JP4974107B2 - Method for producing benzene compound - Google Patents

Description

  The present invention relates to a method for producing a benzene compound.

  Multi-substituted benzene compounds are compounds that are expected to be used in a wide range of industrial fields as useful functional materials such as electroluminescence and redox capacitors.

  For example, hexaarylbenzene and its derivatives are used as an organic electroluminescent element in Patent Document 1 and Patent Document 2, and are used as an additive for a non-aqueous electrolyte of a lithium battery in Patent Document 3.

  Various proposals have been made to date for the production of multi-substituted benzene derivatives. The simplest and most direct synthesis method is the presence of transition metal catalysts such as Ni, Pd, Co, Ti, Ru, Rh, and alkynes. Reaction which heats a compound and carries out cyclic trimerization is reported (nonpatent literature 1-6).

However, in the methods described in Non-Patent Documents 1 to 6, when a cyclic trimerization reaction is performed using an asymmetric disubstituted alkyne compound, a polysubstituted benzene compound is only obtained in a low yield. Asymmetric polysubstituted benzene compounds cannot be selectively produced.
JP 2005-285410 A JP 2006-49438 A JP2001-15158 J. Organomet. Chem., 2003, 683, 295-300 Organometallics, 2002, 21, 5029-5037 J. Mol. Catal., 1985, 32, 101-105 Z. Naturforsch., B: Chem. Sci., 1984, 39B, 180-184 Chem.Ber., 1960, 93, 103-115 J. Mol. Catal., 1987, 40, 337-357

  An object of the present invention is to provide a method by which an alkyne compound can be subjected to cyclic trimerization to produce a corresponding benzene compound in a high yield and, moreover, an asymmetric polysubstituted benzene compound can be produced with high selectivity.

  The present inventors have intensively studied to solve the above problems. As a result, the desired benzene compound is obtained from the alkyne compound by using rhodium halide which is not taught or suggested in Non-Patent Documents 1 to 6 and coexisting rhodium halide and a tertiary amine compound in the reaction system. It was found that can be produced in a high yield, and that an asymmetric polysubstituted benzene compound can be produced in a high yield and with a high selectivity. The present invention has been completed based on such findings.

The present invention provides manufacturing methods according to items 1 to 8 below.
Item 1. In the presence of rhodium halide and a tertiary amine compound, the compound represented by the general formula (1)

[Wherein, R ¹ and R ² are the same or different and each represents a hydrogen atom, a C _1-15 alkyl group, a phenyl group which may have a substituent, a C _1-4 alkoxy C _1-4 alkyl group, C _{1 -4} alkylcarbonyl group, benzoyl group which may have a substituent, C _1-4 alkoxycarbonyl group, tri (C _1-4 alkyl) silyl group, tri (C _1-4 alkoxy) silyl group, cyano group, halogen The heterocyclic group which may have an atom, a nitro group, or a substituent is shown. However, R ¹ and R ² do not represent a hydrogen atom at the same time. ]
The alkyne compound represented by general formula (2)

[Wherein, R ¹ and R ² are the same as defined above. ]
The manufacturing method of a benzene compound which manufactures the benzene compound represented by these.
Item 2. Item 2. The production method according to Item 1, wherein the rhodium halide is at least one selected from the group consisting of rhodium fluoride, rhodium chloride, rhodium bromide, rhodium iodide and hydrates thereof.
Item 3. Item 2. The method according to Item 1, wherein the rhodium halide is at least one selected from the group consisting of rhodium chloride and hydrates thereof.
Item 4. Item 4. The production method according to any one of Items 1 to 3, wherein about 0.015 to 2 mol of rhodium halide is used with respect to 1 mol of the alkyne compound represented by the general formula (1).
Item 5. Item 5. The production method according to any one of Items 1 to 4, wherein the tertiary amine compound is used in an amount of about 1.2 to 10 mol per 1 mol of rhodium halide.
Item 6. In the alkyne compound of the general formula (1), R ¹ and R ² are the same or different and each represents a hydrogen atom, a C _1-8 alkyl group, a phenyl group which may have a substituent, or a C _1-4 alkoxycarbonyl group. The manufacturing method of claim | item 1 which is an alkyne compound to show.
Item 7. 7. The production method according to any one of 1 to 6 above, wherein the reaction is carried out in an aromatic hydrocarbon solvent.
Item 8. 8. The production method according to any one of 1 to 7 above, wherein the reaction is performed under heating and reflux.

