CN103508959A - Synthesis method of 1-methyl-3-ethyl-5-pyrazolyl ethyl carboxylate - Google Patents
Synthesis method of 1-methyl-3-ethyl-5-pyrazolyl ethyl carboxylate Download PDFInfo
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- CN103508959A CN103508959A CN201310495016.XA CN201310495016A CN103508959A CN 103508959 A CN103508959 A CN 103508959A CN 201310495016 A CN201310495016 A CN 201310495016A CN 103508959 A CN103508959 A CN 103508959A
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- C07—ORGANIC CHEMISTRY
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- 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
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Abstract
The invention discloses a synthesis method of 1-methyl-3-ethyl-5-pyrazolyl ethyl carboxylate, relates to a synthesis method of ethyl carboxylate, and aims to solve the technical problem of environment pollution caused by highly-toxic dimethyl sulfate in the synthesis process of the 1-methyl-3-ethyl-5-pyrazolyl ethyl carboxylate. The synthesis method comprises the following steps: adding 3-ethyl-5-pyrazolyl ethyl carboxylate, NaH and dimethyl carbonate into dimethylformamide, and reacting for 4 h at 80-140 DEG C to obtain 1-methyl-3-ethyl-5-pyrazolyl ethyl carboxylate. Non-toxic dimethyl carbonate replaces the highly-toxic dimethyl sulfate, thus eliminating the problems of safety and environment pollution caused by using the highly-toxic raw material; by the synthesis method, the reaction yield can be about 90%, relatively few byproducts are produced during the reaction, and the atom yield in the methylation reaction is greatly increased. The invention belongs to the field of preparation of 1-methyl-3-ethyl-5-pyrazolyl ethyl carboxylate.
Description
Technical field
The present invention relates to a kind of method of synthesis of carboxylic acid ethyl ester.
Background technology
Tolfenpyrad is a kind of novel pyrazole amides insecticidal/acaricidal agent, has Insecticiding-miticiding and composes wide, low, the efficient feature of toxicity.1-methyl-3-ethyl-5-pyrazole carboxylic acid ethyl ester is the key intermediate of Tolfenpyrad in synthetic, and the synthetic route of bibliographical information has two kinds at present, and a kind of is to take methyl-sulfate to react and make with 3-ethyl-5-pyrazole carboxylic acid ethyl ester as methylating reagent.The shortcoming of the method is methyl-sulfate large usage quantity, and reaction process produces a large amount of by products makes atom utilization lower.Another method is that ethyl propionylpyruvate and methyl hydrazine direct polycondensation make, and the shortcoming of present method is the expensive of methyl hydrazine, causes production cost higher than the former.In addition, two kinds of methods also exist a common problem be exactly their raw materials for production methyl-sulfate and methyl hydrazine be all hypertoxic hazardous substance, wherein methyl hydrazine or inflammable and explosive anakinetomer, will there is huge security risk and problem of environmental pollution in their use.The unfriendly reagent of environment of finding alternative these high risks of new eco-friendly poisonous material has important practical value to the suitability for industrialized production of this type of agricultural chemicals.
Methylcarbonate (DMC) is a kind of novel Green Chemistry reagent, and its toxicity is extremely low, is listed in non-toxic chemicals.The methylcarbonate of take as raw material, replaces many poisonous reagents such as phosgene, methyl-sulfate and methyl halide to methylate and the synthetic technology of carbonylation reaction has become one of focus of Green Chemical Technology research.The present invention is exactly a kind of novel method of methylcarbonate as the synthetic 1-methyl-3-ethyl-5-pyrazole carboxylic acid ethyl ester of methylating reagent of take under sodium hydride catalysis.
Summary of the invention
To the object of the invention is the technical problem of using hypertoxic methyl-sulfate to cause environmental pollution in 1-methyl-3-ethyl-5-pyrazole carboxylic acid ethyl ester building-up process in order solving, a kind of method of synthetic 1-methyl-3-ethyl-5-pyrazole carboxylic acid ethyl ester to be provided.
