CN102001903B - 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
- Publication number
- CN102001903B CN102001903B CN 201010518663 CN201010518663A CN102001903B CN 102001903 B CN102001903 B CN 102001903B CN 201010518663 CN201010518663 CN 201010518663 CN 201010518663 A CN201010518663 A CN 201010518663A CN 102001903 B CN102001903 B CN 102001903B
- Authority
- CN
- China
- Prior art keywords
- carbon
- reaction
- microwave
- hydrazine
- reduction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 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 23
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000011203 carbon fibre reinforced carbon Substances 0.000 title abstract description 25
- 238000000034 method Methods 0.000 title abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000003756 stirring Methods 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 8
- RWFHJEVTRVSDNX-UHFFFAOYSA-N phenol;propanoic acid Chemical compound CCC(O)=O.OC1=CC=CC=C1 RWFHJEVTRVSDNX-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 4
- UAGIUNHUUPYKPA-UHFFFAOYSA-N phenol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC1=CC=CC=C1 UAGIUNHUUPYKPA-UHFFFAOYSA-N 0.000 claims description 3
- 238000010189 synthetic method Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 abstract description 18
- 150000001875 compounds Chemical class 0.000 abstract description 14
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 230000035484 reaction time Effects 0.000 abstract description 7
- 238000010438 heat treatment Methods 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 2
- 239000003638 chemical reducing agent Substances 0.000 abstract 1
- 239000000203 mixture 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 37
- 230000009467 reduction Effects 0.000 description 33
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 238000004821 distillation Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 238000003810 ethyl acetate extraction Methods 0.000 description 8
- 230000002194 synthesizing effect Effects 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
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 238000005984 hydrogenation reaction Methods 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 150000003949 imides Chemical class 0.000 description 5
- 230000005855 radiation Effects 0.000 description 5
- 230000002829 reductive effect 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
- 230000007613 environmental effect Effects 0.000 description 4
- 238000006317 isomerization reaction Methods 0.000 description 4
- 230000007246 mechanism Effects 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
- ZQPPMHVWECSIRJ-MDZDMXLPSA-N elaidic acid Chemical compound CCCCCCCC\C=C\CCCCCCCC(O)=O ZQPPMHVWECSIRJ-MDZDMXLPSA-N 0.000 description 3
- 238000003912 environmental pollution Methods 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
- 150000003839 salts Chemical class 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003262 carboxylic acid ester group Chemical group [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- UVJHQYIOXKWHFD-UHFFFAOYSA-N cyclohexa-1,4-diene Chemical compound C1C=CCC=C1 UVJHQYIOXKWHFD-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 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
- -1 hydrazine-hydrazine sodium Chemical compound 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
- 239000012046 mixed solvent Substances 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
- 238000007086 side reaction Methods 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
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 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
- DYUQAZSOFZSPHD-UHFFFAOYSA-N Phenylpropanol Chemical compound CCC(O)C1=CC=CC=C1 DYUQAZSOFZSPHD-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
- 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
- 125000003118 aryl 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
- 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
- CCRCUPLGCSFEDV-UHFFFAOYSA-N cinnamic acid methyl ester Natural products COC(=O)C=CC1=CC=CC=C1 CCRCUPLGCSFEDV-UHFFFAOYSA-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
- 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
- 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
- 150000002431 hydrogen Chemical class 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
- CCRCUPLGCSFEDV-BQYQJAHWSA-N methyl trans-cinnamate Chemical compound COC(=O)\C=C\C1=CC=CC=C1 CCRCUPLGCSFEDV-BQYQJAHWSA-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
- 238000002360 preparation method Methods 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
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 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
- 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
- 125000000101 thioether group Chemical group 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
The invention relates to a novel synchronizing method for preparing a corresponding carbon-carbon single-bond compound by reducing a carbon-carbon double-bond compound. The carbon-carbon single-bond compound is prepared by adopting hydrazine hydrate as a reducing agent and using water or water-alcohol mixture solution as a solvent through a microwave heating carbon-carbon double-bond reducing process, wherein the purity of the carbon-carbon single-bond compound is above 95 percent and the yield reaches above 90 percent. The synchronizing method can shorten the reaction time, improve the reaction yield and the product purity, save energy sources, reduce environment pollution and lower the reaction cost, and has higher application value on the small quantity synthesis and industrial synthesis in a laboratory.