  In this specification, each group shows the following.

Examples of the C _1-8 alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an isopentyl group. And linear or branched alkyl groups having 1 to 8 carbon atoms such as neopentyl group, tert-pentyl group, n-hexyl group, isohexyl group and octyl group.

Examples of the C _1-15 alkyl group include, in addition to the groups exemplified for the C _1-8 alkyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, and an n-tridecyl group. C1-C15 linear or branched alkyl groups, such as n-tetradecyl group and n-pentadecyl group.

Examples of the C _1-4 alkoxy C _1-4 alkyl group include straight chain having 1 to 4 carbon atoms such as methoxymethyl group, methoxyethyl group, ethoxyethyl group, n-propoxymethyl group, isopropoxymethyl group, and the like. C1-C4 linear or branched alkyl group which the branched alkoxy group substituted is mentioned.

Examples of the C _1-4 alkylcarbonyl group include a methylcarbonyl group (acetyl group), an ethylcarbonyl group (propionyl group), an n-propylcarbonyl group (butyryl group), an isopropylcarbonyl group (isobutyryl group), and n-butylcarbonyl. A group in which a linear or branched alkyl group having 1 to 4 carbon atoms such as a group (valeryl group), isobutylcarbonyl group (isovaleryl group), sec-butylcarbonyl group, tert-butylcarbonyl group, and the carbonyl group is bonded Is mentioned.

Examples of the C _1-4 alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, cyclopropyloxycarbonyl group, n-butoxycarbonyl group, sec-butoxycarbonyl group, tert A group in which a linear or branched alkoxy having 1 to 4 carbon atoms such as a butoxycarbonyl group and a carbonyl group are bonded to each other is exemplified.

Examples of the tri (C _1-4 alkyl) silyl group include three linear or branched alkyl groups having 1 to 4 carbon atoms of the same or different types such as a trimethylsilyl group and a tert-butyldimethylsilyl group. Examples include substituted silyl groups.

Examples of the tri (C _1-4 alkoxy) silyl group include three linear or branched alkoxy groups having 1 to 4 carbon atoms of the same type or different types such as a trimethoxysilyl group and a dimethoxyethoxysilyl group. Examples include substituted silyl groups.

  As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example.

  Examples of the heterocyclic group include thienyl, furyl, tetrahydrofuryl, dioxolanyl, pyrrolyl, pyrrolinyl, pyrrolidinyl, oxazolyl, isoxazolyl, oxazolinyl, oxazolidinyl, isoxazolinyl, thiazolyl, isothiazolyl, thiazolinyl, thiazolidinyl, isothiazolidinyl, pyrazolyridylyl, pyrazolidridyl, , Imidazolidinyl, oxadiazolyl, oxadiazolinyl, thiadiazolinyl, triazolyl, triazolinyl, triazolidinyl, tetrazolyl, tetrazolinyl, pyridyl, dihydropyridyl, tetrahydropyridyl, piperidyl, oxazinyl, dihydrooxazinyl, morpholino, thiazinyl, thiazinyl , Dihydropi Dazinyl, tetrahydropyridazinyl, hexahydropyridazinyl, oxadiazinyl, dihydrooxadiazinyl, tetrahydrooxadiazinyl, thiadiazolyl, thiadiazinyl, dihydrothiadiazinyl, tetrahydrothiadiazinyl, pyrimidinyl, dihydropyrimidinyl, tetrahydropyrimidinyl , Hexahydropyrimidinyl, pyrazinyl, dihydropyrazinyl, tetrahydropyrazinyl, piperazinyl, triazinyl, dihydrotriazinyl, tetrahydrotriazinyl, hexahydrotriazinyl, tetrazinyl, dihydrotetrazinyl, indolyl, indolinyl, isoindolyl, Indazolyl, quinazolinyl, dihydroquinazolyl, tetrahydroquinazolyl, carbazolyl, benzoxazolyl, benzoxazo Nyl, benzisoxazolyl, benzoisoxazolinyl, benzothiazolyl, benzisothiazolyl, benzisothiazolinyl, benzimidazolyl, indazolinyl, quinolinyl, dihydroquinolinyl, tetrahydroquinolinyl, isoquinolinyl, dihydroisoquinolinyl , Tetrahydroisoquinolinyl, pyridoindolyl, dihydrobenzooxazinyl, cinnolinyl, dihydrocinnolinyl, tetrahydrocinnolyl, phthalazinyl, dihydrophthalazinyl, tetrahydrophthalazinyl, quinoxalinyl, dihydroquinoxalinyl, tetrahydroquino Xalinyl, purinyl, dihydrobenzotriazinyl, dihydrobenzotetrazinyl, phenothiazinylfuranyl, benzofuranyl, benzothienyl and the like. These heterocyclic groups may include those in the form of oxo or thioketone at any substitutable position, and these heterocyclic groups may be substituted with an appropriate substituent at any substitutable position. Also good.

