CN100400496C - Method of preparing 3,3-dimethyl-4-pentenoic acid methyl ester with industrial scale - Google Patents
Method of preparing 3,3-dimethyl-4-pentenoic acid methyl ester with industrial scale Download PDFInfo
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- CN100400496C CN100400496C CNB2006100481365A CN200610048136A CN100400496C CN 100400496 C CN100400496 C CN 100400496C CN B2006100481365 A CNB2006100481365 A CN B2006100481365A CN 200610048136 A CN200610048136 A CN 200610048136A CN 100400496 C CN100400496 C CN 100400496C
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- 238000000034 method Methods 0.000 title claims abstract description 13
- MKLKDUHMZCIBSJ-UHFFFAOYSA-N methyl 3,3-dimethylpent-4-enoate Chemical compound COC(=O)CC(C)(C)C=C MKLKDUHMZCIBSJ-UHFFFAOYSA-N 0.000 title claims description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- HDPNBNXLBDFELL-UHFFFAOYSA-N 1,1,1-trimethoxyethane Chemical compound COC(C)(OC)OC HDPNBNXLBDFELL-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000000047 product Substances 0.000 claims abstract description 18
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 14
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 10
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 7
- 239000011592 zinc chloride Substances 0.000 claims abstract description 7
- 230000035484 reaction time Effects 0.000 claims abstract description 6
- 229960003280 cupric chloride Drugs 0.000 claims abstract description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 239000000706 filtrate Substances 0.000 claims abstract description 3
- 239000007787 solid Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- ASUAYTHWZCLXAN-UHFFFAOYSA-N prenol Chemical compound CC(C)=CCO ASUAYTHWZCLXAN-UHFFFAOYSA-N 0.000 claims description 39
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 150000002815 nickel Chemical class 0.000 claims description 3
- YMHOBZXQZVXHBM-UHFFFAOYSA-N 2,5-dimethoxy-4-bromophenethylamine Chemical compound COC1=CC(CCN)=C(OC)C=C1Br YMHOBZXQZVXHBM-UHFFFAOYSA-N 0.000 claims description 2
- 241000545067 Venus Species 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- AIYYMMQIMJOTBM-UHFFFAOYSA-L nickel(ii) acetate Chemical compound [Ni+2].CC([O-])=O.CC([O-])=O AIYYMMQIMJOTBM-UHFFFAOYSA-L 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000011949 solid catalyst Substances 0.000 abstract description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 abstract 2
- QVDTXNVYSHVCGW-ONEGZZNKSA-N isopentenol Chemical compound CC(C)\C=C\O QVDTXNVYSHVCGW-ONEGZZNKSA-N 0.000 abstract 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 abstract 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 abstract 1
- 238000007036 catalytic synthesis reaction Methods 0.000 abstract 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 abstract 1
- 239000012467 final product Substances 0.000 abstract 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- MBAHGFJTIVZLFB-UHFFFAOYSA-N methyl pent-2-enoate Chemical compound CCC=CC(=O)OC MBAHGFJTIVZLFB-UHFFFAOYSA-N 0.000 abstract 1
- HNBDRPTVWVGKBR-UHFFFAOYSA-N n-pentanoic acid methyl ester Natural products CCCCC(=O)OC HNBDRPTVWVGKBR-UHFFFAOYSA-N 0.000 abstract 1
- 229940078494 nickel acetate Drugs 0.000 abstract 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 abstract 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 238000004817 gas chromatography Methods 0.000 description 14
- 238000004821 distillation Methods 0.000 description 13
- 239000000126 substance Substances 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HIRWGWMTAVZIPF-UHFFFAOYSA-N nickel;sulfuric acid Chemical compound [Ni].OS(O)(=O)=O HIRWGWMTAVZIPF-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- UMRSVAKGZBVPKD-UHFFFAOYSA-N acetic acid;copper Chemical compound [Cu].CC(O)=O UMRSVAKGZBVPKD-UHFFFAOYSA-N 0.000 description 2
