WU Chunxin, LI Wanxia, LI Yangyang, et al. Process for synthesis of daidzein based on Friedel-Crafts reaction[J]. CIESC Journal, 2011, (5): 1377-1381.DOI:
3-dimethoxybenzene and p-methoxyphenylacetic acid using a process containing chlorination
Friedel-Crafts acylation
demethylation
cyclization and demethylation. Because of methyl protection
reactivity of hydroxy groups was reduced and the yield of Friedel-Crafts reaction reached to 93.6%.Hydrobromic acid(40%)was used as demethylation reagent
and all methyl in 4′
7-dimethoxyisoflavone molecule could be removed.The effect of process parameters such as catalyst amount
reaction temperature and molar ratio of materials were studied
and their optimal values were as follows:(1)in Friedel-Crafts reaction
the ratio of catalyst(aluminum chloride)and 1
3-dimethoxybenzene 1.1∶1
reaction temperature 25℃
(2)in demethylation
the ratio of demethylation reagent(aluminum chloride)and 2
4
4′-trimethoxydeoxybenzoin 1.1∶1
(3)in cyclization reaction
the ratio of triethyl orthoformate and 2-hydroxy-4
4′-dimethoxydeoxybenzoin 2∶1
reaction temperature 135℃
(4)in demethylation reaction of 4′
7-dimethoxyisoflavone
reaction temperature 122℃.The structure of product was characterized by 1H NMR and MS.