CN107043359A - A kind of preparation method of prothioconazoles intermediate - Google Patents
A kind of preparation method of prothioconazoles intermediate Download PDFInfo
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- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
- C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract
The present invention relates to a kind of preparation method of prothioconazoles intermediate, including the following steps carried out successively：Compound I and compound II in the presence of the solvent, are reacted at 20~120 DEG C, and reaction obtains compound III after terminating through post processing；By compound III in the presence of the solvent, compound IV 2 (1 chlorine ring the third 1 base) 1 (2 chlorphenyl) 2 hydroxyl 3 (1 is made with the reaction of XOH, formaldehyde, YSCN and niter cake respectively at 10~80 DEG C, 2, the base of 4 triazolidine, 5 thioketones 1) propane is described prothioconazoles intermediate.Compared with the method reported, can not only it make intermediate more stable by the present invention, and reduce the use of the amount of reagent, simplify operating procedure, it is to avoid the generation of side reaction, improve reaction efficiency, three-waste pollution is few, environmental protection, is suitable for industrialized production.
Description
Technical field
The present invention relates to the preparation method of bactericide prothioconazoles intermediate, more particularly to 2- (the chloro- ring propyl- 1- yls of 1-)-
The preparation method of 1- (2- chlorphenyls) -2- hydroxyls -3- (1,2,4- triazolidine -5- thioketones -1- bases)-propane.
Background technology
Prothioconazoles (prothi DEG C of onazole) are a kind of low toxicity, the efficient, triazolinthione of wide spectrum that Beyer Co., Ltd develops
Series bactericidal agent, is mainly used in preventing and treating numerous diseases such as cereal, wheat class and legume crop.2- (the chloro- ring propyl- 1- yls of 1-) -1- (2- chlorine
Phenyl) -2- hydroxyls -3- (1,2,4- triazolidine -5- thioketones -1- bases)-propane (compound IV) be synthesize prothioconazoles key
Intermediate.Prothioconazoles are synthesized by the intermediate, the generation of isomery solid waste can be not only avoided from source, can also be avoided
Use a series of reaction conditions for not being suitable for industrialized production such as hazardous chemical, high temperature.At present, on 2- (the chloro- rings of 1-
Propyl- 1- yls) -1- (2- chlorphenyls) -2- hydroxyls -3- (1,2,4- triazolidine -5- thioketones -1- bases)-propane preparation method have
Report, for example：US6201128, US6559317 and PCT Int.Appl.2001046158 etc..But there is intermediate in existing method
Unstable, reaction condition is whard to control, waste liquid is more, do not meet the problem of environment protection requirement etc. is unfavorable for industrialized production.
For example：
In US6201128 synthetic route, reaction reagent is used as using large excess of hydrazine hydrate so that waste liquid increases,
And the hydrazine midbody compound of generated free state is relatively unstable, easily occurs side reaction, so as to cause yield to reduce.
In US6559317 synthetic route, large excess of hydrazine hydrate is also using as reaction reagent, is terminated in reaction
Hydrogen chloride is passed through afterwards with into the form stable hydrazine midbody compound of salt, and adding alkali in follow-up reaction is dissociated.No
Operating procedure is increase only, the generation of reaction scheme solid waste is also add.
The content of the invention
It is an object of the invention to provide a kind of economic, environmental protection 2- (chloro- rings of 1- for being suitable for industrialized production
Propyl- 1- yls) -1- (2- chlorphenyls) -2- hydroxyls -3- (1,2,4- triazolidine -5- thioketones -1- bases)-propane (IV) preparation method.
To solve above technical problem, the present invention is adopted the following technical scheme that：
A kind of preparation method of prothioconazoles intermediate, including the following steps carried out successively：
Step (1), compound I 2- (1- chlorine cyclopropyl) the chloro- 1- of -3- (2- chlorphenyls) -2- propyl alcohol and compound II are molten
In the presence of agent, reacted at 20~120 DEG C, reaction obtains compound III after terminating through post processing, is represented with reaction equation
It is as follows：
Wherein, R is methyl, methoxy or ethoxy；
Step (2), the compound III for obtaining step (1) in the presence of the solvent, at 10~80 DEG C respectively with XOH,
Compound IV 2- (the chloro- ring propyl- 1- yls of 1-) -1- (2- chlorphenyls) -2- hydroxyls -3- is made in formaldehyde, YSCN and niter cake reaction
(1,2,4- triazolidine -5- thioketones -1- bases)-propane, is described prothioconazoles intermediate, is expressed as follows with reaction equation：
Wherein, R is methyl, methoxy or ethoxy, and XOH is lithium hydroxide, sodium hydroxide or potassium hydroxide；YSCN is sulphur
Zassol, potassium rhodanide or ammonium thiocyanate.
