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CN112430213A - Synthesis process of trifluoromethylthio pyrazole - Google Patents

Synthesis process of trifluoromethylthio pyrazole Download PDF

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Publication number
CN112430213A
CN112430213A CN202011405564.5A CN202011405564A CN112430213A CN 112430213 A CN112430213 A CN 112430213A CN 202011405564 A CN202011405564 A CN 202011405564A CN 112430213 A CN112430213 A CN 112430213A
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CN
China
Prior art keywords
trifluoromethylthio
synthesizing
trifluoromethylthio pyrazole
mixed solution
pyrazole
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202011405564.5A
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Chinese (zh)
Inventor
谢斌
邱历
倪志伟
江飞
顾佳林
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Jiangsu U Prefer Biochemical Technology Co ltd
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Jiangsu U Prefer Biochemical Technology Co ltd
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Priority to CN202011405564.5A priority Critical patent/CN112430213A/en
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D231/00Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
    • C07D231/18One oxygen or sulfur atom
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D487/00Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04Ortho-condensed systems

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a synthesis process of trifluoromethylthio pyrazole, which comprises the following steps of raw materials of vicinal dipyrazole and trifluoromethyl bromide: A. firstly, reacting the vicinal dipyrazole with trifluoromethyl bromide to generate a mixed solution of trifluoromethylthio pyrazole and sodium bromide; B. b, carrying out phase separation treatment on the mixed solution obtained in the step A to obtain a water phase and an organic phase, and recovering the water phase for later use; C. adding a catalyst and an extracting agent into the organic phase obtained in the step B for extraction reaction to obtain a product; D. adding acid liquor into the product for neutralization, and filtering to obtain filtrate; E. and finally, carrying out filter pressing and drying on the filtrate to obtain the trifluoromethylthio pyrazole.

