CN101602770A - A kind of preparation method of weedicide - Google Patents
A kind of preparation method of weedicide Download PDFInfo
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Abstract
A kind of preparation method of weedicide, the preparation method of the natural herbicide that provide a kind of reaction conditions gentleness, technology is simple, cost is low, easy large-scale industrialization is produced.Terpineol 350 is dissolved in the solvent, add alkali, metal oxide and superoxide, when gas chromatographic analysis show Terpineol 350 content less than total amount 0.5% the time stopped reaction, the filtered and recycled metal oxide, the filtrate distillating recovering solvent gets 1, the 2-epoxide, be dissolved in the solvent again, add acid, gas chromatographic analysis shows 1, the 2-epoxide content is less than 2% o'clock stopped reaction of total amount, the reaction solution distillating recovering solvent gets 1, and 2-epoxide isomerization product is dissolved in the reaction solvent again, adding alkali stirs, add the reaction of 2-methyl benzyl chlorine, gas chromatographic analysis shows the 2% o'clock stopped reaction of isomerate content less than total amount, and reaction solution is poured in the water, transfer pH to neutral, tell organic phase, the water extraction merges organic phase, distillating recovering solvent gets product.
Description
Technical field
The present invention relates to a kind of preparation method of weedicide.
Background technology
Cinmethylin claims Chinese mugwort to cut again, 1-methyl-4-(1-methylethyl)-2-(2-aminomethyl phenyl methoxyl group)-7-Evil two rings [2,2,1] heptane, (1RS, 2SR, 4SR)-1,4-bridging oxygen-right-Meng-2-base-2-methyl-benzylic ether (CAS NO 87818-31-3) belongs to Terpane (cineole) class weedicide, can effectively prevent and kill off most of Gramineae and sedge weed, as barnyard grass, Sheathed Monochoria, Herba Cyperi Difformis etc.As natural herbicide, cinmethylin has numerous good characteristics, obtains people's generally acceptance in the Europe and the U.S., and has entered Europe and market, Australia, obtains good effect, and market is just fast-developing, and huge demand space is arranged.
About synthesizing of cinmethylin, have some documents and patent report both at home and abroad, the method for employing is: trimethylacetic acid, (soil)-terpenes-4-alcohol, two (2, the 4-pentanedioic acid) vanadium (IV) oxide compound reflux 2h in methylene dichloride, drip p-methyl benzenesulfonic acid then, reaction mixture refluxed obtains (soil)-2-extension-hydroxyl-1-methyl-4-sec.-propyl-7-oxabicyclo [2,2,2, ] heptane, react in the presence of sodium hydride with adjacent methyl benzyl chloride again, obtain the product cinmethylin.
All there is deficiency in existing these synthetic methods, are mainly reflected in: 1) use lower boiling poisonous methylene dichloride as solvent in a large number, be difficult for reclaiming and can causing damage to human body, also strengthened production cost; 2) use the organo-metallic oxide compound to be catalyzer in the epoxidation, the process complexity is difficult for reclaiming, and cost is also high; 3) use dangerous high sodium hydride in the condensation reaction, have serious potential safety hazard, be unfavorable for industrial large-scale operation; 4) quality of product still remains to be improved (content＜96%), by product benzyl oxide content higher (＞1.5%).
Summary of the invention
The objective of the invention is to deficiency, the preparation method of the natural herbicide that provide a kind of reaction conditions gentleness, technology is simple, cost is low, easy large-scale industrialization is produced at above-mentioned existing synthetic method existence.
The present invention includes following steps:
1) 1, the preparation of 2-epoxide
Terpineol 350 is dissolved in the solvent, add alkali and metal oxide, drip superoxide then, continue stirring reaction, when gas chromatographic analysis show Terpineol 350 content less than total amount 0.5% the time stopped reaction, reacting liquid filtering reclaims metal oxide, filtrate distillating recovering solvent, get product 1, the 2-epoxide;
2) 1, the isomerization of 2-epoxide
With 1, the 2-epoxide is dissolved in the solvent, adds acid-respons, and gas chromatographic analysis shows 1, and the 2-epoxide content is less than 2% o'clock stopped reaction of total amount, and the reaction solution distillating recovering solvent gets 1,2-epoxide isomerization product;
3) condensation of isomerate
Isomerate is dissolved in the reaction solvent, adds alkali, mixed solution stirs, and in mixed solution, drip 2-methyl benzyl chlorine, continue stirring reaction, gas chromatographic analysis shows the 2% o'clock stopped reaction of isomerate content less than total amount, and reaction solution is directly poured in the water, add acid-conditioning solution pH to neutral, tell organic phase, water extracts with extraction solvent, merges organic phase, distillating recovering solvent gets product natural herbicide cinmethylin.
