CN102001903A - Method for reducing carbon-carbon double bond by hydrazine hydrate through microwave - Google Patents
Method for reducing carbon-carbon double bond by hydrazine hydrate through microwave Download PDFInfo
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- CN102001903A CN102001903A CN2010105186634A CN201010518663A CN102001903A CN 102001903 A CN102001903 A CN 102001903A CN 2010105186634 A CN2010105186634 A CN 2010105186634A CN 201010518663 A CN201010518663 A CN 201010518663A CN 102001903 A CN102001903 A CN 102001903A
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- Prior art keywords
- carbon
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- water
- double bond
- hydrazine hydrate
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- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 title claims abstract description 26
- 239000011203 carbon fibre reinforced carbon Substances 0.000 title claims abstract description 26
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003262 carboxylic acid ester group Chemical group [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 claims description 4
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 125000000101 thioether group Chemical group 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 230000009467 reduction Effects 0.000 abstract description 31
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- 230000035484 reaction time Effects 0.000 abstract description 7
- 238000003912 environmental pollution Methods 0.000 abstract description 6
- 238000010438 heat treatment Methods 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 abstract description 4
- 238000010189 synthetic method Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 2
- 239000003638 chemical reducing agent Substances 0.000 abstract 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 38
- 238000006722 reduction reaction Methods 0.000 description 34
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 20
- 238000004821 distillation Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 230000002829 reductive effect Effects 0.000 description 9
- 238000003810 ethyl acetate extraction Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 238000005984 hydrogenation reaction Methods 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- 230000002194 synthesizing effect Effects 0.000 description 6
- 150000003949 imides Chemical class 0.000 description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 230000005855 radiation Effects 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- 150000003624 transition metals Chemical class 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- IXQGCWUGDFDQMF-UHFFFAOYSA-N 2-Ethylphenol Chemical compound CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 4
- XMIIGOLPHOKFCH-UHFFFAOYSA-N 3-phenylpropionic acid Chemical compound OC(=O)CCC1=CC=CC=C1 XMIIGOLPHOKFCH-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000001143 conditioned effect Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000006317 isomerization reaction Methods 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- RWFHJEVTRVSDNX-UHFFFAOYSA-N phenol;propanoic acid Chemical compound CCC(O)=O.OC1=CC=CC=C1 RWFHJEVTRVSDNX-UHFFFAOYSA-N 0.000 description 4
- SNZXFRFQGXSSGN-UHFFFAOYSA-N phenylsulfanyloxysulfanylbenzene Chemical compound C=1C=CC=CC=1SOSC1=CC=CC=C1 SNZXFRFQGXSSGN-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 3
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- ZQPPMHVWECSIRJ-MDZDMXLPSA-N elaidic acid Chemical compound CCCCCCCC\C=C\CCCCCCCC(O)=O ZQPPMHVWECSIRJ-MDZDMXLPSA-N 0.000 description 3
- -1 hydrazine-hydrazine sodium Chemical compound 0.000 description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 3
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- AQNDDEOPVVGCPG-UHFFFAOYSA-N esmolol Chemical compound COC(=O)CCC1=CC=C(OCC(O)CNC(C)C)C=C1 AQNDDEOPVVGCPG-UHFFFAOYSA-N 0.000 description 2
- 229960003745 esmolol Drugs 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- DZIQUZJSNSZOCH-UHFFFAOYSA-N methyl 2-phenylpropanoate Chemical class COC(=O)C(C)C1=CC=CC=C1 DZIQUZJSNSZOCH-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229960003742 phenol Drugs 0.000 description 2
- UAGIUNHUUPYKPA-UHFFFAOYSA-N phenol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC1=CC=CC=C1 UAGIUNHUUPYKPA-UHFFFAOYSA-N 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000001384 succinic acid Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- CUXYLFPMQMFGPL-UHFFFAOYSA-N (9Z,11E,13E)-9,11,13-Octadecatrienoic acid Natural products CCCCC=CC=CC=CCCCCCCCC(O)=O CUXYLFPMQMFGPL-UHFFFAOYSA-N 0.000 description 1
- NQBWNECTZUOWID-UHFFFAOYSA-N (E)-cinnamyl (E)-cinnamate Natural products C=1C=CC=CC=1C=CC(=O)OCC=CC1=CC=CC=C1 NQBWNECTZUOWID-UHFFFAOYSA-N 0.000 description 1
- NWEGQRHHMGZCHN-UHFFFAOYSA-N 1,3-dinitro-1,3-diphenylpropan-2-one Chemical compound [N+](=O)([O-])C(C1=CC=CC=C1)C(=O)C([N+](=O)[O-])C1=CC=CC=C1 NWEGQRHHMGZCHN-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000006908 Julia-Kocienski olefination reaction Methods 0.000 description 1
- 238000006000 Knoevenagel condensation reaction Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 238000005644 Wolff-Kishner reduction reaction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000005575 aldol reaction Methods 0.000 description 1
- 238000005865 alkene metathesis reaction Methods 0.000 description 1
- CUXYLFPMQMFGPL-SUTYWZMXSA-N all-trans-octadeca-9,11,13-trienoic acid Chemical compound CCCC\C=C\C=C\C=C\CCCCCCCC(O)=O CUXYLFPMQMFGPL-SUTYWZMXSA-N 0.000 description 1
- 125000000746 allylic group Chemical group 0.000 description 1
- 238000009876 asymmetric hydrogenation reaction Methods 0.000 description 1
- NWCHELUCVWSRRS-UHFFFAOYSA-N atrolactic acid Chemical compound OC(=O)C(O)(C)C1=CC=CC=C1 NWCHELUCVWSRRS-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001743 benzylic group Chemical group 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- NQBWNECTZUOWID-QSYVVUFSSA-N cinnamyl cinnamate Chemical compound C=1C=CC=CC=1\C=C/C(=O)OC\C=C\C1=CC=CC=C1 NQBWNECTZUOWID-QSYVVUFSSA-N 0.000 description 1
- 238000006352 cycloaddition reaction Methods 0.000 description 1
- NMGSDTSOSIPXTN-UHFFFAOYSA-N cyclohexa-1,2-diene Chemical compound C1CC=C=CC1 NMGSDTSOSIPXTN-UHFFFAOYSA-N 0.000 description 1
- UVJHQYIOXKWHFD-UHFFFAOYSA-N cyclohexa-1,4-diene Chemical compound C1C=CCC=C1 UVJHQYIOXKWHFD-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- GQTXKEVAUZYHGE-UHFFFAOYSA-N methyl 2-phenylprop-2-enoate Chemical class COC(=O)C(=C)C1=CC=CC=C1 GQTXKEVAUZYHGE-UHFFFAOYSA-N 0.000 description 1
- 238000007144 microwave assisted synthesis reaction Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 1
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 description 1
- 239000001230 potassium iodate Substances 0.000 description 1
- 229940093930 potassium iodate Drugs 0.000 description 1
- 235000006666 potassium iodate Nutrition 0.000 description 1
- POSICDHOUBKJKP-UHFFFAOYSA-N prop-2-enoxybenzene Chemical compound C=CCOC1=CC=CC=C1 POSICDHOUBKJKP-UHFFFAOYSA-N 0.000 description 1
- QGNRLAFFKKBSIM-UHFFFAOYSA-N prop-2-enylsulfanylbenzene Chemical compound C=CCSC1=CC=CC=C1 QGNRLAFFKKBSIM-UHFFFAOYSA-N 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000006340 racemization Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000006561 solvent free reaction Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 150000005671 trienes Chemical class 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及一类碳碳双键化合物还原制备相应碳碳单键化合物的合成新方法。采用水合肼作为还原剂，用水或水-乙醇混合溶液做溶剂，微波加热还原碳碳双键工艺，使制备产品纯度达到95%以上，收率达到90%以上。本发明的合成工艺可缩短反应时间、提高反应收率及产品纯度、节约能源、减少环境污染，降低反应成本，在实验室小量合成及工业合成上有较高的应用价值。The invention relates to a novel synthetic method for preparing corresponding carbon-carbon single bond compounds by reduction of a class of carbon-carbon double bond compounds. Hydrazine hydrate is used as reducing agent, water or water-ethanol mixed solution is used as solvent, and microwave heating is used to reduce carbon-carbon double bonds, so that the purity of the prepared product can reach more than 95%, and the yield can reach more than 90%. The synthesis process of the invention can shorten reaction time, increase reaction yield and product purity, save energy, reduce environmental pollution, and reduce reaction cost, and has high application value in laboratory small-scale synthesis and industrial synthesis.
Description
Technical field
The present invention relates to a kind of carbon-carbon double bond that reduces and prepare the synthetic method of carbon-carbon single bond compound, belong to the organic synthesis field.
Background technology
Since Vanderhoff in 1969 applied microwave radiotechnology in organic synthesis first, had very big development through the technology of the development microwave radiation catalytic synthesis of organic substance of decades.Compare with traditional synthetic method, microwave-assisted synthesis can make the reaction times obviously shorten, and reduces environmental pollution, improves reaction yield, simplifies post-processing step.Can reduce cost in many cases, obtain energy-conservation, consumption reduction and the benefit that reduces discharging.Present under the situation that the mechanism of microwave radiation promotion chemical reaction it be unclear that, microwave irradiation just progressively forms a subject---microwave chemical.Be described as the organic chemistry of 21 century, huge development prospect arranged in the organic synthesis field.
The reduction of carbon-carbon double bond is the important reaction of a class in the organic synthesis.In organic synthesis, usually adopt some reaction to form carbon-carbon double bond, obtain the product of corresponding carbon-carbon single bond again by the certain method reduction, reach the purpose that prolongs carbochain.Some even employing asymmetry catalysis reductive method obtain the hand-type product and reach synthetic purpose.The method of the formation carbon-carbon double bond that has existed comprises: Witting reaction and relevant reaction thereof, Julia-Kocienski reaction, Ramberg-
Reaction, aldol reaction, Knoevenagel reaction, and nearest olefin metathesis reaction and allyl substitution reaction.These reactions have brought unlimited possibility for the reduction reaction of carbon-carbon double bond.
The reduction carbon-carbon double bond uses hydrogen and out-phase transition metal-catalyzed usually, such as: Rh/C, Pd/C, Raney Ni, Adams catalyzer (PtO
2).Another kind is to adopt the homogeneous transition metal complex compound, such as the Wilkinson catalyzer.Most of asymmetric hydrogenations are by the homogeneous catalyst catalyzed reaction.
Though these hydrogenations by the transition metal mediation are very efficient, have very big shortcoming.When using heterogeneous catalyst catalytic reduction benzylic, allylic, when the alcohols of propargyl and aminated compounds, usually invalid.(Wilkinson，H.S.；Hett，R.；Tanoury，G.J.；Senanayake，C.H.；Wald，S.A.Org.Proc.Res.DeV.2000，4，567-570)。When compound has corresponding C bz and Alloc protecting group, can not be with hydrogenation hydrogenation (Galletti, the A.M.R. of transition metal mediation; Bonaccorsi, F.; Calvani, F.; Di Bugno, C.Catal.Commun.2006,7,896-900).And some are similar to nitro, benzyl ketone, and the functional group of fragrant halogen also can very fast being reduced in such reduction system.
Hydrogenation for homogeneous phase and the mediation of heterogeneous transition metal has a very common shortcoming not obtain enough concerns---double-bond isomerization side reaction ((a) Nakai, T.; Yajima, A.; Akasaka, K.; Kaihoku, T.; Ohtaki, M.; Nukada, T.; Ohrui, H.; Yabuta, G.Biosci.Biotechnol.Biochem.2005,69,2401-2408. (b) Schwartz, B.D.; Hayes, P.Y.; Kitching, W.; De Voss, J.J.J.Org.Chem.2005,70,3054-3065. (c) Rakoff, H.; Rohwedder, W.K.Lipids 1992,27,567-569).These double bond isomerization reactions can cause stereoisomers, the racemization of open loopization and more difficult detection.
Except that transition metal-catalyzed reduction, some other method of reducing are also arranged, wherein a kind of for using hydrazine reduction carbon-carbon double bond.Hydrazine at first becomes imide in reaction, imide has avoided reduction to be similar to the two keys of the such polarization of carbonyl or the like by cycloaddition mechanism hydro-reduction carbon-carbon double bond, also can not cause double-bond isomerization.Be a kind of gentleness, the reduction reaction that selectivity is very high.(Pasto，D.J.；Taylor，R.T.Reductions?with?Diimide?in?Organic?Reactions；V?Paquette?L.A.，Ed.；J.Wiley&Sons：New?York，1991；40，91-150)。Because hydrazine can form more stable hydrazine hydrate in water, that sells on the market mostly is the hydrazine hydrate reagent of (40%～80% mass concentration) as reductive reagent hydrazine.Hereinafter be expressed as the hydrazine hydrate that can be regarded as of hydrazine.
Need become imide during hydrazine reduction carbon-carbon double bond, usually need the existence of oxygenant in this process.Hydrazine-the oxidizer systems that has now had is respectively: (1) hydrazine-oxygen system; (2) hydrazine-oxidizer systems, oxygenant commonly used are hydrogen peroxide, Potassium Iodate and potassium bichromate etc.; (3) hydrazine-oxygen-cupric ion system and hydrazine-oxygenant-cupric ion system.Having does not need the hydrazine of oxygenant restoring system report yet, such as: hydrazine-hydrogenation catalyst system, hydrazine-hydrazine sodium system etc.(Zhong Tongsheng etc., the hydrazine utilization in organic synthesis, chemistry circular, 1964,11,39-41) its reaction mechanism is not an imide ring addition hydrogenation mechanism, has the shortcoming of our above-mentioned common reduction reaction.
For hydrazine-oxygen system, the Falciola hydrazine hydrate, uncovered reactor hydrogenation becomes stearic acid to obtain better yield along oleic acid and elaidic acid.(P.Falciola，et?al，Ann.Chim.Appl.1914，2，351；Chem.Zntn，I，1917，926.P.Falciola，et?al，Gazz，Chem.Ital，1920，50，162；Chem.Zntn，III，1920，276)。1956, Aylward used the same method reduction is contained one, and the oleic acid of two two keys is extended for the eleostearic acid (F, Aylward, et al, ibid, 1957,7,137) that reduction contains conjugated triene.It is required long reaction time that these class methods have a bigger shortcoming, reduction efficiency low (about 70%), and practicality is not high.
Hydrazine-oxidizer systems, hydrazine-oxygen-cupric ion system and hydrazine-oxygenant-cupric ion system, the time that responds is short, the reduction efficiency advantages of higher, but have problems such as heavy metal environmental pollution, aftertreatment complexity, production cost height.
Utilization microwave heating hydrazine reductive report has as follows in the existing documents and materials: calendar year 2001 Andr á s Vass etc. has reported that the hydrazine of utilization aluminum oxide support uses method (the Andr á s Vass et al of solvent-free reaction nitro compound reducing under microwave condition, Tetrahedron Letters, 2001,42,5347-5349).E Parquet in 1997 etc. have reported that utilization microwave heating promotes Wolff-Kishner reductive research (E Parquet et al, Journal ofChemical Education, 1997,74,1225).The complex compound of microwave heating hydrazine hydrate and zinc prepare nano zine oxide (D.K.Bhat, Nanoscale Res Lett, 2008,3,31-35).Have in the materials chemistry in recent years the report that uses carry out microwave radiation heating hydrazine hydrate, reduction-oxidation graphite to make Graphene (SuniinPark, Nature Nanotechnology, 2009,4,217-224).
Use microwave radiation, hydrazine reduction carbon-carbon double bond organic compound makes the report of carbon-carbon single bond organic compound and does not see.With respect to using transition metal, single hydrazine reducing environment of using is polluted still less, and more cheap, aftertreatment is simpler, the intact hydrazine of unreacted can be removed by the method that bubbling air makes it to become the nitrogen G﹠W, is the reductive agent (corresponding Green Chemistry oxygenant is a hydrogen peroxide) of Green Chemistry first-selection.And add thermal reduction with respect to hydrazine, and microwave hydrazine reduction required time is shorter, reduction efficiency is higher, and energy consumption still less meets low-carbon economy, the practicality height.More and more receive the concern of the public and government at modern environment, and chemical industry is received very big social pressures as a big source of polluting, this wherein has many-sided reason but makes water can reduce pollution greatly as reaction solvent, and since water be easy to get cheaply can be bigger increase economic efficiency, be the solvent that compound probability is dreamed of.Helpless most reaction can't be used water as solvent, has influenced the development of chemical industry.The reaction of water as solvent has in recent years caused that scientific circles and industry member pay close attention to widely.International magazine Chem.Review goes up even has occurred the summary of water as solvent reaction! This patent adopts water as solvent as far as possible, regulates its solubleness until dissolving for insoluble compound in water with ethanol.Adopt microwave heating to promote reduction, have environmental friendliness, reaction temperature and, characteristics such as economic worth height.
Summary of the invention
Technical problem to be solved by this invention is at the deficiencies in the prior art, and a kind of selectivity height is provided, and the while is the method for reducing of carbon-carbon double bond efficiently.
Concrete technical scheme of the present invention is: add the carbon-carbon double bond compound R in uncovered reaction vessel
1R
2CCHR
3, solvent, hydrazine hydrate, under the microwave condition, 65～95 ℃ of reaction 10～60min.
Reaction formula is as follows:
R
1, R
2Be aryl independently, phenol aryl, alkyl, pure alkyl, ether, thioether group, carboxylic acid group, carboxylic acid ester groups or hydrogen; R
3Be hydrogen, carboxylic acid group or carboxylic acid ester groups.
Further,
Solvent is the mixed solvent of water or second alcohol and water, and in the mixed solvent of second alcohol and water, the volume ratio of second alcohol and water is 2: 1～1: 20.
Solvent adding amount is with every mole of carbon-carbon double bond compound 1000～2500ml.
The consumption of hydrazine hydrate is 4～8 times of molar weights of carbon-carbon double bond compound.
The hydrazine hydrate specification is the hydrazine hydrate of 40～100wt% concentration.
Microwave power is 400W～1200W.
Whether the aftertreatment purification process is dissolved in solvent and difference by product.(1) be dissolved in solvent: water-alcohol mixeding liquid is made solvent, and ethanol is removed in first underpressure distillation, and adding hydrochloric acid again, to transfer pH be 1～4; The hydrochloric acid that directly adds that uses water as solvent is transferred pH to 1～4, uses ethyl acetate extraction again, last fractionation or recrystallization, and vacuum-drying gets product.(2) be insoluble to solvent, can adding hydrochloric acid, to transfer pH be 1～4, filters, and vacuum-drying gets product.
The method utilization solvent and the airborne dioxygen oxidation hydrazine of the utilization microwave hydrazine reduction carbon-carbon double bond of this patent report, microwave radiation itself also can promote the decomposition of hydrazine, become reducing compounds such as imide, improved reduction and renderd a service, reduced the reduction required time, avoided side reaction, reduced environmental pollution and advantages such as post-treating method is simple are arranged.Water or alcohol-water mixing solutions are made solvent, and aftertreatment is simple, and is pollution-free, economy.In sum, the present invention has following beneficial effect: shortening reaction times, raising reaction yield and product purity, save energy, minimizing environmental pollution, reduce reaction cost.
