JPH11255683A - Method for oxidizing organic compounds using amide-bridged platinum complexes - Google Patents

Abstract

(57) [Summary] (Modifications) [PROBLEMS] The present invention provides a novel catalyst in a reaction for oxidizing a carbon-carbon double bond. The present invention also provides a method for selectively producing 1,2-diol by oxidizing a compound having a carbon-carbon double bond in the presence of oxygen. Further, the present invention provides a novel amide (L) -bridged platinum (III) complex. The invention relates to amides represented by the following formula (1) (L) crosslinked platinum (III) ^{_{complex, [Pt III 2 (NH 3}} ) 4 L 2 L 1 L 2] (NO 3) 4 (1 (Wherein, L represents an anionic group consisting of R ¹ CONH group, L ¹ and L ² are the same or different and each represent a water molecule, a neutral ligand or an anionic group, and R ¹ is an organic residue. A method comprising oxidizing a compound having a carbon-carbon double bond in the presence of a catalyst comprising:
The present invention relates to a method for producing a diol and a complex.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for oxidizing a compound having a carbon-carbon double bond, particularly an olefin or cycloolefin, in the presence of a catalyst comprising an amide (L) -bridged platinum (III) complex. Specifically, the present invention oxidizes a compound having a carbon-carbon double bond to 1,
The present invention relates to a method for selectively producing 2-diol. Also,
The present invention relates to amide (L) bridged platinum (III) complexes.

[0002]

2. Description of the Related Art Conventionally, an oxidation reaction of an olefin to a ketone or an aldehyde is carried out by using divalent palladium (Pd) as a catalyst.
(II) (for example, PdCl ₂ or Pd (OAC) ₂ )
Is widely used, Wacker
It is also industrialized as a law. On the other hand, oxidation of olefin to carboxylic acid is generally known to be an equivalent reaction using potassium permanganate or sodium dichromate. Oxidation of olefin to 1,2-diol can be performed by using osmium tetroxide or a derivative thereof,
A method using β zeolite is known. In the former reaction using osmium tetroxide or its derivative as a catalyst, a chiral diol can be synthesized, but a special oxidizing agent such as tertiary amine oxide or K ₃ Fe (CN) ₆ is used for reoxidation of the catalyst. Need. In addition, the latter Ti-β
A method using zeolite as a catalyst also requires aqueous hydrogen peroxide.

[0003] As another method for synthesizing 1,2-diol, a method of oxidizing ethylene to ethylene oxide using Ag as a catalyst and then hydrolyzing it to obtain ethylene glycol is generally performed. It has to go through a two-step process. Pt (II) and Pt (II)
A method for obtaining ethylene glycol from ethanol using a salt of t (IV) has also been reported, but has low catalytic activity and many by-products.

[0004]

SUMMARY OF THE INVENTION The present invention provides a novel catalyst in a reaction for oxidizing a carbon-carbon double bond. Further, the present invention provides a method for oxidizing a compound having a carbon-carbon double bond in one step in the presence of oxygen to form 1,2-
A method for selectively producing a diol is provided. Further, the present invention provides a novel amide (L) -bridged platinum (III) complex.

[0005]

Means for Solving the Problems The present invention is an amide represented by the following formula (1) (L) crosslinked platinum (III) ^{_{complex, [Pt III 2 (NH 3}} ) 4 L 2 L 1 L 2] (NO ₃ ) ₄ (1) (wherein, L represents an anionic group consisting of R ¹ CONH group, and L ¹ and L ² represent the same or different and represent a water molecule, a neutral ligand or an anionic group, respectively. R ¹ represents an organic residue) in the presence of a catalyst comprising a carbon-carbon double bond. The oxidation reaction of the present invention is preferably oxidation with oxygen, and the solvent for the oxidation reaction is preferably a homogeneous or heterogeneous system composed of an organic solvent and / or water. In the formula (1), L ¹ and L ² are the same or different and are each a water molecule, a neutral ligand, NO ₂ ⁻ , NO ₃ ⁻ , X ⁻ or RCOO ⁻ (wherein,
X represents a halogen atom, and R represents an organic residue. ) Is preferable, and L is preferably a group derived from pivalinamide.

