JPH0812681A - Silylpropylamine derivative, its preparation and disinfectant - Google Patents

Abstract

PURPOSE: To obtain a new derivative which is a germicide for fungal diseases due to Alternaria mali, Phytophthora capsici, Phytophora baccae, Botryosphaeria dothidea, Glomerella cingulata, Pyricularia oryzae and Botrytis cinerea of plants.

CONSTITUTION: This derivative is represented by formula I (X¹ and X² are each H, a 1-4C alkyl, pheny or the like; R is H or methyl; Z is direct bond, O, methylene or the like; R¹ and R² are each methyl, allyl, phenyl or the like or R¹ and R² together form a 4-5C alkylene group), e.g. 1-(2,6- dimethylmorpholino)-6-(O- or P-chlorophenyl)-4,4-dimethyl-4-silaheptane. The derivative is obtained by adding NaI as a catalyst to an amine of formula II and a silylpropyl chloride of formula III and reacting the amine with the silylpropyl chloride at 90-100°C.

COPYRIGHT: (C)1996,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel silylpropylamine derivative, a method for producing the same, and a fungicide against fungal diseases of plants.

[0002]

BACKGROUND ART Development of a tertiary amine fungicide was started in the 1970s, and as a representative compound, a morpholine-based compound of the following formula (VI), Fenpropimorph (German Patent No. 2,822,326 and Nos. 2,752,135) and Tridemorph (German Patent No. 2,543,279) represented by the following formula (VII) and Fenpropidin (compound represented by the following formula (VIII) based on piperidine German Patent No. 2,752,135) was commercialized one after another.

[0003]

[Chemical 6]

[0004]

[Chemical 7]

[0005]

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[0006] It has been more than 10 years since the discovery of the excellent bactericidal effect of these tertiary amine compounds.
In 9 years, a new fungicide represented by the following formula (IX) in which a tertiary amine was introduced into an organosilicon compound was reported as a pesticide (European Patent Publication No. 313,353).

[0007]

[Chemical 9]

(In the formula, R ³ represents an alkyl group having 1 to ⁴ carbon atoms, and R ⁴ represents an alkyl group having 1 to ⁴ carbon atoms, an aryloxy group, a halomethyl group or a halogen atom.
May be methyl-substituted (CH ₂ ) _q (q is 3 or 4)
, M is 0 to 5, and p is an integer of 0 to 2, respectively.)

In the above formula, a compound having excellent activity and easily synthesized is represented by the following formula (X).

[0010]

[Chemical 10]

Thereafter, in 1990 and 1992, Shin-Etsu Chemical Co., Ltd. of Japan found that a new compound (XI) having a structure similar to the above formula was effective as a fungicide (Japanese Patent Laid-Open No. 2-270899). And 4-149183).

[0012]

[Chemical 11]

(In the formula, R ⁵ and R ⁶ each represent a hydrogen atom, a halogen atom, a methoxy group or the like, and R ⁷ represents a carbon atom having 1 to 1 carbon atoms.
6 alkyl group, vinyl group, cyclopropyl group or CH
₂ Cl, R ⁸ is an alkyl group having 1 to 4 carbon atoms, a vinyl group, a cyclopropyl group, CH ₂ Cl or C ₆ H ₃ R ⁵
Represents R ⁶ . r represents an integer of 3 to 7, Q represents a pyrrolidinyl group, a piperidinyl group, a morpholino group or a piperazinyl group)

The present inventors used a mixed gas of allyl chloride and hydrogen chloride in a fluidized bed reaction tank or a stirred reaction tank,
It was reported that dichloroallylsilane and trichloroallylsilane can be simultaneously produced by reacting directly with metallic silicon using copper as a catalyst at a reaction temperature of 250 to 350 ° C. When 0.5% by weight of cadmium is added to the total solid, the reactivity becomes high and the selectivity of allyldichlorosilane becomes good. In addition, hydrogen chloride was added to reduce the decomposition of allyl chloride and prevent the formation of diallyldichlorosilane, which easily polymerizes at high reaction temperature, and facilitated the synthesis (Jung, I.
N .; Yeon, SH; Kim, SL; Lee, BW Organmetallic
s, 1993, 12, 4887).

[0015]

[Chemical 12]

Allyldichlorosilane is added to aromatic compounds having various substituents by Friedel-Crafts reaction in the presence of a Lewis acid catalyst such as aluminum chloride to give (2-arylpropyl) dichlorosilane. Generate [Korean Patent Publication No. 92-12996 (1992.7.21)].

[0017]

[Chemical 13]

(In the formula, X ¹ and X ² each represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, a phenoxy group or a halogen atom)

Having the Si--H bond obtained above (2-
Arylpropyl) silane produces 1,4,4-trichloro-6-aryl-4-silaheptane (V) by hydrogen silicidation with allyl chloride in the presence of a platinum catalyst such as chloroplatinic acid [Korea Patent Publication 92-229
96 specification (1992.12.1)].

[0020]

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[0021]

DISCLOSURE OF THE INVENTION The present invention aims to provide a silylpropylamine derivative (I) which is extremely effective against fungal diseases of plants, and at the same time, to provide an effective production method thereof. The purpose is to do.

[0022]

In order to achieve the above object, various propylamine derivatives were synthesized and tested for their effects on fungal diseases of plants. As a result, general formula (I)

[0023]

[Chemical 15]

(Wherein, X ¹ and X ² each represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, a phenoxy group or a halogen atom, R represents a hydrogen atom or a methyl group, and Z represents Z. Represents a methylene group, an ethylene group, an oxygen atom or a direct bond, R ¹ and R ² are each a methyl group, an allyl group, a butyl group, a phenyl group, a 4-chlorophenyl group, 4
-Representing a fluorophenyl group, a hydroxyl group or a trimethylsilyloxy group, or R ¹ and R ² together form an alkylene group having 4 or 5 carbon atoms)

It was found that the novel silylpropylamine derivative (I) represented by the formula (1) has an excellent effect on plant fungal diseases. In the general formula (I), R
^{When 1} and R ² together form an alkylene group having 4 or 5 carbon atoms, it is represented by the following general formula (I ′).

[0026]

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(In the formula, n represents 4 or 5. X ¹ , X
² , R and Z are the same as above)

In the present invention, firstly, 1, 4 of the general formula (V)
Starting from 4-trichloro-6-aryl-4-silaheptane, the silicon-bonded chlorine of this compound is converted into a Grignard reagent of the general formula R ¹ MgX and R ² MgX (wherein X represents a halogen atom). ¹ and R ² are the same as above) to synthesize a compound of the general formula (III) or co-hydrolyze a compound of the general formula (V) with chlorotrimethylsilane, and R ¹ and R ² are trimethylsilyloxy. The compound of formula (III), which is a group, is synthesized.

[0029]

[Chemical 17]

Further, the compound of the general formula (V) is converted to the general formula XM
g (CH _{2) n} MgX (wherein, n is .X representing the 4 or 5 as defined above) is a ring-type compounds, including silicon atom is reacted with Jigurinyaru reagent a compound of general formula (IV) Can be synthesized.

