JPH11246466A - Cyclohexanone derivative and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound useful as an intermediate raw material of monomer for functional polymers (e.g. acrylic resin for resist or polyester) or an intermediate for perfumes, medicines or agrochemicals by introducing an acyl group at 4 position. SOLUTION: This compound is represented by formula I (R<1> to R<5> are each H or a hydrocarbon group and R<1> and R<2> and R<4> and R<5> each may form a ring together with adjacent carbon atom), e.g. 2,3,5-trimethyl-4- propionylcyclohexane-1-one. The compound of formula I is obtained by bringing (A) a compound of formula II into contact with (B) a catalyst comprising a compound of the group 3 or 4 of the periodic table (e.g. a samarium compound or a zirconium compound) in an amount corresponding to 0.00001-1 mol based on 1 mol component A in the presence (or absence) of a solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel cyclohexanone derivative and a method for producing the same. This compound
It is expected to be used as an intermediate raw material for functional polymer monomers, fragrances, and intermediates for pharmaceuticals and agricultural chemicals.

[0002]

2. Description of the Related Art Hydroxyl and hydroxymethyl groups,
Alternatively, the alicyclic compounds having substituents such as oxo group and acyl group, which are precursors thereof, can be used as monomer raw materials, fragrances, and pharmaceutical intermediates of functional polymers (eg, acrylic resins for resists and polyesters). From recently, has been attracting attention. However, a cyclohexanone derivative having an acyl group at the 4-position and a production method thereof are not known.

[0003]

Accordingly, an object of the present invention is to provide a novel cyclohexanone derivative having an acyl group at the 4-position. Another object of the present invention is to provide a method for easily producing a cyclohexanone derivative having an acyl group at the 4-position.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object. As a result, when an α, β-unsaturated ketone is brought into contact with a specific catalyst, it dimerizes to give a corresponding cyclohexanone. The present inventors have found that a derivative is formed and completed the present invention.

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

Embedded image (Wherein, R ¹ , R ² , R ³ , R ⁴ , and R ⁵ are the same or different and represent a hydrogen atom or a hydrocarbon group. R ^1, R ² , R ⁴
And R ⁵ may be combined with adjacent carbon atoms to form a ring). The present invention also provides the following formula (2)

Embedded image (Wherein, R ¹ , R ² , R ³ , R ⁴ , and R ⁵ are the same as described above), and a catalyst comprising an α, β-unsaturated ketone represented by a Group 3 or 4 element compound of the periodic table. And the above formula (1)
A process for producing a cyclohexanone derivative which produces the compound represented by the formula:

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION [Cyclohexanone Derivative] In the above formula (1), the hydrocarbon groups for R ¹ , R ² , R ³ , R ⁴ and R ⁵ include an aliphatic hydrocarbon group and an alicyclic hydrocarbon. And aromatic hydrocarbon groups. Examples of the aliphatic hydrocarbon group include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, hexyl, and decyl groups having 1 to 10 carbon atoms (preferably 1 to 10 carbon atoms).
To 6, more preferably 1 to 4) alkyl groups; 2 to 10 carbon atoms such as vinyl, allyl and 1-butenyl groups
(Preferably 2 to 6, more preferably 2 to 4) alkenyl groups; and 2 carbon atoms such as ethynyl and propynyl groups.
-10 (preferably 2-6, more preferably 2-4)
Alkynyl groups and the like.

The alicyclic hydrocarbon groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,
A cycloalkyl group having about 3 to 12 members (preferably 3 to 8 members, more preferably 5 or 6 members) such as a cyclooctyl group; and a 3 to 12 member (preferably 3 or 12 members) such as a cyclopentenyl or cyclohexenyl group. To 8-membered, more preferably 5 or 6-membered) cycloalkenyl groups. Examples of the aromatic hydrocarbon group include phenyl and naphthyl groups.

Preferred hydrocarbon groups include those having 1 to 10 carbon atoms.
Alkenyl group and alkynyl group having 2 to 10 carbon atoms, and an aromatic hydrocarbon group having 6 to 10 carbon atoms, and an alkyl group having 1 to 10 carbon atoms is particularly preferable.

[0009] The hydrocarbon group may have a substituent. Examples of the substituent include a halogen atom (fluorine, chlorine, bromine atom, etc.), an oxo group, a hydroxyl group, a substituted oxy group [alkoxy group (C _1-4 alkoxy group such as methoxy, ethoxy group, etc.), aryloxy Group (such as phenyloxy group), acyloxy group (such as C _1-6 acyloxy group such as acetoxy and benzoyloxy group), carboxyl group, and substituted oxycarbonyl group (such as methoxycarbonyl and ethoxycarbonyl group).
_C1-4 alkoxy - carbonyl group), a substituted or unsubstituted carbamoyl group (a carbamoyl group; methylcarbamoyl, such mono- or di-C _1-4 alkyl-substituted carbamoyl groups such as dimethylcarbamoyl group), a cyano group, a nitro group, a substituted or Unsubstituted amino group (amino group; mono- or di-C such as N-methylamino, N, N-dimethylamino group, etc.)
_1-4 alkyl-substituted amino group and the like, alkyl group (C _1-4 alkyl group such as methyl and ethyl group), cycloalkyl group (3-8 membered cycloalkyl group such as cyclohexyl group), aryl group (phenyl , A naphthyl group, etc.) and a heterocyclic group (a 5- to 6-membered heterocyclic ring having 1 to 3 heteroatoms selected from nitrogen, oxygen and sulfur atoms such as pyridyl, furyl and thienyl groups).

The ring which may be formed by combining R ¹ and R ² , R ⁴ and R ⁵ together with adjacent carbon atoms includes:
3 to 12 members (preferably 3 to 8 members) such as cyclopropyl, cyclopentyl, cyclohexyl and cyclohexenyl groups.
Member, more preferably about 5 or 6 membered) cycloalkane ring or cycloalkene ring. These rings may have the above substituents.

R ¹ , R ² , R ³ , R ⁴ and R ⁵ are preferably a hydrogen atom or a C _1-10 alkyl group (particularly a C _1-6 alkyl group). Preferred compounds represented by the formula (1) include compounds in which R ¹ , R ² , R ⁴ and R ⁵ are not simultaneously a hydrogen atom. In a preferred embodiment of the present invention, R ¹ and R ²
One is a hydrogen atom, and the other is a hydrocarbon group (for example, the above-mentioned preferred hydrocarbon group, particularly a C _1-10 alkyl group, especially a C _1-6 alkyl group). Preferably, one of R ⁴ and R ⁵ is a hydrogen atom and the other is a hydrocarbon group (for example, the preferred hydrocarbon group, particularly
_1-10 alkyl group, especially C _1-6 alkyl group). R ³
Is preferably a hydrogen atom or a C _1-4 alkyl group, and more preferably a hydrogen atom.

Representative examples of the compound represented by the formula (1) include 4-acetylcyclohexane-1-one, 2-methyl-4-propionylcyclohexane-1-one,
-Acetyl-3,5-dimethylcyclohexane-1-one, 2,3,5-trimethyl-4-propionylcyclohexane-1-one, 2,3,3,5,5-pentamethyl-4-propionylcyclohexane-1-one ON, 2-
Methyl-3,5-dipropyl-4-propionylcyclohexane-1-one, 2-methyl-3,5-diphenyl-4-propionylcyclohexane-1-one, 3,5
-Dicyclohexyl-2-methyl-4-propionylcyclohexane-1-one, 4-butyryl-2-ethyl-
3,5-dimethylcyclohexane-1-one, 4-isobutyryl-2,2,3,5-tetramethylcyclohexane-1-one, 3,5-dimethyl-2-phenyl-4-
Phenylacetylcyclohexane-1-one, 2-cyclohexyl-3,5-dimethyl-4-cyclohexylacetylcyclohexane-1-one, 2,3,4,5,6
-Pentamethyl-4-propionylcyclohexane-1
-One, 4-acetyl-3,5-dipentylcyclohexane-1-one and the like.

The cyclohexanone derivative of the present invention is expected to be used as a raw material for monomers of functional polymers (acrylic resins for resists, polyesters, etc.), perfumes, pharmaceutical intermediates, etc., for example, by reduction as necessary. it can.

[Production of cyclohexanone derivative] In the α, β-unsaturated ketone represented by the above formula (2),
Hydrocarbon groups in R ¹ , R ² , R ³ , R ⁴ and R ⁵ (and
Preferred examples of the ring formed by bonding of R ¹ and R ² , R ⁴ and R ⁵ together with adjacent carbon atoms include the same as those described above.

As typical examples of the α, β-unsaturated ketone represented by the formula (2), 3-buten-2-one, 4-penten-3-one, 3-penten-2-one, -Hexen-3-one, 5-methyl-4-hexen-3-one,
4-octen-3-one, 5-phenyl-4-penten-3-one, 5-cyclohexyl-4-penten-3-
On, 2-hepten-4-one, 2-methyl-4-hexen-3-one, 1-phenyl-3-penten-2-one, 1-cyclohexyl-3-penten-2-one,
-Methyl-4-hexen-3-one, 3-nonen-2-
On and the like.

In the catalyst composed of a compound of the periodic table group 3 element, the group 3 element of the periodic table includes rare earth elements [for example, scandium, yttrium, lanthanoid series elements (lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium). , Gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium)], and actinoid series elements (eg, actinium and the like).
Preferable Group 3 elements of the periodic table include rare earth elements, and in particular, lanthanoid elements, among which samarium is preferable.
Group 4 elements of the periodic table include titanium, zirconium, and hafnium.

In the periodic table group 3 or 4 element compounds,
The valence of the group 3 or 4 element of the periodic table is not particularly limited,
For example, it is often about 0 to 4, especially about 2 to 4.
Examples of the Group 3 or 4 element compound of the periodic table include simple metals, hydroxides, oxides (including composite oxides), halides (fluoride, chloride, bromide, iodide), and oxo acid salts (for example, Inorganic compounds such as nitrates, sulfates, phosphates, borates, carbonates), oxo acids, isopoly acids or salts thereof, heteropoly acids or salts thereof; organic acid salts (eg,
Cyanate; acetate, trichloroacetate, trifluoroacetate, propionate, naphthenate, stearate,
Carboxylate such as maleate and tartrate; sulfonate such as methanesulfonate, trifluoromethanesulfonate, ethanesulfonate, benzenesulfonate, p-toluenesulfonate and the like; Organic compounds may be mentioned. The ligands constituting the complex include OH (hydroxo), alkoxy (methoxy, ethoxy, propoxy, butoxy, etc.), acyl (acetyl, propionyl, etc.), alkoxycarbonyl (methoxycarbonyl, ethoxycarbonyl, etc.), acetylacetonato , Cyclopentadienyl group, C _1-4 alkyl-substituted dicyclopentadienyl (such as pentamethyldicyclopentadienyl), C _1-4 alkyl (such as methyl and ethyl), halogen atom (such as chlorine and bromine), CO, C
N, oxygen atom, H ₂ O (aquo), phosphorus compound of phosphine (triarylphosphine such as triphenylphosphine), NH ₃ (ammine), NO, NO ₂ (nitro), NO ₃ (nitrat), ethylenediamine, Examples include nitrogen-containing compounds such as diethylenetriamine, pyridine and phenanthroline, and oxygen-containing compounds such as tetrahydrofuran.

Specific examples of Group 3 element compounds of the periodic table include:
Taking a samarium compound as an example, samarium hydroxide (I
I), samarium hydroxide (III), samarium oxide (I
I), samarium oxide (III), samarium iodide (I
I), samarium iodide (III), samarium bromide (I
I), samarium (III) bromide, samarium (II) chloride,
Inorganic compounds such as samarium chloride (III), samarium nitrate (II), samarium sulfate (II), samarium phosphate (II), samarium (II) carbonate; samarium acetate (I
I), samarium acetate (III), samarium trichloroacetate (II), samarium trichloroacetate (III), samarium trifluoroacetate (II), samarium trifluoroacetate (III), samarium trifluoromethanesulfonate (II), trifluoromethane Samarium (III) sulfonate, samarium acetylacetonate (II), samarium acetylacetonate (III), chlorobis (η-
Cyclopentadienyl) samarium (III), chlorobis (η-pentamethylcyclopentadienyl) samarium (III) THF adduct, dichlorobis (η-pentadienyl) samarium (III) THF adduct, tetra (allyl) samarium (III) ) ・ Lithium salt, tetra (t-
Butyl) lithium samarium (III) THF adduct,
Tris (η-cyclopentadienyl) samarium (II
I), bis (η-pentamethylcyclopentadienyl)
Samarium (II) / THF adduct, hydridobis (η-
Pentamethylcyclopentadienyl) samarium (II
I) and alkylsamarium iodide (II). As other Group 3 element compounds of the periodic table, compounds corresponding to the samarium compounds can be exemplified.

As a specific example of the group 4 element compound of the periodic table, taking a zirconium compound as an example, zirconium hydroxide (IV), zirconium oxide (IV), zirconium iodide (IV), zirconyl iodide (IV) ), Zirconium bromide (IV), zirconyl bromide (IV), zirconium chloride (IV), zirconyl chloride (IV), zirconium nitrate (I
V), zirconyl nitrate (IV), zirconium sulfate (I
V), zirconyl sulfate (IV), zirconium phosphate (I
V), zirconyl phosphate (IV), zirconium carbonate (I
V), inorganic compounds such as zirconyl carbonate (IV); zirconium oxalate (IV), zirconium acetylacetonato (IV), chlorobis (η-cyclopentadienyl) methyl zirconium (IV), trichloro (η-cyclopentadiene) Enyl) zirconium (IV), trichloro (η-pentamethylcyclopentadienyl) zirconium (I
V), bis (η-pentamethylcyclopentadienyl)
Organic compounds such as diiodozirconium (IV) are exemplified. Compounds corresponding to the above zirconium compounds are exemplified as other Group 4 element compounds of the periodic table.

The catalyst composed of a Group 3 or 4 element compound of the periodic table may be used in any of a homogeneous system and a heterogeneous system. Further, the catalyst can be used in a form supported on a carrier. As the carrier, a porous carrier such as activated carbon, silica, alumina, silica-alumina, or zeolite is often used. The amount of the catalyst component (Group 3 or Group 4 element compound of the periodic table) supported on the carrier is, for example, 0.1 to 50 parts by weight, preferably 0.5 part by weight, per 100 parts by weight of the carrier.
About 30 parts by weight.

The Group 3 or 4 element compounds of the Periodic Table can be used alone or in combination of two or more. The amount of the catalyst composed of a Group 3 or 4 element compound in the periodic table can be selected in a wide range, for example, 0.00001 to 1 mol per 1 mol of the compound represented by the formula (2). Preferably 0.0
01-0.5 mol, more preferably 0.01-0.2
It is about 5 mol.

The contact (reaction) between the compound represented by the formula (2) and the catalyst is carried out in the presence or absence of a solvent. Examples of the solvent include aliphatic hydrocarbons such as hexane and octane; aromatic hydrocarbons such as benzene and toluene; halogenated hydrocarbons such as chloroform, dichloromethane, dichloroethane, carbon tetrachloride, chlorobenzene, and trifluoromethylbenzene; acetone. Ketones such as methyl, ethyl ethyl ketone and cyclohexanone; ethers such as diethyl ether, diisopropyl ether, dimethoxyethane, tetrahydrofuran and dioxane; organic acids such as acetic acid and propionic acid; esters such as ethyl acetate and butyl acetate; acetonitrile and propionitrile , Nitriles such as benzonitrile; dimethylformamide (DMF), dimethylacetamide, N-
Aprotic polar solvents such as methylpyrrolidone and dimethylsulfoxide; and mixed solvents thereof. Preferred solvents include ketones, ethers, aprotic polar solvents and the like.

The reaction temperature is, for example, 0 to 300 ° C., preferably 10 to 150 ° C., more preferably 20 to 100 ° C.
It is about ° C. The reaction time can be appropriately selected, for example, from a range of about 10 minutes to 48 hours. The reaction may be performed in any of a batch system, a semi-batch system, and a continuous system.

By bringing the compound represented by the formula (2) into contact with the catalyst, a so-called double Michael addition reaction proceeds to dimerize the compound represented by the formula (2), that is, the compound represented by the above formula The compound represented by (1) is produced. After completion of the reaction, the reaction product is easily separated and purified by a conventional method, for example, separation and purification means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, and column chromatography, or a combination thereof. it can.

[0025]

According to the present invention, a novel cyclohexanone derivative having an acyl group at the 4-position is provided. Also,
A cyclohexanone derivative having an acyl group at the 4-position can be easily produced.

[0026]

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

Example 1 1 mmol of 4-hexen-3-one, 0.1 mmol of samarium (II) iodide SmI ₂ , 1 mmol of tetrahydrofuran
The ml mixture was stirred at 60 ° C. for 1 hour. When the product in the reaction solution was isolated using column chromatography, 2,3,5-trimethyl-4-propionylcyclohexane-1-one was produced in a yield of 73%. IR (cm ^-1 ): 2970, 2950, 1740, 14
50, 1380, 1220, 1100 ¹ H-NMR (CDCl ₃ ) δ: 0.85-1.13
(M, 12H), 1.68-2.12 (m, 2H),
2.05-2.22 (m, 2H), 2.34-2.46
(M, 2H), 2.50 ( q, 2H) 13 C-NMR (CDCl 3) δ: 7.08,11.3
0, 18.31, 20.40, 36.08, 38.1
5,42.12,48.77,49.80,63.9
5,210.24, 214.43.

Example 2 Instead of samarium (II) iodide, 0.1 mmol of samarium (III) iodide SmI ₃ was used, and the reaction time was 15 minutes.
When the same operation as in Example 1 was performed except for the time, 2,3,5-trimethyl-4-propionylcyclohexane-1-one was produced in a yield of 36%.

Example 3 Instead of samarium (II) iodide, bis (η-pentamethylcyclopentadienyl) samarium (II) .THF
The same operation as in Example 1 was carried out except that the adduct was used in an amount of 0.1 mmol and the reaction time was changed to 15 hours.
3,5-Trimethyl-4-propionylcyclohexane-1-one was produced in a yield of 21%.

Example 4 Instead of samarium (II) iodide, 0.1 mmol of zirconium (IV) chloride ZrCl ₄ was used, and the reaction time was 1
Except for 5 hours, the same operation as in Example 1 was performed. As a result, 2,3,5-trimethyl-4-propionylcyclohexane-1-one was produced at a yield of 15%.

Example 5 The same operation as in Example 1 was carried out except that 1 mmol of 3-nonen-2-one was used instead of 4-hexen-3-one. -Dipentylcyclohexane-1-one was produced in a yield of 13.4%. IR (cm ^-1 ): 2970, 2940, 1750, 14
50, 1380, 1230, 1110

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // C07B 61/00 300 C07B 61/00 300

Claims (5)

[Claims] [Claim 1] The following formula (1) (Wherein, R ¹ , R ² , R ³ , R ⁴ , and R ⁵ are the same or different and represent a hydrogen atom or a hydrocarbon group. R ^1, R ² , R ⁴
And R ⁵ may be combined with adjacent carbon atoms to form a ring). 2. In the formula (1), R ¹ , R ² , R ³ ,
The cyclohexanone derivative according to claim 1, wherein R ⁴ and R ⁵ are the same or different and each is a hydrogen atom or a C _1-10 alkyl group. 3. The following formula (2): (Wherein, R ¹ , R ² , R ³ , R ⁴ , and R ⁵ are the same or different and represent a hydrogen atom or a hydrocarbon group. R ^1, R ² , R ⁴
And R ⁵ may be bonded together with adjacent carbon atoms to form a ring) with an α, β-unsaturated ketone represented by the following formula: Then, the following formula (1) (Wherein R ¹ , R ² , R ³ , R ⁴ , and R ⁵ are the same as described above). 4. The method for producing a cyclohexanone derivative according to claim 3, wherein the Group 3 element compound of the periodic table is a rare earth element compound. 5. The process for producing a cyclohexanone derivative according to claim 4, wherein the rare earth element compound is a samarium compound.