CN103172549A - Preparation method of 2-(2-nitryl-4-methyl sulfuryl-benzoyl) cyclohexane-1,3-diketone - Google Patents
Preparation method of 2-(2-nitryl-4-methyl sulfuryl-benzoyl) cyclohexane-1,3-diketone Download PDFInfo
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Abstract
The invention relates to a preparation method of 2-(2-nitryl-4-methyl sulfuryl-benzoyl) cyclohexane-1,3-diketone (methyl mesotrione, mesotrione). The preparation method adopting 2-nitryl-4-methyl sulfuryl benzaldehyde and 1,3-cyclohexanedione as the materials comprises the following steps of: carrying out the reactions including nucleophilic addition, oxidation and the like to prepare the high-purity 2-(2-nitryl-4-methyl sulfuryl-benzoyl) cyclohexane-1,3-diketone. The preparation method disclosed by the invention is short in route; all steps are free of severe conditions, simple to operate, environment-friendly, remarkable in innovative significance and economic value and extensive in industrial production prospect.
Description
Technical field
the present invention relates to novel pesticide herbicide 2-(2-nitro-4-methylsulfonyl-benzoyl) hexanaphthene-1, preparation method and the production technique of 3-diketone (MST), method of the present invention is with 2-nitro-4-methylsulfonyl-phenyl aldehyde and 1, hydroresorcinol is raw material, through nucleophilic addition(Adn), the reactions such as oxidation prepare 2-(2-nitro-4-methylsulfonyl-benzoyl) hexanaphthene-1, the 3-diketone, product purity is greater than 99%, total recovery is more than 69%, it is brief that preparation method of the present invention has route, reaction conditions is gentle, operation is smooth, the characteristics such as environmental protection, be expected to be applied to actual production.。
Background technology
2-(2-nitro-4-methylsulfonyl-benzoyl) hexanaphthene-1; 3-diketone (MST) has another name called mesotrione, nitre sulphur ketone; it is a three ketones weedicide kind by the exploitation of Switzerland Syngenta Co.,Ltd; it is the inhibitor to oxypyroracemic acid dioxygenase (HPPD), tyrosine can be converted into plastoquinone.Mesotrione is by modifying sulphur humulone structure, and its biological activity surpasses the sulphur humulone more than 10 times, thereby has better exploitation potential quality and the market competitiveness.Novel systemic weedicide as a kind of corn field special use, it with broad weed-killing spectrum, activity is high, miscibility is strong, toxicity is low, environmentally friendly, to succession crop safety, use the characteristics such as flexible to obtain abroad immense success, also have larger exploitation to be worth and to promote the use of preferably prospect in China.
It is raw material that present synthetic report about MST substantially all adopts 2-nitryl-4-thiamphenicol benzoic acid/Benzoyl chloride and hydroresorcinol, and reaction process is as follows:
Wherein hydroresorcinol can be made by the Resorcinol hydro-reduction, and 2-nitryl-4-thiamphenicol benzoic acid/Benzoyl chloride all has more synthetic schemes at home and abroad, and main route gathers as follows:
1) chloroacetic acid route: take chloroacetic acid as raw material, synthesize (Jingxi Huagong Zhongjianti, 35 (2), 50-51,56,2005 through nitrated, methyl oxidation two-step reaction; Zhejiang Polytechnical University's journal, 35 (5), 493-494,2007; CN1995014).Raw materials used being easy to purchased, but needs to use the mixed acid system of concentrated nitric acid/vitriol oil in nitrifying process, and quantity of three wastes is very large.
2) Ortho Nitro Toluene route: take Ortho Nitro Toluene as raw material, further can be divided into the method for MSM oxidation and the method for sulfonating chlorinating → MSM → oxidation
The method steps of MSM oxidation is more brief, but agents useful for same is comparatively special, and yield lower (47%), and practical application also need be carried out a large amount of research work.(Russian?Journal?of?Organic?Chemistry(Translation?of?Zhurnal?Organicheskoi?Khimii),?34(11),?1573-1578,?1998)
Second method: the raw materials used price of sulfonating chlorinating method is easy to get, in production process, quantity of three wastes is less, but there is no at present document and directly synthesize the report of target compound with this route, can only be with reference to the pertinent literature of stepwise reaction and similar reaction, therefore this technique is still not mature enough, and reactions steps is more, still has a large amount of optimize work and need badly and complete.(Bioorganic?&?Medicinal?Chemistry,?10(6),?1841-1854,?2002;?Nippom?Kagaku?Kaishi,?11,?1694-1697,?1977;?J.?Org.?Chem.,?56,?4974-4976,?1991)
3) 4-methyl-3-nitro thioanisole route: take 4-methyl-3-nitro thioanisole as raw material, synthetic through the two-step oxidation reaction.This route there is no bibliographical information at present, just has theoretic possibility, and the raw materials used commercialized supply that not yet forms on market, does not temporarily possess practical value.
