CN114453027B - Catalyst composition, application thereof and method for synthesizing pyraclonil - Google Patents

Catalyst composition, application thereof and method for synthesizing pyraclonil Download PDF

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CN114453027B
CN114453027B CN202111555818.6A CN202111555818A CN114453027B CN 114453027 B CN114453027 B CN 114453027B CN 202111555818 A CN202111555818 A CN 202111555818A CN 114453027 B CN114453027 B CN 114453027B
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catalyst composition
sodium
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CN114453027A (en
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曾润生
张科
孙永辉
苏文豪
陈莉芝
孔繁蕾
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Jiangsu Agrochem Laboratory Co ltd
Suzhou University
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Suzhou University
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Abstract

The invention provides a catalyst composition, application thereof and a method for synthesizing pyraclonil, wherein the method comprises the following steps: under the action of the catalyst composition at 15-20 ℃, the compound shown in the formula (1) reacts with paraformaldehyde and sodium methoxide, and then a reducing agent is added for reduction to obtain a compound shown in the formula (2); reacting a compound shown in a formula (2) with chlorpropyne under the action of the catalyst composition at 25-60 ℃ to obtain a compound shown in a formula (3); the catalyst composition provided by the invention has the advantages of high catalytic efficiency and small pollution to products when catalyzing methylation and/or propargylation reaction; synthesis method of compound (3) pyraclonilThe raw materials are easy to obtain, the yield is higher, the cost is lower, the reaction condition is mild, the method is environment-friendly, and the method meets the requirements of green chemistry; wherein the compounds represented by the formulas (1) to (3) are represented by the following formulas:

Description

Catalyst composition, application thereof and method for synthesizing pyraclonil
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a catalyst composition, application thereof and a method for synthesizing pyraclonil.
Background
Bispyribac-sodium (Pyraclonil) is a protoporphyrinogen oxidase (PPO) inhibiting type paddy field herbicide and has a unique structure of pyrazolopyridine ring.
The bispyraclonil was originally discovered by Ai Gefu company and later developed by Kyoyu agriculture, a japanese agrochemical company. The pyraclonil is used as a PPO inhibitor herbicide, has no problem of cross resistance with sulfonylurea and hormone herbicides, and has good effect on sulfonylurea resistant weeds. In addition, the pyraclonil is generally used for preventing and killing in the early stage of barnyard grass occurrence in rice fields, and meets the requirement of early weed prevention and killing.
The pyraclonil is a herbicide variety with great potential for solving the problem of weeds with rice field resistant to sulfonylurea herbicides, so that the pyraclonil has great significance for developing research of new synthesis processes thereof.
In the prior art, the method for synthesizing the pyraclonil mainly comprises the following two steps:
first kind:
second kind:
however, in the prior art, the method for synthesizing the pyraclonil has the advantages of lower yield, higher cost, harsh reaction conditions, environment friendliness and no compliance with the requirements of green chemistry.
Disclosure of Invention
Aiming at the problems of lower yield, higher cost, harsh reaction conditions and unfriendly environment and not meeting the requirements of green chemistry in the method for synthesizing the biscarfentrazone-ethyl in the prior art, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a catalyst composition for catalyzing methylation and/or propargylation reactions, the catalyst composition comprising, in terms of moles, 50-60 parts of a first composite component, 20-30 parts of a second composite component, and 10-15 parts of a third composite component; wherein,
the first composite component comprises one or two of a 4A molecular sieve, graphene oxide and anion exchange resin;
the second composite component comprises one or more of sodium bromide, potassium bromide, copper chloride, copper bromide, sodium iodide, potassium iodide, copper iodide, cuprous iodide and copper acetate;
the third composite component comprises one or two of triethylbenzyl amine chloride, tetrabutyl amine bromide, tetrabutyl amine iodide, PEG-400, PEG-600 and 18-crown-6.
In a second aspect, the present invention provides the use of the above-described catalyst composition for catalyzing methylation and/or propargylation reactions.
In a third aspect, the invention provides a method for synthesizing pyraclonil, which comprises the following steps:
step one: reacting a compound shown in a formula (1) with paraformaldehyde and sodium alkoxide in a first organic solvent at 15-20 ℃ under the action of a first catalyst composition, adding a reducing agent into a reaction system for reduction reaction after the reaction is finished, and obtaining a compound shown in a formula (2) after the reduction reaction is finished;
step two: reacting a compound shown in a formula (2) with chlorpropyne in a second organic solvent added with an alkaline substance at 25-60 ℃ under the action of a second catalyst composition to obtain a compound shown in a formula (3);
wherein the first catalyst composition and the second catalyst composition are each independently selected from the catalyst compositions of claim 1;
the compounds represented by the formulas (1) to (3) are represented by the following formulas:
further, in the first step, the molar ratio of the compound represented by the formula (1) to paraformaldehyde, sodium methoxide, reducing agent and catalyst composition is 1:2:5:1:1; the reaction time of the compound shown in the formula (1) and paraformaldehyde and sodium methoxide in the first organic solvent is 1-10h; preferably, the reaction time of the reduction reaction is 2 to 4 hours.
