* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Stage #1: at 80 - 110℃; for 3 h; Stage #2: at 90℃; for 3 h;
A process for the production of 2-carboxyethylphenylphosphinic acid in accordance with the present invention without waste water,Next:(1) 1.0 mol of phenylphosphine dichloride was charged into a reaction vessel, stirred, heated to 80 ° C, 1 mol of acrylic acid was added dropwise,Finished warming to 110 deg C , heat 3 hours, cooling to 50 deg C ; (2) To the liquid obtained in the step (1), 2.0 mol of dichloropropane (secondary used mother liquor,Material complement), stirring;(3) to the step (2) to slowly drop 1.0mol of water, acid chloride intermediates and water hydrolysis reaction, drop finishedHeating to 90 DEG C, keeping for 3 hours, cooling to 20 DEG C to produce 2-carboxyethylphenylphosphinic acid, and recovering by-product hydrochloric acid.(4) The solid-liquid mixture obtained in step (3) was filtered, washed with dichloropropane, filtered again, placed in an oven,Baking at 130 ° C for 2 hours to obtain 2-carboxyethylphenylphosphinic acid, and the mother liquor was recovered in the next batch. The yield of 2-carboxyethylphenylphosphinic acid was 98.0percent, the melting point was 160.2 deg C , the acid value (mgKOH / g) was 522, the phosphorus content was 14.35percent, and the product quality was excellent.
93.6%
With 2,2'-azobis(isobutyronitrile) In water
EXAMPLE 4 A 3-l four neck flask having a Dimroth condenser and a thermometer was charged with 1252.9 g (7.0 moles) of dichloro(phenyl)phosphine and 8.3 g (0.0506 mole) of azobisisobutyronitrile, and heated under stirring to raise the liquid temperature to 75° C. Then, 514.7 g (7.0 moles) of acrylic acid was added dropwise to the mixture in one hour. During such dropwise addition, heat was gradually generated, but the liquid temperature was maintained at 85° to 90° C. After the dropwise addition, the reaction was further continued at 90° C. for 6 hours. After completion of the reaction, 2.3 lof water was gradually added to the reaction product with the liquid temperature maintained at 50° C. To prevent heat from being generated during this addition, the reaction product was cooled with ice water to maintain the liquid temperature at 60° to 70° C. After the addition, the reaction product was continuously stirred at the same temperature for one hour. After the liquid temperature was cooled to 10° C., the reaction product was filtered off and the resulting crystal was washed with water and then dried by a vacuum oven (60° C.), thereby to obtain 1403.2 g of 3-[hydroxy(phenyl)phosphinyl]propionic acid in the form of a white crystal (yield: 93.6percent).
Reference：
[1] Patent: CN105541908, 2016, A, . Location in patent: Paragraph 0023; 0024
[2] Patent: US5334760, 1994, A,
[3] Patent: US6090976, 2000, A,
[4] Patent: EP1092722, 2001, A1,
[5] Patent: EP1099705, 2001, A1,
[6] Patent: US5334760, 1994, A,
[7] Patent: US6090976, 2000, A,
[8] Patent: EP1092722, 2001, A1,
2
[ 14576-56-8 ]
[ 14657-64-8 ]
Yield
Reaction Conditions
Operation in experiment
97.2%
With sulfuric acid In water
EXAMPLE 6 A 3-l four neck flask having a Liebig condenser and a thermometer was charged with 1142.3 g (3.5 moles) of butyl 3-[butoxy(phenyl)phosphinyl]propionate obtained in Example 5, and under stirring, 530 g of water and a sulfuric-acid aqueous solution containing 5.7 g of sulfuric acid dissolved in 100 g of water were added. The resulting mixture was heated to raise the liquid temperature to 100° C. The reaction was continued for 6 hours while distilling water and butanol away and while replenishing the same amount of distilled water through a dropping funnel. The reaction product was allowed to stand overnight, and then filtered off. The resulting crystal was washed with water and dried by a vacuum oven (60° C.), thereby to obtain 728.6 g of 3-[hydroxy(phenyl)phosphinyl]propionic acid in the form of a white crystal (yield: 97.2percent).
Reference：
[1] Patent: US5334760, 1994, A,
3
[ 2071-68-3 ]
[ 14657-64-8 ]
Reference：
[1] J. Gen. Chem. USSR (Engl. Transl.), 1992, vol. 62, # 1.2, p. 182 - 183[2] Zhurnal Obshchei Khimii, 1992, vol. 62, # 1, p. 219 - 220
[3] J. Gen. Chem. USSR (Engl. Transl.), 1967, vol. 37, p. 423 - 427[4] Zhurnal Obshchei Khimii, 1967, vol. 37, p. 455 - 460
4
[ 644-97-3 ]
[ 14657-64-8 ]
Reference：
[1] Roczniki Chemii, 1952, vol. 26, p. 593,597,599,601[2] Chem.Abstr., 1955, p. 2345
[3] Roczniki Chemii, 1952, vol. 26, p. 593,597,599,601[4] Chem.Abstr., 1955, p. 2345
[5] Roczniki Chemii, 1952, vol. 26, p. 593,597,599,601[6] Chem.Abstr., 1955, p. 2345
[7] J. Gen. Chem. USSR (Engl. Transl.), 1967, vol. 37, p. 423 - 427[8] Zhurnal Obshchei Khimii, 1967, vol. 37, p. 455 - 460
5
[ 6172-81-2 ]
[ 14657-64-8 ]
Reference：
[1] Roczniki Chemii, 1952, vol. 26, p. 593,597,599,601[2] Chem.Abstr., 1955, p. 2345
[3] Roczniki Chemii, 1952, vol. 26, p. 593,597,599,601[4] Chem.Abstr., 1955, p. 2345
[5] Roczniki Chemii, 1952, vol. 26, p. 593,597,599,601[6] Chem.Abstr., 1955, p. 2345
6
[ 857470-46-3 ]
[ 14657-64-8 ]
Reference：
[1] Roczniki Chemii, 1952, vol. 26, p. 593,597,599,601[2] Chem.Abstr., 1955, p. 2345
7
[ 202477-16-5 ]
[ 14657-64-8 ]
Reference：
[1] Roczniki Chemii, 1952, vol. 26, p. 593,597,599,601[2] Chem.Abstr., 1955, p. 2345
EXAMPLE I In a reactor were placed 396.7 g (2.793 moles) of phenylphosphonous dichloride which was then dropwise added with 500 g (2.793 mole) of phenylphosphonous dichloride at 20 C under a nitrogen atmosphere with stirring. After complete mixing, 556.15 g (6.145 moles) of acryloyl chloride was dropwise added at 20 C for 90 min, and the reaction mixture was further reacted for 30 min. In 1,106 g of water, the resulting condensate was dropwise added at 80 C with vigorous stirring, after which the temperature was cooled to near 10 C to obtaine precipitates. After being allowed to stand at 10 C for 1 hour, the slurry containing the precipitates was filtered,washed and dried in a vacuum dryer to produce 1,147.6 g of 3-(hydroxyphenylphosphinyl)-propanoic acid. Yield 96 %.