In addition, also having document to adopt 2-nitro-4-methylsulfonyltoluene and hydroresorcinol is raw material, through bromo, addition, oxidation three-step reaction synthetic (Jiangsu agricultural journal, 23 (6), 661-662,2006).This route has certain novelty, but needs in process with expensive anhydrous bromine, and high expensive is only suitable for laboratory preparation sample in a small amount at present, and large-scale industrial production is lacked competitiveness.
Summary of the invention
The present invention is on the relative merits basis of serious analysis target compound synthetic method; designed with 2-nitro-4-methylsulfonyl phenyl aldehyde and 1; hydroresorcinol is that starting raw material prepares 2-(2-nitro-4-methylsulfonyl-benzoyl) hexanaphthene-1; the method of 3-diketone (MST); this route is via nucleophilic addition(Adn), oxidation two-step reaction; the target product of the synthesis of high content of high yield; all steps are without severe condition; simple to operate; quantity of three wastes is few; have the original creation meaning, be fit to suitability for industrialized production.
For achieving the above object, a kind of 2-provided by the invention (2-nitro-4-methylsulfonyl-benzoyl) hexanaphthene-1, the synthetic method of 3-diketone (MST) comprises the following steps:
2-(2-nitro-4-methylsulfonyl-benzoyl) hexanaphthene-1, the structural formula of 3-diketone is as follows:
Its synthetic route is:
Concrete operation step is as follows:
Step 1: be under the condition of 5～45 ℃ in temperature, to 2-nitro-4-methylsulfonyl phenyl aldehyde and 1, the mixed solution and dripping alkaline solution of hydroresorcinol, note keeping temperature of reaction, dropwise, continued insulation reaction 0.5～2 hour, stopped reaction, namely get intermediate 2-(2-nitro-4-methylsulfonyl-benzyl hydroxyl) hexanaphthene-1, the mixed solution of 3-diketone can be directly used in next step reaction.
In step 1 of the present invention, solvent can be tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxane, DMF, methyl-sulphoxide, tetramethylene sulfone, ethylene dichloride, toluene etc., consumption be raw materials quality and 2～3 times, preferred toluene.
In step 1 of the present invention, alkaline solution can be mineral alkali, as aqueous sodium hydroxide solution (wt 15%), aqueous sodium carbonate (wt 15%), sodium bicarbonate aqueous solution (wt 20%) etc., also can be organic bases, as triethylamine, N, accelerine, N, N-dimethyl benzylamine, methyl Diisopropylamine, pyridine, 4-(N, N-dimethyl) pyridine, preferred N, the N-dimethyl benzylamine.
In step 1 of the present invention, reaction can be carried out in the temperature range of 5～45 ℃, preferred 10～15 ℃.
Step 2: be under the condition of 35～60 ℃, to 2-(2-nitro-4-methylsulfonyl-benzyl hydroxyl) hexanaphthene-1, to add oxygenant in the mixed solution of 3-diketone in temperature, continue to stir 1～3.5 hour, stopped heating, reaction solution is bathed cooling with cryosel, filter, wash product with water to neutral.Crude product further recrystallization is purified.
In step 2 of the present invention, oxygenant can be PCC, CrO
3/ pyridine, ceric ammonium nitrate-sulfuric acid, aluminum isopropylate, Peracetic Acid, benzoyl hydroperoxide, hydrogen peroxide etc., preferred hydrogen peroxide.
In step 2 of the present invention, reaction can be carried out in the temperature range of 35～60 ℃, preferred 40～45 ℃.
In step 2 of the present invention, recrystallization solvent can be methylene dichloride, chloroform, 1, and 2-ethylene dichloride, methyl acetate, ethyl acetate etc. are preferred 1, the 2-ethylene dichloride.
The invention relates to 2-(2-nitro-4-methylsulfonyl-benzoyl) hexanaphthene-1, the synthetic method of 3-diketone (MST), technical essential is:
(1) in intermediate 2-(2-nitro-4-methylsulfonyl-benzyl hydroxyl) hexanaphthene-1, in 3-diketone synthetic, select appropriate solvent, raw material and alkali there are good miscible effect, be conducive to addition reaction;
(2) in intermediate 2-(2-nitro-4-methylsulfonyl-benzyl hydroxyl) hexanaphthene-1, in 3-diketone synthetic, selects appropriate alkali, control temperature of reaction, the dehydration reaction of inhibition intermediate has improved yield.
The present invention is with 2-nitro-4-methylsulfonyl phenyl aldehyde and 1; hydroresorcinol is starting raw material; explored a preparation 2-capable of being industrialized (2-nitro-4-methylsulfonyl-benzoyl) hexanaphthene-1; the route of 3-diketone; its total recovery is more than 85%; product purity is greater than 99%, and this route institute has important actual application value in steps without severe condition, simple to operate, environmentally friendly.
