JP4475987B2 - Method for producing phosphonate esters - Google Patents

Description

  The present invention relates to a method for producing phosphonic acid esters useful as a metal extractant, a plasticizer, a flame retardant, or a precursor thereof.

  Conventionally, organophosphorus compounds are useful reagents for organic synthesis, and various synthetic methods have been developed. For example, as a method for synthesizing an arylphosphonic acid ester, a method in which a phosphonic acid ester and an aromatic compound are reacted with an excess of CAN (cerium (IV) ammonium nitrate) as an oxidizing agent has been reported (Non-Patent Document). 1). In this method, aryl phosphonates are formed by radical addition of phosphonates to aromatic compounds followed by oxidation / deprotonation. However, in the above method, a large amount of salt by-products cannot be avoided after the reaction.

Synthesis, 1987, page 797.

  An object of the present invention is to provide a method for efficiently obtaining phosphonic acid esters in which atoms constituting a conjugated structure of a conjugated compound are bonded to phosphorus atoms of phosphites by a catalytic radical reaction. is there.

  As a result of intensive studies to achieve the above object, the present inventors have combined oxygen of a periodic table group 5-9 element compound and oxygen, and oxygen functions as an oxidizing agent and the periodic table group 5-9 element compound as a catalyst. The inventors have found that the corresponding phosphonates can be efficiently produced from phosphites and conjugated compounds, and thus completed the present invention.

（式中、Ｒ^a、Ｒ^bは、それぞれ水素原子又は炭化水素基を示す）
で表される亜リン酸エステル類と、下記式（３）

（式中、Ｒ ^c 、Ｒ ^d 、Ｒ ^e 、Ｒ ^f 、Ｒ ^g 、Ｒ ^h は、それぞれ水素原子又は炭化水素基、複素環式基、置換オキシ基、置換オキシカルボニル基、カルボキシル基、置換又は無置換カルバモイル基、シアノ基、ニトロ基、硫黄酸基、硫黄酸エステル基、アシル基から選択される１つを示す。但し、Ｒ ^c 、Ｒ ^d 、Ｒ ^e 、Ｒ ^f 、Ｒ ^g 、Ｒ ^h のうち少なくとも１つは水素原子である。Ｒ ^c 、Ｒ ^d 、Ｒ ^e 、Ｒ ^f 、Ｒ ^g 、Ｒ ^h は、それぞれ互いに結合して又は一体となって隣接する原子又は炭素鎖と共に芳香族性又は非芳香族性の環を形成してもよい）
で表される化合物とを、マンガン化合物及び／又はコバルト化合物、及び酸素の存在下で反応させて、下記式（４）

［式中、Ｒ ¹ は下記式（２）

（式中、Ｒ ^a 、Ｒ ^b は、それぞれ水素原子又は炭化水素基を示す）
で表されるホスホリル基又はＲ ^c を示し、Ｒ ² は上記式（２）で表される基又はＲ ^d を示し、Ｒ ³ は上記式（２）で表される基又はＲ ^e を示し、Ｒ ⁴ は上記式（２）で表される基又はＲ ^f を示し、Ｒ ⁵ は上記式（２）で表される基又はＲ ^g を示し、Ｒ ⁶ は上記式（２）で表される基又はＲ ^h を示す。但し、Ｒ ¹ 、Ｒ ² 、Ｒ ³ 、Ｒ ⁴ 、Ｒ ⁵ 、Ｒ ⁶ のうち少なくとも１つは上記式（２）で表される基である。Ｒ ¹ 、Ｒ ² 、Ｒ ³ 、Ｒ ⁴ 、Ｒ ⁵ 、Ｒ ⁶ は、それぞれ互いに結合して又は一体となって隣接する原子又は炭素鎖と共に芳香族性又は非芳香族性の環を形成してもよい］
で表される化合物を生成させることを特徴とするホスホン酸エステル類の製造法を提供する。 That is, the present invention provides the following formula (1):

(Wherein R ^a and R ^b each represent a hydrogen atom or a hydrocarbon group )
Phosphites represented by the following formula (3)

(Wherein R ^c , R ^d , R ^e , R ^f , R ^g , and R ^h are each a hydrogen atom or a hydrocarbon group, a heterocyclic group, a substituted oxy group, a substituted oxycarbonyl group, a carboxyl group, a substituted or One selected from an unsubstituted carbamoyl group, a cyano group, a nitro group, a sulfur acid group, a sulfur acid ester group, and an acyl group, provided that R ^c , R ^d , R ^e , R ^f , R ^g , R ^h At least one of them is a hydrogen atom, and R ^c , R ^d , R ^e , R ^f , R ^g , and R ^h are each bonded to each other or integrally formed together with an adjacent atom or carbon chain. Or a non-aromatic ring may be formed)
In the presence of a manganese compound and / or a cobalt compound and oxygen , and the following formula (4):

[Wherein R ¹ represents the following formula (2)

(Wherein R ^a and R ^b each represent a hydrogen atom or a hydrocarbon group)
In represented shows a phosphoryl group, or R ^c, R ² represents a group or R ^d is represented by the formula (2), R ³ represents a group or R ^e represented by the formula (2), R ⁴ represents a group represented by the above formula (2) or R ^f , R ⁵ represents a group represented by the above formula (2) or R ^g , and R ⁶ represents the above formula (2). Represents a group or R ^h . However, at least one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ is a group represented by the above formula (2). R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ may be bonded to each other or united together to form an aromatic or non-aromatic ring with adjacent atoms or carbon chains. It is good]
A method for producing a phosphonic acid ester is provided.

