Method for producing alkenyl phosphorus compound

Abstract

Provided is a method for producing an alkenyl phosphorus compound which can produce an alkenyl phosphorus compound efficiently even with a smaller amount of a catalyst used than that used conventionally, and further which can maintain catalytic activity to produce an alkenyl phosphorus compound in high yield even at a larger reaction scale, and which can also be applied to quantity synthesis at an industrial scale using a conventional batch reactor or continuous reactor. A method for producing an alkenyl phosphorus compound, comprising: a step of reacting a compound represented by the following formula (1): ##STR00001## [In formula (1), R.sup.1 represents OR.sup.3 or R.sup.3, R.sup.2 represents OR.sup.4 or R.sup.4, and R.sup.3 and R.sup.4 represent, for example, each independently a substituted or unsubstituted alkyl group.] with a compound represented by the following formula (2): ##STR00002## [In formula (2), R.sup.5 represents, for example, a hydrogen atom, or a substituted or unsubstituted alkyl group.] to produce the phosphorus alkenyl compound presented by at least any of the following formulas (3a) or (3b): ##STR00003## [In formulas (3a) and (3b), R.sup.1 and R.sup.2 have the same meaning as defined in formula (1), and R.sup.5 has the same meaning as defined in formula (2).], In which the compound represented by formula (1) is reacted with the compound represented by formula (2) using a transition metal catalyst, and a phosphorus oxo acid compound having an intramolecular PH bond.

Claims

1. A method for producing an alkenyl phosphorus compound; comprising reacting a compound represented by formula (1): ##STR00016## wherein R.sup.1 represents OR.sup.3 or R.sup.3, R.sup.2 represents OR.sup.4 or R.sup.4, and R.sup.3 and R.sup.4 each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aryl group, and R.sup.3 and R.sup.4 together may form a ring structure, with a compound represented by formula (2): ##STR00017## wherein R.sup.5 represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, or a substituted or unsubstituted silyl group, to produce an alkenyl phosphorus compound represented by at least one formula represented by (3a) or (3b): ##STR00018## wherein R.sup.1 and R.sup.2 the same meaning as defined in formula (1), and R.sup.5 has the same meaning as defined in formula (2), wherein the compound represented by the formula (1) and the compound represented by the formula (2) are reacted using a transition metal catalyst, and a phosphorus oxo acid compound having an intramolecular PH bond.

2. The production method according to claim 1, wherein the phosphorus oxo acid compound is a compound represented by formula (4): ##STR00019## wherein R.sup.6 represents a hydrogen atom, a hydroxyl group, OR.sup.7, or R.sup.7, and R.sup.7 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aryl group.

3. The production method according to claim 1, wherein the phosphorus oxo acid compound is obtained by hydrolyzing a compound represented by Formula (5): ##STR00020## wherein R.sup.8 represents a hydrogen atom, a hydroxyl group, OR.sup.10, or R.sup.10, and R.sup.9 and R.sup.10 each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or substituted aralkyl group, a substituted or substituted aryl group, and when R.sup.8 is OR.sup.10 or R.sup.10, R.sup.9 and R.sup.10 together may form a ring structure.

4. The production method according to claim 3, comprising applying hydrolysis treatment to the compound represented by formula (5), and using the obtained hydrolysis product as the phosphorus oxo acid compound.

5. The production method according to claim 1, wherein the transition metal catalyst is a nickel catalyst.

6. A method for producing an alkenyl phosphorus compound, comprising: applying hydrolysis treatment to a compound represented by formula (1), excluding compounds in which R.sup.1 is R.sup.3, and R.sup.2 is R.sup.4: ##STR00021## wherein R.sup.1 represents OR.sup.3 or R.sup.3, R.sup.2 represents OR.sup.4 or R.sup.4, and R.sup.3 and R.sup.4 each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aryl group, and R.sup.3 and R.sup.4 together may form a ring structure, and contacting a hydrolysis product obtained by the hydrolysis treatment with a compound represented by formula (2): ##STR00022## wherein R.sup.5 represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted, or unsubstituted heteroaryl group, substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, or a substituted or unsubstituted silyl group, and a transition metal catalyst, to produce an alkenyl phosphorus compound represented by at least one formula represented by (3a) or (3b): ##STR00023## wherein R.sup.1 and R.sup.2 have the same meaning as defined in formula (1), and R.sup.5 has the same meaning as defined in formula (2).