The method of synthetic 1-methyl-3-ethyl-5-pyrazole carboxylic acid ethyl ester is as follows:
The NaH and the methylcarbonate that by 3-ethyl-5-pyrazole carboxylic acid ethyl ester, content, are 60% join in dimethyl formamide, obtain mixed solution, then under the condition of 80～140 ℃, react 4h, obtain 1-methyl-3-ethyl-5-pyrazole carboxylic acid ethyl ester;
Wherein the mol ratio of methylcarbonate and 3-ethyl-5-pyrazole carboxylic acid ethyl ester is 3～8 ﹕ 1, and the add-on of NaH is 10～50% of 3-ethyl-5-pyrazole carboxylic acid ethyl ester amount of substance.
Principle of the present invention:
Saturated nitrogen-atoms on pyrazole ring reacts with the methyl of methylcarbonate as nucleophilic reaction center, and the hydrogen atom on methyl substituted nitrogen-atoms completes methylation reaction.In reaction, alkaline sodium hydride first reacts with 3-ethyl-5-pyrazole carboxylic acid ethyl ester and generates the pyrazoles negative ion with strong nucleophilicity, and the latter and dimethyl carbonate generate methylate and carbonic acid monoesters negative ion.Because sodium hydride is catalytic amount, the carbonic acid monoesters negative ion of generation is to provide the needed alkaline condition of reaction, maintains the actual catalyst of the carrying out of reaction.
Method of the present invention has the following advantages:
(1) use nontoxic methylcarbonate to replace hypertoxic methyl-sulfate, eliminated the safety and the problem of environmental pollution that use hypertoxic raw material to produce.
(2) reaction yield of the inventive method can reach 90% left and right, close when using methyl-sulfate for methylating reagent, but because excessive methylcarbonate can reclaim use, the by product of reaction is less, has greatly improved the atom yield of methylation reaction.
Accompanying drawing explanation
Fig. 1 tests 1-methyl-3-ethyl-5-pyrazole carboxylic acid ethyl ester of preparing
1hNMR spectrogram.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: in present embodiment, the method for synthetic 1-methyl-3-ethyl-5-pyrazole carboxylic acid ethyl ester is as follows:
The NaH and the methylcarbonate that by 3-ethyl-5-pyrazole carboxylic acid ethyl ester, purity, are 60% join in dimethyl formamide, obtain mixed solution, then under the condition of 80～140 ℃, react 4h, obtain 1-methyl-3-ethyl-5-pyrazole carboxylic acid ethyl ester;
Wherein the mol ratio of methylcarbonate and 3-ethyl-5-pyrazole carboxylic acid ethyl ester is 3～8 ﹕ 1, and the add-on of NaH is 10～50% of 3-ethyl-5-pyrazole carboxylic acid ethyl ester amount of substance.
In present embodiment, reaction finishes rear underpressure distillation and removes unreacted methylcarbonate and partial solvent (dimethyl formamide), in distillation residuum injected water.Being extracted with ethyl acetate, is neutral by salt water washing to washing lotion after merging organic phase, anhydrous magnesium sulfate drying, filter, ethyl acetate is removed in air distillation, and underpressure distillation obtains pale yellow oily liquid body and is target product (1-methyl-3-ethyl-5-pyrazole carboxylic acid ethyl ester), and yield is 65.1～90.5%.
Embodiment two: present embodiment is different from embodiment one is that the mol ratio of methylcarbonate and 3-ethyl-5-pyrazole carboxylic acid ethyl ester is 4～7 ﹕ 1.Other is identical with embodiment one.
Embodiment three: present embodiment is different from one of embodiment one or two is that the mol ratio of methylcarbonate and 3-ethyl-5-pyrazole carboxylic acid ethyl ester is 6 ﹕ 1.Other is identical with one of embodiment one or two.
Embodiment four: present embodiment is different from one of embodiment one to three is that the mol ratio of methylcarbonate and 3-ethyl-5-pyrazole carboxylic acid ethyl ester is 5 ﹕ 1.Other is identical with one of embodiment one to three.