Further, in the first step, the sodium alkoxide includes sodium methoxide and/or sodium ethoxide; the first solvent comprises methanol and/or ethanol. Further, in the second step, the molar ratio of the compound shown in the formula (2) to chlorpropyne, alkaline substances and the catalyst composition is 1:2-5:5:0.1-0.2; preferably, the reaction time of the second step is 12-24 hours.
Further, the preparation method of the compound shown in the formula (1) comprises the following steps:
step A: reacting a compound shown in a formula (a) with dichloroethylene under the catalysis of a first catalyst at 0-5 ℃ to obtain a compound shown in a formula (b) after the reaction is finished;
and (B) step (B): reacting the compound shown in the formula (b) with hydrazine hydrate at 15-30 ℃, adding an alkaline substance into the reaction solution at 70-90 ℃ after the reaction is finished, continuously reacting, adjusting the pH to 4-9 at 70-90 ℃ after the reaction is finished, adding ethoxymethylenemalononitrile into the reaction solution, continuously reacting, and obtaining the compound shown in the formula (c) after the reaction is finished;
step C: reacting a compound shown in a formula (c) with sulfonyl chloride at a temperature of between 20 ℃ below zero and 0 ℃ below zero, and obtaining a compound shown in a formula (1) after the reaction is finished;
wherein the compounds represented by the formulas (a) - (c) are represented by the following formulas:
further, in the step a, the first catalyst includes one or more combinations of anhydrous aluminum chloride, zinc chloride, ferric chloride and boron trifluoride diethyl etherate solution; the molar ratio of the compound shown in the formula (a), the 1, 1-dichloroethylene and the first catalyst is 1:1.05:1.1, and the reaction solvent comprises one or more of dichloromethane, dichloroethane and tetrahydrofuran; preferably, the reaction time of the above reaction is 8 to 12 hours.
Further, in the step B, the molar ratio of the compound shown in the formula (B) to hydrazine hydrate, alkaline substances and ethoxymethylenemalononitrile is 1:10:2:1.2, and the reaction solvent is one or a combination of more of methanol, ethanol, ethyl acetate and N, N-dimethylformamide; preferably, the reaction time of the compound shown in the formula (b) and the hydrazine hydrate is 3-5h, the reaction time of adding an alkaline substance into the reaction solution for continuous reaction is 8-12h, and the reaction time of adding the ethoxymethylenemalononitrile into the reaction solution for continuous reaction is 5-7h.
Further, in the step C, the molar ratio of the compound shown in the formula (C) to the sulfonyl chloride is 1:1, and the reaction solvent is dichloromethane, preferably, the reaction time is 0.5-1h.
Further, in each step, the alkaline substances are each independently selected from: one or more combinations of sodium hydroxide, potassium hydroxide, sodium ethoxide, sodium tert-butoxide, potassium tert-butoxide, sodium carbonate, potassium carbonate, and sodium hydride; the first organic solvent includes: one or more combinations of methanol, ethanol, and isopropanol; the second organic solvent includes: one or more combinations of methanol, ethanol, t-butanol, ethyl acetate, methylene chloride, tetrahydrofuran, acetone, toluene, and N, N-dimethylformamide; the reducing agent comprises: one or more of sodium borohydride, potassium tetrahydroborate, and sodium hydrosulfite.
The inventors have found through intensive studies that 5-amino-1- (4, 5,6, 7-tetrahydropyrazolo [1,5-a ] pyridin-2-yl) -1H-pyrazole-4-carbonitrile (bispyraclonil) can be synthesized with high efficiency by a one-pot cyclization reaction. The self-made catalyst composition is used for catalytic reaction, so that methylation and propargylation can be smoothly carried out, no bi-methylation and bi-propargylation byproducts are generated in the reaction process, and the bispyraclonil can be obtained in high yield.
By adopting the technical scheme provided by the invention, the method has the following beneficial effects:
1. the catalyst composition provided by the invention has the advantages of high catalytic efficiency and small pollution to products during the catalytic methylation and/or propargylation reaction.