Examples of the substituent of the phenyl group which may have a substituent, the benzoyl group which may have a substituent, and the heterocyclic group which may have a substituent include a halogen atom, a hydroxyl group, C _1-4 Examples thereof include an alkyl group, a C _1-4 haloalkyl group, a C _1-4 alkoxy group, an amino group, a C _1-4 alkoxycarbonyl group, a nitro group, a cyano group, and the like. The plurality of substituents may be the same or different from each other.

Specific examples of the C _1-4 alkoxycarbonyl group are as described above.

Examples of the C _1-4 alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. A linear or branched alkyl group is mentioned.

Examples of the C _1-4 haloalkyl group include a fluoromethyl group, a chloromethyl group, a bromomethyl group, an iodomethyl group, a difluoromethyl group, a trifluoromethyl group, a chlorodifluoromethyl group, a bromodifluoromethyl group, a dichlorofluoromethyl group, 1 -Fluoroethyl group, 2-fluoroethyl group, 2-chloroethyl group, 2-bromoethyl group, 2-iodoethyl group, 2,2,2-trifluoroethyl group, 2,2,2-trichloroethyl group, pentafluoroethyl 1-9, preferably 1-5, such as a group, 1-fluoroisopropyl group, 3-fluoropropyl group, 3-chloropropyl group, 3-bromopropyl group, 4-fluorobutyl group, 4-chlorobutyl group, etc. C1-C4 linear or branched alkyl group substituted with the halogen atom is mentioned.

Examples of the C _1-4 alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, cyclopropyloxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, and n-pentyloxy. C1-C6 linear or branched alkoxy groups, such as a group, an isopentyloxy group, a neopentyloxy group, a tert-pentyloxy group, an n-hexyloxy group, and an isohexyloxy group.

  As shown in the following formula, the benzene compound represented by the general formula (2) of the present invention is a cyclic alkyne compound represented by the general formula (1) in the presence of rhodium halide and a tertiary amine compound. It is produced by a trimerization reaction.

[Wherein, R ¹ and R ² are the same as defined above. ]
When the alkyne compound represented by the general formula (1) is subjected to a cyclic trimerization reaction, an isomer represented by the general formula (3) is produced as a by-product. When present, the by-product of the isomer represented by the general formula (3) can be significantly suppressed, and the benzene compound represented by the general formula (2) can be produced with high selectivity and high yield. .

  Among the alkyne compounds represented by the general formula (1) used as a starting material in the present invention, the following general formula (1a)

[Wherein, R ^1a and R ^2a are the same or different and each represents a hydrogen atom, a C _1-8 alkyl group, a phenyl group which may have a substituent, or a C _1-4 alkoxycarbonyl group. However, R ^1a and R ^2a do not represent a hydrogen atom at the same time. ]
The alkyne compound represented by these can be used conveniently. When the alkyne compound represented by the general formula (1a) is used as a starting material, the following general formula (2a)

[Wherein, R ^1a and R ^2a are the same as above. ]
Is produced.

  Examples of the rhodium halide used in the present invention include rhodium fluoride, rhodium chloride, rhodium bromide, and rhodium iodide. Specific examples of rhodium fluoride include rhodium fluoride (III), rhodium fluoride (IV), rhodium fluoride (V) and the like. Specific examples of rhodium chloride include rhodium (I) chloride, rhodium (II) chloride, rhodium (III) chloride and the like. Specific examples of rhodium bromide include rhodium (III) bromide and basic rhodium bromide. Specific examples of rhodium iodide include rhodium (III) iodide. In the present invention, hydrates of these rhodium halides can also be used. These are used alone or in combination of two or more.

Among the above rhodium halides, rhodium chloride and hydrates thereof can be preferably used. Particularly, rhodium (III) chloride (rhodium trichloride: RhCl ₃ ) and trihydrate thereof (RhCl ₃ .3H ₂ O are preferably used. can do.