7. The production method according to claim 6, wherein the hydrolysis product comprises the compound represented by formula (1), excluding a compound in which is R.sup.1 is R.sup.3, and R.sup.2 is R.sup.4, and a compound represented by formula (6): ##STR00024## wherein R.sup.11 represents a hydroxyl group, OR.sup.12 represents R.sup.12, and R.sup.12 presents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aryl group.

8. The production method according to claim 6, wherein the transition metal catalyst is a nickel catalyst.

Description

EXAMPLES

(1) The present invention is described below in detail with reference to Examples, but the present invention is not limited to the following Examples.

(2) In Examples, acid concentration is measured by neutralization titration using a solution of 0.1 mol/L of potassium hydroxide in ethanol, and whether absorption of acetylene occurs or not is confirmed by changes in the internal pressure of the reactor and flow rate of acetylene.

(3) As a nickel catalyst, A: tetrakis(trimethylphosphine)nickel, B: bis(trimethylphosphine) Nickel (II) hydridophosphate, or C: tetrakis (tributylphosphine) nickel is used.

Reference Example 1: Hydrolysis Example of Dimethyl Phosphonate (1)

(4) To 1000 parts by mass of dimethyl phosphonate A (manufactured by SINOCHEM (China), purity of 99.08%, acid concentration of 0.13 mmol/g), 3.2 parts by mass of ion, exchanged water (2.0 mol % relative to dimethyl phosphonate) was added, and a reaction was performed at room temperature for 96 hours to hydrolyze. An acid concentration of the obtained hydrolysis product A was 0.52 mmol/g. Then, the hydrolysis product A was used as it was in the following Examples 1 and 2.

Reference Example 2: Hydrolysis Example of Dimethyl Phosphonate (2)

(5) To 1000 parts by mass of dimethyl phosphonate (manufactured by SINOCHEM (China) purity of 99.12%, acid concentration of 0.05 mmol/g), 4.9 parts by mass of ion exchanged water (3.0 mol relative to dimethyl phosphonate) was added, and a reaction was performed at 60 C. for 6 hours to hydrolyze. An acid concentration of the obtained hydrolysis product B was 0.58 mmol/g. Then, the hydrolysis product B was used as it was in the following Examples 3 to 5, and 9 to 11.

Reference Example 3: Hydrolysis Example of Dimethyl Phosphonate (3)

(6) The hydrolysis was performed in the same manner as Reference Example 2 except that the amount of ion exchanged water used was 8.1 parts by mass (5.0 mol % relative to dimethyl phosphonate). An acid concentration of the obtained hydrolysis product C was 0.84 mmol/g. Then, the hydrolysis product C was used as it was in the following Examples 6 and 7.

Reference Example 4: Hydrolysis Example of Dimethyl Phosphonate (4)

(7) The hydrolysis was performed in the same manner as Reference Example 2 except that the amount of exchanged water used was 2.4 parts by mass (1.5 mol % relative to dimethyl phosphonate). An acid concentration of the obtained hydrolysis product D was 0.58 mmol/g. Then, the hydrolysis product D was used as it was in the following Example 3.

Example 1: Example for Manufacturing Dimethyl Vinylphosphonate (1)

(8) In a 1 L volume autoclave equipped with an internal thermometer, a pressure gauge, a cooling jacket, an agitator, and a gas inlet tube, 350 g of toluene and 150 g of hydrolysis product A obtained in Reference Example 1 were placed, and the interior of the sys tem was coaled to 0 C. and degassed under reduced pressure.

(9) Then, 0.19 mol %, relative to the unreacted dimethyl phosphonate contained in hydrolysis product A, of nickel catalyst A was added, and the resultant was agitated at a rotation rate of agitating blades of 200 rpm for 15 minutes.

(10) Acetylene was fed into the reaction system at a feed pressure of 0.02 MPa, and the temperature and agitation conditions were kept to proceed a reaction until an absorption of acetylene disappeared. The reaction was performed for 5.5 hours to obtain a desired dimethyl vinylphosphonate at a conversion ratio of 89.5%, and selectivity of 93.9%.

Example 2: Example for Manufacturing Dimethyl Vinylphosphonate (2)

(11) A reaction was performed in the same manner as Example 1 except that the rotation rate of agitating blades was 400 rpm. The reaction was per formed for 4 hours to obtain a desired dimethyl vinylphosphonate at a conversion ratio of 84.7%, and selectivity of 92.9%.