94.3%
16.5:1 Control-Preparation of 2-Carboxyalkyl(phenyl)phosphinic acid Using Acrylation Intermediate of Example 1 Deionized water, 476 grams (26.4 moles), was charged to a reactor purged with a continuous flow of nitrogen and the off gases collected. At ambient temperature, addition of 419 grams of acrylation intermediate from an acrylation step similar to that of Example 1. The ratio of moles of water added per mole of dichlorophenyl-phosphine charged to prepare the 419 grams of acrylation intermediate used was 16.5:1. The exothermic nature of the reaction raised the temperature to 85-90 C. as the addition proceeded. Some solids appeared during the reaction which dissolved as the temperature increased. When the addition was completed, the reaction temperature was raised to 90-95 C. and 4-6 grams of 30% hydrogen peroxide were added to destroy any P4 which may have been present as a contaminant from the original dichlorophenylphosphine. The batch was maintained briefly at 90-95 C. and then cooled to 76 C. where seed crystals were added. After 10-15 minutes (to allow crystallization to occur), cooling was resumed until a temperature of 5 C. was reached. The slurry was held at this temperature for 15-30 minutes and then solid 2-carboxyethyl(phenyl)phosphinic acid was filtered off and washed with a total of 476 grams of cold deionized water (according to methods described in 3(b) and 3(c) hereinafter following). The wet cake was dried and a yield of 323.8 grams of 2-carboxyethyl(phenyl)phosphinic acid or about 94.3% was obtained. Essentially no hydrogen chloride was evolved. The bulk density of the dried solid was analyzed and was about 0.504 g/cc.
94.3%
Example 2 Control Deionized water, 476 g. (26.4 moles), was charged to a reactor purged with a continuous flow of nitrogen and the off gases collected. At ambient temperature, addition of 419 grams of the acrylation intermediates mixture from Example 1 was begun. The moles of water added per mole of dichlorophenylphosphine charged to prepare the 419 g of acrylation intermediate used was 16.5:1. The exothermic nature of the reaction raised the temperature to 85-90 C. as the addition proceeded. Some solids appeared during the reaction which dissolved as the temperature increased. When the addition was completed, the reaction temperature was raised to 90-95 C. and 4-6 grams of 30% hydrogen peroxide were added to destroy any P4 which may have been present from the original dichlorophenylphosphine. The batch was maintained briefly at 90-95 C. and then cooled to about 76 C. where seed crystals were added. After about 10-15 minutes, cooling was resumed until a temperature of 5 C. was reached. The slurry was held at this temperature for 15-30 minutes and then the solid 2-carboxyethyl(phenyl)phosphinic acid was filtered off and washed with a total of 476 grams of cold deionized water. The wet cake was dried and a yield of 323.8 grams of 2-carboxyethyl(phenyl)phosphinic acid or 94.3% was obtained. No hydrogen chloride was removed and collected in this example. The bulk density of the dried solid was 0.504 g/cc.
94.9%
EXAMPLE I In a reactor were placed 895 g (5 moles) of phenylphosphonous dichloride, which was then heated at 80 C. with agitating. 396 g (5.5 moles) of acrylic acid were dropwise added while the reactor was maintained at a temperature of 80~100 C. under a pressure of 1.1 atm. Afer completion of the addition of acrylic acid, the reaction mixture was allowed to stand for 1 hour at 80 C. and then cooled to room temperature. In 1,000 ml of water, the resulting reaction mixture was dropwise added and subjected to hydrolysis at 80 C., after which the temperature was cooled to near 10 C. to obtained precipitates. After being allowed to stand at 10 C. for 1 hour, the slurry containing the precipitates was filtered, washed and dried in a vacuum dryer to produce 1,015 g of 3-(hydroxyphenylphosphinyl)-propanoic acid. Yield 94.9%.
94.2%
EXAMPLE 1 A 3-l four neck flask having a Dimroth condenser and a thermometer was charged with 1252.9 g (7.0 moles) of dichloro(phenyl)phosphine and 8.0 g (0.041 mole) of t-butyl peroxybenzoate, and heated under stirring to raise the liquid temperature to 55 C. Then, 504.4 g (7.0 moles) of acrylic acid was added dropwise to the mixture in one hour. To prevent heat from being generated during the dropwise addition, the reaction product was cooled with water to maintain the liquid temperature at 65 to 70 C. After the dropwise addition, the reaction was further continued at the same temperature for 2 hours. After completion of the reaction, 2.3 l of water was gradually added to the reaction product with the liquid temperature maintained at 50 C. To prevent heat from being generated during this addition, the reaction product was cooled with ice water to maintain the liquid temperature at 60 to 70 C. After the addition, the reaction product was continuously stirred at the same temperature for one hour. After the liquid temperature was cooled to 10 C., the reaction product was filtered off and the resulting crystal was washed with water and then dried by a vacuum oven (60 C.) to obtain 1412.2 g of 3-[hydroxy(phenyl)phosphinyl]propionic acid in the form of a white crystal (yield: 94.2%).