  The amount of rhodium halide used is usually about 0.015 to 2 mol, preferably about 0.02 to 1 mol, more preferably 0.03, per 1 mol of the alkyne compound represented by the general formula (1). About 0.5 mol.

Examples of the tertiary amine compound used in the present invention include N, N, N-tri (C _1- ) such as trimethylamine, dimethylethylamine, triethylamine, tri (n-butyl) amine, diisopropylethylamine, diisobutylmethylamine. ₄ alkyl) amine; N- (C _1-4 alkyl) azacycloalkane such as diethyl (tetramethylsilyl) amine, N-methylpyrrolidine, N-methylpiperidine; N such as N-methylmorpholine, N-ethylmorpholine -(C _1-4 alkyl) azaoxycycloalkane; N-benzyl-N, N-di (C _1-4 alkyl) such as N-benzyl-N, N-dimethylamine and N-benzyl-N, N-diethylamine ) amine; N, N-dimethylaniline or the like of N, N-di (C _1-4 alkyl) aniline; diazabicyclo undecenyl It can include bicyclic amines such as diazabicyclononene. These tertiary amine compounds may be used alone or in combination of two or more.

Among these tertiary amines, N, N, N-tri (C _1-4 alkyl) amines and N- (C _1-4 alkyl) azacycloalkane can be preferably used, and diisopropylmethylamine and tri (n- Butyl) amine is particularly preferably used.

  The amount of the tertiary amine compound used is usually about 1.2 to 10 mol, preferably about 1.5 to 8 mol, more preferably about 2 to 4 mol, particularly preferably 1 mol of rhodium halide. Is about 3 moles.

  The reaction of the present invention is usually carried out in a solvent. Examples of the solvent used include lower alkyl alcohol solvents such as methanol, ethanol, n-propanol, n-butanol, isopropanol, isobutanol, and tert-butanol; methyl formate, ethyl formate, propyl formate, butyl formate, methyl acetate , Lower alkyl ester solvents of lower carboxylic acids such as ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate; ketones such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diethyl ketone Solvents: ethers such as diethyl ether, ethyl propyl ether, ethyl butyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, methyl cellosolve, dimethoxyethane Medium; nitrile solvents such as acetonitrile, propionitrile, butyronitrile, isobutyronitrile, valeronitrile; substituted or unsubstituted aromatic hydrocarbon solvents such as benzene, toluene, xylene, chlorobenzene, anisole; dichloromethane, chloroform, Halogenated hydrocarbon solvents such as dichloroethane, trichloroethane, dibromoethane, propylene dichloride, carbon tetrachloride, and chlorofluorocarbons; aliphatic hydrocarbon solvents such as pentane, hexane, heptane, and octane; cyclopentane, cyclohexane, cycloheptane, cyclo Cycloalkane solvents such as octane; amide solvents such as dimethylformamide, diethylformamide, dimethylacetamide; cyclic amide solvents such as N-methylpyrrolidinone; tetrahydrofuran, di It can be exemplified dimethyl sulfoxide, water and the like; hexane, cyclic ethers dioxolane-based solvent. These solvents may be used alone or in combination of two or more.

  Among these solvents, lower alkyl alcohol solvents, aromatic hydrocarbon solvents, ether solvents and cyclic ether solvents are preferable, and specifically, isopropyl alcohol, toluene, xylene, dimethoxyethane and dioxane are preferable. Aromatic hydrocarbon solvents such as toluene are more preferred.

  The amount of these solvents used is usually about 2 to 200 liters, preferably about 3 to 100 liters per kg of the alkyne compound of the general formula (1).

  The reaction temperature of the present invention may be from room temperature to around the boiling point of the solvent to be used or the reflux temperature, but it is preferable to select the solvent to be used so that the reaction can be carried out in the range of 50 to 150 ° C. The temperature is particularly preferable.

  The reaction time of this reaction varies depending on the type of alkyne compound used and other reaction conditions, and cannot be generally specified, but is generally about 1 to 48 hours, usually about 5 to 24 hours.

  The benzene compound of the general formula (1) obtained by the method of the present invention is isolated from the reaction mixture and purified by known isolation means and purification means.

  By the method of the present invention, a desired benzene compound can be produced in high yield from an alkyne compound.

  According to the method of the present invention, a complex polysubstituted benzene compound (asymmetric polysubstituted benzene compound) can be produced from an alkyne compound in a single step with high selectivity and high yield.

