JP3007958B2 - 1-Alkoxy-1-methylthio-2-oxo compound and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel compound, a 1-alkoxy-1-methylthio-2-oxo compound,
And its manufacturing method.

[0002]

2. Description of the Related Art A 1-alkoxy-1-methylthio-2-oxo compound having an O, S-mixed acetal group at the α-position of a ketone group is a compound not described in the literature.

[0003]

An object of the present invention is to provide a novel compound, a 1-alkoxy-1-methylthio-2-oxo compound, and a method for producing the compound.

[0004]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have made intensive studies on the Pummeler reaction between methylsulfinylmethylketone (II) and a hydroxy compound (R ₂ OH) and found that solid acid The present inventors have found that a 1-alkoxy-1-methylthio-2-oxo compound (I) can be synthesized by using a clay mineral having a catalytic function as a catalyst, and based on this finding, the present invention has been accomplished.

That is, the present invention is as follows. (1) 1-alkoxy-1-methylthio-2-oxo compounds represented by the formula (I). Formula (I)

Embedded image (Wherein, R ₁ and R ₂ represent an alkyl group, an aralkyl group, an aryl group having 6 to 14 carbon atoms , a cycloalkyl group, or a heteroatom having 5
And a 10-membered heterocyclic group. However, if R ₁ is t-
A tyl group , R ₂ is a methyl group, and R ₁ is a phenyl group,
R ₂ excludes a combination of i-propyl groups. (2) 1-alkoxy represented by the formula (I), wherein the methylsulfinyl methyl ketone represented by the formula (II) is reacted with a hydroxy compound (R ₂ OH) in the presence of a clay mineral. A method for producing a 1-methylthio-2-oxo compound. Formula (II)

Embedded image (Wherein, R ₁ and R ₂ represent an alkyl group, an aralkyl group, an aryl group having 6 to 14 carbon atoms , a cycloalkyl group, or a heteroatom having 5
And a 10-membered heterocyclic group. )

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a compound represented by the formula (I) is synthesized by reacting a methylsulfinyl methyl ketone represented by the formula (II) with a hydroxy compound (R ₂ OH) in the presence of a clay mineral. can do. This methylsulfinyl methyl ketone (II) is a β-ketosulfoxide compound having various types of chemical structures from aliphatic to aromatic, heterocyclic and alicyclic. Formula (I)
And in (II), R ₁ or R ₂ is preferably an alkyl group having 1 to 16, more preferably 1 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms,
C7-C12, more preferably C7-C10 aralkyl group, C3-C14, more preferably C3-C10 cycloalkyl group, 5- to 10-membered ring having oxygen, nitrogen and sulfur atoms as hetero atoms And more preferably a 5- to 6-membered heterocyclic group. As R ₁ and R ₂ , for example, an alkyl group such as methyl, ethyl, heptadecyl,
Aryl groups such as phenyl and naphthyl, aralkyl groups such as benzyl and phenylethyl, cycloalkyl groups such as cyclopentyl, cyclohexyl and decahydronaphthyl, heterocyclic groups such as furyl, pyridyl, thienyl, quinolyl, piperidyl and pyranyl, and their substitution Derivatives. Provided that R ₁ is a t-butyl group and R ₂ is
A methyl group and R ₁ are phenyl groups, and R ₂ is i- propyl
Excluding the case of a compound having a combination of But
In the case of the method for producing the compound represented by the formula (1),
It does not exclude the specific combinations described above. The hydroxy compound (R ₂ OH) is preferably an aliphatic alcohol, for example, a primary alcohol such as methanol or ethanol, a secondary alcohol such as 2-propanol or 2-butanol, t-butanol, or the like. t
-Tertiary alcohols such as pentanol can be used, and alicyclic alcohols such as cyclohexanol and aryl alcohols such as phenol can also be used. In the compound of the formula (I) or (II), R ₁
And R ₂ may further have a substituent, such as an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a sulfonyl group, an ester group, and a nitro group. And carboxyl groups.

The clay mineral used in the method for synthesizing the 1-alkoxy-1-methylthio-2-oxo compound of the present invention is not particularly limited as long as it has properties as a solid acid. For example, montmorillonite, beidellite, saponite, Hectorite and the like can be used, and montmorillonite is particularly preferred. The amount of the clay mineral to be used can be appropriately determined, but is usually 0.3 to 1 by weight based on 1 of methylsulfinylmethylketone of the formula (II).

[0008] The above hydroxy compound and formula (I)
I) with methylsulfinyl methyl ketone of I)
The mixture is reacted by heating and stirring. The reaction molar ratio of the methylsulfinyl methyl ketone of the formula (II) to the hydroxy compound is
Although there is no particular limitation, a range of 1: 3 to 1:10 is preferable. The reaction temperature is preferably 60 to 100 ° C, more preferably 70 ° C or higher, and the reaction time is not particularly limited, but is usually 6 to 20 hours. The reaction may be carried out in a solvent or in the absence of a solvent. However, the reaction is preferably carried out in a solvent. In some cases, the hydroxyl compound itself is used in excess as a solvent or a compound other than the hydroxyl compound is used as a solvent. Specific examples of the solvent other than the hydroxyl compound include solvents such as dichloromethane, acetonitrile, and dioxane. After the reaction, the desired 1-alkoxy-1 represented by the formula (I) can be obtained by removing the catalyst clay mineral by a simple filtration operation and removing the solvent.
-Methylthio-2-oxo compound can be obtained.
Although clay minerals are known as environmentally acceptable catalysts, the present invention is the first example applied to the Pummeler reaction.

[0009]

Next, the present invention will be described in more detail with reference to examples. Example 1 Methylsulfinyl methyl ketone (R ₁ = p- (OM
e) phenyl) 0.103 g, clay mineral (Montmorillonite KSF, trade name, manufactured by Aldrich) 0.040
g, 6 ml of ethanol was stirred at 73 ° C. for 7 hours. After the reaction, the catalyst was removed by filtration, and the solvent was removed from the filtrate under reduced pressure. The residue was purified by silica gel chromatography to give 0.102 g of a colorless oil.
(88%) of pure 1-alkoxy-1-methylthio-
2-oxo compound (R ₁ = p- (OMe) phenyl,
R ₂ = C ₂ H ₅ ). NMR of the obtained compound
Table 1 shows the analysis values.

Example 2 Methylsulfinyl methyl ketone (R ₁ = p- (OM
e) A mixture of 0.047 g of phenyl), 0.030 g of the same clay mineral as in Example 1, and 3 ml of 2-propanol was added to 7
Stirred at 8 ° C for 10 hours. After the reaction, the catalyst was removed by filtration, and the solvent was removed from the filtrate under reduced pressure. The residue was purified by chromatography on silica gel, giving 0.044 g (77%) of pure 1-alkoxy-1-methylthio-2-oxo compound (R ₁ = p- as a colorless oil).
(OMe) _phenyl, to obtain a _{R 2 = i-C 3 H} 7).
The analytical values of the obtained compound, such as NMR, are shown in Table 1.

Example 3 Methylsulfinyl methyl ketone (R ₁ = p- (OM
e) A mixture of 0.049 g of phenyl), 0.02 g of the same clay mineral as in Example 1, and 5 ml of t-butanol was added at 80 ° C.
For 15 hours. After the reaction, the catalyst was removed by filtration, and the solvent was removed from the filtrate under reduced pressure. The residue was purified by chromatography on silica gel, affording 0.026 g (40%) of pure 1-alkoxy-1- as a colorless oil.
Methylthio-2-oxo compound (R ₁ = p- (OM
e) _phenyl, to obtain a _{R 2 = t-C 4 H} 9). The analytical values of the obtained compound, such as NMR, are shown in Table 1.

[0012] Example 4 methylsulfinyl methyl ketone used in Example _{1 (R 1 = p- (OMe} ) phenyl) instead of, except for using methyl sulfinyl methyl ketone having various R ₁ shown in Table 1 reactions were carried out in the same manner as in example 1, _{R 1} different 1-alkoxy-1-methylthio -
A 2-oxo compound was synthesized. The obtained compound and the yield,
Table 1 shows the analysis values such as NMR and NMR.

[0013]

[Table 1]

[0015]

As described above, according to the present invention, as a novel compound, 1-alkoxy-1-methylthio-2-
An oxo compound is obtained. Since such a compound has a specific reactivity derived from a sulfur atom, it is used as a reaction material for synthesizing a functional substance, and a hydrophobic group is introduced by a reaction of a carbonyl group of the compound to form a methylthio group. The sulfur atom can be a sulfur-containing hydrophilic group and can be used as a raw material for producing a surfactant. In addition, such a compound can be produced by using a clay mineral as a catalyst by a clean and simple method without environmental pollution.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-49-5961 (JP, A) Agric. Food Chem. , Vol. 33, No. 5, p. 896-907 (1985) Chem. Pharm. Bull. , Vol. 19, No. 10, p. 2207-1209 (1971) (58) Fields investigated (Int. Cl. ⁷ , DB name) CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. A 1-alkoxy-1 represented by the formula (I)
-Methylthio-2-oxo compound. Formula (I) (Wherein, R ₁ and R ₂ represent an alkyl group, an aralkyl group, an aryl group having 6 to 14 carbon atoms, a cycloalkyl group, or a heteroatom having 5
And a 10-membered heterocyclic group. However, if R ₁ is t-
A tyl group , R ₂ is a methyl group, and R ₁ is a phenyl group,
R ₂ excludes a combination of i-propyl groups. ) 2. The compound according to claim 1, wherein the methylsulfinyl methyl ketone represented by the formula (II) is reacted with a hydroxy compound (R ₂ OH) in the presence of a clay mineral. A method for producing the represented 1-alkoxy-1-methylthio-2-oxo compound. Formula (II) (Wherein, R ₁ and R ₂ represent an alkyl group, an aralkyl group, an aryl group having 6 to 14 carbon atoms, a cycloalkyl group, or a heteroatom having 5
And a 10-membered heterocyclic group. )