluble than the racemic form in all solvents examined. When saturated solutions of the d- and Z-modifications in methyl ethyl ketone are mixed an immediate copious precipitate of the racemic form is produced. To show the dependence of the optical activity on the lactonic structure of the compound a solution of the d-acid in approxini-ately 1 per cent. sodium hydrogen carbonate was examined in the polarimeter . The rotation was observed to diminish gradually, sinking to the half value in about twenty-four hours and disappearing completely in about four days. Further experiments on larger quantities of material are in progress in order to extend these observations and particularly to determine the specific rotation of the optically pure acids. One of us (C.R.N.) is indebted to the Department of Scientific and Industrial Research for a grant for which he desires to express his thanks. UNIVERSITY CHEMICAL LABORATORY, CAMBRIDGE. [Received November 2nd 1920.

ISSN:0368-1645    

DOI:10.1039/CT9201701407

出版商:RSC    

年代:1920

数据来源: RSC

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1410 ATKINSON HEYCOCK AND POPE THE PREPARATION AND CLV.- Th e Preparation und Physical Fy opert ies of Carbonyt Chloride. By RALPH HALL ATKINSON CHARLES THO~AS HEYCOCK and WILLIAM JACKSON POPE. ALTHOUGH carbonyl chloride COCl, was discovered by John Davy in 1812 (Phil. Trans. 1812 102 144) and has found extensive scientific and technical applications very little information is contained in the literature concerning its preparation and physical properties; Davy obtained the substance by effecting the combination of carbonic oxide and chlorine under the influence of sunlight and this method of preparation was elaborated by Wilm and Wischin (AnnaZen 1868 147 150). Schutzenberger (BUZZ. SOC. chim. 1869 [ii] 12 198) and Armstrong (Proc. Roy. SOC., 1870 18 504) prepared it by the action of sulphur trioxide on carbon tetrachloride ; the latter method has been recently studied by Grignard and Urbain (Compt.rend. 1919 169 17) and used by Paternb and Mazzucchelli (Gazzetta 1920 50 i 30) in their determination of the physical properties of carbonyl chloride. On the introduction of carbonyl chloride as a weapon of chemica PHYSICATI PROPERTTES O F CARRONYT CHLORIDE. 1411 warfare it became necessary to ascertain which method of pre-paration was most adaptable as a works process for manufacture, and one described by Paternb (Gazzetta 1878 8 233) presented itself as probably the best for this purpose. Paternb states that, on passing a rapid current of mixed carbonic oxide and chlorine a t the ordinary temperature over animal charcoal carbonyl chloride is produced very rapidly with considerable evolution of heat.Difficulties were encountered in carrying out the Paternb method of preparation; a number of samples of commercial animal and vegetable clzarcoalsi proved almost without effect as catalysts. Ultimately a charcoal was prepared which gave quite remarkable results in inducing the combination of carbonic oxide and chlorine ; this was made in the following manner. Fresh ox bones were crushed embedded in sand in a clay crucible and burnt in a muffle furnace; the residual charcoal was then well extracted with hot hydrochloric acid washed with water and heated as before in sand. Finally the bone charcoal was kept a t a red heat for some time in a current of dry chlorine. The charcoal prepared in this way was crushed into small frag-ments and after sifting off the dust 10 grams were filled into a U-tube immersed in a water-bath; a rapid current of mixed carbonic oxide and chlorine in which the former was in rather the greater volume was then passed over the charcoal.Carbonyl chloride was produced freely when the water-jacket was kept a t the ordinary temperature but on raising the bath temperature to between 40" and 50° combination proceeded a t a greater rate than that a t which it was possible to supply the mixed gases. Using the bone charcoal catalyst in the manner described and liquefying the carbonyl chloride by means of a freezing mixture about 10 kilograms of the compound were produced without any sign that the activity of the 10 grams of charcoal had suffered diminution.It is thus shown that Paternb's method for preparing phosgene is correctly stated but that certain precautions are necessary in the preparation of the animal charcoal used. Purther investiga-tfions showed that certain kinds of vegetable charcoal act even more vigorously in inducing the condensation of carbonic oxide and chlorine and the highly activated wood charcoal used in the Army box respirator proved more efficient as a catalyst than the bone charcoal described above. A U-tube containing 10 grams of the box-respirator charcoal which had been heated in a current of chlorine gas proved extremely efficient when the water-jacket was maintained a t 14O and one such tube kept a t this temperature yielded more than 20 kilograms of carbonyl chloride with no sign that the catalytic activity had diminished.I n the wor 1412 ATKINSON IIEYCOCK AND POPE THE PREPARATION subsequently described in this paper this active vegetable charcoal was used. The carbonic oxide required for laboratory work 011 the pre-paration of carbonyl chloride is conveniently prepared by passing carbon dioxide over red-hot coke contained in iron tubes heated in an ordinary combustion furnace; the resultant gas after passing over slaked lime and drying over sulphuric acid is practically pure carbonic oxide. I n industrial operations it is to be expected, however that the available carbonic oxide will contain hydrogen. It thus becomes of importance to compare the reactivity of carbonic oxide and hydrogen with chlorine under the catalytic influence of charcoal.A series of experiments was therefore arranged in which varying proportions of hydrogen were mixed with the carbonic oxide and chlorine passed over the catalyst. It was found that the vegetable charcoal was so active a t 14O in inducing the combination of carbonic oxide and chlorine that no advantage accrued from heab ing it to 90° and that working a t temperatures below 70° no hydrogen chloride was produced; a t SOo a small proportion of hydrogen chloride was formed and this was greatly increased a t 90°. It is thus shown that an active form of charcoal will effect the complete conversion of a mixture of carbonic oxide and chlorine into carbonyl chloride a t a temperature 50° below that a t which it begins to exhibit catalytic activity towards a mixture of hydrogen and chlorine.This conclusion seems of impcrtance in connexion with the manufacture of carbonyl chloride from carbonic oxide containing hydrogen. Carbonyl chloride dissociates into carbonic oxide and chlorine a t moderately high temperatures; Bodenstein and Dunant (Zeitsch. physikal. Chem. 1908 61 437) state that under atmospheric pressure carbonyl chloride dissociates to the extent of 67 80 and 91 por cent. a t 503O 553O and 603O respectively and that dis-sociation is complete a t 800O. The results obtained by these observers indicate that carbonyl chloride is appreciably dissociated a t 300O. A little consideration will show that if carbonyl chloride free from chlorine is to be manufactured from a mixture of carbonic oxide and' chlorine containing an excess by volume of the former, the temperature of the catalyst must be maintained below that a t which carbonyl chloride suffers appreciable dissociation.Further, it may be anticipated that within the dissociation range of temperature the catalyst will act comparatively sluggishly ; the chlorine content of the produced carbonyl chloride should thus be higher than that' indicated by the equilibrium composition and th PHYSICAL PROPERTIES OF CARBONYL CHLORIDE. 141.3 catalyst would become feebler with prolonged use. The following experiments were made for the purpose of further elucidating this question. A mixture of chlorine and carbon monoxide containing 3.5 per cent. excess by volume of the latter and1 standing over brine saturated with chlorine was dried over sulphuric acid and calcium chloride and passed over the absorbent charcoal the latter being contained in a glass tube 45 cm.in length and 1-9 cm. in diameter, a t different temperatures. For temperatures from 20° to 150° the tube was heated in an oil-bath; for temperatures from 150° to 520° the tube was wrapped in three layers of copper gauze encased in heavy iron gas pipe and heated in a gas furnace the gas pressure being carefully regulated. A quill tube was fitted into the axis of the catalyser tube so that the temperature a t any point could be measured by a copper-constantan thermo-couple. Control experiments showed that on sliding tlie thermo-couple along tshe tube the maximum temperature variation from place to place and for a period of several hours was not more than loo when no chemical action was occurring.With this arrangement of apparatus it proved easy to obtain carbonyl chloride free from chlorine a t temperatures between 50° and 200° and to collect 90 to 97 per cent. of the theoretical yield of phosgene. The important point was established however that the major part of the Combination took place at the position in the tube first exposed to contact of the mixed gases. This was further demonstrated by keeping the first or entrance half of the tube a t 18O and the second or exit half of the tube a t looo; the main disengagement of heat occurred a t the junction between the cool and the hot charcoal. By sliding the thermo-couplb along the tube the heat-ing effect of the reaction could be followed as the couple was passed along the tube from the front of the exit half to the front of the entrance half.It would be expected that on subjecting mixtures of carbon monoxide and chlorine to the action of the catalyst a certain maximum temperature would be attained which could not be exceeded-the equilibrium temperature a t which the reverse action absorbed the heat liberated. On passing the mixed gases a t the rates of 0.84 and 2.4 litres per minute the temperature of 464O was attained and remained constant; this is t(o be regarded as the maximum temperature which can be attained in the large-scale catalysing vessels used in the manufacture of carbonyl chloride. Jn the experiments just described it is noteworthy that a t the rate of flow of 0.84 litre per minute the layer of charcoal found to be at 464" was only about 3 mm.long whilst when the ga 1414 ATmNSON HEYCOCK AND POPE THE PREPBATION AND passed through a t 2.4 litres per minute the layer of catalyst main-tained a t 464O was some 10 mm. in thickness. Attempts to prepare carbonyl bromide with t,he aid of charcoal as a catalyst were unsuccessful. The Dissociation of C'arBoi:yl C'hloride. Since the combination of carbon monoxide and chlorine is highly exothermic CO + C1 = COC1 + 26C and the catalyst used is very active it seemed undesirable to attempt the investigation of the dissociation curve of carbonyl chloride by the study of the associa-tion; the foregoing experiments have shown the difficulty of main-taining the catalyst a t an even temperature during the formation of the chloride.A series of experiments was therefore made on the dissociation of carbonyl chloride for the purpose of determining the equilibrium between it and its dissociation products with temperature a t the atmospheric pressure. Since the dissociation is endothermic and must proceed to equilibrium in contact with the catalyst it should be possible to ensure that the catalyst will be kept a t an even temperature and will set up equilibrium a t that temperature. The carbonyl chloride used in all the further work described below was prepared from carbon monoxide and chlorine and pre-served in glass vessels in contact with mercury t o ensure its freedom from chlorine.The absorbent charcoal was maintained a t a constant tempera-ture as described above and a slow steady stream of dry carbonyl chloride was passed over it. The gaseous products were passed through a separating funnel A of 338 C.C. capacity entering a t the bottom and leaving through a side-arm in the shoulder; when all the air had been displaced from A the two taps were closed and a 20 per cent. potassium iodide solution was run in from a dropping funnel B stoppered into the neck of A . After well shaking the whole apparatus further quantities of potassium iodide solution were run in until action was a t an end. The solution was then washed out with water and the iodine titrated against thio-sulphate in order to determine the free chlorine present in the gas.The residual gas consisting of carbon monoxide with some carbonyl chloride and usually a little air was passed into a gas pipette and shaken with sodium hydroxide solution to remove the chloride. The carbon monoxide was determined by absorption in a hydro-chloric acid solution of cuprous chloride ; the residual air was measured and its volume deducted from the volume of the cylinder, A . Direct determinations of the chlorine carbon monoxide an PHYSICAL PROPERTIES OF CaRBONYL CHLORIDE. 1415 carbonyl chloride are thus obtained; the volumes of carbon mon-oxide and chlorine always corresponded closely and in table I, which suminarises the results the mean of the two slightly differing volumes is given. The degree of dissociation 11 of the carbonyl chloride is calcu-lated from the formula and the curve (Fig.1) is drawn by plotting the values of D against the temperature. TABLE I. Dissociation of Car bony1 Chloride. Percentage by weight. T O . l...... 101 2...... 102 3...... 151 4...... 153 5...... 208 6...... 211 7...... 237 8 . . . . . . 239.5 g...... 309 10 ...... 314 11 ...... 318 12 ...... 341 13 ...... 400 14 ...... 406 15 ...... 443 16 ...... 449 17 ...... 460 18 ...... 486 19 ...... 505 20 ...... 505 21 ...... 506 -&...... 517 '? '> 7 coc1,. 99.54 99.50 99-50 99.46 99.16 99.26 98.68 98.86 94.38 94.51 94.37 92.48 78.62 82.56 68-89 66.60 64-05 58.32 66.51 46-77 72.48 70.54 Cl,. 0.32 0.36 0.36 0.38 0.60 0.53 0-94 0.82 4.02 3.94 4-03 5-38 15.34 12.50 22.3 1 23.90 25-78 29.89 24.02 38.17 19.74 21.13 - co.0.13 0.14 0.14 0.15 0.24 0.2 1 0.37 0.33 1.59 1.55 1.59 2.14 6.04 4.94 8-80 9.40 10.17 11.79 9.47 15-05 7-78 8.33 Degreo Volume per cent. of dis-7' - sociation, COCl,. CO & Cl,. D. 99.10 0.45 0.45 99.01 0.50 0-50 99.01 0.50 0.50 99-95 0.53 0.53 98-36 0.82 0.83 98.55 0.73 0.74 97-41 1.30 1.32 97.74 1.13 1.14 89.35 5.31 5.61 89.61 5.20 5.48 89.34 5.33 5-63 68.05 6.98 7.50 64.79 17.60 21.36 70.31 14.84 17.43 52-57 23.71 31-08 49.23 25-39 34.02 47.14 26.43 35.92 41.19 29.41 41.65 49.85 25-08 33-47 30.55 34.72 53-19 56-87 21.57 27-50 54.51 22-76 29.45 The method of experimentation which has been applied has the fault that it does not ensure the dissociation products being cooled so rapidly that their partial recombination is prevented.The effect of this is seen in the fact that certain points namely those from experiments numbered 19 21 and 22 lie off the general course of the graph; in these experiments the gas current was passed much more slowly than in the others. I n consequence,'it may be found later that the degree of dissociation for any particular temperature as now recorded is too low. F o r practical purposes it may be concluded that experiments 1 to 4 referring to temperatures of looo to 150° have give 1416 ATKINSON HEYCOCK AND POPE THE PREPARA9!'TON AND identical results; the results of experiments 5 and 6 made a t t,emperatures just above 200° show a distinct increase in the degree of dissociation indicated a t looo and 150°.This increase is still more marked a t 2 3 7 O and 239O. The accuracy of the suggestion made above that carbonyl chloride free from chlorine can only be produced a t temperatures YlG. 1 . Dissociation of cnrbonyl chloride. 600' 600 400 c, 3 '$ 300 P ry" 200 100 10 20 30 40 50 Pcrccntage degrcc of dissociation. below 200° must be regarded as fully substantiated by the above experimental results. It is noteworthy that dissociation is indicated as occurring even a t 1000 and 150° by the results now recorded. It. will be seen, however that no difference is observable between the degree of dissociation indicated a t 100' and 1 5 0 O ; the indication may there-fore be attributed to some other cause than that of dissociation, possibly t o the slight reaction between potassium iodide in the acid solution and carbonyl chloride referred to below.Such a reaction would not disturb the equal volume ratio found betwee PHYSICAL PROPERTIES OF CARBONYL CHLORIDE. 