CN104592117A - Synthesis method of pyraclostrobin - Google Patents
Synthesis method of pyraclostrobin Download PDFInfo
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- CN104592117A CN104592117A CN201510016425.6A CN201510016425A CN104592117A CN 104592117 A CN104592117 A CN 104592117A CN 201510016425 A CN201510016425 A CN 201510016425A CN 104592117 A CN104592117 A CN 104592117A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic 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
- C07D231/14—Heterocyclic 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
- C07D231/18—One oxygen or sulfur atom
- C07D231/20—One oxygen atom attached in position 3 or 5
- C07D231/22—One oxygen atom attached in position 3 or 5 with aryl radicals attached to ring nitrogen atoms
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Abstract
The invention aims at providing a synthesis method of pyraclostrobin. The method comprises the following steps: with chloroaniline and ortho-nitrotoluene as raw materials, synthesizing, cyclizing, oxidizing, bromizing, etherifying, reducing, esterifying and methylating chlorophenylhydrazine hydrochloride to prepare the pyraclostrobin. The purity of the pyraclostrobin synthesized through the method disclosed by the invention is 98.0% and more, the yield reaches 48%. And the process is low in cost, simple to operate and easy for industrial production.
Description
Technical field
The present invention relates to agricultural bactericide field, be specifically related to a kind of synthetic method of pyraclostrobin.
Background technology
Pyraclostrobin Pyraclostrobin has another name called Strobilurin, is a kind of methoxy methyl acrylate class wide-spectrum bactericide having pyrrazole structure concurrently that BASF Aktiengesellschaft found in 1993, molecular formula C
19h
18clN
3o
4, its structural formula is
Pyraclostrobin has patent right in the country such as the U.S., Europe, has also applied for patent in China, and its synthetic technology is also not open.The domestic and international synthetic route to pyraclostrobin is summed up and is got up can be divided into following two at present: first condensation method and retrude legal, two kinds of synthetic routes are all for starting raw material with Ortho Nitro Toluene and p-Chlorobenzoic acid amide.First condensation method prepares pyraclostrobin by p-hydrochloride synthesis, cyclization, oxidation, bromination, etherificate, reduction, esterification and the eight step reactions that methylate, and this method by product is few, and reaction yield is higher, and condition is gentleer; Retrude legal by by p-hydrochloride synthesis, cyclization, oxidation, reduction, esterification, methylate, bromination and condensation reaction prepare pyraclostrobin, but the productive rate that this method Ortho Nitro Toluene is reduced into azanol is lower, the condensation productive rate of final step is lower, and the finished product purification difficult.Key issue in current pyraclostrobin synthetic route be reduction and bromination reaction time committed step, reaction easily produces by product, is separated quite difficult.
We adopt first condensation method, adopt effective means to decrease the generation of by-product to the committed step bromination in building-up process and reduction, and the purity of the pyraclostrobin of pyraclostrobin prepared by this kind of method is more than 98.0%, and yield can reach 48%.Meanwhile, it is low that technique has production cost, grasps with easy and be easy to the features such as suitability for industrialized production.
Summary of the invention
The object of the invention is to be improved on the basis of traditional first condensation process and optimize, effective means is adopted to the committed step bromination in building-up process and reduction, reduces the generation of by product, thus obtain the highly purified pyraclostrobin product of high yield.
