JP2002226421A - Method for producing organic compound using imide compound and nitric acid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To efficiently produce under milder conditions an organic compound having an oxidized group oxidized with nitric acid. SOLUTION: This method for producing the organic compound is characterized by oxidizing an organic compound (A) having the oxidizable group to be oxidized with the nitric acid in the presence of (i) an imide compound having a cyclic imide skeleton represented by the following formula (I) [wherein, X denotes oxygen atom or an -OR group (R denotes hydrogen atom or a protecting group of the hydroxy group)] as a catalyst and (ii) the nitric acid as an oxidizing agent and forming the organic compound having the oxidized group which is oxidized. The amount of the nitric acid used is 1-3 equivalents based on 1 equivalent of the organic compound (A) having the oxidizable group and the amount of the imide compound used may be 0.001-0.2 equivalent based on 1 equivalent of the organic compound (A) having the oxidizable group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing an organic compound using an imide compound catalyst, and more particularly, to a method for oxidizing an organic compound with nitric acid in the presence of a specific catalytic amount of an imide compound and nitric acid. The present invention relates to a method for producing an organic compound that oxidizes an organic compound having an oxidized group with nitric acid to generate an oxidized organic compound having an oxidized group.

[0002]

2. Description of the Related Art Oxidation reaction with nitric acid (nitric acid oxidation reaction)
Is generally and widely used. In the nitric acid oxidation reaction,
The reaction can be accelerated by increasing the temperature, increasing the amount of nitric acid used, or adding an initiator. However, in the nitric acid oxidation reaction, increasing the temperature is disadvantageous in terms of energy. In addition, it becomes difficult to control the reaction. Particularly, when the nitric acid oxidation reaction is an exothermic reaction, the heat generated in the system increases the temperature in the system, thereby increasing the risk of runaway of the reaction.

On the other hand, increasing the use of nitric acid is disadvantageous in terms of cost. In addition, the amount of nitric oxide produced as a by-product increases with an increase in the use amount of nitric acid, and industrially requires large processing equipment for treating the by-product.

As an initiator used in the nitric acid oxidation reaction, nitrous acid and the like are known. However, nitrogen oxide generated by decomposition of the nitrous acid puts a burden on the environment. Not preferred.

[0005]

Accordingly, it is an object of the present invention to provide an organic compound having an oxidized oxidized group by efficiently oxidizing an organic compound having an oxidizable group with nitric acid under mild conditions. It is an object of the present invention to provide a method capable of manufacturing the same. Another object of the present invention is to provide a method capable of efficiently producing an organic compound having an oxidized oxidized group with excellent selectivity.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that an organic compound having an oxidizable group which is oxidized to nitric acid in the presence of an imide compound having a specific structure and nitric acid. An organic compound having an oxidized oxidized group (such as an oxygen atom-containing group) efficiently under mild conditions and with high reaction selectivity without increasing the amount of nitric acid used by oxidizing the compound with nitric acid. Have been found, and the present invention has been completed.

That is, the present invention provides (i) a catalyst represented by the following formula (I):

Embedded image [Wherein X represents an oxygen atom or an -OR group (R represents a hydrogen atom or a protecting group for a hydroxyl group)], and an imide compound having a cyclic imide skeleton represented by (ii) nitric acid as an oxidizing agent Wherein the organic compound (A) having an oxidizable group oxidized by nitric acid is oxidized with nitric acid in the presence of a nitric acid to produce an organic compound having an oxidized oxidized group. I do.

The imide compound has the following formula (1)

Embedded image [Wherein, R ¹ and R ² are the same or different and are each a hydrogen atom,
A halogen atom, an alkyl group, an aryl group, a cycloalkyl group, a hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or an acyl group; R ¹ and R ² are bonded to each other to form a double bond, or an aromatic or A non-aromatic ring may be formed. X represents an oxygen atom or an -OR group (R represents a hydrogen atom or a hydroxyl-protecting group). R ¹ , R ² , or a double bond or an aromatic or non-aromatic ring formed by bonding R ¹ and R ² to each other is an N-substituted group represented by the above formula (1). One or two cyclic imide groups may be further formed]
Embedded image is included.

The amount of the nitric acid used is, for example, about 1 to 3 equivalents to 1 equivalent of the organic compound (A) having an oxidizable group. The amount of the imide compound used is, for example, about 0.001 to 0.2 equivalent to 1 equivalent of the organic compound (A) having an oxidizable group.

Examples of the organic compound having an oxidizable group (A) include (A1) a compound having a carbon-hydrogen bond adjacent to an aromatic ring, and (A2) a carbon-hydrogen bond adjacent to a hetero atom.
Heteroatom-containing compound having a hydrogen bond, (A3) carbon-
A compound having a heteroatom double bond, (A4) a compound having an aromatic ring carbon-heteroatom bond, (A5) a compound having a carbon-hydrogen bond adjacent to a halogen atom, and (A4)
6) At least one compound selected from the group consisting of compounds having an ester bond can be used.

In the method for producing an organic compound, a metal compound can be used as a co-catalyst.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION [Imide Compound Catalyst] In the present invention, an imide compound having a cyclic imide skeleton represented by the above formula (I) is used as a catalyst. That is, the amount of the imide compound used is a catalytic amount.

In the formula (I), the bond between the nitrogen atom and X is a single bond or a double bond. The imide compound may have a plurality of N-substituted cyclic imide skeletons represented by the formula (I) in the molecule. Also, this imide compound,
When X is an -OR group and R is a protecting group for a hydroxyl group, a plurality of N-substituted cyclic imide skeletons other than R (N-oxy cyclic imide skeleton) are bonded via R. It may be.

In the formula (I), as the hydroxyl-protecting group represented by R, a hydroxyl-protecting group commonly used in the field of organic synthesis can be used. Examples of such a protecting group include an alkyl group (eg, a C _1-4 alkyl group such as a methyl and t-butyl group), an alkenyl group (eg, an allyl group), a cycloalkyl group (eg, a cyclohexyl group). ), Aryl groups (eg,
A 2,4-dinitrophenyl group, an aralkyl group (eg, benzyl, 2,6-dichlorobenzyl, 3-bromobenzyl, 2-nitrobenzyl, triphenylmethyl group, etc.); a substituted methyl group (eg, methoxymethyl, Methylthiomethyl, benzyloxymethyl, t-butoxymethyl, 2-methoxyethoxymethyl, 2,2,2-trichloroethoxymethyl, bis (2-chloroethoxy)
Methyl, 2- (trimethylsilyl) ethoxymethyl group, etc., substituted ethyl group (for example, 1-ethoxyethyl, 1
-Methyl-1-methoxyethyl, 1-isopropoxyethyl, 2,2,2-trichloroethyl group, etc., tetrahydropyranyl group, tetrahydrofuranyl group, 1-hydroxyalkyl group (for example, 1-hydroxyethyl,
A group capable of forming an acetal or hemiacetal group with a hydroxyl group such as -hydroxyhexyl, 1-hydroxydecyl, 1-hydroxyhexadecyl, 1-hydroxy-1-phenylmethyl group and the like; an acyl group (e.g., formyl, C _1-6 aliphatic acyl groups such as acetyl, propionyl, butyryl, isobutyryl, valeryl and pivaloyl groups; acetoacetyl groups; aromatic acyl groups such as benzoyl and naphthoyl groups; and sulfonyl groups (methanesulfonyl, ethanesulfonyl, trifluoro) b methanesulfonyl, benzenesulfonyl, p- toluenesulfonyl, naphthalene sulfonyl group), an alkoxycarbonyl group (e.g., C _1-4 alkoxy such as methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl group - carbonyl group ), Aralkyloxycarbonyl groups (eg, benzyloxycarbonyl group, p-methoxybenzyloxycarbonyl group, etc.), substituted or unsubstituted carbamoyl groups (eg, carbamoyl, methylcarbamoyl, phenylcarbamoyl group, etc.), inorganic acids (sulfuric acid, nitric acid) , Phosphoric acid, boric acid, etc.), a group obtained by removing an OH group, a dialkylphosphinothioyl group (eg, dimethylphosphinothioyl group), a diarylphosphinothioyl group (eg, diphenylphosphinothioyl group, etc.) ), Substituted silyl groups (eg, trimethylsilyl, t
-Butyldimethylsilyl, tribenzylsilyl, triphenylsilyl group, etc.).

