Preparation method for high optical indoxacarb intermediate

Abstract

A field of asymmetric catalytic synthesis, and in particular a preparation method for a high optical indoxacarb intermediate includes reacting 5-chloro-2-methoxycarbonyl-1-indanone ester (or indanone ester for short) with an oxidizing agent in the presence of a chiral Zr-salen polymer to obtain an indoxacarb intermediate (2S)-5-chloro-2,3-dihydro-2-hydroxy-1-oxo-1H-indole-2-carboxylic acid methyl ester. The yield is stabilized between 86% and 90%, and the S-enantiomer content is up to 99%. Such catalyst can replace catalysts such as cinchonine, and greatly increase the content of the effective S-enantiomer of the indoxacarb, so that the content of the hydroxyl intermediate S-enantiomer of the indoxacarb is raised from 75% to 99% or more. In addition, the chiral Zr-salen polymer catalyst is recycled without retreatment, and can be recycled at least 5 times or more, greatly reducing the production cost and laying a foundation for the industrial production of high quality indoxacarb.

Claims

1. A preparation method for a high optical indoxacarb intermediate (2S)-5-chloro-2,3-dihydro-2-hydroxy-1-oxo-1H-indene-2-carboxylic acid methyl ester, wherein an asymmetric synthesis is catalyzed by a chiral Zr-salen polymer, a method of producing the chiral Zr-salen polymer, comprising the steps of: (1) adding a solvent I, 3-tert-butyl-5-styrylsalicylaldehyde and (1S,2S)-()-1,2-diphenylethylenediamine or (1S,2S)-(+)-1,2-cyclohexanediamine into a reaction flask, raising the temperature for reflux reaction, after the reaction is finished, a condensate is obtained after lowering the temperature and filtration, wherein the solvent I is methanol; (2) dissolving the condensate in a solvent II, raising the temperature to 50-60 C., and dripping a reducing agent, removing the solvent II after the reaction, adding water into the system, and a ligand monomer of catalyst A or catalyst B is obtained after extraction, desolvation, crystallization, lowering the temperature and filtration, wherein the solvent II is tetrahydrofuran; (3) putting the ligand monomer of catalyst A or catalyst B into a pressure-resistant reaction flask, adding a solvent III and using azobisisobutyronitrile (AIBN) as an initiator, carrying out hydrothermal polymerization at 110-120 C., then a polymer ligand is obtained after filtration and drying, wherein the solvent III is a mixture of ethanol and water; (4) putting the polymer ligand and a zirconium-containing metal compound in toluene at 50-80 C. to carry out complexation reaction, after the reaction, a toluene system of catalyst A or catalyst B is obtained, wherein the zirconium-containing metal compound is selected from zirconium hydroxide, zirconyl chloride octahydrate, zirconium dioxide, zirconium(IV) acetylacetonate, zirconium trifluoroacetylacetonate, n-propyl zirconate, zirconium(IV) tert-butoxide, zirconium(IV) hydrogenphosphate, zirconium(IV) bromide, and mixtures thereof; and the preparation reaction equation is as follows: ##STR00006## ##STR00007## ##STR00008## ##STR00009## ##STR00010## ##STR00011## wherein: R is ##STR00012## n is 10020000, and ZrX is the zirconium-containing metal compound.

2. The preparation method for the high optical indoxacarb intermediate according to claim 1, comprising the steps of: adding 5-chloro-2-methoxycarbonyl-1-indanone ester in toluene solution into the toluene system of catalyst A or catalyst B obtained by the above method, dripping an oxidant at 50-80 C. to carry out asymmetric synthesis reaction, after the reaction is finished, cooling it to 60-65 C.; Catalyst A or Catalyst B is recovered by hot filtration, after the filtrate is concentrated, cooled and filtered, the high optical indoxacarb intermediate (2S)-5-chloro-2,3-dihydro-2-hydroxy-1-oxo-1H-indene-2-carboxylic acid methyl ester is obtained; at the same time, the recovered Catalyst A or Catalyst B is put into toluene solvent to form a suspension, which can continue to participate in the above asymmetric synthesis reaction.

3. The preparation method for the high optical indoxacarb intermediate (2S)-5-chloro-2,3-dihydro-2-hydroxy-1-oxo-1H-indene-2-carboxylic acid methyl ester according to claim 1, wherein in step (1), a duration of the reflux reaction is 6-7 h; a mole ratio of 3-tert-butyl-5-styrylsalicylaldehyde and (1S,2S)-()-1,2-diphenylethylenediamine or (1S,2S)-(+)-1,2-cyclohexanediamine is 2:1-1.1; a dosage of the solvent I is 8-10 times of the mass of (1S,2S)-()-1,2-diphenylethylenediamine or (1S,2S)-(+)-1,2-cyclohexanediamine.

4. The preparation method for the high optical indoxacarb intermediate (2S)-5-chloro-2,3-dihydro-2-hydroxy-1-oxo-1H-indene-2-carboxylic acid methyl ester according to claim 1, wherein in step (2), the reducing agent is sodium borohydride or sodium cyanoborohydride or potassium borohydride or lithium aluminum hydride; a mole ratio of the reducing agent and the condensate is 2-4:1; a dosage of the solvent II is 4-8 times of the mass of the condensate.

5. The preparation method for the high optical indoxacarb intermediate (2S)-5-chloro-2,3-dihydro-2-hydroxy-1-oxo-1H-indene-2-carboxylic acid methyl ester according to claim 1, wherein a weight of the water added in step (2) is 2-4 times of the weight of the condensate; extraction with ethyl acetate, and a weight of ethyl acetate added is 6-10 times of the weight of the condensate; the crystallization solvent is methanol; a dosage of methanol is 4-8 times of the weight of the condensate.

6. The preparation method for the high optical indoxacarb intermediate (2S)-5-chloro-2,3-dihydro-2-hydroxy-1-oxo-1H-indene-2-carboxylic acid methyl ester according to claim 1, wherein in step (3), a volume ratio of ethanol to water in the solvent III is 3:1; a dosage of the solvent III is 6-10 times of the weight of the ligand monomer of Catalyst A or Catalyst B, and a dosage of AIBN is 0.5%2% of the weight of the ligand monomer of Catalyst A or Catalyst B.

7. The preparation method for the high optical indoxacarb intermediate (2S)-5-chloro-2,3-dihydro-2-hydroxy-1-oxo-1H-indene-2-carboxylic acid methyl ester according to claim 1, wherein in step (3), a particle size of the polymer ligand is 0.1-1 mm.

8. The preparation method for the high optical indoxacarb intermediate (2S)-5-chloro-2,3-dihydro-2-hydroxy-1-oxo-1H-indene-2-carboxylic acid methyl ester according to claim 1, wherein in step (4), a mole ratio of the polymer ligand to the zirconium-containing metal compound is 1-1.5:1; a dosage of the toluene is 4-10 times of the weight of the polymer ligand.

9. The preparation method for the high optical indoxacarb intermediate (2S)-5-chloro-2,3-dihydro-2-hydroxy-1-oxo-1H-indene-2-carboxylic acid methyl ester according to claim 2, wherein the oxidant is tert-butyl hydroperoxide or m-chloroperbenzoic acid or cumyl hydroperoxide; in terms of the mole ratio of pure matter, the oxidant to 5-chloro-2-methoxycarbonyl-1-indanone ester is 1:1.2-3; an added dosage of catalyst A or catalyst B is 1%-5% of the mass of 5-chloro-2-methoxycarbonyl-1-indanone ester; in the 5-chloro-2-methoxycarbonyl-1-indanone ester in toluene solution, a dosage of toluene is 2-4 times of the weight of 5-chloro-2-methoxycarbonyl-1-indanone ester.

10. The preparation method for the high optical indoxacarb intermediate (2S)-5-chloro-2,3-dihydro-2-hydroxy-1-oxo-1H-indene-2-carboxylic acid methyl ester according to claim 1, wherein the reducing agent in the preparation reaction equation is sodium borohydride.

Description

Specific Embodiments

Embodiment 1 (Taking Catalyst A as an Example)

(1) A preparation method for high optical indoxacarb intermediate, the preparation method is as follows:

(2) 1. Adding 28 g (0.1 mol) of 3-tert-butyl-5-styrylsalicylaldehyde and 10.6 g (0.05 mol) of (1S,2S)-()-1,2-diphenylethylenediamine to a reaction flask, then adding 106 g of methanol to the reaction flask and the mixture is heated and refluxed. Cooling the mixture to 05 C. and a pale yellow condensate solid is obtained after filtration. The weight of the condensate solid is weighed as 35 g after drying, and the yield is 95%.

(3) 2. Weighing and dissolving 7.36 g (0.01 mol) of the above dried condensate in 50 g of tetrahydrofuran, raising the temperature to 5060 C., add 1.5 g (0.04 mol) of sodium borohydride in batches. After the reaction, removing the tetrahydrofuran. Adding 20 g of water into the system, extracting with 60 g of ethyl acetate. After removing ethyl acetate, adding 20 g of methanol to crystallize. Lowering the temperature to 05 C. and filtering to obtain 6.66 g of ligand monomer of Catalyst A, with a yield of 90%. The ligand monomer is white solid and its melting point is 165-168 C., .sup.1HNMR (DMSO-d6, D2O 400 MHz): (ppm) 1.39 (s, 18H), 3.57-3.61 (d, J=14.1 Hz, 2H), 3.68-3.72 (d, J=13.8 Hz, 2H), 3.97 (s, 2H), 5.22-5.25 (d, J=11.4 Hz, 2H), 5.79-5.83 (d, J=17.7 Hz, 2H), 6.69-6.76 (m, 2H), 6.97-6.98 (d, J=1.68 Hz, 2H), 7.14-7.23 (m, 10H), 7.32-7.33 (d, J=1.92 Hz, 2H), 7.47 (s, 8H).

(4) 3. Adding 6 g (8 mmol) of Catalyst A ligand monomer into a pressure resistant reaction flask. Adding 60 g of ethanol/water and 0.06 g of AIBN. Hydrothermal polymerization is carried out at 115-120 C. for 24 h to obtain a white-like spherical polymer ligand. The polymerization degree is 900-1500, the particle size is 0.5 mm, and the dry weight is 6 g. The yield is calculated as 100%.

(5) 4. Adding 3 g (4 mmol) of the polymer ligand and 2 g (4 mmol) of zirconium(IV) acetylacetonate to 20 g of toluene. After complexation reaction at 7580 C. for 24 h, a catalyst A toluene suspension system was obtained. The yield of the Catalyst A is calculated as 100% and its weight is 3.3 g.

(6) 5. Dissolving 66 g (0.29 mol) of indanone ester in 132 g of toluene, and then putting the mixture into the above-mentioned 3.3 g (4 mmol) of Catalyst A toluene suspension system. Dripping into the system 45.7 g (0.41 mol) of aqueous solution of tert-butyl hydroperoxide with mass fraction 80%. Dripping time is 2 h and the reaction temperature is 75-80 C.

(7) 6. After the oxidant is dripped, maintaining the temperature at 75-80 C. for 1 h. Taking the sample to inspect the reaction.

(8) 7. After tracking reaction and confirming the reaction is qualified, cooling down to 6065 C., and Catalyst A is recovered by hot filtration.

(9) 8. Concentrating the filtrate and toluene which the weight is 70% of the weight of the added solvent is concentrated from the filtrate. Cooling it to 05 C., and maintaining the temperature for 1 h. 60.6 g (converted to 100% purity calculation, the same below) of white solid (2S)-5-chloro-2,3-dihydro-2-hydroxy-1-oxo-1H-indene-2-carboxylic acid methyl ester is obtained after filtration. The optical detection of a chiral chromatographic column is 99.9%, and the yield is 86.9%.

Embodiment 2 (Taking Catalyst A as an Example)

(10) 1. The polymer ligand is prepared first, which is the same as in Embodiment 1.

(11) 2. Adding 3 g (4 mmol) of the polymer ligand and 1.55 g (4 mmol) of zirconium(IV) tert-butoxide to 20 g of toluene. After complexation reaction at 7580 C. for 20 h, a catalyst A toluene suspension system was obtained. The yield of the Catalyst A is calculated as 100% and its weight is 3.3 g.

(12) 3. Dissolving 66 g (0.29 mol) of indanone ester in 132 g of toluene, and then putting the mixture into the above-mentioned 3.3 g (4 mmol) of Catalyst A toluene suspension system. Dripping into the system 45.7 g (0.41 mol) of aqueous solution of tert-butyl hydroperoxide with mass fraction 80%. Dripping time is 2.5 h and the reaction temperature is 75-80 C.

(13) 4. After the oxidant is dripped, maintaining the temperature at 75-80 C. for 1 h. Taking the sample to inspect the reaction.

(14) 5. After tracking reaction and confirming the reaction is qualified, cooling down to 6065 C., and Catalyst A is recovered by hot filtration.

(15) 6. Concentrating the filtrate and toluene which the weight is 70% of the weight of the added solvent is concentrated from the filtrate. Cooling it to 05 C., and maintaining the temperature for 1 h. 60.96 g of white solid (2S)-5-chloro-2,3-dihydro-2-hydroxy-1-oxo-1H-indene-2-carboxylic acid methyl ester is obtained after filtration. The optical detection of a chiral chromatographic column is 99.5%, and the yield is 87.4%.

(16) The first time for reusing the Catalyst A:

(17) 1. Dissolving 66 g (0.29 mol) of indanone ester in 132 g of toluene, and then putting the above recovered Catalyst A into the system. Dripping into the system 45.7 g (0.41 mol) of aqueous solution of tert-butyl hydroperoxide with mass fraction 80%. Dripping time is 3 h and the reaction temperature is 75-80 C.

(18) 2. After the oxidant is dripped, maintaining the temperature at 75-80 C. for 1 h. Taking the sample to inspect the reaction.

(19) 3. After tracking reaction and confirming the reaction is qualified, cooling down to 6065 C., and Catalyst A is recovered by hot filtration.

(20) 4. Concentrating the filtrate and toluene which the weight is 70% of the weight of the added solvent is concentrated from the filtrate. Cooling it to 05 C., and maintaining the temperature for 1 h. 62.56 g of white solid (2S)-5-chloro-2,3-dihydro-2-hydroxy-1-oxo-1H-indene-2-carboxylic acid methyl ester is obtained after filtration. The optical detection of a chiral chromatographic column is 99.5%, and the yield is 89.7%.

(21) The second time for reusing the Catalyst A:

(22) 1. Dissolving 66 g (0.29 mol) of indanone ester in 132 g of toluene, and then putting the above recovered Catalyst A into the system. Dripping into the system 45.7 g (0.41 mol) of aqueous solution of tert-butyl hydroperoxide with mass fraction 80%. Dripping time is 2 h and the reaction temperature is 75-80 C.

(23) 2. After the oxidant is dripped, maintaining the temperature at 75-80 C. for 1 h. Taking the sample to inspect the reaction.

(24) 3. After tracking reaction and confirming the reaction is qualified, cooling down to 6065 C., and Catalyst A is recovered by hot filtration.

(25) 4. Concentrating the filtrate and toluene which the weight is 70% of the weight of the added solvent is concentrated from the filtrate. Cooling it to 05 C., and maintaining the temperature for 1 h. 61.2 g of white solid (2S)-5-chloro-2,3-dihydro-2-hydroxy-1-oxo-1H-indene-2-carboxylic acid methyl ester is obtained after filtration. The optical detection of a chiral chromatographic column is 99.8%, and the yield is 87.7%.

(26) The third time for reusing the Catalyst A:

(27) 1. Dissolving 66 g (0.29 mol) of indanone ester in 132 g of toluene, and then putting the above recovered Catalyst A into the system. Dripping into the system 45.7 g (0.41 mol) of aqueous solution of tert-butyl hydroperoxide with mass fraction 80%. Dripping time is 2.5 h and the reaction temperature is 75-80 C.

(28) 2. After the oxidant is dripped, maintaining the temperature at 75-80 C. for 1 h. Taking the sample to inspect the reaction.

(29) 3. After tracking reaction and confirming the reaction is qualified, cooling down to 6065 C., and Catalyst A is recovered by hot filtration.

(30) 4. Concentrating the filtrate and toluene which the weight is 70% of the weight of the added solvent is concentrated from the filtrate. Cooling it to 05 C., and maintaining the temperature for 1 h. 62.0 g of white solid (2S)-5-chloro-2,3-dihydro-2-hydroxy-1-oxo-1H-indene-2-carboxylic acid methyl ester is obtained after filtration. The optical detection of a chiral chromatographic column is 99.2%, and the yield is 88.9%.

(31) The fourth time for reusing the Catalyst A:

(32) 1. Dissolving 66 g (0.29 mol) of indanone ester in 132 g of toluene, and then putting the above recovered Catalyst A into the system. Dripping into the system 45.7 g (0.41 mol) of aqueous solution of tert-butyl hydroperoxide with mass fraction 80%. Dripping time is 3 h and the reaction temperature is 75-80 C.

(33) 2. After the oxidant is dripped, maintaining the temperature at 75-80 C. for 1 h. Taking the sample to inspect the reaction.

(34) 3. After tracking reaction and confirming the reaction is qualified, cooling down to 6065 C., and Catalyst A is recovered by hot filtration.

(35) 4. Concentrating the filtrate and toluene which the weight is 70% of the weight of the added solvent is concentrated from the filtrate. Cooling it to 05 C., and maintaining the temperature for 1 h. 61.0 g of white solid (2S)-5-chloro-2,3-dihydro-2-hydroxy-1-oxo-1H-indene-2-carboxylic acid methyl ester is obtained after filtration. The optical detection of a chiral chromatographic column is 99.5%, and the yield is 87.5%.

(36) The fifth time for reusing the Catalyst A:

(37) 1. Dissolving 66 g (0.29 mol) of indanone ester in 132 g of toluene, and then putting the above recovered Catalyst A into the system. Dripping into the system 45.7 g (0.41 mol) of aqueous solution of tert-butyl hydroperoxide with mass fraction 80%. Dripping time is 3 h and the reaction temperature is 75-80 C.

(38) 2. After the oxidant is dripped, maintaining the temperature at 75-80 C. for 1 h. Taking the sample to inspect the reaction.

(39) 3. After tracking reaction and confirming the reaction is qualified, cooling down to 6065 C., and Catalyst A is recovered by hot filtration.

(40) 4. Concentrating the filtrate and toluene which the weight is 70% of the weight of the added solvent is concentrated from the filtrate. Cooling it to 05 C., and maintaining the temperature for 1 h. 61.4 g of white solid (2S)-5-chloro-2,3-dihydro-2-hydroxy-1-oxo-1H-indene-2-carboxylic acid methyl ester is obtained after filtration. The optical detection of a chiral chromatographic column is 99.0%, and the yield is 88.1%.

Embodiment 3 (Taking Catalyst B as an Example)

(41) 1. Adding 28 g (0.1 mol) of 3-tert-butyl-5-styrylsalicylaldehyde and 5.7 g (0.05 mol) of (1S,2S)-(+)-1,2-cyclohexanediamine to a reaction flask, then adding 57 g of methanol to the reaction flask and the mixture is heated and refluxed. Cooling the mixture to 05 C. and a yellow condensate solid is obtained after filtration. The weight of the condensate solid is weighed as 28.75 g after drying, and the yield is 90%.

(42) 2. Weighing and dissolving 12.78 g (0.02 mol) of the above dried condensate in 90 g of tetrahydrofuran, raising the temperature to 5060 C., add 2.26 g (0.06 mol) of sodium borohydride in batches. After the reaction, removing the tetrahydrofuran. Adding 40 g of water into the system, extracting with 100 g of ethyl acetate. After removing ethyl acetate, adding 50 g of methanol to crystallize. Lowering the temperature to 0 C. and filtering to obtain 11.2 g of ligand monomer of Catalyst B, with a yield of 87%.

(43) 3. Adding 5.14 g (8 mmol) of Catalyst B ligand monomer into a pressure resistant reaction flask. Adding 50 g of ethanol/water and 0.05 g of AIBN. Hydrothermal polymerization is carried out at 115-120 C. for 24 h to obtain a white-like spherical polymer ligand. The polymerization degree is 800-1300, the particle size is 0.3-0.5 mm, and the dry weight is 5.2 g.

(44) 4. Adding 2.6 g (4 mmol) of the polymer ligand and 1.68 g (4 mmol) of n-propyl zirconate to 20 g of toluene. After complexation reaction at 7580 C. for 24 h, a catalyst B toluene suspension system was obtained. The yield of the Catalyst A is calculated as 100% and its weight is 2.92 g.

(45) 5. Dissolving 66 g (0.29 mol) of indanone ester in 132 g of toluene, and then putting the mixture into the above-mentioned 2.92 g (4 mmol) of Catalyst B toluene suspension system. Dripping into the system 45.7 g (0.41 mol) of aqueous solution of tert-butyl hydroperoxide with mass fraction 80%. Dripping time is 2.5 h and the reaction temperature is 75-80 C.

(46) 6. After the oxidant is dripped, maintaining the temperature at 75-80 C. for 1 h. Taking the sample to inspect the reaction.

(47) 7. After tracking reaction and confirming the reaction is qualified, cooling down to 6065 C., and Catalyst B is recovered by hot filtration.

(48) 8. Concentrating the filtrate and toluene which the weight is 70% of the weight of the added solvent is concentrated from the filtrate. Cooling it to 05 C., and maintaining the temperature for 1 h. 60.68 g of white solid (2S)-5-chloro-2,3-dihydro-2-hydroxy-1-oxo-1H-indene-2-carboxylic acid methyl ester is obtained after filtration. The optical detection of a chiral chromatographic column is 99.3%, and the yield is 87.0%.

Embodiment 4 (Taking Catalyst B as an Example)

(49) 1. The polymer ligand is prepared first, which is the same as in Embodiment 3.

(50) 2. Adding 2.6 g (4 mmol) of the polymer ligand and 2.81 g (4 mmol) of zirconium trifluoroacetylacetonate to 20 g of toluene. After complexation reaction at 7580 C. for 20 h, a catalyst B toluene suspension system was obtained. The yield of the Catalyst A is calculated as 100%.

(51) 3. Dissolving 66 g (0.29 mol) of indanone ester in 132 g of toluene, and then putting the mixture into the above-mentioned Catalyst B toluene suspension system. Dripping into the system 45.7 g (0.41 mol) of aqueous solution of tert-butyl hydroperoxide with mass fraction 80%. Dripping time is 2.5 h and the reaction temperature is 75-80 C.

(52) 4. After the oxidant is dripped, maintaining the temperature at 75-80 C. for 1 h. Taking the sample to inspect the reaction.

(53) 5. After tracking reaction and confirming the reaction is qualified, cooling down to 6065 C., and Catalyst B is recovered by hot filtration.

(54) 6. Concentrating the filtrate and toluene which the weight is 70% of the weight of the added solvent is concentrated from the filtrate. Cooling it to 05 C., and maintaining the temperature for 1 h. 60.2 g of white solid (2S)-5-chloro-2,3-dihydro-2-hydroxy-1-oxo-1H-indene-2-carboxylic acid methyl ester is obtained after filtration. The optical detection of a chiral chromatographic column is 99.1%, and the yield is 86.3%.

(55) The invention adopts a new catalyst in the preparation of indoxacarb, which is a polymer compound with high catalytic efficiency and is easy to recycle and utilize. For the production of indoxacarb with the same quality, the catalyst consumption is only one-third of that of DuPont Company, and the catalyst can be recycled and utilized for more than 5 times without adding new catalyst. The content of the hydroxyl intermediate S-enantiomer of the indoxacarb is kept above 99%. The cost per ton of high optical indoxacarb is reduced more than RMB 50000 yuan compared with that of DuPont Company, which greatly improves the market competitiveness of the products.