JP2002053516A - Method of producing ketone by oxidative degradation of olefin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of simply and effectively producing a corresponding carbonyl compound from an olefin by an oxidative degradation without using a toxic substance such as ozone or the like and capable of reacting in an aqueous medium. SOLUTION: This method produces a corresponding carbonyl compound by oxidizing an olefin compound with hydrogen peroxide and an iron compound in an aqueous medium in the presence of a metal complex having a hydrophobic space, e.g. M6L4 type three dimensional basket like or bowl like transition metal complex using, e.g. 2,4,6-tris-(4-pyridinyl)-1,3,5-triazine or 2,4,6-tris-(3- pyridinyl)-1,3,5-triazine or the like as a ligand.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel method for producing a carbonyl compound utilizing an oxidative decomposition reaction of an olefin.

[0002]

2. Description of the Related Art As a method of producing a corresponding carbonyl compound by oxidatively decomposing an olefin, a method of decomposing a carbon-carbon double bond using ozone in an organic solvent to produce an ozonide has been described. This is then reduced to a ketone only as the only practical method. However, the above-mentioned conventional method has a problem in that it is essential to use ozone, which is a harmful substance, and the reaction must be carried out in an organic solvent. Not yet.

[0003]

SUMMARY OF THE INVENTION The present invention is a method for producing the corresponding carbonyl compound by oxidatively decomposing an olefin, and does not use harmful substances such as ozone.
Another object of the present invention is to provide a simple and efficient production method capable of performing a reaction in an aqueous medium.

[0004]

The present invention relates to a corresponding carbonyl compound, characterized in that an olefin compound is oxidized with hydrogen peroxide and an iron compound in an aqueous medium in the presence of a metal complex having a hydrophobic space. A method for producing the same.

The metal complex having a hydrophobic space used in the present invention includes, for example, an electron pair which has a substantially planar structure and can form a coordination bond with a transition metal in a molecule. Having three or more compounds. Examples of the transition metal include platinum and palladium. Examples of the electron pair of a ligand capable of forming a coordination bond with a transition metal include an electron pair of a nitrogen atom of a pyridine ring. As the ligand, a compound having 3 to 6 electron pairs capable of forming a coordination bond with a transition metal in the molecule is preferable, and specifically, 2,4,6-
Tris (4-pyridyl) -1,3,5-triazine, 2,4,6-tris (3-pyridyl) -1,3,5-triazine and the like are exemplified as more preferable ligands. Examples of the metal complex having a hydrophobic space used in the present invention include an M ₆ L ₄ type three-dimensional cage-like or bowl-like transition metal complex. M ₆ L ₄ used in the present invention
Type three-dimensional cage-like transition metal complex is disclosed in, for example,
The three-dimensional cage-like transition metal complex described in JP-A-00-86683 is exemplified. Preferred specific examples of the metal complex having a hydrophobic space used in the present invention include, for example, the following formula [1]

[0006]

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The compound represented by the following formula [2]

[0008]

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Compounds represented by the formula: The use amount of the metal complex according to the present invention is usually about 1 to 30 mol%, preferably 3 to 20 mol%, more preferably about 5 to 10 mol% based on 1 mol of the olefin compound.

The olefin compound used in the present invention is preferably an olefin compound having an aromatic group.
Further, as the olefin compound used in the present invention,
Olefin compounds having a carbon-carbon double bond at the terminal of the molecule are preferred. Examples of the hydrogen peroxide used in the present invention include, for example, an aqueous hydrogen peroxide solution having a concentration of about 30%, which is generally used, but the concentration is not particularly limited thereto. Demonstrate
Any concentration may be used as long as the concentration allows the intended oxidation reaction to proceed smoothly. The amount of hydrogen peroxide to be used is generally 0.5 to 50 equivalents, preferably 1 to 10 equivalents, more preferably 1 to 2 equivalents to the olefin compound. As the iron compound used in the present invention, generally, a trivalent iron compound having oxidizing power as it is is preferable,
In this case, even a divalent iron compound is oxidized in the system to be trivalent, so that a divalent iron compound can be used similarly to a trivalent iron compound. Specific examples of the iron compound used in the present invention include, for example, ferric (or ferrous) chloride, ferric (or ferrous) sulfate, ferric (or ferrous) nitrate, and ferric (or ferrous) phosphate. First) iron salts such as iron. The amount of the iron compound to be used is generally about 1 to 50 mol%, preferably about 3 to 20 mol%, more preferably about 5 to 10 mol%, based on the olefin compound.

In the production method of the present invention, the reaction is usually carried out in an aqueous solvent. The reaction temperature in the production method of the present invention is usually about 0 to 100 ° C, preferably about 20 to 50 ° C. The reaction time varies naturally depending on the reaction temperature, the type of the olefin compound, the concentration of hydrogen peroxide in the reaction system, the amount of the metal complex and the amount of the trivalent iron salt used, etc. It takes about 2 to 48 hours.

[0012]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. The complex 1a used in the examples is a complex represented by the above formula [1] in which the transition metal is palladium. The complex 1b is a complex represented by the above formula [1] in which the transition metal is the same. Each of platinum is represented.

