CN109988053A - 一种邻位烯基取代的苄醇衍生物的制备方法 - Google Patents
一种邻位烯基取代的苄醇衍生物的制备方法 Download PDFInfo
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B41/00—Formation or introduction of functional groups containing oxygen
- C07B41/02—Formation or introduction of functional groups containing oxygen of hydroxy or O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
- C07F7/083—Syntheses without formation of a Si-C bond
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
本发明公开了式I所示的邻位烯基取代的苄醇衍生物的制备方法。该方法包括如下步骤:在催化剂、路易斯酸和锌试剂存在的条件下,使式II所示酮与式III所示烯烃经C‑H活化反应,即得式I所示邻位烯基取代的苄醇衍生物。本发明在催化剂、路易斯酸和锌试剂存在的条件下一步实现邻位烯基取代的苄醇衍生物的制备,操作流程简单,使用原料易得,具有很好的原子经济性和环境友好性,同时,本发明具有较广的底物适用范围、较好的官能团容忍性以及较好的反应产率。
Description
技术领域
本发明涉及化学合成技术领域,尤其涉及一种邻位烯基取代的苄醇衍生物的制备方法。
背景技术
苄醇衍生物是合成医药和香料的重要中间体,广泛应用于化妆品、染料、涂料及油墨等领域。由于醇羟基的存在,使得其可以发生氧化、取代等反应而被进一步修饰,在有机合成、医药和化工领域都体现出了重要的研究价值和应用前景。
因此,发展新的简单高效的合成方法制备苄醇衍生物具有重要意义。
发明内容
本发明旨在提供一种邻位烯基取代的苄醇衍生物的制备方法。通过一步合成了苄醇衍生物,具有较大的有机合成价值及应用发展前景。
本发明的目的主要是通过以下技术方案实现的:
式I所示的邻位烯基取代的苄醇衍生物的制备方法,包括如下步骤:
在催化剂、路易斯酸和锌试剂存在的条件下,使式II所示酮与式III所示烯烃经C-H活化反应,即得式I所示邻位烯基取代的苄醇衍生物;
式I、式II和式III中,R1表示苯环上的单取代基或多取代基,其选自氢、取代或未取代的碳原子数为1~10的烷基、取代或未取代的碳原子数为1~10的烷氧基、磺酰基、酯基和卤素中的任意一种或多种;
R2选自取代或未取代的碳原子数为1~10的烷基、碳原子数为3~10的环烷基和芳基中的任意一种;
R3选自取代或未取代的碳原子数为1~10的烷基、取代或未取代的碳原子数为1~10的烷氧基、芳基、硅基和与苯环稠合得到的芳环中的任意一种。
上述取代的碳原子数为1~10的烷基、取代的碳原子数为1~10的烷氧基中的取代基选自下述基团中的任意一种:苯基和卤素(如氯、溴、氟)。
上述芳基可选自下述任意一种:苯基、碳原子数为1~6的烷基取代的苯基、碳原子数为1~6的烷氧基取代的苯基、苯基取代的苯基、卤素取代的苯基、三氟甲基取代的苯基或酯基取代的苯基。
进一步的,R1选自氢、碳原子数为1~6的烷基、碳原子数为1~6的烷氧基、磺酰基、碳原子数为1~6的烷氧基羰基和卤素中的任意一种或多种;所述卤素具体可为氯、溴、氟;
R2选自碳原子数为1~6的烷基、环己基和苯基中的任意一种;
R3选自碳原子数为1~10的烷基、苯基、甲基苯基、苄基、三苯基硅基和2-萘基中的任意一种。
更进一步的,R1选自氢、甲基、甲氧基、甲磺酰基、甲氧基羰基和卤素中的任意一种;所述卤素具体可为氯、溴、氟。
R2选自甲基、乙基、亚丙基、环己基和苯基中的任意一种;
R3选自壬基、苯基、甲基苯基、苄基、三苯基硅基和2-萘基中的任意一种。
选用上述取代基团,都能够以较好的反应产率得到邻位烯基取代的苄醇衍生物。
进一步的,所述催化剂选自五羰基溴化锰和十羰基二锰中的至少一种。
