JP2000119247A - Production of arylalkyl hydroperoxides - Google Patents

Abstract

PROBLEM TO BE SOLVED: To selectively convert an arylalkyl hydrocarbon into the corresponding arylalkyl hydroperoxides at a high reaction rate and high concentration. SOLUTION: An arylalkyl hydrocarbon represented by the general formula [P and Q are each H or an alkyl group which may be mutually same or different; and (x) is an integer of 1-3 and Ar represents an aromatic hydrocarbon group having (x) valence] is oxidized with an oxygen-containing gas while keeping pH of the water phase to 5.0-9.5 in the presence of a transition metal complex catalyst containing a polyvalent amine compound selected from a cyclic polyvalent amine compound having >=3 nitrogen atoms in the molecular chain forming a ring and a linear polyvalent amine compound having >=3 nitrogen atoms in main chain of the molecule in the presence of water phase to selectively convert the hydrocarbon to the corresponding arylalkyl hydroperoxide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyvalent amine, more specifically, a cyclic polyamine compound having three or more nitrogen atoms in a molecular chain forming a ring, or a polyvalent amine compound having three or more nitrogen atoms in a main chain of the molecule.
Using a transition metal complex catalyst having a chain polyvalent amine compound having two or more nitrogen atoms as a ligand as a catalyst,
Arylalkyl hydroperoxides by oxidizing arylalkyl hydrocarbons with oxygen-containing gases under relatively mild reaction conditions to selectively convert them to the corresponding arylalkyl hydroperoxides at high reaction rates and to high concentrations And a method for producing the same. Arylalkyl hydroperoxides are useful as intermediates in the production of various chemicals. For example, cumene monohydroperoxide is used in the production of phenol and acetone.

[0002]

2. Description of the Related Art Various processes for producing corresponding arylalkyl hydroperoxides by oxidizing a hydrocarbon having an arylalkyl group with an oxygen-containing gas in the presence of a catalyst are known in the art.

For example, Japanese Patent Publication No. 55-50020 discloses a water-soluble complex (chelate compound) of cobalt, nickel, manganese, copper or iron having a polyaminocarboxylic acid such as ethylenediaminetetraacetic acid (EDTA) as a ligand. A method of using a catalyst to oxidize methylbenzenes having a secondary alkyl group such as 3,5-dimethylcumene with an oxygen-containing gas in the presence of water to convert them to the corresponding hydroperoxides. Is described. However, according to this method, the oxidation reaction cannot proceed at a practical reaction rate in a relatively low temperature range of about 80 ° C. where thermal decomposition of hydroperoxides can be ignored.

[0004]

SUMMARY OF THE INVENTION Accordingly, the present inventors have developed the above-mentioned problems in the prior art method of producing arylalkyl hydroperoxides by oxidizing arylalkyl hydrocarbons with an oxygen-containing gas. As a result of intensive studies to solve the above, polyamines, specifically, cyclic polyamine compounds having three or more nitrogen atoms in the molecular chain forming the ring, or in the main chain of the molecule A chain polyamine compound having three or more nitrogen atoms or a transition metal complex having any one of the ligands as a ligand oxidizes an arylalkyl hydrocarbon with an oxygen-containing gas under mild reaction conditions. Have been found to be advantageous catalysts for the conversion to arylalkyl hydroperoxides described in JP-A-8-311023 and JP-A-9-40139. However, with the progress of the oxidation reaction of the arylalkyl hydrocarbon, various organic acids including formic acid are produced as by-products, and as a result, the selectivity to the target arylalkyl hydroperoxide is reduced. is there.

The present invention has been made to solve such a problem. In the above reaction, an aqueous phase is present in the reaction system, and the pH of the aqueous phase is kept within a predetermined range. The present invention has been found not only to be able to stabilize the transition metal complex catalyst to be used, but also to increase the selectivity to the target arylalkyl hydroperoxide.

That is, the present invention provides a method of oxidizing an arylalkyl hydrocarbon with an oxygen-containing gas using a transition metal complex having a cyclic or chain-like polyvalent amine compound as a ligand as a catalyst to form a corresponding aryl compound. In the conversion to alkyl hydroperoxides, an aqueous phase is present in the reaction system, and the pH of the aqueous phase is maintained in a predetermined range, whereby the arylalkyl hydrocarbon is selectively and highly concentrated at a high reaction rate. It is an object of the present invention to provide a method for producing an arylalkyl hydroperoxide by converting it to the corresponding arylalkyl hydroperoxide.

[0007]

SUMMARY OF THE INVENTION The process for producing arylalkyl hydroperoxides according to the present invention is directed to a cyclic polyvalent amine compound having three or more nitrogen atoms in a molecular chain forming a ring and a cyclic polyvalent amine compound in the main chain of the molecule. In the presence of a transition metal complex catalyst having a ligand of a polyvalent amine compound selected from a chain-like polyvalent amine compound having three or more nitrogen atoms in the formula (I)

[0008]

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(Wherein P and Q each represent hydrogen or an alkyl group, which may be the same or different, x represents an integer of 1 to 3, and Ar represents an x-valent aromatic compound. An arylalkyl hydrocarbon represented by the following formula: is oxidized with an oxygen-containing gas in the presence of an aqueous phase while maintaining the pH of the aqueous phase in the range of 5.0 to 9.5. It is characterized by being selectively converted to the corresponding arylalkyl hydroperoxides.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION In the process according to the present invention, the arylalkyl hydrocarbon used as a starting material is represented by the general formula

[0011]

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(Wherein P and Q each represent hydrogen or an alkyl group, which may be the same or different, x represents an integer of 1 to 3, and Ar represents an x-valent aromatic compound. Represents a group hydrocarbon group).

According to the present invention, the arylalkyl hydrocarbon represented by the general formula (I) needs to have α hydrogen, and particularly preferably has tertiary hydrogen. Therefore, according to the present invention, in the general formula (I), at least one of P and Q is preferably an alkyl group, and particularly preferably, both are alkyl groups. The alkyl group is particularly preferably a methyl group. Examples of the aromatic hydrocarbon group include, for example, x-valent hydrocarbon groups derived from benzene, naphthalene, biphenyl, diphenyl ether and the like, and preferably x-valent hydrocarbon groups derived from benzene or naphthalene. .

Accordingly, in the present invention, preferred specific examples of the arylalkyl hydrocarbon include, for example, diisopropylbenzenes such as cumene, cymene, m-diisopropylbenzene and p-diisopropylbenzene;
Triisopropylbenzenes such as 3,5-triisopropylbenzene, ethylbenzene, sec-butylbenzene, sec-butylethylbenzene, isopropylnaphthalenes, diisopropylnaphthalenes such as 2,6-diisopropylnaphthalene, isopropylbiphenyls, 4,
Examples thereof include diisopropyl biphenyls such as 4'-diisopropyl biphenyl, and mixtures of two or more thereof. However, it is not limited to these.

According to the method of the present invention, such an arylalkyl hydrocarbon is oxidized with an oxygen-containing gas in the presence of a transition metal complex catalyst having a polyvalent amine compound as a ligand to form a corresponding arylalkyl hydrocarbon. In the conversion to hydroperoxides, an aqueous phase is present in the reaction system, and the pH of the aqueous phase is maintained in the range of 5.0 to 9.5, preferably 6.0 to 9.0. While maintaining the catalyst stable, the arylalkyl hydrocarbons can be selectively converted to the corresponding arylalkyl hydroperoxides at high reaction rates selectively and in high concentrations.

