184 ALDEHYDES AND KETONES : FATTY GROUP [95/B-/ZZB. 



which, on reduction with zinc and 

 sulphuric acid and finally with sodium 

 amalgam, yields an acid apparently 

 identical with sebacic acid (Ibid. 2272). 

 Sebacic acid on heating with lime is 

 said to give, among other products, va- 

 leric aldehyde (Calvi, Ann. 91, no; 

 Petersen, Ann. 103, 1 84 ; Dale and 

 Schorlemmer, Ann. 199, 149). 



[C.] Fiimaric acid [Vol. II] gives 

 dibromsuccinic acid on heating with 

 bromine and water (Kekule, Ann. 

 Suppl. 1, 131 ; Baeyer, Ber. 18, 676), 

 and this can be converted into sebacic 

 acid as above. 



[D.] From adipic acid [Vol. II], which 

 gives sebacic acid (ester) on electrolysis 

 of a solution of the potassium salt of 

 the monoethyl ester (Crum Brown and 

 Walker, Ann. 261, 121). 



[E.] Stearic acid [Vol. II] gives se- 

 bacic acid when heated with nitric acid 

 (Arppe, Zeit. [2] 1, 296). 



[P.] Normal hexoic acid [Vol. II], on 

 bromination and boiling with sodium 

 carbonate solution, gives a-hydroxy- 

 hexoic = 2-hexanolic acid (Jelisafoff, 

 Journ. Russ. Soc. 12, 367), and this, on 

 oxidation with chromic acid mixture, 

 yields valeric aldehyde among other pro- 

 ducts (Ley, Ibid. 9, 139). 



//. Isovaleric Aldehyde ; z-Methyl- 



CH 3 .CH(CH 3 ).CH 2 . CHO 



[A.] From isoamyl alcohol [22] by 

 oxidation (Dumas and Stas, Ann. Chim. 

 [2] 73, 145 ; Parkinson, Ann. 90, 114 ; 

 Kolbe and Guthrie, Ann. 109, 296; 

 Bouveault and Rousset, Bull. Soc. [3] 

 11, 300). 



An amylene from fusel oil (isopropyl- 

 ethylene : see above under butyric alde- 

 hyde [94; H]) gives isopropylethylene 

 glycol (Flawitzky, Ann. 179, 351 ; 

 Wagner, Ber. 21, 1232), and this on 

 heating with phosphorus pentoxide or 

 zinc chloride yields isovaleric aldehyde 

 (Flawitzky, Ber. 10, 2240 : see also 

 Michailenko, Journ. Russ. Soc. 27, 57). 



Isoamyl alcohol gives 30-40 per cent. 

 isovaleric aldehyde by pyrogenic de- 

 composition (Ipatieff, Ber. 34, 598). 



[B.] From isovaleric acid [Vol. II] 

 by the dry distillation of its salts or by 

 distilling the calcium salt with calcium 

 formate [Vol. II] (Chancel, Ann. 60, 

 318 ; Ebersbach, Ann. 106, 262 ; 

 Wurtz, Ann. 134, 302 ; Schmidt, Ber. 

 5, 600; Limpricht, Ann. 97, 370; 

 Dilthey, Ber. 34, 2115). Or isovaleric 

 acid can be converted into isovaleryl 

 chloride, and the latter reduced in moist 

 ethereal solution with sodium amalgam 

 (W. H. Perkin, junr., and Sudborough, 

 Proc. Ch. Soc. 1O, 2 1 6). 



[C.] Leucine [Vol. II] gives isovaleric 

 aldehyde when acted on by sulphur tri- 

 oxide (Schwanert, Ann. 102, 226). 



[D.] Formic aldehyde [9l] and iso- 

 butyric aldehyde [94] combine under the 

 influence of alcoholic potash to form 

 ' pentaglycol,' (CH 3 ) 2 : C(CH 2 . OH) 2 

 (Just, Monats. 17, 76). The latter by 

 the action of 5-20 per cent, sulphuric 

 acid gives, among other products, iso- 

 valeric aldehyde (Fischer and Winter, 

 Monats. 21, 301 : see also Lieben, Ibid. 

 23, 60). 



///. Methyl ethylacetaldehyde ; 

 2 -Methylbn tanal. 



CH 3 .CH 2 .CH(CH 3 ).CHO 



[A.] Tiglic aldehyde [103] gives this 

 valeric aldehyde on reduction with iron 

 and acetic acid (Herzig, Monats. 3, 1 23 ; 

 Lieben and Zeisel, Ibid. 7, 56)- 



[B.] Isoamyl alcohol [22] gives an 

 amylene which, on conversion into 

 bromide and treatment with alcoholic 

 potash, yields a monobromamylene. The 

 latter on further heating with strong 

 alcoholic potash gives (with valerylene) 

 a valeryl ethyl ether, which, on heating 

 with dilute sulphuric acid at 150, yields 

 a valeric aldehyde probably having the 

 above constitution (Eltekoff, Ber. 10, 

 706). ^ 



Or isoamyl alcohol can be converted 

 into isoamyl iodide and amylene, and 

 the latter by the action of chlorine into a- 

 ethylallyl chloride [CH 2 : Cf(C 2 H 5 ) . CH 2 

 Cl] (Kondakoff, Journ. Russ. Soc. 2O, 

 149). This chloride on heating with 

 potassium carbonate solution gives the 

 corresponding a-ethylallyl alcohol, and 