  The polysubstituted benzene compound obtained by the production method of the present invention is used by itself as a functional substance or a functional material, or used as a raw material for producing a functional substance or a functional material.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to these examples.

  The analytical methods and equipment used in the present invention are as follows.

Nuclear magnetic resonance (NMR) spectra were measured using INOVA UNITY 600 (600 MHz) manufactured by Varian, and chemical shifts were expressed in ppm based on the internal standard (tetramethylsilane). Abbreviations for splitting patterns are as follows.
s: singlet, d: doublet, m: multit, br: broad.

  Moreover, the production | generation ratio of the target benzene compound (2) and the by-product isomer (3) was computed from NMR.

  Infrared spectroscopy (IR) spectrum was measured using FT-IR Valor III manufactured by JASCO Corporation. The liquid sample was measured using a liquid film method.

  Example 1

[In the formula, Ph represents a phenyl group, and Et represents an ethyl group. ]
In the reactor, 13.1 mg (0.05 mmol) of rhodium (III) chloride trihydrate (RhCl ₃ .3H ₂ O) was weighed, and the inside of the reactor was purged with argon. Next, 3 ml of toluene and 19.4 mg (0.15 mmol) of diisopropylethylamine (IPEA) were added to the reactor, followed by stirring for 15 minutes under reflux. Next, 87 mg (0.5 mmol) of ethyl phenylpropinate (1-1) was gradually added dropwise, and then the reaction was carried out by stirring for 24 hours while heating under reflux. The reaction mixture was filtered to remove insolubles, and the filtrate was concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography (developing solvent: n-hexane / ethyl acetate = 5/1 (volume ratio)) to obtain a benzene compound (2-1).
Yield: 79.3 mg
Yield: 91%
Content of benzene compound (2-1): 96% by weight or more (content of isomer (3-1): less than 4% by weight)
The NMR spectrum of the benzene compound (2-1) is as follows.
¹ H-NMR (600 MHz) δ ppm: 7.35 (s, 5H), 7.11-7.14 (m, 6H), 7.00-7.04 (m, 4H), 3.98 (q, 2H, J = 7.2 Hz), 3.94 (q, 2H, J = 7.2 Hz), 3.65 (q, 2H, J = 7.2 Hz), 0.90 (t, 3H, J = 7) .2 Hz), 0.87 (t, 3H, J = 7.2 Hz), 0.68 (t, 3H, J = 7.2 Hz)
The IR spectrum of the benzene compound (2-1) is as follows.
IR (Neat): 3057, 2981, 2936, 1729, 1232, 1200 cm ⁻¹ .

Examples 2-5
The reaction and treatment were performed in the same manner as in Example 1 except that the amounts of RhCl ₃ .3H ₂ O and IPEA used were changed to the amounts shown in Table 1. Note that the amount of RhCl ₃ · 3H ₂ O and IPEA showed a molar ratio to phenylpropionate phosphate ethyl 100mmol (mmol%). The results are shown in Table 1.

Examples 6-7 and Comparative Examples 1-9
The reaction and treatment were performed in the same manner as in Example 1 except that IPEA was changed to the amine compounds shown in Table 3 or other compounds. The results are shown in Table 2. In the table, Et represents an ethyl group, Bu represents a butyl group, TMS represents a trimethylsilyl group, TMEDA represents N, N, N ′, N′-tetramethylethylenediamine, and Ph represents a phenyl group. -Means unconfirmed.

Examples 8-11
The reaction and treatment were performed in the same manner as in Example 1 except that toluene was changed to the organic solvent described in Table 3. The results are shown in Table 3. In the table, DME means dimethoxyethane and IPA means isopropyl alcohol.

Examples 12-19
The reaction and treatment were performed in the same manner as in Example 1 except that ethyl phenylpropinate (1-1) was changed to the alkyne compounds shown in Table 4. The results are shown in Table 4. In the table, Me represents a methyl group, Et represents an ethyl group, Pr represents an n-propyl group, Hex represents an n-hexyl group, and Ph represents a phenyl group.

