CN113348161B - Method for producing ester compound - Google Patents
Method for producing ester compound Download PDFInfo
- Publication number
- CN113348161B CN113348161B CN201980090304.2A CN201980090304A CN113348161B CN 113348161 B CN113348161 B CN 113348161B CN 201980090304 A CN201980090304 A CN 201980090304A CN 113348161 B CN113348161 B CN 113348161B
- Authority
- CN
- China
- Prior art keywords
- tetrafluorophenyl
- methoxymethyl
- propenyl
- dimethyl
- methyl
- 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.)
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- -1 ester compound Chemical class 0.000 title claims description 8
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- YMGUBTXCNDTFJI-UHFFFAOYSA-M cyclopropanecarboxylate Chemical compound [O-]C(=O)C1CC1 YMGUBTXCNDTFJI-UHFFFAOYSA-M 0.000 claims abstract description 14
- YFHZSPDQKWFAPH-UHFFFAOYSA-N [2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methanol Chemical compound COCC1=C(F)C(F)=C(CO)C(F)=C1F YFHZSPDQKWFAPH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 11
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 9
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical group CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical group [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 5
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 5
- 239000004289 sodium hydrogen sulphite Substances 0.000 claims description 4
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 claims 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims 1
- 238000005406 washing Methods 0.000 abstract description 9
- 150000001875 compounds Chemical class 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000012535 impurity Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000749 insecticidal effect Effects 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000001256 steam distillation Methods 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
- C07C69/743—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring of acids with a three-membered ring and with unsaturation outside the ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
- C07C69/743—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring of acids with a three-membered ring and with unsaturation outside the ring
- C07C69/747—Chrysanthemumic acid esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B61/00—Other general methods
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
In the case of producing 2, 2-dimethyl-3- ((Z) -1-propenyl) cyclopropanecarboxylic acid [4- (methoxymethyl) -2,3,5, 6-tetrafluorophenyl ] methyl ester by reacting methyl 2, 2-dimethyl-3- ((Z) -1-propenyl) cyclopropanecarboxylate with [4- (methoxymethyl) -2,3,5, 6-tetrafluorophenyl ] methanol in the presence of lithium methoxide in an organic solvent, the object can be produced by washing a mixture of methyl 2, 2-dimethyl-3- ((Z) -1-propenyl) cyclopropanecarboxylate and [4- (methoxymethyl) -2,3,5, 6-tetrafluorophenyl ] methanol with an aqueous bisulfite solution, and then adding lithium methoxide to react the mixture.
Description
Technical Field
The present invention relates to a method for producing an ester compound.
Background
2, 2-dimethyl-3- ((Z) -1-propenyl) cyclopropanecarboxylic acid [4- (methoxymethyl) -2,3,5, 6-tetrafluorophenyl ] methyl ester is known to have insecticidal activity. (patent document 1)
2, 2-dimethyl-3- ((Z) -1-propenyl) cyclopropanecarboxylic acid [4- (methoxymethyl) -2,3,5, 6-tetrafluorophenyl ] methyl ester can be produced by adding lithium methoxide to a mixture of methyl 2, 2-dimethyl-3- ((Z) -1-propenyl) cyclopropanecarboxylate, heptane and [4- (methoxymethyl) -2,3,5, 6-tetrafluorophenyl ] methanol and allowing it to react. (patent document 2)
Prior art literature
Patent literature
Patent document 1: US6225495
Patent document 2: japanese patent laid-open No. 2005-82501
Disclosure of Invention
Problems to be solved by the invention
Patent document 2 discloses a method advantageous in terms of industrially producing 2, 2-dimethyl-3- ((Z) -1-propenyl) cyclopropanecarboxylic acid [4- (methoxymethyl) -2,3,5, 6-tetrafluorophenyl ] methyl ester.
According to this method, the target product can be obtained from the bottom of the rectifying column after the steam distillation, but in some cases, impurities having a large molecular weight, such as a compound represented by the following formula (a), remain.
The present invention provides a method for producing [4- (methoxymethyl) -2,3,5, 6-tetrafluorophenyl ] methyl 2, 2-dimethyl-3- ((Z) -1-propenyl) cyclopropanecarboxylate in a state in which the formation of a compound represented by formula (A) (hereinafter referred to as compound (A)) as an impurity is suppressed.
According to the present invention, when lithium methoxide is added to a mixture of methyl 2, 2-dimethyl-3- ((Z) -1-propenyl) cyclopropanecarboxylate, an organic solvent, and [4- (methoxymethyl) -2,3,5, 6-tetrafluorophenyl ] methanol and reacted to produce [4- (methoxymethyl) -2,3,5, 6-tetrafluorophenyl ] methyl 2, 2-dimethyl-3- ((Z) -1-propenyl) cyclopropanecarboxylate, the mixture is washed with an aqueous bisulfite solution in advance, whereby the formation of compound (a) as an impurity can be suppressed.