In the present specification, the following formula (1)

(Wherein R ^a , R ^b Each represents a hydrogen atom or an organic group)
And a conjugated compound in which at least one hydrogen atom is bonded to an atom constituting a conjugated structure, in the presence of a group 5-9 element compound catalyst and oxygen in the periodic table. And at least one of the hydrogen atoms of the conjugated compound is represented by the following formula (2):

(Wherein R ^a , R ^b Is the same as above)
A method for producing a phosphonic acid ester, characterized in that a corresponding phosphonic acid ester substituted with a phosphoryl group represented by formula (1) is generated, is also described.

  According to the method of the present invention, the atoms constituting the conjugated structure of the conjugated compound are bonded to the phosphorus atom of the phosphite by a catalytic radical reaction using oxygen and a group 5-9 element compound of the periodic table. Bound phosphonates can be obtained efficiently.

[Phosphorous esters]
The compounds represented by formula (1) used as a raw material in the present invention (phosphites) include a wide range of phosphites (phosphonates) having a phosphoryl (V) group in the molecule. included. In addition, phosphorous acid is also contained in the phosphites represented by Formula (1).

In formula (1), as the organic group in R ^a and R ^b , a hydrocarbon group or a heterocyclic group can be preferably used. The hydrocarbon group in the organic group of R ^a and R ^b includes an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group in which a plurality of these are bonded. Examples of the aliphatic hydrocarbon group include carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl, octyl, decyl, tetradecyl, hexadecyl, octadecyl, and allyl groups. Examples thereof include a linear or branched aliphatic hydrocarbon group (an alkyl group, an alkenyl group, and an alkynyl group) of about 1 to 20 (preferably 1 to 10, more preferably 1 to 6).

  Examples of the alicyclic hydrocarbon group include fatty acids having about 3 to 20 carbon atoms (preferably 3 to 15 carbon atoms) such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, cyclooctyl, cyclodecyl, and cyclododecyl groups. Examples thereof include a cyclic hydrocarbon group (a cycloalkyl group, a cycloalkenyl group, etc.).

  Examples of the aromatic hydrocarbon group include aromatic hydrocarbon groups having about 6 to 20 carbon atoms such as phenyl and naphthyl groups.

These hydrocarbon groups may be protected by various substituents such as halogen atoms (fluorine, chlorine, bromine, iodine atoms), oxo groups, hydroxyl groups which may be protected with protecting groups, and protecting groups. A good hydroxymethyl group, an amino group which may be protected with a protecting group, a carboxyl group which may be protected with a protecting group, a substituted oxycarbonyl group, a substituted or unsubstituted carbamoyl group, a nitro group, an acyl group, a cyano group, It may have an alkyl group (for example, a C _1-4 alkyl group such as a methyl or ethyl group), a cycloalkyl group, an aryl group (for example, a phenyl or naphthyl group), a heterocyclic group, or the like. As the protecting group, a protecting group commonly used in the field of organic synthesis can be used.

The heterocyclic ring constituting the heterocyclic group in the organic group of R ^a and R ^b includes an aromatic heterocyclic ring and a non-aromatic heterocyclic ring. As such a heterocyclic ring, for example, a heterocyclic ring containing an oxygen atom as a hetero atom (for example, 5-membered ring such as furan, tetrahydrofuran, oxazole, isoxazole, 4-oxo-4H-pyran, tetrahydropyran, morpholine, etc. 6-membered ring, condensed ring such as benzofuran, isobenzofuran, 4-oxo-4H-chromene, chromane, isochroman, etc.), heterocycle containing a sulfur atom as a hetero atom (for example, 5 such as thiophene, thiazole, isothiazole, thiadiazole, etc.) 5-membered rings, 6-membered rings such as 4-oxo-4H-thiopyran, condensed rings such as benzothiophene, etc.) and heterocycles containing nitrogen atoms as heteroatoms (eg, pyrrole, pyrrolidine, pyrazole, imidazole, triazole, etc.) Ring, pyridine, pyridazine, pyrimi Emissions, pyrazine, piperidine, 6-membered ring such as piperazine, indole, indoline, quinoline, acridine, naphthyridine, quinazoline, other condensed rings purine) and the like. These heterocyclic groups may have a substituent (for example, a group similar to the substituent that the hydrocarbon group may have).

R ^a and R ^b are preferably the same or different and each represents a hydrocarbon group [eg, a C _1-10 aliphatic hydrocarbon group (eg, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, C _1-10 alkyl group such as t-butyl, pentyl, hexyl, octyl, decyl group, etc.), alicyclic hydrocarbon group (for example, C _3-15 cycloalkyl group such as cyclopentyl, cyclohexyl, cyclohexenyl group or cyclo Alkenyl group etc.), C _6-14 aryl group etc.].

