CN1035252C - Aminomethyl formate-1,1,1-trichloro-2-(2,4-dichlorothiophenyl)-ethyl ester and the prepn. method - Google Patents
Aminomethyl formate-1,1,1-trichloro-2-(2,4-dichlorothiophenyl)-ethyl ester and the prepn. method Download PDFInfo
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- CN1035252C CN1035252C CN93115220A CN93115220A CN1035252C CN 1035252 C CN1035252 C CN 1035252C CN 93115220 A CN93115220 A CN 93115220A CN 93115220 A CN93115220 A CN 93115220A CN 1035252 C CN1035252 C CN 1035252C
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Abstract
The present invention relates to a novel bactericide, namely aminomethyl formate-1, 1, 1-trichloro-2-(2, 4-dichlorothiophenyl)-ethylester whose structure formula is shown in (1) and whose molecular formula is C10H3Cl5NSO2. The novel bactericide is prepared by the reaction of equal mol of 2, 4-dichlorophenyl-sulfhydrate and trichloro acetaldehyde to produce 2-(2, 4-dichlorothiophenyl) trichloro-ethyl alcohol and the reaction with the equal mol of aminoformyl chloride.
Description
The invention belongs to the agricultural bactericide field, particularly a kind of novel agrochemical sterilant, aminomethyl formic acid-1,1,1-three chloro-2-(2,4-two chloro thiophenol bases)-ethyl ester and preparation method thereof field.
In China, ginger output is very big, and ground such as Sichuan, Hunan, Shandong are planted the ginger area and reached 6,000 ten thousand mu, but because of ginger is subjected to the harm of canker, the underproduction reaches 20-30%, and weight person reaches 60-80%, even has no harvest.People utilize the sterilant as ginger such as the auspicious malicious MnZn of agricultural chemicals, rizolex, wide bacterium spirit, but the preventive effect ability is not high, adopt biological medicine, the preventive effect instability, viable bacteria is difficult for preserving, therefore, a kind of efficient, the wide spectrum of ginger rot, sterilant of low toxicity of preventing of research becomes the problem of urgent solution.
Task of the present invention is studied a kind of efficient, the wide spectrum of ginger rot, sterilant of low toxicity of preventing exactly.
In order to reach purpose of the present invention, the inventor has studied and has a kind ofly prevented that the sterilant of ginger rot from being the compound that belongs to the methylamino-formate ester, and its structural formula is:
Called after aminomethyl formic acid-1,1,1-three chloro-2-(2,4-two chloro thiophenol bases) ethyl ester.
Molecular formula is: C
10H
8Cl
5NSO
2
Aminomethyl formic acid-1,1 of the present invention, the preparation method of 1-three chloro-2-(2,4-two chloro thiophenol bases) ethyl ester is that the first step utilizes 2, the mol ratio of 4-two chloro thiophenols and trichoro-aldehyde is a solvent with toluene under 1 to 1 condition, TiO
2The super acid catalyzer, the limit leads to the exsiccant hydrogen chloride gas, and the limit drips trichoro-aldehyde solution, and temperature of reaction maintains 80 ± 5 ℃, and the solvent toluene amount is 200 milliliters, catalyzer TiO
2The amount of solid superacid is 10 grams, be reflected in one liter the reactor and carry out, the reaction product that obtains the first step is 2-(2,4-two chloro thiophenol bases) three chloro ethanol, and the sodium hydroxide solution that adds entry and 30% stirs and becomes suspension and at room temperature react with 1 mole urea chloride.Prepare aminomethyl formic acid-1,1,1-three chloro-2-(2,4-two chloro thiophenol bases) ethyl ester.
Aminomethyl formic acid-1,1 of the present invention, the reaction equation of 1-three chloro-2-(2,4-two chloro thiophenol bases) ethyl ester is:
Aminomethyl formic acid-1,1 of the present invention, 1-three chloro-2-(2,4-two chloro thiophenol bases)-ethyl ester through Infrared spectroscopy, confirm that molecular structural formula is:
Accompanying drawing 1 is an aminomethyl formic acid-1,1 of the present invention, the Infrared spectroscopy figure of 1-three chloro-2-(2,4-two chloro thiophenol bases)-ethyl ester.Accompanying drawing 2 is an aminomethyl formic acid-1,1 of the present invention, the ultraviolet spectrogram of 1-three chloro-2-(2,4-two chloro thiophenol bases)-ethyl ester.
In order to further specify the present invention, list below the parsing report of infrared spectrum.