[0031]

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Then, the silylpropyl chloride of the general formula (III), the amine of the general formula (II) and a small amount of NaI as a catalyst are added and reacted at 90 to 100 ° C. to give the silyl of the general formula (I). New organosilicon compounds that are propylamine derivatives can be synthesized.

[0033]

[Chemical 19]

The compound (I) of the present invention is a fungal disease of plants, for example, apple spot foliar fungus, capsicum epidemic bacterium, grape wilt fungus, apple heavy spot rot fungus, apple anthracnose bacterium,
It is effective against rice blast fungus, rice wilt fungus, rice bacillus fungus, rice seedling wilt bacterium, and cucumber gray mold fungus.

Although the compound (I) of the present invention can be used alone, it can be mixed with a carrier, a surfactant, a dispersant, an auxiliary agent, etc. by a conventional method, for example, a powder, emulsion, fine granule, It is preferably prepared and used in a composition such as a granule, a wettable powder, an oily suspension and an aerosol.

[0036]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

Example 1: 1-chloro-6-phenyl-
Preparation of 4,4-dimethyl-4-silaheptane A 3-neck round bottom flask with a capacity of 25 ml equipped with a reflux condenser and a dropping funnel was flash dried with dry nitrogen. to this,
125 ml of THF and 8.9 g (30 mmol) of 1,4,4-trichloro-6-phenyl-4-silaheptane were added and 3M methylmagnesium chloride 3 was added with stirring.
1.2 ml (94 mmol) was added via dropping funnel.
After completion of the dropping, the reaction solvent was refluxed for 2 hours by heating. The content was treated with water, the organic layer was separated with a separatory funnel, dried over anhydrous magnesium sulfate, and the solvent was evaporated. The product obtained was passed through a column packed with silica to give pure 1-chloro-
4.3 g (14.66 mmol) of 6-phenyl-4,4-dimethyl-4-silaheptane were isolated. Product N
The MR data are shown in Table 1.

Example 2: 1-chloro-6- (m- or p
-Methylphenyl) -4,4-dimethyl-4-silaheptane 150 ml THF, 1-chloro-6- (m- or p-methylphenyl) -4,4-dimethyl-4-silaheptane 9.3 g (30 mmol) ) And 3 M methylmagnesium chloride (24 ml, 72 mmol) were used, but the procedure was the same as in Example 1 and 1-chloro-6- (m- or p-) was used.
There was obtained 6.9 g (26 mmol) of -methylphenyl) -4,4-dimethyl-4-silaheptane. The NMR data of the product are shown in Table 1.

Example 3: 1-chloro-6- (m- or p
Preparation of -ethylphenyl) -4,4-dimethyl-4-silaheptane 50 ml THF, 1-chloro-6- (m- or p-ethylphenyl) -4,4-dimethyl-4-silaheptane 1
1-Chloro-6- (m- or p- was carried out as in Example 1, except that 0.5 g (32 mmol) and 26 ml (78 mmol) of 3M methylmagnesium chloride were used.
6.5 g (23 mmol) of -ethylphenyl) -4,4-dimethyl-4-silaheptane were obtained. The NMR data of the product are shown in Table 1.

Example 4: 1-chloro-6- (m- or p
-Isopropylphenyl) -4,4-dimethyl-4-silaheptane Preparation 30 ml THF, 1,4-dichloro-6- (m- or p-
Isopropylphenyl) -4,4-dimethyl-4-silaheptane 5.4 g (16 mmol) and 3M methylmagnesium chloride 13 ml (33 mmol) were used as in Example 1 except that 1-chloro- 6- (m
-Or p-Isopropylphenyl) -4,4-dimethyl-4-silaheptane (3.8 g, 13 mmol) was obtained. The NMR data of the product are shown in Table 1.

Example 5: 1-chloro-6- (o- or p
Preparation of -phenoxyphenyl) -4,4-dimethyl-4-silaheptane THF 150 ml, 1,4,4-trichloro-6- (o
-Or p-phenoxyphenyl) -4-silaheptane 2
Except that 4.7 g (64 mmol) and 51 ml of 3 M methylmagnesium chloride (150 mmol) were used.
The same procedure as in Example 1 was carried out to obtain 1-chloro-6- (o- or p-phenoxyphenyl) -4,4-dimethyl-4-silaheptane (15.2 g, 44 mmol). The NMR data of the product are shown in Table 1.

Example 6: 1-chloro-6- (o- or p
Preparation of -fluorophenyl) -4,4-dimethyl-4-silaheptane 1,4,4-trichloro-6- (o- or p-fluorophenyl) -4-silaheptane 8.8 g (28 mmol)
And 22.2 ml of 3M methylmagnesium chloride (6
The same procedure was followed as in Example 1 except that 0 mmol) was used and 1-chloro-6- (o- or p-fluorophenyl) -4,4-dimethyl-4-silaheptane 7.0 g (2
6 mmol) was obtained. The NMR data of the product are shown in Table 1.

Example 7: 1-chloro-6- (o- or p
Preparation of -chlorophenyl) -4,4-dimethyl-4-silaheptane 1,4,4-trichloro-6- (o- or p-chlorophenyl) -4-silaheptane 5 g (15 mmol) and 3
The procedure was the same as in Example 1 except that 11 ml (33 mmol) of M methylmagnesium chloride was used.
Chloro-6- (o- or p-chlorophenyl) -4,4
-Dimethyl-4-silaheptane 3.3 g (12 mmol)
I got The NMR data of the product are shown in Table 1.

Example 8: 1-chloro-6- (o- or p
-Chlorophenyl) -4-methyl-4-phenyl-4-
Preparation of silaheptane 25 ml of THF, 1.8 g of 1,4,4-trichloro-6- (o- or p-chlorophenyl) -4-silaheptane
(4.5 mmol), 2.3 ml of 2M phenylmagnesium chloride and 2.2 ml (5.4 mmol) of 3M methylmagnesium chloride were continuously reacted in the same apparatus and method as in Example 1 to give 1-chloro. 1.44 g (4.1 mmol) of -6- (o- or p-chlorophenyl) -4-methyl-phenyl-4-silaheptane was obtained. The NMR data of the product are shown in Table 1.

Example 9: 1-chloro-6- (o- or p
-Chlorophenyl) -4-methyl-4-fluorophenyl-4-silaheptane 25 ml THF, 1,4,4-trichloro-6- (o- or p-chlorophenyl) -4-silaheptane 1.4g
Example 4.2, except that 2.3 ml (4.6 mmol) each of 2M 4-fluorophenyl magnesium bromide and methyl magnesium chloride were used.
Was carried out in the same manner as above to obtain 1.35 g (3.5 mmol) of 1-chloro-6- (o- or p-chlorophenyl) -4-methyl-4- (4-fluorophenyl) -4-silaheptane. The NMR data of the product are shown in Table 1.

