CN101481331B - N,N'-bis(4-ethoxy carbonyl phenyl)-N'-benzyl formamidine - Google Patents
N,N'-bis(4-ethoxy carbonyl phenyl)-N'-benzyl formamidine Download PDFInfo
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Abstract
The invention relates to the technical field of fine chemistry industry, in particular to a method for preparing N, N'-di(4-ethoxycarbonylphenyl)-N'-phenylformamidine. Parathesin and benzyl chloride are taken as raw materials. The method comprises a formylation reaction process, an N alkylation reaction process and a condensation reaction process; wherein, in the N alkylation reaction process, 4-formamido ethyl benzoate generated in the formylation reaction process is added into dipolar aprotic solvent, and then inorganic weak base and the benzyl chloride are added, the temperature rises and is preserved and the reaction lasts for 20-25 hours; then the temperature is lowered to the room temperature and suction filtration and washing are carried out on the separated pale yellow solid to obtain pale yellow intermediate; the intermediate and the parathesin are added into halogenated hydrocarbon and then dehydrant is added; after heatingup and reflux for 15-17 hours, the temperature is cooled to the room temperature; NaOH aqueous solution is added to steam out the halogenated hydrocarbon under normal pressure and then separate out offwhite solid; suction filtration, washing by water and drying are carried out on the solid and the white solid of N, N'-di(4-ethoxycarbonylphenyl)-N'-phenylformamidine is obtained by recrystallization and cooling the solid to the room temperature after washing.
Description
Affiliated technical field
The present invention relates to the fine chemical technology field, a kind of N specifically, the preparation method of N '-two (4-ethoxy carbonyl phenyl)-N '-benzyl carbonamidine.
Background technology
N, N '-two (4-ethoxy carbonyl phenyl)-N '-benzyl carbonamidine is a kind of important UV light absorber, in the synthesis technique of multiple organic materials such as plastics, rosin products, makeup, dyestuff, textiles etc., add such absorption agent, can avoid the physicals of the synthetic products that ultraviolet photodegradation effect causes destruction (as product variable color, decolouring or frangible, easily split).1977, US4,021,471 has reported that the formamidine compound can be used as UV light absorber and relevant synthetic technology.This invention utilizes parathesin and trialkyl ortho-formiate reaction preparation intermediate imide ester, makes carbonamidine with the N-alkyl benzene amine by condensation reaction again.But this synthesis technique need be through monoacylated, the alkylation of amide of aniline, amide hydrolysis three-step reaction preparation feedback raw material N-alkyl benzene amine, and synthetic route is longer, has increased production cost.In recent years, CN 1956947A improves synthesis technique, has shortened synthetic route.Take the PABA ethyl ester as raw material, at first carry out formylation reaction, then carry out the N-alkylated reaction with the benzyl bromine, last and parathesin condensation prepares N, N '-two (4-ethoxy carbonyl phenyl)-N '-benzyl carbonamidine.Although synthesis procedure has been simplified in this invention, but N-alkylated reaction step needs to carry out in water and toluene two phase solvent system, employing tertiary butyl bromination ammonium is made phase-transfer catalyst and is used the more expensive benzyl bromine of price as benzyl reagent, and aftertreatment technology is comparatively loaded down with trivial details, the reaction overall yield is also lower, only is 37.8%.Therefore, the method still can not effectively reduce the industrial production cost.
Summary of the invention
The technical problem to be solved in the present invention is: for existing N, the problem of the synthesis technique productive rate of N '-two (4-ethoxy carbonyl phenyl)-N '-benzyl carbonamidine, provide a kind of productive rate high N, N '-two (4-ethoxy carbonyl phenyl)-N '-benzyl carbonamidine synthesis technique.
