CN108707109A - A kind of preparation method of 2- methoxyl groups -4- trifluoromethyl pyridine -3- sulfonic acid chlorides - Google Patents
A kind of preparation method of 2- methoxyl groups -4- trifluoromethyl pyridine -3- sulfonic acid chlorides Download PDFInfo
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- CN108707109A CN108707109A CN201810991672.1A CN201810991672A CN108707109A CN 108707109 A CN108707109 A CN 108707109A CN 201810991672 A CN201810991672 A CN 201810991672A CN 108707109 A CN108707109 A CN 108707109A
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- methoxyl groups
- sulfonic acid
- trifluoromethyl
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/70—Sulfur atoms
- C07D213/71—Sulfur atoms to which a second hetero atom is attached
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- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
Abstract
The present invention provides a kind of preparation methods of the intermediate 2- methoxyl group -4- trifluoromethyl pyridine -3- sulfonic acid chlorides of pyroxsulam, belong to technical field of organic synthesis.2- methoxyl group -3- sulfydryl -4- trifluoromethyl pyridines are obtained by the reaction in the chloro- 4- trifluoromethyl pyridines of 2- methoxyl groups -3- and sodium hydroxide, sulphur and NaHS by this method, then obtain 2- methoxyl group -4- trifluoromethyl pyridine -3- sulfonic acid chlorides with chlorine reaction.Method provided by the invention it is easy to operate, process conditions are simple, safe, and yield is higher, and cost is relatively low, be suitble to industrialized production.
Description
Technical field
The invention belongs to technical field of organic synthesis, and in particular to a kind of 2- methoxyl groups -4- trifluoromethyl pyridine -3- sulphonyl
The preparation method of the intermediate 2- methoxyl group -4- trifluoromethyl pyridine -3- sulfonic acid chlorides of chlorine.
Background technology
Pyroxsulam is the wheat paddock cauline leaf process herbicide of The Dow Agrosciences, LLC., can prevent and kill off a variety of grassy weeds
And broad leaved weed, it is sulfonamides inner sucting conduction type, selective winter wheat field herbicide after seedling, broad weed-killing spectrum, activity of weeding
Height, drug action are fast.Territory of use is extensive.
Chinese patent CN1092195C is introduced, using 2- methoxyl group -4- trifluoromethyl pyridines as raw material and lithium methide, diisopropyl
Amine at -78 DEG C and after dipropyl disulfide reaction, reacts under the conditions of chlorine and 2- methoxyl group -4- trifluoromethyl pyridines-is made
3- sulfonic acid chlorides, this method are disadvantageous in that：Reaction needs Cryogenic Conditions, lithium methide price more demanding to consersion unit
Costliness, production is dangerous high, and product is required for column chromatography to purify, and yield is relatively low, and there are certain difficulty in industrialization.
Invention content
It is an object of the invention to overcome the deficiencies of existing technologies, provide that a kind of yield is higher, and cost is relatively low, safety
Height is suitable for the preparation method of the 2- methoxyl group -4- trifluoromethyl pyridine -3- sulfonic acid chlorides of industrialized production.
Realizing the technical solution of above-mentioned purpose of the present invention is：A kind of 2- methoxyl groups -4- trifluoromethyl pyridine -3- sulfonic acid chlorides
Preparation method, it is characterised in that include the following steps：
(1) sodium hydroxide, sulphur and NaHS are added in organic solvent, and back flow reaction to system dissolved clarification is at homogeneous
Afterwards, stop reaction, cooling；The chloro- 4- trifluoromethyl pyridines of 2- methoxyl groups -3- are added in reaction solution, continue back flow reaction, instead
After answering, removing solvent, acidification purify to obtain 2- methoxyl group -3- sulfydryl -4- trifluoromethyl pyridines；
(2) 2- methoxyl group -3- sulfydryl -4- trifluoromethyl pyridines are formed into suspension in organic solvent and water, is passed through chlorine
Gas is reacted, and after reaction, is layered, and 2- methoxyl group -4- trifluoromethyl pyridine -3- sulfonic acid chlorides are distilled to obtain in washing；
Its reaction route is as follows：
Preferably, organic solvent described in the step (1) is methanol, ethyl alcohol or isopropanol.
Preferably, the molar ratio of sodium hydroxide and the chloro- 4- trifluoromethyl pyridines of 2- methoxyl groups -3- is 1 in the step (1)
~3:1；Further, the molar ratio of sodium hydroxide and the chloro- 4- trifluoromethyl pyridines of 2- methoxyl groups -3- is in the step (1)
1.5~3:1.
Preferably, in the step (1) molar ratio of sulphur and the chloro- 4- trifluoromethyl pyridines of 2- methoxyl groups -3- be 1.5~
3:1；Further, the molar ratio of sulphur and the chloro- 4- trifluoromethyl pyridines of 2- methoxyl groups -3- is 1.5~2 in the step (1):
1。
Preferably, the molar ratio of NaHS and the chloro- 4- trifluoromethyl pyridines of 2- methoxyl groups -3- is in the step (1)
1.5~3:1；Further, in the step (1) NaHS and the chloro- 4- trifluoromethyl pyridines of 2- methoxyl groups -3- molar ratio
It is 2~3:1.
Preferably, purification step includes that crude product is dissolved in aqueous slkali in the step (1), filters out insoluble matter；It is acidified again,
It collects and solid is precipitated.
Preferably, reaction temperature is -5~30 DEG C in the step (2).
Preferably, organic solvent described in the step (2) is dichloromethane, formic acid or acetic acid.
Preferably, the mass ratio of organic solvent and water is 4.5~6 in the step (2):1.
The advantageous effect that the present invention obtains：The present invention's is easy to operate, and process conditions are simple, safe, and yield is higher,
Cost is relatively low, is suitble to industrialized production.
Specific implementation mode
The present invention is further described specifically with reference to embodiments, but not limited to this.
Embodiment 1
By 8.0g (0.2mol) sodium hydroxide, 15.6g (0.28mol) NaHS, 6.4g (0.2mol) sublimed sulfur is added
Into 150g absolute ethyl alcohols, temperature rising reflux, reaction is entirely molten to solid, stops reaction, and the ethanol solution of sodium polysulfide is made.It will
The chloro- 4- trifluoromethyl pyridines of 21.1g (0.1mol) 2- methoxyl groups -3- are added in reaction solution, back flow reaction 4 hours, air-distillation
Ethyl alcohol is removed, it is 2 or so that 10% dilute hydrochloric acid, which is added dropwise, to pH, filters to obtain crude product.
Crude product is dissolved in the NaOH aqueous solutions of 50g10%, 1h is stirred, filters out insoluble matter, filtrate with 10% dilute hydrochloric acid
It is acidified to pH=3, a large amount of yellow solids are precipitated, is filtered.Wet product is added in 140g dichloromethane and 30g water, cools to 0
DEG C, chlorine is passed through to solid dissolved clarification, is layered, organic layer is dried with 20g anhydrous magnesium sulfates, is concentrated to give 2- methoxyl group -4- fluoroforms
Yl pyridines -3- sulfonic acid chlorides 23.4g (two step total recoverys 85.1%).
The product of above-described embodiment confirms through nuclear-magnetism and mass spectrum.
All documents that the present invention refers to are incorporated herein by reference, and are individually drawn just as each document
It is used as with reference to such.
Claims (10)
1. a kind of preparation method of 2- methoxyl groups -4- trifluoromethyl pyridine -3- sulfonic acid chlorides, it is characterised in that include the following steps：
(1) sodium hydroxide, sulphur and NaHS are added in organic solvent, and back flow reaction to system dissolved clarification is stopped at after homogeneous
It only reacts, cools down；The chloro- 4- trifluoromethyl pyridines of 2- methoxyl groups -3- are added in reaction solution, back flow reaction, reaction knot are continued
Shu Hou, removing solvent, acidification purify to obtain 2- methoxyl group -3- sulfydryl -4- trifluoromethyl pyridines；
(2) 2- methoxyl group -3- sulfydryl -4- trifluoromethyl pyridines are formed into suspension in organic solvent and water, be passed through chlorine into
Row reaction is layered after reaction, and 2- methoxyl group -4- trifluoromethyl pyridine -3- sulfonic acid chlorides are distilled to obtain in washing；
Its reaction route is as follows：
2. the preparation method of 2- methoxyl groups -4- trifluoromethyl pyridine -3- sulfonic acid chlorides according to claim 1, feature exist
In organic solvent described in the step (1) is methanol, ethyl alcohol or isopropanol.
3. the preparation method of 2- methoxyl groups -4- trifluoromethyl pyridine -3- sulfonic acid chlorides according to claim 1, feature exist
In the molar ratio of sodium hydroxide and the chloro- 4- trifluoromethyl pyridines of 2- methoxyl groups -3- is 1~3 in the step (1):1.
4. the preparation method of 2- methoxyl groups -4- trifluoromethyl pyridine -3- sulfonic acid chlorides according to claim 1, feature exist
In the molar ratio of sulphur and the chloro- 4- trifluoromethyl pyridines of 2- methoxyl groups -3- is 1.5~3 in the step (1):1.