Example 10: 1-chloro-6- (o- or p-chlorophenyl) -4-butyl-4-phenyl-4
-Preparation of sila heptane 25 ml THF, 1,4-dichloro-6- (o- or p-
Chlorophenyl) -4-phenyl-4-silaheptane was carried out in the same manner as in Example 1 except that 1.5 g (4.5 mmol) of 2M normal butyl lithium was used. -Chloro-6- (o- or p
-Chlorophenyl) -4-butyl-4-phenyl-4-
1.57 g (4.0 mmol) of silaheptane was obtained. The NMR data of the product are shown in Table 1.

Example 11: Preparation of 1-chloro-6- (o- or p-chlorophenyl) -4,4-diallyl-4-silaheptane 25 ml THF, 1,4,4-trichloro-6- (o- or p -Chlorophenyl) -4-silaheptane 3.0 g
(9.1 mmol), allyl magnesium chloride 10 m
1 (20 mmol) was used and 1-chloro-6- (o-
Or p-chlorophenyl) -4,4-diallyl-4-silaheptane (2.83 g, 8.3 mmol) was obtained. The NMR data of the product are shown in Table 1.

Example 12: 1-Chloro-6-phenyl-
Preparation of 4,4-di (trimethylsilyloxy) -4-silaheptane 50 g of water and 100 g of diethyl ether were placed in a 250 ml three-necked round bottom slasco dried in the same manner as in Example 1, and 1,4,4-trichloro was added using a dropping funnel. 4.5 g (15 mmol) of -6-phenyl-4-silaheptane and 8.1 g (75 mmol) of chlorotrimethylsilane were added dropwise with stirring for 15 minutes, and further stirred for 10 minutes. Hexane solvent was added and HCl dissolved in the reaction product was extracted and removed. Remove the solvent and separate to give 1-chloro-6-phenyl-4,4-
2 g of di (trimethylsilyloxy) -4-silaheptane
(5 mmol) was obtained. The NMR data of the product are shown in Table 1.

Example 13: Preparation of 1-chloro-6- (o- or p-chlorophenyl) -4,4-di (trimethylsilyloxy) -4-silaheptane 25 ml THF, 1,4,4-trichloro-6- ( o- or p-chlorophenyl) -4-silaheptane 6.0 g (1
8.2 mmol) and chlorotrimethylsilane 10.8
1-Chloro-6- (o- or p-chlorophenyl) -4,4-di (trimethylsilyloxy) -4- was carried out as in Example 12, except that g (100 mmol) was used.
2.6 g (6 mmol) of silaheptane was obtained. Product N
The MR data are shown in Table 1.

[0050]

[Table 1]

[0051]

[Table 2]

[0052]

[Table 3]

Example 14: 1- (3-chloropropyl)
Preparation of -1- [2- (m- or p-methylphenyl) propyl] -1-silacyclopentane i) Drying a 250 ml round bottom flask equipped with a reflux condenser and dropping funnel under a nitrogen atmosphere. THF in a flask
30 ml, 6.3 g (260 mmol) of magnesium metal and a small amount of I ₂ were added to the mixture, which was passed through a dropping funnel with stirring to give 11.9 g (49 mmol) of 1,4-dichlorobutane.
Was added dropwise over 5 minutes to prepare a diGrignard reagent.

Ii) Example 1 using 150 ml of THF, 21 g (79 mmol) of 1,4,4-trichloro-6- (m- or p-methylphenyl) -4-silaheptane and the diGrignard reagent synthesized in i). 1-
(3-chloropropyl) -1- [2- (m- or p-methylphenyl) propyl] -1-silacyclopentane 1
7.7 g (60 mmol) were obtained. The NMR data of the product are shown in Table 2.

Example 15: 1- (3-chloropropyl)
Preparation of -1- [2- (m- or p-isopropylphenyl) propyl] -1-silacyclopentane 1.8 g (14 mmol) of 1,4-dichlorobutane and 0.9 g (37 mmol) of magnesium metal were used. A Di Grignard reagent was prepared in the same manner as in Example 14 except that the above was performed. Then THF 150 ml, 1,4,4-trichloro-
3.5 g (10 mmol) of 6- (m- or p-isopropylphenyl) -4-silaheptane and the above-mentioned Di Grignard reagent were reacted in the same manner as in Example 14 to give 1- (3-
1.0 g (3.2 mmol) of chloropropyl) -1- [2- (m- or p-isopropylphenyl) propyl] -1-silacyclopentane was obtained. The NMR data of the product are shown in Table 2.

Example 16: 1- (3-chloropropyl)
Preparation of -1- [2- (o- or p-fluorophenyl) propyl] -1-silacyclopentane 2.7 g (21 mmol) 1,4-dichlorobutane and 2.1 g (87 mmol) magnesium metal were used. A Di Grignard reagent was prepared in the same manner as in Example 14 except that the above was performed. Then 60 ml of THF, 1,4,4-trichloro-6
6.8 g (21 mmol) of-(o- or p-fluorophenyl) -4-silaheptane and the above-mentioned DiGrignard reagent were reacted in the same manner as in Example 1 to give 1- (3-chloropropyl) -1- [ 2- (o- or p-fluorophenyl) propyl] -1-silacyclopentane 5.8 g (17
Mmol). The NMR data of the product are shown in Table 2.

[0057]

[Table 4]

Example 17: 1- (3-chloropropyl)
Preparation of -1- [2- (m- or p-methylphenyl) propyl] -1-silacyclohexane 14.8 g (105 mmol) 1,5-dichloropentane, 7.6 g (304 mmol) magnesium metal and 90 ml THF. A DiGrignard reagent was prepared in the same manner as in Example 14 except that it was used. Next, 150 ml of THF,
30 g (84 mmol) of 1,4,4-trichloro-6- (m- or p-methylphenyl) -4-silaheptane and the above-mentioned Di Grignard reagent were reacted in the same manner as in Example 1 to give 1- (3- 20.3 g (60 mmol) of chloropropyl) -1- [2- (m- or p-methylphenyl) propyl] -1-silacyclohexane was obtained. Product NM
R data is shown in Table 3.

Example 18: 1- (3-chloropropyl)
Preparation of -1- [2- (o- or p-fluorophenyl) propyl] -1-silacyclohexane 5.4 g (38 mmol) of 1,5-dichloropentane and 3.1 g (128 mmol) of metallic magnesium were used. A Di Grignard reagent was prepared in the same manner as in Example 14 except for the above. Then 90 ml THF, 1,4,4-trichloro-6
1-g (38 mmol) of-(o- or p-fluorophenyl) -4-silaheptane and the above-mentioned diGrignard reagent were reacted in the same manner as in Example 1 to give 1- (3-chloropropyl) -1- [ 2- (o- or p-fluorophenyl) propyl] -1-silacyclohexane 10.7 g (3
4 mmol) was obtained. The NMR data of the product are shown in Table 3.

[0060]

[Table 5]

Example 19: 1- (2,6-Dimethylmorpholino) -6- (o- or p-chlorophenyl) -4,
Preparation of 4-dimethyl-4-silaheptane In a 25 ml round bottom flask equipped with a reflux condenser, 1-
Chloro-6- (o- or p-chlorophenyl) -4,4
1.75 g (6 mmol) of dimethyl-4-silaheptane, 1.15 g (10 mmol) of 2,6-dimethylmorpholine and a small amount of NaI were added, and an oil bath was used.
The reaction was carried out at -100 ° C for 3 hours. White salt was precipitated as the reaction proceeded. After completion of the reaction, the reaction product was transferred to a separatory funnel, and water was added and shaken. The aqueous layer was extracted with hexane three times and collected in the organic layer. After drying this over anhydrous MgSO ₄ , the solvent was removed. Vacuum distill the residue (140 ℃ / 0.6mmHg),
2.1 g (5.7 mmol) of 1- (2,6-dimethylmorpholino) -6- (o- or p-chlorophenyl) -4,4-dimethyl-4-silaheptane were obtained. Product NM
R data are shown in Table 4.

Example 20: 1- (2,6-Dimethylmorpholino) -6- (o- or p-chlorophenyl) -4-
Preparation of (4-chlorophenyl) -4-hydroxy-4-silaheptane 1-chloro-6- (o- or p-chlorophenyl) -4
As in Example 19, but using 1.8 g (4.7 mmol) of-(4-chlorophenyl) -4-hydroxy-4-silaheptane and 1.63 g (14.1 mmol) of 2,6-dimethylmorpholine. 1- (2,6-dimethylmorpholino) -6- (o- or p-chlorophenyl)-
0.5 g (1.0 mmol) of 4- (4-chlorophenyl) -4-hydroxy-4-silaheptane was obtained (vacuum distillation 175 ° C./0.6 mmHg). 4th NMR data of product
Shown in the table.

Example 21: 1- (2,6-Dimethylmorpholino) -6- (o- or p-chlorophenyl) -4-
Preparation of methyl-4-phenyl-4-silaheptane 1-chloro-6- (o- or p-chlorophenyl) -4
1.44 g of -methyl-4-phenyl-4-silaheptane
(4.1 mmol) and 2,6-dimethylmorpholine (1.18 g, 10.2 mmol) were used, and the same procedure as in Example 19 was carried out to obtain a reaction product. This is passed through a column filled with silica and 1.37 g of pure 1- (2,6-dimethylmorpholino) -6- (o- or p-chlorophenyl) -4-methyl-4-phenyl-4-silaheptane ( 3.3 mmol) was obtained. The NMR data of the product are shown in Table 4.

Example 22: 1- (2,6-Dimethylmorpholino) -6- (o- or p-chlorophenyl) -4-
Preparation of butyl-4-phenyl-4-silaheptane 1-chloro-6- (o- or p-chlorophenyl) -4
-Butyl-4-phenyl-4-silaheptane 1.57 g
(4.0 mmol) and 1.41 g (12.2 mmol) of 2,6-dimethylmorpholine were used, and the same procedure as in Example 19 was carried out to obtain a reaction product. This is passed through a column filled with silica and 1.3 g of pure 1- (2,6-dimethylmorpholino) -6- (o- or p-chlorophenyl) -4-butyl-4-phenyl-4-silaheptane ( (2.7 mmol) was obtained. The NMR data of the product are shown in Table 4.

Example 23: 1- (2,6-Dimethylmorpholino) -6- (o- or p-chlorophenyl) -4-
Preparation of (4-fluorophenyl) -4-hydroxy-4-silaheptane 1-chloro-6- (o- or p-chlorophenyl) -4
Same as Example 19 except that 1.3 g (3.5 mmol) of-(4-fluorophenyl) -4-hydroxy-4-silaheptane and 1.06 g (9.2 mmol) of 2,6-dimethylmorpholine were used. Was carried out in 1- (2,6-dimethylmorpholino) -6- (o- or p-chlorophenyl) -4- (4-fluorophenyl) -4-hydroxy-4-silaheptane 1.0 g (2.3 mmol) ) Got.
The NMR data of the product are shown in Table 4.

Example 24: 1- (2,6-Dimethylmorpholino) -6- (o- or p-chlorophenyl) -4-
Preparation of Methyl-4- (4-fluorophenyl) -4-silaheptane 1-chloro-6- (o- or p-chlorophenyl) -4
As in Example 19, except that 1.35 g (3.5 mmol) of -methyl-4- (4-fluorophenyl) -4-silaheptane and 1.41 g (12.2 mmol) of 2,6-dimethylmorpholine were used. The reaction product was obtained.
Pass this through a column filled with silica to obtain pure 1-
(2,6-Dimethylmorpholino) -6- (o- or p-
Chlorophenyl) -4-methyl-4- (4-fluorophenyl) -4-silaheptane 1.3 g (3.1 mmol)
I got The NMR data of the product are shown in Table 4.

Example 25: 1- (2,6-Dimethylmorpholino) -6- (o- or p-chlorophenyl) -4,
Preparation of 4-diallyl-4-silaheptane 1-chloro-6- (o- or p-chlorophenyl)-
2.8 g (8.3) of 4,4-diallyl-4-silaheptane
Mmol) and 2,6-dimethylmorpholine 2.84 g
A reaction product was obtained in the same manner as in Example 19 except that (23 mmol) was used. This is passed through a column filled with silica to give pure 1- (2,6-dimethylmorpholino) -6- (o- or p-chlorophenyl) -4,4-
3.1 g (7.6 mmol) of diallyl-4-silaheptane
I got The NMR data of the product are shown in Table 4.

Example 26: 1- (2,6-Dimethylmorpholino) -6- (o- or p-fluorophenyl)-
Preparation of 4,4-dimethyl-4-silaheptane 1-chloro-6- (o- or p-fluorophenyl)-
1.2 g (4.3 mmol) of 4,4-dimethyl-4-silaheptane and 2.0 g (16 of 2,6-dimethylmorpholine)
Was carried out in the same manner as in Example 19 to obtain a reaction product. This is passed through a column filled with silica to give pure 1- (2,6-dimethylmorpholino)-
1.1 g (3.1 mmol) of 6- (o- or p-fluorophenyl) -4,4-dimethyl-4-silaheptane was obtained. The NMR data of the product are shown in Table 4.

Example 27: 1- (2,6-Dimethylmorpholino) -6- (m- or p-methylphenyl) -4,
Preparation of 4-dimethyl-4-silaheptane 1-chloro-6- (m- or p-methylphenyl)-
1.5 g (5.5 mmol) of 4,4-dimethyl-4-silaheptane and 2.0 g (16 of 2,6-dimethylmorpholine)
Was carried out in the same manner as in Example 19 to obtain a reaction product. This is passed through a column filled with silica to give pure 1- (2,6-dimethylmorpholino)-
0.9 g (2.6 mmol) of 6- (m- or p-methylphenyl) -4,4-dimethyl-4-silaheptane was obtained. The NMR data of the product are shown in Table 4.

