JPS6340438B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula (However, R is an alkyl group, n is 0, 1 or 2,
X is a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. The present invention relates to an organosilicon compound represented by the following formula and a method for producing the organosilicon compound, and also provides an antibacterial and antifungal agent containing the organosilicon compound as an active ingredient. It is known that organosilicon compounds have been widely used as water repellent treatment agents for fiber surfaces, rust preventive agents, and the like. However, there is relatively little research on the physiological activity of organosilicon compounds, and only the following few examples are known. For example, RSi
Silatlane compound represented by the structural formula (OCH ₂ CH ₂ ) ₃ N (R is various functional groups), R'SiO _1.5
(R′ is various functional groups);
Anticancer activity of organoalkylsilane compounds represented by (CH ₃ ) ₃ SiCH ₂ CH ₂ SCH ₂ CH ₂ NH ₂ ; Organoalkylsilane compounds represented by (C ₂ H ₅ ) ₃ SiCH ₂ CH ₂ CH ₂ NH ₂ is known for its antibacterial activity. In addition, as an organosilicon compound having a heterocycle and a carbon-nitrogen double bond, USP3022270
In the The alkoxysilane compound represented by is known and has been proposed for use as a filtering agent or an ultraviolet absorber, but no research on the physiological activity of this compound is known at all. The present inventors have been conducting intensive research on the synthesis and physiological activities of various useful functional organosilicon compounds for many years. As a result, a novel and useful compound, the general formula (However, R is an alkyl group, n is 0, 1 or 2,
X is a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group. ) We have synthesized the organosilicon compound shown in the following, confirmed its structure and uses, and completed and provided the present invention. The novel organosilicon compound of the present invention has the general formula (However, R is an alkyl group, n is 0, 1 or 2,
X is a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group. ) is a compound represented by In the above formula, R may be an alkyl group without particular limitation, but lower alkyl groups such as methyl, ethyl, and butyl are generally preferably used because of their ease of availability and handling. Moreover, X in the above formula is a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group. The halogen atom is not particularly limited, and chlorine atom, bromine atom, iodine atom, and fluorine atom can be used, but chlorine atom and bromine atom are preferable because of easy availability of raw materials. The alkyl group is not particularly limited, but lower alkyl groups such as methyl, ethyl, and propyl groups are preferred from the viewpoint of easy availability of raw materials.
Furthermore, the alkoxy group is not particularly limited, but lower alkoxy groups such as methoxy, ethoxy, and butoxy groups are preferably used from the viewpoint of ease of raw material availability and ease of handling. Furthermore, in the above general formula, when n becomes large, there are restrictions in terms of production, so it is generally difficult to industrially produce compounds of 3 or more. The organosilicon compound of the present invention generally has the following (a) to (d):
It can be confirmed that the compound is represented by the above general formula. (b) By measuring the infrared absorption spectrum (IR), several absorptions based on CH bonds were detected near 3000 cm ^-1 to 2900 cm ^-1 and -C=N- near 1640 cm ^-1
Absorption, etc. based on bonding appears. Furthermore, when n is 1 or 2 in the above general formula,
Absorption based on NH bonds appears around 3300 cm ^-1 . Moreover, absorption based on Si--O bonds appears at 1100 to 1060 cm ^-1 . (b) ¹ H-Nuclear Magnetic Resonance Spectrum ( ¹ H-NMR)
By measuring , it is possible to know the number of hydrogen atoms and the bonding mode in the organosilicon compound of the present invention. The chemical shift value (based on tetramethylsilane, δ, ppm) of the above-mentioned organosilicon compound varies somewhat depending on the type of substituent, but generally shows the following value. That is, in the following formula, n
When is 0, the proton of methylene (α position) adjacent to silicon is around 0.7 ppm, the proton of methylene (β position) is around 1.9 ppm, and the proton of methylene (β position) is around 1.9 ppm.
Methylene (γ-position proton, 8.1
-N=CH- protons around ~8.5ppm, 7.0
