JPH0326698B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention discloses a novel compound, substituted phenylureidopropyl polysilsesquioxane, which has the general formula: (However, X is a sulfamoyl group or bis(β-
The present invention also provides a substituted phenylureidopropyl polysilsesquioxane having a structural unit represented by the following (chloroethyl) amino group), and an anticancer agent and an antibacterial agent containing the polysilsesquioxane as an active ingredient. Some conventional polysilsesquioxanes have the formula

[Formula] Further abbreviated as O _{1 .5} SiR (where R represents a monovalent organic group), it is known as a polymer containing silsesquioxane as a repeating unit. In addition, the polymer substance is modeled by the following formula: It is known that it is a polymer compound generally having a ladder-like or cage-like skeleton structure, and is used as a water-repellent agent, a lubricant, a catalyst, a synthetic intermediate for organosilicon compounds, etc. In fact, the general formula A siloxane polymer represented by b is an integer from 0 to 2) is known in US Pat. No. 2,907,782, and its use as a lubricant, oil, and surface treatment agent is proposed. The present inventor has synthesized various polysilsesquioxanes and conducted various studies on their physiological activities. As a result, the following general formula To further abbreviate (However, X is a sulfamoyl group or bis(β-
It has been discovered that a novel substituted phenylureidopropyl polysesquioxane having a structural unit represented by (chloroethyl) amino group) has excellent physiological activity, particularly anticancer activity and antibacterial activity,
The present invention has now been completed. That is, the present invention is based on the general formula (However, X is a sulfamoyl group or bis(β-
The present invention provides a novel polysilsesquioxane consisting of a structural unit represented by (chloroethyl)amino group), and an anticancer agent and an antibacterial agent containing the polysilsesquioxane as an active ingredient. The polysilsesquioxane of the present invention is a new compound having a structural unit represented by the above general formula,
It is usually obtained as a white or pale yellowish brown solid polymer, and is often crushed and handled as a powder. The polysilsesquioxane is modeled to be a three-dimensional cage-like polymer as described above, and is generally almost insoluble in ligroin, cyclopentane, hexane, and insoluble in benzene, toluene, chloroform,
It is sparingly soluble in carbon tetrachloride, etc. On the other hand, it is soluble in alcohol, and is further soluble in formamide, N,N
- They are often soluble in polar nonaqueous solvents such as dimethylformamide, dimethylsulfoxide, hexamethylphosphoamide, etc., and their solubility tends to increase markedly especially when heated. Furthermore, since the polysilsesquioxane has a ureido bond in its molecule, it generally tends to produce bubbles and decompose when heated to 200° C. or higher, although this varies somewhat depending on the conditions. It also has the property of decomposing when heated in an aqueous solvent in the presence of an acid or a base. The decomposition tends to become more severe as the base concentration increases and as the temperature rises. It can generally be confirmed by chemical analysis and instrumental analysis that the polysilsesquioxane has a chemical structure having a structural unit represented by the above general formula. In particular, elemental analysis, infrared absorption spectroscopy, and ¹³ C-nuclear magnetic resonance spectroscopy are extremely effective methods. That is, for the synthesized polysilsesquioxane, the weight percent of the elements of carbon, hydrogen, nitrogen, silicon (and halogen or sulfur if the molecule contains a halogen atom or sulfur atom) is determined, and further the recognized By subtracting the sum of the weight percent of each element from 10, the weight percent of the oxygen element can be calculated, and the compositional formula of the polysilsesquioxane sample can be determined. Furthermore, by measuring the infrared absorption spectrum of the sample, it is possible to confirm the characteristic chemical bonds and types of functional groups present in the polysilsesquioxane molecule. Generally, the polysilsesquioxane absorbs around 3300 cm ^-1 based on the NH bond of the ureido group and the OH bond of hydration water, and 1690 to 1630 cm ^-1
It can be confirmed that a characteristic absorption based on the carbonyl bond of the ureido group is exhibited in the vicinity. Furthermore, by measuring ^{the 13} C-nuclear magnetic resonance spectrum, the number of carbon atoms in the compound, the arrangement of carbon chains, and the bonding mode of carbon atoms can be determined. As a representative example, ^13C -nuclear magnetic resonance spectrum measurement results (chemical shift value based on tetramethylsilane, δppm) of r-(p-sulfamoylphenylureido)propylpolysilsesquioxane in methanol are shown. is as follows, and the assignment of each carbon atom present in the molecule can be fixed. Furthermore, as is clear from the results of elemental analysis and infrared absorption spectrum, the polysilsesquioxane usually exists in a monohydrated form or a dihydrated form in the solid state, but it cannot be heated and dried for a long time. By doing so, it is also possible to achieve a nearly anhydrous state. The method for producing the polysilsesquioxane of the present invention is not particularly limited, and any production method may be used. Examples of representative methods that are generally suitably used include the method represented by the following formula (1), which is produced by hydrolyzing and condensing r-(substituted phenylureido)propyltrialkoxysilane;
There is a method represented by the following formula (2), which is produced by reacting r-aminopropyl polysilsesquioxane and substituted phenyl isocyanate. The former, that is, the method represented by formula (1) generally carries out the hydrolysis at -20°C to 120°C, preferably -5°C to
This is preferably carried out at 80° C. for 1 to 80 hours. The solvent used for the hydrolysis is not particularly limited as long as it does not irreversibly react with the r-(substituted phenylureido)propyltrialkoxysilane, and can generally be used to dissolve the silane compound. If,
It can be suitably used regardless of whether it is miscible with water or not. Typical reaction methods include a method of dropping water into a solution of the silane, a method of dropping a solution of the silane into water, a method of dissolving the silane in a solvent containing water, etc. In this case, in order to speed up the reaction, it is preferable to stir or shake the reaction mixture, add a small amount of acid or base, etc.
When the above hydrolysis conditions are relatively mild, for example, when the raw material silane compound is added to water or a mixture of water and an organic solvent and left to stir at room temperature, the organic The group remains unchanged in the product r-(substituted phenylureido)propyl polysilsesquioxane even after hydrolysis of the raw materials. In addition, when adding an acid or a base or heating is used as the hydrolysis conditions, if the conditions are made harsher, the organic groups in the hydrolyzed product, especially the ureido moieties in the organic groups, may be damaged to some extent. Changes may also be seen. However, even if the product contains some changes in some organic groups, it still has sufficient physiological activity. It can be fully used as a physiologically active substance. Furthermore, as mentioned above, the molecular weight of the polysilsesquioxane is difficult to measure accurately because it has a three-dimensional cage or ladder shape. Since it is known that san is a tetra- to dodecamer (for example, "Organosilicon Chemistry" co-authored by Kumada and Okawara, pp. 271-280), the r-(substituted phenylureido)propyl polysilsesquioxane of the present invention is also This is considered to be the case. The method represented by the above formula (2) is generally carried out at 0 to 80°C,
This is preferably carried out in a suitable solvent for 1 to 80 hours with stirring. The solvent is not particularly limited and can be used as long as it does not react with the raw materials r-aminopropylpolysilsesquioxane and substituted phenyl isocyanate. Solvents that easily dissolve propylpolysilsesquioxane and substituted phenyl isocyanate are preferred, such as N,N-dimethylformamide, N-
Polar non-aqueous solvents such as methylpyrrolidone and acetonitrile, high boiling point ether solvents such as diethylene glycol dimethyl ether and triethylene glycol dimethyl ether, etc. are preferably used. After the reaction, the target product, r-(substituted phenylureido)propylpolysilsesquioxane, is isolated in both of the production methods shown by formulas (1) and (2), using a reaction solvent. and low boiling point substances under reduced pressure or vacuum, below 120℃,
Preferably, it is sufficient to carry out distillation at 80° C. or below, followed by drying at the above temperature or below for 1 to 24 hours. If necessary, after the reaction, most of the solvent and low-boiling substances are distilled off, the resulting solid product is washed with water, and the desired product, r-(substituted phenylureido)propyl polysilsesquioxane, is dissolved. Washing with a difficult-to-clean solvent such as hexane, benzene, ether, etc. may be followed by drying. In the method for producing r-(substituted phenylureido)propyl polysilsesquioxane, the raw material r-(substituted phenylureido)propyltrialkoxysilane is also the same as the r-(substituted phenylureido)propyl polysilsesquioxane of the present invention. is itself a novel compound. The r-(substituted phenylureido)propyltrialkoxysilane is The method for producing the compound is as described in detail in the reference examples below. Examples include a method of reacting with enyl isocyanate. in general,
These reactions proceed quantitatively even at room temperature under anhydrous conditions. However, when a salt of substituted aniline (eg, hydrochloride, sulfate, etc.) is used in the above reaction, it is desirable to add a base such as triethylamine or pyridine to the reaction system in order to liberate the substituted aniline from the salt. r-(substituted phenylureido)propyltrialkoxysilane is a white crystalline solid that melts under normal conditions when heated above 100°C.