进一步的,所述路易斯酸选自溴化铜、氯化铜、醋酸酮、三氟甲磺酸酮、硫酸铜、氧化铜、溴化亚铜、氯化亚铜和溴化锌中的至少一种,其用料为式II所示酮的摩尔量的10%~150%(优选为10%~50%),用量增加或减少时,反应产率均有所降低。
进一步的,所述锌试剂为甲基锌试剂,其用料为式II所示酮的摩尔量的150%~200%,用量增加或减少时,反应产率均有所降低。
进一步的,式II所示酮与式III所示烯烃的摩尔比为1:(1~4)。反应产率随酮与烯烃摩尔比的增加而增加直至达到平衡。
优选地,式II所示酮与式III所示烯烃的摩尔比为1:(2~3),此时,产率最高。
进一步的,所述催化剂与式II所示酮的摩尔比为1:(10~50)。反应产率随催化剂用量的增加而增加直至达到平衡。
优选地,所述催化剂与式II所示酮的摩尔比为1:(10~20),此时,产率最高。
进一步的,所述C-H活化反应在溶剂中进行,所述溶剂为二氯乙烷或二氯甲烷。
进一步的,所述C-H活化反应的体系中,式II所示酮的摩尔浓度为0.05~2mol/L。反应产率随摩尔浓度的增大而增加直至达到平衡。
优选地,式II所示酮的摩尔浓度为0.4mol/L。此时,产率最高。
进一步的,所述C-H活化反应的温度范围为60~120℃,时间范围为2~12h。反应产率随温度的升高和时间的延长逐渐增加直至不变。
优选地,所述C-H活化反应在60℃~80℃的条件下反应6h。此时,产率最高。
进一步的,所述C-H活化反应在惰性气氛中进行,所述惰性气氛可为氮气。
本发明在催化剂、路易斯酸和锌试剂存在的条件下一步实现邻位烯基取代的苄醇衍生物的制备,操作流程简单,使用原料易得,具有很好的原子经济性和环境友好性,同时,本发明具有较广的底物适用范围、较好的官能团容忍性以及较好的反应产率。
本发明有益效果如下:
1)本发明利用酮、烯烃在锰催化剂、路易斯酸和锌试剂的存在下在溶剂中进行反应,实现了邻位烯基取代的苄醇衍生物的合成;
2)邻位烯基取代的苄醇衍生物在有机合成、医药和化工领域中有着非常广泛的应用,本发明研发了新的合成策略,具有重要意义;
3)本发明一步合成了邻位烯基取代的苄醇衍生物,底物适用性较广,官能团容忍性较好,具有较大的有机合成价值及应用发展前景。
附图说明
图1为实施例1制备式I-a的反应流程图。
图2为实施例1制备式I-b的反应流程图。
图3为实施例1制备式I-c的反应流程图。
图4为实施例1制备式I-d的反应流程图。
图5为实施例1制备式I-e的反应流程图。
图6为实施例1制备式I-f的反应流程图。
图7为实施例1制备式I-g的反应流程图。
图8为实施例1制备式I-h的反应流程图。
图9为实施例1制备式I-i的反应流程图。
具体实施方式
下面通过具体实施例对本发明的方法进行说明,但本发明并不局限于此,凡在本发明的精神和原则之内所做的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。
下述实施例中所使用的实验方法如无特殊说明,均为常规方法。
下述实施例中所用的材料、试剂等,如无特殊说明,均可从商业途径得到。
实施例1、合成1-(2-苯乙烯基苯基)乙醇(式I-a)
向25mL Schlenk瓶中,在N2的保护下,依次加入五羰基溴化锰(0.025mmol,6.9mg)、溴化酮(0.05mmol,11.3mg)、溶剂二氯乙烷(1.25mL)、苯乙烯(式III-a)(1.0mmol,104.0mg)、苯乙酮(式II-a)(0.5mmol,60.0mg)和甲基锌(0.75mmol,1.2M in toluene,0.625mL),在60℃反应6h后加水(2mL)淬灭,再用二氯甲烷萃取,合并有机相,用无水硫酸钠干燥、过滤、旋干。经柱层析色谱分离(洗脱剂为石油醚:乙酸乙酯=24/1,v/v)后得到目标产物(式I-a)184mg,产率82%,反式产物与顺式产物的比例为11:1。
反式产物的表征如下:1H NMR(CDCl3,400MHz)δ7.58-7.49(m,4H),7.44(d,J=16.0Hz,1H),7.36(t,J=7.6Hz,2H),7.31-7.24(m,3H),6.95(d,J=16.0Hz,1H),5.26(q,J=6.4Hz,1H),2.03(s,1H),1.49(d,J=6.4Hz,3H);13C NMR(CDCl3,100MHz)δ143.1,137.5,135.1,131.3,128.8,128.1,127.9,127.7,126.7,126.3,125.7,125.1,67.2,24.5,为已知化合物,结构正确。