When the pH of the aqueous phase to be present in the reaction system is too low, the ligand is dissociated from the transition metal complex in the reaction system, and the transition metal and the counter ion combine to decompose the complex. On the other hand, when the pH of the aqueous phase is too large, the transition metal complex is decomposed to generate a transition metal hydroxide. Thus, in each case, the catalytic activity decreases, the selectivity to the target arylalkyl hydroperoxide decreases, and the reaction rate also decreases.

In the present invention, in order to maintain the pH of the aqueous phase in the above range, an aqueous solution containing a base such as sodium carbonate or sodium hydroxide is usually added to the reaction system at the start of the reaction. Thereafter, as the pH of the aqueous phase decreases, the aqueous solution of the base may be added to maintain the pH of the aqueous phase within the above range.

More specifically, when the reaction is carried out in a batch system, when an arylalkyl hydrocarbon as a starting material is charged into a reactor before the reaction, an aqueous solution in which a transition metal complex as a catalyst and a base are dissolved is used. May be charged into the reactor at the same time.
Here, in the case of a batch-type reaction, the amount of by-produced organic acid fluctuates depending on the reaction rate, so that the pH of the aqueous phase at the end of the reaction is adjusted to 5.0 to 9. The pH of the aqueous phase at the time of preparation, that is, the amount of the base added may be adjusted so as to fall within the range of 5. However, according to the invention, it is preferred that the pH of the aqueous phase be kept in a predetermined range by continuously adding a base to the reactor according to the reaction rate.

On the other hand, when the reaction is carried out continuously, before the reaction is started, an arylalkyl hydrocarbon as a starting material is charged into a reactor, and an aqueous solution in which a complex and a base are dissolved is added to the reactor. After the start of the reaction, while monitoring the pH of the aqueous phase, an aqueous solution in which the complex and the base are dissolved is continuously added to the reactor together with the arylalkyl hydrocarbon to keep the pH of the aqueous phase of the reaction system constant. Is preferred.

Next, a transition metal complex catalyst having a polyvalent amine compound as a ligand used in the method of the present invention will be described. In the present invention, the polyamine compound is a cyclic polyamine compound having three or more nitrogen atoms in a molecular chain forming a ring, and a chain having three or more nitrogen atoms in a main chain of the molecule. In the general formula representing the transition metal complex, the square brackets indicate a cyclic polyamine compound as a ligand.

First, a transition metal complex having a cyclic polyvalent amine compound as a ligand will be described. A first preferred transition metal complex having such a cyclic polyamine compound as a ligand is represented by general formula (II):

[0022]

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Wherein A is independently an alkylene group having 1 to 6 carbon atoms in the main chain, a phenylene group, a naphthylene group (a naphthalenediyl group), a phenanthrylene group (a phenanthylene diyl group), a pyridinediyl group, a pyrroldiyl group. Group, pyrazinediyl group, pyramidindiyl group or 1,
These are 3,5-triazinediyl groups, and these groups may have a substituent inert to the reaction. R is each independently hydrogen, an alkyl group, an aryl group, an alkylaryl group, or an arylalkyl group;
It may have a substituent inert to the reaction. M represents a + a-valent transition metal ion as a central metal ion;
Represents an oxidatively stable counter ion of -b valence, and a represents 1 to
4 represents an integer, b represents a positive integer, n represents an integer of 1 to 4, n = a / b, and m represents 0 or an integer of 1 or more. ) Is an electrically neutral transition metal complex.

Generally, in the oxidation reaction using such a transition metal complex as a catalyst, the oxidation number of the central metal ion may change during the oxidation of the arylalkyl hydrocarbon. In this case, for example, if the oxidation number of the transition metal ion increases, a suitable anion existing in the reaction system forms a corresponding counter ion.

In the above formula (II), A is independently an alkylene group having 1 to 6 carbon atoms in the main chain, a phenylene group, a naphthylene group, a phenanthrylene group, a pyridinediyl group, a pyrroldiyl group, a pyrazinediyl group, a pyrimidine A diyl group or a 1,3,5-triazinediyl group.

Examples of the alkylene group include an ethylene, trimethylene, tetramethylene, pentamethylene and hexamethylene group. Most preferably, it is an ethylene group. In addition, any of the groups represented by A may have a substituent that is inert to the reaction in the molecule. As a substituent inert to such a reaction, for example, an alkyl group, an alkoxy group, an aryl group,
Examples include alkylaryl, arylalkyl, aryloxy, ethenylene, ether, cyano, amino, amide, sulfonamide, carboxyl, carboxylate, hydroxyl, and ester groups. Can be.

R is each independently hydrogen, an alkyl group, an aryl group, an alkylaryl group or an arylalkyl group, and the above-mentioned alkyl group, aryl group, alkylaryl group or arylalkyl group also reacts as described above. It may have an inert substituent.

The alkyl group is not particularly limited, but usually preferably has 1 to 25 carbon atoms. Therefore, specific examples thereof include, for example,
Methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, undecyl, dodecyl, tridecyl and the like can be mentioned. Examples of the aryl group include phenyl and naphthyl. Examples of the alkylaryl group include, for example, a toluyl group.
For example, a benzyl group can be mentioned.

Further, when R has an inert substituent,
As specific examples thereof, more specifically, for example, hydroxyalkyl groups such as hydroxyethyl, hydroxypropyl and hydroxybutyl groups, alkoxyalkyl groups such as methoxyethyl, methoxypropyl, methoxybutyl and methoxypentyl, acetyloxyethyl, acetyloxy Propyl, acetyloxybutyl, ethoxycarbonylethyl, ethoxycarbonylpropyl, an alkyl group having an ester group such as ethoxycarbonylbutyl, carboxymethyl, carboxyethyl, carboxypropyl,
Carboxyl butyl, acetate, propionate, alkyl group having a carboxyl group such as butyrate or carboxylate group, cyanomethyl, cyanoethyl, cyanopropyl, cyanoalkyl group such as cyanobutyl, aminoethyl, amylpropyl, aminobutyl, aminoalkyl such as aminopentyl Group, acetylaminomethyl, acetylaminoethyl, acetylaminopropyl, benzoylaminoethyl, an alkyl group having an amide group such as benzoylaminopropyl, methylsulfoaminoethyl,
Examples thereof include alkyls having a sulfonamide group such as methylsulfoaminopropyl, methylsulfoaminobutyl, phenylsulfoaminoethyl, phenylsulfoaminopropyl, phenylsulfoaminobutyl, toluylsulfoaminoethyl, and toluylsulfoaminopropyl.

In the present invention, among the cyclic polyamine compounds which are ligands constituting the first transition metal complex represented by the general formula (II), three nitrogen atoms are present in a molecular chain forming a ring. In the triazacrown compound, A is preferably an ethylene group. Therefore, preferred specific examples of the triazacrown compound include, for example, the following (1-01 to 1- 1
8).

[0031]

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[0032]

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The first compound represented by the general formula (II)
Among the cyclic polyamine compounds which are ligands constituting the transition metal complex of the above, preferred specific examples of those having four or more nitrogen atoms in the molecular chain constituting the ring are those wherein A is an ethylene group, a trimethylene group, 2,6-pyridinediyl group, 2,5-
A pyrrolediyl group or a 2,2′-bipyridyl-6,6′-diyl group, wherein m is an integer of 1 to 4.

Accordingly, specific examples of such a cyclic polyvalent amine compound include the following (2-01 to 2-16).

[0035]

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[0036]

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In the above, R represents an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms (for example, phenyl group), or an arylalkyl group having 7 to 14 carbon atoms (for example,
A benzyl group) or an alkylaryl group having 7 to 14 carbon atoms (eg, a toluyl group).