94.9%
EXAMPLE I In a reactor were placed 895g (5 moles) of phenylphosphonous dichloride, which was then heated at 80 C with agitating. 396g (5.5 moles) of acrylic acid were dropwise added while the reactor was maintained at a temperature of 80~100 C under a pressure of 1.1 atm. Afer completion of the addition of acrylic acid, the reaction mixture was allowed to stand for 1 hour at 80 C and thencooled to room temperature. In 1,000 ml of water, the resulting reaction mixture was dropwise added and subjected to hydrolysis at 80 C, after which the temperature was cooled to near 10 C to obtained precipitates. After being allowed to stand at 10 C for 1 hour, the slurry containing the precipitates was filtered, washed and dried in a vacuum dryer to produce 1,015 g of 3-(hydroxyphenylphosphinyl)-propanoic acid. Yield 94.9 %.
94.9%
COMPARATIVE EXAMPLE I In a reactor were placed 895g (5 moles) of phenylphosphonous dichloride, which was then heated at 80 C with stirring. 346g (5.5 moles) of acrylic acid were dropwise added while the reactor was maintained at a temperature of 80-100 C under atmospheric pressure. Afer completion of the addition of acrylic acid, the reaction mixture was allowed to stand for 1 hour at 80 C and then cooled to room temperature. In 1,000 ml of water, the resulting reaction mixture was dropwise added and subjected to hydrolysis at 80 C, after which the temperature was cooled to near 10 C to obtaine precipitates. After being allowed to stand at 10 C for 1 hour, the slurry containing the precipitates was filtered, washed and dried in a vacuum dryer to produce 1,015 g of 3-(hydroxyphenylphosphinyl) -propanoic acid. Yield 94.9 %.
93.2%
Example 4 Deionized water, 119 grams (6.61 moles), was charged to a reactor purged with a continuous flow of nitrogen and the off gases collected. At ambient temperature, addition of 419 grams of the acrylation intermediates mixture from Example 1 was begun. The moles of water added per mole of dichlorophenylphosphine charged to prepare the 419 g of acrylation intermediate used was 4.1: 1. The exothermic nature of the reaction raised the temperature to 85-90 C. as the addition proceeded. Some solids appeared during the reaction which dissolved as the temperature increased. When the addition was completed, the reaction temperature was raised to 90-95 C. and an additional 357 grams of deionized water (19.83 moles) were added while maintaining temperature. Finally, 4-6 grams of 30% hydrogen peroxide were added to destroy any P4 which may have been present from the original dichlorophenylphosphine. The batch was maintained briefly at 90-95 C. and then cooled to about 76 C. where seed crystals were added. After about 10-15 minutes, cooling was resumed until a temperature of 5 C. was reached. The slurry was held at this temperature for 15-30 minutes and then the solid 2-carboxyethyl(phenyl)phosphinic acid was filtered off and washed with a total of 476 grams of cold deionized water. The wet cake is dried and a yield of 319.2 grams of 2-carboxyethyl(phenyl)phosphinic acid or 93.2% was obtained.
93.0%
EXAMPLE 10 A 200-ml four neck flask having a Dimroth condenser and a thermometer was charged with 39.3 g (0.30 mole) of dichloro(ethyl)phosphine and 0.35 g (1.8* 10-3 moles) of t-butyl peroxybenzoate, while carbonic acid gas was blown into the flask. Under stirring, the resulting mixture was heated to maintain the liquid temperature at 55 C. Then, 22.7 g (0.315 mole) of acrylic acid was added dropwise to the mixture. The reaction was carried out at 60 C. for 3 hours. After the reaction, the liquid temperature was lowered to 50 C, and 60 g of water was gradually added to the reaction product. To prevent heat from being generated, the reaction product was cooled with ice water to maintain the liquid temperature at 60 to 70 C. After the dropwise addition, the reaction product was continuously stirred at the same temperature for 1 hour. After the liquid temperature was cooled to 10 C., the reaction product was filtered off and dried by a vacuum oven (60 C.), thereby to obtain 42.4 g of 3-[hydroxy(phenyl)phosphinyl]propionic acid in the form of a white crystal (yield: 93.0%).
93.6%
EXAMPLE 7 The reaction was carried out in the same manner as in Example 5 except for the use of 480 g (15.0 moles) of methanol instead of n-butanol. Then, 873 g of water was added to the resulting reaction product (methyl ester) in its entirety. The liquid temperature was raised to 100 C., and the reaction was continued for 5 hours while distilling water and methanol away and while replenishing the same amount of distilled water through a dropping funnel. The reaction product was allowed to stand overnight, and then filtered off. The resulting crystal was washed with water and dried by a vacuum oven (60 C.), thereby to obtain 1002.3 g of 3-[hydroxy(phenyl)phosphinyl]propionic acid in the form of a white crystal (yield: 93.6%).
Example 3 Deionized water, 214 grams (11.89 moles) was charged to a reactor purged with a continuous flow of nitrogen and the off gases collected. At ambient temperature, addition of 419 grams of the acrylation intermediates mixture from Example 1 was begun. The moles of water added per mole of dichlorophenylphosphine charged to prepare the 419 g of acrylation intermediate used was 7.4:1. The exothermic nature of the reaction raised the temperature to 85-90 C. as the addition proceeded. Some solids appeared during the reaction which dissolved as the temperature increased. When the addition was completed, the reaction temperature was raised to 90-95 C. and an additional 262 grams of deionized water (14.56 moles) were added while maintaining temperature. Finally, 4-6 grams of 30% hydrogen peroxide were added to destroy any P4 which may have been present from the original dichlorophenylphosphine. The batch was maintained briefly at 90-95 C. and then cooled to about 76 C. where seed crystals were added. After about 10-15 minutes, cooling is resumed until a temperature of 5 C. is reached. The slurry was held at this temperature for 15-30 minutes and then the solid 2-carboxyethyl(phenyl)-phosphinic acid was filtered off and washed with a total of 476 grams of cold deionized water. The wet cake is dried and a yield of 318.6 grams of 2-carboxyethyl(phenyl)phosphinic acid or 93.% is obtained.
Example 5 Deionized water, 58 grams (3.22 moles), was charged to a reactor purged with a continuous flow of nitrogen and the off gases collected. The water was heated to 70-75 C. At this temperature, addition of 419 grams of the acrylation intermediates mixture from Example 1 was begun. The moles of water added per mole of dichlorophenylphosphine charged to prepare the 419 g of acrylation intermediate used was 2.01:1. The exothermic nature of the reaction raised the temperature to 90-95 C. as the addition proceeded. The water was preheated in this example because the solids which appear during the reaction can cause agitation problems until they dissolve as the temperature increases. The reaction can be initiated at ambient if care is taken to allow for the solids. When the addition was complete, the reaction temperature was raised to 125-130 C., held briefly at this temperature, and then an additional 418 grams of deionized water (23.22 moles) were added. The temperature was allowed to lower to 90-95 C. during this addition and was maintained at 90-95 C. until the addition was completed. Finally, 4-6 grams of 30% hydrogen peroxide were added to destroy any P4 which may have been present from the original dichlorophenylphosphine. The batch is maintained briefly at 90-95 C. and then cooled to about 76 C. where seed crystals were added. After about 10-15 minutes, cooling was resumed until a temperature of 5 C. is reached. The slurry was held at this temperature for 15-30 minutes and then the solid 2-carboxyethyl(phenyl)-phosphinic acid was filtered off and washed with a total of 476 grams of cold deionized water. The wet cake was dried and a yield of 318.5 grams of 2-carboxy-ethyl(phenyl)phosphinic acid or 93% is obtained.
5
[ 644-97-3 ]
μ.μ-bis-diphenylacetylene-bis-<tricarbonyl iron (<i>Fe</i>-<i>Fe</i>)[ No CAS ]
A process for the production of 2-carboxyethylphenylphosphinic acid in accordance with the present invention without waste water,Next:(1) 1.0 mol of phenylphosphine dichloride was charged into a reaction vessel, stirred, heated to 80 C, 1 mol of acrylic acid was added dropwise,Finished warming to 110 deg C , heat 3 hours, cooling to 50 deg C ; (2) To the liquid obtained in the step (1), 2.0 mol of dichloropropane (secondary used mother liquor,Material complement), stirring;(3) to the step (2) to slowly drop 1.0mol of water, acid chloride intermediates and water hydrolysis reaction, drop finishedHeating to 90 DEG C, keeping for 3 hours, cooling to 20 DEG C to produce 2-carboxyethylphenylphosphinic acid, and recovering by-product hydrochloric acid.(4) The solid-liquid mixture obtained in step (3) was filtered, washed with dichloropropane, filtered again, placed in an oven,Baking at 130 C for 2 hours to obtain 2-carboxyethylphenylphosphinic acid, and the mother liquor was recovered in the next batch. The yield of 2-carboxyethylphenylphosphinic acid was 98.0%, the melting point was 160.2 deg C , the acid value (mgKOH / g) was 522, the phosphorus content was 14.35%, and the product quality was excellent.
96.8%
With acetic anhydride;
EXAMPLE 8 A 3-l four neck flask having a Dimroth condenser and a thermometer was charged with 895.0 g (5.0 moles) of dichloro(phenyl)phosphine, and heated under stirring to raise the liquid temperature to 55 C. Then, 367.5 g (5.1 moles) of acrylic acid was added dropwise to the mixture. To prevent heat from being generated, the reaction product was cooled with water to maintain the liquid temperature at 65 to 70 C. After the dropwise addition, the reaction was further continued at 70 to 75 C. for 2 hours. With the liquid temperature lowered to 25 C., 510.0 g (5.0 moles) of acetic anhydride was added to the reaction product. After the reaction was carried out at 55 C. for 5 hours, the reaction product was distilled at the same temperature under reduced pressure to distill away acetyl chloride as a by-product and the residual acetic anhydride, thereby to obtain 948.7 g of 3-[hydroxy(phenyl)phosphinyl]propionic acid in the form of a cyclic anhydride (yield: 96.8%).
94.2%
Comparative Example II A procedure was carried out following Example I except that 895 g (5 moles) of phenylphosphonous dichloride were placed in the reactor, heated to 80 C. with agitating, and dropwise added with 386 g (5.35 moles) of acrylic acid while maintaining a reaction temperature at 80~100 C. under 1 atm, after which the reaction mixture was heated up to 130 C., allowed to stand for 1 hour, and cooled to room temperature, to produce 1,008 g of 3-(hydroxyphenylphosphinyl)-propanoic acid. Yield 94.2%.
94.2%
COMPARATIVE EXAMPLE II A procedure was carried out following Example I except that 895 g (5 moles) of phenylphosphonous dichloride were placed in the reactor, heated to 80 C with agitating, and dropwise added with 386 g (5.35 moles) of acrylic acid while maintaining a reaction temperature at 80~100 C under 1 atm, after which the reaction mixture was heated up to 130 C, allowed to stand for 1 hour, and cooled to room temperature, to produce 1,008 g of 3-(hydroxyphenylphosphinyl)-propanoic acid. Yield 94.2 %.
94.2%
COMPARATIVE EXAMPLE II A procedure was carried out following Example I except that 895 g (5 moles) of phenylphosphonous dichloride were placed in the reactor, heated to 80 C with stirring, anddropwise added with 386 g (5.35 moles) of acrylic acid while maintaining a reaction temperature at 80-100 C under 1 atm, after which the reaction mixture was heated up to 130 C, allowed to stand for 1 hour, and cooled to room temperature, to produce 1,008 g of 3-(hydroxyphenylphosphinyl)-propanoic acid. Yield 94.2 %.
93.6%
With 2,2'-azobis(isobutyronitrile); In water;
EXAMPLE 4 A 3-l four neck flask having a Dimroth condenser and a thermometer was charged with 1252.9 g (7.0 moles) of dichloro(phenyl)phosphine and 8.3 g (0.0506 mole) of azobisisobutyronitrile, and heated under stirring to raise the liquid temperature to 75 C. Then, 514.7 g (7.0 moles) of acrylic acid was added dropwise to the mixture in one hour. During such dropwise addition, heat was gradually generated, but the liquid temperature was maintained at 85 to 90 C. After the dropwise addition, the reaction was further continued at 90 C. for 6 hours. After completion of the reaction, 2.3 lof water was gradually added to the reaction product with the liquid temperature maintained at 50 C. To prevent heat from being generated during this addition, the reaction product was cooled with ice water to maintain the liquid temperature at 60 to 70 C. After the addition, the reaction product was continuously stirred at the same temperature for one hour. After the liquid temperature was cooled to 10 C., the reaction product was filtered off and the resulting crystal was washed with water and then dried by a vacuum oven (60 C.), thereby to obtain 1403.2 g of 3-[hydroxy(phenyl)phosphinyl]propionic acid in the form of a white crystal (yield: 93.6%).
85.4%
Comparative Example I The same procedure as in Example I was repeated except that 895 g (5 moles) of phenylphosphonous dichloride were placed in the reactor, heated to 80 C. with agitating, and dropwise added with 468 g(6.5 moles) of acrylic acid while maintaining a reaction temperature at 80~100 C. under 1 atm, to produce 998 g of 3-(hydroxyphenylphosphinyl)-propanoic acid. Yield 85.4%.
85.4%
COMPARATIVE EXAMPLE I The same procedure as in Example I was repeated except that 895 g (5 moles) of phenylphosphonous dichloride were placed in the reactor, heated to 80 C with agitating, and dropwise added with 468 g(6.5 moles) of acrylic acid while maintaining a reaction temperature at 80~100 C under 1 atm, to produce 998 g of 3-(hydroxyphenylphosphinyl)-propanoic acid. Yield 85.4 %.
EXAMPLE 6 A 3-l four neck flask having a Liebig condenser and a thermometer was charged with 1142.3 g (3.5 moles) of butyl 3-[butoxy(phenyl)phosphinyl]propionate obtained in Example 5, and under stirring, 530 g of water and a sulfuric-acid aqueous solution containing 5.7 g of sulfuric acid dissolved in 100 g of water were added. The resulting mixture was heated to raise the liquid temperature to 100 C. The reaction was continued for 6 hours while distilling water and butanol away and while replenishing the same amount of distilled water through a dropping funnel. The reaction product was allowed to stand overnight, and then filtered off. The resulting crystal was washed with water and dried by a vacuum oven (60 C.), thereby to obtain 728.6 g of 3-[hydroxy(phenyl)phosphinyl]propionic acid in the form of a white crystal (yield: 97.2%).
Comparative Example 3 In 500 ml of water at 80 C. was dissolved 149.8 g of the rinse-purified 3-[hydroxy(phenyl)phosphinyl]propionic acid obtained in Comparative Example 2 to prepare an aqueous solution. This aqueous solution was cooled to 10 C. and the resulting crystals were harvested by filtration, rinsed with water, and dried in a vacuum dryer at 60 C. to provide 111.3 g of a recrystallization-purified 3-?hydroxy(phenyl)[phosphinyl]propionic acid.
11
hydroxyethyl 3-[hydroxy(phenyl)phosphinyl]propionate[ No CAS ]
[ 14657-64-8 ]
Yield
Reaction Conditions
Operation in experiment
Reference Example 1 Except that the recrystallization-purified 3-[hydroxy(phenyl)phosphinyl]propionic acid obtained in Comparative Example 3 was used in lieu of the rinse-purified 3-[hydroxy(phenyl)phosphinyl]propionic acid, the procedure of Comparative Example 4 was repeated to provide 102.81 g of an ethylene glycol solution of hydroxyethyl 3-[hydroxy(phenyl)phosphinyl]propionate. In addition, using 13 parts of this ethylene glycol solution of hydroxyethyl 3-[hydroxy(phenyl)phosphinyl]propionate, the procedure of Example 7 was repeated to provide 63 parts of polyester resin (P-4). This polyester resin (P-4) was colorless and transparent and showed a Tg of 52 C.
With sodium hydroxide; In water; at 20℃; for 0.166667h;
General procedure: A mixture of NaOH (0.15 mmol) with Ph-PO2H-C2H4-COOH (0.30 mmol) in 4 mL distilled water was stirred for 10 min and then stood at room temperature, colorless block-shaped crystals of 1 were obtained after 2 days later, in an approximately 66% yieldbased on Na. Anal. Calcd. for C9H10.5O4P1Na0.5: C 48.01, H 4.70%. Found: C 47.94, H 4.83%. IR data (KBr, cm-1): 3422(s), 3070(m), 2913(m), 2439(m), 1898(m), 1685(s), 1645(s), 1438(m), 1340(m), 1298(m), 1265(m), 1135(s), 1038(s), 997(s), 958(m), 859(m), 812(m), 754(m), 728(m), 696(m), 618(m), 531(s).
With potassium hydroxide; In water; at 20℃; for 0.166667h;
General procedure: A mixture of NaOH (0.15 mmol) with Ph-PO2H-C2H4-COOH (0.30 mmol) in 4 mL distilled water was stirred for 10 min and then stood at room temperature, colorless block-shaped crystals of 1 were obtained after 2 days later, in an approximately 66% yieldbased on Na. Anal. Calcd. for C9H10.5O4P1Na0.5: C 48.01, H 4.70%. Found: C 47.94, H 4.83%. IR data (KBr, cm-1): 3422(s), 3070(m), 2913(m), 2439(m), 1898(m), 1685(s), 1645(s), 1438(m), 1340(m), 1298(m), 1265(m), 1135(s), 1038(s), 997(s), 958(m), 859(m), 812(m), 754(m), 728(m), 696(m), 618(m), 531(s).
A mixture of Cu(CH3CO2)2·H2O (0.30 mmol) with H2L (0.35 mmol) and phen (0.30 mmol) in 15 mL distilled water was evaporated in air at ca. 80-90 C until green plate-shaped crystals precipitated. These crystals were collected in approximately 78% yield based on Cu, and the final pH value of the solution was ?4. Anal. Calc. for C21H25N2O8P1Cu1 (Mr = 527.94): C, 47.77; H, 4.77; N, 5.31. Found: C, 44.81; H, 4.68; N, 5.35%. IR data (KBr, cm-1): 3334(s), 3060(m), 2921(m), 1560(s), 1512(m), 1425(s), 1383(m), 1297(m), 1155(s), 1137(m), 1045(s), 1028(m), 949(m), 854(m), 802(m), 723(m), 700(m), 648(m), 538(m), 523(m).
A mixture of Cd(CH3CO2)2·2H2O (0.30 mmol) with H2L (0.30 mmol) and phen (0.30 mmol) in 15 mL distilled water was evaporated in air at ca. 80-90 C until colorless plate-shaped crystals precipitated. These crystals were collected in approximately 72% yield based on Cd, and the final pH value of the solution was ?5. Anal. Calc. for C63H64N6O18.5P3Cd3 (Mr = 1631.31): C, 46.38; H, 3.95; N, 5.15. Found: C, 46.29; H, 4.09; N, 5.07%. IR data (KBr, cm-1): 3524(m), 3377(m), 3070(s), 2916(m), 1621(m), 1564(s), 1515(m), 1428(s), 1305(m), 1152(s), 1127(s), 1037(m), 1024(m), 939(m), 854(m), 798(m), 730 (m), 697(m), 639(m), 541(m), 520(m).
A mixture of Cd(NO3)2·4H2O (0.30 mmol), H2L (0.30 mmol) and phen (0.40 mmol) in 12 mL distilled water was sealed in a Parr Teflon-lined autoclave (23 mL) and heated at 150 C for 3 days, then the resultant clear yellow solution was left to stand at room temperature. Yellow block-shaped crystals of 5 were obtained 2 days later in ca. 61% yield based on Cd. The final pH value of the solution was ?4. Anal. Calc. for C21H23N2O7P1Cd1 (Mr = 558.78): C, 45.14; H, 4.15; N, 5.01. Found: C, 45.05; H, 4.30; N, 4.92%. IR data (KBr, cm-1): 3408(s), 3048(m), 2967(m), 1633(s), 1581(s), 1425(m), 1348(m), 1309(m), 1144(s), 1309(m), 1273(m), 1221(m), 1144(s), 1126(s), 1039(m), 1022(m), 998(m), 860(s), 730(m), 700(m), 635(m), 540(m).
A mixture of Mn(CH3CO2)2·4H2O (0.30 mmol) with H2L (0.30 mmol) and phen (0.30 mmol) in 10 mL distilled water was stirred for half an hour and then stood at room temperature. Pale yellow brick-shaped crystals of 1 were obtained after one day, in approximately 56% yield based on Mn, and the final pH value of the solution was ?5. Anal. Calc. for C21H23N2O7P1Mn1 (Mr = 501.32): C, 50.31; H, 4.62; N, 5.59. Found: C, 50.25; H, 4.73; N, 5.53%. IR data (KBr, cm-1): 3394(s), 3051(m), 2922(m), 2856(m), 1558(s), 1512(m), 1427(s), 1398(m), 1311(m), 1205(m), 1178(s), 1136(s), 1078(m), 1048(m), 1027(m), 931(m), 852(m), 756(m), 735(m), 638(m), 555(m), 513(m).
A mixture of Mn(CH3CO2)2·4H2O (0.30 mmol), H2L (0.30 mmol), phen (0.30 mmol) and urea (0.30 mmol) in 12 mL of distilled water was sealed in a Parr Teflon-lined autoclave (23 mL) and heated at 110 C for 3 days. The final pH value was ?6 and yellow column-shaped crystals of 2 were collected in ca. 70% yield based on Mn. Anal. Calc. for C21H19N2O5P1Mn1 (Mr = 465.29): C, 54.21; H, 4.12; N, 6.02. Found: C, 54.12; H, 4.21; N, 5.96%. IR data (KBr, cm-1): 3073(s), 2921(m), 1564(s), 1514(m), 1425(s), 1306(m), 1198(m), 1157(s), 1128(m), 1043(s), 1028(m), 937(m), 856(m), 798(m), 735(m), 638(m), 543(m), 521(m).
With urea; In water; at 150℃; for 72h;pH 7;Autoclave;
A mixture of Cd(NO3)2·4H2O (0.30 mmol), H2L (0.30 mmol), phen (0.30 mmol) and urea (0.30 mmol) in 12 mL distilled water was sealed in a Parr Teflon-lined autoclave (23 mL) and heated at 150 C for 3 days. The final pH value was ?7 and pale yellow club-shaped crystals of 4 were obtained in ca. 81% yield based on Cd. Anal. Calc. for C21H17N2O4P1Cd1 (Mr = 504.74): C, 49.97; H, 3.39; N, 5.55. Found: C, 49.85; H, 3.51; N, 5.46%. IR data (KBr, cm-1): 3059(m), 2952(m), 2919(m), 1623(m), 1564(s), 1512(m), 1427(s), 1414(m), 1315(m), 1205(m), 1147(s), 1139(s), 1101(m), 1062(s), 1033(m), 949(m), 862(m), 846(s), 812(s), 752(m), 729(s), 696(m), 636(m), 541(s), 520(m).
A mixture of LiOH (0.30 mmol) with H2L (0.30 mmol) in 5 mL distilled water was evaporated in air at ca. 50 C until colorless column-shaped crystals precipitated. These crystals were collected in approximately 45% yield based on Li. The powder XRD for bulky crystals indicated that the experiment pattern matches well with the simulated one (see ESI, Fig. S1). Anal. Calc. for C9H10O4P1Li1 (Mr = 220.08): C, 49.12; H, 4.58. Found: C, 49.26; H, 4.72%. IR data (KBr, cm-1): 3080(m), 2911(m), 2756(m), 2506(m), 1896(m), 1695(s), 1456(m), 1419(m), 1368(m), 1275(s), 1139(s), 1046(s), 799(m), 753(m), 695(m), 538(s), 489(m). Note: The integral and differential titration curves for the ?H2L-LiOH? system is shown in Fig. S2. We have also tried to prepared the Li(I) carboxylate-phosphinite with the molar ratio of LiOH:H2L = 2:1, but the final product behaved as an amorphous precipitate. Hence, we did not take further investigation on it.
