114 A.] 



BENZOIC ALDEHYDE 



207 



the dehydration of the latter by heat or phos- 

 phorus pentoxide, &c. (Dumas, Comp. Rend. 

 35, 383 ; Buckton and Hofmann, Journ. Ch. 

 Soc. 9, 242 ; Henry, Ann. 152, 149 ; Wallach, 

 Ann. 184, 21 ; Demarcay, Bull. Soc. [2] 33, 

 456). Also from methyl alcohol [13] by distil- 

 ling methyl sulphates with potassium cyanide or 

 ferrocyanide[172'] (Dumas, Malaguti, and Leblanc, 

 Comp. Rend. 25, 474 ; Frankland and Kolbe, 

 Mem. Ch. Soc. 3, 386 ; Ann. 65, 288). Hydro- 

 gen cyanide [172] and diazomethane combine to 

 form acetonitrile (v. Pechmann, Ber. 28, 857). 

 Ethylamine [Vol. II] gives acetonitrile among 

 the products of oxidation by monopersulphuric 

 acid (Bamberger, Ber. 35, 4293). 



Benzonitrile can be obtained from benzene 

 by the action of cyanogen chloride [172] in 

 presence of aluminium chloride (Friedel and 

 Crafts, Ann. Chim. [6] 1, 528) ; by the action 

 of aluminium chloride on a mixture of benzene 

 vapour and cyanogen [172] (Desgrez, Bull. Soc. 

 [3] 13> 735) > by distilling beuzenesulphonates 

 with potassium cyanide (Merz, Zeit. [2] 4, 33) 

 or (practically) by the diazo-method through 

 nitrobenzene, aniline, &c. (Sandmeyer, Ber. 17, 

 2653). 



Also from benzene and formic or oxalic acid 

 [Vol. II], aniline and oxalic acid giving benzo- 

 nitrile on distillation (Hofmann, Ann. 142, 125) 

 and formanilide giving the nitrile on distilla- 

 tion over zinc dust (Gasiorowski and Merz, 

 Ber. 17, 73 ; 18, 1001). 



Also from aniline and acetic acid [VoL II] by 

 the action of sodium hydroxide on aniline 

 dichloracetate (Cech and Sehwebel, Ch. Centr. 

 '877, 134) ; from chlor.- or brombenzene and 

 potassium fcrrocyanide [172] at 400 (Merz and 

 Weith, Ber. 8, 918 ; 10, 749) ; from iodobenzene 

 and silver cyanide (Merz and Schelnberger, Bor. 

 8, 1630) ; from benzene and cyanogen [172] by 

 pyrogenic synthesis (Ibid. ; Merz and Weith, 

 Ber. 10, 753) ; from aniline and methyl alcohol 

 [13] through dimethylaniline and the action 

 of heat on the Litter (Nietzki, Ber. 10, 474) ; 

 or from aniline through phenyl isocyanide and 

 isomeric transformation at 220 (Weith, Ber. 

 6, 213) and from aniline and carbon dieulphlde 

 [160] through phenyl thiocarbimide and the 

 action of copper on the latter (Ibid, and 7, 7 2 5) > 

 from magnesium nitride and benzoic anhydride 

 (Emmerling, Ber. 29, 1635) ; from benzoic acid 

 and ethylene cyanide (Mathews, Journ. Am. Ch. 

 800.20,650) ; fr>imbenzoyJ chloride and methyla mine 

 through benzenylmethylimido-chloride (v. 

 Pechmann, Ber. 33, 6u). 



From benzene and acetic acid through 

 acetophenone, by the action of acetyl 

 chloride on benzene in presence of 

 aluminium or ferric chloride (Friedel 

 and Crafts, Ann. Chim. [6] 1, 507 ; 

 14 455 ; Nencki and Stoeber, Ber. 30, 

 1768 ; Boeseken, Rec. Tr. Ch. 20, 102), 

 and then as under G- and C below. 



From benzene and ethyl alcohol [14]. 

 The latter, on treatment with nitric acid 

 in presence of mercury, gives mercury 

 fulminate (Howard, Phil. Trans, ittoo ; 

 Liebig, Ann. 95, 284 ; Steiner, Ber. 9, 



787; Lobry de Bruyn, Ber. 19, 1370). 

 The fulminate interacts with benzene 

 in presence of a mixture of aluminium 

 chloride and hydroxide, giving benzalde- 

 hyde (with its oxime, benzonitrile and 

 benzamide) (S choll,Ber. 32, 349 2; 36, i o) . 



Or from benzene and methyl alcohol 

 [13] through nitromethane by the 

 interaction of methyl iodide and silver 

 nitrite (see under glycerol [48 ; L]). 

 Sodium-nitromethane on treatment with 

 mercuric chloride solution gives a com- 

 pound which yields mercury fulminate on 

 treatment with hydrochloric acid (Jones, 

 Am. Ch. Journ. 20, 33 ; also Nef, Ann. 

 28Q, 276). Subsequent steps as above. 



Or from benzene and ethyl alcohol 

 [14] through ethylbenzene and styrene 

 bromide (see under styrene [7 ; A] and 

 under phlorol [64 ; A]). The latter 

 can be converted into styrene glycol 

 or into phenyl-/3-lactic acid, and either 

 of these into benzaldehyde as below 

 under B. Or ethylbenzene can be con- 

 verted into acetophenone by oxidation 

 with chromic and acetic acids, or by 

 decomposing its chromoxychloride with 

 water (Friedel and Balsohn, Bull. Soc. 

 [2] 32, 616; v. Miller and Rohde, Ber. 



23, 1078), and the ketone treated as 

 under Gr. (See also Fournier, Comp. 

 Rend. 133, 634). 



Or from benzene and normal or isopro- 

 pyl alcohol [15 ; 16] through isopropyl- 

 benzene by the interaction of the alkyl 

 bromide and benzene in presence of 

 aluminium bromide, or of the alkyl 

 chloride and benzene in presence of 

 aluminium chloride (see under cymene 

 [6; A]), or of brombenzene and the 

 iso-alkyl iodide by sodium (Jacobsen, 

 Ber. 8, 1260). Isopropylbenzene gives 

 acetophenone (with hydratropic alde- 

 hyde) on oxidation with chromium 

 oxychloride (v. Miller and Rohde, Ber. 



24, 1358). 



Trimethylene bromide [15 ; E] from 

 glycerol [43] and benzene condense under 

 the influence of aluminium chloride with 

 the formation of diphenylpropane and 

 propyl and isopropylbenzene. Propylene 

 bromide produces the same hydrocarbons 

 (Bodroux, Comp. Rend. 132, 155). 



NOTE : Generators of isopropylbenzene are 

 also given under cymene [6 ; A, note]. 



