CN100537530C - Synthesis process of sulcoatrione - Google Patents
Synthesis process of sulcoatrione Download PDFInfo
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- CN100537530C CN100537530C CNB200710069245XA CN200710069245A CN100537530C CN 100537530 C CN100537530 C CN 100537530C CN B200710069245X A CNB200710069245X A CN B200710069245XA CN 200710069245 A CN200710069245 A CN 200710069245A CN 100537530 C CN100537530 C CN 100537530C
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- chloro
- methyl
- preparation
- reaction
- sulphur humulone
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Abstract
The process of preparing sulcotrione includes the following steps: the acyl chlorination of 2-chloro-4-mesyl benzoic acid and solid phosgene in ionic liquid system in the presence of organic base A to obtain resultant liquid containing 2-chloro-4-mesyl benzoyl chloride; adding organic base B and cyclohexyl dione into the resultant liquid to produce serial reaction at 90-110 deg.c, and treating the resultant to obtain the target product sulcotrione. The present invention has simple technological process, short synthesis path, simple operation, high yield and environment friendship.
Description
(1) technical field
The present invention relates to a kind of new synthetic method of weedicide sulphur humulone.
(2) background technology
Sulphur humulone (2-(2-chloro-4-methylsulfonyl benzoyl)-hydroresorcinol) is a kind of cyclohexyl diketone weedicide that is used for control of maize field broadleaf weeds and gramineous weeds.Former medicine is filbert solid, and per os, through skin or inhalation test is all very low to toxicity such as Mammals, bird, fish and honeybees, does not also find residually in crop, and soil microorganisms is not had harmful effect yet, uses as safe as a house.
The sulphur humulone is the new herbicides that grows up over nearly 20 years; contain functional groups such as phenyl ring, methylsulfonyl, chlorine atom, benzoyl and cyclohexanedione in the structure; synthetic route relates generally to reactions steps such as alkylation, chlorination, oxidation, chloride and condensation, and it is more that synthetic route is reported.
For the environmental friendliness and the green chemical industry technology of developing a circular economy, reach energy saving purposes, we just had been devoted to the research of Green Chemistry synthetic technology in recent years, in the present invention, and to the methylbenzene thiophenol to be the new synthetic method that raw material has been studied preparation sulphur humulone.With use in the original traditional synthesis the big harmful chemical feedstocks of environmental influence is substituted with green chemical, simplified synthesis technique, shortened the reaction times, reduced raw materials cost, improved product yield, reduced the generation of the three wastes.
(3) summary of the invention
The objective of the invention is to be to provide work simplification, synthetic route is short, easy and simple to handle, yield is high and the sulphur humulone new synthetic method of greenization.
For reaching the object of the invention, the technical solution used in the present invention is as follows:
A kind of preparation method of sulphur humulone, carry out as follows: 2-chloro-4-methyl sulfonylbenzoic acid is in ion liquid system, in the presence of organic bases a, utilize solid phosgene to carry out acyl chloride reaction and make the reaction solution that contains 2-chloro-4-methylsulfonyl Benzoyl chloride accordingly at 50～110 ℃, add organic bases b, cyclohexanedione and carry out cascade reaction in 90～110 ℃ in described reaction solution, reaction product obtains target compound sulphur humulone after handling; The amount of substance ratio that feeds intake of described acyl chloride reaction is 2-chloro-4-methyl sulfonylbenzoic acid: solid phosgene: organic bases a is 1:0.4:0.3～1.5; 2-chloro-4-methyl sulfonylbenzoic acid amount of substance in organic bases b in the described cascade reaction, cyclohexanedione charging capacity and the acyl chloride reaction is than being 1:0.1～1.2:1; Described ion liquid consumption is that every mole of 2-chloro-4-methyl sulfonylbenzoic acid is with 100～1000 milliliters.
Described organic bases a or b independently are one of following separately: acid amides, pyridine or triethylamine, preferred triethylamine.
Described ionic liquid is one of following: imidazole salt, pyridine salt or ion liquid of quaternaries, respectively suc as formula shown in (I), (II), (III):
R in formula (I), formula (II), the formula (III)
1, R
6, R
11Be hydrogen or phenyl ring; R
2～R
5, R
7～R
10, R
12～R
14Independent separately is the alkyl of hydrogen or C1～C18, and L is BF
4, PF
6, OA
C, CF
3SO
3Or N (SO
2CF
3)
2
Further again, described ionic liquid is 1-alkyl-3-methyl imidazolium tetrafluoroborate or 1-alkyl-3-Methylimidazole hexafluorophosphate, is preferably 1-butyl-3-methyl imidazolium tetrafluoroborate or 1-ethyl-3-methyl imidazolium tetrafluoroborate or 1-butyl-3-Methylimidazole hexafluorophosphate or 1-ethyl-3-Methylimidazole hexafluorophosphate.Ion liquid consumption be every equimolar acid with 100～1000 milliliters, preferred every equimolar acid is with 500 milliliters.
Described solid phosgene has another name called triphosgene, and chemical name is two (trichloromethyl) carbonic ether, and molecular formula is C
3Cl
6O
3, molecular weight 296.75.Structural formula is suc as formula shown in (IV):
Further, described acyl chloride reaction is recommended in 50～110 ℃ and carried out 3～5 hours.
Described cascade reaction is recommended in 90～110 ℃ to carry out 3～5 hours.
Concrete, described sulphur humulone preparation method carries out according to following steps:
2-chloro-4-methyl sulfonylbenzoic acid is in 1-butyl-3-methyl imidazolium tetrafluoroborate ion liquid system, in the presence of triethylamine a, utilize solid phosgene to carry out acyl chloride reaction and made corresponding 2-chloro-4-methylsulfonyl Benzoyl chloride in 5 hours at 60 ℃, make in the 2-chloro-4-methylsulfonyl Benzoyl chloride ion liquid system toward above-mentioned acyl chloride reaction again, add triethylamine b, cyclohexanedione and carried out cascade reaction 5 hours in 100 ℃, reaction product obtains target compound sulphur humulone after handling; The amount of substance ratio that feeds intake of described acyl chloride reaction is 2-chloro-4-methyl sulfonylbenzoic acid: solid phosgene: triethylamine a is 1:0.4:1; 2-chloro-4-methyl sulfonylbenzoic acid amount of substance in organic bases b in the described cascade reaction, cyclohexanedione charging capacity and the acyl chloride reaction is than being 1:0.1～1.2:1; Described ion liquid consumption is that every mole of 2-chloro-4-methyl sulfonylbenzoic acid is with 500 milliliters.
Described 2-chloro-4-methyl sulfonylbenzoic acid makes by following A or B method:
The A method: compare methyl thiobenzoxide according to amount of substance: oxygenant: hydrochloric acid is that 1:3～8:2～6 feed intake; earlier in hydrochloric acid; adding is to methyl thiobenzoxide; 0～100 ℃ of control reaction temperature; slowly add oxygenant; reacted 5～10 hours, and be cooled to room temperature, separate out solid product and be described 2-chloro-4-methyl sulfonylbenzoic acid.
The B method: compare methylsulfonyl toluene according to amount of substance: oxygenant: hydrochloric acid is that 1:3～8:2～6 feed intake; earlier in hydrochloric acid; adding is to methylsulfonyl toluene; 0～100 ℃ of control reaction temperature; slowly add oxygenant; reacted 5～10 hours, and be cooled to room temperature, separate out solid product and be described 2-chloro-4-methyl sulfonylbenzoic acid.
Above 2-chloro-4-methyl sulfonylbenzoic acid prepares in A or the B method, and oxygenant is hydrogen peroxide, nitric acid, potassium permanganate, potassium bichromate or sodium dichromate 99, preferred hydrogen peroxide and potassium permanganate.
