CN112047859B - Method for preparing N, N '-di (4-ethoxycarbonylphenyl) -N' -benzyl formamidine from waste residues generated in production of UV-1 - Google Patents
Method for preparing N, N '-di (4-ethoxycarbonylphenyl) -N' -benzyl formamidine from waste residues generated in production of UV-1 Download PDFInfo
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- CN112047859B CN112047859B CN202010753548.9A CN202010753548A CN112047859B CN 112047859 B CN112047859 B CN 112047859B CN 202010753548 A CN202010753548 A CN 202010753548A CN 112047859 B CN112047859 B CN 112047859B
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- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000002699 waste material Substances 0.000 title claims abstract description 36
- BRLPHWMHLVBHEG-UHFFFAOYSA-N ethyl 4-(n'-benzylcarbamimidoyl)benzoate Chemical compound C1=CC(C(=O)OCC)=CC=C1C(=N)NCC1=CC=CC=C1 BRLPHWMHLVBHEG-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 240000003864 Ulex europaeus Species 0.000 claims abstract description 16
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229940073608 benzyl chloride Drugs 0.000 claims abstract description 13
- 238000007126 N-alkylation reaction Methods 0.000 claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- 239000003880 polar aprotic solvent Substances 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 239000012043 crude product Substances 0.000 claims description 13
- 238000000967 suction filtration Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- BLFLLBZGZJTVJG-UHFFFAOYSA-N benzocaine Chemical compound CCOC(=O)C1=CC=C(N)C=C1 BLFLLBZGZJTVJG-UHFFFAOYSA-N 0.000 abstract description 10
- 238000006482 condensation reaction Methods 0.000 abstract description 5
- -1 4-ethoxycarbonylphenyl Chemical group 0.000 abstract description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000012065 filter cake Substances 0.000 description 8
- 238000002386 leaching Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- GKASDNZWUGIAMG-UHFFFAOYSA-N triethyl orthoformate Chemical compound CCOC(OCC)OCC GKASDNZWUGIAMG-UHFFFAOYSA-N 0.000 description 4
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 2
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 208000034874 Product colour issue Diseases 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229960005274 benzocaine Drugs 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- GQCWLVKRYZIQBN-UHFFFAOYSA-N ethyl 4-[(4-ethoxycarbonylphenyl)iminomethylamino]benzoate Chemical compound C1=CC(C(=O)OCC)=CC=C1NC=NC1=CC=C(C(=O)OCC)C=C1 GQCWLVKRYZIQBN-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C257/00—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines
- C07C257/10—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines
- C07C257/12—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines having carbon atoms of amidino groups bound to hydrogen atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application discloses a method for preparing N, N '-di (4-ethoxycarbonylphenyl) -N' -benzyl formamidine by using waste residues generated in the production of UV-1, which is obtained by carrying out reaction treatment or separation treatment on NE waste residues generated in the production of N- (4-ethoxycarbonylphenyl) -N '-methyl-N' -phenyl formamidine and then carrying out N-alkylation reaction with benzyl chloride; dissolving NE waste residue in a polar aprotic solvent, treating by active carbon, adding ethyl p-aminobenzoate for condensation reaction, and finally carrying out N-alkylation reaction with benzyl chloride; the separation treatment is to dissolve NE waste residue in toluene solvent, separate NE, then dissolve in polar aprotic solvent, treat with active carbon, and then carry out N-alkylation reaction with benzyl chloride. The reaction method of the present application can obtain more NEPA, while the separation method can obtain NEPA with higher purity.
Description
The application is a divisional application of patent application with the application number of 201810385261.8 and the application date of 2018, 4 and 26, and the application creates a method for preparing N, N '-bis (4-ethoxycarbonylphenyl) -N' -benzyl formamidine by using waste residues for producing UV-1.
Technical Field
The application belongs to the technical field of fine chemical engineering, and particularly relates to a method for preparing N, N '-di (4-ethoxycarbonylphenyl) -N' -benzyl formamidine from waste residues generated in the production of UV-1.