实施例2、合成1-(4-甲基-2-苯乙烯基苯基)乙醇(式I-b)
向25mL Schlenk瓶中,在N2的保护下,依次加入五羰基溴化锰(0.05mmol,13.8mg)、溴化酮(0.05mmol,11.3mg)、溶剂二氯乙烷(1.25mL)、苯乙烯(式III-a)(1.5mmol,156.0mg)、4-甲基苯乙酮(式II-b)(0.5mmol,67.0mg)和甲基锌(0.75mmol,1.2M intoluene,0.625mL),在80℃反应6h后加水(2mL)淬灭,再用二氯甲烷萃取,合并有机相,用无水硫酸钠干燥、过滤、旋干。经柱层析色谱分离(洗脱剂为石油醚:乙酸乙酯=24/1,v/v)后得到目标产物(式I-b)202mg,产率85%,反式产物与顺式产物的比例为10:1。
反式产物的表征如下:1H NMR(CDCl3,400MHz)δ7.49(d,J=7.6Hz,2H),7.44-7.32(m,5H),7.25(t,J=7.2Hz,1H),7.10(d,J=8.8Hz,1H),6.94(d,J=16.0Hz,1H),5.22(q,J=6.4Hz,1H),2.35(s,3H),2.06(s,1H),1.46(d,J=7.2Hz,3H);13C NMR(CDCl3,100MHz)δ140.3,137.6,137.2,134.9,131.0,128.9,128.8,127.8,126.8,126.7,125.8,125.2,67.0,24.5,21.2;
HRMS(ESI)Calculated for C17H17O-([M-H]-):237.12739,found:237.12807,结构正确。
实施例3、合成1-(4-氯-2-苯乙烯基苯基)乙醇(式I-c)
向25mL Schlenk瓶中,在N2的保护下,依次加入五羰基溴化锰(0.05mmol,13.8mg)、溴化酮(0.05mmol,11.3mg)、溶剂二氯乙烷(1.25mL)、苯乙烯(式III-a)(1.5mmol,156.0mg)、4-氯苯乙酮(式II-c)(0.5mmol,77.0mg)和甲基锌(0.75mmol,1.2M in toluene,0.625mL),在80℃反应6h后加水(2mL)淬灭,再用二氯甲烷萃取,合并有机相,用无水硫酸钠干燥、过滤、旋干。经柱层析色谱分离(洗脱剂为石油醚:乙酸乙酯=24/1,v/v)后得到目标产物(式I-c)237mg,产率92%,反式产物与顺式产物的比例为12:1。
反式产物的表征如下:1H NMR(CDCl3,400MHz)δ7.53(d,J=2.0Hz,1H),7.49(d,J=7.8Hz,2H),7.45(d,J=8.4Hz,1H),7.39-7.26(m,4H),7.24(dd,J1=8.4Hz,J2=2.0Hz,1H),6.94(d,J=16.4Hz,1H),5.24-5.18(m,1H),2.07(d,J=3.2Hz,1H),1.46(d,J=6.4Hz,3H);13C NMR(CDCl3,100MHz)δ141.5,137.0,136.7,133.4,132.4,128.9,128.3,127.9,126.9,126.8,126.0,124.2,66.8,24.6;HRMS(EI)Calculated for C16H15OCl+([M]+):258.0811,found:258.0815,结构正确。
实施例4、合成1-(2-苯乙烯基苯基)-1-丙醇(式I-d)
向25mL Schlenk瓶中,在N2的保护下,依次加入五羰基溴化锰(0.025mmol,6.9mg)、溴化酮(0.05mmol,11.3mg)、溶剂二氯乙烷(1.25mL)、苯乙烯(式III-a)(1.0mmol,104.0mg)、苯丙酮(式II-d)(0.5mmol,66.5mg)和甲基锌(0.75mmol,1.2M in toluene,0.625mL),在60℃反应6h后加水(2mL)淬灭,再用二氯甲烷萃取,合并有机相,用无水硫酸钠干燥、过滤、旋干。经柱层析色谱分离(洗脱剂为石油醚:乙酸乙酯=24/1,v/v)后得到目标产物(式I-d)209mg,产率88%,反式产物与顺式产物的比例为10:1。