In order to set forth using value of the present invention and superiority better, existing synthetic explanation as an example with esmolol intermediate para hydroxybenzene propionic acid.
The synthetic common method of para hydroxybenzene propionic acid is: palladium carbon hydrogenating reduction (PCT Int.Appl.2008147553.04Dec2008).Raney Ni adds the hydrogen reduction.Produce hydrogen and directly do not feed hydrogen with highly basic and hydrazine, add Raney Ni reduction (Zou Pei etc., contemporary Chinese is used pharmaceutical journal, 1999,16,6).Have recently the report that uses 1 palladium carbon microwave reduction (JohnF Quinn et al.Tetrahedron Letters, 2008,49,6137-6140).These method of reducing use metal as catalyzer without exception, and shortcomings such as isomerization that we say previously and environmental pollution are arranged.Simultaneously because solvent how with organic solvent reaction cost height such as alcohol, pollutes big.And adopt hydrogen to do to go back that original reagent need pressurize and special reaction unit has risk of explosion.
The present invention adopts hydrazine hydrate to make reductive agent, water as solvent, the reduction paired hydroxy phenylpropionic acid of p-hydroxybenzene vinylformic acid (seeing embodiment 1), with respect to 1,4-cyclohexadiene palladium carbon microwave reduction (reaction times 5min) is though many 10min of reaction times, but avoided using 1 of costliness, the 4-cyclohexadiene, palladium metal, organic solvent.Superiority in the environmental protection is arranged economically.There is the tangible reaction times short with respect to other three kinds of method of reducing equally, the productive rate height, good in economic efficiency, environment protection, advantages such as convenient post-treatment.Be a kind of advanced person, practical reduction mode.
Embodiment:
Further introduce the present invention by following embodiment, but do not limit protection scope of the present invention.
Embodiment 1
Synthesizing of esmolol intermediate para hydroxybenzene propionic acid: adding p-hydroxybenzene vinylformic acid in microwave reactor (1g, 6.05mmol), distilled water (6mL), (reconcile temperature of reaction is 80 ℃ to the 80wt% hydrazine hydrate for 3.05g, 48.4mmol) vigorous stirring, microwave power is 600W, reaction 15min.Reaction finish to wait for that system temperature reduces to room temperature, and the cryosel acid for adjusting pH that adds 2mol/L is 1, leaves standstill, filter white solid, get distilled water and clean solid (2mL * 2), vacuum-drying, product para hydroxybenzene propionic acid (0.915g, 5.51mmol).Productive rate 91%, purity 98%.Fusing point 126-130 ℃,
1H NMR (400MHz, DMSO) δ 9.33 (s, 1H), 7.04 (d, J=8.5Hz, 2H), 6.70 (d, J=8.5Hz, 2H), 2.74 (t, J=7.6Hz, 2H), 2.49 (t, J=7.6Hz, 2H).
Embodiment 2
Succinic Acid synthetic: in microwave reactor, add maleic acid (1g, 8.62mmol), water (20mL), (reconcile temperature of reaction is 65 ℃ to the 40wt% hydrazine hydrate for 4.32g, 34.5mmol) vigorous stirring, and microwave power is 400W, reaction 10min.Reaction finishes the wait system temperature and reduces to room temperature, and the hydrochloric acid adjusting pH that adds 2mol/L is 1, ethyl acetate extraction 3 times (25ml * 3), anhydrous sodium sulfate drying 2h, ethyl acetate is removed in underpressure distillation, vacuum-drying, the product Succinic Acid (0.916g, 7.76mmol).Productive rate 90%, purity 95%
1H NMR (400MHz, CDCl
3) δ 1.35 (t, J=6.9Hz, 4H).
Embodiment 3
Synthesizing of 3-phenylpropionic acid formicester: adding styracin formicester in microwave reactor (1g, 6.17mmol), distilled water and alcohol mixeding liquid (1: 1,6mL), 80wt% hydrazine hydrate (3.09g, 49.4mmol) vigorous stirring, reconciling temperature of reaction is 70 ℃, and microwave power is 600W, reaction 20min.Reaction finishes the wait system temperature and reduces to room temperature, and ethanol is removed in underpressure distillation, and the hydrochloric acid adjusting pH that adds 2mol/L is 4, ethyl acetate extraction 3 times (15mL * 3), anhydrous sodium sulfate drying 2h, ethyl acetate is removed in underpressure distillation, product 3-phenylpropionic acid formicester (0.973g, 5.92mmol).Productive rate 96%, purity 97%.
1HNMR(400MHz，CDCl
3)δ7.21(dd，J＝13.3，6.0Hz，3H)，7.13(t，J＝6.2Hz，3H)，3.59(s，3H)，2.90-2.85(m，2H)，2.56(t，J＝7.9Hz，2H)。
Embodiment 4
Synthesizing of 2-phenylpropionic acid methyl esters: adding 2-phenylacrylic acid methyl esters in microwave reactor (1g, 6.2mmol), alcohol-water (1: 1,6mL), 80wt% hydrazine hydrate (3.08g, 49.3mmol) vigorous stirring, reconciling temperature of reaction is 70 ℃, and microwave power is 600W, reaction 20min.Reaction finishes the wait system temperature and reduces to room temperature, and ethanol is removed in underpressure distillation, and the hydrochloric acid adjusting pH that adds 2mol/L is 4, ethyl acetate extraction 3 times (15ml * 3), anhydrous sodium sulfate drying 2h, ethyl acetate is removed in underpressure distillation, product 2-phenylpropionic acid methyl esters (0.947g, 5.77mmol).Productive rate 93%, purity 98%.
1HNMR?(400MHz，CDCl
3)δ7.23±7.35(m，5H)，3.72(q，J＝7.2Hz，1H)，3.65(s，3H)，1.50(d，J＝7.2Hz，3H)。
Embodiment 5
Synthesizing of 2-ethylphenol: adding 2-phenol ethylene in microwave reactor (1g, 7.45mmol), alcohol-water (1: 20,6ml), 100wt% hydrazine hydrate (2.98g, 59.6mmol) vigorous stirring, the conditioned reaction temperature is 95 ℃, and microwave power is 1200W, reaction 60min.Reaction finishes the wait system temperature and reduces to room temperature, and ethanol is removed in underpressure distillation, and the hydrochloric acid accent pH that adds 2mol/L is 3, ethyl acetate extraction 3 times (15ml * 3), anhydrous sodium sulfate drying 2h, ethyl acetate is removed in underpressure distillation, product 2-ethylphenol (0.994g, 7.30mmol).Productive rate 98%, purity 98%.
1H?NMR(400MHz，CDCl
3)δ7.01(dd，J＝7.4，1.4Hz，1H)，6.93(td，J＝7.7，1.7Hz，1H)，6.71(ddd，J＝12.6，9.5，4.4Hz，2H)，6.29(s，1H)，2.53-2.46(m，2H)，1.61-1.49(m，2H)，0.87(t，J＝7.4Hz，3H)。
Embodiment 6
Synthesizing of propyl group phenyl thioether: adding allyl phenyl thioether in microwave reactor (1g, 6.66mmol), alcohol-water (1: 1,6ml), 80wt% hydrazine hydrate (3.33g, 53.2mmol) vigorous stirring, the conditioned reaction temperature is 85 ℃, and microwave power is 800W, reaction 30min.Reaction finishes the wait system temperature and reduces to room temperature, ethanol is removed in underpressure distillation, the hydrochloric acid accent pH that adds 2mol/L is 3, ethyl acetate extraction 3 times (15ml * 3), anhydrous sodium sulfate drying 2h, ethyl acetate is removed in underpressure distillation, vacuum-drying, product propyl group phenyl thioether (0.943g, 6.19mmol).Productive rate 93%, purity 96%.
1H?NMR?(400MHz，CDCl
3)δ7.22～7.34(m，4H)，7.10～7.19(m，1H)，2.89(t，J＝7.3Hz，2H)，1.66(tq，J＝7.4，7.3Hz，2H)，1.01(t，J＝7.4Hz，3H)
Embodiment 7
Propyl group phenyl ether synthetic: in microwave reactor, add allyl phenyl ether (1g, 7.45mmol), alcohol-water (2: 1,6ml), 80wt% hydrazine hydrate (3.73g, 59.6mmol) vigorous stirring, the conditioned reaction temperature is 85 ℃, and microwave power is 800W, reaction 30min.Reaction finishes the wait system temperature and reduces to room temperature, ethanol is removed in underpressure distillation, the hydrochloric acid accent pH that adds 2mol/L is 3, ethyl acetate extraction 3 times (15ml * 3), anhydrous sodium sulfate drying 2h, ethyl acetate is removed in underpressure distillation, vacuum-drying, product propyl group phenyl thioether (0.954g, 7.00mmol).Productive rate 94%, purity 96%.
1H?NMR?(400MHz，CDCl
3)δ7.20～7.35(m，5H)，4.49(s，2H)，3.42(t，J＝6.8Hz，2H)，1.63(tq，J＝6.8，7.4Hz，2H)，0.94(t，J＝7.4Hz，3H)
Embodiment 8
Synthesizing of 1-phenyl-1-propyl alcohol: adding 1-phenyl-2-alkene-1-propyl alcohol in microwave reactor (1g, 7.45mmol), alcohol-water (1: 10,6ml), 80wt% hydrazine hydrate (3.73g, 59.6mmol) vigorous stirring, the conditioned reaction temperature is 95 ℃, and microwave power is 1000W, reaction 30min.Reaction finishes the wait system temperature and reduces to room temperature, and the hydrochloric acid accent pH that adds 2mol/L is 4, ethyl acetate extraction 3 times (15ml * 3), anhydrous sodium sulfate drying 2h, ethyl acetate is removed in underpressure distillation, vacuum-drying, product propyl group phenyl thioether (0.923g, 6.78mmol).Productive rate 91%, purity 96%.
1H?NMR(400MHz，CDCl
3)δ7.23～7.35(m，5H)，4.58(t，J＝6.6Hz，1H)，2.71(s，1H)，1.64～1.92(m，2H)，0.90(t，J＝7.4Hz，3H)
Claims (7)
1. the method for reducing of a carbon-carbon double bond is characterized by: add the carbon-carbon double bond compound R in uncovered reaction vessel
1R
2CCHR
3, solvent, hydrazine hydrate, under the microwave condition, 65 ~ 95
OCReaction 10 ~ 60min, wherein R
1, R
2Be aryl independently, phenol aryl, alkyl, pure alkyl, ether, thioether group, carboxylic acid group, carboxylic acid ester groups or hydrogen; R
3Be hydrogen, carboxylic acid group or carboxylic acid ester groups.
2. method according to claim 1 is characterized in that described solvent is the mixture of water or second alcohol and water.
3. method according to claim 2 is characterized in that in the mixed solvent of second alcohol and water that the volume ratio of second alcohol and water is 2:1 ~ 1:20.
4. method according to claim 1 and 2, the consumption that it is characterized in that hydrazine hydrate are 4 ~ 8 times of molar weights of carbon-carbon double bond compound.
5. method according to claim 1 and 2 is characterized in that solvent adding amount is every mole of carbon-carbon double bond compound 1000 ~ 2500ml.
6. method according to claim 1 and 2 is characterized in that described hydrazine hydrate is the hydrazine hydrate of 40 ~ 100wt% concentration.
7. method according to claim 1 and 2 is characterized in that microwave power is 400W ~ 1200W.
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