In step 1), press mass ratio, Terpineol 350: solvent is 1: (1～4); By mass percentage, the amount that adds alkali and metal oxide is respectively 0.2%～2.0% of Terpineol 350, and the temperature of described adding alkali and reactive metal oxide can be 20～60 ℃, and the best is 20～40 ℃; In molar ratio, the amount of splashing into of superoxide is 1.1～1.8 times of Terpineol 350, and the described time that splashes into superoxide is 20～100min, and the best is 40～60min; The time of described continuation stirring reaction can be 2～7h, and the best is 4h; Described solvent is selected from a kind of in methylene dichloride, the trimethyl carbinol, toluene, benzene, ethyl acetate, tetrahydrofuran (THF), the dioxane etc., and the best is an ethyl acetate; Press mass ratio, Terpineol 350: solvent the best is 1: 2; Described alkali is selected from yellow soda ash, triethylamine, salt of wormwood, diisopropylethylamine, 1, a kind of in 3-propylene diamine, the trolamine etc., and the best is a diisopropylethylamine; By mass percentage, the amount of adding alkali is preferably 1.5% of Terpineol 350; Described metal oxide is selected from a kind of in cupric oxide, ferric oxide, Vanadium Pentoxide in FLAKES, two (2, the 4-pentanedioic acid) barium oxide etc., and the best is a ferric oxide; By mass percentage, the amount of adding metal oxide is preferably 0.5% of Terpineol 350; Described superoxide is selected from peroxy tert-butyl alcohol, metachloroperbenzoic acid, the di-tert-butyl hydrogen peroxide etc. a kind of, and the best is a peroxy tert-butyl alcohol; In molar ratio, the amount of splashing into of superoxide is preferably 1.5 times of Terpineol 350.
In step 2) in, press mass ratio, 1, the 2-epoxide: solvent is 1: (2～5); By mass percentage, the add-on of acid is 1,0.5%～5% of 2-epoxide; The temperature of described adding acid-respons can be 20～60 ℃, and the time that adds acid-respons can be 4～12h, and the temperature that adds acid-respons is preferably 20～40 ℃, and the time that adds acid-respons is preferably 8h; Described solvent is selected from a kind of in methylene dichloride, toluene, benzene, ethyl acetate, tetrahydrofuran (THF), the dioxane etc., and the best is a toluene; Press mass ratio, 1, the 2-epoxide: solvent is preferably 1: 3; Described acid is selected from a kind of in Sulphanilic Acid, acetate, Phenylsulfonic acid, the tosic acid etc., and the best is a tosic acid; By mass percentage, Suan add-on is preferably 1,1% of 2-epoxide.
In step 3), press mass ratio, isomerate: reaction solvent can be 1: (2～5) are preferably 1: 2; In molar ratio, isomerate: alkali can be 1: (1.1～1.8) are preferably 1: 1.2; In molar ratio, isomerate: 2-methyl benzyl chlorine can be 1: (1.2～1.8) are preferably 1: 1.3; The time of described dropping 2-methyl benzyl chlorine is preferably 20～100min, the temperature of described continuation stirring reaction can be 20～80 ℃, the time of continuing stirring reaction can be 2～8h, and the temperature of described continuation stirring reaction is preferably 30～50 ℃, and the time of continuing stirring reaction is preferably 5h; Press mass ratio, isomerate: water can be 1: (2～5) are preferably 1: 3; Press mass ratio, isomerate: extraction solvent can be 1: (5～9) are preferably 1: 6; Described reaction solvent is selected from a kind of in methylene dichloride, toluene, benzene, the ethyl acetate etc., and the best is an ethyl acetate; Described alkali selects a kind of in white sodium hydroxide, sodium hydride, sodium amide, potassium hydroxide, potassium tert.-butoxide, the sodium tert-butoxide etc., and the best is a sodium hydroxide; Described acid is selected from a kind of in hydrochloric acid, sulfuric acid, acetate, the phosphoric acid etc., and the best is a hydrochloric acid; Described extraction solvent is selected from a kind of in methylene dichloride, toluene, benzene, the ethyl acetate etc., and the best is an ethyl acetate.
