WO2003055600A1 - Catalyseurs renfermant des composes d'acyluree cycliques, et procedes d'elaboration de composes organiques reposant sur l'utilisation de ces catalyseurs - Google Patents

Catalyseurs renfermant des composes d'acyluree cycliques, et procedes d'elaboration de composes organiques reposant sur l'utilisation de ces catalyseurs Download PDF

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WO2003055600A1
WO2003055600A1 PCT/JP2002/012794 JP0212794W WO03055600A1 WO 2003055600 A1 WO2003055600 A1 WO 2003055600A1 JP 0212794 W JP0212794 W JP 0212794W WO 03055600 A1 WO03055600 A1 WO 03055600A1
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group
compound
reaction
formula
acid
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PCT/JP2002/012794
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English (en)
French (fr)
Japanese (ja)
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Yasutaka Ishii
Naruhisa Hirai
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Daicel Chemical Industries, Ltd.
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Priority to AU2002361079A priority Critical patent/AU2002361079A1/en
Priority to US10/495,645 priority patent/US7091342B2/en
Priority to JP2003556171A priority patent/JP4413009B2/ja
Priority to EP02791966A priority patent/EP1459804B1/en
Priority to DE60236619T priority patent/DE60236619D1/de
Publication of WO2003055600A1 publication Critical patent/WO2003055600A1/ja
Priority to US11/233,017 priority patent/US7288649B2/en

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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0245—Nitrogen containing compounds being derivatives of carboxylic or carbonic acids
    • B01J31/0249—Ureas (R2N-C(=O)-NR2)
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C201/06—Preparation of nitro compounds
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
    • C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
    • C07C45/36—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in compounds containing six-membered aromatic rings
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/385—Saturated compounds containing a keto group being part of a ring
    • C07C49/417—Saturated compounds containing a keto group being part of a ring polycyclic
    • C07C49/423—Saturated compounds containing a keto group being part of a ring polycyclic a keto group being part of a condensed ring system
    • C07C49/453—Saturated compounds containing a keto group being part of a ring polycyclic a keto group being part of a condensed ring system having three rings
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    • C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
    • C07C49/657—Unsaturated compounds containing a keto groups being part of a ring containing six-membered aromatic rings
    • C07C49/665—Unsaturated compounds containing a keto groups being part of a ring containing six-membered aromatic rings a keto group being part of a condensed ring system
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
    • C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/31—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting
    • C07C51/313—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting with molecular oxygen
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/29—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of oxygen-containing functional groups
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/30—Only oxygen atoms
    • C07D251/34—Cyanuric or isocyanuric esters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/323—Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C2603/58—Ring systems containing bridged rings containing three rings
    • C07C2603/70—Ring systems containing bridged rings containing three rings containing only six-membered rings
    • C07C2603/74—Adamantanes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

Definitions

  • the present invention relates to a catalyst useful for reactions such as oxidation, nitration, carboxylation, and carbon-carbon bond formation reaction, and a method for producing an organic compound using the catalyst.
  • the oxidation reaction is one of the most basic reactions in the organic chemical industry, various oxidation methods have been developed.
  • the preferred oxidation method is a catalytic oxidation method using molecular oxygen or air directly as oxidant.
  • the catalytic oxidation method usually requires high temperature and high pressure to activate oxygen, and requires reaction in the presence of a reducing agent such as aldehyde to react under mild conditions. is there. Therefore, it has been difficult to easily and efficiently produce alcohols and carboxylic acids under mild conditions using the catalytic oxidation method.
  • nitration of lower hydrocarbons such as methane and ditan is performed at a high temperature of 250 to 300 ° C using nitric acid and nitrogen dioxide.
  • nitric acid and nitrogen dioxide a mixture of nitric acid and sulfuric acid
  • this method requires the use of large amounts of high concentrations of strong acids. Also, little is known about a method for directly introducing a carboxyl group into hydrocarbons under mild conditions.
  • JP-A-8-38909 and JP-A-9-327626 disclose an imid having a specific structure as a catalyst for oxidizing an organic substrate with molecular oxygen.
  • an oxidation catalyst comprising an oxide compound or the above-mentioned imide compound and a transition metal compound.
  • Japanese Patent Application Laid-Open (JP-A) No. 11-239,730 discloses that, in the presence of the imide compound, a substrate and a mixture of (i) nitrogen oxides and (ii) carbon monoxide and oxygen are selected.
  • a method is disclosed in which at least one type of functional group selected from a nitrogen group and a carboxyl group is introduced into a substrate by contacting at least one type of reactive agent.
  • WO 358 / 35,35 is reacted with two compounds in the presence of a specific imid compound and a radical generator for the imid compound, and is added by a radical mechanism.
  • a method for producing a substitution reaction product or an oxidation product thereof is disclosed. According to the method using these imido compounds as catalysts, under relatively mild conditions, a hydroxyl-containing group such as a hydroxyl group, a nitro group or a carboxyl group can be introduced into the substrate, It is possible to form a single carbon bond.
  • the yield of the target compound, the stability of the catalyst, the amount of the catalyst used, and the like were not always satisfactory. Disclosure of the invention
  • an object of the present invention is to provide a catalyst capable of producing an organic compound with a high selectivity and a high yield by an addition or substitution reaction under mild conditions, and a method for producing an organic compound using the same. .
  • Another object of the present invention is to introduce an oxygen atom-containing group into an organic substrate under mild conditions.
  • An object of the present invention is to provide a catalyst that can be used and a method for producing an organic compound using the catalyst.
  • Still another object of the present invention is to provide a catalyst which is excellent in stability and can maintain catalytic activity for a long time.
  • Another object of the present invention is to provide a radical reaction catalyst that exhibits high catalytic activity in a small amount.
  • Still another object of the present invention is to provide a novel cyclic acyl peryl compound having the above-mentioned characteristics and useful as a catalyst.
  • the present inventors have conducted intensive studies in order to achieve the above object.As a result, when a compound capable of generating a radical and a radical-scavenging compound are reacted in the presence of a cyclic acylpurea-based compound having a specific structure, under mild conditions, The present inventors have found that a corresponding addition or substitution reaction product or a derivative thereof can be obtained, and completed the present invention.
  • R represents a hydrogen atom or a protecting group for a hydroxyl group
  • G represents a carbon atom or a nitrogen atom.n represents 1 or 2, and when n is 2, two Gs may be the same. May be different,
  • a catalyst comprising a cyclic acetyl perea-based compound having a cyclic acetyl perea skeleton represented by the formula:
  • R represents a hydrogen atom or a protecting group for a hydroxy group.
  • RR 4 is the same or different and is a hydrogen atom, an alkyl group, an aryl group, a cycloalkyl group, or a protecting group which may be protected by a protecting group.
  • a substituted oxycarbonyl group, an acyl group or an acyloxy group At least two of R 1 , R 2 , R 3 , and R 4 are bonded to each other to form a double bond or an aromatic or non-aromatic ring together with the atoms constituting the ring in the formula. R 2 and R 3 may together form an oxo group.
  • the compound represented by is included.
  • cyclic acyl perea-based compound examples include a compound represented by the following formula (la)
  • R, R 5 , and R s are the same or different and each represent a hydrogen atom or a hydroxyl-protecting group
  • the catalyst is a combination of a cyclic acetyl perea compound and a metal compound. It may be composed of
  • (A) a compound capable of generating a radical and (B) a radical-scavenging compound are reacted in the presence of the catalyst to form the compound (A) with the compound (B).
  • a method for producing an organic compound which comprises producing an addition or substitution reaction product or a derivative thereof.
  • (A) capable of generating a radical (A1) a compound containing a heteroatom having a carbon-hydrogen bond adjacent to a heteroatom, (A2) a compound having a carbon-to-carbon double bond, ( (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) a conjugated compound, (A7) an amine, A compound selected from (A8) an aromatic compound, (A9) a linear alkane, and (A10) an olefin can be used.
  • the radical scavenging compound (B) is selected from (B1) an unsaturated compound, (B2) a compound having a methine carbon atom, (B3) a compound containing a hetero atom, and (B4) a reactant containing an oxygen atom.
  • the used compounds can be used.
  • the oxygen atom-containing reactant (B4) includes oxygen, carbon monoxide, nitrogen oxide, sulfur oxide, nitric acid or nitrous acid, or a salt thereof.
  • the reaction between the radical-generating compound (A) and the radical-scavenging compound (B) includes, for example, an oxidation reaction, a carboxylation reaction, a nitration reaction, a sulfonation reaction, a coupling reaction, or a combination thereof. Can be illustrated.
  • the present invention also provides the following formula (lb) o
  • R 7 , R 8 and R 9 are the same or different and are each a hydrogen atom or the following formula (1,
  • R x represents an alkyl group, an anoreckeninole group, a cycloalkynole group, an aryl group, or an aralkyl group].
  • At least one of R 7 , R 8 and R 9 represents an acyl group represented by the formula (lc)).
  • the “addition or substitution” reaction is used in a broad sense including oxidized and sulfonated.
  • the cyclic acyl perylene compound also includes a salt thereof (eg, an alkali metal salt, an alkaline earth metal salt, and the like).
  • This cyclic acetyl perea compound may have a plurality of cyclic acetyl perea skeletons represented by the formula (I) in the molecule.
  • the cyclic acylarea compound of the formula (I) has a portion (N-oxycyclic acylaurea skeleton) other than R in the cyclic acylarea skeleton represented by the formula (I). A plurality of them may be linked via R.
  • the atom G constituting the cyclic acyl perylene skeleton and the nitrogen atom bonded to the G may have various substituents, and the cyclic acyl perrea skeleton has a non-aromatic or aromatic ring. May be condensed. Further, the cyclic isperyl skeleton may have a double bond in the ring.
  • hydroxy-protecting group for R a hydroxy-protecting group commonly used in the field of organic synthesis can be used.
  • a protecting group include an alkyl group (for example, a C alkyl group such as a methyl or butyl group), an alkenyl group (for example, an aryl group), a cycloalkyl group (for example, a cyclohexyl group).
  • Aryl group for example, 2,4-dinitrophenyl group
  • aralkyl group for example, benzyl, 2,6-dichlorobenzene, 3-bromobenzinole, 2-nitrobenzyl, triphenylmethyl group, etc.
  • Substituted methyl groups for example, methoxymethinole, methinorethiomethyl, benzylinoleoxymethinole, savetoxmethyl, 2-methoxetoxymethinole, 2,2,2—trichloromouth ethoxymethinole, bis (2 —Cross-ethoxy) methyl, 2— (trimethylsilyl) ethoxymethyl group, etc.
  • 1-ethoxyquinonele 1-methinocinole 1-methoxinetinole, 1-isopropoxinetinole, 2,2,2-trichloroethyl, 2-methoxinetyl group, etc.
  • tetrahidrobilanyl group tetrahidrofurael
  • 1-hydroxylalkyl groups eg, 1-hydroxyl, 1-hydroxyhexyl, 1-hydroxydecyl, 1-hydroxyhexadecyl, 1-hydroxyl 1-phenylmethyl group, etc.
  • a group capable of forming an acetal or hemiacetal group with a group an acyl group (eg, formyl, acetinole, propionyl, butylinole, isobutylinole, valle renole, vivaloyl, hexanoinole, heptanoinole, otanoinole, nonanoinole, decananoinole Inore, Lauroyl, Miris Toinole, No ,.
  • an acyl group eg, formyl, acetinole, propionyl, butylinole, isobutylinole, valle renole, vivaloyl, hexanoinole, heptanoinole, otanoinole, nonanoinole, decananoinole Inore, Lauroyl, Miris Toinole, No ,
  • Aliphatic saturated or unsaturated acyls such as C-aliphatic acyls such as Lumi Toinole and Stearonole; acetoacetinole; cyclopentanecanoleboninole, cyclohexancanoleboninole, and other cyclic carbonyls
  • Alicyclic acyl groups such as benzoyl and naphthoinole groups, etc., sulfonole groups (methansulfone diolenes, ethanesolelegnoninole, trifnorolelometanesolelehoninele, benzenesolelenonyl, p-tonolene sulphoninole, naphthalene solephoninole group, etc., anorecoxycanoleboninole group (for example, methoxyl / reponinole, ethoxycanolebonyl, t-butoxycarbonyl group,
  • the R may be, for example, oxalyl, Polyvalent carboxylic acid groups such as malonyl, succinyl, glutarinole, aziboyl, phthalinole, isophthaloinole, terephthaloyl; carbonyl; methylene, ethylidene, isopropylidene, cyclopentylidene, cyclohexylidene, benzylidene, etc.
  • Hydrocarbon group (particularly, a group that forms an acetal bond with two hydroxyl groups).
  • Preferred R includes, for example, a hydrogen atom; a group capable of forming an acetal or hemiacetal group with a hydroxyl group; an acid such as a carboxylic acid, a sulfonic acid, a carbonic acid, a sulfuric acid, a phosphoric acid, a boric acid, and a boric acid; And a hydrolyzable protecting group which can be eliminated by hydrolysis, such as a group obtained by removing an OH group from the above (such as an acyl group, a snolephonyl group, an alkoxycarbonyl group, and a carbamoyl group).
  • R is a hydrogen atom; an unsubstituted or substituted Ci- 4 aliphatic acetyl group such as acetyl, propionyl, and butyryl; a substituent on the aromatic ring such as benzoyl, naphthyl, and phenylacetyl groups.
  • the cyclic acylprea skeleton represented by the formula (I) has a 3-hydroxy (or 3-substituted oxy) hydantoin skeleton represented by the following formula (la) and a 4-hydroxy skeleton represented by the formula (lb).
  • Droxy (or 4-substituted oxy) 1-1,2,4—triazolidin-1,3,5-dione skeleton [4-hydroxy (or 4-substituted oxy) 1-1,2,4_triazolin-1 3,5 -Including a dione skeleton], a 3-hydroxy (or 3-substituted oxy) -11,3-diazine-12,4-dione skeleton represented by the formula (Ic) [Hexahydr-1-1-1 Si (or 1-substituted oxy) 1,1,3-diazine-1,2,4,6-trion skeleton, hexahydro 1, 3-dihydroxy (or 1,3-bissubstituted oxy) 1,3 Diazine- 1, 2, 4, 6-trion skeleton, 3-hydroxy (or 3-substituted oxy) peracyl skeleton And a 4-, hydroxy (or 4-substituted oxy) -11,2,4-triazine-1,3,5-dione ske
  • hydroxy-1—hydroxy (or 1-substituted oxy) -11,3,5—triazine-12,6 represented by the formula (1) — Dione compounds.
  • R in the formula (1) is the same as R in the formula (I).
  • the alkyl group in R ⁇ includes, for example, methyl, ethyl, propynole, isopropynole, butynole, isobutynole, s-puthynole, t-butynole, hexyl, decyl, dodecyl, tetradecyl, hexadecyl and the like.
  • the aryl group includes phenyl, torinole, xylinole, and naphthyl groups
  • the cycloalkyl group includes cyclopentyl and cyclohexyl groups.
  • the protecting group for the hydroxyl group include those described above.
  • Examples of the carboxyl-protecting group include protecting groups commonly used in the field of organic synthesis such as alkoxy groups (for example, methoxy, ethoxy, butoxy, etc.).
  • C 6 alkoxy group, etc. C 6 alkoxy group, etc.
  • cycloalkyloxy group aryloxy group (eg, phenoxy group, etc.) aralkyloxy group (eg, benzyloxy group, etc.), trialkylsilyloxy group (eg, trimethylsilyloxy group, etc.), substituent (For example, an amino group; a mono- or di-C! -6 alkylamino group such as a methylamino group and a dimethylamino group); and the like.
  • acyl group examples include formyl, acetyl, propionyl, butylinole, isop'tilinole, linolein, linolein, hexanoinole, heptanolyl, octanoyl, nonanoyl, decanoyl, lauroyl, myristyl.
  • C! -3 such as palmitoyl and stearoyl groups.
  • Aliphatic Ashiru group (particularly, c WINCH 2 aliphatic Ashiru group.) And aliphatic saturated or unsaturated Ashiru group; ⁇ Se Tasechiru group; cyclopentane Kano levo Nino les, consequent opening Al force down such Kisankanoreboni Le group cycloheteroalkyl
  • Alicyclic acyl groups such as carbonyl groups; aromatic acyl groups such as benzoyl and naphthoyl groups;
  • Alkyl group in RR 3, ⁇ Li Lumpur group, a cycloalkyl group, in the ⁇ shea group, the R ', the same alkyl group for R are exemplified.
  • the halogen atoms in R 2 and R 3 include iodine, bromine, chlorine and fluorine atoms.
  • Alkoxy groups include, for example, 1 to 3 carbon atoms such as methoxy, ethoxy, isopropoxy, butoxy, t-butoxy, hexyloxy, octyloxy, decyloxy, dodecyloxy, tetradecyloxy, octadecyloxy and the like. About 0 (particularly about 1 to 20 carbon atoms) alkoxy groups are included.
  • Substituted oxycarbonyl groups include, for example, methoxycarbonyl, ethoxycanoleboninole, isopropoxy phenol, butoxycanoleboninole, t-one Butoxycanolepo'Ninole, Hexinoleoxycanoleponinole, Heptinoleoxycanolebonyl, Octyloxycanoleponyl, Decyloxycarbonyl, Dodecyloxycarbonyl, Tetradecyloxycarbonyl, To C 130 alkoxy carbonyl group (especially C 0 alkoxy monocarbonyl group) such as xadecyloxycanoleponinole, octadecyloxycarbonyl group, etc .; pentopenyloxycanoleboninole, Cycloalkyloxy group olevonyl group such as levoninole group (especially 3- to 20-membered cycloalkynoleoxycarbonyl group
  • -Asyloxy groups include, for example, formyloxy, acetyloxy, propioninoleoxy, butylinoleoxy, isobutylyl / reoxy, valerinolexy, vivaloyloxy, hexanoyloxy, heptanoylenoxy, octanoyloxy, oxynanolyl, oxynanolyl, oxynanoloxy, and nonoxyloxy.
  • C 1-3 such as, myristoyloxy, norremityloxy, stearoyloxy groups.
  • Aliphatic saturated or unsaturated acyloxy group such as aliphatic acyloxy group (especially CL-2; aliphatic acyloxy group); acetate cinoleoxy group; cycloalkane such as cyclopentanecanoleponinoleoxy and cyclohexanecagrebonyloxy group
  • Aliphatic siloxy groups such as carbonyloxy groups
  • aromatic siloxy groups such as benzoyloxy and naphthoyloxy groups.
  • R 1 , R 2 , R 3 and R 4 are bonded to each other to form a ring represented by the formula (carbon atom and / or nitrogen atom). Double bond or aromatic or non-aromatic ring And R 2 and R 3 may together form an oxo group.
  • Preferred aromatic or non-aromatic rings are 5- to 12-membered rings, especially hydrocarbon rings of about 6 to 10-membered rings (including condensed carbocycles and bridged carbons) or heterocycles (. Ring and bridged heterocyclic ring).
  • Such a ring is, for example, an anoalkyl group, a haloalkyl group, a hydroxyl group, an alkoxy group, a canoleboxyl group, a substituted oxycarbonyl group, an acyl group, an acyloxy group, a nitro group, a cyano group, an amino group, a halogen atom And the like.
  • the protecting group for the hydroxy group and the preferred protecting group for R 5 and R s are the same as those described above for the hydroxy group for R.
  • at least one of R 7 , R 8 and R 9 represents an acyl group represented by the formula (lc).
  • the alkyl group for R ′ includes, for example, methyl, ethyl, propynole, isopropyl, butyl, isobutyl, s-butynole, t-butyl, hexinole, decinole, dodecyl, te About 1 to 2 ⁇ carbon atoms such as toradecyl and hexadecyl groups (preferably Or about 1 to 6 carbon atoms).
  • the alkenyl group includes an alkenyl group having about 2 to 20 carbon atoms (preferably, about 2 to 6 carbon atoms) such as bier, 1-propenyl, and aryl groups, and a cycloalkyl group includes cyclopentyl. And a cycloalkyl group having about 3 to 20 carbon atoms (preferably about 5 to 8 carbon atoms) such as a cyclohexyl group.
  • the aryl group includes an aryl group having about 6 to 20 carbon atoms (preferably, about 6 to 14 carbon atoms) such as phenyl, tolyl, xylyl, and naphthyl groups.
  • 1,3,5-triacetoxy-hexahydro 1,3,5-triazine-2,4,6-trion is particularly preferred.
  • cyclic acyladiarea-based compounds include, for example, 3-hydroxyhydantoin, 1,3-dihydroxyhydantoin, 3-hydroxy-1-methylhydantoin, 3-acetoxyhydantoin, 1,3— Formulas such as diacetoxyhydantoin, 3—acetoxy-1 1—methylhydantoin, 3—benzoinoleoxyhydantoin, 1,3—bis (benzoyloxy) hydantoin, and 3—benzoyloxy_1-methylhydantoin
  • HexahydroDraw 5 Hydroxy-1, 2,3—Trimethyl-1, 2 , 3,5—Tetrazine-4,6-dione, 5-acetoxyhexahydro 1,2,3,5—Tetrazine-1,4,6-dione, 5-acetoxyhexahi Draw 1, 2, 3—trim Chill 1,2,3,5—Tetrazine-1,4,6-dione, 5-benzoyloxyhexaDraw 1,2,3,5—Tetrazine-1,4,6-dione, 5-benzoinoleoxy-1-hexahi Examples thereof include compounds having a skeleton represented by the formula (If), such as 1,1,2,3-trimethino 1,1,2,3,5-tetrazine-14,6-dione.
  • a skeleton represented by the formula (If) such as 1,1,2,3-trimethino 1,1,2,3,5-tetrazine-14,6-dione.
  • R is a hydrogen atom among the cyclic acyl perea compounds
  • compounds in which R is a protecting group for a hydroxyl group can be prepared by introducing a conventional protecting group into a compound in which R is a hydrogen atom (N-hydroxy compound). Thus, it can be prepared by introducing a desired protecting group.
  • the cyclic acetyl-rea compound having a cyclic acryl-rea structure represented by the formula (I) can be used alone or in combination of two or more.
  • the cyclic acyl peria compound may be formed in a reaction system.
  • a cyclic acyl-urea-based compound having a cyclic acyl-urea skeleton represented by the formula (I) and an imido-based compound can be used in combination.
  • Examples of the imide compounds include N-hydroxyphthalimid, N-hydroxysuccinic imid, N-hydroxydaltarimide, and N-hydroxy-1,8-naphthalene range Carboxylic acid imido, N-hydroxy-1,2,3-naphthalenedicarboxylic acid imid, N, N'-Dihydroxypyrromelite Acid diimide, N, N-dihydroxy 1,8; 4,5-naphthalene-tetracarboxylic acid diimide, N, N'-dihydroxy-l 2,3; 6,7-naphthalene-tetracarboxylic acid diimide An N-hydroxy cyclic imide compound such as a compound (for example, a compound described in Japanese Patent Application Laid-Open No.
  • the hydroxy group of the N-hydroxy cyclic imide compound is an acyl group Imine having an N-substituted cyclic imido skeleton such as a compound protected with a protecting group (for example, an acetyl group or the like) or the like (for example, those exemplified as the protecting group for the hydroxy group in R above).
  • a protecting group for example, an acetyl group or the like
  • the amount of the cyclic acyl peria compound used can be selected in a wide range, for example, 0.001 to 0.001 to 1 mol, preferably 0.00 to 1 mol per 1 mol of the reaction component (substrate). It is about 0.1 to 0.5 mol, more preferably about 0.001 to 0.4 mol, and often about 0.001 to 0.35 mol.
  • a co-catalyst can be used together with the cyclic acyl perylene compound.
  • the co-catalyst include a metal compound.
  • the metal element constituting the metal compound is not particularly limited, but a metal element belonging to Groups 1 to 15 of the periodic table is often used. Note that, in this specification, boron B is also included in the metal element.
  • a periodic table group 1 element Na, K, etc.
  • a group 2 element Mg, Ca, Sr, Ba, etc.
  • a group 3 element Sc, lanthanide element
  • Actinide elements, etc. Group 4 elements (Ti, Zr, Hf, etc.), Group 5 elements (V, etc.), Group 6 elements (Cr, ⁇ Vio, W, etc.), Group 7 elements ( Mn, etc.), Group 8 elements (Fe, Ru, etc.), Group 9 elements (C 0, Rh, etc.), Group 10 elements (N 1, P d, Pt, etc.), Group 11 elements (Cu, etc.), Group 12 elements (Zn, etc.), Group 13 elements (B, A1, In, etc.), Group 14 elements (Sn, Pb) And group
  • Preferred metal elements include transition metal elements (groups 3 to 12 elements of the periodic table). Among these, elements of the Periodic Tables 5 to 11 and especially elements of the Groups 5 to 9 are preferable, and particularly, Zr, V, Mo, Mn, and Co are preferable.
  • the activity may be improved by the combined use of a transition metal element and a Group 1 or 2 element in the periodic table.
  • the valence of the metal element is not particularly limited and is, for example, about 0-6.
  • the metal compound examples include simple substances, hydroxides, oxides (including composite oxides), halides (fluoride, chloride, bromide, iodide), oxo acid salts (for example, nitrate, Inorganic compounds such as sulfates, phosphates, borates, carbonates, etc., salts of isopoly acids, salts of heteropoly acids; organic-acid salts (eg, acetates, propionates, cyanates, naphthenic acids) Organic compounds such as salts, stearate and the like.
  • the ligands constituting the complex include OH (hydroxy), alkoxy (such as methoxy, ethoxy, propoxy, butoxy), acyl (such as acetyl, propioninole), and anorecoxycano.
  • Reboninore main Tokishikarubo two Honoré, etc.
  • Cobalt compounds include cobalt hydroxide, cobalt oxide, cobalt chloride, cobalt bromide, cobalt nitrate, cobalt nitrate, cobalt sulfate, and phosphoric acid.
  • Inorganic compounds such as cobalt; Coba acetate Organic acid salts such as noreto, cobalt naphthenate, and cobalt stearate; and divalent or trivalent cobalt compounds such as complexes such as konole acetoacetyl acetate.
  • vanadium compounds include inorganic compounds such as vanadium hydroxide, vanadium oxide, vanadium chloride, vanadyl chloride, vanadium sulfate, vanadyl sulfate, and sodium vanadate; Examples thereof include divalent to pentavalent vanadium compounds such as a complex such as acetyl acetonato.
  • examples of sodium compounds include inorganic compounds such as sodium, sodium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium chloride, sodium sulfate, and the like. (Including simple metals); organic compounds such as sodium methoxide, sodium ethoxide, sodium acetate, sodium benzoate, and sodium p_toluenesulfonate.
  • zirconium compounds include zirconium oxyacetate.
  • the compound of another metal element include a compound corresponding to the above-mentioned cobalt compound, vanadium compound, sodium compound or zirconium compound.
  • the metal compounds can be used alone or in combination of two or more. In particular, the combination of a covanolate compound with a manganese compound, and in some cases, a zirconium compound, often significantly improves the reaction rate. It is also preferable to use a combination of a plurality of metal compounds having different valences (for example, a divalent metal compound and a trivalent metal compound).
  • a transition metal element compound such as a cobalt compound and a group 1 element or a group 2 element of the periodic table are used as the metal compound.
  • a high catalytic activity can be obtained even in a reaction in a non-acidic solvent or non-protonic solvent, and the reaction between the substrate and the catalyst can be suppressed.
  • the amount of the metal compound used is, for example, The amount is 0.0001 to 10 moles, preferably about 0.05 to 3 moles, per 1 sample.
  • the amount of the metal compound used is, for example, 0.0001 mol 0 / mol per reaction component (substrate). ⁇ 1 0 mole 0/0, preferably 0. 1 mol% to 5 mol 0 /. It is about.
  • a polyatomic cation or anion and a counter ion 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.
  • the organic salt as a promoter, the reaction rate and the selectivity of the reaction can be improved.
  • the Group 15 elements of the periodic table include N, P, As, Sb, and Bi.
  • Group 16 elements in the periodic table include ⁇ , S, Se, Te, and the like.
