5-溴-7,7-二甲基-7H-苯并[C]芴的合成

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

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。

5-Bromo-7,7-dimethyl-7H-benzo [ C ] fluorine was prepared from 1-bromonaphthalene in 63.1% yield. The synthetic process of intermediates 2-（1-naphthalenyl） benzaldehyde, 7-methyl-7H- benzo[ C ~ fluorene and ,7-dimethyl-TH-benzo[ C ] fluorene were optimized. The optimum conditions were as follows. In the synthesis of 2-（1-naphthalenyl） benzaldehyde, when the amount of catalyst Pd （dppf） C1z 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-benzo [ C ] 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-7 H-benzo [ C ] fluorene, when n （ methyl 4-methylbenzenesulfinate ） ： tr （ 7- methyl-7H-benzo [ C ] 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.