1417 the carbon monoxide and chlorine and it is recorded by Bessoa (Compt. rend. 1896 122 140) that carbonyl chloride dissolves hydriodic acid with liberation of iodine. Whilst Bodenstein and Dunant (Zoc. cit.) found that carbonyl chloride is dissociated to the extent of 67 per cent a t 503O the smoothed curve (Fig. 1) expressing the Cambridge results indicates the dissociation to be 55 to 56 per cent. a t this temperature. The former workers analysed the mixture of gases by bubbling it through aqueous potassium iodide solution and it is known that pure carbonyl chloride liberates a small amount of iodine in such a solution and that the quantity of iodine formed increases on keeping (DelBpine and Ville BUZZ.SOC. chim. 1920 [iv] 27 283). It is significant that Bodenstein and Dunant obtained higher values for the dissociation in those experiments which lasted the longest (45 80 and 120 minutes) and that the dissociation-temperature curve plotted from their results slopes a t an improbable angle. The heat of formation of gaseous carbonyl chloride calculated from the degree of dissociation is +25*4 C. a t 475O and +23*4 C. a t 425O according to the Cambridge results and + 19.2 C. a t 528O and +26-6 C.a t 578O calculated from the results of Bodenstein and Dunant. Thomsen (“ Thermochemkhe Untersuchungen,” 1882, 11 364; Ber. 1883 16 2619) gives the value +26*14 C. a t the ordinary temperature and criticises adversely the value + 18.8 C. previously obtained by Berthelot. Vayour Pressure of C’arbonyl Chloride between - looo and + looo. The boiling point of carbonyl chloride is given by Beckmann (Zeitsch. anorg. Chem. 1907 55 370) as 8*2O/756 mm.; no other data concerning the vapour pressure of this compound were avail-able before the recent publication of Paternb and Mazzucchelli (Zoc. cit.) who made a series of determinations a t temperatures between - 1 9 O and +24O. We have determined the vapour pressure at temperatures from -183O to + 1 8 O in one type of apparatus and by means of another have extended the results up to +looo.The apparatus used in the determination of the vapour pressure between - 1 8 3 O and + 1 8 O is depicted diagrammatically in Fig. 2. The distillation flask F of about 60 C.C. capacity is connected with a differential manometer HB placed in front of a silvered mirror on which a millimetre scale is engraved so as to avoid parallax. Through the neck of the flask passes a thistle funnel, S for the purpose of sealing the leads of the thermo-couple air-tight by means of Faraday wax at the point where the bulb joins VOL. CXVII. 3 1418 ATKINSON HEYCOCK AND POPE THE PREPARATION AND the stem. A joint thus made was found to be very satisfactory and quite unattacked by carbonyl chloride vapour.The thermo-couple used was of copper-constantan ; one junction was kept in ice and the other in the liquid carbonyl chloride. The couple was connected to a delicate millivoltmeter which could be read with accuracy to 0.01 millivolt. For the graduation of the couple the following temperatures were assumed : TABLE 11. Melting ice ................................. - 0.00 Millivolts. Steam a t 760 mm. pressure ............ 100" + 4-07 Freezing point of mercury ............... - 38 - 1.38 Solid carbon dioxide and ether ......... - 79 - 2-65 Boiling liquid oxygen ..................... - 183 -5.12 FIG. 2. The millivolts corresponding with each of these temperatures were read off on the instrument and the results plotted. The accuracy of the calibration was confirmed by determining with the aid of the couple the boiling point of a very pure sample of ethylene; this gave the value -104O which compares well with the standard value of -103.50 given by Wroblewski and Witkowski.After some preliminary trials the following procedure was adopted. About 50 C.C. of pure liquid carbonyl chloride was dis-tilled into the flask F ; the mercury was then run out of the mano PHYSICAL PROPERTIES O F CARBONYL CHLORIDE. 1419 meter and the whole apparatus exhausted while the contents of the flask were maintained a t -80'. The temperature of the carbanyl chloride was then allowed to rise until vapour was freely given off. This process was repeated several times during the three days occupied by the experiments so as to ensure the complete absence of air.A series of observations of the pressure and temperature of the carbonyl chloride was made a t the selected temperatures with the follc~wing results (table 111) : TABLE 111. Temperature. Water-bath .................................... + 100" , , .................................... , , .................................... Z K 5 Melting ice .................................... -Ice and salt mixture - 19 Freezing point of mercury - 39 Solid carbon dioxide and ether ............ - 79 Boiling liquid oxygen ........................ - 183 ........................ .................. Pressure mm. of Hg. 16.07 x 760 5.1 1 x 760 1105-5 568.3 236.0 89.5 4-0 0 mm. These results have been plotted on the curve (Fig.3) from which the vapour pressures of carbonyl chloride for each loo between +20° and -looo have been taken; these values are included in table V. After the vapour pressure of carbonyl chloride had been measured over the range -183O to + 1 8 O recourse was had to a different form of apparatus in order to extend the observations up to looo. A sealed tube containing carbonyl chloride and a special type of manometer was heated in a water-bath to the desired temperature and kept there for two to three hours. The glass manometer is shown in Fig. 4. The graduated tube AB was carefully calibrated by means of mercury. At the same time the volume of the manometer was measured by weighing the amount of mercury which it contained. After the manometer had been thoroughly cleaned the tube AB was silvered internally.The slight difference in the weight of the manometer before and after silvering proved that the amount of silver deposited was so small that its eflect could be neglected. The manometer having been carefully cleaned and dried was filled with dry air and lowered into a hard glass tube containing about 10 C.C. of dry mercury (see Fig. 5). A wire F served to keep the manometer upright in the centre of the tube. The tube was drawn off and finally sealed after 30 C.C. of pure liquid carbonyl chloride had been introduced in the usual manner; due care was taken to ensure that the space above the liquid contained 3 s 1420 ATKINSON HEYCOCK AND POPE THE PREPARATION AND carbonyl chloride vapour only and that air was absent.The pressure tube placed inside an iron tube was kept a t 50° for two hours in a water-bath. As the pressure of the vapour increases it forces the mercury into the manometer thereby compressing the air. When FIG. 3. Vapour pressure of carbonyl chloride. 1 IT. 0.005 0.004 0.003 0.002 0.001 4- 40" + 20 0 - 20 Q u s E E - 40 F4 h - 60 - 80 - 100 _- . -- 120 0 200 400 600 800 1000 1200 14 t h e 1 2 n, Q 9 3 4 0 Pressure in mm. of mercury. mercury rises into the silvered part of the tube it dissolves the silver as far as the highest point it reaches. Thus a record is made of the volume of the compressed air at the temperature of the experiment. After the tube had cooled and a note been made of the point to which the mercury had dissolved the silver the experiment wa PHYSICAL PROPERTIES OF CARBONYL CHLORIDE.1421 repeated a t looo. The following data were obtained volume of manometer 4.675 C.C. ; barometer 758 mm. ; temperature 16.6'. Volume of compressed air at 50° = 1.038 c.c. and a t loo0'= 0.380 C.C. The following results were calculated after applying corrections for the pressure of the columns of carbonyl chloride and mercury: Vapour pressure of carbonyl chloride at 50" = 5.11 x 760 mm. Y 9 Y ? Y 9 ) 100" = 16.07 x 760mm. It was noticed that the surface of the mercury was slightly dirty FIG. 4. FIG. 5. FIa. 6. after these experiments; it is suggested that some chemical change occurs in accordance with the equation 2Hg + COCl = CO + Hg,Cb, and that the two values last given may be rather high by reason of the formation of a trace of carbonic oxide.From the vapour-pressure determinations now recorded the molecular heat of evaporation (without performance of external work) of carbonyl chloride between Oo and So is calculated as approximately 5500 calories. A molecular heat of evaporation of 5500 calories for carbonyl chloride gives a value of 2 8 O to 2 9 O for the molecular rise in boiling point of this solvent; Beckmann (Zeitsch. anorg. Ghent. 1907 55 371) has determined thi 1422 ATKINSON HEYCOCK AND POPE THE PREPARATION AND quantity experimentally as 29O. Since the lahter value is obtained as the mean of six values lying between 27-2O and 30*8O the agreement between his value and ours may be considered satisfactory.Our values for the vapour pressure of carbonyl chloride at the higher temperature are rather higher than the Italian ones whilst a t Oo and below the reverse is the case. That oiir values arc con-cordant among themselves is seen from the fact that the curve plotted between the reciprocal of the absolute temperature and the logarithm of the observed vapour pressure is pra,ctically a straight. line; this curve is indeed drawn as a straight line in Fig. 3. Since the vapour-pressure curve for carbonyl chloride only begins to fall rapidly at below -40° it is clear that considerable losses will occur in the preparation unless the effluent gas saturated with carbonyl chloride is cooled well below -4OO. The solubility of the chloride in a number of liquids from which it' might be sub-sequently recovered by evaporation was therefore ascertained in order to learn whether washing the effluent gas with a solvent would lead to economy.Solubility of Carbonyl Chloride in Or?qanic Liquids. Two or three C.C. of the solvent to be used are placed in a glass bulb of about 10 C.C. capacity immersed in a constant-temperature bath and a slow current of the gas evolved from gently boiling carbonyl chloride is passed through the bulb until no further absorption occurs. Saturation was generally complete in about three hours and the contents of the bulb were then hermetically sealed. The weight of the saturated solution was given by direct weighing and the quantity of carbonyl chloride present determined by breaking the bulb in a closed bottle containing 50 or 100 C.C.of standard sodium hydroxide solution and titrating with standard acid. The number of grams of carbonyl chloride dissolved by 100 grams of solvent are notw stated. Toluene.-At 17*0° 23.5O 30-5O and 31-5O 244.7 124.2 79.38, and 74-48 respectively. Coal-tur Xy1ene.-At 12.307 16-4O 16*9O 23.8O and 29'8O : 457.3 225.6 217.9 103-4 and 71.24 respectively. Creosote Oil.-At 1 6 ~ 2 ~ 77.42. Petroleum boiling at 180-280°.-At 12*3O 15-8O 16*7O 22-4O, 23*7O 29*9O and 30° 263.8 163.1 143.4 79-5 71-2 49.2 and 48.6 respectively. Heavy Lubricating Oil.-At 1 5 * 6 O 23*5O and 31.0° '79.7 39.3, and 24.5 respectively PHYSICAL PROPERTIES 08 CARBONYL CHLORIDE. 1423 Nitrobenzene.-106.4 a t 16.8O. a-CRloronaphthalene.-lO4-5 a t 17.0O.Ch1orobenxene.-At 12.307 16'6O 16*7O 24*2" and 29-7O 422.1, 204.3 221.6 99.9 and 81-9 respectively. Acetylene Tetrachloride.-At 16.807 25.1° and 29.9O 149.7, 89.4 and 74.9 respectively. The solubility of carbonyl chloride differs widely according to the solvent. Toluene coal-tar xylene and chlorobenzene are by far the best solvents of those examined and in view of their elevated boiling points would appear to offer most advantages as scrubbing agents for efluent gases containing carbonyl chloride. Ordinary burning petroleum boiling a t 180° to 280O' is the next best solvent and heavy mineral lubricating oil and acetylene tetrachloride are not quite so good. MeZti?ag and Freezing Points of Carbonyl Chloride. The only recorded melting point for carbonyl chloride is that given by Erdmann (Annalen 1908 362 148) as -118O.Our determinations were made by immersing the bare junction of a standardised copper-constantan thermo-couple in pure liquid carbonyl chloride; on cooling in a bath of liquid air the carbonyl chloride solidified to a white crystalline mass and on allowing the temperature to rise slowly the temperature as recorded by a milli-voltmeter remained steady a t -126O throughout the melting of the substance. On cooling the liquid very slowly with constant shaking the carbonyl chloride commenced to crystallise at - 128O. Density of Liquid Car bony1 Chloride. The density of liquid carbonyl chloride was determined by Emmerling and Lengyel (Annalen Supp. 1870 7 106) as 1.432 a t 0°/40 and as 1.392 a t 18*6O/4O; Paternb and Mazzucchelli (loc.cit .) have quite recently made a series of careful determinations between - 15'4O and + 5 9 ~ 9 ~ . We have determined the density a t -104*Oo -79O O" and +49*90 with the aid of weight thermo-meters of transparent silica; two such thermometers A and B, were used. After filling the thermometers with mercury and repeatedly boiling out they were cooled for some hours in ice dried in a vacuum desiccator and weighed precautions being taken to collect the mercury overflow; thermometer A contained 80.1054 grams of mercury a t Oo whilst B contained 67.2640 grams. Assumin 1424 ATKINSON HEYCOCK AND POPE THE PREPARATION AND Regnault's value of 13.5955 grams for t3he weight of 1 C.C. of mercury at Oo the capacities of A and B are calculated as 5.8920 and 4.9475 C.C.respectively. Thermometer A was filled with mercury a t Oo heated in a steam hypsometer (Bar. 768 mm.) for an hour and then weighed; it contained 78.6835 grams of mercury a t 100-3O. From these values, the coefficient of apparent expansion of mercury in silica is calcu-lated as (1.4219) / (78.6835 x 100.3) = 0~000,180,17 ; assuming Regnault's value of 0*000,180,92 for the coefficient of absolute expansion of mercury between 00 and looo the coefficient of cubic expansion of transparent silica becomes 0*000,000,75 a quantity which is small enough to be neglected. I n making the density determinations a t Oo and lower tempera-tures the thermometer A was filled with liquid carbonyl chloride in the ordinary way and kept a t the steady low temperature for for half to one hour; no attempt was made to weigh the vessel on account of the difficulty of preventing moisture from the air con-densing on it during transference.The weight of carbonyl chloride was found by removing the tube from the cooling bath and lower-ing it into a bottle containing 200 C.C. of ice-cold standard ( 2 N ) sodium hydroxide which was then stoppered and clamped. The liquid in the thermometer slowly boiled off usually taking from one to two1 hours and when all had evaporated and reacted with the alkali the excess of the latter was determined by titration with an acid; the weight of carbonyl chloride was then calculated. I n making the determination at +49*9O the weight thermo-meter B was filled a t -79O and was then lowered nose down-wards into a stout combustion tube the lower end of which contained mercury.Cold carbonyl chloride was poured into the tube which was then drawn off and placed inside an iron tube (see Fig. 6) gradually heated to 4 9 ~ 9 ~ in a water-bath and kept a t that temperature for three hours. The tube was then slowly cooled finally in ice and salt and opened in the same way as in an ordinary pressure-tube experiment. The thermometer, which now contained mercury and carbonyl chloride was with-drawn from the tube drenched on the outside with cold ether, placed in the standard sodium hydroxide solution and allowed to become warm slowly; the titration was then performed as before. All errors due to the deformation of the silica tube by pressure were in this way eliminated as the pressure within and without the tube was practically the same.The density of carbonyl chloride (that is weight in grams of 1 c.c.) was determined a t -104O (boiling point of ethylene) -79O (solid carbon dioxide wetted with ether) Oo (ice) and +49*9 PHYSICAL PROPERTIES OF CARBONYL CHLORIDE. 1425 (thermo-regulator) ; the results of the actual experiments are given in tabular form (table IV). TABLE IV. Weight Weight of COCl, Temperature. thermometer. in grams. C A -104'0" t(Vo1. 5.892 c.c.)) 9'892 - 79 Y ? 9.519 - 79 Y Y 9-503 0 9 9 8463 0 8.443 6-502 i5 +49.9 { (Vol. 4.948 c.c.)} Density of COC1,. (Weight of 1 C.C. of liquid. ) 1-679 1-616 1.613 1.436 1.433 1.314 From these results a smooth curve was drawn and a table (table V) constructed giving the density of carbonyl chloride for each loo from -looo to +50°.TABLE V. Density and Vapour Pressure of Liquid Car bony1 Chloride. Tempera-ture. -110O - 100 - 90 - 80 - 70 - 60 - 50 - 40 - 30 Density. Grams per C.C. 1.685 1-663 1.640 1-617 1.594 1.572 1 $49 1,526 1.504 Vapour pressure. Mm. of mercury -4 11 24 47.5 85 141 Tempera- Density. ture. Grams per C.C. - 20 1-481 - 10 1.459 0 1.435 1.412 $-lo 1.388 +" + 30 1.363 + 40 1.338 + 50 1.314 Vapour pressure. Mm. of mercury. 226 361 568 844 1212 -I 5-11 x 760 The mean coefficient of cubical expansion of carbonyl chloride between -79O and +49*9O is calculated as (1.6145 - 1*3140)/(1*3140 x 129) =0*001,77. The values for the temperature ranges -1040 to -79O -79O to Oo and Oo to +49*9O are 0~001,60 0*001,59 and 0.001,84 respectively. The values for the density of liquid carbonyl chloride which we now give are slightly higher than those obtained by the Italian workers; the latter obtained their product by the action of sulphur trioxide on carbon tetrachloride and it is curious that Ernmerling and Lengyel who prepared their material as we did by the com-bination of carbonic oxide and chlorine obtained results for the densities which are almost identical with ours for the two tempera-3 F 1426 PYMAN AND RAVALD: tures a t which they worked. The discrepancies Letween the results obtained by Paterni and Mazzucchelli and by ourselves may possibly be traced to the presence of some characteristic impurity in the carbonyl chloride made by one or the other method. The work described in the present paper was carried out for the purposes of the Chemical Warfare Department and permission for its publication has been given by the General Staff. Our thanks are due to our assistant Mr. George Hall for much help in experimental work. THE CHEMICAL LABORATORY, UNIVERSITY OF CAMBRIDGE. [Received October lBth 1920.

