METHOD FOR MANUFACTURING ALKENYL PHOSPHORUS COMPOUND

Abstract

[Problem]

To provide an alkenyl phosphorus compound.

[Means to Solve the Problem]

The method for manufacturing an alkenyl phosphorus compound according to the present invention is a method in which a specific phosphorus compound and a specific alkynyl compound are reacted in the presence of a transition metal complex and a Lewis acid, thereby giving an alkenyl phosphorus compound.

Claims

1. A method for manufacturing an alkenyl phosphorus compound by reacting a phosphorus compound represented by the following general formula (1): ##STR00007## wherein R.sup.1 and R.sup.2 each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aryloxy group; and R.sup.1 and R.sup.2 may be bonded to each other to form a cyclic structure; and an alkynyl compound represented by the following general formula (2): ##STR00008## wherein R.sup.3 and R.sup.4 each independently 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, in the presence of a transition metal complex and a Lewis acid, wherein the alkenyl phosphorus compound is represented by the following general formula (3): ##STR00009## wherein, R.sup.1 and R.sup.2 are synonymous with R.sup.1 and R.sup.2 in general formula (1), and R.sup.3 and R.sup.4 are synonymous with R.sup.3 and R.sup.4 in general formula (2).

2. The manufacturing method according to claim 1, wherein the transition metal complex is a complex of nickel.

3. The manufacturing method according to claim 2, wherein the transition metal complex is a zero valent nickel complex of nickel and phosphines.

4. The manufacturing method according to claim 3, wherein the phosphines are phosphines having an aromatic substituent.

5. The manufacturing method according to claim 1, wherein the Lewis acid is a metal compound.

6. The manufacturing method according to claim 5, wherein the metal compound is at least one compound selected from the group consisting of zinc chloride, zinc bromide, and iron (II) chloride.

7. The manufacturing method according to claim 1, wherein R.sup.1 and R.sup.2 in general formulae (1) and (3) are each independently a substituted or unsubstituted alkoxy group or a substituted or unsubstituted aryl group having 1 to 10 carbons.

8. The manufacturing method according to claim 1, wherein R.sup.3 and R.sup.4 in general formulae (2) and (3) are each independently a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group or a substituted or unsubstituted aralkyl group having 1 to 10 carbons.

9. The manufacturing method according to claim 1, wherein the reaction is carried out at 20° C. to 60° C.

Description

EXAMPLES

[0048] The present invention shall be described in details below with reference to the Examples and Comparative Examples; however, the present invention shall not be limited to these Examples.

Synthesis of Alkenyl Phosphorus Compound

Example 1

[0049] 1.35 mmol of bis(triphenylphosphine)nickel (II) dichloride, 1.35 mmol of zinc powder, and 2.7 mmol of triphenylphosphine were metered in a glass Schlenk tube and the container was substituted with nitrogen. To this was added 1.5 mL of acetone, and the mixture was heated and stirred at 40° C. for 3 hours to obtain an orange precipitate. The pressure in the flask was reduced, acetone was removed from the precipitate, and subsequently 90 mol of a phosphorus compound ((MeO).sub.2P(O)H) and 2.7 mmol of zinc chloride were added, and the mixture was stirred at 40° C. for 4 hours in an acetylene gas atmosphere to obtain an alkenyl compound (MeO).sub.2P(O)CH═CH.sub.2. The conversion rate from the phosphorus compound to the alkenyl phosphorus compound was 81%.

Example 2

[0050] An alkenyl phosphorus compound ((MeO).sub.2P(O)CH═CH.sub.2) was obtained in the same manner as in Example 1 except that the reaction time was changed to 6 hours. The conversion rate from the phosphorus compound to the alkenyl phosphorus compound was 95%.

Example 3

[0051] An alkenyl phosphorus compound ((MeO).sub.2P(O)CH═CH.sub.2) was obtained in the same manner as in Example 1 except that 5.4 mmol of zinc chloride was used as the Lewis acid. The conversion rate from the phosphorus compound to the alkenyl phosphorus compound was 98%.

Example 4

[0052] An alkenyl phosphorus compound ((MeO).sub.2P(O)CH═CH.sub.2) was obtained in the same manner as in Example 1 except that only 1.35 mmol of zinc chloride precipitated as a by-product in the preparation of the zero valent nickel complex was used as the Lewis acid and the reaction time was changed to 18 hours. The conversion rate from the phosphorus compound to the alkenyl phosphorus compound was 54%.

Example 5

[0053] An alkenyl phosphorus compound ((MeO).sub.2P(O)CH═CH.sub.2) was obtained in the same manner as in Example 4 except that the reaction temperature was changed to 50° C. The conversion rate from the phosphorus compound to the alkenylphosphorus compound was 82%.

