48 L-49 A.] 



GLYCEROL 



99 



with formic aldehyde (2 mols.) to give 

 trimethylenebromnitroglycol, which by 

 reduction yields trimethyleneaminogly- 

 col, and the latter by the action of nitrous 

 acid is converted into glycerol (Henry, 

 Rec. Tr. Ch. 16, 250; Bull. Acad. Roy. 

 Belg. 30, 25). 



Or nitromethane and formic aldehyde 

 may be combined so as to form ( nitro- 

 isobutylglycerol/ (CH 2 . OH) 3 C . NO 2 

 (Henry, loc. cit. ; Piloty and Ruff, Ber. 

 80, 1656), from which the correspond- 

 ing- hydroxylamine derivative can be 

 obtained and converted by oxidation 

 with mercuric oxide into the oxime of 

 dihydroxy acetone. Bromine converts 

 the latter into diltydroxy acetone [151], 

 and this by reduction with sodium 

 amalgam in presence of aluminium 

 sulphate gives glycerol (Piloty, Ber. 

 30, 3161). 



NOTE : Methyl alcohol gives nitromethane 

 also by the interaction of dimethyl sulphate 

 and a nitrite (Kaufler and Pomeranz, Monats. 

 22, 492). 



[M.] Citric acid [Vol. II] by the 

 action of sulphuric acid gives acetone- 

 dicarboxylic acid (v. Pechmann, Ber. 

 17, 2543; Ann. 261, 157: see also 

 Peratoner and Strazzeri, Gazz. 21, 295, 

 and under, orcinol [75 ; C]), which by the 

 action of sodium nitrite yields diisonitro- 

 soacetone (v. Pechmann and Wehsarg, 

 Ber. 19, 2465). The latter on reduction 

 gives diaminoacetone (Gabriel, Ber. 27, 

 1043; Kalischer, Ber. 28, 1519), which 

 by the action of nitrous acid is con- 

 verted into dihydroxyacetone (Ibid. 

 1521), and this can be reduced to 

 glycerol as under L above. 



[N.] llippuric acid [Vol. II] when 

 its ethyl ester is heated with dry sodium 

 ethoxide gives with another product 

 ' dibenzaminodioxytetrol ' (Rugheimer, 

 Ber. 21, 3325), which on heating with 

 sulphuric and acetic acids and water 

 yields diaminoacetone (Ibid. 3328). The 

 latter can be converted into dihydroxy- 

 acetone and glycerol as above. The 

 other product, ' a-oxy-/3-benzamirio-/3- 

 oxypyrroline/ also gives diaminoacetone 

 by the same method {Ibid. 22, 1955). 



[O.] From mannitol [5l], which gives 

 acroltin [lOl] among the products of 

 oxidation by sulphuric acid and man- 



H 



ganese dioxide (Backhaus, Jahresber. 

 1860, 522). Subsequent steps through 

 allyl alcohol, &c., as above under E. 

 Or through n-hexane and propylene (as 

 under isopropyl alcohol [16 ; I]). 



NOTE : All generators of n-hexane (see under 

 n-hexyl alcohol [23 ; A, &c.]) thus become 

 generators of glycerol. 



[P.] Uric acid [Vol. II] gives glycerol 

 among the products of reduction by 

 heating with aqueous hydriodic acid 

 (Strecker, Zeit. [2] 4, 315). 



[Q.] From isobutyl alcohol [18] 

 through isobutyl chloride or bromide. 

 The haloids give propylene among other 

 products when passed over lime heated 

 above 600 (Nef, Ann. 318, 22). 



Or from isobutyl or tertiary butyl 

 alcohol [19] through isobutylene and 

 propylene (see under isopropyl alcohol 

 [16 ; D ; E]). Isobutyl alcohol gives 

 propylene and isobutylene among the 

 products of partial combustion by air 

 in contact with heated platinum (v. 

 Stepski, Monats. 23, 773). 



49. Glyceropliosplioric Acid. 

 CH 2 (OH) . CH(OH) . CH 2 . . P . 0(OH) 2 



NATUKAL SOUECES. 



Has been found in small quantity in 

 human urine, in certain (animal) gall- 

 stones, in the juices of the spleen and 

 other organs and tissues. In all cases 

 it is probably a product of decomposi- 

 tion of lecithin (Sotnitschewsky, Zeit. 

 physiol. Ch.4,2i4; Robin, Arch. Pharm. 

 2,532; Ch. Centr. 1888, 1 86; Lepine, 

 Eymonnet, and Aubert, Comp. Rend. 

 98, 238; in leucsemic blood, Salamon 

 and Kossel as quoted by Hammarsten, 

 'Lehrb. d. physiol. Ch/ 1895, p. 152). 



Lecithin, a complex substance related 

 to natural fats and obtained from many 

 animal and vegetable sources, is a choline 

 ester of palmito-stearo-glycerophos- 

 phoric acid. 



SYNTHETICAL PROCESS. 



[A.] From glycerol [48] by heating 

 with metaphosphoric acid or phosphoric 

 anhydride (Pelouze, Journ. pr. Chem. 



