102 



POLYHYDRIC ALCOHOLS 



[50 E-G. 



Ann. 208,59) and boiling 1 the y-hydroxy- 

 isohexoic anhydride with dilute nitric 

 acid (Ibid. 62). 



[F.] From malonic acid [Vol. II] and 

 glycerol [48] through allylmalonic acid 

 by the action of allyl iodide on sodio- 

 malonic ester and hydrolysis (Conrad 

 and Bischoff, Ann. 204, 168), allylacetic 

 acid by heating allylmalonic acid (Ibid. 

 1 70), and y8-dibromvaleric acid by the 

 addition of bromine (Messerschmidt, 

 Ann. 208, 100). The dibromo-acid on 

 boiling- with water gives (with much 

 dihydroxyvaleric acid) lavulic acid 

 (Fittig and Urban, Ann. 268, 64), 

 which can be treated as under D. 



Or from malonic acid, glycerol, and 

 methylamine [Vol. II] (with ethyl al- 

 cohol as accessory) through ethyl brom- 

 propyl malonate by the action of trime- 

 thylene bromide (see under propylene 

 glycol [46 ; A]) on sodio-malonic ester. 

 Ethylbrompropyl malonate on bromina- 

 tion gives ethyl- a8-dibrompropyl ma- 

 lonate, and this on treatment with 

 methylamine yieldsamethylamide which 

 on hydrolysis gives among other pro- 

 ducts N-methylpyrollidine-2-carboxylic 

 = hygric acid (Willstatter, Ber. 33, 

 1160; W. and Ettlinger, Ber. 35, 620). 

 The latter on dry distillation yields N- 

 methylpyrollidine (Liebermann and Cy- 

 bulski, Ber. 28, 582), which can be 

 treated as above under C. 



Malonic acid and acrolein [lOl] from 

 glycerol condense in presence of pyridine 

 to form /3-vinylacrylic acid, and this is 

 reduced by sodium amalgam to allyl- 

 acetic acid (Doebner, Ber. 35, 1136: 

 according to Thiele and Jehl, Ber. 35, 

 2320, the acid thus formed is /3y-pen- 

 tenoic acid). 



[G.] From acetic acid [Vol. II], gly- 

 cerol [48], and ethyl alcohol [14] through 

 allylacetoacetic ester by the action of 

 allyl iodide on sodio-acetoacetic ester 

 (Zeidler, Ann. 187, 33), allylacetic ester 

 by the action of sodium ethoxide (Ibid. 

 39), allylacetic acid by hydrolysis, and 

 then as under P. 



Or allylacetoacetic ester can be hydro- 

 lysed to allylacetone (Zeidler, Ann. 

 187,35; Conrad, Ann. 192, 153; Mer- 

 ling, Ann. 264, 323), which gives Ise- 

 vulic acid on oxidation with potassium 



permanganate (v. Braun and Stechele, 

 Ber. 33, 1472). 



Or glycerol can be converted into 

 trimethylene bromide (see under propyl- 

 ene glycol [46 ; A]) and the latter con- 

 densed with sodio-acetoacetic ester to 

 form brombutylmethyl ketone (Lipp, 

 Ber. 18, 3278). The latter on decom- 

 position by alkali gives allylacetone (v. 

 Braun and Stechele, foe. cit. 1473), which 

 can be oxidised to Isevulic acid as 

 above. 



Or from acetic acid or ethyl acetate 

 and acetone [106] through acetylacetone 

 (see under n-primary amyl alcohol [20 ; 

 B ; C]). The latter by the action of 

 ethyl chloracetate on the sodium deri- 

 vative gives 0/3-diacetylpropionic ethyl 

 ester (March, Comp. Rend. 130, 1192), 

 and this on treatment with strong caus- 

 tic soda solution yields Isevulic acid (Ibid. 

 132, 697). 



Or sodio-acetylacetone and etliyl-a- 

 brompropionate (see under aldehyde [92; 

 E]) interact to form /3/3-diacetyl-a-me- 

 thylpropionic ethyl ester, which is de- 

 composed by alkali as above into Ia3- 

 vulic acid and ester (March, loc. cit. 

 134, 179 : see also Ann. Chim. [7] 26, 



295). 



Also from glycerol through allylamine 

 by the interaction of allyl iodide and 

 silver cyanate, and decomposition of the 

 allyl cyanate with alkali (Cahours and 

 Hofmann, Phil. Trans. 1857, 555 ; Ann. 

 102, 301). Allylamine by the action 

 of ethyl iodide gives ethylallylamine 

 (Rinne, Ann. 168, 261), and the vapour 

 of the latter yields (among other pro- 

 ducts), when passed over heated lead 

 oxide, pyrrole (Konigs, Ber. 12, 2344), 

 which can be treated as under C. 



Or from glycerol through allyl al- 

 cohol, allyl chloride (Tollens, Ann. 156, 

 154; Eltekoff, Journ. Russ. Soc. 14, 

 394), and trimethylene-chlorobromide= 

 i : 3-chlorbrompropane (Reboul, Ann. 

 Chim. [5] 14, 487). The latter by 

 the action of potassium cyanide gives 

 y-chlorbutyronitrile (Henry, Bull. Soc. 

 [2] 45, 341; Gabriel, Ber. 23, 1771), 

 and the chlornitrile by interaction with 

 sodium phenolate yields y-phenoxy- 

 butyronitrile (Gabriel, Ber. 24, 3231), 

 which by reduction with sodium in 