Example 3: Example for Manufacturing Dimethyl Vinylphosphonate (3)

(12) In a 1 L volume autoclave equipped with an internal thermometer, a pressure gauge, a cooling jacket, an agitator, and a gas inlet tube, 75 g of hydrolysis product B obtained in Reference Example 2, 75 g of dimethyl phosphonate B (manufactured by SINOCHEM (China), purity of 99.12%, acid concentration of 0.05 mmol/g), and 350 g of toluene were placed, and the interior of the system was cooled to 0 C. and degassed under reduced pressure.

(13) Then, 0.19 mol %, relative to dimethyl phosphonate, of nickel catalyst B was added, and the resultant was agitated at a rotation rate of agitating blades of 400 rpm for 15 minutes.

(14) Acetylene was fed into the reaction system at a feed pressure of 0.02 MPa, and the temperature and agitation conditions were kept to proceed a reaction until an absorption of acetylene disappeared. The reaction was performed for 3 hours to obtain a desired dimethyl vinylphosphonate at a conversion ratio of 78.8%, and selectivity of 95.2%.

Example 4: Example for Manufacturing Dimethyl Vinylphosphonate (4)

(15) In a 600 L volume reaction tank equipped with an internal thermometer, a pressure gauge, a cooling jacket, an agitator, and a gas inlet tube, 63 kg of hydrolysis product B obtained in Reference Example 2, 63 kg of dimethyl phosphonate B (manufactured by SINOCHEM (China), purity of 99.12%, acid concentration of 0.05 mmol/g), and 249 kg of toluene were introduced, and the interior of the system was regulated at 5 C. 5 C. and degassed under reduced pressure.

(16) Then, 0.9mol %, relative to dimethyl phosphonate, of nickel catalyst A was added, and the resultant was agitated at a rotation rate of agitating blades of 150 rpm for 15 minutes.

(17) Acetylene was fed into the reaction system at a feed pressure of 0.02 MPa, and the temperature and agitation conditions were kept to proceed a reaction until an absorption of acetylene disappeared. The reaction was performed for 6.6 hours to obtain a desired dimethyl vinylphosphonate at a conversion ratio of 76.6%, and selectivity of 95.5% (yield: 114 kg).

Example 5: Example for Manufacturing Dimethyl Vinylphosphonate (5)

(18) In a 1200 L volume reaction tank equipped with an internal thermometer, a pressure gauge, a cooling jacket, an agitator, and a gas inlet tube, 120 kg of hydrolysis product B obtained in Reference Example 2, 120 kg of dimethyl phosphonate B (manufactured by SINOCHEM (China), purity of 99.12%, acid concentration of 0.05 mmol/g) and 560 kg of toluene were introduced, and the interior of the system was regulated at 5 C. 5 C. and degassed under reduced pressure.

(19) Then, 0.19 mol %, relative to dimethyl phosphonate, of nickel catalyst A was added, and the resultant was agitated at a rotation rate of agitating blades of 150 rpm for 15 minutes.

(20) Acetylene was fed into the reaction system at a feed pressure of 0.02 MPa, and the temperature and agitation conditions were kept to proceed a reaction until an absorption of acetylene disappeared. The reaction as performed for 8 hours to obtain a desired dimethyl vinylphosphonate at a conversion ratio of 71.4%, and selectivity of 93.0% (yield: 197 kg)

Example 6: Example for Manufacturing Dimethyl Vinylphosphonate (6)

(21) In a 1 L volume autoclave equipped with an internal thermometer, a pressure gauge, a cooling jacket, an agitator, and a gas inlet tube, 40 g of hydrolysis product C obtained in Reference Example 3, 110 g of dimethyl phosphonate B (manufactured by SINOCHEM (China), purity of 99.12%, acid concentration of 0.05 mmol/g), and 350 g of toluene were placed, and the interior of the system was cooled to 0 C. and degassed under reduced pressure.

(22) Then, 0.19 mol %, relative to dimethyl phosphonate, of nickel catalyst A was added, and the resultant was agitated at a rotation rate of agitating blades of 400 rpm for 15 minutes.

(23) Acetylene Baas fed into the reaction system at a feed pressure of 0.02 MPa, and the temperature and agitation conditions were kept to proceed a reaction until an absorption of acetylene disappeared. The reaction was performed for 4 hours to obtain a desired dimethyl vinylphosphonate at a conversion ratio of 81.1%, and selectivity of 96.0%.

Example 7: Example for Manufacturing Dimethyl Vinylphosphonate (7)

(24) In a 1 L volume autoclave equipped with an internal thermometer, a pressure gauge, a cooling jacket, an agitator, and a gas inlet tube, 90 g of hydrolysis product C obtained in Reference Example 3, 60 g of dimethyl phosphonate B (manufactured by SINOCHEM (China), purity of 99.12%, acid concentration of 0.05 mmol/g), and 350 g of toluene were placed, and the interior of the system was cooled to 0 C. and degassed under reduced pressure.

(25) Then, 0.19 mol %, relative to dimethyl phosphonate, of nickel catalyst A was added, and the resultant was agitated at a rotation rate of agitating blades of 400 rpm for 15 minutes.

(26) Acetylene was fed into the reaction system at a feed pressure of 0.02 MPa, and the temperature and agitation conditions were kept to proceed a reaction until an absorption of acetylene disappeared. The reaction was performed for 4 hours to obtain a desired dimethyl vinylphosphonate at a conversion ratio of 73.2%, and selectivity of 93.8%.

Example 8: Example for Manufacturing Dimethyl Vinylphosphonate (8)

(27) A reaction was performed in the same manner as Example 2 except that 150 g of hydrolysis product D obtained in Reference Example 4 was used instead of hydrolysis product A, and nickel catalyst C was used instead of nickel catalyst A. The reaction was performed for 4 hours to obtain a desired dimethyl vinylphosphonate at a conversion ratio of 79.7%, and selectivity of 95.4%.

Example 9: Example for Manufacturing Dimethyl Vinylphosphonate (9)

(28) In a 1 L volume autoclave equipped with an internal thermometer, a pressure gauge, a cooling jacket, an agitator, and a gas inlet tube, 42 g of a hydrolysis product B obtained in Reference Example 2, 208 g of dimethyl phosphonate A (manufactured by SINOCHEM (China), purity of 99.08%, acid concentration of 0.13 mmol/g), and 250 g of toluene were placed, and the interior of the system was cooled to 0 C. and degassed under reduced pressure.

(29) Then, 0.10 mol %, relative to dimethyl phosphonate, of a nickel catalyst A was added, and the resultant was agitated at a rotation rate of agitating blades of 400 rpm for 15 minutes.

(30) Acetylene was fed into the reaction system at a feed pressure of 0.02 MPa, and the temperature and agitation conditions were kept to proceed a reaction until an absorption of acetylene disappeared. The reaction was performed for 4 hours to obtain a desired dimethyl vinylphosphonate at a conversion ratio of 64.1%, and selectivity of 95.8%.

Example 10: Example for Manufacturing Dimethyl Vinylphosphonate (10)

(31) A reaction was performed in the same manner as Example 9 except that an amount of a nickel catalyst A used was 0.19 mol % a relative to dimethyl phosphonate. A reaction was performed for 6 hours to obtain a desired dimethyl vinylphosphonate at a conversion ratio of 91.1%, and selectivity of 95.4%.

Example 11 Example for Manufacturing Dimethyl Vinylphosphonate (11)

(32) In a 1 L volume autoclave equipped with an internal thermometer, a pressure gauge, a cooling jacket, an agitator, and a gas inlet tube, 35 g of a hydrolysis product B obtained in Reference Example 2, 315 g of dimethyl phosphonate A (manufactured by SINOCHEM (China), purity of 99.08%, acid concentration of 0.13 mmol/g), and 150 g of toluene were placed, and the interior of the system was cooled to 0 C. and degassed under reduced pressure.

(33) Then, 0.10 mol %, relative to dimethyl phosphonate, of a nickel catalyst A was added, and the resultant was agitated at a rotation rate of agitating blades of 400 rpm for 15 minutes.

(34) Acetylene was fed into the reaction system at a feed pressure of 0.02 MPa, and the temperature and agitation conditions were kept to proceed a reaction until an absorption of acetylene disappeared. The reaction was performed for 5 hours to obtain a desired dimethyl vinylphosphonate at a conversion ratio of 65.9%, and selectivity of 94.4%.