Preferably, the reaction temperature of step (1) is 20~80 DEG C.
Preferably, the reaction temperature of step (2) is 20~60 DEG C.
Preferably, in step (1), described compound I, described compound II molar ratio are 1：1.0~
3.0, more preferably 1：1~2.5, more preferably 1：1~2, most preferably 1：1~1.5.
Preferably, in step (2), described compound III, described XOH, described formaldehyde, described YSCN and institute
The molar ratio for the niter cake stated is 1:1.0~3.0:1.0~3.0:1.0~2.0:1.0~3.0, more preferably
1:1.0~2.5:1.0~2.0:1.0~2.0:1.0~3.0, more preferably 1:1.0~2.0:1.0~1.8:1.0~1.8:
1.0~2.5, most preferably 1:1.0~2.0:1.0~1.5:1.0~1.5:1.5~2.0.
Preferably, the reaction described in step (1) is carried out in the presence of base, and described alkali is n-BuLi, hydroxide
In sodium, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, potassium tert-butoxide, sodium tert-butoxide, triethylamine, diisopropyl ethyl amine
It is one or more；It is further preferred that alkali described in step (1) is sodium hydroxide, potassium hydroxide, potassium carbonate, potassium tert-butoxide,
One kind in triethylamine.
It is further preferred that in step (1), described compound I, the molar ratio of described alkali are 1：0.1~
1.5, more preferably 1：0.5~1.2.
Preferably, the solvent described in step (1) be toluene, dichloromethane, 1,2- dichloroethanes, acetonitrile, tetrahydrofuran,
One or more in dimethyl sulfoxide, N,N-dimethylformamide, 1-METHYLPYRROLIDONE, n-butanol, isobutanol, the tert-butyl alcohol；
It is further preferred that in step (1), described solvent is toluene, acetonitrile, dimethyl sulfoxide, DMF, N- methyl
One kind in pyrrolidones.
Preferably, the solvent described in step (2) is in methyl tertiary butyl ether(MTBE), tetrahydrofuran, ethyl acetate, toluene, water
One or more；It is further preferred that in step (2), described solvent is one kind or several in tetrahydrofuran, toluene, water
Kind.
Preferably, the specific reaction method of step (1) is：Described compound I is dissolved in described solvent, then
Sequentially add alkali and described compound II, reacted 2~16 hours under conditions of 20~120 DEG C.
Preferably, in step (1), described post processing mode is：With organic after the reaction solution reacted after terminating is added water
Solvent extraction, dries the crude product that described compound III is recrystallized to give after concentration or is dried after concentration and is directly used in step
(2)。
Preferably, in step (2), described compound III first reacts with described XOH, then anti-with described formaldehyde
Should, finally reacted with described YSCN and described niter cake.
Preferably, the specific reaction method of step (2) is：Described compound III is dissolved in described solvent, so
Described XOH is added afterwards, is stirred 1~3 hour at 10~60 DEG C, described formaldehyde is subsequently added into, and is stirred at 10~80 DEG C
20~40min, is subsequently added into described YSCN and described niter cake, is reacted 2~16 hours at 10~80 DEG C.
It is further preferred that the specific reaction method of step (2) is：Described compound III is dissolved in described molten
In agent, described XOH is then added, is stirred 1~3 hour at 20~60 DEG C, described formaldehyde is subsequently added into, at 20~60 DEG C
20~40min of lower stirring, is subsequently added into described YSCN and described niter cake, is reacted 2~16 hours at 20~60 DEG C
Preferably, the post processing mode described in step (2) is：The reaction solution reacted after terminating is washed with water, dried
Recrystallized after concentration, obtain described compound IV.
Due to the implementation of above technical scheme, the present invention has following advantage compared with prior art：
The present invention can not only make intermediate more stable, and reduce the use of the amount of reagent, simplify operating procedure,
The generation of side reaction is avoided, reaction efficiency is improved, three-waste pollution is few, environmental protection is suitable for industrialized production；In addition,
The preparing raw material of the present invention is cheap and easy to get, and the yield and content of final products are higher.
Embodiment
The present invention is described in further details below in conjunction with specific embodiment.It should be understood that these embodiments are to be used to say
The bright basic principles, principal features and advantages of the present invention, and the present invention is not limited by the following examples.Used in embodiment
Implementation condition can do further adjustment according to specific requirement, and unreceipted implementation condition is usually the condition in normal experiment.
Embodiment 1
2- (the chloro- ring propyl- 1- yls of 1-) -1- (2- chlorphenyls) -2- hydroxyls -3- (1,2,4- triazolidine -5- sulphur of the present embodiment
Ketone -1- bases) preparation method of-propane has steps of：
Step (1), 2- (1- chlorine cyclopropyl) the chloro- 1- of -3- (2- chlorphenyls) -2- propyl alcohol I (28.0g, 0.10mol) are dissolved in
In acetonitrile (50mL), potassium carbonate (13.8g, 0.10mol) and ethyl carbazate II (11.5g, 0.11mol) are subsequently added.Instead
Liquid is answered to be stirred 4 hours at 80 DEG C.After reaction terminates, water (50mL) is added into reaction solution, is then extracted with ethyl acetate
(extraction three times, each 50mL), organic phase is concentrated after being dried after merging with sodium sulphate.Obtain crude product 36.8g, content 83.4%.Institute
Obtain crude product and compound III (30.7g), faint yellow solid, content 95%, yield 84% are obtained with ethyl alcohol recrystallization.Compound III's
Nuclear magnetic data is as follows：
1H NMR(400MHz,CDCl3)δ(ppm)7.60-7.64(1H,m),7.11-7.18(3H,m),4.96(1H,s),
4.35 (1H, s), 4.10 (2H, d, J=8.0Hz), 2.56-2.98 (4H, m), 1.80 (1H, s), 1.21 (3H, t, J=
8.0Hz),0.84-0.99(2H,m),0.65-0.80(2H,m)。
Step (2), into compound III (30.7g, 0.08mol) toluene (50mL) and water (10mL) solution add hydrogen
Sodium oxide molybdena (3.36g, 0.08mol).Reaction solution is down to room temperature after being stirred 2 hours at 60 DEG C.Then added into reaction system
36.5% formalin (5.8mL, 0.08mol), and stirred 30 minutes at 25 DEG C.Then sulphur cyanogen is added into reaction system
Sour sodium (6.81g, 0.08mol) and niter cake (15.6g, 0.13mol), and stirred 3 hours at 25 DEG C.Divide after reaction completely
Layer, after organic phase is washed with saturated aqueous common salt (30mL), is dried with sodium sulphate, is concentrated.Obtain crude product (31.2g), content 81%.Institute
Crude product recrystallized with dichloromethane and methyl tertiary butyl ether(MTBE) 2- (the chloro- ring propyl- 1- yls of 1-) -1- (2- chlorphenyls) -2- hydroxyls -
3- (1,2,4- triazolidine -5- thioketones -1- bases)-propane IV (24.5g), faint yellow solid, content 95%, yield 80%.Chemical combination
Thing IV nuclear magnetic data is as follows：
1H NMR(600MHz,CDCl3)δ(ppm)7.55-7.56(1H,m),7.35-7.37(1H,m),7.16-7.26
(2H, m), 6.11 (1H, s), 5.11 (1H, t, J=17.4Hz), 4.57-4.60 (2H, m), 4.45-4.50 (1H, m), 4.17
(2H, s), 3.63 (1H, d, J=21.0Hz), 3.08 (1H, d, J=21.0Hz), 1.21-1.26 (1H, m), 0.99-1.04
(1H,m),0.86-0.94(2H,m)。
Embodiment 2
2- (the chloro- ring propyl- 1- yls of 1-) -1- (2- chlorphenyls) -2- hydroxyls -3- (1,2,4- triazolidine -5- sulphur of the present embodiment
Ketone -1- bases) preparation method of-propane has steps of：
Step (1), 2- (1- chlorine cyclopropyl) the chloro- 1- of -3- (2- chlorphenyls) -2- propyl alcohol I (28.0g, 0.10mol) are dissolved in
In acetonitrile (50mL), triethylamine (10.1g, 0.10mol) and ethyl carbazate II (11.5g, 0.11mol) are subsequently added.Instead
Liquid is answered to be stirred 3 hours at 80 DEG C.After reaction terminates, water (50mL) is added into reaction solution, is then extracted with ethyl acetate
(extraction three times, each 50mL), organic phase is concentrated after being dried after merging with sodium sulphate.Obtain crude product 37.5g, content 86%.Gained
Crude product obtains compound III (33.1g), faint yellow solid, content 95%, yield 91% with ethyl alcohol recrystallization.
Step (2), into compound III (33.1g, 0.09mol) toluene (60mL) and water (15mL) solution add hydrogen
Sodium oxide molybdena (3.60g, 0.09mol).Reaction solution is down to room temperature after being stirred 2 hours at 60 DEG C.Then added into reaction system
36.5% formalin (6.5mL, 0.09mol), and stirred 30 minutes at 25 DEG C.Then sulphur cyanogen is added into reaction system
Sour sodium (7.66g, 0.09mol) and niter cake (18.0g, 0.15mol), and stirred 3 hours at 25 DEG C.Divide after reaction completely
Layer, after organic phase is washed with saturated aqueous common salt (40mL), is dried with sodium sulphate, is concentrated.Obtain crude product (35.3g), content 82%.Institute
Crude product recrystallized with dichloromethane and methyl tertiary butyl ether(MTBE) 2- (the chloro- ring propyl- 1- yls of 1-) -1- (2- chlorphenyls) -2- hydroxyls -
3- (1,2,4- triazolidine -5- thioketones -1- bases)-propane IV (26.6g), faint yellow solid, content 95%, yield 81%.
Embodiment 3
2- (the chloro- ring propyl- 1- yls of 1-) -1- (2- chlorphenyls) -2- hydroxyls -3- (1,2,4- triazolidine -5- sulphur of the present embodiment
Ketone -1- bases) preparation method of-propane has steps of：
Step (1), 2- (1- chlorine cyclopropyl) the chloro- 1- of -3- (2- chlorphenyls) -2- propyl alcohol I (28.0g, 0.10mol) are dissolved in
In acetonitrile (50mL), triethylamine (10.1g, 0.10mol) and acethydrazide II (8.15g, 0.11mol) are subsequently added.Reaction solution exists
Stirred 3 hours at 80 DEG C.After reaction terminates, water (50mL) is added into reaction solution, (extraction three is then extracted with ethyl acetate
It is secondary, each 50mL), organic phase is concentrated after being dried after merging with sodium sulphate.Obtain crude product 36.3g, content 81%.Gained crude product second
Alcohol recrystallizes to obtain compound III (30.0g), faint yellow solid, content 95%, yield 90%.
Step (2), into compound III (30.0g, 0.09mol) toluene (60mL) and water (15mL) solution add hydrogen
Potassium oxide (5.05g, 0.09mol).Reaction solution is down to room temperature after being stirred 2 hours at 60 DEG C.Then added into reaction system
36.5% formalin (6.5mL, 0.09mol), and stirred 30 minutes at 25 DEG C.Then sulphur cyanogen is added into reaction system
Sour ammonium (6.85g, 0.09mol) and niter cake (18.0g, 0.15mol), and stirred 3 hours at 25 DEG C.Divide after reaction completely
Layer, after organic phase is washed with saturated aqueous common salt (40mL), is dried with sodium sulphate, is concentrated.Obtain crude product (32.4g), content 81%.Institute
Crude product recrystallized with dichloromethane and methyl tertiary butyl ether(MTBE) 2- (the chloro- ring propyl- 1- yls of 1-) -1- (2- chlorphenyls) -2- hydroxyls -
3- (1,2,4- triazolidine -5- thioketones -1- bases)-propane IV (25.6g), faint yellow solid, content 95%, yield 78%.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar can understand present disclosure and implement according to this, and it is not intended to limit the scope of the present invention, all according to the present invention
The equivalent change or modification that Spirit Essence is made, should all be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of prothioconazoles intermediate, it is characterised in that：Including the following steps carried out successively：
Step (1), compound I and compound II in the presence of the solvent, are reacted at 20~120 DEG C, after reaction terminates
It is post-treated to obtain compound III, it is expressed as follows with reaction equation：
Wherein, R is methyl, methoxy or ethoxy；
Step (2), the compound III for obtaining step (1) in the presence of the solvent, at 10~80 DEG C respectively with XOH, first
Compound IV is made in aldehyde, YSCN and niter cake reaction, is described prothioconazoles intermediate, is expressed as follows with reaction equation：
Wherein, R is methyl, methoxy or ethoxy, and XOH is lithium hydroxide, sodium hydroxide or potassium hydroxide；YSCN is thiocyanic acid
Sodium, potassium rhodanide or ammonium thiocyanate.
