7 C-L] 



STYRENE 



33 



aldehyde, and w-phenylethylamine (see 

 under phenylethyl mustard oil [170; 

 D]). 



Or from benzoic aldehyde w&&hydrogen 

 cyanide [172] through mandelonitrile 

 and phenylethylamine (references as 

 before). 



Or from benzoic aldehyde and chloro- 

 form [l ; D, &c.], which condense in 

 the presence of alkali to form trichlor- 

 methylphenyl carbinol (Jocitsch, Journ. 

 Russ. Soc. 29, 97). The latter by the 

 action of zinc dust on the alcoholic 

 solution gives styrene (Jocitsch and 

 Faworsky, Ibid. 30, 920). 



[D.] From benzoic and acetic acids 

 [Vol.11] through acetophenone (Friedel, 

 Ann. 108, 122). Or from benzoic acid 

 and methyl alcohol [13] through benzoyl 

 chloride and zinc methyl, which yield 

 acetophenone by interaction (Popoff, 

 Ber. 4,720; Ann. 161, 296) ; or benzoyl 

 chloride and sodio-acetoacetic ester [Vol. 

 II] give benzoylacetoacetic ester, which 

 yields acetophenone among other pro- 

 ducts on hydrolysis (Bonne, Ann. 187, 

 I ; Nef, Ann. 266, 99). Acetophenone 

 gives styrene as above under A. 



NOTE : Since ethylbenzene gives a-toluic 

 aldehyde and the latter phenylethylamine, 

 which is a generator of styrene (see above 

 under A), generators of a-toluic aldehyde be- 

 come generators of styrene (see below and 

 under phenylethyl mustard oil [170]). 



[E.] From phenylacetic and formic 

 acids [Vol. II] through a-toluic aldehyde 

 [170; H]. 



[F.J From fi-pkenylpropionic acid 



[Vol. II] through co-phenylethylamine 

 170; I]. 



[G.] From phenylalanine [Vol. II] 

 through co-phenylethylamine [17O ; J]. 



[H.] From cinnamic acid [Vol. II], 

 which gives styrene by heating per se 

 or with lime or baryta or by heating 

 the copper salt (Gerhardt and Cahours, 

 Ann. Chim. [3] 1, 96 ; Ann. 38, 96 ; 

 Kopp, Comp. Rend. 53, 634 ; Simon, 

 Ann. 31, 265 ; Howard, Journ. Ch. Soc. 

 13, 135; Hempel, Ann. 69, 318 ; Miller, 

 Ann. 189, 338 ; Kramer, Spilker, and 

 Eberhardt, Ber. 23, 3269). 



Or cinnamic acid on combination 

 with hydrogen iodide gives iodhydro- 

 cinnamic = phenyliodopropionic acid, 



D2 



and this gives styrene on boiling with 

 sodium carbonate solution (Fittig and 

 Binder, Ann. 195, 137). 



Cinnamic acid (or ester) combines 

 with bromine to form phenyldibrom- 

 propionic acid, which by the action of 

 alcoholic potash is converted into u- 

 brom- = i 2 -bromcinnamic acid and 

 finally into phenylpropiolic acid (Glaser, 

 Ann. 143, 32,5; 330; Barisch, Journ. 

 pr. Ch. [2] 20, 182; Kinnicutt, Am. 

 Ch. Journ. 4, 26; Stockmeier, Inaug. 

 Diss. 1883, 52 ; Glaser, Zeifr [2] 4, 328 ; 

 Ann. 154, 140; W. H. Perkin, junr., 

 Trans. Ch. Soc. 45, 173; Weger, Ann. 

 221,70; Roser,Ann.247, 138; Michael, 

 Ber. 34 ; 3648 : see also Liebermann 

 and Sachse, Ber. 24, 4113, note). 

 Phenylpropiolic acid on heating with 

 water at 1 20 or by distilling the barium 

 salt gives phenylacetylene (Glaser, Ann. 

 154, 155; Weger, loc. cit.: see also 

 Holleman, Ber. 20, 3081). 



Or phenylbrompropionic acid on boil- 

 ing with sodium carbonate solution gives 

 co-bromstyrene, which, on heating with 

 alcoholic potash, gives phenylacetylene 

 (Nef, Ch. Centr. 1899, 2, 933, from 

 Ann. 308, 264, &c. : for conversion of 

 /3-bromcinnamic acid into phenylacety- 

 lene see Michael, Ber. 34, 4226). 



Cinnamic acid by the action of iodine 

 in presence of pyridine gives pyridine 

 /3-iodocinnamate, which, by the action of 

 sulphurous acid on the sodium hydroxide 

 solution, gives /3-iodocinnamic acid. The 

 silver salt of the latter gives phenyl- 

 acetylene on heating (Ortoleva, Gazz. 

 29, 503). Phenylacetylene can be re- 

 duced to styrene as above under A. 



From cinuamic acid through phenyl- 

 a-chlorlactic acid, a-toluic aldehyde, 

 and oj-phenylethylamine (phenylethyl 

 mustard oil [170 ; A and E] and above 

 under A) ; or through a-oxyphenyl- 

 propionic lactone and a-toluic alde- 

 hyde [17O ; E] ; or through phenyl- 

 gly eerie acid (benzaldehyde [114 ; E]), 

 phenyl-^S-chlor- or bromlactic acid, and 

 a-toluic aldehyde (phenylethyl mustard 

 oil [170 ; E]). 



[I.] Benzoylacetic ester [Vol. II] gives 

 phenyl-/9-lactic acid on reduction with 

 sodium amalgam (W. H. Perkin, junr., 

 Trans. Ch. Soc. 47, 254). This acid 