- XMOKRCSXICGIDD-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O XMOKRCSXICGIDD-UHFFFAOYSA-N 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- NSPPRYXGGYQMPY-UHFFFAOYSA-N 3-Methylbuten-2-ol-1 Natural products CC(C)C(O)=C NSPPRYXGGYQMPY-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 235000007516 Chrysanthemum Nutrition 0.000 description 1
- 244000189548 Chrysanthemum x morifolium Species 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000881 depressing effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the industrial scale production methods for methyl pentenoate, involving a synthesis method for methyl pantenate through a reaction of isopentenol with methyl orthoacetate through catalytic synthesis under pressure. The molar ratio of isopentenol : methyl orthoacetate : catalyst is 1:1.0~2.0 : 0.01~0.1. The reaction conditions include stirring pressure of 1~3.2MPa and temperature of 150~250DEG C, and the reaction time of 6~10h. The catalysts are removed after cooling and the final product is obtained by distilling the filtrate. The catalyst is solid anhydrous zinc chloride, nickel sulfate, nickel acetate, copper acetate, anhydrous cupric chloride, or anhydrous ferric chloride. The invention has the advantages of simple catalyst separation as using solid catalyst, short reaction time as reacting at high temperature and pressure, high yield of 88%, low production cost, high product content above 99%, simple process, and less wastes.
Description
Technical field
The invention belongs to isocyclic compound preparation, be specifically related to a kind of utilize prenol and trimethyl orthoacetate in catalysis, add the method for depressing synthetic 3,3-dimethyl-4-pentenoic acid methyl ester.
Background technology
3,3-dimethyl-4-pentenoic acid methyl ester (4-Pentenoic acid, 3,3-dimethyl-, methyl ester), chemical name: 3,3-dimethyl-4-amylene-4 acid methyl ester (3,3-Dimethyl-4-pentenoic acid methyl ester); Molecular formula C
8H
14O
4Structural formula:
3,3-dimethyl-4-pentenoic acid methyl ester is a kind of important Organic Chemicals, it is an intermediate of making fluorine, chlorine, bromine three big chrysanthemum lipid agricultural chemicals, also can make the number of chemical product, takes the lead in the beginning of the seventies by Britain prompt sharp Kanggong department realization suitability for industrialized production, domestic also had production in recent years, but copy category belong to more.
Document " study on the synthesis of 3,3-dimethyl-4-pentenoic acid methyl ester " (Zou Jun, Li Junqing: " agricultural chemicals " 1996 the 09th phases) to the synthetic literature review of having carried out of 3,3-dimethyl-4-pentenoic acid methyl ester, in the prior art, mainly be to adopt synthesis under normal pressure, its deficiency is the reaction times to reach 15h, temperature of reaction is about 120 ℃, in the reaction proportioning of trimethyl orthoacetate bigger 1: 2.5～3.0, the catalyzer that uses in the domestic production generally is phosphoric acid, propionic acid, tosic acid, phenylformic acid and phenol etc., (proportioning 1～5%), reaction yield is generally about 65～85%.
Up to now, do not see the method report that utilizes solid catalyst and compressive reaction.
Summary of the invention
The objective of the invention is to look for another way, seek prenol and trimethyl orthoacetate when synthesizing 3,3-dimethyl-4-pentenoic acid methyl ester, improve its yield, method for quality.
The present invention implements by following technical proposals:
Develop a kind of method of preparing 3,3-dimethyl-4-pentenoic acid methyl ester with industrial scale, make prenol and trimethyl orthoacetate, the synthetic 3,3-dimethyl-4-pentenoic acid methyl ester of compressive reaction under catalysis is characterized in that:
(1) the reaction mass mol ratio is: prenol: trimethyl orthoacetate: catalyzer=1: 1.0～2.0: 0.01～0.1;
(2) condition of building-up reactions is, stirs down pressure 1～3.2Mpa, 150～250 ℃ of temperature, reaction times 6～10h;
(3) reaction is finished, cooling, and the reaction mass filtration catalizer, filtrate rectifying obtains the 3,3-dimethyl-4-pentenoic acid methyl ester product.