The second preferred transition metal complex used in the method of the present invention is represented by the general formula (III):

[0039]

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Wherein B is a group represented by the general formula (IV)

[0041]

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(In the formula, Y ¹ and Y ² each independently represent an alkylene group having 1 to 6 carbon atoms or a phenylene group in the main chain, and each of these groups has a substituent which is inactive in the reaction. R is each independently hydrogen, an alkyl group, an aryl group, an alkylaryl group or an arylalkyl group, and the alkyl group, the aryl group, the alkylaryl group or the arylalkyl group is M may represent a + a-valent transition metal ion as a central metal ion, and X represents an oxidatively stable -b-valent pair. Represents an ion, a represents an integer of 1 to 4, b represents a positive integer,
n represents an integer of 1 to 4, n = a / b, and m represents 0 or an integer of 1 or more. ). ).

In particular, Y ¹ and Y ² are preferably ethylene or trimethylene, and R is preferably hydrogen.

Therefore, preferred specific examples of the cyclic polyamine compound which is a ligand constituting such a second transition metal complex include, for example, the following (3-01)
To 3-08).

[0045]

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A third preferred transition metal complex used in the method of the present invention is represented by the general formula (V):

[0047]

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(In the formula, B represents an alkylene group having 1 to 3 carbon atoms in the main chain, and the alkylene group and the 2,5-pyrrolediyl group have a substituent which is inactive in the above-described reaction. A transition metal complex represented by the formula:

Particularly, a third preferred transition metal complex is a porphyrin in which B is a methylene group which may have an alkyl or phenyl substituent, or an alkyl or phenyl substituted porphyrin in the above general formula (V). is there.

Accordingly, preferred specific examples of the cyclic polyamine compound which is a ligand constituting such a third transition metal complex are as follows (4-01 to 4-
09).

[0051]

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[0052]

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A fourth preferred transition metal complex used in the method of the present invention is represented by the general formula (VI):

[0054]

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Wherein A is independently an alkylene group having 1 to 6 carbon atoms in the main chain, a phenylene group, a naphthylene group, a phenanthrylene group, a pyridinediyl group, a pyrroldiyl group, a pyrazinediyl group, a pyrimidinediyl group or
A 1,3,5-triazinediyl group, B is a bisalkylidene group having 2 to 10 carbon atoms in the main chain,

[0056]

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And these groups may have a substituent inert to the reaction. R is each independently hydrogen, an alkyl group, an aryl group, an alkylaryl group or an arylalkyl group, and these groups may have a substituent inert to the reaction. M represents a + a-valent transition metal ion as a central metal ion, and X represents
Represents an oxidatively stable counter ion having a valence of -b, a represents an integer of 1 to 4, b represents a positive integer, n represents an integer of 1 to 4, and n = a / b; m represents 0 or an integer of 1 or more. ).

Here, the following can be exemplified as preferred bisalkylidene groups.

[0059]

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Preferred specific examples of the bisalkylidene group containing a heteroaromatic ring include the following.

[0061]

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Accordingly, specific examples of the cyclic polyamine compound which is a ligand constituting such a fourth transition metal complex include the following (5-01 to 5-04). Can be.

[0063]

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In the above, R is an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms (for example, phenyl group), and an arylalkyl group having 7 to 14 carbon atoms (for example,
A benzyl group) or an alkylaryl group having 7 to 14 carbon atoms (eg, a toluyl group).

Further, a fifth preferred transition metal complex used in the method of the present invention has the general formula (VII)

[0066]

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(Wherein A is each independently an alkylene group having 1 to 6 carbon atoms in the main chain, a phenylene group, a naphthylene group, a phenanthrylene group, a pyridinediyl group, a pyrroldiyl group, a pyrazinediyl group, a pyrimidinediyl group or
A 1,3,5-triazinediyl group, B is a bisalkylidene group having 2 to 10 carbon atoms in the main chain,

[0068]

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All of these groups may have a substituent inert to the reaction. R is each independently hydrogen, an alkyl group, an aryl group, an alkylaryl group or an arylalkyl group, and these groups may have a substituent inert to the reaction. M represents a + a-valent transition metal ion as a central metal ion, and X represents
Represents an oxidatively stable counter ion having a valence of -b, a represents an integer of 1 to 4, b represents a positive integer, n represents an integer of 1 to 4, and n = a / b; m and q are each 0 or 1
The following integers are shown. ).

Here, preferred bisalkylidene groups include those exemplified above for the fourth transition metal complex.

Accordingly, specific examples of the cyclic polyamine compound which is a ligand constituting such a fifth transition metal complex include the following (6-01 to 6-04). Can be.

[0072]

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In the above, R is an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms (for example, phenyl group), and an arylalkyl group having 7 to 14 carbon atoms (for example,
A benzyl group) or an alkylaryl group having 7 to 14 carbon atoms (eg, a toluyl group).

In the present invention, among the various transition metal complex catalysts having the above-mentioned cyclic polyamine compound as a ligand, the first transition metal complex catalyst is particularly preferably used.

Therefore, among the first transition metal complexes,
When the cyclic polyvalent amine compound as a ligand is a triazacrown compound, for example, (1,4,7-
Triazanonane) manganese (II) sulfate, (N, N ', N''-
Tributyl-1,4,7-triazanonane) manganese (II)
Sulfate, (N, N ′, N ″ -tribenzyl-1,4,7-triazanonane) manganese (II) sulfate, [N, N ′, N ″ -tris (3-hydroxypropyl) -1, [4,7-Triazanonane] manganese (II) sulfate, [N, N ', N "-tris (potassium propionate) -1,4,7-triazanonane] manganese (II) sulfate and the like. it can.

In the first transition metal complex, a cyclic polyvalent amine compound as a ligand has four molecules in a molecular chain forming a ring.
When the compound has two or more nitrogen atoms, specific examples thereof include [1,4,8,11-tetraazacyclotetradecane] manganese (II) sulfate, [1,4,8,11-tetraaza Cyclotetradecane] cobalt (III) chloride, [1,4,
8,11-tetraazacyclotetradecane] copper (II) sulfate, [1,4,8,11-tetraazacyclotetradecane] ruthenium (II) chloride, [1,4,8,11-tetraazacyclo] [Tetradecane] nickel (II) sulfate, [1,4,8,11-tetraazacyclotetradecane] manganese (II) benzoate, [1,4,8,11-tetraazacyclotetradecane] cobalt (II) benzoate Acid salt, [1,4,8,12-tetraazacyclopentadecane] manganese (II) sulfate, [N, N ′, N ″,
N '''-tetrakis (2-ethoxycarbonylethyl)
[1,4,8,11-tetraazacyclotetradecane] cobalt (II) sulfate, [1,4,8,11-tetraazacyclotetradecane] manganese (II) stearate, [1,4,8, 11-tetraazacyclotetradecane] cobalt (II) stearate, [N, N ′, N ″, N ″ ′-tetra-n-butyl-1,4,
8,11-tetraazacyclotetradecane] manganese (II)
Sulfate, the cyclic polyamine compound 3-01, 3-0
8, 4-01 to 4-09 copper sulfate complex, copper benzoate complex, cobalt sulfate complex, cobalt acetate complex, ruthenium chloride complex and the like.

Next, a transition metal complex having a chain polyvalent amine compound as a ligand will be described. The first preferred transition metal complex having such a linear polyamine compound as a ligand is represented by the general formula (VIII):

[0078]

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Wherein A ² is independently an alkylene group having 1 to 6 carbon atoms in the main chain, an o-phenylene group, an m-
Phenylene group, p-phenylene group, 1,8-naphthylene group, 9,10-phenanthrylene group, 2,6-pyridinediyl group, 3,6-acridinediyl group, 2,2′-bipyridyl-6,
6'-diyl group, 1,10-phenanthrone-2,9-diyl group, 2,6-pyrimidinediyl group, 4,5-pyrimidinediyl group, 2,6-pyrazinediyl group, 2-phenyl-1,3, 5
-A triazine-2,6-diyl group,

[0080]

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(In the above formula, R¹Is an alk having 1 to 8 carbon atoms
Represents a len group;^TwoIs an alkylene group having 1 to 8 carbon atoms,
Aryl group having 6 to 14 primes, aryl having 7 to 14 carbons
An alkyl group or an alkylaryl group having 7 to 14 carbon atoms
Show. ). ) And these groups
May have a substituent that is inert to the reaction.
No. K ^{twenty one}, K^{twenty two}, K^{twenty three}And K^{twenty four}Are each independently water
Element, alkyl group, aryl group, alkylaryl group,
Reel alkyl group, pyridyl group, pyridylalkyl group or
Represents a quinolyl group, of which an alkyl group, an aryl
Group, alkylaryl group, arylalkyl group, pyridi
, Pyridylalkyl or quinolyl groups do not interfere with the reaction.
It may have an active substituent. M is the central metal ion
X represents a transition metal ion having a valence of + a,
Shows a stable counter ion of -b valence, a is an integer of 1 to 4
And b represents a positive integer, and n represents an integer of 1 to 4.
And n = a / b, and m represents an integer of 2 or more. )
Is an electrically neutral compound represented by

In the above general formula (VIII), K ²¹ ,
K ²² , K ²³ and K ²⁴ each independently represent hydrogen, an alkyl group, an aryl group, an alkylaryl group, an arylalkyl group, a pyridyl group, a pyridylalkyl group or a quinolyl group.

Here, the alkyl group is not particularly limited, but usually preferably has 1 to 25 carbon atoms. Therefore, specific examples thereof include, for example,
Methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, undecyl, dodecyl, tridecyl and the like can be mentioned. Examples of the aryl group include phenyl and naphthyl. Examples of the alkylaryl group include a toluyl group and the like.
In addition, examples of the arylalkyl group include a benzyl group.

Examples of the pyridyl group include a 2-pyridyl group, a 3-pyridyl group and a 6-methyl-2-pyridyl group. Examples of the pyridylalkyl group include a 2-pyridylmethyl group, a 3-pyridylmethyl group, a 2-pyridylethyl group, and a 3-pyridylmethyl group. Also, as the quinolyl group,
For example, an 8-quinolyl group and the like can be mentioned.

The above-mentioned alkyl group, aryl group, alkylaryl group, arylalkyl group, pyridyl group, pyridylalkyl group and quinolyl group may all have a substituent inert to the reaction. Examples of the substituent inert to such a reaction include a hydroxyl group, an ether group, an ester group, a cyano group, an amino group, an amide group, a sulfonamide group, a carboxyl group, and a carboxylate group.

A ² is a group as described above. When A ² is an alkylene group having 1 to 6 carbon atoms, specific examples thereof include an ethylene, trimethylene, tetramethylene, pentamethylene and hexamethylene group. be able to.

As described above, any of A ² may have a substituent which is inactive in the reaction. Examples of the substituent which is inactive in the reaction include, for example, a hydroxyl group. , An ether group, an ester group, a cyano group, an amino group, an amide group, a sulfonamide group, a carboxyl group, and a carboxylate group.

In the present invention, specific examples of the chain polyvalent amine compound which is a ligand constituting the first transition metal complex represented by the general formula (VIII) include compounds 5-01 to 5 -25. 5-01 diethylenetriamine 5-02 triethylenetetramine 5-03 tetraethylenepentamine 5-04 pentaethylenehexamine 5-05 hexaethyleneheptamine 5-06 heptaethyleneoctamine 5-07 octaethylenenonamine 5-08 N, N ' -Bis (2-aminoethyl) -1,3-propanediamine 5-09 N- (3-aminopropyl) -1,3-propanediamine 5-10 N, N'-bis (2-aminopropyl) -1 , 3-
Propanediamine 5-11 1,5,9,13,17-pentaazaheptadecane 5-12 1,5,9,13,17,21-hexaazaheneicosane 5-13 N, N, N ', N '-Tetramethyltriethylenetetramine 5-14 N, N', N ", N"'-Tetramethyltriethylenetetramine 5-15 N, N', N ", N"'-Tetraethyltriethylenetetramine 5-16 N , N ', N ", N"'-tetrapropyltriethylenetetramine 5-17 N, N ', N ", N"'-tetrabutyltriethylenetetramine 5-18 N, N ', N ", N"' -Tetrapentyltriethylenetetramine 5-19 N, N ', N ", N"'-tetrakis (2-cyanoethyl) triethylenetetramine 5-20 N, N ', N ", N"'-tetrakis (2-ethoxy Carbonylethyl) triethylenetetramine 5-21 N, N ', N ", N"'-tetrakis (2-methoxycarbonylethyl) triethylenetetramine 5-22 N, N ', N ", N"'-tetrakis (3-hydroxypropyl) triethylenetetramine 5-23 N, N ', N ", N"'-tetrakis (3-tosylaminoethyl) triethylenetetramine 5- 24 N, N ', N ", N"'-tetrakis (3-acetylaminopropyl) triethylenetetramine 5-25 N, N ', N ", N"'-tetrakis (3-acetoxypropyl) triethylenetetramine In addition to the above 5-01 to 5-25, the following (5-26 to 5-29 and 11-01 to 11
-70).

[0089]

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[0090]

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[0091]

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[0092]

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[0093]

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[0094]

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Among such chain polyamines, those in which A ² is an ethylene group or trimethylene group and m is 2 or 3 are particularly preferred in the present invention. The second preferred transition metal complex used in the method of the present invention
Is represented by the general formula (IX) [K ³¹ = N−A ³ −N = K ³² ] M ^{a +} (X ^b− ) n (IX) (where A ³ is each independently a carbon number of 1 in the main chain. ~ 6
Alkylene group, o-phenylene group, m-phenylene group, p-phenylene group, 1,8-naphthylene group, 9,10-phenanthrylene group, 2,6-pyridinediyl group, 3,6-acridinediyl group, 2 , 2'-Bipyridyl-6,6'-diyl group, 1,10-phenanthrone-2,9-diyl group, 2,6-pyrimidinediyl group, 4,5-pyrimidinediyl group, 2,6-
A pyrazinediyl group, a 2-phenyl-1,3,5-triazine-2,6-diyl group,

[0096]

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(In the above formula, R¹Is an alk having 1 to 8 carbon atoms
Represents a len group;^TwoIs an alkylene group having 1 to 8 carbon atoms,
Aryl group having 6 to 14 primes, aryl having 7 to 14 carbons
An alkyl group or an alkylaryl group having 7 to 14 carbon atoms
Show. ). ) And these groups
May have a substituent that is inert to the reaction.
No. K ³¹And K³²Is a 2-aminobenzylidene group.
And may have a substituent that is inert to the reaction. M is
Shows + a-valent transition metal ion as central metal ion
X represents an oxidatively stable -b valent counter ion;
Represents an integer of 1 to 4, b represents a positive integer, and n represents 1 to 4.
4 is an integer, n = a / b, and m is an integer of 2 or more.
Indicates a number. ).

Specific examples of the chain polyamine compound constituting the ligand in the second transition metal complex include:
For example, the following (6-01 to 6-10) can be mentioned.

