228 



AROMATIC ALDEHYDES AND KETONES [129 D-130 E. 



fusion with potash gives m-(y)-cresotic 

 acid (Weber, Ber. 25, 1743). Subse- 

 quent steps as above under C. 



NOTE : Toluene [54] gives 3-sulpho-p-toluic 

 acid through p-nitrotoluene, p-toluidine, p- 

 toluidinesulphonic acid, cyanotoluenesulphonic 

 acid by the diazo-method, the sulphonamide 

 and sulphaminotoluic acid, which on heating 

 gives the imide (methylsaccharin). The latter 

 on evaporating with hydrochoric acid yields 

 the ammonium salt of 3-sulpho-p-toluic acid 

 (Bad. An. Sod. Fab. Germ. Pat. 48583 of 1889 ; 

 Ber. 22, Ref. 719 ; Weber, Ibid. 25, 1741). 



Or p-toluidine can be acetylated, nitrated, 

 and the o-nitro-p-toluidine converted into the 

 iiitrile by the diazo-method. The nitrile on 

 reduction gives 3-amino-p-cyanotoluene, and 

 this by hydrolysis 3-amino-p-toluic = homo- 

 anthranilic acid (Niementowski, Journ. pr. 

 Ch. [2] 40, 6; 15 ; Glock, Ber. 21, 2662). 



Or the nitrocyano-derivative can be hydro- 

 lysed to 3-nitro-p-toluic acid and then reduced 

 to 3-amino-p-toluic acid (Niementowski and 

 Rozanski, Ber. 21, 1997 ; Noyes, Am. Ch. 

 Journ. 10, 479). The latter gives m-(7>cresotic 

 acid by the diazo-method (N. and R. loc, cit. 

 1998 : see also under m-cresol [62, pp. 128, 

 1 29] for further details). 



[E.] From pulegone [128] and iso- 

 propyl alcohol [16]. Pulegone on boil- 

 ing with formic acid gives methylcyclo- 

 hexanone = g-keto-i-methylhexahydro- 

 benzene (see under phenol [60; Sj), 

 and this on treatment with sodium and 

 ethyl acetate gives acetylmethylcyclo- 

 hexanone (Leser, Bull. Soc. [3] 23, 

 370). The potassium derivative of the 

 latter condenses with isopropyl iodide 

 to form acetylmenthone, and this yields 

 menthone on hydrolysis with methyl 

 alcoholic potassium hydroxide (Ibid. 

 Comp. Rend. 134, 1115). 



130. Orthohydroxyacetopheiioiie ; 



Ortlio-Acetylpheiiol ; 



2-Ethanoylphenol. 



CO . CH S 

 /\>H 



\/ 



NATURAL SOURCE. 



In the volatile oil from the wood and 

 bark of C/tione glabra, W. Indies (Dun- 

 stan and Henry, Trans. Ch. Soc. 75, 

 66). The methyl ether probably occurs 

 also in the oil (Ibid. 71). 



SYNTHETICAL PROCESSES. 



[A.] From cinnamic acid [Vol. II] 

 through the o-nitro-acid (see under 

 quinol [71; E] and salicylic aldehyde 

 [117; E]),thedibromide by bromination, 

 o-nitrophenylpropiolic acid by the action 

 of alkali, and o-nitrophenylacetylene by 

 heating the latter acid with water 

 (Baeyer, Ber. 13, 2259). o-Amino- 

 phenylacetylene obtained by reduction 

 of the nitro-compound (Baeyer and 

 Landsberg, Ber. 15, 60 ; Baeyer and 

 Bloem, Ber. 17, 964) gives o-amino- 

 acetophenone on treatment with sul- 

 phuric acid and water (Baeyer and 

 Bloem, loc. cit. Kippenberg, Ber. 3O, 

 1130), from which o-hydroxyacetophe- 

 none can be obtained by the diazo- 

 method (Friedlander and Neudorfer, 

 Ber. 30, 1080; Dunstan and Henry, 

 loc. cit. 71). 



Or o-nitrophenylpropiolic acid can be 

 reduced to the amino-acid (Baeyer and 

 Bloem, Ber. 15, 2147 ; Richter, Ibid. 

 16, 679), and this on heating with water 

 gives o-aminoacetophenone (B. and B. 

 loc. cit. 2153). 



Or from cinnamic acid through 

 phenylpropiolic acid, phenylacetylene, 

 and acetophenone (see under benzoic 

 aldehyde [114 ; E]), and then through 

 the o-nitro- and o-amino-ketone (see 

 under salicylic aldehyde [117 ; D]), and 

 o-hydroxyacetophenone as above. 



[B.] From benzoic and acetic acids 



[Vol. II] through acetophenone [114; 



A and G-], and then as under salicylic 



aldehyde [117 ; D] and A above. 



Or from benzoic acid and zinc methyl 



[13] through acetophenone [114 ; C], 



and then as above. 



Or from benzoic acid and acetoacetic 



ester [Vol. II] through o-nitro- and o- 



aminoacetophenone [117; P and D], 



and then as above under A. 



[C.] From salicylic acid [Vol. IT] 



and acetic ester through 2-methoxyben- 



zoylacetic ester, &c., as under salicylic 



aldehyde [117 ; G]. 



[D.] From coumarin [Vol. II] through 



o-coumarilic acid as under salicylic 



aldehyde [117; H]. 



[E.] From orthocoumaric acid [Vol. II] 



through dibrom-melilotic acid and o- 