ISSN:0368-1645    

DOI:10.1039/CT9201701410

出版商:RSC    

年代:1920

数据来源: RSC

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1426 PYMAN AND RAVALD: CLVI.-o- and p - Tol?~eneaxoglyoxalines. By FRANK LEE PYYAN and LEONARD ALLAN RAVALD. IN continuation of previous work on arylazoglyoxalines (Fargher and Pyman T. 1919 115 217) the interaction of 0- and p-toluenediazonium chlorides and glyoxaline has been studied. The methods employed and the products obtained are generally similar to those described in the previous communication. o-Toluenediazonium chloride combines with glyoxaline in aqueous sodium carbonate giving 2-0-toZueneuzogZyoxali~ne (I) in poor yield a considerable amount of bis-o-tolueneazo-o-cresol being produced as a by-product. On replacing the sodium carbonate by sodium hydroxide the yield was very little better but the by-products were of different character whilst when sodium hydrogen carbonate was used in the place of sodium carbonate bis-o-toluens azo-o-cresol was again produced but no tolueneazoglyoxaline.2 - o - Tolueneazoglyoxaline resembles 2 - benzeneazoglyoxaline closely in physical and chemical properties. On reduction with stannous chlo’ride it gives 2 @-diamir~o-4-m- tolylylyoxuline (11). The combination of p-toluenediazonium chloride with glyoxaline in aqueous sodium carbonate leads to the formation of 2-p-toluene-azoglyoxaline (111) in good yield together with a small amoun 0- AND P-TOLUENEAZOGLYOXANES. 1427 of an ~somericie doubtless 4-p-tolueneazoglyoxaline (IV) and a quantity of p-tulueneazo-p-cresol. We had expected that (111.) w. 1 2-p-tolueneazoglyoxaIine would resemble 2-y-bromobenzeneazo-glyoxaline in giving a good yield of 2-aminoglyoxaline when reduced.with stannous chloride under the condit>ions employed by Fargher and Pyman (loc. cit. p. 244) but this was not the case, 2-aminoglyoxaline being produced in a yield of less than 15 per cent. of the theoretical together with p-toluidine guanidine, ammonia and unidentified products. When 2-p-tolueneazo-glyoxaline is reduced with zinc dust and acetic acid under tho conditions previously employed for the reduction of 2-benzeneazo-glyoxaline (ibid. p. 241) p-toluidine and glycocyamidine were obtained in yields amounting to 97 and 42 per cent. of the theoretical respectively. EXP EB I M E N TAL. 2-0- Tolueneazoglyoxa.line. o-Toluidine (10.7 grams) was diazotised and the product added to a solution of 6.8 grams of glyoxaline and 20 grams of anhydrous sodium carbonate in 500 C.C.of water at 5O. After keeping over-night the brown deposit was collected and extracted with 5 per cent. hydrochloric acid. On the addition of sodium carbonate, the extract deposited 4.8 grams of crude 2-o-tolueneazoglyoxaline melting at 165q the yield amounting to 26 per cent. of the theoretical. The material insoluble in dilute hydrochloric acid amounted' to 7 grams and melted a t 120'; after recrystallisation from alcohol it gave 3.3 grams of pure bis-o-tulueneazo-o-cresol, which melted a t 147O (corr.) and was! identified by analysis [Found (mean) C = 72-4; H = 6.0 ; N = 16.6. Calc. C = 72.2 ; H=6.1; N=16*9 per cent.] and by comparison with a specimen preparedl by the action of o-toluenediazonium chloride on 0-crwl (Noelting and Werner Ber.1890 23 3260). 2-o-27olueneazoglyoxaline crystallises from alcohol in brownish-yellow crystals of indeterminate shape which melt a t 185-186O (mrr.). It is very readily soluble in alcohol or chloroform less readily so in ether or benzene (Found C=64.6 64.4; H=5.4, 5-7; N=30.1. Cl,Hl,N4 requires C=64.5; H=5*4; N=30-1 per cent.) 1428 0- AND P-TOLUENEAZOQLYOXALINES. Reduction of 2-o-Tolueneazoglyoxaline with Stafinous Chloride. Zsolation of 2 4/-Uiamino-4-m-tolylglyoxaline. TWO grams of 2-o-tolueneazoglyoxaline were dissolved in 20 C.C. of hot 2.5 per cent. hydrochloric acid and mixed with 12 C.C. of stannous chloride (40 per cent. w/v) in hydrochloric acid. On cooling the solution and adding 20 C.C.of concentrated hydrochloric acid 4 grams of a crystalline stannichloride were deposited which, after the removal of the tin gave 2 grams of 2 4l-diamino-4-m-tolylglyoxaline dihydrochloride that is 67 per cent. of the theoretical yield. 2 4~-Diamino-4-m-toZylglyoxaline dihydrochloride separates from dilute hydrochloric acid in microscopic needles which form a white spongy mass. It is readily soluble in cold very readily so in hot water [Found (in substance dried a t 50O) C=43*0; H=5-8; N=19*9 20'1; C1= 25.7 ; H20 = 6.9. C,,H,2N,,2HC1,H,0 requires C = 43.0 ; H=5*8; N=20.1; C1=25*5; H20=6-5 per cent.]. Its reactions with potassium permanganate sodium nitro-prusside sodium diazobenzen~~-sulphonate and nitrous acid are similar to those of t.he lower homologue (T.1919 115 240). The base appears to be unstable for on the addition of ammonia to an aqueous solution of the dihydrochloride a white flocculent precipitate is formed which rapidly darkens when separated from the solution. The sparingly soluble sulphate separates as a mass of woolly needles on the addition of sulphuric acid to an aqueous solution of the salt. The dipicrute separates as a crystalline powder which melts at about 210° (corr.) after sintering earlier. It is sparingly soluble in boiling water. After drying a t 50° it contains lH20. 2- and 4-p-Tolueneazoglyoxalines. p-Toluidine (10.7 grams) was diazotised and the product added to a solution of 6.8 grams of glyoxaline and 20 grams of anhydrous sodium carbonate in 500 C.C. of water a t 5O.After keeping over-night the yellowish-brown insoluble product was collected and extracted with 5 per cent. hydrochloric acid. One gram of dark red amorphous matter remained undissolved and on crystallisa-tion from alcohol yielded p-tolueneazo-p-cresol which melted a t 1 1 2 O (corr.) and was identified by analysis (Found C=73*7; H=6*8; N=12-5. Calc. C=74-3; H=6.3; N=12*4 per cent.) and by comparison with a specimen prepared by the action o THE SULPHONATION OF GLYOXALINES. 1429 p-toluenediazonium chloride on pcresol (Noelting and Kohn Ber., 1884 17 354). The hydrochloric acid extract was basified with sodium carbonate and deposited 15-2 grams of the mixed toluene-azoglyoxalines melting a t 220'. that is 86 per cent. of the theoretical yield. On recrystallisation from alcohol 11.6 grams of 2-p-tolueneazoglyoxaline were obtained in .a pure state and small crops of impure material. From the final filtrate, 4-p-tolueneazoglyoxaline was isolated in the form of its hydro-chloride. 2-p-Tolueneazogtyo:ti~~e crystallises from alcohol in yellow leaflets which melt a t 235O (corr.). It is soluble in boiling alcohol to the extent of rather less than 5 per cent. (Found C=64*1, 64.4 ; H = 5.6 5.6 ; N =3O*1. C,,,R,,N4 requires C= 64.5 ; R = 5.4 ; N=30-1 per cent.). The hydrochloride was crystalline but deliquescent. 4-p-Totueneazoglyo~alin e prepared from the pure hydrochloride. crystallised from alcohol in vellow leaflets which melted a t 152O (corr.) (Found C=63.9; R = 5 * 5 ; N=31-0. C,,HI,N requires C=64-5; H = 5 * 4 ; N=30*1 per cent.). The hylrochloride crystallises from dilute hydrochloric acid in fine yellow needles forming a felted mass. The air-dried salt melts first a t 76O (corr.) loses 2H,O at. about 117O and melts again after darkening a t 185O (corr.). It is very readily soluble in water [Found (in air-dried salt) C1 = 13.8; H,O = 13.5. C,,H,,N4,RC1,2H,O requires C1= 13.7 ; H,O = 13.9 per cent.]. We desire to thank the Salters' Institute of Industrial Chemistry for the grant of a fellowship which has enabled one of US (L.A.R.) to take part in the investigation. MUNICIPAL COLLEGE OF TECHNOLOGY, UNIVERSITY OF MANCHESTER. [Receiued October 16th 1920.

ISSN:0368-1645    

DOI:10.1039/CT9201701426

出版商:RSC    

年代:1920

数据来源: RSC

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THE SULPHONATION OF GLYOXALINES. 1429 CLVI1.-The Sulphonation qf G'lyoxalines. By FRANK LEE PYMAN and LEONARD ALLAN RAVALD. DIRECT sulphonation of glyosalinasl has not been decked previously, but in two cases derivatives of glyoxaline2-sulphonic acid ha,ve been prepaxed i n d i r d y . Thus Anschutz (,4nnalen 1895 284 18) obtained 4 5 -diphenylglyoxadine2-~ulphmia said by the oxidation of 2-thioll-4 5diphenylglyoxaline whilst mlh of c;a$~ine-8-sulphoni 1430 PYMAN AND RAVALD: acid are formed by the adim of holt aqueous sulphita on 8-chlom-d e i n e (D.R.-P. 74045). In view of the stability and pronounced aromatic a h r d e r of glyoxaline it seemed prolbable that this base like pyrazole and pyridine would be siismptible to direct sulphonation 'and this has praved to 6e the &e it glyozalinesutphimic acid being obtained in goad yield under suitable conditions.PrBsumably sulphonation takea plam in the 4-pmitim as dms nitration (Fargher and Pyman, T. 1919 115 217; Fargher this vol. p. 668) and the investigation will be continued and extended to alkylglycsxalines to elucidate this point. E x P E R I M E N TAL. Glyaxaline in the form of its sulphate was added to snlphuric a&d cw fuming sulphuric acid and the mixture heated. The diluted solution was treated with barium hydroxide and subsequently with carbon dioxide evaporated to dryneas and extracted wit.h chloro-form. This removed the unchanged glyoxaline and left crude barium glyoxalines;ulphmate. The consequences of varying the conditions appear in the follow-ing table: 8trength gly- sulphurio Propor.of tion of fuming oxdine acid in of fuming of free No. (base) to percentage experi- sulphuria sulphur Tem-ment. acid. trioxide. perature. 1 1 2 (98%R,S04) 100' 2 1 3 12 Y 3 4 A 6 7 1 ) 260 9 99 9* 160 10 11 9 9 99 12 I9 Y Y 99 13 .f $9 9 9 9 9 9 9 4; lib '1 99 9 9 9 ) 9 9 2;o 8 99 d 6 0 100 1Y4 9 ) 99 Yield of Duration nulphonate. Glv-of heating (hours). 3 9. 9 9 6 3 9 9 9 5 9 9 9. Y9 9 9 9. Percentage oxaline of theo- recovered. reticd. Per cent. Nil. 86 Nil. 74 4 98 18.5 Ti7 9 89 I1 86 2 46 20 46 52 Trace. 55 26 78 Trace. 70 9 9 8.3 9 9 The crude barium glymalineeulphcsnate qshllised almoet m-pletely 0111 treatmeBt with waster.From the pure salt the free acid and the sodium and ammonium s a l t s were prepared by treatment with the equivalent quantit.ies of sulphuric acid and its db. G!?/o.m2i;nesitlwh.on.?:c acid crystallises from watm in large mlmr-less cubes which are anhydrous. It beejns to soften at 290° and i THE SULPHONATION OF GLYOXALINES. 1431 entirely molten a t 307O (corr.). It! is soluble in about 5 parts of cold olr 2 parta oif hotl water butl is almost insoluble in aloohol. (Found C=24*2; H=2*6 ; N=18.9. C,H,O,N,S requirea C=24*3; H=2*7; N=18*9 per cent.) Glyoxalinesulphonic acid is strongly acid to litmus whilst its salts are only faintly alkaline. It does not combine with strong aqueous acids. On adding sodium diazobenzene-p-sulphonate to glyoxaline-sulphonic acid in excess of aqueous sodium carbonate no immediate coloration is produced but a deep red colour develops in the course of a few minutes.I n the presence of sodium hydroxide the solu-tion remains pale yellow even on keeping. An attempt to nitrate glyoxalinesulphonic acid by boiling 1.1 grams with a mixture of 1 C.C. of fuming nitric acid and 1 C.C. of sulphuric acid was un-successful the glyoxalinesulphonic acid being recovered unchanged. Tbe barizim salt crystallisea frolm watler in colourless octahedra, whiclh are anhydrous soluble in 3 parts of hot water and littde less soluble in cold water butl insoluble in alcohol. (Found Ba = 34.2. (C,H,O,N,S),Ba requires ]Bas = 34.1 per ceintl.) The sodkm saltl crystallises from water in large! colourless tlableta, which contain 2H,O. I t is v e r y readily soluble in water but almost insoluble in alcohol. (Found in air-dried salt Na= 11.2; H,O = 17.7. C3H,03N,SNa,2H,0 reqniree Na= 11.2 ; H,O = 17.5 per cent.) Tbe ammonium salt crystallises from watelr in large colmrless prisms. It is very reladily sollubla in water and easily so1 in hot moist alcolhol but almsst insoluble in absohtel alcohol. It 1-ammonia atl temperatures above looo letaving the frele acid. The air-dried salt lo& 1.5 pelr cent,. of water in it vaouum ovelr sulphurio acid. (Found in salt dried in a vacuum N=25*4; loss a t 120°= 10.5. C3H,03N,S*NH requires N=25'4; low of NH,=10.3 per cent.) We desire ta thank the Salters' InstlitUte of Industrial Chemistry for t$e grant of a fellowship which has eaabled one1 of us (L. A. R.) t'o take part in tlhe investigation. MUNICIPAL COLLEGE OF TECHNOLOGY, THE UNIVERSITY OF MANCHESTER. [ReCeiVd October 10& 1920.