Example 1 Synthesis of acetophenone using complex 1a Complex 1a (15.0 mg, 0.005 ml) was placed in a 5 mL test tube.
5 mmol) and iron nitrate nonahydrate (2.0 mg, 0.1 mg).
005 mmol) and dissolved by heating with water (1 mL). After cooling this with tap water, α with a micro syringe
-Methylstyrene 0.0065mL (0.05mmo
l) and 34% aqueous hydrogen peroxide 0.005 mL (0.05
mmol), and the mixture was sealed and stirred at 50 ° C. for 24 hours. After the stirring reaction, extraction was performed with heavy chloroform.
^The amount of acetophenone produced was quantified by ¹ H NMR (66% yield).

Example 2 Synthesis of acetophenone using complex 1b Complex 1b (17.6 mg, 0.005 mL) was placed in a 5 mL test tube.
5 mmol) and iron nitrate 9-hydrate (2,2.0 mg,
0.005 mmol) and dissolved by heating with water (1 mL). After cooling this with tap water, 0.0065 mL of α-methylstyrene (0.05 m
mol) and 0.005 mL of 34% aqueous hydrogen peroxide (0.
05 mmol), and sealed at 50 ° C. for 24 hours.
Stirred for hours. After the stirring reaction, extraction was performed with deuterated chloroform,
From the ¹ H NMR, the amount of acetophenone produced was quantified (yield 15%).

Comparative Example 1 Synthesis of acetophenone in a system from which iron nitrate 9-hydrate was removed Into a 5 mL test tube, complex 1a (15.0 mg, 0.00
5 mmol) and dissolved by heating with water (1 mL).
After cooling this with tap water, 0.0065 mL (0.05 mmol) of α-methylstyrene was obtained with a microsyringe.
And 34% hydrogen peroxide solution 0.005 mL (0.05 mm
ol), and the mixture was sealed, followed by stirring at 50 ° C for 24 hours. After stirring the reaction was extracted with deuterochloroform, The ¹ H
The amount of acetophenone produced was quantified by NMR (1% yield).

Comparative Example 2 Synthesis of Acetophenone in a System Excluding Complex 1a Into a 5 mL test tube, iron nitrate 9-hydrate (2.0 mg,
0.005 mmol) and dissolved in water (1 mL). Add α-methylstyrene with a micro syringe
0.0065 mL (0.05 mmol) and 0.005 mL (0.05 mmol) of 34% aqueous hydrogen peroxide were sequentially added, and the mixture was sealed, followed by stirring at 50 ° C. for 24 hours. After the stirring reaction, extraction was performed with deuterated chloroform, and the amount of acetophenone produced was quantified from its ¹ H NMR (4% yield).

Comparative Example 3 Synthesis of acetophenone in a system from which hydrogen peroxide had been removed Into a 5 mL test tube, complex 1a (15.0 mg, 0.00
5 mmol) and iron nitrate nonahydrate (2.0 mg,
0.005 mmol) and dissolved by heating with water (1 mL). After cooling this with tap water, 0.0065 mL of α-methylstyrene (0.05 m
mol) and 0.005 mL of 34% aqueous hydrogen peroxide (0.
05 mmol), and sealed at 50 ° C. for 24 hours.
Stirred for hours. After the stirring reaction, extraction was performed with deuterated chloroform,
From the ¹ H NMR, the amount of acetophenone produced was quantified (yield 1%).

Example 3 Synthesis of 4-methoxyacetophenone using complex 1a In a 5 mL test tube, complex 1a (15.0 mg, 0.005
mmol) and iron nitrate nonahydrate (2.0 mg, 0.1 mg).
005 mmol), and dissolved by heating in water (1 mL) to prepare an aqueous solution. Add 4-methoxy- to another test tube in advance.
7.4 mg (0.05 mmol) of α-methylstyrene
, And the aqueous solution prepared above and 0.005 mL (0.05 mmol) of 34% aqueous hydrogen peroxide were sequentially added thereto, and the mixture was sealed, followed by stirring at 50 ° C. for 24 hours. After the stirring reaction, the mixture was extracted with heavy chloroform, and the amount of 4-methoxyacetophenone produced was quantified from its ¹ H NMR (yield 61%).

Example 4 Synthesis of 4-methylacetophenone using complex 1a Complex 1a (15.0 mg, 0.005 ml) was placed in a 5 mL test tube.
5 mmol) and iron nitrate nonahydrate (2.0 mg,
0.005 mmol) and dissolved by heating with water (1 mL). After cooling this with tap water, 4-methyl-α-methylstyrene 0.0066 mL with a microsyringe.
(0.05 mmol) and 34% aqueous hydrogen peroxide 0.00
After adding 5 mL (0.05 mmol) sequentially and sealing,
Stirred at 50 ° C. for 24 hours. After the stirring reaction, extraction was performed with deuterated chloroform, and the amount of 4-methylacetophenone produced was quantified from its ¹ H NMR (yield 53%).