The method of above-mentioned preparing 3,3-dimethyl-4-pentenoic acid methyl ester with industrial scale is characterized in that catalyzer is a solid anhydrous zinc chloride, single nickel salt, nickelous acetate, venus crystals, anhydrous cupric chloride or FERRIC CHLORIDE ANHYDROUS;
The method of above-mentioned preparing 3,3-dimethyl-4-pentenoic acid methyl ester with industrial scale is characterized in that building-up reactions carries out under 2.5～3.2Mpa.
The method of above-mentioned preparing 3,3-dimethyl-4-pentenoic acid methyl ester with industrial scale is characterized in that the reaction mass mol ratio is:
Prenol: trimethyl orthoacetate: catalyzer=1: 1.5～2.0: 0.03～0.1.
The course of this reaction is:
Wherein, catalyzer refers to zinc chloride, single nickel salt, neutralized verdigris etc., and pressurization is to say that reaction refers to carry out under the certain pressure
Advantage of the present invention is, uses solid catalyst, and catalyst separating is simple; The reaction of employing pressurized high-temperature, the reaction times shortens, and reaction yield can be up to 88%, and production cost is lower, product content 〉=99%, technology is simple and direct, and discharging " three wastes " is few.
Embodiment
The present invention is further elaborated below in conjunction with embodiment.
Embodiment 1:
Mole proportioning: prenol: trimethyl orthoacetate: catalyzer=1: 1.2: 0.05
Raw material: (all adopting the commodity of commercially available commercial size)
Commercial goods prenol (Prenyl alcohol, chemical name 3-methyl-2-butene-1-alcohol 3-methyl-2-buten-1-ol) 86.9kg (content 99%, pure 86.031kg 1gkmol)
Commercial goods trimethyl orthoacetate (Trimethyl orthoacetate, chemical name: 1.1.1-trimethoxy-ethane, 1.1.1-Trimethoxyethane) 145.5kg (content 99%, pure 144.05kg 1.2kgmol)
Catalyzer Zinc Chloride Anhydrous 6.8kg (content 98%, pure 6.664kg, 0.05kgmol)
Operation:
Raw material and catalyzer add autoclave, heating, and in still 150～160 ℃, under the pressure 2.5Mpa, reaction 6～7h; Reaction is finished, and reduces to room temperature, and the still internal pressure drops to normal pressure naturally; Vacuum sucking-off material, the reaction mass filtration catalizer, reclaim the methyl alcohol of by-product and excessive trimethyl orthoacetate, the colourless transparent liquid that 60～62 ℃/2kPa of boiling range is collected in rectifying is a 3,3-dimethyl-4-pentenoic acid methyl ester, must measure 117kg, gas chromatography determination content 99.53%, pure 116.45kg, yield 82.01%.
Embodiment 2:
Mole proportioning: prenol: trimethyl orthoacetate: catalyzer=1: 1.5: 0.03
Prenol 86.9kg (content 99%, pure 86.031kg 1kgmol) and trimethyl orthoacetate 181.8kg (content 99%, pure 179.98kg 1.5kgmol), catalyst sulfuric acid nickel 7.7kg (content 98%, pure 7.55kg, 0.03kgmol) in autoclave 190～200 ℃, 3.0MPa reaction 8～9h, observation pressure no longer increase the back and are reaction end.Distillation operation goes out product 3,3-dimethyl-4-pentenoic acid methyl ester 126kg at last with embodiment 1, gas chromatography determination content 99.26%, pure 125.07kg, yield 88.08%.