5. the preparation method of 2- methoxyl groups -4- trifluoromethyl pyridine -3- sulfonic acid chlorides according to claim 1, feature exist
In the molar ratio of NaHS and the chloro- 4- trifluoromethyl pyridines of 2- methoxyl groups -3- is 1.5~3 in the step (1):1.
6. according to the preparation method of claim 3~5 any one of them 2- methoxyl group -4- trifluoromethyl pyridine -3- sulfonic acid chlorides,
It is characterized in that, sodium hydroxide, sulphur, NaHS and the chloro- 4- trifluoromethyl pyridines of 2- methoxyl groups -3- in the step (1)
Molar ratio be 1.5~3:1.5~2:2~3:1.
7. the preparation method of 2- methoxyl groups -4- trifluoromethyl pyridine -3- sulfonic acid chlorides according to claim 1, feature exist
In purification step includes that crude product is dissolved in aqueous slkali in the step (1), filters out insoluble matter；It is acidified again, collects and be precipitated admittedly
Body.
8. the preparation method of 2- methoxyl groups -4- trifluoromethyl pyridine -3- sulfonic acid chlorides according to claim 1, feature exist
In reaction temperature is -5~30 DEG C in the step (2)..
9. the preparation method of 2- methoxyl groups -4- trifluoromethyl pyridine -3- sulfonic acid chlorides according to claim 1, feature exist
In organic solvent is dichloromethane, formic acid or acetic acid in the step (2).
10. the preparation method of 2- methoxyl groups -4- trifluoromethyl pyridine -3- sulfonic acid chlorides according to claim 9, feature exist
In the mass ratio of organic solvent and water is 4.5~6 in the step (2)：1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020139740A1 (en) * | 2018-12-27 | 2020-07-02 | Dow Agrosciences Llc | Preparation of sulfonamide herbicide process intermediates |
| WO2020139734A1 (en) * | 2018-12-27 | 2020-07-02 | Dow Agrosciences Llc | Preparation of sulfonamide herbicide process intermediates |
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| CN1206416A (en) * | 1996-09-24 | 1999-01-27 | 道农业科学公司 | N-([1,2,4] triazoloazinyl- benzenesulfonamide and pyridinesulfonamide composes and their use as herbicides |
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| CN1094490C (en) * | 1995-09-15 | 2002-11-20 | 圣诺菲合成实验室公司 | Quinolein-2(1H)-one derivatives as serotonin antagonists |
| CN1206416A (en) * | 1996-09-24 | 1999-01-27 | 道农业科学公司 | N-([1,2,4] triazoloazinyl- benzenesulfonamide and pyridinesulfonamide composes and their use as herbicides |
| CN1930164A (en) * | 2004-03-26 | 2007-03-14 | 美国陶氏益农公司 | Process for the preparation of n-([1,2,4]triazolopyrimidin-2-yl)aryl sulfonamides |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020139740A1 (en) * | 2018-12-27 | 2020-07-02 | Dow Agrosciences Llc | Preparation of sulfonamide herbicide process intermediates |
| WO2020139734A1 (en) * | 2018-12-27 | 2020-07-02 | Dow Agrosciences Llc | Preparation of sulfonamide herbicide process intermediates |
| CN113227052A (en) * | 2018-12-27 | 2021-08-06 | 科迪华农业科技有限责任公司 | Sulfonamide herbicide process intermediates preparation |
| CN113272277A (en) * | 2018-12-27 | 2021-08-17 | 科迪华农业科技有限责任公司 | Sulfonamide herbicide process intermediates preparation |
| US11390587B2 (en) | 2018-12-27 | 2022-07-19 | Corteva Agriscience Llc | Preparation of sulfonamide herbicide process intermediates |
| JP7489390B2 (en) | 2018-12-27 | 2024-05-23 | コルテバ アグリサイエンス エルエルシー | Preparation of sulfonamide herbicide process intermediates |
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Effective date of registration: 20220908 Address after: Room 205, Office Building, Qiaochang Modern Agriculture Co., Ltd., east of Bohai Second Road, north of Wutong Seventh Road, Binbei Street, Bincheng District, Binzhou City, Shandong Province, 256600 Applicant after: Shandong Tengbin Technology Co.,Ltd. Address before: 213012 No. 2188 Longcheng Road, bell tower area, Jiangsu, Changzhou Applicant before: CHANGZHOU WATSON FINE CHEMICAL CO.,LTD. |
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Application publication date: 20181026 |