The technical solution adopted for the present invention to solve the technical problems is: N, the preparation method of N '-two (4-ethoxy carbonyl phenyl)-N '-benzyl carbonamidine, the raw material that adopts is parathesin and benzyl chlorine, has following process formylation reaction process, N alkylation process and condensation reaction, described formylation reflection process is that parathesin is dissolved in the toluene, then heat up, in solution, drip formic acid, drip off and stir after two minutes, being warmed up to 90～120 ℃ makes system keep stopped reaction after little the boiling about 8～10 hours, reaction solution slowly cools to room temperature, obtain 4-formamido-ethyl benzoate, described N alkylation process is that the 4-formamido-ethyl benzoate that will generate in the formylation reaction process joins in the non-proton property dipole solvent and forms solution I, in solution I, add inorganic weak bases and benzyl chlorine, be warmed up to 50～70 ℃ and insulation reaction and be down to room temperature after 20～25 hours, separate out light yellow solid and carry out filtering and washing, obtain lurid N-benzyl-4-formamido-ethyl benzoate; Described condensation reaction will form solution II in N-benzyl-4-formamido-ethyl benzoate and the parathesin adding halohydrocarbon exactly, in solution II, add dewatering agent, be warmed up to 65～75 ℃ of backflows and be cooled to room temperature after 15～17 hours, add again and separate out the rice white solid NaOH aqueous solution steams halohydrocarbon under normal pressure after, suction filtration, washing drying with water obtains solid and is obtaining white solid N with washing with alcohol by the re-crystallizing in ethyl acetate cool to room temperature, N '-two (4-ethoxy carbonyl phenyl)-N '-benzyl carbonamidine.
The technical process reaction formula is as follows among the present invention:
PABA ethyl ester and formic acid mol ratio are 1: 1～1: 10 in the formylation reaction process of the present invention, preferred 1: 1～1: 3.Solvent load is with respect to the amount of PABA ethyl ester, and mass ratio is 1: 1～10: 1, preferred 1: 1～4: 1.
Inorganic weak bases described in the N alkylation process of the present invention is yellow soda ash, salt of wormwood, potassiumphosphate or sodium hydride, and described non-proton property dipole solvent is N, N-dimethylformamide, N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone or methyl-sulphoxide.
The preferred yellow soda ash of inorganic weak bases described in the N alkylation process of the present invention, the preferred N of described non-proton property dipole solvent, N-dimethylformamide.
(mol ratio is 1: 1～6: 1 for inorganic weak bases and 4-formamido-ethyl benzoate in the N alkylation process of the present invention, benzyl chlorine and 4-formamido-ethyl benzoate mol ratio are 1: 1～5: 1, described non-proton property dipole solvent consumption is with respect to the amount of 4-formamido-ethyl benzoate, and mass ratio is 2: 1～10: 1.
Inorganic weak bases and 4-formamido-ethyl benzoate mol ratio are preferred 1: 1～3: 1 in the N alkylation process of the present invention, preferred 1: 1～3: 1 of benzyl chlorine and 4-formamido-ethyl benzoate mol ratio, described non-proton property dipole solvent consumption preferred 3: 1～5: 1 with respect to the mass ratio of the amount of 4-formamido-ethyl benzoate.
Halohydrocarbon in the condensation reaction of the present invention is chloroform, methylene dichloride, ethylene dichloride or trichloroethane.
The preferred chloroform of halohydrocarbon in the condensation reaction of the present invention.
The invention has the beneficial effects as follows: the present invention is about N, and the preparation method of N '-two (4-ethoxy carbonyl phenyl)-N '-benzyl carbonamidine has following advantage:
1, the N-alkylated reaction adopts non-proton property dipole solvent, make alkali with yellow soda ash, salt of wormwood, potassiumphosphate, sodium hydride etc., replace traditional use sodium hydroxide to make alkali, tertiary butyl bromination ammonium and made the water of phase-transfer catalyst/toluene two-phase reaction system, greatly improved the productive rate of this step reaction, can be up to 99%.
2, intermediate and the finished product separation and purification process are easy, and technique is simple.The last handling process of synthetic intermediate 4-formamido-ethyl benzoate and N-benzyl-4-formamido-ethyl benzoate only needs simple solid-liquid separation, washing to get final product, productive rate is up to 99%, product purity can reach 99%, need not extra purifying and can be directly used in next step reaction.Directly pour into condensation reaction solution in the alkali lye; steam organic solvent and separate out solid, after filtration, washing, recrystallization can obtain the finished product N, N '-two (4-ethoxy carbonyl phenyl)-N '-benzyl carbonamidine; product purity reaches more than 99%, is fit to the mass-producing batch production.
3, when the reaction of N-benzyl, adopting inexpensive benzyl chlorine is raw material, has avoided the use of the more expensive benzyl bromine of price.
4, in halohydrocarbon, carry out condensation reaction, significantly improved the yield of this step reaction.
5, present method technique is simple, and is easy to operate, and total recovery reaches 55%, and cost is low, is easy to large-scale industrialization production.
Embodiment
Embodiment 1
Under stirring 50g PABA ethyl ester is dissolved in the 104g toluene, then be warmed up to 43 ℃, drip 18g formic acid in this solution, about 10min drips off, stir after two minutes, be warmed up to 100 ℃ and make system keep stopped reaction after little the boiling about 8 hours, reaction solution slowly cools to room temperature, separates out white solid.Suction filtration washes solid with water three times, and drying obtains 56g white intermediate 4-formamido-ethyl benzoate, and productive rate is 96%.
Gained intermediate 4-formamido-ethyl benzoate is dissolved in 233gDMF obtains light yellow transparent solution, again to wherein adding 104gK
2CO
3With 42g benzyl chlorine, then be warmed up to 60 ℃, cool to room temperature behind the reaction 23h is poured into water reaction solution, separate out light yellow solid, suction filtration washes solid with water three times, drying obtains the light yellow intermediate N benzyl of 78g-4-formamido-ethyl benzoate, and productive rate is 95%.
In reaction flask, add not purified intermediate N benzyl-4-formamido-ethyl benzoate and 45g4-subcutin, add 360gCHCl
3Make it be dissolved as clear solution, then in reaction solution, add 53gPOCl
3, be warmed up to 65 ℃ of back flow reaction 15h, be cooled to room temperature.Reaction mixture is poured in the 250mL20%NaOH aqueous solution, and normal pressure steams CHCl
3, leaving standstill a moment, the rice white solid appears, and suction filtration washes solid with water three times, and drying obtains light yellow solid, with 15g washing with alcohol solid secondary, obtains the 66g white solid.Solid 139g re-crystallizing in ethyl acetate, cool to room temperature (25 ℃) obtains white solid product 63g, and overall yield is take the first step starting raw material PABA ethyl ester as benchmark as 48%, and purity is 99%.
Embodiment 2
Under stirring the 99g4-subcutin is dissolved in the 217g toluene, then be warmed up to 43 ℃, drip 36g formic acid in this solution, about 20min drips off, stir after two minutes, be warmed up to 100 ℃ and make system keep stopped reaction after little the boiling about 10 hours, reaction solution slowly cools to room temperature, separates out white solid.Suction filtration washes solid with water three times, and drying obtains 115g white intermediate 4-formamido-ethyl benzoate, and productive rate is 99%.
Gained intermediate 4-formamido-ethyl benzoate is dissolved in 378gDMF obtains light yellow transparent solution, again to wherein adding 190g K
2CO
3With 79g benzyl chlorine, then be warmed up to 60 ℃, cool to room temperature behind the reaction 20h is poured into water reaction solution, separate out light yellow solid, suction filtration washes solid with water three times, drying obtains the light yellow intermediate N benzyl of 162g-4-formamido-ethyl benzoate, and productive rate is 96%.
In reaction flask, add not purified intermediate N benzyl-4-formamido-ethyl benzoate and 94g4-subcutin, add 653gCHCl
3Make it be dissolved as clear solution, then in reaction solution, add 101gPOCl
3, be warmed up to 65 ℃ of back flow reaction 15h, be cooled to room temperature.Reaction mixture is poured in the 440mL20%NaOH aqueous solution, and normal pressure steams CHCl
3, leaving standstill a moment, the rice white solid appears, and suction filtration washes solid with water three times, and drying obtains light yellow solid, with 29g washing with alcohol solid secondary, obtains the 138g white solid.Solid 351g re-crystallizing in ethyl acetate, cool to room temperature (25 ℃) obtains white solid product 134g, and overall yield is take the first step starting raw material PABA ethyl ester as benchmark as 52%, and purity is 99.5%.
Embodiment 3
Under stirring the 99g4-subcutin is dissolved in the 217g toluene, then be warmed up to 43 ℃, drip 36g formic acid in this solution, about 20min drips off, stir after two minutes, be warmed up to 100 ℃ and make system keep stopped reaction after little the boiling about 10 hours, reaction solution slowly cools to room temperature, separates out white solid.Suction filtration washes solid with water three times, and drying obtains 109g white intermediate 4-formamido-ethyl benzoate, and productive rate is 94%.
Gained intermediate 4-formamido-ethyl benzoate is dissolved in 378gDMF obtains light yellow transparent solution, again to wherein adding 200g K
2CO
3With 81g benzyl chlorine, then be warmed up to 60 ℃, cool to room temperature behind the reaction 23h is poured into water reaction solution, separate out light yellow solid, suction filtration washes solid with water three times, drying obtains the light yellow intermediate N benzyl of 158g-4-formamido-ethyl benzoate, and productive rate is 99%.
In reaction flask, add not purified intermediate N benzyl-4-formamido-ethyl benzoate and 92g4-subcutin, add 638gCHCl
3Make it be dissolved as clear solution, then in reaction solution, add 95gPOCl
3, be warmed up to 65 ℃ of back flow reaction 15h, be cooled to room temperature.Reaction mixture is poured in the 430mL20%NaOH aqueous solution, and normal pressure steams CHCl
3, leaving standstill a moment, the rice white solid appears, and suction filtration washes solid with water three times, and drying obtains light yellow solid, with 35g washing with alcohol solid secondary, obtains the 132g white solid.Solid 317g re-crystallizing in ethyl acetate, cool to room temperature (25 ℃) obtains white solid product 129g, and overall yield is take the first step starting raw material PABA ethyl ester as benchmark as 50%, and purity is 99.5%.
Embodiment 4
Under stirring the 25g4-subcutin is dissolved in the 52g toluene, then be warmed up to 43 ℃, drip 9g formic acid in this solution, about 6min drips off, stir after two minutes, be warmed up to 100 ℃ and make system keep stopped reaction after little the boiling about 10 hours, reaction solution slowly cools to room temperature, separates out white solid.Suction filtration washes solid with water three times, and drying obtains 29g white intermediate 4-formamido-ethyl benzoate, and productive rate is 98%.
Gained intermediate 4-formamido-ethyl benzoate is dissolved in 123gDMF obtains light yellow transparent solution, again to wherein adding 52gK
2CO
3With 25g benzyl chlorine, then be warmed up to 60 ℃, cool to room temperature behind the reaction 20h is poured into water reaction solution, separate out light yellow solid, suction filtration washes solid with water three times, drying obtains the light yellow intermediate N benzyl of 40g-4-formamido-ethyl benzoate, and productive rate is 95%.
In reaction flask, add not purified intermediate N benzyl-4-formamido-ethyl benzoate and 23g4-subcutin, add 89gCHCl
3Make it be dissolved as clear solution, then in reaction solution, add 26gPOCl
3, be warmed up to 65 ℃ of back flow reaction 15h, be cooled to room temperature.Reaction mixture is poured in the 60mL20%NaOH aqueous solution, and normal pressure steams CHCl
3, leaving standstill a moment, the rice white solid appears, and suction filtration washes solid with water three times, and drying obtains light yellow solid, with 8g washing with alcohol solid secondary, obtains the 34g white solid.Solid 71g re-crystallizing in ethyl acetate, cool to room temperature (25 ℃) obtains white solid product 29g, and overall yield is take the first step starting raw material PABA ethyl ester as benchmark as 45%, and purity is 99%.
Embodiment 5
Under stirring the 25g4-subcutin is dissolved in the 52g toluene, then be warmed up to 43 ℃, drip 9g formic acid in this solution, about 6min drips off, stir after two minutes, be warmed up to 100 ℃ and make system keep stopped reaction after little the boiling about 10 hours, reaction solution slowly cools to room temperature, separates out white solid.Suction filtration washes solid with water three times, and drying obtains 29g white intermediate 4-formamido-ethyl benzoate, and productive rate is 99%.
Gained intermediate 4-formamido-ethyl benzoate is dissolved in 123gDMF obtains light yellow transparent solution, again to wherein adding 50gK
2CO
3With 21g benzyl chlorine, then be warmed up to 60 ℃, cool to room temperature behind the reaction 20h is poured into water reaction solution, separate out light yellow solid, suction filtration washes solid with water three times, drying obtains the light yellow intermediate N benzyl of 41g-4-formamido-ethyl benzoate, and productive rate is 97%.
In reaction flask, add not purified intermediate N benzyl-4-formamido-ethyl benzoate and 24g4-subcutin, add 89gCHCl
3Make it be dissolved as clear solution, then in reaction solution, add 29gPOCl
3, be warmed up to 65 ℃ of back flow reaction 15h, be cooled to room temperature.Reaction mixture is poured in the 60mL20%NaOH aqueous solution, and normal pressure steams CHCl
3, leaving standstill a moment, the rice white solid appears, and suction filtration washes solid with water three times, and drying obtains light yellow solid, with 4g washing with alcohol solid secondary, obtains the 38g white solid.Solid 67g re-crystallizing in ethyl acetate, cool to room temperature (25 ℃) obtains white solid product 32g, and overall yield is take the first step starting raw material PABA ethyl ester as benchmark as 49%, and purity is 99%.
Embodiment 6
Under stirring the 330g4-subcutin is dissolved in the 693g toluene, then be warmed up to 43 ℃, drip 120g formic acid in this solution, about 40min drips off, stir after two minutes, be warmed up to 100 ℃ and make system keep stopped reaction after little the boiling about 10 hours, reaction solution slowly cools to room temperature, separates out white solid.Suction filtration washes solid with water three times, and drying obtains 374g white intermediate 4-formamido-ethyl benzoate, and productive rate is 97%.
Gained intermediate 4-formamido-ethyl benzoate is dissolved in 1322gDMF obtains light yellow transparent solution, again to wherein adding 662gK
2CO
3With 273g benzyl chlorine, then be warmed up to 60 ℃, cool to room temperature behind the reaction 25h is poured into water reaction solution, separate out light yellow solid, suction filtration washes solid with water three times, drying obtains the light yellow intermediate N benzyl of 537g-4-formamido-ethyl benzoate, and productive rate is 98%.
In reaction flask, add not purified intermediate N benzyl-4-formamido-ethyl benzoate and 313g4-subcutin, add 2000gCHCl
3Make it be dissolved as clear solution, then in reaction solution, add 319gPOCl
3, be warmed up to 65 ℃ of back flow reaction 15h, be cooled to room temperature.Reaction mixture is poured in the 1350mL20%NaOH aqueous solution, and normal pressure steams CHCl
3, leaving standstill a moment, the rice white solid appears, and suction filtration washes solid with water three times, and drying obtains light yellow solid, with 110g washing with alcohol solid secondary, obtains the 480g white solid.Solid 1120g re-crystallizing in ethyl acetate, cool to room temperature (25 ℃) obtains 473g white solid product, and overall yield is take the first step starting raw material PABA ethyl ester as benchmark as 55%, and purity is 99.5%.
Embodiment 7
Under stirring the 330g4-subcutin is dissolved in the 693g toluene, then be warmed up to 43 ℃, drip 120g formic acid in this solution, about 40min drips off, stir after two minutes, be warmed up to 100 ℃ and make system keep stopped reaction after little the boiling about 10 hours, reaction solution slowly cools to room temperature, separates out white solid.Suction filtration washes solid with water three times, and drying obtains 378g white intermediate 4-formamido-ethyl benzoate, and productive rate is 98%.
Gained intermediate 4-formamido-ethyl benzoate is dissolved in 1450gDMF obtains light yellow transparent solution, again to wherein adding 676gK
2CO
3With 292g benzyl chlorine, then be warmed up to 60 ℃, cool to room temperature behind the reaction 25h is poured into water reaction solution, separate out light yellow solid, suction filtration washes solid with water three times, drying obtains the light yellow intermediate N benzyl of 549g-4-formamido-ethyl benzoate, and productive rate is 99%.
In reaction flask, add not purified intermediate N benzyl-4-formamido-ethyl benzoate and 320g4-subcutin, add 2150gCHCl
3Make it be dissolved as clear solution, then in reaction solution, add 330gPOCl
3, be warmed up to 65 ℃ of back flow reaction 17h, be cooled to room temperature.Reaction mixture is poured in the 1450mL20%NaOH aqueous solution, and normal pressure steams CHCl
3, leaving standstill a moment, the rice white solid appears, and suction filtration washes solid with water three times, and drying obtains light yellow solid, with 106g washing with alcohol solid secondary, obtains the 462g white solid.Solid 1026g re-crystallizing in ethyl acetate, cool to room temperature (25 ℃) obtains white solid product 456g, and overall yield is take the first step starting raw material PABA ethyl ester as benchmark as 53%, and purity is 99.5%.
Claims (7)
1. one kind
N, N'-two (4-ethoxy carbonyl phenyl)-
N'The preparation method of-benzyl carbonamidine; the raw material that adopts is parathesin and benzyl chlorine; has following process: the formylation reaction process; N alkylation process and condensation reaction; described formylation reaction process is that parathesin is dissolved in the toluene; then heat up; in solution, drip formic acid; drip off and stir after two minutes; being warmed up to 90～120 ℃ makes system keep stopped reaction after little the boiling 8～10 hours; reaction solution slowly cools to room temperature; it is characterized in that: described N alkylation process is that the 4-formamido-ethyl benzoate that will generate in the formylation reaction process joins formation solution I in the non-proton property dipole solvent; in solution I, add inorganic weak bases and benzyl chlorine; be warmed up to 50～70 ℃ and insulation reaction and be down to room temperature after 20～25 hours; separate out light yellow solid and carry out filtering and washing, obtain lurid
N-benzyl-4-formamido-ethyl benzoate; Described condensation reaction is exactly will
N-benzyl-4-formamido-ethyl benzoate and parathesin add formation solution II in the halohydrocarbon, in the solution II, add dewatering agent, be warmed up to 65～75 ℃ of backflows and be cooled to room temperature after 15～17 hours, add again and separate out the rice white solid NaOH aqueous solution steams halohydrocarbon under normal pressure after, suction filtration washes drying with water and obtains solid and obtaining white solid with washing with alcohol by the re-crystallizing in ethyl acetate cool to room temperature
N, N'-two (4-ethoxy carbonyl phenyl)-
N'-benzyl carbonamidine.
2. as claimed in claim 1
N, N'-two (4-ethoxy carbonyl phenyl)-
N'The preparation method of-benzyl carbonamidine is characterized in that: PABA ethyl ester and formic acid mol ratio are 1:1～1:3 in the described formylation reaction process, and solvent load is with respect to the amount of PABA ethyl ester, and mass ratio is 1:1～4:1.
3. as claimed in claim 1
N, N'-two (4-ethoxy carbonyl phenyl)-
N'The preparation method of-benzyl carbonamidine is characterized in that: described
NInorganic weak bases described in the-alkylation process is yellow soda ash, salt of wormwood or sodium phosphate, and described non-proton property dipole solvent is
N, N-dimethyl formamide, N,N-DIMETHYLACETAMIDE,
N-methyl-2-pyrrolidone or methyl-sulphoxide.
4. as claimed in claim 3
N, N'-two (4-ethoxy carbonyl phenyl)-
N'The preparation method of-benzyl carbonamidine is characterized in that: described
NThe preferred yellow soda ash of inorganic weak bases described in the alkylation process, described non-proton property dipole solvent is preferred
N, N-dimethyl formamide.
5. as claimed in claim 1
N, N'-two (4-ethoxy carbonyl phenyl)-
N'The preparation method of-benzyl carbonamidine is characterized in that: described
NInorganic weak bases and 4-formamido-ethyl benzoate mol ratio are 1:1～6:1 in the alkylation process, benzyl chlorine and 4-formamido-ethyl benzoate mol ratio are 1:1～5:1, described non-proton property dipole solvent consumption is with respect to the amount of 4-formamido-ethyl benzoate, and mass ratio is 2:1～10:1.
6. as claimed in claim 5
N, N'-two (4-ethoxy carbonyl phenyl)-
N'The preparation method of-benzyl carbonamidine is characterized in that: described
NInorganic weak bases and the preferred 1:1～3:1 of 4-formamido-ethyl benzoate mol ratio in the alkylation process, benzyl chlorine and the preferred 1:1～3:1 of 4-formamido-ethyl benzoate mol ratio, described non-proton property dipole solvent consumption is with respect to the preferred 3:1～5:1 of mass ratio of the amount of 4-formamido-ethyl benzoate.
7. as claimed in claim 1
N, N'-two (4-ethoxy carbonyl phenyl)-
N'The preparation method of-benzyl carbonamidine is characterized in that: the halohydrocarbon in the described condensation reaction is chloroform, methylene dichloride, ethylene dichloride or trichloroethane.
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| CN2009100290075A CN101481331B (en) | 2009-01-20 | 2009-01-20 | N,N'-bis(4-ethoxy carbonyl phenyl)-N'-benzyl formamidine |
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| CN103420873B (en) * | 2013-09-06 | 2014-10-08 | 安徽工业大学 | N, N'-di (4-ethyoxyl carbonyl phenyl)-N'-benzyl formamidine preparation method |
| CN112047859B (en) * | 2018-04-26 | 2023-11-03 | 常州永和精细化学有限公司 | Method for preparing N, N '-di (4-ethoxycarbonylphenyl) -N' -benzyl formamidine from waste residues generated in production of UV-1 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4021471A (en) * | 1974-04-18 | 1977-05-03 | Givaudan Corporation | Formamidines useful as ultraviolet light absorbers |
| CN1956947A (en) * | 2004-05-27 | 2007-05-02 | 知科株式会社 | Benzylformamidine compounds and plastic products containing the benzylformamidine compounds as ultraviolet light absorbers |
-
2009
- 2009-01-20 CN CN2009100290075A patent/CN101481331B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4021471A (en) * | 1974-04-18 | 1977-05-03 | Givaudan Corporation | Formamidines useful as ultraviolet light absorbers |
| CN1956947A (en) * | 2004-05-27 | 2007-05-02 | 知科株式会社 | Benzylformamidine compounds and plastic products containing the benzylformamidine compounds as ultraviolet light absorbers |
Non-Patent Citations (3)
| Title |
|---|
| Medicinal Chemistry》.2004,第12卷423–438. * |
| Taketoshi Okubo et al.Design, synthesis and structure–affinity relationships of aryloxyanilide derivatives as novel peripheral benzodiazepine receptor ligands.《Bioorganic & * |
| TaketoshiOkuboetal.Design synthesis and structure–affinity relationships of aryloxyanilide derivatives as novel peripheral benzodiazepine receptor ligands.《Bioorganic & Medicinal Chemistry》.2004 |
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