CN1277806C - Process for preparing transfluthrin - Google Patents
Process for preparing transfluthrin Download PDFInfo
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- CN1277806C CN1277806C CN 200310121743 CN200310121743A CN1277806C CN 1277806 C CN1277806 C CN 1277806C CN 200310121743 CN200310121743 CN 200310121743 CN 200310121743 A CN200310121743 A CN 200310121743A CN 1277806 C CN1277806 C CN 1277806C
- Authority
- CN
- China
- Prior art keywords
- transfluthrin
- processing method
- preparation
- hydride
- solvent
- 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 - Lifetime
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- DDVNRFNDOPPVQJ-HQJQHLMTSA-N transfluthrin Chemical compound CC1(C)[C@H](C=C(Cl)Cl)[C@H]1C(=O)OCC1=C(F)C(F)=CC(F)=C1F DDVNRFNDOPPVQJ-HQJQHLMTSA-N 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title description 3
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- AGWVQASYTKCTCC-UHFFFAOYSA-N (2,3,5,6-tetrafluorophenyl)methanol Chemical compound OCC1=C(F)C(F)=CC(F)=C1F AGWVQASYTKCTCC-UHFFFAOYSA-N 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 238000006722 reduction reaction Methods 0.000 claims description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 230000002829 reductive effect Effects 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 6
- -1 normal-butyl Chemical group 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 150000001263 acyl chlorides Chemical class 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 3
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 230000032050 esterification Effects 0.000 claims description 3
- 238000005886 esterification reaction Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052987 metal hydride Inorganic materials 0.000 claims description 3
- 150000004681 metal hydrides Chemical class 0.000 claims description 3
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 claims description 2
- 229910000105 potassium hydride Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 125000005208 trialkylammonium group Chemical group 0.000 claims description 2
- 238000003672 processing method Methods 0.000 claims 11
- 238000000034 method Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 description 3
- 239000012279 sodium borohydride Substances 0.000 description 3
- PBIJFSCPEFQXBB-UHFFFAOYSA-N 1,1-dimethylcyclopropane Chemical compound CC1(C)CC1 PBIJFSCPEFQXBB-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000002728 pyrethroid Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- WRWPPGUCZBJXKX-UHFFFAOYSA-N 1-fluoro-4-methylbenzene Chemical compound CC1=CC=C(F)C=C1 WRWPPGUCZBJXKX-UHFFFAOYSA-N 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- GFAUNYMRSKVDJL-UHFFFAOYSA-N formyl chloride Chemical compound ClC=O GFAUNYMRSKVDJL-UHFFFAOYSA-N 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a preparation method applied to the synthesis of (2, 3, 5, 6)-tetrafluorobenzyl(1R, 3S)-(2, 2-2-dichloroethenyl)-2, 2-dimethylcyclopropane-carboxylic acid esters, namely a preparation method applied to a transfluthrin intermediate 2, 3, 5, 6-tetrafluorobenzyl alcohol. Transfluthrin synthesized by the 2, 3, 5, 6-tetrafluorobenzyl alcohol and obtained by the method has the characteristics of safe and reliable technological lines and high quality yield.
Description
Technical field
The present invention relates to the preparation method of a kind of polyfluoro for pyrethroid.
Background technology
Transfluthrin [(2,3,5,6)-ptfe benzyl (1R, 3S)-(2, the 2-dichloroethylene)-2,2-dimethyl cyclopropane carboxylic acid ester], be a kind of important hygienic insecticide, have efficiently, low toxicity is the characteristics of low residue especially.The method of the synthetic transfluthrin of more existing at present reports, the present invention has highlighted a kind of capable of being industrialized, simple and effective novel process, by 2,3,5, the reduction of 6-tetrafluorobenzoic aid ester obtains 2,3,5, and the 6-. tetrafluorobenzyl alcohol prepares transfluthrin.
Summary of the invention
Here introduce a kind of novel process and be by reductive agent 2,3,5,6-tetrafluorobenzoic aid ester changes 2,3,5 into, and the 6-tetrafluorobenzyl alcohol obtains transfluthrin again behind over-churning.Following scheme has illustrated reaction of the present invention:
The R that mentions among the present invention is the alkyl of 1-6 carbon atom, is preferably any in methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, sec.-propyl, isobutyl-, the tertiary butyl or the neo-pentyl.It most preferably is methyl.
The used reductive agent of this technology is a kind of to be metal hydride, is preferably any in the hydroborate of lithium, sodium, potassium or calcium, and another kind is the aluminum hydride metal, is preferably any in potassium hydride KH aluminium, the lithium aluminium hydride etc.Need to add the reduction auxiliary agent in addition in the reductive agent, make reaction more complete, selectable reduction auxiliary agent has ammonium formate, trialkyl ammonium formate, any in the tetrahydrobenzene etc.
The used more suitable selection of solvent of this technology is an alcohols: be preferably any in methyl alcohol, ethanol, the Virahol etc.; Ethers is preferably tetrahydrofuran (THF), 1, any in 4-dioxane, ether, the glycol dimethyl ether etc.; The mixture of aromatics and water is preferably the mixture of toluene and water.
Reduction reaction can be carried out in the scope of solvent boiling point at-20 ℃, is preferably 20 ℃-100 ℃, and most preferred temperature of reaction is 30 ℃-60 ℃.
Reduction reaction uses the amount of reductive agent to depend on the character of reductive agent itself, is preferably 0.5-2 with the mol ratio of methyl esters: 1, most preferably be 0.75-1.25: 1.The amount of reduction auxiliary agent is generally the 10%-30% of reduction dosage.
Through above step obtain 2,3,5, the 6-tetrafluorobenzyl alcohol and (1R, 3S)-(2, the 2-dichloroethylene)-2, the synthetic transfluthrin that obtains of pyridine method that 2-dimethylcyclopropane base esterification of acyl chloride is promptly conventional.
Embodiment
From different aspects the present invention is described with some concrete examples below, but the present invention not only is confined to following embodiment:
Embodiment 1:2,3,5, the preparation method of 6-tetrafluorobenzyl alcohol (1)
Add tetrahydrofuran (THF) and the 37g sodium borohydride of 300ml in the four-hole boiling flask of 1500ml, be heated to 50 ℃, be added dropwise to 2,3,5 of 208g, 6-tetrafluorobenzoic aid propyl ester is incubated 5 hours, is cooled to room temperature again.The reaction material drop is gone in the sulfuric acid of 200ml30%, and the extraction of 500ml toluene is washed to neutrality.Can obtain the crystal 2 of white after the underpressure distillation, 3,5,6-tetrafluorobenzyl alcohol 155.6g, the purity of this product is 95.8%, yield is 82.8%.
Embodiment 2:2,3,5, the preparation method of 6-tetrafluorobenzyl alcohol (2)
In the four-hole boiling flask of 1500ml, add tetrahydrofuran (THF) and the 37g sodium borohydride of 300ml, be heated to 50 ℃, splash into the methyl 4-fluorobenzene of 208g, add the ammonium formate of 5g again.Be incubated and be cooled to room temperature after 3 hours.The reaction material drop is gone in the sulfuric acid of 200ml30%, and the extraction of 500ml toluene is washed to neutrality.Can obtain tetrafluorobenzyl alcohol 165.4g after the underpressure distillation, purity is 97.3%, and yield is 89.4%
Embodiment 3:2,3,5, the preparation method of 6-tetrafluorobenzyl alcohol (3)
In the four-hole boiling flask of 1500ml, add the tetrahydrofuran (THF) of 200ml, methyl alcohol and the 37g sodium borohydride of 100ml, be heated to 50 ℃, splash into the tetrafluorobenzoic aid butyl ester of 208g, be incubated and be cooled to room temperature after 3 hours.In the sulfuric acid of reaction feed liquid 200ml30%, toluene extraction after washing is to neutral.Underpressure distillation obtains tetrafluorobenzyl alcohol 162.1g, and purity is 97.1%, and yield is 87.44%.
2,3,5,6-tetrafluorobenzyl alcohol and (1R, 3S))-(2, the 2-dichloroethylene)-2,2 dimethylcyclopropane base acyl chloride reactions can get transfluthrin.
Following example has been described the preparation process of transfluthrin [(2,3,5,6)-ptfe benzyl (1R, 3S)-(2, the 2-dichloroethylene)-2,2 dimethyl cyclopropane carboxylic acid's esters]:
Embodiment 4:
Add toluene 300ml in the four-hole boiling flask of 1000ml, pyridine 22.8g, tetrafluorobenzyl alcohol 45g stirs.Add toluene 56.9g in another flask, (1R, 3S))-(2, the 2-dichloroethylene)-2,2 dimethylcyclopropane base formyl chloride 56.9g mix the back and keep 40 ℃-45 ℃ of temperature.Drip acyl chlorides to alcohol, temperature is controlled at 40-55 ℃.Drip and finish, be incubated 3 hours, slough toluene after the washing and get white crystallization transfluthrin 91.5g, content is 97%, and yield is 95.7%.
The applicant has invented a kind of new preparation method of intermediate of pyrethroid compound, this intermediate 2,3,5, the 6-tetrafluorobenzyl alcohol obtains transfluthrin by esterification, this technology has the advantages that operational path is simple, safe and reliable, mass yield is high, cost is low, is fit to very much suitability for industrialized production.
Claims (10)
1, a kind of processing method for preparing transfluthrin is characterized by by 2,3,5, and with reductive agent and aids reduction preparation 2,3,5, the 6-tetrafluorobenzyl alcohol obtains the processing method of transfluthrin to 6-tetrafluorobenzoic aid ester after esterification in solvent; Following scheme has illustrated reaction of the present invention:
The R that mentions among the present invention is the alkyl of 1-6 carbon atom;
Used reductive agent is any in metal hydride or the aluminum hydride metal;
Used reduction auxiliary agent is any in ammonium formate, trialkyl ammonium formate or the tetrahydrobenzene.
2, the processing method of preparation transfluthrin according to claim 1 is characterized in that R is any in methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, sec.-propyl, isobutyl-, the tertiary butyl or the neo-pentyl.
3, the processing method of preparation transfluthrin according to claim 2 is characterized in that R is a methyl.
4, the processing method of preparation transfluthrin according to claim 1 is characterized in that the used solvent of reduction reaction has any in the mixture of alcohols, ethers or aromatics and water.
5, the processing method of preparation transfluthrin according to claim 4 is characterized in that solvent is methyl alcohol, ethanol, Virahol, tetrahydrofuran (THF), 1, any in the mixture of 4-dioxane, ether, glycol dimethyl ether or toluene and water.
6, the processing method of preparation transfluthrin according to claim 1 is characterized in that the reductive agent metal hydride is any in the hydroborate of lithium, sodium, potassium or calcium, and the aluminum hydride metal is any in potassium hydride KH aluminium or the lithium aluminium hydride.
7, the processing method of the described preparation transfluthrin of claim 1 is characterized in that the reduction reaction temperature scope is-20 ℃ and carries out in the scope of solvent boiling point.
8,, it is characterized in that the reduction reaction temperature scope is 20-100 ℃ according to the processing method of the described preparation transfluthrin of claim 1.
9,, it is characterized in that the reduction reaction temperature scope is 30-60 ℃ according to the processing method of the described preparation transfluthrin of claim 1.
10, the processing method of preparation transfluthrin according to claim 1 is characterized in that 2,3,5,6-tetrafluorobenzyl alcohol and (1R, 3S)-(2, the 2-dichloroethylene)-2,2-dimethylcyclopropane base acyl chloride reaction obtains transfluthrin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310121743 CN1277806C (en) | 2003-12-22 | 2003-12-22 | Process for preparing transfluthrin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310121743 CN1277806C (en) | 2003-12-22 | 2003-12-22 | Process for preparing transfluthrin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1631869A CN1631869A (en) | 2005-06-29 |
| CN1277806C true CN1277806C (en) | 2006-10-04 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200310121743 Expired - Lifetime CN1277806C (en) | 2003-12-22 | 2003-12-22 | Process for preparing transfluthrin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1277806C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113797977B (en) * | 2020-06-12 | 2022-11-29 | 沈阳中化农药化工研发有限公司 | Ruthenium catalyst and application thereof |
| CN115259996B (en) * | 2022-08-29 | 2024-02-02 | 浙江中欣氟材股份有限公司 | Synthesis method of 2,3,5, 6-tetrafluorobenzyl alcohol |
-
2003
- 2003-12-22 CN CN 200310121743 patent/CN1277806C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1631869A (en) | 2005-06-29 |
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Address after: No. 39, Wenfeng Road, Jiangsu, Yangzhou Province, China: 225009 Co-patentee after: JIANGSU YOUTH CHEMICAL Co.,Ltd. Patentee after: JIANGSU YANGNONG CHEMICAL Co.,Ltd. Address before: No. 39, Wenfeng Road, Yangzhou, Jiangsu Patentee before: JIANGSU YANGNONG CHEMICAL Co.,Ltd. |
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Granted publication date: 20061004 |