Detailed Description
The production method of the present invention can be carried out with reference to Japanese patent application laid-open No. 2005-82501.
That is, lithium methoxide is added to a mixture of methyl 2, 2-dimethyl-3- ((Z) -1-propenyl) cyclopropanecarboxylate, an organic solvent, and [4- (methoxymethyl) -2,3,5, 6-tetrafluorophenyl ] methanol and the reaction is carried out, however, it is necessary to wash the mixture with an aqueous bisulfite solution in advance.
The bisulphite is not particularly limited as long as it is a water-soluble salt, and an alkali metal salt, particularly a sodium salt having good availability, is usually used. Particularly preferably, 1 to 10% by weight aqueous solution of sodium bisulphite is used.
In the case of washing with an aqueous solution of a bisulfite, a sulfite such as sodium sulfite may be added to the aqueous solution.
Methyl 2, 2-dimethyl-3- ((Z) -1-propenyl) cyclopropanecarboxylate is usually used in a proportion of 1 to 3 moles relative to 1 mole of [4- (methoxymethyl) -2,3,5, 6-tetrafluorophenyl ] methanol, and 1 to 10 parts by weight of an organic solvent is usually used relative to 1 part by weight of [4- (methoxymethyl) -2,3,5, 6-tetrafluorophenyl ] methanol.
Examples of the organic solvent include aliphatic hydrocarbons, aromatic hydrocarbons, and halogenated hydrocarbons, and heptane is preferable.
Lithium methoxide is added to the mixture washed with the aqueous bisulfite solution and reacted, preferably at a temperature of 50 to 200℃and preferably at a temperature of 80 to 150℃for a further 10 to 48 hours.
After the completion of the reaction, the reaction mixture is washed with water or alkaline water, and then, if necessary, the oil phase is taken out by washing with acidic water, and steam distillation is performed in a distillation apparatus equipped with a rectifying column, whereby 2, 2-dimethyl-3- ((Z) -1-propenyl) cyclopropanecarboxylic acid [4- (methoxymethyl) -2,3,5, 6-tetrafluorophenyl ] methyl ester can be obtained as an oil phase remaining in the bottom of the rectifying column.
Examples
Methyl 2, 2-dimethyl-3- ((Z) -1-propenyl) cyclopropanecarboxylate 9.38g, [4- (methoxymethyl) -2,3,5, 6-tetrafluorophenyl ] methanol 10.2g, 2, 6-di-tert-butyl-p-cresol 0.15g, heptane 10.2g, 1 wt% sodium bisulphite aqueous solution 10.0g were mixed, and after washing at 40-50℃for 30 minutes, the mixture was separated to remove the aqueous layer. After washing with 5.0g of water in the same manner, 30.6g of heptane and 0.059g of lithium methoxide were added thereto, and the resultant methanol was removed at 102℃and heated under reflux until [4- (methoxymethyl) -2,3,5, 6-tetrafluorophenyl ] methanol was 2% or less relative to [4- (methoxymethyl) -2,3,5, 6-tetrafluorophenyl ] methyl 2, 2-dimethyl-3- ((Z) -1-propenyl) cyclopropanecarboxylate. After cooling to room temperature and washing with water, the heptane solution was concentrated under reduced pressure to give 17.3g of 2, 2-dimethyl-3- ((Z) -1-propenyl) cyclopropanecarboxylic acid [4- (methoxymethyl) -2,3,5, 6-tetrafluorophenyl ] methyl ester as an oil. The content of the compound (A) was determined by liquid chromatography analysis of the obtained 2, 2-dimethyl-3- ((Z) -1-propenyl) cyclopropanecarboxylate. Similarly, the concentration of the sodium bisulfite solution was changed to measure the content of the compound (a). In the case of washing with an aqueous sodium bisulphite solution, the subsequent washing with water is also omitted.
| NaHSO 3 | Yield is good | Compound (A) |
| 1％ | 92.8％ | 0.02％ |
| 1％(＊) | 94.4％ | 0.02％ |
| 2.5％ | 92.9％ | 0.01％ |
| 5％ | 95.3％ | 0.03％ |
| 10％ | 93.1％ | 0.01％ |
| - | 93.0％ | 0.42％ |
Used in the presence of 1% NaHSO 3 Contains 0.5% Na 2 SO 3 Is an aqueous solution of (a)
From the above table, it was observed that the generation of the compound (a) as an impurity can be suppressed by washing with an aqueous bisulfite solution.
Industrial applicability
By the production method of the present invention, 2-dimethyl-3- ((Z) -1-propenyl) cyclopropanecarboxylic acid [4- (methoxymethyl) -2,3,5, 6-tetrafluorophenyl ] methyl ester having insecticidal activity can be produced.
