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EP-4293002-B1 - METHOD FOR PRODUCING ALKENYL PHOSPHORUS COMPOUND

EP4293002B1EP 4293002 B1EP4293002 B1EP 4293002B1EP-4293002-B1

Inventors

  • SAGA YUTA

Dates

Publication Date
20260513
Application Date
20220208

Claims (10)

  1. A method of producing an alkenyl phosphorus compound represented by the general formula (4) shown below, comprising allowing a phosphorus compound represented by the following general formula (1): wherein, in general formula (1), each of R 1 and R 2 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; wherein R 1 and R 2 may be bonded with each other to form a cyclic structure to react with an alkynyl compound represented by the following general formula (2): wherein, in general formula (2), each of R 3 and R 4 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, a Lewis acid and a low-polarity additive, to produce the alkenyl phosphorus compound represented by the general formula (4): wherein, in general formula (4), the definitions of R 13 and R 14 are the same as those of R 1 and R 2 in the general formula (1), and the definitions of R 15 and R 16 are the same as those of R 3 and R 4 in the general formula (2), wherein the Lewis acid is at least one selected from the group consisting of zinc chloride, zinc bromide and iron (II) chloride, and wherein the low-polarity additive is at least one selected from the group consisting of an aromatic hydrocarbon, an aliphatic hydrocarbon and an alicyclic hydrocarbon.
  2. The production method according to claim 1, wherein the transition metal complex is a nickel complex.
  3. The production method according to claim 2, wherein the transition metal complex is a zero-valent nickel complex of nickel and a phosphine.
  4. The production method according to claim 3, wherein the phosphine is a phosphine containing an aromatic substituent.
  5. The production method according to any one of claims 1 to 4, wherein each of R 1 and R 2 in the general formula (1) independently represents a substituted or unsubstituted alkoxy group having from 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group; and each of R 13 and R 14 in the general formula (4) independently represents a substituted or unsubstituted alkoxy group having from 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group.
  6. The production method according to any one of claims 1 to 5, wherein both of R 3 and R 4 in the general formula (2) are hydrogen atoms, and both of R 15 and R 16 in the general formula (4) are hydrogen atoms.
  7. The production method according to any one of claims 1 to 6, wherein the reaction is carried out at a temperature of from 10 to 60°C.
  8. The production method according to any one of claims 1 to 7, wherein the low-polarity additive is at least one selected from the group consisting of toluene, tetralin and methylnaphthalene.
  9. The production method according to any one of claims 1 to 8, wherein the amount of the low-polarity additive added is 1% by mass or more and 70% by mass or less with respect to the total amount of the reaction system other than the alkynyl compound.
  10. The production method according to any one of claims 1 to 9, wherein the rate of generation of a by-product is 10% or less.

Description

BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to a method of producing an alkenyl phosphorus compound. More particularly, the present invention relates to a method of producing an alkenyl phosphorus compound by a hydrophosphorylation reaction, in the presence of a transition metal complex, a Lewis acid and a low-polarity additive. Background Art Organic phosphorus compounds are chemical substances widely used in a variety of products, such as flame retardants, plasticizers, insecticides, pharmaceutical and agricultural chemicals, ligands for metal complexes and the like. In recent years, organic phosphorus compounds are particularly attracting industrial attention as functional materials, also in the fields of constituent materials for metal surface treatment agents, flame retardant resins and the like, and electronic materials. Since phosphonic acid derivatives, among organic phosphorus compounds, are useful precursor substances of a variety of chemical substances described above, various production methods thereof have been conventionally investigated. For example, the production of a phosphonic acid derivative by the addition reaction (hereinafter, referred to as "hydrophosphorylation reaction") of the P(O)-H bond of phosphonic acid to an alkyne, using a catalyst, has been performed. For example, Patent Document 1 proposes a technique of producing a phosphonic acid derivative in which a phosphonic acid diester compound that has been partially hydrolyzed in advance, is used as a raw material. Further, Non-patent Document 1 proposes a technique of producing a phosphonic acid derivative using any of various zero-valent nickel catalysts. Non-patent Document 2 describes the catalytic addition of O-methyl(adamant-2-ylmethyl)phosphonite to phenylacetylene in the presence of complexes of Pd, Cu, and Ni. Citation List Patent Document Patent Document 1: WO 2017/043552 Non-patent Document Non-patent Document 1: J. AM. CHEM. SOC. 2004, 126, 5080 to 5081Non-patent Document 2: RUSS. J. GEN. CHEM. 2014, 84, 1737 to 1741 SUMMARY OF THE INVENTION Technical Problem However, there have been problems in the reaction conditions disclosed in Patent Document 1, such as that a hydrolysis reaction as a pretreatment needs to be performed, making it necessary to perform one additional step, and that a large amount of reaction heat is generated while requiring a low reaction temperature, making it difficult to perform temperature control in order to achieve mass production. In addition, catalysts to be used in the hydrophosphorylation reaction are expensive, unstable and ignitable, and have a bad odor, and thus, a safe and inexpensive catalyst has been demanded. On the other hand, Non-patent Document 1 discloses a technique of carrying out a hydrophosphorylation reaction with a nickel complex using inexpensive triphenylphosphine. However, this results in a low reactivity, and a phosphonic acid derivative can be obtained only at a low yield even if a large amount of catalyst is used. Moreover, many of phosphine compounds and nickel compounds are difficult to obtain industrially, leading to another problem that the range for the selection of raw materials is narrow. Therefore, an object of the present invention is to provide a method of producing an alkenyl phosphorus compound, which method is capable of controlling a catalyst in the reaction system to allow a hydrophosphorylation reaction to proceed efficiently at room temperature or at room temperature with slight heating, using a divalent nickel compound which is easily available as an industrial raw material, stable in air and inexpensive, and a phosphine having an aromatic substituent which is stable in air and inexpensive. Solution to Problem The present inventors have found out, as a result of intensive studies to solve the above-mentioned problems, that it is possible to produce an alkenyl phosphorus compound efficiently, by carrying out the hydrophosphorylation reaction of a specific phosphorus compound with a specific alkynyl compound, in the presence of a transition metal complex, a Lewis acid and a low-polarity additive, thereby completing the present invention. Specifically, the present invention provides the following inventions. [1] A method of producing an alkenyl phosphorus compound represented by the general formula (4) shown below, comprising allowing a phosphorus compound represented by the following general formula (1): wherein, in general formula (1), each of R1 and R2 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; wherein R1 and R2 may be bonded with each other to form a cyclic structure)to react with an alkynyl compound represented by the following general formula (2): (wher