CN100526303C - preparation process of safe herbicide preparation of N-dichloroacetyl oxazolidine herbicide - Google Patents
preparation process of safe herbicide preparation of N-dichloroacetyl oxazolidine herbicide Download PDFInfo
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- CN100526303C CN100526303C CNB2007100718943A CN200710071894A CN100526303C CN 100526303 C CN100526303 C CN 100526303C CN B2007100718943 A CNB2007100718943 A CN B2007100718943A CN 200710071894 A CN200710071894 A CN 200710071894A CN 100526303 C CN100526303 C CN 100526303C
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Abstract
The present invention provides preparation process of new N-dichloroacetyl-1, 3-oxazolidine compound. The preparation process includes the following steps: 1. dissolving 2-methyl-2-amino propanol and aldehyde or ketone of different structure in the molar ratio of 1 to 1-1 to 1.5 in solvent; 2. stirring at 33-38 deg.c, refluxing and separating out water, cooling the reaction system to -10 deg.c, adding acid-binding agent, and dropping dichloroacetyl chloride slowly to maintain the pH value of the reaction system in over 12; 3. washing the organic phase with water to neutrality, drying with anhydrous magnesium sulfate and distilling off solvent; and 4. adding solvent to re-crystallize or column chromatography to separate so as to obtain white crystal. Compared with available technology, the present invention has the advantages of mild reaction cn, short reaction period, less side products and high yield.
Description
Technical field
The present invention relates to belong to organic synthesis and agricultural chemicals study on the synthesis field, be specifically related to a kind of synthetic method of herbicide-safener.
Background technology
The dichloroacetyl oxazolidine compound
It is a kind of novel herbicide-safener; it is the good toxinicide of chloro acetanilide class and dithiocarbamate herbicide; and can be as sulfonylurea and imidazolinone herbicide safener gramineous crop Tanaka; can protect crops such as corn, Chinese sorghum and paddy rice to avoid the injury of chloro acetanilide class (as acetochlor) and dithiocarbamate herbicide (as EPTC) preferably; especially sulfonylurea and imidazolinone herbicide there are detoxifying effect preferably, can reduce the caused poisoning of weedicide.Abroad just having begun one's study from the seventies, it synthesizes and application, United States Patent (USP) U.S.P.4, and 038,284 has reported a kind of synthetic method and bioactive measuring method of dichloroacetyl oxazolidine compound.It adds amino alcohol and ketone in the benzene, stirs down at 33-34 ℃, and reflux water-dividing 4hr is cooled to below 0 ℃, is acid binding agent with the triethylamine, drips dichloroacetyl chloride, and drip and finish, washing, drying, decompression steams benzene, recrystallization.The shortcoming of this method is a long reaction time, complicated operation, and the temperature of reaction height is an acid binding agent by-product object height with the triethylamine, yield is low, the cost height.At present China is also about the patent of the synthetic method of dichloroacetyl oxazolidine compound, and only relevant for the preparation method (CN200410012505.6) of oxazolidine, but reaction conditions is still than the condition height of present method, method complexity, long reaction time.
Summary of the invention
The object of the present invention is to provide a kind of reaction times short, simple to operate, temperature of reaction is low, the preparation method of the new diethylamino ethanol caproate that by product is few.
The object of the present invention is achieved like this:
(1) aldehydes or ketones with 2-methyl-2-aminopropanol, different structure is that raw material is put into container, and the mol ratio of the two is 1:1～1:1.5, adds solvent;
(2) stir under 33～38 ℃ of envrionment temperatures, stir the back reflux water-dividing, reaction system is cooled to-10 ℃, add acid binding agent, slowly drip dichloroacetyl chloride, the pH value of keeping reaction system is more than 12;
(3) drip after, wash organic phase with water to neutral, the organic phase anhydrous magnesium sulfate drying steams solvent;
(4) add solvent and carry out recrystallization, or adopt column chromatography method to separate to obtain white crystal.
The present invention also has some technical characterictics like this:
1, the described aldehydes or ketones of step 1 is respectively formaldehyde, butyraldehyde-n, cyclopentanone, pimelinketone;
2, the described reaction solvent of step 1 is a chloroform;
3, the described churning time of step 2 is 0.5-1.5 hour, and the reflux water-dividing time is 1-2 hour;
4, the described acid binding agent of step 2 is the 33%NaOH aqueous solution;
5, the consumption of the described dichloroacetyl chloride of step 2 is: 2-methyl-2-aminopropanol: dichloroacetyl chloride (mol ratio) is 1:1.1～1:1.3;
6, the control temperature of reaction system maintains in-10～0 ℃ of scopes during the described dropping dichloroacetyl chloride of step 2;
7, the described recrystallization solvent of step 4 is a hexanaphthene;
8, the stationary phase used of the described column chromatography of step 4 is a silica gel, and eluent is ethyl acetate and sherwood oil mixed solution, and volume ratio is 1:6～1:12;
9, the described container of step 1 is a three-necked bottle, and three-necked bottle is provided with thermometer, reflux condensing tube and dropping funnel.
The present invention prepares N-dichloro-acetyl-1; the method of 3-oxazolidine; comprise that (1) raw material chooses: with 2-methyl-2-aminopropanol; the aldehydes or ketones of different structure is a raw material; the mol ratio of the two is 1:1～1:1.5; chloroform is a solvent; (2) reaction process: stirred 1 hour at 33～38 ℃, about 1.5 hours of reflux water-dividing is cooled to reaction system-10 ℃; add the 33%NaOH aqueous solution; slowly drip dichloroacetyl chloride, make the reaction system temperature control in-10～0 ℃ of scope, the pH value of keeping reaction system is more than 12; after dripping; wash organic phase with water to neutral, the organic phase anhydrous magnesium sulfate drying steams solvent.(3) separation method: according to the compound of different structure select for use different solvents carry out recrystallization or column chromatography method separate white crystal.
The present invention prepares N-dichloro-acetyl-1, and the synthetic route of the method for 3-oxazolidine is:
The invention has the advantages that: overcome long reaction time at present synthetic this compounds technology; complicated operation; the temperature of reaction height; shortcomings such as by product is many; by the preparation method synthetic N-of institute dichloro-acetyl-1 of the present invention; the reaction conditions gentleness of 3-oxazolidine; reaction times is short; the productive rate height; have that cost is low, energy consumption is low and advantage such as easy suitability for industrialized production; has high promotional value, for suitability for industrialized production dichloroacetyl oxazolidine herbicide-safener from now on provides certain foundation.
Test of many times result of the present invention shows: institute of the present invention synthetic compound can protect corn to avoid the grand injury of green sulphur to a certain extent, has the certain protection effect.
Embodiment
The present invention is further illustrated below in conjunction with specific embodiment:
Embodiment 1:
0.067mol 2-methyl-2-aminopropanol, 0.067mol butyraldehyde-n, 20.0mL chloroform are added in the three-necked bottle, thermometer, reflux condensing tube and dropping funnel are housed on the three-necked bottle, and temperature control stirs 1hr, the about 1.5h of reflux water-dividing down for 33～34 ℃, be cooled to-10 ℃, add 7.5mL33%NaOH solution, drip dichloroacetyl chloride, the control rate of addition, make the reaction system temperature control in-10～0 ℃ of scope, after dripping, wash organic phase with water to neutral, the organic phase anhydrous magnesium sulfate drying.Filter the back decompression and steam solvent, thick product hexanaphthene recrystallization gets Compound I, productive rate 58.2%.
Embodiment 2:
With 0.067mol2-methyl-2-aminopropanol, 0.067mol Paraformaldehyde 96,1.5mL water, 20.0mL chloroform is added in the three-necked bottle, thermometer, reflux condensing tube and dropping funnel are housed on the three-necked bottle, temperature control stirs 1hr down for 33～34 ℃, the about 1.5h of reflux water-dividing, be cooled to-10 ℃, add 7.5mL33%NaOH solution, drip dichloroacetyl chloride, the control rate of addition makes the reaction system temperature control in-10～0 ℃ of scope, after dripping, wash organic phase with water to neutral, the organic phase anhydrous magnesium sulfate drying.Reduce pressure after filtering and steam solvent, thick product separates with silica gel column chromatography, and decompression steams solvent, gets white crystal, gets Compound I I, productive rate 60.4%.
Embodiment 3:
0.067mol 2-methyl-2-aminopropanol, 0.067mol cyclopentanone, 20.0mL chloroform are added in the three-necked bottle, thermometer, reflux condensing tube and dropping funnel are housed on the three-necked bottle, temperature control stirs 1hr down for 33～34 ℃, the about 1.5h of reflux water-dividing, be cooled to-10 ℃, add 7.5mL33%NaOH solution, drip dichloroacetyl chloride, the control rate of addition makes the reaction system temperature control in-10～0 ℃ of scope, adds small amount of N aOH solution, the pH value of keeping reaction system is more than 12, after dripping, wash organic phase with water to neutral, the organic phase anhydrous magnesium sulfate drying.Reduce pressure after filtering and steam solvent, thick product separates with silica gel column chromatography, and decompression steams solvent, uses the hexanaphthene recrystallization again, gets white crystal, gets compound III, productive rate 43.5%.
Embodiment 4:
0.067mol 2-methyl-2-aminopropanol, 0.067mol pimelinketone, 20.0mL chloroform are added in the three-necked bottle, thermometer, reflux condensing tube and dropping funnel are housed on the three-necked bottle, temperature control stirs 1hr down for 33～34 ℃, the about 1.5h of reflux water-dividing, be cooled to-10 ℃, add 7.5mL33%NaOH solution, drip dichloroacetyl chloride, the control rate of addition makes the reaction system temperature control in-10～0 ℃ of scope, adds small amount of N aOH solution, the pH value of keeping reaction system is more than 12, after dripping, wash organic phase with water to neutral, the organic phase anhydrous magnesium sulfate drying.Decompression steams solvent after the filtration,, thick product separates with silica gel column chromatography, steams solvent, gets white crystal, gets compound IV, productive rate 68.9%.
