CN102285900B - Method for preparing 3-(2,6-dichlorophenyl)-2,3-dioxy ethyl propionate-2-(4-chlorphenyl) hydrazone - Google Patents
Method for preparing 3-(2,6-dichlorophenyl)-2,3-dioxy ethyl propionate-2-(4-chlorphenyl) hydrazone Download PDFInfo
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- CN102285900B CN102285900B CN 201110192400 CN201110192400A CN102285900B CN 102285900 B CN102285900 B CN 102285900B CN 201110192400 CN201110192400 CN 201110192400 CN 201110192400 A CN201110192400 A CN 201110192400A CN 102285900 B CN102285900 B CN 102285900B
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- dichlorophenyl
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- ethyl propionate
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Abstract
The invention discloses a method for preparing 3-(2,6-dichlorophenyl)-2,3-dioxy ethyl propionate-2-(4-chlorphenyl) hydrazone. In the method, 2,6-dichlorophenyl formoxyl ethyl acetoacetate and parachloroaniline diazonium salt are used as raw materials, sodium bicarbonate is used as a neutralizing agent, the materials are filled in an organic solvent to react for 1-5 hours by controlling the temperature at 0-50 DEG C; and then an organic acid is added to perform acidification reaction for 1-24 hours by controlling the temperature at 10-100 DEG C to obtain a target product, namely the 3-(2,6-dichlorophenyl)-2,3-dioxy ethyl propionate-2-(4-chlorphenyl) hydrazone. The method provided by the invention is easy and convenient to operate and has mild reaction conditions, and the used auxiliary rawmaterial, namely the sodium bicarbonate, is low in cost, so that the production cost can be reduced, and the method is convenient for industrial production.
Description
Technical field
The present invention relates to Chemicals, relate in particular to a kind of 3-(2,6-dichlorophenyl)-2, the preparation method of 3-dioxy ethyl propionate-2-(4-chloro-phenyl-) hydrazone.
Background technology
3-(2,6-dichlorophenyl)-2,3-dioxy ethyl propionate-2-(4-chloro-phenyl-) hydrazone is a kind of chemistry of pesticide intermediate, can be used for the synthetic of plant-growth regulator sintofen.
Document EP 0519; 140; agricultural chemicals the 40th volume the 6th phase (2001) has been reported a kind of 3-(2; the 6-dichlorophenyl)-2; the preparation method of 3-dioxy ethyl propionate-2-(4-chloro-phenyl-) hydrazone; this method is with 2; 6-dichloro-benzoyl base methyl aceto acetate is raw material; in methyl alcohol/acetic acid/Potassium ethanoate buffered soln backflow 16-20 hour; concentrate through solvent; solvent extraction; get intermediate 2 behind the solvent reconcentration; 6-dichloro-benzoyl guanidine-acetic acid ethyl ester (productive rate: 80%, purity: 85～90%), then with 2; 6-dichloro-benzoyl guanidine-acetic acid ethyl ester and p-Chlorobenzoic acid amide diazonium salt are placed in Potassium ethanoate and the ethanolic soln and reacted 10 hours under 30 degree; filter; washing; dry product 3-(2,6-dichlorophenyl)-2,3-dioxy ethyl propionate-2-(4-chloro-phenyl-) hydrazone (yield: 74% of getting; content: 90%), two step overall yields about 60%.Reaction formula is as follows:
Aforesaid method relates to two-step reaction, and aftertreatment is loaded down with trivial details, overall yield is lower, and used auxiliary material Potassium ethanoate price is more expensive, and production cost is higher.
Us5,183,891 also disclose same method.
Summary of the invention
Purpose of the present invention in order to overcome the problems referred to above that prior art exists, provides a kind of 3-(2,6-dichlorophenyl)-2, the preparation method of 3-dioxy ethyl propionate-2-(4-chloro-phenyl-) hydrazone exactly.
In order to achieve the above object, the present invention has adopted following technical scheme: a kind of 3-(2, the 6-dichlorophenyl)-2, the preparation method of 3-dioxy ethyl propionate-2-(4-chloro-phenyl-) hydrazone is to be raw material with 2,6-dichloro-benzoyl base methyl aceto acetate and p-Chlorobenzoic acid amide diazonium salt, be neutralizing agent with the sodium bicarbonate, place organic solvent, the control temperature is 0～50 ℃, reacts 1-5 hour; Add organic acid then and carry out acidifying, the control temperature is 10-100 ℃, reacts 1～24 hour, namely obtains target product 3-(2,6-dichlorophenyl)-2,3-dioxy ethyl propionate-2-(4-chloro-phenyl-) hydrazone.
Described 2, the mol ratio of 6-dichloro-benzoyl base methyl aceto acetate and p-Chlorobenzoic acid amide diazonium salt is 1: 1～2,2, and the mol ratio of 6-dichloro-benzoyl base methyl aceto acetate and sodium bicarbonate is 1: 2～10.
Described organic solvent is selected from one or both in methyl alcohol or the ethanol.
Described organic acid is selected from one or both in formic acid or the acetic acid.
Adopt 3-of the present invention (2,6-dichlorophenyl)-2, the preparation method of 3-dioxy ethyl propionate-2-(4-chloro-phenyl-) hydrazone, related reaction formula is as follows:
Method of the present invention is easy and simple to handle, reaction conditions is gentle, and productive rate is greater than 90%, and content is greater than 98%.Used auxiliary material sodium bicarbonate is cheap, therefore can reduce production costs, and is convenient to suitability for industrialized production.
Embodiment
Embodiment 1
In three mouthfuls of reaction flasks of the 1L that agitator and thermometer are housed, add 300 milliliters of ethanol, 60.6 grams 2,6-dichloro-benzoyl base methyl aceto acetate (0.2mol) and 50.4 gram sodium bicarbonates (0.6mol), the control temperature is 15～20 ℃, stirring reaction adds 0.2 mole of p-Chlorobenzoic acid amide diazonium salt after half an hour; Be incubated 15～20 ℃, the restir reaction added 50 milliliters of acetic acid after 2 hours.After the stirring at room 12 hours, add 150 ml waters.Filtration, washing, drying obtain 74.8 gram 3-(2,6-dichlorophenyl)-2, and 3-dioxy ethyl propionate-2-(4-chloro-phenyl-) hydrazone (content: 98.7%, productive rate: 92.4%).Product is yellow powder shape solid, fusing point: 123 ℃.
0.2 the preparation method of mole p-Chlorobenzoic acid amide diazonium salt is as follows:
In being housed, 500 milliliters of three mouthfuls of reaction flasks of agitator and thermometer add 100 milliliters of ethanol, 25.5 gram (0.2mol) p-Chlorobenzoic acid amide and 45 milliliters of concentrated hydrochloric acids, stir, cool off, drip sodium nitrite solution (16 gram Sodium Nitrites are dissolved in 25 ml waters) down at-5～0 ℃, after dripping end, be incubated half an hour at-5～0 ℃, get p-Chlorobenzoic acid amide diazonium salt mixed solution.
Embodiment 2
In three mouthfuls of reaction flasks of the 1L that agitator, reflux condensing tube and thermometer are housed, add 300 ml methanol, 60.6 grams 2,6-dichloro-benzoyl base methyl aceto acetate (0.2mol) and 134.1 gram sodium bicarbonates (1.6mol), stir half an hour down at 15～20 ℃, add 0.2 mole of p-Chlorobenzoic acid amide diazonium salt then; Be incubated 15～20 ℃, restir adds 40 milliliters of formic acid after 2 hours.Stirring and refluxing is cooled to 20 ℃ after 2 hours, add 150 ml waters.Filtration, washing, the dry 58.5 gram 3-(2,6-dichlorophenyl)-2 that get, and 3-dioxy ethyl propionate-2-(4-chloro-phenyl-) hydrazone (content: 88.4%, productive rate: 64.7%).Product is yellow powder shape solid, fusing point: 119～120 ℃.
0.2 the preparation method of mole p-Chlorobenzoic acid amide diazonium salt is as follows:
In being housed, 500 milliliters of three mouthfuls of reaction flasks of agitator and thermometer add 100 milliliters of ethanol, 25.5 gram (0.2mol) p-Chlorobenzoic acid amide and 45 milliliters of concentrated hydrochloric acids, stir, cool off, drip sodium nitrite solution (16 gram Sodium Nitrites are dissolved in 25 ml waters) down at-5～0 ℃, after dripping end, be incubated half an hour at-5～0 ℃, get p-Chlorobenzoic acid amide diazonium salt mixed solution.
Embodiment 3
In three mouthfuls of reaction flasks of the 1L that agitator and thermometer are housed, add 400 milliliters of ethanol, 60.6 grams 2,6-dichloro-benzoyl base methyl aceto acetate (0.2mol) and 100.8 gram sodium bicarbonates (1.2mol) after stirring half an hour under 0～5 ℃, add 0.3 mole of p-Chlorobenzoic acid amide diazonium salt; After stirring 5 hours under 5～10 ℃, add 80 milliliters of formic acid.After the stirring at room 24 hours, add 200 ml waters.Filtration, washing, the dry 73.6 gram 3-(2,6-dichlorophenyl)-2 that get, and 3-dioxy ethyl propionate-2-(4-chloro-phenyl-) hydrazone (content: 96.1%, productive rate: 88.5%).Product is yellow powder shape solid, fusing point: 123 ℃.
0.3 the preparation method of mole p-Chlorobenzoic acid amide diazonium salt is as follows:
In being housed, 500 milliliters of three mouthfuls of reaction flasks of agitator and thermometer add 150 milliliters of ethanol, 38.5 gram (0.3mol) p-Chlorobenzoic acid amide and 68 milliliters of concentrated hydrochloric acids, stir, cool off, drip sodium nitrite solution (24 gram Sodium Nitrites are dissolved in 40 ml waters) down at-5～0 ℃, drip the end back and be incubated half an hour down at-5～0 ℃, get p-Chlorobenzoic acid amide diazonium salt mixed solution.
Embodiment 4
In three mouthfuls of reaction flasks of the 1L that agitator and thermometer are housed, add 200 milliliters of ethanol and 100 ml methanol, 60.6 grams 2,6-dichloro-benzoyl base methyl aceto acetate (0.2mol) and 67 gram sodium bicarbonates (0.8mol), the control temperature is 15～20 ℃, stirring reaction adds 0.4 mole of p-Chlorobenzoic acid amide diazonium salt after half an hour; Be incubated 15～20 ℃, the restir reaction added 30 milliliters of acetic acid and 20 milliliters of formic acid after 2 hours.After the stirring at room 12 hours, add 150 ml waters.Filtration, washing, drying obtain 74.8 gram 3-(2,6-dichlorophenyl)-2, and 3-dioxy ethyl propionate-2-(4-chloro-phenyl-) hydrazone (content: 98.7%, productive rate: 92.4%).Product is yellow powder shape solid, fusing point: 123 ℃.
0.4 the preparation method of mole p-Chlorobenzoic acid amide diazonium salt is as follows:
In being housed, 500 milliliters of three mouthfuls of reaction flasks of agitator and thermometer add 200 milliliters of ethanol, 51 gram (0.4mol) p-Chlorobenzoic acid amide and 90 milliliters of concentrated hydrochloric acids, stir, cool off, drip sodium nitrite solution (32 gram Sodium Nitrites are dissolved in 50 ml waters) down at-5～0 ℃, drip the end back and be incubated half an hour down at-5～0 ℃, get p-Chlorobenzoic acid amide diazonium salt mixed solution.
Embodiment 5
In three mouthfuls of reaction flasks of the 1L that agitator, reflux condensing tube and thermometer are housed, add 200 milliliters of ethanol and 100 ml methanol, 60.6 grams 2,6-dichloro-benzoyl base methyl aceto acetate (0.2mol) and 33.6 gram sodium bicarbonates (0.4mol), stir half an hour down at 15～20 ℃, add 0.3 mole of p-Chlorobenzoic acid amide diazonium salt then; Be incubated 15～20 ℃, restir adds 40 milliliters of acetic acid after 2 hours.Stirring and refluxing is cooled to 20 ℃ after 2 hours, add 150 ml waters.Filtration, washing, the dry 58.5 gram 3-(2,6-dichlorophenyl)-2 that get, and 3-dioxy ethyl propionate-2-(4-chloro-phenyl-) hydrazone (content: 88.4%, productive rate: 64.7%).Product is yellow powder shape solid, fusing point: 119～120 ℃.
