CN109651151B - 一种多取代菲衍生物及其制备方法 - Google Patents
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- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
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- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C67/347—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to unsaturated carbon-to-carbon bonds
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- C07C2603/00—Systems containing at least three condensed rings
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Abstract
本发明公开了一种多取代菲衍生物及其制备方法,以不同的取代苯乙炔底物通过串联反应构筑多取代菲衍生物,该反应克服了以往反应中路线过长、底物和反应条件要求苛刻,取代官能团扩展有限的等缺点,该反应不但底物合成简单、试剂比较便宜,并且具有高原子经济性、绿色环保的得到目标分子,给多取代菲衍生物的工业化生产提供了一种很有价值的途径。
Description
技术领域
本发明属于有机化合物合成技术领域,具体涉及一种多取代菲衍生物及其制备方法。
背景技术
菲可用于合成树脂、植物生长激素、还原染料、鞣料等方面,菲经氢化制得全氢菲可用于生产喷气飞机的燃料。溶液有蓝色荧光。用于制造染料和农药等,并用作无烟火药的稳定剂。菲经氧化制菲醌、经氧化得到的联苯酸可用于制聚酯树脂、醇酸树脂;菲氧化可以得到苯酐、环已酮、苯酚;在造纸上,菲可作纸浆防雾剂;在医药上,菲可合成生物碱;在染料工业上,菲可制取2-氨基菲醌,苯绕蒽酮,硫化还原染料(蓝BO,黑BB及棕色)等;菲在高温高压下加氢可得到氢菲,是高级喷气式飞机的燃料。
但是天然产物中含多个取代基的菲衍生物含量较少,分离提取的数量有限,其产量根本满足不了人们的需求。因此,人工合成含多取代菲衍生物更是显得尤为重要。
发明内容
本发明目的在于提供一种多取代菲衍生物,其具有多环存在,结构更复杂,有广阔的应用前景。
本发明还提供了一种多取代菲衍生物衍生物的制备方法,所述制备方法简单、所得产物产率高,具有较高原子经济性。
本发明采取的技术方案为:
一种多取代菲衍生物,所述多取代菲衍生物的结构式为:
其中,R为四个C以内的直链烷基或支链烷基;R1为氢、卤素、或四个C以内烷基,R2为三个C以内的烷氧基。
进一步优选为,R为甲基、乙基或异丙基;R1为氯、甲基或乙基;R2为甲氧基或乙氧基。
进一步地,所述多取代菲衍生物的结构式优选为:
本发明所述的多取代菲衍生物的制备方法,所述制备方法包括以下步骤:
步骤(2)中,所述前体化合物与取代苯乙炔的物质的量之比为1:1。
步骤(2)中,所述前体化合物在甲苯中的浓度为0.1mmol/L。
步骤(2)中,所述分离纯化的方法为:将粗产物用乙酸乙酯和水萃取分离,浓缩后,用体积比为1:60~80的乙酸乙酯:石油醚为洗脱剂进行柱层析分离纯化。
与现有技术相比,本发明提供了一种全新的多取代菲衍生物的合成方法,该方法克服了以往反应中路线过长,底物和反应条件要求苛刻,取代官能团扩展有限的等缺点,该反应不但底物合成简单、试剂比较便宜,并且具有高产率、高原子经济性、绿色环保的得到目标分子,给多取代菲衍生物的工业化生产提供了一种很有价值的途径,具有一定的运用前景。
附图说明
图1为多取代菲衍生物的结构式;
图2为多取代菲衍生物的合成路线图;
图3为实施例1制备的多取代菲衍生物c-1的合成路线图;
图4为实施例2制备的多取代菲衍生物c-2的合成路线图;
图5为实施例3制备的多取代菲衍生物c-3的合成路线图;
图6为实施例1制备的多取代菲衍生物c-1的核磁共振氢谱;
图7为实施例1制备的多取代菲衍生物c-1的核磁共振碳谱;
图8为实施例1制备的多取代菲衍生物c-2的核磁共振氢谱;
图9为实施例1制备的多取代菲衍生物c-2的核磁共振碳谱;
图10为实施例1制备的多取代菲衍生物c-3的核磁共振氢谱;
图11为实施例1制备的多取代菲衍生物c-3的核磁共振碳谱;
图12为多取代菲衍生物的合成机理图。
