5-溴-7,7-二甲基-7H-苯并[C]芴的合成

以1-溴萘为原料,合成了5-溴-7,7-二甲基-7H-苯并C]芴,总产率为63.1%。其中,对中间体2-(1-萘基)苯甲醛、7-甲基-7H-苯并C]芴和7,7-二甲基-7H-苯并C]芴的合成工艺进行了优化。优化反应条件为:2-(1-萘基)苯甲醛合成中,催化剂Pd(dppf)Cl2质量分数3.0%,反应温度40℃,反应时间2 h,产率96.8%;7-甲基-7H-苯并C]芴合成中,催化剂Amberlyst 15型离子交换树脂的质量分数0.6%,反应温度110℃,反应时间4 h,产率95.4%;7,7-二甲基-7H-苯并C]芴合成中,n(对甲苯磺酸甲酯)∶n(7-甲基-7H-苯并C]芴)=2.5∶1,反应温度40℃,产率91.0%。产品结构通过1HNMR和ESI-MS进行了表征。

Synthesis of 5-Bromo-7,7-dimethyl-7H-benzo[c]fluorene

5-Bromo-7,7-dimethyl-7H-benzoC]fluorine was prepared from 1-bromonaphthalene in 63.1% yield.The synthetic process of intermediates 2-(1-naphthalenyl)benzaldehyde,7-methyl-7H-benzoC]fluorene and,7-dimethyl-7H-benzoC]fluorene were optimized.The optimum conditions were as follows.In the synthesis of 2-(1-naphthalenyl)benzaldehyde,when the amount of catalyst Pd(dppf)Cl2 was 3.0%,reaction temperature was 40 ℃ and reaction time was 2 h,the yield was 96.8%.In the synthesis of 7-methyl-7H-benzoC]fluorene,when the amount of catalyst Amberlyst 15 ion-exchange resin was 0.6%,reaction temperature was 110 ℃ and reaction time was 4 h,the yield was 95.4%.In the synthesis of 7,7-dimethyl-7H-benzoC]fluorene,when n(methyl 4-methylbenzenesulfinate)∶n(7-methyl-7H-benzoC]fluorene)=2.5∶1 and reaction temperature was 40 ℃,the yield was 91.0%.The product was characterized by means of 1HNMR and ESI-MS.