  • Preferred elements include N, P, As, Sb, and S. In particular, N, P, and S are preferred.
  • the organic group bonded to the atom of the element includes a hydrocarbon group which may have a substituent, a substituted oxy group, and the like.
  • the hydrocarbon group include methyl, ethynole, propynole, isopropynole, butynole, isobutynole, s-butynole, t-butyl, pentyl, hexyl, octyl, decyl, tetradecinole, hexadecyl, octadecyl, and allyl.
  • hydrocarbon groups include alkyl groups having about 1 to 30 carbon atoms, aromatic hydrocarbon groups having about 6 to 14 carbon atoms (particularly, phenyl or naphthyl).
  • the substituted oxy group includes an alkoxy group, an aryloxy group, an aralkyloxy group and the like.
  • organic salt examples include organic ammonium salts such as organic ammonium salts, organic phosphonium salts, and organic sulfonium salts.
  • organic ammonium salts include tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, tetrahexylammonium chloride, and triotachi.
  • Quaternary ammonium chlorides such as trimethylammonium chloride, triethylammonium chloride, tributyl (hexadecyl) ammonium chloride and di (octadecyl) dimethylammonium chloride
  • quaternary ammonium salts such as quaternary ammonium bromide and the corresponding quaternary ammonium bromide; a quaternary ammonium salt in which four hydrocarbon groups are bonded to a nitrogen atom; And quaternary ammonium salts.
  • organic phosphonium salt examples include tetramethylphosphonium chloride, tetrabutylphosphonium chloride, tributyl (hexadecyl) phosphonium chloride, and triethylphenylphosphonyl chloride.
  • examples include quaternary phosphonium chlorides such as dimethyl chloride and quaternary phosphonium salts in which four hydrocarbon groups are bonded to a phosphorus atom, such as the corresponding quaternary phosphonium bromide.
  • organic sulfonium salts include, for example, triethylsulfonimide, and ethyldiphenylsulfonimide.
  • organic salt examples include alkyl sulfonates such as methanesulfonate, ethanesulfonate, octanesulfonate, and dodecanesulfonate. (e.g., C 6 8 alkyl sulfonate);.
  • benzenesulfonate, p - toluenesulfonate, naphthalate Rensuru Hong salts, Deshirubenze Nsuruhon salts are substitution with an alkyl group such as dodecyl benzene sulfonate which may be ⁇ Li one Rusuruhon salts (e.g., C 6 - 1 8 alkyl one ⁇ reel sulfonate); sulfonic acid type ion exchange resins (ion exchangers); phosphonic acid type ion exchange resins (ion exchangers) Is also included.
  • the amount of the organic salt to be used is, for example, about 0.01 to 0.1 mol, preferably 0.05 to 0 to 0.08 mol, per mol of the cyclic acylurea compound. It is about a mole.
  • a strong acid for example, a compound having a pKa of 2 (25 ° C.) or less
  • Preferred strong acids include, for example, hydrogen halide, hydrohalic acid, sulfuric acid, heteropoly acids, and the like.
  • the amount of the strong acid to be used is, for example, about 0.01 to 3 moles per 1 mole of the cyclic isperyl compound.
  • a compound having a carbonyl group to which an electron-withdrawing group is bonded can be used as a promoter.
  • Representative examples of compounds having a carbonyl group to which an electron-withdrawing group is bonded include hexafluoroacetone, triphenylenoacetoacetic acid, pentaphnoleolopheninole (methinole) ketone, and pentaphnoleolophenyl ( Trifonoleolomethinole) Ketones and benzoic acid.
  • the amount of the compound to be used is, for example, about 0.001 to 3 mol per 1 mol of the reaction component (substrate).
  • a radical generator (a radical polymerization initiator is added to the system).
  • a radical reaction accelerator Such components include, for example, halogens (chlorine, bromine, etc.), peracids (peracetic acid, m-chloroperbenzoic acid, etc.), peroxides (hydrogen peroxide; dibenzoylperoxide, t —Organic peroxides such as butynolephine dropoperoxide (TBHP), cumoxide, peroxyl, lauroyl baroxide, etc .; nitric acid or nitrous acid or salts thereof; aldehydes such as nitrogen dioxide, benzaldehyde; Ketones such as lohexanone; and azo compounds such as 2,2'-azobisisobutyronitrile (AIBN) and azobisisovaleronitrile.
  • the presence of these components in the system may accelerate the reaction.
  • the amount of the component to be used is, for example, about 0.00
  • an acid anhydride may be present in the system.
  • the acid anhydrides include aliphatic monocarboxylic anhydrides such as acetic anhydride and propionic anhydride; aromatic monocarboxylic anhydrides such as benzoic anhydride; aliphatic polyhydric acids such as succinic anhydride and maleic anhydride.
  • the amount of the acid anhydride to be used is, for example, from 0.01 mol to the amount of the solvent based on 1 mol of the reaction component (substrate).
  • the catalyst of the present invention is useful, for example, as a radical reaction catalyst.
  • the catalyst of the present invention not only exhibits the same kind of catalytic action as to the reaction in which an N-hydroxycyclic imide compound such as N-hydroxyphthalimide exhibits a catalytic action, but also the above-mentioned N-hydroxycyclic imide. Compared to mid-compounds, (i) exhibits high catalytic activity in small amounts, and (ii) maintains catalytic activity for a long time You. Therefore, the catalyst of the present invention can be applied to all reactions in which the N-hydroxy cyclic imide compound exhibits a catalytic action, and is more effective than when the N-hydroxy cyclic imide compound is used as a catalyst. But also great benefits.
  • reaction in which the catalyst of the present invention exhibits a catalytic action include the reactions described in the following literature relating to the N-hydroxy cyclic imide compound catalyst.
  • JP-A-8-38909, JP-A-9-326276, JP-A-10-286647, JP-A-10-316166 Japanese Patent Application Laid-Open No. H10-309469, Japanese Patent Laid-open No. Hei 10-3161625, Japanese Patent Laid-open No. Hei 11-23997, Japanese Patent Laid-open No. Hei 10 Japanese Patent Application Laid-Open No. 315043, Japanese Unexamined Patent Publication No. Hei 11-114, Japanese Unexamined Patent Publication No.
  • a reaction between (A) a compound capable of generating a radical and (B) a radical-scavenging compound is performed.
  • a reaction product of the compound (A) and the compound (B) or a derivative thereof can be produced.
  • 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, and typical examples thereof include (A1) a carbon atom adjacent to a hetero atom. Heteroatom-containing compound having hydrogen bond, (A2) Compound having carbon-heteroatom double bond, (A3) Compound having methine carbon atom, (A4) Carbon-hydrogen bond adjacent to unsaturated bond (A5) non-aromatic cyclic hydrocarbon, (A6) conjugated compound, (A7) amines, (A8) aromatic compound, (A9) linear alkane, and (A1 G) orefin And the like.
  • These compounds may have various substituents as long as the reaction is not inhibited.
  • substituents 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, and a substituted group.
  • the compound (A) capable of generating a radical functions as a radical-donating compound in this reaction.
  • hetero atom-containing compound (A1) having a carbon-hydrogen bond at the position adjacent to the hetero atom examples include (A1-1) a primary or secondary alcohol or a primary or secondary thiol, and (A1- 2) an ether having a carbon-hydrogen bond adjacent to the oxygen atom or a sulfide having a carbon-hydrogen bond adjacent to the sulfur atom; (A1-3) an acetate having a carbon-hydrogen bond adjacent to the oxygen atom (Including hemiacetal) or thioacetal having a carbon-hydrogen bond adjacent to the sulfur atom (including theohemiacetal).
  • the primary or secondary alcohol in the above (A1-1) is , Contains a wide range of alcohol.
  • the alcohol may be any of mono-, di- or polyhydric alcohols.
  • Typical primary alcohols are methanol, ethanol, 1-propanol, 1-butanol, 2-methino 1 1-propano, 1 pentano, 1-hexano, 1-octano, 1 1 to 30 (preferably 1 to 2) carbon atoms such as —decanonore, 1—hexadenole, 2-butene-1-oneole, ethylene glycol cornole, trimethylene glycol, hexamethylene glycol cornole, and pentaerythritol.
  • a typical secondary alcohol is 2-prono.
  • aliphatic hydrocarbon groups and alicyclic hydrocarbons such as cycloalkyl groups
  • the carbon atoms to which the hydroxy groups are bonded such as pentynoleethanol and 1-cyclohexynoleethanol, are used.
  • cyclobutano mono cyclopentano mono, cyclohexano nore, cyclo octanonor, cyclo dodecano mono, 2-cyclohexene 1-1 mono-norole, 2-adamantanol, hydroxy group at the bridgehead 3- to 20-members (preferably 3- to 15-members, more preferably 5- to 15-members) such as 2-adamantanol having 1 to 4 and 2-adamantanol having an oxo group on the adamantane ring.
  • saturated or unsaturated alicyclic secondary alcohols including bridged cyclic secondary alcohols
  • heterocyclic secondary alcohols such as 1_ (2-pyridyl) ethanol.
  • typical alcohols include 1-adamantane methanol,-methyl-1-adamantane methanol, ⁇ -ethinol 1-adamantan methanol, ⁇ ;-isopropynole 1-1-adamantane methanol, and 3-hydroxy-1- ⁇ .
  • Methinolone 1 Adamantane methanole, 3—Hydroxy 1 ⁇ —Methyl-1 adamantane methanole, 1-Methinole 3a—Perhydrodindenemethanol, ⁇ -Methyl-4a-decaline methanol, 8 a —Hydroxy ⁇ -Methynole 4a —Decalinmethanol, ⁇ —Methynole 4a 1 ⁇ 0 —Hydro Fnoleo Renme Tanole, Hymechinole 1 4a —No ⁇ ° Hydroan Thracenme Tanoole, ⁇ -Methylenole 8 a — Perhydric phenanthrene methanol, ⁇ — Le one 2- Application Benefits consequent b [...
  • Preferred alcohols include secondary alcohols (eg, aliphatic secondary alcohols such as 2-propanol and s-butyl alcohol; 1-cyclohexyl alcohols such as hexyl ethanol). family hydrocarbon group (for example, C alkyl group, C 6 - 1 4 etc. Ariru group) and non-aromatic carbocyclic group (e.g., C 1 5 cycloalkyl group or Shikuroa alkenyl group) and are attached Secondary alcohols; cyclopentano monocyclic, cyclohexanol, 2-adamantanol, etc. 3- to 15-membered alicyclic secondary alcohols; 1-Aromatic secondary alcohols, such as phenylethanol) , And alcohols having the above-mentioned bridged ring hydrocarbon group.
  • secondary alcohols eg, aliphatic secondary alcohols such as 2-propanol and s-butyl alcohol; 1-cyclohexyl alcohols such as hexy
  • Examples of the primary or secondary thiol in (Al-1) include thiols corresponding to the primary or secondary alcohol.
  • 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, dimethinol ether, getyl ether, zipper pill ether, diisopro pinoreeteneol, dibutinoleate Aliphatic ethers such as tenore, methinole ethenoleatenole, methinolebutinoleatenoetre, etinolebutinoreetenore, jarinoreete ter, methinolebininoleethenore, ethyla linolee ether, etc .; Aromatic ethers such as phenetole, dibenzyl ether, and phenyl benzyl ether; cyclic compounds such as dihydrofuran, tetrahydr
  • 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, an acetal derived from an aldehyde and an alcohol or an acid anhydride. Includes cyclic acetal and acyclic acetal.
  • aldehyde examples include aliphatic aldehydes such as formaldehyde, acetate aldehyde, propion aldehyde, butyl aldehyde, isobutyl aldehyde, pentanal, hexanal, and decanal; cyclopentane carbaldehyde; Alicyclic aldehydes such as mouth hexanecarbaldehyde; aromatic aldehydes such as benzaldehyde and phenylacetaldehyde; Examples of the alcohol include methanol, ethanol, and 1-prono.
  • aliphatic aldehydes such as formaldehyde, acetate aldehyde, propion aldehyde, butyl aldehyde, isobutyl aldehyde, pentanal, hexanal, and decanal
  • cyclopentane carbaldehyde Alicyclic aldehydes such as mouth
  • Typical acetals include 1,3-dioxolane compounds such as 1,3-dioxolane, 2-methyl-1,3-dioxolane, 2-ethyl-1,3-dioxolane; and 2-methyl-1,3-dioxane. 1,3-Dioxane compounds; dialkyl acetal compounds such as acetoaldehyde dimethyl acetal;
  • the thioacetal having a carbon-hydrogen bond at a position adjacent to a sulfur atom in the IJ-I (A1-3) is defined as a thioacetal corresponding to an acetal having a carbon-hydrogen bond at a position adjacent to the oxygen atom. Is mentioned.
  • the carbonyl group-containing compound (A2-1) includes ketones and aldehydes, and includes, for example, acetone, methylethylketone, methylisopropylketone, methylisobutinoreketone, methylenole s-ptynoleketone, and methylinole t-butylketone.
  • Examples of the thiocarbonyl group-containing compound (A2-2) include a thiocarbonyl group-containing compound corresponding to the above-mentioned carbonyl group-containing compound (A2-1).
  • Imines (A2-3) include: The carbonyl group-containing compound (A2-1) and an amine or an amine (for example, methylamine, ethylamine, propylamine, butylamine, hexinoleamine, benzylamine, cyclohexylamine, aniline) Hydramines such as hydrazine, O-methyl hydroxylamine and the like; hydrazines such as hydrazine, methinorehydrazine, phenylhydrazine and the like; Oxim ⁇ hydrazone).
  • the compound (A3) having a methine carbon atom includes (A3-1) a cyclic compound containing a methine group (that is, a methine carbon-hydrogen bond) as a ring constituent unit, and (A3-2) a methine carbon atom.
  • a chain compound having an atom is included.
  • the cyclic compound (A3-1) includes (A3-la) a bridged cyclic compound having at least one methine group, and a (A3-lb) non-aromatic cyclic compound having a hydrocarbon group bonded to the ring ( Alicyclic hydrocarbons, etc.).
  • 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.