Background
N, N '-bis (4-ethoxycarbonylphenyl) -N' -benzylformamidine (hereinafter referred to as NEPA) is an important ultraviolet absorber, and the ultraviolet absorber is added in the synthesis process of various organic materials such as plastic products, resin products, cosmetics, fuels, textiles and the like, so that the damage of physical properties (such as product discoloration, decoloration or fragile and easy cracking) of the synthetic products caused by the photodegradation of ultraviolet rays can be avoided, and the ultraviolet absorber has wide market prospect.
At present, the method for preparing the NEPA is divided into a two-step access method and a one-step access method according to the difference of access of 4-ethoxycarbonylphenyl, wherein the one-step access method uses ethyl p-aminobenzoate (excessive) as a starting material, and the ethyl p-aminobenzoate and trialkylorthoformate are subjected to condensation reaction to obtain N, N' -di (4-ethoxycarbonylphenyl) formamidine (hereinafter referred to as NET for short) and then subjected to N-alkylation reaction with benzyl chloride to obtain the NEPA (see Chinese patent document CN 103709073A).
N- (4-ethoxycarbonylphenyl) -N '-methyl-N' -phenylformamidine (hereinafter abbreviated as UV-1) is also an important ultraviolet absorber, and can efficiently absorb ultraviolet light in the wavelength range of 240 to 340 nm. The UV-1 has good compatibility with organic macromolecules and good photo-thermal stability, and is widely applied to high polymer materials such as polyurethane, adhesives, foam and the like. The UV-1 is liquid at normal temperature, has better processing performance, and has more excellent ultraviolet resistance compared with the ultraviolet absorbent of benzophenone or benzotriazole, and has wide market prospect.
At present, the method for preparing the UV-1 mainly comprises a one-step condensation method and a two-step condensation method, wherein the two-step condensation method uses ethyl p-aminobenzoate as a starting material, and the ethyl p-aminobenzoate is firstly condensed with trialkyl orthoformate (excessive) to obtain N- (4-ethoxycarbonylphenyl) -ethyl iminoformate (hereinafter, the ethyl N-ethoxycarbonylphenyl) -ethyl iminoformate is also simply referred to as NE), and then condensed with N-methylaniline to obtain the UV-1 (see Chinese patent documents CN101481330A and CN 105315176A).
As known from chinese patent document CN105315176 a: the first condensation reaction usually produces more NET, but the NET production cannot be completely avoided although the NET amount can be effectively reduced by extending the reaction time. In addition, this document also mentions that the residual NE residue (i.e., NET) can be used as a raw material for NEPA after collection and recovery. However, this document does not disclose a specific recycling method.
Disclosure of Invention
The present application has been made to solve the above problems, and an object of the present application is to provide a method for preparing N, N '-bis (4-ethoxycarbonylphenyl) -N' -benzylformamidine from waste residues of UV-1 production.
The technical scheme for realizing the aim of the application is as follows: a process for preparing N, N '-bis (4-ethoxycarbonylphenyl) -N' -benzylformamidine from the waste dregs generated in preparing UV-1 includes such steps as treating the waste dregs of NE generated in preparing N- (4-ethoxycarbonylphenyl) -N '-methyl-N' -phenylformamidine, and N-alkylating with benzyl chloride.
The treatment method is divided into a reaction method and a separation method.
The reaction method comprises the following steps:
(1) dissolving NE waste residue in a solvent A, and treating the NE waste residue by active carbon to obtain a solution A containing NE and NET;
(2) and (3) adding ethyl p-aminobenzoate into the solution A obtained in the step (1) to perform condensation reaction, and then adding benzyl chloride to perform N-alkylation reaction to obtain NEPA.
The separation method comprises the following steps:
(1) dissolving NE waste residue in the solvent B, stirring and dissolving, filtering, and drying to obtain a NET crude product;
(2) dissolving the NET crude product obtained in the step (1) in a solvent A, and treating the NET crude product by activated carbon to obtain a solution A containing NET;
(3) and (3) adding benzyl chloride into the solution A obtained in the step (2) to carry out N-alkylation reaction to obtain NEPA.
The solvent A is a polar aprotic solvent, preferably DMF, DMAc, NMP, DMSO, more preferably DMF.
The dosage of the solvent A is 1 to 3 times of the weight of the NE waste residue or the NET crude product.
The solvent B is toluene.
The dosage of the solvent B is 1 to 5 times of the weight of the NE waste residue.
The dosage of the activated carbon is 1-5% of the weight of the NE waste residue or the NET crude product.
The activated carbon treatment temperature is 50-80 ℃, preferably 60-65 ℃.
The dosage of the ethyl aminobenzoate is 5-25% of the weight of the NE waste residue.
The condensation reaction temperature is 70 to 100 ℃, preferably 80 to 90 ℃.
The N-alkylation reaction temperature is 30 to 60 ℃, preferably 40 to 45 ℃.
The application has the positive effects that: (1) Although the reaction method of the application can obtain more NET, thereby obtaining more NEPA, the purity of the NEPA is relatively low; (2) The isolation method of the present application allows obtaining NEPA of higher purity, which is critical in that it surprisingly has been found that toluene can dissolve NE but not NET, which has not been reported in the prior art.
Detailed Description
Example 1
272kg of triethyl orthoformate (1.84 kmol) is pumped into a reaction kettle, 45.4kg of ethyl paraaminobenzoate (0.275 kmol) is added, the temperature is raised to 90+/-2 ℃, distilled liquid appears at the moment, ethanol is recovered by introducing the distilled liquid into a receiving tank, the temperature of the materials is raised to 140+/-2 ℃, the reaction is kept for 1 hour, and after the reaction is finished, the triethyl orthoformate is recovered by reduced pressure distillation, so that 57.5kg of NE and 4.3kg of NE waste residues (about 20wt% of NE and 80wt% of NET) are respectively obtained.
Example 2
272kg of triethyl orthoformate (1.84 kmol) is pumped into a reaction kettle, 45.4kg of ethyl paraaminobenzoate (0.275 kmol) is added, the temperature is raised to 90+/-2 ℃, distilled liquid appears at the moment, ethanol is recovered by introducing the distilled liquid into a receiving tank, the temperature of the materials is raised to 140+/-2 ℃, the reaction is kept for 4 hours, and after the reaction is finished, the triethyl orthoformate is recovered by reduced pressure distillation, so that 59.6kg of NE and 1.6kg of NE waste residues (about 10wt% of NE and 90wt% of NET) are respectively obtained.
Example 1
The method for preparing N, N '-bis (4-ethoxycarbonylphenyl) -N' -benzylformamidine from the waste residue for producing UV-1 in this example is an isolation method, which comprises the following steps:
(1) 1kg of NE waste residue obtained in example 1 is added into 3kg of toluene, stirred for 2-3 h, filtered and dried to obtain 796g of light yellow solid NET crude product with purity of 98.2%.
(2) 796g of NET crude product obtained in the step (1) is added into 2kg of DMF, 25g of active carbon is then added, the temperature is raised to 60-65 ℃, the temperature is kept for 2h, suction filtration is carried out, the filter cake is leached by 150g of DMF, and the leaching solution and the filtrate are combined to obtain a DMF solution containing NET.
(3) And (3) controlling the temperature of the DMF solution containing NET obtained in the step (2) at 40-45 ℃, adding 480g of benzyl chloride and 610g of potassium carbonate, keeping the temperature at 40-45 ℃ for 24 hours after the addition, carrying out suction filtration, and leaching the filter cake by using 150g of DMF.
Adding the obtained filtrate and leaching solution into 8kg of 3wt% potassium carbonate aqueous solution under stirring, slowly heating to 65 ℃, preserving heat for 2 hours, slowly cooling to room temperature, starting to precipitate white solid in the cooling process, carrying out suction filtration, adding the filter cake into 2.7kg of water, stirring and heating to 50 ℃, preserving heat for 2 hours, slowly cooling to room temperature, carrying out suction filtration, leaching the filter cake with a small amount of water for three times, and drying to obtain 945g of white solid NEPA with the purity of 99.2%.
Example 2 to example 4
The procedure of each example was essentially the same as in example 1, except that table 1 was followed.
TABLE 1
| Example 1 | Example 2 | Example 3 | Example 4 | |
| NE waste residue | 1kg example 1 | 1kg example 2 | 500g example 1 | 500g example 2 |
| Toluene (toluene) | 3kg | 3kg | 1kg | 2kg |
| NET crude product/purity | 796g/98.2% | 886g/98.4% | 397g/98.3% | 445g/98.5 |
| Activated carbon | 25g | 25g | 10g | 15g |
| DMF for reaction | 2kg | 2kg | 0.5kg | 1.5kg |
| DMF for rinsing | 150g+150g | 150g+150g | 70g+70g | 80g+80g |
| Benzyl chloride | 480g | 495g | 235g | 250g |
| Potassium carbonate | 610g | 630g | 300g | 320g |
| Aqueous potassium carbonate solution | 8kg、3wt% | 8kg、3wt% | 4kg、3wt% | 4kg、3wt% |
| Water and its preparation method | 2.7kg | 2.7kg | 1.3kg | 1.4kg |
| NEPA/purity | 945g/99.2% | 1069g/99.3% | 476g/99.2% | 535g/99.3% |
Example 5
The method for preparing N, N '-bis (4-ethoxycarbonylphenyl) -N' -benzylformamidine from the waste residue for producing UV-1 in this example is a reaction method, which comprises the following steps:
(1) 1kg of the NE waste residue obtained in example 1 is added into 2kg of DMF, 25g of active carbon is then added, the temperature is raised to 60-65 ℃, the temperature is kept for 2h, suction filtration is carried out, the filter cake is leached by 150g of DMF, and the leaching solution and the filtrate are combined to obtain a DMF solution containing NE and NET.
(2) 154g of ethyl p-aminobenzoate is added into the DMF solution containing NE and NET obtained in the step (1), the temperature is raised to 85+/-2 ℃, the temperature is kept for 4 hours, then the temperature is reduced to 40-45 ℃, 507g of benzyl chloride and 644g of potassium carbonate are added, the temperature is kept for 24 hours at 40-45 ℃, suction filtration is carried out, and the filter cake is leached by 150g of DMF.
Adding the obtained filtrate and the leaching solution into 8kg of 3wt% potassium carbonate aqueous solution under stirring, slowly heating to 65 ℃, preserving heat for 2 hours, slowly cooling to room temperature, starting to precipitate white solid in the cooling process, carrying out suction filtration, adding the filter cake into 3kg of water, stirring and heating to 50 ℃, preserving heat for 2 hours, slowly cooling to room temperature, carrying out suction filtration, leaching the filter cake with a small amount of water for three times, and drying to obtain 1281g of white solid NEPA with the purity of 98.3%.
Example 6 to example 8
The procedure of each example was essentially the same as in example 5, except that it is shown in Table 2.
TABLE 2
| Example 5 | Example 6 | Example 7 | Example 8 | |
| NE waste residue | 1kg example 1 | 1kg example 2 | 500g example 1 | 500g example 2 |
| Activated carbon | 25g | 25g | 10g | 15g |
| DMF for reaction | 2kg | 2kg | 0.5kg | 1.5kg |
| DMF for rinsing | 150g+150g | 150g+150g | 70g+70g | 80g+80g |
| Para aminobenzoic acid ethyl ester | 154g | 80g | 80g | 40g |
| Benzyl chloride | 507g | 500g | 250g | 240g |
| Potassium carbonate | 644g | 640g | 320g | 310g |
| Aqueous potassium carbonate solution | 8kg、3wt% | 8kg、3wt% | 4kg、3wt% | 4kg、3wt% |
| Water and its preparation method | 3kg | 3kg | 1.4kg | 1.6kg |
| NEPA/purity | 1281g/98.3% | 1205g/98.5% | 639g/98.2% | 600g/98.4% |
Claims (5)
1. A method for preparing N, N '-di (4-ethoxycarbonylphenyl) -N' -benzyl formamidine from waste residues generated in the production of UV-1, which is characterized in that: the method is that NE waste residue generated in the production of UV-1 is treated and then is subjected to N-alkylation reaction with benzyl chloride to obtain the catalyst; the treatment method is a separation method; the method comprises the following steps: (1) dissolving NE waste residue in toluene, stirring and dissolving, and then carrying out suction filtration and drying to obtain a NET crude product; (2) dissolving the NET crude product obtained in the step (1) in a polar aprotic solvent, and treating the NET crude product by active carbon to obtain a solution A containing NET; (3) adding benzyl chloride into the solution A obtained in the step (2) to carry out N-alkylation reaction to obtain NEPA; the dosage of toluene is 1-5 times of the weight of the NE waste residue.