The structure of the trialkoxysilane can be confirmed by the same means as for fixing the r-(substituted phenylureido)propyl polysilsesquioxane of the present invention, such as the following methods (a) to (d). (b) By measuring the infrared absorption spectrum,
The strong absorption near 3300 cm ^-1 indicates the presence of NH groups, and the strong characteristic absorption near 1680 to 1630 cm ^-1 indicates the presence of ureido carbonyl groups. (b) Carbon, hydrogen, nitrogen, silicon,
(and halogen or sulfur if the molecule contains a halogen atom or sulfur atom)
By finding the weight percent of the element and further subtracting the sum of the weight percent of each recognized element from 100,
The weight percent of elemental oxygen can be calculated and therefore the compositional formula of the product can be determined. (c) By measuring ^{the 13} C-nuclear magnetic resonance spectrum, it is possible to show the number of carbon atoms, the arrangement of carbon chains, and the bonding mode of carbon atoms in the compound. A typical example is r-(p-sulfamoylphenylureido)propyltriethoxysilane in ^dimethyl sulfoxide.
-Nuclear magnetic resonance spectrum measurement results (chemical shift value based on tetramethylsilane, δppm)
is shown below, and the carbon atoms present in the molecule can be identified. (d) By measuring the mass spectrum, calculate the composition formula corresponding to each observed peak (generally the mass number expressed as m/e, which is the ion molecular weight m divided by the ion charge number e). By doing so, it is possible to know the molecular weight of the compound subjected to measurement and the bonding mode of each atomic group within the molecule. That is, the sample subjected to measurement is expressed by the general formula, When expressed as , a molecular ion peak (hereinafter abbreviated as M) is generally observed, so the molecular weight of the compound subjected to measurement can be determined. Furthermore, a strong peak corresponding to (RO) ₃ Si is generally observed. The r-(substituted phenylureido)propyl polysilsesquioxane of the present invention is a new compound,
When the present inventor conducted a physiological activity test on the polysilsesquioxane, it was confirmed that the polysilsesquioxane has a particularly remarkable anticancer effect. That is, since the polysilsesquioxane exhibits an extremely strong anticancer effect, the polysilsesquioxane having the above structural unit can be used as an anticancer agent for the prevention, treatment, or treatment of various cancers. Therefore, the anticancer agent of the present invention can be administered to patients orally, parenterally (for example, intraperitoneally, intrarectally), or locally, and the effectiveness of polysilsesquioxane, the active ingredient, The dosage varies depending on the patient's age, weight, severity of symptoms, type of cancer, etc., but in general, 800
~0.002mg/Kg/day, preferably 500~0.01mg/
It can be Kg/day. The daily dose is 1
It can be administered only once a day or divided into several times (3 to 5 times) a day. In addition, the above dosages are only a guideline and are subject to the judgment of the treating physician.
It goes without saying that it is also possible to administer doses exceeding the above range. When administering the active ingredient, the polysilsesquioxane can be formulated into various dosage forms depending on the desired administration method (oral, parenteral, or topical). For example, for oral administration, it can be formulated into tablets, pills, sugar-coated tablets, powder packets, granules, syrups, capsules, etc., and for parenteral administration, it can be formulated into suspensions, suppositories, etc. Furthermore, for topical administration, it can be formulated into dosage forms such as ointments, plasters, and creams. The concentration of the active ingredient in these preparations is not particularly limited and can vary widely depending on the dosage form, but it is generally about 0.05 to 90% by weight, preferably 1 to 60% by weight. be able to. As excipients that can be used in the above formulation, any excipient commonly used in the field can be used, and for solid form formulations, for example, lactose,
Examples include sucrose, starch, glycine, crystalline cellulose, mannitrate, magnesium stearate, liquid paraffin, calcium carbonate, sodium hydrogen carbonate, etc. For liquid form preparations,
For example, physiological saline, surfactant solution, glucose solution,
Examples include alcohols and esters. Specific examples of such formulations are as follows. Formulation Example 1: Capsule 0.6 parts by weight of magnesium stearate and 4.5 parts by weight of lactose
Add parts by weight and stir and mix to make the mixture uniform.Furthermore, 5 parts by weight of lactose and 10 parts by weight of crystalline cellulose are added and mixed. 20 parts by weight of polysilsesquioxane, which had been previously pulverized, was added to this mixture.
A prepared powder is obtained by mixing again. Capsules may be produced by filling this powder into gelatin capsules using a capsule filling machine. Formulation Example 2: Ointment After heating and dissolving 10 parts by weight of stearyl alcohol, 20 parts by weight of liquid paraffin, and 160 parts by weight of petrolatum, 0.5 parts by weight of cholesterol and 10 parts by weight of polysilsesquioxane, which had been pulverized in advance, were added. It is recommended to add the mixture with good stirring, and after further stirring, leave it at room temperature to obtain an appropriate hardness. Formulation Example 3: Tablet 25 parts by weight of polysilsesquioxane and mannite
After thoroughly mixing and pulverizing 20 parts by weight, 4.7 parts by weight of potato starch was added as starch paste and granulated. The particles are passed through a 60-mesh sieve, dried to a predetermined weight, and passed through a 16-mesh sieve. Next, the particles may be mixed with 0.3 parts by weight of magnesium stearate, smoothed, and compressed using a tablet machine in a conventional manner to form uncoated tablets of an appropriate size. Furthermore, the polysilsesquioxane of the present invention exhibits a remarkable growth-inhibiting effect on bacteria and fungi, as evidenced in the Examples below. As already mentioned, r-(substituted phenylureido)propyltrialkoxysilane, which is a raw material for the polysilsesquioxane, is converted into the polysilsesquioxane of the present invention by hydrolysis. In this case, the silane can be easily attached to the surface by reacting with a material that has a hydroxyl group or an amino group on its surface that can react with the silane, such as an inorganic material such as glass or mortar; or an organic material such as paper, wood, cellulose, or silk. I can do it. The attached compound has a property that it is difficult to be removed even by washing,
In addition, since it imparts antibacterial and antifungal properties to the surface to which it is attached, it is possible to make the treated surface semi-permanently resistant to germs. 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, and therefore can be used as an antibacterial agent, antifungal agent, and 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. Reference Example 1 While cooling a mixture of sulfanilamide (5.17 g, 0.03 mole) and dimethoxyethane (26.3 g) in an ice water bath, r-isocyanatopropyltriethoxysilane (7.42 g, 0.03 mole) was added dropwise. After stirring at room temperature for 3 hours, the mixture was heated to 80°C on an oil bath for 1 hour. The solvent was distilled off under reduced pressure, ether was added to the residue, and the insoluble matter was filtered to obtain a white solid.
11.77g was obtained. When the infrared absorption spectrum of this product was measured, it showed a strong and broad absorption based on NH and NH ₂ bonds at 3360 cm ^-1 and 1680 cm ^-1
showed an absorption based on the carbonyl bond of the ureido group. Its elemental analysis values are C45.43%, H6.84%,
N10.14%, and C ₁₆ H ₂₉ N ₃ O ₆ SSi (419.57)
The calculated values for the composition formula are C45.80%, H6.97%,
It matched well with N10.02%. Further, when the mass spectrum was measured, a molecular ion peak (M) corresponding to the molecular weight was observed at m/e420, and a peak corresponding to (Eto) ₃ Si was observed at m/e163. Further, ^{the 13} C-nuclear magnetic resonance spectrum of the compound was measured in dimethyl sulfoxide using tetramethylsilane as a reference, and the results were as follows (chemical shift value δ, ppm). From the above results, the obtained white solid is r-
It was revealed that it was (p-sulfamoyl phenyl ureido) propyltriethoxysilane. The yield was 93.5%. Reference Example 2 Add r-isocyanatopropyltriethoxysilane (5.07g) to a mixture of p-(bischloroethyl)aminoaniline hydrochloride (5.39g, 0.02mole), triethylamine (3.04g, 0.03mole) and hexane (120ml). , 0.02 mole) was added dropwise under ice water cooling, and then left at room temperature for 6 days. The white precipitate present in the reaction mixture was suction filtered, thoroughly washed with hexane and dried to obtain 11.60 g of white solid.