Example 28: 1- (2,6-Dimethylmorpholino) -6- (m- or p-ethylphenyl) -4,
Preparation of 4-dimethyl-4-silaheptane 1-chloro-6- (m- or p-ethylphenyl)-
1.3 g (4.5 mmol) of 4,4-dimethyl-4-silaheptane and 2.0 g (16 g of 2,6-dimethylmorpholine)
Was carried out in the same manner as in Example 19 to obtain a reaction product. This is passed through a column filled with silica to give pure 1- (2,6-dimethylmorpholino)-
1.4 g (3.8 mmol) of 6- (m- or p-ethylphenyl) -4,4-dimethyl-4-silaheptane was obtained. The NMR data of the product are shown in Table 4.

Example 29: 1- (2,6-Dimethylmorpholino) -6- (m- or p-isopropylphenyl)
Preparation of -4,4-dimethyl-4-silaheptane 1.2 g of 1-chloro-6- (m- or p-isopropylphenyl) -4,4-dimethyl-4-silaheptane
A reaction product was obtained in the same manner as in Example 19 except that (4.1 mmol) and 1.5 g (12 mmol) of 2,6-dimethylmorpholine were used. This is passed through a column filled with silica and pure 1- (2,6-dimethylmorpholino) -6- (m- or p-isopropylphenyl) -4,4-dimethyl-4-silaheptane 1.3 g
(3.4 mmol) was obtained. The NMR data of the product are shown in Table 4.

Example 30: 1- (2,6-Dimethylmorpholino) -6- (m- or p-phenoxyphenyl)-
Preparation of 4,4-dimethyl-4-silaheptane 1-chloro-6- (m- or p-phenoxyphenyl)
3.1 g (8.8 g of -4,4-dimethyl-4-silaheptane)
Mmol) and 2,6-dimethylmorpholine 4.4 g (3
A reaction product was obtained in the same manner as in Example 19 except that 5 mmol) was used. Pass this through a column filled with silica to obtain pure 1- (2,6-dimethylmorpholino).
-6- (m- or p-phenoxyphenyl) -4,4-
Dimethyl-4-silaheptane 3.1 g (7.3 mmol)
I got The NMR data of the product are shown in Table 4.

Example 31: Preparation of 1- (2,6-dimethylmorpholino) -6-phenyl-4,4-di (trimethylsilyloxy) -4-silaheptane 1-chloro-6-phenyl-4,4-di The reaction product was obtained in the same manner as in Example 19 except that 3.6 g (9.0 mmol) of (trimethylsilyloxy) -4-silaheptane and 4.4 g (35 mmol) of 2,6-dimethylmorpholine were used. It was This is passed through a column filled with silica to give pure 1- (2,6-dimethylmorpholino) -6-
Phenyl-4,4-di (trimethylsilyloxy) -4
-3.0 g (6.2 mmol) of silaheptane was obtained. The NMR data of the product are shown in Table 4.

[0074]

[Table 6]

[0075]

[Table 7]

[0076]

[Table 8]

[0077]

[Table 9]

Example 32: 1- [3- (2,6-dimethylmorpholino) propyl] -1- [2- (m- or p-
Preparation of methylphenyl) propyl] -1-silacyclopentane 1- (3-chloropropyl) -1- [2- (m- or p
-Methylphenyl) propyl] -1-silacyclopentane The procedure of Example 19 was repeated except that 1.9 g (6.5 mmol) and 2,6-dimethylmorpholine 2.4 g (19 mmol) were used. A reaction product was obtained. This is passed through a column filled with silica to obtain pure 1- [3- (2,
6-Dimethylmorpholino) propyl] -1- [2- (m
0.92 g (2.5 mmol) of -or p-methylphenyl) propyl] -1-silacyclopentane was obtained. The NMR data of the product are shown in Table 5.

[0079]

[Table 10]

Example 33: 1- [3- (2,6-dimethylmorpholino) propyl] -1- [2- (o- or p-
Preparation of fluorophenyl) propyl] -1-silacyclohexane 1- (3-chloropropyl) -1- [2- (o- or p
-Fluorophenyl) propyl] -1-silacyclohexane 1.9 g (6.2 mmol) and 2,6-dimethylmorpholine 3.0 g (24 mmol) were used, except that the same procedure as in Example 19 was carried out. I got a thing. This is passed through a column filled with silica to obtain pure 1- [3- (2,
6-dimethylmorpholino) propyl] -1- [2- (o
1.6 g (4.1 mmol) of -or p-fluorophenyl) propyl] -1-silacyclohexane were obtained. The NMR data of the product are shown in Table 6.

Example 34: 1- [3- (2,6-Dimethylmorpholino) propyl] -1- [2- (m- or p-
Preparation of methylphenyl) propyl] -1-silacyclohexane 1- (3-chloropropyl) -1- [2- (m- or p
-Methylphenyl) propyl] -1-silacyclohexane 3.1 g (10.0 mmol) and 2,6-dimethylmorpholine 4.7 g (41 mmol) except that the reaction was carried out in the same manner as in Example 19. The product was obtained. This is passed through a column filled with silica to obtain pure 1- [3-
(2,6-Dimethylmorpholino) propyl] -1- [2
2.8 g (7.5 mmol) of-(m- or p-methylphenyl) propyl] -1-silacyclohexane was obtained. The NMR data of the product are shown in Table 6.

[0082]

[Table 11]

Example 35: Preparation of 1- (hexamethyleneimino) -4,4-dimethyl-6-phenyl-4-silaheptane 1.8 g of 1-chloro-4,4-dimethyl-6-phenyl-4-silaheptane A reaction product was obtained in the same manner as in Example 19 except that 2.1 g (21 mmol) of hexamethyleneimine (7.1 mmol) was used. This is passed through a column filled with silica to give pure 1- (hexamethyleneimino) -4,4-dimethyl-6-phenyl-4-.
1.9 g (5.9 mmol) of silaheptane was obtained. The NMR data of the product are shown in Table 7.

Example 36: Preparation of 1- (hexamethyleneimino) -4,4-dimethyl-6- (o- or p-chlorophenyl) -4-silaheptane 1-chloro-4,4-dimethyl-6- ( The reaction product was prepared in the same manner as in Example 19 except that 0.94 g (3.2 mmol) of o- or p-chlorophenyl) -4-silaheptane and 1.4 g (14 mmol) of hexamethyleneimine were used. Obtained. This was passed through a column filled with silica to give 1.0 g (2.8 mmol) of pure 1- (hexamethyleneimino) -4,4-dimethyl-6- (o- or p-chlorophenyl) -4-silaheptane. Got The NMR data of the product are shown in Table 7.

Example 37: Preparation of 1- (hexamethyleneimino) -4,4-dimethyl-6- (o- or p-fluorophenyl) -4-silaheptane 1-chloro-4,4-dimethyl-6- Reaction was carried out in the same manner as in Example 19 except that 1.4 g (5.2 mmol) of (o- or p-fluorophenyl) -4-silaheptane and 2.0 g (19.6 mmol) of hexamethyleneimine were used. The product was obtained. This is passed through a column filled with silica to give pure 1- (hexamethyleneimino) -4,4-
Dimethyl-6- (o- or p-fluorophenyl) -4
1.7 g (5.1 mmol) of silaheptane were obtained. The NMR data of the product are shown in Table 7.

