CN100447131C - Method for preparing 1-tert butyl-3-(2,6-diisopropyl-4-phenyl cxypheny) thiourea - Google Patents
Method for preparing 1-tert butyl-3-(2,6-diisopropyl-4-phenyl cxypheny) thiourea Download PDFInfo
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- CN100447131C CN100447131C CNB2005100470277A CN200510047027A CN100447131C CN 100447131 C CN100447131 C CN 100447131C CN B2005100470277 A CNB2005100470277 A CN B2005100470277A CN 200510047027 A CN200510047027 A CN 200510047027A CN 100447131 C CN100447131 C CN 100447131C
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Abstract
The present invention is process of preparing 1-tertbutyl-3-(2, 6-diisopropyl-4-phenoxyl phenyl) thiourea. The preparation process includes the following steps: 1. the reaction of 4-phenoxyl-2, 6- diisopropyl aniline or its salt, CS2 and one kind of organic alkali or inorganic alkali in solvent to produce corresponding 4- phenoxyl-2, 6-diisopropyl aniline dithio formate; and 2. the reaction of 4- phenoxyl-2, 6-diisopropyl aniline dithio formate and tert-butylamine inside organic solvent to produce 1-tertbutyl-3-(2, 6-diisopropyl-4-phenoxyl phenyl) thiourea. The preparation process of the present invention has less reaction steps, high total yield, simple operation, mild reaction condition and facile cheap material, and is suitable for industrial production.
Description
Technical field
The invention provides a kind of preparation method with Thiourea organic compound of unsymmetrical structure.Specifically, the method that relates to a kind of preparation 1-tertiary butyl-3-(2,6-di-isopropyl-4-Phenoxyphenyl) thiocarbamide (Chinese popular name: methamidophos, English popular name: Diafenthiuron is hereinafter to be referred as methamidophos).
Background technology
Methamidophos is a kind of organosulfur ureas Insecticidal and acaricidal agent with unsymmetrical structure of vapour Ba-Jia Ji company the eighties exploitation, and its structure is as follows:
Patent FR2465720 has reported synthetic and desinsection, the acaricidal activity of this compound.
Patent FR2465720, BE888179, EP210487 have reported by 4-phenoxy group-2,6-diisopropyl aniline and the synthetic lsothiocyanates of thio phosgene reaction, 4-phenoxy group-2,6-diisopropyl phenyl lsothiocyanates make the general preparation method of methamidophos again with the TERTIARY BUTYL AMINE reaction.
The thio phosgene market value height that this method is used during lsothiocyanates because of preparation, toxicity are difficult to the mass preparation methamidophos greatly.
Patent US4997967 has reported 4-phenoxy group-2,6-diisopropyl benzene amine hydrochlorate and Sodium Thiocyanate 99 are solvent with dimethylbenzene in the presence of aqueous hydrochloric acid, the substituting thioureido that reaction generates is in high boiling aromatic hydrocarbon solvent, be heated to reaction generation 4-phenoxy group-2 more than 150 ℃, 6-diisopropyl phenyl lsothiocyanates.
This method is raw materials used cheap and easy to get, is suitable for the mass preparation methamidophos.By 2,6-diisopropyl benzene amine hydrochlorate sets out synthetic methamidophos need the reaction of 3 steps with this method.But owing to need higher temperature of reaction in thermolysis, general low-pressure steam heating is inaccessible, and energy consumption is higher when being applied to suitability for industrialized production; Reaction also is easy to generate the tarry by product.
At document J.Agric.Food Chem.1992, reported 4-phenoxy group-2 in 40,908～913, the isocyanic ester that 6-diisopropyl aniline and phosgene reaction obtain replacing, be reacted into corresponding urea with TERTIARY BUTYL AMINE again, make the method for methamidophos again through Vanadium Pentoxide in FLAKES dehydration and hydrogen sulfide addition.This route is many because of step, and yield is low and do not have industrial value.