Shows a peak based on benzene ring protons around ~8.0 ppm. When n is 1 or 2, in addition to the peaks based on each proton mentioned above, 2.3 to 2.
A peak based on the methylene proton adjacent to -NH- is shown at around 2.7 ppm, and a peak based on the NH proton at around 4.3 to 4.8 ppm. In addition, when the alkoxy group adjacent to silicon is an ethoxy group,
A peak based on methyl protons is shown around 1.2 ppm, a peak based on methylene protons is shown around 3.8 ppm, and in the case of methoxy group, a peak based on methyl protons is shown around 3.4 to 3.6 ppm. Furthermore, when the substituent (X) is an alkyl group or an alkoxy group, a peak unique to the alkyl group or alkoxy group is shown. (c) By measuring the mass spectrum (ms) and calculating the composition formula corresponding to each observed peak (generally the mass number expressed as m/e, which is the molecular weight of the ion divided by the number of charges e), The molecular weight and binding mode of the sample subjected to measurement can be estimated. In other words, the sample subjected to measurement is expressed by the general formula When expressed as , in addition to the corresponding molecular ion peak (M), M-
A peak corresponding to the mass number of OR, a peak of (RO) ₃ Si, etc. appear. (d) Calculate the weight percent of oxygen by determining the weight percent of each of carbon, hydrogen, nitrogen, halogen, and silicon by elemental analysis, and then subtracting the sum of the weight percent of each recognized element from 100. Therefore, the compositional formula of the sample subjected to analysis can be determined. The organosilicon compound represented by the above general formula is
Although its properties vary somewhat depending on the types of R and
Further, the compound may decompose or polymerize by being left at room temperature for a long time or by heating. The compound is highly soluble in common organic solvents such as benzene, ether and alcohol.
Furthermore, since the organosilicon compound of the present invention contains a trialkoxysilyl group that is easily condensed by hydrolysis in its molecule, it can be hydrolyzed alone or together with other organic or inorganic silicon compounds to form a polysilyl group. Sesquioxane derivatives can also be obtained. The hydrolysis reaction proceeds at room temperature in water or a mixture of water and an organic solvent (eg, alcohol, benzene, etc.). The rate of the hydrolysis reaction is increased by heating or adding a small amount of acid or base into the reaction system. The method for producing the organosilicon compound of the present invention is not particularly limited, and any method may be used. Typical manufacturing methods that are generally suitably used will be explained below. That is, an aminoalkyltritriate represented by the general formula (RO) ₃ SiCH ₂ CH ₂ CH ₂ (-NHCH ₂ CH ₂ )- _o NH ₂ (wherein R is an alkyl group and n is 0, 1 or 2). Alkoxysilane compounds and general formulas (However, X is a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group.) By dehydrating and condensing the substituted (3-chloro)benzofurfural represented by Silicon compounds can be obtained. Although the molar ratio of the charges in the above reaction is not particularly limited, it is usually desirable to use equimolar amounts.
Further, it is preferable to use a reaction solvent in the above reaction, and for example, a solvent that is azeotropic with water such as benzene, toluene, ethanol, and chloroform is preferably used. The reaction temperature can be, for example, -20°C to 150°C, but it is preferably carried out within a suitable temperature range, taking into consideration the thermal stability of the desired organosilicon compound. Although the reaction time varies depending on the reaction temperature, it can generally be selected from several minutes to several days. In order to promote the dehydration condensation reaction of the above reaction, a means of adding an acid such as acetic acid or formic acid to the reaction system is often suitably used. Another effective method is to add calcium chloride, molecular sieve, etc. as a dehydrating agent into the reaction system. The organosilicon compound of the present invention exhibits a remarkable growth-inhibiting effect on bacteria and mold, as evidenced in the Examples below. Furthermore, the organosilicon compound can be easily attached to the surface by reacting with a material having a hydroxyl group or the like on the surface that can react with the compound, such as an inorganic material such as glass or mortar; or an organic material such as paper, wood, or cellulose. be able to. The attached compound has a property that it is difficult to be removed even by washing, and in addition, it imparts antibacterial and antifungal properties to the surface to which it is attached, making the treated surface semipermanently resistant to germs. be able to. Therefore, the organosilicon compound of the present invention has excellent antibacterial and antifungal properties not only alone but also in various objects whose surfaces are treated with the compound, so it can be used as an antibacterial agent, an antifungal agent, and a disinfectant. It is a useful compound that can be used as a sanitary finishing agent for rugs and clothing. EXAMPLES In order to explain the present invention more specifically, Examples will be given below, but the present invention is not limited to these Examples. Example 1 Azeotropic dehydration was carried out by heating and refluxing a mixture of γ-aminopropyltriethoxysilane (2.70 g), 3-chlorobenzofurfural (2.17 g) and benzene (50 ml) on an oil bath for 2 hours. . After removing volatile components under reduced pressure, a pale and colored viscous liquid (4.27 g) was obtained by vacuum drying. When the infrared absorption spectrum of the compound was measured, it was found to be 3000 to 2900 cm ^-1 as shown in Figure 1 of the attached drawing.
Absorption based on C-H bonds was observed at 1,640 cm ^-1 , absorption based on C=N bonds was observed at 1100 to 1080 cm ^-1 , and strong absorption based on Si-O bonds was observed at 1100 to 1080 cm -1 . When the ¹ H-nuclear magnetic resonance spectrum (tetramethylsilane standard, δ, ppm) was measured, a spectrum as shown in Figure 2 of the attached drawings was observed. The analysis results of the chemical shift values of each peak were as follows. In addition, when mass spectra were measured, m/
Molecular ion peak (M) at e383, M at m/e338
A peak corresponding to -EtO and a peak corresponding to (Eto) ₃ Si were shown at m/e163. Its elemental analysis values are C56.29%, H6.85%,
N3.63%, Cl9.18%, Si7.35%, composition formula
The theoretical value for C ₁₈ H ₂₆ NClO ₄ Si (383.94),
C56.31%, H6.83%, N3.65%, Cl9.24%, Si7.32
% was in good agreement. From the above results, it is clear that the product is N
It was revealed that it was -(3-chlorobenzofluridene)γ-aminopropyltriethoxysilane. Example 2 After completing dropwise addition of 3-chlorobenzofurfural (1.96 g) to a solution of γ-(2-aminoethyl)aminopropyltrimethoxysilane (2.42 g) in anhydrous tetrahydrofuran (50 ml) with stirring under ice cooling,
The mixture was stirred at 50°C for 4 hours. After removing volatile components under reduced pressure, a colored viscous liquid (3.80 g) was obtained by vacuum drying. When the infrared absorption spectrum of the compound was measured, it was found that the absorption based on the N-H bond was at 3350 cm ^-1 and the absorption at 2950 -
Absorption based on C-H bond at 2800 cm ^-1 , absorption based on C=H bond at 1640 cm ^-1 , Si- at 1100 to 1070 cm ^-1
It showed strong absorption based on O bonds. When the ¹ H-nuclear magnetic resonance spectrum (tetramethylsilane standard, δ, ppm) was measured, a spectrum as shown in Figure 3 of the attached drawings was observed. In addition, when we measured the mass spectrum, m/e384
Molecular ion peak (M) at m/e349, M- at m/e349
Peak corresponding to Cl, m/e121 (CH ₃ O) ₃₃ Si
The peak corresponding to The analysis value is C53.09
%, H6.53%, N3.68%, Cl9.18%, Si7.28%, and the theoretical values for the composition formula C ₁₇ H ₂₅ N ₂ ClO ₄ Si (384.94) are C53.04%, H6. 55%, N3.64%, Cl9.21
% and Si7.30%. From the above results, the product is N-(3-chlorobenzofluridene)γ-(2-
It was revealed that it was aminoethyl)aminopropyltrimethoxysilane. Example 3 A nutrient medium containing 1.5% agar was sterilized by heating at 121°C for 15 minutes, then cooled to 50°C, and pre-grown cells or spores suspended in sterile water were added thereto. The mixture was mixed well, poured into a sheerle, and solidified into a flat plate. N-(3-
A circular paper with a diameter of 8 mm was immersed in a methanol solution containing about 1% of γ-aminopropyltriethoxysilane (chlorobenzoflufridene), the excess was removed on a piece of paper, and the mixture was placed on a solidified agar medium. .
After incubation at approximately 30°C for 24-28 hours, the diameter of the inhibition zone was measured. As a bacterium, Staphylococcus aureus
aureus, Staphylococcus aureus), black mold (Aspergillus niger, Aspergillus niger), athlete's foot fungus (Trichophyton
mentagrophytes, Trichophyton mentagrophytes, Candida
Table 1 shows the results of tests conducted using Candida albicans (Candida albicans).

[Table] Example 4 Using N-(3-chlorobenzofluridene)γ-(2-aminoethyl)aminopropyltrimethoxysilane obtained in Example 2, antibacterial and antifungal tests were carried out in the same manner as in Example 3. I conducted a test. The results are shown in Table 2.

[Table] Example 5 An 8 mm diameter tube was added to a methanol solution containing 1% of N-(3-chlorobenzofluridene)γ-(2-aminoethyl)aminopropyltrimethoxysilane synthesized in Example 2. Soak a circular piece of paper,
After removing the excess on the paper, the circular paper was immersed in an aqueous hydrochloric acid solution and dried to fix the organosilicon compound on the paper. When the paper was washed with benzene, about 8% of the raw organosilicon compound was eluted. Using the sample paper prepared by the above method, an antibacterial and antifungal test was conducted in the same manner as in Example 3, and the diameter of the inhibition circle was measured. The results are listed in Table 3.

[Table] *) After being immersed in the paper, it was fixed on the paper by hydrochloric acid treatment.
Example 6 In the same manner as described in Examples 1 and 2,
Various organosilicon compounds were synthesized. The structural formula and elemental analysis values of the product are listed in Table 4. In addition, in the same manner as the method described in Example 3,
Antibacterial and antifungal tests were conducted. The results are also listed in Table 4. Note that R, n, and X in Table 4 correspond to R, n, and X in the following formula, respectively. Furthermore, for the following representative compounds among the organosilicon compounds listed in Table 4, the analysis values of their properties, infrared absorption spectra (hereinafter abbreviated as IR), and mass spectra (hereinafter abbreviated as ms) are listed. No. 2: Pale brown viscous liquid Absorption based on C=H bond at IR 1640 cm ^-1 Peak corresponding to molecular ion (M) at ms m/e 418 Peak corresponding to M−C ₂ H ₅ O at m/e 373 Peak No. 5 corresponding to (C ₂ H ₅ O) ₃ Si at m/e163: Yellow viscous liquid IR Absorption based on C=N bond at 1650cm ^-1 ms Corresponding to molecular ion (M) at m/e413 Peak m/e378 corresponds to M−C ₂ H ₅ O Peak m/e163 corresponds to (C ₂ H ₅ O) ₃ Si Peak No. 11: Brown viscous liquid C=N bond at IR 1640 cm ^-1 Absorption based on N-H bond at 3300 cm ^-1 ms Peak corresponding to molecular ion (M) at m/e455 M-C ₂ H ₅ O peak at m/e 410 (C ₂ H ₅ O) ₃ Peak No. 22 corresponding to Si: Light brown viscous liquid IR Absorption based on C=N bond at 1630 cm ^-1 ms Peak corresponding to molecular ion (M) at m/e 420 M at m/e 389 - Peak corresponding to CH ₃ O at m/e121 Peak No. 27 corresponding to (CH ₃ O) ₃ Si: Yellow viscous liquid Absorption based on C=N bond at IR 1640cm ^-1 Molecular ion at ms m/e385 Peak No. 30 corresponding to (CH 3 O) 3 Si: Peak No. 30 corresponding to (CH ₃ O) ₃ Si: M-Peak corresponding to CH ₃ O at m/e 354: C = Brown viscous liquid IR 1650 cm ^-1 Absorption based on N bonds At 3300cm ^-1 Absorption based on N-H bonds ms Peak corresponding to molecular ion (M) at m/e398 m/e367 Peak corresponding to M-CH ₃ O At m/e121 (CH ₃ O) Peak corresponding to _3Si

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【table】 [Brief explanation of drawings]

1 and 2 show the infrared absorption spectrum and nuclear magnetic resonance spectrum of the organosilicon compound obtained in Example 1, respectively. FIG. 3 shows a nuclear magnetic resonance spectrum of the organosilicon compound obtained in Example 2.

Claims (1)

[Claims] 1. General formula (However, R is an alkyl group, n is 0, 1 or 2,
X is a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. ) An organosilicon compound represented by 2 Aminoalkyltrialkoxy represented by the general formula (RO) ₃ SiCH ₂ CH ₂ CH ₂ (-NHCH ₂ CH ₂ )- _o NH ₂ (wherein, R is an alkyl group and n is 0, 1 or 2) Silane compounds and general formula (However, X is a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group.) A general formula characterized by dehydration condensation with a substituted benzofurfural represented by (However, R is an alkyl group, n is 0, 1 or 2,
X is a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. ) A method for producing an organosilicon compound shown in 3 General formula (However, R is an alkyl group, n is 0, 1 or 2,
X is a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. ) An antibacterial and antifungal agent containing an organosilicon compound as an active ingredient.