A mixture of Zn(CO3)2 (0.30 mmol) with H2L (0.35 mmol) in 12 mL of distilled water was sealed into a Parr Teflon-lined autoclave (23 mL) and heated at 150 C for 3 days. The final pH value was ?5 and colorless block-shaped crystals of 2 were collected in ca. 78% yield based on Zn. The powder XRD for bulky crystals indicated that the experiment pattern matches well with the simulated one (Fig. S3). Anal. Calc. for C9H9O4P1Zn1 (Mr = 277.50): C, 38.95; H, 3.27. Found: C, 38.80; H, 3.41%. IR data (KBr, cm-1): 3057(m), 2931(m), 2367(m), 1586(s), 1446(m), 1417(m), 1334(m), 1199(s), 1131(m), 1061(s), 953(m), 822(s), 746(m), 696(m), 543(s), 496(m), 458(m).
Into a 1 L flask equipped with a reflux condenser, a thermometer, a stirrer, a dropping funnel, 192.7 g (0.9 mol) of <strong>[14657-64-8]2-carboxyethyl(phenyl)phosphinic acid</strong> and 300 ml of ethanol were put to obtain a solution. Then, 133.4 g (1 .8 mol) of glycidol was dropped into the ethanol solution of 2- carboxyethyl(phenyl)phosphinic acid over 30 min. After the dropping, the reaction was further performed at 50oC for another 8 hours to complete the reaction. After the reaction ended, the flask was connected to a vacuum system to remove ethanol leaving 319.6 g of a colorless, transparent liquid product at a yield of 98%.
Zn(2-carboxyethyl(phenyl)phosphinate)(1,10-phenanthroline)*5H2O[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
60%
With sodium hydroxide; In water; at 150℃; for 73h;pH 5;Autoclave;
Zn(NO3)2·6H2O(0.297 g, 1 mmol), <strong>[14657-64-8]2-carboxyethyl(phenyl)phosphinic acid</strong> (0.214 g,1 mmol) and 1,10-phenanthroline (0.198 g, 1 mmol) were dissolved in distilled water(20 mL). To the above mixture with stirring, an aqueous solution of sodium hydroxide(1 mol·L-1) was added dropwise adjusting the pH value to 5. The mixture was furtherstirred for 1 h, and heated at 150C for 72 h in a 25 mL Teflon-lined stainless steel vessel,followed by slowly cooling down to ambient temperature. The colorless block crystals ofthe complex were collected by filtration, washed with ethanol and dried in air. The yield of product was 60% in weight based on zinc. The ICP-AES and elemental analysis resultsare listed as follows: For C21H27N2O9PZn, Anal. Calc.(%) Zn, 11.87; P, 5.66; C, 46.00;N, 5.11; H, 4.93. Found(%): Zn, 11.98; P, 5.73; C, 46.32; N, 5.36; H, 5.26. IR data (KBr,cm-1): 3431 (O-H), 1728 (C = O), 1609, 1435(Ar-P), 1154 (P = O), 1613(C = C), 1524(C = N), 740(C-H) cm-1. 1H NMR (DMSO) delta13.02 (1H, O-H), 7.71 to 8.32 (5H, Ar-H),3.3 to 4.5 (4H, -CH2CH2-). 31P NMR (DMSO) delta31.4.20
A mixture of Cd(CH3COO)2H2O (0.3 mmol), H2L(0.3 mmol) and phen (0.3 mmol) was dissolved in 10 mLdistilled water at room temperature for 2 days. The final pHvalue was about 5 and colorless plate-like crystals of 2were collected in an approximately 45 % yield based on Cd.
A mixture of CdCl2 (0.3 mmol) and H2L (0.3 mmol) wasdissolved in 8 mL distilled water, then was transferred into the sealed Parr Teflon-lined autoclave (23 mL) and heatedat 150 C for 3 days, colorless rod-shaped crystals of 1were obtained, with an approximate yield of 40 % based onCd. The final pH value was about 2.5.
In water; at 160℃; for 72h;Autoclave; High pressure;
A mixture of CdCl2 2.5H2O (0.2 mmol) with H2L (0.1 mmol) in 8 mL H2Owas stirred at room temperature for half an hour andthen sealed in a 15 mL Teflon-lined stainless steelautoclave and heated at 160C for 3 days. After coolingto room temperature at a rate of 10C h-1, colorlesscrystals of I were obtained in 68% yield based on H2L.IR (KBr; nu, cm-1): 3438, 1662, 1350, 1274, 1201,1040, 799.
With triethylamine; at 160℃; for 72h;pH 5;Autoclave; High pressure;
Synthesis of compound II was carried out by thesimilar method described for I with the same componentsin the same molar ratio. The pH value of thesolution was adjusted to 5.00 by addition of 24 muL triethylamine.Colorless crystals of II were isolated byfiltration and washed by water in 87% yield basedon H2L.IR (KBr; nu, cm-1): 3623, 1408, 1297, 1145, 1124,1031, 951.
With sodium hydroxide; In water; at 50℃; for 40h;pH 3 - 4;
430 g (2 mol) of 3-hydroxyphenylphosphoryl propionic acid (CEPPA), 27 g of aluminum complex of high purity aluminum powder and 1371 ml of water were charged into a reactor equipped with a heating and stirring paddle, With a certain amount of 0. 1mol / L NaOH slowly adjust the pH of the solution between 3-4 , and then slowly warming, heating to 50 C, incubation reaction 40 hours; after the end of the reaction, Cooling down,And the mixture was filtered, washed and dried to obtain 315.67 g of the intermediate product phenylethylphosphinic acid, and the yield was 92.8%.
2-Carboxyethyl phenylphosphinic acid and dihydric alcohol1: 2 molar ratio,Catalyst 4-methylbenzenesulfonate was addedAcid, 2-carboxyethyl phenyl phosphinic acid and the catalyst molar ratio of 1: 0.01, under inert gas argon protection and mechanical stirring under the conditions of melt condensation reaction, the mechanical stirring speed of stirring 440rpm, melt-condensation reaction The temperature is 185 C, the reaction time is 2h, to obtain the end groups containing hydroxyl DADA; 3) The DAPER obtained in step 1) was added to the system in step 2), the molar ratio of DAPER and DADA was 1: 4, keeping the temperature of the system constant, continuously purging with inert gas argon, Under the conditions of melt esterification reaction, the mechanical stirring speed of stirring 400rpm, melt esterification reaction time 4h, the product was collected, crushed, dissolved, filtered, washed and dried in a vacuum oven at 32 C 12h ester Chemicals
[Bi2(μ3-O)(2-carboxyethyl(phenyl)phosphinite)2]n[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
11.7%
With 3-amino-1,2,4-triazole-5-carboxylic acid; In water; at 120℃; for 120h;Autoclave; High pressure;
0.2 mmol, 0.0257 g 3-amino-1H-1,2,4-triazole-5-carboxylic acid,0.2 mmol, 0.0978 g Bi(NO3)3*6H2O, and 0.2 mmol, 0.0429 g H2CEPPA mixed with 15 ml H2O were placed in a crystallization vial placed in a 25 ml Teflon-lined stainless-steel autoclave. The mixture was kept inside the furnace at120C for 5 days, and then naturally cooled to ambient temperature. The colorless platelet crystals of 1 suitable for X-ray diffraction were collected after soak clearing with water and ethanol. Yield based on H2CEPPA: 20.1 mg, 11.7%. IR data (inKBr, cm-1) for 1: 3434(m), 3057(w), 2922(w), 1642(w), 1527(s), 1412(s), 1380(s), 1310(s), 1271(w), 1207(w), 1105(s),1066(w), 1009(s), 939(w), 823(w), 791(w), 753(s), 695(m).
With 1,2,4-Triazole; In water; at 120℃; for 120h;Autoclave; High pressure;
The similar process as that of 1 using 0.2 mmol, 0.0140 g 1H-1,2,4-triazole,0.2 mmol, 0.0428 g H2CEPPA, 0.2 mmol, 0.0618 g Cd(NO3)24H2O in 20 ml H2O produced colorless prism crystals. Yieldbased on H2CEPPA: 9.2 mg, 8.5%. IR data (in KBr, cm-1) for 2: 3440(m), 3069(w), 2916(w), 2846(w), 1873(m), 1662(s),1463(w), 1437(m), 1348(m), 1310(w), 1277(s), 1150(s), 1021(s), 798(m), 753(m), 689(m).
1) Selecting 1 part by mass of 2-carboxyethylphenylphosphinic acid,Adding to 3 parts of aqueous solution, and stirring at 70 C to dissolve into a colorless transparent liquid; 2) Select 3 parts of melamine and add to step 1)a solution of 2-carboxyethylphenylphosphinic acid in a solution which is sufficiently stirred at room temperature to produce a white precipitate which is insoluble in water; 3) Cooling the solution containing the white precipitate in step 2) to room temperature,After vacuum filtration, a solid product CEPPM is obtained; 4) The solid product CEPPM is dried at 80 C, and then dried and dehydrated at 160 C.At 15 minutes, a light yellow new organophosphorus nitrogen flame retardant was obtained with a yield of 93%.
(i) 2-carboxyethylphenylphosphinic acid, After mixing sodium hydroxide and X uniformly, the mixture was stirred at a temperature of 55 C for 0.5 hour. X is ethanol; (ii) dissolving tin tetrachloride in ethanol to obtain a mixed solution. Then added dropwise to the system of step (i), Keep the temperature unchanged, continue to stir for 4 hours, Y is ethanol; (iii) filtration, Washing and drying to obtain tin 2-carboxyethylphenylphosphinate
stannous 2-carboxyethylphenylphosphinate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
(i) 2-carboxyethylphenylphosphinic acid, sodium hydroxide and X were uniformly mixed and stirred at a temperature of 55 C for 1.5 hours, and X was water; (ii) firstly dissolving stannous chloride in Y to obtain a mixed solution, and then adding the mixed solution dropwise to the system of step (i), keeping the temperature constant, stirring is continued for 1.5 hours, and Y is water; (iii) filtering, washing and drying to obtain stannous 2-carboxyethylphenylphosphinate;
stannous 2-carboxyethylphenylphosphinate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
(i) 2-carboxyethylphenylphosphinic acid, sodium hydroxide and X are uniformly mixed and stirred at a temperature of 60 C for 0.5 hours, and X is ethanol; (ii) a solution obtained by dissolving stannous sulfate in Y is added dropwise to the system of step (i), keeping the temperature constant, stirring is continued for 2 hours, and Y is ethanol; (iii) filtering, washing and drying to obtain stannous 2-carboxyethylphenylphosphinate;
In water; at 120℃; for 48h;Autoclave; High pressure;
A mixture of MnSO4 (0.151 g, 1 mmol) and H2L (0.214 g,1 mmol) in distilled water (10 mL) was sealed in a Teflon lined autoclave (15 mL) and heated at 120 C for 2 d; orangecrystals of compound 1 were obtained when the sample wascooled to room temperature. The crystals were recoveredby filtering, washed with distilled water, and dried in air(yield: 82% based on Mn). Elem. Anal. Calcd. (%) forC18H20MnO8P2: C44.92, H4.16. Found (%): C44.96, H4.49.IR (m, cm1) 1664, 1600, 1435, 1409, 1385, 1351, 1275, 1161,1141, 1122, 1037, 1008, 995, 793, 745, 688.
With sodium hydroxide; In ethanol; water; at 140℃; for 48h;pH Ca. 6;Autoclave; High pressure;
A mixture of H2L (214 mg, 1 mmol), Zn(NO3)2 * 6H2O (297 mg, 1 mmol), 4,4'-bipy (156 mg, 1 mmol), ethanol (10 mL) and H2O (10 mL) was adjusted to pH ca. 6.0 with 0.1M NaOH solution and transferred into a Teflon reactor (30 mL), which was heated to 140 C for 2 days, followed by slow cooling (10 C * h-1) to room temperature. Colorless block crystals of compound 1 were collected in a yield of 65%. IR (KBr, nu/cm-1): 1602, 1379, 1322, 1168, 1137, 1046, 1023, 816, 754, 696, 664. Anal. Calcd. for C14H13NO4PZn (355.59): C, 47.28; H, 3.66; N, 3.94. Found: C, 47.36; H, 3.87; N, 4.13%.
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