Benzene compounds (2-2), (2-3), (2-4), (2-5), (2-6), (2-7), (2- The NMR spectrum data and IR spectrum data of 8) and (2-9) are shown below.
Benzene compound (2-2);
¹ H-NMR (600 MHz) δ ppm: δ = 6.96-7.46 (m, 15H), 2.05 (s, 3H), 2.04 (s, 3H), 1.72 (s, 3H)
IR (Neat): 3055, 2956, 2918, 2849 cm ⁻¹
Benzene compound (2-3);
¹ H-NMR (600 MHz) δ ppm: 4.40 (q, 2H, J = 7.2 Hz), 4.33 (q, 2H, J = 7.2 Hz), 4.32 (q, 2H, J = 7) .2 Hz), 2.30 (s, 3H), 2.26 (s, 3H), 2.22 (s, 3H), 1.38 (t, 3H, J = 7.2 Hz), 1.36 ( t, 3H, J = 7.2 Hz), 1.35 (t, 3H, J = 7.2 Hz)
IR (Neat): 2982, 2938, 2906, 1731, 1576 cm ⁻¹
Benzene compound (2-4);
¹ H-NMR (600 MHz) δ ppm: 2.46-2.48 (m, 12H), 1.49-1.57 (m, 12H), 1.04 (t, 18H, J = 7.2 Hz), 1.87 (s, 3H)
IR (Neat): 2952, 2928, 2890, 2869 cm ⁻¹
Benzene compound (2-5);
¹ H-NMR (600 MHz) δ ppm: 6.83 to 6.86 (m, 30H)
IR (Neat): 3056, 3024, 2925 cm ⁻¹
Benzene compound (2-6);
¹ H-NMR (600 MHz) δ ppm: 7.17-7.69 (m, 18H)
IR (Neat): 3075, 3056, 3027 cm ⁻¹
Benzene compound (2-7);
¹ H-NMR (600 MHz) δ ppm: 7.56-7.62 (m, 4H), 7.46 (dd, 1H, J = 7.8 Hz, J = 0.6 Hz), 7.26 (dd, 2H) , J = 7.8 Hz, J = 0.6 Hz), 7.03-7.10 (m, 8H), 2.40 (s, 3H), 2.33 (s, 3H), 2.32 (s , 3H)
IR (Neat): 3025, 2917, 2863 cm ⁻¹
Benzene compound (2-8);
¹ H-NMR (600 MHz) δ ppm: 6.81-7.05 (m, 3H), 2.52-2.58 (m, 6H), 1.54-1.59 (m, 6H), 28-1.39 (m, 18H), 0.87-0.91 (m, 9H)
IR (Neat): 2926, 2856 cm ⁻¹
Benzene compound (2-9);
¹ H-NMR (600 MHz) δ ppm: 8.40 (dd, 1H, J = 1.2 Hz, J = 0.6 Hz, 8.19 (dd, 1H, J = 8.4 Hz, J = 1.2 Hz), 7.76 (dd, 1H, J = 8.4 Hz, J = 0.6 Hz), 4.37-4.43 (m, 6H), 1.37-1.59 (m, 9H)
IR (Neat): 2983, 2938, 1727, 1244 cm ⁻¹
Comparative Examples 10-13
The reaction and treatment were carried out in the same manner as in Example 1 except that RhCl ₃ .3H ₂ O was changed to the rhodium compounds shown in Table 5. The results are shown in Table 5. In the table, cod means 1,6-cyclooctadiene, and acac means acetylacetonate.

Claims (4)

In the presence of rhodium halide and a tertiary amine compound, the compound represented by the general formula (1)

[Wherein, R ¹ and R ² are the same or different and each represents a hydrogen atom, a C _1-15 alkyl group, a phenyl group which may have a substituent, a C _1-4 alkoxy C _1-4 alkyl group, C _{1 -4} alkylcarbonyl group, benzoyl group which may have a substituent, C _1-4 alkoxycarbonyl group, tri (C _1-4 alkyl) silyl group, tri (C _1-4 alkoxy) silyl group, cyano group, halogen The heterocyclic group which may have an atom, a nitro group, or a substituent is shown. However, R ¹ and R ² do not represent a hydrogen atom at the same time. ]
The alkyne compound represented by general formula (2)

[Wherein, R ¹ and R ² are the same as defined above. ]
The manufacturing method of a benzene compound which manufactures the benzene compound represented by these.   The production method according to claim 1, wherein the rhodium halide is at least one selected from the group consisting of rhodium fluoride, rhodium chloride, rhodium bromide, rhodium iodide and hydrates thereof.   The manufacturing method of Claim 1 or 2 which uses about 0.015-2 mol of rhodium halides with respect to 1 mol of alkyne compounds represented by General formula (1). The production method according to any one of claims 1 to 3, wherein the tertiary amine compound is used in an amount of about 1.2 to 10 moles per mole of rhodium halide.