CN109456243B - 一种(Z)-β-硒氰酸酯基丙烯酸酯化合物及其制备方法 - Google Patents
一种(Z)-β-硒氰酸酯基丙烯酸酯化合物及其制备方法 Download PDFInfo
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- CN109456243B CN109456243B CN201811532590.7A CN201811532590A CN109456243B CN 109456243 B CN109456243 B CN 109456243B CN 201811532590 A CN201811532590 A CN 201811532590A CN 109456243 B CN109456243 B CN 109456243B
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- 238000003786 synthesis reaction Methods 0.000 claims abstract description 8
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- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 150000002367 halogens Chemical group 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims description 8
- 235000019743 Choline chloride Nutrition 0.000 claims description 8
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims description 8
- 229960003178 choline chloride Drugs 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
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- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 5
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- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
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- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 238000001308 synthesis method Methods 0.000 claims description 2
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- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 125000000623 heterocyclic group Chemical group 0.000 claims 1
- 229910052740 iodine Inorganic materials 0.000 claims 1
- 239000011630 iodine Substances 0.000 claims 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims 1
- CRDYSYOERSZTHZ-UHFFFAOYSA-M selenocyanate Chemical compound [Se-]C#N CRDYSYOERSZTHZ-UHFFFAOYSA-M 0.000 claims 1
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- 239000000543 intermediate Substances 0.000 abstract 1
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 4
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- XRICQFIKNMMXTF-UPHRSURJSA-N (Z)-3-selenocyanatoprop-2-enoic acid Chemical compound C(=C\[Se]C#N)\C(=O)O XRICQFIKNMMXTF-UPHRSURJSA-N 0.000 description 3
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- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
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- 125000002947 alkylene group Chemical group 0.000 description 2
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 2
- 229960003237 betaine Drugs 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
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- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
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- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 2
- 229940116357 potassium thiocyanate Drugs 0.000 description 2
