JP3582867B2 - Method for producing unsaturated carbonyl compound - Google Patents

Description

[0001]
[Industrial applications]
The present invention relates to a method for producing an unsaturated carbonyl compound. More specifically, the present invention relates to a new method for producing an unsaturated carbonyl compound useful in the fields of various organic industrial products, pharmaceuticals, agricultural chemicals, fragrances, polymer products, and the like, and to a useful compound obtained by this method. .
[0002]
[Prior art and its problems]
Unsaturated carbonyl compounds having a carbon-carbon unsaturated bond that binds a carbonyl group are important as raw materials, intermediate products and various useful products of the chemical industry. Further, it was not so easy to produce a structure having a structure in which a carbon chain was added or an adduct structure in which various functional groups were bonded to the carbon chain.
[0003]
This means that it is extremely difficult to directly add a bond between carbon and hydrogen at an unsaturated bond site of an olefin or an aromatic ring to an unsaturated bond of another olefin or the like. This is because, in the case of a structure having a carbonyl group of an electron-withdrawing group, such a direct addition reaction is considered to be almost impossible. As a reaction method for directly adding a carbon-hydrogen bond at an unsaturated bond site to an unsaturated bond such as an olefin, only very limited examples have been known so far. Although a dimerization reaction of an acrylate ester is known, in this case, the reaction is limited to a specific compound called an acrylate ester and lacks generality as a reaction.
[0004]
Further, as a similar example, a reaction of sequentially adding a carbon-hydrogen bond of a pyridine ring to carbon monoxide and then to 1-octene or the like using ruthenium carbonyl as a catalyst is known (J. Amer. Chem. Soc., 114 , 5888 (1992)), but this reaction does not give products with carbon-hydrogen bonds added directly to the olefin. Further, the carbon of the pyridine ring - reaction to be added to propylene is known hydrogen bonding of thin b cyclopentadienyl zirconium complexes as catalysts (... J. Amer Chem Soc , 111 -778 (1989)). However, these reactions are limited to carbon-hydrogen bonds on the pyridine ring. Under such circumstances, the production of a carbonyl unsaturated compound in which various functional carbon chains or the like are added to an unsaturated bond having a carbonyl group has to be produced by a very troublesome method. For example, a halogen atom is introduced into an unsaturated bond site, an alkyl group or a functional alkyl group is introduced by a substitution reaction of the halogen atom, or an acylation reaction method using a Friedel-Frafts catalyst. Not only are these processes cumbersome, but also the reaction selectivity and efficiency are limited, and they are not practically satisfactory, and the target substances that can be produced are extremely limited. Did not.
[0005]
Thus, the inventor of the present invention has solved the above-mentioned drawbacks of the prior art, and has made it possible to produce a compound which has been difficult to synthesize by a simple means, with high reactivity and selectivity. A new method for producing an unsaturated carbonyl compound has been studied.
As a result, the inventor of the present invention has the following formula:
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[0007]
An olefinic carbon-carbon double bond structure is added to the carbonyl-substituted unsaturated bond structure represented by the following formula in the presence of a transition metal catalyst to give the following formula:
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[0009]
A process for producing an unsaturated carbonyl compound characterized by the formation of an additional structure represented by the following formula has been developed and has already been proposed (Japanese Patent Application No. 5-232504). This method is a new method in which the carbon-hydrogen bond at the unsaturated bond site having a carbonyl group is directly added to the olefin bond, and it is difficult to synthesize by a complicated and cumbersome process. It has been possible to produce unsaturated carbonyl compounds with high reactivity and selectivity.
[0010]
The produced compounds are extremely useful as various industrial raw materials, pharmaceuticals, agricultural chemicals, fragrances, polymer products and the like.
Since this addition reaction is very interesting and has great expectations for industrial applicability, the inventor of the present invention has further studied the expansion of the application of this reaction technology.
[0011]
In the process, attention was paid to the case where an acetylenic compound was used in place of the olefin, and a new addition reaction was realized. This indicates that compounds having a triple bond as an acetylenically unsaturated compound as compared with olefins have attracted attention as exhibiting different reactivity from olefins, but their studies have not necessarily been sufficiently advanced. It was also based on the perception that it had not.
[0012]
The present invention has been made in view of the above background, and has added a structure of an acetylenic carbon-carbon triple bond to an unsaturated bond structure by simpler means with high reactivity and selectivity. It is an object of the present invention to provide a new addition reaction method which can be carried out. More specifically, the present invention is based on the technical development of the addition reaction of the olefinic carbon-carbon double bond structure already proposed by the inventor. -To provide a new method for performing an addition reaction of a carbon double bond structure.