Embodiment five: present embodiment is different from one of embodiment one to four is that the add-on of NaH is 15～45% of 3-ethyl-5-pyrazole carboxylic acid ethyl ester amount of substance.Other is identical with one of embodiment one to four.
Embodiment six: present embodiment is different from one of embodiment one to five is that the add-on of NaH is 20～40% of 3-ethyl-5-pyrazole carboxylic acid ethyl ester amount of substance.Other is identical with one of embodiment one to five.
Embodiment seven: present embodiment is different from one of embodiment one to six is that the add-on of NaH is 30% of 3-ethyl-5-pyrazole carboxylic acid ethyl ester amount of substance.Other is identical with one of embodiment one to six.
Embodiment eight: what present embodiment was different from one of embodiment one to seven is to react 4h under the condition of 90～130 ℃.Other is identical with one of embodiment one to seven.
Embodiment nine: what present embodiment was different from one of embodiment one to eight is to react 4h under the condition of 100～120 ℃.Other is identical with one of embodiment one to eight.
Embodiment ten: what present embodiment was different from one of embodiment one to nine is to react 4h under the condition of 110 ℃.Other is identical with one of embodiment one to nine.
Adopt following experimental verification effect of the present invention:
Experiment one:
The method of synthetic 1-methyl-3-ethyl-5-pyrazole carboxylic acid ethyl ester is as follows:
3-ethyl-5-pyrazole carboxylic acid the ethyl ester, the 20ml dimethyl formamide that in three-necked bottle, add 50mmol add 0.8g NaH in batches, then add the methylcarbonate of 300mmol, then under the condition of 110 ℃, react 4h;
Reaction finishes rear underpressure distillation and removes unreacted methylcarbonate and partial solvent (dimethyl formamide), and distillation residuum injects 50ml water.With 20ml ethyl acetate extraction 3 times, after merging organic phase, by salt water washing to washing lotion, be neutral respectively, adopt anhydrous magnesium sulfate drying, filter, ethyl acetate is removed in air distillation, and underpressure distillation obtains pale yellow oily liquid body 8.2g(1-methyl-3-ethyl-5-pyrazole carboxylic acid ethyl ester), yield 90.1%.
This experiment gained 1-methyl-3-ethyl-5-pyrazole carboxylic acid ethyl ester embodiments data are as follows:
IR(cm
-1)：3413，3335，2931，1642。
1h-NMR (300Hz, CDCl
3) (seeing accompanying drawing 1): δ 1.22～1.27 (t, 3H ,-CH
3), 1.35～1.40 (t, 3H ,-CH
3), 2.61～2.69 (q, 2H ,-CH
2), 4.13 (s, 3H, N-CH
3), 4.30～4.37 (q, 2H, O-CH
2).
Experiment two:
The method of synthetic 1-methyl-3-ethyl-5-pyrazole carboxylic acid ethyl ester is as follows:
3-ethyl-5-pyrazole carboxylic acid the ethyl ester, the 20ml dimethyl formamide that in three-necked bottle, add 50mmol add 0.8g NaH in batches, then add the methylcarbonate of 200mmol, then under the condition of 110 ℃, react 4h;
Reaction finishes rear underpressure distillation and removes unreacted methylcarbonate and partial solvent (dimethyl formamide), and distillation residuum injects 50ml water.With 20ml ethyl acetate extraction 3 times, after merging organic phase, by salt water washing to washing lotion, be neutral respectively, adopt anhydrous magnesium sulfate drying, filter, ethyl acetate is removed in air distillation, and underpressure distillation obtains pale yellow oily liquid body 7.4g(1-methyl-3-ethyl-5-pyrazole carboxylic acid ethyl ester), yield 81.3%.