Concrete, described 2-chloro-4-methyl sulfonylbenzoic acid preparation method carries out according to following steps:
The A method: according to the amount of substance ratio be to methyl thiobenzoxide: oxygenant: hydrochloric acid is that 1:6:6 feeds intake, and in hydrochloric acid, adds methyl thiobenzoxide earlier; 60 ℃ of control reaction temperature slowly add oxygenant, react 10 hours; be cooled to room temperature, separate out solid 2-chloro-4-methyl sulfonylbenzoic acid.
The B method: according to amount of substance to methylsulfonyl toluene: oxygenant: hydrochloric acid is that 1:4:4 feeds intake, and in hydrochloric acid, adds methyl thiobenzoxide earlier; 80 ℃ of control reaction temperature slowly add oxygenant, react 10 hours; system is cooled to room temperature, separates out solid 2-chloro-4-methyl sulfonylbenzoic acid.
The A method is described also can be by the described method of document by methylbenzene thiophenol and methyl-sulfate reaction are made to methyl thiobenzoxide.The B method described to methylsulfonyl toluene can being that raw material makes with p-methyl benzenesulfonic acid or p-methyl benzene sulfonic chloride by the described method of document.These materials also can be directly from buying from commercially available.
The present invention compared with prior art, beneficial effect of the present invention is:
1) in ion liquid system, utilize solid phosgene to make corresponding acyl chlorides by 2-chloro-4-methyl sulfonylbenzoic acid, carry out cascade reaction with cyclohexanedione then and obtain sulphur humulone target compound.Simplify experimental procedure, reduced production cost.
2) provide by the method that the methyl thiobenzoxide one kettle way is made 2-chloro-4-methyl sulfonylbenzoic acid.
3) provide by the method that methylsulfonyl toluene one kettle way is made 2-chloro-4-methyl sulfonylbenzoic acid.
(4) embodiment
Below with specific embodiment technical scheme of the present invention is described, but protection scope of the present invention is not limited thereto.
The preparation of embodiment 1:2-chloro-4-methyl sulfonylbenzoic acid
In 1 liter of three-necked bottle, add methyl thiobenzoxide 42 gram (0.3 mole), hydrochloric acid 60 milliliters of (0.6 mole), 137 milliliters of 30% hydrogen peroxide (1.2 moles); control reaction temperature is at 80 ℃; reacted 10 hours; be cooled to room temperature; separate out 2-chloro-4-methyl sulfonylbenzoic acid solid product 42 grams, yield 60%.190～192 ℃ of fusing points.IR(KBr)：3007，1716，1317，1151，769cm
-1.
1H?NMR(DMSO-d
6)：δ：3.34(s，3H)，7.95～8.08(m，3H)，14.02(s，1H).MS?m/z：233(M
+-1，9.89)。
The preparation of embodiment 2:2-chloro-4-methyl sulfonylbenzoic acid
In 1 liter of three-necked bottle, add methylsulfonyl toluene 51 grams (0.3 mole); hydrochloric acid 60 milliliters of (0.6 mole), 105 milliliters of 30% hydrogen peroxide (0.9 mole); control reaction temperature is at 80 ℃; reacted 10 hours; be cooled to room temperature; separate out 2-chloro-4-methyl sulfonylbenzoic acid solid product 49 grams, yield 69%.
The preparation of embodiment 3:2-chloro-4-methyl sulfonylbenzoic acid
In 1 liter of three-necked bottle, add methylsulfonyl toluene 51 grams (0.3 mole); hydrochloric acid 120 milliliters of (1.2 moles), 245 milliliters of 30% hydrogen peroxide (2.1 moles); control reaction temperature is at 0 ℃; reacted 7 hours; be cooled to room temperature; separate out 2-chloro-4-methyl sulfonylbenzoic acid solid and produce 43 grams, yield 61%.
