CN105061362A - Preparation method of bentazon - Google Patents
Preparation method of bentazon Download PDFInfo
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- CN105061362A CN105061362A CN201510564067.2A CN201510564067A CN105061362A CN 105061362 A CN105061362 A CN 105061362A CN 201510564067 A CN201510564067 A CN 201510564067A CN 105061362 A CN105061362 A CN 105061362A
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- bentazone
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- isopropylamine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
- C07D285/15—Six-membered rings
- C07D285/16—Thiadiazines; Hydrogenated thiadiazines
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- Organic Chemistry (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
The invention relates to the field of pesticide synthesis, and discloses a preparation method of bentazon. The method comprises the following steps: mixing triethylamine, dichloroethane and isopropylamine, cooling, dropwisely adding chlorosulfonic acid, keeping the temperature for 0.5 hour, naturally heating, adding methyl anthranilate, dropwisely adding phosphorus oxychloride, and distilling under reduced pressure to remove the solvent, thereby obtaining an intermediate o-isopropylaminosulfamido methyl benzoate; and adding an alcohol solvent into the intermediate, dissolving by stirring, dropwisely adding sodium alkoxide at room temperature, and dropwisely adding dilute hydrochloric acid while cooling with ice water, thereby preparing the finished bentazon product. The synthesis process for synthesizing the intermediate o-isopropylaminosulfamido methyl benzoate has the advantages of short time, fewer steps, simple technique and high yield (up to 90%), and is easy to implement. The method does not need to adopt isopropylamino sulfonyl chloride which is difficult to purify as the raw material, and can easily implement industrial production. The raw material methanol can be recycled. Therefore, the method has wide application prospects in industrial production.
Description
Technical field
The present invention relates to a kind of preparation method of weedicide, particularly relate to a kind of preparation method of bentazone.
Background technology
Bentazone (bentazone), has another name called bentazone, is a kind of tool optionally contact killing type herbicide after seedling, for the process of weeds cauline leaf in seedling stage.Be mainly used in the crops such as paddy rice, soybean, peanut, wheat, prevent and kill off broadleaf weeds and sedge weed, invalid to gramineous weeds.Chemistry 3-sec.-propyl (1H)-benzo-2,1,3-thiadiazine-4-(3H)-one 2,2 dioxide by name.It is researched and developed successfully by BASF Corp. of Germany and worldwide a large amount of use at first.
According to DE2710382 and CN1063688A, be that raw material and Isopropylamine react and generate N-sec.-propyl anthranilamide with isatoic anhydride, then react with sulphur trioxide and form mixture, then with phosphorus oxychloride reaction, closed loop obtains product.The method is not refined intermediate N sec.-propyl anthranilamide in process of production further, thus there is the impurity such as anthranilic acid, and these impurity could not be removed in follow-up acid-alkali refining process, like this after being made into aquae concentrate, storage period one, namely length can be separated out, and impact uses.This technological reaction is complicated, is difficult to control, and use a large amount of picoline for acid binding agent, reclaim very difficult, cost is high, and the shortcoming such as wastewater flow rate is large.Germany Patent document DE2357063 discloses a kind of preparation method of bentazone, and it reacts by methyl o-aminobenzoate and isopropylamino SULPHURYL CHLORIDE, then obtain bentazone with sodium methylate pass ring.Germany Patent document DE2105687 also discloses similar approach in addition, just finally obtains bentazone with light air to close ring.But above-mentioned two kinds of methods are difficult to realize industrialization, mainly because the isopropylamino SULPHURYL CHLORIDE purification difficult of one of raw material.Niu Lizhong report a kind of bentazone production method (Niu Lizhong. the synthesising process research [D] of weedicide bentazone. Heilungkiang: Heilongjiang University, 2009), that chlorsulfonic acid is added triethylamine, in the solution of Isopropylamine and ethylene dichloride, it is allowed to react 1h, methyl o-aminobenzoate is added after having reacted, phosphorus oxychloride, synthetic intermediate N-(2-methoxy phosphinylidyne phenyl)-N '-sec.