Description

Synthesis process of trifluoromethylthio pyrazole
Technical Field
The invention relates to the technical field of trifluoromethylthio pyrazole synthesis, and particularly relates to a process for synthesizing trifluoromethylthio pyrazole.
Background
The prior art has low yield of the trifluoromethylthio pyrazole synthesized by the prior art, and has more waste water and poor environmental protection performance in the synthesis process, so the improvement is necessary.
Disclosure of Invention
The invention aims to provide a process for synthesizing trifluoromethylthio pyrazole, which aims to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme: a process for synthesizing trifluoromethylthio pyrazole (CTPMO) from raw materials including vicinal dipyrazole and trifluoromethyl bromide comprises the following steps:
A. firstly, reacting the vicinal dipyrazole with trifluoromethyl bromide to generate a mixed solution of trifluoromethylthio pyrazole and sodium bromide;
B. b, carrying out phase separation treatment on the mixed solution obtained in the step A to obtain a water phase and an organic phase, and recovering the water phase for later use;
C. adding a catalyst and an extracting agent into the organic phase obtained in the step B for extraction reaction to obtain a product;
D. adding acid liquor into the product for neutralization, and filtering to obtain filtrate;
E. and finally, carrying out filter pressing and drying on the filtrate to obtain the trifluoromethylthio pyrazole.
Preferably, the reaction temperature in the step A is 45-55 ℃, and the reaction time is 15-25 min.
Preferably, in the step B, dilute hydrochloric acid and methyl isobutyl ketone are added into the mixed solution to perform phase separation treatment.
Preferably, the catalyst in the step B adopts tetrabutylammonium hydrogen sulfate, trioctylmethylammonium chloride or dodecyltrimethylammonium chloride.
Preferably, the extractant in the step C is prepared from 30% of trioctylamine, 40% of n-octanol and 30% of sulfonated kerosene.
Preferably, the acid solution in the step D is oxalic acid or dilute hydrochloric acid.
Preferably, the drying in the step E adopts a vacuum drying mode, and the drying temperature is 80-90 ℃.
Compared with the prior art, the invention has the beneficial effects that: the synthesis process adopted by the invention is simple to operate, and the obtained trifluoromethylthio pyrazole has high purity; wherein, the catalyst and the extracting agent added into the organic phase can improve the single extraction efficiency and further improve the synthesis efficiency.
Drawings
FIG. 1 is a diagram of the synthesis process of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The first embodiment is as follows:
referring to fig. 1, the present invention provides the following technical solutions: a process for synthesizing trifluoromethylthio pyrazole (CTPMO) from raw materials including vicinal dipyrazole and trifluoromethyl bromide comprises the following steps:
A. firstly, reacting the vicinal dipyrazole with trifluoromethyl bromide to generate a mixed solution of trifluoromethylthio pyrazole and sodium bromide;
B. b, carrying out phase separation treatment on the mixed solution obtained in the step A to obtain a water phase and an organic phase, and recovering the water phase for later use;
C. adding a catalyst and an extracting agent into the organic phase obtained in the step B for extraction reaction to obtain a product;
D. adding acid liquor into the product for neutralization, and filtering to obtain filtrate;
E. and finally, carrying out filter pressing and drying on the filtrate to obtain the trifluoromethylthio pyrazole.
In this example, the reaction temperature in step A was 45 ℃ and the reaction time was 15 min.
In this embodiment, in step B, dilute hydrochloric acid and methyl isobutyl ketone are added to the mixed solution to perform phase separation treatment.
In this example, tetrabutylammonium hydrogen sulfate was used as the catalyst in step B.
In this example, the extractant in step C was made from 30% trioctylamine, 40% n-octanol, and 30% sulfonated kerosene.
In this embodiment, the acid solution in step D is oxalic acid.
In this example, the drying in step E was performed in a vacuum drying mode at a temperature of 80 ℃.
Example two:
a process for synthesizing trifluoromethylthio pyrazole comprises the following steps:
A. firstly, reacting the vicinal dipyrazole with trifluoromethyl bromide to generate a mixed solution of trifluoromethylthio pyrazole and sodium bromide;
B. b, carrying out phase separation treatment on the mixed solution obtained in the step A to obtain a water phase and an organic phase, and recovering the water phase for later use;
C. adding a catalyst and an extracting agent into the organic phase obtained in the step B for extraction reaction to obtain a product;
D. adding acid liquor into the product for neutralization, and filtering to obtain filtrate;
E. and finally, carrying out filter pressing and drying on the filtrate to obtain the trifluoromethylthio pyrazole.
In this example, the reaction temperature in step A was 55 ℃ and the reaction time was 25 min.
In this embodiment, in step B, dilute hydrochloric acid and methyl isobutyl ketone are added to the mixed solution to perform phase separation treatment.
In this example, the catalyst used in step B was trioctylmethylammonium chloride.
In this example, the extractant in step C was made from 30% trioctylamine, 40% n-octanol, and 30% sulfonated kerosene.
In this embodiment, the acid solution in step D is diluted hydrochloric acid.
In this example, the drying in step E was performed in a vacuum drying mode at a drying temperature of 90 ℃.
Example three:
a process for synthesizing trifluoromethylthio pyrazole comprises the following steps:
A. firstly, reacting the vicinal dipyrazole with trifluoromethyl bromide to generate a mixed solution of trifluoromethylthio pyrazole and sodium bromide;
B. b, carrying out phase separation treatment on the mixed solution obtained in the step A to obtain a water phase and an organic phase, and recovering the water phase for later use;
C. adding a catalyst and an extracting agent into the organic phase obtained in the step B for extraction reaction to obtain a product;
D. adding acid liquor into the product for neutralization, and filtering to obtain filtrate;
E. and finally, carrying out filter pressing and drying on the filtrate to obtain the trifluoromethylthio pyrazole.
In this example, the reaction temperature in step A was 48 ℃ and the reaction time was 18 min.
In this embodiment, in step B, dilute hydrochloric acid and methyl isobutyl ketone are added to the mixed solution to perform phase separation treatment.
In this example, dodecyl trimethyl ammonium chloride was used as the catalyst in step B.
In this example, the extractant in step C was made from 30% trioctylamine, 40% n-octanol, and 30% sulfonated kerosene.
In this embodiment, the acid solution in step D is oxalic acid.
In this example, the drying in step E was performed in a vacuum drying mode at a temperature of 82 ℃.
Example four:
a process for synthesizing trifluoromethylthio pyrazole comprises the following steps:
A. firstly, reacting the vicinal dipyrazole with trifluoromethyl bromide to generate a mixed solution of trifluoromethylthio pyrazole and sodium bromide;
B. b, carrying out phase separation treatment on the mixed solution obtained in the step A to obtain a water phase and an organic phase, and recovering the water phase for later use;
C. adding a catalyst and an extracting agent into the organic phase obtained in the step B for extraction reaction to obtain a product;
D. adding acid liquor into the product for neutralization, and filtering to obtain filtrate;
E. and finally, carrying out filter pressing and drying on the filtrate to obtain the trifluoromethylthio pyrazole.
In this example, the reaction temperature in step A was 52 ℃ and the reaction time was 22 min.
In this embodiment, in step B, dilute hydrochloric acid and methyl isobutyl ketone are added to the mixed solution to perform phase separation treatment.
In this example, dodecyl trimethyl ammonium chloride was used as the catalyst in step B.
In this example, the extractant in step C was made from 30% trioctylamine, 40% n-octanol, and 30% sulfonated kerosene.
In this embodiment, the acid solution in step D is oxalic acid.
In this example, the drying in step E was performed in a vacuum drying mode at 88 ℃.
Example five:
a process for synthesizing trifluoromethylthio pyrazole comprises the following steps:
A. firstly, reacting the vicinal dipyrazole with trifluoromethyl bromide to generate a mixed solution of trifluoromethylthio pyrazole and sodium bromide;
B. b, carrying out phase separation treatment on the mixed solution obtained in the step A to obtain a water phase and an organic phase, and recovering the water phase for later use;
C. adding a catalyst and an extracting agent into the organic phase obtained in the step B for extraction reaction to obtain a product;
D. adding acid liquor into the product for neutralization, and filtering to obtain filtrate;
E. and finally, carrying out filter pressing and drying on the filtrate to obtain the trifluoromethylthio pyrazole.
In this example, the reaction temperature in step A was 50 ℃ and the reaction time was 20 min.
In this embodiment, in step B, dilute hydrochloric acid and methyl isobutyl ketone are added to the mixed solution to perform phase separation treatment.
In this example, tetrabutylammonium hydrogen sulfate was used as the catalyst in step B.
In this example, the extractant in step C was made from 30% trioctylamine, 40% n-octanol, and 30% sulfonated kerosene.
In this embodiment, the acid solution in step D is oxalic acid.
In this example, the drying in step E was performed in a vacuum drying mode at a drying temperature of 85 ℃.
Experimental example:
the trifluoromethylthio pyrazole synthesized by the examples of the present invention was used for purity testing, and the data obtained are as follows:
purity (%)
Example one 98.2
Example two 98.2
EXAMPLE III 98.6
Example four 98.4
EXAMPLE five 98.7
In conclusion, the synthesis process adopted by the invention is simple to operate, and the obtained trifluoromethylthio pyrazole has high purity; wherein, the catalyst and the extracting agent added into the organic phase can improve the single extraction efficiency and further improve the synthesis efficiency.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.

Claims (7)

1. A process for synthesizing trifluoromethylthio pyrazole, which comprises raw materials of vicinal dipyrazole and trifluoromethyl bromide, and is characterized in that: the method comprises the following steps:
A. firstly, reacting the vicinal dipyrazole with trifluoromethyl bromide to generate a mixed solution of trifluoromethylthio pyrazole and sodium bromide;
B. b, carrying out phase separation treatment on the mixed solution obtained in the step A to obtain a water phase and an organic phase, and recovering the water phase for later use;
C. adding a catalyst and an extracting agent into the organic phase obtained in the step B for extraction reaction to obtain a product;
D. adding acid liquor into the product for neutralization, and filtering to obtain filtrate;
E. and finally, carrying out filter pressing and drying on the filtrate to obtain the trifluoromethylthio pyrazole.
2. The process for synthesizing trifluoromethylthio pyrazole according to claim 1, wherein: in the step A, the reaction temperature is 45-55 ℃ and the reaction time is 15-25 min.
3. The process for synthesizing trifluoromethylthio pyrazole according to claim 1, wherein: and in the step B, dilute hydrochloric acid and methyl isobutyl ketone are added into the mixed solution for phase separation treatment.
4. The process for synthesizing trifluoromethylthio pyrazole according to claim 1, wherein: and the catalyst in the step B adopts tetrabutylammonium hydrogen sulfate, trioctylmethylammonium chloride or dodecyl trimethyl ammonium chloride.
5. The process for synthesizing trifluoromethylthio pyrazole according to claim 1, wherein: and the extracting agent in the step C is prepared from 30 percent of trioctylamine, 40 percent of n-octanol and 30 percent of sulfonated kerosene.
6. The process for synthesizing trifluoromethylthio pyrazole according to claim 1, wherein: and D, adopting oxalic acid or dilute hydrochloric acid as the acid solution in the step D.
7. The process for synthesizing trifluoromethylthio pyrazole according to claim 1, wherein: and D, drying in the step E in a vacuum drying mode, wherein the drying temperature is 80-90 ℃.
CN202011405564.5A 2020-12-03 2020-12-03 Synthesis process of trifluoromethylthio pyrazole Pending CN112430213A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005023774A1 (en) * 2003-09-11 2005-03-17 Cheminova A/S Process for the preparation of a trifluoromethylthioether
CN101445483A (en) * 1999-10-22 2009-06-03 拜尔农科股份有限公司 Process for preparing pesticides
CN101544607A (en) * 2009-04-30 2009-09-30 宁波中化化学品有限公司 Method for synthesizing 1-aryl pyrazole compound containing trifluoromethylsulfinyl

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101445483A (en) * 1999-10-22 2009-06-03 拜尔农科股份有限公司 Process for preparing pesticides
WO2005023774A1 (en) * 2003-09-11 2005-03-17 Cheminova A/S Process for the preparation of a trifluoromethylthioether
CN101544607A (en) * 2009-04-30 2009-09-30 宁波中化化学品有限公司 Method for synthesizing 1-aryl pyrazole compound containing trifluoromethylsulfinyl

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
RI-YUAN TANG等: "A convenient conversion of pyrazolyl disulfide to sulfides by sodium dithionite and synthesis of sulfoxides", 《JOURNAL OF FLUORINE CHEMISTRY》 *
蒋富国等: "氟虫腈的催化氧化合成研究", 《上海化工》 *

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Application publication date: 20210302