CN114805227A - Preparation method of dithio-bis-triazole compound - Google Patents

Preparation method of dithio-bis-triazole compound Download PDF

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CN114805227A
CN114805227A CN202210619382.0A CN202210619382A CN114805227A CN 114805227 A CN114805227 A CN 114805227A CN 202210619382 A CN202210619382 A CN 202210619382A CN 114805227 A CN114805227 A CN 114805227A
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周先峰
王同波
王旭
矫立鹏
王凯
葛家成
王良清
李建国
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Shandong Hailir Chemicals Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • 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 invention provides a preparation method of a dithiobis-triazole compound, which is characterized by reacting a compound containing a carbonyl bond with an oxidant in the presence of a solvent, and carrying out post-treatment to obtain the dithio compound, wherein the oxidant is a composition of metal acid salt or metal oxide of VIB or VIIB group elements and peroxide. The method has the advantages of high product yield and high purity, and can be applied to the production and detection of the original medicine without excessive purification steps.

Description

Preparation method of dithio-bis-triazole compound
Technical Field
The invention belongs to the technical field of organic synthesis, and relates to a preparation method of a dithiobis-triazole compound.
Technical Field
Prothioconazole is a sterol demethylation (ergosterol biosynthesis) inhibitor developed by Bayer company, has systemic fungicide for protection, treatment and eradication activity, and has long lasting period; the bactericidal composition is usually used for crops such as wheat, barley and the like, and is sprayed on leaf surfaces to prevent and control various diseases such as eye spot, fusarium wilt, leaf spot, rust disease, powdery mildew and the like. And (3) seed treatment, which is used for preventing and treating diseases caused by smut, tilletia, fusarium and snow mold blight. The prothioconazole has good safety, good systemic property, excellent protection, treatment and eradication effects, good prevention and treatment effect, long lasting period and obvious yield increase. Dithioprothioconazole, namely: the bis- {1- [2- (1-chloro-cyclopropyl) -3- (2-chlorophenyl) -2-hydroxy-propyl-1 ] -1,2, 4-triazole-5-yl } disulfide has the CAS number of 199391-98-5, is a related impurity of prothioconazole, is generated in self-polymerization of a prothioconazole raw material in a preparation or storage process, needs to pay attention to the content of the prothioconazole in an analysis and detection process of the raw material due to certain biological toxicity, and the synthesis method of the prothioconazole is less reported at present.
Bayer corporation in the patent application No. CN97194671.X discloses the preparation of bis- {1- [2- (1-chlorocyclopropyl) -3- (2-chlorophenyl) -2-hydroxy-propyl-1 ] -1,2, 4-triazol-5-yl } disulfide (melting point 128- -chlorophenyl) -2-hydroxy-propyl-1 ] -1,2, 4-triazol-5-yl } disulfide (melting point 129-131 ℃ C.) (100% of theory). However, both of the above methods have problems that the reaction time is too long and the purity of the product is not sufficiently satisfactory.
Suxian bin et al of Nanjing Industrial university disclose a method of dissolving mercapto-1, 2, 4-triazole in DCM and reacting with benzenesulfonyl chloride in the presence of pyridine to obtain 5, 5' -dithio-bis (1,2, 4-triazole) in patent application No. CN201611264830.0, and a method for preparing bis- {1- [2- (1-chlorocyclopropyl) -3- (2-chlorophenyl) -2-hydroxy-propyl-1 ] -1,2, 4-triazole-5-yl } disulfide by reacting 5, 5' -dithiol-bis (1,2, 4-triazole) with 2- (1-chlorocyclopropyl) -3-chloro-1- (2-chlorophenyl) -2-propanol. However, the method has the problems that reaction reagents such as pyridine, sulfonyl chlorides and the like have large odor and are not beneficial to environmental protection and large-scale production, and the combined yield is only about 52 percent.
Disclosure of Invention
The invention provides a preparation method of a dithiobis-triazole compound, which effectively solves the problems that the method for synthesizing bis- {1- [2- (1-chloro-cyclopropyl) -3- (2-chloro-phenyl) -2-hydroxy-propyl-1 ] -1,2, 4-triazole-5-yl } disulfide in the prior art consumes long time and the product purity cannot meet the standard sample purity in analysis and detection work.
The technical scheme of the invention is as follows:
a preparation method of a dithio-bis-triazole compound comprises the steps of reacting a compound shown in a formula (II) with an oxidant in the presence of a solvent, carrying out post-treatment to obtain a compound shown in a formula (I), wherein the oxidant is a composition of a metal acid salt or a metal oxide of a VIB or VIIB group element and peroxide,
Figure BDA0003675595410000021
further, the solvent is any one or a mixture of several of water, methanol, ethanol, isopropanol, n-butanol, acetonitrile and acetone.
Still further, the solvent is selected from the group consisting of water, methanol, isopropanol, n-butanol, acetonitrile, acetone, a mixture of water and methanol, a mixture of water and isopropanol, a mixture of water and n-butanol, a mixture of water and acetonitrile, and a mixture of water and acetone.
Further, the group VIB or VIIB metal acid salt or metal oxide includes potassium permanganate, manganese dioxide, sodium chromate, potassium chromate, sodium dichromate, or potassium dichromate;
the peroxide comprises m-chloroperoxybenzoic acid or tert-butyl hydroperoxide.
Further, the oxidizing agent is a composition of any one of potassium permanganate, manganese dioxide, sodium chromate, potassium chromate, sodium dichromate or potassium dichromate and any one of m-chloroperoxybenzoic acid or tert-butyl hydroperoxide in a mass ratio of 1-5: 1-2.
Further, the reaction temperature is 0 to 60 ℃.
Further, the reaction temperature is 0 to 20 ℃.
Further, the mass ratio of the compound of the formula (II) to the oxidant is 1: 1-5.
Further, the mass ratio of the compound of the formula (II) to the solvent is 1: 3-10.
Further, the oxidant is a composition of metal acid salt or metal oxide of VIB or VIIB group element and peroxide with the mass ratio of 1-5: 1-2.
Further, the reaction time is 2 to 20 hours.
Due to the adoption of the technology, compared with the prior art, the invention has the remarkable advantages that:
1) the synthesis method is simple and convenient, one-step reaction synthesis and simple process;
2) the reaction temperature is mild, the reaction time is short, the post-treatment operation is simple and convenient, and the product yield is high;
3) by using the compound oxidant, the purity of the product is obviously improved, and the product can be used as an impurity standard substance for analysis and detection of the prothioconazole original drug without complex purification steps.
Drawings
FIG. 1 is a mass spectrum of bis- {1- [2- (1-chlorocyclopropyl) -3- (2-chlorophenyl) -2-hydroxy-propyl-1 ] -1,2, 4-triazol-5-yl } disulfide;
FIG. 2 is bis- {1- [2- (1-chlorocyclopropyl) -3- (2-chlorophenyl) -2-hydroxy-propyl-1]Process for preparing (E) -1,2, 4-triazol-5-yl) disulfides 1 HNMR spectrogram.
Detailed Description
In order to make the technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments, it should be understood that the specific embodiments described herein are only for explaining the present invention and are not used to limit the present invention.
Example 1
Synthesis of bis- {1- [2- (1-chlorocyclopropyl) -3- (2-chlorophenyl) -2-hydroxy-propyl-1 ] -1,2, 4-triazol-5-yl } dithio (formula I):
Figure BDA0003675595410000031
adding 14g (40mmol, 1eq) of the formula (II) into a four-neck flask, adding 60ml of acetone and 60ml of water, starting stirring, slowly adding 9.48g of potassium permanganate (60mmol) and 9.0g m-CPBA m-chloroperoxybenzoic acid (52mmol) into the four-neck flask in batches, controlling the reaction temperature to be 15-20 ℃, continuing to keep the temperature and stirring for 3 hours after the addition is finished, and finishing the reaction. After the reaction is finished, adding water into a four-mouth bottle, filtering, leaching a filter cake by using a small amount of water to obtain the bis- {1- [2- (1-chlorocyclopropyl) -3- (2-chlorophenyl) -2-hydroxy-propyl-1]13.85g of-1, 2, 4-triazol-5-yl } dithio product with the content of 98.3 percent and the yield of 97.5 percent, the mass spectrum of the product is shown in figure 1, 1 the H NMR spectrum is shown in FIG. 2.