[0006] The present invention also relates to a method for selectively producing 1,2-diol by oxidizing a compound having a carbon-carbon double bond. Further, the present invention relates to an oxidation catalyst for a compound having a carbon-carbon double bond, comprising an amide (L) -bridged platinum (III) complex represented by the formula (1). Further, the present invention provides the following formula (2) [Pt ^III ₂ (NH ₃ ) ₄ (Me ₃ CCONH) ₂ L ¹ L ² ] (NO ₃ ) ₄ (2) (wherein Me represents a methyl group; L ¹ and L ² are the same or different and each represent a water molecule, a neutral ligand or an anionic group.) L ¹ and L ² in the formula (2) may be the same or different and each may be a water molecule, a neutral ligand, NO ₂ ⁻ , NO
₃ ^-, X ^- or RCOO ^- (. Wherein, X represents a halogen atom, R is showing an organic residue) is preferred.

An amide (L) -bridged platinum (III) complex represented by the following formula (1): [Pt ^III ₂ (NH ₃ ) ₄ L ₂ L ¹ L ² ] (NO ₃ ) ₄ (1) (1) In the formula, L represents an anionic group consisting of R ¹ CONH group, L ¹ and L ² are the same or different and each represent a water molecule, a neutral ligand or an anionic group, and R ¹ represents an organic residue. Is a binuclear complex of platinum (III) cross-linked with amide L, which is different from known tetranuclear complexes.

The ligand L of the amide (L) -bridged platinum (III) complex represented by the above formula (1) of the present invention is represented by the following general formula (3): R ¹ CONH ₂ (3) . ¹ the amide represented by showing the organic residue) is deprotonated, R ¹ CONH ^- is obtained by negative ionization represented by. The amide of the formula (3) is not particularly limited as long as it can deprotonate to form a stable anion. For example, the organic residue of R ¹ in the amide of the formula (3) has 1 to 30 carbon atoms, preferably 1 to 1 carbon atoms.
2, more preferably 3 to 10 linear or branched alkyl groups, 2 to 30 carbon atoms, preferably 2 to 12, more preferably 3 to 10 linear or branched alkenyl groups, 2 to 30, preferably 2 to 12, more preferably 3 to
10 straight-chain or branched alkynyl groups, having 3 to 3 carbon atoms
0, preferably 5 to 12, more preferably 5 to 10 monocyclic, polycyclic or condensed cycloalkyl or cycloalkenyl groups, 6 to 30 carbon atoms, preferably 6 to 12, more preferably 6 to 10 monocyclic, polycyclic or condensed cyclic aryl groups, each ring having 5 to 15 members, preferably 5 to 10 members
And more preferably 5 to 7 members, and a monocyclic, polycyclic or condensed-ring heteroaryl group having at least one nitrogen atom, oxygen atom or sulfur atom in the ring. These groups may be optionally substituted with substituents that do not interfere with the stability of the anion.

Further, the amide of the present invention may be a lactam in which a ring is formed by the entire amide. further,
The following equation (4)

[0010]

Embedded image

Wherein R ¹ and R ² are the same or different and each represents an organic residue. As the organic residue of R ² in the formula (4), the same organic residue as the above-described organic residue of R ¹ can be exemplified. R ¹ and R ² may be different organic residues, but are preferably the same organic residues. Further, the imide of the formula (4) may form a ring with the entire imide.

The amide used in the present invention includes, for example, propionamide, pivalamide, benzamide, p-methylbenzamide, phthalimide, 3,3
-Dimethylglutarimide, glutarimide, α-pyrrolidone, α-pyridone, trifluoroacetamide, acetamido, uracil, thymine, N-methyl-uracil, N-methyl-thymine, hydantoin and the like.

Further, L ¹ and L ² of the ligand of the above formula (1) are the same or different and each is a water molecule, a neutral ligand or an anionic group. The neutral ligand is not particularly limited as long as it has a portion of the ligand in which there is an excess or deficiency of electrons and has no charge. Solvents are preferred. The anionic group is not particularly limited as long as it does not inhibit the stability of the complex of the present invention. As the anionic group,
For example, NO ₂ ⁻ , NO ₃ ⁻ , X ⁻ or RCOO ⁻ (where X is
Represents a halogen atom, and R represents an organic residue. Is preferred. Wherein anionic groups RCOO ^- groups represented by R
May be the organic residues described above.
Examples of the halogen atom for X include chlorine, bromine, and fluorine.