  Specifically, the phosphites represented by the formula (1) are preferably phosphites (phosphonates). Examples of the phosphite include phosphite monoester and phosphite diester. More specifically, typical examples of phosphite monoesters include, for example, methyl phosphite, ethyl phosphite, propyl phosphite, isopropyl phosphite, butyl phosphite, isobutyl phosphite. S-butyl phosphite, t-butyl phosphite, pentyl phosphite, hexyl phosphite, heptyl phosphite, octyl phosphite, 2-ethylhexyl phosphite, nonyl phosphite, phosphorous acid Phosphorous such as decyl, undecyl phosphite, dodecyl phosphite, tridecyl phosphite, tetradecyl phosphite, pentadecyl phosphite, hexadecyl phosphite, heptadecyl phosphite, octadecyl phosphite, nonadecyl phosphite Acid monoalkyl esters; Phosphorous acid monocycloalkyl esters such as cyclohexyl phosphite; Phenyl phosphite, Naphthite phosphite Like phosphite monoaryl esters such.

  On the other hand, representative examples of phosphite diesters include, for example, dimethyl phosphite, diethyl phosphite, dipropyl phosphite, diisopropyl phosphite, dibutyl phosphite, diisobutyl phosphite, diphosphite diphosphite. s-butyl, di-t-butyl phosphite, dipentyl phosphite, dihexyl phosphite, diheptyl phosphite, dioctyl phosphite, di-2-ethylhexyl phosphite, dinonyl phosphite, didecyl phosphite, Phosphorous acid such as diundecyl phosphite, didodecyl phosphite, ditridecyl phosphite, ditetradecyl phosphite, dipentadecyl phosphite, dihexadecyl phosphite, diheptadecyl phosphite, dioctadecyl phosphite, dinonadecyl phosphite Dialkyl esters; dicycloalkyl phosphites such as dicyclohexyl phosphite; Phosphorus diaryl esters such as diphenyl phosphate and dinaphthyl phosphite; methyl phenyl phosphite, ethyl phenyl phosphite, propyl phenyl phosphite, butyl phenyl phosphite, pentyl phenyl phosphite, hexyl phosphite Phenyl, heptylphenyl phosphite, octylphenyl phosphite, 2-ethylhexylphenyl phosphite, nonylphenyl phosphite, decylphenyl phosphite, dodecylphenyl phosphite, tetradecylphenyl phosphite, phosphorous acid In addition to alkyl aryl phosphites such as octadecyl phenyl, alkyl cycloalkyl phosphites, cycloalkyl aryl phosphites and the like.

[Conjugated compounds]
The conjugated compound is not particularly limited as long as it is a compound in which at least one hydrogen atom is bonded to an atom constituting the conjugated structure. The conjugated compound includes a compound having a conjugated double bond (a compound having a conjugated system in which two or more carbon-carbon double bonds are bonded by a single bond) and a compound having a conjugated triple bond (two or more carbon-carbon triples). Compounds having a conjugated system in which the bonds are bonded by a single bond, and compounds having a conjugated system in which a carbon-carbon triple bond and a carbon-carbon double bond are bonded by a single bond), as well as α, β-unsaturated carboxylic acids Or derivatives thereof (α, β-unsaturated carboxylic acid, α, β-unsaturated carboxylic acid ester, α, β-unsaturated carboxylic acid amide, α, β-unsaturated nitrile, etc.), α, β-unsaturated ketone , Α, β-unsaturated aldehydes, α, β-unsaturated imines, and the like. Examples of the compound having a conjugated double bond include conjugated dienes, polyenes, and aromatic compounds (aromatic carbocyclic compounds and aromatic heterocyclic compounds). Examples of the compound having a conjugated triple bond include vinyl acetylenes, And diacetylenes.

A typical example of the conjugated compound is a compound represented by the formula (3). In formula (3), R ^c , R ^d , R ^e , R ^f , R ^g , and R ^h each represent a hydrogen atom or an organic group. However, at least one of R ^c , R ^d , R ^e , R ^f , R ^g , and R ^h is a hydrogen atom.

  The organic group may be any group that does not impair the reaction, for example, a hydrocarbon group, a heterocyclic group, a hydroxyl group, a mercapto group, a substituted oxy group, a halogen atom, an N-substituted or unsubstituted amino group. An acyl group and a protected carbonyl group in the acyl group, substituted oxycarbonyl group, carboxyl group, substituted or unsubstituted carbamoyl group, cyano group, substituted or unsubstituted iminoalkyl group, nitro group, sulfur acid group, sulfur acid ester group And a haloalkyl group. Hydroxyl group, carboxyl group, amino group and the like may be protected with a conventional protecting group.

The hydrocarbon group in R ^c and the like includes a hydrocarbon group similar to the hydrocarbon group in R ^a and R ^b (an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a plurality of these Group bonded to each other). These hydrocarbon groups in R ^{c and the} like may have various substituents (for example, the same groups as the substituents that the hydrocarbon groups in R ^a and R ^b may have).