2. The method for synthesizing the pyraclonil has the advantages of easily obtained raw materials, higher yield, lower cost, mild reaction conditions, environmental friendliness and meeting the requirements of green chemistry.
The foregoing description is only an overview of the present invention, and is intended to provide a better understanding of the present invention, as it is embodied in the following description, with reference to the preferred embodiments of the present invention.
Detailed Description
The following describes the embodiments of the present invention in further detail with reference to examples. The following examples are illustrative of the invention and are not intended to limit the scope of the invention.
In the examples of the present invention, the raw materials and chemicals used are all commercially available unless otherwise specified.
Example 1
The present example provides a catalyst composition comprising, in mole number, the following components:
60 parts of a first composite component, 30 parts of a second composite component and 10 parts of a third composite component; wherein the first composite component comprises a 4A molecular sieve and graphene oxide (molar ratio 1:1); the second composite component comprises sodium bromide and copper chloride (molar ratio 1:1); the third composite component comprises triethylbenzylamine chloride and PEG-400 (molar ratio 1:1).
The catalyst composition is prepared by weighing according to a formula and uniformly mixing.
Example two
The present example provides a catalyst composition comprising, in mole number, the following components:
60 parts of a first composite component, 30 parts of a second composite component and 10 parts of a third composite component; wherein the first composite component comprises a 4A molecular sieve and an anion exchange resin (molar ratio 1:1); the second composite component comprises potassium bromide and cuprous iodide (molar ratio 1:1); the third composite component included tetrabutyl iodinated amine and 18-crown-6 (molar ratio 1:1).
The catalyst composition is prepared by weighing according to a formula and uniformly mixing.
Example III
The present example provides a catalyst composition comprising, in mole number, the following components:
60 parts of a first composite component, 30 parts of a second composite component and 10 parts of a third composite component; wherein the first composite component comprises graphene oxide and anion exchange resin (molar ratio 1:1); the second composite component comprises copper chloride and copper acetate (molar ratio 1:1); the third composite component included tetrabutyl iodinated amine and PEG-600 (molar ratio 1:1).
The catalyst composition is prepared by weighing according to a formula and uniformly mixing.
Example IV
The present example provides a catalyst composition comprising, in mole number, the following components:
60 parts of a first composite component, 30 parts of a second composite component and 10 parts of a third composite component; wherein the first composite component comprises a 4A molecular sieve and graphite oxide (molar ratio 1:1); the second composite component comprises sodium iodide and copper iodide (molar ratio 1:1); the third composite component comprises triethylbenzylamine chloride and 18-crown-6 (molar ratio 1:1).
The catalyst composition is prepared by weighing according to a formula and uniformly mixing.
Example five
Preparation of 1,1,7-trichloro-1-hept-3-one (b):
a mixture of 0.68mol of anhydrous aluminum chloride (as the first catalyst) and 150ml of dichloromethane was cooled to 5 ℃. 0.62mol of 5-chlorovaleryl chloride (a) is dripped, 0.65mol of mixed solution of dichloroethylene and 25ml of dichloromethane is dripped after no solid exists in the system, the reaction is continued for 10 hours, water is added for decomposition, an organic phase is separated, washing, drying and concentration are carried out to obtain 123.8g of oily product, and the yield of the reaction step is 93.3 percent through calculation.
The reaction process in this example is shown in the following formula:
example six
Preparation of 5-amino-1- (4, 5,6, 7-tetrahydropyrazolo [1,5-a ] pyridin-2-yl) -1H-pyrazole-4-carbonitrile (c)
After 2.5mol of hydrazine hydrate and 400ml of ethanol were mixed, a mixed solution of 0.25mol of 1,1,7-trichloro-1-hept-3-one (b) and 100ml of ethanol was added dropwise. After reacting for 4 hours at normal temperature, adding 0.5mol of alkaline substance into the reaction liquid, refluxing and reacting for 10 hours at 80 ℃, then adjusting the pH to 7-8, adding 0.3mol of ethoxymethylene malononitrile and reacting for 6 hours at 80 ℃; after the reaction is finished, the solution is concentrated, crystallized, washed and dried to obtain the product 5-amino-1- (4, 5,6, 7-tetrahydropyrazolo [1,5-a ] pyridin-2-yl) -1H-pyrazole-4-carbonitrile (c).
The reaction process in this example is shown in the following formula:
example seven
Preparation of 5-amino-1- (3-chloro-4, 5,6, 7-tetrahydropyrazolo [1,5-a ] pyridin-2-yl) -1H-pyrazole-4-carbonitrile (1)
A mixture of 0.08mol of 5-amino-1- (4, 5,6, 7-tetrahydropyrazolo [1,5-a ] pyridin-2-yl) -1H-pyrazole-4-carbonitrile (c) and 150ml of dichloromethane was cooled to-10 ℃. 0.08mol of sulfonyl chloride is added dropwise and reacted for 0.5h. After the completion of the reaction, the reaction mixture was washed with saturated sodium hydrogencarbonate, and then the organic phase was separated, and dried and concentrated to obtain 18.7g of the product (1), and the yield in the reaction step was calculated to be 88.9%.
The reaction process in this example is shown in the following formula:
example eight
Preparation of 1- (3-chloro-4, 5,6, 7-tetrahydropyrazolo [1,5-a ] pyridin-2-yl) -5- (methylamino) -1H-pyrazole-4-carbonitrile (2)
A mixture of 65ml of methanol containing 5mmol of 5-amino-1- (3-chloro-4, 5,6, 7-tetrahydropyrazolo [1,5-a ] pyridin-2-yl) -1H-pyrazole-4-carbonitrile (1.310 g, 2), 25mmol of paraformaldehyde (0.750 g,1.250g of the catalyst composition provided in example IV above (in the following reaction scheme, the composite catalyst is equivalent to the catalyst composition herein, hereinafter) was cooled to 15 ℃. 1.350g (25 mmol) of sodium methoxide was added to carry out the reaction, and after the completion of the reaction, 0.570g (15 mmol) of sodium borohydride was added thereto, and the reaction was continued at 15℃for 3 hours. Finally, the solvent was concentrated, 100ml of water and 100ml of methylene chloride were added, the organic phase was separated, and the product 1- (3-chloro-4, 5,6, 7-tetrahydropyrazolo [1,5-a ] pyridin-2-yl) -5- (methylamino) -1H-pyrazole-4-carbonitrile (2) 1.387g was obtained by drying and concentrating.
The reaction process in this example is shown in the following formula:
example nine
Preparation of Bispyribac-sodium (3)
1.38g (5 mmol) of the above-mentioned 1- (3-chloro-4, 5,6, 7-tetrahydropyrazolo [1,5-a ] pyridin-2-yl) -5- (methylamino) -1H-pyrazole-4-carbonitrile (2), 1.85g (25 mmol) of chloropropene, 25mmol of the basic substance, 0.335g of the catalyst composition provided in example four and 10ml of the solvent were prepared as a reaction solution, and reacted at room temperature (15 to 25 ℃) to reflux for 24 hours, then 200ml of water and 100ml of methylene chloride were added to the reaction solution, after three extractions, washed twice with 100ml of water, dried over anhydrous sodium sulfate, filtered, concentrated to give a crude product (3) 1.915g, and purified by column chromatography to give a product (3) 1.52g, calculated that in example five and example six of the present invention, the total yield of the two reaction steps was about 96.0%.
The reaction process in this example is shown in the following formula:
characterization data for compounds (1), (2) and (3) are as follows:
(1) 1 H NMR(400MHz,Chloroform-d)δ7.64(s,1H),5.74(s,2H),4.07(t,J＝6.1Hz,2H),2.76(t,J＝6.4Hz,2H),2.12–2.02(m,2H),1.96–1.85(m,2H)； 13 C NMR(101MHz,Chloroform-d)δ141.55,98.49,74.76,48.50,22.97,21.10,19.25；HRMS(ESI-TOF):[M+Na] + m/zcalcd for C 11 H 11 N 6 ClNa + :285.0631,found:285.0643.
(2) 1 H NMR(400MHz,Chloroform-d)δ7.64(s,1H),6.59(s,1H),4.05(t,J＝6.1Hz,2H),3.23(s,3H),2.74(t,J＝6.4Hz,2H),2.10–2.02(m,2H),1.94–1.86(m,2H)； 13 C NMR(101MHz,Chloroform-d)δ152.01,142.93,142.49,138.89,115.79,98.44,72.23,48.45,31.10,22.96,21.09,19.24.
(3) 1 H NMR(400MHz,Chloroform-d)δ7.76(s,1H),4.13(t,J＝6.1Hz,2H),3.84(d,J＝2.4Hz,2H),3.06(s,3H),2.76(t,J＝6.4Hz,2H),2.31(t,J＝2.4Hz,1H),2.12–2.04(m,2H),1.96–1.89(m,2H)； 13 C NMR(101MHz,Chloroform-d)δ154.87,143.51,141.97,138.24,114.43,102.83,81.63,77.44,74.13,48.76,44.35,39.30,22.96,21.15,19.29；HRMS(ESI-TOF):[M+Na] + m/z calcd for C 15 H 15 N 6 ClNa + :337.0944,found:337.0959.
based on the above examples, it is clear that the catalyst composition provided by the invention has higher catalytic efficiency in catalyzing methylation and/or propargylation reactions; the method for synthesizing the pyraclonil has the advantages of easily obtained raw materials, higher yield, lower cost, mild reaction conditions, environmental friendliness, meeting the requirements of green chemistry, being more feasible in the process route and suitable for industrial mass production.