2. The method for preparing N, N '-bis (4-ethoxycarbonylphenyl) -N' -benzylformamidine from the waste residue from the production of UV-1 according to claim 1, wherein: the dosage of the polar aprotic solvent is 1 to 3 times of the weight of the NE waste residue or the NET crude product.
3. The method for preparing N, N '-bis (4-ethoxycarbonylphenyl) -N' -benzylformamidine from the waste residue from the production of UV-1 according to claim 1, wherein: the polar aprotic solvent is DMF.
4. The method for preparing N, N '-bis (4-ethoxycarbonylphenyl) -N' -benzylformamidine from the waste residue from the production of UV-1 according to claim 1, wherein: the dosage of the activated carbon is 1-5% of the weight of the NE waste residue or the NET crude product; the treatment temperature of the activated carbon is 50-80 ℃.
5. The method for preparing N, N '-bis (4-ethoxycarbonylphenyl) -N' -benzylformamidine from the waste residue from the production of UV-1 according to claim 1, wherein: the temperature of the N-alkylation reaction is 30-60 ℃.
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| CN202010753548.9A CN112047859B (en) | 2018-04-26 | 2018-04-26 | Method for preparing N, N '-di (4-ethoxycarbonylphenyl) -N' -benzyl formamidine from waste residues generated in production of UV-1 |
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| CN201810385261.8A CN108484445A (en) | 2018-04-26 | 2018-04-26 | N, N '-two are prepared with the waste residue of production UV-1（4- carboethoxyphenyls）The method of-N '-benzyl carbonamidines |
| CN202010753548.9A CN112047859B (en) | 2018-04-26 | 2018-04-26 | Method for preparing N, N '-di (4-ethoxycarbonylphenyl) -N' -benzyl formamidine from waste residues generated in production of UV-1 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005115973A1 (en) * | 2004-05-27 | 2005-12-08 | Ziko Ltd. | Benzylformamidine compounds and plastic products containing the benzylformamidine compounds as ultraviolet light absorbers |
| CN101481331A (en) * | 2009-01-20 | 2009-07-15 | 常州市阳光医药原料有限公司 | Process for preparing N, N'-bis (4-ethoxycarbonylphenyl)-N'-benzylformamidine |
| CN103420873A (en) * | 2013-09-06 | 2013-12-04 | 安徽工业大学 | N, N'-di (4-ethyoxyl carbonyl phenyl)-N'-benzyl formamidine preparation method |
| CN103709073A (en) * | 2014-01-02 | 2014-04-09 | 常州永和精细化学有限公司 | Preparation method of N,N'-bis (4-ethoxycarbonylphenyl)-N'-benzyl formamidine |
| CN105315176A (en) * | 2015-11-27 | 2016-02-10 | 常州永和精细化学有限公司 | Environment-friendly preparation process of N-(4-ethoxy carbonyl phenyl)-N'-methyl-N'-phenyl formamidine |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101481330B (en) * | 2009-01-20 | 2012-06-20 | 常州市阳光药业有限公司 | Preparation of N-(4-ethoxy carbonyl phenyl)-N'-methyl-N'-phenyl formamidine |
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| Publication number | Publication date |
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| CN108484445A (en) | 2018-09-04 |
| CN112047859A (en) | 2020-12-08 |
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