The preparation of embodiment 4:2-chloro-4-methylsulfonyl Benzoyl chloride
In 1 liter of three-necked bottle, add solid phosgene 119 grams (0.4 mole); 500 milliliters of 1-butyl-3-methyl imidazolium tetrafluoroborate ionic liquid; 2-chloro-4-methyl sulfonylbenzoic acid 235 grams (1 mole); pyridine 80 grams (1 mole); 110 ℃ of heating 5 hours; be cooled to room temperature, make 2-chloro-4-methylsulfonyl Benzoyl chloride as the next step.
The preparation of embodiment 5:2-chloro-4-methylsulfonyl Benzoyl chloride
In 1 liter of three-necked bottle, add solid phosgene 119 grams (0.4 mole); 100 milliliters of 1-butyl-3-methyl imidazolium tetrafluoroborate ionic liquid; 2-chloro-4-methyl sulfonylbenzoic acid 235 grams (1 mole); pyridine 24 grams (0.3 mole); 90 ℃ of heating 10 hours; be cooled to room temperature, make 2-chloro-4-methylsulfonyl Benzoyl chloride as the next step.
Embodiment 6: the preparation of sulphur humulone
In the 2-chloro-4-methylsulfonyl Benzoyl chloride ion liquid system that embodiment 4 makes, add cyclohexanedione 112 grams (1 mole), pyridine 80 grams (1 mole); 110 ℃ of reactions 5 hours, with toluene extraction, washing; concentrate, ethyl alcohol recrystallization gets target product 230 grams, yield 70%.138～140 ℃ of fusing points.IR(KBr)：3006，1657，1593，1552，1307，1154，779cm
-1.
1H?NMR(DMSO-d
6)：δ：2.05～2.84(m，6H)，3.10(s，3H)，7.37～7.96(m，3H)，16.07(s，1H).MS?m/z：327(M
+-1，9.89)。
The preparation of embodiment 7:2-chloro-4-methyl sulfonylbenzoic acid
In 1 liter of three-necked bottle, add methyl thiobenzoxide 42 gram (0.3 mole), hydrochloric acid 200 milliliters of (1.8 moles), 274 milliliters of 30% hydrogen peroxide (2.4 moles); control reaction temperature is at 20 ℃; reacted 10 hours; be cooled to room temperature; separate out 2-chloro-4-methyl sulfonylbenzoic acid solid product 47 grams, yield 66%.
The preparation of embodiment 8:2-chloro-4-methyl sulfonylbenzoic acid
In 1 liter of three-necked bottle, add methylsulfonyl toluene 51 grams (0.3 mole); hydrochloric acid 60 milliliters of (1.5 moles), 170 milliliters of 30% hydrogen peroxide (1.5 moles); control reaction temperature is at 50 ℃; reacted 5 hours; be cooled to room temperature; separate out 2-chloro-4-methyl sulfonylbenzoic acid solid product 44 grams, yield 64%.
The preparation of embodiment 9:2-chloro-4-methylsulfonyl Benzoyl chloride
In 1 liter of three-necked bottle, add solid phosgene 119 grams (0.4 mole); 200 milliliters of 1-butyl-3-methyl imidazolium tetrafluoroborate ionic liquid; 2-chloro-4-methyl sulfonylbenzoic acid 235 grams (1 mole); pyridine 120 grams (1.5 moles); 110 ℃ of heating 5 hours; be cooled to room temperature, make 2-chloro-4-methylsulfonyl Benzoyl chloride as the next step.
The preparation of embodiment 10:2-chloro-4-methylsulfonyl Benzoyl chloride
In 1 liter of three-necked bottle, add solid phosgene 119 grams (0.4 mole); 800 milliliters of 1-butyl-3-Methylimidazole hexafluorophosphate ionic liquid; 2-chloro-4-methyl sulfonylbenzoic acid 235 grams (1 mole); triethylamine 151 grams (1.5 moles); 110 ℃ of heating 5 hours; be cooled to room temperature, make 2-chloro-4-methylsulfonyl Benzoyl chloride as the next step.