Embodiment 3:
Mole proportioning: prenol: trimethyl orthoacetate: catalyzer=1: 1.2: 0.02
Prenol 86.9kg (content 99%, pure 86kg 1kgmol) and trimethyl orthoacetate 145.5kg (content 99%, pure 144.05kg 1.2kgmol), catalyst acetic acid nickel 5.3kg (content 98%, pure 5.19kg, 0.02kgmol) the adding autoclave, 160～170 ℃, 2.5MPa, reaction 9～10h, observation pressure no longer increase the back and are reaction end.Distillation operation goes out product 3,3-dimethyl-4-pentenoic acid methyl ester 122kg at last with embodiment 1, gas chromatography determination content 99.43%, pure 121.31kg, yield 85.43%.All the other are with embodiment 1.
Embodiment 4:
Mole proportioning: prenol: trimethyl orthoacetate: catalyzer=1: 2.0: 0.01
Prenol 8b.9kg (content 99%, pure 86.03kg, 1kgmol) with trimethyl orthoacetate 242.42kg (content 99%, pure 240kg 2kgmol), (content 99%, pure 1.99kg 0.01kgmol) add autoclave to catalyst acetic acid copper 2.01kg, 180～190 ℃, 2.8MPa reaction 8～9h, observation pressure no longer increase the back and are reaction end.Distillation operation goes out product 3,3-dimethyl-4-pentenoic acid methyl ester 120.5kg at last with embodiment 1, gas chromatography determination content 99.56%, pure 119.97kg, yield 84.49%.All the other are with embodiment 1.
Embodiment 5:
Mole proportioning: prenol: trimethyl orthoacetate: catalyzer=1: 2.0: 0.1
Prenol 86.9kg (content 99%, pure 86.03kg 1kgmol) and trimethyl orthoacetate 242.42kg (content 99%, pure 240kg 2kgmol), catalyzer anhydrous cupric chloride 13.67kg (content 98%, pure 13.4kg, 0.1kgmol) at autoclave, 240～250 ℃, 3.2MPa, reaction 6～7h, observation pressure no longer increase the back and are reaction end.Distillation operation goes out product 3,3-dimethyl-4-pentenoic acid methyl ester 126.39kg at last with embodiment 1, gas chromatography determination content 99.66%, pure 125.96kg, yield 88.70%.All the other are with embodiment 1.
Embodiment 6:
Mole proportioning: prenol: trimethyl orthoacetate: catalyzer=1: 1.8: 0.01
Prenol 86.9kg (content 99%, pure 86.03kg 1kgmol) and trimethyl orthoacetate 218.18kg (content 99%, pure 216kg 1.8kgmol), catalyst sulfuric acid nickel 2.67kg (content 98%, pure 2.62kg, 0.01kgmol) add autoclave, at 240～250 ℃, 2.5MPa, reaction 9～10h, observation pressure no longer increase the back and are reaction end.Distillation operation goes out product 3,3-dimethyl-4-pentenoic acid methyl ester 127kg at last with embodiment 1, gas chromatography determination content 99.11%, pure 125.87kg, yield 88.64%.All the other are with embodiment 1.
Embodiment 7:
Mole proportioning: prenol: trimethyl orthoacetate: catalyzer=1: 1.8: 0.05
Prenol 86.9kg (content 99%, pure 86.031kg 1kgmol) and trimethyl orthoacetate 218.18kg (content 99%, pure 216kg 1.8kgmol), catalyzer FERRIC CHLORIDE ANHYDROUS 8.44kg (content 96%, pure 8.10kg, 0.05kgmol) in autoclave 240～250 ℃, 1.0MPa reaction 8～9h, observation pressure no longer increase the back and are reaction end.Distillation operation goes out product 3,3-dimethyl-4-pentenoic acid methyl ester 123.59kg at last with embodiment 1, gas chromatography determination content 99.26%, pure 122.94kg, yield 86.58%.All the other are with embodiment 1.