反式产物的表征如下:1H NMR(CDCl3,300MHz)δ7.59-7.26(m,10H),6.94(d,J=15.9Hz,1H),5.00(t,J=6.3Hz,1H),1.99(s,1H),1.85-1.75(m,2H),0.95(t,J=7.5Hz,3H);13C NMR(CDCl3,75MHz)δ142.0,137.6,135.5,131.2,128.8,127.9,127.9,127.6,126.7,126.3,126.0,125.9,72.6,31.4,10.5;HRMS(EI)Calculated for C17H18O+([M]+):238.1358,found:238.1361,结构正确。
实施例5、合成2-甲基-1-(2-苯乙烯基苯基)-1-丙醇(式I-e)
向25mL Schlenk瓶中,在N2的保护下,依次加入五羰基溴化锰(0.025mmol,6.9mg)、溴化酮(0.05mmol,11.3mg)、溶剂二氯乙烷(1.25mL)、苯乙烯(式III-a)(1.0mmol,104.0mg)、苯基异丙基酮(式II-e)(0.5mmol,73.5mg)和甲基锌(0.75mmol,1.2M intoluene,0.625mL),在60℃反应6h后加水(2mL)淬灭,再用二氯甲烷萃取,合并有机相,用无水硫酸钠干燥、过滤、旋干。经柱层析色谱分离(洗脱剂为石油醚:乙酸乙酯=24/1,v/v)后得到目标产物(式I-e)239mg,产率95%,反式产物与顺式产物的比例为12:1。
反式产物的表征如下:1H NMR(CDCl3,300MHz)δ7.60-7.56(m,1H),7.52-7.44(m,4H),7.37(d,J=7.5Hz,2H),7.30-7.23(m,3H),6.94(d,J=15.9Hz,1H),4.76(dd,J1=6.9Hz,J2=2.7Hz,1H),2.11-1.99(m,1H),1.84(d,J=3.0Hz,1H),1.02(d,J=6.6Hz,3H),0.84(d,J=6.6Hz,3H);13C NMR(CDCl3,75MHz)δ141.5,137.7,135.8,131.0,128.9,127.8,127.8,127.6,126.9,126.7,126.3,126.3,76.6,35.0,19.8,18.0;HRMS(EI)Calculatedfor C18H20O+([M]+):252.1514,found:252.1510,结构正确。
实施例6、合成环己基(2-苯乙烯基苯基)甲醇(式I-f)
向25mL Schlenk瓶中,在N2的保护下,依次加入五羰基溴化锰(0.05mmol,13.8mg)、溴化酮(0.05mmol,11.3mg)、溶剂二氯乙烷(1.25mL)、苯乙烯(式III-a)(1.5mmol,156.0mg)、苯基环己基酮(式II-f)(0.5mmol,93.5mg)和甲基锌(0.75mmol,1.2M intoluene,0.625mL),在80℃反应6h后加水(2mL)淬灭,再用二氯甲烷萃取,合并有机相,用无水硫酸钠干燥、过滤、旋干。经柱层析色谱分离(洗脱剂为石油醚:乙酸乙酯=24/1,v/v)后得到目标产物(式I-f)242mg,产率83%,反式产物与顺式产物的比例为11:1。
反式产物的表征如下:1H NMR(CDCl3,400MHz)δ7.58-7.55(m,1H),7.50-7.41(m,4H),7.36(d,J=7.6Hz,2H),7.30-7.23(m,3H),6.93(d,J=16.0Hz,1H),4.77(d,J=7.2Hz,1H),2.00(d,J=12.8Hz,1H),1.95(s,1H),1.64-1.61(m,4H),1.36(d,J=12.4Hz,1H),1.18-0.96(m,5H);13C NMR(CDCl3,100MHz)δ141.3,137.7,135.9,130.9,128.8,127.8,127.7,127.5,127.0,126.7,126.2,126.2,75.6,44.9,29.8,28.8,26.5,26.3,26.1;HRMS(ESI)Calculated for C21H23O-([M-H]-):291.17434,found:291.17540,结构正确。
实施例7、合成1-(2-(4-甲基苯乙烯基)苯基)乙醇(式I-g)