-propyl sulphamide, after reacting completely, add water stirring, make the triethylamine hydrochloride of generation, phosphoric acid salt is soluble in water, moisture is removed, organic layer distillation obtains intermediate N (2-methoxy phosphinylidyne phenyl)-N '-sec.-propyl sulphamide, then in methanol solution, sodium methylate closed loop is used, use HCl acidifying, obtain bentazone product.Chinese patent literature CN101830866, disclose similar production method, author first adds sulphonating agent SO3 or chlorsulfonic acid in organic solvent ethylene dichloride, then at low temperatures (-10 ~ 0 DEG C) adds triethylamine, it is allowed to generate sulphur trioxide/triethylamine double salt, then Isopropylamine is added, synthesizing isopropamide base sulfonic acid, again with methyl o-aminobenzoate, phosphorus oxychloride reaction, synthetic intermediate N-(2-methoxycarbonyl phenyl)-N '-sec.-propyl sulphonamide, distillation, washing, obtain solid intermediate, last in methanol solution, sodium methylate is used to make its closed loop, obtain target product bentazone.In bentazone synthesis technique disclosed in Chinese patent CN101863858, first allow methyl o-aminobenzoate react with chlorsulfonic acid under triethylamine exists, and then with Isopropylamine, phosphorus oxychloride reaction synthetic intermediate, then be added to the water, stir, the inorganic salt of triethylamine are soluble in water, leave standstill, water layer is separated, water layer ethylene dichloride extracts once, merges organic layer, distillation, obtain intermediate N (2-methoxy phosphinylidyne phenyl)-N '-sec.-propyl sulphamide, then obtain bentazone by sodium methylate closed loop.
In sum, also there are some problems in the preparation technology of current existing bentazone, and need to research and develop a kind of low in raw material price, the reaction times is short, and technique is simple, the preparation method of the bentazone of easy suitability for industrialized production.
Summary of the invention
Technical problem to be solved by this invention is, adopt picoline to reclaim the difficult problem such as difficulty, high, the seriously polluted and raw material isopropylamino SULPHURYL CHLORIDE purification difficult of cost for the method preparing bentazone in prior art, the invention provides a kind of cost low, pollute less, yield is high, be applicable to the preparation method of the bentazone of suitability for industrialized production.
In order to solve the problems of the technologies described above, the invention provides a kind of preparation method of bentazone, concrete adopted technical scheme is:
S1, add triethylamine, ethylene dichloride and Isopropylamine successively in a kettle.;
S2, icy salt solution are cooled to-10 ~ 0 DEG C, drip chlorsulfonic acid, are added dropwise to complete rear insulation 0.5h;
S3, be naturally warming up to 50 DEG C and add methyl o-aminobenzoate, reaction 0.5h;
S4, be cooled to 20 ~ 25 DEG C, drip phosphorus oxychloride, be warming up to 80 DEG C after dropwising and react;
S5, the product of S4 carried out to underpressure distillation except desolventizing, the crystallisation by cooling that adds water, filtration, washing, oven dry, obtain intermediate isopropyl sulfanilamide (SN);
S6, the product in S5 and methanol solvate to be joined in reactor successively, stirring and dissolving;
S7, add sodium methylate carry out ring-closure reaction at 20 ~ 25 DEG C, dropwise temperature rising reflux 1h, normal pressure reclaims methanol solvate;
S8, frozen water are cooled to-5 ~ 0 DEG C, drip dilute hydrochloric acid, drip finish centrifugal, washing, dry, obtain bentazone product.
The reaction end mark of described S4 is that raw material dissolves completely.
When preparing adjacent isopropylamine base sulfamoylbenzoic acid methyl esters, the mol ratio of each reaction raw materials is triethylamine: ethylene dichloride: Isopropylamine: chlorsulfonic acid: methyl o-aminobenzoate=4:20:1.5:1.44.
The molar weight of described methyl alcohol is 16 times of isopropyl sulfanilamide (SN).
The molar weight of described sodium methylate is 2 times of isopropyl sulfanilamide (SN).
Methanol solvate in described S6 can also replace with alcohol solvent.
Sodium methylate in described S7 can also replace with sodium ethylate or sodium hydroxide.
Reaction process of the present invention is as follows:
The first step: the preparation of adjacent isopropylamine base sulfamoylbenzoic acid methyl esters
Second step: cyclization and acidifying
The invention has the beneficial effects as follows:
1) to prepare reaction times of intermediate adjacent isopropylamine base sulfamoylbenzoic acid methyl esters shorter in the present invention;
2) to prepare the step of intermediate adjacent isopropylamine base sulfamoylbenzoic acid methyl esters few in the present invention, and technique is simple, easily realize, and yield reaches 90%;
3) the present invention does not need to adopt the isopropylamino SULPHURYL CHLORIDE being difficult to purify as raw material, is easy to suitability for industrialized production;
4) methyl alcohol used in ring-closure reaction of the present invention can be recycled at normal temperatures.
Embodiment
For making the object, technical solutions and advantages of the present invention clearly, below the present invention is described in further detail.
Embodiment 1
A preparation method for bentazone, is characterized in that first triethylamine, ethylene dichloride and Isopropylamine being added in reaction vessel, then adds chlorsulfonic acid, methyl o-aminobenzoate and phosphorus oxychloride successively, prepares intermediate adjacent isopropylamine base sulfamoylbenzoic acid methyl esters; Then in intermediate adjacent isopropylamine base sulfamoylbenzoic acid methyl esters, add methyl alcohol, after stirring and dissolving, add sodium methylate, dilute hydrochloric acid synthesis bentazone successively.
The preparation method of above-mentioned bentazone, comprises the following steps:
(1) triethylamine, ethylene dichloride and Isopropylamine are added successively in reaction vessel, icy salt solution drips chlorsulfonic acid at being cooled to 0 DEG C, adds rear insulation 0.5h, adds methyl o-aminobenzoate after naturally heating up, in 50 DEG C of reaction 0.5h.The mol ratio of each reaction raw materials is triethylamine: ethylene dichloride: Isopropylamine: chlorsulfonic acid: methyl o-aminobenzoate=4:20:1.5:1.44.Be cooled to room temperature, drip phosphorus oxychloride, be warmed up to about 80 DEG C reactions after adding to raw material does not have, underpressure distillation is except desolventizing, add water crystallisation by cooling, filtration, washing, oven dry, obtains intermediate adjacent isopropylamine base sulfamoylbenzoic acid methyl esters, yield 90%;
(2) adjacent isopropylamine base sulfamoylbenzoic acid methyl esters, methyl alcohol successively in another reaction vessel, the molar weight of methyl alcohol is 16 times of adjacent isopropylamine base sulfamoylbenzoic acid methyl esters, stirring and dissolving, at room temperature add sodium methylate, the molar weight of sodium methylate is 2 times of adjacent isopropylamine base sulfamoylbenzoic acid methyl esters, adds rear temperature rising reflux 1h, and normal pressure reclaims methyl alcohol, add suitable quantity of water, drip dilute hydrochloric acid under frozen water cooling, drip complete centrifugal, washing, dry to obtain bentazone finished product, yield 80%.
The invention has the beneficial effects as follows:
1) to prepare reaction times of intermediate adjacent isopropylamine base sulfamoylbenzoic acid methyl esters shorter in the present invention;
2) to prepare the step of intermediate adjacent isopropylamine base sulfamoylbenzoic acid methyl esters few in the present invention, and technique is simple, easily realize, and yield reaches 90%;
3) the present invention does not need to adopt the isopropylamino SULPHURYL CHLORIDE being difficult to purify as raw material, is easy to suitability for industrialized production;
4) methyl alcohol used in ring-closure reaction of the present invention can be recycled at normal temperatures.