The flat 4-312568 of Japanese Patent has introduced a kind of new preparation method of Thiourea organic compound with symmetrical structure: with 2, the N that 6-diisopropyl aniline and dithiocarbonic anhydride react in the presence of solvent, one-step synthesis has symmetrical structure, N-is two 2,6-diisopropyl phenyl thiocarbamide.But the Thiourea organic compound that uses this method preparation to have unsymmetrical structure does not appear in the newspapers so far.
Summary of the invention
The object of the present invention is to provide and a kind ofly be applicable to the preparation method of the Thiourea organic compound with unsymmetrical structure of suitability for industrialized production, especially provide a kind of method for preparing methamidophos, big to solve the cost of material height, the toxicity that exist in the prior art, problems such as byproduct of reaction is many, energy consumption height.
Technical scheme of the present invention is as follows: be raw material, obtain corresponding substituted-amino dithio formate with dithiocarbonic anhydride and alkali reaction with a kind of organic amine, have the Thiourea organic compound of unsymmetrical structure accordingly with another kind of organic amine reaction generation again.
The present invention specifically provides a kind of and has prepared the method for methamidophos through above-mentioned two-step reaction, specifically may further comprise the steps:
A.4-phenoxy group-2,6-diisopropyl aniline and salt thereof and dithiocarbonic anhydride and a kind of organic bases or mineral alkali react in solvent, generate corresponding 4-phenoxy group-2,6-diisopropyl benzene amido dithio formate.
B.4-phenoxy group-2,6-diisopropyl phenyl Aminodithioformate and TERTIARY BUTYL AMINE react in organic solvent and generate methamidophos.
Reaction formula is as follows:
In the formula: B is an alkali, B
+Positively charged ion for alkali
The above 4-phenoxy group-2, the salt of 6-diisopropyl aniline can be selected from its hydrochloride, hydrobromate or acetate etc.Described organic bases can be selected from triethylamine, pyridine, piperidines or hexamethylenetetramine etc.Described mineral alkali can be selected to be selected from ammoniacal liquor, ammonia, sodium hydroxide, potassium hydroxide or calcium hydroxide etc.The used solvent of the first step reaction can be selected from water, toluene, dimethylbenzene, methyl alcohol, ethanol, acetone, dioxane or tetrahydrofuran (THF), also can be selected from the mixed solvent of above-mentioned two or more solvent composition; Be reaction solvent preferably with toluene, water.The used organic solvent of second step reaction can be selected from organic solvents such as triethylamine, TERTIARY BUTYL AMINE, toluene, dimethylbenzene, acetone, dioxane or tetrahydrofuran (THF), also can be selected from the mixed solvent of above-mentioned two or more solvent composition, preferably with triethylamine, toluene or raw material TERTIARY BUTYL AMINE as reaction solvent.
By the proportioning of suitable control reaction conditions and reaction raw materials, can control two kinds of generations effectively with Thiourea organic compound (by product) of symmetrical structure.For example,, be aided with liquid chromatography monitoring reaction process, can in reaction, suppress two kinds of generations effectively with by products such as thiocarbamide of symmetrical structure by the proportioning that increases dithiocarbonic anhydride, the temperature of reaction of selecting suitable reaction solvent, control to suit.
Preparation 4-phenoxy group-2, during 6-diisopropyl phenyl Aminodithioformate, suitable proportioning raw materials is: 4-phenoxy group-2, mol ratio=1: 1～20: 1～20 of 6-diisopropyl aniline (or salt) and dithiocarbonic anhydride and alkali; Mol ratio=1: 1～10: 1～10 more preferably; Preferred mol ratio=1: 2～5: 2～5.The weightmeasurement ratio of raw material and solvent is 1: 1～100; Preferred weightmeasurement ratio is 1: 1～50.Suitable temperature of reaction is the reflux temperature of 0 ℃～reaction solution; More preferably temperature of reaction is 0 ℃～50 ℃; Preferred temperature of reaction is 20 ℃～25 ℃.
During the preparation methamidophos, 4-phenoxy group-2, the mol ratio of 6-diisopropyl phenyl Aminodithioformate and TERTIARY BUTYL AMINE is 1: 1～100; More preferably mol ratio is 1: 1～50; Preferred mol ratio is 1: 1～10.The weightmeasurement ratio of raw material and solvent is 1: 1～100; More preferably weightmeasurement ratio is 1: 1～50; Preferred weightmeasurement ratio is 1: 2～30.Suitable temperature of reaction is 0 a ℃～reflux temperature; More preferably temperature of reaction is 0 ℃～50 ℃; Preferred temperature of reaction is 20 ℃～25 ℃.
Through product purity 〉=96% that above-mentioned two-step reaction obtains, overall yield of reaction 〉=81% (with 4-phenoxy group-2,6-diisopropyl aniline meter).
The reaction solvent for use can recycled, and reaction can carry out at normal temperatures smoothly, and therefore can economize in raw materials greatly cost and running cost of technical scheme provided by the invention saved the energy.Compare with existing methamidophos synthetic method, the present invention has that reactions steps is few, total recovery is high, simple to operate, reaction conditions is gentle, raw materials used cheap and easy to get, be fit to advantages such as suitability for industrialized production.
Embodiment
Following examples are used to further specify the present invention, but do not limit the present invention.Wherein 2,6-diisopropyl aniline and hydrochloride thereof can be according to patent FR2465720, US4997967, JP56-81558 and J.Agric.Food Chem.1992, reported method preparation in 40,908～913.
Embodiment 1:
(1) in reaction flask, adds 4-phenoxy group-2,6-diisopropyl aniline 4.2g (content 91%, 0.014mol), dithiocarbonic anhydride 4g (content 99%, 0.052mol), triethylamine 5.3g (content 99%, 0.052 and toluene 10ml mole), 20～25 ℃ of stir abouts 14 hours, HPLC monitored raw material 4-phenoxy group-2,6-diisopropyl benzene amine content was less than 1% o'clock, and reaction finishes.There is yellow solid to separate out in the reaction flask, filters.Filtrate is waited until next time and is applied mechanically; Obtaining the 6.2g solid after filter cake dries is dithio (4-phenoxy group-2,6-di-isopropyl phenylamino) formic acid triethylamine salt.
(2) will go up step gained dithio (4-phenoxy group-2,6-di-isopropyl phenylamino) formic acid triethylamine salt solid drops in the reaction flask, add 10ml TERTIARY BUTYL AMINE and 10ml triethylamine 20～25 ℃ of following stir abouts 24 hours, HPLC monitoring raw material dithio (4-phenoxy group-2,6-di-isopropyl phenylamino) formic acid triethylamine salt content was less than 1% o'clock, and reaction finishes.Excessive TERTIARY BUTYL AMINE is removed in underpressure distillation, waits until down the step and applies mechanically; 10 minutes after-filtration of the residual adding of still 10ml petroleum ether and stirring are methamidophos after filter cake dries, and must measure 4.6g.95.8%, two step of HPLC quantitative analysis content total recovery 81.8% (with 4-phenoxy group-2,6-diisopropyl aniline meter).
Embodiment 2:
(1) in the 250ml autoclave, add 4-phenoxy group-2,6-diisopropyl aniline 21.0g (content 93%, 0.07mol), dithiocarbonic anhydride 21.6g (content 99%, 0.28mol) and toluene 100ml, after the ammonia displacement, at 20～25 ℃, 8kg/cm
2Pressure continues about 24 hours of logical ammonia stirring reaction down, HPLC monitoring raw material 4-phenoxy group-2, and 6-diisopropyl benzene amine hydrochlorate content was less than 1% o'clock, and reaction finishes.There is yellow dithio (4-phenoxy group-2,6-di-isopropyl phenylamino) formic acid ammonium salt solid to separate out in the reaction mixture.