The method for producing the amide (L) -bridged platinum (III) complex represented by the above formula (1) of the present invention includes, for example, the following amide-bridged platinum (II, III) having a mixed valence of platinum (II, III). A small excess of Na ₂ S is added to the tetranuclear complex represented by the formula (5) [Pt ₄ (NH ₃ ) ₈ L ₄ ] ^{n +} (5) (where n = 5 or 6, L is the same as described above). After adding ₂ O ₈ and reacting for several minutes, HNO ₃ and NaNO ₃ were added and reacted with a small excess.
When left at room temperature, the desired product can be produced as crystals. In the oxidation reaction of the present invention, an amide (L) -bridged platinum (III) complex used as a catalyst, which is produced by the above-mentioned method can be used. It can also be used without.

The following formula (2) of the present invention [Pt ^III ₂ (NH ₃ ) ₄ (Me ₃ CCONH) ₂ L ¹ L ² ] (NO ₃ ) ₄ (2) (wherein Me represents a methyl group; L ¹ and L ² are the same or different and each represent a water molecule, a neutral ligand or an anionic group.) The amide (L) -bridged platinum (III) complex represented by the formula (I) is a novel compound. As L ¹ and L ² in the formula (2), the same as those described in the formula (1) can be used.

The compound having a carbon-carbon double bond as a raw material used in the oxidation reaction of the present invention has a carbon-carbon double bond subjected to the oxidation reaction, and has an adverse effect on the oxidation reaction of the present invention. There is no particular limitation as long as it does not provide, but it has 2 to 30, preferably 2 to 12, more preferably 2 carbon atoms.
Linear or branched olefin of 10 to 10 or C4 to C3
0, preferably 5 to 12, more preferably 6 to 10, monocyclic, polycyclic or condensed cyclic cycloolefins are preferred.
These olefins or cycloolefins may be substituted with a substituent that does not adversely affect the oxidation reaction of the present invention. Examples of the compound having a carbon-carbon double bond of the present invention include ethylene, propylene, butene, and 2,3.
-Dimethylbutene, cyclopentene, cyclohexene,
Cycloheptene, butadiene, cyclohexadiene and the like can be mentioned.

The oxidation reaction of the present invention preferably uses a solvent. As the solvent, water is preferable, but ether,
Tetrahydrofuran, methylene chloride, t-butanol,
An organic solvent such as dichloroethane and trichloroethane may be added to form a multiphase solvent. The oxidation reaction can be performed while blowing oxygen into the catalyst and the starting compound, but can also be performed by incorporating oxygen into the reaction mixture by simply stirring in air. When the raw material is a gas, the reaction can be performed while simultaneously blowing the raw material gas and oxygen. The oxygen to be blown in may be pure oxygen, or may be nitrogen or an inert gas added as a carrier. Air can be used, and the use of air is economically preferable. In the case of reacting while simultaneously blowing the raw material gas and oxygen, the partial pressures of the raw material gas and oxygen can be appropriately adjusted, but it is preferable to perform the reaction at about 1: 1.

The reaction temperature of the oxidation reaction can be appropriately set depending on the starting compounds and the oxidation conditions.
100 ° C., preferably room temperature to 60 ° C., more preferably room temperature to about 40 ° C. The reaction pressure may be any of reduced pressure, normal pressure, and pressurized. The pH of the reaction mixture is also not particularly limited, and a wide range of pH can be selected. Further, in the oxidation reaction of the present invention, there is no change in pH due to the progress of the reaction, or there is little change, so there is no particular need to use a buffer such as potassium carbonate.

The products of the oxidation reaction of the present invention include:
There are diol derivatives, aldehyde derivatives, ketone derivatives, carboxylic acid derivatives, and the like corresponding to the compound having a carbon-carbon double bond used as a raw material, but the method of the present invention is characterized by high selectivity of the diol derivative. is there.
When a cycloolefin is used as a starting compound, a product with a change in the ring skeleton can be produced.