ISSN:0368-1645    

DOI:10.1039/CT9201701429

出版商:RSC    

年代:1920

数据来源: RSC

摘要:

1432 FARMER THE VELOCITY OF DECOMPOSITION OF CLVI 11.-The Velocity of Decomposition of High Explosives in a Vacuum. Part I. By ROBERT CROSBIE FARMER. PREVIOUS work on the stability of explosives has been devoted almost entirely to the nitric esters. The methods used depend for the most part on the detection and estimation of the oxides of nitrogen evolved on heating and are not in general applicable to nitro-aromatic compounds or to mercuric fulminate azides etc. I n order to meet the need for a simple quantitative stability test for such compounds the vacuum test described below was developed. This has been widely used for high explosives more particularly for trinitrophenylmethylnitroamine. It has proved itself so simple in use after some thousands of tests that it may be of interest for the investigation of other reactions in which gases are evolved.Some measurements of the rate of decomposi-tion in a vacuum have been made on guncotton (Obermiiller M i t t . B e d . Bezirksuer. 1904 1 30; Dupr6 Ann. Rep. I m p . of Explosives 1903 26; 1904 28'; 1905 29; Hodgkinson and Coote, Chem. News 1905 91 194; Robertson and Napper T. 1907 91, 764; Willcox J . Amer. Chem. Soc. 1907 30 271; Pleus, Zeitsch. yes. Schiess. u. Sprengstofw. 1910 5 121) on silver oxalate (Hoitsema Zeitsch. physilcal. Chem. 1896 21 137) tri-nitrotoluene (Verola Mkm. poud. Salp. 1911-1912 16 40) and tetryl (Knowles J . Tnd. Eng. Chem. 1920 12 246). The methods described were not however convenient as standard tests for high explosives. From measurements on a large number of explosives it appears that these are in all cases subject to a gradual decomposition with evolution of gas a t temperatures below their ignition points.The velocity decreases strongly as the temperature is lowered butl there can be little doubt that a very slow decomposition must occur even a t the ordinary temperature. As in the case of nitric esters (Farmer this vol. p. Sll) the decomposition is partly catalytic and partly non-catalytic ; when catalytic influences are eliminated the velocity sinks to a minimum. I n many cases the catalytic decomposition outweighs the intrinsic decomposition of the pure substance and it is frequently difficult to purify the explosive to such a degree that the catalytic influences are completely removed.For the same reason different prepar-ations of the same substance often differ considerably in their ratas of decomposition Frequently the avolution of gas proceed H-IGH EXPLOSIVES I N A VACUUM. PART I. 1433 with an acceleration due to autocatalysis whilst in other cases it becomes slower after a time owing to the decomposition and con-sequent elimination of impurities. In many cases the presence of moisture gives rise to very erratic results and special steps are therefore taken to eliminate this influence. As a rule the decom-position has been carried only to the extent of a small evolution of gas. The measurement of small volumes of gas has it is true, the disadvantage that the measurements are more affected by traces of volatile matter etc. but if the decomposition is carried further, the products formed are liable to have a very disturbing effect and frequently a very rapid evolution of gas sets in.The nitro-aromatic compounds are in general very much more stable than the nitric ester explosives. Whilst guncotton shows a marked decomposition in Will's test a t 1 3 5 O in four hours and nitroglycerin a t a lower temperature the trinitrobenzene deriv-atives require in general temperatures of 140° to 180° in order to give readily measurable volumes of p s on heating for 100 hours. The dinitro-compounds show scarcely any measurable decomposi-tion. The nitroaminw such as tetryl on the other hand are less stable and decompose sufficiently rapidly for measurements at 1 20°. I n order to give an approximate idea of the relative stability, the temperatures may be calculated by extrapolation a t which the gas evolution amounts to 1 C.C.per gram in 100 hours: Trinitrobenzene .............................. 190-195' Trinitrophenol ................................. 150-158" 2 4 6-Trinitrotoluene ..................... 135-140' 2:3:4- ..................... 135-140" 3:4:6- 11 130-135' Trinitrophenylmethylnitroamine ......... 115-1 20' Cellulose nitrate (N= 13 per cent) ...... Approx. looo 11 ..................... Trinitrotoluenes gave 0.8 to 1.8 C.C. of gas per gram in 100 hours a t 140O. The differences in velocity between different samples indicated the presence of traces of catalysts although most of the samples were very pure. There was practically no parallelism between the melting point and stability.The rate of evolution showed no acceleration ; hence no autocatalysis occurred within limits measured. From the results obtained it is evident that pure trinitrotoluene could be kept indefinitely a t the ordinary temperature but the actual rate of decomposition cannot be ascer-tained by direct extrapolation as the results obtained in the case of tetryl have shown that a great increase in stability occurs on pasging from the molten to the solid condition. The isomeric trinifrotoluenes which accompany the symmetrical compound in small proportion on nitration of toluene were als 1434 FARMER THE VELOCITY OF DECOMPOSITION OF examined. The commercial products contained impurities which decreased their stability. When these were removed by crystal-lisation 2 3 4-trinitrotoluene showed about the same stability as the 2 4 6-isomeride whilst 3 4 6-trinitrotoluene was somewhat less stable.The stability of 2 4 6-trinitrotoluene was not sensibly affected by the addition of 1 per cent. of the other pure isomerides, but 5 per cent. of the 3 4 6-isomeride caused a slight increase of velocity. Mixtures of picric acid and trinitrotoluene showed a lower rate of decomposition at 140° than trinitrotoluene alone. This was somewhat surprising since the general experience is that acids decrease the stability. It is possible that the trinitrotoluene exists as an ec;rnilibrium in which a small quantity of an isonitro-compound is present the latter being the cause of the instability observed.Picric acid miqht readily cause the isonitro-compound to revert to the normal nitro-compound thus increasing the stability. As an example of an unsaturated substance castor oil was mixed with trinitrotoluene and with picric acid and the mixtures were tested. The castor oil depressed the stability very strongly in both cases. Trinitrophenol showed a stabilitv intermediate between that of trinitrobenzene and that of trinitrotoluene. Trinitrobenzene showed extreme stability even a t the boiling point of aniline and the stability was not perceptibly affected by wet and dry storage trials. This is of interest as showing that notwithstanding the difficulty of introducing the third nitro-group the trinitro-compound when once prepared is very stable.EX P E R I M E N T A L . A pparatus.-The thermostat (Fig. 1) consists of a cylindrical copper bath. which is maintained a t the required temperature by a boiling liquid. The cover consists of a thin brass casting with six orifices for the heating tubes and a short column to support the condenser. These all form part of the casting thus avoiding joints which are otherwise very apt to Teak during protracted tests. The connexion with the condenser is made by a conical joint' surmounted by a cap which can be filled with vaselin or other material to lute the joint. The brass column also projects about 0-5 cm. into the interior of the bath and is connected with a cylinder of coarse copper gauze of the same diameter as the tube and about 15 cm. in length. The object of this is to convey the condensed liquid down the centre of the bat,h and ensure unifor HIGH EXPLOSIVES IN A VACUUM.PART I. 1435 heating. This is fitted with a cap and a cup for luting. laggiiig material surrounds the bath. The lid has also1 a small opening for filling the bath. A cylinder of The top of the bath is also F I G . 1.A. -- ,----I I I I I I I 1 'i---;-y I 1436 FARMER THE VELOCITY OF DECOMPOSITION OF covered with a loose cake of asbestos lagging material about 3 cm. thick with holes corresponding with those in the brass cover. The condenser (Fig. 2) is of the multitubular pattern and the water inlet tube is fitted with a funnel as shown so that the flow of water can be seen. For temperatures from 800 to 1000 mixtures of alcohol and water were used.From looo to about 1 3 5 O solutions of calcium chloride were generally taken. In the latter case the addition of a little lime is advisable to avoid corrosion of the copper. The temperature of the boiling calcium chloride solution is FIG. 1 ~ . readily adjusted by adding water if too high or by allowing water to evaporate if too low. The level of the liquid should be main-tained a t about 5 cm. from the lid of the bath. Safety Precautions.-To guard against damage by explosion, steel tubes with closed bottoms were provided; these fitted loosely into the brass orifices and were packed round with fine copper fillings to give good contact with the bath. They were made rather short (Fig. 3) since it was found that if they extended nearly to the surface of the bath they became cooled by radiation, and irregular temperatures were obtained HIGH EXPLOSIVES IN A VACUUM.PART I. 1437 The thermostats were surrounded by screens and placed in a A cistern was provided to guard against failure fire-proof shed. of the water sup-ply and an auto-m a t i c ball-cock tap was fitted to cut off the gas supply in case the cistern b e c a m e empty. Heating Tubes. - T h e g l a s s apparatus passed through numerous modifications i n the course of a large number of m e a s u r e m ents. The earlier pat-terns were fitted with glass taps for exhaustion but it was found much better to avoid these and the s i m p 1 e device shown in Fig. 3 was found to be a g r e a t improve-ment.In order to exhaust the tube a quantity of mercury suffi-cient to fill the upright limb of the capillary tube is placed in the lower cup. This cup is connected with the pump by FIG. 2. means of a rubber stopper. The apparatus is then inclined so that the cup is horizontal and the mercury lies in a pool in the cup, leaving a free passage between t,he pump and the capillary tube 1438 FARMER TITE VELOCITY OF DECOMPOSITION OF After exhaustion the apparatus is returned t o the upright posi-tion and on releasing the vacuum the mercury rises in the F I G . 3. capillary tube which acts as a manometer during the test. The cup a t the top of the' heating tube is luted with mercury, and the apparatus is then ready to be transferred to the thermostat.It is i m p o r t a n t that the stopper be very well ground and lubricated as thinly as possible with a non-reactive lubricant. The thermometer is embedded in sand in a similar heating tube, which is introduced into one of the steel tubes and placed in the bath. Accuracy of the tempera-ture readings is of great importance in view of t h high t e m p e r a t u r e-cosfficients of the decom-positions. Met hod of Working.-Very thorough cleaning of the apparatus is neces-sary as traces of foreign matter have a marked catalytic effect. T h e tubes were cleaned suc-cessively with acetone, benzene and hot chromic acid and were then sub-jected to prolonged wash-ing with water. The manometers were simi-larly cleansed.The corn-plete removal of moisture is also of importance since this frequently gives rise to abnormal accelerations. The explosive is dried a t a temperature well below its decomposition point and weighed quantities are introduced into tho t,est-tubes. These ar HIGH EXPLOSI.VES IN A VACUUM. PART I. 1439 then connected with the capillary tubes the ground stoppers being thinly lubricated. The apparatus is then exhausted to about, ti mm. of mercury by nieans of a Geryk pump and is heated t o a temperature a t which no measurable decomposition will occur (generally SOo) for some hours to remove water. The apparatus is then again exhausted dry air is allowed to enter through a three-way cock attached to the pump and removed onca more by the pump and the apparatus is inserted in the thermostat.The time a t which the heating commences is noted and an arbitrary period is allowed to permit the pressure to settle down before the first reading is taken. This is necessary on account of minute traces of residual volatile matter and in some cases the volatility of the compound itself. In general one and a-half hours have been found sufficient. The height of the mercury column is then read a t intervals in comparison with the baro-metric height. It is convenient to use as barometer a similar tube exhausted and placed near the apparatus. This automatic-ally corrects the reading _for temperature of the mercury and capillary depression. To avoid differences in the level of the mercury in the lower cup it is convenient to fill this up so that it overflows into a dish as the mercury descends in the capillary tube.In taking a number of readings a sliding scale may be used with advantage. The zero1 is set to the mercury level in the baro-meter and the difference between manometer and barometer can then be read off directly. Calculation of Gas Fo1ume.-The calibration of the apparatus includes measurements of the volume of the test-tube the volume of unit length of the capillary and the total length of the three limbs of the capillary tube from the stopper to1 a point on the capillary-tube level with the average height of mercury in the cup. The volume of explosive is deducted from the volume of the heating tube to obtain the net volume. I n calculating repeated readings with the same explosive and Lhe same bath temperature the following shortened method of calculation is useful The bath temperature is practically constant ; the ordinary temperature alters somewhat but as this oiily affects the correction of the volume in the capillary tube it may also be taken as constant (it was in general about 30O).I f the difference between barometer and manometer reading be p mrn. the corrected volume of gas in the heating tube is equal to: A little asbestos wool is packed round the stopper. x y 273 Net gas space x 273 + bath temp. 760 1440 FARMER THE VELOCITY OF DECOMPOSITION OF The corrected volume of gas in the capillary tube is equal to (total 273 p 303 r60 length - 760 +p) x (vol. of 1 mm.) x ~ x = p (total length - 760) x 1 1 (vol.of 1 mm.) x - +pa (vol. of 1 mm.) x -. 843 8 43 Hence the corrected volume is equal to p (a + b) +p2c, net gas space x 373 where (I= 760 (273 +bath temp.) 1 843 b = (length of capillary tube - 760) x (vol. of 1 mm.) 1 843 c = - (vol. of 1 mm.). These constants can be determined for the whole series of measure-ments and the calculation is then very simple. The constants b and c depend only on the calibration of the apparatus; a depends also on the volume of explosive and the bath temperature. Correction for Fluctuations in Bath Temperature.-The fluctuations due to alteration of boiling point with variations of the barometric pressure are of importance as the velocity of decomposition usually increases approximately 100 per cent.for each 5 degrees or 15 per cent. per degree. It is better to apply the correction to the time readings rather than to correct the FIG. 4. Hours. 2 4 6-Tr$nitrotoluene (various samples) at 140'. volume of gas from the individual tubes in the bath. If the deviation of temperature is within about 0*3O it is generally sufficient to calculate a time correction for each day's readings, based on the mean temperature of the bath. Thus a deviation of 0*lo corresponds with a difference of 1.4 per cent. in the velocity, or 0.34 hour per day HIGH EXPLOSIVES IN A VACUUM. PART I. 1441 Measurements of Gas Evolution. 2 4 6-Z1rinitroto1uene.-Measurements at 120° gave very low results (about 0.15 C.C. in 100 hours). A t 180° the evolution was too rapid and gave erratic accelerations which made the measure-ments untrustworthy for comparison.Convenient velocities were obtained at 140° and the fo1lo;wing measurements were made on trinitrotoluenes from different sources (Fig. 4). FIG. 5. t 10 20 30 40 50 60 70 80 90 100 Hours. Trinitrotoluene isomerides at 140". Gas Evolution at 140° (c.c. per gram). Melting point. 20 hours. 40 hours. 60 hours. 81.1" .................. 0.35 0.69 1.04 81.05 .................. 0.39 0.78 1.16 81.05 .................. 0.13 0.33 0.70 81-0 .................. 0.14 0.28 0-54 81.0 .................. 0.16 0-32 0.55 81-0 .................. 0-16 0.35 0.58 81.0 .................. 0-12 0.22 0.37 80.95 ............... s.. 0.25 0-50 0.86 80.95 .................. 0.14 0-28 0.52 110.76 .......... ...... .. 0.33 0.68 0.8ti 80.65 0.26 0.54 0.85 80.65 .................. 0.33 0.7 1 @!)O 78.80 ......,..,. ,,... 0.36 0.71 1-0t) . . . . . . . . . . . . . . . . . . 80 hours. 1.31 1.47 0.94 0.85 0-85 0.78 0.57 1.21 0.83 1.01 1-13 1.017 1-45 100 hours 1.56 1-75 1-13 1-13 1.13 0.99 0.77 1.50 1.10 1-26 1.36 1-24 1.8 1442 FARMER THE VELOCITY O F DECOMPOSITION OF Comparative measurements on dinitrotoluene gave no perceptible decomposition in 100 hours. 2 3 4-Trinitrotoluene.-The following figures show the gas evolution after one and two crystallisations respectively. The purification reduced the rate of decomposition slightly. Cas Evolutioi~ a t 140° (c.c. per yram). 20 40 60 80 100 hours. hours. hours.hours. hours. One crystallisation ... 0.44 0.78 1.07 1.40 1.75 Fig. 5 (4) Two crystallisations ... 0.18 0.46 0.76 1-05 1-36 , (3) Y ? 9 9 0.22 0.37 0.67 1.01 1-38 , ( 2 ) ... 2 4 6-T.N.T. (mean) 0.24 0.40 0.77 1.04 1-29 . ( 1 ) 3 4 6-Trinit~otoluene .-The commercial product was much less stable than the above and decomposed so rapidly a t 140° that the measurement had to be made at 1 2 0 O . The results after one crystallisation are given a t both temperatures. Gas Evolution at 120° (c.c. per g r a m ) . 20 40 60 80 100 hours. hours. hours. hours. hours. - - - Original (sample a) ............... 2.2 3.3 One crystallisation ............... 0.55 1.08 1-58 2.05 2-48 Gas E,Liolutz'on at 140° (c.c. per gram). 20 40 60 80 100 hours. hours. hours.hours. hours. Sample (a) One cryst. 4.7 7-9 - - - Fig. 5 (8) Sample (5) One cryst. 0.89 1-80 2.80 4-10 5-70 , (6) ? 9 9 (7) 9 9 TWO , 0.76 1.38 1.99 2.60 3.23 , ( 5 ) - - TWO , 1.50 3.00 -Even after purification this isa'meride was much less stable than 2 3 $-trinitrotoluene. Mixtures of the Isomeric Trinitrotoluenes.-In order to ascer-tain whether the unsymmetrical isomerides which always accom-pany 2 4 6-trinitrotoluene in small quantity in the crude pro-duct affect the stability the following mixtures were examined HIGII EXPLOSIVES IN A VACUUM. PART I. 1443 Gas Evolution at 140° (c.c. per y a m ) . 2 ~ 3 ~ 4 - 3 ~ 4 ~ 6 - 2"::-T.N.T. T.N.T. Puri- T.N.T., per Sam-cent. ple. - -- a b z, a b b 1 b 1 a 1 h 5 a 5 a 5 b --- a ---fica-tion.. -_ corn]. coml. 2 crysts. coml. 1 cryst. 1 cryst. 1 cryst. 2 cryste. 2 crysts. 2 crysts. 2 cryste. 2 crysts. 2 crysts. Per cent. 100 99 9 8 99 95 95 95 95 99 99 99 95 95 95 20 40 60 80 100 hours. hours. hours. hours. hours. 0-16 0.34 0-57 0.78 0.99 1.03 1.55 2.12 2.60 3.01 0-23 0.80 1.40 2.01 2.53 0.15 0-33 0.65 0.79 0.98 2.23 3.34 4.21 4.99 5.78 0-31 0.77 0.98 1-23 1-52 0-54 0.87 1-10 1-36 1*€9 0.17 0.44 0.52 0.78 0.98 0.48 1.11 1-61 2-10 2.53 0.10 0.67 1.02 1.37 1.62 1.28 2.01 2-85 3.45 4.02 4.60 1-56 2-51 3.22 3.86 4.44 2.7 1 - - - -- - - -Influence of Picric A cicl o n the Stability of 2 4 6-Trinitro-toluene.-A trinitrotoluene was tested alone and in admixture with picric acid.The evolution from the1 mixture was less than from Irinitrotoluene alone. C.C. of gas (corr.) (140"). , Picric 2 4 6- 20 40 GO 80 100 150 200 acid. T.N.T. hours. hours. hours. hours. hours. hours. hours. 2 - 0.14 0.25 0.29 0.35 0.44 0.62 0.83 2 2 0.14 0.22 0.25 0-32 0.42 0-62 0-81 2 2 0.15 0.23 0.28 0.34 0.43 0.68 0.95 - 2 0.25 0.50 0.74 0.96 1.19 1-94 2.88 Iiifluerbce of Unsaturated Compounds.-To avoid a disturbing effect on the gas volume due to vapour pressure castor oil was chosen as a fairly non-volatile unsaturated substance. This increased the rate of decomposition very strongly; even a t 12Q0, the gas evolution from trinitrotoluene containing 5 per cent. of castor oil was readily measurable. C.C. of gas (corr ) (120").1 2 4 6- Castor 20 40 60 80 100 150 200 T.N.T. oil. hours. hours. hours. hours. hours. hours. hours. 5 0.25 0-65 1.00 1.90 2.80 3.75 7.60 11.10 Naphthalene under similar conditions gave no measurable gas evolution in admixture with trinitrotoluene even when present t o the extent of 40 per cent. Picric Acid.-Measurements were made a t 140° and 183" on picric acid crystallised from water. The gas evolution was very rapid a t the higher temperature but showed some decrease in velocity as the decomposition proceeded from which it woul 1444 FARMER THE VELOCITY OF DECOMPOSITION OE' appear that some catalyst was being gradually eliminated. The successive crystallisations did not reduce the rate of decomposi-tion a t 183O' but at 140° some stabilisation was noticeable in the latter crystallisations.Gas Evolution at 140° ( c . c . per gram). 100 hours. 150 hours. 200 hours. 300 hours. Original .................. 0-1 1 0.27 0.44 0.88 Cryst. No. 2 ............ 0.13 0.35 0.51 0-92 , , 4 ............... 0.04 0.12 0.23 0.50 , , 5 ............... 0.06 0.2 1 0.31 0.58 Gas Evolution at 183O ( c . c . per gram). 1 2 3 5 10 15 20 hour. hours. hours. hours. hours. hours. hours. Cryst. No. 1 2-90 4-50 5.45 6.45 - - -) , 2 2.95 4.85 6.10 7.30 - - -, , 3 2-30 3.95 5.20 6.15 8.35 10.60 12.80 ) , 4 1.90 3.80 5.50 6-65 9.00 11-35 13.65 , ,) 5 2.05 3.90 6-65 6.95 9.20 11-50 13-80 As in the case of trinitrotoluene castor oil increased the decom-position. Whereas picric acid alone gave practically no measur-able decomposition a t 120° a mixture of picric acid with 5 per cent.of castor oil gave t.he following evolution : Picric Acid 5 grams. Castor Oil 0.25 gram. 50 hours. 100 hours. 150 hours. 200 hours. C.c at! 120" ............... 0.85 2.50 4.70 6.85 1 3 5-Trinitrobeltzene.-The gas evolution from this compound The following was very low even a t 1 8 3 O (boiling aniline bath). rates of decomposition were obtained with different samples : Gas Evolution at 183O ( c . c . per gram). Mean.. .... 20 hours. 40 hours. 0.05 0.14 0.04 0.09 0.03 0.07 - 0.10 - 0.10 - 0.15 0-04 0.11 60 hours. 0.20 0-13 0.10 0-13 0.13 0.19 0.15 80 hours. 0-27 0.18 0.14 0.15 0.15 0.25 0.19 100 hours. 0.33 0.23 0.19 0.18 0.18 0.30 0.23 I n order to ascertain the effect of storage on the stability, samples were kept for a year a t 50° and tested as above a t 183O HIGH EgPLOSIVES IN A VACUUM.PART I. 1445 20 hours. 40 hours. 60 hours. 80 hours. 100 hours. 0-07 0.13 0.18 0.24 0.30 0.08 0.13 0.17 0.23 0.28 0.06 0.10 0.17 0-22 0.27 0.06 0.07 0.16 0.22 0.26 Mean ...... 0.07 0.11 0.17 0.23 0.28 for a year in a saturated atmosphere a t 4 5 O ' and testing a t 183O. The influence of hydrolysis was examined by keeping samples 20 hours. 40 hours. 60 hours. 80 hours. 100 hours. 0.04 0-08 0.13 0-17 0.17 0-02 0.04 0.12 0.25 0.24 0.01 0.02 0.10 0.11 0.16 Mean.. . . . . 0-02 0.05 0.12 0.18 0.19 The effect of an admixture of picric acid on trinitrobenzene was tried at 150° as the decompmition of picric acid itself is too rapid a t 1 8 3 O . Gas Evolution at 1 5 0 O . a 100 200 300 400 500 hours. hours. hours. hours. hours. Picric acid 0.2 gram Trinitrobenzene 1-8 grams ...... 0.07 0-07 0.20 0-28 0.60 nitrob benzene 1.8 grEtms }.*. 0.07 0.26 0.86 1.45 2-22 Summary. An apparatus is deslcribed for the determination of stability of high explosives by the velocity of evolution of gas on heating in a vacuum. All explosives appear to be liable to a gradual decomposition a t temperatures considerably below their ignition points. The velocity is highly affected by temperature and by the catalytic action of impurities. Trinitrotoluene and the isomerides which accompany it on nitra-tion of toluene do not differ greatly in stability when purified. Trinitrobenzene is much more stable notwithstanding the difficulty with which it is prepared by nitration and trinitrophenol shows an intermediate stability. The t.hanks of the author are due to the Director of Artillery for permission to publish these results. ROYAL ARSENAL WOOLWICH. RESEARCH DEPARTMENT, [Received November 3rd 1920.