Embodiment
In order to be illustrated more clearly in the present invention, hereinafter adopt indefiniteness embodiment to be described further.
Embodiment one:
(1) 2-(2-nitro-4-methylsulfonyl-benzyl hydroxyl) hexanaphthene-1,3-diketone (MST01) synthetic
Add successively 2-nitro-4-methylsulfonyl phenyl aldehyde (114.5g/0.5mol), 1 in the four-hole boiling flask of 2L, hydroresorcinol (67.2g/0.6mol) and 400ml toluene, stirring and evenly mixing, control temperature of reaction system at 10～15 ℃, drip N, N-dimethyl benzylamine (94.5g/0.7mol), dropwise, continue insulation reaction 1.5h, stopped reaction, to neutral, namely get the mixed solution of intermediate MST01 with dilute sulphuric acid (wt 20%) regulation system, can be directly used in next step reaction.
(2) 2-(2-nitro-4-methylsulfonyl-benzoyl) hexanaphthene-1,3-diketone (MST) synthetic
Control the mixeding liquid temperature of MST01 at 40～45 ℃, add 30% hydrogen peroxide (62.33g/0.55mol), stirring and evenly mixing, drip 120ml dilute sulphuric acid (wt 20%), dropwise, continue insulation reaction 2h, stopped heating, reaction solution is bathed with cryosel and is cooled to below 0 ℃, filter, filter cake with clear water drip washing until washings is neutrality, oven dry, obtain MST crude product 163.7g, content 95.7% (HPLC-outer marking quantitative), structure warp
1H-NMR, MS conclusive evidence.Select the further recrystallization of ethylene dichloride to purify to content greater than 99% (HPLC-outer marking quantitative) MST product 153.7g.
Two-step reaction yield 86.8%.
Embodiment two:
(1) 2-(2-nitro-4-methylsulfonyl-benzyl hydroxyl) hexanaphthene-1,3-diketone (MST01) synthetic
Add successively 2-nitro-4-methylsulfonyl phenyl aldehyde (114.5g/0.5mol), 1 in the four-hole boiling flask of 2L, hydroresorcinol (67.2g/0.6mol) and 400ml tetrahydrofuran (THF), stirring and evenly mixing, control temperature of reaction system at 35～40 ℃, drip 400ml aqueous sodium hydroxide solution (wt 5%), dropwise, continue insulation reaction 40min, stopped reaction, extremely neutral with dilute sulphuric acid (wt 20%) regulation system, namely get the mixed solution of intermediate MST01, can be directly used in next step reaction.
(2) 2-(2-nitro-4-methylsulfonyl-benzoyl) hexanaphthene-1,3-diketone (MST) synthetic
Control the mixeding liquid temperature of MST01 at 55～60 ℃, drip Peracetic Acid (41.5g/0.55mol), stirring and evenly mixing, dropwise, continue insulation reaction 1h, stopped heating, reaction solution are bathed with cryosel and are cooled to below 0 ℃, filter, until washings is neutral, oven dry obtains MST crude product 156.4g to filter cake with clear water drip washing, content 93.9% (HPLC-outer marking quantitative), the structure warp
1H-NMR, MS conclusive evidence.Further the methyl acetate recrystallization purifies to content greater than 99% (HPLC-outer marking quantitative) product 146.4g.
Two-step reaction yield 81.1%.
Embodiment three:
(1) 2-(2-nitro-4-methylsulfonyl-benzyl hydroxyl) hexanaphthene-1,3-diketone (MST01) synthetic
Add successively 2-nitro-4-methylsulfonyl phenyl aldehyde (114.5g/0.5mol), 1 in the four-hole boiling flask of 2L, hydroresorcinol (67.2g/0.6mol) and 400ml tetramethylene sulfone, stirring and evenly mixing, control temperature of reaction system at 10～15 ℃, drip 300ml aqueous sodium carbonate (wt 15%), dropwise, continue insulation reaction 2h, stopped reaction, extremely neutral with dilute sulphuric acid (wt 20%) regulation system, namely get the mixed solution of intermediate MST01, can be directly used in next step reaction.
(2) 2-(2-nitro-4-methylsulfonyl-benzoyl) hexanaphthene-1,3-diketone (MST) synthetic
Under room temperature condition, add ceric ammonium nitrate (164.4g/0.3mol), stirring and evenly mixing to the mixed solution of MST01, drip 50ml dilute sulphuric acid (wt 20%), dropwise, continue room temperature reaction 3h, stopped heating, reaction solution is bathed with cryosel and is cooled to below 0 ℃, filter, filter cake with clear water drip washing until washings is neutrality, oven dry, obtain MST crude product 160.8g, content 96.1% (HPLC-outer marking quantitative), structure warp
1H-NMR, MS conclusive evidence.Further Gossypol recrystallized from chloroform purifies to content greater than 99% (HPLC-outer marking quantitative) product 151.2g.