Thus, in the method of the present invention, platinum (I
II) The compound having a carbon-carbon double bond can be catalytically oxidized to 1,2-diol or carboxylic acid in a single step by using an amide-bridged binuclear complex containing platinum in an abnormal oxidation state as a catalyst. it can. Further, since O ₂ is used for reoxidation of the catalyst using water as a solvent, no special oxidizing agent is required. Further, the selectivity of the reaction is extremely high, the amount of by-products is small, and the reaction is more economical and safe than the conventional method.

[0021]

EXAMPLES Next, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

Example 1 (Synthesis of amide-bridged binuclear platinum (III) complex) [Pt ₄ (NH ₃ ) ₈ ((CH ₃ ) ₃ CCONH) ₄ ] (CF
Dissolve 40 mg of ₃ SO ₃ ) ₅ in 2 ml of 0.01 M HClO ₄ , add 8.3 mg of Na ₂ S ₂ O ₈ and add
Heat for a minute. After cooling, 0.2 ml of concentrated nitric acid (HN
O ₃ ) and 0.4 ml of 0.1 M sodium nitrite (N
aNO ₂ ) and the solution is filtered. After leaving the filtrate at 5 ° C. for several days, [Pt ₂ (NH ₃ ) ₄ (C ₅ H ₁₀ NO) ₂ (NO ₃ )
₂ ] (NO ₃ ) ₂ .H ₂ O yellow crystals are obtained. Yield 48
%. Elemental analysis: Calculated: C, 13.22; H, 3.77; N, 15.42 Experimental: C, 13.20; H, 3.79; N, 15.45

Examples 2 to 7 (Catalytic oxidation reaction of olefin to 1,2 diol and carboxylic acid in aqueous solution) 2.5 µmol of [Pt ₄ (NH ₃ ) in 1 ml of D ₂ O]
₈ L ₄ ] ^{n +} (n = 5 or 6) or 5 μmol of [Pt
^III ₂ (NH ₃ ) ₄ L ₂ L ¹ L ² ] ^{n +} is dissolved. When the former is used as a catalyst, H ₂ SO ₄ or HClO ₄ is added at 0.0
3.75 μmol of Na ₂ S ₂ O ₈
And heated at 50 ° C. for 5 minutes, and after oxidation to the latter, a 5 mM solution per Pt ^III binuclear complex is used as it is. Examples of the olefin include ethylene (Example 2), propylene (Example 3), 2,3-dimethyl-2-butene (Example 4), cyclopentene (Example 5), cyclohexene (Example 6), and cycloheptene (Example Example 7) was used. In the case of ethylene and propylene, the partial pressure of the gas was set to oxygen: source gas = 1: 1, the total pressure was 5 kgf / cm ² (each gas amount was 1.28 mmol), and the reaction was performed at 35 ° C. For cyclopentene, cyclohexene, and cycloheptene, 1 ml (11.4 mmol) was added, and the reaction was performed at room temperature with vigorous stirring in air. Two weeks later, the reaction product was quantified by ¹ HNMR for diol and by gas chromatography (GC) for acetaldehyde and acetic acid. Table 1 shows the results.

[0024]

[Table 1]

The turnover number in Table 1 indicates that the platinum complex 1
Numerical values indicating how many equivalents of product were produced per equivalent indicate how many times the catalyst has been turned. In Table 1, the aldehyde produced by Example 6 was cyclopentanecarbaldehyde having a modified ring skeleton, and the aldehyde produced by Example 7 was cyclohexanecarbaldehyde having a modified ring skeleton. Further, the aldehyde product which is a product of propylene of Example 2 was acetone.

Examples 8 to 10 (Catalytic oxidation reaction of olefin to 1,2-diol and carboxylic acid in aqueous solution / dichloroethane two-layer system) A mixed solvent of 1 ml of 0.01 MH ₂ SO _{4 and} 1 ml of dichloroethane was added to the above solvent. The same amount of platinum complex as in the examples, 5 to 6
A double equivalent of sodium dodecanesulfonate and a substrate were added and reacted at 50 ° C. Table 2 shows the results.

[0027]

[Table 2]

The remaining 38% of the selectivity for cyclohexene of Example 9 in Table 2 was cyclohexene oxide. The product of the diol form of 2,3-dimethyl-2-butene in Example 10 was pinacol.