ISSN:0368-1645    

DOI:10.1039/CT9201701432

出版商:RSC    

年代:1920

数据来源: RSC

摘要:

1446 THE PREPARATION OF PURE CARBON DIOXIDE. CLIX.-The Preparation oj' Pure Carbon Dioxide. By ROBERT CROSBIE FARMER. THE diffimlty of prepa;ring carbon dioixidel completely free1 frolm air is frequently eacoant,eireld. Nolt,wit$stlaading thah a,ll sollutlioas used for making the1 gas are prelviously boileld tlhe elliminatioln of t'he last D D traces oC air is velry diflimlh and the same1 applies tot carboln diolxide from cylinders even though moist of the gasi is bloiwn to waste1 belforehand to eliminate the air as far as possible. The difficulty is especially notiioeable in the1 testing of the stability oif gun-coltton by Will's method (Zeitsch. angew. C'hem. 1901 14 743 774), in which a rela,tivedy large quantity of carboln dioxide is used to sweep o a t the1 nitrogenous gas= and the air-correction forms a veiry high pro-portion ojf the unabsorbed gases.By the f ollloiwing simple metlhod, which haa belen useid velry satisfae torily for sobme time1 in aolnneon with tbe Will test the propolrtioln of air in carbon dioxide can be reduced ta such a degree that it is praatically immeasurable. The1 metihold depends u p n the principle that a dissodved gas can be very completely removed frolm a liquid by bubbling a selcond gas through the liquid. The carbon dioxide is prepared from solutioins of potassium hydrogen oarbolna,te and sulphurio acid each of which is freeid from air by bubbling carboin dioxide throlugh it{ belfore the ttwoi a're broughtl togethelr. The pear-shaped funnels, A A colntain potassium hydrogen caxbolnahe (300 grams to 1 litre od waf,elr) and sulphuric acid (120 0.0.to 1 litIra oC water) rmpeo-tively. Thel sohtions should be prelviously filtered throlugh glass-wooll. From the funnels thew soilutiolns pass down the1 b r a d velrti-The1 genelratolr is shown in the figure TRIPHENYLARSINE AND DIPHENYLARSENIOUS SALTS ]I 447 ca.1 tubes into1 the gelnetratling boktls. The bulk od the carbon diolxide is dra,wn olff a4t U a,nd ussd as required. A small propolrtion olf the gaa is however allowed t'o pass t,hrough the1 tube C and bubbles through t,he collumns of liquid in t'hel tlwo uprightl tubes thus remov-ing all tsa.cels of dissollve,d air. If desireld a selpara4ta solurm of carboln dioixide can be1 used for tlhis purpose). As soon as the1 air originally prelsent in t,he Woiulf e's boltltds has beisin ediminatleld the carbon dioxide! relaches a sta,te of extreme purity a.nd give@ pranti-cally no1 residue1 olf gas on absorptioln with potassium hydroxide so'lu ti on.The fit,tings of the1 Woulfel's bolt& must be absolutely frete from leaks; the b,otltlle niay if desire#d be immelrseld in water covered witah a layelr of pasa.ffin wax. The feed tlubw dip below the surfaoe of inerc$ury tlol a.vodd ba,ck-diffusioln. If the1 wholle appasa,tus is mounted on at stand it ca.n be tilted slightdy to equalise t,he back pressure in the1 two feeid tubw but. no very aacrurats balancing is neaessasy. A lit.tlle melthyl-orangel in tlhe sollutlim seirvea tlol sholw tha,t the sollutlions amre( being mixed in aboat t'he right proiportlions. When t4he tap B is turned off the intaoductioln od the reagents autIoma,ti-cally ceases. The t,aps DD which regulate the b,ubbles od gas ghauld, however be dosed when the appara.tus is not in use. The spent liquor ca,n be drawn off atl E as the fresh soJutiom. a,re addeld. The rate of eivolutiota ca.n be1 incretaseld almost in.definitslly by using a somewhat 1 a,rger ap p ar ahus. Onmi stlartad the ampparaflus need nevetr be1 discolnnected. The thanks of tlhe aut'holr are duel to the1 Director of Artillery for RESEARCH DEPARTMENT, pelrmission to publish tlhis note. ROYAL ARSENAL WOOLWICH. [Received November 3rd. 1920.

