64 J-66.] 



PHLOROL 



135 



acid (Doebner, Ber. 23, 2379 ; 24, 



1746), which gives ethylbenzene on 



distilling- the calcium salt (Ibid. 23> 

 238 ). 



NOTE : The generators of pyroracemic acid 

 referred to under benzyl alcohol [54 ; F ; I ; 

 O ; P] thus become, with n-propyl alcohol, 

 generators of phlorol. 



[K ] Aceloplienone [7; D and 114; A] 

 gives dypnone [CH 3 . C(C 6 H 5 ) : C : 

 CH . CO . C 6 H 6 ] as the first product of 

 condensation, and this, on heating for 

 80 hours at 280, yields ethylbenzene 

 (Ameye, Bull. Acad. Roy. Belg. [3] 37, 

 227 ; Delacre, Ibid. [3] 39, 68 ; Ch. 

 Centr. 1900, 2, 256). 



Ethylbenzene is also among the pro- 

 ducts of reduction of acetophenone by 

 sodium in alcohol (Klages and Allen- 

 dorff, Ber. 31, 1003). 



65. 3-Etliylpheiiol ; Meta-ethyl- 



phenol. 



HO 



NATURAL SOURCE. 



A phlorol probably occurs as isobutyr- 

 ate in oil of arnica root from Arnica 

 montana (Sigel, Ann. 170, 354) which 

 may be m-ethylphenol, but this requires 

 confirmation. 



SYNTHETICAL PROCESSES. 



[A.] From etliyllenzene (see under 

 phlorol [64 ; A]) by bromination and 

 sulphonation, whereby (with the 4- 

 brom-2-sulphonic acid) there is formed 

 ethyl-2-brombenzene-3- or 5-sulphonic 

 acid. The latter on debromination with 

 zinc dust and ammonia gives ethyl- 

 benzene-m-sulphonic acid (Sempotowski, 

 Ber. 22, 2673), which yields m-ethyl- 

 phenol on potash fusion (Ibid. 2674). 



Or the ethyl-p-nitrobenzene (obtained 

 as under phlorol [64 ; A]) can be re- 

 duced to ethyl-p-aminobenzene, acetyl- 

 ated, nitrated, and hydrolysed so as to 

 form 3-nitro-4-aminoethylbenzene, the 

 amino-group replaced by hydrogen by 



the diazo-method, the ethyl-m-nitro- 

 benzene reduced to ethyl -m-amino- 

 benzene. and the latter converted into 

 m-ethylphenol by the diazo- method 

 (Behal and Choay, Bull. Soc. [3] 11, 

 212). 



66. Carvacrol ; Cymophenol ; 



6-Methyl-3-Isopropylpheiiol ; 



1 : 4-Methylmeth.oetkyl-2-Pheiiol. 



CH, 



OH 



Oxi 3 . Oxi . G-tig 



NATURAL SOURCES. 



Occurs in oils of Origanum hirtum 

 from Trieste and 0. zmyrneeum from 

 Smyrna (Jahns, Arch. Pharm. 215, I ; 

 Gildemeister, Ibid. 231, 182); in oil 

 from the pepperwort or summer savory, 

 Satureia hortensis, and the mountain 

 savory, S. montana (Jahns, Ber. 15, 

 816; Haller, Com p. Rend. 94, 132; 

 Bull. Soc. [2] 37, 411) ; in oil of thyme 

 from Thijmns serpyllum (Jahns, Arch. 

 Pharm. 216, 277; Ber. 15, 819); in 

 oil of wild bergamot from Monarda 

 Jistulosa (Kremers, Ch. Centr. 1897, 

 2, 41 ; Pharm. Rund. 13, 207 ; Melzner 

 and Kremers, Pharm. Rev. 14, 198; 

 Kremers and Hendricks, Pharm. Arch. 

 2, 73); and in the oil from Pycnant/iemum 

 lanceolatum T/iymus virginicus (Correll, 

 Pharm. Rev. 14, 32; Ch. Centr. 1898, 

 1, 123). 



Occurs in small quantity in the 

 ethereal oil from the fruit of the Mexi- 

 can ScJdnus molle (Gildemeister and 

 Stephan, Arch. Pharm. 235, 582). 



According to Duyk carvacrol occurs 

 with thymol in oil of thyme from T. 

 vnlgaris (Ch. Centr. 1898, 1, 783; 

 Journ. Pharm. [6] 7, 190). The oil 

 of Monarda punctata (from Wisconsin) 

 probably contains (with thymol) carva- 

 crol (Kremers and Hendricks, Ch. Centr. 

 1899, 2, 125; Pharm. Arch. 2, 73). 

 The oil from the N. American wild 

 mint, Mentha canadensis, may contain 

 carvacrol (Gage, Pharm. Rev. 16, 412). 



Carvacrol is among the phenolic con- 