[0013]
[Means for Solving the Problems]
The present invention solves the above-mentioned problems by providing the following formula ( I )
[0014]
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[0015]
(R ^a and R ^c are bonded to each other to form an aromatic hydrocarbon group or a heterocyclic substituent, and R ^b is an alkyl group and may be bonded to R ^c to form a ring. Good)
In the presence of a ruthenium complex, a carbonyl-substituted unsaturated bond represented by the following formula (II)
[0016]
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[0017]
(R ^d and ^Re are the same or different and each represents an alkyl group, a phenyl group or a silyl group, and these may be further substituted with an alkyl group or an alkyl-substituted siloxy group )
And an acetylenic carbon-carbon triple bond structure represented by the following formula (III):
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^{(Wherein, R a, R b, R} c, R d and R ^e are all SANYO of the wavy line in the formula represents a cis isomer, a mixture of trans isomers, or cis form and trans form)
A process for producing an unsaturated carbonyl compound, characterized by producing an addition structure represented by the formula: Further, the present invention provides the following formula (III) which can be obtained by the above production method.
[0018]
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[0019]
(R ^a and R ^c are bonded to each other to form an aromatic hydrocarbon group or a heterocyclic substituent, and R ^b is an alkyl group and may be bonded to R ^c to form a ring. R ^d and R ^e are the same or different and each represents an alkyl group, a phenyl group or a silyl group, which may be further substituted with an alkyl group or an alkyl-substituted siloxy group. Cis, trans, or a mixture of cis and trans isomers ).
[0020]
These compounds are attracting attention as unsaturated carbonyl compounds useful in the fields of various organic industrial products, pharmaceuticals, agricultural chemicals, fragrances, polymer products and the like.
[0021]
[Action]
In the present invention, the "unsaturated CH compound" represented by the above formula ( I ) having a carbonyl group bonded thereto is reacted with an acetylene compound of the formula ( II ) to form an additional structure represented by the formula ( III ) or the like. Produce compound. This is noted as a direct addition of an "unsaturated CH bond" to the alkyne.
[0022]
In carrying out this addition reaction, the acetylene compound having the structure of the formula ( II ) is reacted intermolecularly or intramolecularly with the compound of the formula ( I ) as a different molecule or as the same molecule.
In the intermolecular reaction, the molar ratio of the acetylene compound of the formula ( II ) to the structural compound of the formula ( I ) is usually about 0.01 to 1000, more preferably 0.1 to 20. A transition metal catalyst is used for the reaction, and these can be appropriately used as a metal or a compound or complex thereof. The metal element is preferably a noble metal, particularly preferably ruthenium, a ruthenium compound or a ruthenium complex. When ruthenium metal is used, it can be used alone or with a carrier such as activated carbon or alumina. As the ruthenium compound, an organometallic compound of ruthenium is suitably used, and various organic complexes are also used as the ruthenium complex.
[0023]
The ruthenium complexes such as _{H 2 Ru (PPh 3) 4} , H 2 Ru (CO) (PPh 3) 3, Ru n (CO) m (PPh 3) x, Ru (CH 2 = CH 2) (PPh 3 ₃ ) and the like. These catalysts can be used in combination of two or more kinds, and these catalysts can also be used in combination with other generally known types of ligands. Further, a ruthenium salt can be used in combination with a reducing agent.
[0024]
The amount of these catalysts to be used is generally 0.0001 to 0.1, preferably 0.001 to 0.01 in terms of molar ratio with respect to the unsaturated compound of the formula (1).
The reaction proceeds without solvent, but a solvent can also be used. The solvent used may be any solvent that is inert to the reaction, and is usually a fatty acid hydrocarbon solvent such as n-hexane, n-heptane, cyclohexane, an aromatic hydrocarbon solvent such as benzene or toluene, diethyl ether, THF. And the like.
[0025]
The reaction temperature is usually from room temperature to 200 ° C, preferably about 50 to 160 ° C. The reaction time is generally about 0.5 minute to 200 hours, preferably about 3 minutes to 50 hours.
After completion of the reaction, the desired addition product can be obtained by various separation and purification means, for example, separation by column chromatography, or distillation separation.
[0026]
Unsaturated carbonyl compounds of the invention obtained by direct addition reaction described above, for example, those exemplified by the above formula (III), specific ones of this, the R ^a and R ^c bonded to form a ring, for example, it forms a ring this ring is a benzene ring (substituted) acetophenone and (substituted) benzophenones, further by bonding R ^b and R ^c, constitute a condensed ring Examples thereof include (substituted) acetylnaphthalenes and those forming a heterocyclic ring via a hetero atom.
[0027]
Furthermore, R ^a and R ^c are may form an alicyclic structure combined with. Such a ring further includes a halogen atom, an amino group, a substituted amino group, a nitro group, a cyano group, a carboxyl group, an ester group, a hydroxyl group, an ether group, a thiol group, a thioether group, a carbamoyl group, a thiocarbamoyl group, and a silyl group. It may have a functional group consisting of a group, a metal atom-containing group, a heterocyclic group, and other appropriate atoms and atomic groups.
[0028]
Hereinafter, the present invention will be described in more detail with reference to Examples. Of course, this invention is not limited at all by the following examples.
[0029]
【Example】
Examples 1 to 7
[0030]
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[0031]
Α-tetralone represented by the following formula was reacted with various acetylene compounds.
That is, RuH ₂ (CO) (PPh ₃ ) ₃ (0.12 mmol), toluene (3 mL) and α-tetralone (2 mmol) were reacted with an acetylene compound (4 mmol) while vigorously refluxing at 135 ° C. in an oil bath.
[0032]
The product was analyzed by gas chromatography.
Table 1 shows the acetylene compound used in the reaction, the reaction time (hr), the reaction product, and the isolation yield of the reaction product.
However, in Example 2, the amount of the Ru complex used as a catalyst was 0.04 mmol.
[0033]
Table 1 shows that an unsaturated carbonyl compound having an additional structure of an acetylene compound was obtained with excellent selectivity and yield.
[0034]
[Table 1]
[0035]
The physical properties of the products obtained in Examples 1 to 7 were as shown in Tables 2 to 8 below.
[0036]
[Table 2]
[0037]
[Table 3]
[0038]
[Table 4]
[0039]
[Table 5]
[0040]
[Table 6]
[0041]
[Table 7]
[0042]
[Table 8]
[0043]
Example 8
The following equation
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[0045]
The reaction was carried out along.
That is, using RuH ₂ (CO) (PPh ₃ ) ₃ (0.12 mmol), 2-acetylfuran (2 mmol) and trimethylsilyl-phenylacetylene (4 mmol) were mixed with toluene (3 ml), and the mixture was heated at a bath temperature of 135 ° C. The reaction was performed for 24 hours.
[0046]
As a result, α-adduct 2-acetyl-3- (1-phenyl-2-trimethylsilylethenyl) furan was obtained at an isolation yield of 83%. The physical properties of this product were as shown in Table 9.
[0047]
[Table 9]
[0048]
Example 9
The following equation
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[0050]
The reaction was carried out along. That is, the reaction was carried out in the same manner as in Example 8 using 3-acetylthiophene instead of 2-acetylfuran in Example 8. 3-Acetyl-2- (1-phenyl-2-trimethylsilylethenyl) thiophene was obtained at an isolation yield of 90%.
The physical properties of this product were as shown in Table 10.
[0051]
[Table 10]
[0052]
Example 10
The following equation:
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[0054]
Along, 3,4-dihydro-6-pivaloyl-2H-pyran (2 mmol) was reacted with each of diphenylacetylene and trimethylsilyl-phenylacetylene (4 mmol).
In isolation yields of 71% and 86%, respectively, 3,4-dihydro-5- [1,2- (diphenyl) ethenyl] -6-pivaloyl-2H-pyran and 3,4-dihydro-5- [ (1-Phenyl-2-trimethylsilyl) ethenyl] -6-pivaloyl-2H-pyran was obtained.
[0055]
The physical properties of these products were as shown in Tables 11 and 12.
[0056]
[Table 11]
[0057]
[Table 12]
[0058]
【The invention's effect】
As explained in detail above, according to the present invention, a C—H bond of an unsaturated bond having a carbonyl group can be directly added to acetylenes by a simple means. Are provided.

Claims (2)

The following formula (I)
(R ^a and R ^c are bonded to each other to form an aromatic hydrocarbon group or a heterocyclic substituent, and R ^b is an alkyl group and may be bonded to R ^c to form a ring. Good)
In the presence of a ruthenium complex, a carbonyl-substituted unsaturated bond represented by the following formula (II)
(R ^d and ^Re are the same or different and each represents an alkyl group, a phenyl group or a silyl group, and these may be further substituted with an alkyl group or an alkyl-substituted siloxy group )
And an acetylenic carbon-carbon triple bond structure represented by the following formula (III):
^{(Wherein, R a, R b, R} c, R d and R ^e are all SANYO of the wavy line in the formula represents a cis isomer, a mixture of trans isomers, or cis form and trans form)
A process for producing an unsaturated carbonyl compound, characterized by producing an addition structure represented by the formula: The following formula (III) produced by the production method according to claim 1.
(R ^a and R ^c are bonded to each other to form an aromatic hydrocarbon group or a heterocyclic substituent, and R ^b is an alkyl group and may be bonded to R ^c to form a ring. R ^d and R ^e are the same or different and each represents an alkyl group, a phenyl group or a silyl group, which may be further substituted with an alkyl group or an alkyl-substituted siloxy group. , Cis-form, trans-form, or a mixture of cis-form and trans-form )
An unsaturated carbonyl compound represented by the formula: