XXII.—On the nitration of chloroform

Edmund J. Mills
1871 Journal of the Chemical Society (Resumed)  
THE nitration of chloroform has been attempted, but, aecording to the ordinary statements, without success. I find, however, that the task is not altogether impossible of accomplishment. 16 vols. hydric nitrate containing much nitric peroxide are sealed up with 7 vols. chloroform, and heated to 90"-100" for 120 hours. The digesting tubes should lie at an angle of about 30" with the bottom of the bath, as it appears that a more nearly horizontal position involves the destruction of any
more » ... on of any nitro-compound that may be formed, whilc an upright position causes the reaction t o proceed with excessive slowness. When the digestion is ended, the apparent volume of the chloroform is much greater than before, on account of the liquefied gases, especially nitric peroxide, which it now holds in solution. The tubes are best opened by meams of a flame, and allowed to stand about 12 hours; their contents are then poured into water (with which they are mashed) and are afterwards dried over calcic chloride and fractionally distilled. In the course of the distillation, much chloroform comes over first, and is followed by a very small quantity of a liquid, whose nature is not easily mistaken. This second distillate has the extremely pungent and highly characteristic smell of chloropicrin, is nearly colourless, and much heavier than water ; a specimen of it boiled at 110.5" in an apparatus in which chloropicrin, prepared from picrate, boiled at 111.6" (corrected temperatures). The determination of chlorine in this specimen furnished the following results :-Substance. hgentic chloride. Chlorine per cent. 0.3287 0.8714 65.54 0.2661 0,7063 65-62 0.6955 grm. chloride from the second estimation yielded 0.5239 grm. silver = 75.33 per cent. (theoretically, 75.28 per cent.), sllowing that no appreciable quantity of cyanide mas present. Another preparatiolz gave the following numbers :-Substance. Argentic chloride, Chlorine per cent. 0.3245 0.8545 65.10 [The theoretical percentage of chlorine in chloropicrin is 64.74. Chloroform contains 89.12 per cent. of chlorine ; dinitromethylenic chloride, 4 0 5 7 per cent.] f Watts's Dictionwy# i, 920.
doi:10.1039/js8712400641 fatcat:wkeludjvzzbmlebwys233cnrxq