The preparation of embodiment 11:2-chloro-4-methylsulfonyl Benzoyl chloride
In 1 liter of three-necked bottle, add solid phosgene 119 grams (0.4 mole); 1000 milliliters of 1-butyl-3-Methylimidazole hexafluorophosphate ionic liquid; 2-chloro-4-methyl sulfonylbenzoic acid 235 grams (1 mole); triethylamine 80 grams (0.8 mole); 100 ℃ of heating 8 hours; be cooled to room temperature, make 2-chloro-4-methylsulfonyl Benzoyl chloride as the next step.
Embodiment 12: the preparation of sulphur humulone
In the 2-chloro-4-methylsulfonyl Benzoyl chloride ion liquid system that embodiment 9 makes, add cyclohexanedione 112 grams (1 mole), pyridine 8 grams (0.1 mole); 100 ℃ of reactions 10 hours, with toluene extraction, washing; concentrate, ethyl alcohol recrystallization gets target product 197 grams, yield 60%.
Embodiment 13: the preparation of sulphur humulone
In the 2-chloro-4-methylsulfonyl Benzoyl chloride ion liquid system that embodiment 10 makes, add cyclohexanedione 112 grams (1 mole), triethylamine 121 grams (1.2 moles); 90 ℃ of reactions 8 hours, with toluene extraction, washing; concentrate, ethyl alcohol recrystallization gets target product 256 grams, yield 78%.
Claims (8)
1. the preparation method of a sulphur humulone, it is characterized in that carrying out as follows: 2-chloro-4-methyl sulfonylbenzoic acid is in ion liquid system, in the presence of organic bases a, utilize solid phosgene to carry out acyl chloride reaction and make the reaction solution that contains 2-chloro-4-methylsulfonyl Benzoyl chloride accordingly at 50～110 ℃, add organic bases b, cyclohexanedione and carry out cascade reaction in 90～110 ℃ in described reaction solution, reaction product obtains target compound sulphur humulone after handling; The amount of substance ratio that feeds intake of described acyl chloride reaction is 2-chloro-4-methyl sulfonylbenzoic acid: solid phosgene: organic bases a is 1:0.4:0.3～1.5; 2-chloro-4-methyl sulfonylbenzoic acid amount of substance in organic bases b in the described cascade reaction, cyclohexanedione charging capacity and the acyl chloride reaction is than being 1:0.1～1.2:1; Described ion liquid consumption is that every mole of 2-chloro-4-methyl sulfonylbenzoic acid is with 100～1000 milliliters;
Described ionic liquid is: formula (I) imidazole salt or formula (II) pyridine salt:
In formula (I), the formula (II), R
1, R
6Independent is hydrogen or phenyl ring; R
2～R
5, R
7～R
10Independent separately is the alkyl of hydrogen or C1～C18; L is BF
4, PF
6, OA
C, CF
3SO
3Or N (SO
2CF
3)
2
2. the preparation method of sulphur humulone as claimed in claim 1 is characterized in that described ionic liquid is alkyl-3-methyl imidazolium tetrafluoroborate of 1-C1～C18 or the alkyl of 1-C1～C18-3-Methylimidazole hexafluorophosphate.
3. the preparation method of sulphur humulone as claimed in claim 1 is characterized in that described ionic liquid is 1-butyl-3-methyl imidazolium tetrafluoroborate, 1-ethyl-3-methyl imidazolium tetrafluoroborate, 1-butyl-3-Methylimidazole hexafluorophosphate or 1-ethyl-3-Methylimidazole hexafluorophosphate.
4. the preparation method of sulphur humulone as claimed in claim 1 is characterized in that described organic bases a or organic bases b are separately independently for one of following: acid amides, pyridine or triethylamine.
5. the preparation method of sulphur humulone as claimed in claim 1 is characterized in that described acyl chloride reaction carried out 3～5 hours at 50～110 ℃.
6. the preparation method of sulphur humulone as claimed in claim 1 is characterized in that described cascade reaction carried out 3～5 hours at 90～110 ℃.
