CN104447337B - 一种肉桂酸酯类衍生物及其制备方法 - Google Patents
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- WBYWAXJHAXSJNI-VOTSOKGWSA-M trans-cinnamate Chemical class [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 36
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 18
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims abstract description 18
- AZQCFLDDJHERFZ-UHFFFAOYSA-N Br.C#Cc1ccccc1 Chemical compound Br.C#Cc1ccccc1 AZQCFLDDJHERFZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 239000012265 solid product Substances 0.000 claims abstract description 9
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims abstract description 6
- YORCIIVHUBAYBQ-UHFFFAOYSA-N propargyl bromide Chemical compound BrCC#C YORCIIVHUBAYBQ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000012312 sodium hydride Substances 0.000 claims abstract description 6
- 229910000104 sodium hydride Inorganic materials 0.000 claims abstract description 6
- WJIFKOVZNJTSGO-UHFFFAOYSA-N 1-bromo-3-methylbenzene Chemical compound CC1=CC=CC(Br)=C1 WJIFKOVZNJTSGO-UHFFFAOYSA-N 0.000 claims abstract description 5
- HBMGEXMZDMAEDN-UHFFFAOYSA-N 2-bromo-3-phenylprop-2-enoic acid Chemical group OC(=O)C(Br)=CC1=CC=CC=C1 HBMGEXMZDMAEDN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003513 alkali Substances 0.000 claims abstract description 4
- 229940114081 cinnamate Drugs 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 45
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 12
- 238000004440 column chromatography Methods 0.000 claims description 10
- 229940125904 compound 1 Drugs 0.000 claims description 10
- 229940125782 compound 2 Drugs 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 230000006837 decompression Effects 0.000 claims description 9
- 239000003208 petroleum Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 239000006227 byproduct Substances 0.000 claims description 7
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- 238000005406 washing Methods 0.000 claims description 7
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- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
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- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 229940126214 compound 3 Drugs 0.000 claims description 3
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- 229910052736 halogen Inorganic materials 0.000 claims description 3
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- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001851 cinnamic acid derivatives Chemical class 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- RUROFEVDCUGKHD-UHFFFAOYSA-N 3-bromoprop-1-enylbenzene Chemical group BrCC=CC1=CC=CC=C1 RUROFEVDCUGKHD-UHFFFAOYSA-N 0.000 claims 1
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- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical class OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 6
- 229930016911 cinnamic acid Natural products 0.000 description 6
- 235000013985 cinnamic acid Nutrition 0.000 description 6
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzenecarboxaldehyde Natural products O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000001211 (E)-4-phenylbut-3-en-2-one Substances 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 241001597008 Nomeidae Species 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- -1 benzaldehyde ketone Chemical class 0.000 description 3
- 229930008407 benzylideneacetone Natural products 0.000 description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- BWHOZHOGCMHOBV-BQYQJAHWSA-N trans-benzylideneacetone Chemical compound CC(=O)\C=C\C1=CC=CC=C1 BWHOZHOGCMHOBV-BQYQJAHWSA-N 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 description 1
- QSSXJPIWXQTSIX-UHFFFAOYSA-N 1-bromo-2-methylbenzene Chemical compound CC1=CC=CC=C1Br QSSXJPIWXQTSIX-UHFFFAOYSA-N 0.000 description 1
- BIKWEMFTJVYFAM-VPROQMLRSA-N C=C/C1=C/C=C\C=C/C=C/C1=[BrH] Chemical compound C=C/C1=C/C=C\C=C/C=C/C1=[BrH] BIKWEMFTJVYFAM-VPROQMLRSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- AXMVYSVVTMKQSL-UHFFFAOYSA-N UNPD142122 Natural products OC1=CC=C(C=CC=O)C=C1O AXMVYSVVTMKQSL-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 description 1
- 229940117916 cinnamic aldehyde Drugs 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
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- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- DXIHILNWDOYYCH-UHDJGPCESA-M sodium;(e)-3-phenylprop-2-enoate Chemical compound [Na+].[O-]C(=O)\C=C\C1=CC=CC=C1 DXIHILNWDOYYCH-UHDJGPCESA-M 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
- C07C69/757—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- 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
- C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- 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
- C07C67/333—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
- 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
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- 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
- C07C67/333—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
- 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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- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/04—One of the condensed rings being a six-membered aromatic ring
- C07C2602/08—One of the condensed rings being a six-membered aromatic ring the other ring being five-membered, e.g. indane
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Abstract
本发明涉及一种肉桂酸酯类衍生物及其制备方法。肉桂酸酯衍生物结构式为:制备方法包括在氢化钠催化下,将甲二酸酯与炔丙基溴在无水乙腈反应得到白色固体产物;将白色固体产物与苯乙炔基溴或取代的苯乙炔基溴在Pd(PPh3)2Cl2/CuI催化下,以三乙胺作碱,在无水乙腈中反应得到浅棕色固体产物;在90‑110℃的条件下,将浅棕色固体产物在间溴甲苯中与邻溴肉桂酸反应得肉桂酸酯类衍生物。本发明提供了生成一系列新的肉桂酸酯类衍生物。相对于普通肉桂酸酯类衍生物,本发明制备的肉桂酸酯类衍生物有多环的存在,其结构更加复杂多样,在化工生产、临床医药中也将表现出更加广阔的用途前景。
Description
技术领域
本发明涉及有机化合物领域,具体涉及一种肉桂酸酯类衍生物及其制备方法。
背景资料
肉桂酸及其酯类衍生物广泛用于工业生产和科学研究,例如:肉桂酸及其酯类衍生物广泛应用于化工、医药、农用化学品、食品添加剂、香料香精以及有机合成化工生产等,是重要的有机原料,绝大多数的芳胺都来自相应的硝基化合物。芳胺作为一重要化工产品,必将随着我国经济发展,特别是医药、农药、染料等的发展,需求量呈现迅速增长趋势。鉴于肉桂酸及其酯类衍生物的特殊重要性,如何去拓展肉桂酸及其衍生物的合成路径引起了无数有机合成家和化学家积极思考,并且得出了一些很有效的方法。
常见的肉桂酸的合成方法有perkin法,苯甲醛—酮缩合法,苄叉丙酮合成法。
1.perkin法
2.苯甲醛—酮缩合法
3.卞叉丙酮合成法
第一步:苯甲醛与丙酮在纯碱或其它碱性缩合剂存在下,在室温进行缩合反应得苄叉丙酮,其产率很高。
第一步:苄叉丙酮与次氯酸钠反应生成肉桂酸钠,氯仿,氢氧化钠,然后蒸馏出氯仿。
第二步:用无机酸将反应物酸化而得到肉桂酸。
现有技术制备肉桂酸酯类的方法,存在成本高、效率低和环境不友好等缺点。在工艺上有许多缺点,如流程长、反应温度高、能耗高、收率低、副产物多、分离困难和对环境污染严重等;而肉桂醛氧化法,要以浓度达到90%-100%的H2O2和NaClO2等无机氧化剂进行氧化,如此高浓度的H2O2是危险品,还需要大量的有机溶剂如丙腈、苯等,也不利于工业化生产。
发明内容
针对现有技术存在的不足,本发明提供一种肉桂酸酯类衍生物及其制备方法。
本发明采用的技术方案是:
一种肉桂酸酯衍生物,其结构式为:
其中E1=E2=CO2R,R为直链烷基;R1、R2为氢、直链烷基、支链烷基、卤素、烷氧基以及其相应的衍生物。进一步地,所述R为甲基,R1、R2为氢。
一种肉桂酸衍生物的制备方法,包括以下步骤:
(1)以氢化钠为催化剂,将甲二酸酯与炔丙基溴加入到无水乙腈中冰水浴,搅拌反应,纯化分离后得到白色固体产物,即化合物1;
所述氢化钠、甲二酸酯、炔丙基溴的物质的量比为4-5:1:2.2-3.2;
所述甲二酸酯在无水乙腈中的浓度为0.4-0.8mol/L;
所述甲二酸酯选自甲二酸烷基酯、甲二酸不饱和烃基酯、甲二酸芳香烃基酯;
所述纯化分离为将产物加水洗涤,用乙酸乙酯萃取,减压旋干,用体积比为1:100的乙酸乙酯:石油醚柱层析分离;
所述反应时间为5h以上;
(2)将化合物1与苯乙炔基溴或取代的苯乙炔基溴混合在Pd(PPh3)2Cl2/CuI的无水无氧催化体系中,以三乙胺作碱,以无水乙腈为溶剂,室温下搅拌反应,纯化分离后得到浅棕色固体产物,即前体化合物2;
所述化合物1、苯乙炔基溴或取代的苯乙炔基溴、Pd(PPh3)2Cl2、三乙胺的物质的量为1:2.2-3.2:0.0085-0.014:4-5;
所述取代的苯乙炔基溴的取代基为直链烷基、支链烷基、卤素或烷氧基及其相应的衍生物;
所述化合物1在无水乙腈中的浓度为0.3-0.65mol/L;
所述Pd(PPh3)2Cl2/CuI的无水无氧催化体系中,Pd(PPh3)2Cl2与CuI的物质的量比为3:1;
所述纯化分离为将产物加水洗涤,用乙酸乙酯萃取,减压旋干,用体积比为1:100的乙酸乙酯:石油醚柱层析分离;
所述反应时间为8h以上;
(3)在90-110℃的条件下,将步骤(2)所制备的前体化合物2在间溴甲苯中与邻溴肉桂酸反应10小时以上,将产物纯化分离后得到化合物3,即目标产物肉桂酸酯类衍生物;
所述前体化合物2与邻溴肉桂酸的物质的量比为1:1.0-1.5;
前体化合物2在间溴甲苯中的浓度为0.20-0.50mol/L;
所述纯化分离为将产物用水洗涤,乙酸乙酯萃取,减压旋干,用体积比为1:40的乙酸乙酯:石油醚柱层析分离。
与现有技术相比,本发明提供了生成一系列新的肉桂酸酯类衍生物。相对于普通肉桂酸酯类衍生物,本发明制备的肉桂酸酯类衍生物有多环的存在,其结构更加复杂多样,在化工生产、临床医药中也将表现出更加广阔的用途前景。
具体实施方式
一种肉桂酸酯类衍生物,其结构式为:
一种肉桂酸酯类衍生物的制备方法,所述的制备方法包括以下步骤:
a、前体合成;
b、目标产物合成;
c、纯化。
其中,a、前体合成,包括以下步骤:
(1)以830mmol氢化钠为催化剂,将200mmol甲二酸二甲酯与440mmol炔丙基溴加入到无水乙腈中冰水浴,搅拌反应8小时,产物加水洗涤,用乙酸乙酯萃取,减压旋干,柱层析(体积比乙酸乙酯:石油醚=1:100)得到白色固体产物,即化合物1;
(2)将80mmol化合物1与200mmol苯乙炔基溴混合在1.6g Pd(PPh3)2Cl2/CuI的无水无氧催化体系中,Pd(PPh3)2Cl2与CuI的物质的量比为3:1,以三乙胺作碱,以200ml无水乙腈为溶剂,室温下搅拌反应12小时,产物用水洗涤,用乙酸乙酯萃取,减压旋干,柱层析(体积比乙酸乙酯:石油醚=1:100)得到浅棕色固体产物,即前体化合物2。
其中b、目标产物合成,包括以下步骤:
在100℃的条件下,将0.65g前体化合物2与0.43g邻溴肉桂酸在5ml邻溴甲苯中反应24小时,得化合物3,即肉桂酸酯类衍生物的粗产物。
其中,c、纯化,包括以下步骤:
将步骤b制备的肉桂酸酯类衍生物的粗产物用水洗涤,乙酸乙酯萃取,减压旋干,柱层析(体积比乙酸乙酯:石油醚=1:40)分离得到浅黄色固体产物,即肉桂酸酯类衍生物,柱层析产率约为52.9%。
浅黄色固体产物结构通过1H NMR;13C NMR来测定。
浅黄色固体产物:
1H NMR(300MHz,CDCl3)δ8.30-8.25(d,1H),7.68-7.65(m,4H),7.42–7.31(m,10H),7.14(s,1H),6.63-6.57(d,1H),3.90-3.65(t,10H).
13C NMR(75MHz,CDCl3)δ117.72,163.81,146.38,145.72,145.45,144.50,139.60,131.43,127.98,127.74,123.29,119.44,115.86,96.00,86.63,59.60,53.27,41.37,38.42。
Claims (8)
1.一种肉桂酸衍生物的制备方法,包括以下步骤:
(1)以氢化钠为催化剂,将甲二酸二甲酯与炔丙基溴加入到无水乙腈中冰水浴,搅拌反应5h以上,纯化分离后得到白色固体产物,即化合物1;
(2)将化合物1与苯乙炔基溴或取代的苯乙炔基溴混合在Pd(PPh3)2Cl2/CuI的无水无氧催化体系中,以三乙胺作碱,以无水乙腈为溶剂,室温下搅拌反应8h以上,纯化分离后得到浅棕色固体产物,即前体化合物2;所述前体化合物的结构式为:
(3)在90-110℃的条件下,将步骤(2)所制备的前体化合物2在间溴甲苯中与邻溴肉桂酸反应10小时以上,将产物纯化分离后得到化合物3,即目标产物肉桂酸酯类衍生物;
所述肉桂酸酯衍生物,其结构式为:
其中E1=E2=CO2R,R为甲基,R1、R2为氢。
2.如权利要求1所述的制备方法,其特征在于:所述步骤(1)中氢化钠、甲二酸二甲酯、炔丙基溴的物质的量比为4-5:1:2.2-3.2;所述甲二酸二甲酯在无水乙腈中的浓度为0.4-0.8mol/L。
3.如权利要求1所述的制备方法,其特征在于:所述步骤(1)中纯化分离为将产物加水洗涤,用乙酸乙酯萃取,减压旋干,用体积比为1:100的乙酸乙酯:石油醚柱层析分离。
4.如权利要求1所述的制备方法,其特征在于:所述步骤(2)中化合物1、苯乙炔基溴或取代的苯乙炔基溴、Pd(PPh3)2Cl2、三乙胺的物质的量为1:2.2-3.2:0.0085-0.014:4-5;化合物1在无水乙腈中的浓度为0.30-0.60mol/L;Pd(PPh3)2Cl2/CuI的无水无氧催化体系中,Pd(PPh3)2Cl2与CuI的物质的量比为3:1。
5.如权利要求1所述的制备方法,其特征在于:所述步骤(2)中取代的苯乙炔基溴的取代基为直链烷基、支链烷基、卤素或烷氧基。
6.如权利要求1所述的制备方法,其特征在于:所述步骤(2)中纯化分离为将产物加水洗涤,用乙酸乙酯萃取,减压旋干,用体积比为1:100的乙酸乙酯:石油醚柱层析分离。
7.如权利要求1所述的制备方法,其特征在于:所述步骤(3)中所述前体化合物2与邻溴肉桂酸的物质的量比为1:1.0-1.5;前体化合物2在间溴甲苯中的浓度为0.2-0.5mol/L。
8.如权利要求1所述的制备方法,其特征在于:所述步骤(3)中纯化分离为将产物用水洗涤,乙酸乙酯萃取,减压旋干,用体积比为1:40的乙酸乙酯:石油醚柱层析分离。
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