Example 5 Synthesis of 4-nitroacetophenone using complex 1a In a 5 mL test tube, complex 1a (15.0 mg, 0.00
5 mmol) and iron nitrate nonahydrate (2.0 mg,
0.005 mmol), and dissolved by heating in water (1 mL) to prepare an aqueous solution. In another test tube, 8.2 mg (0.05 mmol) of 4-nitro-α-methylstyrene was previously prepared.
l), and add the aqueous solution prepared above with 34%
After 0.005 mL (0.05 mmol) of aqueous hydrogen peroxide was sequentially added and the mixture was sealed, the mixture was stirred at 50 ° C. for 24 hours.
After the stirring reaction, extraction was performed with deuterated chloroform, and the ¹ H NM
The amount of 4-nitroacetophenone produced from R was quantified (75% yield).

Example 6 Methyl-2-using complex 1a
Synthesis of Naphthyl Ketone In a 5 mL test tube, complex 1a (15.0 mg, 0.00
5 mmol) and iron nitrate nonahydrate (2.0 mg,
0.005 mmol), and dissolved by heating in water (1 mL) to prepare an aqueous solution. In another test tube, 8.2 mg (0.05 mmol) of isopropenylnaphthalene was put in advance, and the aqueous solution prepared above and 0.005 mL (0.05 mmol) of 34% hydrogen peroxide solution were sequentially added thereto, followed by sealing. Thereafter, the mixture was stirred at 50 ° C. for 24 hours. After stirring the reaction was extracted with chloroform-methyl-2 from its ¹ HNMR
-The amount of naphthyl ketone produced was quantified (40% yield).

Example 7 Methyl-2-using complex 1a
Synthesis of naphthyl ketone (scale-up synthesis) In a 100 mL eggplant-shaped flask, 168.1 mg (1.0 mmol) of isopropenylnaphthalene was placed, and the separately prepared complex 1a (299.3 mg, 0.1 mmol) was added thereto.
l) and iron nitrate nonahydrate (40.4 mg, 0.1 m
mol)) (30 mL) and stirred for 10 minutes. Add 34% hydrogen peroxide solution with a micro syringe
After adding 0.11 mL (1.0 mmol) and sealing,
Stirred at 50 ° C. for 24 hours. After the stirring reaction, hexane 50
The mixture was extracted with 3 mL × 3 and 50 mL × 2 chloroform, and the extract was dried over anhydrous magnesium sulfate. After drying, this was concentrated and separated by GPC to obtain methyl-2-naphthyl ketone (78.9 mg, yield 47%). At the same time, the raw material (52.2 mg) was recovered.

[0023]

The oxidative decomposition (cleavage) reaction of olefins is a basic synthesis reaction, but it is a bottleneck that ozone must be used and that the reaction is carried out in an organic solvent. And did not reach general public use. According to the method of the present invention, no harmful substances such as ozone are used, and the reaction proceeds in an aqueous medium.
We can expect great progress in the future.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07C 49/84 C07C 49/84 C 201/12 201/12 205/45 205/45 // C07B 61/00 300 C07B 61/00 300 (72) Inventor Hirokazu Ito 9-9 Inokachi Shinmachi, Okazaki City, Aichi Prefecture Urban Square II 201 F term (reference) 4G069 BA27A BA27B BC72A BC72B BC75A BC75B BE13A BE13B BE38A BE38B BE39A BE39B CB11 4H006 AA02 AC BA26 BA46 BE32 4H039 CA62 CC30

Claims (12)

[Claims] 1. In the presence of a metal complex having a hydrophobic space,
A method for producing a corresponding carbonyl compound, comprising oxidizing an olefin compound with hydrogen peroxide and an iron compound in an aqueous medium. 2. The method according to claim 1, wherein the olefin compound is an olefin compound having an aromatic group. 3. The production method according to claim 1, wherein the olefin compound is an olefin compound having a carbon-carbon double bond at a molecular terminal. 4. A compound in which a metal complex having a hydrophobic space has a ligand having a substantially planar structure and three or more electron pairs in a molecule capable of forming a coordinate bond with a transition metal. The method according to any one of claims 1 to 3, wherein 5. The method according to claim 4, wherein the transition metal is platinum or palladium. 6. The method according to claim 4, wherein the electron pair of the ligand capable of forming a coordination bond with the transition metal is an electron pair of a nitrogen atom of a pyridine ring. 7. The method according to claim 4, wherein the ligand is a compound having 3 to 6 electron pairs capable of forming a coordination bond with a transition metal in the molecule. 8. The method according to claim 7, wherein the ligand is 2,4,6-tris (4-pyridyl) -1,3,5-triazine. 9. The method according to claim 7, wherein the ligand is 2,4,6-tris (3-pyridyl) -1,3,5-triazine. 10. The metal complex having a hydrophobic space is M ₆
The process according to any one of claims 1 to 7 L is a _4-inch three-dimensional cage or bowl-shaped transition metal complex. 11. A metal complex having a hydrophobic space is represented by the following formula [1]: The method according to claim 4, which is a compound represented by the formula: 12. The metal complex having a hydrophobic space is represented by the following formula [2]: The method according to claim 4, which is a compound represented by the formula: