JP2002088077A - Method for producing organic compound using imide compound and nitric acid compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce an organic compound in high selectivity and yield by addition reaction or substitution reaction or the like under mild conditions. SOLUTION: The method for producing the objective organic compound is characterized by comprising reaction between (A) a radical-forming compound and (B) a radical-scavenging compound in the presence of (i) an imide compound of the formula (1) (wherein, R1 and R2 are each an alkyl, aryl or the like, or may be bound to each other to form a double bond, or aromatic or nonaromatic ring; and X is O or OH) and (ii) nitric acid or nitrous acid or a salt thereof to form the addition or substitution reaction product of the compounds (A) and (B) or a derivative thereof.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[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 producing two kinds of compounds in the presence of a specific imide compound and nitric acid or nitrous acid or a salt thereof. The present invention relates to a method for reacting and producing an addition or substitution reaction product or a derivative thereof by a radical mechanism.

[0002]

2. Description of the Related Art It is known to obtain a useful organic compound by adding various compounds to an unsaturated compound having a carbon-carbon double bond or a hetero atom-containing compound. For example, when an active methylene compound such as malonic acid diester is reacted with an olefin having an electron withdrawing group such as acrylonitrile in the presence of a base, a carbon-carbon bond is formed by a nucleophilic addition reaction to form an addition product. (Michael addition reaction). In addition, in the presence of an acid or a base,
Upon treatment of one carbonyl compound, one carbonyl compound will nucleophilically add to the other carbonyl compound,
A carbon-carbon bond is formed and an aldol condensate is obtained.

[0003] However, these methods are usually applied in the presence of an acid or a base, and therefore cannot be applied to a compound having a weak substituent in an acid or a base. In addition, a hydroxymethyl group, an alkoxymethyl group, an acyl group, a tertiary carbon atom, or the like is directly bonded to a carbon atom forming an unsaturated bond of an unsaturated compound or a methine carbon atom of a bridged cyclic compound. It is difficult.

[0004] Further, addition reactions to carbon-carbon double bonds by a radical mechanism and coupling reactions for forming carbon-carbon bonds are also known. However, there is almost no method for obtaining an addition or substitution reaction product or a derivative thereof efficiently under mild conditions, for example, with molecular oxygen.

[0005] Several methods are known for producing hydroxy-γ-butyrolactone derivatives. For example, EP-A-2103686 states that
A method for synthesizing pantolactone by reacting glyoxylic acid and isobutylene is disclosed. JP-A-61-
No. 282373 discloses glyoxylic acid hydrate and t-
A method for producing pantolactone by reacting with butyl alcohol is also disclosed. Tetrahedron (Te
trahedron), 933 (1979) discloses that 4-hydroxy-2-methyl-5,5,5-trichloro-1-pentene is hydrolyzed to 2-hydroxy-4-methyl-4-pentenoic acid, A method has been reported for synthesizing pantolactone by cyclizing the compound in the presence of hydrochloric acid. In addition, the Chemical Society of Japan Spring Meeting Preliminary Lectures II, 10
On page 15 (1998), α-acetoxy-α, β-
It has been reported that when a mixture of unsaturated carboxylic acid ester and 2-propanol is irradiated with light, a corresponding α-acetoxy-γ, γ-dimethyl-γ-butyrolactone derivative is formed. However, in each of the above-mentioned methods, it is generally difficult to obtain raw materials or special conditions are required for the reaction.

[0006] Since the oxidation reaction is one of the most basic reactions in the organic chemical industry, various oxidation methods have been developed. From a resource and environmental point of view, a preferred oxidation method is a catalytic oxidation method using molecular oxygen or air directly as an oxidizing agent. However, in the catalytic oxidation method, usually, high temperature and high pressure are required for activating oxygen, and the reaction needs to be performed in the coexistence of a reducing agent such as aldehyde for performing the reaction under mild conditions. For this reason, it has been difficult to easily and efficiently produce alcohols and carboxylic acids under mild conditions using a catalytic oxidation method.

On the other hand, nitration of lower hydrocarbons such as methane and ethane is carried out using nitric acid and nitrogen dioxide in the range of 250 to 300.
It is performed at high temperature of ° C. However, when nitration of a hydrocarbon having a large number of carbon atoms is carried out under the above conditions, the substrate is decomposed and the desired nitro compound cannot be obtained in good yield. In addition, a method using a mixed acid (a mixture of nitric acid and sulfuric acid) is widely used as nitration of hydrocarbons. However, this method requires the use of large amounts of high concentrations of strong acids.

Various methods are known for producing organic sulfuric acids and salts thereof. For example, as a method for producing sulfonic acid, a method of oxidizing thiol or disulfide with an oxidizing agent, a method of utilizing a Friedel-Crafts reaction of reacting an aromatic hydrocarbon with anhydrous SO ₃ -pyridine or chlorosulfuric acid, a method of producing an unsaturated compound, And the like. However, these methods have problems such as strict reaction conditions and co-production of a large amount of by-products. In addition, a method for directly and efficiently sulfonating non-aromatic hydrocarbons has not been known.

JP-A-8-38909 and JP-A-9-909
JP-A-327626 proposes, as a catalyst for oxidizing an organic substrate by molecular oxygen, an imide compound having a specific structure, or an oxidation catalyst composed of the imide compound and a transition metal compound. . JP-A-11-239730 discloses that in the presence of the imide compound, a substrate and at least one type of reactant selected from (i) a nitrogen oxide and (ii) a mixture of carbon monoxide and oxygen. To introduce at least one functional group selected from a nitro group and a carboxyl group into a substrate. According to the method using these imide compounds as catalysts, an oxygen-containing group such as a hydroxyl group, a nitro group or a carboxyl group can be introduced into a substrate under relatively mild conditions. However, this method was not always satisfactory in terms of the yield of the target compound. In addition, the imide compound may be decomposed depending on the type of reaction or reaction conditions.

[0010]

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a method capable of producing an organic compound with a high selectivity and a high yield by an addition or substitution reaction under mild conditions. Another object of the present invention is to directly provide a hydroxymethyl group, an alkoxymethyl group, an acyl group, a tertiary carbon atom to a carbon atom forming an unsaturated bond of an unsaturated compound or a methine carbon atom of a bridged cyclic compound. It is an object of the present invention to provide a method for producing an organic compound which can bind to such compounds. Still another object of the present invention is to provide a method for obtaining a corresponding 1,3-dihydroxy compound from an alcohol, an unsaturated compound and oxygen in a high yield. It is another object of the present invention to provide α-hydroxy-γ-
An object of the present invention is to provide a method for producing a butyrolactone derivative. Still another object of the present invention is to provide a method for easily and selectively producing an organic compound having an oxygen atom-containing group under milder conditions. Another object of the present invention is to provide a method for producing an organic compound with high production efficiency while suppressing the decomposition of the catalyst and maintaining the catalytic activity for a long period of time.

[0011]

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 imide compound having a specific structure and a nitric acid or a nitrous acid or a salt thereof can generate a radical. It has been found that the reaction of a compound with a radical-scavenging compound yields a corresponding addition or substitution reaction product or a derivative thereof under mild conditions, thus completing the present invention.

That is, the present invention provides (i) the following formula (1)

Embedded image (Wherein R ¹ and R ² are the same or different and each represents 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 a hydroxyl group. R ¹ , R ² , or R ¹ and R ²
Are bonded to each other to form a double bond or an aromatic or non-aromatic ring represented by the above formula (1).
And (ii) a compound capable of producing (A) a radical in the presence of nitric acid or nitrous acid or a salt thereof. And (B) a radical scavenging compound to produce an addition or substitution reaction product of the compound (A) and the compound (B) or a derivative thereof. I will provide a.

The compound (A) capable of forming a radical includes, for example, (A1) a heteroatom-containing compound having a carbon-hydrogen bond adjacent to a heteroatom, and (A2) a carbon-heteroatom double bond. A compound, (A3) a compound having a methine carbon atom, (A4) a compound having a carbon-hydrogen bond at a position adjacent to an unsaturated bond, (A5) a non-aromatic cyclic hydrocarbon,
(A6) Conjugated compounds, (A7) amines, (A8) aromatic compounds, (A9) linear alkanes, and (A10) olefins.

The radical scavenging compound (B) includes, for example, (B1) an unsaturated compound, (B2) a compound having a methine carbon atom, (B3) a compound containing a hetero atom, and (B4)
Oxygen atom-containing gas and the like are included. As the oxygen atom-containing gas (B4), at least one selected from oxygen, carbon monoxide, nitrogen oxides and sulfur oxides can be used.

In the above method, (A11) an imide compound represented by the following formula (2) in the presence of (i) an imide compound represented by the formula (1) and (ii) nitric acid or nitrous acid or a salt thereof.

Embedded image (Wherein R ^a and R ^b are the same or different and each represent a hydrogen atom or an organic group. R ^a and R ^b may be bonded to each other to form a ring together with adjacent carbon atoms) Alcohol represented by formula (B11) and the following formula (3)

Embedded image ^{(Wherein, R c, R d, R} e may be the same or different and each represents a hydrogen atom or an organic group, Y represents an electron-withdrawing group .R ^c,
R ^d , R ^e , and Y may combine with each other to form a ring together with an adjacent carbon atom or a carbon-carbon bond), and react with an active olefin represented by the following formula (B41): Equation (4)

Embedded image (Wherein, R ^a , R ^b , R ^c , R ^d , R ^e , and Y are the same as described above)
1,3-dihydroxy compound represented by the following formula:

In addition, (A11) an imide compound represented by the following formula (2) in the presence of (i) an imide compound represented by the formula (1) and (ii) nitric acid or nitrous acid or a salt thereof.

Embedded image (Wherein R ^a and R ^b are the same or different and each represent a hydrogen atom or an organic group. R ^a and R ^b may be bonded to each other to form a ring together with adjacent carbon atoms) Alcohol represented by the formula (B12) and the following formula (5)

Embedded image (Wherein, R ^c , R ^d , R ^e , and R ^f are the same or different and each represent a hydrogen atom or an organic group. R ^c , R ^d , and R ^e are bonded to each other to form an adjacent carbon atom or -Which may form a ring together with the carbon bond), and (B41) oxygen.
The following equation (6)

Embedded image (Wherein, R ^a , R ^b , R ^c , R ^d , and ^Re are the same as described above).

Further, (i) an imide compound represented by the formula (1), (ii) a compound capable of forming a radical in the presence of nitric acid or nitrous acid or a salt thereof, and (B4)
By reacting with an oxygen atom-containing gas, an organic compound containing an oxygen atom-containing group can be obtained.

In each of the above reactions, a metal compound can be used as a co-catalyst. In the present specification, the “addition or substitution” reaction is used in a broad sense including oxidation, sulfonation, and the like.

[0019]

DETAILED DESCRIPTION OF THE INVENTION [Imide compound] In the present invention, an imide compound represented by the above formula (1) is used as a catalyst. In this imide compound, the halogen atom among the substituents R ¹ and R ² includes iodine, bromine, chlorine and fluorine atoms. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl,
It includes a linear or branched alkyl group having about 1 to 10 carbon atoms, such as s-butyl, t-butyl, hexyl and decyl 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 groups 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, hexyloxycarbonyl and the like. included. Preferred alkoxycarbonyl 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. The preferred aromatic or non-aromatic ring is a 5- to 12-membered ring, particularly a 6- to 10-membered ring, and may be a heterocyclic ring or a fused heterocyclic ring, but is often a hydrocarbon ring. 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. In the formula (1), X represents an oxygen atom or a hydroxyl group, and the bond between the nitrogen atom N and X is a single bond or a double bond.

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 are 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 to include 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, R ^{3 to} R ⁶ may be mutually adjacent groups to form an aromatic or non-aromatic ring, and in formula (1f), A represents a methylene group or Represents an oxygen atom, R ¹ ,
R ² and R 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 the 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, and examples of the halogen atom include fluorine, chlorine, and bromine atoms. Substituent R ³
To R ⁶ is 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 combining R ^{3 to} R ⁶ with each other is the same as the ring formed by combining R ¹ and R ² with 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
-Hydroxytetrachlorophthalimide, N-hydroxyhettimide, N-hydroxyhymic imide, N-hydroxytrimellitic imide, N, N'-
Examples thereof include dihydroxypyromellitic imide and N, N'-dihydroxynaphthalenetetracarboxylic imide.

The imide compound is prepared by a conventional imidization reaction, for example, by reacting the 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.

The acid anhydrides include, for example, saturated or unsaturated aliphatic dicarboxylic anhydrides such as succinic anhydride and maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride (1,2-cyclohexanedicarboxylic anhydride). Or saturated, unsaturated non-aromatic cyclic polycarboxylic anhydrides such as 1,2,3,4-cyclohexanetetracarboxylic acid 1,2-anhydride, methylcyclohexenetricarboxylic anhydride, etc. (Polycarboxylic anhydride), cross-linked cyclic polycarboxylic anhydride (alicyclic polycarboxylic anhydride), such as hetic anhydride and hymic anhydride, phthalic anhydride, tetrabromophthalic anhydride, tetrachloroanhydride Phthalic acid, nitrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, melitic anhydride, 1,8;
Aromatic polycarboxylic anhydrides such as 4,5-naphthalenetetracarboxylic dianhydride are included.

Particularly preferred imide compounds are alicyclic polycarboxylic acid anhydrides or aromatic polycarboxylic acid anhydrides, and especially N-derivatives derived from aromatic polycarboxylic acid anhydrides.
Hydroxyimide compounds, such as N-hydroxyphthalimide, are included. The imide compounds represented by the formula (1) can be used alone or in combination of two or more. 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, the compound (A) capable of generating a radical
And 0.0000001 to 1 mol, preferably 0.00001 to 0.5 mol, more preferably about 0.0001 to 0.4 mol, per 1 mol of the compound used in a smaller amount among the radical-scavenging compound (B). And 0.001 to
It is often about 0.35 mol.

[Nitric acid or nitrous acid or a salt thereof] In the present invention, nitric acid or nitrous acid or a salt thereof (hereinafter sometimes simply referred to as "nitric acid") is used as the other catalyst. These may be used alone or in combination of two or more.

The salts of nitric acid and nitrous acid include alkali metal salts such as sodium salt and potassium salt; alkaline earth metal salts such as magnesium salt, calcium salt and barium salt; and other salts such as silver salt, aluminum salt and zinc salt. And the like. Preferred salts include alkali metal nitrates or nitrites.

The nitric acid may be supplied to the reaction system as it is, but may be supplied to the reaction system in the form of a solution such as an aqueous solution. They can also be generated in a reaction system and used for the reaction.

The amount of the nitric acid used is, for example, from 0.1 to 1 mole of the compound (A) capable of generating a radical and the radical scavenging compound (B) which is used in a smaller amount.
00000-0.8 mol (for example, 0.00001-
0.8 mol), preferably 0.0004 to 0.1 mol,
More preferably, it is about 0.001 to 0.05 mol. If the amount of nitric acid is too large, the desired reaction may not proceed due to the decomposition of the imide compound.

[Co-catalyst] In the present invention, a co-catalyst can be used in addition to the catalyst comprising the imide compound and nitric acid. Metal compounds can be mentioned as co-catalysts. By using the catalyst and the metal compound together, the reaction rate and the selectivity of the reaction can be improved.

As the metal element constituting the metal compound,
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 periodic table group 2 element (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). Among them, elements of the 5 to 11 groups of the periodic table, particularly elements of the 5th to 9th groups 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.

Examples of the metal compound include simple substances, hydroxides, oxides (including complex oxides), halides (fluoride, chloride, bromide, iodide), oxo acid salts (for example, nitrate) of the above metal elements. , Sulfate, phosphate, borate,
Inorganic compounds such as carbonates, salts of isopolyacids and salts of heteropolyacids; organic acid salts (eg, acetates, propionates, cyanates, naphthenates, octanoates, stearates, etc.), complexes And other organic compounds. The ligands constituting the complex include OH (hydroxo), alkoxy (methoxy, ethoxy, propoxy,
Butoxy), acyl (acetyl, propionyl, etc.), alkoxycarbonyl (methoxycarbonyl, ethoxycarbonyl, etc.), acetylacetonato, cyclopentadienyl group, halogen atom (chlorine, bromine, etc.),
CO, CN, oxygen atom, H ₂ O (aquo), phosphorus compound of phosphine (triarylphosphine such as triphenylphosphine), NH ₃ (ammine), NO, N
Examples include nitrogen-containing compounds such as O ₂ (nitro), NO ₃ (nitrat), ethylenediamine, diethylenetriamine, pyridine, and phenanthroline.

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, cobalt octanoate, and cobalt stearate; and divalent or trivalent cobalt compounds such as complexes such as cobalt acetylacetonate. Examples of the vanadium compound include vanadium hydroxide, vanadium oxide, vanadium chloride, vanadyl chloride, vanadium sulfate, vanadyl sulfate,
Inorganic compounds such as sodium vanadate; divalent to pentavalent vanadium compounds such as complexes such as vanadium acetylacetonate and vanadyl acetylacetonate; Examples of the compound of another metal element include a compound corresponding to the aforementioned cobalt or vanadium compound.
The metal compounds can be used alone or in combination of two or more.

The amount of the metal compound used is, for example, about 0.001 to 10 mol, preferably about 0.005 to 3 mol, per 1 mol of the imide compound. Also,
The amount of the metal compound used is 0.0000001 to 0.001 mol per 1 mol of the compound (A) capable of forming a radical and the radical scavenging compound (B) which is used in a small amount.
It is about 0.1 mol, preferably about 0.000001 to 0.02 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, elements of Group 15 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 group, alkenyl group and alkynyl group); 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 (for example, 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 4 aromatic hydrocarbon groups (particularly, phenyl group or 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 corresponding quaternary ammonium bromides; and quaternary ammonium salts having four hydrocarbon groups bonded to a nitrogen atom; dimethylpiperidinium chloride, hexadecylpyridinium chloride, And 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 for 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.

Further, the organic salt includes methanesulfonic acid.
Salt, ethane sulfonate, octane sulfonate, dode
Alkylsulfonates such as cansulfonates (eg,
If C _6-18Alkyl 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_6-18Alkyl-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 0.001 to 10 mol per 1 mol of the imide compound.
Preferably it is about 0.005 to 3 mol.

In the method of the present invention, a radical generator or a radical reaction accelerator may be present in the system. Such components include, for example, halogens (such as chlorine and bromine), peracids (such as peracetic acid and m-chloroperbenzoic acid), and peroxides (such as hydrogen peroxide and t-butyl hydroperoxide (TBHP)). Peroxide and the like). The presence of these components in the system may accelerate the reaction. The amount of the component used is, for example, about 0.001 to 10 mol per 1 mol of the imide compound.

[Compound (A) capable of generating a radical] The compound (A) capable of generating a radical is not particularly limited as long as it is a compound capable of generating a stable radical.
As typical examples, (A1) a compound containing a hetero atom having a carbon-hydrogen bond adjacent to a hetero atom, (A2) a compound having a carbon-hetero atom double bond, and (A3) a compound having a methine carbon atom , (A4) a compound having a carbon-hydrogen bond adjacent to an unsaturated bond, (A5) a non-aromatic cyclic hydrocarbon, (A6) conjugated compound, (A7) amines, (A8)
Aromatic compounds, (A9) linear alkanes, and (A10) olefins.

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 Examples include an amino group, a sulfo group, an alkyl group, an alkenyl group, an alkynyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a heterocyclic group. The compound (A) capable of generating a radical functions as a radical-donating compound in this reaction.

The heteroatom-containing compound (A1) having a carbon-hydrogen bond at a position adjacent to the heteroatom includes (A1-1) a primary or secondary alcohol or a primary or secondary alcohol.
Grade thiol, (A1-2) ether having a carbon-hydrogen bond adjacent to an oxygen atom or sulfide having a carbon-hydrogen bond adjacent to a sulfur atom, (A1-3) carbon-hydrogen adjacent to an oxygen atom Examples thereof include an acetal having a bond (including hemiacetal) and a thioacetal having a carbon-hydrogen bond at a position adjacent to a sulfur atom (including thiohemiacetal).

The first or second grade in the above (A1-1)
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, 2-phenylethyl alcohol,
-Aromatic primary alcohols such as -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, Carbon atoms 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; Cyclopentanol, cyclohexanol, cyclooctanol, cyclododecanol, 2-cyclohexen-1-ol, 2-adamantanol, 2-adamantanol having 1 to 4 hydroxyl groups at the bridgehead,
A saturated or unsaturated cycloaliphatic secondary compound having about 3 to 20 members (preferably 3 to 15 members, more preferably 5 to 15 members, particularly 5 to 8 members) such as 2-adamantanol having an oxo group on the adamantane ring. Primary alcohols (including bridged cyclic secondary alcohols); aromatic secondary alcohols such as 1-phenylethanol, 1-phenylpropanol, 1-phenylmethylethanol and diphenylmethanol;
Heterocyclic secondary alcohols such as (2-pyridyl) ethanol and the like are included.

Further, typical alcohols include 1-adamantane methanol, α-methyl-1-adamantane methanol, α-ethyl-1-adamantane methanol, α-isopropyl-1-adamantane methanol,
3-hydroxy-α-methyl-1-adamantane methanol, 3-carboxy-α-methyl-1-adamantane methanol, α-methyl-3a-perhydroindenemethanol, α-methyl-4a-decalinmethanol, 8
a-hydroxy-α-methyl-4a-decalinmethanol, α-methyl-4a-perhydrofluorenemethanol, α-methyl-4a-perhydroanthracenemethanol, α-methyl-8a-perhydrophenanthrenemethanol, α-methyl- 2-tricyclo [5.2.1.
0 ^2,6 ] decanemethanol, 6-hydroxy-α-methyl-2-tricyclo [5.2.1.0 ^2,6 ] decanemethanol, α-methyl-2a-perhydroacenaphthenemethanol, α-methyl- 3a-perhydrophenalenemethanol, α-methyl-1-norbornanemethanol,
Also included are alcohols having a bridging ring hydrocarbon group such as α-methyl-2-norbornene-1-methanol (compounds having a bridging ring hydrocarbon group bonded to a carbon atom to which a hydroxyl group is bonded). .

Preferred alcohols include secondary alcohols
(For example, 2-propanol, s-butyl alcohol
Aliphatic secondary alcohols such as 1-cyclohexyl
Fatty oils on carbon atoms with hydroxyl groups such as
Aliphatic hydrocarbon groups (for example, C _1-4Alkyl group, C_6-14A
Reel group) and a non-aromatic carbocyclic group (eg, C_Three
-15A cycloalkyl group or a cycloalkenyl group)
Secondary alcohol to which is bound; cyclopentano
, Cyclohexanol, 2-adamantanol, etc.
Alicyclic secondary alcohol of about 3 to 15 members; 1-phenyl
Aromatic secondary alcohols such as ethanol), and
Alcohols having a crosslinked ring hydrocarbon group are included.

The first or second grade in the above (A1-1)
Grade thiols include thiols corresponding to the primary or secondary alcohols. Examples of the ether having a carbon-hydrogen bond at the position adjacent to the oxygen atom in the above (A1-2) include, for example, dimethyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, methyl ethyl ether, methyl butyl ether, ethyl butyl ether, Aliphatic ethers such as diallyl ether, methyl vinyl ether and ethyl allyl ether; aromatic ethers such as anisole, phenetole, dibenzyl ether and phenylbenzyl ether; dihydrofuran, tetrahydrofuran,
Cyclic ethers such as pyran, dihydropyran, 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 at the position adjacent to the sulfur atom in the above (A1-2) include sulfides corresponding to ethers having a carbon-hydrogen bond at the position adjacent to the oxygen atom.

Examples of the acetal having a carbon-hydrogen bond at the position adjacent to the oxygen atom in the above (A1-3) include, for example,
Acetals derived from aldehydes, alcohols, acid anhydrides and the like are mentioned, and the acetal includes cyclic acetal and acyclic acetal. As the aldehyde, for example, formaldehyde, acetaldehyde,
Aliphatic aldehydes such as propionaldehyde, butyraldehyde, isobutyraldehyde, pentanal, hexanal, and decanal; alicyclic aldehydes such as cyclopentanecarbaldehyde and cyclohexanecarbaldehyde; and aromatic aldehydes such as benzaldehyde and phenylacetaldehyde. Further, as the alcohol, for example, methanol, ethanol,
Monohydric alcohols such as 1-propanol, 1-butanol and benzyl alcohol; ethylene glycol, propylene glycol, 1,3-propanediol, 2,2-
And dihydric alcohols such as dibromo-1,3-propanediol. As a representative acetal,
1,3 such as 1,3-dioxolan, 2-methyl-1,3-dioxolan, 2-ethyl-1,3-dioxolan
-Dioxolane compounds; 1,3-dioxane compounds such as 2-methyl-1,3-dioxane; dialkylacetal compounds such as acetaldehyde dimethyl acetal;

The thioacetal having a carbon-hydrogen bond adjacent to the sulfur atom in (A1-3) includes a thioacetal corresponding to the acetal having a carbon-hydrogen bond adjacent to the oxygen atom.

Examples of the compound (A2) having a carbon-heteroatom double bond include (A2-1) a carbonyl group-containing compound, (A2-2) a thiocarbonyl group-containing compound, and (A2-3) imines. No. Carbonyl group-containing compound (A2
-1) includes ketones and aldehydes, 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 Chain ketones such as butyl ketone, methyl vinyl ketone, methyl isopropenyl ketone, methyl cyclohexyl ketone, acetophenone, methyl (2-methylphenyl) ketone, methyl (2-pyridyl) ketone, cyclohexyl phenyl ketone; cyclopropanone, cyclobutanone , Cyclopentanone, cyclohexanone, 4-methylcyclohexanone, 4-chlorocyclohexanone, isophorone, cycloheptanone, cyclooctanone, cyclodecanone, cyclo Decanone, cyclopentadecanone, 1,3-cyclohexanedione, 1,4-cyclohexanedione, 1,4-octane-dione, 2,2
Cyclic ketones such as -bis (4-oxocyclohexyl) propane, bis (4-oxocyclohexyl) methane, 4- (4-oxocyclohexyl) cyclohexanone and 2-adamantanone; biacetyl (2,3-butanedione); 1,2-dicarbonyl compounds such as 3-pentanedione, 3,4-hexanedione, bibenzoyl (benzyl), acetylbenzoyl, cyclopentane-1,2-dione, and cyclohexane-1,2-dione (α-diketones) Α-keto alcohols such as acetoin and benzoin; aliphatic aldehydes such as acetaldehyde, propionaldehyde, butanal, hexanal, succinaldehyde, glutaraldehyde, and adipaldehyde; cyclohexylaldehyde, citral, and citronella Alicyclic aldehydes such as benzoyl, nitrobenzaldehyde, cinnamaldehyde, salicylaldehyde, anisaldehyde, phthalaldehyde, isophthalaldehyde, and terephthalaldehyde; and heterocyclic aldehydes such as furfural and nicotinaldehyde.

The thiocarbonyl group-containing compound (A2-2) includes a thiocarbonyl group-containing compound corresponding to the carbonyl group-containing compound (A2-1). The imines (A2-3) include the carbonyl group-containing compound (A2-1)
And ammonia or amines (eg, methylamine,
Amines such as ethylamine, propylamine, butylamine, hexylamine, benzylamine, cyclohexylamine and aniline; hydroxylamines such as hydroxylamine and O-methylhydroxylamine; hydrazines such as hydrazine, methylhydrazine and phenylhydrazine) Includes derived imines (including oximes and hydrazones).

The compound having a methine carbon atom (A3)
Include (A3-1) a cyclic compound containing a methine group (ie, a methine carbon-hydrogen bond) as a structural unit of the ring, (A3-
2) Includes chain compounds having a methine carbon atom.

The cyclic compound (A3-1) includes (A3-1a) a bridged cyclic compound having at least one methine group, (A3
-1b) Non-aromatic cyclic compounds having a hydrocarbon group bonded to the ring (such as alicyclic hydrocarbons). The bridged cyclic compound also includes a compound in which two rings share two carbon atoms, for example, a hydrogenated product of a condensed polycyclic aromatic hydrocarbon.

As the bridged cyclic compound (A3-1a), for example, decalin, bicyclo [2.2.0] hexane, bicyclo [2.2.2] octane, bicyclo [3.2.
1] octane, bicyclo [4.3.2] undecane, bicyclo [3.3.3] undecane, tsujon, karan,
Pinane, pinene, bornane, bornylene, norbornane, norbornene, camphor, camphoric acid, camphene, tricyclene, tricyclo [5.2.1.
0 ^3,8 ] decane, tricyclo [4.2.1.1 ^2,5 ] decane, exotricyclo [5.2.1.0 ^2,6 ] decane,
Endotricyclo [5.2.1.0 ^2,6 ] decane, tricyclo [4.3.1.1 ^2,5 ] undecane, tricyclo [4.2.2.1 ^2,5 ] undecane, endotricyclo [5.2.2.0 ^2,6 ] undecane, adamantane, 1
-Adamantanol, 1-chloroadamantane, 1-methyladamantane, 1,3-dimethyladamantane, 1
-Methoxy adamantane, 1-carboxy adamantane, 1-methoxy carbonyl adamantane, 1-nitro adamantane, tetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] dodecane, perhydroanthracene, perhydroacenaphthene, perhydrophenanthrene, perhydrophenalene, perhydroindene, quinuclidine, and the like; And derivatives thereof. These bridged cyclic compounds have a methine carbon atom at the bridgehead position (corresponding to the junction if two rings share two atoms).

Examples of the non-aromatic cyclic compound (A3-1b) having a hydrocarbon group bonded to the ring include 1-methylcyclopentane, 1-methylcyclohexane, limonene, menten,
About 3 to 15 membered alicyclic hydrocarbon in which a hydrocarbon group having about 1 to 20 (preferably 1 to 10) carbon atoms (such as an alkyl group) is bonded to a ring, such as menthol, carbomentone, or menthol; And derivatives thereof. Non-aromatic cyclic compound having a hydrocarbon group bonded to the ring (A3-1
b) has a methine carbon atom at the bonding site between the ring and the hydrocarbon group.

A chain compound having a methine carbon atom (A3-
As 2), chain hydrocarbons having a tertiary carbon atom, for example, isobutane, isopentane, isohexane, 3-methylpentane, 2,3-dimethylbutane,
4-2 carbon atoms such as -methylhexane, 3-methylhexane, 3,4-dimethylhexane, and 3-methyloctane;
About 0 (preferably 4 to 10) aliphatic hydrocarbons and derivatives thereof can be exemplified.

The compound (A4) having a carbon-hydrogen bond adjacent to the unsaturated bond includes (A4-1) an aromatic compound having a methyl group or a methylene group at the adjacent position (so-called benzyl position) of an aromatic ring. Group compound, (A4-2) unsaturated bond (for example, carbon-carbon unsaturated bond, carbon-oxygen double bond, etc.)
And a non-aromatic compound having a methyl group or a methylene group at the adjacent position.

In the aromatic compound (A4-1), the aromatic ring may be any of an aromatic hydrocarbon ring and an aromatic heterocyclic ring. The aromatic hydrocarbon ring includes a benzene ring,
Fused carbocycles (eg, naphthalene, azulene, indacene, anthracene, phenanthrene, triphenylene,
A condensed carbocycle in which 2 to 10 4- to 7-membered carbocycles such as pyrene are condensed, and the like. Examples of the aromatic heterocyclic ring include, for example, 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, isobenzofuran, 4-oxo-4H-
A fused ring such as chromene, etc.), a heterocyclic ring containing a sulfur atom as a hetero atom (for example, thiophene, thiazole,
5-membered rings such as isothiazole and thiadiazole, 6-membered rings such as 4-oxo-4H-thiopyran, condensed rings such as benzothiophene, etc., heterocycles containing a nitrogen atom as a hetero atom (for example, pyrrole, pyrazole, imidazole, 5-membered ring such as triazole, 6-membered ring such as pyridine, pyridazine, pyrimidine and pyrazine, indole,
Condensed rings of quinoline, acridine, naphthyridine, quinazoline, purine and the like) and the like.

The methylene group adjacent to the aromatic ring may be a methylene group constituting a non-aromatic ring fused to the aromatic ring. In the above (A4-1), both a methyl group and a methylene group may be present at positions adjacent to the aromatic ring.

Examples of the aromatic compound having a methyl group at a position adjacent to the aromatic ring include aromatic hydrocarbons having about 1 to 6 methyl groups substituted on the aromatic ring (for example, toluene, xylene, -Ethyl-4-methylbenzene, 1-
Ethyl-3-methylbenzene, 1-t-butyl-4-methylbenzene, 1-methoxy-4-methylbenzene, mesitylene, durene, methylnaphthalene, methylanthracene, 4,4'-dimethylbiphenyl, etc.) Heterocyclic compounds substituted with about 1 to 6 methyl groups (for example, 2-methylfuran, 3-methylfuran, 3-methylthiophene, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,4 -Dimethylpyridine,
2,4,6-trimethylpyridine, 4-methylindole, 2-methylquinoline, etc.).

Examples of the aromatic compound having a methylene group at the adjacent position of the aromatic ring include aromatic hydrocarbons having an alkyl group or a substituted alkyl group having 2 or more carbon atoms (eg, ethylbenzene, propylbenzene, , 4-diethylbenzene, diphenylmethane, etc.), aromatic heterocyclic compounds having an alkyl group or a substituted alkyl group having 2 or more carbon atoms (eg, 2-ethylfuran, 3-propylthiophene, 4-ethylpyridine, 4-butylquinoline) Etc.), 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 among the non-aromatic rings (dihydronaphthalene,
Indene, indane, tetralin, fluorene, acenaphthene, phenalene, indanone, xanthene and the like).

The non-aromatic compound (A4-2) having a methyl group or a methylene group at the position adjacent to the unsaturated bond includes, for example,
(A4-2a) So-called chain-like unsaturated hydrocarbons having a methyl group or a methylene group at an allyl position, and (A4-2b) compounds having a methyl group or a methylene group at a position adjacent to a carbonyl group can be exemplified.

The linear unsaturated hydrocarbons (A4-2a) include, for example, propylene, 1-butene, 2-butene,
1-pentene, 1-hexene, 2-hexene, 1,5-
Examples thereof include chain unsaturated hydrocarbons having about 3 to 20 carbon atoms, such as hexadiene, 1-octene, 3-octene, and undecatriene. The compound (A4-2b) includes ketones (for example, chain ketones such as acetone, methyl ethyl ketone, 3-pentanone, and acetophenone; cyclic ketones such as cyclohexanone), carboxylic acids and derivatives thereof (for example, acetic acid, propion and the like). Acids, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, phenylacetic acid, malonic acid, succinic acid, glutaric acid, and esters thereof).

The non-aromatic cyclic hydrocarbon (A5) includes
(A5-1) cycloalkanes and (A5-2) cycloalkenes are included.

The cycloalkanes (A5-1) include 3 to
Compounds having a 30-membered cycloalkane ring, such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cyclododecane, cyclotetradecane, cyclohexadecane, cyclotetracosane, cyclotriacontan, and These derivatives can be exemplified. Preferred cycloalkane rings include 5 to 30 membered, especially 5 to 20 membered cycloalkane rings.

The cycloalkenes (A5-2) include 3 to 30
Compounds having a membered cycloalkene ring, such as cyclopropene, cyclobutene, cyclopentene, cyclooctene, cyclohexene, 1-methyl-cyclohexene,
In addition to isophorone, cycloheptene, cyclododecaene and the like, cycloalkadienes such as cyclopentadiene, 1,3-cyclohexadiene and 1,5-cyclooctadiene, cycloalkatrienes such as cyclooctatriene, and derivatives thereof and the like Is included. Preferred cycloalkenes include compounds having a 3-20 membered ring, especially a 3-12 membered ring.

The conjugated compound (A6) includes conjugated dienes (A6-1), α, β-unsaturated nitriles (A6-2), α, β-
Unsaturated carboxylic acids or derivatives thereof (eg, esters,
Amide, acid anhydride, etc.) (A6-3).

The conjugated dienes (A6-1) include, for example,
Butadiene, isoprene, 2-chlorobutadiene, 2-
Ethyl butadiene and the like can be mentioned. Note that the conjugated dienes (A6-1) include compounds in which a double bond and a triple bond are conjugated, for example, vinyl acetylene and the like.

Examples of the α, β-unsaturated nitrile (A6-2) include (meth) acrylonitrile. α, β-unsaturated carboxylic acid or derivative thereof (A6-3)
Examples of (meth) acrylic acid include: (methyl) (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate. (Meth) acrylic acid esters; (meth) acrylamide, (meth) acrylamide derivatives such as N-methylol (meth) acrylamide, and the like.

The amines (A7) include primary or secondary amines such as methylamine, ethylamine, propylamine, butylamine, dimethylamine, and the like.
Diethylamine, dibutylamine, ethylenediamine,
Aliphatic amines such as 1,4-butanediamine, hydroxylamine and ethanolamine; alicyclic amines such as cyclopentylamine and cyclohexylamine; aromatic amines such as benzylamine and toluidine; cyclic such as pyrrolidine, piperidine, piperazine and indoline Examples thereof include amines (an aromatic or non-aromatic ring may be condensed) and the like.

Examples of the aromatic hydrocarbon (A8) include benzene, naphthalene, acenaphthylene, phenanthrene,
Aromatic compounds having at least one benzene ring, such as anthracene, naphthacene, aceanthrylene, triphenylene, pyrene, chrysene, naphthacene, picene, perylene, pentacene, coronene, pyranthrene, and ovalene, preferably having at least one benzene ring For example, 2 to 10 condensed condensed polycyclic aromatic compounds and the like can be mentioned. These aromatic hydrocarbons may have one or more substituents. Specific examples of the aromatic hydrocarbon having a substituent include, for example, 2-chloronaphthalene, 2-methoxynaphthalene, 1-methylnaphthalene, 2-methylnaphthalene, 2-methylanthracene,
Examples thereof include 2-t-butylanthracene, 2-carboxyanthracene, 2-ethoxycarbonylanthracene, 2-cyanoanthracene, 2-nitroanthracene, and 2-methylpentalene. Further, a non-aromatic carbon ring, an aromatic hetero ring, or a non-aromatic hetero ring may be fused to the benzene ring.

The linear alkane (A9) includes, for example, about 1 to 30 carbon atoms such as methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, dodecane, tetradecane and hexadecane ( A linear alkane having preferably about 1 to 20 carbon atoms) is exemplified.

The olefin (A10) may be any of an α-olefin which may have a substituent (for example, the above-mentioned substituent such as a hydroxyl group and an acyloxy group) and an internal olefin. Often, olefins having a plurality of carbon-carbon double bonds such as dienes are also included. For example, as olefins (A10), ethylene, propylene, 1-butene, 2-butene, isobutene, 1-pentene, 2-pentene, 2,4,4-trimethyl-2-pentene, 1-hexene, 2-hexene ,
2,3-dimethyl-2-butene, 3-hexene, 3-hexen-1-ol, 2-hexen-1-ol, 1-
Octen-3-ol, 1-heptene, 1-octene,
2-octene, 3-octene, 4-octene, 1-nonene, 2-nonene, 1-decene, 1-undecene, 1-dodecene, 1-hexadecene, 1-octadecene, 1,5
-Hexadiene, 1,6-heptadiene, 1,7-octadiene, 1-acetoxy-3,7-dimethyl-2,6
Chain olefins such as octadiene, styrene, vinyltoluene, α-methylstyrene, 3-vinylpyridine, 3-vinylthiophene; cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, cycloundecene , Cyclododecene, 1,4-cyclohexadiene, 1,4-cycloheptadiene, cyclodecadiene, cyclododecadiene, limonene, 1-p-menthene, 3-p-menthene, carveol, bicyclo [2.
2.1] Hept-2-ene, bicyclo [3.2.1] oct-2-ene, α-pinene, 2-bornene, and other cyclic olefins.

The above compounds capable of generating a radical may be used alone or in combination of two or more of the same or different ones. When two or more of these compounds are used, particularly two or more of different compounds are used in combination, for example, when reacting with an oxygen atom-containing gas such as oxygen, one of the substrates is a co-reactant (a co-oxidant) of the other substrate. Etc.), and the reaction rate may be significantly improved.

[Radical Scavenging Compound (B)] The radical scavenging compound (B) may be any compound which can react with a radical to form a stable compound. Typical examples of the compound include (B1) Unsaturated compounds, (B2) compounds having a methine carbon atom, (B3) heteroatom-containing compounds, and (B4) oxygen-atom-containing gases. These compounds may be used alone or in combination of two or more.

Further, these compounds may have various substituents as long as the reaction is not inhibited. Examples of the substituent include a halogen atom, a hydroxyl group, a mercapto group, an oxo group, a substituted oxy group (for example, an alkoxy group, an aryloxy group, an acyloxy group, etc.), a substituted thio group, a carboxyl group, a substituted oxycarbonyl group, a substituted or Examples include an unsubstituted carbamoyl group, a cyano group, a nitro group, a substituted or unsubstituted amino group, a sulfo group, an alkyl group, an alkenyl group, an alkynyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a heterocyclic group. .

The unsaturated compound (B1) includes a wide range of compounds having an unsaturated bond. Examples of such compounds include (B1-1) unsaturated compounds having an electron withdrawing group at a position adjacent to a carbon-carbon unsaturated bond [active unsaturated compounds such as active olefins (electron-deficient olefins)], (B1-
2) Compound having a carbon-carbon triple bond, (B1-3) Compound having an aromatic ring, (B1-4) Ketene, (B1-5) Isocyanate or thiocyanate compound, (B1-6) Inactive olefin And the like.

The active unsaturated compounds (B1-1) include:
For example, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, (meth)
Phenyl acrylate, methyl crotonate, ethyl crotonate, methyl 3-methyl-2-butenoate, 3-methyl-
Ethyl 2-butenoate, methyl 2-pentenoate, ethyl 2-pentenoate, methyl 2-octenoate, ethyl 2-octenoate, methyl cinnamate, ethyl cinnamate, 4,4,4-trifluoro-2-butane Α such as methyl acrylate, ethyl 4,4,4-trifluoro-2-butanoate, dimethyl maleate, diethyl maleate, dimethyl fumarate, diethyl fumarate, methyl 3-cyanoacrylate, and ethyl 3-cyanoacrylate Α, β-unsaturated ketones such as vinyl methyl ketone, vinyl ethyl ketone and methyl-1-propenyl ketone; α, β-unsaturated aldehydes such as propenal and crotonaldehyde; acrylonitrile; Α, β-unsaturated nitriles such as methacrylonitonyl; α, β-unsaturated such as (meth) acrylic acid and crotonic acid Carboxylic acids; (meth) alpha, such as acrylamide, beta-unsaturated carboxylic acid amides; N-(2-propenylidene) methylamine, N-
Α, β-unsaturated imines such as (2-butenylidene) methylamine; aryl groups adjacent to carbon-carbon unsaturated bonds such as styrene derivatives such as styrene, vinyltoluene, α-methylstyrene and β-methylstyrene Conjugated dienes such as butadiene, isoprene, 2-chlorobutadiene, 2-ethylbutadiene, vinylacetylene, and cyclopentadiene derivatives (including compounds in which a double bond and a triple bond are conjugated); Is mentioned.

Examples of the compound having a carbon-carbon triple bond (B1-2) include methylacetylene and 1-butyne. Compounds having an aromatic ring (B1-3) include compounds having an aromatic carbon ring such as a benzene ring and a naphthalene ring; compounds having an aromatic heterocyclic ring such as a pyrrole ring, a furan ring and a thiophene ring. Is included. Ketene (B1-4) includes ketene, 2-methylketene and the like. The isocyanate or thiocyanate compound (B1-5) includes methyl isocyanate, ethyl isocyanate, phenyl isocyanate, methyl thiocyanate, ethyl thiocyanate, phenyl thiocyanate and the like.

As the non-activated olefin (B1-6), α-
Any of olefins and internal olefins may be used,
Further, olefins having a plurality of carbon-carbon bonds such as dienes are also included. Representative examples of the non-activated olefin (B1-6) include, for example, ethylene, propylene, 1-butene, 2-butene, isobutene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, 3-hexene , 1
-Heptene, 1-octene, 2-octene, 3-octene, 4-octene, 1-nonene, 1-decene, 1-dodecene, 1,5-hexadiene, 1,6-heptadiene,
Chain olefins such as 1,7-octadiene (alkenes); and cyclic olefins such as cyclopentene, cyclohexene, cyclooctene, cyclodecene, and cyclododecene (cycloalkenes).

Examples of the compound (B2) having a methine carbon atom include the compounds exemplified as the above (A3). In the reaction, the same compound may be used as the compound (A3) and the compound (B2).

The heteroatom-containing compound (B3) includes (B3-
1) compounds having a sulfur atom, (B3-2) compounds having a nitrogen atom, (B3-3) compounds having a phosphorus atom, (B3-
4) Includes compounds having an oxygen atom. Examples of the compound having a sulfur atom (B3-1) include sulfides and thiols. Examples of the compound having a nitrogen atom (B3-2) include amines. Examples of the compound having a phosphorus atom (B3-3) include phosphites. Examples of the compound having an oxygen atom (B3-4) include N-oxides.

The oxygen atom-containing gas (B4) includes those having a boiling point (or sublimation point) of 45 ° C. or less, and typical examples thereof include (B4-1) oxygen and (B4-2) Carbon monoxide,
(B4-3) nitrogen oxides, (B4-4) sulfur oxides and the like. These gases can be used alone or in combination of two or more.

The oxygen (B4-1) may be either molecular oxygen or active oxygen. Molecular oxygen is not particularly limited,
Pure oxygen may be used, or oxygen or air diluted with an inert gas such as nitrogen, helium, argon, or carbon dioxide may be used. In many cases, molecular oxygen is used as oxygen.

As the carbon monoxide (B4-2), pure carbon monoxide may be used, or one diluted with an inert gas may be used. When carbon monoxide and oxygen are used in combination, a carboxylic acid can be obtained in a high yield by the reaction with the compound (A).

The nitrogen oxide (B4-3) includes a compound represented by NxOy (where x is 1 or 2, and y is an integer of 1 to 6). In this compound, when x is 1, y is usually an integer of 1 to 3, and when x is 2, y is usually an integer of 1 to 6.

As typical examples of nitrogen oxides, N 2 O,
NO, N2O3, NO2, N2O4, N2O5, NO
3, N2O6 and the like. These nitrogen oxides can be used alone or in combination of two or more. The nitrogen oxide may be pure or a mixture containing nitrogen oxide as a main component. As a mixture containing nitrogen oxides as a main component, for example, exhaust gas from a nitric acid oxidation process can be used.

Preferred nitrogen oxides include NO, N 2 O
3, NO2, N2O5 and the like. N2O3 can be easily obtained by reacting nitrous oxide (N2O) and / or nitric oxide (NO) with oxygen. More specifically,
It can be prepared by introducing nitrogen monoxide (or nitrous oxide) and oxygen into a cooled reactor to produce a blue liquid N2O3. Therefore, the reaction of the present invention may be performed by introducing nitrous oxide (N2O) and / or nitric oxide (NO) and oxygen into the reaction system without generating N2O3 in advance. Nitrogen oxides can be used with oxygen. For example, by using NO2 and oxygen together, the yield of a product (for example, a nitro compound) can be further improved.

The sulfur oxide (B4-4) includes a compound represented by SpOq (where p is 1 or 2, and q is an integer of 1 to 7). In this compound, when p is 1, q is usually an integer of 1 to 4, and when p is 2, q is usually 3 or 7.

As typical examples of the sulfur oxide, for example,
SO, S2O3, SO2, SO3, S2O7, SO4 and the like. These sulfur oxides can be used alone or in combination of two or more. Note that fuming sulfuric acid containing sulfur trioxide may be used as sulfur trioxide.

Preferred sulfur oxides include sulfur dioxide (S
O2) and sulfur trioxide (SO3). Sulfur oxides can also be used with oxygen. For example,
When sulfur dioxide (SO2) is used in combination with oxygen, the corresponding sulfonic acid can be obtained in high yield by the reaction with the compound (A).

The reaction between the radical-forming compound (A) and the radical-scavenging compound (B) is carried out in the presence or absence of a solvent. Examples of the solvent include organic acids such as acetic acid and propionic acid; nitriles such as acetonitrile, propionitrile and benzonitrile; formamide, acetamide, dimethylformamide (DMF),
Amides such as dimethylacetamide; aliphatic hydrocarbons such as hexane and octane; chloroform, dichloromethane, dichloroethane, carbon tetrachloride, chlorobenzene,
Halogenated hydrocarbons such as trifluoromethylbenzene; nitro compounds such as nitrobenzene, nitromethane and nitroethane; esters such as ethyl acetate and butyl acetate; mixed solvents thereof. As a solvent,
Organic acids such as acetic acid, nitriles such as acetonitrile and benzonitrile, halogenated hydrocarbons such as trifluoromethylbenzene, and esters such as ethyl acetate are often used.

The ratio between the radical-generating compound (A) and the radical-scavenging compound (B) can be appropriately selected depending on the kind (price, reactivity) and combination of both compounds. For example, the compound (A) may be used in excess (for example, about 2 to 50 times by mole) with respect to the compound (B), and conversely, the compound (B) may be used in excess with respect to the compound (A). Is also good.

The method of the present invention is characterized in that the reaction proceeds smoothly under mild conditions. The reaction temperature can be appropriately selected depending on the type of the compound (A) and the compound (B), the type of the target product, and the like.
° C, preferably 5 to 120 ° C, more preferably 10 to
It is about 80 ° C, and usually reacts at about 20 to 70 ° C in many cases. In addition, depending on the type of reaction, 70 to 120
C. or so may be preferable. The reaction can be performed under normal pressure or under pressure. When the reaction is performed under pressure, it is usually 1 to 100 atm [0.1 to 10 MPa] (for example, 1.5 to 80 atm [0.15 to 8 MPa]). ), Preferably about 2 to 70 atm [0.2 to 7 MPa]. The reaction time depends on the reaction temperature and pressure, for example,
It can be appropriately selected from a range of about 30 minutes to 48 hours.

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 is easily separated and purified by a conventional method, for example, separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, and column chromatography, or a separation means combining these. it can.

According to the method of the present invention, an addition or substitution reaction product (carbon-carbon bond product, oxidation product) is added depending on the combination of the radical-forming compound (A) and the radical-scavenging compound (B). , Carboxylation products, nitration products, sulfonation products, etc.) or derivatives thereof.

For example, when a compound (A1) containing a hetero atom having a carbon-hydrogen bond at a position adjacent to a hetero atom is used as the compound (A), an unsaturated compound (B1 ), The compound (B2) having a methine carbon atom, the methine carbon atom of the compound having a methine carbon atom, or the heteroatom of the compound containing a hetero atom (B3). A substitution reaction product or a derivative thereof is provided.

When a compound having a carbon-heteroatom double bond (for example, a compound having a carbonyl group) (A2) is used as the compound (A), the carbon atom ( The bond between the carbonyl carbon atom) and an atom adjacent to the carbon atom is cleaved, and an atomic group (for example, an acyl group) containing the carbon-heteroatom double bond is converted to the compound (B1), (B2) Or (B3)
To give an addition or substitution reaction product or a derivative thereof.

Further, when the compound (A3) having a methine carbon atom is used as the compound (A) capable of forming a radical, the methine carbon atom is replaced with the compound (B)
1), (B2) or (B3) binds to the above site to produce a corresponding addition or substitution reaction product or a derivative thereof.

Usually, when the unsaturated compound (B1) is used as the radical-scavenging compound (B), the addition reaction product is used. When the compound (B2) having a methine carbon atom is used, the substitution reaction product ( For example, coupling products)
Is generated.

When the oxygen-containing gas (B4) is used as the radical-scavenging compound (B) and is reacted with the compound (A) capable of forming a radical, the oxygen-containing gas according to the type of the oxygen-containing gas is obtained. Groups (eg, hydroxyl groups,
Oxo, carboxyl, nitro, sulfuric acid, etc.)
Is produced.

Further, in the method of the present invention, by using two or more kinds of the compounds (A) and the radical-scavenging compounds (B) capable of generating radicals, substitution or addition reactions occur sequentially, and complex organic compounds are produced. Can be obtained in one step. For example, when an unsaturated compound (B1) and oxygen (B4-1) are used as the radical-scavenging compound (B) to react with the compound (A), an unsaturated bond is formed.
Among the two carbon atoms, a group derived from the compound (A) can be bonded to one carbon atom as described above, and a hydroxyl group derived from oxygen can be introduced to the other carbon atom.

In the method of the present invention, although the details of the reaction mechanism are not always clear, nitrate acts on the imide compound under mild conditions to produce imide N-oxy radical (> NO.), Which is Hydrogen is abstracted from compound (A). For example, compound (A1) is substituted with a carbon atom adjacent to a hetero atom, compound (A2) is substituted with a carbon atom related to a carbon-heteroatom double bond, and compound (A3) is modified with methine. In the compound (A4), a radical is generated at a carbon atom adjacent to an unsaturated bond in the compound (A4), and the radical thus generated reacts with the compound (B),
It is presumed that the corresponding substitution or addition reaction product is formed.

The addition or substitution reaction product produced in the above reaction may further undergo a dehydration reaction, a cyclization reaction, a decarboxylation reaction, a rearrangement reaction, an isomerization reaction, etc. in the reaction system depending on its structure and reaction conditions. Proceeding can produce the corresponding derivative.

The compound (A) capable of forming a radical
The reaction between the compound and the radical-scavenging compound (B) is preferably carried out under a condition in which a so-called polymerization inhibitor (such as hydroquinone) is as small as possible. For example, the amount of the polymerization inhibitor in the reaction system is preferably 1000 ppm or less, more preferably 100 ppm or less. When the amount of the polymerization inhibitor exceeds 1000 ppm, the reaction rate tends to decrease, and it may become necessary to use a large amount of the imide compound represented by the formula (1) or the cocatalyst. Conversely, when the amount of the polymerization inhibitor in the reaction system is small, there is an advantage that the reaction rate is increased and the yield is improved, the reproducibility of the reaction result is high, and the target compound can be produced stably. . Therefore, it is preferable that the (B1) unsaturated compound or the like which is sold with a polymerization inhibitor added thereto is subjected to a reaction after removing the polymerization inhibitor by distillation or the like. This applies to any reaction in which the compound (A) and the compound (B) are reacted in the presence of the imide compound.

In the present invention, the following various organic compounds can be obtained by appropriately combining the radical-forming compound (A) and the radical-scavenging compound (B) and reacting them.

1.1 Production of 1,3-Dihydroxy Compound The first example will be described. The imide compound represented by the above formula (1) and nitric acid are used as catalysts and the compound is represented by the above formula (2). By reacting an alcohol with the active olefin represented by the formula (3) and oxygen, the formula (4)
1,3-dihydroxy compound represented by

[Alcohol] In the above formula (2), Ra, R
The organic group in b may be any organic group that does not inhibit the present reaction (for example, an organic group that is non-reactive under the reaction conditions in the present method), and examples thereof include a hydrocarbon group and a heterocyclic group. No.

The hydrocarbon group includes an aliphatic hydrocarbon group,
An alicyclic hydrocarbon group and an aromatic hydrocarbon group are included. Examples of the aliphatic hydrocarbon group include those having 1 carbon atom such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl, octyl, decyl, tetradecyl, hexadecyl, octadecyl, and allyl. About 20 to 20 (preferably 1 to 10, more preferably 1 to 6) linear or branched aliphatic hydrocarbon groups (alkyl, alkenyl, and alkynyl).

Examples of the alicyclic hydrocarbon group include those having 3 to 20 (preferably 3 to 15) carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, cyclooctyl, cyclodecyl and cyclododecyl groups. A monocyclic alicyclic hydrocarbon group (cycloalkyl group, cycloalkenyl group, etc.); a bridged ring hydrocarbon group;

Examples of the bridged ring hydrocarbon group include 2-4
Ring-based cross-linked hydrocarbon groups, among which,
A bicyclic or tricyclic bridged ring hydrocarbon group is preferred. Representative examples of the cross-linked ring in the cross-linked hydrocarbon group include, for example, adamantane ring, perhydroindene ring, decalin ring, perhydrofluorene ring, perhydroanthracene ring, perhydrophenanthrene ring, tricyclo [5. 2.1.02,6] decane ring, perhydroacenaphthene ring, perhydrophenalene ring, norbornane ring, norbornene ring and the like. In the bridged ring hydrocarbon group, the bonding site of the hydroxyl group in the formula to the carbon atom to which the hydroxyl group is bonded may be any of the carbon atoms constituting the bridged ring. Position) carbon atom.

Examples of the aromatic hydrocarbon group include an aromatic hydrocarbon group having about 6 to 14 carbon atoms, such as a phenyl and naphthyl group.

These hydrocarbon groups may be protected with various substituents, for example, a halogen atom (fluorine, chlorine, bromine, iodine atom), an oxo group, a hydroxyl group which may be protected with a protecting group, or a protecting group. An optionally substituted hydroxymethyl group, an amino group which may be protected with a protecting group, a carboxyl group which may be protected with a protecting group, a substituted oxycarbonyl group, a substituted or unsubstituted carbamoyl group, a nitro group, an acyl group, It may have a cyano group, an alkyl group (for example, a C1-4 alkyl group such as a methyl or ethyl group), a cycloalkyl group, an aryl group (for example, a phenyl or naphthyl group), a heterocyclic group, or the like. . As the protecting group, a protecting group commonly used in the field of organic synthesis can be used.

Examples of the protecting groups for the hydroxyl group and the hydroxymethyl group include conventional protecting groups such as an alkyl group (eg, a C1-4 alkyl group such as a methyl and t-butyl group) and an alkenyl group (eg, an allyl group). Group), a cycloalkyl group (eg, a cyclohexyl group), an aryl group (eg, a 2,4-dinitrophenyl group), an aralkyl group (eg, benzyl, 2,6-
Dichlorobenzyl, 3-bromobenzyl, 2-nitrobenzyl, triphenylmethyl group and the like; substituted methyl group (for example, 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-iso Propoxyethyl, 2,2,2-
Trichloroethyl group), tetrahydropyranyl group,
A group capable of forming an acetal or hemiacetal group with a hydroxyl group such as a tetrahydrofuranyl group, a 1-hydroxyalkyl group (eg, 1-hydroxyethyl, 1-hydroxyhexyl, 1-hydroxydecyl, 1-hydroxyhexadecyl group, etc.) And the like; acyl group (for example,
C1-6 aliphatic acyl groups such as formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl and pivaloyl groups; acetoacetyl groups; aromatic acyl groups such as benzoyl and naphthoyl groups; and alkoxycarbonyl groups (for example, methoxycarbonyl, C1-4 alkoxy-carbonyl groups such as ethoxycarbonyl and t-butoxycarbonyl groups, etc., aralkyloxycarbonyl groups (eg, benzyloxycarbonyl group, p-methoxybenzyloxycarbonyl group, etc.), and substituted or unsubstituted carbamoyl groups (eg, Carbamoyl, methylcarbamoyl, phenylcarbamoyl, etc.), dialkylphosphinothioyl groups (eg, dimethylphosphinothioyl groups), diarylphosphinothioyl groups (eg, diphenylphosphinothioyl groups). And a substituted silyl group (eg, trimethylsilyl, t-butyldimethylsilyl, tribenzylsilyl, triphenylsilyl group, etc.), and two or more hydroxyl groups (including a hydroxymethyl group) in the molecule. Sometimes, a divalent hydrocarbon group which may have a substituent (methylene, ethylidene, isopropylidene, cyclopentylidene, cyclohexylidene, benzylidene group, etc.) can be exemplified. Preferred hydroxyl-protecting groups include a C1-4 alkyl group; a group capable of forming an acetal or hemiacetal group with a hydroxyl group such as a substituted methyl group, a substituted ethyl group, and a 1-hydroxyalkyl group; an acyl group, a C1-4 Examples include an alkoxy-carbonyl group, a substituted or unsubstituted carbamoyl group, a substituted silyl group, and a divalent hydrocarbon group which may have a substituent.

Examples of the amino-protecting group include the alkyl, aralkyl, acyl, alkoxycarbonyl, aralkyloxycarbonyl, dialkylphosphinothioyl, and diarylphosphinothio groups exemplified as the hydroxyl-protecting group. And an oil group. Preferred amino-protecting groups include a C1-4 alkyl group, a C1-6 aliphatic acyl group, an aromatic acyl group, and a C1-
4 alkoxy-carbonyl group and the like.

The protective group for the carboxyl group includes, for example, an alkoxy group (for example, a C1-6 alkoxy group such as methoxy, ethoxy, butoxy, etc.), a cycloalkyloxy group, and an aryloxy group (for example, a phenoxy group, etc.). ), An aralkyloxy group (eg, a benzyloxy group), a trialkylsilyloxy group (eg, a trimethylsilyloxy group), an optionally substituted amino group (eg, an amino group; a methylamino group, a dimethyl group) A mono- or di-C1-6 alkylamino group such as an amino group), a hydrazino group, an alkoxycarbonylhydrazino group, an aralkyloxycarbonylhydrazino group and the like. Preferred carboxyl-protecting groups include C1-6 alkoxy groups (particularly C1-4 alkoxy groups) and mono- or di-C1-6 alkylamino groups (particularly mono- or di-C1-4 alkylamino groups). .

The heterocyclic ring constituting the heterocyclic group for Ra and Rb includes an aromatic heterocyclic ring and a non-aromatic heterocyclic ring. As such a heterocyclic ring, for example, a heterocyclic ring containing an oxygen atom as a hetero atom (for example, a 5-membered ring such as furan, tetrahydrofuran, oxazole and isoxazole, 4-oxo-4H-pyran, tetrahydropyran, morpholine and the like) 6-membered ring, benzofuran, isobenzofuran, 4-oxo-4H-chromene, chroman,
A condensed ring such as isochroman, 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), a heterocyclic ring containing a nitrogen atom as a hetero atom (for example, a 5-membered ring such as pyrrole, pyrrolidine, pyrazole, imidazole, and triazole; 6-membered rings such as pyridazine, pyrimidine, pyrazine, piperidine and piperazine, and condensed rings such as indole, indoline, quinoline, acridine, naphthyridine, quinazoline and purine). These heterocyclic groups may have a substituent (for example, the same group as the substituent which the hydrocarbon group may have).

Examples of the ring formed by Ra and Rb bonded together with an adjacent carbon atom include, for example, cyclopropane, cyclobutane, cyclopentane, cyclopentene, cyclohexane, cyclohexene, cyclooctane, cyclodecane, cyclododecane, decalin, Non-aromatic carbon rings (cycloalkane ring, cycloalkene ring, etc.) of about 3 to 20 members (preferably 3 to 15 members, more preferably 5 to 15 members, especially 5 to 8 members) such as an adamantane ring
A bridged carbon ring). These rings may have a substituent (for example, the same group as the substituent which the hydrocarbon group may have), and may have another ring (a non-aromatic ring or an aromatic ring). Ring) may be condensed.

Preferred Ra is a hydrogen atom; C1-4 such as methyl, ethyl, propyl, isopropyl, butyl and the like.
Examples include an alkyl group and a C6-14 aryl group. Preferred Rb includes a hydrogen atom, a C1-10 aliphatic hydrocarbon group (methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl,
Hexyl, octyl, decyl group and the like; in particular, C1-10 alkyl group), alicyclic hydrocarbon group (for example, C3- such as cyclopentyl, cyclohexyl and cyclohexenyl group)
15 cycloalkyl groups or cycloalkenyl groups; bridged ring hydrocarbon groups and the like). It is also preferable that Ra and Rb be bonded to each other to form a non-aromatic carbon ring of about 3 to 15 members (particularly 5 to 8 members) together with adjacent carbon atoms.

Examples of the alcohol represented by the formula (2) include the alcohols exemplified as the primary or secondary alcohol in the above (A1-1).

Preferred alcohols include secondary alcohols (for example, aliphatic secondary alcohols such as 2-propanol and s-butyl alcohol); aliphatic hydrocarbons such as 1-cyclohexylethanol and the like. Groups (for example, C1-4 alkyl group, C6-
Secondary alcohol in which a non-aromatic carbocyclic group (for example, a C3-15 cycloalkyl group or a cycloalkenyl group) is bonded; cyclopentanol, cyclohexanol, 2-adaman About 3 to 15 membered alicyclic secondary alcohol such as tanol; 1
Aromatic secondary alcohols such as phenylethanol), and alcohols in which Rb is a bridged ring hydrocarbon group.

[Active olefin] In the active olefin represented by the above formula (3), as the organic group for Rc, Rd and Re, an organic group which does not inhibit the present reaction (for example, under the reaction conditions in the present method) Non-reactive organic group)
For example, a halogen atom, a hydrocarbon group, a heterocyclic group, a substituted oxycarbonyl group (alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, cycloalkyloxycarbonyl group, etc.), a carboxyl group, Or unsubstituted carbamoyl group (N-substituted or unsubstituted amide group), cyano group, nitro group, sulfuric acid group (sulfonic acid group, sulfinic acid group), sulfuric acid ester group (sulfonic acid ester group, sulfinic acid ester group) , An acyl group, a hydroxyl group, an alkoxy group, an N-substituted or unsubstituted amino group, and the like. The carboxyl group, hydroxyl group and amino group may be protected with a conventional protecting group.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms. Examples of the hydrocarbon group include the groups exemplified as the hydrocarbon group for Ra and Rb, and these hydrocarbon groups may have the substituent. Preferred hydrocarbon groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, vinyl, allyl groups and the like having about 1 to 6 carbon atoms (particularly about 1 to 4 carbon atoms). Linear or branched aliphatic hydrocarbon group (alkyl group, alkenyl group and alkynyl group); aromatic hydrocarbon group having about 6 to 14 carbon atoms such as phenyl group and naphthyl group; cycloalkyl group; 1-6 carbon atoms such as methyl group
About (particularly about 1 to 4 carbon atoms) haloalkyl groups.

Examples of the heterocyclic group include the aforementioned Ra, Rb
And the like groups exemplified as the heterocyclic group in
These heterocyclic groups may have the above substituents.
Examples of the alkoxycarbonyl group include a C1-6 alkoxy-carbonyl group such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, and t-butoxycarbonyl group. The aryloxycarbonyl group includes, for example, a phenyloxycarbonyl group, and the aralkyloxycarbonyl group includes, for example, a benzyloxycarbonyl group. Examples of the cycloalkyloxycarbonyl group include a cyclopentyloxycarbonyl group and a cyclohexyloxycarbonyl group.

The substituted carbamoyl group includes, for example, N-methylcarbamoyl, N, N-dimethylcarbamoyl and the like. The sulfonic acid ester group includes sulfonic acid C1-4 such as methyl sulfonate and ethyl sulfonate.
It includes an alkyl ester group and the like. The sulfinic acid ester group includes a sulfinic acid C1-4 alkyl ester group such as a methyl sulfinic acid group and an ethyl sulfinic acid group. Examples of the acyl group include aliphatic acyl groups such as acetyl and propionyl groups (for example, C2-7
Aliphatic acyl group) and aromatic acyl groups such as benzoyl group. Examples of the alkoxy group include alkoxy groups having about 1 to 6 carbon atoms, such as methoxy, ethoxy, propoxy, and butoxy groups.
The N-substituted amino group includes, for example, N, N-dimethylamino, N, N-diethylamino, piperidino group and the like.

Preferred Rc, Rd and Re include a hydrogen atom, a hydrocarbon group [for example, a C1-6 aliphatic hydrocarbon group (especially a C1-4 aliphatic hydrocarbon group), and a C6-14 aryl group (phenyl group). Etc.), cycloalkyl groups (3 to
A cycloalkyl group of about 8 members), a haloalkyl group (for example, a C1-6 haloalkyl group such as a trifluoromethyl group, especially a C1-4 haloalkyl group), a heterocyclic group, a substituted oxycarbonyl group (for example, C1 -6 alkoxy-carbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, cycloalkyloxycarbonyl group, etc.), carboxyl group, substituted or unsubstituted carbamoyl group, cyano group, nitro group, sulfuric acid group,
It includes a sulfuric acid ester group, an acyl group and the like. Rc, R
Particularly preferred groups for d include a hydrogen atom, a C1-6 aliphatic hydrocarbon group (especially a C1-4 aliphatic hydrocarbon group, etc.),
6-14 aryl group (such as phenyl group), cycloalkyl group (such as about 3 to 8 membered cycloalkyl group), haloalkyl group (for example, C1-
6 haloalkyl group, particularly a C1-4 haloalkyl group), a substituted oxycarbonyl group (for example, a C1-6 alkoxy-carbonyl group, an aryloxycarbonyl group,
Aralkyloxycarbonyl group, cycloalkyloxycarbonyl group, etc.), cyano group and the like. Particularly preferred Re includes a hydrogen atom, a C1-6 aliphatic hydrocarbon group (particularly, a C1-4 aliphatic hydrocarbon group, and the like).

Rc, Rd, Re (Rc and Rd, Rc and R
e, Rd and Re, or Rc and Rd and Re) are bonded to each other to form a ring together with an adjacent carbon atom or a carbon-carbon bond, for example, cyclopropane, cyclobutane, cyclopentane, cyclopentene, cyclohexane, cyclohexene, cyclooctane , Cyclododecane ring, etc.
Alicyclic carbocycles (cycloalkane ring, cycloalkene ring, etc.) of about 20 to about 20 members; These rings may have a substituent, and other rings (non-aromatic rings or aromatic rings) may be condensed. Examples of the electron withdrawing group Y include, for example, an alkoxycarbonyl group such as a methoxycarbonyl group and an ethoxycarbonyl group; an aryloxycarbonyl group such as a phenoxycarbonyl group;
Acyl groups such as acetyl, propionyl and benzoyl groups; cyano groups; carboxyl groups; carbamoyl, N, N
-A substituted or unsubstituted carbamoyl group such as a dimethylcarbamoyl group; -CH = NR (R is an alkyl group or the like);
Aryl groups such as phenyl and naphthyl groups; vinyl, 1-
1-alkenyl group such as propenyl and ethynyl group or 1
-Alkynyl group and the like.

The ring which may be formed by bonding at least one of Rc, Rd and Re and Y together with an adjacent carbon atom or a carbon-carbon bond includes, for example, a cyclopentadiene ring, a pyrrole ring and a furan ring And a thiophene ring.

Representative examples of the active olefin represented by the formula (3) include the compounds exemplified as the active unsaturated compound (B1-1).

[Reaction] The reaction between the alcohol represented by the formula (2) and the active olefin represented by the formula (3) and oxygen is carried out by the method described for the reaction between the compound (A) and the compound (B). Can be performed according to

In this reaction, the 1-hydroxyalkyl radical corresponding to the alcohol represented by the formula (2) formed in the system is converted into two unsaturated bonds of the active olefin represented by the formula (3). The 1,3-dihydroxy compound represented by the formula (4) is obtained by attacking and adding a carbon atom at the β-position of the group Y among the carbon atoms and by oxygen attacking a radical generated at the α-position by the addition. Is assumed to be generated.

In the compound represented by the above formula (4) produced by the reaction, when Y is an ester group such as an alkoxycarbonyl group or an aryloxycarbonyl group, or a carboxyl group, as described later, The cyclization reaction further proceeds within the above, and the furanone derivative represented by the formula (6) (α-hydroxy-γ-butyrolactone derivative)
Can be generated. The yield of the furanone derivative is, for example,
It can be improved by adjusting the type and amount of the cocatalyst or by further aging after the addition reaction (or subsequent oxidation). The reaction temperature during the ripening period may be set higher than the reaction temperature during the addition reaction. Further, the furanone derivative can also be produced by isolating the compound represented by the formula (4), dissolving the compound in a solvent, and heating as necessary. The solvent is not particularly limited and includes, in addition to the solvents described below, aromatic hydrocarbons such as benzene and toluene; alicyclic hydrocarbons such as cyclohexane;
Ketones such as cyclohexanone; ethers such as diethyl ether and tetrahydrofuran; alcohols such as methanol, ethanol and isopropanol can be used. The reaction temperature in this case is, for example, about 0 to 150 ° C, preferably about 30 to 100 ° C.

[0142] 2. Production of α-hydroxy-γ-butyrolactone derivative An imide compound represented by the above formula (1) and a nitric acid are used as catalysts, and an alcohol represented by the above formula (2) and a compound represented by the above formula (5) are used. By reacting an α, β-unsaturated carboxylic acid derivative with oxygen, an α-hydroxy-γ-butyrolactone derivative represented by the above formula (6) can be obtained.

[Alcohol] As the alcohol represented by the formula (2), the same alcohol as used in the production of the 1,3-dihydroxy compound can be used.

[Α, β-Unsaturated Carboxylic Acid Derivative] Rc, Rd and Re in the above formula (5) are the same as Rc, Rd and Re in the above formula (3). Examples of the organic group for Rf include an organic group that does not inhibit the reaction (for example, an organic group that is nonreactive under the reaction conditions in the present method), such as a hydrocarbon group and a heterocyclic group. When the compound represented by the formula (5) has a substituted oxycarbonyl group in addition to the -CO2Rf group shown in the formula (5), the -CO2Rf group participates in a cyclization reaction. However, other substituted oxycarbonyl groups are included in the non-reactive organic groups, since other substituted oxycarbonyl groups may remain in the product in its original form.

At least one of Rc and Rd is an electron-withdrawing organic group such as a haloalkyl group, a substituted oxycarbonyl group, a carboxyl group, a substituted or unsubstituted carbamoyl group, a cyano group, a nitro group, a sulfuric acid group, and a sulfuric ester group. When it is a group, the target α-hydroxy-γ-butyrolactone derivative can be obtained with a particularly high yield.

Rf is often a hydrogen atom or a hydrocarbon group, for example, a C1-6 alkyl group (particularly C1-
4 alkyl groups), C2-6 alkenyl groups (particularly C2-4
Alkenyl group) and C6-10 aryl group.

As typical examples of the α, β-unsaturated carboxylic acid derivative represented by the formula (5), for example, (meth) acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, ( (Meth) isopropyl acrylate, (meth)
(Meth) acrylic acid esters such as phenyl acrylate; crotonic acid; crotonic acid esters such as methyl crotonic acid and ethyl crotonate; 3-methyl-2-butenoic acid; 3-methyl-2-butenoic acid methyl; -2
3-methyl-2-butenoic acid ester such as ethyl butenoate; 2-pentenoic acid: 2-pentenoic acid ester such as methyl 2-pentenoate, ethyl 2-pentenoate; 2-octenoic acid; 2-methyl octenoate 2-octenoic acid esters, such as ethyl 2-octenoate; cinnamic acid; cinnamic acid esters, such as methyl cinnamate and ethyl cinnamate; 4,4,4-
Trifluoro-2-butenoic acid; methyl 4,4,4-trifluoro-2-butenoate, 4,4,4-trifluoro-
4,4,4-trifluoro- such as ethyl 2-butenoate
2-butenoic acid ester; maleic acid; maleic acid ester such as dimethyl maleate and diethyl maleate; fumaric acid; fumaric acid ester such as dimethyl fumarate and diethyl fumarate; 3-cyanoacrylic acid; methyl 3-cyanoacrylate , 3-ethyl ethyl cyanoacrylate, etc.
An α, β-unsaturated carboxylic acid having about 2 to 15 carbon atoms such as a cyanoacrylate or an ester thereof (C1-
6 alkyl esters, C2-6 alkenyl esters, aryl esters, etc.).

[Reaction] The reaction of the alcohol represented by the formula (2) with the α, β-unsaturated carboxylic acid derivative represented by the formula (5) and oxygen is carried out by reacting the compound (A) with the compound (B). Can be performed according to the method described for the reaction with.

In the method of the present invention, the following intermediate (7) is used as a reaction intermediate product.

Embedded image (In the formula, Ra, Rb, Rc, Rd, Re, and Rf are the same as described above), thereby producing an α, γ-dihydroxycarboxylic acid derivative (a kind of the compound represented by the formula (4)). . In this compound, a 1-hydroxyalkyl radical corresponding to the alcohol represented by the above formula (2) generated in the system changes the β-position of the α, β-unsaturated carboxylic acid derivative represented by the formula (5). It is presumed that the compound is formed by attacking and adding, and by oxygen attacking the radical generated at the α-position by the addition. Then, the resulting α, γ-dihydroxycarboxylic acid derivative represented by the formula (7) undergoes ring closure under the reaction conditions, whereby the target α-hydroxy-γ-butyrolactone derivative represented by the formula (6) is obtained. Generate.

When a primary alcohol is used as the alcohol represented by the formula (2) (when Ra is a hydrogen atom), the acyl radical [RbC (＝ O)
•], or in addition to the compound represented by the formula (6), the following formula (8)

Embedded image (Wherein Rb, Rc, Rd, Re, and Rf are the same as described above)
In some cases, a β-acyl-α-hydroxycarboxylic acid derivative represented by the formula: In addition, α-hydroxy-γ-
As described above, the butyrolactone derivative can also be produced by isolating the α, γ-dihydroxycarboxylic acid derivative represented by the formula (7), dissolving the derivative in a solvent, and heating as necessary.

[0151] 3. Production of Conjugated Unsaturated Compound The imide compound represented by the above formula (1) and nitric acid are used as a catalyst, and the following formula (2a)

Embedded image (Wherein, Ri and Rj are the same or different and each represent a hydrogen atom or an organic group. Ri and Rj may be bonded to each other to form a ring together with an adjacent carbon atom). Alcohol and the following formula (3a)

Embedded image (In the formula, Rd and Re are the same or different and each represent a hydrogen atom or an organic group, and Y represents an electron-withdrawing group.
Y may combine with each other to form a ring together with an adjacent carbon atom or a carbon-carbon bond) and react with an active olefin represented by the following formula (9):

Embedded image (Wherein, Rd, Re, Ri, Rj, and Y are the same as described above).

In the formula (2a), the organic group for Ri and Rj is the same as the organic group for Ra and Rb. The ring formed by bonding Ri and Rj together with the adjacent carbon atom is as follows: The same ring as Ra and Rb are combined with each other to form a ring together with an adjacent carbon atom.

Preferred Ri is a hydrogen atom; C1-4 such as methyl, ethyl, propyl, isopropyl and butyl.
Examples include an alkyl group and a C6-14 aryl group. Preferred Rj include a hydrogen atom, a C1-10 aliphatic hydrocarbon group (methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl,
Hexyl, octyl, decyl group and the like; in particular, C1-10 alkyl group), alicyclic hydrocarbon group (for example, C3- such as cyclopentyl, cyclohexyl and cyclohexenyl group)
15 cycloalkyl groups or cycloalkenyl groups; bridged ring hydrocarbon groups and the like). It is also preferred that Ri and Rj be bonded to each other to form a non-aromatic carbon ring of about 3 to 15 members (particularly 5 to 8 members) together with adjacent carbon atoms.

The alcohol represented by the formula (2a) includes a wide range of primary alcohols. Representative examples thereof include ethanol, 1-propanol, 1-butanol, 2-methyl-1-propanol, 1-pentanol, 1-hexanol, 1-octanol, 1-decanol, 1-hexadecanol, Saturated or unsaturated aliphatic primary alcohols having about 2 to 30 (preferably 2 to 20, more preferably 2 to 15) carbon atoms such as buten-1-ol; cyclopentylmethyl alcohol, cyclohexylmethyl alcohol, 2-cyclohexyl A saturated or unsaturated alicyclic primary alcohol such as ethyl alcohol; an aromatic primary such as 2-phenylethyl alcohol, 3-phenylpropyl alcohol, and cinnamon alcohol;
Secondary alcohols include heterocyclic alcohols such as 2- (2-hydroxyethyl) pyridine.

The compound represented by the formula (3a) corresponds to the compound represented by the formula (3) wherein Rc is a hydrogen atom. Rd, Re, and Y in the formula (3a) are the same as those in the formula (3).

The reaction can be carried out according to the production of the 1,3-dihydroxy compound. In this reaction,
In addition to the conjugated unsaturated compound represented by the formula (9), a compound corresponding to the formula (4) (in the formula (4), Ra =
When a compound of the formula (3a) where Y = CO2Rf is used as the compound of the formula (3a), a compound corresponding to the formula (6) (in the formula (6), = RiRjCH group, Rb = Rc =
H).

For example, when n-propyl alcohol is reacted with ethyl acrylate, ethyl sorbate, which is the target product, is formed, and depending on conditions, 2,4-dihydroxyhexane corresponding to the formula (4) is obtained. Ethyl acid and 4-ethyl-2-hydroxy-γ-butyrolactone corresponding to formula (6) are formed.

The conjugated unsaturated compound represented by the formula (9) is
First, a dihydroxy compound corresponding to the above formula (4) (in formula (4), Ra = RiRjCH group, Rb = Rc =
H) is produced, and then two molecules of water are desorbed from this compound. The reaction product can be separated and purified by the same separation means as described above.

4. Production of β-hydroxyacetal compound Using the imide compound represented by the above formula (1) and nitrates as catalysts, the following formula (10)

Embedded image (Wherein, Rk, Rm, and Rn are the same or different and each represent a hydrogen atom or an organic group. Rm and Rn are bonded to each other to form, together with two adjacent oxygen atoms and carbon atoms shown in the formula, By reacting an acetal represented by the following formula (3) with an active olefin represented by the formula (3) and oxygen:

Embedded image (Wherein, Rc, Rd, Re, Rk, Rm, Rn, and Y are the same as described above).

In the formula (10), examples of the organic group for Rk, Rm, and Rn include the same as the organic group for Ra and Rb. Examples of the ring formed by Rm and Rn together with two adjacent oxygen atoms and carbon atoms by bonding to each other include a 1,3-dioxolane ring and a 1,3-dioxane ring. A substituent such as an alkyl group or a halogen atom may be bonded to these rings.

Preferred Rk includes a hydrogen atom; methyl, ethyl, propyl, isopropyl, butyl, isobutyl,
C1-10 aliphatic hydrocarbon groups (particularly, C1-4 alkyl groups) such as s-butyl, t-butyl, pentyl, hexyl, octyl, and decyl groups; C3 such as cyclopentyl, cyclohexyl, cyclohexenyl, and adamantyl groups.
About -15 alicyclic hydrocarbon groups (cycloalkyl group, cycloalkenyl group, bridged ring hydrocarbon group); phenyl,
And a C6-14 aryl group such as a naphthyl group. Preferred Rm and Rn are a hydrogen atom; methyl,
C1-6 aliphatic hydrocarbon groups (especially C1-4 alkyl groups) such as ethyl, propyl, isopropyl, butyl, isobutyl and hexyl groups; C3-10 alicyclic hydrocarbon groups such as cyclopentyl and cyclohexyl groups Is mentioned. It is also preferable that Rm and Rn be bonded to each other to form a ring together with two adjacent oxygen atoms and carbon atoms.

As the acetal represented by the formula (10),
The compounds exemplified as the acetal having a carbon-hydrogen bond at the position adjacent to the oxygen atom in the above (A1-3). Typical examples include 1,3-dioxolan, 2
-Methyl-1,3-dioxolan, 2-ethyl-1,3
1,3-dioxolane compounds such as dioxolane; 2
1,3-dioxane compounds such as -methyl-1,3-dioxane; dialkyl acetal compounds such as acetaldehyde dimethyl acetal;

The active olefin represented by the formula (3) is the same as described above. The reaction can be carried out according to the method for producing an organic compound of the present invention. The reaction product can be separated and purified by the same separation means as described above.

In this reaction, first, a 1,1-disubstituted oxyalkyl radical corresponding to the acetal represented by the formula (10) is generated, and this is the unsaturated bond of the active olefin represented by the formula (3). Of the group Y among the two carbon atoms constituting the group by attacking and adding, and by attacking the radical generated at the position α by the addition, oxygen attacks the β atom represented by the formula (11). -It is assumed that a hydroxyacetal compound is formed.

5. Production of hydroxy compound Using an imide compound represented by the above formula (1) and nitric acid as a catalyst, the following formula (12)

Embedded image (In the formula, Ro, Rp, and Rq are the same or different and each represents an organic group. Ro, Rp, and Rq may be bonded to each other to form a ring together with adjacent carbon atoms.) By reacting a compound having a methine carbon atom with an active olefin represented by the above formula (3) and oxygen, the following formulas (13) and (14)

Embedded image (Wherein, Rc, Rd, Re, Ro, Rp, Rq, and Y are the same as described above).

In the formula (12), examples of the organic group for Ro, Rp, and Rq include the same as the organic group for Ra and Rb. Preferred organic groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s
C1-10 aliphatic hydrocarbon groups (especially C1-4 alkyl groups) such as -butyl, t-butyl, pentyl, hexyl, octyl, and decyl groups; C3 such as cyclopentyl, cyclohexyl, cyclohexenyl, and adamantyl groups.
About -15 alicyclic hydrocarbon groups (cycloalkyl group, cycloalkenyl group, bridged ring hydrocarbon group); phenyl,
And a C6-14 aryl group such as a naphthyl group.

Ro, Rp, Rq (Ro and Rp, Rp and R
q, Ro and Rq, or Ro and Rp and Rq) bond to each other to form a ring together with adjacent carbon atoms, for example, cyclopropane, cyclobutane, cyclopentane,
Monocyclic alicyclic having about 3 to 20 members (preferably 3 to 15 members, more preferably 5 to 15 members, particularly 5 to 8 members) such as cyclopentene, cyclohexane, cyclohexene, cyclooctane, cyclodecane and cyclododecane rings. Carbocycle (cycloalkane ring, cycloalkene ring); for example, adamantane ring, perhydroindene ring, decalin ring, perhydrofluorene ring, perhydroanthracene ring, perhydrophenanthrene ring, tricyclo [5.2.1.
[02,6] About 2 to 4 bridged cyclic carbon rings such as decane ring, perhydroacenaphthene ring, perhydrophenalene ring, norbornane ring and norbornene ring. These rings may have a substituent (for example, the same group as the substituent which the hydrocarbon group in Ra and Rb may have).

When Ro, Rp and Rq are bonded to each other to form a bridged cyclic carbocycle together with adjacent carbon atoms, the methine carbon atom represented by the formula (12) is preferably a carbon atom at the bridgehead position. .

As the compound having a methine carbon atom represented by the formula (12), the compound having a methine carbon atom (A3), for example, a bridged cyclic compound (A3-1a), and a ring having a hydrocarbon group in the ring. A bonded non-aromatic cyclic compound (A3-1b),
The compounds exemplified as the chain compound having a methine carbon atom (A3-2) can be mentioned.

The active olefin represented by the formula (3) is the same as described above. The reaction can be carried out according to the method for producing an organic compound of the present invention. The reaction product can be separated and purified by the same separation means as described above.

In this reaction, a radical is generated at the methine carbon site of the compound represented by the formula (12), and a radical is formed between the two carbon atoms constituting the unsaturated bond of the active olefin represented by the formula (3). Of the group Y by attacking the β-position carbon atom or the α-position carbon atom, and adding
It is considered that the hydroxyl compound represented by the formula (13) or the hydroxy compound represented by the formula (14) is generated by oxygen attacking the radical generated at each of the β-position and the β-position.

Among the hydroxy compounds represented by the formula (13) thus produced, preferred compounds include R
o, Rp and Rq are bonded to each other to form a bridged cyclic carbocycle (for example, an adamantane ring) together with adjacent carbon atoms, and Rc, Rd and Re are each a hydrogen atom or C1
-4 alkyl group, and Y is an alkoxycarbonyl group (for example, C1-4 alkoxy-carbonyl group), an aryloxycarbonyl group, an acyl group (for example, C1-4
Compounds that are an acyl group, a benzoyl group, etc.) or a carboxyl group. Such compounds are useful as raw materials for fine chemicals such as pharmaceuticals and agricultural chemicals and as raw materials for functional polymers.

6. Production of carbonyl compound (1) A compound having a methine carbon atom represented by the above formula (12) using the imide compound represented by the above formula (1) and nitrates as catalysts, and a compound represented by the following formula (3b)

Embedded image (Wherein, Rc and Rd are the same or different and each represent a hydrogen atom or an organic group, and Y represents an electron withdrawing group. Rc, Rd,
Y may combine with each other to form a ring together with an adjacent carbon atom or a carbon-carbon bond), and react with an active olefin represented by the following formula (15)

Embedded image (Wherein Rc, Rd, Ro, Rp, Rq, and Y are the same as described above) can be obtained.

In this method, in the production of the hydroxy compound, the active olefin represented by the formula (3) is represented by R
This corresponds to the case where a compound in which e is a hydrogen atom is used. In this case, a compound corresponding to the formula (13) (Re =
H) and / or compounds corresponding to formula (14) (Re = H)
Instead of or in addition to the above compound, a carbonyl compound represented by the formula (15) is formed. The formation ratio of both compounds is, for example, the reaction temperature, the amount of catalyst, the co-catalyst (metal compound)
It can be adjusted by appropriately selecting the reaction conditions such as the type of.

The carbonyl compound represented by the formula (15) is
It is considered that the compound (Re = H) corresponding to the formula (13) is further oxidized in the system to form.

Among the carbonyl compounds represented by the formula (15) thus produced, preferred compounds include Ro and R
p and Rq are bonded to each other to form a bridged cyclic carbocycle (for example, an adamantane ring or the like) together with adjacent carbon atoms, Rc and Rd are each a hydrogen atom or a C1-4 alkyl group, and Y is an alkoxycarbonyl Groups (eg, C
Compounds that are a 1-4 alkoxy-carbonyl group), an aryloxycarbonyl group, an acyl group (eg, a C1-4 acyl group, a benzoyl group, etc.) or a carboxyl group are included. Such compounds are useful as raw materials for fine chemicals such as pharmaceuticals and agricultural chemicals and as raw materials for functional polymers.

[0177] 7. Production of Electron-Withdrawing Group-Containing Compound A compound having a methine carbon atom represented by the formula (12) using the imide compound represented by the formula (1) and nitric acid as a catalyst, and a compound represented by the following formula (3c)

Embedded image (Wherein, Re represents a hydrogen atom or an organic group, and Y represents an electron-withdrawing group) by reacting with an active olefin represented by the following formula (16):

Embedded image (Wherein, Re, Ro, Rp, Rq, and Y are the same as described above).

In this method, in the production of the hydroxy compound, the active olefin represented by the formula (3) is represented by R
This corresponds to the case where a compound in which c and Rd are hydrogen atoms is used. In this case, the compound corresponding to the formula (13) (Rc = Rd = H), the compound corresponding to the formula (14) (Rc = Rd = H), and the compound corresponding to the formula (15) (Rc = Rd = H, Re = H only)
Alternatively, in addition to the compound, a compound represented by the formula (16) is generated. The production ratio of each compound can be adjusted by appropriately selecting reaction conditions such as the reaction temperature, the amount of catalyst, and the type of cocatalyst (metal compound).

In the compound represented by the formula (16), the methylol group of the compound (Rc = Rd = H) corresponding to the formula (14) is further oxidized in the system to form a carboxyl group, which is decarboxylated. It is considered to be generated.

Among the carbonyl compounds represented by the formula (16) thus produced, preferred compounds include Ro and R
p and Rq are bonded to each other to form a bridged cyclic carbocycle (for example, an adamantane ring or the like) together with adjacent carbon atoms, Re is a hydrogen atom or a C1-4 alkyl group, and Y is
Is an alkoxycarbonyl group (for example, C1-4 alkoxy-carbonyl group), an aryloxycarbonyl group, an acyl group (for example, C1-4 acyl group, benzoyl group and the like) or a carboxyl group. Such compounds are useful as raw materials for fine chemicals such as pharmaceuticals and agricultural chemicals and as raw materials for functional polymers.

8. Production of alcohol The imide compound represented by the formula (1) and nitric acid are used as catalysts, and the alcohol represented by the formula (2) is represented by the formula (12) in the presence of oxygen if necessary. By reacting with a compound having a methine carbon atom

Embedded image (Wherein Ra, Rb, Ro, Rp, Rq, and Y are the same as described above) can be obtained.

As the alcohol represented by the formula (2),
The same ones as in the case of producing the 1,3-dihydroxy compound can be used. In addition, as the compound having a methine carbon atom represented by the formula (12), the same compound as in the case of producing the hydroxy compound can be used. In this method, the compound having a methine carbon atom represented by the formula (12) is considered to function as a radical-scavenging compound (B2).

The reaction can be carried out according to the method for producing an organic compound of the present invention. The reaction product can be separated and purified by the same separation means as described above.

In this reaction, the 1-hydroxyalkyl radical corresponding to the alcohol of the formula (2) generated in the system attacks the methine carbon atom of the compound represented by the formula (12), whereby the compound represented by the formula (17) ) Is considered to be produced.

9. Production of Coupling Product The imide compound represented by the above formula (1) and nitric acid are used as catalysts, and if necessary, in the presence of oxygen, the following formula (12a)

Embedded image (In the formula, Ro1, Rp1, and Rq1 are the same or different and each represents an organic group. Ro1, Rp1, and Rq1 may be bonded to each other to form a ring together with adjacent carbon atoms.) A compound having a methine carbon atom, and a compound represented by the following formula (12b)

Embedded image (In the formula, Ro2, Rp2, and Rq2 are the same or different and each represents an organic group. Ro2, Rp2, and Rq2 may be bonded to each other to form a ring together with adjacent carbon atoms.) By reacting with a compound having a methine carbon atom, the following formula (18)

Embedded image (Wherein, Ro1, Rp1, Rq1, Ro2, Rp2, R
q2 is the same as described above) to obtain a coupling product (hydrocarbons).

In the formulas (12a) and (12b), Ro1, Rp
1, Rq1, Ro2, Rp2, and the organic group in Rq2 include the same organic groups as those described above for Ro, Rp, and Rq. Also, Ro1, Rp1,
Rq1 (Ro1 and Rp1, Rp1 and Rq1, Ro1 and R
q1, or a ring in which Ro1, Rp1, and Rq1) are bonded to each other to form an adjacent carbon atom, Ro2, Rp2,
Rq2 (Ro2 and Rp2, Rp2 and Rq2, Ro2 and R
q2 or a ring formed by Ro2 and Rp2 and Rq2) together with an adjacent carbon atom includes the above-mentioned R
The same ring as o, Rp, and Rq are combined with each other to form a ring together with an adjacent carbon atom.

As the compound having a methine carbon atom represented by the formula (12a) or (12b), the compound having a methine carbon atom (A3), for example, a bridged cyclic compound (A3-1
a), a non-aromatic cyclic compound having a hydrocarbon group bonded to the ring (A3-1b), a chain compound having a methine carbon atom (A3-
The compounds exemplified as 2) are mentioned. The compound represented by the formula (12a) and the compound represented by the formula (12b) may be the same compound or different compounds.

The reaction can be carried out according to the method for producing an organic compound of the present invention. The reaction product can be separated and purified by the same separation means as described above.

In this reaction, a radical is generated at the methine carbon site of the compound represented by the formula (12a), and this radical attacks the methine carbon atom of the compound represented by the formula (12b). It is considered that a coupling product represented by 18) is produced.

10. Production of carbonyl compound (2) The imide compound represented by the above formula (1) and nitric acid are used as catalysts, and if necessary, in the presence of oxygen, the following formula (19)

Embedded image (Wherein, Rg represents a hydrogen atom or an organic group) and an aldehyde represented by the following formula (20):

Embedded image (Wherein, Rc, Rd, Re, and Rh are the same or different and represent a hydrogen atom or an organic group. Rc, Rd, Re, R
h may be bonded to each other to form a ring together with an adjacent carbon atom or carbon-carbon) to react with an olefin represented by the following formula (21)

Embedded image (In the formula, Rc, Rd, Re, Rh, and Rg are the same as described above.)
Can be obtained.

In the formula (19), examples of the organic group for Rg include the same as the organic groups for Ra and Rb. As the aldehyde represented by the formula (19), the aldehyde exemplified in the carbonyl group-containing compound (A2-1) can be used.

In the formula (20), Rc, Rd and Re are the same as described above, and the organic group in Rh is the same as that of Rc, Rd and R
Same as e. As the olefins represented by the formula (20), for example, the compounds exemplified as the inactive olefin (B1-6) and the active unsaturated compound (B1-1) can be used.

The reaction can be carried out according to the method for producing an organic compound of the present invention. The reaction product can be separated and purified by the same separation means as described above.

In this reaction, a corresponding acyl radical is generated from the compound represented by the formula (19), and this is converted to a compound represented by the formula (20).
It is considered that the carbonyl compound represented by the formula (21) is formed by attacking the carbon atom constituting the double bond of the compound represented by the formula (21).

11. Production of Organic Compound Containing Oxygen Atom-Containing Group The compound (A) capable of generating the radical and the oxygen atom-containing gas (B4) are produced by using the imide compound represented by the formula (1) and nitric acid as catalysts. By reacting, an organic compound containing an oxygen atom-containing group can be produced.

This reaction is carried out in the presence or absence of a solvent. As the solvent, the above-mentioned solvents can be used. The amount of the imide compound catalyst to be used is, for example, 0.0000001 to 1 mol, preferably 0.00001 to 0.5 mol, more preferably 0.0 mol to 1 mol of compound (A).
001 to 0.4 mol, and often about 0.001 to 0.3 mol. The amount of the nitric acid used is, for example, 0.000001 to 1 mol of the compound (A).
About 0.8 mol, preferably about 0.0004 to 0.1 mol. In this reaction, when a co-catalyst such as the above-mentioned metal compound (for example, a vanadium compound, a molybdenum compound, a manganese compound, a cobalt compound, etc.) is used in combination,
The reaction is often significantly accelerated.

The oxygen atom-containing gas (B4) may be used after being diluted with an inert gas such as nitrogen or argon.
Further, the oxygen atom-containing gas (B4) may be used alone,
Two or more kinds may be used as a mixture. By using two or more kinds of oxygen atom-containing gas (B4) in combination, two or more kinds of different functional groups selected from a hydroxyl group, an oxo group, a carboxyl group, a nitro group, a sulfonic acid group and the like can be formed in the molecule. Can be introduced. In this case, two or more oxygen atom-containing gases (B4) may be used at the same time,
They may be used sequentially.

The amount of the oxygen atom-containing gas (B4) varies depending on the type of the gas, and can be appropriately selected in consideration of reactivity, operability, and the like. For example, when oxygen (B4-1) is used as the oxygen atom-containing gas (B4), the amount of oxygen used is 0.5 mol or more (eg, 1 mol or more), preferably 1 mol, per 1 mol of the compound (A). It is about 1 to 100 mol, and more preferably about 2 to 50 mol. In many cases, an excess molar amount of oxygen is used relative to compound (A). The blowing rate of oxygen is 1 to 30 as oxygen per mole of compound (A).
0 ml / min, preferably about 10 to 250 ml / min.

When carbon monoxide (B4-2) and oxygen (B4-1) are used in combination as the oxygen atom-containing gas (B4), the compound (A)
1 mole or more (for example, about 1 to 100 moles) of carbon monoxide and 0.5 mole or more (for example, 0.5 to
(About 50 mol) of oxygen is often used. in this case,
The ratio of carbon monoxide to oxygen is as follows: carbon monoxide / oxygen (molar ratio) = 1/99 to 99.99 / 0.01, preferably 1
It is about 0/90 to 99/1.

When a nitrogen oxide (B4-3) is used as the oxygen atom-containing gas (B4), the amount of the nitrogen oxide used is appropriately selected according to the type of the nitrogen oxide and the type of the compound (A). The amount may be 1 mol or more, or may be less than 1 mol, per 1 mol of compound (A). The amount of the nitrogen oxide (for example, nitrogen dioxide or the like) used is changed by the amount of compound (A) 1
Less than 1 mole (eg, 0.0001 mole or more and less than 1 mole), preferably 0.001 to 0.8 mole,
If it is more preferably about 0.005 to 0.25 mol, the conversion of nitrogen oxides and the selectivity of the reaction are greatly improved.

When nitrogen dioxide (NO2) and oxygen are used in combination, the reaction rate such as nitration reaction is greatly improved. In this case, the amount of oxygen used is 0.5 mol or more (for example, 1 mol or more), preferably 1 to 100 mol, more preferably about 2 to 50 mol per 1 mol of nitrogen dioxide.

As the oxygen atom-containing gas, sulfur oxide (B4-
When 4) is used, the amount of the sulfur oxide can be appropriately selected according to the type of the sulfur oxide, the type of the compound (A), and the like. 50
Mol, preferably in the range of about 1.5 to 30 mol. The reaction may be performed under a large excess atmosphere of sulfur oxides. When a sulfur oxide (for example, sulfur dioxide) and oxygen are used in combination, the ratio is, for example, former / latter (molar ratio) = 10/90 to 90/10, and more preferably former / latter (molar ratio). ) = About 30/70 to 70/30.

The reaction temperature can be appropriately selected according to the type of the compound (A) and the gas containing an oxygen atom. For example, when oxygen (B4-1) is used as the oxygen atom-containing gas, the reaction temperature is about 0 to 300 ° C, preferably about 20 to 250 ° C, and more preferably about 30 to 150 ° C. In particular, when the corresponding hydroxy compound is produced from the compound (b) having a methine carbon atom, such as when adamantane diols are obtained from adamantanes, the reaction temperature is set at 3 ° C.
By setting the temperature in the range of about 0 to 100 ° C., particularly about 45 to 65 ° C., the selectivity of the target hydroxy compound is improved, and the compound can be obtained in a high yield.

As an oxygen atom-containing gas, carbon monoxide (B4-
When using 2) and oxygen (B4-1), the reaction temperature is
For example, it is about 0 to 200 ° C, preferably about 10 to 150 ° C. When the nitrogen oxide (B4-3) or the sulfur oxide (B4-4) is used as the oxygen atom-containing gas (including the case where oxygen is used in combination), the reaction temperature is, for example, 0 to 150.
C., and preferably about 10 to 125.degree. The reaction pressure may be normal pressure or under pressure. When it is performed under pressure, the pressure is usually about 0.1 to 10 MPa, 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 is easily separated and purified by conventional separation and purification means, for example, filtration, concentration, distillation, extraction, crystallization, recrystallization, adsorption, column chromatography and the like, or a combination thereof. Can be separated and purified.

According to this method, under mild conditions, a reaction product corresponding to the type of the oxygen atom-containing gas can be obtained with a high yield.

More specifically, when oxygen (B4-1) is used as the oxygen atom-containing gas, the oxidation reaction proceeds and a corresponding oxidation product is obtained. For example, when a hetero atom-containing compound (A1) having a carbon-hydrogen bond adjacent to the hetero atom is used as the compound (A), the carbon atom adjacent to the hetero atom is oxidized. For example, a primary alcohol produces a corresponding aldehyde or carboxylic acid, and a secondary alcohol produces a corresponding ketone or the like.

When the compound (A2) having a carbon-heteroatom double bond is used as the compound (A), an oxidation reaction product corresponding to the kind of the hetero atom or the like is obtained. For example, when a ketone is oxidized, it is cleaved to form a carboxylic acid or the like, and a dicarboxylic acid such as adipic acid is obtained from a cyclic ketone such as cyclohexanone. Also,
When a heteroatom-containing compound (A1) having a carbon-hydrogen bond at a position adjacent to a heteroatom such as a secondary alcohol (for example, benzhydrol) is used as a co-reactant (co-oxidant), mild conditions can be obtained. As a result, a Bayer-Villiger-type reaction proceeds, and a corresponding lactone can be obtained from a cyclic ketone and a corresponding ester can be obtained from a chain ketone in good yield. In addition, a corresponding carboxylic acid is generated from the aldehyde.

When the compound (A3) having a methine carbon atom is used as the compound (A), an alcohol derivative having a methine carbon to which a hydroxyl group has been introduced can be obtained in high yield. For example, when a bridged cyclic hydrocarbon (A3-1a) such as adamantane is oxidized, an alcohol derivative having a hydroxyl group introduced at the bridgehead, for example, 1-
Adamantanol, 1,3-adamantanediol and 1,3,5-adamantanetriol can be obtained with high selectivity. From a chain compound having a methine carbon atom (A3-2) such as isobutane, a tertiary alcohol such as t-butanol can be obtained in high yield.

When the compound (A4) having a carbon-hydrogen bond at a position adjacent to the unsaturated bond is used as the compound (A), the position at the position adjacent to the unsaturated bond is efficiently oxidized to produce an alcohol or a carboxylic acid. . For example, a primary alcohol or a carboxylic acid can be obtained in a high yield from a compound having a methyl group at a position adjacent to an unsaturated bond. Specifically, for example, benzoic acid and the like can be obtained in good yield from toluene. In addition, secondary alcohols or ketones can be obtained from a compound having a methylene group at the position adjacent to the unsaturated bond.

When the non-aromatic cyclic hydrocarbon (A5) is used as the compound (A), alcohols or ketones having a hydroxy or oxo group introduced into the carbon atom constituting the ring,
Alternatively, depending on the reaction conditions, the ring is oxidatively cleaved to form the corresponding dicarboxylic acid. For example, from cyclohexane, cyclohexyl alcohol, cyclohexanone or adipic acid can be obtained with good selectivity by appropriately selecting the conditions.

When the conjugated compound (A6) is used as the compound (A), various compounds are produced depending on the structure. For example, oxidation of conjugated dienes produces alkenediol and the like. Specifically, when butadiene is oxidized,
Butene-1,4-diol, 1-butene-3,4-diol and the like are obtained. α, β-unsaturated nitrile and α, β
Oxidation of the unsaturated carboxylic acid or its derivative gives α,
The β-unsaturated bond site is selectively oxidized so that the unsaturated bond becomes a single bond, and the β-position is a formyl group, an acetal group (when reacted in the presence of an alcohol) or an acyloxy group (in the presence of a carboxylic acid). (If reacted below). More specifically, for example, oxidizing acrylonitrile and methyl acrylate in the presence of methanol produces 3,3-dimethoxypropionitrile and methyl 3,3-dimethoxypropionate, respectively.

When amines (A7) are used as compound (A), corresponding Schiff bases, oximes and the like are formed.
When an aromatic compound (A8) is used as the compound (A), a compound having a carbon-hydrogen bond at a position adjacent to an unsaturated bond (eg, fluorene) (A4) or the like is used as a co-reactant (co-oxidant). When coexisting, the corresponding quinones are produced in good yield. Alcohol and the like are produced from the linear alkane (A9).

Further, when an olefin (A10) is used as the compound (A), a heteroatom-containing compound (A1) having a carbon-hydrogen bond at a position adjacent to a heteroatom such as a secondary alcohol or an unsaturated bond is used. When a compound having a carbon-hydrogen bond at the position (A4) or the like coexists as a co-reactant (co-oxidant), the epoxidation reaction proceeds under mild conditions, and the corresponding epoxide can be obtained in good yield. it can.

As the oxygen atom-containing gas, carbon monoxide (B4-
When 2) and oxygen (B4-1) are used, the carboxylation reaction proceeds smoothly, and the corresponding carboxylic acid can be obtained in good yield. For example, when a compound (A3) having a methine carbon atom is used as the compound (A), a compound (A4) having a carboxyl group introduced into the methine carbon atom and having a carbon-hydrogen bond adjacent to an unsaturated bond (A4 )
A carboxyl group is introduced into a carbon atom involved in the carbon-hydrogen bond. Further, a non-aromatic cyclic hydrocarbon (A5) such as cyclohexane generates a carboxylic acid in which a carboxyl group is bonded to a carbon atom constituting the ring.

As an oxygen atom-containing gas, nitrogen oxide (B4-
When 3) is used, a nitration reaction mainly proceeds, and a corresponding nitro compound or the like is obtained. For example, when the compound (A3) having a methine carbon atom is used as the compound (A), the compound (A4) in which the methine carbon atom is nitrated and which has a carbon-hydrogen bond adjacent to the unsaturated bond is used. The carbon atom involved in the carbon-hydrogen bond is nitrated. In addition, from a non-aromatic cyclic hydrocarbon (A5) such as cyclohexane, a corresponding cyclic nitro compound in which a nitro group is bonded to a carbon atom constituting the ring is formed, and further a linear alkane (A9) such as hexane is produced. ), The corresponding nitroalkane is formed.

When a compound (eg, toluene) having a methyl group at a position adjacent to the aromatic ring (so-called benzyl position) is used as the compound (A), a nitro group is introduced into the carbon atom of the methyl group. However, depending on the conditions, a corresponding aromatic aldehyde (for example, benzaldehyde) in which the methyl group is formylated or a compound in which a nitro group is introduced into an aromatic ring may be produced. Furthermore, when a compound having a methylene group at the adjacent position of the aromatic ring (for example, ethylbenzene) is used as a substrate, a nitro compound in which the methylene group is nitrated (for example, α-nitroethylbenzene) is formed, and the reaction proceeds. Depending on the conditions, an oxime compound in which the methylene group is oxime-formed (for example, acetophenone oxime) may be generated.

As an oxygen atom-containing gas, sulfur oxide (B4-
When 4) is used, a sulfonation or sulfination reaction proceeds, and a corresponding organic sulfur acid or a salt thereof is obtained.
For example, when a compound (A3) having a methine carbon atom is used as the compound (A), a compound (A4) in which a sulfur acid group is introduced into the methine carbon atom and has a carbon-hydrogen bond at a position adjacent to the unsaturated bond, When used, a sulfur atom (sulfonic acid group, sulfinic acid group, etc.) is added to the carbon atom related to the carbon-hydrogen bond.
Is introduced. Further, from a non-aromatic cyclic hydrocarbon (A5) such as cyclohexane, an organic sulfuric acid in which a sulfuric acid group is bonded to a carbon atom constituting the ring is generated. The produced organic sulfuric acid can be prepared by a conventional method, for example, in a suitable solvent such as water, in an alkali metal hydroxide, an alkali metal carbonate, an alkali metal bicarbonate, an alkaline earth metal hydroxide, an alkaline earth metal. By reacting with metal carbonates, amines, thioureas, isothioureas, etc., they can be converted to the corresponding organic sulfur salts.

[0219]

According to the method of the present invention, since an imide compound having a specific structure and nitric acid are used as a catalyst in combination, an active radical is generated under mild conditions. Thus, various organic compounds can be easily produced under extremely easy operation conditions. In addition, since the reaction can be carried out under mild conditions, the selectivity of the reaction is high, and even if a sublimable substance such as adamantane is used as a reaction component, troubles due to sublimation and a decrease in yield can be prevented. Further, since the decomposition and deactivation of the imide compound catalyst are suppressed by the action of nitric acids, the catalyst life is long, the cost of the catalyst can be reduced, and the target compound can be stably produced for a long period of time.

According to the method of the present invention, a hydroxymethyl group, an alkoxymethyl group or an alkoxymethyl group is added under mild conditions to a carbon atom forming an unsaturated bond of an unsaturated compound or a methine carbon atom of a bridged cyclic compound. Groups, acyl groups, tertiary carbon atoms, etc. can be directly attached. Furthermore, the corresponding 1,3-dihydroxy compound can be obtained from the alcohol, the unsaturated compound, and oxygen in good yield. Also,
Α-hydroxy-γ under mild conditions from readily available raw materials
-Butyrolactone derivatives can be produced.

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, a nitro group or a sulfonic acid group can be easily and easily selected under very mild conditions. It can be manufactured with good quality.

In particular, in the present invention, in an oxidation reaction using a carbon-carbon bond product or a derivative thereof (a cyclized derivative, etc.) and oxygen, a low-order oxidation product such as an alcohol can be obtained with a high selectivity. It is.

[0223]

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. The reaction product was identified by NM
Performed by R, IR, and GC-MS.

Example 1 3 mmol of ethyl acrylate, 9 mmol of 2-propanol, 0.3 mmol of N-hydroxyphthalimide, 0.06 mmol of cobalt (II) acetate, and 60% by weight nitric acid (0.03 mmol as nitric acid) Was stirred at 40 ° C. for 3 hours under an air atmosphere (1 atm = 0.1 MPa). The product in the reaction mixture was analyzed by gas chromatography to find that ethyl 2,4-dihydroxy-4-methylpentanoate had a yield of 30% (based on ethyl acrylate) and α-hydroxy-γ, γ-dimethyl- γ-butyrolactone was produced in a yield of 41% (based on ethyl acrylate). The conversion of ethyl acrylate was 95%. Further, when the mixture was stirred at the same temperature for 3 hours, the yield of α-hydroxy-γ, γ-dimethyl-γ-butyrolactone was 68% (based on ethyl acrylate). [Spectral data of α-hydroxy-γ, γ-dimethyl-γ-butyrolactone] 1H-NMR (CDCl 3) δ: 1.42 (s, 3
H), 1.51 (s, 3H), 2.06 (dd, 1
H), 2.52 (dd, 1H), 3.03 (brs, 1
H), 4.63 (t, 1H).

Example 2 3 mmol of ethyl acrylate, 9 mmol of 2-propanol, 0.3 mmol of N-hydroxyphthalimide, 0.06 mmol of cobalt (II) acetate, and 60% by weight nitric acid (0.03 mmol as nitric acid) Was stirred at 25 ° C. for 6 hours under an air atmosphere (1 atm = 0.1 MPa). The product in the reaction mixture was analyzed by gas chromatography to find that ethyl 2,4-dihydroxy-4-methylpentanoate had a yield of 41% (based on ethyl acrylate) and α-hydroxy-γ, γ-dimethyl- γ-butyrolactone was produced in a yield of 32% (based on ethyl acrylate). The conversion of ethyl acrylate was 92%. When the temperature was further stirred at 40 ° C. for 3 hours, the yield of α-hydroxy-γ, γ-dimethyl-γ-butyrolactone was 71% (based on ethyl acrylate).

Example 3 3.0 g of adamantane, 0.72 g (20 mol%) of N-hydroxyphthalimide, 0.09 g of 60% by weight nitric acid
(4 mol%), vanadium acetylacetonate V (ac
ac) 3 0.023 g (0.3 mol%) and acetic acid 2
7.0 g was placed in the flask, and one atmosphere of oxygen (0.1MP
In the atmosphere of a), the mixture was stirred at 55 ° C. for 6 hours. When the reaction mixture was analyzed by gas chromatography, the yield of 1-adamantanol was 35.7%, the yield of 1,3-adamantanediol was 23.5%, and the yield of 1,3,5-adamantanetriol was 2. 2% and 2-adamantanone were produced in a yield of 6.2%. Adamantane conversion is 8
It was 5.0%. Comparative Example 1 The same operation as in Example 3 was carried out except that nitric acid was not added. As a result, the reaction did not proceed, and adamantane was recovered 100%.

Example 4 Adamantane 3.0 g, N-hydroxyphthalimide 0.36 g (10 mol%), 60% by weight nitric acid 0.009
g (0.4 mol%), vanadium acetylacetonate V
(Acac) 3 0.038 g (0.5 mol%) and acetic acid 27.0 g were placed in a flask, and one atmosphere of oxygen (0.1 atm.
Under an atmosphere of MPa), the mixture was stirred at 55 ° C. for 18 hours. When the reaction mixture was analyzed by gas chromatography, 1
-Adamantanol yield 31.6%, 1,3-adamantanediol yield 31.9%, 1,3,5-adamantanetriol yield 5.2%, 2-adamantanone yield 6. It was formed at 2%. The conversion of adamantane was 94.8%.

Comparative Example 2 The same operation as in Example 4 was carried out except that nitric acid was not added, and the yield of 1-adamantanol was 29.3.
%, 1,3-adamantanediol yield 11.7%,
2-adamantanone was produced in a yield of 3.8%. In addition, 1,3,5-adamantanetriol was not generated. The conversion of adamantane was 66.7%.

Example 5 In an autoclave, 1200 g of adamantane, 287.4 g (20 mol%) of N-hydroxyphthalimide, 60 g of N-hydroxyphthalimide were added.
37.1 g (4 mol%) of nitric acid by weight, 9.2 g (0.3 mol%) of vanadium acetylacetonate V (acac) 3, and 8000 g of acetic acid were charged and stirred at 55 ° C. 1.96 MPa (20 kgf / cm) while blowing air at a flow rate of 200 L (standard state) / h.
The reaction was performed under the pressure of 2) for 12 hours. When the reaction mixture was analyzed by gas chromatography, the yield of 1-adamantanol was 21.6%, the yield of 1,3-adamantanediol was 40.1%, and the yield of 1,3,5-adamantanetriol was 9. 1%, 2-adamantanone yield 5.
It was formed at 4%. The conversion of adamantane is 99.1
%Met.

Example 6 3.0 g of adamantane, 0.36 g (10 mol%) of N-hydroxyphthalimide, 0.11 g of sodium nitrate
(0.5 mol%), vanadium acetylacetonate V
(Acac) 3 0.024 g (0.3 mol%) and acetic acid 27.0 g were placed in a flask, and one atmosphere of oxygen (0.1 atm.
Under an atmosphere of MPa), the mixture was stirred at 55 ° C. for 18 hours. When the reaction mixture was analyzed by gas chromatography, 1
-Adamantanol yield 33.4%, 1,3-adamantanediol yield 33.4%, 1,3,5-adamantanetriol yield 5.0%, 2-adamantanone yield 6. It was formed at 1%. The conversion of adamantane was 94.0%.

Example 7 A gas inlet tube equipped with a filter was installed so that the bubble diameter was 1 mm or less, and a cooling tube was provided at the gas outlet of the reactor to cool and reflux the volatilized gas. In a 1-L glass autoclave equipped with a pressure-holding valve at the gas outlet of the cooling pipe to apply pressure inside the reactor, 2 mol of cyclohexane, 26 mmol of N-hydroxyphthalimide, cobalt octoate 0.3 mmol of (cobalt octylate), 3 mmol of nitric acid, and 248 g of acetonitrile were added, and the pressure was adjusted to 0.9 MPa. 450m of 9-14% oxygen diluted with nitrogen
The mixture was stirred at 90 ° C. for 4.3 hours while feeding at 1 / min. When the reaction mass was analyzed by gas chromatography, the conversion of cyclohexane was 10%, the selectivity of cyclohexanone was 41%, and the selectivity of cyclohexanol was 0.1%.
% Or less, and cyclohexyl hydroperoxide was formed at a selectivity of 40%. When the remaining N-hydroxyphthalimide was analyzed by high performance liquid chromatography, the retention (residual) of N-hydroxyphthalimide was 89%.

Comparative Example 3 The same operation as in Example 7 was performed except that nitric acid was not added. With a reaction time of 3.7 hours, the conversion of cyclohexane was 10%, the selectivity of cyclohexanone was 56%,
Cyclohexanol was formed at a selectivity of 7%, and cyclohexyl hydroperoxide was formed at a selectivity of 16%. When the remaining N-hydroxyphthalimide was analyzed by high performance liquid chromatography, the retention (residual) of N-hydroxyphthalimide was 36%.

Example 8 The same operation as in Example 7 was performed except that the reaction temperature was changed to 100 ° C. After a reaction time of 2.4 hours, the conversion of cyclohexane was 10% and the selectivity of cyclohexanone was 40%.
%, Cyclohexanol was formed at a selectivity of 0.1% or less, and cyclohexyl hydroperoxide was formed at a selectivity of 40%. When the remaining N-hydroxyphthalimide was analyzed by high performance liquid chromatography, the retention (residual) of N-hydroxyphthalimide was 87%.

Example 9 The same operation as in Example 7 was carried out except that 17 mmol of N-hydroxyphthalimide, 0.2 mmol of cobalt octoate, 2 mmol of nitric acid, 107 g of acetonitrile and the reaction temperature were changed to 100 ° C. Was done. Reaction time 3.
At 9 hours, the conversion of cyclohexane was 10%, the selectivity of cyclohexanone was 43%, the selectivity of cyclohexanol was 0.1% or less, and the selectivity of cyclohexyl hydroperoxide was 36%. When the remaining N-hydroxyphthalimide was analyzed by high performance liquid chromatography, the retention (residual) of N-hydroxyphthalimide was 87%.

Claims (8)

[Claims] (I) The following formula (1): (Wherein R ¹ and R ² are the same or different and each represents 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 a hydroxyl group. R ¹ , R ² , or R ¹ and R ²
Are bonded to each other to form a double bond or an aromatic or non-aromatic ring represented by the above formula (1).
And (ii) a compound capable of producing (A) a radical in the presence of nitric acid or nitrous acid or a salt thereof. And (B) a radical scavenging compound to produce an addition or substitution reaction product of the compound (A) and the compound (B) or a derivative thereof. . 2. A compound (A) capable of generating a radical,
(A1) a heteroatom-containing compound having a carbon-hydrogen bond at a position adjacent to a heteroatom, (A2) a compound having a carbon-heteroatom double bond, (A3) a compound having a methine carbon atom, (A4) an unsaturated bond A compound having a carbon-hydrogen bond at the adjacent position of (A5) a non-aromatic cyclic hydrocarbon, (A6) conjugated compound, (A7) amines, (A8) aromatic compound, (A9)
The method for producing an organic compound according to claim 1, which is a compound selected from a linear alkane and an olefin (A10). 3. The method according to claim 1, wherein the radical-scavenging compound (B) is (B1)
Unsaturated compounds, (B2) compounds having a methine carbon atom,
The method for producing an organic compound according to claim 1, wherein the compound is selected from (B3) a compound containing a hetero atom and (B4) a gas containing an oxygen atom. 4. The method for producing an organic compound according to claim 3, wherein the oxygen atom-containing gas (B4) is at least one selected from oxygen, carbon monoxide, nitrogen oxides and sulfur oxides. (5) In the presence of (i) an imide compound represented by the formula (1) and (ii) nitric acid or nitrous acid or a salt thereof, (A11) a compound represented by the following formula (2): (Wherein R ^a and R ^b are the same or different and each represent a hydrogen atom or an organic group. R ^a and R ^b may be bonded to each other to form a ring together with adjacent carbon atoms) An alcohol represented by the following formula (B11): ^{(Wherein, R c, R d, R} e may be the same or different and each represents a hydrogen atom or an organic group, Y represents an electron-withdrawing group .R ^c,
R ^d , R ^e , and Y may combine with each other to form a ring together with an adjacent carbon atom or a carbon-carbon bond), and react with oxygen (B41) represented by the following formula: (4) (Wherein, R ^a , R ^b , R ^c , R ^d , R ^e , and Y are the same as described above)
The method for producing an organic compound according to claim 1, wherein a 1,3-dihydroxy compound represented by the following formula is produced. 6. In the presence of (i) an imide compound represented by the formula (1) and (ii) nitric acid or nitrous acid or a salt thereof, (A11) a compound represented by the following formula (2): (Wherein R ^a and R ^b are the same or different and each represent a hydrogen atom or an organic group. R ^a and R ^b may be bonded to each other to form a ring together with adjacent carbon atoms) An alcohol represented by the formula (B12) and the following formula (5): (In the formula, R ^c , R ^d , R ^e , and R ^f are the same or different and each represents a hydrogen atom or an organic group. R ^c , R ^d , and R ^e are bonded to each other to form an adjacent carbon atom or carbon atom. -Which may form a ring together with a carbon bond), and (B41) oxygen to react with an α, β-unsaturated carboxylic acid derivative represented by the following formula (6): The method for producing an organic compound according to claim 1, wherein an α-hydroxy-γ-butyrolactone derivative represented by the formula: wherein R ^a , R ^b , R ^c , R ^d , and ^Re are the same as above, is produced. 7. (i) an imide compound represented by the formula (1), (ii) a compound capable of generating a radical in the presence of nitric acid or nitrous acid or a salt thereof, and (B4) oxygen The method for producing an organic compound according to claim 1, wherein the organic compound containing an oxygen atom-containing group is formed by reacting the compound with an atom-containing gas. 8. The method for producing an organic compound according to claim 1, wherein a metal compound is used as a co-catalyst.