The heterocyclic ring constituting the heterocyclic group in R ^c and the like includes the same heterocyclic ring as the heterocyclic ring constituting the heterocyclic group in R ^a and R ^b (aromatic heterocyclic ring and non-aromatic heterocyclic ring). ) Is included. These heterocyclic groups in R ^{c and the} like may have a substituent (for example, the same group as the substituent which the hydrocarbon group in R ^a and R ^b may have).

Examples of the substituted oxy group in R ^c include alkoxy groups such as methoxy, ethoxy, propoxy and butoxy groups; alkenyloxy groups such as allyloxy groups; cycloalkyloxy groups such as cyclohexyloxy groups; phenoxy, naphthyloxy groups and the like Aryloxy groups; aralkyloxy groups such as benzyloxy groups; acyloxy groups such as acetoxy, propionyloxy, and benzoyloxy groups. Examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms. N-substituted amino groups include, for example, N, N-dimethylamino, N, N-diethylamino, piperidino groups and the like.

  Representative examples of acyl groups and protected carbonyl groups in the acyl groups include, for example, formyl, acetyl, propionyl, butyryl, (meth) acryloyl, cyclopentanecarbonyl, cyclohexanecarbonyl, benzoyl, naphthoyl, and pyridylcarbonyl groups. And aliphatic, alicyclic, aromatic or heterocyclic acyl groups and their protected carbonyl groups. Substituted oxycarbonyl groups include, for example, methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, vinyloxycarbonyl, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl, pyridyloxycarbonyl groups and the like. Examples of the substituted or unsubstituted carbamoyl group include carbamoyl, N-methylcarbamoyl, N-phenylcarbamoyl, N, N-dimethylcarbamoyl, 1-pyrrolidinylcarbonyl, piperidinocarbonyl and the like. Examples of sulfur acid groups include sulfonic acid groups and sulfinic acid groups. Examples of sulfur acid ester groups (sulfonic acid ester groups and sulfinic acid ester groups) include methyl sulfonate, ethyl sulfonate, and sulfinic acid. Examples include methyl and ethyl sulfinate groups. Examples of the haloalkyl group include a trifluoromethyl group. In addition, as a protected body of an acyl group, a form in which a carbonyl group is protected with a conventional protective group (for example, acetal bodies such as dimethyl acetal, diethyl acetal, 1,3-dioxane, 1,3-dioxolane; S, S And dithioacetals such as' -dimethyldithioacetal).

R ^c , R ^d , R ^e , R ^f , R ^g , and R ^h are bonded to each other or united to form an aromatic or non-aromatic ring with adjacent atoms or carbon chains. Also good. Examples of the aromatic ring include an aromatic carbocyclic ring such as a benzene ring; and a furan ring, a thiophene ring, a pyrrole ring, an oxazole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, and a pyridazine ring. And an aromatic heterocycle having at least one heteroatom selected from a nitrogen atom, an oxygen atom and a sulfur atom. Non-aromatic rings include, for example, cyclohexane, cyclobutane, cyclopentane, cyclopentene, cyclohexane, cyclohexene, cyclooctane, cyclododecane and norbornene rings. A cyclic carbocycle (cycloalkane ring, cycloalkene ring, bridged carbocycle, etc.); at least one selected from nitrogen, oxygen and sulfur atoms such as tetrahydrofuran, pyrrolidine, piperazine, piperidine and morpholine A non-aromatic heterocyclic ring having about 3 to 20 members having one hetero atom is exemplified. These rings substituents (e.g., the R ^a, groups exemplified as the organic group in R ^b, wherein R ^a, such as the same group and hydrocarbon group substituent which may be possessed by the R ^b) Yu Or other ring (non-aromatic ring or aromatic ring) may be condensed.

When R ^c and R ^h are combined or united to form an aromatic ring with the adjacent carbon chain, the compound represented by the formula (3) is an aromatic compound (aromatic carbocyclic compound). Or an aromatic heterocyclic compound).

Preferred R ^c , R ^d , R ^e , R ^f , R ^g and R ^h are a hydrogen atom, a hydrocarbon group [for example, a C _1-20 aliphatic hydrocarbon group (particularly a C _1-10 aliphatic hydrocarbon group). Etc.), C _6-20 aryl group (phenyl group, naphthyl group, etc.), cycloalkyl group (about 3-8 membered cycloalkyl group, etc.), haloalkyl group (for example, C _1-6 haloalkyl such as trifluoromethyl group, etc.) Group, especially C _1-4 haloalkyl group)], heterocyclic group, substituted oxy group (for example, C _1-6 alkoxy group, C _2-6 alkenyloxy group, aryloxy group, C _7-15 aralkyloxy group) and C _1-10 acyloxy group), substituted oxycarbonyl group (e.g., C _1-6 alkoxy - carbonyl group, an aryloxycarbonyl group, an aralkyloxycarbonyl group, such as cycloalkyl alkyloxycarbonyl group), a carboxyl group,換又 unsubstituted carbamoyl group, a cyano group, a nitro group, sulfur acid groups, sulfur acid ester groups, and the like acyl groups. It is also preferred that R ^c and R ^h are combined or united to form an aromatic ring with the adjacent carbon chain.