2. the preparation method of prothioconazoles intermediate according to claim 1, it is characterised in that：It is described in step (1)
Compound I, described compound II molar ratio are 1：1.0~3.0；It is described compound III, described in step (2)
XOH, described formaldehyde, the molar ratio of described YSCN and described niter cake be 1:1.0~3.0:1.0~3.0:
1.0~2.0:1.0~3.0.
3. the preparation method of prothioconazoles intermediate according to claim 1 or 2, it is characterised in that：Described in step (1)
Reaction carry out in the presence of base, described alkali is n-BuLi, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, carbon
One or more in sour caesium, potassium tert-butoxide, sodium tert-butoxide, triethylamine, diisopropyl ethyl amine.
4. the preparation method of prothioconazoles intermediate according to claim 3, it is characterised in that：It is described in step (1)
Compound I, the molar ratio of described alkali are 1：0.1~1.5.
5. the preparation method of prothioconazoles intermediate according to claim 1, it is characterised in that：Described in step (1)
Solvent is toluene, dichloromethane, 1,2- dichloroethanes, acetonitrile, tetrahydrofuran, dimethyl sulfoxide, N,N-dimethylformamide, N- first
One or more in base pyrrolidones, n-butanol, isobutanol, the tert-butyl alcohol；Solvent described in step (2) is methyl tertbutyl
One or more in ether, tetrahydrofuran, ethyl acetate, toluene, water.
6. the preparation method of prothioconazoles intermediate according to claim 1, it is characterised in that：Step (1) it is specific anti-
Induction method is：Described compound I is dissolved in described solvent, then sequentially adds alkali and described compound II,
Reacted 2~16 hours under conditions of 20~120 DEG C.
7. the preparation method of prothioconazoles intermediate according to claim 1, it is characterised in that：It is described in step (1)
Post processing mode is：Extracted after the reaction solution reacted after terminating is added water with organic solvent, institute is recrystallized to give after drying concentration
The compound III stated or the crude product dried after concentration are directly used in step (2).
8. the preparation method of prothioconazoles intermediate according to claim 1, it is characterised in that：It is described in step (2)
Compound III first reacts with described XOH, is then reacted with described formaldehyde, finally with described YSCN and described sulfuric acid
Hydrogen sodium reacts.
9. the preparation method of the prothioconazoles intermediate according to claim 1 or 8, it is characterised in that：Step (2) it is specific
Reaction method is：Described compound III is dissolved in described solvent, described XOH is then added, at 10~60 DEG C
Stirring 1~3 hour, is subsequently added into described formaldehyde, and 20~40min is stirred at 10~80 DEG C, is subsequently added into described YSCN
With described niter cake, reacted 2~16 hours at 10~80 DEG C.
10. the preparation method of prothioconazoles intermediate according to claim 1, it is characterised in that：Described in step (2)
Post processing mode is：The reaction solution reacted after terminating is washed with water, dries and is recrystallized after concentration, obtain described compound
IV。
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109824611A (en) * | 2019-02-27 | 2019-05-31 | 江苏苏利精细化工股份有限公司 | A kind of novel synthesis of prothioconazoles |
| CN110218196A (en) * | 2019-05-20 | 2019-09-10 | 江苏蓝丰生物化工股份有限公司 | The preparation method of prothioconazoles intermediate triazole alkane derivatives |
| CN111100081A (en) * | 2018-10-26 | 2020-05-05 | 江苏七洲绿色化工股份有限公司 | Continuous preparation method of prothioconazole |
| CN113185470A (en) * | 2021-04-12 | 2021-07-30 | 江苏七洲绿色科技研究院有限公司 | Preparation method of prothioconazole |
| CN113429357A (en) * | 2021-06-16 | 2021-09-24 | 江苏七洲绿色科技研究院有限公司 | Synthesis method of prothioconazole |
| CN114702455A (en) * | 2022-03-29 | 2022-07-05 | 江苏托球农化股份有限公司 | Environment-friendly production process of prothioconazole |
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| CN111100081A (en) * | 2018-10-26 | 2020-05-05 | 江苏七洲绿色化工股份有限公司 | Continuous preparation method of prothioconazole |
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|---|---|
| CN107043359B (en) | 2019-08-09 |
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