7. the preparation method of sulphur humulone as claimed in claim 1; it is characterized in that described 2-chloro-4-methyl sulfonylbenzoic acid makes as follows: according to amount of substance comparison methyl thiobenzoxide or to methylsulfonyl toluene: oxygenant: hydrochloric acid is that 1:3～8:2～6 feed intake; earlier in hydrochloric acid; adding is to methyl thiobenzoxide or to methylsulfonyl toluene; 0～100 ℃ of control reaction temperature; slowly add oxygenant; reacted 5～10 hours; be cooled to room temperature, separate out solid product and be described 2-chloro-4-methyl sulfonylbenzoic acid.
8. the preparation method of sulphur humulone as claimed in claim 7 is characterized in that described oxygenant is hydrogen peroxide, nitric acid, potassium permanganate, potassium bichromate or sodium dichromate 99.
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|---|---|---|---|
| CNB200710069245XA CN100537530C (en) | 2007-06-08 | 2007-06-08 | Synthesis process of sulcoatrione |
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|---|---|---|---|
| CNB200710069245XA CN100537530C (en) | 2007-06-08 | 2007-06-08 | Synthesis process of sulcoatrione |
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| CN101066944A CN101066944A (en) | 2007-11-07 |
| CN100537530C true CN100537530C (en) | 2009-09-09 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103772243B (en) * | 2013-12-30 | 2016-03-23 | 北京英力精化技术发展有限公司 | A kind of preparation method of mesotrione |
| GB2530838B (en) * | 2015-06-08 | 2020-01-22 | Rotam Agrochem Int Co Ltd | Process for purifying mesotrione |
| CN114805240B (en) * | 2022-06-28 | 2022-09-16 | 湖南速博生物技术有限公司 | Method for synthesizing fluoro-olefine sulfone by one-pot method |
Citations (5)
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|---|---|---|---|---|
| US5650373A (en) * | 1989-10-18 | 1997-07-22 | Hoechst Aktiengesellschaft | Herbicidal active substance combinations comprising a triketone and a second herbicide |
| US5886231A (en) * | 1995-01-25 | 1999-03-23 | Zeneca Limited | Process for the production of 2-(substituted benzoyl) 1,3 cyclohexanediones |
| US6218579B1 (en) * | 1997-11-27 | 2001-04-17 | Zeneca Limited | Process for the preparation of acylated cyclic 1,3-dicarbonyl compounds |
| US6291400B1 (en) * | 1987-03-19 | 2001-09-18 | Zeneca Limited | Herbicidal compounds |
| CN1860102A (en) * | 2003-10-02 | 2006-11-08 | 辛根塔参与股份公司 | Process for purifying mesotrione |
-
2007
- 2007-06-08 CN CNB200710069245XA patent/CN100537530C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6291400B1 (en) * | 1987-03-19 | 2001-09-18 | Zeneca Limited | Herbicidal compounds |
| US5650373A (en) * | 1989-10-18 | 1997-07-22 | Hoechst Aktiengesellschaft | Herbicidal active substance combinations comprising a triketone and a second herbicide |
| US5886231A (en) * | 1995-01-25 | 1999-03-23 | Zeneca Limited | Process for the production of 2-(substituted benzoyl) 1,3 cyclohexanediones |
| US6218579B1 (en) * | 1997-11-27 | 2001-04-17 | Zeneca Limited | Process for the preparation of acylated cyclic 1,3-dicarbonyl compounds |
| CN1860102A (en) * | 2003-10-02 | 2006-11-08 | 辛根塔参与股份公司 | Process for purifying mesotrione |
Non-Patent Citations (3)
| Title |
|---|
| 新型玉米除草剂甲基磺草酮的合成研究. 田学芳等.河北化工，第5期. 2005 * |
| 甲基磺草酮开发与使用. 苏少泉.农药，第43卷第5期. 2004 * |
| 除草剂磺草酮的合成方法. 郭胜等.农药，第40卷第7期. 2001 * |
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