63 F-64 C.] 



PARACRESOL 



133 



dorff, Terrasse, and Morton, Am. Ch. 

 Journ. 19, 845). 



NOTE : Puracresol can be converted into p- 

 cresylsulphuric acid (potassium salt) by heating 

 the potassium salt with a solution of potassium 

 pyrosulphate (Baumann, Ber. 9, 1389). 



64. Phlorol; 2-Ethylphenol. 

 HO 



NATURAL SOURCES. 



The phlorol complex probably occurs 

 in gum-ammoniac, the dried sap of 

 Dorema ammoniacum, which yields 

 phlorol methyl ether on distillation 

 with zinc dust (Ciamician, Ber. 12, 

 1658). _ 



Hlasiwetz obtained a phlorol by dis- 

 tilling- barium phloretate with lime 

 (Ann. 102, 166), but since phloretic 

 acid is a para-hydroxybenzene deriva- 

 tive, it is doubtful whether the phlorol 

 thus obtained is the ortho-ethyl phenol, 

 although Oliveri concludes that it is 

 identical with this modification (Gazz. 

 13, 263). 



SYNTHETICAL PROCESSES. 



[A.] Benzene [6 ; I, &c.] can be con- 

 verted into ethylbenzene by several 

 processes : 



By the action of sodium on a mixture 

 of brombenzene and ethyl bromide (Fit- 

 tig 1 , Ann. 131, 310; 133, 223; 144, 

 378 ; Schramm, Ber. 24, 1333). 



From benzene, ethyl iodide, bromide 

 or chloride, and aluminium chloride 

 (Friedel and Crafts, Ann. Chim. [6] 

 1, 457; Sollscher, Ber. 15, 1680 ; 

 Sempotowski, Ber. 22, 2662; Behal 

 and Choay, Bull. Soc. [3] 11, 207 ; 

 Radziewanowski, Ber. 27, 3235). 



From benzene and ethylene in the 

 presence of aluminium chloride (Bal- 

 sohn, Bull. Soc. [2] 31, 540), or by 

 heating- benzene with ethyl ether and 

 zinc chloride (Ibid. 32, 618). 



From benzene and chloracetic or 

 chloroformic ester and aluminium 

 chloride (Friedel and Crafts, Ann. Chim. 



[6] 1, 527; Rennie, Trans. Ch. Soc. 



41, 33)- 



From benzene and ethylene through 

 thedibromideof the latter, vinyl bromide, 

 and the action of the latter on benzene 

 in presence of aluminium chloride (An- 

 schiitz, Ann. 235, 331). 



Ethylbenzene when brominated (in 

 the dark) in presence of iodine gives a 

 mixture of o- and p-ethylbrombenzene 

 (Schramm, Ber. 18, 1273; Sempotowski, 

 Ber. 22, 2668). The latter on sulphona- 

 tion yields ethyl-4-brombenzene-2-sul- 

 phonic acid (Sempotowski, loc. cit.), 

 which on debromination by zinc dust 

 and ammonia gives ethyl benzene- o- 

 sulphonic acid (Ibid.}. The latter yields 

 phlorol on fusion with potash (Beilstein 

 and Kuhlberg, Ann. 156, 311 j Sempo- 

 towski, loc. cit. 2,672). 



Or ethylbenzene may be nitrated, 

 the o-nitro-derivative reduced, and the 

 amino- ethylbenzene converted into 

 phlorol by the diazo-method (Suida and 

 Plohn, Monats. 1, 175; Belial and 

 Choay, Bull. Soc. [3] 11, 209 ; Sempo- 

 towski, loc. eit. 2672 ; for nitration of 

 ethylbenzene and separation of isomer- 

 ides see Schultz and Flachslander, 

 Journ. pr. Ch. [2] 66, 153). 



[B.] From styrene [?] through ethyl- 

 benzene by heating with hydriodic acid 

 (Berthelot, Bull. Soc. [2] 9, 455), or by 

 passing the vapour mixed with hydrogen 

 over heated copper (Sabatier and Sen- 

 derens, Comp. Rend. 130, 1761 ; 132, 

 1254; 134, 1127). Also by reduction 

 with sodium in alcoholic solution 

 (Klages and Keil, Ber. 36, 1632), and 

 then as under A. 



[C.] Phenol [60] when heated with 

 absolute alcohol and zinc chloride gives 

 a mixture of ethylphenols (Auer, Ber. 

 17, 670 ; Errera, Gazz, 14, 484), among 

 which phlorol is present. 



Or phenol may be converted into 

 phenoxylacetal by heating sodium 

 phenate with chloracetal at 160 

 (Autenrieth, Ber. 24, 162 ; Pomeranz, 

 Monats. 15, 739). 



[Chloracetal is prepared by the action 

 of chlorine on ethyl alcohol (Lieben, 

 Ann. 104, 114; Fritsch, Ann. 279, 

 288 : see also 54, p. m).] 



Phenoxylacetal when heated with zinc 