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 large 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 environmental contamination reduction 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 in 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, in the organic synthesis field huge development prospect arranged.
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 again the product of corresponding carbon-carbon single bond by certain method reduction, reach the purpose that prolongs carbochain.Some even the method that adopts asymmetry catalysis to reduce 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 to 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.
Although these hydrogenations by the transition metal mediation are very efficient, have very large 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 Cbz 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 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 etc. by cycloaddition mechanism hydro-reduction carbon-carbon double bond, also can not cause double-bond isomerization.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, the reagent hydrazine as reduction of selling on the market mostly is the hydrazine hydrate reagent of (40%～80% mass concentration).Hereinafter be expressed as the hydrazine hydrate that can be regarded as of hydrazine.
Need to 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, the chemistry circular, 1964,11,39-41) its reaction mechanism is not 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 larger 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 the heavy metal environmental pollution, aftertreatment is complicated, the problems such as production cost height.
Use the report of microwave heating hydrazine reduction to have as follows in the existing documents and materials: calendar year 2001 Andr á s Vass etc. has reported that the hydrazine that uses aluminum oxide to 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 and have used microwave heating to promote the research (E Parquet et al, Journal ofChemical Education, 1997,74,1225) of Wolff-Kishner reduction.The complexes preparation nano zine oxide of microwave heating hydrazine hydrate and zinc (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-made to get 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, alone hydrazine reducing environment is polluted still less, and more cheap, aftertreatment is simpler, the complete hydrazine of unreacted can make it to become by passing into air the method for nitrogen G﹠W and remove, and is the reductive agent (corresponding Green Chemistry oxygenant is hydrogen peroxide) of Green Chemistry first-selection.And with respect to the hydrazine heat reduction, microwave hydrazine reduction required time is shorter, reduction efficiency is higher, and energy consumption still less meets low-carbon economy, and practicality is high.More and more receive the concern of the public and government at modern environment, and chemical industry is received very large social pressures as a large source of polluting, this wherein has many-sided reason but makes water can reduce greatly pollution as reaction solvent, and since water be easy to get cheaply can be larger increase economic efficiency, be the solvent that compound probability is dreamed of.Helpless most reaction can't be used water as solvent, has affected the development of chemical industry.The in recent years reaction of water as solvent has 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 with ethanol until dissolving for compound insoluble in water.Adopt microwave heating to promote reduction, have environmental friendliness, reaction temperature and, the economic worth high.
Summary of the invention
Technical problem to be solved by this invention is for the deficiencies in the prior art, provides a kind of selectivity high, the method for reducing of simultaneously efficient carbon-carbon double bond.
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, to transfer pH be 1～4 again; 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 of the utilization microwave hydrazine reduction carbon-carbon double bond of this patent report is used solvent and airborne dioxygen oxidation hydrazine, microwave radiation itself also can promote the decomposition of hydrazine, become the reducing compounds such as imide, improved reduction and renderd a service, reduced the reduction required time, avoided side reaction, reduced environmental pollution and the 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: Reaction time shorten, raising reaction yield and product purity, save energy, environmental contamination reduction, reduce reaction cost.
In order to set forth better using value of the present invention and superiority, existing synthetic as an example explanation 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 pass into hydrogen with highly basic and hydrazine, add Raney Ni reduction (Zou Pei etc., Chinese Journal of Modern Applied Pharmacy magazine, 1999,16,6).Have recently the report that uses 1，4-cyclohexadiene 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 the shortcomings such as isomerization that we say previously and environmental pollution are arranged.Because the multiplex alcohol of solvent waits the organic solvent reaction cost high, pollute large simultaneously.And adopt hydrogen to do to go back that original reagent need to 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 although 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.Have the obvious reaction times short with respect to other three kinds of method of reducing equally, productive rate is high, and is good in economic efficiency, environment protection, the advantages such as convenient post-treatment.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: in microwave reactor, add p-hydroxybenzene vinylformic acid (1g, 6.05mmol), distilled water (6mL), 80wt% hydrazine hydrate (3.05g, 48.4mmol) vigorous stirring, reconciling temperature of reaction is 80 ℃, and microwave power is 600W, reaction 15min.Reaction finishes the wait system temperature and reduces to room temperature, and the cryosel acid for adjusting pH that adds 2mol/L is 1, leaves standstill, and filters to get white solid, gets distilled water and cleans solid (2mL * 2), and vacuum-drying gets 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
Synthesizing of Succinic Acid: in microwave reactor, add maleic acid (1g, 8.62mmol), water (20mL), 40wt% hydrazine hydrate (4.32g, 34.5mmol) vigorous stirring, reconciling temperature of reaction is 65 ℃, microwave power is 400W, reaction 10min.Reaction finishes the wait system temperature and reduces to room temperature, and the salt acid for 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, get 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: in microwave reactor, add methyl cinnamate (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 ℃, microwave power is 600W, reaction 20min.Reaction finishes the wait system temperature and reduces to room temperature, ethanol is removed in underpressure distillation, the salt acid for 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, gets 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: in microwave reactor, add 2-phenylacrylic acid methyl esters (1g, 6.2mmol), alcohol-water (1: 1,6mL), 80wt% hydrazine hydrate (3.08g, 49.3mmol) vigorous stirring, reconciling temperature of reaction is 70 ℃, microwave power is 600W, reaction 20min.Reaction finishes the wait system temperature and reduces to room temperature, ethanol is removed in underpressure distillation, the salt acid for 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, gets 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: in microwave reactor, add 2-phenol ethylene (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, get 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 aralkyl sulfid: in microwave reactor, add allyl phenyl thioether (1g, 6.66mmol), alcohol-water (1: 1,6ml), 80wt% hydrazine hydrate (3.33g, 53.2mmol) vigorous stirring, conditioned reaction temperature are 85 ℃, 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, get product propyl group aralkyl sulfid (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
Synthesizing of propyl group phenyl ether: 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, get product propyl group aralkyl sulfid (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-propanol: in microwave reactor, add 1-phenyl-2-alkene-1-propyl alcohol (1g, 7.45mmol), alcohol-water (1: 10,6ml), 80wt% hydrazine hydrate (3.73g, 59.6mmol) vigorous stirring, conditioned reaction temperature are 95 ℃, 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, get product propyl group aralkyl sulfid (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 (1)
1. the synthetic method of a para hydroxybenzene propionic acid is characterized in that, adds p-hydroxybenzene vinylformic acid 1g in microwave reactor, distilled water 6mL, and 80wt% hydrazine hydrate 3.05g, vigorous stirring, reconciling temperature of reaction is 80