Compare with existing weedicide preparation technology, the present invention has following outstanding advantage:
1) the present invention is raw material with the Terpineol 350, the tool higher ethyl acetate of low toxicity again is a solvent, adopt the inorganic, metal oxide ferric oxide as epoxidation catalyst, the mineral alkali sodium hydroxide of safety is as condensation reagent, high yield makes the natural herbicide cinmethylin at low cost, and purity is more than 96%.
2) solvent and metal oxide are all recyclable, and pollute for a short time, have reduced production cost.
3) peroxy tert-butyl alcohol and 2-methyl benzyl chlorine add with the dropping form, and adopt mineral alkali sodium hydroxide as condensation reagent, have reduced the content (＜0.7%) of by product benzyl oxide, have improved quality product (content＞96%) and reaction yield.
4) adopt mineral alkali sodium hydroxide to replace sodium hydride commonly used, significantly reduce the potential safety hazard in the production.
5) reaction conditions gentleness, simple, easy to operate, the easy industrialized production of technology.
Embodiment
Embodiment 1
The preparation of (1) 1,2-epoxide
77g (0.5mol) Terpineol 350 is dissolved in the flask that fills the 77g ethyl acetate, and the diisopropylethylamine of adding 1.54g and the ferric oxide of 0.15g, stir down at 20 ℃, drip 70.4g (0.55mol) peroxy tert-butyl alcohol (content 70%), the dropping time is controlled at 40～60min, and continue stirring reaction 7h, gas chromatographic analysis shows that Terpineol 350 content was less than 0.5% o'clock stopped reaction.Reacting liquid filtering reclaims ferric oxide, and ethyl acetate is reclaimed in the filtrate distillation, gets product 1,2-epoxide, 70.5g, content 97.8%.
The isomerization of (2) 1,2-epoxide
(97.8%, 0.395mol) 1, the 2-epoxide is dissolved in the flask that fills 141g toluene, and adds the 0.35g tosic acid, and at 60 ℃ of following stirring reaction 4h, gas chromatographic analysis shows 1, and the 2-epoxide content was less than 2% o'clock stopped reaction with 70.5g.Toluene is reclaimed in the reaction solution distillation, gets 1,2-epoxide isomerization product, 62.5g, content 98.1%.
(3) condensation of isomerate
With 62.5g (98.1%, 0.361mol) isomerate is dissolved in the flask that fills the 188g ethyl acetate, the sodium hydroxide that adds 15.9g (0.397mol), mixed solution stirs, and in mixed solution, drip 60.7g (0.433mol) 2-methyl benzyl chlorine, the dropping time is controlled at 40～60min, and then at 20 ℃ of following stirring reaction 8h, gas chromatographic analysis shows that isomerate content was less than 2% o'clock stopped reaction.Reaction solution is directly poured in the water of 125g, adds hydrochloric acid conditioning solution pH to neutral.Tell organic phase, water divides three extractions with the ethyl acetate of 312g, merges organic phase, and ethyl acetate is reclaimed in distillation, gets product natural herbicide cinmethylin, 91.6g, content 96.2%.
Embodiment 2
The preparation of (1) 1,2-epoxide
77g (0.5mol) Terpineol 350 is dissolved in the flask that fills the 154g ethyl acetate, and the diisopropylethylamine of adding 0.2g and the ferric oxide of 0.4g, stir down at 30 ℃, drip 96g (0.75mol) peroxy tert-butyl alcohol (content 70%), the dropping time is controlled at 40～60min, and continue stirring reaction 4h, gas chromatographic analysis shows that Terpineol 350 content was less than 0.5% o'clock stopped reaction.Reacting liquid filtering reclaims ferric oxide, and ethyl acetate is reclaimed in the filtrate distillation, gets product 1,2-epoxide, 81.1g, content 98.5%.