The Assignment of Infrared Spectrum report
Each peak ownership (1) 2870.9Cm of spectrum peak conclusion infrared spectrum-1Be CH3The flexible 2929.8Cm of C-H in the structure-1Vibration performance band 3000.8Cm-1
(2)3381.7Cm
-1For＞-1591.2Cm is arranged in the N-H stretching vibration band decision structure-1Be NH bending vibration band 1014.8Cm-1Be C-N stretching vibration band＞NH-CH3Structure (3) 1061.1Cm-1For ester group C-O stretching vibration band decision structure has＞CH-O-C-1005.2Cm-1Group is 1200Cm-1690.8Cm wherein-1For ester group C=O stretching vibration is in the said structure
Characteristic strip＞CH-O-1200.0Cm-1Be C-O stretching vibration characteristic strip stretching vibration peak (4) 1399.9Cm-1For
C-S stretching vibration band (5) 775.8Cm in the structure-1Be phenol ortho C-H distortion 710.0Cm-1Vibration performance bands of a spectrum 750.7Cm-1Be to have in 2 C-H deformation vibration band decision structures
1491.3Cm
-1Be C=O 1608.2Cm in the phenyl ring-1Stretching vibration band 3002.7Cm-1Band be in the phenyl ring C-H stretching vibration band in sum again according to molecular formula C10H
8Cl
5NSO
2Getting molecular structure is:
Infrared (IR) spectrum that stores in the stochastic retrieval database does not have this spectrum, proves to belong to the new invention product.
By Assignment of Infrared Spectrum report proof molecular formula of the present invention be
C
10H
8Cl
5NSO
2Getting molecular structure is:
Belong to neoteric product.
By aminomethyl formic acid-1,1 of the present invention, the UV spectrum map analysis of 1-three chloro-2-(2,4-two chloro thiophenol bases)-ethyl ester, (a) 218.2nm is
Characteristic peak during benzene ring structure π in the molecule-π transition carries out quantitative analysis with the peak height and the peak area of this characteristic peak.(b) 265.7nm is in the molecular structure of the present invention
The characteristic peak of the n-π transition of the C=O in the unit.
Aminomethyl formic acid-1 of the present invention, 1,1-three chloro-2-(2,4-two chloro thiophenol bases)-quantitative analysis of ethyl ester is that the table one that peak height and peak area according to UV spectrum 218.2nm characteristic peak carry out is an aminomethyl formic acid-1 of the present invention, 1,1-three chloro-2-(2,4-two chloro thiophenol bases)-each results of elemental analyses of ethyl ester.
Table one: aminomethyl formic acid-1,1 of the present invention, the results of elemental analyses of 1-three chloro-2-(2,4 trichlorothiophenol base)-ethyl ester.
Chlorine: (Cl) 46.20 ± 0.50
Sulphur: (S) 8.40 ± 0.50
Nitrogen: (N) 3.62 ± 0.50
Oxygen: (O) 8.48 ± 0.50
Hydrogen: (H) 1.98 ± 0.50
Carbon (C) 31.22 ± 0.50
Table two is ammonia toluic acids-1,1 of the present invention, 1-three chloro-2-(2,4-trichlorothiophenol base)-each the element theory value of ethyl ester and the comparing result of experimental value.
The theoretical value experimental value
Chlorine: (Cl) 46.28 46.20 ± 0.50
Sulphur: (S) 8.34 8.40 ± 0.50
Nitrogen: (N) 3.65 3.62 ± 0.50
Oxygen: (O) 8.34 8.48 ± 0.50
Hydrogen: (H) 2.09 1.98 ± 0.50
Carbon (C) 31.29 31.22 ± 0.50
By ultimate analysis, further confirmed structural formula of the present invention.
Aminomethyl formic acid-1,1 of the present invention, 1-three chloro-2-(2,4-two chloro thiophenol bases)-ethyl ester as the sterilant of ginger in Shandong many places, be applied, every mu of ginger ground can increase production more than 1200 kilograms.
Embodiment:
Example 1 in one one liter four-hole bottle, adds two chloro thiophenols of 1 mole (179.2 gram), adds 200 milliliters of solvent toluenes, adds the TiO of about 10 grams
2The super acid catalyzer, the limit feeds the exsiccant hydrogen chloride gas, the limit drips the trichoro-aldehyde and the reaction of two chloro thiophenols of 1 mole (160 gram), and temperature of reaction maintains 80 ± 5 ℃, after trichoro-aldehyde drips, continue reaction 30 minutes, isolate solvent, reaction product 2-(2,4 two chloro thiophenol base) three chloro ethanol 288 grams in the step of winning, purity is 91.5%, and transformation efficiency is calculated as 80.8% with thiophenol.The reactant of the first steps of 288 grams placed in one 1000 milliliters the four-hole bottle, the distilled water or the deionized water that add 360 grams, stir down, sodium hydroxide solution 115 grams of adding 30%, one mole of (87.8 gram) Methylaminoformyl chloride that will dissolve again is added in the four-hole bottle and reacts, temperature of reaction maintains 20 ± 10 ℃, after 1 hour, reaction finishes, and does isolating method processing reaction product with routine, obtains the aminomethyl formic acid-1 of 297 grams, 1,1-three chloro-2-(2,4-two chloro thiophenols)-ethyl ester, purity is 89.7%.
Example 2 adds two chloro thiophenols of 900 grams in one 5 liters reactor, add 1 liter solvent toluene, adds the TiO of 50 grams
2The super acid catalyzer, the hydrogen chloride gas that the limit feeds, the limit drips the trichoro-aldehyde of 805 grams, temperature of reaction maintains 80 ± 5 ℃, after dripping trichoro-aldehyde, continue reaction after 30 minutes, isolate solvent, get reaction product 2-(2,4 two chloro thiophenol bases) dichloro-ethanol 1460 grams, purity is 90.8%, adds 1800 gram deionized waters or distilled water in the reaction product that the first step is obtained and stirs down that (70 rev/mins) add 30% sodium hydroxide solution, 570 grams, and Methylaminoformyl chloride 440 grams that will dissolve again add in the reactors, terminal point is controlled with basicity, reaction finishes the back blowing, through separate 1481.4 gram aminomethyl formic acid-1,1,1-three chloro-2-(2,4-two chloro thiophenol bases)-and ethyl ester, purity is about 88.6%, again through separation and purification, get the aminomethyl formic acid-1 of elaboration, 1, (2,4-two chloro thiophenol bases)-ethyl ester purity is 99% to 1-three chloro-2-.
Claims (2)
1, a kind of compound of aminomethyl formate ester, its structural formula is
Called after aminomethyl formic acid-1,1,1-three chloro-2-(2,4-two chloro thiophenol bases)-ethyl ester
Molecular formula is: C
10H
8Cl
5NSO
2
2, aminomethyl formic acid-1,1, the preparation method of 1-three chloro-2-(2,4-two chloro thiophenol bases)-ethyl ester is characterized in that the first step utilizes 2, the mol ratio of 4-two chloro thiophenols and trichoro-aldehyde is a solvent with toluene under 1 to 1 condition, TiO
2The solid superacid catalyzer, the limit leads to the exsiccant hydrogen chloride gas, the limit drips trichoro-aldehyde solution, temperature of reaction maintains 80 ± 5C, the solvent toluene amount is 200 milliliters, the amount of catalyzer is 10 grams, be reflected in 1 liter the reactor and carry out, obtaining the first step reaction product is 2-(2,4-two chloro thiophenol bases) three chloro ethanol are again with reaction product 2-(2,4-two chloro thiophenol bases) the three chloro ethanol of the first step, the Methylaminoformyl chloride that adds the stirring becoming of entry and 30% sodium hydroxide solution suspension and 1 mole reacts.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93115220A CN1035252C (en) | 1993-11-23 | 1993-11-23 | Aminomethyl formate-1,1,1-trichloro-2-(2,4-dichlorothiophenyl)-ethyl ester and the prepn. method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93115220A CN1035252C (en) | 1993-11-23 | 1993-11-23 | Aminomethyl formate-1,1,1-trichloro-2-(2,4-dichlorothiophenyl)-ethyl ester and the prepn. method |
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| Publication Number | Publication Date |
|---|---|
| CN1100718A CN1100718A (en) | 1995-03-29 |
| CN1035252C true CN1035252C (en) | 1997-06-25 |
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| CN93115220A Expired - Fee Related CN1035252C (en) | 1993-11-23 | 1993-11-23 | Aminomethyl formate-1,1,1-trichloro-2-(2,4-dichlorothiophenyl)-ethyl ester and the prepn. method |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2078741A (en) * | 1980-06-23 | 1982-01-13 | Chevron Res | Process for Preparing Gamma- butyrothiolactone Derivatives and Intermediates Therefor |
| EP0115997A2 (en) * | 1983-02-07 | 1984-08-15 | Roussel-Uclaf | Derivatives of omega mercaptopropanamides, and their homologues, process for their preparation, their use as medicines, compositions containing them and intermediates obtained |
-
1993
- 1993-11-23 CN CN93115220A patent/CN1035252C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2078741A (en) * | 1980-06-23 | 1982-01-13 | Chevron Res | Process for Preparing Gamma- butyrothiolactone Derivatives and Intermediates Therefor |
| EP0115997A2 (en) * | 1983-02-07 | 1984-08-15 | Roussel-Uclaf | Derivatives of omega mercaptopropanamides, and their homologues, process for their preparation, their use as medicines, compositions containing them and intermediates obtained |
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| Publication number | Publication date |
|---|---|
| CN1100718A (en) | 1995-03-29 |
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