oC, microwave power are 600 W, reaction 15min; Reaction finishes the wait system temperature and reduces to room temperature, and the cryosel acid for adjusting pH that adds 2mol/L is 1, leaves standstill, and filters to get white solid, and get distilled water and clean solid, totally 2 times, each 2mL, vacuum-drying gets product para hydroxybenzene propionic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010518663 CN102001903B (en) | 2010-10-25 | 2010-10-25 | Method for reducing carbon-carbon double bond by hydrazine hydrate through microwave |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010518663 CN102001903B (en) | 2010-10-25 | 2010-10-25 | Method for reducing carbon-carbon double bond by hydrazine hydrate through microwave |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102001903A CN102001903A (en) | 2011-04-06 |
| CN102001903B true CN102001903B (en) | 2013-04-03 |
Family
ID=43809647
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010518663 Expired - Fee Related CN102001903B (en) | 2010-10-25 | 2010-10-25 | Method for reducing carbon-carbon double bond by hydrazine hydrate through microwave |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102001903B (en) |
-
2010
- 2010-10-25 CN CN 201010518663 patent/CN102001903B/en not_active Expired - Fee Related
Non-Patent Citations (4)
| Title |
|---|
| Bimbisar Desai et al..Thermal- and microwave-assisted hydrogenation of electron-deficient alkenes using a polymer-supported hydrogen donor.《Tetrahedron Letters》.2001,第42卷5963–5965. |
| Thermal- and microwave-assisted hydrogenation of electron-deficient alkenes using a polymer-supported hydrogen donor;Bimbisar Desai et al.;《Tetrahedron Letters》;20011231;第42卷;5963–5965 * |
| 以水合肼为还原剂由癸烯酸制取癸酸的研究;梁本熹等;《湖南大学学报》;19881231;第15卷(第1期);17-22 * |
| 梁本熹等.以水合肼为还原剂由癸烯酸制取癸酸的研究.《湖南大学学报》.1988,第15卷(第1期),17-22. |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102001903A (en) | 2011-04-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wu et al. | A redox-neutral catechol synthesis | |
| Maresh et al. | Chemoselective Zinc/HCl reduction of halogenated β-nitrostyrenes: synthesis of halogenated dopamine analogues | |
| CN108727161B (en) | A kind of method for preparing phenol by efficient on-site hydroxylation of phenylboronic acid | |
| CN102001903B (en) | Method for reducing carbon-carbon double bond by hydrazine hydrate through microwave | |
| CN104788326A (en) | Synthesis method of ambroxol hydrochloride | |
| CN113831318A (en) | Synthetic method of piperonylethylamine | |
| CN103274982B (en) | Levulinic acid transforms the method generating lactan | |
| CN106146277B (en) | Method for synthesizing naphthoquinone compound by photocatalytic oxidation of naphthol compound | |
| CN101704701A (en) | Method for reducing alkyne into cis-form olefin | |
| Li et al. | Direct Deoxygenative Intramolecular Acylation of Biarylcarboxylic Acids | |
| CN102786403A (en) | Preparation method for 4-tertiary butyl-4'-methoxy dibenzoyl methane | |
| CN103435477B (en) | A kind of method of synthesizing p-ethoxybenzoic acid | |
| CN102336656B (en) | High-selectivity synthesis method of benzoyl formic acid | |
| Suzuki et al. | Tishchenko reaction using an iridium-ligand bifunctional catalyst | |
| CN108129269B (en) | Method for synthesizing 1, 3-diphenyl-1-propanol from 1, 3-diphenyl-1-propanol and nitromethane | |
| CN115232013A (en) | Preparation method of aromatic amine compound | |
| Reddy et al. | Palladium (II)-catalyzed auxiliary-directed CH activation for the regioselective ortho arylation of N-(2-benzoylphenyl) benzamides | |
| CN114210332A (en) | Preparation method of cobalt metal-nitrogen co-doped carbon material catalyst | |
| CN109369394B (en) | Photocatalytic oxidation synthesis method of diphenylcarbinol ester | |
| CN111393338A (en) | A kind of dofetilide-d3 medicine and preparation method thereof | |
| CN109422625A (en) | The method and its application of intramolecular single step reaction synthesizing o-dihydroxybenzene class compound | |
| CN101544564A (en) | Chemical synthetic method for para-methyl catechol diacetoxyl dimethyl ester | |
| CN107903158B (en) | A kind of synthetic method of 1,2,3-triphenylpropan-1-one | |
| CN111704577A (en) | A kind of preparation method of cinacalcet hydrochloride | |
| CN106905122B (en) | Method for preparing alicyclic ketone from alicyclic alcohol through Oppenauer oxidation reaction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130403 Termination date: 20181025 |