- KYEKHFSRAXRJBR-UHFFFAOYSA-M potassium;selenocyanate Chemical compound [K+].[Se-]C#N KYEKHFSRAXRJBR-UHFFFAOYSA-M 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
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- KIUKXJAPPMFGSW-DNGZLQJQSA-N (2S,3S,4S,5R,6R)-6-[(2S,3R,4R,5S,6R)-3-Acetamido-2-[(2S,3S,4R,5R,6R)-6-[(2R,3R,4R,5S,6R)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylic acid Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 KIUKXJAPPMFGSW-DNGZLQJQSA-N 0.000 description 1
- PEGAWOWRHSBZGQ-FPLPWBNLSA-N (4-prop-1-en-2-ylcyclohexen-1-yl)methyl (Z)-3-selenocyanatoprop-2-enoate Chemical compound CC(=C)C1CCC(=CC1)COC(=O)/C=C\[Se]C#N PEGAWOWRHSBZGQ-FPLPWBNLSA-N 0.000 description 1
- ZTACFNMYOSEQST-ARJAWSKDSA-N 1,3-benzodioxol-5-yl (Z)-3-selenocyanatoprop-2-enoate Chemical compound C1OC2=C(O1)C=C(C=C2)OC(=O)/C=C\[Se]C#N ZTACFNMYOSEQST-ARJAWSKDSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
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- JQWXPJCOTIKBKQ-RJRFIUFISA-N 2-bromoethyl (Z)-3-selenocyanatoprop-2-enoate Chemical compound C(CBr)OC(=O)/C=C\[Se]C#N JQWXPJCOTIKBKQ-RJRFIUFISA-N 0.000 description 1
- NZWYEWGRDJYBKE-DJWKRKHSSA-N 2-cyanoethyl (Z)-3-selenocyanatoprop-2-enoate Chemical compound C(COC(=O)/C=C\[Se]C#N)C#N NZWYEWGRDJYBKE-DJWKRKHSSA-N 0.000 description 1
- WMDCHDLJZCMJEZ-TWGQIWQCSA-N 2-phenylmethoxyethyl (Z)-3-selenocyanatoprop-2-enoate Chemical compound C1=CC=C(C=C1)COCCOC(=O)/C=C\[Se]C#N WMDCHDLJZCMJEZ-TWGQIWQCSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 description 1
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- 150000005840 aryl radicals Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- NHOUSJCXAJGJGK-SREVYHEPSA-N benzyl (Z)-3-selenocyanatoprop-2-enoate Chemical compound C1=CC=C(C=C1)COC(=O)/C=C\[Se]C#N NHOUSJCXAJGJGK-SREVYHEPSA-N 0.000 description 1
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- 230000000052 comparative effect Effects 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- MUSYMEAZFRXRMG-HYXAFXHYSA-N ethyl (E)-3-bromo-3-selenocyanatoprop-2-enoate Chemical compound CCOC(=O)/C=C(\[Se]C#N)/Br MUSYMEAZFRXRMG-HYXAFXHYSA-N 0.000 description 1
- UHARDDOCXZDBGM-XQRVVYSFSA-N ethyl (Z)-3-selenocyanatobut-2-enoate Chemical compound CCOC(=O)/C=C(/C)\[Se]C#N UHARDDOCXZDBGM-XQRVVYSFSA-N 0.000 description 1
- SDJHFDZHPMFBDT-HYXAFXHYSA-N ethyl (Z)-4,4,4-trifluoro-3-selenocyanatobut-2-enoate Chemical compound CCOC(=O)/C=C(/C(F)(F)F)\[Se]C#N SDJHFDZHPMFBDT-HYXAFXHYSA-N 0.000 description 1
- 229920002674 hyaluronan Polymers 0.000 description 1
- 229960003160 hyaluronic acid Drugs 0.000 description 1
- ANAHCPHBNVJFKU-IHWYPQMZSA-N methyl (Z)-3-selenocyanatoprop-2-enoate Chemical compound COC(=O)/C=C\[Se]C#N ANAHCPHBNVJFKU-IHWYPQMZSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- AHZUUWPNXZJAAE-FPLPWBNLSA-N naphthalen-2-yl (Z)-3-selenocyanatoprop-2-enoate Chemical compound C1=CC=C2C=C(C=CC2=C1)OC(=O)/C=C\[Se]C#N AHZUUWPNXZJAAE-FPLPWBNLSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- QUECYMRCFCDIMW-SREVYHEPSA-N phenyl (Z)-3-selenocyanatoprop-2-enoate Chemical compound C1=CC=C(C=C1)OC(=O)/C=C\[Se]C#N QUECYMRCFCDIMW-SREVYHEPSA-N 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- AQPZTWQIOCPAOC-PLNGDYQASA-N tert-butyl (Z)-3-selenocyanatoprop-2-enoate Chemical compound CC(C)(C)OC(=O)/C=C\[Se]C#N AQPZTWQIOCPAOC-PLNGDYQASA-N 0.000 description 1
- RRBBVWTUHSMDSD-UHFFFAOYSA-N thiophen-2-ylmethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CS1 RRBBVWTUHSMDSD-UHFFFAOYSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C391/00—Compounds containing selenium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/42—Singly bound oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/58—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4
- C07D311/70—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4 with two hydrocarbon radicals attached in position 2 and elements other than carbon and hydrogen in position 6
- C07D311/72—3,4-Dihydro derivatives having in position 2 at least one methyl radical and in position 6 one oxygen atom, e.g. tocopherols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
- C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
- C07D317/62—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring 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 atoms of the carbocyclic ring
- C07D317/64—Oxygen atoms
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- 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
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种超声波辅助合成(Z)‑β‑硒氰酸酯基丙烯酸酯化合物的方法。在超声波作用下，生物质低共熔溶剂催化丙炔酸酯、硒氰酸钾和水进行加成反应，合成(Z)‑β‑硒氰酸酯基丙烯酸酯化合物。(Z)‑β‑硒氰酸酯基丙烯酸酯化合物具有重要生理活性的硒氰酸官能团以及可修饰的酯基和烯基团等，为药物及有机物合成提供重要的有机中间体，且其方法原料易得，反应条件简便、温和、绿色节能，反应选择性及产率高，底物官能团兼容性优异。
Description
技术领域
本发明涉及一种(Z)-β-硒氰酸酯基丙烯酸酯化合物及其合成方法，特别涉及一种超声波辅助生物质低共熔溶剂催化丙炔酸酯化合物、硫氰酸盐和水一步加成反应合成(Z)-β-硒氰酸酯基丙烯酸酯化合物的方法，属于有机中间体合成技术领域。
背景技术
(Z)-β-硒氰酸酯基丙烯酸酯化合物由于具有非常重要生理活性的含硒官能团以及可修饰酯基、烯基团等，是一类非常重要的药物及有机合成中间体化合物。但是，目前尚无文献报道相关类似化合物及其合成方法。
发明内容
针对现有技术中未见(Z)-β-硒氰酸酯基丙烯酸酯化合物的相关化合物，本发明的第一个目的是在于提供一种具有重要生理活性的含硒氰酸酯官能团以及可修饰烯基和酯基的(Z)-β-硒氰酸酯基丙烯酸酸酯化合物，为药物及有机物合成提供重要的有机中间体。
针对现有技术中(Z)-β-硒氰酸酯基丙烯酸酯化合物的合成存在技术空白，本发明的第二个目的是在于提供一种利用生物质低共熔溶剂催化丙炔酸酯化合物、硫氰酸盐和水一锅反应合成(Z)-β-硒氰酸酯基丙烯酸酯化合物的方法，该方法高收率，低成本，环境友好，有利于工业化生产应用。
为了实现上述技术目的，本发明提供了一种(Z)-β-硒氰酸酯基丙烯酸酯化合物，其具有式1结构：
其中，
R1选自H、C1～C10的烷基、卤素取代基、三氟甲基、C1～C10的酯基或C2～C10的烯烃基；
R2选自C1～C10的烷基、含取代基的C1～C10的烷基或芳基。
上述式1中，R1的选择范围较广，R1可以为氢。R1也可以为常见取代基团，如烷基、卤素取代基、三氟甲基、酯基等。R1可以为C1～C10的烷基，如可以为直链烷基或带支链的烷基，也可以为C3～C7的环烷基，具体如甲基、乙基、异丁基、环己基等等。R1可以为氟、氯或溴等卤素取代基。R1可以为C1～C10的酯基，如甲氧酰基、乙氧酰基、丁氧酰基等。R1可以为C2～C10的烯烃基，可以含有至少一个烯烃基。如丙烯基、己烯、环己烯等。