具体实施方式
下面结合实施例和说明书附图对本发明进行详细说明。
实施例1
一种多取代菲衍生物,所述多取代菲衍生物的结构式为:
所述多取代菲衍生物的制备方法为:
(1)以以830mmol氢化钠为催化剂,将200mmol丙二酸二异丙酯与440mmol炔丙基溴加入到210mL无水乙腈中,冰水浴中搅拌反应8.5小时,产物加水洗涤,用乙酸乙酯萃取,减压旋干,以体积比为乙酸乙酯:石油醚=1:90为洗脱剂进行柱层析,减压浓缩干燥后,得到白色固体产物化合物a-1;
(2)将80mmol化合物a-1与200mmol对氯苯乙炔基溴混合,在Pd(PPh3)2Cl2/CuI的无水无氧催化体系中,摩尔比Pd(PPh3)2Cl2:CuI=3:1;Pd(PPh3)2Cl2、CuI的物质的量分别为2.56mmol、0.85mmo,,以336mmol三乙胺作碱,以150mL无水乙腈为溶剂,室温下搅拌反应11小时,产物用水洗涤,用乙酸乙酯萃取,减压旋干,以体积比为乙酸乙酯:石油醚=1:70为洗脱剂进行柱层析,减压浓缩干燥后,得到淡黄色固体产物前体化合物b-1;
(3)将前体化合物b-1与4-乙氧基苯乙炔按照1:1的摩尔比溶解在甲苯中,前体化合物b-1在甲苯中的浓度为0.1mmol/L,95℃反应3.5~4h,将粗产物用乙酸乙酯和水萃取分离,浓缩后,用体积比为1:70的乙酸乙酯:石油醚为洗脱剂进行柱层析分离纯化,减压浓缩干燥后,即可得到白色粉末状的多取代菲衍生物c-1,其产率为89.5%。
所述多取代菲衍生物c-1的合成路线图如图3所示。
产物结构通过1H NMR、13C NMR来测定,分别如图6、图7所示,结果如下:
1H NMR(500MHz,CDCl3)δ7.73(dd,J=16.1,8.7Hz,2H),7.60(d,J=8.8Hz,1H),7.58–7.54(m,2H),7.43–7.39(m,2H),7.28(s,1H),7.25(s,1H),7.19(d,J=2.4Hz,1H),7.09–7.08(m,1H),7.08–7.04(m,2H),5.15–5.09(m,2H),4.06(s,2H),3.95(s,2H),3.41(q,J=7.0Hz,2H),1.31(s,6H),1.30(s,6H),1.27(d,J=7.0Hz,3H)。
13C NMR(125MHz,CDCl3)δ171.28,156.62,142.55,140.82,139.02,136.60,134.20,133.31,132.52,131.86,130.03,129.82,129.17,128.85,128.66,127.77,127.37,121.71,120.60,119.09,117.86,109.43,96.59,88.79,69.50,62.60,59.22,41.48,40.51,21.59,14.87。
实施例2
一种多取代菲衍生物,所述多取代菲衍生物的结构式为:
所述多取代菲衍生物的制备方法为:
(1)以以830mmol氢化钠为催化剂,将200mmol丙二酸二异丙酯与440mmol炔丙基溴加入到210mL无水乙腈中,冰水浴中搅拌反应8.5小时,产物加水洗涤,用乙酸乙酯萃取,减压旋干,以体积比为乙酸乙酯:石油醚=1:90为洗脱剂进行柱层析,减压浓缩干燥后,得到白色固体产物化合物a-2;
(2)将80mmol化合物a-2与200mmol对甲基苯乙炔基溴混合,在Pd(PPh3)2Cl2/CuI的无水无氧催化体系中,摩尔比Pd(PPh3)2Cl2:CuI=3:1;Pd(PPh3)2Cl2、CuI的物质的量分别为2.56mmol、0.85mmol,,以336mmol三乙胺作碱,以150mL无水乙腈为溶剂,室温下搅拌反应11小时,产物用水洗涤,用乙酸乙酯萃取,减压旋干,以体积比为乙酸乙酯:石油醚=1:70为洗脱剂进行柱层析,减压浓缩干燥后,得到淡黄色固体产物前体化合物b-2;
(3)将前体化合物b-2与4-乙氧基苯乙炔按照1:1的摩尔比溶解在甲苯中,前体化合物b-1在甲苯中的浓度为0.1mmol/L,95℃反应3.5~4h,将粗产物用乙酸乙酯和水萃取分离,浓缩后,用体积比为1:65的乙酸乙酯:石油醚为洗脱剂进行柱层析分离纯化,减压浓缩干燥后,即可得到白色粉末状的多取代菲衍生物c-2,其产率为91.2%。
所述多取代菲衍生物c-2的合成路线图如图4所示。
产物结构通过1H NMR、13C NMR来测定,分别如图8、图9所示,结果如下:
1H NMR(400MHz,CDCl3)δ7.70(dd,J=11.7,8.8Hz,2H),7.60(d,J=8.8Hz,1H),7.39–7.33(m,5H),7.09–7.00(m,5H),5.12(dt,J=12.5,6.2Hz,2H),4.06(s,2H),3.97(s,2H),3.34(q,J=7.0Hz,2H),2.48(s,3H),2.33(s,3H),1.31(s,6H),1.29(s,6H),1.22(t,J=7.0Hz,3H)。
13C NMR(100MHz,CDCl3)δ171.39,156.34,142.16,141.14,138.94,138.10,136.58,135.86,132.16,131.30,130.16,129.73,129.61,129.47,128.91,128.36,127.68,127.56,120.65,120.50,119.78,117.56,109.59,97.50,87.67,76.70,69.36,62.34,59.21,41.57,40.51,21.59,21.51,21.23,14.86。
实施例3
一种多取代菲衍生物,所述多取代菲衍生物的结构式为:
所述多取代菲衍生物的制备方法为:
(1)以以830mmol氢化钠为催化剂,将200mmol丙二酸二乙酯与440mmol炔丙基溴加入到210mL无水乙腈中,冰水浴中搅拌反应8.5小时,产物加水洗涤,用乙酸乙酯萃取,减压旋干,以体积比为乙酸乙酯:石油醚=1:90为洗脱剂进行柱层析,减压浓缩干燥后,得到白色固体产物化合物a-3;
(2)将80mmol化合物a-3与200mmol对乙基苯乙炔基溴混合,在Pd(PPh3)2Cl2/CuI的无水无氧催化体系中,摩尔比Pd(PPh3)2Cl2:CuI=3:1;Pd(PPh3)2Cl2、CuI的物质的量分别为2.56mmol、0.85mmo,,以336mmol三乙胺作碱,以150mL无水乙腈为溶剂,室温下搅拌反应11小时,产物用水洗涤,用乙酸乙酯萃取,减压旋干,以体积比为乙酸乙酯:石油醚=1:70为洗脱剂进行柱层析,减压浓缩干燥后,得到淡黄色固体产物前体化合物b-3;
(3)将前体化合物b-3与4-甲氧基苯乙炔按照1:1的摩尔比溶解在甲苯中,前体化合物b-1在甲苯中的浓度为0.1mmol/L,95℃反应3.5~4h,将粗产物用乙酸乙酯和水萃取分离,浓缩后,用体积比为1:80的乙酸乙酯:石油醚为洗脱剂进行柱层析分离纯化,减压浓缩干燥后,即可得到白色粉末状的多取代菲衍生物c-3,其产率为89.7%。
所述多取代菲衍生物c-3的合成路线图如图5所示。
产物结构通过1H NMR、13C NMR来测定,分别如图10、图11所示,结果如下:
1H NMR(400MHz,CDCl3)δ7.71(dd,J=12.8,8.8Hz,2H),7.60(d,J=8.8Hz,1H),7.41(dd,J=13.7,1.9Hz,5H),7.10–7.02(m,5H),4.28(q,J=7.0Hz,4H),4.10(s,2H),4.01(s,2H),3.22(s,3H),2.77(q,J=7.6Hz,2H),2.62(q,J=7.6Hz,2H),1.37–1.30(m,9H),1.21(t,J=7.6Hz,3H)。
13C NMR(101MHz,CDCl3)δ171.87,156.98,144.48,143.14,142.32,141.39,138.84,135.79,132.17,131.43,130.29,129.78,129.43,128.56,128.36,127.76,127.70,127.54,120.75,120.67,119.93,117.26,108.95,97.66,87.66,76.70,61.96,59.26,54.26,41.65,40.54,28.86,28.84,16.16,15.43,14.10。
上述参照实施例对一种多取代菲衍生物及其制备方法进行的详细描述,是说明性的而不是限定性的,可按照所限定范围列举出若干个实施例,因此在不脱离本发明总体构思下的变化和修改,应属本发明的保护范围之内。
Claims (5)
3.根据权利要求1所述的多取代菲衍生物的制备方法,其特征在于,步骤(2)中,所述前体化合物与取代苯乙炔的物质的量之比为1:1。
4.根据权利要求1所述的多取代菲衍生物的制备方法,其特征在于,步骤(2)中,所述前体化合物在甲苯中的浓度为0.1mmol/L。
5.根据权利要求1所述的多取代菲衍生物的制备方法,其特征在于,步骤(2)中,所述分离纯化的方法为:将粗产物用乙酸乙酯和水萃取分离,浓缩后,用体积比为1:60~80的乙酸乙酯:石油醚为洗脱剂进行柱层析分离纯化。
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