# US 10,479,809 B2 · Method for producing alkenyl phosphorus compound

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- Number: US 10,479,809 B2
- Document ID: US10479809B2
- Status: Granted
- Kind: B2
- Application number: 15/759,020
- Filed: 2016-09-08
- Published: 2019-08-29
- Granted: 2019-11-19
- Earliest claimed: 2015-09-11
- Assignees: Maruzen Petrochemical Co., Ltd.
- Applicants: Maruzen Petrochemical Co., Ltd.
- Inventors: Yu Kinami; Ryuichi Tenjimbayashi; Yusuke Yokoo; Ichiro Kimura; Tomohiko Sato; Hiroyoshi Fujino; Tomoko Watanabe; Yuta Saga
- Web page: https://patentgrep.com/patent/US10479809B2

## CPC

- C07F 9/40: Esters thereof
- C07F 9/4015: {Esters of acyclic unsaturated acids}
- B01J 31/0257: {Phosphorus acids or phosphorus acid esters}
- B01J 31/24: Phosphines {, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands}
- B01J 31/2404: {Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring}
- C07F 9/142: with hydroxyalkyl compounds without further substituents on alkyl
- B01J 2231/32: Addition reactions to C=C or C-C triple bonds
- B01J 2531/847: Nickel
- C07B 61/00: Other general methods
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07B: GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR (preparation of carboxylic acid esters by telomerisation C07C67/47; telomerisation C08F)

## 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): [In formula (1), R1 represents OR3 or R3, R2 represents OR4 or R4, and R3 and R4 represent, for example, each independently a substituted or unsubstituted alkyl group.] with a compound represented by the following formula (2): [In formula (2), R5 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): [In formulas (3a) and (3b), R1 and R2 have the same meaning as defined in formula (1), and R5 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 P—H bond.

## Claims

### Claim 1

A method for producing an alkenyl phosphorus compound; comprising
reacting a compound represented by formula (1):
wherein R1 represents OR3 or R3, R2 represents OR4 or R4, and R3 and R4 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 R3 and R4 together may form a ring structure,
with a compound represented by formula (2):
wherein R5 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):
wherein R1 and R2 the same meaning as defined in formula (1), and R5 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 P—H bond.

### Claim 2 (depends on 1)

The production method according to claim 1, wherein the phosphorus oxo acid compound is a compound represented by formula (4):
wherein R6 represents a hydrogen atom, a hydroxyl group, OR7, or R7, and R7 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.

### Claim 3 (depends on 1)

The production method according to claim 1, wherein the phosphorus oxo acid compound is obtained by hydrolyzing a compound represented by Formula (5):
wherein R8 represents a hydrogen atom, a hydroxyl group, OR10, or R10, and R9 and R10 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 R8 is OR10 or R10, R9 and R10 together may form a ring structure.

### Claim 4 (depends on 3)

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.

### Claim 5 (depends on 1)

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

### Claim 6

A method for producing an alkenyl phosphorus compound, comprising:
applying hydrolysis treatment to a compound represented by formula (1), excluding compounds in which R1 is R3, and R2 is R4:
wherein R1 represents OR3 or R3, R2 represents OR4 or R4, and R3 and R4 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 R3 and R4 together may form a ring structure, and
contacting a hydrolysis product obtained by the hydrolysis treatment with a compound represented by formula (2):
wherein R5 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):
wherein R1 and R2 have the same meaning as defined in formula (1), and R5 has the same meaning as defined in formula (2).

### Claim 7 (depends on 6)

The production method according to claim 6, wherein the hydrolysis product comprises the compound represented by formula (1),
excluding a compound in which is R1 is R3, and R2 is R4, and a compound represented by formula (6):
wherein R11 represents a hydroxyl group, OR12 represents R12, and R12 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.

### Claim 8 (depends on 6)

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