Embodiment 8:
Mole proportioning: prenol: trimethyl orthoacetate: catalyzer=1: 1.6: 0.1
Prenol 86.9kg (content 99%, pure 86kg 1kgmol) and trimethyl orthoacetate 193.94kg (content 99%, pure 192kg 1.6kgmol), catalyzer FERRIC CHLORIDE ANHYDROUS 16.53kg (content 98%, pure 16.2kg, 0.1kgmol) the adding autoclave, 150～160 ℃, 3.2MPa, reaction 9～10h, observation pressure no longer increase the back and are reaction end.Distillation operation goes out product 3,3-dimethyl-4-pentenoic acid methyl ester 121.68kg at last with embodiment 1, gas chromatography determination content 99.43%, pure 120.73kg, yield 85.02%.All the other are with embodiment 1.
Embodiment 9:
Mole proportioning: prenol: trimethyl orthoacetate: catalyzer=1: 1.0: 0.1
Prenol 86.9kg (content 99%, pure 86.03kg, 1kgmol) with trimethyl orthoacetate 121.21kg (content 99%, pure 120kg 1kgmol), (content 99%, pure 1.34kg 0.1kgmol) add autoclave to catalyzer anhydrous cupric chloride 1.35kg, 180～190 ℃, 2.5MPa reaction 7～8h, observation pressure no longer increase the back and are reaction end.Distillation operation goes out product 3,3-dimethyl-4-pentenoic acid methyl ester 121.63kg at last with embodiment 1, gas chromatography determination content 99.56%, pure 120.37kg, yield 84.77%.All the other are with embodiment 1.
Embodiment 10:
Mole proportioning: prenol: trimethyl orthoacetate: catalyzer=1: 1.0: 0.1
Prenol 86.9kg (content 99%, pure 86.03kg 1kgmol) and trimethyl orthoacetate 121.21kg (content 99%, pure 120kg 1kgmol), catalyzer Zinc Chloride Anhydrous 1.39kg (content 97%, pure 1.35kg, 0.1kgmol) at autoclave, 240～250 ℃, 1.0MPa, reaction 9～10h, observation pressure no longer increase the back and are reaction end.Distillation operation goes out product 3,3-dimethyl-4-pentenoic acid methyl ester 119.53kg at last with embodiment 1, gas chromatography determination content 98.89%, pure 118.20kg, yield 83.24%.All the other are with embodiment 1.
Embodiment 11:
Mole proportioning: prenol: trimethyl orthoacetate: catalyzer=1: 1.2: 0.08
Prenol 86.9kg (content 99%, pure 86.03kg 1kgmol) and trimethyl orthoacetate 145.46kg (content 99%, pure 144kg 1.2kgmol), catalyst sulfuric acid nickel 2.14kg (content 98%, pure 2.096kg, 0.08kgmol) add autoclave, at 240～250 ℃, 1.0MPa, reaction 9～10h, observation pressure no longer increase the back and are reaction end.Distillation operation goes out product 3,3-dimethyl-4-pentenoic acid methyl ester 118.18kg at last with embodiment 1, gas chromatography determination content 98.98%, pure 116.97kg, yield 82.37%.All the other are with embodiment 1.
Embodiment 12:
Mole proportioning: prenol: trimethyl orthoacetate: catalyzer=1: 1.2: 0.08
Prenol 86.9kg (content 99%, pure 86.03kg, 1kgmol) with trimethyl orthoacetate 145.46kg (content 99%, pure 144kg 1.2kgmol), (content 98%, pure 19.84kg 0.08kgmol) add autoclave to catalyst acetic acid nickel 20.25kg, 200～210 ℃, 1.5MPa reaction 9～10h, observation pressure no longer increase the back and are reaction end.Distillation operation goes out product 3,3-dimethyl-4-pentenoic acid methyl ester 118.21kg at last with embodiment 1, gas chromatography determination content 99.66%, pure 117.80kg, yield 82.96%.All the other are with embodiment 1.
Embodiment 13:
Mole proportioning: prenol: trimethyl orthoacetate: catalyzer=1: 1.5: 0.03
Prenol 86.9kg (content 99%, pure 86.03kg 1kgmol) and trimethyl orthoacetate 181.82kg (content 99%, pure 180kg 1.5kgmol), catalyst acetic acid copper 6.03kg (content 99%, pure 5.97kg, 0.03kgmol) at autoclave, 240～250 ℃, 1.0MPa, reaction 9～10h, observation pressure no longer increase the back and are reaction end.Distillation operation goes out product 3,3-dimethyl-4-pentenoic acid methyl ester 118.85kg at last with embodiment 1, gas chromatography determination content 99.01%, pure 117.68kg, yield 82.87%.All the other are with embodiment 1.
Embodiment 14:
Mole proportioning: prenol: trimethyl orthoacetate: catalyzer=1: 1.6: 0.02
Prenol 86.9kg (content 99%, pure 86.03kg 1kgmol) and trimethyl orthoacetate 193.94kg (content 99%, pure 192kg 1.6kgmol), catalyzer Zinc Chloride Anhydrous 2.75kg (content 98%, pure 2.7kg, 0.02kgmol) add autoclave, at 230～240 ℃, 2.0MPa, reaction 8～9h, observation pressure no longer increase the back and are reaction end.Distillation operation goes out product 3,3-dimethyl-4-pentenoic acid methyl ester 118.38kg at last with embodiment 1, gas chromatography determination content 99.03%, pure 117.24kg, yield 82.56%.All the other are with embodiment 1.
Claims (3)
1. the method for a preparing 3,3-dimethyl-4-pentenoic acid methyl ester with industrial scale makes prenol and trimethyl orthoacetate, and the synthetic 3,3-dimethyl-4-pentenoic acid methyl ester of compressive reaction under catalysis is characterized in that:
(1) the reaction mass mol ratio is: prenol: trimethyl orthoacetate: catalyzer=1: 1.0～2.0: 0.01～0.1;
Catalyzer is a solid anhydrous zinc chloride, single nickel salt, nickelous acetate, venus crystals, anhydrous cupric chloride or FERRIC CHLORIDE ANHYDROUS;
(2) condition of building-up reactions is, stirs down pressure 1～3.2MPa, 150～250 ℃ of temperature, reaction times 6～10h;
(3) reaction is finished, cooling, and the reaction mass filtration catalizer, filtrate rectifying obtains the 3,3-dimethyl-4-pentenoic acid methyl ester product.
2. according to the method for the described preparing 3,3-dimethyl-4-pentenoic acid methyl ester with industrial scale of claim 1, it is characterized in that building-up reactions carries out under 2.5～3.2MPa.
3. according to the method for the described preparing 3,3-dimethyl-4-pentenoic acid methyl ester with industrial scale of claim 1, it is characterized in that the reaction mass mol ratio is:
Prenol: trimethyl orthoacetate: catalyzer=1: 1.5～2.0: 0.03～0.1.
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| CN102001940B (en) * | 2010-12-31 | 2013-07-24 | 江苏优士化学有限公司 | Continuous synthesis method for methyl 3,3-dimethyl pentenoate |
| CN102001941B (en) * | 2010-12-31 | 2013-11-13 | 江苏优士化学有限公司 | Method for synthesizing 3,3-dimethyl-4-pentenoic acid methyl ester |
| CN102633632B (en) * | 2011-04-02 | 2014-06-18 | 南通天泽化工有限公司 | Pentenoic acid methylester preparation process |
| CN102557934A (en) * | 2012-01-17 | 2012-07-11 | 山东高新润农化学有限公司 | Method for continuously synthesizing 3,3-dimethyl-4-pentenoic acid methylester |
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| JPS52111513A (en) * | 1976-03-16 | 1977-09-19 | Kuraray Co Ltd | Preparation of 3,3-dimethyl-4-penthnoic acid methyl ester |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52111513A (en) * | 1976-03-16 | 1977-09-19 | Kuraray Co Ltd | Preparation of 3,3-dimethyl-4-penthnoic acid methyl ester |
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| 贲亭酸甲酯的合成研究. 邹军，李俊卿.农药，第35卷第9期. 1996 |
| 贲亭酸甲酯的合成研究. 邹军，李俊卿.农药，第35卷第9期. 1996 * |
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