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Chloride. by JOHNEDWIN MACKENZIE, D.Sc., PI1.D

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Chloride. by JOHNEDWIN MACKENZIE, D.Sc., PI1.D View Article Online / Journal Homepage / Table of Contents for this issue I204 MACKENZIE: THE ACTlON OF SODIUM MEETHOXIDE ON Published on 01 January 1901. Downloaded by University of Connecticut 18/01/2018 18:50:42. CXXVIIL-The Action of Sodium Nethoxide and its Homologues on Benxophenone Chlo&le and Bmxal Chloride. By JOHNEDWIN MACKENZIE, D.Sc., PI1.D. INa previous communication to the Society (Trans., 1896, 69, 985), a description was givsn of the preparation of dimebhoxydi phenylmethane by the action of sodium methoxide on benzophenone chloride according to the equation (C,H,),CCI, + 2CH,*ONa= (C,H,),C(O*CH,), + 2NaC1, and of di-ethoxy- and dibeazoxy-diphenylmethane,using sodium ethoxide View Article Online BENZOPHENONE CHLORIDE AND BENZAL CHLORIDE. 1205 and benzoxide respectively instead of methoxide. In continuing this investigation, dipropyloxy-, diisobutyloxy-, and dihydroxy-tetraphenyl- methane have been prepared, and for the sake of comparison a number of experiments with benzal chloride have been carried out. The action of sodium methoxide and its homologues on benzal chloride was first investigated by Wicke (Anncden, 1857, 102, 356), who prepared dimethoxy-, diethoxy-, and diamyloxy-benzylidenes, the reaction pro- ceeding thus : C,H,*CHCI, + 2CH,*ONa = C,H,-CH(O*CH,), + 2NaCI. Some years later, Limpricht, in a research on the chlorine substitution products of toluene (Anncderh, 1886, 139, 319), repeated Wicke's work, but was unable to obtain products free from chlorine. This being so, and no record of the yield of the products obtained by Wicke being given, it was thought advisable to try these experiments agzin under various conditions. Following Wicke's instructions, it was found that the reaction took place under the ordinary pressure as represented, but that the benzal chloride only disappeared on repeated treatment with sodium methoxide." On the other hand, when benzal chloride mas heated with sodium ethoxide under pressure, a different reaction took place, ethyl chloride, benzaldehyde, and sodium chloride being the products. The change may be represented thus : C,H5*CHC12+ C,H,*ONa = C2H,C1 + C6H5*CH0+ NaCl. By using the sodium compounds of different alcohols, the corresponding chlorides mere produced. That this reaction does not apply to phenols would appear from the work of Fosse (Compt. rend., 1900, 130, 725 and 1194), who obtained diphenoxyethylidene by heating ethylidene chloride and sodium phenate in sealed tubes at 120°, according to the equation,? Published on 01 January 1901. Downloaded by University of Connecticut 18/01/2018 18:50:42. CH,*CHCJ, + 2C,H,*ONa = CH,,*CH(O*C,H,), + 2NaCl. As in benzophenone chloride and benzal chloride both halogen atoms are attached to the same carbon atom, it was thought that itl would be interesting to see what happened when the halogen atoms * In the case of sodium benzoxide, the only product separated was stilbene, and that only in minute quantity, The reaction would thus appear to be expressed in part by the equation : 2C,H5*CHCI, + 4C,H;CH;ONa = 4NaC1 f C,H,*CH:CH-C',H, + 2CGH,*CH,*OH -t- C,H,*CHO. .t. That this should be so is rather curions in view of the fact that when benzal chloride and phenol are heated together, they form clihydroxytriphenylmethane according to the equation : CGH,*CHCI, + BC,H,*OH = CGH,*CH(CGH,'OH), + 2HCl9 and that benzophenone chloride gives n similar componiid with either phenol or s'oclinm phenoxidc. View Article Online 1206 MACKENZIE: THE ACTION OF SODIUM METHOXIDE ON are attached to different carbon atoms. In the case of ethylene di- bromide, the reaction would be expected to take place thus : CH2Br*CH2Br + 2C,H5*ONn = CH,(O*C,H,)*CH,(O*C,H,) + ZNaBr, but no record of experiment showing this to be so is known to the author. Diethoxyethylidene has, however, been prepared by Henry (Compt. rend., 1885, 100, 1007) from an intermediate product in this way: CH,I*CH,(O*C,H,) + C,H;ONa = CH,(O~C,H,)*CH,(O*C,H,) t NaI. On heating ethylene dibromide with sodium ethoxide under pres- sure, however, it was found that acetylene was produced, reaction taking place thus : CH,Br*CH,Br + 2C,H,*ONa = CH:CH + 2C,H,*OH + 2NaBr. The production of acetylene in a similar fashion, using sodium isoamyloxide instead of ethoxide, is recorded by Sawitch (Juhresber., 1861, 646). I. Action of Xodium AlkyZoxides on Benxoyhenons CI'LZoride. Diln.o~~yZoxydipT~enzylmetl~url.le,(CGBs),C!O.C)H,*CHz'C)H,),. In preparing this substance, 3.7 grams of sodium were dissolved in 40 grams of propyl alcohol, and to the cold product 19 grams of benzo- phenone chloride were added. The mixture was gradually heated to a temperature of 95O, when a violent action took place, and then kept at 120° for 7 hours, at the end of which time the supernatant liquid still gave an alkaline reaction. The liquid was filtered from the salt which had separated, the latter being washed three times with small Published on 01 January 1901. Downloaded by University of Connecticut 18/01/2018 18:50:42. quantities of propyl alcohol. The filtrate mas then distilled under reduced pressure to remove the excess of propyl alcohol. The residue, which was a viscous, brown oil, was diluted by the addition of a little ethyl alcohol, filtered from some salt, and distilled, 7.9 grnma of a colourless oil boiling at 200-210° under 40 mm. pressure being col- lected. The yellowish, semi-solid, strongly alkaline substance remain- ing in the distilling flask was distilled with steam, From the milky distillate, crystals separated which melted at 32-34O, and boiled at 204O under 40 mm,pressure. They amounted to nearly 1 gram. By cooling the fraction boiling at 200-210° under 40 mm. pres- sure in a freezing mixture, a white, powdery mass wasobtained, which on recrystallisation from light petroleum formed colourless, prismatic crystals melting at 33-34.5'. On analysis : 0.2026 gave 0.5982 GO, and 0.1576 H,O. C= $0.53 ; H= 8.64. C19H2402requires C = 80.28 ; H = 8.46 per cent. View Article Online HENZOPHENONE CHLORIDE AND BENZAL CEILORIDE. 1 20'9 Dipropyloxydiphenylrnethane is insoluble in water, but extremely easily soluble in methyl or ethyl alcohol, ether, benzene, light petroleum, $c. It is rather unstable, the faces of crystals very soon becoming dull. Well formed crystals are very difficult to obtain. The amount of the fraction boiling at 2UO-21O0 under 40 mm. pressure corresponds to 35 per cent. of the theoretical yield. The preparation of this substance mas effected in the way previously described, the quantities taken being 3.7 grams of sodium, 41 grams of isobutyl alcohol, and 19 grams of benzopheaone chloride, When the sodium compound melted, a brisk action took place, but was not complete after heating to 130--150° for 7 hours, the liquid still show- ing an alkaline reaction. The salt was removed by filtration, and the liquid then distilled under diminished pressure. After removal of the excess of isobutyl alcohol, the temperature rose rapidly to 199O, and 16.5 grams of a thick oil were collected, having a boiling point between 199' and 210" under 35 mm. pressure. When placed in a freezing mixture, this oil became a thick jelly in which minute needles appeared on scratching, After standing at the ordinary temperature for 18 days, the small bunches of needles, which had grown, were filtered off, dried on a porous plate, and, as they showed no sharp melting point, dissolved in ether., The ethereal solution deposited silky needles after being kept in a desiccator for a week. The dried crystals, which weighed 0% gram, now melted at 62--64O, but on exposure to the air the melting point fell, and, as mill be shown later, the substance decomposed with the formation of benzophenone. A combustion per- Published on 01 January 1901. Downloaded by University of Connecticut 18/01/2018 18:50:42. formed a week after the separation of the crystals gave the following figures : 0.2682 gave 0.8313 CO, and 0.1657 H20. C = 84.5 ; H = GbS6. C,,H,,O, requires C = 80.76 ; 13 = 8-97 per cent. C13€Ilo0 ,, C=S5.71 ; €I=5*49 ,, The quantity being so small, no experiments could be carpied out to ascertain the reason for the difference in melting point between these crystals and those described below. The oil from these crystals was again distilled under a pressure of 35 mm., when eleven grams, or 44 per cent. of the theoretical quantity obtainable, came over between 203" and 215", mostly at 210'. By cooling in a freezing mixture, small, diamond shaped plates crystsllised from the oil, which gradually became solid throughout. After drying on a porous plate, the solid melted at 36-38', but the melting point was lowered by exposure to the air. From an ethereal solution, View Article Online 120s MACKENZIE: THE ACTION OF SODIUM METHOXIDE ON crystals melting at 35-37", and from light petroleum, crystals melting at 35-36', were obtained. On analysis of the crystals melting at 36-38', the following numbers were obtained : 0,2041 gave 0.6017 CO, and 0,1644 H,O. C = 80.40 ; H = S.95. 0,2076 ,, 0.6131 CO, ,, 0.1669 H20. C=80.54; H=8*92. C,,H,,O, requires C = 80.76 ; H = 8.97 per cent, The following experiment is a further proof that the substance has the formula attributed to it. 0.2660 gram of the crystals in a platinum boat was placed in a desiccator over sulphuric acid and weighed every second day. The crystals soon deliquesced, then became entirely liquid, meanwhile steadily losing weight for nearly three weeks.
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