Example 38: Preparation of 1- (hexamethyleneimino) -4,4-dimethyl-6- (o-, m- or p-methylphenyl) -4-silaheptane 1-chloro-4,4-dimethyl 1.9 g of -6- (o-, m- or p-methylphenyl) -4-silaheptane (7.
(1 mmol) and hexamethyleneimine (2.1 g, 21 mmol) were used, and the same procedure as in Example 19 was carried out to obtain a reaction product. This is passed through a column filled with silica to give pure 1- (hexamethyleneimino) -4,4-
Dimethyl-6- (o-, m- or p-methylphenyl)
1.7 g (5.2 mmol) of -4-silaheptane was obtained.
The NMR data of the product are shown in Table 7.

Example 39: Preparation of 1- (hexamethyleneimino) -4,4-dimethyl-6- (m- or p-ethylphenyl) -4-silaheptane 1-chloro-4,4-dimethyl-6- The reaction product was prepared in the same manner as in Example 19 except that 1.1 g (3.9 mmol) of (m- or p-ethylphenyl) -4-silaheptane and 1.5 g (15 mmol) of hexamethyleneimine were used. Got This is passed through a column filled with silica and 0.9 g (2.6 mmol) of pure 1- (hexamethyleneimino) -4,4-dimethyl-6- (m- or p-ethylphenyl) -4-silaheptane. ) Got. The NMR data of the product are shown in Table 7.

Example 40: Preparation of 1- (hexamethyleneimino) -4,4-dimethyl-6- (m- or p-isopropylphenyl) -4-silaheptane 1-chloro-4,4-dimethyl-6- 1.5 g of (m- or p-isopropylphenyl) -4-silaheptane (5.
(1 mmol) and hexamethyleneimine (1.5 g, 15 mmol) were used, and the reaction product was obtained in the same manner as in Example 19. This is passed through a column filled with silica to give pure 1- (hexamethyleneimino) -4,4-
Dimethyl-6- (m- or p-isopropylphenyl)
1.4 g (3.9 mmol) of -4-silaheptane was obtained.
The NMR data of the product are shown in Table 7.

Example 41: Preparation of 1- (hexamethyleneimino) -4,4-dimethyl-6- (o- or p-phenoxyphenyl) -4-silaheptane 1-chloro-4,4-dimethyl-6- 2.3 g (6.6) of (o- or p-phenoxyphenyl) -4-silaheptane
The reaction product was obtained in the same manner as in Example 19 except that 2.6 g (26 mmol) of hexamethyleneimine was used. This is passed through a column filled with silica to give pure 1- (hexamethyleneimino) -4,4-
Dimethyl-6- (o- or p-phenoxyphenyl)-
2.6 g (6.4 mmol) of 4-silaheptane was obtained. The NMR data of the product are shown in Table 7.

Example 42: 1- (Hexamethyleneimino) -4,4-di (trimethylsilyloxy) -6-
Preparation of (m- or p-methylphenyl) -4-silaheptane 1-chloro-4,4-di (trimethylsilyloxy)-
The reaction product was prepared in the same manner as in Example 19 except that 4.2 g (10 mmol) of 6- (m- or p-methylphenyl) -4-silaheptane and 3.0 g (30 mmol) of hexamethyleneimine were used. Got This is passed through a column filled with silica to give pure 1- (hexamethyleneimino) -4,4-di (trimethylsilyloxy) -6-.
3.5 g (7.0 mmol) of (m- or p-methylphenyl) -4-silaheptane was obtained. The NMR data of the product are shown in Table 7.

[0091]

[Table 12]

[0092]

[Table 13]

Example 43: Preparation of 1- [3- (hexamethyleneimino) propyl] -1- [2- (m- or p-methylphenyl) propyl] -4-silacyclopentane 1- (3-chloro Propyl) -1- [2- (m- or p
-Methylphenyl) propyl] -1-silacyclopentane (2.1 g, 7.2 mmol) and hexamethyleneimine (4.4 g, 44 mmol) were used, except that the reaction product was prepared in the same manner as in Example 19. Obtained. This is passed through a column filled with silica to give pure 1- [3- (hexamethyleneimino) propyl] -1- [2- (m- or p-methylphenyl) propyl] -1-silacyclopentane 1.
7 g (4.9 mmol) were obtained. The NMR data of the product are shown in Table 8.

Example 44: Preparation of 1- [3- (hexamethyleneimino) propyl] -1- [2- (m- or p-isopropylphenyl) propyl] -1-silacyclopentane 1- (3-chloro Propyl) -1- [2- (m- or p
-Isopropylphenyl) propyl] -1-silacyclopentane 1.0 g (3.2 mmol) and hexamethyleneimine 1.0 g (10 mmol) were used, except that the reaction product was prepared in the same manner as in Example 19. Obtained. This is passed through a column filled with silica to give pure 1- [3- (hexamethyleneimino) propyl] -1- [2- (m- or p
1.07 g (2.8 mmol) of -isopropylphenyl) propyl] -1-silacyclopentane was obtained. The NMR data of the product are shown in Table 8.

[0095]

[Table 14]

Example 45: Preparation of 1- [3- (hexamethyleneimino) propyl] -1- [2- (m- or p-methylphenyl) propyl] -1-silacyclohexane 1- (3-chloropropyl ) -1- [2- (m- or p
-Methylphenyl) propyl] -1-silacyclohexane 2.5 g (8.0 mmol) and hexamethyleneimine 4.4 g (44 mmol) were used, except that the reaction product was obtained in the same manner as in Example 19. It was This is passed through a column filled with silica to give pure 1- [3- (hexamethyleneimino) propyl] -1- [2- (m- or p-methylphenyl) propyl] -1-silacyclohexane 2.
0 g (5.4 mmol) was obtained. The NMR data of the product are shown in Table 9.

Example 46: Preparation of 1- [3- (hexamethyleneimino) propyl] -1- [2- (o- or p-fluorophenyl) propyl] -4-silacyclohexane 1- (3-chloropropyl ) -1- [2- (o- or p
Example 19 except that 1.0 g (6.1 mmol) of -fluorophenyl) propyl] -1-silacyclohexane and 2.4 g (24 mmol) of hexamethyleneimine were used.
A reaction product was obtained in the same manner as in. This is passed through a column filled with silica to give 0.88 g of pure 1- [3- (hexamethyleneimino) propyl] -1- [2- (o- or p-fluorophenyl) propyl] -1-silacyclohexane. (2.4 mmol) was obtained. The NMR data of the product are shown in Table 9.

[0098]

[Table 15]

Example 47: 1- (Piperidino) -4,4
-Dimethyl-6- (m- or p-methylphenyl) -4
-Preparation of silaheptane 1-chloro-4,4-dimethyl-6- (m- or p-methylphenyl) -4-silaheptane 1.6 g (6.0 mmol) and piperidine 2.1 g (25 mmol) were used. A reaction product was obtained in the same manner as in Example 19 except for the above. Pass this through a column filled with silica to obtain a pure 1
-(Piperidino) -4,4-dimethyl-6- (m- or p-methylphenyl) -4-silaheptane 0.8 g (2.
7 mmol) was obtained. The NMR data of the product are shown in Table 10.

Example 48: 1- (Piperidino) -4,4
-Dimethyl-6- (o- or p-fluorophenyl)-
Preparation of 4-silaheptane 2.7 g (9.8 mmol) 1-chloro-4,4-dimethyl-6- (o- or p-fluorophenyl) -4-silaheptane and 2.6 g (31 mmol) piperidine were used. A reaction product was obtained in the same manner as in Example 19 except for the above. Pass this through a column filled with silica to obtain a pure 1
2.6 g of-(piperidino) -4,4-dimethyl-6- (o- or p-fluorophenyl) -4-silaheptane
(2.7 mmol) was obtained. The NMR data of the product are shown in Table 10.

Example 49: 1- (Piperidino) -4,4
-Dimethyl-6- (o- or p-chlorophenyl) -4
-Preparation of silaheptane 1-chloro-4,4-dimethyl-6- (o- or p-chlorophenyl) -4-silaheptane 1.7 g (9.8 mmol) and piperidine 1.7 g (20 mmol) were used. A reaction product was obtained in the same manner as in Example 19. Pass this through a column filled with silica to obtain a pure 1
1.4 g (4.-piperidino) -4,4-dimethyl-6- (o- or p-chlorophenyl) -4-silaheptane.
2 mmol) was obtained. The NMR data of the product are shown in Table 10.

Example 50: 1- (Piperidino) -4,4
-Dimethyl-6- (o- or p-phenoxyphenyl)
Preparation of -4-silaheptane 1-chloro-4,4-dimethyl-6- (o- or p-phenoxyphenyl) -4-silaheptane 2.5 g (7.2
Mmol) and 2.6 g (31 mmol) of piperidine were used and a reaction product was obtained in the same manner as in Example 19. This is passed through a column filled with silica to give pure 1- (piperidino) -4,4-dimethyl-6- (o- or p-phenoxyphenyl) -4-silaheptane 2.3.
g (5.8 mmol) was obtained. The NMR data of the product are shown in Table 10.

Example 51: 1- (Piperidino) -4,4
-Di (trimethylsilyloxy) -6- (o- or p-
Preparation of chlorophenyl) -4-silaheptane 1-chloro-4,4-di (trimethylsilyloxy)-
A reaction product was obtained in the same manner as in Example 19 except that 3.9 g (9 mmol) of 6- (o- or p-chlorophenyl) -4-silaheptane and 2.6 g (31 mmol) of piperidine were used. . This is passed through a column filled with silica and pure 1- (piperidino) -4,4-di (trimethylsilyloxy) -6- (o- or p-chlorophenyl) -4-silaheptane 3.1 g (6 mmol) Got
The NMR data of the product are shown in Table 10.

[0104]

[Table 16]

Example 52: Preparation of 1- (3-piperidinopropyl) -1- [2- (m- or p-methylphenyl) propyl] -1-silacyclopentane 1- (3-chloropropyl) -1- [2- (m- or p
-Methylphenyl) propyl] -1-silacyclopentane 5.7 g (17 mmol) and pyrrolidine 4.3 g (51
Was carried out in the same manner as in Example 19 to obtain a reaction product. This is passed through a column filled with silica to give pure 1- (3-piperidinopropyl) -1-
[2- (m- or p-methylphenyl) propyl] -1
3.5 g (10 mmol) of silacyclopentane were obtained.
The NMR data of the product are shown in Table 11.

Example 53: Preparation of 1- (3-piperidinopropyl) -1- [2- (o- or p-chlorophenyl) propyl] -1-silacyclopentane 1- (3-chloropropyl)- 1- [2- (o- or p
-Chlorophenyl) propyl] -1-silacyclopentane 4.1 g (13 mmol) and pyrrolidine 3.3 g (39
A reaction product was obtained in the same manner as in Example 19 except that (mmol) was used. This is passed through a column filled with silica to give pure 1- (3-piperidinopropyl) -1.
-[2- (o- or p-chlorophenyl) propyl]-
3.3 g (9 mmol) of 1-silacyclopentane was obtained.
The NMR data of the product are shown in Table 11.

[0107]

[Table 17]

Example 54: Preparation of 1- (3-piperidinopropyl) -1- [2- (m- or p-methylphenyl) propyl] -1-silacyclohexane 1- (3-chloropropyl)- 1- [2- (m- or p
-Methylphenyl) propyl] -1-silacyclohexane 4.3 g (13 mmol) and pyrrolidine 3.3 g (39
Was carried out in the same manner as in Example 19 to obtain a reaction product. This is passed through a column filled with silica to give pure 1- (3-piperidinopropyl) -1-
[2- (m- or p-methylphenyl) propyl] -1
-2.9 g (8 mmol) of silacyclohexane were obtained. The NMR data of the product are shown in Table 12.

Example 55: Preparation of 1- (3-piperidinopropyl) -1- [2- (o- or p-fluorophenyl) propyl] -1-silacyclohexane 1- (3-chloropropyl)- 1- [2- (o- or p
-Fluorophenyl) propyl] -1-silacyclohexane 3.8 g (12 mmol) and pyrrolidine 3.3 g (3
A reaction product was obtained in the same manner as in Example 19 except that 9 mmol) was used. This is passed through a column filled with silica to give pure 1- (3-piperidinopropyl) -1.
-[2- (o- or p-fluorophenyl) propyl]
2.7 g (7 mmol) of -1-silacyclohexane was obtained. The NMR data of the product are shown in Table 12.

[0110]

[Table 18]

Example 56: 1-Pyrrolidino-4,4-dimethyl-6- (o- or p-fluorophenyl) -4-
Preparation of silacycloheptane 1-chloro-4,4-dimethyl-6- (o- or p-fluorophenyl) -4-silaheptane 0.6 g (2.1 mmol) and pyrrolidine 0.6 g (8.0 mmol) A reaction product was obtained in the same manner as in Example 19 except that was used. This is passed through a column filled with silica to obtain pure 1-pyrrolidino-4,4-dimethyl-6- (o- or p-
-Fluorophenyl) -4-silaheptane 0.5 g (0.
5 mmol) was obtained. The NMR data of the product are shown in Table 13.

Example 57: Preparation of 1-pyrrolidino-4,4-dimethyl-6- (o- or p-chlorophenyl) -4-silaheptane 1-chloro-4,4-dimethyl-6- (o- or p A reaction product was obtained in the same manner as in Example 19 except that 1.2 g (4.0 mmol) of -chlorophenyl) -4-silaheptane and 1.2 g (16 mmol) of pyrrolidine were used. Pass this through a column filled with silica to obtain a pure 1
-Pyrrolidino-4,4-dimethyl-6- (o- or p-
1.2 g (3.8 mmol) of chlorophenyl) -4-silaheptane was obtained. The NMR data of the product are shown in Table 13.