Further, when X is -OR group,
When a plurality of portions (N-oxycyclic imide skeleton) other than R in the N-substituted cyclic imide skeleton are bonded via R, for example, oxalyl, malonyl, succinyl, glutaryl, phthaloyl, isophthaloyl, Polycarboxylic acyl groups such as terephthaloyl group; carbonyl groups; polyvalent hydrocarbon groups such as methylene, ethylidene, isopropylidene, cyclopentylidene, cyclohexylidene, and benzylidene groups (particularly, they form an acetal bond with two hydroxyl groups) Group).

R represents an alkyl group (eg, a methyl group)
Other protecting groups are more preferred. Particularly preferred R is, for example, a hydrogen atom; a group capable of forming an acetal or hemiacetal group with a hydroxyl group; Preferred are hydrolyzable protecting groups which can be eliminated by hydrolysis, such as the removed groups (acyl group, sulfonyl group, alkoxycarbonyl group, carbamoyl group, etc.).

A typical example of the imide compound is an imide compound represented by the formula (1). In this imide compound, the halogen atom among the substituents R ¹ and R ² includes iodine, bromine, chlorine and fluorine atoms. The alkyl group includes, for example, 1 to 1 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, hexyl, and decyl.
It contains about 10 linear or branched alkyl groups.
Preferred alkyl groups include, for example, lower alkyl groups having about 1 to 6 carbon atoms, particularly about 1 to 4 carbon atoms.

The aryl group includes phenyl and naphthyl groups, and the cycloalkyl group includes cyclopentyl and
And a cyclohexyl group. The alkoxy group includes
For example, methoxy, ethoxy, isopropoxy, butoxy, t-butoxy, hexyloxy group and other C1-C1
About 10 carbon atoms, preferably about 1 to 6 carbon atoms, particularly 1 carbon atom
About 4 lower alkoxy groups are included.

The alkoxycarbonyl group includes, for example, an alkoxycarbonyl group having about 1 to 10 carbon atoms in the alkoxy moiety such as methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, t-butoxycarbonyl and hexyloxycarbonyl. included. Preferred carbonyl groups include lower alkoxycarbonyl groups having about 1 to 6, particularly about 1 to 4 carbon atoms in the alkoxy moiety. Examples of the acyl group include acyl groups having about 1 to 6 carbon atoms, such as formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, and pivaloyl groups.

The substituents R ¹ and R ² may be the same or different. In the formula (1), R ¹ and R ² may be bonded to each other to form a double bond or a ring having an aromatic or non-aromatic attribute. Preferred aromatic or non-aromatic rings have about 5 to 12 membered rings, especially about 6 to 10 membered rings, and may be heterocyclic rings or condensed heterocyclic rings, but are often hydrocarbon rings. Such rings include, for example,
Non-aromatic alicyclic ring (cycloalkane ring optionally having a substituent such as cyclohexane ring, cycloalkene ring optionally having a substituent such as cyclohexene ring), non-aromatic bridge A bridged ring (eg, a bridged hydrocarbon ring which may have a substituent such as a 5-norbornene ring),
An aromatic ring (including a condensed ring) which may have a substituent such as a benzene ring and a naphthalene ring is included. The ring is
Often composed of aromatic rings. The ring is an alkyl group, a haloalkyl group, a hydroxyl group, an alkoxy group,
Carboxyl group, alkoxycarbonyl group, acyl group,
It may have a substituent such as a nitro group, a cyano group, an amino group, and a halogen atom.

The above-mentioned R ¹ , R ² , or a double bond or an aromatic or non-aromatic ring formed by bonding R ¹ and R ² to each other is represented by the above formula (1). One or two N-substituted cyclic imide groups may be further formed. For example, when R ¹ or R ² is an alkyl group having 2 or more carbon atoms, the N-substituted cyclic imide group may be formed to include two adjacent carbon atoms constituting the alkyl group. When R ¹ and R ² are bonded to each other to form a double bond, the N-substituted cyclic imide group may be formed to include the double bond. Further, when R ¹ and R ² are bonded to each other to form an aromatic or non-aromatic ring, the N-substituted cyclic imide group is formed containing two adjacent carbon atoms constituting the ring. It may be.

Preferred imide compounds include compounds represented by the following formula:

Embedded image (Wherein, R ^{3 to} R ⁶ are the same or different and each represents a hydrogen atom, an alkyl group, a haloalkyl group, a hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, an acyl group, a nitro group, a cyano group, an amino group, In the formula (1f), A represents a methylene group or a halogen atom, wherein R ^{3 to} R ⁶ may be such that adjacent groups are bonded to each other to form an aromatic or non-aromatic ring. Represents an oxygen atom, R ¹ ,
R ² and X are the same as above. (In the benzene ring of the formula (1c), one or two N-substituted cyclic imide groups shown in the formula (1c) may be further formed.)

In the substituents R ^{3 to} R ⁶ , the alkyl group includes the same alkyl groups as those exemplified above, particularly an alkyl group having about 1 to 6 carbon atoms, and the haloalkyl group includes trifluoromethyl The haloalkyl group having about 1 to 4 carbon atoms such as a group, an alkoxy group includes the same alkoxy group as described above, particularly a lower alkoxy group having about 1 to 4 carbon atoms,
The alkoxycarbonyl group includes the same alkoxycarbonyl group as described above, particularly a lower alkoxycarbonyl group having about 1 to 4 carbon atoms in the alkoxy moiety. Examples of the acyl group include the same acyl groups as described above, particularly those having 1 carbon atom.
About 6 to about 6 acyl groups are exemplified. Examples of the halogen atom include fluorine, chlorine and bromine atoms. Substituent R ³
To R ⁶ you are often a hydrogen atom, a lower alkyl group having about 1 to 4 carbon atoms, a carboxyl group, a nitro group, or a halogen atom. The ring formed by R ^{3 to} R ⁶ bonded to each other is the same as the ring formed by bonding R ¹ and R ² to each other, and is particularly preferably an aromatic or non-aromatic 5 to 12 ring.
Member rings are preferred.

Representative examples of preferred imide compounds include, for example, N-hydroxysuccinimide, N-hydroxymaleimide, N-hydroxyhexahydrophthalimide, N, N'-dihydroxycyclohexanetetracarboxylic imide, N-hydroxyphthalimide, N-hydroxytetrabromophthalimide, N
-Hydroxytetrachlorophthalic imide, N-hydroxyhetic imide, N-hydroxyhymic imide, N-hydroxytrimellitic imide, N, N'-
X such as dihydroxypyromellitic imide, N, N'-dihydroxynaphthalenetetracarboxylic imide is-
A compound having an OR group and R being a hydrogen atom; N-acetoxysuccinimide, N-acetoxymaleimide,
N-acetoxyhexahydrophthalimide, N, N '
-Diacetoxycyclohexanetetracarboxylic imide, N-acetoxyphthalimide, N-acetoxytetrabromophthalimide, N-acetoxytetrachlorophthalimide, N-acetoxyhetimide, N
X such as -acetoxyhymic imide, N-acetoxytrimellitic imide, N, N'-diacetoxypyromellitic imide, N, N'-diacetoxynaphthalenetetracarboxylic imide, wherein X is an -OR group and R is A compound which is an acyl group such as an acetyl group; X such as N-methoxymethyloxyphthalimide, N- (2-methoxyethoxymethyloxy) phthalimide is an -OR group and R
Is a group capable of forming an acetal or hemiacetal bond with a hydroxyl group; X such as N-methanesulfonyloxyphthalimide, N- (p-toluenesulfonyloxy) phthalimide is an -OR group and R is Compounds that are sulfonyl groups; compounds in which X is an -OR group and R is a group obtained by removing an OH group from an inorganic acid, such as a sulfate, nitrate, phosphate or borate of N-hydroxyphthalimide. Is mentioned.

Among the above imide compounds, those in which X is an —OR group and R is a hydrogen atom can be prepared by a conventional imidization reaction, for example, by reacting a corresponding acid anhydride with hydroxylamine N
It can be prepared by a method of reacting with H ₂ OH and imidizing via ring opening and ring closing of an acid anhydride group. Examples of the acid anhydride include succinic anhydride, saturated or unsaturated aliphatic dicarboxylic anhydride such as maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride (1,2-cyclohexanedicarboxylic anhydride), Saturated or unsaturated non-aromatic cyclic polycarboxylic anhydrides (alicyclic polycarboxylic anhydrides) such as 1,2,3,4-cyclohexanetetracarboxylic acid 1,2-anhydride; Cyclic polycarboxylic anhydrides (alicyclic polycarboxylic anhydrides) such as carboxylic acid, hymic anhydride, alicyclic polycarboxylic anhydride, phthalic anhydride, tetrabromophthalic anhydride, tetrachlorophthalic anhydride, nitrophthalic anhydride, trimellitic anhydride Acid, methylcyclohexenetricarboxylic anhydride, pyromellitic anhydride, melitic anhydride, 1,8; 4,5-naphthalenetetracarboxylic acid Aromatic polycarboxylic anhydrides such as anhydrides are included.

Among the above imide compounds, those in which X is an -OR group and R is a protecting group for a hydroxyl group include compounds in which the corresponding R is a hydrogen atom (N-hydroxy cyclic imide compounds), It can be prepared by introducing a desired protecting group using a group introduction reaction. For example, N-acetoxyphthalimide can be obtained by reacting N-hydroxyphthalimide with acetic anhydride or reacting acetyl halide in the presence of a base.

Particularly preferred imide compounds are alicyclic polycarboxylic acid anhydrides or aromatic polycarboxylic acid anhydrides, and in particular, N-derivatives derived from aromatic polycarboxylic acid anhydrides.
Hydroxyimide compounds (eg, N-hydroxyphthalimide, N, N'-dihydroxypyromellitic imide); and compounds obtained by introducing a protecting group into the hydroxyl group of the N-hydroxyimide compound. .

The imide compound having an N-substituted cyclic imide skeleton represented by the formula (I) can be used alone or in combination of two or more in the reaction. The imide compound may be generated in a reaction system.

The amount of the imide compound to be used can be selected in a wide range, for example, 0.0001 to 0.2 equivalent, preferably 0.001 to 0.2 equivalent to 1 equivalent of the reaction component (substrate).
It is about 0.2 equivalent.

[Nitric acid] In the present invention, nitric acid (HNO ₃ ) is used as an oxidizing agent. The nitric acid is not particularly limited, and commercially available nitric acid, fuming nitric acid, aqueous nitric acid (aqueous nitric acid) and the like can be used. Nitric acid may be used after being diluted with water or an inert organic solvent. That is,
Nitric acid may be supplied to the reaction system as it is, or may be supplied to the reaction system in the form of a solution such as an aqueous solution. In particular, nitric acid can be generated in a reaction system and used for a nitric acid oxidation reaction.

The amount of nitric acid used is, for example, about 1 to 5 equivalents, preferably about 1 to 3 equivalents, per equivalent of the organic compound (A) (substrate) having an oxidizable group. Too much nitric acid is disadvantageous in terms of cost and equipment.

The equivalent of the substrate is determined based on the oxidized oxidized group formed after nitric acid oxidation. For example, when the oxidizable group of the substrate is an ether group, when two nitric acid-oxidized groups (carboxyl group, aldehyde group, etc.) are generated with respect to one ether group by nitric acid oxidation, the two oxidations are performed. The equivalent is based on the group, and when one nitric acid oxidized group is generated, the equivalent is based on this one oxidized group. More specifically, when phthalane having one ether group is subjected to nitric acid oxidation,
Since o-phthalaldehyde having two oxidized groups (aldehyde groups) is generated, the equivalent of the substrate can be determined based on the aldehyde group, which is the two oxidized groups after nitric acid oxidation.

[Co-catalyst] In the present invention, a co-catalyst can be used in addition to the catalyst containing the imide compound. Metal compounds can be mentioned as co-catalysts. The combined use of an imide compound and a metal compound as the catalyst can improve the reaction rate and the selectivity of the reaction.

The metal elements constituting the metal compound include:
Although not particularly limited, metal elements of Groups 2 to 15 of the periodic table are often used. Note that, in this specification, boron B is also included in the metal element. For example, as the metal element, a Group 2 element of the periodic table (Mg, Ca, Sr, Ba, etc.),
Group 3 element (Sc, lanthanoid element, actinoid element, etc.), Group 4 element (Ti, Zr, Hf, etc.), Group 5 element (V, etc.), Group 6 element (Cr, Mo, W, etc.), Group 7 element ( Mn, etc.), Group 8 elements (Fe, Ru, etc.), Group 9 elements (Co, Rh, etc.), Group 10 elements (Ni, Pd, Pt)
), Group 11 elements (such as Zn), Group 13 elements (such as B, Al, In), Group 14 elements (such as Sn and Pb), and Group 15 elements (such as Sb and Bi). And the like. Preferred metal elements include transition metal elements (groups 3 to 12 of the periodic table). Above all, elements of Groups 5 to 11 of the periodic table, particularly elements of Groups 5 to 9, are preferable, and V, Mo, Mn, Co and the like are particularly preferable. The valence of the metal element is not particularly limited, and is, for example, about 0 to 6 valence.

As the metal compound, a simple one of the above metal elements can be used.
Body, hydroxide, oxide (including complex oxide), halogen
(Fluoride, chloride, bromide, iodide), oxo
Acid salts (e.g., nitrates, sulfates, phosphates, borates,
Carbonates), salts of isopoly acids, salts of heteropoly acids, etc.
Inorganic salts; organic acid salts (eg, acetate, propion
Acid salts, cyanates, naphthenates, stearates, etc.),
Organic compounds such as a complex may be used. Constituting the complex
OH (hydroxo), alkoxy
(Methoxy, ethoxy, propoxy, butoxy, etc.),
Acyl (acetyl, propionyl, etc.), alkoxyca
Rubonyl (methoxycarbonyl, ethoxycarbonyl, etc.
), Acetylacetonato, cyclopentadienyl group,
Halogen atom (chlorine, bromine, etc.), CO, CN, oxygen source
Child, H_TwoO (Aquo), phosphine (triphenylphosphine)
Compounds such as triarylphosphines such as
Object, NH _Three(Ammin), NO, NO_Two(Nitro), NO
_Three(Nitrato), ethylenediamine, diethylenetria
Nitrogen-containing compounds such as min, pyridine and phenanthroline
Things.

Specific examples of metal compounds include, for example, cobalt compounds, inorganic compounds such as cobalt hydroxide, cobalt oxide, cobalt chloride, cobalt bromide, cobalt nitrate, cobalt sulfate, and cobalt phosphate; Organic salts such as cobalt, cobalt naphthenate, and cobalt stearate; and divalent or trivalent cobalt compounds such as complexes such as cobalt acetylacetonate.
Examples of vanadium compounds include vanadium hydroxide, vanadium oxide, vanadium chloride, vanadyl chloride,
Inorganic compounds such as vanadium sulfate, vanadyl sulfate, and sodium vanadate; and divalent to pentavalent vanadium compounds such as complexes of vanadium acetylacetonate and vanadyl acetylacetonate. Examples of the compound of another metal element include a compound corresponding to the cobalt or vanadium compound. The metal compounds can be used alone or in combination of two or more.

The amount of the metal compound to be used is, for example, from 0.000001 to 0.1 mol per mol of the substrate (reaction component).
It is about 1 mol, preferably about 0.00001 to 0.01 mol. The amount of the metal compound used is, for example, 0.001 to 0.1 with respect to 1 mol of the imide compound.
It is about mol, preferably about 0.005 to 0.08 mol.

In the present invention, as a co-catalyst, an organic salt composed of a polyatomic cation or polyanion containing a group 15 or 16 element of the periodic table to which at least one organic group is bonded, and a counter ion. Can also be used.
By using the organic salt as a promoter, the reaction rate and the selectivity of the reaction can be improved.

In the above-mentioned organic salts, Group 15 elements of the periodic table include N, P, As, Sb and Bi. Periodic Table 16
Group elements include O, S, Se, Te, and the like. Preferred elements include N, P, As, Sb, and S, and particularly preferred are N, P, and S.

The organic group bonded to an atom of the element includes a hydrocarbon group which may have a substituent, a substituted oxy group, and the like. Examples of the hydrocarbon group include about 1 to 30 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl, octyl, decyl, tetradecyl, hexadecyl, octadecyl, and allyl ( Preferably 1 to 2 carbon atoms
0) linear or branched aliphatic hydrocarbon groups (alkyl, alkenyl, and alkynyl groups); cyclopentyl, cyclohexyl and other alicyclic hydrocarbon groups having about 3 to 8 carbon atoms; phenyl, naphthyl 6-1 such as carbon number
About four aromatic hydrocarbon groups are exemplified. Examples of the substituent which the hydrocarbon group may have include, for example, a halogen atom, an oxo group, a hydroxyl group, a substituted oxy group (eg, an alkoxy group, an aryloxy group, an acyloxy group, etc.), a carboxyl group, a substituted oxycarbonyl group A substituted or unsubstituted carbamoyl group, a cyano group, a nitro group, a substituted or unsubstituted amino group, an alkyl group (for example, methyl,
Examples thereof include a C _1-4 alkyl group such as an ethyl group, a cycloalkyl group, an aryl group (eg, a phenyl and naphthyl group), and a heterocyclic group. Preferred hydrocarbon groups include alkyl groups having about 1 to 30 carbon atoms, and 6-1 to carbon atoms.
About four aromatic hydrocarbon groups (particularly, a phenyl group or a naphthyl group) are included. The substituted oxy group includes an alkoxy group, an aryloxy group, an aralkyloxy group and the like.

Representative examples of the organic salts include organic onium salts such as organic ammonium salts, organic phosphonium salts, and organic sulfonium salts. Specific examples of the organic ammonium salt include tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, tetrahexylammonium chloride, trioctylmethylammonium chloride, triethylphenylammonium chloride, tributyl (hexadecyl) ammonium chloride, and di (octadecyl) Quaternary ammonium chlorides such as dimethylammonium chloride, and the corresponding quaternary ammonium bromides; quaternary ammonium salts having four hydrocarbon groups bonded to a nitrogen atom; dimethylpiperidinium chloride, hexadecylpyridinium chloride, Cyclic quaternary ammonium salts such as methylquinolinium chloride; Specific examples of the organic phosphonium salt include quaternary phosphonium chlorides such as tetramethylphosphonium chloride, tetrabutylphosphonium chloride, tributyl (hexadecyl) phosphonium chloride, and triethylphenylphosphonium chloride, and corresponding quaternary phosphonium bromides. , 4 in the phosphorus atom
And quaternary phosphonium salts in which two hydrocarbon groups are bonded. Specific examples of the organic sulfonium salt include a sulfonium salt in which three hydrocarbon groups are bonded to a sulfur atom, such as triethylsulfonium iodide and ethyldiphenylsulfonium iodide.

The organic salt includes methanesulfonic acid
Salt, ethane sulfonate, octane sulfonate, dode
Alkylsulfonates such as cansulfonates (eg,
If C _1-18Alkyl sulfonate); benzene sulfone
Acid salt, p-toluenesulfonic acid salt, naphthalene sulfone
Acid salt, decylbenzene sulfonate, dodecylbenzene
It may be substituted with an alkyl group such as a sulfonate
Aryl sulfonates (eg, C_1-18Alkyl-ant
Sulfonate); sulfonic acid type ion exchange resin (a
On-exchanger); phosphonic acid type ion exchange resin (ion exchange)
Conversion).

The amount of the organic salt used is, for example, about 0.000001 to 0.1 mol, preferably about 0.00001 to 0.01 mol, per 1 mol of the substrate. The amount of the organic salt used is, for example, about 0.001 to 0.1 mol, and preferably about 0.005 to 0.08 mol, per 1 mol of the imide compound.

In the present invention, sodium nitrite, nitrogen dioxide, benzoyl peroxide and azobisisobutyronitrile, which are known as radical initiators, can be used as the initiator in the nitric acid oxidation reaction.

[Organic Compound Having Oxidizable Group (A)] The organic compound having an oxidizable group (A) is not particularly limited as long as it is an organic compound having an oxidizable group that is oxidized by nitric acid. A typical example is (A1)
A compound having a carbon-hydrogen bond at a position adjacent to the aromatic ring,
(A2) a heteroatom-containing compound having a carbon-hydrogen bond at the adjacent position of a heteroatom, (A3) a compound having a carbon-heteroatom double bond, (A4) a compound having an aromatic ring carbon-heteroatom bond, A5) Carbon-
Examples include a compound having a hydrogen bond and a compound having an (A6) ester bond. The organic compound (A) having an oxidizable group can be used alone or in combination of two or more.

In these compounds (A1 to A7), the aromatic ring may be any of an aromatic hydrocarbon ring and an aromatic heterocyclic ring. The aromatic hydrocarbon ring includes a benzene ring, a condensed carbocycle (for example, a condensed carbocycle in which 2 to 10 4- to 7-membered carbocycles such as naphthalene, azulene, indacene, anthracene, phenanthrene, triphenylene, pyrene and the like are condensed) ) Is included. Examples of the aromatic heterocyclic ring include a heterocyclic ring containing an oxygen atom as a hetero atom (for example, a 5-membered ring such as furan, oxazole and isoxazole, a 6-membered ring such as 4-oxo-4H-pyran, benzofuran, Benzofuran, 4-oxo-4
A condensed ring such as H-chromene or the like; a heterocyclic ring containing a sulfur atom as a hetero atom (for example, a 5-membered ring such as thiophene, thiazole, isothiazole, and thiadiazole;
A 6-membered ring such as -oxo-4H-thiopyran, a condensed ring such as benzothiophene, etc., a heterocyclic ring containing a nitrogen atom as a hetero atom (for example, a 5-membered ring such as pyrrole, pyrazole, imidazole or triazole, pyridine, pyridazine, 6-membered rings such as pyrimidine and pyrazine, and condensed rings such as indole, quinoline, acridine, naphthyridine, quinazoline and purine).

In the organic compound (A) having an oxidizable group, the oxidizable group oxidized by nitric acid is not particularly limited as long as it is a group oxidized by nitric acid. Examples of such an oxidizable group include, in addition to a carbon atom in a methyl group, a methylene group, and a methine group bonded to an aromatic ring carbon, a hydroxyl group, a mercapto group, an ether group, a sulfide group, an oxo group, and a halogen atom. Examples include carbon atoms having a functional group such as an atom, an amino group, and a nitro group. That is, such carbon atoms are oxidized by nitric acid.

These compounds may have various substituents as long as the reaction is not inhibited. As a substituent, for example, a halogen atom, a hydroxyl group, a mercapto group,
Oxo group, substituted oxy group (for example, alkoxy group, aryloxy group, acyloxy group, etc.), substituted thio group, carboxyl group, substituted oxycarbonyl group, substituted or unsubstituted carbamoyl group, cyano group, nitro group, substituted or unsubstituted Amino group, sulfo group, unsubstituted alkyl group, substituted alkyl group (eg, halogenated alkyl group), substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, alicyclic hydrocarbon group, aromatic hydrocarbon group, heterocyclic group And a ring group.

The organic compound (A) having an oxidizable group
Functions as a substrate in this reaction.

The compound (A1) having a carbon-hydrogen bond adjacent to the aromatic ring includes (A1-1) an aromatic compound having a methyl group adjacent to the aromatic ring (so-called benzyl position). And (A1-2) an aromatic compound having a methylene group at a position adjacent to an aromatic ring, and (A1-3) an aromatic compound having a methine group at a position adjacent to an aromatic ring.

The methylene group adjacent to the aromatic ring may be a methylene group constituting a non-aromatic ring fused to the aromatic ring. In addition, (A1-1), (A1
In -2) and (A1-3), a plurality of groups such as a methyl group, a methylene group, and a methine group may coexist at a position adjacent to the aromatic ring.

Specifically, as the aromatic compound (A1-1) having a methyl group at a position adjacent to the aromatic ring, for example, an aromatic compound in which about 1 to 6 methyl groups are substituted on the aromatic ring is used. Hydrogens (for example, toluene, xylene, 1-ethyl-4-
Methylbenzene, 1-ethyl-3-methylbenzene, 1
-T-butyl-4-methylbenzene, 1-methoxy-4
-Methylbenzene, mesitylene, durene, methylnaphthalene, methylanthracene, 4,4'-dimethylbiphenyl, etc., a heterocyclic compound in which a heterocyclic ring is substituted with about 1 to 6 methyl groups (for example, 2-methylfuran, -Methylfuran, 3-methylthiophene, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,4
-Dimethylpyridine, 2,4,6-trimethylpyridine, 4-methylindole, 2-methylquinoline, etc.)
And the like.

Examples of the aromatic compound (A1-2) having a methylene group adjacent to the aromatic ring include aromatic hydrocarbons having an alkyl group having 2 or more carbon atoms or a substituted alkyl group (eg, , Ethylbenzene, propylbenzene, 1,4-diethylbenzene, diphenylmethane, etc.), aromatic heterocyclic compounds having an alkyl group or a substituted alkyl group having 2 or more carbon atoms (for example, 2-ethylfuran, 3-propylthiophene, Ethyl pyridine, 4
-Butylquinoline), a compound in which a non-aromatic ring is fused to an aromatic ring, and a compound having a methylene group at a site adjacent to the aromatic ring in the non-aromatic ring (dihydronaphthalene, indene , Indane, tetralin, fluorene, acenaphthene, phenalene, indanone, xanthene, etc.).

Examples of the aromatic compound (A1-3) having a methine group at the position adjacent to the aromatic ring include, for example, aromatic hydrocarbons having an alicyclic hydrocarbon group (eg, cyclohexylbenzene, etc.), In addition to an aromatic heterocyclic compound having an aromatic heterocyclic group (for example, nicotine), an aromatic heterocyclic compound having an alicyclic hydrocarbon group and an aromatic hydrocarbon having a non-aromatic heterocyclic group Examples include hydrogens.

As the hetero atom-containing compound (A2) having a carbon-hydrogen bond at a position adjacent to the hetero atom, (A2-1) a primary or secondary alcohol or a primary or secondary alcohol
Grade thiol, (A2-2) an ether having a carbon-hydrogen bond adjacent to an oxygen atom or a sulfide having a carbon-hydrogen bond adjacent to a sulfur atom (including disulfide), (A2
-3) an acetal having a carbon-hydrogen bond adjacent to the oxygen atom (including hemiacetal) or a thioacetal having a carbon-hydrogen bond adjacent to the sulfur atom (including thiohemiacetal), (A2-4) Examples thereof include amines or hydrazos having a carbon-hydrogen bond adjacent to the nitrogen atom, and (A2-5) nitro compounds having a carbon-hydrogen bond adjacent to the nitrogen atom.

The primary or secondary in (A2-1)
Grade alcohols include a wide range of alcohols. The alcohol may be a monohydric, dihydric or polyhydric alcohol.

Representative primary alcohols include methanol, ethanol, 1-propanol, 1-butanol, 2-methyl-1-propanol, 1-pentanol, 1-hexanol, 1-octanol, 1-decanol, About 1 to 30 (preferably 1 to 20, more preferably 1 to 15) carbon atoms such as 1-hexadecanol, 2-buten-1-ol, ethylene glycol, trimethylene glycol, hexamethylene glycol, and pentaerythritol. Saturated or unsaturated aliphatic primary alcohols; saturated or unsaturated alicyclic primary alcohols such as cyclopentylmethyl alcohol, cyclohexylmethyl alcohol and 2-cyclohexylethyl alcohol; benzyl alcohol, 1,2-benzenedimethanol,
Aromatic primary alcohols such as -phenylethyl alcohol, 3-phenylpropyl alcohol and cinnamon alcohol; and heterocyclic alcohols such as 2-hydroxymethylpyridine.

Representative secondary alcohols include 2-
Propanol, s-butyl alcohol, 2-pentanol, 3-pentanol, 3,3-dimethyl-2-butanol, 2-octanol, 4-decanol, 2-hexadecanol, 2-penten-4-ol, , Such as vicinal diols such as 2,2-propanediol, 2,3-butanediol and 2,3-pentanediol;
To 30 (preferably 3 to 20, more preferably 3 to 1)
5) a degree of saturated or unsaturated aliphatic secondary alcohol; 1
Secondary alcohols in which an aliphatic hydrocarbon group and an alicyclic hydrocarbon (such as a cycloalkyl group) are bonded to a carbon atom to which a hydroxyl group is bonded, such as cyclopentylethanol and 1-cyclohexylethanol; cyclobutanol; 3 to 2 such as cyclopentanol, cyclohexanol, cyclooctanol, cyclododecanol, 2-cyclohexen-1-ol and 2-adamantanol
0 members (preferably 3 to 15 members, more preferably 5 to 1
5 or more, especially 5 to 8 member) saturated or unsaturated alicyclic second
Secondary alcohols (including bridged cyclic secondary alcohols);
1-phenylethanol, 1-phenylpropanol,
Aromatic secondary alcohols such as 1-phenylmethylethanol and diphenylmethanol; 1- (2-pyridyl)
Heterocyclic secondary alcohols such as ethanol are included.

Preferred alcohols include primary alcohols (such as aliphatic primary alcohols) and secondary alcohols (such as aliphatic secondary alcohols).

The primary or secondary in (A2-1)
Grade thiols include thiols corresponding to the primary or secondary alcohols.

Examples of the ether having a carbon-hydrogen bond at a position adjacent to an oxygen atom in the above (A2-2) include, for example, dimethyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, methyl ethyl ether, methyl butyl ether, Aliphatic ethers such as ethyl butyl ether, diallyl ether, methyl vinyl ether, ethyl allyl ether, methyl (1-methylheptyl) ether (2-methoxyoctane); alicyclic ethers such as methoxycyclohexane (methylcyclohexyl ether); anisole ,
Aromatic ethers such as phenetole, dibenzyl ether and phenylbenzyl ether; dihydrofuran, tetrahydrofuran, phthalane, pyran, dihydropyran,
And cyclic ethers such as tetrahydropyran, morpholine, chroman and isochroman (an aromatic ring or a non-aromatic ring may be condensed).

Examples of the sulfide having a carbon-hydrogen bond adjacent to the sulfur atom in the above (A2-2) include sulfides corresponding to ethers having a carbon-hydrogen bond adjacent to the oxygen atom. Further, the sulfide having a carbon-hydrogen bond at a position adjacent to a sulfur atom in (A2-2) also includes a disulfide. Examples of the disulfide include dimethyl disulfide.

Examples of the acetal having a carbon-hydrogen bond at a position adjacent to an oxygen atom in the above (A2-3) include, for example,
Acetals derived from aldehydes, alcohols, acid anhydrides and the like are mentioned, and the acetal includes cyclic acetal and acyclic acetal. Examples of the aldehyde include aliphatic aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, pentanal, hexanal, and decanal; alicyclic aldehydes such as cyclopentanecarbaldehyde and cyclohexanecarbaldehyde; benzaldehyde, phenylacetaldehyde And the like. Examples of the alcohol include monohydric alcohols such as methanol, ethanol, 1-propanol, 1-butanol and benzyl alcohol; ethylene glycol, propylene glycol, 1,3-propanediol,
And dihydric alcohols such as 2-dibromo-1,3-propanediol. Representative acetals include 1,3-dioxolan compounds such as 1,3-dioxolan, 2-methyl-1,3-dioxolan and 2-ethyl-1,3-dioxolan; 2-methyl-1,3-dioxane and the like And dialkyl acetal compounds such as acetaldehyde dimethyl acetal.

The thioacetal having a carbon-hydrogen bond adjacent to the sulfur atom in the above (A2-3) includes a thioacetal corresponding to the acetal having a carbon-hydrogen bond adjacent to the oxygen atom.

The amines in the above (A2-4) include:
Primary or secondary amines, for example, aliphatic amines such as methylamine, ethylamine, propylamine, butylamine, dimethylamine, diethylamine, dibutylamine, ethylenediamine, 1,4-butanediamine, hydroxylamine, ethanolamine; cyclopentyl Alicyclic amines such as amine and cyclohexylamine; aromatic amines such as benzylamine; pyrrolidine;
Examples thereof include cyclic amines such as piperidine, piperazine and indoline (an aromatic or non-aromatic ring may be condensed) and the like.

The hydrazos in the above (A2-4) include, for example, hydrazobenzene, N-methyl-N'-phenylhydrazine, N, N'-dimethylhydrazine and the like.

Examples of the nitro compound in the above (A2-5) include aliphatic nitro compounds such as nitromethane and nitroethane, and alicyclic nitro compounds such as nitrocyclohexane.

As the compound (A3) having a carbon-heteroatom double bond, (A3-1) a carbonyl group-containing compound, (A3-2) a thiocarbonyl group-containing compound, (A3-
3) Imines and the like. The carbonyl group-containing compound (A3-1) includes ketone and aldehyde, for example, acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl s-butyl ketone, methyl t-butyl ketone, 3-pentanone, methyl decyl ketone , Ethyl isopropyl ketone, isopropyl butyl ketone, methyl vinyl ketone, methyl isopropenyl ketone, methyl cyclohexyl ketone, acetophenone, methyl (2-methylphenyl) ketone, methyl (2-pyridyl) ketone, chain ketones such as cyclohexyl phenyl ketone ; Cyclopropanone, cyclobutanone, cyclopentanone, cyclohexanone, 4-
Methylcyclohexanone, 4-chlorocyclohexanone, isophorone, cycloheptanone, cyclooctanone, cyclodecanone, cyclododecanone, cyclopentadecanone, 1,3-cyclohexanedione, 1,4-cyclohexanedione, 1,4-cyclooctanedione ,
2,2-bis (4-oxocyclohexyl) propane,
Bis (4-oxocyclohexyl) methane, 4- (4-
(Oxocyclohexyl) cyclohexanone, cyclic ketones such as 2-adamantanone; biacetyl (2,3-butanedione), 2,3-pentanedione, 3,4-hexanedione, bibenzoyl (benzyl), acetylbenzoyl, cyclopentane-1 1,2-dicarbonyl compounds such as 1,2-dione and cyclohexane-1,2-dione (α-diketones and the like); α-keto alcohols such as acetoin and benzoin; acetaldehyde, propionaldehyde, butanal, hexanal, succinyl Aliphatic aldehydes such as synaldehyde, glutaraldehyde and adipine aldehyde; cyclohexyl aldehyde,
Alicyclic aldehydes such as citral and citronellal;
Benzaldehyde, nitrobenzaldehyde, cinnamaldehyde, salicylaldehyde, anisaldehyde,
Aromatic aldehydes such as phthalaldehyde, isophthalaldehyde and terephthalaldehyde; and heterocyclic aldehydes such as furfural and nicotinaldehyde.

Examples of the thiocarbonyl group-containing compound (A3-2) include thiocarbonyl group-containing compounds corresponding to the carbonyl group-containing compound (A3-1).

The imines (A3-3) include the carbonyl group-containing compound (A3-1), ammonia or amines (eg, methylamine, ethylamine, propylamine, butylamine, hexylamine, benzylamine, cyclohexylamine). And amines such as aniline; hydroxylamines such as hydroxylamine and O-methylhydroxylamine; hydrazines such as hydrazine, methylhydrazine and phenylhydrazine) and imines (including oximes and hydrazones). .

Examples of the compound having an aromatic ring carbon-hetero atom bond in the above (A4) include (A4-1) phenols having an aromatic ring carbon-oxygen atom bond or ethers thereof, and (A4-2) Examples thereof include thiophenols having an aromatic ring carbon-sulfur atom bond or sulfides thereof, and (A4-3) aminobenzenes or nitrobenzenes having an aromatic ring carbon-nitrogen atom bond.

Examples of the phenol having an aromatic ring carbon-oxygen atom bond in the above (A4-1) include (o-, p-) dihydroxybenzene such as pyrocatechol and hydroquinone, as well as o-aminophenol, (o-, p-) alkoxyphenols such as p-aminophenol, o-nitrophenol, p-nitrophenol, o-methoxyphenol, p-methoxyphenol, o-
(Chloromethyl) phenol, p- (chloromethyl) phenol and the like. Examples of the ether of the phenol having an aromatic ring carbon-oxygen bond in the above (A4-1) include the phenol having an aromatic ring carbon-oxygen bond, an aliphatic hydrocarbon and an alicyclic hydrocarbon. And ethers.

Examples of the thiophenols having an aromatic ring carbon-sulfur atom bond in the above (A4-2) include thiophenols corresponding to the phenols having an aromatic ring carbon-oxygen atom bond. . The above (A4-2)
Examples of sulfides of thiophenols having an aromatic ring carbon-sulfur atom bond include thiophenols having an aromatic ring carbon-sulfur atom bond and sulfides of aliphatic or alicyclic hydrocarbons. Can be In addition, disulfide is also included in sulfide.

The aminobenzenes having an aromatic ring carbon-nitrogen atom bond in the above (A4-3) include, for example,
Examples include aniline, toluidine, (o-, p-) diaminobenzene, (o-, p-) anisidine, (o-, p-) phenetidine and the like. In addition, the nitrobenzenes having an aromatic ring carbon-nitrogen atom bond in the above (A4-3) include nitrobenzene, (o-, p-) dinitrobenzene and the like.

Examples of the compound having a carbon-hydrogen bond at the position adjacent to the halogen atom in the above (A5) include: aliphatic halogenated alkyl such as chloromethyl and chloroethyl; alicyclic halogenated alkyl such as chloromethylcyclohexane; And aromatic alkyl halides such as chloromethylbenzene and di (chloromethyl) benzene.

Examples of the compound (ester) having an ester bond in the above (A6) include an ester derived from an alcohol and a carboxylic acid.
In the ester, the alcohol can be appropriately selected from aliphatic alcohols, alicyclic alcohols, aromatic alcohols, and the like. The carboxylic acid can be appropriately selected from aliphatic carboxylic acids, alicyclic carboxylic acids, aromatic carboxylic acids, and the like. Specific examples of the ester include alkyl carboxylic acid alkyl esters such as methyl acetate, ethyl acetate, methyl propionate, and ethyl propionate; alkyl carboxylic acid alkyl esters such as methyl benzoate and ethyl benzoate; cyclohexane methyl ester And alicyclic carboxylic acid alkyl esters. Also, as an ester,
Aliphatic carboxylic acid aryl esters, aliphatic carboxylic acid cycloalkyl esters, aromatic carboxylic acid aryl esters, aromatic carboxylic acid cycloalkyl esters, alicyclic carboxylic acid aryl esters, alicyclic carboxylic acid cycloalkyl esters, and the like may also be used. Can be.

The above-mentioned organic compound having an oxidizable group (A)
May be used alone, or two or more of the same or different may be used in combination.

In the present invention, examples of the organic compound (A) having an oxidizable group include a compound (A1) having a carbon-hydrogen bond adjacent to an aromatic ring (toluene, benzene dimethanol, etc.), a heteroatom Heteroatom-containing compound (A2) having an adjacent carbon-hydrogen bond (alcohols, ethers, etc.) can be preferably used.

The organic compound (A) having an oxidizable group
Is reacted with nitric acid to perform nitric acid oxidation, whereby an organic compound having an oxidized group (oxidized group) containing an oxygen atom derived from nitric acid can be obtained. Examples of such an oxidizing group include oxygen atom-containing groups such as a carboxyl group, an aldehyde group, a carbonyl group, a sulfonic acid group, and a sulfoxide group, and an azo group.

[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, propionic acid, and trifluoroacetic acid; acetonitrile,
Nitriles such as propionitrile and benzonitrile;
Amides such as formamide, acetamide, dimethylformamide (DMF) and dimethylacetamide; aliphatic hydrocarbons such as hexane and octane; chloroform, dichloromethane, dichloroethane, carbon tetrachloride, chlorobenzene, trifluoromethylbenzene (trifluorotoluene) and the like Halogenated hydrocarbons; nitro compounds such as nitrobenzene, nitromethane and nitroethane; esters such as ethyl acetate and butyl acetate; water; As the solvent, organic acids such as acetic acid and trifluoroacetic acid, nitriles such as acetonitrile and benzonitrile, and halogenated hydrocarbons such as trifluoromethylbenzene are often used.

When the substrate is alcohol or the like, if the solvent is acetic acid alone, the esterification reaction of the substrate may proceed and the target product may not be obtained, and if water alone is used, the reactivity is significantly reduced. There are cases. In such a case, by using a mixture of acetic acid and water (acetic acid-water-based solvent), alcohol can be efficiently oxidized with nitric acid, and an organic compound having an oxidized group as a target substance can be prepared.

The reaction temperature can be appropriately selected according to the type of the organic compound (A) having an oxidizable group and the imide compound as a catalyst. The reaction temperature is, for example, 0 to 3
The temperature can be selected from the range of about 00 ° C, preferably about 20 to 200 ° C, more preferably about 50 to 90 ° C.

In the present invention, the reaction can be performed in an atmosphere of a gas inert to the nitric acid oxidation reaction. Examples of such an inert gas include nitrogen, carbon dioxide, and air. In some cases, the generation of by-products is reduced in a nitrogen atmosphere than in an air atmosphere.

The reaction pressure may be normal pressure or under pressure. When performed under pressure, usually 0.1 to 10M
Pa, preferably about 0.2 to 7 MPa. The reaction can be carried out by a conventional method such as a batch system, a semi-batch system, and a continuous system.

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

According to the method of the present invention, the organic compound (A) having a group to be oxidized as a substrate is oxidized with nitric acid under mild conditions to obtain a high conversion, an efficient oxidation reaction product, The organic compound (A) having the oxidized group can be obtained.

More specifically, for example, as the organic compound (A) as a substrate, a carbon-
When the compound having a hydrogen bond (A1) is used, the adjacent position of the aromatic ring is efficiently oxidized even under mild conditions, and carboxylic acid, aldehyde, ketone, and the like are generated.
For example, from a compound having a methyl group at a position adjacent to an aromatic ring (for example, toluene), a corresponding aromatic carboxylic acid (for example, benzoic acid) can be obtained in a high yield. Similarly, aromatic carboxylic acids such as benzoic acid can be obtained at a high yield from a compound having a methylene group or a methine group at a position adjacent to the aromatic ring.

When a hetero atom-containing compound (A2) having a carbon-hydrogen bond adjacent to the hetero atom is used as the organic compound (A), the carbon atom adjacent to the hetero atom is oxidized. For example, a primary alcohol produces a corresponding aldehyde, a carboxylic acid or the like, and a secondary alcohol produces a corresponding ketone or the like. Sulfonic acid and the like are generated from the primary or secondary thiol (A2-1). These carboxylic acids, aldehydes, ketones and sulfonic acids can also be obtained in high yield.

From ethers, carboxylic acids, ketones and the like are formed at high conversion. In such an ether, two kinds of carboxylic acids, aldehydes or ketones may be produced from one ether, or dicarboxylic acids or dialdehydes may be produced. Specifically, when two adjacent positions of the oxygen atom of the ether are a carbon atom having a carbon-hydrogen bond, and the carbon atom is a carbon atom constituting an aliphatic hydrocarbon, that is, the ether is an aliphatic hydrocarbon In the case of a group ether, two carbon atoms adjacent to these oxygen atoms are each subjected to nitric acid oxidation to generate a carboxylic acid, a ketone or the like corresponding to each. Further, when two adjacent positions of the oxygen atom of the ether are carbon atoms having a carbon-hydrogen bond, and the carbon atom is a carbon atom constituting one alicyclic hydrocarbon, that is, when the ether is cyclic In the case of ether, these two carbon atoms adjacent to the oxygen atom are each oxidized with nitric acid to open the ring, thereby producing a dicarboxylic acid, a dialdehyde or the like. These carboxylic acids and ketones can also be obtained in high yield. More specifically, from phthalane,
The nitric acid oxidation produces o-phthalaldehyde at a high conversion.

For example, from hydrazos, the corresponding azo compound can be obtained in high yield.

When the compound (A3) having a carbon-heteroatom double bond is used as the organic compound (A), an oxidation reaction product corresponding to the type of heteroatom and the like can be obtained in high yield. For example, when a ketone is oxidized with nitric acid, it is cleaved to generate a carboxylic acid or the like. For example, a dicarboxylic acid such as adipic acid can be obtained from a cyclic ketone such as cyclohexanone in a high yield.

When the compound (A4) having an aromatic ring carbon-hetero atom bond is used as the organic compound (A),
The aromatic ring carbon atom bonded to the hetero atom is oxidized with nitric acid. For example, phenols having the same oxidizable group (hydroxyl group) or another oxidizable group (amino group, nitro group, halogenated alkyl group, etc.) at the ortho or para position of the hydroxyl group of phenol ( From p-aminophenol and the like), the corresponding quinone is formed at a high conversion.

When a compound (A5) having a carbon-hydrogen bond adjacent to a halogen atom is used as the organic compound (A), the carbon atom adjacent to the halogen atom is oxidized with nitric acid,
The corresponding carboxylic acids and the like are formed at high conversions.

When the compound (A6) having an ester bond is used as the organic compound (A), the carbon atom relating to the ester bond is oxidized with nitric acid, and the corresponding carboxylic acid or the like is obtained in high yield.

[0095]

According to the method of the present invention, nitric acid is used as an oxidizing agent using an imide compound having a specific structure as a catalyst. An organic compound containing the oxidized group can be produced. Further, since the reaction can be performed under mild conditions, the selectivity of the reaction is excellent. In addition, deactivation of the imide compound catalyst used can be suppressed.

Further, according to the method of the present invention, an organic compound having an oxygen atom-containing group such as a hydroxyl group, an oxo group, a carboxyl group or a sulfonic acid group can be easily and selectively produced under very mild conditions. can do.

[0097]

The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the invention thereto.

Example 1 Phthalane 1.0 was added to a flask.
g (8.3 mmol), 0.14 g (0.86 mmol) of N-hydroxyphthalimide (NHPI), 60%
0.87 g (8.3 mmol) of nitric acid and 9.0 g of acetic acid
And stirred at 60 ° C. for 30 minutes in an air atmosphere.
When the obtained reaction mixture was analyzed by gas chromatography, 70 mol% of orthophthalaldehyde and 11 mol% of phthalide were produced. The conversion of phthalane was 100%.

(Comparative Example 1) A reaction was carried out in the same manner as in Example 1 except that NHPI was not added. The obtained reaction mixture was analyzed by gas chromatography to find that 2 mol% of orthophthalaldehyde was formed. And the conversion of phthalane was 3%.

Example 2 A reaction was carried out in the same manner as in Example 1 except that the atmosphere was changed to a nitrogen atmosphere instead of an air atmosphere, and the obtained reaction mixture was analyzed by gas chromatography. Aldehyde 72 mol
% And phthalide were generated at 8 mol%. The conversion of phthalane was 100%.

Example 3 1.0 g (7.2 mmol) of 1,2-benzenedimethanol and NHPI were placed in a flask.
0.12 g (0.74 mmol), 1.5 g of 60% nitric acid
(14.3 mmol), 5.0 g of acetic acid, and 4.0 g of water.
And stirred at 60 ° C. for 3 hours under an air atmosphere. When the obtained reaction mixture was analyzed by gas chromatography, 75 mol% of orthophthalaldehyde and 12 mol% of phthalide were produced. The conversion of 1,2-benzenedimethanol was 100%.

One hour after the start of the reaction, in the reaction mixture, 51 mol% of orthophthalaldehyde and 10 mol% of phthalide were produced, and the conversion of 1,2-benzenedimethanol was 100%. .

(Comparative Example 2) A reaction was carried out in the same manner as in Example 3 except that NHPI was not added. The obtained reaction mixture was analyzed by gas chromatography to find that 3 mol% of orthophthalaldehyde was formed. Yes, 1,
The conversion of 2-benzenedimethanol was 100%. In addition, 1,2-benzenedimethanol acetate ester and the like were generated.

Example 4 1.0 g (7.2 mmol) of 1,2-benzenedimethanol and NHPI were placed in a flask.
0.12 g (0.74 mmol), 1.5 g of 60% nitric acid
(14.3 mmol), 4.5 g of acetic acid, and 4.5 g of water.
And stirred at 80 ° C. for 3 hours in an air atmosphere. When the obtained reaction mixture was analyzed by gas chromatography, 75 mol% of orthophthalaldehyde and 12 mol% of phthalide were produced. The conversion of 1,2-benzenedimethanol was 100%.

One hour after the start of the reaction, in the reaction mixture, ortho-phthalaldehyde was produced in an amount of 73 mol% and phthalide in an amount of 11 mol%, and the conversion of 1,2-benzenedimethanol was 100%. .

Example 5 A flask was charged with 1.0 g (7.2 mmol) of 1,2-benzenedimethanol and NHPI
0.012 g (0.074 mmol), 60% nitric acid
5 g (14.3 mmol), 4.5 g of acetic acid, and 4.
5 g was added and stirred at 80 ° C. for 3 hours under an air atmosphere. The resulting reaction mixture was analyzed by gas chromatography to find that orthophthalaldehyde contained 87 mol
%, And 11 mol% of phthalide. Also, 1,
The conversion of 2-benzenedimethanol was 100%.

(Comparative Example 3) A reaction was carried out in the same manner as in Example 5 except that NHPI was not added. The obtained reaction mixture was analyzed by gas chromatography to find that 2 mol% of orthophthalaldehyde was formed. Yes, 1,
The conversion of 2-benzenedimethanol was 100%. In addition, acetic acid ester of 1,2-benzenedimethanol and the like were generated.

Example 6 A flask was charged with 1.0 g (9.8 mmol) of 1-hexanol and 0.16 g of NHPI.
(0.98 mmol), 1.0 g of 60% nitric acid (9.5 m
mol) and 9.0 g of acetonitrile, and stirred at 70 ° C. for 3 hours in an air atmosphere. The obtained reaction mixture was analyzed by gas chromatography to find that 0.7 mol% of capronaldehyde was produced. Also, 1
Conversion of hexanol was 10%.

(Comparative Example 4) A reaction was carried out in the same manner as in Example 6 except that NHPI was not added, and the obtained reaction mixture was analyzed by gas chromatography to find that 0.1 mol% of caproaldehyde was formed. And 1-
Hexanol conversion was 6%.

Example 7 A reaction was carried out in the same manner as in Example 6 except that 5.0 g of acetic acid and 4.0 g of water were added instead of 9.0 g of acetonitrile, and the obtained reaction mixture was subjected to gas chromatography. When analyzed by chromatography, capronaldehyde was 1.1 mol% and caproic acid was 0.3 m
ol%. The conversion of 1-hexanol was 83%.

(Comparative Example 5) A reaction was carried out in the same manner as in Example 7 except that NHPI was not added. The obtained reaction mixture was analyzed by gas chromatography to find that 0.1 mol% of caproaldehyde was formed. No formation of caproic acid was observed. The conversion of 1-hexanol was 65%.

Claims (6)

[Claims] (1) (i) The following formula (I) as a catalyst: [Wherein X represents an oxygen atom or an -OR group (R represents a hydrogen atom or a protecting group for a hydroxyl group)], and an imide compound having a cyclic imide skeleton represented by (ii) nitric acid as an oxidizing agent Wherein the organic compound (A) having an oxidizable group which is oxidized by nitric acid is oxidized with nitric acid in the presence of the above to produce an organic compound having an oxidized oxidized group. 2. An imide compound represented by the following formula (1): [Wherein, R ¹ and R ² are the same or different and are each a hydrogen atom,
A halogen atom, an alkyl group, an aryl group, a cycloalkyl group, a hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or an acyl group; R ¹ and R ² are bonded to each other to form a double bond, or an aromatic or A non-aromatic ring may be formed. X represents an oxygen atom or an -OR group (R represents a hydrogen atom or a hydroxyl-protecting group). R ¹ , R ² , or a double bond or an aromatic or non-aromatic ring formed by bonding R ¹ and R ² to each other may be an N-substituted group represented by the formula (1) (One or two cyclic imide groups may be further formed.)
The method for producing an organic compound according to claim 1, which is a compound represented by the formula: 3. The process for producing an organic compound according to claim 1, wherein the amount of nitric acid used is 1 to 3 equivalents relative to 1 equivalent of the organic compound having an oxidizable group (A). 4. The use amount of the imide compound is 0.001 to 1 equivalent of the organic compound (A) having an oxidizable group.
The method for producing an organic compound according to any one of claims 1 to 3, which is 0.2 equivalent. 5. The organic compound (A) having an oxidizable group,
(A1) a compound having a carbon-hydrogen bond at a position adjacent to an aromatic ring, (A2) a hetero atom-containing compound having a carbon-hydrogen bond at a position adjacent to a hetero atom, and (A3) a carbon-hetero atom double bond. (A4) a compound having an aromatic ring carbon-heteroatom bond, (A5) a compound having a carbon-hydrogen bond at a position adjacent to a halogen atom, and (A6) a compound having an ester bond. The method for producing an organic compound according to claim 1, which is at least one compound. 6. The method for producing an organic compound according to claim 1, wherein a metal compound is used as a cocatalyst.