The object of the invention is to be realized by following technical scheme:
A kind of synthetic method of pyraclostrobin, it is characterized in that: with p-Chlorobenzoic acid amide and Ortho Nitro Toluene for raw material, prepare pyraclostrobin by synthesis, cyclization, oxidation, bromination, etherificate, reduction, the esterification of p-hydrochloride and the eight steps reactions that methylate, concrete operations are as follows:
1) synthesis of p-hydrochloride: p-Chlorobenzoic acid amide, mineral acid and Sodium Nitrite add in reactor successively, the mol ratio of p-Chlorobenzoic acid amide, mineral acid and Sodium Nitrite is 1:2 ~ 4.5:0.5 ~ 2.5, temperature of reaction is at 1 ~ 10 DEG C, reaction times is 1 ~ 4h, then in reactor, add sodium sulphite anhydrous 99.3, the mol ratio of p-Chlorobenzoic acid amide and sodium sulphite anhydrous 99.3 is 1:1.5 ~ 4.5, and the time for adding of diazonium salt controls at 2 ~ 5h, temperature at 50 ~ 80 DEG C, then at 60 ~ 90 DEG C of salifies;
2) ring-closure reaction: p-hydrochloride, sodium alkoxide and cyclization reagent are added in reactor, the mol ratio of sodium alkoxide, p-hydrochloride and cyclization reagent is 1:1.5 ~ 3.5:1.5 ~ 4.5, using toluene as solvent, under 60 ~ 80 DEG C of conditions, react 1 ~ 5h;
3) oxidizing reaction: 1-(4-chloro-phenyl-)-3-pyrazolone, catalyzer and DMF are dropped in reactor, pass into oxygen, at 20 ~ 55 DEG C, react 20h, the mol ratio of 1-(4-chloro-phenyl-)-3-pyrazolone, catalyzer and DMF is 1:0.005 ~ 0.35:5 ~ 10;
4) bromination reaction: Ortho Nitro Toluene, hydrogen peroxide, initiator and bromide reagent are dropped in reactor successively, at 60 ~ 65 DEG C, react 4 ~ 8h, in bromination reaction, the mol ratio of Ortho Nitro Toluene, hydrogen peroxide, initiator and bromide reagent is 1:0.3 ~ 2.5:0.01 ~ 1.5:0.3 ~ 3.5;
5) etherification reaction: by 1-(4-chloro-phenyl-)-3-pyrazoles alcohol), adjacent nitro bromobenzyl, alkali and catalyzer add in reactor successively, at 65 ~ 85 DEG C of reaction 4 ~ 10h, 1-(4-chloro-phenyl-)-3-pyrazoles alcohol), the mol ratio of adjacent nitro bromobenzyl, alkali and catalyzer is 1:0.5 ~ 3.5:0.5 ~ 5.0:0.001 ~ 1.2;
6) reduction reaction: 2-[(N-rubigan)-3-pyrazoles oxygen ylmethyl] oil of mirbane, reductive agent and catalyzer are added in reactor successively, the mol ratio of reacting 3 ~ 5h, 2-[(N-rubigan)-3-pyrazoles oxygen ylmethyl] oil of mirbane, reductive agent and catalyzer at 20 ~ 50 DEG C is 1:3.2 ~ 8.5:0.001 ~ 0.356;
7) esterification: 2-[(N-rubigan)-3-pyrazoles oxygen ylmethyl] oil of mirbane, solvent and methyl-chloroformate are added in reactor successively, the mol ratio of reacting 2 ~ 5h, 2-[(N-rubigan)-3-pyrazoles oxygen ylmethyl] oil of mirbane, solvent and methyl-chloroformate at 10 ~ 45 DEG C is 1:10 ~ 35:0.2 ~ 4.5;
8) methylation reaction: by N-hydroxy-n-2-[N-(rubigan) pyrazoles-3-oxygen ylmethyl] phenylcarbamate, methyl-sulfate, K
2cO
3add successively in reactor with solvent, at 30 ~ 60 DEG C of reaction 4 ~ 7h, N-hydroxy-n-2-[N-(rubigan) pyrazoles-3-oxygen ylmethyl] phenylcarbamate, methyl-sulfate, K
2cO
3be 1:0.2 ~ 5.5:0.5 ~ 4.5:15 ~ 50 with the mol ratio of solvent.
Step 1) described in mineral acid be selected from sulfuric acid, hydrochloric acid, the one crossed in chloric acid and fluoroboric acid.
Step 2) cyclization reagent described in ring-closure reaction is selected from one in methyl acrylate, ethyl propenoate and acrylamide; Described sodium alkoxide is that sodium methylate, sodium ethylate, sodium Metal 99.5 and methyl alcohol or ethanol replace.
Step 3) catalyzer described in oxidizing reaction is FeCl
3or CuCl.
Step 4) bromide reagent described in bromination reaction is one in HBr, bromine and N-bromo-succinimide; Described initiator is the one in azoisobutyl cyanide, benzoyl peroxide, isopropyl benzene hydroperoxide, 2,2'-Azobis(2,4-dimethylvaleronitrile) and di-t-butyl peroxide.
Step 5) catalyzer described in etherification reaction be in PEG-600, benzyltriethylammoinium chloride (TEBA), Tetrabutyl amonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate (TBAB), tri-n-octyl methyl ammonium chloride, Dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride one or more mixing.
Step 6) catalyzer described in reduction reaction is one in Ni, Pd/C, Ni-Ce-P; Described reductive agent is sulfide, H
2, hydrazine hydrate, CO, Zn powder/NH
4one in Cl.
Step 7) solvent described in esterification is the mixing of the one or both in ethylene dichloride, methylene dichloride.
Step 8) solvent described in methylation reaction is the mixing of the one or both in ethylene dichloride and DMF.
Beneficial effect
We adopt first condensation method, adopt effective means to decrease the generation of by-product to the committed step bromination in building-up process and reduction, and the purity of the pyraclostrobin of pyraclostrobin prepared by this kind of method is more than 98.0%, and yield can reach 48%.Meanwhile, it is low that technique has production cost, grasps with easy and be easy to the features such as suitability for industrialized production.
Embodiment
Below by example, the present invention is described, but the present invention is not limited to these embodiments.
Embodiment 1:
Embodiment 2:
Embodiment 3:
Embodiment 4:
Embodiment 5:
Embodiment 6:
Claims (9)
1. the synthetic method of a pyraclostrobin, it is characterized in that: with p-Chlorobenzoic acid amide and Ortho Nitro Toluene for raw material, prepare pyraclostrobin by synthesis, cyclization, oxidation, bromination, etherificate, reduction, the esterification of p-hydrochloride and the eight steps reactions that methylate, concrete operations are as follows:
1) synthesis of p-hydrochloride: p-Chlorobenzoic acid amide, mineral acid and Sodium Nitrite add in reactor successively, the mol ratio of p-Chlorobenzoic acid amide, mineral acid and Sodium Nitrite is 1:2 ~ 4.5:0.5 ~ 2.5, temperature of reaction is at 1 ~ 10 DEG C, reaction times is 1 ~ 4h, then in reactor, add sodium sulphite anhydrous 99.3, the mol ratio of p-Chlorobenzoic acid amide and sodium sulphite anhydrous 99.3 is 1:1.5 ~ 4.5, and the time for adding of diazonium salt controls at 2 ~ 5h, temperature at 50 ~ 80 DEG C, then at 60 ~ 90 DEG C of salifies;
2) ring-closure reaction: p-hydrochloride, sodium alkoxide and cyclization reagent are added in reactor, the mol ratio of sodium alkoxide, p-hydrochloride and cyclization reagent is 1:1.5 ~ 3.5:1.5 ~ 4.5, using toluene as solvent, under 60 ~ 80 DEG C of conditions, reacts 1 ~ 5h;
3) oxidizing reaction: 1-(4-chloro-phenyl-)-3-pyrazolone, catalyzer and DMF are dropped in reactor, pass into oxygen, at 20 ~ 55 DEG C, react 20h, the mol ratio of 1-(4-chloro-phenyl-)-3-pyrazolone, catalyzer and DMF is 1:0.005 ~ 0.35:5 ~ 10;
4) bromination reaction: Ortho Nitro Toluene, hydrogen peroxide, initiator and bromide reagent are dropped in reactor successively, at 60 ~ 65 DEG C, react 4 ~ 8h, in bromination reaction, the mol ratio of Ortho Nitro Toluene, hydrogen peroxide, initiator and bromide reagent is 1:0.3 ~ 2.5:0.01 ~ 1.5:0.3 ~ 3.5;
5) etherification reaction: by 1-(4-chloro-phenyl-)-3-pyrazoles alcohol), adjacent nitro bromobenzyl, alkali and catalyzer add in reactor successively, at 65 ~ 85 DEG C of reaction 4 ~ 10h, 1-(4-chloro-phenyl-)-3-pyrazoles alcohol), the mol ratio of adjacent nitro bromobenzyl, alkali and catalyzer is 1:0.5 ~ 3.5:0.5 ~ 5.0:0.001 ~ 1.2;
6) reduction reaction: 2-[(N-rubigan)-3-pyrazoles oxygen ylmethyl] oil of mirbane, reductive agent and catalyzer are added in reactor successively, the mol ratio of reacting 3 ~ 5h, 2-[(N-rubigan)-3-pyrazoles oxygen ylmethyl] oil of mirbane, reductive agent and catalyzer at 20 ~ 50 DEG C is 1:3.2 ~ 8.5:0.001 ~ 0.356;
7) esterification: 2-[(N-rubigan)-3-pyrazoles oxygen ylmethyl] oil of mirbane, solvent and methyl-chloroformate are added in reactor successively, the mol ratio of reacting 2 ~ 5h, 2-[(N-rubigan)-3-pyrazoles oxygen ylmethyl] oil of mirbane, solvent and methyl-chloroformate at 10 ~ 45 DEG C is 1:10 ~ 35:0.2 ~ 4.5;
8) methylation reaction: by N-hydroxy-n-2-[N-(rubigan) pyrazoles-3-oxygen ylmethyl] phenylcarbamate, methyl-sulfate, K
2cO
3add successively in reactor with solvent, at 30 ~ 60 DEG C of reaction 4 ~ 7h, N-hydroxy-n-2-[N-(rubigan) pyrazoles-3-oxygen ylmethyl] phenylcarbamate, methyl-sulfate, K
2cO
3be 1:0.2 ~ 5.5:0.5 ~ 4.5:15 ~ 50 with the mol ratio of solvent.
2. the synthetic method of pyraclostrobin as claimed in claim 1, is characterized in that: the mineral acid described in step 1) is selected from sulfuric acid, hydrochloric acid, the one crossed in chloric acid and fluoroboric acid.
3. the synthetic method of pyraclostrobin as claimed in claim 1, is characterized in that: step 2) cyclization reagent described in ring-closure reaction is selected from one in methyl acrylate, ethyl propenoate and acrylamide; Described sodium alkoxide is that sodium methylate, sodium ethylate, sodium Metal 99.5 and methyl alcohol or ethanol replace.
4. the synthetic method of pyraclostrobin as claimed in claim 1, is characterized in that: the catalyzer described in step 3) oxidizing reaction is FeCl
3or CuCl.
5. the synthetic method of pyraclostrobin as claimed in claim 1, is characterized in that: the bromide reagent described in step 4) bromination reaction is the one in HBr, bromine and N-bromo-succinimide; Described initiator is the one in azoisobutyl cyanide, benzoyl peroxide, isopropyl benzene hydroperoxide, 2,2'-Azobis(2,4-dimethylvaleronitrile) and di-t-butyl peroxide.
6. the synthetic method of pyraclostrobin as claimed in claim 1, its feature exists: the catalyzer described in step 5) etherification reaction is one or more mixing in PEG-600, benzyltriethylammoinium chloride (TEBA), Tetrabutyl amonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate (TBAB), tri-n-octyl methyl ammonium chloride, Dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride.
7. the synthetic method of pyraclostrobin as claimed in claim 1, is characterized in that: the catalyzer described in step 6) reduction reaction is the one in Ni, Pd/C, Ni-Ce-P; Described reductive agent is sulfide, H
2, hydrazine hydrate, CO, Zn powder/NH
4one in Cl.
8. the synthetic method of pyraclostrobin as claimed in claim 1, its feature exists: the solvent described in step 7) esterification is the mixing of the one or both in ethylene dichloride, methylene dichloride.
9. the synthetic method of the pyraclostrobin stated as claim 1, is characterized in that: the solvent described in step 8) methylation reaction is the mixing of the one or both in ethylene dichloride and DMF.
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