(2) will go up step gained yellow reaction mixture and drop in the reaction flask, and add the 10ml TERTIARY BUTYL AMINE 20～25 ℃ of following stir abouts 24 hours, HPLC monitoring raw material dithio (4-phenoxy group-2,6-di-isopropyl phenylamino) ammonium formiate salts contg was less than 1% o'clock, and reaction finishes.Excessive TERTIARY BUTYL AMINE and solvent toluene are removed in underpressure distillation, wait until down the step and apply mechanically; 10 minutes after-filtration of the residual adding of still 40ml petroleum ether and stirring are methamidophos after filter cake dries, and must measure 23.1g.Analyze 95.1%, two step of content total recovery 81.6% (with 4-phenoxy group-2,6-diisopropyl benzene amine hydrochlorate meter).
Embodiment 3:
(1) in reaction flask, adds 4-phenoxy group-2,6-diisopropyl benzene amine hydrochlorate 23.7g (content 93%, 0.072mol), then add ammoniacal liquor 20ml (content 25%) and water 25ml, and dropping dithiocarbonic anhydride 21.6g under stirring (content 99%, 0.28mol), 20～25 ℃ of stir abouts 24 hours, HPLC monitoring raw material 4-phenoxy group-2,6-diisopropyl benzene amine hydrochlorate content was less than 1% o'clock, and reaction finishes.There is yellow solid to separate out in the reaction flask, filters.Filtrate is waited until next time and is applied mechanically; Obtaining the 25.9g solid after filter cake dries is dithio (4-phenoxy group-2,6-di-isopropyl phenylamino) formic acid ammonium salt.
(2) will go up step gained solid and drop in the reaction flask, and add 30 milliliters of TERTIARY BUTYL AMINE 20～25 ℃ of following stir abouts 24 hours, HPLC monitoring raw material dithio (4-phenoxy group-2,6-di-isopropyl phenylamino) ammonium formiate salts contg is less than 1% o'clock, the reaction end.Excessive TERTIARY BUTYL AMINE is removed in underpressure distillation, waits until down the step and applies mechanically; 10 minutes after-filtration of the residual adding of still 40ml petroleum ether and stirring are methamidophos after filter cake dries, and must measure 23.3g.Analyze 96.3%, two step of content total recovery 81.0% (with 4-phenoxy group-2,6-diisopropyl benzene amine hydrochlorate meter).
Embodiment 4:
(1) in reaction flask, adds 4-phenoxy group-2,6-diisopropyl benzene amine hydrochlorate 23.7g (content 93%, 0.072mol), (content 96% is 0.1mol) with water 45ml then to add sodium hydroxide 4.2g, stir and drip dithiocarbonic anhydride 21.6g (content 99% down, 0.28mol), 20～25 ℃ of stir abouts 24 hours, HPLC monitoring raw material 4-phenoxy group-2,6-diisopropyl benzene amine hydrochlorate content was less than 1% o'clock, and reaction finishes.There is yellow solid to separate out in the reaction flask, filters.Filtrate is waited until next time and is applied mechanically; Obtaining the 26.4g solid after filter cake dries is dithio (4-phenoxy group-2,6-di-isopropyl phenylamino) formic acid sodium salt.
(2) will go up step gained solid and drop in the reaction flask, and add 30ml TERTIARY BUTYL AMINE stir about 24 hours at normal temperatures, HPLC monitoring raw material dithio (4-phenoxy group-2,6-di-isopropyl phenylamino) sodium formiate salts contg was less than 1% o'clock, and reaction finishes.Excessive TERTIARY BUTYL AMINE is removed in underpressure distillation, waits until down the step and applies mechanically; 10 minutes after-filtration of the residual adding of still 40ml petroleum ether and stirring are methamidophos after filter cake dries, and must measure 23.8g.Analyze 95.3%, two step of content total recovery 81.9% (with 4-phenoxy group-2,6-diisopropyl benzene amine hydrochlorate meter).
