164 



AROMATIC ALCOHOLS AND PHENOLS '[87B-89A. 



acids (Cahours, Ann. 6 9, 23 8), the 2:4:6- 

 trinitroanisole reduced by tin and hy- 

 drochloric acid to diaminohydroxyani- 

 sole and the latter (hydrochloride) heated 

 with dilute stannous chloride in an 

 atmosphere of carbon dioxide (Kohner, 

 Monats. 2O, 933). 



Or from phenol through picric acid 

 (see under phloroglucinol [86 ; B]) and 

 the methyl ether of the latter by 

 methylation. Subsequent steps as 

 above. 



NOTE : Generators of picric acid, viz. sali- 

 cylic aldehyde [117], saligenin [55], salicylic acid, 

 coumarin, and indigo [Vol. II], thus become 

 generators of iretol (see under phloroglucinol 

 [86 ; B]). 



[B.] Anisic acid [Vol. II] gives trini- 

 troanisole on nitration as under A 

 (Cahours, loc. cit.). Subsequent steps 

 as above. 



Germ. Pat. 109789 of 1898; Ch. 

 Centr. 1900, 2, 460). The monomethyl 

 ether might be converted into the tri- 

 methyl ether by further methylation, 

 and then treated as above. 



[C.] From phloroglucinol [86] through 

 the trimethyl ether by methylation 

 (Will, Ber. 21, 603; Pollak, Monats. 

 18, 736), 3 : 5-dimethoxyquinone by 

 oxidation with chromic acid (Ciamician 

 and Silber, Ber. 26, 786), and then as 

 under A. 



[D.] From benzene [6] through 1:3: 

 5-trinitrobenzene (see under phloro- 

 glucinol [86 ; H]), which, on heating 

 with sodium methoxide, gives 3 : 5-di- 

 nitroanisole (Lobry de Bruyn, Bee. Tr. 

 Ch. 9, 209). The latter on reduction 

 yields diaminoanisole, and this,onheating 

 with water, gives phloroglucinol methyl 

 ether (Herzig and Aigner, Monats. 21, 



433)- 



88. Iretol; l-Methoxy-2 : 4 : 6 



trihydroxybenzene ; 2:4:6- 



Triliydroxyanisole ; 1:2:4:6- 



Fhenetetrol 1- Methyl Ether. 



NATURAL SOURCE. 



The complex is possibly contained in 

 orris root from Iris florentina, which 

 contains a glucoside, iridin, which is 

 decomposed, on heating with dilute sul- 

 phuric acid and alcohol, into glucose 

 and irigenin. The latter gives iretol 

 among other products (iridic and formic 

 acids) on heating with strong potash 

 solution (G. de Laire and Tiemann, 

 Ber. 26, 2015). 



SYNTHETICAL PROCESSES. 



[A.] From phenol [60] and methyl 

 alcohol [13] through anisole (see under 

 anisic aldehyde [120 ; B]). The latter 

 is nitrated with nitric and sulphuric 



89. Asarone ; 



! 1 -Fropenyl-2 : 4 : 5-trimethoxy- 

 benzene. 



CH : CH . CH 3 

 / \OCH 3 



CH,ol / 

 OCH 3 



NATURAL SOURCES. 



In the root of Asarum europaum 

 (Petersen, Ber. 21, 1057). Also in 

 certain matico oils from the leaves of 

 Piper angustifolium (Schimmers Ber. 

 Oct. 1898; Ch. Centr. 1898, 2, 985), 

 in sweet flag oil from the root of Acorus 

 calamus (Thorns and Beckstroem, Ber. 

 34, ]O2i; Thorns, Zeit. angew. Ch. 

 14, 1019; T. and B. Ber. 35, 3190), 

 and in the oil of Asarum arfolium 

 (Miller, Arch. Pharm. 240, 371). 



SYNTHETICAL PROCESSES. 



[A.] From phenol [60~], propionic acid 

 [Vol. II], methyl alcohol [13], and 

 hydrogen cyanide [172]. Phenol is 

 nitrated, the o-nitrophenol converted 