The above is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Claims (7)
1. a preparation method for bentazone, is characterized in that, comprises the following steps:
S1, add triethylamine, ethylene dichloride and Isopropylamine successively in a kettle.;
S2, icy salt solution are cooled to-10 ~ 0 DEG C, drip chlorsulfonic acid, are added dropwise to complete rear insulation 0.5h;
S3, be naturally warming up to 50 DEG C and add methyl o-aminobenzoate, reaction 0.5h;
S4, be cooled to 20 ~ 25 DEG C, drip phosphorus oxychloride, be warming up to 80 DEG C after dropwising and react;
S5, the product of S4 carried out to underpressure distillation except desolventizing, the crystallisation by cooling that adds water, filtration, washing, oven dry, obtain intermediate isopropyl sulfanilamide (SN);
S6, the product in S5 and methanol solvate to be joined in reactor successively, stirring and dissolving;
S7, add sodium methylate carry out ring-closure reaction at 20 ~ 25 DEG C, dropwise temperature rising reflux 1h, normal pressure reclaims methanol solvate;
S8, frozen water are cooled to-5 ~ 0 DEG C, drip dilute hydrochloric acid, drip finish centrifugal, washing, dry, obtain bentazone product.
2. the preparation method of bentazone according to claim 1, is characterized in that, the reaction end mark of described S4 is that raw material dissolves completely.
3. the preparation method of bentazone according to claim 1 and 2, it is characterized in that, when preparing described intermediate isopropyl sulfanilamide (SN), the mol ratio of each reaction raw materials is triethylamine: ethylene dichloride: Isopropylamine: chlorsulfonic acid: methyl o-aminobenzoate=4:20:1.5:1.44.
4. the preparation method of bentazone according to claim 3, is characterized in that, the molar weight of described methyl alcohol is 16 times of isopropyl sulfanilamide (SN).
5. the preparation method of the bentazone according to claim 1,2 or 4, is characterized in that, the molar weight of described sodium methylate is 2 times of isopropyl sulfanilamide (SN).
6. the preparation method of bentazone according to claim 5, is characterized in that, the methanol solvate in described S6 can also replace with alcohol solvent.
7. the preparation method of the bentazone according to claim 1,4 or 6, is characterized in that, the sodium methylate in described S7 can also replace with sodium ethylate or sodium hydroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201510564067.2A CN105061362A (en) | 2015-09-07 | 2015-09-07 | Preparation method of bentazon |
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| CN201510564067.2A CN105061362A (en) | 2015-09-07 | 2015-09-07 | Preparation method of bentazon |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111269198A (en) * | 2020-02-18 | 2020-06-12 | 浙江工业大学 | Method for continuously preparing bentazon |
| CN111704592A (en) * | 2020-05-28 | 2020-09-25 | 山东潍坊润丰化工股份有限公司 | Production process for continuously preparing bentazon |
| CN112521344A (en) * | 2020-12-04 | 2021-03-19 | 宁夏蓝田农业开发有限公司 | Method for producing bentazone |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104693142A (en) * | 2015-03-31 | 2015-06-10 | 中国石油大学(华东) | Improved bentazone production method |
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2015
- 2015-09-07 CN CN201510564067.2A patent/CN105061362A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104693142A (en) * | 2015-03-31 | 2015-06-10 | 中国石油大学(华东) | Improved bentazone production method |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111269198A (en) * | 2020-02-18 | 2020-06-12 | 浙江工业大学 | Method for continuously preparing bentazon |
| CN111704592A (en) * | 2020-05-28 | 2020-09-25 | 山东潍坊润丰化工股份有限公司 | Production process for continuously preparing bentazon |
| CN112521344A (en) * | 2020-12-04 | 2021-03-19 | 宁夏蓝田农业开发有限公司 | Method for producing bentazone |
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Application publication date: 20151118 |