Claims (4)
1, the method for a kind of preparation 1-tertiary butyl-3-(2,6-di-isopropyl-4-Phenoxyphenyl) thiocarbamide is characterized in that: may further comprise the steps:
A., 4-phenoxy group-2,6-diisopropyl aniline or its salt and dithiocarbonic anhydride and a kind of organic bases or mineral alkali react in solvent, generate corresponding 4-phenoxy group-2,6-diisopropyl benzene amido dithio formate; Described solvent is selected from water, toluene, dimethylbenzene, methyl alcohol, ethanol, acetone, dioxane, tetrahydrofuran (THF), perhaps is selected from the mixed solvent of above-mentioned solvent composition;
B, 4-phenoxy group-2,6-diisopropyl phenyl Aminodithioformate and TERTIARY BUTYL AMINE react in organic solvent and generate 1-tertiary butyl-3-(2,6-di-isopropyl-4-Phenoxyphenyl) thiocarbamide; Described solvent is selected from triethylamine, TERTIARY BUTYL AMINE, toluene, dimethylbenzene, acetone, dioxane, tetrahydrofuran (THF), perhaps is selected from the mixed solvent of above-mentioned solvent composition.
2, preparation method according to claim 1 is characterized in that: 4-phenoxy group-2, the mol ratio of 6-diisopropyl aniline or its salt and dithiocarbonic anhydride and alkali=1: 1～20: 1～20; 4-phenoxy group-2, the mol ratio of 6-diisopropyl phenyl Aminodithioformate and TERTIARY BUTYL AMINE are 1: 1～100; The first step reaction solvent is selected from toluene or water, and the second step reaction solvent is selected from triethylamine, toluene or TERTIARY BUTYL AMINE, and the weightmeasurement ratio of two-step reaction raw material and solvent is respectively 1: 1～100; Temperature of reaction is the reflux temperature of 0 ℃～reaction solution.
3, preparation method according to claim 2 is characterized in that: 4-phenoxy group-2, the mol ratio of 6-diisopropyl aniline or its salt and dithiocarbonic anhydride and alkali=1: 1～10: 1～10; 4-phenoxy group-2, the mol ratio of 6-diisopropyl phenyl Aminodithioformate and TERTIARY BUTYL AMINE are 1: 1～50; The weightmeasurement ratio of two-step reaction raw material and solvent is respectively 1: 1～50; Temperature of reaction is 0 ℃～50 ℃.
4, preparation method according to claim 3 is characterized in that: 4-phenoxy group-2, the mol ratio of 6-diisopropyl aniline or its salt and dithiocarbonic anhydride and alkali=1: 2～5: 2～5; 4-phenoxy group-2, the mol ratio of 6-diisopropyl phenyl Aminodithioformate and TERTIARY BUTYL AMINE are 1: 1～10; The weightmeasurement ratio of the second step reaction raw materials and solvent is 1: 2～30; Temperature of reaction is 20 ℃～25 ℃.
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| CN102993075A (en) * | 2012-11-29 | 2013-03-27 | 江苏长青农化股份有限公司 | Synthesis process for diafenthiuron as thiourea insecticide and acaricide |
| CN103724213B (en) * | 2014-01-04 | 2015-08-12 | 新发药业有限公司 | A kind of synthetic method of 2,6-di-isopropyl-4-phenoxybenzamine |
| CN111978227A (en) * | 2020-09-04 | 2020-11-24 | 山西省化工研究所（有限公司） | Synthetic method of thiourea |
| CN114957066A (en) * | 2022-06-07 | 2022-08-30 | 江苏长青农化南通有限公司 | Energy-saving and efficient synthesis method of diafenthiuron |
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| US4328247A (en) * | 1979-09-19 | 1982-05-04 | Ciba-Geigy Corporation | Phenoxyphenylisothioureas, production thereof and use thereof in pest control, and phenoxyphenylthioureas as intermediates for the production of the phenoxyphenylisothioureas and use thereof in pest control |
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