The above-claimed cpd biological activity determination:
Corn variety: agricultural 248 corn hybrid seeds in east
Bioassay method:
Get 50 ℃ of 30min that hot water treatment of seeds of corn seed, derosal is cleaned with clear water after soaking 30min, is placed in the culture dish of the different concns that safener is housed, and puts into 26 ℃ of incubators and soaks 12h, then vernalization 24h.Get the oven-dried soil that 300g crosses 2mm sieve, become the pesticide-clay mixture of the grand 2 μ g/kg of green sulphur by medicine soil proportional arrangement, the corn seed that selects uniformity evenly pendulum at soil surface, umbilical region down, on cover about pesticide-clay mixture 30g.All handle 4 times parallel, triplicate.Take out after 7 days.Measure various growth indexes.
Table 1: each compound is to the relative inhibition of corn seedling strain fresh weight, root fresh weight
Test-results shows: institute of the present invention synthetic compound can protect corn to avoid the grand injury of green sulphur to a certain extent, has the certain protection effect.
Claims (5)
1, the preparation method of a kind of N-dichloroacetyl oxazolidine herbicide-safener is characterized in that:
(1) with a kind of container of putting in 2-methyl-2-aminopropanol and formaldehyde, butyraldehyde-n, cyclopentanone or the pimelinketone, the mol ratio of the two is 1:1～1:1.5, and the adding chloroform is a solvent;
(2) stirred 0.5-1.5 hour under 33～38 ℃ of envrionment temperatures, stirred the back reflux water-dividing 1-2 hour, reaction system is cooled to-10 ℃, add the acid binding agent 33%NaOH aqueous solution, slowly drip dichloroacetyl chloride, the pH value of keeping reaction system is more than 12;
(3) drip after, wash organic phase with water to neutral, the organic phase anhydrous magnesium sulfate drying steams solvent chloroform;
(4) add solvent and carry out recrystallization, or adopt column chromatography method to separate to obtain white crystal.
2, the preparation method of a kind of N according to claim 1-dichloroacetyl oxazolidine herbicide-safener, it is characterized in that the described dichloroacetyl chloride consumption of step (2) is: the mol ratio of 2-methyl-2-aminopropanol and dichloroacetyl chloride is 1:1.1～1:1.3.
3, the preparation method of a kind of N according to claim 2-dichloroacetyl oxazolidine herbicide-safener, the control temperature of reaction system maintains in-10～0 ℃ of scopes when it is characterized in that the described dropping dichloroacetyl chloride of step (2).
4, the preparation method of a kind of N according to claim 3-dichloroacetyl oxazolidine herbicide-safener is characterized in that the described recrystallization solvent of step (4) is a hexanaphthene.
5, the preparation method of a kind of N according to claim 4-dichloroacetyl oxazolidine herbicide-safener; it is characterized in that the stationary phase that the described column chromatography of step (4) is used is a silica gel; eluent is ethyl acetate and sherwood oil mixed solution, and volume ratio is 1:6～1:12.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100718943A CN100526303C (en) | 2007-03-16 | 2007-03-16 | preparation process of safe herbicide preparation of N-dichloroacetyl oxazolidine herbicide |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2007100718943A CN100526303C (en) | 2007-03-16 | 2007-03-16 | preparation process of safe herbicide preparation of N-dichloroacetyl oxazolidine herbicide |
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| CN101019538A CN101019538A (en) | 2007-08-22 |
| CN100526303C true CN100526303C (en) | 2009-08-12 |
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| CNB2007100718943A Expired - Fee Related CN100526303C (en) | 2007-03-16 | 2007-03-16 | preparation process of safe herbicide preparation of N-dichloroacetyl oxazolidine herbicide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103070477B (en) * | 2013-01-16 | 2014-06-11 | 湖南中烟工业有限责任公司 | Application of aminopropanol compound |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4038284A (en) * | 1975-07-28 | 1977-07-26 | Stauffer Chemical Company | N-acylation of oxazolidines |
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2007
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4038284A (en) * | 1975-07-28 | 1977-07-26 | Stauffer Chemical Company | N-acylation of oxazolidines |
Non-Patent Citations (4)
| Title |
|---|
| Simple,Mild and Convenient synthesis of two novelN-dichloroacetyl oxazolidines and their biological activities. Chao CHAI et al.Chinese chemical letters,Vol.15 No.10. 2004 |
| Simple,Mild and Convenient synthesis of two novelN-dichloroacetyl oxazolidines and their biological activities. Chao CHAI et al.Chinese chemical letters,Vol.15 No.10. 2004 * |
| 两种二氯乙酰基取代噁唑烷的一步合成. 李绍锋等.化学工程，第29卷第6期. 2001 |
| 两种二氯乙酰基取代噁唑烷的一步合成. 李绍锋等.化学工程，第29卷第6期. 2001 * |
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Granted publication date: 20090812 Termination date: 20110316 |