Example 2
Synthesis of bis- {1- [2- (1-chlorocyclopropyl) -3- (2-chlorophenyl) -2-hydroxy-propyl-1 ] -1,2, 4-triazol-5-yl } dithio (formula I):
Figure BDA0003675595410000032
adding 14g (40mmol, 1eq) of the formula (II) into a four-neck flask, adding 60ml of acetonitrile and 40ml of water, starting stirring, slowly adding 9.48g of potassium permanganate (60mmol) and 6.90g m-CPBA m-chloroperoxybenzoic acid (40mmol) into the four-neck flask in batches, controlling the reaction temperature to be 0-5 ℃, continuing stirring for 2 hours under heat preservation after the addition is finished, and finishing the reaction. After the reaction, the reaction solution was filtered, and the filter cake was rinsed with a small amount of water to obtain 13.9g of bis- {1- [2- (1-chlorocyclopropyl) -3- (2-chlorophenyl) -2-hydroxy-propyl-1 ] -1,2, 4-triazol-5-yl } dithio-product, the content of which was 97.6%, and the yield was 97.2%.
Example 3
Synthesis of bis- {1- [2- (1-chlorocyclopropyl) -3- (2-chlorophenyl) -2-hydroxy-propyl-1 ] -1,2, 4-triazol-5-yl } dithio (formula I):
Figure BDA0003675595410000041
adding 14g (40mmol, 1eq) of the formula (II) into a four-neck flask, adding 60ml of isopropanol and 60ml of water, starting stirring, slowly adding 9.48g of potassium permanganate (60mmol) and 3.6g of tert-butyl hydroperoxide (40mmol) into the four-neck flask in batches, controlling the reaction temperature to be 0-5 ℃, continuing to keep the temperature and stirring for 2 hours after the addition is finished, and finishing the reaction. After the reaction, the reaction solution was filtered, and the filter cake was rinsed with a small amount of water to obtain 14.2g of bis- {1- [2- (1-chlorocyclopropyl) -3- (2-chlorophenyl) -2-hydroxy-propyl-1 ] -1,2, 4-triazol-5-yl } dithio-product with a content of 96.9% and a yield of 98.6%.
Example 4
Synthesis of bis- {1- [2- (1-chlorocyclopropyl) -3- (2-chlorophenyl) -2-hydroxy-propyl-1 ] -1,2, 4-triazol-5-yl } dithio (formula I):
Figure BDA0003675595410000042
14g (40mmol) of the formula (II), 80ml of methanol and 80ml of water are added into a four-neck flask, stirring is started, 11.77g of potassium dichromate (40mmol) and 6.90g m-CPBA m-chloroperoxybenzoic acid (40mmol) are slowly added into the four-neck flask in batches, the reaction temperature is controlled to be 20-25 ℃, and after the addition is finished, heat preservation stirring is continuously carried out for 4 hours, thus completing the reaction. After the reaction was completed, water was added to the four-necked flask, and the mixture was filtered, and the filter cake was rinsed with a small amount of water, to obtain 13.77g of bis- {1- [2- (1-chlorocyclopropyl) -3- (2-chlorophenyl) -2-hydroxy-propyl-1 ] -1,2, 4-triazol-5-yl } dithio-product, the content of which was 96.2%, and the yield was 94.9%.
Comparative example 1
A mixture of 3.42g (10mmol)2- (1-chloro-cyclopropyl) -1- (2-chlorophenyl) -3- (5-mercapto-1, 2, 4-triazol-1-yl) -propan-2-ol and 1.27g (0.01 gram atom) iodine in 50ml anhydrous dichloromethane was stirred for 46 hours at room temperature under nitrogen. The reaction mixture was then extracted with saturated aqueous sodium carbonate solution and then dried over sodium sulfate. The organic phase was concentrated under reduced pressure to give 3.23g of bis- {1- [2- (1-chlorocyclopropyl) -3- (2-chlorophenyl) -2-hydroxy-propyl-1 ] -1,2, 4-triazol-5-yl } disulfide in solid form with a purity of 90.2%.