Claims (4)
1. A process for the manufacture of [4- (methoxymethyl) -2,3,5, 6-tetrafluorophenyl ] methyl 2, 2-dimethyl-3- ((Z) -1-propenyl) cyclopropanecarboxylate,
a process for producing 2, 2-dimethyl-3- ((Z) -1-propenyl) cyclopropanecarboxylic acid [4- (methoxymethyl) -2,3,5, 6-tetrafluorophenyl ] methyl ester by reacting methyl 2, 2-dimethyl-3- ((Z) -1-propenyl) cyclopropanecarboxylate with [4- (methoxymethyl) -2,3,5, 6-tetrafluorophenyl ] methanol in the presence of lithium methoxide in an organic solvent, wherein a mixture of methyl 2, 2-dimethyl-3- ((Z) -1-propenyl) cyclopropanecarboxylate and [4- (methoxymethyl) -2,3,5, 6-tetrafluorophenyl ] methanol is washed with an aqueous bisulfite solution, and lithium methoxide is added to the mixture and reacted.
2. The method of claim 1, wherein,
the bisulphite is sodium bisulphite.
3. The method of claim 1, wherein,
the hydrosulfite aqueous solution is a sodium hydrosulfite aqueous solution with a concentration of 1-10 wt%.
4. The method according to claim 1 to 3, wherein,
the organic solvent is heptane.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019016771A JP6652205B1 (en) | 2019-02-01 | 2019-02-01 | Method for producing ester compound |
| JP2019-016771 | 2019-02-01 | ||
| PCT/JP2019/038081 WO2020158047A1 (en) | 2019-02-01 | 2019-09-27 | Method for producing ester compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113348161A CN113348161A (en) | 2021-09-03 |
| CN113348161B true CN113348161B (en) | 2023-11-28 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201980090304.2A Active CN113348161B (en) | 2019-02-01 | 2019-09-27 | Method for producing ester compound |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP6652205B1 (en) |
| CN (1) | CN113348161B (en) |
| WO (1) | WO2020158047A1 (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003267915A (en) * | 2002-01-10 | 2003-09-25 | Sumitomo Chem Co Ltd | Method for producing 3,3-dimethyl-2- formylcyclopropanecarboxylic acid derivative |
| CN1622929A (en) * | 2002-01-10 | 2005-06-01 | 住友化学工业株式会社 | Process for production of 3,3-dimethyl-2-formylcyclopropanecarboxylic acid derivatives |
| CN1930111A (en) * | 2004-03-25 | 2007-03-14 | 住友化学株式会社 | Preparation method for purified 3-methyl-2-butenyl acetate |
| WO2008020639A1 (en) * | 2006-08-18 | 2008-02-21 | Sumitomo Chemical Company, Limited | Process for production of trans-2,2-dimethyl- 3-formylcyclopropane carboxylic acid ester |
| JP2008069145A (en) * | 2006-08-18 | 2008-03-27 | Sumitomo Chemical Co Ltd | Method for producing trans-2,2-dimethyl-3-formylcyclopropanecarboxylic acid ester |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4604339B2 (en) * | 2000-11-29 | 2011-01-05 | 住友化学株式会社 | Method for producing ester compound |
| JP2004269507A (en) * | 2003-02-17 | 2004-09-30 | Sumitomo Chem Co Ltd | Method for producing fluorine-containing ester compound |
| JP2005082501A (en) * | 2003-09-05 | 2005-03-31 | Sumitomo Chemical Co Ltd | Method for manufacturing purified benzyl ester compound |
-
2019
- 2019-02-01 JP JP2019016771A patent/JP6652205B1/en active Active
- 2019-09-27 CN CN201980090304.2A patent/CN113348161B/en active Active
- 2019-09-27 WO PCT/JP2019/038081 patent/WO2020158047A1/en active Application Filing
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003267915A (en) * | 2002-01-10 | 2003-09-25 | Sumitomo Chem Co Ltd | Method for producing 3,3-dimethyl-2- formylcyclopropanecarboxylic acid derivative |
| CN1622929A (en) * | 2002-01-10 | 2005-06-01 | 住友化学工业株式会社 | Process for production of 3,3-dimethyl-2-formylcyclopropanecarboxylic acid derivatives |
| CN1930111A (en) * | 2004-03-25 | 2007-03-14 | 住友化学株式会社 | Preparation method for purified 3-methyl-2-butenyl acetate |
| WO2008020639A1 (en) * | 2006-08-18 | 2008-02-21 | Sumitomo Chemical Company, Limited | Process for production of trans-2,2-dimethyl- 3-formylcyclopropane carboxylic acid ester |
| JP2008069145A (en) * | 2006-08-18 | 2008-03-27 | Sumitomo Chemical Co Ltd | Method for producing trans-2,2-dimethyl-3-formylcyclopropanecarboxylic acid ester |
| CN101506142A (en) * | 2006-08-18 | 2009-08-12 | 住友化学株式会社 | Process for production of trans-2,2-dimethyl- 3-formylcyclopropane carboxylic acid ester |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6652205B1 (en) | 2020-02-19 |
| JP2020125244A (en) | 2020-08-20 |
| CN113348161A (en) | 2021-09-03 |
| WO2020158047A1 (en) | 2020-08-06 |
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