[0099]

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A third preferred transition metal complex used in the method of the present invention is represented by the general formula (X) [K ⁴¹ = N−A ⁴ -N = K ⁴² ] M ^{a +} (X ^b− ) n (X) In the formula, A ⁴ independently represents 1 to 6 carbon atoms in the main chain.
Alkylene group, o-phenylene group, m-phenylene group, p-phenylene group, 1,8-naphthylene group, 9,10-phenanthrylene group, 2,6-pyridinediyl group, 3,6-acridinediyl group, 2 , 2'-Bipyridyl-6,6'-diyl group, 1,10-phenanthrone-2,9-diyl group, 2,6-pyrimidinediyl group, 4,5-pyrimidinediyl group, 2,6-
A pyrazinediyl group, a 2-phenyl-1,3,5-triazine-2,6-diyl group,

[0101]

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(In the above formula, R¹Is an alk having 1 to 8 carbon atoms
Represents a len group;^TwoIs an alkylene group having 1 to 8 carbon atoms,
Aryl group having 6 to 14 primes, aryl having 7 to 14 carbons
An alkyl group or an alkylaryl group having 7 to 14 carbon atoms
Show. ). ) And these groups
May have a substituent that is inert to the reaction.
No. K ⁴¹And K⁴²Is a 2-pyridylmethylene group or 6-
A methyl-2-pyridylmethylene group,
May have a substituent that is inert to the reaction.
No. M is a + a-valent transition metal ion as a central metal ion.
X represents an oxidatively stable -b valent counter ion.
A represents an integer of 1 to 4, b represents a positive integer,
n represents an integer of 1 to 4, n = a / b, and m represents 2
The following integers are shown. ) Is a transition metal complex represented by
You.

Specific examples of the chain polyvalent amine compound constituting the ligand of the third transition metal complex include the following (7-01 to 7-22). Can be.

[0104]

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A fourth preferred transition metal complex used in the method of the present invention is represented by the general formula (XI):

[0106]

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Wherein A ^{51 to} A ⁵³ are each independently
It represents an alkylene group having 1 to 6 carbon atoms and may have a substituent inert to the reaction. K ^{51 to} K ⁵³ are a 2-pyridylmethylene group, a 6-methyl-2-pyridylmethylene group or a benzylidene group, and any of these groups may have a substituent inert to the reaction. . M represents a + a-valent transition metal ion as a central metal ion, and X represents
Represents an oxidatively stable counter ion having a valence of -b, a represents an integer of 1 to 4, b represents a positive integer, n represents an integer of 1 to 4, and n = a / b; m represents an integer of 2 or more. ).

As specific examples of the chain polyamine compound constituting the ligand in the fourth transition metal complex,
For example, the following (8-01 to 8-03) can be mentioned.

[0109]

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The fifth of the preferred transition metal complexes used in the method of the present invention is represented by the general formula (XII) [K ⁶¹ -N = A ⁶ = ^{NK 62} ] M ^{a +} (X ^b- ) n (XII) in, a ⁶ is,

[0111]

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And these groups may have a substituent which is inactive in the reaction. K ⁶¹
And K ⁶² are a 2-pyridyl group, a 3-pyridyl group, an 8-quinolyl group or an aminoalkyl group (the alkyl group is
4 ), And any of these groups may have a substituent inert to the reaction. M represents a + a-valent transition metal ion as a central metal ion, and X represents
Represents an oxidatively stable counter ion having a valence of -b, a represents an integer of 1 to 4, b represents a positive integer, n represents an integer of 1 to 4, and n = a / b; m represents an integer of 2 or more. ).

Specific examples of the chain polyamine compound constituting the ligand in the fifth transition metal complex include:
For example, the following (9-01 to 9-18) can be mentioned.

[0114]

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The sixth preferred transition metal complex used in the method of the present invention has the general formula (XIII)

[0116]

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(Where A ⁷ is

[0118]

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And these groups may have a substituent inert to the reaction. K ⁷¹
~K ⁷⁴ are 2-pyridyl, 3-pyridyl group, a 2-pyridylmethyl group or 3-pyridylmethyl group, none of these groups may have substituent groups inert to the reaction Good. M represents a + a-valent transition metal ion as a central metal ion, X represents an oxidatively stable -b-valent counter ion, a represents an integer of 1 to 4, and b represents a positive integer. And n represents an integer of 1 to 4; n = a / b;
Represents an integer of 2 or more. ).

Specific examples of the chain polyamine compound constituting the ligand in the sixth transition metal complex include:
For example, the following (10-01 to 10-15)
Can be mentioned.

[0121]

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The seventh preferred transition metal complex used in the method of the present invention is represented by the general formula (XIV) [K ⁸¹ ＮNA ⁸ -N = K ⁸² ] M ^{a +} (X ^b- ) n (XIV) In the formula, A ⁸ is each independently a carbon number of 1 to 6 in the main chain.
Alkylene group, o-phenylene group, m-phenylene group, p-phenylene group, 1,8-naphthylene group, 9,10-phenanthrylene group, 2,6-pyridinediyl group, 3,6-acridinediyl group, 2 , 2'-Bipyridyl-6,6'-diyl group, 1,10-phenanthrone-2,9-diyl group, 2,6-pyrimidinediyl group, 4,5-pyrimidinediyl group, 2,6-
A pyrazinediyl group, a 2-phenyl-1,3,5-triazine-2,6-diyl group,

[0123]

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(In the above formula, R¹Is an alk having 1 to 8 carbon atoms
Represents a len group;^TwoIs an alkylene group having 1 to 8 carbon atoms,
Aryl group having 6 to 14 primes, aryl having 7 to 14 carbons
An alkyl group or an alkylaryl group having 7 to 14 carbon atoms
Show. ). ) And these groups
May have a substituent that is inert to the reaction.
No. K ⁸¹And K⁸²Is the general formula TN = CR⁸¹-CR⁸²= Wherein T is a hydroxyl group, an amino group or a general formula -NR^FourR
^Five(Where R^FourAnd R^FiveAre each independently 1 carbon atom
Represents an alkyl group of 1 to 6 and having a substituent inert to the reaction
May be. ) Represents a group represented by⁸¹And R⁸²
Are each independently a hydrogen atom, an alkyl having 1 to 6 carbon atoms.
A phenyl group or an alkyl group or a phenyl group
May have a substituent that is inert to the reaction. M is
Shows + a-valent transition metal ion as central metal ion
X represents an oxidatively stable -b valent counter ion;
Represents an integer of 1 to 4, b represents a positive integer, and n represents 1 to 4.
4 is an integer, n = a / b, and m is an integer of 2 or more.
Indicates a number. ).

Specific examples of the chain polyvalent amine compound constituting the ligand in the seventh transition metal complex include:
For example, the following (12-01 to 12-26)
Can be mentioned.

[0126]

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[0127]

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In the present invention, in any of the above transition metal complexes, M represents + as the central metal ion.
a represents a transition metal ion having a valence (a represents a positive integer), and preferred specific examples thereof include ions such as iron, nickel, manganese, cobalt, copper, chromium, ruthenium, rhodium, vanadium, titanium, and zirconium. And among these transition metal ions,
In particular, iron, nickel, manganese, cobalt, copper or ruthenium is preferred.

X is an oxidatively stable -b value (b is
Indicates a positive integer. )), A preferred specific example
For example, halo such as chloride ion and bromide ion
Genion, SO_Four ^2-, NO_Three ^-, BF_Four ^-, P
F₆ ^-, ClO_Four ^-, CO_Three ^2-, P _TwoO₇ ^Four-, S_TwoO₆
^2-, Formate ion, acetate ion, trifluoroacetate ion
, Propionate ion, naphthenate ion, benzoic acid
Organic carboxylate anions such as ion and naphthoate ion
Methanesulfonate ion, trifluoromethanesulfur
Phonate ion, benzenesulfonic acid ion, p-tolue
Organic sulfonic acid anions such as sulfonic acid ion
Peroxide anions such as
And acetyl acetate.
List settato ions and squarate ions
Can be.

In the transition metal complex used in the present invention, a represents an integer of 1 to 4, n represents an integer of 1 to 4, b represents a positive integer, n = a / b, and m represents an integer. It is an integer of 2 or more, preferably 2 or 3. The counter ion in the transition metal complex need not be unique.

The transition metal complex used in the present invention includes a metal salt corresponding to the central metal ion, a carboxylate,
It can be easily obtained by coordinating the cyclic or chain polyamine compound with a sulfonate or the like.
More specifically, an inorganic salt, a carboxylate, a sulfonate, or the like of the metal corresponding to the central metal ion may be reacted with a cyclic or chain polyvalent amine compound in an appropriate solvent. The transition metal complex thus obtained may be purified, if necessary, by ordinary means such as recrystallization, extraction, chromatography and the like.

In the method of the present invention, among the transition metal complexes, those having a cyclic polyamine compound as a ligand are usually used as starting arylalkyl hydrocarbons 10 as starting materials.
It is used in the range of 0.000001 to 10 parts by weight, preferably 0.000001 to 1 part by weight with respect to 0 parts by weight.
In particular, among the first transition metal complexes, those having a ligand of a cyclic polyamine compound having three nitrogen atoms in the molecule are preferably 0.000001 to 100 parts by weight of the arylalkyl hydrocarbon. 5.0 parts by weight, preferably 0.00
The compound used in the range of from 0.1 to 0.1 part by weight and having a ligand of a cyclic polyvalent amine compound having four or more nitrogen atoms in the molecule has an amount of 0 to 100 parts by weight of the arylalkyl hydrocarbon. 0.000001 to 5.0 parts by weight, preferably 0.1 to 5.0 parts by weight.
It is used in the range of 00001 to 0.1 parts by weight.

On the other hand, a transition metal complex having a chain polyvalent amine compound as a ligand is usually used in an amount of 0.000001 based on 100 parts by weight of the starting arylalkyl hydrocarbon.
To 5.0 parts by weight, preferably 0.000 parts by weight.
It is used in the range of 1 to 0.1 part by weight.

In the method of the present invention, the transition metal complex may be used as a solid or may be used after being dissolved in a reaction solution. That is, the transition metal catalyst can be used in any of a heterogeneous reaction and a homogeneous reaction.

As the oxygen-containing gas as an oxidizing agent, air is usually used, but oxygen or any mixed gas of oxygen and nitrogen may be used. The reaction may be usually carried out under normal pressure, but may be carried out under pressure if necessary.
The reaction temperature is usually in the range of 40 to 130 ° C, preferably in the range of 50 to 110 ° C.

In the present invention, the reaction can be carried out in either a batch system or a continuous system. When the reaction is carried out batchwise, if the starting arylalkyl hydrocarbon is liquid at the reaction temperature, an aqueous solution in which a catalyst and a base are dissolved is charged into the reactor together with the arylalkyl hydrocarbon, and the mixture is heated and stirred. The oxidation reaction is usually performed by blowing air. If necessary, an organic solvent or water inert to the reaction may be used as the reaction solvent. As described above, the base may be added to the reactor all at once during the preparation, but preferably, the base is continuously added to the reactor according to the reaction rate to adjust the pH of the aqueous phase to a predetermined range. It is preferable to keep. On the other hand, if the starting arylalkyl hydrocarbon is solid at the reaction temperature, it may be dissolved in an organic solvent inert to the reaction and used as a solution.

Further, in the present invention, if necessary,
At the start of the reaction, a small amount of the corresponding arylalkyl hydroperoxide or the like may be present as an initiator in the arylalkyl hydrocarbon. Alternatively, the catalyst may be formed in a fixed bed, and the mixture may be passed through the fixed bed while mixing the starting material arylalkyl hydrocarbon or a solution thereof with air.

On the other hand, when the reaction is carried out continuously, before the reaction is started, an arylalkyl hydrocarbon as a starting material is charged into a reactor, and an aqueous solution in which a complex and a base are dissolved is added to the reactor. After the start of the reaction, while monitoring the pH of the aqueous phase, an aqueous solution in which the complex and the base are dissolved is continuously added to the reactor together with the arylalkyl hydrocarbon to keep the pH of the aqueous phase of the reaction system constant. Is preferred.

In the present invention, when the reaction is carried out in a continuous mode, there is an advantage that an optimum pH range for improving the selectivity can be maintained.

According to the method of the present invention, the desired arylalkyl hydroperoxide can be easily recovered from the reaction mixture after the completion of the reaction by ordinary means such as distillation of the resulting reaction mixture.

[0141]

According to the present invention, when an arylalkyl hydrocarbon is oxidized by an oxygen-containing gas using a transition metal complex having a cyclic or chain-like polyvalent amine compound as a ligand as a catalyst, the reaction system And maintaining the pH of the aqueous phase in a predetermined range to stably maintain the transition metal complex catalyst and selectively and at high concentration of the arylalkyl hydrocarbon at a high reaction rate. It can be converted to the corresponding arylalkyl hydroperoxides.

[0142]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited by these examples. In the following, the concentration of cumene hydroperoxide in the reaction mixture after completion of the reaction was determined by iodometry and gas chromatography. The selectivity of the produced cumene hydroperoxide was determined by gas chromatography.

Example 1 5.6 g of an aqueous solution obtained by adding 0.54 mg of a catalyst to a 0.3% by weight aqueous solution of sodium carbonate was prepared, and 130.9 g of cumene was prepared.
And 49.1 g of cumene hydroperoxide (CHP) were charged to the reactor. The oil-water mixture is added to 0.6
Heat to 105 ° C under 9MPa pressure and with strong stirring,
Air is blown into this at a rate of 400 mL / min.
130.9 g of cumene and 49.1 g of cumene hydroperoxide
And a solution obtained by adding 96.4 ppm of a catalyst to an aqueous solution of 0.3% by weight of sodium carbonate at a rate of 0.093 g / min. Was continuously added to the reactor at a rate of 3 g / min. Cumene was oxidized by continuous reaction.

The reaction solution that overflowed from the overflow line of the reactor was collected in a sampling pot provided downstream, and the samples collected at 4 hours, 5 hours, and 6 hours after the start of the reaction were analyzed for cumene and cumene hydroperoxide. The concentration was determined by iodometry and gas chromatography and found to be 2.2% by weight / hour on average. Further, the selectivity of cumene hydroperoxide formed during this period was determined by high performance liquid chromatography, and was found to be 92.2 mol% on average.

The residence time, the reaction temperature, the catalyst used and its amount (relative to cumene), the concentration of cumene hydroperoxide in the oil phase before and after the reaction, the rate of accumulation and selectivity of cumene hydroperoxide, the steady-state (ie, The pH of the aqueous phase (after) is shown in Table 1.

Examples 2 to 4 and Comparative Examples 1 to 4 As shown in Table 1, the reaction was carried out under various reaction conditions.
Table 1 shows the results.

[0147]

[Table 1]

[0148]

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 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Nariwa Matsui 6-1-2, Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture Inside Mitsui Chemicals, Inc. (72) Toshihiro Takai Waki-Roku, Waki-cho, Kuga-gun, Yamaguchi Prefecture 1-2 1-2, Mitsui Chemicals Co., Ltd. (72) Inventor Hideto Matsuoka 6-1-2, Waki-machi, Kuga-gun, Yamaguchi Prefecture In-house Mitsui Chemicals Co., Ltd. (72) Inventor Yoji Kagayama Waki-cho, Kuga-gun, Yamaguchi Prefecture 6-1-2 Waki, Mitsui Chemicals, Inc. (72) Inventor Terunori Fujita 1-2-1, Waki, Waki-cho, Kuga-gun, Yamaguchi F-term in Mitsui Chemicals, Inc. 4G069 AA15 BA27A BA27B BB10B BC31A BC31B BC50A BC51A BC58A BC62A BC66A BC67A BC68A BC70A BC71A BD08B BE14A BE14B CB70 4H006 AA02 AB84 AC13 AC90 BA05 BA10 BA14 BA16 BA19 BA20 BA21 BA23 BA24 BA46 BB31 BC16 BE30 4H039 CA64 CC60

Claims (16)

[Claims] (1) a cyclic polyamine compound having three or more nitrogen atoms in a molecular chain forming a ring, and a cyclic polyamine compound having three or more nitrogen atoms in a main chain of the molecule;
In the presence of a transition metal complex catalyst having a ligand of a polyvalent amine compound selected from a chain polyvalent amine compound having two or more nitrogen atoms, a compound of the general formula (I) (Wherein, P and Q represent hydrogen or an alkyl group and may be the same or different from each other, and x is 1 to
An integer of 3 is shown, and Ar represents an x-valent aromatic hydrocarbon group. ) Is oxidized with an oxygen-containing gas in the presence of an aqueous phase while maintaining the pH of the aqueous phase in the range of 5.0 to 9.5, to form the corresponding arylalkyl hydroperoxide. A process for producing arylalkyl hydroperoxides, which is selectively converted to 2. The method for producing an arylalkyl hydroperoxide according to claim 1, wherein the reaction is carried out in a continuous manner. 3. The transition metal complex represented by the general formula (II): Wherein A is independently an alkylene group having 1 to 6 carbon atoms in the main chain, a phenylene group, a naphthylene group, a phenanthrylene group, a pyridinediyl group, a pyrroldiyl group, a pyrazinediyl group, a pyrimidinediyl group, or a 1,3, A 5-triazinediyl group, which may have a substituent inert to the reaction, wherein R is independently hydrogen, an alkyl group, an aryl group, an alkylaryl group, or an arylalkyl group; And an alkyl group, an aryl group,
The alkylaryl group or the arylalkyl group may have a substituent inert to the reaction. M represents a + a-valent transition metal ion as a central metal ion, X represents an oxidatively stable -b-valent counter ion, a represents an integer of 1 to 4, and b represents a positive integer. And n represents an integer of 1 to 4, n = a / b, and m represents 0 or an integer of 1 or more. 2. The method according to claim 1, which is a transition metal complex represented by the formula: 4. The transition metal complex represented by the general formula (III): (Wherein B is a group represented by the general formula (IV): (Wherein, Y ¹ and Y ² each independently represent an alkylene group having 1 to 6 carbon atoms or a phenylene group in the main chain, and any of these groups has a substituent that is inert to the reaction. R is each independently hydrogen, an alkyl group, an aryl group, an alkylaryl group or an arylalkyl group, and the alkyl group, the aryl group, the alkylaryl group or the arylalkyl group is a substituent inert to the reaction. And M represents a + a-valent transition metal ion as a central metal ion;
Represents an oxidatively stable counter ion of -b valence, and a represents 1 to
4 represents an integer, b represents a positive integer, n represents an integer of 1 to 4, n = a / b, and m represents 0 or an integer of 1 or more. ). 2. The method according to claim 1, which is a transition metal complex represented by the formula: 5. The transition metal complex catalyst of the formula (V) (Wherein B represents an alkylene group having 1 to 3 carbon atoms in the main chain, and the alkylene group and the 2,5-pyrrolediyl group are
It may have a substituent inert to the reaction. 2. The method according to claim 1, which is a transition metal complex represented by the formula: 6. The transition metal complex represented by the general formula (VI): Wherein A is independently an alkylene group having 1 to 6 carbon atoms in the main chain, a phenylene group, a naphthylene group, a phenanthrylene group, a pyridinediyl group, a pyrroldiyl group, a pyrazinediyl group, a pyrimidinediyl group, or a 1,3, B is a bisalkylidene group having 2 to 10 carbon atoms in the main chain, and each of these groups may have a substituent inert to the reaction. And any of these groups may have a substituent inert to the reaction. R is each independently hydrogen, an alkyl group, an aryl group, an alkylaryl group or an arylalkyl group, and these groups may have a substituent inert to the reaction. M represents a + a-valent transition metal ion as a central metal ion, X represents an oxidatively stable -b-valent counter ion, a represents an integer of 1 to 4,
b represents a positive integer, n represents an integer of 1 to 4, and n = a
/ B, and m represents 0 or an integer of 1 or more. 2. The method according to claim 1, which is a transition metal complex represented by the formula: 7. The transition metal complex represented by the general formula (VII): Wherein A is independently an alkylene group having 1 to 6 carbon atoms in the main chain, a phenylene group, a naphthylene group, a phenanthrylene group, a pyridinediyl group, a pyrroldiyl group, a pyrazinediyl group, a pyrimidinediyl group, or a 1,3, A 5-triazinediyl group, each of which may have a substituent inert to the reaction, B is a bisalkylidene group having 2 to 10 carbon atoms in the main chain, And any of these groups may have a substituent inert to the reaction. R is each independently hydrogen, an alkyl group, an aryl group, an alkylaryl group or an arylalkyl group, and these groups may have a substituent inert to the reaction. M represents a + a-valent transition metal ion as a central metal ion, X represents an oxidatively stable -b-valent counter ion, a represents an integer of 1 to 4,
b represents a positive integer, n represents an integer of 1 to 4, and n = a
/ B, and m and q each represent 0 or an integer of 1 or more. 2. The method according to claim 1, which is a transition metal complex represented by the formula: 8. The transition metal complex represented by the general formula (VIII):(Where A^TwoAre each independently 1 to 6 carbon atoms in the main chain.
Alkylene group, o-phenylene group, m-phenylene
Group, p-phenylene group, 1,8-naphthylene group, 9,10-phenyl group
Enanthrylene group, 2,6-pyridinediyl group, 3,6-a
Clidinediyl group, 2,2'-bipyridyl-6,6'-diyl
Group, 1,10-phenanthrone-2,9-diyl group, 2,6-pi
Limidinediyl group, 4,5-pyrimidinediyl group, 2,6-
Pyrazinediyl group, 2-phenyl-1,3,5-triazine
-2,6-diyl group,(In the above formula, R¹Represents an alkylene group having 1 to 8 carbon atoms
Then R^TwoIs an alkyl group having 1 to 8 carbon atoms, 6 to 14 carbon atoms
An aryl group, an arylalkyl group having 7 to 14 carbon atoms or
Represents an alkylaryl group having 7 to 14 carbon atoms. )
It is a group forgotten. ), And each of these groups is
It may have a substituent inert to the reaction. K ^{twenty one},
K^{twenty two}, K^{twenty three}And K^{twenty four}Are independently hydrogen,
Group, aryl group, alkylaryl group, arylal
Kill, pyridyl, pyridylalkyl or quinolyl
Groups, of which alkyl, aryl, and alkyl
Aryl, arylalkyl, pyridyl, pyri
A zylalkyl group or a quinolyl group is a substituent inert to the reaction.
It may have a group. M represents a central metal ion
+ A represents a transition metal ion, and X represents an oxidatively stable
A represents a counter ion having a valence of b, a represents an integer of 1 to 4,
Represents a positive integer, n represents an integer of 1 to 4, and n = a /
b and m represents an integer of 2 or more. )
The method according to claim 1, which is a transition metal complex. 9. The transition metal complex represented by the general formula (IX) [K³¹= NA^Three-N = K³²] M^{a +}(X^b-) N (IX) (where A^ThreeAre each independently 1 to 6 carbon atoms in the main chain.
Alkylene group, o-phenylene group, m-phenylene
Group, p-phenylene group, 1,8-naphthylene group, 9,10-phenyl group
Enanthrylene group, 2,6-pyridinediyl group, 3,6-a
Clidinediyl group, 2,2'-bipyridyl-6,6'-diyl
Group, 1,10-phenanthrone-2,9-diyl group, 2,6-pi
Limidinediyl group, 4,5-pyrimidinediyl group, 2,6-
Pyrazinediyl group, 2-phenyl-1,3,5-triazine
-2,6-diyl group,(In the above formula, R¹Represents an alkylene group having 1 to 8 carbon atoms
Then R^TwoIs an alkylene group having 1 to 8 carbon atoms, 6 to 1 carbon atoms
4 aryl groups, arylalkyl groups having 7 to 14 carbon atoms
Or an alkylaryl group having 7 to 14 carbon atoms. )so
It is a group represented. ), And any of these groups
May also have a substituent that is inert to the reaction. K ³¹Passing
And K³²Is a 2-aminobenzylidene group,
It may have an inert substituent. M is the central metal
X represents a + a-valent transition metal ion as on, and X represents an acid
Represents a chemically stable -b valent counter ion, wherein a is an integer of 1 to 4
Represents a number, b represents a positive integer, n represents an integer of 1 to 4
And n = a / b, and m represents an integer of 2 or more. )
The method according to claim 1, which is a transition metal complex represented by the following formula: 10. The transition metal complex represented by the general formula (X) [K⁴¹= NA^Four-N = K⁴²] M^{a +}(X^b-) N (X) (where A^FourAre each independently 1 to 6 carbon atoms in the main chain.
Alkylene group, o-phenylene group, m-phenylene
Group, p-phenylene group, 1,8-naphthylene group, 9,10-phenyl group
Enanthrylene group, 2,6-pyridinediyl group, 3,6-a
Clidinediyl group, 2,2'-bipyridyl-6,6'-diyl
Group, 1,10-phenanthrone-2,9-diyl group, 2,6-pi
Limidinediyl group, 4,5-pyrimidinediyl group, 2,6-
Pyrazinediyl group, 2-phenyl-1,3,5-triazine
-2,6-diyl group,(In the above formula, R¹Represents an alkylene group having 1 to 8 carbon atoms
Then R^TwoIs an alkylene group having 1 to 8 carbon atoms, 6 to 1 carbon atoms
4 aryl groups, arylalkyl groups having 7 to 14 carbon atoms
Or an alkylaryl group having 7 to 14 carbon atoms. )so
It is a group represented. ), And any of these groups
May also have a substituent that is inert to the reaction. K ⁴¹Passing
And K⁴²Is a 2-pyridylmethylene group or 6-methyl-2
-A pyridylmethylene group, any of which
May also have a substituent that is inert to the reaction. M is
Shows + a-valent transition metal ion as central metal ion
X represents an oxidatively stable -b valent counter ion;
Represents an integer of 1 to 4, b represents a positive integer, and n represents 1 to 4.
4 is an integer, n = a / b, and m is an integer of 2 or more.
Indicates a number. 2) a transition metal complex represented by the formula:
The described method. 11. The transition metal complex represented by the general formula (XI): (Wherein, A ^{51 to} A ⁵³ each independently have 1 to 6 carbon atoms)
And may have a substituent inert to the reaction. K ^{51 to} K ⁵³ are a benzylidene group, a 2-pyridylmethylene group or a 6-methyl-2-pyridylmethylene group, and any of these groups may have a substituent that is inert to the reaction. . M represents a + a-valent transition metal ion as a central metal ion, X represents an oxidatively stable -b-valent counter ion, a represents an integer of 1 to 4,
b represents a positive integer, n represents an integer of 1 to 4, and n = a
/ B, and m represents an integer of 2 or more. 2. The method according to claim 1, which is a transition metal complex represented by the formula: 12. A transition metal complex represented by the general formula (XII) [K ⁶¹ -N = A ⁶ = ^{NK 62} ] M ^{a +} (X ^b- ) n (XII) wherein A ⁶ is ] And any of these groups may have a substituent inert to the reaction. ^K61 and ^K62 are
A 2-pyridyl group, a 3-pyridyl group, an 8-quinolyl group or an aminoalkyl group (the alkyl group has 2 to 4 carbon atoms), each of which has a substituent that is inert to the reaction. It may be. M represents a + a-valent transition metal ion as a central metal ion, X represents an oxidatively stable -b-valent counter ion, a represents an integer of 1 to 4, and b represents a positive integer. And n represents an integer of 1 to 4;
= A / b, and m represents an integer of 2 or more. 2. The method according to claim 1, which is a transition metal complex represented by the formula: 13. The transition metal complex represented by the general formula (XIII): (Wherein A ⁷ is And any of these groups may have a substituent inert to the reaction. K ^{71 to} K ⁷⁴ are 2
A -pyridyl group, a 3-pyridyl group, a 2-pyridylmethyl group or a 3-pyridylmethyl group, each of which may have a substituent that is inert to the reaction. M
Represents a + a-valent transition metal ion as a central metal ion, X represents an oxidatively stable -b-valent counter ion,
a represents an integer of 1 to 4, b represents a positive integer, and n represents 1
And n is a / b, and m is an integer of 2 or more. 2. The method according to claim 1, which is a transition metal complex represented by the formula: 14. The transition metal complex represented by the general formula (XIV) [K⁸¹= NA⁸-N = K⁸²] M^{a +}(X^b-) N (XIV)) where A⁸Are each independently 1 to 6 carbon atoms in the main chain.
Alkylene group, o-phenylene group, m-phenylene
Group, p-phenylene group, 1,8-naphthylene group, 9,10-phenyl group
Enanthrylene group, 2,6-pyridinediyl group, 3,6-a
Clidinediyl group, 2,2'-bipyridyl-6,6'-diyl
Group, 1,10-phenanthrone-2,9-diyl group, 2,6-pi
Limidinediyl group, 4,5-pyrimidinediyl group, 2,6-
Pyrazinediyl group, 2-phenyl-1,3,5-triazine
-2,6-diyl group,(In the above formula, R¹Represents an alkylene group having 1 to 8 carbon atoms
Then R^TwoIs an alkylene group having 1 to 8 carbon atoms, 6 to 1 carbon atoms
4 aryl groups, arylalkyl groups having 7 to 14 carbon atoms
Or an alkylaryl group having 7 to 14 carbon atoms. )so
It is a group represented. ), And any of these groups
May also have a substituent that is inert to the reaction. K ⁸¹Passing
And K⁸²Is the general formula TN = CR⁸¹-CR⁸²= Wherein T is a hydroxyl group, an amino group or a general formula -NR^FourR
^Five(Where R^FourAnd R^FiveAre each independently 1 carbon atom
Represents an alkyl group of 1 to 6 and having a substituent inert to the reaction
May be. ) Represents a group represented by⁸¹And R⁸²
Are each independently a hydrogen atom, an alkyl having 1 to 6 carbon atoms.
A phenyl group or an alkyl group or a phenyl group
May have a substituent that is inert to the reaction. M is
Shows + a-valent transition metal ion as central metal ion
X represents an oxidatively stable -b valent counter ion;
Represents an integer of 1 to 4, b represents a positive integer, and n represents 1 to 4.
4 is an integer, n = a / b, and m is an integer of 2 or more.
Indicates a number. 2) a transition metal complex represented by the formula:
The described method. 15. The oil phase comprising the arylalkyl hydrocarbon and the formed arylalkyl hydroperoxides and the aqueous phase, wherein the aqueous phase is in the range of 5.0 to 9.5.
The method described in. 16. The method according to claim 1, wherein the transition metal ion is an ion of iron, nickel, manganese, cobalt, copper, chromium, ruthenium, rhodium, titanium or zirconium.