Example 12: Example for Manufacturing Dimethyl Vinylphosphonate (12)

(35) In a 1 L volume autoclave equipped with an internal thermometer, a pressure gauge, a cooling jacket, an agitator, and a gas inlet tube, 42 g of a hydrolysis product B obtained in Reference Example 2, and 458 g of dimethyl phosphonate A (manufactured by SINOCHEM (China) purity of 99.08%, acid concentration of 0.13 mol/g) were placed, and the interior of the system was cooled to 0 C. and degassed under reduced pressure.

(36) Then, 0.10 mol %, relative to dimethyl phosphonate, of a nickel catalyst A was added, and the resultant was agitated at a rotation rate of agitating blades of 400 rpm for 15 minutes.

(37) Acetylene was fed into the reaction system at a feed pressure of 0.02 MPa, and the temperature and agitation conditions kept to proceed a reaction until an absorption of acetylene disappeared. The reaction was performed for 6 hours to obtain a desired dimethyl vinylphosphonate at a conversion ratio of 61.8%, and selectivity of 98.5%.

Comparative Example 1: Example for Manufacturing Dimethyl Vinylphosphonate (13)

(38) In a 1 L volume autoclave equipped with an internal thermometer, a pressure gauge, a cooling jacket, an agitator, and a gas inlet tube, 150 g of dimethyl phosphonate B (manufactured by SINOCHEM (China), purity of 99.12%, acid concentration of 0.05 mmol/g) and 350 g of toluene were placed, and the interior of the system was cooled to 0 C. and degassed under reduced pressure.

(39) Then, 0.17 mol %, relative to dimethyl phosphonate, of nickel catalyst A was added, and the resultant was agitated at a rotation rate of agitating blades of 200 rpm for 15 minutes.

(40) Acetylene was fed into the reaction system at a feed pressure of 0.04 mPa, and the temperature and agitation conditions were kept to proceed a reaction until an absorption of acetylene disappeared. The reaction performed for 5 hours to obtain a desired dimethyl vinylphosphonate at a conversion ratio of 27.5%, and selectivity of 85.8%.

(41) Comparative Example 2: Example for Manufacturing Dimethyl Vinylphosphonate (14)

(42) A reaction was performed in the same manner as Comparative Example 1 except that 150 g of dimethyl phosphonate A (manufactured by SINOCHEM (China) purity of 99.08% acid concentration of 0.13 mmol/g) was used instead of dimethyl phosphonate B, and 1.5 g of 85% phosphoric acid aqueous solution (manufactured by KANTO CHEMICAL CO., INC.) was also added when dimethyl phosphonate A was placed. The reaction was performed for 2 hours to obtain a desired di ethyl vinylphosphonate a conversion ratio of 33.2%, and selectivity of 81.3%.

Comparative Example 3: Example for Manufacturing Dimethyl Vinylphosphonate (15)

(43) A reaction was performed in the same manner as Comparative Example 1 except that 1.2 g of phosphoric acid (solid) (manufactured by Sigma-Aldrich, purity of 99%) was also added when dimethyl phosphonate B was placed. The reaction was performed for 2 hours to obtain a desired dimethyl vinylphosphonate at a conversion ratio of 34.8%, and selectivity of 89.5%.

Example 13: Example for Manufacturing Dimethyl Vinylphosphonate (16)

(44) A reaction was performed in the same manner as Comparative Example 1 except that 150 g of dimethyl phosphonate A (manufactured by SINOCHEM (China), purity of 99.08%, acid concentration of 0.13 mmol/g) was used instead of dimethyl phosphonate 3, and 1 g of phosphonic acid (manufactured by Wako Pure Chemical Industries, Ltd., purity of 97%) was also added when dimethyl phosphonate A was placed. The reaction was performed for 5 hours to obtain a desired dimethyl vinylphosphonate at a conversion ratio of 61.6%, and selectivity of 98.1%.

Example 14: Example for Manufacturing Dimethyl Vinylphosphonate (17)

(45) A reaction was performed in the same manner as Example 13 except that feed pressure of acetylene was 0.02 MPa. The reaction was performed for 6 hours to obtain a desired dimethyl vinylphosphonate at a conversion. ratio of 71.2%, and selectivity of 97.6%.