Comparative Example 1

[0054] 1.35 mmol of 1,5-bis(cyclooctadiene)nickel (O), 5.4 mmol of triphenylphosphine, and 1.5 mL of acetone were added to a glass Schlenk tube, and the mixture was heated and stirred at 40° C. for 3 hours to obtain an orange precipitate. The pressure in the flask was reduced, acetone was removed from the precipitate, then 90 mol of a phosphorus compound ((MeO).sub.2P(O)H) was added, and the mixture was stirred at 40° C. for 4 hours in an acetylene gas atmosphere, thereby obtaining an alkenyl compound (MeO).sub.2P(O)CH═CH.sub.2. The conversion rate from the phosphorus compound to the alkenyl phosphorus compound was 27%.

Comparative Example 2

[0055] When the reaction time in Comparative Example 1 was changed to 18 hours, the conversion rate from the phosphorus compound to the alkenyl phosphorus compound was 27%.

[0056] The results of Examples 1-5 and Comparative Example 1 are listed in Table 1.

TABLE-US-00001 TABLE 1 Addition Starting Starting Amount of Substance Substance Type of Catalyst Reaction Reaction Synthesized Substance Conversion (Phosphorus (Alkynyl Lewis of Lewis Temperature Time (Alkenyl Phosphorus Rate Compound) Compound) Acid Acid (eq) (° C.) (hours) Compound) (%) Ex. 1 (MeO).sub.2P(O)H Acetylene ZnCl.sub.2 3 20-25 4 (MeO).sub.2P(O)CH═CH.sub.2 81 Ex. 2 (MeO).sub.2P(O)H Acetylene ZnCl.sub.2 3 20-25 6 (MeO).sub.2P(O)CH═CH.sub.2 95 Ex. 3 (MeO).sub.2P(O)H Acetylene ZnCl.sub.2 5 20-25 4 (MeO).sub.2P(O)CH═CH.sub.2 98 Ex. 4 (MeO).sub.2P(O)H Acetylene ZnCl.sub.2 1 20-25 18 (MeO).sub.2P(O)CH═CH.sub.2 54 Ex. 5 (MeO).sub.2P(O)H Acetylene ZnCl.sub.2 1 50 4 (MeO).sub.2P(O)CH═CH.sub.2 82 Comp. (MeO).sub.2P(O)H Acetylene — 0 20-25 4 (MeO).sub.2P(O)CH═CH.sub.2 27 Ex. 1 Comp. (MeO).sub.2P(O)H Acetylene — 0 20-25 18 (MeO).sub.2P(O)CH═CH.sub.2 27 Ex. 2

Example 6

[0057] An alkenyl phosphorus compound ((MeO).sub.2P(O)CH═CH.sub.2) was obtained in the same manner as in Example 1 except that 1.35 mmol of nickel chloride was used instead of bis(triphenylphosphine)nickel (II) dichloride, and the amount of triphenylphosphine used was changed to 5.4 mmol. The conversion rate from the phosphorus compound to the alkenyl phosphorus compound was 94%.

Example 7

[0058] An alkenyl phosphorus compound ((MeO).sub.2P(O)CH═CH.sub.2) was obtained in the same manner as in Example 6 except that 2.70 mmol of 1,4-diphenylphosphinobutane (dppb) was used instead of triphenylphosphine. The conversion rate from the phosphorus compound to the alkenyl phosphorus compound was 64%.

Example 8

[0059] An alkenyl phosphorus compound ((MeO).sub.2P(O)CH═CH.sub.2) was obtained in the same manner as in Example 6 except that 5.40 mmol of diphenylmethylphosphine was used in place of triphenylphosphine. The conversion rate from the phosphorus compound to the alkenyl phosphorus compound was 40%.

Example 9

[0060] An alkenyl phosphorus compound ((MeO).sub.2P(O)CH═CH.sub.2) was obtained in the same manner as in Example 6, except that 4.05 mmol of iron (II) chloride (FeCl.sub.2) was used as a Lewis acid. The conversion rate from the phosphorus compound to the alkenyl phosphorus compound was 41%.

Example 10

[0061] An alkenyl phosphorus compound ((MeO).sub.2P(O)CH═CH.sub.2) was obtained in the same manner as in Example 6 except that 4.05 mmol of zinc bromide (ZnBr.sub.2) was used as the Lewis acid. The conversion rate from the phosphorus compound to the alkenyl phosphorus compound was 51%.

[0062] A list of the results of Examples 6 to 10 are listed in Table 2.