ISSN:0368-1645    

DOI:10.1039/CT9201701446

出版商:RSC    

年代:1920

数据来源: RSC

摘要:

TRIPHENYLARSINE AND DIPHENYLARSENIOIJS SALTS ]L 447 CLX.- Triphenylarsine and Dipheszylursenious Salts. By WILLIAM JACKSON POPE and EUSTACE EBENEZER TUBNEB. THE intro'duction of aromatic arsenic compounds as materials for chemical warfare rendered necessary the working out of satis-factory methods for preparing triphenylarsine (C,H,),As and diphenylchloroarsine (C,H,),AsCl. The former of these two' corn-pounds is conveniently prepared by Michaelis and Reess's method (Ber. 1882 15 2876) which consists in treating an ethereal solution of arsenic trichloride and bromobenzene with sodium ; i 1448 POPE AND TURNBBi a later paper (Ber. 1886 19 1031) Philips showed that chloro-benzene can be substituted for bromobenzene and that the reac-tion is stimulated by the addition of a small proportion of ethyl acetate but more recently (Annulen 1902 321 160) Michaelis claimed that a cleaner product is obtained by the use of bromo-benzene than of chlorobenzene.The several workers on this reaction used ether as a solvent, and itl was important to ascertain whether this could be replaced by some less volatile and less inflammable diluent. Preliminary experiments showed that the reaction proceeds better in benzene than in ethereal solution and that contrary to Michaelis’s sugges-tion chlorobenzene gives a cleaner product than does bromo-benzene. It was thus shown that triphenylarsine is readily p r e pared by the action of sodium on a mixture of arsenic trichloride and chlorobenzene in benzene solution to which a little ethyl acetate had been added; this method was described in a report to the Chemical Warfare Department dated January 28th 1918 and formed the basis of the larger-scale work done by Morgan and others (this vol.p. 777) in the conversion of the laboratory method into a works process. It was observed that the use of ether as a diluent is dis-advantageous in that the violent reaction tends to pass out of control and that when this happens pyrophoric sodium remains after the evaporation of the ether causing dangerous fires. The repetition of the method of Philips gave a yield of 71 per cent. of the theoretical; Michaelis’s later method gave a yield of 67 per cent,. of the theoretical. In the absence of a diluent sodium acts on a mixture of arsenic trichloride and chlorobenzene causing incandescence.Experiments were next carried out for the purpose of ascertain-ing how the yield of triphenylarsine is influenced by the propor-tions of the reacting materials and by the conditions. The general method adopted was to weigh outl the sodium in slices (s) granules (g) powder ( p ) or wire into a large flask cover with benzene containing I or 2 per cent of ethyl acetate allow to remain for half an hour to activate the metal and then slowly run in the arsenic trichloride and chlorobenzene. After a few minutes, a vigorous reaction sets in which when sodium wire is used must be controlled by the use of a freezing mixture; when sliced sodium is used no external cooling is necessary and indeed once the reaction is checked by cooling it can only be started again with considerable difficulty.The mixture is then left overnight, filtered and the inorganic residue well washed with hot benzene; the filtrate and washing are distilled until a thermometer place TRIPHENY LARSJNE AND DIPHENYLARSENIOUS SALTS. 1449 in the liquid registers 200c’. crystalline mass and is almost pure triphenylarsine ; in general it melts a t above 56O. The following table gives the results of a series of experiments, in each of which 136 grams of chlorobenzene were used; this quantity requires theoretically 60 grams of arsenic trichloride and 46 grams of sodium for complete conversion into triphenylarsine. The residue solidifies on cooling to No. of experi -ment. I 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 It) 19 20 21 Volume of benzene.C.C. 400 7 9 9 9 7 9 9 9 9 7 . 7 9 9 9 9 1 7 ) G O 350 9 9 7 1 7 9 9 , 9 9 , Sodium. Grams. 68 7 7 9 7 9 9 7 7 7 9 3 . 1 . 9 9 69 G.3 60 60 67 1 9 9 9 55.5 9 9 9 9 ASCl,. Grams. 72 7 7 7 9 9 , 9 7 9 9 i b 85 90 80 9 9 $0 $0 85 85 90 95 90 Percentage of theoretical yield of C,H,Cl used. 67.5 69 66 64 62.5 71 83 91.5 95.5 93.5 80 75 83.5 81 88 93 89 80 83 74.5 84 Experiments 1 to 3 were carried o u t just as described above; 4 and 5 were carried out as rapidly as possible and the product was worked up immediately without remaining overnight. In numbers 6 and 7 the product was gently boiled under reflux for several hours after the spontaneous reaction had ended.It is thus shown that the yield is not improved by hastening the reac-tion but that itl does increase when the reaction is continued further by boiling; the operation of boiling under reflux was there-fore introduced in all the later experiments. A consideration of the further experiments shows that the yield of triphenylarsine, calculated on the amount of chlorobenzene used is appreciably raised by increasing the amount of arsenic trichloride to 85 grams, and is practically unaffected by diminishing the weight of sodium to 57 grams; it appears further that the volume of benzene used can be reduced to 300 C.C. without ill-effect on the yield. The most satisfactory results seem to be obtained by using 300 C.C.of benzene for each 136 grams of chlorobenzene 85 grams of arsenic trichloride and 57 grams of sodium but since the VOL. CXVIT. 3 1450 POPE AND TURNER: reaction proceeds well with considerable fluctuations of the pro-portions the appropriate quantities of materials to be used depend on the relative cost of the latter. The reaction between chlorobenzene and arsenic trichloride is not promoted by boiling with copper or aluminium powder the copper-zinc couple or magnesium or calcium turnings. The copper arsenide obtained by digesting a hydrochloric acid solution c,f arsenic trichloride collecting the black powder washing i t with water and acetone and drying is without action on chlorobenzene, but when heated with iodobenzene yields diphenyl.Conversion of Triphetiylnrsine into Di- and Jfono-phenylarsine Derivatives. Michaelis and Reese showed (Bcr. 1882 15 2876) that phenyl-arsenious dichloride is produced on heating triphenylarsine with arsenic trichloride under pressure; it is to be concluded that diphenylarsenious chloride is formed as an intermediate stage and particulars have been given by Morgan and Vining (this vol., p. 780) of a convenient means for preparing diphenylarsenious chloride by heating triphenylarsine with arsenic trichloride a t 250-280° under pressure. This method involves however the use of an autoclave and i t seemed of interest to ascertain whether the same reaction could be carried out under the ordinary atmo-spheric pressure.Triphenylarsine (30.6 grams) was maintained a t 350° while, arsenic trichloride (25.5 c.c.) was very slowly run in by means of a long capillary tube; the arsenic trichloride which distilled over was returned to the reaction vessel. The first addition of the arsenic trichloride occupied one and threequarter hours. On carefully distilling the product under 12-15 mm. pressure the following fractions were obtained a t above 1200 ( a ) 120-160°, 17.7 grams; ( b ) 160-200° 22.2 grams; ( c ) 200-250° 2.2 grams; (d) residue 2.2 grams. The fraction (a) is fairly pure phenyl-arsenious dichloride (ij) is pure diphenylarsenious chloride whilst ( c ) and (d) consist of nearly pure triphenylarsine; allowing for the recovery of the latter the yield of phenylarsenious dichloride and diphenylarsenious chloride is 97 per cent.of the theoretical. In the experiment just described the arsenic trichloride was added fairly rapidly and another may be quoted to show the effect of running it in more slowly. Using the same quantities as before but taking seven hours for the addition of the arsenic trichloride the following fractions were obtained on distilling the product under 12-15 mm. pressure ( a ) 120-160° 1 2 grams o TRIPHENYLARSINE AND DIPHENYLARSENIOUS SALTS. 1451 moderately pure pheiiylarsenious dichloride; ( b ) 160-205° 31.5 grams of practically pure diphenylarsenious chloride ; and a resi-due (c) of 7.2 grams of impure triphenylarsine. I n this case a larger proportion of diphenylarsenious chloride was produced. The general conclusion is drawn from the above and other experiments that under atmospheric pressure the following reac-tions occur (C,H,)3As + 2AsC13= 3(C6H5)AsClz and ~(C,H,)~AS + AsCl,= 3(C,H5)2AsCl.I n addition to the foregoing the reaction represented by the following equation may also occur: and experiment showed this reaction to take place almost quantitatively. On heating a mixture of triphenylarsine (15.3 grams) and phenylarsenious dichloride (11-2 grams) for four hours a t 300° in an open flask and distilling the resulting pasty mass under diminished pressure nearly pure diphenylarsenious chloride (20 grams) distilled a t 185O/15 mm.; this corresponds with a yield of about 80 per cent. of the theoretical; under the conditions stated a small amount of chlorobenzene was produced and practically no action occurs a t 250'.It is thus prsved that the reaction between arsenic trichloride and triphenylarsine proceeds very satisfactorily under atmospheric pressure and that the product is an equilibrium mixture resulting from the simultaneous occurrence of several reactions. In view of the possible importance of the observation that triphenylarsine can 'be converted into phenylarsenious dichloride and diphenyl-arsenious chloride by the action of arsenic trichloride under the ordinary pressure the above and analogous reactions were pro-tected by secret Patent No. 142880 of June l l t h 1918 of which the specification has now been published. (C,H,)AsC& + (CdHj)&s= 2(C,H,)&sCl, Dip h e uylnrs e nious Bromide (C,H&AsBr.Diphenylarsenious oxide [(C6H,)2As]20 was prepared by Michaelis and La Coste (AnnaZen 1880 201 229) but the follow-ing is a more expeditious method for obtaining it in a pure state. Potassium hydroxide (12 grams) dissolved in water (10 c.c.) is added to rectified spirit (200 c.c.) ; a solution of diphenylarsenious chloride (53 grams) in spirit (100 c.c.) is added and the mixture boiled for an hour. The solvents are then distilled off and the solid residue is extracted with chloroform ; on drying filtering, and evaporating the extract a quantitative yield of pure diphenyl-arsenious oxide remains as a colourless crystalline solid melting a t 8 9-9 lo. 3 a 1452 TRIPHENYLARSINE AND DIPHENYLARSENIOUS SALTS. On heating the oxide at looo with hydrobromic acid in a sealed tube and allowing to cool diphenylarsenious bromide (C&€,),AsBr, separates as a colourless crystalline solid melting a t 55-56O; this compound is described by Michaelis and La Coste as a yellow oily liquid.The bromide is also obtained by heating triphenylarsine (30.6 grams) with arsenic tribromide (15.8 grams) for three hours a t 300-350O; on distilling the product under 14 mm. pressure, the following fractions resulted below 170° 2 grams of a mixture of benzene and bromobenzene; 170-205O 26 grams of crude diphenylarsenious bromide and a residue of 15 grams of mixed diphenylarsenious bromide and triphenylarsine. By redistillation, pure diphenylarsenious bromide was readily obtained. Diphenylarsenious Iodide (Diphenpliodoarsine) (C&I&AsI. This previously undescribed substance is obtained by heating diphenylarsenious oxide (25 grams) with fuming hydriodic acid (30 grams) for two hours in a sealed tube a t looo; on cooling the crude iodide (29.5 grams) solidifies and melts at 4 2 4 5 O . On crystallisation from benzene the compound is obtained in yellow, crystalline scales melting a t 4 5 - 4 6 " (Found I = 35.6. C,,H,,IAs requires I=35*6 per cent.). On heating triphenylarsine (30.6 grams) with arsenic tri-iodide (22.8' grams) for six hours in an open flask a t 350-360° and dis-tilling the resulting mass under diminished pressure practically pure diphenylarsenious iodide (25 grams) distils a t 204-218O/ 10 mm.; the yield is less than 50 per cent. of the theoretical and the reaction does not proceed so satisfactorily as in the case of the corresponding bromo-derivative. The work described in the present paper was carried out for the purposes of the Chemical Warfare Department and permission for its publication has been given by the General Staff. THE CHEMICAL LABORATORY, UNIVEREITY OF CAMBRIDGE. [Received October 16th 1920.

ISSN:0368-1645    

DOI:10.1039/CT9201701447

出版商:RSC    

年代:1920

数据来源: RSC

摘要:

INTERACTION OF ETHYLENE ETC. 1453 CLXI.--Interaction of Ethylene and Selenium lionochloride . By HAROLD WILLIAM BAUSOR CHARLES STANLEY GIBSON and WILLIAM JACKSON POPE. IN a previous paper (this vol. p. 271) we have shown that ethylene is absorbed by sulphur monochloride giving a quantitative yield of @'-dichloroethyl sulphide in accordance with the following equation : 2CHz:CH + S,Cl = (CH,Cl*CH,),S + S, It is now shown that ethylene reacts with selenium monochloride to give /3B'-dichloroethyl selenide dichloride and selenium ; the reaction proceeds in good accord with the following equation: 2CH,:CH + 2Sc3ClZ= (CH,Cl*CH,),SeCl + 3Se. Whilst it thus appears that sulphur monochloride and selenium monochloride are acted on quite differently by ethylene it is possible that the action proceeds analogously in both cases so as to yield BB'-dichloroethyl sulphide or selenide but that the selenide is further acted on by selenium monochloride giving selenium and the new derivative of quadrivalent selenium now described ; this suggestion is supported by the observations of Evans and Ramsay (T.1884 45 64) which indicate that selenium nionochloride readily decomposes into selenium and chlorine. Preparation of Selenium Monochloride, Selenium monochloride is conveniently prepared in quantity by a modification of the method described by Divers and Shimose (T. 1884 45 198'). Finely powdered selenium (80 grams) is added with constant shaking to fuming sulphuric acid (320 c.c.) containing 15 per cent. of dissolved sulphur trioxide; the mixture is warmed to 45-50° with shaking allowed to cool and treated with a current of dry hydrogen chloride.When the gas is no longer absorbed the product is poured into concentrated sulphuric acid (450 c.c.) and the residue washed in with the same liquid (35 c.c.); the lower layer of cruds selenium monochloride contain-ing suspended selenium is drawn off mixed with fuming sulphuric acid (containing 15 per cent. of sulphur trioxide) (100 c.c.) and treated with a brisk stream of dry hydrogen chloride for an hour and a-half. The product is now poured into concentrated sulphuric acid (150 c.c.) when much hydrogen chloride is evolved 1454 BAUSOR UIBSON AND POPE INTERACTION OP and the lower layer of selenium monochloride (99 grains) drawn off. Thus obtained it forms a deep red liquid containing a little free selenium in suspension; i t is further purified by keeping over dry potassium chloride and filtering in a dry atmosphere./3fi/-Dichloroethyl Selenide Dichloride (CH,Cl*CH,),SeCl,. Selenium monochloride (55.5 grams) is dissolved in dry benzene (50 c.c.) and a current of dry ethylene passed through the solu-tion; considerable evolution of heat occurs and the liquid should be kept cool. Absorption commences rapidly and selenium is almost immediately precipitated ; i t is desirable to add further quantities of dry benzene (20 c.c.) to prevent blockage of the delivery tube. When no further absorption occurs more benzene is added and the liquid filtered boiling hot the residue being extracted with boiling benzene until the filtrate deposits no more crystalline product on evaporation.P,B’-Dichloroethyl seleiiide dichloride (27.5 grams) remains in the form of white crystalline needles after distilling off the benzene and may be purified from slight admixture with selenium by recrystallisation from boiling benzene. From observation of the quantity of selenium recovered (30.0 grams) it is concluded that the reaction proceeds in accordance with the equation given above. Bfi’-Dichloroethyl sdenide dichloride is about ten times as soluble in boiling benzene as in the cold solvent; it’ crystallises in long, colourless prisms (see figure) which melt a t 122’5O and are slightly hygroscopic. The crystallographic description given below was furnished by Miss I. E. Knaggs working under the direction of Mr.A. Hutchinson. Crystal System.-Monosymmetric holohedral. A xial Ratios.-a ; b c = 0.6345 1 0.5359. Forms Observed.-C(OOl) m(110) of(ll1). P = 75O5Of. No. of mertsiite-Angle. ments. Limits. Observed. Calculated. - mm=iio y o ...... 9 62’38’- 63’46’ 63’12’ rnn%=_llO :?lo ...... 9 116 14-117 22 116 52 116’48’ O‘C = E l l 001 ...... 7 66 24- 66 43 66 2 65 69.6 - mo’-llO 111 ...... 9 35 2 5 - 36 24 36 2.5 mC =110 001 ...... t i 101 40 -102 23 102 2 -Cm =001 Ti0 ...... 7 77 2 5 - 78 28 77 49 77 58 No cleavage was observed. The crystal habit is prismatic and is terminated by small basal and pyramidal planes. The crystal faces are very much rounded and badly developed arid it was only possible to obtain approximate angular measurements.The1 opti ETHYLENE AND SELENIUM MONOCHLORIDE. 1455 axial plane is perpendicular to the plane c;f symmetry and the acute bisectrix lies in the plane of symmetry being inclined at 22O to the z-axis in the acute axial angle. The refractive index P, was found by the immersion method to bs approximately 1-65; the index a is slightly less than this and y is somewhat higher than 1.75 and could not be determined. The double refraction is hence strong and positive in sign; this was verified by observa-tion on a section cut nearly perpendicular to the acute bisectrix. The optical axial angle was measured as 31O13’ for sodium light in a liquid of refractive index 1-65. Moderate dispersion of the optic axes was observed the angle for red being greater than that for blue light ; horizontal dispersion was not observed.The compound dissolves freely in cold water t o an acid liquid, which gives a precipitate of silver chloride with the nitrate; a viscous liquid remains on evaporating the aqueous solution. One half of the chlorine present is hydrolysed to hydrogen chloride by the action of water (Found C=17*5; H,=2.70; C1=51.4; Se=29*1. 0.1591 required 11.5 C.C. N/lO-AgNO,. Hydrolysable chlorine = 25-7. C,H,Cl,Se requires C = 17.3 ; H = 2.89 ; C1= 51.3 per cent.). On passing sulphur dioxide into a cold dilute aqueous solution of the dichloride a heavy oil separates; this when collected and left in a coo1 place crystallises to a mass of almost colourless, prismatic needles. This compound is very readily soluble in benzene and when crystallised from a small quantity of this solvent melts a t 23-25O ; it is possibly @P’-dichloroethyl selenide 1456 MORGAN AND DREW RESEARCHES ON RESIDUAL and as special precautions must be observed in handling such a substance its further examination will be continued later. We are engaged on the further study of the interaction of ethylene and other non-metallic chlorides. The work described in the preeent paper was carried out for the purposes of the Chemical Warfare Department and permission for its publication has been given by the General Staff. THE CEEMICAL LABORATORY, UNIVERSITY OF CAJTBRIDOE. [Rrc~iucd Octobpr 1.5th 1920.

