178 



ALDEHYDES AND KETONES : FATTY GROUP [92 J-L. 



by addition of hydrogen chloride (Ibid. 

 Journ. Russ. Soc. 13, 157); and then as 

 above. 



Glycerol may also be converted into 

 a-chlorlactic acid through a/3-dichlor- 

 propyl alcohol by the action of chlorine 

 on allyl alcohol (Tollens, Ann. 156, 

 164; Hiibner and Miiller, Ann. 159, 

 1 68), by the addition of hypochlorous 

 acid to allyl chloride (v. Gegerfeldt, 

 Ann. 154, 347 ; Ber. Q, 720 ; Henry, 

 Ber. 3, 352 ; 7, 414), or by the direct 

 action of dry hydrogen chloride (Faucon- 

 nier and Sanson, Bull. Soc. [2] 48, 236). 

 The a/3-dichlorpropyl alcohol gives a/3- 

 dichlorpropionic acid on oxidation 

 (Henry, Ber. 7, 414; Werigo and 

 Melikoff, Ber. 10, 1500), and the latter 

 yields a-chlorlactic acid by the action of 

 water (Melikoff, Ber. 12, 2227). 



Or glyceric acid may be converted 

 into /3-iodopropionic acid by the action 

 of phosphorus iodide (Beilstein, Ann. 

 12O, 226 ; 122, 366 ; Erlenmeyer, Ann. 

 101, 284; Meyer, Ber. 19, 3294; 21, 

 24). The iodo-acid gives acrylic acid 

 by the action of alcoholic potash, or by 

 heating with lead oxide (Schneider and 

 Erlenmeyer, Ber. 3, 339 ; Wislicenus, 

 Ann. 166, 2), and this can be converted 

 into ^3-chlorlactic acid and aldehyde as 

 above. 



Or from glycerol through a-epichlor- 

 hydrin by the action of phosphorus 

 pentachloride, or by the action of hydro- 

 chloric acid or alkali on dichlorhydrin 

 (Berthelot, Ann. Chim. [3] 41, 299 ; 

 Reboul, Ann. Suppl. 1, 221 ; Prevost, 

 Journ. pr. Ch. [2] 12, 160 ; Fauconnier, 

 Bull. Soc. [2] 50, 213). Epichlorhydrin 

 on oxidation with nitric acid gives 

 /3-chlorlactic acid (Richter, Journ. pr. 

 Ch. [2] 20, 193), from which aldehyde 

 can be obtained as above. 



Acetic aldehyde is among the pro- 

 ducts of the dry distillation of the 

 calcium derivative of glycerol (Destrem, 

 Ann. Chim. [5] 27, 20). 



[K.] From normal butyric acid [Vol. II] 

 through a-crotonic acid (see under benzyl 

 alcohol [54 ; K]), and /3-methylglycerie 

 = a/3 -dihydroxy butyric acid (see under 

 formic aldehyde [91 ; J]), and then as 

 above under J. 



Or a-crotonic acid gives aldehyde 



directly by oxidation with chromic acid 

 mixture (Kekule, Ann. 162, 315). 



Or from isobutyric acid [Vol. II] 

 through a-hydroxyisobutyric = 2-me- 

 thyl-2-propanolic acid by oxidation 

 with potassium permanganate (Meyer, 

 Ann. 219, 240). The acid gives alde- 

 hyde among other products by the 

 action of heat or dehydrating agents 

 (Scholtz, 'Der Einfluss der Raumerfiil- 

 lung der Atomgruppen auf den Verlauf 

 chemischer Reaktionen/ 1899, p. 363; 

 Bischoff and Walden, Ann. 279, ill). 



Or isobutyric acid can be brominated 

 (Markownikoff, Ann. 153, 229 ; Hell 

 and Waldbauer, Ber. 10, 448), the 

 a-bromo-acid converted into the hydroxy- 

 acid by treatment with barium hy- 

 droxide or sodium carbonate solution 

 (Markownikoff, loc. cit.; Fittig, Ann. 

 200, 70), and then as above. 



Or isobutyric acid (or chloride) on 

 chlorination gives, with other products, 

 a-chlorisobutyric acid (Balbiano, Ber. 

 11, 1693 ; Michael and Garner, Ber. 34, 

 4054), and this yields the hydroxy-acid 

 on heating with water at 180 (Ostrop- 

 jatoff, Journ. Russ. Soc. 28, 51). 



[L.] From acetoacetic ester [Vol. II] 

 through a-crotonic acid (see under 

 benzyl alcohol [54; l]), or through 

 /3-methylglyceric acid (see under formic 

 aldehyde [91 ; L and J]), and then as 

 above under J and K. 



Or acetoacetic ester may be con- 

 verted into its methylpropyl-derivative 

 by the alternate introduction of methyl 

 and propyl by the action of the alkyl 

 iodides on sodio-acetoacetic ester (Lie- 

 bermann and Kleemann, Ber. 17, 918; 

 Jones, Ann. 226, 287). Methylpropyl- 

 acetoacetic ester on reduction with 

 sodium amalgam gives a-methylpropyl- 

 /3-hydroxy butyric (3-methyl-2-hexanol- 

 3-carboxylic) acid (Jones, loc. cit,. 288), 

 and this on dry distillation breaks down 

 into acetic aldehyde and methylpropyl- 

 acetic acid. 



Or instead of methyl and propyl two 

 other alkyls may be introduced into 

 acetoacetic ester, such as two ethyls, 

 giving rise to a-diethyl-/3-hydroxy- 

 butyric (3-ethyl-2-pentanol-3-carboxy- 

 lic) acid by reduction with sodium amal- 

 gam as above (Schnapp, Ann. 201, 65). 