0.3 the preparation method of mole p-Chlorobenzoic acid amide diazonium salt is as follows:
In being housed, 500 milliliters of three mouthfuls of reaction flasks of agitator and thermometer add 150 milliliters of ethanol, 38.5 gram (0.3mol) p-Chlorobenzoic acid amide and 68 milliliters of concentrated hydrochloric acids, stir, cool off, drip sodium nitrite solution (24 gram Sodium Nitrites are dissolved in 40 ml waters) down at-5～0 ℃, drip the end back and be incubated half an hour down at-5～0 ℃, get p-Chlorobenzoic acid amide diazonium salt mixed solution.
Embodiment 6
In three mouthfuls of reaction flasks of the 1L that agitator and thermometer are housed, add 400 ml methanol, 60.6 grams 2,6-dichloro-benzoyl base methyl aceto acetate (0.2mol) and 168 gram sodium bicarbonates (2mol), 0～5 ℃ is stirred half an hour, adds 0.4 mole of p-Chlorobenzoic acid amide diazonium salt then half an hour; After stirring 5 hours under 5～10 ℃, add 80 milliliters of formic acid.After the stirring at room 24 hours, add 200 ml waters.Filtration, washing, the dry 73.6 gram 3-(2,6-dichlorophenyl)-2 that get, and 3-dioxy ethyl propionate-2-(4-chloro-phenyl-) hydrazone (content: 96.1%, productive rate: 88.5%).Product is yellow powder shape solid, fusing point: 123 ℃.
0.4 the preparation method of mole p-Chlorobenzoic acid amide diazonium salt is as follows:
In being housed, 500 milliliters of three mouthfuls of reaction flasks of agitator and thermometer add 200 milliliters of ethanol, 51 gram (0.4mol) p-Chlorobenzoic acid amide and 90 milliliters of concentrated hydrochloric acids, stir, cool off, drip sodium nitrite solution (32 gram Sodium Nitrites are dissolved in 50 ml waters) down at-5～0 ℃, drip the end back and be incubated half an hour down at-5～0 ℃, get p-Chlorobenzoic acid amide diazonium salt mixed solution.
Claims (1)
1. 3-(2, the 6-dichlorophenyl)-2,3-dioxy ethyl propionate-2-(4-chloro-phenyl-) preparation method of hydrazone, it is characterized in that: be with 2,6-dichloro-benzoyl base methyl aceto acetate and p-Chlorobenzoic acid amide diazonium salt are raw material, are neutralizing agent with the sodium bicarbonate, place organic solvent, the control temperature is 0 ~ 50 ℃, reacts 1-5 hour; Add organic acid then and carry out acidifying, the control temperature is 10-100 ℃, reacts 1 ~ 24 hour, namely obtains target product 3-(2,6-dichlorophenyl)-2,3-dioxy ethyl propionate-2-(4-chloro-phenyl-) hydrazone;
Described 2, the mol ratio of 6-dichloro-benzoyl base methyl aceto acetate and p-Chlorobenzoic acid amide diazonium salt is 1:1 ~ 2,2, and the mol ratio of 6-dichloro-benzoyl base methyl aceto acetate and sodium bicarbonate is 1:2 ~ 10;
Described organic solvent is selected from one or both in methyl alcohol or the ethanol; Described organic acid is selected from one or both in formic acid or the acetic acid.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5144057A (en) * | 1990-10-15 | 1992-09-01 | Lonza Ltd. | Process for the production of 3-oxocarboxylic acid esters |
| US5183891A (en) * | 1989-11-09 | 1993-02-02 | Orsan | Method for the preparation of substituted 1,4-dihydro-4-oxo-cinnoline-3-carboxylic acid, esters and salts thereof, and intermediates used in their preparation |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5183891A (en) * | 1989-11-09 | 1993-02-02 | Orsan | Method for the preparation of substituted 1,4-dihydro-4-oxo-cinnoline-3-carboxylic acid, esters and salts thereof, and intermediates used in their preparation |
| US5144057A (en) * | 1990-10-15 | 1992-09-01 | Lonza Ltd. | Process for the production of 3-oxocarboxylic acid esters |
Non-Patent Citations (2)
| Title |
|---|
| 小麦杀雄剂杀雄啉的合成及生物活性;耿丽文 等;《农药》;20011231;第40卷(第6期);16-17 * |
| 耿丽文 等.小麦杀雄剂杀雄啉的合成及生物活性.《农药》.2001,第40卷(第6期),16-17. |
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