上述式1中，R2选自烷基、含取代基的烷基或芳基等。R2可以选自C1～C10的烷基，烷基可以为直链烷基或带支链的烷基，也可以为C3～C7的环烷基，具体如甲基、乙基、异丁基、环己基等等。R2可以选自含取代基的C1～C10烷基，烷基可以为直链烷基，也可以为带支链的烷基或者为C3～C7的环烷基，在烷基链上的任意碳原子上可以含有常见取代基，取代基可以为芳基、芳杂环基、卤素取代基、氰基、硝基、羟基等常见的取代基；具体来说芳基如苯基或苯环上含常见取代基的取代苯基，常见取代苯基如C1～C5短链烷基、C1～C5烷氧基、卤素取代基(氟、氯、溴等)、三氟甲基基或氰基等，取代基数量可以为一个或多个，取代基位置不限；芳杂环基如五元或六元杂环取代基，如呋喃、噻吩、吡啶等；卤素取代基如氟、氯、溴等。R2可以选自芳基，芳基可以为苯基、萘基，或者由苯基衍生的取代苯基，取代苯基如C1～C5短链烷基取代苯基、C1～C5烷氧基取代苯基、卤素取代苯基、三氟甲基取代苯基或氰基取代苯基等。
本发明还提供了一种超声波辅助合成(Z)-β-硒氰酸酯基丙烯酸酯化合物的方法，该方法是在超声波作用下，生物质低共熔溶剂催化丙炔酸酯化合物、硫氰酸盐和水进行加成反应，合成(Z)-β-硒氰酸酯基丙烯酸酯化合物。
所述丙炔酸酯化合物具有式2结构；
其中，
R1选自H、C1～C10的烷基、卤素取代基、三氟甲基、C1～C10酯基或C2～C10的烯烃基；
R2选自C1～C10的烷基、含取代基的C1～C10的烷基或芳基。R2的具体选择范围如上式1。
优选的方案，所述生物质低共熔溶剂为氯化胆碱与乙醇酸组合。较优选的生物质低共熔溶剂由氯化胆碱与乙醇酸按摩尔比1:1～3组合。最优选为由氯化胆碱与乙醇酸按摩尔比1:2组合。而其他类似的生物质低共熔溶剂反应效果远远低于氯化胆碱/乙醇酸，如氯化胆碱/草酸(两者摩尔比1:2)，氯化胆碱/尿素(两者摩尔比1:2)，甜菜碱/乙醇酸(两者摩尔比1:2)等。本发明采用的生物质低共熔溶剂在反应中同时作为催化剂和反应介质。
优选的方案，丙炔酸酯化合物与硫氰酸钾、水及生物质低共熔溶剂的摩尔比为1:1～2:1～2:1～10。最优选的摩尔比为1:1.2:1:5。
优选的方案，所述加成反应的条件为：在室温下，超声功率为25～45W，超声频率为28KHz～80KHz，反应时间为15～40min。更进一步优选的超声功率为35W。更进一步优选的超声频率为40KHz。本发明在超声辅助下进行生物质低共熔溶剂催化丙炔酸酯化合物、硫氰酸盐和水进行加成反应，不仅可以在缩短反应时间，还能提升转化率。
本发明的硫氰酸盐可以为常见的硫氰酸钾、硫氰酸钠等易溶性盐。
本发明由丙炔酸酯化合物、硫氰酸盐和水进行加成反应的路线如下：
相对现有技术，本发明的技术方案带来的有益技术效果：
1)本发明首次由丙炔酸酯化合物与硫氰酸盐和水通过加成反应一步合成(Z)-β-硒氰酸酯基丙烯酸酯化合物。
2)本发明采用生物质低共熔溶剂作为反应介质和催化剂，易循环使用，环境友好，价格低廉；
3)本发明在室温条件下反应，条件温和；
4)本发明对丙炔酸酯化合物的选择性广，官能团兼容性好，易于各种基团修饰；
5)本发明使用超声波促进反应，在缩短反应时间的同时，提高反应产率。
6)本发明的(Z)-β-硒氰酸酯基丙烯酸酯化合物具有重要生理活性的硒氰酸官能团以及可修饰酯基和烯基，为药物及有机物合成提供重要的有机中间体。
附图说明
图1为ethyl(Z)-3-selenocyanatoacrylate的核磁氢谱图；
图2为ethyl(Z)-3-selenocyanatoacrylate的核磁碳谱图；
图3为2-hydroxyethyl(Z)-3-selenocyanatoacrylate的核磁氢谱图；
图4为2-hydroxyethyl(Z)-3-selenocyanatoacrylate的核磁碳谱图。
具体实施方式
以下具体实施例旨在进一步说明本发明内容，而不是限制本发明权利要求的保护范围。
对照实施例：
以下对照实验组1～30均按以下反应方程式反应：
具体操作步骤为：在10mL圆底烧瓶中，依次加入丙炔酸乙酯(1当量，0.3mmol)、硒氰酸钾、水，以及溶剂或者生物质低共熔溶剂，所得混合液在的超声反应装置中反应，或者搅拌反应。乙酸乙酯萃取反应物，最后，用旋转蒸发器浓缩滤液，用石油醚(PE)/乙酸乙酯(EA)作为洗脱剂，采用硅胶(200-300目筛)进行柱色谱纯化。
上表中实验组1～10考察了各种反应介质对丙炔酸乙酯、硒氰酸钾、水三组份加成反应的影响，从实验数据可以看出，在ChCl/glycolic acid介质中反应相对其他反应介质，可以明显提高三组份加成反应的效率。虽然在Betaine/glycolic acid、ChCl/oxalic acid等反应介质中共加成反应也能顺利进行，但是目标产物的收率并不理想。同时也可以看出，采用单一的ChCl或glycolic acid均达不到很好的共加成反应效果，两者之间存在明显的协同增效作用。
上表中实验组7、11及12考察了反应介质ChCl/glycolic acid中生物质酸和生物质碱摩尔比例对丙炔酸乙酯、硒氰酸钾、水三组份共加成反应的影响，通过实验表明ChCl/glycolic acid的最佳摩尔比例为1:2，过高或过低都会降低目标产物收率。
上表中实验组7、13及14考察了反应原料KSeCN用量对丙炔酸乙酯、硒氰酸钾、水三组份加成反应的影响，通过实验表明KSeCN的最佳摩尔用量为1.2当量，过高时目标产物的收率增加并不明显，而过低时，目标产物的收率降低明显。
上表中实验组7及15考察了反应原料水的用量对丙炔酸乙酯、硒氰酸钾、水三组份加成反应的影响，通过实验表明水的最佳摩尔用量为1当量，增加水的用量，目标产物的产率没有提高。
上表中实验组7、16及17考察了生物质低共熔溶剂用量对丙炔酸乙酯、硒氰酸钾、水三组份加成反应的影响，通过实验表明生物质低共熔溶剂的最佳摩尔用量为5当量；增加生物质低共熔溶剂的用量，目标产物的产率没有提高；当生物质低共熔溶剂用量低于5当量时，目标产物的收率降低明显。
上表中实验组18～22考察了超声辅助对对丙炔酸乙酯、硒氰酸钾、水共加成反应的影响，通过实验表明通过超声辅助反应，能够大大缩短反应时间，提高反应效率，特别是超声功率为35W/频率为40KHz时，共加成反应效果最佳，可以在较短时间内获得最佳的目标产物收率。
实施例1～22
以下实施例1～22均按以下反应方程式反应：
具体操作步骤为：在10mL圆底烧瓶中，依次加入炔酸酯(0.3mmol)、硒氰酸钾(1.2当量，0.36mmol，516mg)、水(1当量)，生物质低共熔溶剂ChCl/glycolic acid(5当量，1.5mmol)，所得混合液在35W/40KHz的超声反应装置中反应35分钟。乙酸乙酯萃取反应物，最后，用旋转蒸发器浓缩滤液，用石油醚(PE)/乙酸乙酯(EA)作为洗脱剂，采用硅胶(200-300目筛)进行柱色谱纯化。
实施例1
原料：
目标产物：
ethyl(Z)-3-selenocyanatoacrylate:Colorless oil.产率:93％.