ISSN:0368-1645    

DOI:10.1039/CT9201701453

出版商:RSC    

年代:1920

数据来源: RSC

摘要:

1456 MORGAN AND DREW RESEARCHES ON RESIDUAL CLXI1.-Researches on Residual A f l n i t y and CP ordination. Part I I . Acetylacetonev of Selenium and Tellurium. By GJLBERT T. MORGAN and HARRY DUGALD KEITH DREW. THE acetyla.cetolne derivahives of t,he metals metlallaids and non-metals ma,y be classified into three main groups. I. Meta.llic ac:eltylacelttosnea in which t'he principal valeaoiee of t$hel metal are complet,ely satisfied by the univalent a.cetylamtone radidel, C5H702 such as t'he thallous glucinum oupric zinc sca,ndium, aluminium chromic ferric a.nd t,horium derivatives amd numerous others. In many instances aoetylacehm has gimn wings to the metals for certain of these compoanda are va1a;tilei without decom-pmit(ion (Combes C'om.pt. rend. 1894 117 1222 ; Kurwski Ber., 1910 63 1078; T.1913 103 81; 1914 105 189). 11. Aceltylaaekmes of thel noln-rnet$als and metlalloids in which the principad vadenues oC the delment8 as@ only pastdy &isfied by tthe univalent amtylamtonel radicle. Such are the colmpaunds of boron, silicon and tit,anium B (C,H70,),Cl Si(C,H,O,),Cl and Ti(C,H70,),C1 which function. a8 meltdlic ahlorides givin,g rise t,o rema,rkable double salts (Dilthey AnmaZen 1905 344 326). 111. Aeet4ylamtones o f . sulphur whiah behave as true olrganic deriva.tives of sulphur carbon being attacheld d i r e d y to this non-metlal and not through the intmmediasy of obxygen as in the two1 preceding classes (Angelli and Magnani Gazzetfn 1893 23 ii 415; 1894 24 i 342; Vaillanb Compt. rend. 1894 119 647). There is also a t<ransitioa group of metallio ac&ylawbnes behween tqhe+ maSn groups I and 11 in which the prindpa*l valendes of t,he met a1 aTet only pastly satisfied by t,he acetylaeelt'one complen.Thi AFFINITY AND CO-ORDINATION. PART II. 1457 transition group includes the complex amtylacebnes of plakkmm (Werner Ber. 1901 34 2584) and the colbaltia amtylaceitone corn-pounds of the general type [C,H,O,Col e%]X (Werner Helv. Chirn. A cta 191 8 1 78) wheret en = elthylenediamine. The latter series of acetylacetone detrivativm axhibits optical activity and the existence of enantiomorphous pairs of isolmerides aff olrds definite information as to the arrangement of the1 acetylacetom nucleus in these sub-st8ances and justifies .the belief tlhat the univalent group CH,-CO* CEI C (CH,) 0 fun d i o n s as two asc oci a t i ng uni tg,* forming a ring structure in which the inetallia atom is implicated.The relsearah described below which is still in a preliminary stage shofws that the intelractisns of acetylacetone and the tetlra-chlorides olf selenium and tellurium lead to prolducte differing considerably in type1 frofm thoset classified above. Altholugh there are many points of differcmm bertwelen the1 various members of the three main groups of acekylacetone delrivakives they possess one attribute) in common namely the univalent acetylacetone radicle of which oiie or morel arg present) in the moletcule of every one oC thew derivatives hikhelrta described. I n the acetylacetones of selenium and tellurium these metalloids are found to be associatled with a bivalent radicle @,H,O,”.Selenium tetrachloride and acetylacetone interact in ethereal solutioln in aocordancel with the following equation : (1) 2SeCl,+ 4C,H80 = [C,H,O,:Sej + 2C,H7C10 + 6HC1, the products being seleniicm acetylacetone a well-detfind pale yellolw orystalline compolund chloroacetylacetone and hydrogen chloride. This seileniuni acetylacetone which is bimo~lmlar in benzene1 solution is readily decomposed by concentrated hydro+ chloiric acid and by reducing agents such as the alkali hydrogen sulphitea. The former of these decompositions takes plam readily, giving rise to1 elonieatal selenium and chlolrolacetylaceltonel, (2) [C513[602:Se]2 + 2HC1= 2Se+ 2C,H702C1. * The adjective “ chelate,” derived from the great claw or “ chela” (“ chely ”) of the lobster and other crustaceans is suggested for these caliper-like groups which function as two associating units and fasten on to the central metallic atom so as to produce heterocyclic rings.Among the compounds which by virtue of their residual affinity function a.s chelate groups are ethylenecliamine (en) propylenecliamine aa-dipyridyl and dimethylethylene sulphide (T. 1912 101 1798). Many unsaturated radicles also function as chelate groups partly owing t o their principal valencies and partly owing to residual affinity for example. the acetylacetone and oxdate groups and the univalent groups in dimethylglyoxime, CH;C( :NOH)*C(CH,I:NO*, izitroso-p-naphthol 0 :C,,H,:NO’ and many other lake-forming complexes. In the present communication tho bivalent radicle C,H,02” functions as a chelate group entirely owing t o its principal vnloncies 1468 MORGAN AND DREW RESEARCHES ON RESIDUAL The latter demmpodtion which proceeds quantitatively is an interestling example of the1 way in which organic reselarch sometimes leads tlo improvelmeata in inorgania syntlheses.Four moilecular prol-portions of alkali hydrogen sulphitel reduce the1 dimeric setlenium amtylaceitoae quantlitlaflive~ly into amtylacetonel and alkali seletnudi-thiolna#k : (3) [C,H,O,:Se] + 4KHS0 = 2C5H802 + 2Se<s0:K. SO. K I n the earlier preparations these selenodithionates were obtained in a laborious manner together with alkali thioselenates by digesting sulphites with selenium or selenious acid (Rathke J .pr. Chem., 1865 95 8 ; 1866 97 56; Schultze ibid. 1885 [ii] 32 399). The acetplacettonel setj free in the forelgoing reduction and in other similas reactioizs is convenielntly mtima8teld by coupling with sodium iso-p-nitrobenzenediaxo-oxidel to f o m the sparingly soluble p-nitro-b~nzen~soaceityla~t~ne N02*C,H,*N,*C5H702 (Bulow and Schlot-t.erb& Ber. 1902 35 2191). The foregoing equatJolns representing the farmatian and quanti-tat,ive decolmpositim of selenium acekylacetone are acEnsistenti witlh the view that this associateid compound may be represented by ths graphio formula 0 0 /\ /\ \/ \/ CH,*S Se==Se C*CH, I I 11 HA CH CH CH co co /\ /\ - . S- 'HA CHn CHn ' \7 (1.1 This canalusion is confirmed by the rwults obtained in studying the intoradion of tellurium tstraclhlolride and acetylacetme.In moder rately concentrated chlorolform solution theae reagents give rise t o a cololurleas substance tellurium acetylacetone dichloride, (4) TeC1 + C5H80 = C5HG0,:TeC1 + 2HC1. The didhlotride when cautiously reduced with sulphurous acid or alkali hydrogen sulphites 1mes its ohlorine and yields tellurium acetylacetme a golden-yellow compolund whioh unlike its selenium analogue does notl exhibit association in organic solvelnts : (5) C,R,O,:TeCl2 + H,S03 + H,O = C5H602:Te + 2HC1+ H2S04. Tellurium acetylamtone is decomposed quantitatively into tellurium and acetlylacetoine by suah reducing ageinta as an aluminium-mer-cury coluplei or alkali hydrogen sulphites. In the1 l a t h case a tellurium analogue of tlhO alkali sele~ndithio~natlw was not detected : (6) C,H,O,:Tel + 2KHS0 = C,H,O + TO + li,SO + SO, AFFINITY AND CO-ORDINATION.PART 11. 1459 Tellurium acetylacotone differs from the selenium analogue in its dwompolsition with colld concentrated hydrochloric acid (compare equation 2); it yiellds acetylacetone a8nd half the tellurium as the1 tetrachloride : (7) 2C5H,02:Te + 4HC1= 2C,H80 + Tel+ TeC1,. These1 relactioas support the view thatl tellurium aceltylacet\one didloride (11) and tellurium acetylacetolne (111) may be repre-sented respectively by the following folrmulaa : 0 0 0 /\ \/ CH,*C X /\ \/ Ct'l,*C Te /\ \/ H& CH C CH~*C ?<:; (nascent Fi?) II I RC CH, UO 7+ -- a II HC aCC2 CO dK (111.) (IV.) Selemium and tdlurium acet;ylacetoirx?s f unatiofn as weiak aaids and dissolve in aqueous alkali hydroxides.It is therefore evident that they may have an alternative einolic configuration (IV) which would correspoad with that of their unstable a,lkali salts. E X P E R I M E N T A L . * Se 1 e nium ,4 c e t y lac e t one [ C5H602 Se],. Sellenium tetlrachlomridel was preIpa,red by passing dry chlorine in elxoe,ss over coasselly polwdefred sellelnium at tlhe ordina,ry temperature, t,he da,rk red mo~nochlo,ride being f olrmeld as a,n intleme~diacte phase. The pale yelllolw crystiallinel tet'rachlolridel (14.3 grams) suspended in 140 C.G. of dry sther was tseatled at the oBrrdina8ry. temperature witlh 13 grams of aceltylaceitsne (2 molls.) dissollved in 30 G.C. of the same solveliit8.Hydrogen chlolride was f olrhhwith emlved the solution reddelneld t8her t'eltlra,chloiride slolwly passeld intlol sollution while a yellolw pre8cipit'atte appea,red asld reldissollveld in about tlhirty minutes to a tsanspa8rentl pa,lel red f Liming la.chryma.t,ory sollution which was elvaporat'ed rapidly a t the1 oirdinasy tlempesature in a cu'rreat of air. Hydro'gen chloride elthetr and ohlo~rooacet~la,aet~oins were1 t'hus remowd; tlhe reaidueb a palei red oil sollidified on stbrring. The product (10 gra,ms yield 90 per eetntf.) cryst,allis,eld from benzene in pale primroseyellow glistening plates or lath-like needles giving yellow ,solutjiolns in 0rgani.c me.dia.; oln exposure] t'ol light far pro+ longed pelrio*ds its surface. becamel thinly colated with pink selenium.* The authors are indebted t o Dr. Scott for a gift of pure tellurium, and to Professor Ling for specimens of this metalloid and of selenium 1460 MORGAN AND DREW RESEARCHES ON RESIDUAL During this incipient decomposition the odour which at first was pleasing and fa8rinacwus beoamei fainbly nauseiatling a result whioh was due pro*bably tIo liberation of traces ojf hydrogen selenide. The substance reddened atl about 140° and subsequently melted and demmposeld atl 175O. In a sealed capillary tlube heated from 150° it meltled to an orangel-red liquid at 185O. The selenium was determined by heating the weighed substance with 5 a.0. of fuming nitria acrid in a flask with ground-in air con-denser. Oxidatioln being ao~mpleted the soilution was boiled with exoe~s of hydrolchloria acid untdl all nitIraus coimpolunds were destroyed the metlalloid pre&pittated as the red moldifiaatim tsam-forming into the dark grey variety oln warming with sodium sulphitle or aqueous sulphurous acid was colllelded and weighed.Carbon and hydrogen atimatiolns were made in mmbustion tubee charged with fine copper oxide a long length oC lelad ahramate and a spiral of aopper oxide a lit& of this oxide! beling also placed in the polrcelain boat. In the eombustioln od sellenium and tellurium deriva,tivea more acwuratx resulbs were obtained by burning with oxygen alme than with air follolwed by oxygen (Found C = 34.23, 33-74 ; H =3-45 3.72 ; Se= 44.10 44-17. (C,H,02Se) requires C = 33-86 ; H = 3.41 ; Se= 44.68 per cent.). Molemlar determinations by the elbullimaopia method in benzene gave 316 312 (0.65 and 1-18 grams per 100 C.C.respectively) thus indioating association n = 1 o r 2 requirea 177 or 354. Selenium aaeltyla8wtone is notl obtained unless the presaribed elxperimelntal conditions are followed aloselly in regard to tempelra-tlure concentration proportion of reagents and remowal of the volatile pr0duat.e a t the ordinary temperature. The proportion of two molecules of amtlylacetone to me of selenium tetraahloride has been found t a give the optimum yield whereas ratios of m e or four mo~leaulee of the dikebne do not give rise to any crystalline product. Experiments carried out in chloroifmm or with selenium dibrolmide, S%Br, and acetylwetolne in ether have led 50( far to dimination of selenium and to( the production of lauhrymahry oils.A preliminary experimentl with benzoylacetonne and selemium tetraahloride in cold ether indicated the formation of a pale yellolw selenium benzoyl-acetone (m. p. 212O) having similar properties to1 seilenium amtyl-aceltonel. Selenium acetylacetone which has a faintly acidic sweetish taste, di-lves slightly in holt waker the solution being distinctly acid; it is somewhat sparingly soluble in boiling ethm ethyl alcohol amhne or chloroform and dissolves more freely in hot glacial acetic acid. Its solubility in boiling benzene is about 1.5 grams in 100 c.c. but is ten times less in the cold AFFINITY AND CO-ORDINATION. PART 11. 