向25mL Schlenk瓶中,在N2的保护下,依次加入五羰基溴化锰(0.025mmol,6.9mg)、溴化酮(0.05mmol,11.3mg)、溶剂二氯乙烷(1.25mL)、4-甲基苯乙烯(式III-b)(1.0mmol,118.0mg)、苯乙酮(式II-a)(0.5mmol,60.0mg)和甲基锌(0.75mmol,1.2M intoluene,0.625mL),在60℃反应6h后加水(2mL)淬灭,再用二氯甲烷萃取,合并有机相,用无水硫酸钠干燥、过滤、旋干。经柱层析色谱分离(洗脱剂为石油醚:乙酸乙酯=24/1,v/v)后得到目标产物(式I-g)190mg,产率80%,反式产物与顺式产物的比例为8:1。
反式产物的表征如下:1H NMR(CDCl3,400MHz)δ7.57-7.52(m,2H),7.41-7.36(m,3H),7.32-7.25(m,2H),7.17(d,J=7.6Hz,2H),6.96-6.91(m,1H),5.29-5.27(m,1H),2.36(s,3H),1.90(s,1H),1.50(d,J=6.4Hz,3H);13C NMR(CDCl3,100MHz)δ143.0,137.9,135.3,134.8,131.3,129.6,127.9,127.7,126.7,126.3,125.1,124.7,67.2,24.5,21.4;HRMS(EI)Calculated for C17H18O+([M]+):238.1358,found:238.1360,结构正确。
实施例8、合成1-(2-(3-苯基-1-丙烯基)苯基)乙醇(式I-h)
向25mL Schlenk瓶中,在N2的保护下,依次加入五羰基溴化锰(0.05mmol,13.8mg)、溴化酮(0.05mmol,11.3mg)、溶剂二氯乙烷(1.25mL)、烯丙基苯(式III-c)(1.5mmol,177.0mg)、苯乙酮(式II-a)(0.5mmol,60.0mg)和甲基锌(0.75mmol,1.2M intoluene,0.625mL),在80℃反应6h后加水(2mL)淬灭,再用二氯甲烷萃取,合并有机相,用无水硫酸钠干燥、过滤、旋干。经柱层析色谱分离(洗脱剂为石油醚:乙酸乙酯=24/1,v/v)后得到目标产物(式I-h)190mg,产率80%,反式产物与顺式产物的比例为12:1。
反式产物的表征如下:1H NMR(CDCl3,300MHz)δ7.50(d,J=7.2Hz,1H),7.40(d,J=7.2Hz,1H),7.34-7.20(m,7H),6.76(d,J=15.6Hz,1H),6.26-6.15(m,1H),5.19(dq,J1=6.0Hz,J2=3.0Hz,1H),3.57(d,J=6.9Hz,2H),1.79(d,J=3.9Hz,1H),1.47(d,J=6.3Hz,3H);13C NMR(CDCl3,75MHz)δ142.6,140.2,135.3,132.1,128.7,128.7,128.2,127.7,127.5,126.6,126.4,124.8,67.0,39.7,24.3;HRMS(ESI)Calculated forC17H17O-([M-H]-):237.12739,found:237.12807,结构正确。
实施例9、合成1-(2-(2-(三苯基硅基)乙烯基)苯基)乙醇(式I-i)
向25mL Schlenk瓶中,在N2的保护下,依次加入五羰基溴化锰(0.05mmol,13.8mg)、溴化酮(0.05mmol,11.3mg)、溶剂二氯乙烷(1.25mL)、三苯基乙烯基硅烷(式III-d)(1.5mmol,429.0mg)、苯乙酮(式II-a)(0.5mmol,60.0mg)和甲基锌(0.75mmol,1.2M intoluene,0.625mL),在80℃反应6h后加水(2mL)淬灭,再用二氯甲烷萃取,合并有机相,用无水硫酸钠干燥、过滤、旋干。经柱层析色谱分离(洗脱剂为石油醚:乙酸乙酯=24/1,v/v)后得到目标产物(式I-i)296mg,产率73%,反式产物与顺式产物的比例为6:1。