I got it. When we measured the infrared absorption spectrum, we found that
An absorption based on the NH bond was observed at 3300 cm ^-1 and an absorption based on the carbonyl bond of the ureido group was observed at 1630 cm ^-1 . Its elemental analysis values are C49.20%, H7.97%,
N9.36%, Cl18.83%, Si4.09%
Calculated values for the composition formula C ₂₆ H ₅₁ N ₄ O ₄ Cl ₃ Si (618.16) C50.51%, H8.32%, N9.06%, Cl17.21%,
It matched well with Si4.54%. Further, ^{the 13} C-nuclear magnetic resonance spectrum of the compound was measured in deuterated chloroform using tetramethylsilane as a reference, and the results were as follows (chemical shift value δ, ppm). [46.0] and (CH ₂ CH ₂ ) ₃ N.HCl [8.6] From the above results, the obtained white solid is r-[p
-(Bis-β-chloroethyl)aminophenylureido] It was found to be a 1:1 molar mixture of propyltriethoxysilane and triethylamine hydrochloride. Transfer the white solid (7.12 g) to a mortar and add water (50 g) to a mortar.
ml) was added, crushed well and stirred, followed by suction filtration. The same operation was repeated three more times on the solids collected by filtration. White needle-like crystals were obtained by distilling off water from the filtrate under reduced pressure. When elemental analysis was performed, the measured values were C51.35%, H11.71%, and N10.08%, and the calculated values were C52.35% and H11 for the composition formula C ₆ H ₁₆ NCl (137.66). 72%, N10.18%
It matched well. Furthermore, by measuring an infrared absorption spectrum and comparing it with a standard product, it was revealed that the crystals obtained from the filtrate were triethylamine hydrochloride. Furthermore, when ^{the 13} C-nuclear magnetic resonance spectrum of the filtered solid was measured in deuterated chloroform, the results were in good agreement with the measurement results described above, except that the peaks at 46.0 ppm and 8.6 ppm disappeared. From the above results, it is clear that the solid obtained by washing with water does not contain triethylamine hydrochloride.
It was revealed that it was (bis-β-chloroethyl)aminophenylureido]propyltriethoxysilane. Example 1 Methanol (50 ml) and water (30 ml) were added to r-(p-sulfamoylphenylureido)propyltriethoxysilane (9.07 g, 0.022 mole) obtained in Reference Example 1, and the mixture was stirred at room temperature overnight. After that,
Heated to 60°C on a water bath for 1 hour. Low-boiling substances were distilled off from the reaction mixture under reduced pressure, and then vacuum-dried at 70°C for 5 hours to obtain 6.32 g of a white solid. When the infrared absorption spectrum of this isolated product was measured, a spectrum as shown in Figure 1 was obtained, with a broad absorption based on the OH and NH bonds of hydration water at 3300 cm ^-1 and ureid absorption at 1685 cm ^-1 . It showed an absorption based on the carbonyl bond of the group. Its elemental analysis values are C34.95%, H5.27%, N12.23%, Si8.34
%, C ₁₀ H ₁₄ N ₃ O _{4 .5} SSi・2H ₂ O (344.42)
The calculated values for the composition formula are C34.87%, H5.27%,
It was in good agreement with N12.20% and Si8.16%. Furthermore, ^{the 13} C-nuclear magnetic resonance spectrum of the compound was measured in methanol using tetramethylsilane as a reference, and the results were as follows (chemical shift value δ,
ppm). From the above results, the obtained white solid is r-(p
-sulfamoyl phenyl ureido) propyl polysilsesquioxane. The molecular weight of the product was determined to be 2,700 by vapor osmometry (tetrahydrofuran solution). Example 2 A 1:1 mixture (4.00 g) of r-[p-(bis-β-chloroethyl)aminophenylureido]propyltriethoxysilane obtained in Reference Example 2 and triethylamine hydrochloride was added to methanol (200 ml).
The mixture was dissolved in water, water (50 ml) was added, and the mixture was stirred at room temperature for 2 days. Methanol was removed under reduced pressure and water was decanted from the residue. Water (approximately 100 ml) was added to wash away the gum-like substance adhering to the flask. After repeating the washing operation four times, the gum-like material was vacuum-dried to obtain a pink solid (2.11 g). As is clear from the infrared absorption spectrum (Figure 2), 3300
Absorption based on the OH and NH bonds of hydration water was observed at cm ^-1 , and absorption based on the carbonyl bond of the ureido group was observed at 1640 cm ^-1 . Its elemental analysis value is C43.89
%, H5.73%, N10.86%, Si7.56%.
Calculated values for the composition formula C ₁₄ H ₂₀ N ₃ O _2.5 Cl ₂ Si・H ₂ O (387.34) _: C43.41%, H5.73%, N10.85%,
It matched well with Si7.25%. The above results revealed that the obtained solid was r-[p-(bis-β-chloroethyl)aminophenylureido]propylpolysilsesquioxane. The molecular weight of the product was measured in the same manner as in Example 1 and was found to be 3560. Example 3 Six types of suspensions (3981, 3981, 3981, 3162, 2512, 1995,
1585 and 1259 mg/Kg). This sample solution was intraperitoneally injected into 36 female CDF ₁ mice weighing around 20 g for 20 days, and the acute toxicity value (LD ₅₀ ) was determined by the method of Richfield and Wilcoxon. , the average survival time is more than 20 days in all cases, and the LD ₅₀ is
It was confirmed that the amount was 3981mg/Kg or higher. Example 4 The r-(p-sulfamoylphenylureido)propyl polysilsesquioxane obtained in Example 1 was added to physiological saline (0.85%) containing the surfactant Tween 80 to prepare a specified amount of sample. A suspension containing The sample solution was mixed with 5 Ehrlichi cancer cells.
Six Swiss mice (male) containing ×10 ⁶ cells were continuously injected intraperitoneally in 0.5 ml doses for 9 days. From the results of the survival effect over 60 days, the mean survival days (MST) was determined and compared with the mean survival days of the control group (30 animals) to accurately calculate T/C% using a computer. The results are shown in Table 1.

[Table] Example 5 The r-(p-sulfamoylphenylureido)propyl polysilsesquioxane obtained in Example 1 was suspended in a saline solution (0.85%) containing the surfactant Tween 80. A sample solution was prepared so that the dose was 400 mg/Kg. Inject this sample solution into the peritoneal cavity of Walker Carcinoma Sarcoma 256.
Intraperitoneal injections were administered to 6 Sprague-Dawley rats (female) containing 1×10 ⁵ cancer cells for 5 consecutive days, and the survival effect was investigated over a period of 1 month. As a result, the number of survivors out of 6 rats was 2, and the T/C% was 315. Example 6 Using r-[p-(bis-β-chloroethyl)aminophenylureido]propylpolysilsesquioxane obtained in Example 2, mice were infected by a method similar to that described in Example 4. An anticancer activity test against Ehrlichi cancer revealed that the dosage
T/C (%) was 144 at 200 mg/Kg. Example 7 A nutrient medium containing 1.5% agar was sterilized by heating at 121°C for 15 minutes, then cooled to 50°C, and a suspension of pre-grown bacterial cells or spores in sterile water was added thereto. The mixture was mixed, poured into a shear plate, and solidified into a flat plate. A circular piece of paper with a diameter of 8 mm was immersed in a methanol solution containing about 3% of the r-(p-sulfamoylphenylureido)propyl polysilsesquioxane obtained in Example 1. The excess was removed and placed on a solidified agar medium. about 30
After incubation for 24-48 hours at °C, the diameter of the inhibition circle was measured. As a result, rice blast disease (Pyrichlaria
oryqae), 26mmφ, Escherichia coli (Escherichia
An inhibition zone of 17 mmφ was observed for Staphylococcus aureus (coli) and 15 mmφ for Staphylococcus aureus. Example 8 Antibacterial properties were determined using r-[p-(bis-β-chloroethyl)aminophenylureido]propyl polysilsesquioxane obtained in Example 2 by a method similar to that described in Example 7. Tests showed that 18mm against black mold (Aspergillus niger)
φ, an inhibition circle of 15 mmφ was observed for E. coli. Example 9 A tube with a diameter of 8 mm was added to a methanol solution containing 3% of r-(p-sulfamoylphenylureido)propyltriethoxysilane synthesized in Reference Example 1.
After soaking a round filter paper and removing the excess on a filter paper,
The filter paper was immersed in an aqueous hydrochloric acid solution and dried to fix the organosilicon compound on the filter paper. Using the sample filter paper, an antibacterial test against rice blast disease was conducted in the same manner as in Example 7, and the inhibition circle was 24 mm.
It was φ.

[Brief explanation of drawings]

The accompanying drawings FIG. 1 is a chart showing the infrared absorption spectra of the compound obtained in Example 1, and FIG. 2 is a chart showing the infrared absorption spectra of the compound obtained in Example 2.

Claims (1)

[Claims] 1 General formula, (However, X is a sulfamoyl group or bis(β-
A substituted phenylureidopropyl polysilsesquioxane having a molecular weight of 1,400 to 4,800 and consisting of a structural unit represented by (chloroethyl) amino group). 2 general formula, (However, X is a sulfamoyl group or bis(β-
An antibacterial agent whose active ingredient is substituted phenylureidopropyl polysilsesquioxane with a molecular weight of 1,400 to 4,800 and consisting of a structural unit represented by (chloroethyl) amino group.