1H NMR(400MHz,CDCl3)δ7.82(d,J＝8.4Hz,1H),6.62(t,J＝8.4Hz,1H),4.28(q,J＝7.2Hz,2H),1.33(t,J＝7.2Hz,3H).
13C NMR(100MHz,CDCl3)δ168.7,140.9,120.0,105.6,62.2,14.1.
HRMS Calcd(EI)m/z for C6H7NO2Se:[M]+204.9642,found:204.9638.
实施例2
原料：
目标产物：
methyl(Z)-3-selenocyanatoacrylate:Colorless oil.产率:94％.
H NMR(400MHz,CDCl3)δ7.85(d,J＝8.4Hz,1H),6.64(d,J＝8.4Hz,1H),3.84(s,3H).
13C NMR(100MHz,CDCl3)δ169.2,141.3,119.6,105.5,52.9.
HRMS Calcd(EI)m/z for C5H5NO2Se:[M]+190.9486,found:190.9485.
实施例3
原料：
目标产物：
tert-butyl(Z)-3-selenocyanatoacrylate:Colorless oil.产率:89％
1H NMR(400MHz,CDCl3)δ7.74(d,J＝8.4Hz,1H),6.54(d,J＝8.4Hz,1H),1.51(s,9H).
13C NMR(100MHz,CDCl3)δ168.2,139.4,121.5,106.2,83.5,28.0.
HRMS Calcd(EI)m/z for C8H11NO2Se:[M]+232.9955,found:232.9950.
实施例4
原料：
目标产物：
phenyl(Z)-3-selenocyanatoacrylate:Colorless oil.产率:91％
1H NMR(400MHz,CDCl3)δ8.05(d,J＝8.4Hz,1H),7.45–7.41(m,2H),7.32–7.28(m,1H),7.17–7.14(m,2H),6.88(d,J＝8.4Hz,1H).
13C NMR(100MHz,CDCl3)δ167.2,149.9,143.7,129.6,126.6,121.0,119.4,105.0.HRMS Calcd(EI)m/z for C10H7NO2Se:[M]+252.9642,found:252.9644.
实施例5
原料：
目标产物：
benzyl(Z)-3-selenocyanatoacrylate:Light yellow oil.产率:93％
1H NMR(400MHz,CDCl3)δ7.87(d,J＝8.4Hz,1H),7.41–7.37(m,5H),6.67(d,J＝8.4Hz,1H),5.25(s,2H).
13C NMR(100MHz,CDCl3)δ168.5,141.6,134.5,128.8,128.7,128.6,119.8,105.5,67.8.
HRMS Calcd(EI)m/z for C11H9NO2Se:[M]+266.9799,found:266.9793.
实施例6
原料：
目标产物：
cyclohexyl(Z)-3-selenocyanatoacrylate:White solid,m.p.68-70℃.产率:86％
1H NMR(400MHz,CDCl3)δ7.81(d,J＝8.4Hz,1H),7.61(d,J＝8.4Hz,1H),4.89–4.84(m,1H),1.92–1.88(m,2H),1.77–1.74(m,2H),1.50–1.27(m,6H).
13C NMR(100MHz,CDCl3)δ168.3,140.6,120.4,105.9,75.2,31.5,25.1,23.6.HRMSCalcd(EI)m/z for C10H13NO2Se:[M]+259.0112,found:259.0109.
实施例7
原料：
目标产物：
phenethyl(Z)-3-selenocyanatoacrylate:White solid,m.p.89-90℃.产率:86％
1H NMR(400MHz,CDCl3)δ7.81(d,J＝8.4Hz,1H),7.33–7.30(m,2H),7.27–7.20(m,3H),6.60(d,J＝8.4Hz,1H),4.43(t,J＝6.8Hz,2H),2.99(t,J＝6.8Hz,2H).13C NMR(100MHz,CDCl3)δ168.6,141.2,136.9,128.8,128.6,126.8,119.8,105.5,66.4,34.8.
HRMS Calcd(EI)m/z for C12H11NO2Se:[M]+280.9955,found:280.9949.
实施例8
原料：
目标产物：
2-hydroxyethyl(Z)-3-selenocyanatoacrylate(2h):Colorless oil.产率:81％
1H NMR(400MHz,CDCl3)δ7.89(d,J＝8.4Hz,1H),6.69(d,J＝8.4Hz,1H),4.37(t,J＝4.8Hz,2H),3.90(t,J＝4.8Hz,2H).
13C NMR(100MHz,CDCl3)δ168.8,142.0,119.6,105.3,67.4,60.7.
HRMS Calcd(EI)m/z for C6H7NO3Se:[M]+220.9591,found:220.9593.
实施例9
原料：
目标产物：
2-(benzyloxy)ethyl(Z)-3-selenocyanatoacrylate:White solid,m.p.102-104℃.
产率:90％
1H NMR(400MHz,CDCl3)δ7.86(d,J＝8.4Hz,1H),7.37–7.33(m,5H),6.68(d,J＝8.4Hz,1H),4.57(s,2H),4.40(t,J＝6.8Hz,2H),3.73(t,J＝6.8Hz,2H).13CNMR(100MHz,CDCl3)δ168.6,141.4,137.5,128.5,127.8,127.7,119.8,105.4,73.2,67.4,66.1.
HRMS Calcd(EI)m/z for C13H13NO3Se:[M]+311.0061,found:311.0055.
实施例10
原料：
目标产物：
2-cyanoethyl(Z)-3-selenocyanatoacrylate:Colorless oil.产率:92％
1H NMR(400MHz,CDCl3)δ7.94(d,J＝8.4Hz,1H),6.68(d,J＝8.4Hz,1H),4.42(t,J＝6.4Hz,2H),2.78(t,J＝6.4Hz,2H).
13C NMR(100MHz,CDCl3)δ167.8,143.0,119.0,116.3,104.8,60.0,17.8.
HRMS Calcd(EI)m/z for C7H6N2O2Se:[M]+229.9594,found:229.9591.
实施例11
原料：
目标产物：
2-bromoethyl(Z)-3-selenocyanatoacrylate:Light yellow oil.产率:89％
1H NMR(400MHz,CDCl3)δ7.91(d,J＝8.4Hz,1H),6.68(d,J＝8.4Hz,1H),4.52(t,J＝6.4Hz,2H),3.55(t,J＝6.4Hz,2H).
13C NMR(100MHz,CDCl3)δ168.0,142.3,119.4,105.1,65.1,27.8.
HRMS Calcd(EI)m/z for C6H6BrNO2Se:[M]+282.8747,found:282.8741.
实施例12
原料：
目标产物：
naphthalen-2-yl(Z)-3-selenocyanatoacrylate:White solid,m.p.123-124℃.产率:86％1H NMR(400MHz,CDCl3)δ8.08(d,J＝8.4Hz,2H),7.91–7.82(m,3H),7.64(d,J＝2.0Hz,1H),7.55–7.49(m,2H),7.29–7.26(m,1H),6.93(d,J＝8.4Hz,2H).
13C NMR(100MHz,CDCl3)δ167.4,147.5,143.9,133.5,131.7,129.8,127.8,127.7,126.9,126.2,120.2,119.4,118.3,105.0.
HRMS Calcd(EI)m/z for C14H9NO2Se:[M]+302.9799,found:302.9797.
实施例13
原料：
目标产物
furan-2-ylmethyl(Z)-3-selenocyanatoacrylate:Colorless oil.产率:90％
1H NMR(400MHz,CDCl3)δ7.87(d,J＝8.4Hz,1H),7.46–7.45(m,1H),6.64(d,J＝8.4Hz,1H),6.47(d,J＝3.2Hz,1H),6.40–6.38(m,1H),5.21(s,2H).
13C NMR(100MHz,CDCl3)δ168.2,148.1,143.7,141.8,119.6,111.7,110.7,105.3,59.3.
