54 R-Y.] 



BENZYL ALCOHOL 



115 



Ann. 42, 215 ; Haussermann, Jahresber. 

 1877, 763 ; 1158 ; Fischer, Ber. 11, 738 ; 

 Depouilly, Ann. 137, 373 ; Beilstein 

 and Kurbatoff, Ann. 2O2, 215; Liid- 

 dens, Chem. Zeit. 15, 585 ; Fuchs, Ibid. 

 735 ; Graebe, Ber. 29, 2806 ; Pro- 

 chazka, Ber. 30, 3108; Tcherniac, Ber. 

 31, 139 : for electrolytic oxidation see 

 Darmstadter, Germ. Pat. 109012 of 

 1897; Ch. Centr. 1900, 2, 151: for 

 technical process see Germ. Pat. 91202 

 of the Bad. An. Sod. Fab. and Brunck, 

 Ber. 33, Suppl. Ixxx : for production 

 by oxidation of the naphthols see Eng. 

 Pat. 15527 of 1901, Basle Ch. Co.; 

 from a-nitronaphthalene via the 2- and 

 4-nitronaphthols, Ibid. Germ. Pat. 

 136410 of 1901; Ch. Centr. 1902, 2, 

 1371). Phthalic acid on distillation 

 with phosphorus pentachloride is con- 

 verted into phthaloyl chloride (Miiller, 

 Zeit. 1863, 257; Graebe, Ann. 238, 

 329 ; Auger, Ann. China. [6] 22, 295 ; 

 Glaus and Hoch, Ber. 19, 1187), which 

 by reduction with zinc and hydrochloric 

 acid or magnesium and acetic acid gives 

 phthalide (Kolbe and Wischin, Zeit. 

 [2] 2, 315; Journ. Ch. Soc. 19, 339; 

 Hessert, Ber. 1O, 1445; Baeyer, Zeit. 

 [2] 5, 399 ; 10, 123; 1445; U, 637). 



Or phthalic acid can be converted 

 into phthalide through phthalimide by 

 heating the acid ammonium salt (Lau- 

 rent, Ann. 41, 1 10; Ann. China. [2] 

 61, 121; [3] 23, 119; Lansberg, Ann. 

 215, 181 : also Matthews, Journ. Am. 

 Ch. Soc. 18, 679), reduction to phthal- 

 imidine by tin and hydrochloric acid 

 (Graebe, Ber. 17, 2598 ; Ann. 247, 

 291), formation of nitroso-derivative 

 by the action of sodium nitrite and acid 

 (Ibid. Ann. 247, 297), and action of 

 sodium hydroxide solution on the ni- 

 troso-derivative (Ibid. 292). By heating 

 phthalide with hydriodic acid solution 

 and phosphorus, orthotoluic acid is 

 formed (Hessert, Ber. 11, 238 ; Racine, 

 Ann. 239, 72), and this by distillation 

 with lime or soda-lime gives toluene. 



Naphthalene also can be sulphonated 

 so as to give a mixture of disulphonic 

 acids, the product nitrated and reduced, 

 and the 1:3: 8-naphthylamine-disul- 

 phonic acid converted into I : 3-naph- 

 thylaminesulphonic acid by sodium 



amalgam, or by heating with sulphuric 

 acid of 75 per cent. (Friedlander and 

 Lucht, Ber. 26, 3028 ; Kalle & Co., 

 Germ. Pat. 64979 of 1892). The I : 3- 

 sulpho-acid is converted by potash fusion 

 into i : 3-aminonaphthol (Friedlander, 

 Ber. 28, 1952). The latter on sul- 

 phonation gives I : 3-aminonaphthol-4- 

 sulphonic acid, and this on heating with 

 water or dilute sulphuric acid at 120 

 yields i : 3-dihydroxynaphthalene (Ibid. 

 29, 1609), which on heating with 60 

 per cent, sodium hydroxide solution at 

 180-190 breaks down into o-toluic and 

 acetic acids (Ibid. 1611). 



Other naphthalene derivatives such 

 as the I : 3-disulphonic acid, i : 3-naph- 

 thylamine-sulphonic acid, &c., give 

 o-toluic acid on heating with alkali 

 (Kalle & Co., Germ. Pat. 79028 of 

 1893; Ber. 28, Ref. 364). 



[S.] Cymene [6] on oxidation with 

 dilute nitric acid gives paratoluic acid 

 (Noad, Phil. Mag. [3] 32, 19 ; Ann. 

 63, 289), which on distillation with 

 baryta gives toluene (Ibid. Ann. 63, 

 305)- 



Miscellaneous Generators of Toluene. 



[T.] Heptane [2] gives toluene among 

 other products when the vapour is 

 heated to 900 (Worstall and Burwell, 

 Am. Ch. Journ. 19, 815). 



[U.] Mannoheptol [53] on heating 

 with hydriodic acid gives among other 

 products a ' heptine/ C 7 H 12 (Maquenne, 

 Bull. Soc. [2] 50, 548). If, as is 

 probable, this hydrocarbon is tetra- 

 hydrotoluene, it can be converted (par- 

 tially) into toluene by the action of 

 strong sulphuric acid. 



[V.] From the cresols [61 ; 62 ; 63] 

 through toluene (see under quinol 

 [71; O]). 



[W.] From pkenylacetic acid [Vol. II] 

 through toluene by the action of heat 

 on the acid (Engler and Low, Ber. 26, 



1438). 



[X.] From aconitic acid [Vol. II] 

 through itaconic acid (Pebal, Ann. 98, 

 94), and then as above under M, &c. 



[Y.] From pulegone [128] through 

 methylcyclohexanone (see under phenol 

 [60; SJ). The latter gives an oxime 