Two-step reaction yield 85.5%.
Claims (5)
1. claimed a kind of 2-(2-nitro-4-methylsulfonyl-benzoyl) hexanaphthene-1, the preparation method of 3-diketone (MST), react as follows:
Step 1: be under the condition of 5～45 ℃ in temperature, to 2-nitro-4-methylsulfonyl phenyl aldehyde and 1, the mixed solution and dripping alkaline solution of hydroresorcinol, note keeping temperature of reaction, dropwise, continued insulation reaction 0.5～2 hour, stopped reaction, namely get intermediate 2-(2-nitro-4-methylsulfonyl-benzyl hydroxyl) hexanaphthene-1, the mixed solution of 3-diketone can be directly used in next step reaction;
Step 2: be under the condition of 35～60 ℃ in temperature, to 2-(2-nitro-4-methylsulfonyl-benzyl hydroxyl) hexanaphthene-1, add oxygenant in the mixed solution of 3-diketone, continue to stir 1～3.5 hour, stopped heating, reaction solution is bathed cooling with cryosel, filter, wash product with water to neutral, crude product further recrystallization is purified.
2. according to claim 1 method, in step 1 of the present invention, solvent can be tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxane, DMF, methyl-sulphoxide, tetramethylene sulfone, ethylene dichloride, toluene etc., consumption be raw materials quality and 2～3 times; Alkaline solution can be aqueous sodium hydroxide solution (wt 5%), aqueous sodium hydroxide solution (wt 10%), aqueous sodium hydroxide solution (wt 15%), aqueous sodium carbonate (wt 15%), sodium bicarbonate aqueous solution (wt 20%) etc.; Reaction can be carried out in the temperature range of 5～45 ℃.
3. according to claim 2 method, is characterized in that solvent for use is toluene; Alkaline solution is aqueous sodium hydroxide solution (wt 5%); Reaction is carried out in the temperature range of 10～15 ℃.
4. according to claim 1 method, is characterized in that in described step 2, oxygenant can be PCC, CrO
3/ pyridine, ceric ammonium nitrate-sulfuric acid, aluminum isopropylate, Peracetic Acid, benzoyl hydroperoxide, hydrogen peroxide etc.; Reaction can be carried out in the temperature range of 35～60 ℃; Recrystallization solvent can be methylene dichloride, chloroform, 1,2-ethylene dichloride, methyl acetate, ethyl acetate etc.
5. according to claim 4 method, be characterised in that oxygenant is hydrogen peroxide; Reaction can be carried out in the temperature range of 40～45 ℃; Recrystallization solvent is 1,2-ethylene dichloride.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103965084A (en) * | 2014-05-14 | 2014-08-06 | 江苏常隆农化有限公司 | Production method of mesotrione |
| CN104086438A (en) * | 2014-06-30 | 2014-10-08 | 浙江中山化工集团股份有限公司 | Recycling process of methyl sulcotrione solvent |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1169139A (en) * | 1995-01-25 | 1997-12-31 | 曾尼卡有限公司 | Process for prodn. of 2-(substd. Benzyl)-1,3-cyclohexanediones |
| CN1169140A (en) * | 1995-01-25 | 1997-12-31 | 曾尼卡有限公司 | Process for prodn. of 2-(substd. benzoyl)-1,3-cyclohexanediones |
-
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1169139A (en) * | 1995-01-25 | 1997-12-31 | 曾尼卡有限公司 | Process for prodn. of 2-(substd. Benzyl)-1,3-cyclohexanediones |
| CN1169140A (en) * | 1995-01-25 | 1997-12-31 | 曾尼卡有限公司 | Process for prodn. of 2-(substd. benzoyl)-1,3-cyclohexanediones |
Non-Patent Citations (2)
| Title |
|---|
| 余刚，等: "玉米田除草剂甲基磺草酮的合成", 《江苏农业学报》, vol. 23, no. 6, 31 December 2007 (2007-12-31), pages 661 - 662 * |
| 田学芳，等: "新型玉米田除草剂甲基磺草酮的合成研究", 《河北化工》, no. 5, 31 December 2005 (2005-12-31), pages 32 - 33 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103965084A (en) * | 2014-05-14 | 2014-08-06 | 江苏常隆农化有限公司 | Production method of mesotrione |
| CN104086438A (en) * | 2014-06-30 | 2014-10-08 | 浙江中山化工集团股份有限公司 | Recycling process of methyl sulcotrione solvent |
| CN104086438B (en) * | 2014-06-30 | 2016-07-06 | 浙江中山化工集团股份有限公司 | A kind of mesotrione solvent recovery process |
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