1461 Selenium amtylambnet dissollves readily in cold aqueous alkali hydroxides or ammonia to bright yellow solutions which regenerate the ampound if neutralised a t onm with dilute a&d.The alkaline solutions speedily decampme red sellenium being precipitated whilst a nauseating odolur is devdopd. Although insoluble in aqueous soIciium earboiiatle prollonged treatment witIh this reagentl leads tto the foregoing demmpoaition. The orgalliu product of theee alkaline decmmpositioas is an oil having a plelasaiit ketonic odour. Dilute mineral acids are without &eot on selenium awtylacetone, concentsated nitric and sulphurio adds have 8 destructive adioln, whelreas odd concentrated hydrochloric acid decomposes itl smoohhly into red selenium and ahlolroaoetylaaetone identified by its bailing point lachrymatory properties and grwn copper derivative.Ferria chloride &her in aqueom or alcoholic solution giveis no reld cololration with selenium acetylamtone even a f k two hours. I n twenty-four hours ~JI orange tint is discernible and this coloration is dwelopeld more quickly on holdmg but selenium is set frw simul-taneously. When distilled with zinc dust selenium acetylacetone loses selenium evolves a nauseating vapour and gives rise to an oil whioh after rectificatioa gives a red mloration with ferria ahloride and has a pleasant ketonic; udour. Iodine in chloroform solution has no action on selenium ac&ylamtone but chlorine in the same solvent gives selenium teltrachlorida and chlolr mcety1mt8one whereas bromine yields Iachrymatory produate and a wlourlm crystalline substance (m.p. 1 8 0 O ) . Aqueous hydrogen sulphide decomposes it slowly in the cold with liberat\ion of sulphur and selenium. Hydr-oxylamine phenylhydrazine p - brolmophenylhydrazinel 11 - nitro-phenylhydrazine and 6-chlolro4 4-tollylenediamine induce a mom or less rapid elimir?;ttion of selenium. By-products of the Formution of Selenizcm A eety1acetime.-The amount of hydrogen chloride set free in the condensation was wti-mated and found to be equivalent to tIhhree-fourths of the ahlorhe originally present in the) selenium tetrachloride. The chlarmaetyl-acetone (b. p. 148-150°) of whioh morel than two-thirds of the oal-culatd amount were obtained in a purified condition was further identified by conversion into its green copper derivative soluble in chloroform.Thew reaulk support the view expressed by equation 2 (p. 1457). Quantitative Decomposition of Selenium Acetylacetone Alkali Selenodithionates. Two grams of powdered selenium aceltylmtme were added t'o 18 0.0. of water containing 3 grams od potassium meltabisulphite (Z+ mols. oif KHSO equivalentl to 1 atom o t Se) and the mixtur 1462 MORGAN AND DREW RESEARCHES ON RESIDUAL was shaken nielcbafnically for olne hour. A colourless crystlalline prel-cipit'ate o,f pot,assiunn selenodithioaate K,S,SeO, was) then col-lecteld t,hel filtmhe elxtsacted with etther to1 remove a.celtyla,cstsne, and t8hel aqueiolus layer mixed witlh akoho'l tlol complete t.he delposit'ion olf the inolrganic prolduct8 (yield 3.5 gra,ms = 97 per aelnt. olf the t,heoL reticad). Wheln sepa,ra.tdng rapidly f ro'm aquelous soduti.oln tbe sellenoc dithiomte appeare'd in lust,rous scales oc thin pla,t>es ; when cryst8a81-lising slowly itl was o'bt'ain ed in loag transpa,re'nt silky ne1edle.s.Botb folrms o,f the1 saltl were quite collolurlelss a.nd &able when expweld to air a,nd light. On heatJng tlhezy colmmelnced tlo redden a t 190° and a,tl 250° t'he reld sellenium tarneld grey. Mela.nwhile sulphur diolxidel was evollved aad finally a residue of potaasium sulpha.te was ledt (Foand K= 24.59 ; S = 20.06 20.58 ; Se= 25.06, 25.07. Calc. K = 24.63 ; S = 20.19 ; Sel= 24.95 pelr ce8ntl.). Sodium selenodithionut e Na2SzSei06 was prolduce'd by a.dding sellelnium aceltyla.cetloae to! a. cold colncelntsatleld solutlioln of sodium hydrogeln sulphitle (24 moils.) the mixture beling s h a h n until the osga,l.c cotmpound ha3d dissolved and preoipi,t,a,tled by a,dding alcohol in colloarless lust,rous anhydrous scatlels rela,dily solluble in water (Foand Na,= 16.24.Na2S,Sei06 requires Na= 16-12 pelr cent:.). Aqueolus sulphur diolxide ha,d a simila,r a'ctioln 0111 sedelnium aaeltyl-aceltone dissollving it in the cofld t'o a' co1loiurle:ss solution ccmt4ainiag amtyla.cetolne elxt,raoteld by ether a<nd selenodithiolnic acid which slo,wly deconiposeid into1 se'lenium sulphur dio(xi.de amnd sulphuric acid. Estimation of Acety1acetone.-The amty1a.cetone set free in the foregoing cieeompositionst wa8s idelntified by conversion into its pale blue copper a,nd coloarless a,luminium derivatlives. Itl wa,s elsttimalted by coupling witlh s,oldium iso-p-nitlrolbenzeneldiazol-o,xide.Seilelnium anety.laoeltone (0.2 gmm) was sh&e:n for f ojur hours with 0.25 gra,m od polt.assi,um metlabisulphitte aad 3 C.O. oC wa,tleir. Pot'ass-ium selelnolditlhionatete was precipittated by alcolhoil and t,he filtira.te tlr ea,ted wit'h 0 * 2 3 gr a,m od sobdium is o -pnit;l-olbeazelneldi azo+olxide, (NO,*C,H,*N,*ONa,,H,O). The pale olralnge-reld preidpitate of ~n;itsolbeinzeneazola,~~tylacelt'olne aftw wa'shing witlh dilute1 alcohol, wedgheld 0.2 gram (mlc. 0.28 gram) a,nd gave tlhel colrrectl rnellting pointl 219-222O. Tellurium reactsd wit'h dry chlodne evolving heat and fo'rming tellurium tetrachlocide as a yellowish-whit\e liquid in which excess od the1 metallolid dissolved to an almost black solution probably eolntaining tho diclhlmidel.Witlh exoelssl of chlorine tlhe whole! sdidi AFFINITY AND CO-ORDINATION. PART 11. 1463 lied to a yellaw crystlalline ma.ss of tet,rachloride which was purified by sublimahioln. Sublimed t'edlurium t&rachloride (10.3 gra.ms) was mixed with 7.6 gra?ms olf amtylaaet~o~ne (2 molls.) in. 55 C.C. off dry chloroform and the1 ora,iige sollution heat'ed undelr reflux an the wat'er-bath. The evolution od hydrogeln chloride ce.ased aSter tlwol hours' boliling ; tvhe solution was filtered frolm a heavy dark grey oil and conmntmtod over lime in a desicoator. Crystlals olf tellurium amtylacetone dichloride separahed ; the concent,ra,ted filtrate6 yielded further crops (yiedd 7 grams or 62 per cent'. aaloulateid on TeC1,).The proldud was spasingly solluble in ether benze'ne or ohlolrodorm, ratlhelr moire 501 in hot ahholl and very readily soluble in cold acetone. It! crystadlised from alcohol or benzene1 in a.ciaular forms, and separat'ed slolwly from acetom i n large tlra,mparent hexagonad prisms olft,en twinned. Both forms we're mlourless; they darkened a,t 155-160O a'nd melted and dmmpofjed between 169O and 173O, libelrating t#eJlurium aad evolving hydrogen chloride and a la,chry-matory olil which deivellolpeld a red coloration with aqueous f errio chloride. The tlellurium was wtima,tIed by warming a weighed amountl with i-uming nitlric acid (5 c.c.) in a reflux appa.ratus. After boiling with concentrated hydrochloric acid (25 c.c.) to re8motve nit'rolus compounds the sollution Wacs emaepora8ted ta dryness.The residue dissoIlveld in 15 c.a. od 10 per cent. hydrmhlolric a,cid was wa,rmed with 10 aa. of 15 per ceatl. hydrazine hydrochloride and 35 C.C. of saturated sulphurous acid gradually added the liberated tellurium being dried a t 107O. The chlorine was estimated by alka,line hydrolysis and pre.cipiia,tbn as silvelr chlolridel ; the com-bustions webe carried out as in t,ha case1 ob sedemium aoettylaaeltoae (Foand C=20.72; H=2.07; C1=24.01 23.95; Te=42.87. (C,H,O,Cl,Tel) requires C=20*24; H=2.04; Cl=23.92; Te=43*00 per oelnt,.). ~~o~le~clulas.welightl-weight~ det.elrmina,tlions by the eibullioscolpic method in acet,onel (1.846 and 4.207 grams per 100 c.c.) ga,ve 241 and 255 (Ill = 296.5). Telluriwm acetylncetone dichlom'de does not beaome discoloured on exposure to lightl.It rmdily loses chlorine with hot water or aqueolus a.cids or alkalis. Tellurium is not selt free by bodling wit,h a,queous p&a,ssium hydro'xide. With aquetolus f erria chloride a red collolration is developed only very slowly. When warmed with considerable excess olf aqueous sulphurolw acid this wmpolund i4s decolmpoaeid aompletely yielding tellurium and a.cetyla,mt80me; 1464 RESEARCHES ON RESIDUAL AFFINITY ETC. Tellwium A cetylacet one C,H,O,:Te. The foregoing dichloride (2.2 grams) when tiiturated for ten minutes witlh 1.8 grams of potassium metabisulphite (1 mol.) and 20 C.C. of water yielded a small amountl of tellurium and 1 gram (yield 60-70 per cent.) of a yellow compoand whioh was purified by crystallisatlioa from benzene o r hot water.This product was dsol olbtaind with less libelration of tellurium by boiling the dichloride with a slightl excless of aqueolus sulphur dioxide (Found C= 27-14, 26.62; H=2-88 2.92; Te=56*55. (C,H,O,Te)n relquires C=26.61; H=2.68; Te1=56'52 per cent.). Malemlar-weightt detelrminatbns in boiling benzene and amtone (0.462 and 0.879 gram per 100 c.o.) gave respectively 262 and 185. M.W. for n = l is 225.6. Tellurium acetylacet m e forms heavy goldeln-yelllow needles spar-ingly soluble in water ehher chloroform or alcolhol and demmpoe-iag indefinitely a t 145-180°. I n a sealed tube it melts to a yellow liquid which partly sublimes in yellow needles and on further heating decomposes with elimination of tellurium and pruducrtjon of an oil resembling acetylacetone.Under reduced pressure the compound subl'imes a t about 160° in glistening yellow needles. Tellurium acetylamtone resem blels the selenium compound in its chemical reactions. It dissolves in cold aqueolus potassium hydr-oxide t o a bright yellow sodution from which immeldiatle neutral-isatioa with acid regenerates the original colmpolund but after B few minutes the alkaline solutIioln deposits tellurium. Cold concantrated hydroahloria acid decomposes the1 compound with elimination of tellurium. Ferric ahloride develops a reld coloration but only after a long time[. Hydrogeln peroxidel decolorisea immediately the yellow aqueous solutmn of tellurium acetylaoetone giving a white precipi-tlate; hydrogen sulphide produces at once! a black deposit (T& ?), alcoholic mermrio iodide yidds a yellow precipitate and warm aqueous sulphur diolxide reduces the compound with elimination af tellurium.Quun t it at i.v e Decompositions of T el1u.rizl.m A ce t y lace t one. (a) With Bisulphit e.-Tdlurium amtylamtone (0.4 gram) shaken for five hours witlh 0-4 gra,m of potassium metabisulphite~ and 3 0.0. of water yielded sulphur dioxide 0.2 gram of tellurium and 0.3 gram of potassium sulphate the latter pr&pitlakd by alcohol after extracting the aaetylaaetone with ether. Waxm aqueous sulphur dioxide brought about a similar rcwtuc-tion yielding acetyla&tme tehrium and sulphuric acid THE FORMATION AND REACTIONS OF IMINO-COMPOUNDS. 1465 (b) Il/-ith a n A lum.iniicm-Mercwy 6'ouyZe.-Tellurium acetyl-aceltolne (0-4 gram) i n 50 C.C.of hot water was shaken with an aluminium-n:e8rcury co,uple and t'hs solut'io1n filterred from precipi-tlat8ed tlellurium was treated with sodium iso-pnitmbenzadiazo-olxidel (0.37 gmm) in 8 C.C. od glacial acetic acid and 20 C.C. oC abso-lute alcohol. Af telr three; holurs t,he olrangered p-nit3robenzeneam-acetylacetone was collected (0.35 gram yieild 80 per cent.) and crystallised from glacia.1 aceltlic acid; itl then mellt,d at 220O. (c) With Cowentrated Hydrochloric L4 cid.-A preliminaxy experime,nt showed t'hat tellurium a8cetylacetlone unlike its selenium a.n alogue yielded a.celtylan=et olnel and not chloroac&yla,uetoln,e on dscolmposition witlh concentrat'eld hydroahloric acid a polrtion only of the tellurium beling precipi,t,atled whilst the relmainder was left1 in sotlution as t'elluriiim t8etfrachlolride. Tellurium aceltylaaetone (0.1558 gram) was stirred with colld concenttrated hydrochloric acid folr severa,l ho1ul.s. The precipita,teld tellurium which was theln col-lect,etd a,nd washe'd successive'ly wit'h a little mare conceintrated acid a,nd waf,er weigheid 0.0432 gram. The filtsates were then t s e a t d witlh aqueolus hydrazine hydroahloride saturated with sulphur dioxide. 'These relducing agelnts precipita,ted the remainder of the t,ellurium whiah welighed 0.0427 gram (total a.molunt of tellurium found = 0.0859 gram. ; cak. 0.0880). These results confirm equation 7 (p. 1459). The authors desire to enprelss their thanks to the Advisory Council for Scientific and Industrial Research for grant8 which hame partly defrayed tbe expelnses of this iiivwtigation. CHEMICAL DEPARTMENT, UNIVERSITY OF BIRMINGHAM, EDGBASTON. [Received October 25th 1920.

ISSN:0368-1645    

DOI:10.1039/CT9201701456

出版商:RSC    

年代:1920

数据来源: RSC