[0113]

[Table 19]

Example 58: Preparation of 1- (3-pyrrolidinopropyl) -1- [2- (m- or p-methylphenyl) propyl] -1-silacyclopentane 1- (3-chloropropyl)- 1- [2- (m- or p
2.1 g (7.1 mmol) of -methylphenyl) propyl] -1-silacyclopentane and 1.5 g (2
A reaction product was obtained in the same manner as in Example 19 except that 1.2 mmol) was used. Pass this through a column filled with silica to obtain pure 1- (3-pyrrolidinopropyl).
0.7 g (2.2 mmol) of -1- [2- (m- or p-methylphenyl) propyl] -1-silacyclopentane was obtained. The NMR data of the product are shown in Table 14.

Example 59: Preparation of 1- (3-pyrrolidinopropyl) -1- [2- (m- or p-ethylphenyl) propyl] -1-silacyclopentane 1- (3-chloropropyl)- 1- [2- (m- or p
-Ethylphenyl) propyl] -1-silacyclopentane 2.2 g (7.0 mmol) and pyrrolidine 1.0 g (1
A reaction product was obtained in the same manner as in Example 19 except that 4.1 mmol) was used. Pass this through a column filled with silica to obtain pure 1- (3-pyrrolidinopropyl).
-1- [2- (m- or p-ethylphenyl) propyl] -1-silacyclopentane 3.5 g (10 mmol)
I got The NMR data of the product are shown in Table 14.

[0116]

[Table 20]

Example 60: Preparation of 1- (3-pyrrolidinopropyl) -1- [2- (m- or p-methylphenyl) propyl] -1-silacyclohexane 1- (3-chloropropyl) -1 -[2- (m- or p
-Methylphenyl) propyl] -1-silacyclohexane 2.2 g (7.1 mmol) and pyrrolidine 1.5 g (2
A reaction product was obtained in the same manner as in Example 19 except that 1 mmol) was used. This is passed through a column filled with silica to give pure 1- (3-pyrrolidinopropyl) -1.
-[2- (m- or p-methylphenyl) propyl]-
2.2 g (6.4 mmol) of 1-silacyclohexane was obtained. The NMR data of the product are shown in Table 15.

[0118]

[Table 21]

Example 61: Biological activity test The tertiary amine-based organosilicon compounds of the present invention were tested for antifungal activity. The strains used in the bioactivity test are as follows. AM = Alternaria mali PC = Phytophthora capsici PB = Phytophora baccae BD = Botryosphaeria dothidea GC = Apple anthracnose PO (ulata ulcerella) = Rice blast fungus (Pyricularia oryzae) RS = Rhizoctonia solani FM = Rice bacillus seedling fungus (Fusarium moniliforme) RS = Rhizopus Sp BC = Cucumber gray mold fungus (Botrytis cinerea)

The test method was as follows: A drug was dissolved in acetone in vitro and mixed with PDA medium at a concentration of 200 ppm to prepare a drug solution plate medium. Inoculated on medium. Then, the cells were cultured in an incubator (28 ° C.), and the degree of culture was compared with the degree of growth of untreated hyphae to obtain the hyphal growth inhibition rate (%). The results are shown in Tables 16 to 27.

[0121]

[Table 22]

[0122]

[Table 23]

[0123]

[Table 24]

[0124]

[Table 25]

[0125]

[Table 26]

[0126]

[Table 27]

[0127]

[Table 28]

[0128]

[Table 29]

[0129]

[Table 30]

[0130]

[Table 31]

[0131]

[Table 32]

[0132]

[Table 33]

[0133]

The novel silylpropylamine derivative of the present invention is a fungicide against fungal diseases of plants.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location A01N 55/00 C C07F 7/12 R (72) Inventor Ishi Mei, Doh-gu, Seoul, Republic of Korea 5 Ji 5 Dong 519-59 (72) Inventor Lee Ji 9 1-53 Anchon-dong, Jongno-gu, Seoul, Republic of Korea

Claims (9)

[Claims] 1. A silylpropylamine derivative represented by the following general formula (I). Embedded image (In the formula, X ¹ and X ² each represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, a phenoxy group or a halogen atom, R represents a hydrogen atom or a methyl group, Z represents a methylene group, Represents an ethylene group, an oxygen atom or a direct bond, R ¹ and R ² each represent a methyl group, an allyl group, a butyl group, a phenyl group, a 4-chlorophenyl group, a 4-fluorophenyl group, a hydroxyl group or a trimethylsilyloxy group, Or R ¹ and R ² together form an alkylene group having 4 or 5 carbon atoms) 2. The silylpropylamine derivative according to claim 1, wherein Z is a methylene group. 3. The silylpropylamine derivative according to claim 1, wherein Z is an ethylene group. 4. The silylpropylamine derivative according to claim 1, wherein Z is an oxygen atom. 5. The silylpropylamine derivative according to claim 1, wherein Z is a direct bond. 6. The method for producing a silylpropylamine derivative according to claim 1, wherein the amine represented by the general formula (II) is reacted with the silylpropyl chloride represented by the general formula (III) using NaI as a catalyst. Embedded image (In the formula, each R represents a hydrogen atom or a methyl group, and Z represents a methylene group, an ethylene group, an oxygen atom or a direct bond.) (In the formula, each of X ¹ and X ² represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, a phenoxy group or a halogen atom. R ¹ and R ² are each a methyl group, an allyl group, a butyl group, Represents a phenyl group, a 4-chlorophenyl group, a 4-fluorophenyl group, a hydroxyl group or a trimethylsilyloxy group, or R ¹ and R ² together form an alkylene group having 4 or 5 carbon atoms) 7. A silylpropyl chloride derivative represented by the following general formula (III). [Chemical 4] (In the formula, each of X ¹ and X ² represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, a phenoxy group or a halogen atom. R ¹ and R ² are each a methyl group, an allyl group, a butyl group, Represents a phenyl group, a 4-chlorophenyl group, a 4-fluorophenyl group, a hydroxyl group or a trimethylsilyloxy group, or R ¹ and R ² together form an alkylene group having 4 or 5 carbon atoms) 8. A 1,4 represented by the following general formula (V):
4-trichloro-6-aryl-4-silaheptane,
The general formulas R ¹ MgX, R ² MgX and XMg (CH ₂ ) _n M
gX (wherein R ¹ and R ² are each a methyl group, an allyl group, a butyl group, a phenyl group, a 4-chlorophenyl group,
Represents a 4-fluorophenyl group, a hydroxyl group or a trimethylsilyloxy group, X represents a halogen atom, and n
Is a compound represented by 4 or 5) and at least one compound selected from chlorotrimethylsilane, and the method for producing a silylpropyl chloride derivative according to claim 7. Embedded image (In the formula, X ¹ and X ² each represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, a phenoxy group, or a halogen atom) 9. A plant fungicide containing the silylpropylamine derivative of claim 1 as an active ingredient.