TABLE-US-00002 TABLE 2 Starting Starting Substance Substance Type of Synthesized Substance Conversion (Phosphorus (Alkynyl Type of Lewis (Alkenyl Phosphorus Rate Compound) Compound) Phosphine Acid Compound) (%) Ex. 6 (MeO).sub.2P(O)H Acetylene PPh.sub.3 ZnCl.sub.2 (MeO).sub.2P(O)CH═CH.sub.2 94 Ex. 7 (MeO).sub.2P(O)H Acetylene dppb ZnCl.sub.2 (MeO).sub.2P(O)CH═CH.sub.2 64 Ex. 8 (MeO).sub.2P(O)H Acetylene PMePh.sub.2 ZnCl.sub.2 (MeO).sub.2P(O)CH═CH.sub.2 40 Ex. 9 (MeO).sub.2P(O)H Acetylene PPh.sub.3 FeCl.sub.2 (MeO).sub.2P(O)CH═CH.sub.2 41 Ex. 10 (MeO).sub.2P(O)H Acetylene PPh.sub.3 ZnBr.sub.2 (MeO).sub.2P(O)CH═CH.sub.2 51

Example 11

[0063] An alkenyl phosphorus compound (Ph.sub.2P(O)CH═CH.sub.2) was obtained in the same manner as in Example 6 except that 90 mmol of diphenylphosphine oxide (Ph.sub.2P(O)H) as the phosphorus compound and 54 mL of tetrahydrofuran (THF) were used. The conversion rate from the phosphorus compound to the alkenyl phosphorus compound was 100%.

Example 12

[0064] 0.225 mmol of nickel chloride, 0.225 mmol of zinc powder, and 0.9 mmol of methyldiphenylphosphine were metered in a glass Schlenk tube, and the container was substituted with nitrogen. To this, 1.5 mL of acetone was added, and the mixture was heated and stirred at 40° C. for 3 hours to obtain an orange precipitate. The pressure in the flask was reduced, acetone was distilled off from the precipitate, then 15 mol of a phosphorus compound ((MeO).sub.2P(O)H), 0.45 mmol of zinc chloride, and 15 mmol of 1-octyne were added, and the mixture was stirred at 40° C. for 4 hours to obtain an alkenyl compound (a mixture of (MeO).sub.2P(O)C(C.sub.6H.sub.13)═CH.sub.2 and (MeO).sub.2P(O)CH═CHC.sub.6H.sub.13). The conversion of the phosphorus compound to the alkenyl phosphorus compound was 97%.

Example 13

[0065] An alkenyl compound (a mixture of Ph.sub.2P(O)C(C.sub.6H.sub.13)═CH.sub.2 and Ph.sub.2P(O)CH═CHC.sub.6H.sub.13) was obtained in the same manner as in Example 12, except that 15 mmol of diphenylphosphine oxide (Ph.sub.2P(O)H) was used as a phosphorus compound, 0.9 mmol of triphenylphosphine was used as a phosphine, and 6 mL of THF was used as a solvent. The conversion of the phosphorus compound to the alkenyl compound was 100%.

Comparative Example 3

[0066] 0.225 mmol of bis (1,5-cyclopentadiene)nickel and 0.9 mmol of triphenylphosphine were metered in a glass Schlenk tube under a nitrogen atmosphere, 1 mL of THF was added, and the mixture was stirred at room temperature for 3 hours to obtain an orange precipitate. The precipitate was washed with 1 mL of n-hexane three times, dried under reduced pressure, and a catalyst was prepared. The entire amount of this catalyst, 15 mmol of diphenylphosphine oxide (Ph.sub.2P(O)H), 15 mmol of 1-octyne and 6 mL of THF were added and the mixture was stirred at 40° C. for 4 hours to give an alkenyl compound (a mixture of Ph.sub.2P(O)C(C.sub.6H.sub.13)═CH.sub.2 and Ph.sub.2P(O)CH═CHC.sub.6H.sub.13). The conversion of the phosphorus compound to the alkenyl phosphorus compound was 15%.

[0067] The results of Examples 11-13 and Comparative Example 3 are listed in Table 3.

TABLE-US-00003 TABLE 3 Starting Starting Substance Substance Type of Synthesized Substance Conversion (Phosphorus (Alkynyl Type of Lewis (Alkenyl Phosphorus Rate Compound) Compound) Phosphine Acid Compound) (%) Ex. 11 Ph.sub.2P(O)H Acetylene PPh.sub.3 ZnCl.sub.2 Ph.sub.2P(O)CH═CH.sub.2 100 Ex. 12 (MeO).sub.2P(O)H 1-octyne PMePh.sub.2 ZnCl.sub.2 (MeO).sub.2P(O)CH═CHC.sub.6H.sub.13 97 (MeO).sub.2P(O)C(C.sub.6H.sub.13)═CH.sub.2 Ex. 13 Ph.sub.2P(O)H 1-octyne PPh.sub.3 ZnCl.sub.2 Ph.sub.2P(O)CH═CHC.sub.6H.sub.13 100 Ph.sub.2P(O)C(C.sub.6H.sub.13)═CH.sub.2 Comp. Ph.sub.2P(O)H 1-octyne PPh.sub.3 — Ph.sub.2P(O)CH═CHC.sub.6H.sub.13 15 Ex. 3 Ph.sub.2P(O)C(C.sub.6H.sub.13)═CH.sub.2