The above is only a preferred embodiment of the present invention, and it should be noted that it should be understood by those skilled in the art that several improvements and modifications can be made without departing from the technical principle of the present invention, and these improvements and modifications should also be considered as the protection scope of the present invention.

Claims (8)

1. The method for synthesizing the pyraclonil is characterized by comprising the following steps of:
step one: reacting a compound shown in a formula (1) with paraformaldehyde and sodium methoxide in a first solvent organic solvent at 15-20 ℃ under the action of a first catalyst composition, adding a reducing agent into a reaction system for reduction reaction after the reaction is finished, and obtaining a compound shown in a formula (2) after the reduction reaction is finished;
step two: reacting a compound shown in a formula (2) with chlorpropyne in a second organic solvent added with an alkaline substance at 25-60 ℃ under the action of a second catalyst composition to obtain a compound shown in a formula (3);
wherein the first catalyst composition and the second catalyst composition are respectively and independently catalyst compositions for catalyzing methylation and/or propargylation reaction, and the catalyst compositions comprise 50-60 parts of a first composite component, 20-30 parts of a second composite component and 10-15 parts of a third composite component in terms of mole number; wherein,
the first composite component comprises one or two of a 4A molecular sieve, graphene oxide and anion exchange resin;
the second composite component comprises one or two of sodium bromide, potassium bromide, copper chloride, copper bromide, sodium iodide, potassium iodide, copper iodide, cuprous iodide and copper acetate;
the third composite component comprises one or two of triethylbenzyl ammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, PEG-400, PEG-600 and 18-crown-6;
the compounds represented by the formulas (1) to (3) are represented by the following formulas:
。
2. the synthetic method according to claim 1, wherein in the first step, the molar ratio of the compound represented by the formula (1) to paraformaldehyde, sodium methoxide, reducing agent and catalyst composition is 1:2:5:1:1.
3. The synthesis method according to claim 1, wherein in the second step, the molar ratio of the compound represented by the formula (2) to chlorpropyne, the alkaline substance and the catalyst composition is 1:2-5:2-6:0.1-0.2.
4. The synthetic method according to claim 1, wherein the preparation method of the compound represented by formula (1) comprises the steps of:
step A: reacting a compound shown in a formula (a) with 1, 1-dichloroethylene under the catalysis of a first catalyst at 0-5 ℃ to obtain a compound shown in a formula (b);
and (B) step (B): reacting the compound shown in the formula (b) with hydrazine hydrate at 15-30 ℃, adding an alkaline substance into the reaction solution at 70-90 ℃ after the reaction is finished, continuously reacting, adjusting the pH to 4-9 at 70-90 ℃ after the reaction is finished, adding ethoxymethylenemalononitrile into the reaction solution, continuously reacting, and obtaining the compound shown in the formula (c) after the reaction is finished;
step C: reacting a compound shown in a formula (c) with sulfonyl chloride at a temperature of between-10 and 0 ℃ to obtain a compound shown in a formula (1);
wherein the compounds represented by the formulas (a) - (c) are represented by the following formulas:
。
5. the method of synthesis according to claim 4, wherein in step a, the first catalyst comprises one or more of aluminum chloride, zinc chloride, ferric chloride and boron trifluoride etherate solution; the molar ratio of the compound shown in the formula (a), the 1, 1-dichloroethylene and the first catalyst is 1:1.05:1.1.
6. The method according to claim 4, wherein in the step B, the molar ratio of the compound represented by the formula (B) to hydrazine hydrate, the basic substance and ethoxymethylenemalononitrile is 1:10:2:1.2, and the reaction solvent is one or more of methanol, ethanol, ethyl acetate and N, N-dimethylformamide.
7. The method according to claim 4, wherein in the step C, the molar ratio of the compound represented by the formula (C) to the sulfonyl chloride is 1:1.
8. The synthetic method of any one of claims 1 to 7 wherein in each step, the alkaline material is independently selected from the group consisting of: one or more combinations of sodium hydroxide, potassium hydroxide, sodium ethoxide, sodium tert-butoxide, potassium tert-butoxide, sodium carbonate, potassium carbonate, and sodium hydride; the reducing agent comprises: one or more of sodium borohydride, potassium borohydride, and sodium hydrosulfite.
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