The isomerization of (2) 1,2-epoxide
(98.5%, 0.470mol) 1, the 2-epoxide is dissolved in the flask that fills 243g toluene, and adds the 0.81g tosic acid, and at 30 ℃ of following stirring reaction 8h, gas chromatographic analysis shows 1, and the 2-epoxide content was less than 2% o'clock stopped reaction with 81.1g.Toluene is reclaimed in the reaction solution distillation, gets 1,2-epoxide isomerization product, 72.6g, content 98.8%.
(3) condensation of isomerate
With 72.6g (98.8%, 0.422mol) isomerate is dissolved in the flask that fills the 145g ethyl acetate, the sodium hydroxide that adds 20.3g (0.506mol), mixed solution stirs, and in mixed solution, drip 76.8g (0.549mol) 2-methyl benzyl chlorine, the dropping time is controlled at 40～60min, and then at 40 ℃ of following stirring reaction 5h, gas chromatographic analysis shows that isomerate content was less than 2% o'clock stopped reaction.Reaction solution is directly poured in the water of 218g, adds hydrochloric acid conditioning solution pH to neutral.Tell organic phase, water divides three extractions with the ethyl acetate of 436g, merges organic phase, and ethyl acetate is reclaimed in distillation, gets product natural herbicide cinmethylin, 107.4g, content 96.6%.
Embodiment 3
The preparation of (1) 1,2-epoxide
77g (0.5mol) Terpineol 350 is dissolved in the flask that fills the 308g ethyl acetate, and the diisopropylethylamine of adding 0.77g and the ferric oxide of 1.54g, stir down at 60 ℃, drip 115g (0.9mol) peroxy tert-butyl alcohol (content 70%), the dropping time is controlled at 40～60min, and continue stirring reaction 2h, gas chromatographic analysis shows that Terpineol 350 content was less than 0.5% o'clock stopped reaction.Reacting liquid filtering reclaims ferric oxide, and ethyl acetate is reclaimed in the filtrate distillation, gets product 1,2-epoxide, 78.2g, content 98.2%.
The isomerization of (2) 1,2-epoxide
(98.2%, 0.452mol) 1, the 2-epoxide is dissolved in the flask that fills 391g toluene, and adds the 3.91g tosic acid, and at 20 ℃ of following stirring reaction 12h, gas chromatographic analysis shows 1, and the 2-epoxide content was less than 2% o'clock stopped reaction with 78.2g.Toluene is reclaimed in the reaction solution distillation, gets 1,2-epoxide isomerization product, 65.2g, content 98.5%.
(3) condensation of isomerate
With 65.2g (98.5%, 0.377mol) isomerate is dissolved in the flask that fills the 326g ethyl acetate, the sodium hydroxide that adds 27.2g (0.679mol), mixed solution stirs, and in mixed solution, drip 95.1g (0.679mol) 2-methyl benzyl chlorine, the dropping time is controlled at 40～60min, and then at 60 ℃ of following stirring reaction 2h, gas chromatographic analysis shows that isomerate content was less than 2% o'clock stopped reaction.Reaction solution is directly poured in the water of 326g, adds hydrochloric acid conditioning solution pH to neutral.Tell organic phase, water divides three extractions with the ethyl acetate of 587g, merges organic phase, and ethyl acetate is reclaimed in distillation, gets product natural herbicide cinmethylin, 96.7g, content 96.6%.
Embodiment 4
The preparation of (1) 1,2-epoxide
77g (0.5mol) Terpineol 350 is dissolved in the flask that fills the 308g methylene dichloride, and the triethylamine of adding 1.54g and the Vanadium Pentoxide in FLAKES of 1.54g, stir down at 20 ℃, drip 83.2g (0.65mol) peroxy tert-butyl alcohol (content 70%), the dropping time is controlled at 40～60min, and continue stirring reaction 3h, gas chromatographic analysis shows that Terpineol 350 content was less than 0.5% o'clock stopped reaction.Reacting liquid filtering reclaims Vanadium Pentoxide in FLAKES, and methylene dichloride is reclaimed in the filtrate distillation, gets product 1,2-epoxide, 76.4g, content 98.1%.
The isomerization of (2) 1,2-epoxide
(98.1%, 0.441mol) 1, the 2-epoxide is dissolved in the flask that fills the 153g ethyl acetate with 76.4g, and adding 0.8g Sulphanilic Acid, at 60 ℃ of following stirring reaction 5h, gas chromatographic analysis shows 1, and the 2-epoxide content was less than 2% o'clock stopped reaction.Ethyl acetate is reclaimed in the reaction solution distillation, gets 1,2-epoxide isomerization product, 66.2g, content 98.6%.
(3) condensation of isomerate
With 66.2g (98.6%, 0.384mol) isomerate is dissolved in the flask that fills the 132g methylene dichloride, the sodium amide that adds 16.5g (0.422mol), mixed solution stirs, and in mixed solution, drip 64.5g (0.461mol) 2-methyl benzyl chlorine, the dropping time is controlled at 40～60min, and then at 20 ℃ of following stirring reaction 8h, gas chromatographic analysis shows that isomerate content was less than 2% o'clock stopped reaction.Reaction solution is directly poured in the water of 265g, adds acetate regulator solution pH to neutral.Tell organic phase, water divides three extractions with the methylene dichloride of 331g, merges organic phase, and methylene dichloride is reclaimed in distillation, gets product natural herbicide cinmethylin, 93.6g, content 96.2%.
Embodiment 5
The preparation of (1) 1,2-epoxide
77g (0.5mol) Terpineol 350 is dissolved in the flask that fills 308g toluene, and the yellow soda ash of adding 1.2g and the Vanadium Pentoxide in FLAKES of 0.4g, stir down at 60 ℃, drip 97g (0.55mol) metachloroperbenzoic acid, the dropping time is controlled at 40～60min, and continue stirring reaction 3h, gas chromatographic analysis shows that Terpineol 350 content was less than 0.5% o'clock stopped reaction.Reacting liquid filtering reclaims Vanadium Pentoxide in FLAKES, and toluene is reclaimed in the filtrate distillation, gets product 1,2-epoxide, 76.1g, content 98.2%.
The isomerization of (2) 1,2-epoxide
(98.2%, 0.440mol) 1, the 2-epoxide is dissolved in the flask that fills the 152g methylene dichloride with 76.1g, and adding 0.38g Sulphanilic Acid, at 40 ℃ of following stirring reaction 10h, gas chromatographic analysis shows 1, and the 2-epoxide content was less than 2% o'clock stopped reaction.Methylene dichloride is reclaimed in the reaction solution distillation, gets 1,2-epoxide isomerization product, 71.6g, content 98.8%.
(3) condensation of isomerate
With 71.6g (98.8%, 0.416mol) isomerate is dissolved in the flask that fills the 358g methylene dichloride, the sodium amide that adds 29.2g (0.749mol), mixed solution stirs, and in mixed solution, drip 87.4g (0.624mol) 2-methyl benzyl chlorine, the dropping time is controlled at 40～60min, and then at 30 ℃ of following stirring reaction 6h, gas chromatographic analysis shows that isomerate content was less than 2% o'clock stopped reaction.Reaction solution is directly poured in the water of 286g, adds sulfuric acid regulation solution pH to neutral.Tell organic phase, water divides three extractions with the methylene dichloride of 358g, merges organic phase, and benzene is reclaimed in distillation, gets product natural herbicide cinmethylin, 102.4g, content 96.3%.
Embodiment 6
The preparation of (1) 1,2-epoxide
77g (0.5mol) Terpineol 350 is dissolved in the flask that fills 231g benzene, and add two (2 of the trolamine of 1.2g and 0.3g, the 4-pentanedioic acid) barium oxide, stir down at 60 ℃, drip 158g (0.9mol) metachloroperbenzoic acid, the dropping time is controlled at 40～60min, and continues stirring reaction 3h, and gas chromatographic analysis shows that Terpineol 350 content was less than 0.5% o'clock stopped reaction.Reacting liquid filtering reclaims two (2, the 4-pentanedioic acid) barium oxides, and benzene is reclaimed in the filtrate distillation, gets product 1,2-epoxide, 74.8g, content 98.6%.
The isomerization of (2) 1,2-epoxide
(98.6%, 0.434mol) 1, the 2-epoxide is dissolved in the flask that fills the 374g methylene dichloride, and adds 3.74g acetate, and at 40 ℃ of following stirring reaction 6h, gas chromatographic analysis shows 1, and the 2-epoxide content was less than 2% o'clock stopped reaction with 74.8g.Methylene dichloride is reclaimed in the reaction solution distillation, gets 1,2-epoxide isomerization product, 68.2g, content 98.4%.
(3) condensation of isomerate
With 68.2g (98.4%, 0.395mol) isomerate is dissolved in the flask that fills 273g benzene, the sodium hydride that adds 17g (0.711mol), mixed solution stirs, and in mixed solution, drip 83g (0.592mol) 2-methyl benzyl chlorine, the dropping time is controlled at 40～60min, and then at 80 ℃ of following stirring reaction 4h, gas chromatographic analysis shows that isomerate content was less than 2% o'clock stopped reaction.Reaction solution is directly poured in the water of 205g, adds phosphoric acid regulator solution pH to neutral.Tell organic phase, water divides three extractions with the benzene of 341g, merges organic phase, and benzene is reclaimed in distillation, gets product natural herbicide cinmethylin, 96.8g, content 96.4%.
Embodiment 7
The preparation of (1) 1,2-epoxide
77g (0.5mol) Terpineol 350 is dissolved in the flask that fills the 231g trimethyl carbinol, and add 1 of 1.2g, the oxydone of 3-propylene diamine and 0.4g, stir down at 60 ℃, drip 96g (0.75mol) peroxy tert-butyl alcohol (content 70%), the dropping time is controlled at 40～60min, and continues stirring reaction 3h, and gas chromatographic analysis shows that Terpineol 350 content was less than 0.5% o'clock stopped reaction.Reacting liquid filtering reclaims cupric oxide, and the trimethyl carbinol is reclaimed in the filtrate distillation, gets product 1,2-epoxide, 73.6g, content 98.5%.
The isomerization of (2) 1,2-epoxide
(98.5%, 0.426mol) 1, the 2-epoxide is dissolved in the flask that fills the 241g dioxane, and adds the 0.8g Phenylsulfonic acid, and at 60 ℃ of following stirring reaction 4h, gas chromatographic analysis shows 1, and the 2-epoxide content was less than 2% o'clock stopped reaction with 73.6g.Dioxane is reclaimed in the reaction solution distillation, gets 1,2-epoxide isomerization product, 68.2g, content 98.7%.
(3) condensation of isomerate
With 68.2g (98.7%, 0.396mol) isomerate is dissolved in the flask that fills 205g toluene, the sodium tert-butoxide that adds 57.6g (0.594mol), mixed solution stirs, and in mixed solution, drip 77.6g (0.554mol) 2-methyl benzyl chlorine, the dropping time is controlled at 40～60min, and then at 80 ℃ of following stirring reaction 3h, gas chromatographic analysis shows that isomerate content was less than 2% o'clock stopped reaction.Reaction solution is directly poured in the water of 205g, adds acetate regulator solution pH to neutral.Tell organic phase, water divides three extractions with the toluene of 477g, merges organic phase, and toluene is reclaimed in distillation, gets product natural herbicide cinmethylin, 100.6g, content 96.7%.
Embodiment 8
The preparation of (1) 1,2-epoxide
77g (0.5mol) Terpineol 350 is dissolved in the flask that fills the 154g ethyl acetate, and the diisopropylethylamine of adding 1.2g and the ferric oxide of 0.4g, stir down at 40 ℃, drip 96g (0.75mol) peroxy tert-butyl alcohol (content 70%), the dropping time is controlled at 40～60min, and continue stirring reaction 4h, gas chromatographic analysis shows that Terpineol 350 content was less than 0.5% o'clock stopped reaction.Reacting liquid filtering reclaims ferric oxide, and ethyl acetate is reclaimed in the filtrate distillation, gets product 1,2-epoxide, 81.2g, content 98.3%.
The isomerization of (2) 1,2-epoxide
(98.3%, 0.470mol) 1, the 2-epoxide is dissolved in the flask that fills 243g toluene, and adds the 0.81g tosic acid, and at 40 ℃ of following stirring reaction 8h, gas chromatographic analysis shows 1, and the 2-epoxide content was less than 2% o'clock stopped reaction with 81.2g.Toluene is reclaimed in the reaction solution distillation, gets 1,2-epoxide isomerization product, 73.5g, content 98.4%.
(3) condensation of isomerate
With 73.5g (98.4%, 0.425mol) isomerate is dissolved in the flask that fills the 147g ethyl acetate, the sodium hydroxide that adds 20.4g (0.511mol), mixed solution stirs, and in mixed solution, drip 77.5g (0.553mol) 2-methyl benzyl chlorine, the dropping time is controlled at 40～60min, and then at 50 ℃ of following stirring reaction 5h, gas chromatographic analysis shows that isomerate content was less than 2% o'clock stopped reaction.Reaction solution is directly poured in the water of 221g, adds hydrochloric acid conditioning solution pH to neutral.Tell organic phase, water divides three extractions with the ethyl acetate of 442g, merges organic phase, and ethyl acetate is reclaimed in distillation, gets product natural herbicide cinmethylin, 107.8g, content 96.5%.
Embodiment 9
The preparation of (1) 1,2-epoxide
77g (0.5mol) Terpineol 350 is dissolved in the flask that fills the 154g ethyl acetate, and the diisopropylethylamine of adding 1.2g and the ferric oxide of 0.4g, stir down at 20 ℃, drip 96g (0.75mol) peroxy tert-butyl alcohol (content 70%), the dropping time is controlled at 40～60min, and continue stirring reaction 4h, gas chromatographic analysis shows that Terpineol 350 content was less than 0.5% o'clock stopped reaction.Reacting liquid filtering reclaims ferric oxide, and ethyl acetate is reclaimed in the filtrate distillation, gets product 1,2-epoxide, 80.2g, content 98.6%.
The isomerization of (2) 1,2-epoxide
(98.6%, 0.465mol) 1, the 2-epoxide is dissolved in the flask that fills 241g toluene, and adds the 0.8g tosic acid, and at 20 ℃ of following stirring reaction 8h, gas chromatographic analysis shows 1, and the 2-epoxide content was less than 2% o'clock stopped reaction with 80.2g.Toluene is reclaimed in the reaction solution distillation, gets 1,2-epoxide isomerization product, 73.4g, content 98.7%.
(3) condensation of isomerate
With 73.4g (98.7%, 0.426mol) isomerate is dissolved in the flask that fills the 147g ethyl acetate, the sodium hydroxide that adds 20.5g (0.512mol), mixed solution stirs, and in mixed solution, drip 77.6g (0.554mol) 2-methyl benzyl chlorine, the dropping time is controlled at 4O～60min, and then at 30 ℃ of following stirring reaction 5h, gas chromatographic analysis shows that isomerate content was less than 2% o'clock stopped reaction.Reaction solution is directly poured in the water of 220g, adds hydrochloric acid conditioning solution pH to neutral.Tell organic phase, water divides three extractions with the ethyl acetate of 440g, merges organic phase, and ethyl acetate is reclaimed in distillation, gets product natural herbicide cinmethylin, 107.5g, content 96.6%.
Claims (10)
1. the preparation method of a weedicide is characterized in that comprising the steps:
1) 1, the preparation of 2-epoxide
Terpineol 350 is dissolved in the solvent, after adding alkali and reactive metal oxide, splash into superoxide, continue stirring reaction, when gas chromatographic analysis show Terpineol 350 content less than total amount 0.5% the time stopped reaction, reacting liquid filtering reclaims metal oxide, filtrate distillating recovering solvent, get product 1, the 2-epoxide;
2) 1, the isomerization of 2-epoxide
With 1, the 2-epoxide is dissolved in the solvent, adds acid-respons, and gas chromatographic analysis shows 1, and the 2-epoxide content is less than 2% o'clock stopped reaction of total amount, and the reaction solution distillating recovering solvent gets 1,2-epoxide isomerization product;
3) condensation of isomerate
Isomerate is dissolved in the reaction solvent, adds alkali, mixed solution stirs, and in mixed solution, drip 2-methyl benzyl chlorine, continue stirring reaction, gas chromatographic analysis shows the 2% o'clock stopped reaction of isomerate content less than total amount, and reaction solution is directly poured in the water, add acid-conditioning solution pH to neutral, tell organic phase, water extracts with extraction solvent, merges organic phase, distillating recovering solvent gets product natural herbicide cinmethylin.
2. the preparation method of a kind of weedicide as claimed in claim 1, it is characterized in that pressing mass ratio in step 1), Terpineol 350: solvent is 1: 1～4; By mass percentage, the amount of adding alkali and metal oxide is respectively 0.2%～2.0% of Terpineol 350; In molar ratio, the amount of splashing into of superoxide is 1.1～1.8 times of Terpineol 350.
3. the preparation method of a kind of weedicide as claimed in claim 1 is characterized in that in step 1), and the temperature of described adding alkali and reactive metal oxide is 20～60 ℃; The described time that splashes into superoxide is 20～100min; The time of described continuation stirring reaction is 2～7h.
4. the preparation method of a kind of weedicide as claimed in claim 1 is characterized in that in step 1), and described solvent is selected from a kind of in methylene dichloride, the trimethyl carbinol, toluene, benzene, ethyl acetate, tetrahydrofuran (THF), the dioxane; Described alkali is selected from yellow soda ash, triethylamine, salt of wormwood, diisopropylethylamine, 1, a kind of in 3-propylene diamine, the trolamine; Described metal oxide is selected from a kind of in cupric oxide, ferric oxide, Vanadium Pentoxide in FLAKES, two (2, the 4-pentanedioic acid) barium oxide; Described superoxide is selected from a kind of in peroxy tert-butyl alcohol, metachloroperbenzoic acid, the di-tert-butyl hydrogen peroxide.
5. the preparation method of a kind of weedicide as claimed in claim 1 is characterized in that in step 2) in, press mass ratio, 1, the 2-epoxide: solvent is 1: 2～5; By mass percentage, the add-on of acid is 1,0.5%～5% of 2-epoxide.
6. the preparation method of a kind of weedicide as claimed in claim 1 is characterized in that in step 2) in, the temperature of described adding acid-respons is 20～60 ℃, the time that adds acid-respons is 4～12h.
7. the preparation method of a kind of weedicide as claimed in claim 1 is characterized in that in step 2) in, described solvent is selected from a kind of in methylene dichloride, toluene, benzene, ethyl acetate, tetrahydrofuran (THF), the dioxane; Described acid is selected from a kind of in Sulphanilic Acid, acetate, Phenylsulfonic acid, the tosic acid.
8. the preparation method of a kind of weedicide as claimed in claim 1, it is characterized in that pressing mass ratio in step 3), isomerate: reaction solvent is 1: 2～5; In molar ratio, isomerate: alkali is 1: 1.1～1.8; In molar ratio, isomerate: 2-methyl benzyl chlorine is 1: 1.2～1.8; Press mass ratio, isomerate: water is 1: 2～5; Press mass ratio, isomerate: extraction solvent is 1: 5～9.
9. the preparation method of a kind of weedicide as claimed in claim 1 is characterized in that in step 3), and the time of described dropping 2-methyl benzyl chlorine is 20～100min, and the temperature of described continuation stirring reaction is 20～80 ℃, and the time of continuing stirring reaction is 2～8h.
10. the preparation method of a kind of weedicide as claimed in claim 1 is characterized in that in step 3), and described reaction solvent is selected from a kind of in methylene dichloride, toluene, benzene, the ethyl acetate; Described alkali is selected from a kind of in sodium hydroxide, sodium hydride, sodium amide, potassium hydroxide, potassium tert.-butoxide, the sodium tert-butoxide; Described acid is selected from a kind of in hydrochloric acid, sulfuric acid, acetate, the phosphoric acid; Described extraction solvent is selected from a kind of in methylene dichloride, toluene, benzene, the ethyl acetate.
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| US4670041A (en) * | 1981-12-16 | 1987-06-02 | E. I. Du Pont De Nemours And Company | Oxabicycloalkane herbicides |
| US4487945A (en) * | 1981-12-16 | 1984-12-11 | Shell Oil Company | Preparation of 2-exo-Hydroxy-7-oxabicyclo[2.2.1]heptanes |
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