HRMS Calcd(EI)m/z for C9H7NO3Se:[M]+256.9591,found:256.9594.
实施例14
原料：
目标产物
thiophen-2-ylmethyl(Z)-3-selenocyanatoacrylate:Light yellow solid,m.p.85-86℃.产率:92％
1H NMR(400MHz,CDCl3)δ7.86(d,J＝8.4Hz,1H),7.36–7.33(m,2H),7.12–7.10(m,1H),6.65(d,J＝8.4Hz,1H),5.26(s,2H).
13C NMR(100MHz,CDCl3)δ168.4,141.6,135.3,127.6,126.6,125.4,119.8,105.4,62.6.
HRMS Calcd(EI)m/z for C9H7NO2SSe:[M]+272.9363,found:272.9359.
实施例15
原料：
目标产物
benzo[d][1,3]dioxol-5-yl(Z)-3-selenocyanatoacrylate:
White solid,m.p.95-97℃.产率:82％
1H NMR(400MHz,CDCl3)δ8.04(d,J＝8.4Hz,1H),6.84(d,J＝8.4Hz,1H),6.81(d,J＝8.4Hz,1H),6.66(d,J＝2.4Hz,1H),6.60(dd,J＝2.4,8.4Hz,1H),6.01(s,2H).
13C NMR(100MHz,CDCl3)δ167.6,148.2,146.0,144.1,143.9,119.3,113.5,108.1,105.0,103.1,101.9.
HRMS Calcd(EI)m/z for C11H7NO4Se:[M]+296.9540,found:296.9534.
实施例16
原料：
目标产物
cinnamyl(Z)-3-selenocyanatoacrylate:Colorless oil.产率:84％
1H NMR(400MHz,CDCl3)δ7.87(d,J＝8.4Hz,1H),7.42–7.29(m,5H),6.71(d,J＝16.0Hz,1H),6.67(d,J＝8.4Hz,1H),6.33–6.26(m,1H),4.88(dd,J＝1.2,6.8Hz,2H).
13C NMR(100MHz,CDCl3)δ168.5,141.5,135.7,135.6,128.7,128.4,126.7,121.6,119.8,105.5,66.7.
HRMS Calcd(EI)m/z for C13H11NO2Se:[M]+292.9955,found:292.9953.
实施例17
原料：
目标产物
(4-(prop-1-en-2-yl)cyclohex-1-en-1-yl)methyl(Z)-3-selenocyanatoacrylate:
Colorless oil.产率:82％
1H NMR(400MHz,CDCl3)δ7.84(d,J＝8.4Hz,1H),6.65(d,J＝8.4Hz,1H),5.82(s,1H),4.74–4.71(m,2H),4.61(s,2H),2.21–1.84(m,6H),1.74(s,3H),1.53–1.47(m,1H).
13C NMR(100MHz,CDCl3)δ168.7,149.3,141.2,131.6,127.5,119.9,108.9,105.6,70.1,40.6,30.4,27.2,26.3,20.7.
HRMS Calcd(EI)m/z for C14H17NO2Se:[M]+311.0425,found:311.0418.
实施例18
原料
目标产物:
(R)-2,5,7,8-tetramethyl-2-((4R,8R)-4,8,12-trimethyltridecyl)chroman-6-yl
(Z)-3-selenocyanatoacrylate:
White solid,m.p.105-107℃.产率:87％
1H NMR(400MHz,CDCl3)δ8.05(d,J＝8.4Hz,1H),6.95(d,J＝8.8Hz,1H),2.62–2.58(m,2H),2.10(s,3H),2.00(s,3H),1.96(s,3H),1.83–1.77(m,2H),1.55–1.50(m,2H),1.40–1.37(m,4H),1.29–1.24(m,11H),1.15–1.01(m,6H),0.88–0.84(m,13H).
13C NMR(100MHz,CDCl3)δ167.8,150.0,143.7,140.0,126.2,124.5,123.4,119.1,117.7,105.4,75.3,39.4,37.5,37.4,37.3,32.8,32.7,28.0,24.8,24.8,24.4,22.7,22.7,20.6,19.7,13.0,12.1,11.9.
HRMS Calcd(EI)m/z for C33H51NO3Se:[M]+589.3034,found:589.3031.
实施例19
原料：
目标产物:
ethyl(Z)-3-selenocyanatobut-2-enoate:Colorless oil.产率:79％
1H NMR(400MHz,CDCl3)δ6.38(d,J＝0.8Hz,1H),4.24(q,J＝7.2Hz,2H),2.62(d,J＝0.8Hz,3H),1.31(t,J＝7.2Hz,3H).
13C NMR(100MHz,CDCl3)δ168.2,152.0,117.3,104.6,61.8,27.3,14.1.
HRMS Calcd(EI)m/z for C7H9NO2Se:[M]+218.9799,found:218.9801.
实施例20
原料：
目标产物:
ethyl(E)-3-bromo-3-selenocyanatoacrylate:
White solid,m.p.131-133℃.产率:91％
1H NMR(400MHz,CDCl3)δ6.98(s,1H),4.27(q,J＝7.2Hz,2H),1.33(t,J＝7.2Hz,3H).
13C NMR(100MHz,CDCl3)δ167.8,126.5,124.6,105.3,62.4,14.0.
HRMS Calcd(EI)m/z for C6H6BrNO2Se:[M]+282.8747,found:282.8741.
实施例21
原料：
目标产物:
ethyl(Z)-4,4,4-trifluoro-3-selenocyanatobut-2-enoate:
Colorless oil.产率:86％
1H NMR(400MHz,CDCl3)δ6.97(s,1H),4.34(q,J＝7.2Hz,2H),1.36(t,J＝7.2Hz,3H).
13C NMR(100MHz,CDCl3)δ166.5,140.3(q,J＝36.0Hz),122.7(q,J＝6.0Hz),120.9(q,J＝273.0Hz),101.0,63.3,14.0.
19F NMR(376MHz,CDCl3)δ-62.0.
HRMS Calcd(EI)m/z for C7H6F3NO2Se:[M]+272.9516,found:272.9512.
实施例22
原料：
目标产物
diethyl 2-selenocyanatofumarate:White solid,m.p.82-83℃.产率:91％
1H NMR(400MHz,CDCl3)δ6.85(s,1H),4.38(q,J＝7.2Hz,2H),4.28(q,J＝7.2Hz,2H),1.39(t,J＝7.2Hz,3H),1.32(t,J＝7.2Hz,3H).
13C NMR(100MHz,CDCl3)δ167.1,163.0,143.0,122.9,102.8,63.7,62.7,14.0,13.8.HRMS Calcd(EI)m/z for C9H11NO4Se:[M]+276.9853,found:276.9851.
Claims (5)
1.一种超声波辅助合成(Z)-β-硒氰酸酯基丙烯酸酯化合物的方法，其特征在于：在超声波作用下，生物质低共熔溶剂催化丙炔酸酯化合物、硒氰酸盐和水进行加成反应，合成(Z)-β-硒氰酸酯基丙烯酸酯化合物；
所述生物质低共熔溶剂为氯化胆碱与乙醇酸组合；
所述(Z)-β-硒氰酸酯基丙烯酸酯化合物具有式1结构：
所述丙炔酸酯化合物具有式2结构；
其中，
R1选自H、C1～C10的烷基、卤素取代基、三氟甲基、C1～C10的酯基或C2～C10的烯烃基；
R2选自C1～C10的烷基、含取代基的C1～C10的烷基或芳基。
2.根据权利要求1所述的一种超声波辅助合成(Z)-β-硒氰酸酯基丙烯酸酯化合物的方法，其特征在于：
所述卤素取代基为氟、氯、溴或碘；
所述含取代基的C1～C10的烷基包含的取代基为羟基、氰基、卤素取代基、苯基或杂环基；
所述芳基为苯、萘，或含C1～C5的烷基、羟基、卤素、氰基或硝基取代基的苯基。
3.根据权利要求1所述的一种超声波辅助合成(Z)-β-硒氰酸酯基丙烯酸酯化合物的方法，其特征在于：所述生物质低共熔溶剂由氯化胆碱与乙醇酸按摩尔比1:1～3组合。
4.根据权利要求1～3任一项所述的一种超声波辅助合成(Z)-β-硒氰酸酯基丙烯酸酯化合物的方法，其特征在于：丙炔酸酯化合物与硒氰酸钾、水及生物质低共熔溶剂的摩尔比为1:1～2:1～2:1～10。
5.根据权利要求1～3任一项所述的一种超声波辅助合成(Z)-β-硒氰酸酯基丙烯酸酯化合物的方法，其特征在于：所述加成反应的条件为：在室温下，超声功率为25～45W，超声频率为28KHz～80KHz，反应时间为15～40min。
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