  Representative examples of the compound represented by the formula (3) include conjugated dienes such as butadiene, isoprene, chloroprene, 1,3-hexadiene, 2,4-hexadiene; benzene, toluene, xylene, mesitylene, ethylbenzene, isopropyl Benzene, 1,4-diisopropylbenzene, 1,3,5-triisopropylbenzene, anisole, chlorobenzene, acetoxybenzene, acetophenone, benzophenone, ethyl benzoate, cyanobenzene (benzonitrile), nitrobenzene, indane, tetralin, naphthalene, anthracene Aromatic carbocyclic compounds such as fluorene, phenalene, naphthoquinone, anthraquinone, fluorenone, biphenyl, styrene, phenanthrene, C60 (fullerene); furan, benzofuran, thiophene , Pyrrole, oxazole, imidazole, pyrazole, pyridine, picoline, quinoline, pyrazine, pyrimidine, aromatic heterocyclic compounds such as pyridazine and the like.

[Periodic Table Group 5-9 Element Compound Catalyst]
In this invention, the periodic table group 5-9 element compound is used as a catalyst. Periodic Table 5-9 elements include group 5 elements such as vanadium V, niobium Nb, tantalum Ta; group 6 elements such as chromium Cr, molybdenum Mo, tungsten W; group 7 elements such as manganese Mn, technetium Tc, rhenium Re, etc. Elements: Group 8 elements such as iron Fe, ruthenium Ru, and osmium Os; Group 9 elements such as cobalt Co, rhodium Rh, and iridium Ir are included. Among these, group 7 elements such as manganese Mn are preferable. Further, preferred elements include fourth-period metal elements (vanadium V, chromium Cr, manganese Mn, iron Fe, cobalt Co). Moreover, as a catalyst, the metal element compound which shows activity in 1 electron oxidation is preferable.

Examples of the periodic table group 5-9 element compounds include the metal element simple substance, hydroxide, oxide (including complex oxide), halide (fluoride, chloride, bromide, iodide), oxo acid salt ( For example, nitrates, sulfates, phosphates, borates, carbonates, etc.) inorganic compounds such as oxo acids, isopolyacids, heteropolyacids; organic acid salts (eg acetates, propionates, cyanates, naphthenes) Acid compounds, stearates, etc.) and organic compounds such as complexes. The ligands constituting the complex include OH (hydroxo), alkoxy (methoxy, ethoxy, propoxy, butoxy, etc.), acyl (acetyl, propionyl, etc.), alkoxycarbonyl (methoxycarbonyl, ethoxycarbonyl, etc.), acetylacetonato , Cyclopentadienyl group, halogen atom (chlorine, bromine, etc.), CO, CN, oxygen atom, H ₂ O (aquo), phosphine (triarylphosphine such as triphenylphosphine), phosphorus compound, NH ₃ (ammine) ), NO, NO ₂ (nitro), NO ₃ (nitrato), nitrogen-containing compounds such as ethylenediamine, diethylenetriamine, pyridine and phenanthroline.

  As specific examples of Group 5-9 element compounds of the periodic table, for example, when a manganese compound is taken as an example, manganese hydroxide, manganese oxide, manganese halide such as manganese chloride and manganese bromide, manganese nitrate, manganese sulfate, phosphorus Inorganic compounds such as manganese polyacids, manganese carbonates, manganese salts, permanganates, heteropolyacids containing manganese such as manganese molybdate, or salts thereof; manganese formate, manganese acetate, manganese propionate, manganese naphthenate, manganese stearate Examples thereof include organic compounds such as organic acid salts such as manganese thiocyanate and complexes such as manganese acetylacetonate. The valence of manganese may be either divalent or trivalent. Of these, organic manganese compounds such as organic acid salts such as manganese acetate and complexes such as manganese acetylacetonate are preferable.

  Representative examples of cobalt compounds include, for example, cobalt hydroxide, cobalt oxide, cobalt halides such as cobalt chloride and cobalt bromide, and heteropolycarbonates containing cobalt such as cobalt nitrate, cobalt sulfate, cobalt phosphate, and cobalt molybdate. Examples include inorganic compounds such as acids or salts thereof; organic compounds such as organic acid salts such as cobalt formate, cobalt acetate, cobalt naphthenate, and cobalt stearate; and complexes such as cobalt acetylacetonate. The valence of cobalt may be either bivalent or trivalent. Among these, organic acid compounds such as cobalt acetate and organic cobalt compounds such as complexes such as cobalt acetylacetonate are preferable.

  Examples of vanadium compounds include inorganic compounds such as vanadium hydroxide, vanadium oxide, vanadium chloride, vanadyl chloride, vanadium sulfate, vanadyl sulfate, and sodium vanadate; complexes such as vanadium acetylacetonate and vanadylacetylacetonate Examples thereof include divalent to pentavalent vanadium compounds.