  • Examples of the cyclic compound (A3-la) include, for example, .decalin, bicyclo
  • non-aromatic cyclic compound (A3-lb) having a hydrocarbon group bonded to the ring examples include 1-methinolecyclohexane, 1-methinolecyclohexane, limonene, menthen, menthol, carbomentone, An alicyclic hydrocarbon of about 3 to 15 members, such as a hydrocarbon, in which a hydrocarbon group having about 1 to 20 (preferably 1 to 10) carbon atoms (eg, an alkyl group) is bonded to a ring. And derivatives thereof.
  • a non-aromatic cyclic compound in which a hydrocarbon group is bonded to a ring is a chain compound having a methine carbon atom having a methine 'carbon atom at the bonding site between the ring and the hydrocarbon group ( A3 -2 )
  • A3 -2 is a tertiary carbon source
  • hydrocarbons having a substituent for example, isobutane, isopentane, isohexane, 3-methinolepentane, 2,3-dimethinolebutane, 2-methinolehexane, 3-methinolehexane, 3,4-dimethinolehexane, 3 —
  • Examples of the compound (A4) having a carbon-hydrogen bond adjacent to the unsaturated bond include (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. And (A4-2) a non-aromatic compound having a methyl group or a methylene group at a position adjacent to an unsaturated bond (for example, a carbon-carbon unsaturated bond, a carbon-oxygen double bond, etc.).
  • the aromatic ring may be any of an aromatic hydrocarbon ring and an aromatic heterocyclic ring.
  • Aromatic hydrocarbon rings include benzene rings and condensed carbocyclic rings (for example, naphtalene, azulene, indacene, anthracene, phenanthrene, triphenylene, triene, pyrene, etc.). And condensed carbocycles in which carbocycles are condensed.
  • aromatic heterocyclic ring examples include, for example, a complex ring containing an oxygen atom as a hetero atom (for example, a 5-membered ring such as furan, oxazole, and isooxazole, and a 6-membered ring such as 4-oxo-14H-pyran).
  • a complex ring containing an oxygen atom as a hetero atom for example, a 5-membered ring such as furan, oxazole, and isooxazole, and a 6-membered ring such as 4-oxo-14H-pyran).
  • Ring benzofuran, isobenzofuran, condensed ring such as 4-oxo-14H-chromene, etc.), and heterocyclic ring containing io atom as a hetero atom (for example, thiophene, thiazole, isothiazole, thiadiazole, etc.)
  • aromatic compound having a methyl group at the adjacent position of an aromatic ring examples include, for example, aromatic hydrocarbons in which about 1 to 6 methyl groups are substituted on the aromatic ring (for example, toluene, 4-chlorobenzene).
  • aromatic compound having a methylene group at the adjacent position of the aromatic ring examples include, for example, aromatic hydrocarbons having an alkyl group or a substituted alkyl group having 2 or more carbon atoms (eg, ethylbenzene, propylbenzene, 1,4-ethylbenzene, diphenyl-methane, etc.), alkyl groups having 2 or more carbon atoms or Is an aromatic heterocyclic compound having a substituted alkyl group (for example, 2-ethylfuran, 3-propylthiophene, 4-ethynolepyridine, 4-butylquinoline, etc.), a non-aromatic ring fused to an aromatic ring A compound having a methylene group at a site adjacent to the aromatic ring in the non-aromatic ring (dihydronaphthalene, indene, indane, tetralin, fluorene, acenaphthene, phenalene,
  • the non-aromatic compound (A4-2) having a methyl group or a methylene group adjacent to the unsaturated bond includes, for example, (A4-2a) a methyl group or a methylene group at the so-called aryl position.
  • examples thereof include linear unsaturated hydrocarbons and compounds having a methyl group or a methylene group at the adjacent position of (A4-2b) carbonyl group.
  • chain unsaturated hydrocarbons (A4-2a) examples include, for example, propylene, 1-butene, 2-butene, 1-pentene, 1-hexene, 2-hexene, 1,5— Examples thereof include linear unsaturated hydrocarbons having about 3 to 20 carbon atoms, such as xadiene, 1-octene, 3-otaten, and dendecatriene.
  • the compound (A4-2b) includes ketones (for example, chain ketones such as acetone, methylethylketone, 3-pentanone, and acetophenone; cyclic ketones such as cyclohexanone).
  • Carboxylic acids or derivatives thereof for example, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, phenylacetic acid, malonic acid, succinic acid, glutanoleic acid, and esters thereof.
  • the non-aromatic cyclic hydrocarbon (A5) includes (A5-1) cycloalkanes and (A5-2) cycloalkenes.
  • Cycloalkanes (A5-1) are compounds having a 3- to 30-membered cycloalkane ring, for example, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane , Siculo Nona , Cyclodecane, cyclododecane, cyclotetradecane, cyclohexadecane, cyclotetracosane, cyclotriacontane, and derivatives thereof.
  • Preferred cycloalkane rings include 5- to 30-membered, especially 5- to 20-membered, cycloalkane rings.
  • Cycloalkenes (A5-2) include 3- to 30-membered compounds having a cycloalkene ring, for example, cyclopropene, cyclobutene, cyclopentene, cyclooctene, cyclohexene, 1-methylenolecyclohexene, and isophorone. Cyclopentagenes such as cycloheptene and cyclododekaene, cycloalkadienes such as 1,3-cyclohexadiene, 1,5-cyclobutadiene, cycloalkadienes such as cyclooctatriene, and derivatives thereof Is included.
  • Preferred cycloalkenes include compounds having a 3- to 20-membered ring, especially a 3- to 12-membered ring.
  • the conjugated compound (A6) includes a conjugated diene (A6-1), a,) 3-unsaturated nitril (A6-2), a, -unsaturated carboxylic acid or a derivative thereof (for example, ester, And acid anhydrides) ( ⁇ 6-3).
  • conjugated diene ( ⁇ 6-1) examples include butadiene, isoprene, 2-butadiene, 2-ethylbutadiene and the like.
  • the conjugated diene (A6-1) includes a compound in which a double bond and a triple bond are conjugated, for example, bier acetylene and the like.
  • Examples of unsaturated trilinole (A6-2) include (meth) atalylonitrile.
  • Unsaturated carboxylic acid or its derivative (A6-3) includes (meth) acrylic acid; (meth) methyl acrylate, + (meth) acrylic acid ethyl ester, and (meth) acrylic acid.
  • (Meth) acrylic acid esters such as isopropyl acrylate, (meth) butyl acrylate, (meth) acrylic acid 12-hydroxyl, etc .; (meth) acrylamide, N-methyl Mouth (meta) acrylamide and the like (meta) acrylamide derivative.
  • Examples of the amines (A7) include primary or secondary amines, for example, methinoreamin, ethylamine, propylamine, butinoleamine, dimethylamine, getylamine, dibutylamine, ethylenediamine, 1, 4 Aliphatic amines such as butanediamine, hydroxylamine and ethanolanol; Alicyclic amines such as pen-pentylamine and silk-hexylamine; Aromatic amines such as benzylamine and toluidine; pyrrolidine, pyrididine And cyclic amines such as piperazine and indolin (an aromatic or non-aromatic ring may be condensed) and the like.
  • primary or secondary amines for example, methinoreamin, ethylamine, propylamine, butinoleamine, dimethylamine, getylamine, dibutylamine, ethylenediamine, 1, 4 Aliphatic amines such as butanediamine, hydroxyl
  • aromatic hydrocarbon (A8) examples include benzene, naphthalene, acenaphthylene, phenanthrene, anthracene, naphthacene, acethrylene, triphenylene, pyrene, tarisene, naphthacene, picene, and perylene.
  • Aromatic compounds having at least one benzene ring such as pentacene, coronene, pyranthrene, and ovalene, and preferably a condensed polycyclic ring in which at least two (for example, 2 to 10) benzene rings are condensed
  • aromatic hydrocarbons may have one or more substituents.
  • aromatic hydrocarbon having a substituent examples include, for example, 2-chloronaphthalene, 2-methoxynaphthalene, 1-methylinorenaphthalene, 2-methinorenaphthalene, 2-methinolenanethracene, 2-t-butylanthracene, Examples include 2-carboxyanthracene, 2-ethoxyethoxyvinylalanthracene, 2-cyanoanthracene, 2-nitroanthracene, and 2-methylpentalene.
  • the benzene ring may be condensed with a non-aromatic carbon ring, an aromatic hetero ring, or a non-aromatic hetero ring.
  • linear alkane (A9) examples include methane, ethane, and , Butane, pentane, hexane, heptane, octane, nonane, decane, dodecane, tetradecane, hexadecane, etc., having about 1 to 30 carbon atoms (preferably about 1 to 20 carbon atoms) linear alkane Is mentioned.
  • the olefins (A10) may be any of ⁇ -olefins and internal olefins which may have a substituent (for example, the above-mentioned substituents such as a hydroxyl group and an acyloxy group).
  • olefins having a plurality of carbon-carbon double bonds such as gen are also included.
  • 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-dimethinolate 2-butene, 3-hexene, 3-hexene 1 1-one, 2-hexene 1 1-ol, 1 1-otaten 1 3 -one 1—Heptene, 1 octene, 2—octene, 3—otaten, 4—otaten, 1 mononone, 2-nonene, 1—decene, 1—undecene, 1—dodecene, 1—hexadecene, 1—octadecene 1,5-hexadiene, 1,6-heptadiene, 1,
  • Ottata 21-, Hi-binene, 2-borene 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 in combination, and in particular, 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.
  • 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.
  • the radical scavenging compound (B) may be any compound that can generate a stable compound by reacting with a radical.
  • Typical examples of the compound include (B 1) an unsaturated compound, and (B 2) A compound having a methine carbon atom, (B3) a compound containing a hetero atom, and (B4) a reactant containing an oxygen atom (such as an oxygen atom-containing gas). These compounds may be used alone or in combination of two or more.
  • these compounds may have various substituents as long as the reaction is not inhibited.
  • substituents 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 unsubstituted rubamoyl 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, Examples include a heterocyclic group.
  • the unsaturated compound (B 1) includes a wide range of compounds having an unsaturated bond.
  • examples of such a compound include an unsaturated compound having an electron-withdrawing group at a position adjacent to a carbon-carbon unsaturated bond (an active unsaturated compound such as an active olefin (electron-deficient olefin)).
  • an active unsaturated compound such as an active olefin (electron-deficient olefin)
  • ] a compound having a carbon-carbon triple bond
  • B1-3 a compound having an aromatic ring
  • Tens, (B1-5) isocyanate or thiosinate compounds, (B1-6) inactive olefins and the like can be exemplified.
  • Examples of the active unsaturated compound (B1-1) include methyl (meth) acrylate, methyl (meth) acrylate, isopropanol (meth) atalinoleate, and phenyl (meth) acrylate.
  • Ketene (B1-4) includes ketene and 2-methylketene.
  • the isocyanate or thiocyanate compound (B1-5) includes methyl isocyanate, ethyl isocyanate, phenyl succinate, methyl thiosinate, methyl thiosinate, phenyl thiosinate, phenyl thiosinate, and the like.
  • the non-active orefin (B1-6) may be any of an ⁇ -olefin and an internal ore, and also includes an ore having a plurality of carbon-carbon double bonds such as gen.
  • Representative examples of non-activated orefins (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 —Otaten, 4 —Octene, 1 —Nonene, 1 —Decene, 1 —Dodecene, 1,5 —Hexadiene, 1,, 6-Chain olefins (alkenes) such as hebutadiene and 1,7-octadiene; cyclic olefins (cycloalkenes
  • Examples of the compound having a methine carbon atom ( ⁇ 2) include the compounds exemplified as the above (A3). In the reaction, the same compound may be used as the compound (A3) and the compound ( ⁇ 2).
  • the heteroatom-containing compound ( ⁇ 3) includes (B3-1) a compound having a zeo atom: ( ⁇ 3-2) a compound having a nitrogen atom, ( ⁇ 3-3) a compound having a phosphorus atom, ( ⁇ 3-4) )
  • Compounds having an oxygen atom are included.
  • Examples of the compound having a zeo atom ( ⁇ 3-1) include sulfides, thiols, and the like. Is mentioned.
  • 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 reactant (B4) includes an oxygen atom-containing gas, nitric acid or nitrous acid, or a salt thereof (hereinafter sometimes referred to as nitric acid).
  • the oxygen atom-containing gas includes those having a boiling point (or sublimation point) of 45 ° C. or less, and typical examples thereof include (B4-1) oxygen, (B4-2) Carbon monoxide, (B4-3) nitrogen oxides, (B4-4) sulfur oxides and the like. These oxygen atom-containing reactants can be used alone or in combination of two or more.
  • Oxygen (B4-1) may be either molecular oxygen or active oxygen.
  • the molecular oxygen is not particularly limited, and 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.
  • carbon monoxide (B4-2) pure carbon monoxide may be used, or one diluted with an inert gas may be used.
  • 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 N x ⁇ y (where X represents 1 or 2, and y represents an integer of 1 to 6). In this compound, when X is 1, y is usually an integer from 1 to 3, and when X is 2, y is usually an integer from 1 to 6.
  • nitrogen oxides As a representative example of a nitrogen oxide, N 2 ⁇ , NO, NO, NON ⁇ , N 2 ⁇ 5, NO 3, N 2 or the like ⁇ 6. These nitrogen oxides can be used alone or in combination of two or more. Nitrogen oxides are pure Or a mixture containing nitrogen oxides 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.
  • N 2 ⁇ 3 can be easily obtained by the reaction of nitrous oxide (N 2 ⁇ ) and nitrogen or nitric oxide (NO) with oxygen.
  • the yo Ri Specifically, by introducing the oxygen and nitrogen monoxide (or dinitrogen oxide) in cooled reaction ⁇ be prepared by forming a blue liquids N 2 ⁇ 3.
  • nitrogen oxide can be used together with oxygen.
  • it by the combination child and N0 2 and the oxygen product (e.g. two Toro compound) can be improved Ri by the yield of.
  • the sulfur oxide (B4-4) includes a compound represented by S P 1 (1 wherein p is 1 or 2, and q is an integer of 1 to 7.) In this compound, P When is 1, q is usually an integer from 1 to 4, and when p is 2, q is usually 3 or 7.
  • sulfur oxides e.g., SO, S 2_Rei 3, S_ ⁇ 2, S 0 3, etc. S 2_Rei 7, SO 4 and the like.
  • SO, S 2_Rei 3, S_ ⁇ 2, S 0 3, etc. S 2_Rei 7, SO 4 and the like can be used alone or in combination of two or more.
  • fuming sulfuric acid containing sulfur trioxide may be used as sulfur trioxide.
  • Preferred sulfur oxides include sulfur dioxide (so 2 ) and sulfur trioxide (S
  • Sulfur oxides containing at least one selected from (3) as a main component.
  • Sulfur oxides can also be used with oxygen.
  • Salts of nitric acid and nitrous acid include sodium salts and potassium salts such as alkali metal salts; magnesium salts, calcium salts and alkaline earth metal salts such as potassium salts; silver salts and aluminum salts. And other metal salts such as zinc salt.
  • Preferred salts include the alkali metal nitrates or nitrites.
  • Nitric acid may be supplied to the reaction system as it is, but can be supplied to the reaction system in the form of a solution such as an aqueous solution. They can also be produced in a reaction system and used for the reaction.
  • the reaction between the radical-generating compound (A) and the radical-scavenging compound (B) is carried out in the presence or absence of a solvent.
  • a solvent include organic acids such as acetic acid and propionic acid; nitriles such as acetonitril, propionitrile and benzonitrile; formamide, acetoamide, and dimethylformamide Amides such as methane (DMF) and dimethylacetamide; aliphatic hydrocarbons such as hexane and octane; carbon form, dichloromethane, dichloroethane, carbon tetrachloride, carbon benzene, trifluoromethylbenzene, etc.
  • Halogenated hydrocarbons nitro compounds such as benzene, nitromethane, nitroethane, etc .; esters such as ethyl acetate and butyl acetate; water; mixed solvents thereof.
  • Organic solvents such as acetic acid, nitriles such as acetonitrile and benzonitrile, halogenated hydrocarbons such as trifluoromethylbenzene, and esters such as ethyl acetate are used as solvents. Often.
  • the ratio between the radical-generating compound (A) and the radical-scavenging compound (B) can be appropriately selected according to the type (price, reactivity) and combination of both compounds.
  • compound (A) may be used in excess of compound (B) (for example, about 2 to 50 times by mole), and conversely, compound (B) may be used in excess of compound (A). It may be used in excess.
  • the method of the present invention is characterized in that the reaction proceeds smoothly under mild conditions.
  • the reaction temperature can be appropriately selected according to the type of the compound (A) and the compound (B), the type of a target product, and the like. For example, 0 to 300 ° (:, preferably, 20 to 25) 0 ° C., more preferably about 20 to 200 ° C.
  • the reaction can be carried out under normal pressure or under pressure.
  • OMPa for example, 0.1 to 8 MPa, especially l to 8 MPa
  • the reaction time is, for example, 10 minutes to 48 hours depending on the reaction temperature and pressure. It can be appropriately selected from the range of the degree.
  • the reaction can be carried out by a conventional method such as a batch system, a semi-batch system, and a continuous system.
  • a conventional method such as a batch system, a semi-batch system, and a continuous system.
  • the target compound can often be obtained with a higher conversion and selectivity.
  • reaction product After completion of the reaction, the reaction product can be separated and purified by a separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or a combination thereof.
  • a separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or a combination thereof.
  • an addition or substitution reaction product [carbon-carbon bond product (coupling reaction product) is added depending on the combination of the radical-forming compound (A) and the radical-scavenging compound (B). Etc.), oxidation products, sulfoxylation products, nitration products, sulfonation products, etc.] or derivatives thereof.
  • the unsaturated compound (B1) to form an unsaturated bond (eg, a carbon atom), a methine carbon atom of the compound having a methine carbon atom (B2), or a hetero atom of the heteroatom-containing compound (B3). Addition or substitution reaction products or derivatives thereof are provided.
  • a compound having a carbon-heteroatom double bond for example, a compound containing a carbonyl group
  • A2 a carbon atom related to the carbon-heteroatom double bond is used.
  • a bond between an atom (for example, a carbonyl carbon atom) and an atom adjacent to this carbon atom is cleaved, and an atomic group (for example, an acyl group) containing a carbon-to-carbon double bond, the compound (B1), (B2) or (B3) is bonded to the above site to give an addition or substitution reaction product or a derivative thereof.
  • an atom for example, a carbonyl carbon atom
  • an atomic group for example, an acyl group
  • the unsaturated compound (B1) is used as the radical-scavenging compound (B)
  • the addition reaction product is used.
  • the substitution reaction product is used. (Eg, coupling products) are produced.
  • radical-capturing compound (B) is used as the radical-capturing compound (B4) to react with the radical-generating compound (A), an oxygen atom corresponding to the type of the oxygen-atom-containing reactant is obtained.
  • An organic compound containing an atom-containing group for example, a hydroxyl group, an oxo group, a carboxyl group, a nitro group, a sulfuric acid group, etc. is formed.
  • the substitution or addition reaction occurs sequentially by using two or more radical-capturing compounds (A) and radical-capturing compounds (B).
  • A radical-capturing compounds
  • B radical-capturing compounds
  • B1 unsaturated compound
  • oxygen (B4-1) oxygen
  • B4-1 oxygen
  • two carbon atoms forming an unsaturated bond are formed.
  • one of the carbon atoms As described above, the group derived from the compound (A) is bonded, and a hydroxy group derived from oxygen can be introduced into the other carbon atom.
  • an oxidizing active species for example, N-oxy radical (> N ⁇ .)] Is generated in the course of the reaction, and this is converted from the compound (A) to hydrogen.
  • N-oxy radical > N ⁇ .
  • compound (A1) a carbon atom adjacent to a hetero atom
  • compound (A2) a carbon atom related to a carbon-heteroatom double bond
  • compound ( A3 ) a methine carbon atom
  • a radical is generated at each carbon atom adjacent to the unsaturated bond, and the radical thus generated reacts with the compound (B) to form a corresponding substitution or addition reaction. It is assumed that a product is formed.
  • addition or substitution reaction product generated in the above reaction further undergoes dehydration reaction, cyclization reaction, decarboxylation reaction, rearrangement reaction, isomerization reaction, etc. in the reaction system depending on its structure and reaction conditions.
  • the corresponding derivative may be formed.
  • the reaction between the radical-generating compound (A) and the radical-scavenging compound (B) is preferably carried out under conditions where a so-called polymerization inhibitor (such as hydroquinone) is as small as possible.
  • a so-called polymerization inhibitor such as hydroquinone
  • the amount of the polymerization inhibitor in the reaction system is preferably 100 ppm or less, more preferably 100 ppm or less.
  • the amount of the polymerization inhibitor exceeds 10 ppm, the reaction rate tends to decrease, and it may be necessary to use a large amount of the cyclic acyl perylene compound or the cocatalyst.
  • the following various organic compounds can be obtained by appropriately combining the radical-forming compound (A) with the radical-scavenging compound (B) and reacting them.
  • R a and R b are the same or different and each represent a hydrogen atom or an organic group.
  • R ⁇ R b may be bonded to each other to form a ring together with adjacent carbon atoms
  • R, Rd , and Re are the same or different and each represent a hydrogen atom or an organic group; Y represents an electron-withdrawing group; Re , Rd , and R ⁇ Y are bonded (A ring may be formed together with an adjacent carbon atom or a carbon-carbon bond)) and (B41) oxygen to react with the following formula (4)
  • R a is an organic group in R b, an organic group that does not inhibit the reaction (e.g., non-reactive organic under the reaction conditions in the process Group), and examples thereof include a hydrocarbon group and a heterocyclic group.
  • the hydrocarbon group includes an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.
  • the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group having about 1 to 20 carbon atoms (an alkyl group, an alkenyl group, and an alkynyl group).
  • the alicyclic hydrocarbon group include, for example, a monocyclic alicyclic hydrocarbon group having about 3 to 20 (preferably 3 to 15) carbon atoms (such as a cycloalkyl group and a cycloalkenyl group).
  • a bridged ring hydrocarbon group examples include an aromatic hydrocarbon group having about 6 to 14 carbon atoms. These hydrocarbon groups may have various substituents.
  • the heterocyclic ring constituting the heterocyclic group in R ⁇ Rb includes an aromatic heterocyclic ring and a non-aromatic heterocyclic ring.
  • a heterocyclic ring include, for example, a heterocyclic ring containing an oxygen atom as a hetero atom and a heterocyclic atom as a hetero atom.
  • heterocycles containing a nitrogen atom as a hetero atom may have a substituent.
  • R ⁇ R B are linked to each other, is a ring formed together with the adjacent carbon atoms, for example, sik Ropentan, hexane sik Russia, cyclododecane, Dekari down, 3-2 0-membered such Adamantan ring ( Non-aromatic carbon rings (cycloalkane ring, cycloalkene ring, bridged carbon ring) having about 3 to 15 members, more preferably 5 to 15 members, and especially 5 to 8 members are preferable. . These rings may have a substituent, and other rings (non-aromatic rings or aromatic rings) may be condensed.
  • Non-aromatic carbon rings cycloalkane ring, cycloalkene ring, bridged carbon ring
  • These rings may have a substituent, and other rings (non-aromatic rings or aromatic rings) may be condensed.
  • R H a hydrogen atom, d - 4 alkyl group, C 6 - etc.
  • Ariru groups include.
  • An aliphatic hydrocarbon group, an alicyclic hydrocarbon group and the like are included.
  • R A is preferable to form a non-aromatic carbocyclic ring of about 3 to 1 5-membered together with the carbon atom to which R B is adjacent bonded to each other (especially 5-8 membered).
  • 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 (eg, aliphatic secondary alcohols such as 2-propanol and s-butyl alcohol; 1-cyclohexyl), and the like.
  • aliphatic hydrocarbon group e.g., alkyl group, C B - Ariru group, etc.
  • non-aromatic carbocyclic group e.g., C 3 - 1 including 5 cycloalkyl group or Shikuroa alkenyl group
  • Secondary alcohols 3- to 15-membered alicyclic secondary alcohols such as cyclopentanol, cyclohexanol and 2-adamantanol; aromatics such as 1-phenylethanol Alcohols wherein R b is a bridged ring hydrocarbon group Nore is included.
  • R c , R d , and R are used.
  • the organic group in the reaction may be any organic group that does not inhibit the present reaction (eg, an organic group that is non-reactive under the reaction conditions in the present method), and examples thereof include a halogen atom, a hydrocarbon group, and a complex group.
  • Cyclic group substituted oxycarbonyl group (an ethoxycarbonyl carbonyl group, aryloxy carbonyl group, aralkyloxycarbonyl group, cycloalkynoleoxycanolebonyl group, etc.), carboxy group, substituted or unsubstituted rubamoyl group (N-substituted or unsubstituted amide group), cyano group, nitro group, sulfuric acid group (sulfonic acid group, sulfinic acid group), sulfuric acid ester group (snolephonic acid ester group, snorrefonic acid ester group), Examples thereof include an acyl group, a hydroxyl group, an alkoxy group, and an N-substituted or unsubstituted amino group.
  • the carboxyl group, hydroxy group and amino group may be protected with a conventional protecting group.
  • Examples of the halogen atom include a fluorine, chlorine, bromine and iodine atom.
  • the hydrocarbon group include the groups exemplified as the hydrocarbon group for R a and R b , and these hydrocarbon groups may have a substituent.
  • the heterocyclic group include the groups exemplified as the heterocyclic group for R "and Rb , and these heterocyclic groups may have a substituent.
  • Roh the record alkoxycarbonyl group for example, main Bok Kishikarubo two Honoré, et Toki Shikano levo Nino les, propoxy Kano levo Nino les, isopropoxy force Noreboniru, butoxide Shikano repo cycloalkenyl, t - butoxide Shikano levo Nino C 6 alkoxy one such record group
  • Aryloxycarbonyl groups include, for example, phenyloxycarbonyl groups
  • aralkyloxycarbonyl groups include, for example, benzyloxycarbonyl groups.
  • Examples of the cycloalkyloxycarbonyl group include: For example, cyclopentinoleoxy canoleboninole, cyclohexinole xylcarbonyl group and the like can be mentioned.
  • Substituting power rubamoyl groups include, for example, N-methylcarbamoyl, N, N-dimethylcarbamoyl and the like.
  • the sulfonic acid ester group includes a methyl sulfonic acid group, a C-alkynoleestenole group such as a snolefonic acid ethyl group and a snolefonic acid ethyl group.
  • Examples of the sunolefinic acid ester group include a snorerefic acid Ci-alkyl ester group such as methinole sunolefinate and an ethyl sulfonate group.
  • Examples of the acryl group include an aliphatic acryl group such as an acetyl group and a propionyl group (for example, a C aliphatic acryl group), and an aromatic acryl group such as a 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-getylamino, piperidino group and the like.
  • the R e represents a hydrogen atom, a hydrocarbon group [e.g., d - (such as in particular fact aliphatic hydrocarbon group) 6 aliphatic hydrocarbon group, C e - (such as Fuyuniru group) Ari group, a cycloalkyl An alkyl group (eg, a 3- to 8-membered cycloalkyl group), a haloalkyl group (eg, a C ⁇ 6- nitroalkyl group such as a trifluoromethyl group, particularly a C haloalkyl group), a heterocyclic group, and a substituted oxycarbonyl group.
  • a hydrocarbon group e.g., d - (such as in particular fact aliphatic hydrocarbon group) 6 aliphatic hydrocarbon group, C e - (such as Fuyuniru group) Ari group
  • a cycloalkyl An alkyl group eg, a 3- to 8-membere
  • Group for example, C 6 alkoxy monocarbonyl group, aryloxycarbonyl group, aralkyloxy carbonyl group, cycloalkyloxycarbonyl group, etc.
  • carboxyl group substituted or unsubstituted rubamoyl group, cyano group, nitro group Group, sulfuric acid group, sulfuric acid ester group, and acyl group.
  • R e especially preferred groups as the R d is hydrogen atom, C i - (such as in particular C aliphatic hydrocarbon group) 6 aliphatic hydrocarbon group, C 6 _ 1 4 Ariru group (such as phenyl group), a cycloalkyl Alkyl group (about 3 to 8 members Such as a cycloalkyl group), a haloalkyl group (e.g., C 6 haloalkyl group such as Application Benefits Furuorome butyl group, in particular C 4 Nono Roarukinore group), etc.], substituted O alkoxycarbonyl group (e.g., C, - 6 alkoxy - carbonyl group An aryloxycarbonyl group, an aryloxycarbonyl group, a cycloalkyloxycarbonyl group, etc.), and a cyano group.
  • Particularly preferred RS includes a hydrogen atom, a d-aliphatic hydrocarbon group (especially an alipha
  • R c , R d , R e (R c and R d , R c and R e , R d and R e , or R c and R d and R e ) are bonded to each other and are adjacent carbon atoms or carbon-carbon
  • the ring formed together with the bond is a 3- to 20-membered ring such as cyclopropane, cyclobutane, cyclopentane, cyclopentene, cyclohexane, cyclohexene, cyclooctane, cyclooctane, etc.
  • Alicyclic carbocycle (cycloalkane ring, cycloalkene ring, etc.); 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: alkoxycarbonyl groups such as methoxycarbonyl and ethoxycarbonyl; aryloxycanolepodinole such as phenoxycarbonyl; honolemil, acetinol, and propionyl.
  • Acinole group such as phenol group, benzoyl group, etc .; cyano group; carboxy group; substituted or unsubstituted carpamoyl group such as carbamoyl, N, N_dimethylcarbamoyl group; — CH2NR—R
  • An aryl group such as a phenyl or naphthyl group; a alkenyl group or an alkynyl group such as bier, 1-propenyl or ethynyl group.
  • the adjacent may be formed together with the carbon atom or carbon one-carbon bond to ring, for example, cyclopentadiene ring, pyrrole ring, furan Ring, Chiophane ring, etc. I can do it.
  • active olefins represented by the formula (3) include the compounds exemplified as the active unsaturated compounds (B1-1).
  • the reaction between the alcohol represented by the formula (2) and the active olefin and the oxygen represented by the formula (3) can be performed according to the method described for the reaction between the compound (A) and the compound (B). .
  • the 1-hydroxyalkyl radical corresponding to the alcohol represented by the formula (2) formed in the system forms an unsaturated bond of the active olefin represented by the formula (3). Attack the carbon atom at the position of the group Y among the two carbon atoms and add it, and the oxygen attacks the radical generated at the ⁇ -position by the addition, whereby the 1,3-dihydroxyl represented by the formula (4) is obtained. It is presumed that a compound is formed.
  • ⁇ 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, and a furanone derivative represented by the above formula (6) —a hydroxy ⁇ -butyrolactone derivative) can be produced.
  • the yield of the furanone derivative can be improved, for example, 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 of the addition reaction.
  • 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.
  • aromatic hydrocarbons such as benzene and toluene
  • alicyclic hydrocarbons such as cyclohexane
  • acetone and cyclohexanone such as Ketone
  • getyl ether And ethers such as tetrahydrofuran
  • alcohols such as methanol, ethanol and isopropanol.
  • the reaction temperature in this case is, for example, 0 to 15 ° C., preferably about 30 to 100 ° C.
  • R e, R d, R ⁇ R ' are the same or different and are each a hydrogen atom or an organic group.
  • R e, R d, and binding R e are each, adjacent carbon atoms or carbon-containing May form a ring with one carbon bond
  • ⁇ - hydroxyl-lactose lactone derivative represented by the following formula can be obtained.
  • This reaction can be carried out according to the method described in WO 00/35853 (method using a ⁇ -hydroxy cyclic imide compound catalyst).
  • R C, R D in the formula (5) is set to R E, the formula (3) definitive R ⁇ R D, which is the same as R E.
  • the organic group for R ′ include an organic group that does not inhibit the reaction (for example, an organic group that is not reactive under the reaction conditions in the present method), for example, a hydrocarbon group, a heterocyclic group, and the like. .
  • At least one of R c and R d is an electron such as a haloalkyl group, a substituted oxy group, a carbonyl group, a carboxyl group, a substituted or unsubstituted rubamoyl group, a cyano group, a nitro group, a sulfuric acid group, or a sulfuric acid ester group.
  • the compound is an attractive organic group, the target ⁇ -hydroxy ⁇ -petit mouth ratatotone derivative can be obtained with a particularly high yield.
  • R ' is often a hydrogen atom or a hydrocarbon group, for example C LS alkyl group (especially C i alkyl group), C 2 - 6 alkenyl (especially C 2 - 4 alkenyl group), C 6 -. And an aryl group.
  • Representative examples of the ⁇ , -unsaturated carboxylic acid derivative represented by the formula (5) include, for example, (meth) acrylic acid; methyl (meth) acrylate, and (meth) ethyl acrylate.
  • (Meth) atalinoleic acid esters such as isopropyl (meth) acrylate, and (meth) acrylic acid fuel; crotonic acid; —Methyl-2-butenoic acid; 3-methyl_2-methyl butenoate, 3—methyl-2—ethyl butenoate, etc .; 3-methyl-2-butenoate; —2 such as ethynole pentenoate 2,2-Octenoic acid ester; 2—Octenoic acid ester; 2—Octenoic acid ester; 2—Octenoic acid ester Trifluoro-2-butenoic acid; 4,4,4—Trifluoro-1-2-butenoic acid, 4,4,4—Trifnorole
  • Rho 2 Estenole butenoate; Maleic acid; Estenole maleate such as dimethinole maleate and Jetinole maleate; Fumanolate acid; three to Shianoaku acrylic acid methyl, 3'Shianoata 3 such as acrylic acid Echiru - Shianoaku carbon atoms, such as acrylic acid esters 2-1 of about 5 alpha, beta Unsaturated carboxylic acid or its ester (C alkyl Honoré esters, C 2 - 6 alkenyl glycol ester, such as ⁇ re Ruesuteru), and the like.
  • dihydric mud carboxy acid derivative is represented by the formula generated in the system (2)
  • 1-Hydroxyalkyl radical corresponding to an alcohol is substituted at the 3-position of the ⁇ , —unsaturated carboxylic acid derivative represented by the formula (5). It is presumed that they are formed by attacking and adding oxygen, and by oxygen attacking radicals generated at the tertiary position by the addition. And the generated expression
  • alpha is expressed by, .gamma. dihydric mud carboxymethyl Ichihi Dorokishi _ gamma _ Puchiroraku tons derivative represented by the formula (6) to obtain a carboxylic acid derivative is cyclized under the reaction conditions to produce .
  • hydroxycarboxylic acid derivatives have if produced.
  • the hydroxy, 1-butyrolactone derivative is obtained by isolating the ⁇ - dihydroxycarboxylic acid derivative represented by the formula (7), dissolving it in a solvent, for example, It can also be manufactured by heating.
  • R 'and Rj are the same or different and each represent a hydrogen atom or an organic group. May be
  • R d and R s are the same or different and each represent a hydrogen atom or an organic group, Y represents an electron withdrawing group. R d and RY are bonded to each other to form (A ring may be formed with one carbon bond.)
  • a conjugated unsaturated compound represented by the following formula can be obtained.
  • This reaction can be performed according to the method described in WO 00/35853 (a method using an N-hydroxy cyclic imide compound catalyst).
  • the organic group in RR ′ is the same as the organic group in R a and R b , and is a ring in which RR j is bonded together to form an adjacent carbon atom. And the same ring as RR b forms together with adjacent carbon atoms by bonding to each other.
  • R i a hydrogen atom, C, - 4 alkyl group, C 6 - contained etc. ⁇ Li Ichiru group.
  • Preferred R j is a hydrogen atom, C t .
  • R i and R j 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. Typical examples are ethanol, 1-propanol, 1-butano, and 2-methyl_1-prono. Primary or non-saturated aliphatic primary alcohols having about 2 to 30 (preferably 2 to 20 and more preferably 2 to 15) carbon atoms such as nonole, 1-pentanol, and 1-hexanol.
  • Saturated or unsaturated alicyclic primary alcohols such as cyclopentinolemethinoleanolone, cyclohexenolemethinoleanolecole, and the like; Aromatic primary alcohols such as phenylpropynole alcohol and cinnamon alcohol; and heterocyclic alcohols such as 2- (2-hydroxyhexyl) pyridine.
  • the compound represented by the formula (3a) is R among the compounds represented by the formula (3). Is a hydrogen atom. R d and R ⁇ 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.
  • the reaction product can be separated and purified by the same separation means as described above.
  • R k , R m , and R n are the same or different and each represent a hydrogen atom or an organic group.
  • R m and R n are bonded to each other to form two adjacent acids shown in the formula.
  • a ring may be formed together with an element atom and a carbon atom.
  • a j3-hydroxyacetal compound represented by the following formula can be produced. This reaction can be carried out according to the method described in WO 00/35853 (a method using an N-hydroxy cyclic imide compound catalyst).
  • R k, R m is an organic group represented by R '1, wherein R u, those similar to the organic group in R b.
  • R ra and R n combine with each other Examples of the ring formed with two adjacent oxygen atoms and carbon atoms include a 1,3-dioxolan 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 R k is a hydrogen atom; C 1.
  • Aliphatic hydrocarbon group (especially, alkyl group); C 3 - 15 about alicyclic hydrocarbon group (cycloalkyl group, shea Kuroarukeniru group, bridged cyclic hydrocarbon group); ⁇ 6 - like 14 Ariru group included.
  • Preferred R m and R n include a hydrogen atom, a C- 6 aliphatic hydrocarbon group (particularly, d- 4 alkyl group), and C 3 -i. And a degree of alicyclic hydrocarbon group. It is also preferable that R ra and R ⁇ are bonded to each other to form a ring together with two adjacent oxygen atoms and carbon atoms.
  • Examples of the acetal represented by the formula (10) include the compounds exemplified as the acetal having a carbon-hydrogen bond at a position adjacent to an oxygen atom in the above (A1-3).
  • Typical examples are 1,3-dioxolane compounds such as 1,3-dioxolane, 2-methyl-1,3-dioxolane, 2-ethyl-1,3-dioxolane, and 1,3-dioxolane compounds; 2-methyl-1,3-dioxane 1,3-dioxane compounds; dialkyl acetal compounds such as acetoaldehyde dimethyl acetal.
  • the active olefins represented by the formula (3) are 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.
  • a 1,1-disubstituted oxyalkyl radical corresponding to the acetal represented by the formula (10) is generated, which forms an unsaturated bond of the active olefin represented by the formula (3).
  • the carbon atom at the position ⁇ of the group ⁇ ⁇ is attacked and added, and the oxygen is attacked on the radical generated at the position by the addition. It is presumed that a hydroxyacetal compound is formed.
  • R °, RR q are the same or different and are each an organic group.
  • R., R p, R q is bonded to each other, may form a ring together with the adjacent carbon atoms
  • R c , R d , R ⁇ R., R p , and R ⁇ Y are the same as above.
  • examples of the organic group in R °, R p , and R q include the same organic groups as those in R a and R b .
  • Preferred organic groups include d-,. Aliphatic hydrocarbon group (in particular, d-alkyl), C 3 - 15 about alicyclic hydrocarbon group (cycloalkyl group, cycloalkenyl group, bridged ring hydrocarbons Element group); C 6 -aryl group and the like.
  • a monocyclic ring of about 3 to 20 members preferably 3 to 15 members, more preferably 5 to 15 members, particularly 5 to 8 members
  • Alicyclic carbocycles cycloalkane ring, cycloalkene ring
  • Examples of the compound having a methine carbon atom represented by the formula (12) include the compound (A3) having the methine carbon atom, for example, a bridged cyclic compound (A3-1a), and a hydrocarbon group in the ring. And a chain compound having a methine carbon atom (A3-2).
  • the active olefins represented by the formula (3) are 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.
  • a radical is formed at the methine carbon site of the compound represented by the formula (12), and this radical is formed from the two carbon atoms constituting the unsaturated bond of the active olefin represented by the formula (3).
  • Carbon atom at position 3) or carbon at position ⁇ of group Y) Atoms are added by attacking, and oxygen is attacked on the radicals generated at the ⁇ -position or ⁇ -position by the addition, whereby the hydroxy compound represented by the formula (13) or the hydroxyl compound represented by the formula (14) It is thought that droxy compounds are formed.
  • R.R. And R ⁇ and R q are bonded to each other to form a bridged cyclic carbocyclic ring (for example, an adamantane ring) together with an adjacent carbon atom, and R e , R d , and R e are each a hydrogen atom or a C alkyl group.
  • Y is an alkoxycarbonyl group (for example, C t -alkoxymonocarbonyl group)
  • Aryloxycarbonyl group for example, Ci-acyl group
  • Benzoyl group 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.
  • R d is the same or different and represents a hydrogen atom or an organic group
  • Y represents an electron-withdrawing group.
  • RR d and Y are mutually bonded to form an adjacent carbon atom or carbon-carbon May form a ring with the bond
  • This reaction can be carried out according to the method described in WO 00/35853 (a method using an N-hydroxy cyclic imide compound catalyst).
  • This method is the manufacturing of the heat Dorokishi compound corresponds to a case of using a compound R e is a hydrogen atom and an active Orefin of the formula (3).
  • a compound represented by the formula: A carbonyl compound represented by (15) is produced.
  • the production ratio of both compounds can be adjusted by appropriately selecting reaction conditions such as, for example, reaction temperature, amount of catalyst, and type of cocatalyst (metal compound).
  • a preferred compound is R.
  • R and R combine with each other to form a bridged cyclic carbocycle (eg, an adamantane ring) with adjacent carbon atoms;
  • ⁇ R d is a hydrogen atom or a C alkyl group, respectively, and Y is an alkoxycarbonyl group (eg, a C ⁇ alkoxy-carbonyl group), an aryloxycarbonyl group, an acyl group (eg, a C> -acyl group, Benzoyl group) or a carboxyl group.
  • alkoxycarbonyl group eg, a C ⁇ alkoxy-carbonyl group
  • aryloxycarbonyl group eg, an acyl group (eg, a C> -acyl group, Benzoyl group) or a carboxyl group.
  • acyl group eg, a C> -acyl group, Benzoyl group
  • This reaction can be carried out according to the method described in WO 00/35853 (method using a catalyst of ⁇ -hydroxy cyclic imide).
  • This method is the manufacturing of the heat Dorokishi compound, as a active Orefin of the formula (3)
  • R e and R d is equivalent to the case of using a compound having a hydrogen atom.
  • a compound represented by formula (16) is produced.
  • the production ratio of each compound can be adjusted by appropriately selecting reaction conditions such as, for example, reaction temperature, amount of catalyst, and type of cocatalyst (metal compound).
  • a preferred compound is R.
  • R p and R q are bonded to each other to form a bridged cyclic carbocyclic ring (for example, an adamantane ring) together with adjacent carbon atoms
  • R e is a hydrogen atom or a C i alkyl group
  • Y is an alkoxycarbonyl
  • compounds that are a group eg, a C ⁇ 4 alkoxy-carbonyl group
  • an aryloxycarbonyl group eg, a Ci- 4 acyl group, a benzoyl group, etc.
  • Such compounds are useful as raw materials for fine chemicals such as pharmaceuticals and agricultural chemicals and as raw materials for functional polymers.
  • This reaction can be carried out according to the method described in WO 00/35853 (method using an N-hydroxy cyclic imide compound catalyst).
  • the same alcohol as used in the production of the 1,3-dihydroxy compound can be used.
  • equation (12) As the compound having a methine carbon atom, the same compounds as those used in the production of 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.
  • R ° ', R pl, R ql are the same or different and are each an organic group.
  • R ° 2, R p R q 2 are the same or different and are each an organic group.
  • R "2 R p 2 are linked together to form a ring together with the adjacent carbon atoms You can do it)
  • the coupling product (hydrocarbons) represented by can be obtained.
  • This reaction can be carried out according to the method described in WO 00/35853 (a method using an N-hydroxy cyclic imide compound catalyst).
  • R Q l is set to R pl, R " ⁇ R a R p 2, the definitive organic group and preferred organic groups, wherein R °, R p, of R q If those similar to the. also, R Q l, R p ' , R ql (R.' and R pl, R p l and R q ', R Q 1 and R ql, or R "and R pl And R q are bonded together to form a ring with adjacent carbon atoms, R ° 2 , R p 2 , R q 2 (R ° 2 and R p 2 , R p 2 and R ", R ° 2 and R q 2 or R.
  • Examples of the compound having a methine carbon atom represented by the formula (12a) or (12b) include a compound (A3) having the methine carbon atom, for example, Bridged cyclic compound (A3-la), with a hydrocarbon group bonded to the ring
  • the compound represented by the formula (12a) and the compound represented by the formula (12a) include a non-aromatic cyclic compound (A 3-lb) described above and a chain compound having a methine carbon atom (A3-2).
  • the compounds represented by 12b) may be the same compounds 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.
  • R g represents a hydrogen atom or an organic group
  • R e , R d , and RR h are the same or different and each represent a hydrogen atom or an organic group.
  • R, R d , and R ⁇ R h are bonded to each other to form an adjacent carbon atom or carbon atom. May form a ring with carbon
  • examples of the organic group for R s include the same organic groups as those described above for R a and R b .
  • the aldehyde represented by the formula (19) the aldehyde exemplified in the carbonyl group-containing compound (A2-1) can be used.
  • RR d is the same as described above, and the organic group for R h is the same as R e , R d , and R e .
  • the orfins represented by the formula (20) for example, the compounds exemplified as the inactive orefin (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.
  • R., R d are the same or different and each represents a hydrogen atom or an organic group, R el, or indicates the same or different, a hydrogen atom, a hydrocarbon group or a heterocyclic group. R e , R d may be bonded to each other to form a ring together with adjacent carbon atoms)
  • ⁇ -Acyoxycarboxylic acid or ⁇ -acyoxyketone represented by the formula [Japanese Patent Application No. 2000-648] (Example using a catalyst of ⁇ -hydroxy imide compound) ].
  • Examples of the ring formed by the organic group, the hydrocarbon group, the heterocyclic group, R e and R d together with the adjacent carbon atom include the same groups as described above.
  • 3-acetoxy-13-methylbutanoic acid is obtained, for example, by reacting 2-propanol with methylvinylketone. By reacting 2-propanol and acrolein, 3-formyloxy-13-methylbutanoic acid is obtained.
  • 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.
  • R el is a hydrocarbon group or a heterocyclic group.
  • ⁇ -unsaturated carbonyl compound is used as a raw material. If used, the corresponding —Ashyloxyketone is generated.
  • the unsaturated carboxylic acid amides are polymerized under mild conditions to form the corresponding polyacrylamide compound.
  • a polymer is obtained [refer to Japanese Patent Application No. 2000-0-34582 (an example using a ⁇ -hydroxy cyclic imide compound catalyst)].
  • ⁇ , 0-unsaturated carboxylic acid amides include, for example, (meth) acrylamide, ⁇ -methyl (meth) acrylamide, ⁇ , ⁇ -dimethyl (meta) Linoleamide, ⁇ -isopropyl (meta) acrylamide, ⁇ -phenyl (meta) atalinoleamide, crotonic acid amide, and the like.
  • the reaction temperature can be appropriately selected according to the type of the raw materials, and is, for example, 0 to It is about 150 ° C, preferably about 10 to 100 ° C.
  • the molecular weight of the polymer can be controlled by adjusting the reaction temperature.
  • the reaction product can be separated and purified by, for example, precipitation, reprecipitation, or the like.
  • An organic compound containing an oxygen atom-containing group is produced by reacting the compound (A) capable of generating the radical with the oxygen atom-containing reactant (B4) using the cyclic acyl peria compound as a catalyst. be able to.
  • This reaction is performed in the presence or absence of a solvent.
  • a solvent the above-mentioned solvents can be used.
  • the amount of the cyclic acyl perylene compound catalyst to be used is, for example, 0.0000 to 1 mol, preferably 0.0000 to 1 mol, per 1 mol of the compound (A). The amount is 5 mol, more preferably 0.0001 to 0.4 mol, and often about 0.001 to 0.3 mol.
  • a co-catalyst such as the above metal compound (for example, a vanadium compound, a molybdenum compound, a manganese compound, a cobalt compound, a zirconium compound, etc.) is used in combination, the reaction is often remarkably accelerated.
  • the agent (B4) When the agent (B4) is in a gaseous state, for example, it may be used after being diluted with an inert gas such as nitrogen argon. Further, the oxygen atom-containing reactant (B4) may be used alone, or two or more kinds may be used in combination. By using two or more oxygen atom-containing reactants (B4) together, two molecules selected from, for example, a hydroxyl group, an oxo group, a carboxyl group, a nitro group, a sulfonate group, etc. The above heterofunctional groups can be introduced. In this case, two or more oxygen-containing reactants (B4) may be used simultaneously or sequentially. .
  • the amount of the oxygen atom-containing reactant (B4) used varies depending on its type, and can be appropriately selected in consideration of reactivity, operability, and the like.
  • an oxygen atom-containing reactant When oxygen (B4-1) is used as (B4), the amount of oxygen used is 0.5 mol or more (eg, 1 mol or more), preferably 1 to 10 mol per 1 mol of compound (A). 0 mol, more preferably about 2 to 50 mol. In many cases, an excessive molar amount of oxygen is used for the compound (A).
  • carbon monoxide (B4-2) and oxygen (B4-1) are used in combination as the oxygen atom-containing reactant (B4)
  • 1 mole or more (for example, 1 to 10 moles) per mole of compound (A) (About 0 mol) of carbon monoxide and 0.5 mol or more (for example, about 0.5 to 50 mol) of oxygen are often used.
  • the amount of the nitrogen oxide used is appropriately selected according to the type of the nitrogen oxide, the type of the compound (A), and the like.
  • 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) used is less than 1 mol (for example, 0.001 mol or more and less than 1 mol) per 1 mol of the compound (A), preferably When the amount is about 0.001 to 0.8 mol, and more preferably about 0.005 to 0.25 mol, the conversion of nitrogen oxides and the selectivity of the reaction are significantly improved.
  • the reaction rate such as the nitration reaction is greatly improved.
  • the amount of oxygen used is 0.5 mol or more (for example, 1 mol or more), preferably 1 to 100 mol, and more preferably about 2 to 50 mol per mol of nitric oxide. is there.
  • the sulfur oxide (B4-4) is used as the oxygen atom-containing reactant, the amount of the sulfur oxide used can be appropriately selected according to the type of the sulfur oxide, the type of the compound (A), and the like. In general, it can be selected from a range of about 1 to 50 mol, preferably about 1.5 to 30 mol, per 1 mol of compound (A).
  • the reaction may be performed under a large excess atmosphere of the product.
  • a sulfur oxide for example, sulfur dioxide
  • oxygen for example, oxygen
  • the reaction temperature can be appropriately selected according to the type of the compound (II) and the oxygen-containing reactant.
  • the reaction temperature is 0 to 300 ° C., preferably 20 to 250 ° C., and more preferably 2 to 250 ° C. It is about 0 to 200 ° C.
  • the reaction temperature is, for example, about 0 to 200 ° C., preferably 10 to 100 ° C. It is about 150 ° C.
  • the reaction temperature is, for example, 0 to 150 ° C.
  • the reaction pressure may be either normal pressure or under pressure. When the reaction is performed under pressure, usually 0.1 to 10 MPa, preferably 0.2 to 7 MPa
  • the reaction can be carried out by a conventional method such as a batch system, a semi-batch system, or a continuous system.
  • reaction product can be separated and purified by, for example, separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, adsorption, and column chromatography, or a combination thereof.
  • separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, adsorption, and column chromatography, or a combination thereof.
  • a reaction product corresponding to the type of the oxygen atom-containing gas can be obtained with a good yield under mild conditions.
  • primary alcohols produce the corresponding aldehydes or carboxylic acids
  • secondary alcohols produce the corresponding ketones
  • the corresponding hydroxyketone can be obtained from 1,3-diol
  • the corresponding carboxylic acid can be obtained from 1,2-diol by oxidative cleavage
  • Japanese Patent Application Laid-Open No. 2000-219652 an example using an N-hydroxy cyclic imide compound catalyst
  • a corresponding ester or acid anhydride can be obtained from ether [see Japanese Patent Application Laid-Open No. 10-31610 (example using N-hydroxy cyclic imid compound catalyst)].
  • hydrogen peroxide can also be generated from primary or secondary alcohols [see WO 00/46145 (Example using N-hydroxy cyclic imide compound catalyst)] ].
  • the compound (A2) having a carbon-heteroatom double bond is used as the compound (A), an oxidation reaction product corresponding to the type of the hetero atom or the like is obtained.
  • ketones when ketones are oxidized, they are cleaved to generate carboxylic acids and the like.
  • cyclic ketones such as cyclohexanone give dicarboxylic acids such as adipic acid.
  • a compound containing a heteroatom (A1) having a carbon-hydrogen bond at a position adjacent to a hetero atom such as a secondary alcohol (for example, benzohydrol) is used as a co-reactant (co-oxidant).
  • a bridged cyclic hydrocarbon (A3-la) ' such as adamantane
  • an alcohol derivative having a hydroxyl group introduced at the bridgehead position for example, 1-adamantanol, 1,3-adada Mantandiol and 1,3,5-adamantantriol
  • a chain compound (A3-2) having a methine carbon atom such as isobutane
  • a tertiary alcohol such as t-butanol can be obtained in a high yield
  • Japanese Patent Application Laid-Open No. H10-310543 Example using N-hydroxy cyclic imide compound catalyst
  • the adjacent position of the unsaturated bond is efficiently oxidized, and the alcohol, carboxylic acid, or ketone is oxidized. Tons are generated.
  • 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 [JP-A-8-38909, See, for example, Japanese Patent Application Laid-Open No. 9-3227626 and Japanese Patent Application Laid-Open No. H11-106370 (an example using an N-hydroxy cyclic imide compound catalyst)].
  • a secondary or tertiary alcohol, ketone or carboxylic acid can be obtained in good yield depending on the reaction conditions. .
  • an aromatic ring in which an alkyl group or a lower oxidized group thereof (a hydroxyalkyl group, a honoleminolele group, a honoleminoleanolyl group, or an alkyl group having an oxo group) is bonded to an aromatic ring.
  • an alkyl group or a lower oxidized group thereof a hydroxyalkyl group, a honoleminolele group, a honoleminoleanolyl group, or an alkyl group having an oxo group
  • —Picoline gives nicotinic acid.
  • Acetoxybenzoic acid can be obtained from triacetate
  • cyanobenzoic acid and cyanobenzaldehyde can be obtained from tolitol
  • 4-t-butynolebenzoic acid can be obtained from 4-t-t-butyltoluene.
  • 1-t-Butylbenzaldehyde is obtained.
  • Black mouth benzoic acid is obtained from black mouth toluene
  • nitrobenzoic acid is obtained from black mouth toluene.
  • the corresponding arylalkyl hydroperoxide is generated from an aromatic compound in which an alkyl group is bonded to an aromatic ring.
  • cumene yields tamenhydroperoperoxide
  • di-isop-mouth pinolebenzene yields p-diisopropylbenzenebenzene hydroperoxide
  • p-diisopropinolebenzene monohydrobenoleoxide 1,3,5-triisopropylbenzene.
  • 1,3,5_triisopropylbenzene trihydroperoxide, 1,3,5-triisopropylbenzenedihydroperoxide, and 1,3,5-triisopropylbenzenemonohydroperoxide are obtained.
  • secondary alcohols or ketones can be obtained from a compound having a methylene group at a position adjacent to a carbon-carbon double bond.
  • the pK a 8.0 of cobalt (II) acetate or cobalt ( ⁇ ) nitrate is used.
  • a cobalt (II) salt of the following acid is used as a cocatalyst, a corresponding conjugated unsaturated carbonyl compound having an oxo group introduced into the carbon atom of the methylene group can be obtained in high yield. More specifically, nutoton can be obtained from Valensen in high yield.
  • a non-aromatic cyclic hydrocarbon (A5) is used as the compound (A)
  • an alcohol, a hydroperoxide or a ketone in which a hydroxy group, a hydroperoxy group or an oxo group is introduced into a carbon atom constituting the ring.
  • the ring is oxidatively cleaved to form the corresponding dicarboxylic acid.
  • cyclohexane, cyclohexyl alcohol, cyclohexynolenoleoxide, cyclohexanone or adipic acid can be obtained with good selectivity by appropriately selecting the conditions. it can.
  • bis (1-hydroxycyclohexynole) ⁇ noreo.oxide or other bis (1-hydroxycycloalkyl) peroxide can be obtained from cycloanolecan power such as cyclohexane [Japanese Patent Application 200]. 0—3 4 5 8 2 4 (Example using N-hydroxy cyclic imide compound catalyst)]. Furthermore, adamantanone can be obtained in good yield from adamantan by using a strong acid as a co-catalyst [Japanese Patent Application Laid-Open No. H10-309496] (N-hydroxycyclic imidase). Example using compound catalyst)].
  • conjugated compound (A6) When the conjugated compound (A6) is used as the compound (A), various compounds are generated depending on the structure. For example, oxidation of conjugated gens produces alkeneddiols and the like. Specifically, when butadiene is oxidized, 2-butene-11,4-diol, 1-butene-13,4-diol, and the like are obtained.
  • the ./3-unsaturated bond site is selectively oxidized, so that the unsaturated bond becomes a single bond and Is a formyl group, an acetal group (when reacted in the presence of alcohol) or an acyloxy group (with carboxylic acid).
  • oxidation of acrylonitrile and methyl atalinoleate in the presence of methanol yields methyl 3,3-dimethoxypropionitol and methyl 3,3-dimethoxypropionate, respectively.
  • an olefin (A10) is used as the compound (A)
  • a corresponding epoxy compound can be obtained [Japanese Patent Laid-Open No. 11-97464, WO99 / 5 ⁇ 20]. 4 (Example using N-hydroxy cyclic imide compound catalyst)].
  • co-reaction of compounds containing a heteroatom with a carbon-hydrogen bond adjacent to a heteroatom such as a secondary alcohol (A1) and compounds having a carbon-hydrogen bond adjacent to an unsaturated bond (A4) When coexisting as an agent (co-oxidizing agent), the epoxidation reaction proceeds under mild conditions, and the corresponding epoxide can be obtained in good yield.
  • At least one compound selected from cycloalkanes, cycloalkanols and cycloalkynones and oxygen (B4-1) as an oxygen atom-containing reactant in the presence of the cyclic acylperarea compound catalyst When reacted with ammonia, the corresponding lactam is formed [see Japanese Patent Application No. 2000-349528 (Example using N-hydroxy cyclic imide compound catalyst)]. More specifically, in the presence of the catalyst, cyclohexane, cyclohexane The reaction of oxygen and ammonia with at least one compound selected from hexanol and hexanone gives f-prolactam.
  • nitrogen oxide (B4-3) is used as the oxygen atom-containing reactant, the nitration reaction mainly proceeds, and the corresponding nitro compound is obtained [Japanese Patent Application Laid-Open No. Hei 11-23]. No. 9730 (Example using N-hydroxy cyclic imide compound catalyst)].
  • the compound (A3) having a methine carbon atom is used as the compound (A)
  • the compound (A4) is obtained by nitrifying the methine carbon atom and having a carbon-hydrogen bond at the adjacent position of the unsaturated bond.
  • carbon is used, the carbon atom related to the carbon-hydrogen bond is converted to nitrogen.
  • non-aromatic cyclic hydrocarbons (A5) such as cyclohexane form the corresponding cyclic nitro compound in which a nitro group is bonded to the carbon atom that constitutes the ring, and hexane.
  • linear alkane (A9) produces corresponding nitroalkane.
  • a compound having a methylene group at the adjacent position of an aromatic ring eg, ethylbenzene
  • a nitrone compound in which the methylene group is nitrated eg, ⁇ - nitroethylbenzene
  • an oxime compound in which the methylene group is oximed eg, acetophenoxynoxime
  • a corresponding aldehyde or the like formed by cleavage of an ether bond can be obtained from ether [Japanese Patent Application Laid-Open No. H11-31503]. No. 6, Japanese Patent Application No. 11-2549977 (Example using a catalyst of a hydroxy-imid compound)]].
  • phthalaldehyde can be obtained from phthalane in a high yield.
  • the corresponding cycloalkanone oxime can be obtained from cycloalkane [Japanese Patent Application No. 2000-1577356].
  • Example using a droxy cyclic imide catalyst For example, cyclohexanone oxime is formed from cyclohexane.
  • a nitrogen oxide such as nitrogen monoxide in the presence of a halogen (chlorine or the like) or a Beckmann rearrangement catalyst, the corresponding amide or ratatum [Refer to Japanese Patent Application No. 11-3772 1777 (Example using a catalyst for the formation of a hydroxy-imidated product)].
  • cyclohexane gives f-prolactam.
  • the nitration reaction mainly proceeds to obtain the corresponding nitro compound.
  • Japanese Patent Application No. 2000-58080 N-hydroxycyclic Example using an imido compound catalyst
  • the carbon atom related to the carbon-hydrogen bond is nitrated.
  • a compound having a methine carbon atom (A3) is used as a substrate, the methine carbon atom is converted into a nitrogen atom.
  • a nitrogen atom is introduced into a carbon atom constituting the ring, and, for example, from a cycloalkane such as cyclohexane, The corresponding dicyclocycloalkanes are formed.
  • a non-aromatic heterocyclic compound having a carbon-hydrogen bond at a position adjacent to a hetero atom the carbon atom related to the carbon-hydrogen bond is converted into a nitrogen atom, and is converted from a linear alkane (A9) such as hexane. Corresponds to ⁇ Nitroal force is generated.
  • the cyclic acyl peria compound reacts with nitrates to generate an N-oxy radical, which extracts a hydrogen atom from the substrate to form a radical, and this radical is converted into nitrogen dioxide generated in the system.
  • this radical is converted into nitrogen dioxide generated in the system.
  • the corresponding nitrogen compound is formed.
  • a sulfur oxide (B4-4) is used as the oxygen atom-containing reactant, a sulfonation / sulfination reaction proceeds, and a corresponding organic sulfur acid or a salt thereof is obtained.
  • a compound (A3) having a methine carbon atom is used as the compound (A)
  • a compound having a sulfur atom group introduced into the methine carbon atom and having a carbon-hydrogen bond adjacent to the unsaturated bond When A4) is used, a sulfuric acid group (such as a sulfonic acid group or a sulfinic acid group) is introduced into a carbon atom involved in the carbon-hydrogen bond.
  • non-aromatic cyclic hydrocarbons such as cyclohexane
  • organic sulfuric acid in which a sulfur acid group is bonded to a carbon atom constituting the ring is generated.
  • the generated organic sulfuric acid is used in a conventional manner, such as water.
  • Alkali metal hydroxide, alkali metal carbonate, alkali metal bicarbonate, alkali earth metal hydroxide, alkali earth metal carbonate, amines, thiourea Can be converted to the corresponding organic sulphate by reacting with thioureas and isothioureas.
  • an organic compound having an oxygen atom-containing group such as a hydroxyl group, an oxo group, a phenol group, a nitrole group, a nitrole group, etc.
  • a carbon-carbon bond product or a derivative thereof eg, a cyclized derivative
  • an oxygen atom-containing group can be introduced into an organic substrate under mild conditions.
  • the catalyst of the present invention has excellent stability and can maintain the catalytic activity for a long time. In addition, in a radical reaction, a small amount shows high catalytic activity.
  • reaction product was identified by NMR, IR, and GC-MS. “Ar” represents an aryl group.
  • the inside of the autoclave was pressurized with 2 MPa of oxygen and 2 MPa of nitrogen, placed in a heated oil bath, and stirred for 1 hour while maintaining the reaction temperature at 150 ° C. After the reaction, the autocrepes were quenched by immersing them in cold water. The obtained product was analyzed by high performance liquid chromatography, and as a result, terephthalic acid was obtained in a yield of 63%. The conversion of p-toluic acid was 68%.
  • Example 2 The same operation as in Example 1 was performed except that the reaction temperature was set at 17 ° C. As a result, terephthalic acid was obtained in a yield of 67%. The conversion of p-toluic acid was 71%.
  • the inside of the autoclave was pressurized with 2 MPa of oxygen and 2 MPa of nitrogen, placed in a heated oil bath, and stirred for 1 hour while maintaining the reaction temperature at 150 ° C. After the reaction was completed, the autoclave was quenched by immersing it in cold water. As a result of analyzing the obtained product by high performance liquid chromatography, terephthalic acid was obtained in a yield of 90%. The conversion of p-toluic acid was 93%.
  • Example 3 The same operation as in Example 3 was performed except that the reaction temperature was set at 170 ° C. As a result, terephthalic acid was obtained at a yield of 89%. The conversion of p-toluic acid is 91. /. Met. Comparative Example 1
  • a mixture of 0.008 g of tetrahydrate and 0.007 g of manganese (II) acetate tetrahydrate was added under an atmosphere of oxygen at 1 atm (0.1 MPa) at 120 °. The mixture was stirred at C for 6 hours.
  • the product in the reaction mixture was analyzed by gas chromatography, and as a result, fluorenone was obtained in a yield of 93%. The conversion of fluorene was 99%.
  • the inside of the autoclave was pressurized with 2 MPa of oxygen and 2 MPa of nitrogen, put in a heated oil bath, stirred for 1 hour while keeping the reaction temperature at 150 ° C, and then quenched by putting the autoclave in cold water.
  • 1,3,5—Triacetoxyhexahydro 1,3,5—Triazine 1,2,4,6 _ Trion 0.14 g (p-xylene Te 0.3 3 mol 0 /.) was added, oxygen 2 MP a, pressurized with nitrogen 2MP a, immersed in a heated oil bath, was stirred for 1 hour maintaining the reaction temperature 1 5 0 ° C, O one Toku The lave was quenched by immersing it in cold water. The same operation was repeated once more.
  • terephthalic acid was obtained in a yield of 92%.
  • the conversion of p-xylene was 100%.
  • 0 g, acetate Kobanoreto (II ) A mixture of 0.015 g of tetrahydrate and 0.015 g of manganese (II) acetate tetrahydrate was added at 100 ° C. under an atmosphere of oxygen at 1 atm (0.1 MPa). The mixture was stirred at C for 8 hours. The product in the reaction mixture was analyzed by gas chromatography.
  • Tonolen Hexahydro 1,3,5 — Trihydroxy 1,1,3,5 —Triazine 1,2,4,6 — 0.05 g of Trion (1 mol% based on tonolene), 5 g of acetic acid, and 0.0004 g of cobalt (II) acetate tetrahydrate were added under an oxygen atmosphere of 1 atm (0. The mixture was stirred at 0 ° C for 6 hours. The product in the reaction mixture was analyzed by gas chromatography. As a result, benzoic acid was obtained at a yield of 49% and benzaldehyde was obtained at a yield of 3%. The conversion of toluene was 53%.
  • the product in the reaction mixture was analyzed by gas chromatography, and as a result, was obtained with a yield of 85% of benzotobenzoic acid and a yield of 1% of 412 trobenzaldehyde.
  • the conversion of toluene was 91%.
  • the mixture was stirred at 100 ° C. for 14 hours under an oxygen atmosphere of 1 atm (0.1 MPa).
  • the product in the reaction mixture was analyzed by high-performance liquid chromatography. As a result, terephthalic acid was obtained in a yield of 95%.
  • the conversion of p-xylene was 100%. .
  • duren hexahydro 1,3,5—trihydroxy 1,3,5—triazine 2,4,6—trion 0.0 3 5 g (1 0 mol 0/0 for durene), acetic acid 4 g, acetic 1 g anhydride, acetic cobalt (II) tetrahydrate 0. 0 l 0 g, manganese (II) acetate four hydrated 0.03 g of the product and 0.003 g of zirconium oxyacetate were charged. Pressurize the inside of the autoclave with 3MPa of air, and And stirred for 14 hours. After the completion of the reaction, the autoclave was quenched by immersing it in cold water. As a result of analyzing the product in the reaction mixture by high performance liquid chromatography, pyromellitic acid was obtained in a yield of 90%. The conversion of durene was 100%.

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EP02791966A EP1459804B1 (en) 2001-12-25 2002-12-05 Catalysts comprising cyclic acylurea compounds and oxidation and nitration reactions of organic compounds in the presence of the same
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US7994330B2 (en) 2005-03-28 2011-08-09 Daicel Chemical Industries, Ltd. Method for producing organic compound and method for decomposing compound having dicarboximide skeleton
CN114814065A (zh) * 2022-04-12 2022-07-29 上海交通大学 幽门螺旋杆菌的唾液中voc标志物及其在制备诊断试剂中的应用

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WO2005023784A1 (ja) * 2003-09-02 2005-03-17 Daicel Chemical Industries, Ltd. Ｎ，ｎ'，ｎ"－トリ置換イソシアヌル酸の製造方法
US7524986B2 (en) 2004-04-08 2009-04-28 Daicel Chemical Industries, Ltd. Methods for producing aromatic carboxylic acids
WO2005100294A1 (ja) * 2004-04-08 2005-10-27 Daicel Chemical Industries, Ltd. 芳香族カルボン酸の製造法
JP2006273722A (ja) * 2005-03-28 2006-10-12 Daicel Chem Ind Ltd 有機化合物の製造方法
US7994330B2 (en) 2005-03-28 2011-08-09 Daicel Chemical Industries, Ltd. Method for producing organic compound and method for decomposing compound having dicarboximide skeleton
JP2006273793A (ja) * 2005-03-30 2006-10-12 Daicel Chem Ind Ltd 環状アシルウレア系触媒を用いた有機化合物の製造方法
JP2009521514A (ja) * 2005-12-27 2009-06-04 エクソンモービル・ケミカル・パテンツ・インク アルキルベンゼンの選択的酸化
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JP2009297620A (ja) * 2008-06-11 2009-12-24 Daicel Chem Ind Ltd 酸化触媒系
CN114814065A (zh) * 2022-04-12 2022-07-29 上海交通大学 幽门螺旋杆菌的唾液中voc标志物及其在制备诊断试剂中的应用
CN114814065B (zh) * 2022-04-12 2023-12-01 上海交通大学 幽门螺旋杆菌的唾液中voc标志物及其在制备诊断试剂中的应用

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