[0029]

According to the method of the present invention, a compound having a carbon-carbon double bond can be catalytically oxidized to 1,2-diol or carboxylic acid in one step, and the compound having a high selectivity can be obtained. , 2-diols or aldehydes can be produced. Further, since water is used as a solvent and oxygen is used as an oxidizing agent, it is not necessary to use a special oxidizing agent. Furthermore, there is no need to use a buffer to maintain the pH as the oxidation reaction of the conventional O _S O ₄ and its related substances to diol olefin with the catalyst. The selectivity of the oxidation reaction of the present invention is extremely high, and the generation of by-products is small, and the reaction is more economical and safe than the conventional method. Also,
After the reaction is O _S O ₄ method, it is necessary to remove the product from the oxidant (such as K ₃ Fe (CN) ₆ and trialkylamine oxides), such an operation is not necessary in the process of the present invention .

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07C 31/20 C07C 31/20 Z 35/06 35/06 35/14 35/14 C07F 15/00 C07F 15 / 00F // C07B 61/00 300 C07B 61/00 300

Claims (14)

[Claims] An amide (L) -bridged platinum (III) complex represented by the following formula (1): [Pt ^III ₂ (NH ₃ ) ₄ L ₂ L ¹ L ² ] (NO ₃ ) ₄ (1) In the formula, L represents an anionic group consisting of R ¹ CONH groups, L ¹ and L ² are the same or different and each represent a water molecule or a neutral ligand or an anionic group, and R ¹ represents an organic residue ) In the presence of a catalyst comprising a carbon-carbon double bond. 2. The method according to claim 1, wherein the oxidizing agent is oxygen. 3. The method according to claim 1, wherein the solvent for the oxidation reaction is a homogeneous or heterogeneous system comprising an organic solvent and / or water. 4. The method according to claim 1, wherein the compound having a carbon-carbon double bond is an olefin or a cycloolefin. 5. The method according to claim 4, wherein the oxidation product is a 1,2-diol derivative. 6. L ¹ and L ² may be the same or different and each is a water molecule, a neutral ligand, NO ₂ ⁻ , NO ₃ ⁻ , X ⁻ or RC
OO - ^(wherein, X represents a halogen atom, R represents an organic residue.) The method according to any one of claims 1 to 5 is. 7. The method according to claim 1, wherein L is a group derived from pivalinamide. 8. The method according to claim 1, wherein the compound having a carbon-carbon double bond is 1,2-
A method for producing a diol. 9. The method according to claim 8, wherein the compound having a carbon-carbon double bond is an olefin or a cycloolefin. 10. An amide (L) -bridged platinum (III) complex represented by the following formula (1): [Pt ^III ₂ (NH ₃ ) ₄ L ₂ L ¹ L ² ] (NO ₃ ) ₄ (1) In the formula, L represents an anionic group composed of a R ¹ CONH group, L ¹ and L ² represent the same or different and represent a water molecule, a neutral ligand or an anionic group, respectively, and R ¹ represents an organic residue ), An oxidation catalyst for a compound having a carbon-carbon double bond. 11. L ¹ and L ² may be the same or different and each is a water molecule, a neutral ligand, NO ₂ ⁻ , NO ₃ ⁻ , X ⁻ or R
COO - ^(wherein, X represents a halogen atom, R represents an organic residue.) The oxidation catalyst of claim 10 which is. 12. The oxidation catalyst according to claim 10, wherein L is a group derived from pivalinamide. 13. The following formula (2) [Pt ^III ₂ (NH ₃ ) ₄ (Me ₃ CCONH) ₂ L ¹ L ² ] (NO ₃ ) ₄ (2) wherein Me represents a methyl group and L ¹ and L ² are the same or different and each represent a water molecule, a neutral ligand or an anionic group.) 14. L ¹ and L ² may be the same or different and each is a water molecule, a neutral ligand, NO ₂ ⁻ , NO ₃ ⁻ , X ⁻ or R
COO ^- (. Wherein, X represents a halogen atom, R is showing an organic residue) amide (L) crosslinked platinum (III) complex according to claim 13.