CN105777463B - 一种β,γ–不饱和酯化合物的制备方法 - Google Patents
一种β,γ–不饱和酯化合物的制备方法 Download PDFInfo
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- CN105777463B CN105777463B CN201610202260.6A CN201610202260A CN105777463B CN 105777463 B CN105777463 B CN 105777463B CN 201610202260 A CN201610202260 A CN 201610202260A CN 105777463 B CN105777463 B CN 105777463B
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- -1 esters compound Chemical class 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 71
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 37
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 35
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 24
- SBLSVQAUPIHUAM-UHFFFAOYSA-N 2,3-dimethylhept-6-ene-2,3-diol Chemical compound C(C=C)CC(O)(C)C(C)(C)O SBLSVQAUPIHUAM-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 51
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 24
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 23
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 17
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- 235000003270 potassium fluoride Nutrition 0.000 claims description 12
- 239000011698 potassium fluoride Substances 0.000 claims description 12
- 229910052763 palladium Inorganic materials 0.000 claims description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 8
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical group [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 claims description 8
- 230000008859 change Effects 0.000 claims description 7
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 7
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 claims description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 6
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical group [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 6
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims description 5
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 5
- QBVXKDJEZKEASM-UHFFFAOYSA-M tetraoctylammonium bromide Chemical compound [Br-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC QBVXKDJEZKEASM-UHFFFAOYSA-M 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 125000004185 ester group Chemical group 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 125000001072 heteroaryl group Chemical group 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 4
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 claims description 4
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- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical group C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 claims description 3
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- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
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- 229910052731 fluorine Inorganic materials 0.000 claims description 2
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
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- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical group C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 claims 1
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- ITCMXBVIXVDAKR-UHFFFAOYSA-M azanium tetrabutylazanium diacetate Chemical compound C(C)(=O)[O-].[NH4+].C(CCC)[N+](CCCC)(CCCC)CCCC.C(C)(=O)[O-] ITCMXBVIXVDAKR-UHFFFAOYSA-M 0.000 claims 1
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 42
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 30
- 229960004424 carbon dioxide Drugs 0.000 description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 29
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 239000000741 silica gel Substances 0.000 description 14
- 229910002027 silica gel Inorganic materials 0.000 description 14
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- 238000005160 1H NMR spectroscopy Methods 0.000 description 13
- 229910000831 Steel Inorganic materials 0.000 description 13
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 241000790917 Dioxys <bee> Species 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
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- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 3
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- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
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- DMHZDOTYAVHSEH-UHFFFAOYSA-N 1-(chloromethyl)-4-methylbenzene Chemical compound CC1=CC=C(CCl)C=C1 DMHZDOTYAVHSEH-UHFFFAOYSA-N 0.000 description 1
- XMWGTKZEDLCVIG-UHFFFAOYSA-N 1-(chloromethyl)naphthalene Chemical compound C1=CC=C2C(CCl)=CC=CC2=C1 XMWGTKZEDLCVIG-UHFFFAOYSA-N 0.000 description 1
- IRSVDHPYXFLLDS-UHFFFAOYSA-N 2,4-dichloro-1-(chloromethyl)benzene Chemical compound ClCC1=CC=C(Cl)C=C1Cl IRSVDHPYXFLLDS-UHFFFAOYSA-N 0.000 description 1
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- OKUSWAGOKUGEDX-UHFFFAOYSA-N C(CCC)Br(CCCC)(CCCC)CCCC Chemical compound C(CCC)Br(CCCC)(CCCC)CCCC OKUSWAGOKUGEDX-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- IWTYTFSSTWXZFU-QPJJXVBHSA-N [(e)-3-chloroprop-1-enyl]benzene Chemical compound ClC\C=C\C1=CC=CC=C1 IWTYTFSSTWXZFU-QPJJXVBHSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
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- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Substances ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B41/00—Formation or introduction of functional groups containing oxygen
- C07B41/12—Formation or introduction of functional groups containing oxygen of carboxylic acid ester groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
- C07D333/16—Radicals substituted by singly bound hetero atoms other than halogen by oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D333/28—Halogen atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明属于医药化工中间体及相关化学技术领域,涉及一种β,γ–不饱和酯化合物的制备方法。其特征是通过使用原位生成的过渡金属钯纳米粒子作为催化剂,实现卤代甲基(杂)芳烃化合物、烯丙基硼酸频哪醇酯以及二氧化碳三组分之间羧化反应,生成不饱和酯化合物。不饱和酯类化合物是一类非常重要的化学中间体,可用于合成多种非常有用的化合物。该方法操作简便、原料易得、环境友好,对二氧化碳的应用研究具有重要的意义。
Description
技术领域
本发明属于医药化工中间体及相关化学技术领域,涉及到一种使用原位生成的过渡金属纳米粒子作为催化剂,经过卤代甲基(杂)芳烃化合物、烯丙基硼酸频哪醇酯以及二氧化碳三组分之间羧化反应,制备β,γ–不饱和酯化合物的方法。
背景技术
与其它金属-碳键相比,B-C键稳定,不容易断裂,常常需要过渡金属催化剂在膦、氮配体的存在下,促进反应的发生。但是有机硼试剂绿色低毒、官能团兼容性广泛的优点,使其在构筑C-C键的反应中有着重要的应用。不饱和酯类化合物是一类重要的化学中间体,广泛的应用在医药、农药等与人们生活息息相关的领域中。CO2是温室气体,过量的存在严重影响了人们的生存环境,但是CO2储量丰富,是廉价的C1源,若能变废为宝,将有广阔的应用前景。
2011年,Hazari课题组报道了钯催化硼烷与二氧化碳的羧化反应。该反应中使用氮杂环卡宾配体和π-烯丙基配体,催化剂结构复杂,不利于应用[Wu,J.;Hazari,N.Chem.Commun.2011,47,1069.]。同年,该课题组报道了使用烯丙基桥连一价钯二聚体作为催化剂,硼烷与二氧化碳的羧化反应。该反应催化剂制备复杂,底物范围狭窄[Hruszkewycz D.P.,Wu J.,Hazari N.,et al.J.Am.Chem.Soc.2011,133,3280.]。2013年,Duong等人报道了使用氮杂环卡宾铜作为催化剂,硼烷与二氧化碳的羧化反应。该反应需要前期复杂的催化剂制备过程,并且反应结束后需要质子化的后处理过程,不利于应用[Duong H.A.,Huleatt P.B.,Tan Q.,et al.Org.Lett.2013,15,4034.]。
发明内容
本发明提供了一种由原位生成的纳米钯催化剂催化卤代甲基(杂)芳烃化合物、烯丙基硼酸频哪醇酯以及二氧化碳三组分之间羧化反应,制备β,γ–不饱和酯化合物的方法。该方法无需加入额外的配体,在温和条件下可以得到较高收率的产物,具有一定的应用价值。
以二氧化碳、卤代甲基(杂)芳香烃和烯丙基硼酸频哪醇酯为原料,在钯催化剂的作用下,合成一系列β,γ–不饱和酯化合物;合成路线如下:
该方法采用的技术方案如下:
(1)将钯催化剂、添加剂、氟盐、卤代甲基(杂)芳香烃、烯丙基硼酸频哪醇酯和有机溶剂加入高压釜中,冲入二氧化碳0.1atm~20atm,封闭高压釜,将反应釜置于20~150℃、装有磁力搅拌的油浴中反应12~36h,反应结束后冷却至室温,放出剩余二氧化碳。
卤代甲基芳香烃上的R1选自氟、氯、溴、硝基、酯基、甲基、甲氧基、乙氧基、炔丙氧基;R1在芳环的邻位、间位或对位;芳环是苯环、萘环;所述的卤代甲基杂芳香烃上的R2选自甲基、溴、硝基、酯基、甲基;R2在杂芳环的3位、4位或5位;杂芳环是噻吩环(X=S)、苯并呋喃环(X=S)、呋喃环(X=O)、苯并呋喃环(X=O)、吡咯环(X=NTs)或苯并吡咯环(X=NTs);卤代甲基(杂)芳烃上的Y选自溴、氯;卤代甲基(杂)芳香烃化合物和烯丙基硼酸频哪醇酯 的摩尔比为1:0.5~1:10.0。
钯催化剂选自三(二亚苄基丙酮)二钯、氯化钯、醋酸钯、乙酰丙酮钯、二乙腈二氯化钯;卤代甲基(杂)芳香烃与钯催化剂的摩尔比为1:0.01~1:0.1。
添加剂使用季铵盐,选自四丁基氯化铵、四丁基溴化铵、四丁基碘化铵、四丁基醋酸铵、四辛基溴化铵、四丁基六氟磷酸铵、十六烷基三甲基溴化铵、苄基三甲基溴化铵;卤代甲基(杂)芳香烃与添加剂的摩尔比为1:0.1~1:10。
氟盐选自四丁基氟化铵、氟化钾、氟化铯;卤代甲基(杂)芳香烃与氟盐的摩尔比为1:0.1~1:10。
有机溶剂选自四氢呋喃、甲苯、乙腈、乙醇、N,N-二甲基甲酰胺或1,4-二氧六环,是单一溶剂或混合溶剂;卤代甲基(杂)芳香烃在有机溶剂中的摩尔浓度为0.01mmol/mL~2mmol/mL。
(2)将步骤(1)得到的反应液经硅胶柱层析分离得到不饱和酯产物。
柱分离中使用的硅胶型号为100~200目或200~300目,柱高5~30cm。柱分离中使用的洗脱剂为选自石油醚和乙酸乙酯、正己烷和二氯甲烷、石油醚和二氯甲烷按照一定比例配置的一定浓度的混合试剂。浓度比例选自5:1、10:1、20:1、30:1、40:1、50:1或100:1。
附图说明
图1是实施例1中3-丁烯酸苯甲酯的1H核磁谱图。
图2是实施例2中3-丁烯酸-4-氟苯甲酯的1H核磁谱图。
图3是实施例3中3-丁烯酸-2-氯苯甲酯的1H核磁谱图。
图4是实施例4中3-丁烯酸-2,4-二氯苯甲酯的1H核磁谱图。
图5是实施例5中3-丁烯酸-4-甲基苯甲酯的1H核磁谱图。
图6是实施例6中3-丁烯酸-4-甲氧基苯甲酯的1H核磁谱图。
图7是实施例7中3-丁烯酸-4-炔丙氧基苯甲酯的1H核磁谱图。
图8是实施例7中3-丁烯酸-4-炔丙氧基苯甲酯的13C核磁谱图。
图9是实施例8中3-丁烯酸肉桂酯的1H核磁谱图。
图10是实施例8中3-丁烯酸肉桂酯的13C核磁谱图。
图11是实施例9,10中3-丁烯酸-1-萘甲酯的1H核磁谱图。
图12是实施例11中3-丁烯酸-2-甲基-1-萘甲酯的1H核磁谱图。
图13是实施例12中3-丁烯酸-2-噻吩甲酯的1H核磁谱图。
图14是实施例13中3-丁烯酸-5-溴-2-噻吩甲酯的1H核磁谱图。
具体实施方式
本发明是通过使用原位生成的过渡金属纳米粒子作为催化剂,实现了卤代甲基(杂)芳烃化合物、烯丙基硼酸频哪醇酯以及二氧化碳三组分反应,合成β,γ-不饱和酯化合物,具有反应条件温和、实验操作简单、底物兼容性好等优点,具有出良好的应用前景。
下面结合具体实施例,进一步阐述本发明。这些实施例仅用于说明本发明而不用于限制本发明的范围。在本领域内的技术人员对本发明所做的简单替换或改进均属于本发明所保护的技术方案之内。
实施例1:3-丁烯酸苯甲酯的合成
在25mL的高压釜中,加入乙酰丙酮钯(7.6mg,0.025mmol),四辛基溴化铵(820.0mg,1.5mmol),氟化铯(151.9mg,1.0mmol),且装入一个搅拌磁子,氮气置换三次后,向高压釜中加入苄氯(126.6mg,1.0mmol,)、1,4-二氧六环(2mL)、烯丙基硼酸频哪醇酯(184.8mg,1.1mmol),然后关闭加料口以及充气口。连接二氧化碳高压钢瓶之后充入5个大气压的二氧化碳气体。将高压釜置于100℃油浴中搅拌反应24小时。
反应结束后,慢慢释放多余的二氧化碳,将反应液转移至5cm高的硅胶柱上,用石油醚:乙酸乙酯为50:1的展开剂过柱,分离得纯的产物,此反应收率为90%。
3-丁烯酸苯甲酯
1H NMR(400MHz,CDCl3):δ7.38–7.29(m,5H),5.99–5.89(m,1H),5.19–5.15(m,2H),5.13(s,2H),3.12(d,J=7.2Hz,2H).
实施例2:3-丁烯酸-4-氟苯甲酯
在25mL的高压釜中,加入三(二亚苄基丙酮)二钯(22.8mg,0.025mmol),四丁基溴化铵(322.4mg,1.0mmol),氟化铯(151.9mg,1.0mmol),且装入一个搅拌磁子,氮气置换三次后,向高压釜中加入4-氟苄氯(144.6mg,1.0mmol,)、1,4-二氧六环(4mL)、烯丙基硼酸频哪醇酯(184.8mg,1.1mmol),然后关闭加料口以及充气口。连接二氧化碳高压钢瓶之后充入1个大气压的二氧化碳气体。将高压釜置于90℃油浴中搅拌反应24小时。
反应结束后,慢慢释放多余的二氧化碳,将反应液转移至30cm高的硅胶柱上,用石油醚:乙酸乙酯为50:1的展开剂过柱,分离得纯的产物,此反应收率为95%。
3-丁烯酸-4-氟苯甲酯
1H NMR(400MHz,CDCl3):δ7.36–7.30(m,2H),7.08–7.01(m,2H),5.99–5.87(m,1H),5.21–5.13(m,2H),5.09(s,2H),3.13(d,J=6.8Hz,2H).
实施例3:3-丁烯酸-2-氯苯甲酯
在25mL的高压釜中,加入乙酰丙酮钯(7.6mg,0.025mmol),四辛基溴化铵(546.8mg,1.0mmol),氟化钾(116.2mg,2.0mmol),且装入一个搅拌磁子,氮气置换三次后,向高压釜中加入2-氯苄氯(161.0mg,1.0mmol,)、四氢呋喃(4mL)、烯丙基硼酸频哪醇酯(168.0mg,1.0mmol),然后关闭加料口以及充气口。连接二氧化碳高压钢瓶之后充入3个大气压的二氧化碳气体。将高压釜置于90℃油浴中搅拌反应24小时。
反应结束后,慢慢释放多余的二氧化碳,将反应液转移至10cm高的硅胶柱上,用石油醚:乙酸乙酯为50:1的展开剂过柱,分离得纯的产物,此反应收率为92%。
3-丁烯酸-2-氯苯甲酯
1H NMR(400MHz,CDCl3):δ7.42–7.37(m,2H),7.29–7.24(m,2H),5.99–5.91(m,1H),5.28–5.17(m,4H),3.18(d,J=6.8Hz,2H).
实施例4:3-丁烯酸-2,4-二氯苯甲酯的合成
在25mL的高压釜中,加入醋酸钯(11.22mg,0.05mmol),四辛基溴化铵(546.8mg,1.0mmol),氟化钾(116.2mg,2.0mmol),且装入一个搅拌磁子,氮气置换三次后,向高压釜中加入2,4-二氯苄氯(195.5mg,1.0mmol,)、四氢呋喃(2mL)、烯丙基硼酸频哪醇酯(168.0mg,1.0mmol),然后关闭加料口以及充气口。连接二氧化碳高压钢瓶之后充入3个大气压的二氧化碳气体。将高压釜置于90℃油浴中搅拌反应24小时。
反应结束后,慢慢释放多余的二氧化碳,将反应液转移至15cm高的硅胶柱上,用石油醚:乙酸乙酯为100:1的展开剂过柱,分离得纯的产物,此反应收 率为90%
3-丁烯酸-2,4-二氯苯甲酯
1H NMR(400MHz,CDCl3):δ7.41(s,1H),7.35(d,J=8.0Hz,1H),7.25(d,J=8.0Hz,1H),6.00–5.88(m,1H),5.25–5.15(m,4H),3.17(d,J=7.2Hz,2H).
实施例5:3-丁烯酸-4-甲基苯甲酯的合成
在25mL的高压釜中,加入醋酸钯(11.22mg,0.05mmol),四丁基溴化铵(322.4mg,1.0mmol),氟化钾(58.1mg,2.0mmol),且装入一个搅拌磁子,氮气置换三次后,向高压釜中加入4-甲基苄氯(140.6mg,1.0mmol,)、N,N-二甲基甲酰胺(2mL)、烯丙基硼酸频哪醇酯(168.0mg,1.0mmol),然后关闭加料口以及充气口。连接二氧化碳高压钢瓶之后充入3个大气压的二氧化碳气体。将高压釜置于80℃油浴中搅拌反应24小时。
反应结束后,慢慢释放多余的二氧化碳,将反应液转移至25cm高的硅胶柱上,用石油醚:乙酸乙酯为20:1的展开剂过柱,分离得纯的产物,此反应收率为90%。
3-丁烯酸-4-甲基苯甲酯
1H NMR(400MHz,CDCl3):δ7.25(d,J=8.0Hz,2H),7.16(d,J=8.0Hz,2H),5.99–5.88(m,1H),5.20–5.12(m,2H),5.09(s,2H),3.12(d,J=6.8Hz,2H),2.35(s,3H).
实施例6:3-丁烯酸-4-甲氧基苯甲酯的合成
在25mL的高压釜中,加入氯化钯(8.87mg,0.05mmol),四丁基溴化铵 (644.7mg,2.0mmol),四丁基氟化铵(261.5mg,1.0mmol),且装入一个搅拌磁子,氮气置换三次后,向高压釜中加入4-甲氧基苄氯(156.6mg,1.0mmol,)、四氢呋喃(5mL)、烯丙基硼酸频哪醇酯(168.0mg,1.0mmol),然后关闭加料口以及充气口。连接二氧化碳高压钢瓶之后充入1个大气压的二氧化碳气体。将高压釜置于20℃油浴中搅拌反应24小时。
反应结束后,慢慢释放多余的二氧化碳,将反应液转移至25cm高的硅胶柱上,用石油醚:乙酸乙酯为100:1的展开剂过柱,分离得纯的产物,此反应收率为80%。
3-丁烯酸-4-甲氧基苯甲酯
1H NMR(400MHz,CDCl3):δ7.29(d,J=8.4Hz,2H),6.88(d,J=8.4Hz,2H),5.99–5.87(m,1H),5.19–5.12(m,2H),5.02(s,2H),3.80(s,3H),3.11(d,J=7.2Hz,2H).
实施例7:3-丁烯酸-4-炔丙氧基苯甲酯的合成
在25mL的高压釜中,加入氯化钯(8.87mg,0.05mmol),四丁基溴化铵(322.4mg,1.0mmol),氟化钾(58.1mg,1.0mmol),且装入一个搅拌磁子,氮气置换三次后,向高压釜中加入4-炔丙氧基苄氯(180.1mg,1.0mmol,)、乙腈(2mL)、烯丙基硼酸频哪醇酯(168.0mg,1.0mmol),然后关闭加料口以及充气口。连接二氧化碳高压钢瓶之后充入1个大气压的二氧化碳气体。将高压釜置于90℃油浴中搅拌反应24小时。
反应结束后,慢慢释放多余的二氧化碳,将反应液转移至30cm高的硅胶柱上,用石油醚:乙酸乙酯为100:1的展开剂过柱,分离得纯的产物,此反应收 率为90%。
3-丁烯酸-4-炔丙氧基苯甲酯
1H NMR(400MHz,CDCl3):δ7.31(d,J=8.0Hz,2H),6.97(d,J=8.0Hz,2H),5.98–5.88(m,1H),5.19–5.14(m,2H),5.07(s,2H),4.69(s,2H),3.12(d,J=6.8Hz,2H),2.52(s,1H);13C NMR(100MHz,CDCl3):δ171.6,157.7,130.3,130.2,129.1,118.8,115.1,78.5,75.8,66.3,56.0,39.3;IR(neat):3287,3079,2922,1731,1642,1611,1512,1375,1218,1163,1026,973,922,822,674,639cm-1;HRMS(EI,m/z)calcd for C14H14O3:230.0943[M+],found:230.0953.
实施例8:3-丁烯酸肉桂酯的合成
在25mL的高压釜中,加入乙酰丙酮钯(15.2mg,0.05mmol),四丁基氯化铵(277.9mg,1.0mmol),氟化钾(58.1mg,1.0mmol),且装入一个搅拌磁子,氮气置换三次后,向高压釜中加入肉桂基氯(152.6mg,1.0mmol,)、四氢呋喃(2mL)、烯丙基硼酸频哪醇酯(168.0mg,1.0mmol),然后关闭加料口以及充气口。连接二氧化碳高压钢瓶之后充入1个大气压的二氧化碳气体。将高压釜置于90℃油浴中搅拌反应24小时。
反应结束后,慢慢释放多余的二氧化碳,将反应液转移至30cm高的硅胶柱上,用石油醚:乙酸乙酯为100:1的展开剂过柱,分离得纯的产物,此反应收率为95%。
3-丁烯酸肉桂酯
1H NMR(400MHz,CDCl3):δ7.40(d,J=7.6Hz,2H),7.33(dd,J=7.6,7.6Hz, 2H),7.29–7.23(m,1H),6.66(d,J=15.6Hz,1H),6.33–6.26(m,1H),6.02–5.91(m,1H),5.22–5.17(m,2H),4.76(d,J=6.4Hz,2H),3.16(d,J=7.2Hz,2H);13C NMR(100MHz,CDCl3):δ171.3,136.2,134.4,130.2,128.6,128.1,126.7,123.0,118.7,65.3,39.2;IR(neat):3083,3027,2941,1736,1642,1599,1495,1449,1324,1254,1166,967,922,745,692cm-1;HRMS(EI,m/z)calcd for C13H14O2:202.1002[M+],found:202.0994.
实施例9:3-丁烯酸-1-萘甲酯的合成
在25mL的高压釜中,加入醋酸钯(11.22mg,0.05mmol),四丁基碘化铵(369.4mg,1.0mmol),氟化钾(87.2mg,1.5mmol),且装入一个搅拌磁子,氮气置换三次后,向高压釜中加入1-氯甲基萘(176.6mg,1.0mmol,)、四氢呋喃(2mL)、烯丙基硼酸频哪醇酯(168.0mg,1.0mmol),然后关闭加料口以及充气口。连接二氧化碳高压钢瓶之后充入1个大气压的二氧化碳气体。将高压釜置于90℃油浴中搅拌反应24小时。
反应结束后,慢慢释放多余的二氧化碳,将反应液转移至30cm高的硅胶柱上,用石油醚:乙酸乙酯为50:1的展开剂过柱,分离得纯的产物,此反应收率为92%。
3-丁烯酸-1-萘甲酯
1H NMR(400MHz,CDCl3):δ8.00(d,J=8.4Hz,1H),7.90–7.83(m,2H),7.60–7.50(m,3H),7.47–7.42(m,1H),5.99–5.89(m,1H),5.51(s,2H),5.18–5.13(m,2H),2.93(d,J=6.8Hz,2H).
实施例10:3-丁烯酸-1-萘甲酯的合成
在25mL的高压釜中,加入醋酸钯(11.22mg,0.05mmol),四丁基碘化铵(369.4mg,1.0mmol),氟化钾(87.2mg,1.5mmol),且装入一个搅拌磁子,氮气置换三次后,向高压釜中加入1-溴甲基萘(221.1mg,1.0mmol,)、四氢呋喃(2mL)、烯丙基硼酸频哪醇酯(168.0mg,1.0mmol),然后关闭加料口以及充气口。连接二氧化碳高压钢瓶之后充入1个大气压的二氧化碳气体。将高压釜置于90℃油浴中搅拌反应24小时。
反应结束后,慢慢释放多余的二氧化碳,将反应液转移至30cm高的硅胶柱上,用石油醚:乙酸乙酯为50:1的展开剂过柱,分离得纯的产物,此反应收率为87%。
3-丁烯酸-1-萘甲酯
1H NMR(400MHz,CDCl3):δ8.00(d,J=8.4Hz,1H),7.90–7.83(m,2H),7.60–7.50(m,3H),7.47–7.42(m,1H),5.99–5.89(m,1H),5.51(s,2H),5.18–5.13(m,2H),2.93(d,J=6.8Hz,2H).
实施例11:3-丁烯酸-2-甲基-1-萘甲酯的合成
在25mL的高压釜中,加入醋酸钯(11.22mg,0.05mmol),四丁基氟化铵(522.9mg,2.0mmol),氟化钾(87.2mg,1.5mmol),且装入一个搅拌磁子,氮气置换三次后,向高压釜中加入2-甲基-1-氯甲基萘(190.6mg,1.0mmol,)、四氢呋喃(3mL)、烯丙基硼酸频哪醇酯(168.0mg,1.0mmol),然后关闭加料口以及充气口。连接二氧化碳高压钢瓶之后充入7个大气压的二氧化碳气体。将高压釜置于70℃油浴中搅拌反应24小时。
反应结束后,慢慢释放多余的二氧化碳,将反应液转移至30cm高的硅胶 柱上,用石油醚:乙酸乙酯为50:1的展开剂过柱,分离得纯的产物,此反应收率为90%。
3-丁烯酸-2-甲基-1-萘甲酯
1H NMR(400MHz,CDCl3):δ8.02(d,J=8.4Hz,1H),7.78(d,J=8.4Hz,1H),7.73(d,J=8.4Hz,1H),7.50(dd,J=7.6,7.6Hz,1H),7.41(dd,J=7.6,7.6Hz,1H),7.29(d,J=8.4Hz,1H),5.99–5.84(m,1H),5.63(s,2H),5.14–5.10(m,2H),3.08(d,J=7.2Hz,2H),2.57(s,3H).
实施例12:3-丁烯酸-2-噻吩甲酯的合成
在25mL的高压釜中,加入乙酰丙酮钯(15.2mg,0.05mmol),苄基三甲基溴化胺(229.1mg,1mmol),氟化钾(87.2mg,1.5mmol),且装入一个搅拌磁子,氮气置换三次后,向高压釜中加入2-氯甲基噻吩(132.6mg,1.0mmol,)、四氢呋喃(6mL)、烯丙基硼酸频哪醇酯(168.0mg,1.0mmol),然后关闭加料口以及充气口。连接二氧化碳高压钢瓶之后充入7个大气压的二氧化碳气体。将高压釜置于70℃油浴中搅拌反应20小时。
反反应结束后,慢慢释放多余的二氧化碳,将反应液转移至30cm高的硅胶柱上,用石油醚:乙酸乙酯为50:1的展开剂过柱,分离得纯的产物,此反应收率为87%。
3-丁烯酸-2-噻吩甲酯
1H NMR(400MHz,CDCl3):δ7.31(dd,J=5.2,1.2Hz,1H),7.09(d,J=2.8Hz, 1H),6.98(dd,J=5.2,3.6Hz,1H),5.96–5.85(m,1H),5.28(s,2H),5.19–5.13(m,2H),3.12(d,J=6.8Hz,2H).
实施例13:3-丁烯酸-5-溴-2-噻吩甲酯的合成
在25mL的高压釜中,加入乙酰丙酮钯(15.2mg,0.05mmol),苄基三甲基溴化胺(229.1mg,1.0mmol),氟化钾(87.2mg,1.5mmol),且装入一个搅拌磁子,氮气置换三次后,向高压釜中加入5-溴-2-氯甲基噻吩(209.9mg,1.0mmol,)、四氢呋喃(6mL)、烯丙基硼酸频哪醇酯(168.0mg,1.0mmol),然后关闭加料口以及充气口。连接二氧化碳高压钢瓶之后充入7个大气压的二氧化碳气体。将高压釜置于70℃油浴中搅拌反应20小时。
反应结束后,慢慢释放多余的二氧化碳,将反应液转移至30cm高的硅胶柱上,用石油醚:乙酸乙酯为50:1的展开剂过柱,分离得纯的产物,此反应收率为93%。
3-丁烯酸-5-溴-2-噻吩甲酯
1H NMR(400MHz,CDCl3):δ6.92(d,J=3.6Hz,1H),6.84(d,J=4.0Hz,1H),5.97–5.85(m,1H),5.25–5.05(m,4H),3.11(d,J=6.8Hz,2H)。
Claims (1)
1.一种β,γ–不饱和酯化合物的制备方法,其特征在于:
以二氧化碳、卤代甲基(杂)芳香烃和烯丙基硼酸频哪醇酯为原料,在钯催化剂的作用下,合成一系列β,γ–不饱和酯化合物;合成路线如下:
(1)将钯催化剂、添加剂、氟盐、卤代甲基(杂)芳香烃、烯丙基硼酸频哪醇酯和有机溶剂加入高压釜中,冲入二氧化碳0.1atm~20atm,封闭高压釜,将反应釜置于20~150℃、装有磁力搅拌的油浴中反应12~36h,反应结束后冷却至室温,放出剩余二氧化碳;
(2)将步骤(1)得到的反应液经柱分离得到不饱和酯化合物;
所述的卤代甲基芳香烃上的R1选自氟、氯、溴、硝基、酯基、甲基、甲氧基、乙氧基、炔丙氧基;R1在芳环的邻位、间位或对位;芳环是苯环、萘环;所述的卤代甲基杂芳香烃上的R2选自甲基、溴、硝基、酯基;R2在杂芳环的3位、4位或5位;杂芳环是噻吩环(X=S)、苯并噻吩环(X=S)、呋喃环(X=O)、苯并呋喃环(X=O)、吡咯环(X=NTs)或苯并吡咯环(X=NTs);卤代甲基(杂)芳烃上的Y选自溴、氯;卤代甲基(杂)芳香烃化合物和烯丙基硼酸频哪醇酯的摩尔比为1:0.5~1:10.0;
所述钯催化剂选自三(二亚苄基丙酮)二钯、氯化钯、醋酸钯、乙酰丙酮钯、二乙腈二氯化钯;卤代甲基(杂)芳香烃与钯催化剂的摩尔比为1:0.01~1:0.1;所述添加剂使用季铵盐,选自四丁基氯化铵、四丁基溴化铵、四丁基碘化铵、四丁基醋酸铵、四辛基溴化铵、四丁基六氟磷酸铵、十六烷基三甲基溴化铵、苄基三甲基溴化铵;卤代甲基(杂)芳香烃与添加剂的摩尔比为1:0.1~1:10;所述氟盐选自四丁基氟化铵、氟化钾、氟化铯;卤代甲基(杂)芳香烃与氟盐的摩尔比为1:0.1~1:10;
所述有机溶剂选自四氢呋喃、甲苯、乙腈、乙醇、N,N-二甲基甲酰胺或1,4-二氧六环,是单一溶剂或混合溶剂;卤代甲基(杂)芳香烃在有机溶剂中的摩尔浓度为0.01mmol/mL~2mmol/mL。
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