Example 15: Example for Manufacturing Dimethyl Vinylphosphonate (18)

(46) In a 30 L volume autoclave equipped with an internal thermometer, a pressure gauge, a cooling jacket, an agitator, and a gas inlet tube, 4,500 g of dimethyl phosphonate A (manufactured by SINOCHEM (China), purity of 99.08%, acid concentration of 0.13 mmol/g), 30 g of phosphonic acid (manufactured by Wako Pure Chemical Industries, Ltd., purity of 97%), and 10,500 g of toluene were placed, and the interior of the system was cooled to 0 C. and degassed under reduced pressure.

(47) Then, 0.19 mol %, relative to dimethyl phosphonate, of nickel catalyst A was added, and the resultant was agitated at a rotation rate of agitating blades of 200 rpm for 15 minutes.

(48) Acetylene was fed into the reaction system at a feed pressure of 0.02 MPa, and the temperature and agitation conditions were kept to proceed a reaction until an absorption of acetylene disappeared. The reaction was performed for 16 hours to obtain a desired dimethyl vinylphosphonate at a conversion ratio of 66.2%, and selectivity of 95.4%.

(49) TABLE-US-00001 TABLE 1 Example 1 2 3 4 5 6 7 8 Hydrolysis A A B B B C C D product (type) Hydrolysis 150 150 75 63000 120000 40 90 150 product (g) Phosphonic acid (g) Phosphoric acid solution (g) Phosphoric acid (solid) (g) Catalyst A A B A A A A C Catalyst 0.19 0.19 0.19 0.19 0.19 0.19 0.19 0.19 concentration (mol %) Volume (L) 1 1 1 600 1200 1 1 1 Conversion 89.5 84.7 78.8 76.6 71.4 81.1 73.2 79.7 ratio (%) Selectivity 93.9 92.9 95.2 95.5 93.0 96.0 93.8 95.4 (%)

(50) TABLE-US-00002 TABLE 2 Example 9 10 11 12 Hydrolysis product (type) B B B B Hydrolysis product (g) 42 42 35 42 Phosphonic acid (g) Phosphoric acid solution (g) Phosphoric acid (solid) (g) Catalyst A A A A Catalyst concentration 0.10 0.19 0.10 0.10 (mol %) Volume (L) 1 1 1 1 Conversion ratio (%) 64.1 91.1 65.9 61.8 Selectivity (%) 95.8 95.4 94.4 98.5

(51) TABLE-US-00003 TABLE 3 Comparative Example Example 1 2 3 13 14 15 Hydrolysis product (type) Hydrolysis product (g) Phosphonic 1 1 30 acid (g) Phosphoric 1.5 acid solution (g) Phosphoric 1.2 acid (solid) (g) Catalyst A A A A A A Catalyst 0.17 0.17 0.17 0.17 0.17 0.19 concentration (mol %) Volume (L) 1 1 1 1 1 30 Conversion 27.5 33.2 34.8 61.6 71.2 66.2 ratio (%) Selectivity (%) 85.8 81.3 89.5 98.1 97.6 95.4

(52) As shown in Examples 1 to 15, by performing a reaction using a phosphorus oxo acid compound having an intramolecular PH bond, the reaction proceeded at high conversion ratio and/or selectivity (conversion ratio: 61.6 to 91.1%, and selectivity: 92.9 to 98.5%) even when a catalyst was used in half or less of the amount of that used conventionally (about 0.1 to 0.2 mol %), and thus the desired alkenyl phosphorus compound was obtained efficiently. Accordingly, according to the production method of the present invention, an amount of an expensive catalyst used can be reduced, and thus an alkenyl phosphorus compound can be produced industrially advantageously. When a reaction was performed using phosphoric acid having no PH bond (Comparative Examples 2, and 3), or when no acid was added (Comparative Example 1), conversion ratio and/or selectivity was low (conversion ratio: 27.5 to 34.8%, and selectivity: 81.3 to 89.5%) using a catalyst in an amount of about 0.2 mol %, and thus the present invention is obviously superior.

(53) As shown in Examples 4, 5, and 15, according to the production method of the present invention, even at a reaction scale larger than a laboratory scale, that is, 30 L or more in reactor volume (a total weight of materials charged of 15 kg or more), an alkenyl phosphorus compound can be obtained in a yield comparable to that at a laboratory scale, and thus one can understand that the production method of the present invention is also suitable for quantity synthesis at an industrial scale.