  Further, examples of the molybdenum compound include inorganic compounds such as molybdenum hydroxide, molybdenum oxide, molybdenum chloride, molybdenum bromide, molybdenum sulfide, molybdic acid or a salt thereof, phosphomolybdic acid or a salt thereof, silicomolybdic acid or a salt thereof; 0- to 6-valent molybdenum compounds such as complexes of molybdenum carbonyl, bis (acetylacetonato) dioxomolybdenum, chlorotricarbonyl (η-cyclopentadienyl) molybdenum, dibromobis (η-cyclopentadienyl) molybdenum, etc. Can be mentioned. Examples of other metal element compounds include compounds corresponding to the manganese, vanadium or molybdenum compounds. The valence of the Group 5-9 elements of the periodic table is not particularly limited, but is often about 0-6 valence.

  The periodic table 5-9 group element compound can be used individually or in combination of 2 or more types. When two or more kinds of compounds having different elements among the periodic table group 5-9 element compounds are used in combination, the reaction rate and the selectivity of the reaction may be improved. Examples of such a combination include a combination of a manganese compound and a cobalt compound.

  The amount of the periodic table group 5-9 element compound catalyst used is, for example, 0.0001-0 with respect to 1 mol of the compound used in a small amount among the phosphites and conjugated compounds represented by the formula (1). .2 mol, preferably 0.0002 to 0.1 mol, more preferably about 0.0005 to 0.05 mol.

  In addition, when using in combination with a manganese compound and a cobalt compound, the usage-amount of a manganese compound is with respect to 1 mol of compounds of the one used in small quantities among the phosphites and conjugated compounds represented by Formula (1). For example, 0.0001 to 0.2 mol, preferably 0.0002 to 0.1 mol, more preferably about 0.0005 to 0.08 mol, and the amount of cobalt compound used is represented by the formula (1). For example, 0.00005 to 0.2 mol, preferably 0.0001 to 0.1 mol, and more preferably 0.001 mol to 1 mol of the compound to be used in a small amount among the phosphites and conjugated compounds. It is about 0002-0.05 mol. When a manganese compound and a cobalt compound are used in combination, the ratio is usually the former / the latter (molar ratio) = 1/99 to 99/1, preferably 5/95 to 98/2, more preferably 20 / 80 to 95/5, especially about 40/60 to 95/5.

  In the present invention, in order to improve the reaction rate and reaction selectivity, the periodic table group 5-9 element compound and other metal element compounds (for example, cerium, titanium, zirconium, nickel, palladium, platinum, copper, zinc, etc.) Transition metal compounds, etc.) can also be used in combination.

  Also, polymerization initiators such as azobisisobutyronitrile (AIBN), radical generators and radical reaction accelerators [halogen (chlorine, bromine, etc.), peracids, peroxides, etc.], etc., are present in the system. May be. When such a component is present in the system, the reaction may be accelerated. In addition, the reaction rate may be improved by irradiating light or applying ultrasonic waves.

  In the present invention, a base may be added to the system in order to improve the reaction rate and reaction selectivity. The base may be any of an inorganic base, an organic base, a Lewis base and the like. Examples of the inorganic base include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide; alkali metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, and cesium carbonate; hydrogen carbonate Alkali metal hydrogen carbonates such as sodium, potassium hydrogen carbonate and cesium hydrogen carbonate; Alkaline earth metal hydroxides such as magnesium hydroxide, calcium hydroxide and barium hydroxide; Alkaline earth such as magnesium carbonate, calcium carbonate and barium carbonate Metal group carbonates; Group 3 element compounds of periodic table such as cerium carbonate (for example, carbonates) and the like.

  Examples of the organic base include alkali metal alkoxides such as sodium methoxide and sodium ethoxide; alkali metal organic acid salts such as sodium acetate; amines such as triethylamine, piperidine, N-methylpiperidine and pyridine (tertiary amine and the like) And nitrogen-containing heterocyclic compounds.

  The amount of base added varies depending on the type of raw material, the type of catalyst, etc., but usually 1 mol of the compound used in a small amount among the phosphites and conjugated compounds represented by formula (1) used as the raw material The amount is about 0.01 to 5 mol, preferably about 0.5 to 1.0 mol.

[oxygen]
As oxygen, molecular oxygen is usually used. The molecular oxygen is not particularly limited, and pure oxygen may be used. In order to improve operability and safety, oxygen diluted with an inert gas such as nitrogen, helium, argon, carbon dioxide (air) Etc.) may be used. Depending on the type of substrate and other conditions, the yield of the target compound will be higher when a mixed gas of oxygen and inert gas (such as nitrogen) is used than when pure oxygen is used. There is. The ratio of oxygen to inert gas in the mixed gas is, for example, the former / the latter (molar ratio) = 10/90 to 95/5, preferably 15/85 to 90/10, more preferably 25/75 to 80. / 20 or so.

  The amount of oxygen used can be appropriately selected depending on the type of substrate, but is usually 0 with respect to 1 mol of the compound used in a small amount among the phosphites and conjugated compounds represented by formula (1). 0.5 mol or more (for example, 1 mol or more), preferably 1 to 100 mol, more preferably about 2 to 50 mol. Often an excess of oxygen is used relative to the substrate.

[reaction]
The reaction is carried out in the presence or absence of a solvent. Examples of the solvent include organic acids such as acetic acid and propionic acid; nitriles such as acetonitrile and benzonitrile; amides such as formamide, acetamide, dimethylformamide (DMF) and dimethylacetamide; and aliphatic carbonization such as hexane and octane. Hydrogen; halogenated hydrocarbons such as chloroform, dichloromethane, dichloroethane, carbon tetrachloride, chlorobenzene and trifluoromethylbenzene; nitro compounds such as nitrobenzene; and mixed solvents thereof. A substrate (reaction raw material) can also be used as a solvent.

  The ratio of the phosphites represented by the formula (1) (such as phosphonates) and the conjugated compound can be appropriately selected depending on the type and combination of both compounds. From the point of reactivity, the former / The latter (molar ratio) = about 0.5 to 30, preferably about 0.8 to 10, and more preferably about 1 to 5.

  The reaction temperature can be appropriately selected according to the types of the phosphites (phosphonic acid esters, etc.) and the conjugated compound, and is, for example, about 0 to 150 ° C., preferably about 10 to 100 ° C. The reaction can be carried out at normal pressure or under pressure. When the reaction is carried out under pressure, the reaction is usually about 1 to 100 atm (0.101 to 10.1 MPa), preferably 1.5 to 80 atm (0. 152 to 8.08 MPa). The reaction time can be appropriately selected from the range of about 30 minutes to 48 hours, for example, depending on the reaction temperature and pressure. The reaction can be carried out by a conventional method such as a batch system, a semi-batch system, or a continuous system in the presence of oxygen or in the circulation of oxygen.

  Corresponding phosphonates in which at least one of the hydrogen atoms bonded to the atoms constituting the conjugated structure of the conjugated compound used as a raw material is replaced by the phosphoryl group represented by the formula (2) by the above method Is produced in good yield. The number of phosphoryl groups introduced into the conjugated compound can be adjusted by appropriately selecting reaction conditions such as the amount of phosphite used. In this reaction, a phosphonyl radical generated by the action of oxygen and a group 5-9 element compound catalyst of the periodic table such as a manganese catalyst attacks the atoms constituting the conjugated structure of the conjugated compound to form a corresponding conjugated structure. It is presumed that phosphonic acid esters having a containing group are produced.

In particular, when the compound represented by the formula (3) is used as the conjugated compound, the compound represented by the formula (4) is produced with a good yield. In the formula (4), R ¹ represents a phosphoryl group or R ^c represented by the above formula (2), R ² represents a group represented by the above formula (2) or R ^d , and R ³ represents the above formula. R 2 represents a group represented by (2) or R ^e , R ⁴ represents a group represented by the above formula (2) or R ^f , and R ⁵ represents a group represented by the above formula (2) or R ^g . R ⁶ represents a group represented by the above formula (2) or R ^h . However, at least one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ is a group represented by the above formula (2). R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ may be bonded to each other or united together to form an aromatic or non-aromatic ring with adjacent atoms or carbon chains. Also good. This ring is the same as the ring formed by R ^c , R ^d , R ^e , R ^f , R ^g , R ^h , which are bonded to each other or united together with an adjacent atom or carbon chain.

  After completion of the reaction, the reaction product can be separated and purified by separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, etc., or a separation means combining these.

  Phosphonic acid esters [arylphosphonic acid (mono or di) ester etc.] having a group containing a conjugated structure obtained by the production method of the present invention are suitable as a metal extractant, a plasticizer, a flame retardant, or a precursor thereof. Can be used.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. The reaction product was analyzed by gas chromatography. The yield is a value based on the conjugated compound used in the reaction.

Example 1
In a reactor, diethyl phosphite (diethyl phosphonate) 6 mmol, benzene 2 mmol, manganese acetate (II) (5 mol% with respect to benzene), cobalt acetate (II) (0.3 mol% with respect to benzene), acetonitrile 1 ml The reaction was carried out at 45 ° C. for 15 hours under a mixed gas atmosphere of oxygen / nitrogen (0.05 MPa / 0.05 MPa). After the reaction, the reaction solution was analyzed by gas chromatography. As a result, it was found that diethyl phenylphosphonate was 57%, diethyl [2- (diethoxyphosphoryl) phenyl] phosphonate and diethyl [4- (diethoxyphosphoryl) phenyl] phosphonate. It was produced at a ratio of approximately 4: 6 in a yield of 34%.

Example 2
The same procedure as in Example 1 was performed except that 1 ml of propionic acid was used instead of acetonitrile. As a result, 64% diethyl phenylphosphonate, diethyl [2- (diethoxyphosphoryl) phenyl] phosphonate and [4- Diethyl (diethoxyphosphoryl) phenyl] phosphonate was produced in a ratio of approximately 4: 6 in a yield of 23%.

Example 3
The same operation as in Example 1 was conducted except that acetonitrile was not used. As a result, diethyl phenylphosphonate was 50%, [2- (diethoxyphosphoryl) phenyl] phosphonate diethyl and [4- (diethoxyphosphoryl). Diethyl phenyl] phosphonate was produced in a ratio of approximately 4: 6 in 18% yield.

Example 4
The same operation as in Example 1 was performed except that cobalt (II) acetate was not used. As a result, 49% of diethyl phenylphosphonate, diethyl [2- (diethoxyphosphoryl) phenyl] phosphonate and [4- ( Diethoxyphosphoryl) phenyl] diethyl phosphonate was produced in a ratio of 4: 6 in a yield of 7%.

Example 5
The same operation as in Example 1 was conducted except that mesitylene was used instead of benzene and the reaction was performed at 75 ° C. As a result, 69% of diethyl 2,4,6-trimethylphenylphosphonate was found to be [3- (di Ethoxyphosphoryl) -2,4,6-trimethylphenyl] diethyl phosphonate was produced in 3% yield.

Example 6
The same procedure as in Example 1 was performed except that anisole was used instead of benzene. As a result, diethyl 2-methoxyphenylphosphonate and diethyl 4-methoxyphenylphosphonate had a yield of 65% in a ratio of 4: 6. Was generated at a rate.

Example 7
Except that naphthalene was used instead of benzene, the same operation as in Example 1 was performed. As a result, a mixture of diethyl naphthalen-1-ylphosphonate and diethyl naphthalen-2-ylphosphonate was produced in a yield of 76%. It was.

Example 8
Except that pyridine was used instead of benzene, the same operation as in Example 1 was carried out. As a result, diethyl pyridin-2-ylphenylphosphonate, diethyl pyridin-3-ylphenylphosphonate and pyridin-4-ylphenylphosphone were used. A mixture of diethyl acids was produced in a yield of 32%.

Example 9
In the reactor, diethyl phosphite (diethyl phosphonate) 6 mmol, 1,3,5-triisopropylbenzene 2 mmol, manganese (II) acetate (5 mol% with respect to 1,3,5-triisopropylbenzene), cobalt acetate (II) (1 mol% with respect to 1,3,5-triisopropylbenzene), 1 ml of propionic acid, and reaction at 45 ° C. for 5 hours in an oxygen / nitrogen (0.05 MPa / 0.05 MPa) mixed gas atmosphere Went. After the reaction, the reaction solution was analyzed by gas chromatography. As a result, diethyl 2,4,6-triisopropylphenylphosphonate was produced at a yield of 45%.

Example 10
To the reactor, 6 mmol of diethyl phosphite (diethyl phosphonate), 2 mmol of 1,4-diisopropylbenzene, manganese (II) acetate (5 mol% with respect to 1,4-diisopropylbenzene), cobalt (II) acetate (1, 1 mol% with respect to 4-diisopropylbenzene) and 1 ml of propionic acid were added, and the reaction was performed at 45 ° C. for 5 hours in an oxygen / nitrogen (0.05 MPa / 0.05 MPa) mixed gas atmosphere. When the reaction solution was analyzed by gas chromatography after the reaction, diethyl 2,5-diisopropylphenylphosphonate was produced at a yield of 80%.

Example 11
In the reactor, 6 mmol of diethyl phosphite (diethyl phosphonate), 2 mmol of benzonitrile, manganese (II) acetate (5 mol% with respect to benzonitrile), cobalt acetate (II) (1 mol% with respect to benzonitrile), propion 1 ml of acid was added, and the reaction was carried out at 45 ° C. for 10 hours under an oxygen / nitrogen (0.05 MPa / 0.05 MPa) mixed gas atmosphere. After the reaction, the reaction solution was analyzed by gas chromatography. As a result, diethyl cyanophenylphosphonate was obtained as a mixture of positional isomers in a yield of 63%, and a product in which the phosphoryl group was substituted with another molecular phenyl group was obtained in a yield of 12%. Was generated at a rate.

Claims (1)

Following formula (1)

(Wherein R ^a and R ^b each represent a hydrogen atom or a hydrocarbon group )
Phosphites represented by the following formula (3)

(Wherein R ^c , R ^d , R ^e , R ^f , R ^g , and R ^h are each a hydrogen atom or a hydrocarbon group, a heterocyclic group, a substituted oxy group, a substituted oxycarbonyl group, a carboxyl group, a substituted or One selected from an unsubstituted carbamoyl group, a cyano group, a nitro group, a sulfur acid group, a sulfur acid ester group, and an acyl group, provided that R ^c , R ^d , R ^e , R ^f , R ^g , R ^h At least one of them is a hydrogen atom, and R ^c , R ^d , R ^e , R ^f , R ^g , and R ^h are each bonded to each other or integrally formed together with an adjacent atom or carbon chain. Or a non-aromatic ring may be formed)
In the presence of a manganese compound and / or a cobalt compound and oxygen , and the following formula (4):

[Wherein R ¹ represents the following formula (2)

(Wherein R ^a and R ^b each represent a hydrogen atom or a hydrocarbon group)
In represented shows a phosphoryl group, or R ^c, R ² represents a group or R ^d is represented by the formula (2), R ³ represents a group or R ^e represented by the formula (2), R ⁴ represents a group represented by the above formula (2) or R ^f , R ⁵ represents a group represented by the above formula (2) or R ^g , and R ⁶ represents the above formula (2). Represents a group or R ^h . However, at least one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ is a group represented by the above formula (2). R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ may be bonded to each other or united together to form an aromatic or non-aromatic ring with adjacent atoms or carbon chains. It is good]
A method for producing a phosphonic acid ester, characterized in that a compound represented by the formula: