CN101386601B - Method for preparing thidiazuron - Google Patents
Method for preparing thidiazuron Download PDFInfo
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- CN101386601B CN101386601B CN 200810157079 CN200810157079A CN101386601B CN 101386601 B CN101386601 B CN 101386601B CN 200810157079 CN200810157079 CN 200810157079 CN 200810157079 A CN200810157079 A CN 200810157079A CN 101386601 B CN101386601 B CN 101386601B
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- thidiazuron
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- thiadiazoles
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Abstract
The invention disclosed a method for preparing Thidiazuron. The method comprises the following steps: (1) adding a reactant of 5-amino-1, 2, 3-thiadiazole to a butanone solvent while stirring, keeping stirring the mixed solution until the 5-amino-1, 2, 3-thiadiazole is completely dissolved; (2) adding reactants of phenyl isocyanate and a triethylamine catalyst to the solution obtained in the step (1), so that the 5-amino-1, 2, 3-thiadiazole has catalytic synthesis reaction with the phenyl isocyanate, and then filtering the reactant after the reaction is complete to obtain a filter cake which is the Thidiazuron finished product. With the method, the yield of the Thidiazuron can be more than 92 percent and the purity can be more than 98 percent; besides, the used butanone solvent has low price and easy reclaiming, and is applicable to industrial production.
Description
Technical field
The present invention relates to the preparation method of a plant growth regulators, particularly relate to a kind of preparation method of thidiazuron.
Background technology
Thidiazuron is a kind of novel efficient plant growth regulator, and its chemical name is 1-phenyl-3-(1,2,3-thiadiazoles-5-yl) urea, and English name is Thidiazuron, is called for short TDZ.Its pure product are the no color or smell crystal, and fusing point is 210.5～212.5 ℃ (decomposition).Thidiazuron has extremely strong cell fission activity, can promote photosynthesis of plants, improves fruit quality, increases the fruit storage tolerance.On cotton planting, make agents for defoliating and use, after being absorbed by the cotton plant leaf, can impel chorista between handle and the stem to form naturally early and fall leaves, help machinery and receive cotton, and can make cotton receipts tiller shift to an earlier date about 10 days, help to improve Cotton Grade.
U.S. Pat 4294605 discloses a kind of preparation method of thidiazuron, this method is solvent with the tetrahydrofuran (THF), with the triethylamine is catalyzer, with 5-amino-1,2,3-thiadiazoles and phenylcarbimide standing and reacting are also spent the night, and removing desolvates can obtain thidiazuron, the yield of this method is 76.7%, and product purity is 90.5%.
Chinese patent CN1196354 improves the method for this United States Patent (USP), and it is controlled at 8～12 ℃ with temperature of reaction, and 24h is left standstill in reaction, and its yield can reach 88.74%, does not report its product purity.The main deficiency of above-mentioned two kinds of methods is to be solvent with the tetrahydrofuran (THF), and the product purity that obtains is not high.
Japanese Patent JP59048473 discloses the another kind of preparation method of thidiazuron, it is solvent that this method is selected glycol dimethyl ether for use, make catalyzer with triethylamine, with 5-amino-1,2,3-thiadiazoles and phenylcarbimide be 40 ℃ of following stirring reactions 6 hours, filter thidiazuron, the yield of this method is 84%, and product purity can reach more than 98%.Though this method has solved the purity problem of thidiazuron, because the solvent for use selling at exorbitant prices causes production cost higher.
Summary of the invention
The objective of the invention is above-mentioned deficiency, the preparation method of all higher and thidiazuron that production cost is lower of a kind of yield and product purity is provided at prior art.
The technical scheme that realizes the object of the invention is: a kind of preparation method of thidiazuron has following steps: 1. under agitation with reactant 5-amino-1,2, the 3-thiadiazoles joins in the solvent butanone, continues to be stirred to 5-amino-1,2, and the 3-thiadiazoles dissolves fully.2. in the solution that 1. step obtains, add reactant phenylcarbimide and catalyst of triethylamine, make 5-amino-1,2,3-thiadiazoles and phenylcarbimide generation catalytic synthesis, the after-filtration that reacts completely, the gained filter cake is the thidiazuron finished product.
The mol ratio of the 5-amino-1,2 of above-mentioned steps in 1., 3-thiadiazoles and the step phenylcarbimide in 2. is 1: 1.02～1: 1.1.
The mol ratio of the 5-amino-1,2 of above-mentioned steps in 1., 3-thiadiazoles and the step triethylamine in 2. is 1: 0.005～1: 0.01.
Above-mentioned steps 2. in when carrying out catalytic synthesis, earlier under 50 ℃～80 ℃ temperature, react 2h～6h, be cooled to 15 ℃～25 ℃ then, restir 0.5h～1.5h makes it to react completely.
The temperature of the catalytic synthesis before the 2. middle cooling of above-mentioned steps is 60 ℃～65 ℃, and the time of reaction is 3h～4h.
The present invention has positive effect: preparation method of the present invention can make the yield of thidiazuron reach more than 92%, purity reaches more than 98%, and solvent for use butanone cheap (its market value is 1/3rd of a tetrahydrofuran (THF), be glycol dimethyl ether 1/4th), be easy to suitability for industrialized production, and solvent reclaims easily.
Embodiment
(embodiment 1)
The preparation method of the thidiazuron of present embodiment is as follows:
1. under agitation with the reactant 5-amino-1,2 of 50.5g, 3-thiadiazoles (0.5mol) joins in the solvent butanone of 200ml, and until 5-amino-1,2, the 3-thiadiazoles dissolves fully about continuation stirring 10min.
2. in solution, add the reactant phenylcarbimide (0.53mol) of 64g and the catalyst of triethylamine (0.003mol) of 0.5ml, under 60～65 ℃ temperature, make 5-amino-1,2,3-thiadiazoles and phenylcarbimide generation catalytic synthesis, reaction times is 3h, is cooled to 20 ℃ then, and restir reaction 1h makes it to react completely, filter target product thidiazuron 102g, mother liquor reclaims (applying mechanically after the drying), and yield reaches 92.7%, and product purity reaches 98.5%.
(embodiment 2～embodiment 6)
Each embodiment is substantially the same manner as Example 1, and difference sees Table 1.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| 5-amino-1,2, the 3-thiadiazoles | 50.5g、 0.5mol | 101g、 1mol | 50.5g、 0.5mol | 50.5g、 0.5mol | 101g、 0.5mol | 50.5g、 0.5mol |
| Butanone | 200ml | 500ml | 200ml | 200ml | 500ml | 200ml |
| Churning time | 10min | 15min | 10min | 10min | 15min | 10min |
| Phenylcarbimide | 64g、 0.53mol | 128g、 1.06mol | 64g、 0.53mol | 61.6g、 0.51mol | 132.8g、 1.1mol | 66.4g、 0.55mol |
| Triethylamine | 0.5ml、 0.003mo l | 1ml、 0.006mo l | 0.67ml、 0.004mo l | 0.42ml、 0.0025mol | 1.67ml、 0.01mol | 0.83ml、 0.005mol |
| Temperature of reaction | 60℃ | 65℃ | 60℃ | 50℃ | 65℃ | 80℃ |
| Reaction times | 4h | 3h | 4h | 6h | 3h | 2h |
| Cooling temperature | 20℃ | 20℃ | 15℃ | 20℃ | 25℃ | 18℃ |
| Churning time | 1h | 0.8h | 1h | 1.5h | 1.2h | 0.5h |
| Target product weight | 102g | 208g | 103 | 101.2 | 203 | 101.3 |
| Yield | 92.7％ | 94.5％ | 93.6％ | 92.0％ | 92.2％ | 92.1％ |
| Purity | 98.5％ | 98.2％ | 98.3％ | 98.1％ | 98.0％ | 98.0％ |
Claims (4)
1. the preparation method of a thidiazuron is characterized in that having following steps:
1. under agitation with reactant 5-amino-1,2, the 3-thiadiazoles joins in the solvent butanone, continues to be stirred to 5-amino-1,2, and the 3-thiadiazoles dissolves fully;
2. in the solution that 1. step obtains, add reactant phenylcarbimide and catalyst of triethylamine, make 5-amino-1,2, catalytic synthesis 2h～6h takes place in 3-thiadiazoles and phenylcarbimide under 50 ℃～80 ℃ temperature, be cooled to 15 ℃～25 ℃ then, restir 0.5h～1.5h makes it to react completely, the after-filtration that reacts completely, and the gained filter cake is the thidiazuron finished product.
2. the preparation method of thidiazuron according to claim 1 is characterized in that: the mol ratio of the 5-amino-1,2 of step in 1., 3-thiadiazoles and the step phenylcarbimide in 2. is 1: 1.02～1: 1.1.
3. the preparation method of thidiazuron according to claim 1 is characterized in that: the mol ratio of the 5-amino-1,2 of step in 1., 3-thiadiazoles and the step triethylamine in 2. is 1: 0.005～1: 0.01.
4. the preparation method of thidiazuron according to claim 1 is characterized in that: step 2. in the temperature of catalytic synthesis before the cooling be 60 ℃～65 ℃, the time of reaction is 3h～4h.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200810157079 CN101386601B (en) | 2008-09-24 | 2008-09-24 | Method for preparing thidiazuron |
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| CN 200810157079 CN101386601B (en) | 2008-09-24 | 2008-09-24 | Method for preparing thidiazuron |
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| CN101386601A CN101386601A (en) | 2009-03-18 |
| CN101386601B true CN101386601B (en) | 2010-12-22 |
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| CN105851033B (en) * | 2016-04-28 | 2019-06-18 | 江苏省农用激素工程技术研究中心有限公司 | Composition pesticide for cotton defoliation |
| CN107197870A (en) * | 2017-07-06 | 2017-09-26 | 中国科学院合肥物质科学研究院 | A kind of Chinese tallow tree grows conditioning agent and its application |
| CN111763183A (en) * | 2020-06-30 | 2020-10-13 | 河南源博新材料有限公司 | Preparation method of 1-phenyl-3- (1,2, 3-thiadiazole-5-yl) urea |
| CN111972425A (en) * | 2020-09-07 | 2020-11-24 | 安徽省四达农药化工有限公司 | Thidiazuron single agent, thidiazuron and brassinolide compound composition and preparation process thereof |
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