54 H-I.J 



BENZYL ALCOHOL 



111 



of the sodium salt with the formation 

 of aa-dichlorpropylene ; the latter on 

 heating- with alcoholic potash at 150 

 gives allylene (Valentin, Ber. 28, 2661). 

 Butyrochloral also on treatment with 

 caustic alkali gives an allylene dichloride 

 which yields allylene by the action of 

 sodium (Kramer and Pinner, Ann. 158, 

 47 ; Pinner, Ann. 179, 44 ; Ber. 8, 898 ; 

 14, 1081). The aa/3-trichlorbutyric acid 

 also gives the same allylene dichloride 

 when the silver salt is boiled with water 

 (Ibid.}. 



Or aa/3-trichlorbutyric acid by the 

 action of caustic potash gives a/3-dichlor- 

 crotonic acid (Garzarolli, Ber. 9, 1209) 

 which, on heating with zinc and water, 

 yields tetrolic acid (SzenicandTaggesell, 

 Ber. 28, 1671). The latter decomposes 

 at 210 with the formation of allylene 

 (see below under I). 



Or the acetic aldehyde can be con- 

 verted into crotonic aldehyde [102] (see 

 under normal butyl alcohol [17 ; G]) 

 and the latter oxidised to u-crotonic acid 

 (Kekule, Ber. 3, 604; Zeit. [2] 6, 705), 

 which can be converted into allylene,&c., 

 as under G. 



NOTE : Other generators of crotonic aldehyde 

 [102] are given under that compound, viz. 



malic acid, acetylene, formic and acetic esters. 



Or acetic aldehyde and hydrogen 

 cyanide [172] give a cyanhydrin which by 

 the action of phosphorus pentachloride 

 yields a chlorcyanhydrin, and this by 

 hydrolysis a-chlorpropionicacid (Michael 

 and Garner, Ber. 34, 4049). The latter 

 on heating with barium hydroxide gives 

 acrylic acid (Ibid. 4050). From the latter 

 through a-chlorlactic acid, glyceric acid, 

 &c., as above under E, P, &c. 



Or from the aldehyde through glyoxal 

 (see under hydrogen cyanide [172 ; O]) : 

 the latter combines with hydrogen 

 cyanide to form pyroracemic nitrile, 

 from which the acid can be obtained 

 and treated as under I below. 



[I.] From ethyl alcohol [14] and acetic 

 acid through acetoacetic ester [Vol. II], 

 which gives a-crotonic acid by reduction 

 with sodium amalgam (Beilstein and 

 Wiegand, Ber. 18, 482). The acid can 

 be converted into allylene as under G. 



Ethyl alcohol on treatment with iodine 



in the presence of alkali gives iodoform, 

 which by the action of sodium ethylate 

 yields acrylic acid (Butleroff, Ann. 114, 

 204). The latter combines with hypo- 

 chlorous acid to form a-chlorlactic acid 

 (Melikoff, Ber. 12, 2227), which by treat- 

 ment with silver oxide gives glyceric 

 acid (Ibid. 13, 272) : from the latter 

 pyrotartaric acid, citrabrompyrotartaric 

 acid, allylene, &c., can be obtained as 

 under P and M. 



Ethyl ether (from ethyl alcohol) on 

 chlorination gives dichlorether (D'Arcet, 

 Ann. 28, 82 ; Malaguti, Ann. Chim. 

 [2] 70, 338 ; [3] 16, 5 ; 19 ; Regnault, 

 Ibid. [2] 71, 392; Lieben, Ann. Ill, 121 ; 

 123, 130; 133, 287; 141, 236; 146, 

 180; 150, 87; Abeljanz, Ann. 164, 

 197), which by the action of strong sul- 

 phuric acid yields chloracetaldehyde 

 (Jacobsen, Ber. 4, 216). The latter 

 can be converted into /3-chlorlactic acid, 

 glyceric acid, &c., as under A. 



Or ethyl alcohol can be converted 

 into chloracetal by chlorination (Lieben, 

 Ann. 1O4, 114), and the latter into 

 chloracetaldehyde by heating with acetic 

 acid, dilute sulphuric, or dry oxalic acid 

 (Natterer, Monats. 3, 446). The 

 chloracetaldehyde is treated as above. 



Or ethyl alcohol can be converted 

 into chloral by chlorination, into chloral 

 cyanhydrin (Hagemann, Ber. 5, 151 ; 

 Pinner and Bischoff, Ann. 179, 77; 

 Pinner, Ber. 17, 1997), trichlorlactic 

 acid by hydrolysis (Pinner and Bischoff, 

 loc. cit. 179; Pinner, loc. cit.}, dichlor- 

 acetaldehyde by heating the sodium salt 

 with water (Reisse, Ann. 257, 331), 

 dichlorlactic acid by forming the cyan- 

 hydrin of dichloracetaldehyde andhydro- 

 lysing (Grimaux and Adam, Ber. 10, 

 903; Bull. Soc. [2] 34, 29), chloracetalde- 

 hyde by heating sodium dichlorlactate 

 with water (Reisse, Ann. 257, 335), and 

 then as above. 



Or ethyl alcohol can be converted 

 into ethyl cyanide (propionitrile : see 

 under normal propyl alcohol [15 ; A]), 

 aa-dichlorpropionic acid by chlorination 

 of the nitrile and hydrolysis (Otto, Ann. 

 132, 181 ; Beckurts and Otto, Ber. 

 9, 1877), pyroracemic (propanonic) acid 

 by heating dichlorpropionic ester with 

 water or the acid with water and silver 