Experiment three:
The method of synthetic 1-methyl-3-ethyl-5-pyrazole carboxylic acid ethyl ester is as follows:
3-ethyl-5-pyrazole carboxylic acid the ethyl ester, the 20ml dimethyl formamide that in three-necked bottle, add 50mmol add 0.8g NaH in batches, then add the methylcarbonate of 250mmol, then under the condition of 110 ℃, react 4h;
Reaction finishes rear underpressure distillation and removes unreacted methylcarbonate and partial solvent (dimethyl formamide), and distillation residuum injects 50ml water.With 20ml ethyl acetate extraction 3 times, after merging organic phase, by salt water washing to washing lotion, be neutral respectively, adopt anhydrous magnesium sulfate drying, filter, ethyl acetate is removed in air distillation, and underpressure distillation obtains pale yellow oily liquid body 7.9g(1-methyl-3-ethyl-5-pyrazole carboxylic acid ethyl ester), yield 86.8%.
Experiment four:
The method of synthetic 1-methyl-3-ethyl-5-pyrazole carboxylic acid ethyl ester is as follows:
3-ethyl-5-pyrazole carboxylic acid the ethyl ester, the 20ml dimethyl formamide that in three-necked bottle, add 50mmol add 0.8g NaH in batches, then add the methylcarbonate of 350mmol, then under the condition of 110 ℃, react 4h;
Reaction finishes rear underpressure distillation and removes unreacted methylcarbonate and partial solvent (dimethyl formamide), and distillation residuum injects 50ml water.With 20ml ethyl acetate extraction 3 times, after merging organic phase, by salt water washing to washing lotion, be neutral respectively, adopt anhydrous magnesium sulfate drying, filter, ethyl acetate is removed in air distillation, and underpressure distillation obtains pale yellow oily liquid body 8.2g(1-methyl-3-ethyl-5-pyrazole carboxylic acid ethyl ester), yield 90.1%.
Experiment five:
The method of synthetic 1-methyl-3-ethyl-5-pyrazole carboxylic acid ethyl ester is as follows:
3-ethyl-5-pyrazole carboxylic acid the ethyl ester, the 20ml dimethyl formamide that in three-necked bottle, add 50mmol add 0.8g NaH in batches, then add the methylcarbonate of 400mmol, then under the condition of 110 ℃, react 4h;
Reaction finishes rear underpressure distillation and removes unreacted methylcarbonate and partial solvent (dimethyl formamide), and distillation residuum injects 50ml water.With 20ml ethyl acetate extraction 3 times, after merging organic phase, by salt water washing to washing lotion, be neutral respectively, adopt anhydrous magnesium sulfate drying, filter, ethyl acetate is removed in air distillation, and underpressure distillation obtains pale yellow oily liquid body 8.1g(1-methyl-3-ethyl-5-pyrazole carboxylic acid ethyl ester), yield 89.0%.
Experiment six:
The method of synthetic 1-methyl-3-ethyl-5-pyrazole carboxylic acid ethyl ester is as follows:
3-ethyl-5-pyrazole carboxylic acid the ethyl ester, the 20ml dimethyl formamide that in three-necked bottle, add 50mmol add 0.2g NaH in batches, then add the methylcarbonate of 200mmol, then under the condition of 110 ℃, react 4h;
Reaction finishes rear underpressure distillation and removes unreacted methylcarbonate and partial solvent (dimethyl formamide), and distillation residuum injects 50ml water.With 20ml ethyl acetate extraction 3 times, after merging organic phase, by salt water washing to washing lotion, be neutral respectively, adopt anhydrous magnesium sulfate drying, filter, ethyl acetate is removed in air distillation, and underpressure distillation obtains pale yellow oily liquid body 7.2g(1-methyl-3-ethyl-5-pyrazole carboxylic acid ethyl ester), yield 79.1%.
Experiment seven:
The method of synthetic 1-methyl-3-ethyl-5-pyrazole carboxylic acid ethyl ester is as follows:
3-ethyl-5-pyrazole carboxylic acid the ethyl ester, the 20ml dimethyl formamide that in three-necked bottle, add 50mmol add 0.4g NaH in batches, then add the methylcarbonate of 200mmol, then under the condition of 110 ℃, react 4h;
Reaction finishes rear underpressure distillation and removes unreacted methylcarbonate and partial solvent (dimethyl formamide), and distillation residuum injects 50ml water.With 20ml ethyl acetate extraction 3 times, after merging organic phase, by salt water washing to washing lotion, be neutral respectively, adopt anhydrous magnesium sulfate drying, filter, ethyl acetate is removed in air distillation, and underpressure distillation obtains pale yellow oily liquid body 7.3g(1-methyl-3-ethyl-5-pyrazole carboxylic acid ethyl ester), yield 85.7%.
Experiment eight:
The method of synthetic 1-methyl-3-ethyl-5-pyrazole carboxylic acid ethyl ester is as follows:
3-ethyl-5-pyrazole carboxylic acid the ethyl ester, the 20ml dimethyl formamide that in three-necked bottle, add 50mmol add 0.6g NaH in batches, then add the methylcarbonate of 200mmol, then under the condition of 110 ℃, react 4h;
Reaction finishes rear underpressure distillation and removes unreacted methylcarbonate and partial solvent (dimethyl formamide), and distillation residuum injects 50ml water.With 20ml ethyl acetate extraction 3 times, after merging organic phase, by salt water washing to washing lotion, be neutral respectively, adopt anhydrous magnesium sulfate drying, filter, ethyl acetate is removed in air distillation, and underpressure distillation obtains pale yellow oily liquid body 7.8g(1-methyl-3-ethyl-5-pyrazole carboxylic acid ethyl ester), yield 85.7%.
Experiment nine:
The method of synthetic 1-methyl-3-ethyl-5-pyrazole carboxylic acid ethyl ester is as follows:
3-ethyl-5-pyrazole carboxylic acid the ethyl ester, the 20ml dimethyl formamide that in three-necked bottle, add 50mmol add 1.0g NaH in batches, then add the methylcarbonate of 200mmol, then under the condition of 110 ℃, react 4h;
Reaction finishes rear underpressure distillation and removes unreacted methylcarbonate and partial solvent (dimethyl formamide), and distillation residuum injects 50ml water.With 20ml ethyl acetate extraction 3 times, after merging organic phase, by salt water washing to washing lotion, be neutral respectively, adopt anhydrous magnesium sulfate drying, filter, ethyl acetate is removed in air distillation, and underpressure distillation obtains pale yellow oily liquid body 8.1g(1-methyl-3-ethyl-5-pyrazole carboxylic acid ethyl ester), yield 89.0%.
Experiment ten:
The method of synthetic 1-methyl-3-ethyl-5-pyrazole carboxylic acid ethyl ester is as follows:
3-ethyl-5-pyrazole carboxylic acid the ethyl ester, the 20ml dimethyl formamide that in three-necked bottle, add 50mmol add 0.8g NaH in batches, then add the methylcarbonate of 200mmol, then under the condition of 80 ℃, react 4h;
Reaction finishes rear underpressure distillation and removes unreacted methylcarbonate and partial solvent (dimethyl formamide), and distillation residuum injects 50ml water.With 20ml ethyl acetate extraction 3 times, after merging organic phase, by salt water washing to washing lotion, be neutral respectively, adopt anhydrous magnesium sulfate drying, filter, ethyl acetate is removed in air distillation, and underpressure distillation obtains pale yellow oily liquid body 5.9g(1-methyl-3-ethyl-5-pyrazole carboxylic acid ethyl ester), yield 64.8%.
Test 11:
The method of synthetic 1-methyl-3-ethyl-5-pyrazole carboxylic acid ethyl ester is as follows:
3-ethyl-5-pyrazole carboxylic acid the ethyl ester, the 20ml dimethyl formamide that in three-necked bottle, add 50mmol add 0.8g NaH in batches, then add the methylcarbonate of 200mmol, then under the condition of 90 ℃, react 4h;
Reaction finishes rear underpressure distillation and removes unreacted methylcarbonate and partial solvent (dimethyl formamide), and distillation residuum injects 50ml water.With 20ml ethyl acetate extraction 3 times, after merging organic phase, by salt water washing to washing lotion, be neutral respectively, adopt anhydrous magnesium sulfate drying, filter, ethyl acetate is removed in air distillation, and underpressure distillation obtains pale yellow oily liquid body 6.8g(1-methyl-3-ethyl-5-pyrazole carboxylic acid ethyl ester), yield 74.7%.
Test 12:
The method of synthetic 1-methyl-3-ethyl-5-pyrazole carboxylic acid ethyl ester is as follows:
3-ethyl-5-pyrazole carboxylic acid the ethyl ester, the 20ml dimethyl formamide that in three-necked bottle, add 50mmol add 0.8g NaH in batches, then add the methylcarbonate of 200mmol, then under the condition of 100 ℃, react 4h;
Reaction finishes rear underpressure distillation and removes unreacted methylcarbonate and partial solvent (dimethyl formamide), and distillation residuum injects 50ml water.With 20ml ethyl acetate extraction 3 times, after merging organic phase, by salt water washing to washing lotion, be neutral respectively, adopt anhydrous magnesium sulfate drying, filter, ethyl acetate is removed in air distillation, and underpressure distillation obtains pale yellow oily liquid body 7.9g(1-methyl-3-ethyl-5-pyrazole carboxylic acid ethyl ester), yield 86.8%.
Test 13:
The method of synthetic 1-methyl-3-ethyl-5-pyrazole carboxylic acid ethyl ester is as follows:
3-ethyl-5-pyrazole carboxylic acid the ethyl ester, the 20ml dimethyl formamide that in three-necked bottle, add 50mmol add 0.8g NaH in batches, then add the methylcarbonate of 200mmol, then under the condition of 120 ℃, react 4h;
Reaction finishes rear underpressure distillation and removes unreacted methylcarbonate and partial solvent (dimethyl formamide), and distillation residuum injects 50ml water.With 20ml ethyl acetate extraction 3 times, after merging organic phase, by salt water washing to washing lotion, be neutral respectively, adopt anhydrous magnesium sulfate drying, filter, ethyl acetate is removed in air distillation, and underpressure distillation obtains pale yellow oily liquid body 8.0g(1-methyl-3-ethyl-5-pyrazole carboxylic acid ethyl ester), yield 87.9%.
Test 14:
The method of synthetic 1-methyl-3-ethyl-5-pyrazole carboxylic acid ethyl ester is as follows:
3-ethyl-5-pyrazole carboxylic acid the ethyl ester, the 20ml dimethyl formamide that in three-necked bottle, add 50mmol add 0.8g NaH in batches, then add the methylcarbonate of 200mmol, then under the condition of 130 ℃, react 4h;
Reaction finishes rear underpressure distillation and removes unreacted methylcarbonate and partial solvent (dimethyl formamide), and distillation residuum injects 50ml water.With 20ml ethyl acetate extraction 3 times, after merging organic phase, by salt water washing to washing lotion, be neutral respectively, adopt anhydrous magnesium sulfate drying, filter, ethyl acetate is removed in air distillation, and underpressure distillation obtains pale yellow oily liquid body 7.6g(1-methyl-3-ethyl-5-pyrazole carboxylic acid ethyl ester), yield 83.5%.
Test 15:
The method of synthetic 1-methyl-3-ethyl-5-pyrazole carboxylic acid ethyl ester is as follows:
3-ethyl-5-pyrazole carboxylic acid the ethyl ester, the 20ml dimethyl formamide that in three-necked bottle, add 50mmol add 0.8g NaH in batches, then add the methylcarbonate of 200mmol, then under the condition of 140 ℃, react 4h;
Reaction finishes rear underpressure distillation and removes unreacted methylcarbonate and partial solvent (dimethyl formamide), and distillation residuum injects 50ml water.With 20ml ethyl acetate extraction 3 times, after merging organic phase, by salt water washing to washing lotion, be neutral respectively, adopt anhydrous magnesium sulfate drying, filter, ethyl acetate is removed in air distillation, and underpressure distillation obtains pale yellow oily liquid body 7.2g(1-methyl-3-ethyl-5-pyrazole carboxylic acid ethyl ester), yield 79.1%.
Claims (10)
1. synthesize the method for 1-methyl-3-ethyl-5-pyrazole carboxylic acid ethyl ester, it is characterized in that the method for synthetic 1-methyl-3-ethyl-5-pyrazole carboxylic acid ethyl ester is as follows:
The NaH and the methylcarbonate that by 3-ethyl-5-pyrazole carboxylic acid ethyl ester, purity, are 60% join in dimethyl formamide, obtain mixed solution, then under the condition of 80～140 ℃, react 4h, obtain 1-methyl-3-ethyl-5-pyrazole carboxylic acid ethyl ester;
Wherein the mol ratio of methylcarbonate and 3-ethyl-5-pyrazole carboxylic acid ethyl ester is 3～8 ﹕ 1, and the add-on of NaH is 10～50% of 3-ethyl-5-pyrazole carboxylic acid ethyl ester amount of substance.
2. synthesize according to claim 1 the method for 1-methyl-3-ethyl-5-pyrazole carboxylic acid ethyl ester, it is characterized in that the mol ratio of methylcarbonate and 3-ethyl-5-pyrazole carboxylic acid ethyl ester is 4～7 ﹕ 1.
3. synthesize according to claim 1 the method for 1-methyl-3-ethyl-5-pyrazole carboxylic acid ethyl ester, it is characterized in that the mol ratio of methylcarbonate and 3-ethyl-5-pyrazole carboxylic acid ethyl ester is 6 ﹕ 1.
4. synthesize according to claim 1 the method for 1-methyl-3-ethyl-5-pyrazole carboxylic acid ethyl ester, it is characterized in that the mol ratio of methylcarbonate and 3-ethyl-5-pyrazole carboxylic acid ethyl ester is 5 ﹕ 1.
5. synthesize according to claim 1 the method for 1-methyl-3-ethyl-5-pyrazole carboxylic acid ethyl ester, the add-on that it is characterized in that NaH is 15～45% of 3-ethyl-5-pyrazole carboxylic acid ethyl ester amount of substance.
6. synthesize according to claim 1 the method for 1-methyl-3-ethyl-5-pyrazole carboxylic acid ethyl ester, the add-on that it is characterized in that NaH is 20～40% of 3-ethyl-5-pyrazole carboxylic acid ethyl ester amount of substance.
7. synthesize according to claim 1 the method for 1-methyl-3-ethyl-5-pyrazole carboxylic acid ethyl ester, the add-on that it is characterized in that NaH is 30% of 3-ethyl-5-pyrazole carboxylic acid ethyl ester amount of substance.
8. synthesize according to claim 1 the method for 1-methyl-3-ethyl-5-pyrazole carboxylic acid ethyl ester, it is characterized in that reacting 4h under the condition of 90～130 ℃.
9. synthesize according to claim 1 the method for 1-methyl-3-ethyl-5-pyrazole carboxylic acid ethyl ester, it is characterized in that reacting 4h under the condition of 100～120 ℃.
10. synthesize according to claim 1 the method for 1-methyl-3-ethyl-5-pyrazole carboxylic acid ethyl ester, it is characterized in that reacting 4h under the condition of 110 ℃.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02292263A (en) * | 1989-05-08 | 1990-12-03 | Mitsubishi Kasei Corp | Production of 1-methyl-3-alkyl-5-pyrazole carboxylate |
| JP2000044541A (en) * | 1998-08-03 | 2000-02-15 | Mitsui Chemicals Inc | Production of 1,3-dialkylpyrazole-4-carboxylic acid ester |
| CN103102307A (en) * | 2013-03-04 | 2013-05-15 | 黑龙江大学 | Method for synthesizing tolfenpyrad |
-
2013
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02292263A (en) * | 1989-05-08 | 1990-12-03 | Mitsubishi Kasei Corp | Production of 1-methyl-3-alkyl-5-pyrazole carboxylate |
| JP2000044541A (en) * | 1998-08-03 | 2000-02-15 | Mitsui Chemicals Inc | Production of 1,3-dialkylpyrazole-4-carboxylic acid ester |
| CN103102307A (en) * | 2013-03-04 | 2013-05-15 | 黑龙江大学 | Method for synthesizing tolfenpyrad |
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Application publication date: 20140115 |