Comparative example 2
A mixture of 1.7g (5mmol)2- (1-chloro-cyclopropyl) -1- (2-chlorophenyl) -3- (5-mercapto-1, 2, 4-triazol-1-yl) -propan-2-ol, 25ml water and 0.6g (10mmol) acetic acid was mixed with 1.1ml (10mmol) 35% strength hydrogen peroxide at room temperature and stirred at room temperature for 96 hours. The precipitated solid product was suction-filtered off, washed with water and dried under reduced pressure to give 1.64g of bis- {1- [2- (1-chlorocyclopropyl) -3- (2-chlorophenyl) -2-hydroxy-propyl-1 ] -1,2, 4-triazol-5-yl } disulfide in the form of a solid with a purity of 92.1%.
Comparative example 3
Adding 14g (40mmol, 1eq) of the formula (II) into a four-neck flask, adding 60ml of acetonitrile and 40ml of water, starting stirring, slowly adding 18.96g of potassium permanganate (120mmol) into the four-neck flask in batches, controlling the reaction temperature to be 10-15 ℃, continuing to stir for 3 hours under heat preservation after the addition is finished, and finishing the reaction. After the reaction was completed, water was added to the four-necked flask, and the mixture was filtered, and the filter cake was rinsed with a small amount of water, to obtain 13.72g of bis- {1- [2- (1-chlorocyclopropyl) -3- (2-chlorophenyl) -2-hydroxy-propyl-1 ] -1,2, 4-triazol-5-yl } dithio-product, the content of which was 93.2%, and the yield was 91.6%.
Comparative example 4
Adding 14g (40mmol, 1eq) of the formula (II) into a four-neck flask, adding 60ml of methanol and 60ml of water, starting stirring, slowly adding 20.7g m-CPBA m-chloroperoxybenzoic acid (120mmol) into the four-neck flask in batches, controlling the reaction temperature to be 10-15 ℃, continuing to keep the temperature and stirring for 3 hours after the addition is finished, and finishing the reaction. After the reaction was completed, water was added to the four-necked flask, and the mixture was filtered, and the filter cake was rinsed with a small amount of water, to obtain 13.64g of bis- {1- [2- (1-chlorocyclopropyl) -3- (2-chlorophenyl) -2-hydroxy-propyl-1 ] -1,2, 4-triazol-5-yl } dithio-product, the content of which was 90.7%, and the yield was 88.6%.
The above-mentioned embodiments are merely preferred embodiments of the present invention, and should not be construed as limiting the present invention, and the scope of the present invention should be defined by the claims, and equivalents including technical features of the claims, i.e., equivalent modifications within the scope of the present invention.

Claims (10)

1. A preparation method of a dithio-bis-triazole compound comprises the steps of reacting a compound shown in a formula (II) with an oxidant in the presence of a solvent, and carrying out post-treatment to obtain the compound shown in the formula (I), wherein the oxidant is a composition of a metal acid salt or a metal oxide of a VIB or VIIB group element and peroxide,
Figure FDA0003675595400000011
2. the preparation method according to claim 1, wherein the solvent is any one or a mixture of water, methanol, ethanol, isopropanol, n-butanol, acetonitrile and acetone.
3. The method of claim 1, wherein the group VIB or VIIB metal salt or metal oxide comprises potassium permanganate, manganese dioxide, sodium chromate, potassium chromate, sodium dichromate, or potassium dichromate;
the peroxide comprises m-chloroperoxybenzoic acid or tert-butyl hydroperoxide.
4. The preparation method according to claim 3, wherein the oxidizing agent is a composition in which the mass ratio of any one of potassium permanganate, manganese dioxide, sodium chromate, potassium chromate, sodium dichromate, or potassium dichromate to any one of m-chloroperoxybenzoic acid or tert-butyl hydroperoxide is 1-5: 1-2.
5. The method according to claim 1, wherein the reaction temperature is 0 to 60 ℃.
6. The method according to claim 5, wherein the reaction temperature is 0 to 20 ℃.
7. The process according to claim 1, wherein the mass ratio of the compound of formula (II) to the oxidizing agent is 1:1 to 5.
8. The process according to claim 1, wherein the mass ratio of the compound of formula (II) to the solvent is 1:3 to 10.
9. The preparation method according to claim 1, wherein the oxidant is a composition of a metal acid salt or a metal oxide of a group VIB or VIIB element and a peroxide in a mass ratio of 1-5: 1-2.
10. The method according to claim 1, wherein the reaction time is 2 to 20 hours.
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