反式产物的表征如下:1H NMR(CDCl3,300MHz)δ7.62-7.56(m,7H),7.50-7.46(m,1H),7.41-7.32(m,9H),7.27-7.21(m,3H),6.86(d,J=18.9Hz,1H),4.98(q,J=6.3Hz,1H),1.83(s,1H),1.30(d,J=6.3Hz,3H);13C NMR(CDCl3,75MHz)δ146.3,143.2,136.1,135.8,134.5,129.8,128.8,128.1,127.5,126.3,126.2,124.7,66.6,24.7;HRMS(ESI)Calculatedfor C28H25OSi-([M-H]-):405.16692,found:405.16818,结构正确。
综上所述,本发明实施例提供了一种邻位烯基取代的苄醇衍生物的制备方法,利用酮、烯烃在催化剂、路易斯酸和锌试剂存在的条件下在溶剂中进行反应,实现了邻位烯基取代的苄醇衍生物的合成。
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,可轻易想到的变化或替换,都应涵盖在本发明的保护范围之内。
Claims (10)
1.式I所示的邻位烯基取代的苄醇衍生物的制备方法,包括如下步骤:
在催化剂、路易斯酸和锌试剂存在的条件下,使式II所示酮与式III所示烯烃经C-H活化反应,即得式I所示邻位烯基取代的苄醇衍生物;
式I、式II和式III中,R1表示苯环上的单取代基或多取代基,其选自氢、取代或未取代的碳原子数为1~10的烷基、取代或未取代的碳原子数为1~10的烷氧基、磺酰基、酯基和卤素中的任意一种或多种;
R2选自取代或未取代的碳原子数为1~10的烷基、碳原子数为3~10的环烷基和芳基中的任意一种;
R3选自取代或未取代的碳原子数为1~10的烷基、取代或未取代的碳原子数为1~10的烷氧基、芳基、硅基和与苯环稠合得到的芳环中的任意一种;
其中,取代的碳原子数为1~10的烷基、取代的碳原子数为1~10的烷氧基中的取代基选自下述基团:苯基和卤素;
所述芳基选自下述任意一种:苯基、碳原子数为1~6的烷基取代的苯基、碳原子数为1~6的烷氧基取代的苯基、苯基取代的苯基、卤素取代的苯基、三氟甲基取代的苯基和酯基取代的苯基。
2.根据权利要求1所述的制备方法,其特征在于:
R1选自氢、碳原子数为1~6的烷基、碳原子数为1~6的烷氧基、磺酰基、碳原子数为1~6的烷氧基羰基和卤素中的任意一种或多种;
R2选自碳原子数为1~6的烷基、环己基和苯基中的任意一种;
R3选自碳原子数为1~10的烷基、苯基、甲基苯基、苄基、三苯基硅基和2-萘基中的任意一种。
优选的,R1选自氢、甲基、甲氧基、甲磺酰基、甲氧基羰基和卤素中的任意一种;
R2选自甲基、乙基、亚丙基、环己基和苯基中的任意一种;
R3选自壬基、苯基、甲基苯基、苄基、三苯基硅基和2-萘基中的任意一种。
3.根据权利要求1或2所述的制备方法,其特征在于:所述催化剂选自五羰基溴化锰和十羰基二锰中的至少一种;所述催化剂与式II所示酮的摩尔比为1:(10~50),优选摩尔比为1:(10~20)。
4.根据权利要求1-3任一项所述的制备方法,其特征在于:所述路易斯酸选自溴化铜、氯化铜、醋酸酮、三氟甲磺酸酮、硫酸铜、氧化铜、溴化亚铜、氯化亚铜和溴化锌中的至少一种,其用量为式II所示酮的摩尔量的10%~150%,优选10%~50%。
5.根据权利要求1-4中任一项所述的制备方法,其特征在于:所述锌试剂为甲基锌试剂,其用量为式II所示酮的摩尔量的150%~200%。
6.根据权利要求1-5中任一项所述的制备方法,其特征在于:所述式II所示酮与式III所示烯烃的摩尔比为1:(1~4),优选摩尔比为1:(2~3)。
7.根据权利要求1-6中任一项所述的制备方法,其特征在于:所述C-H活化反应在溶剂中进行,所述溶剂为二氯乙烷或二氯甲烷。
8.根据权利要求1-7中任一项所述的制备方法,其特征在于:所述C-H活化反应的温度范围为60~120℃,时间范围为2~12h;所述C-H活化反应优选在60℃~80℃的条件下反应6h。
9.根据权利要求1-8中任一项所述的制备方法,其特征在于:所述C-H活化反应的体系中,式II所示酮的摩尔浓度为0.05~2mol/L。
10.根据权利要求1-9中任一项所述的制备方法,其特征在于:所述C-H活化反应在惰性气氛中进行。
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