JPH02270889A - Organic silicon compound and production thereof - Google Patents

Abstract

NEW MATERIAL:The cyclic aminoalkylsilane of formula I [R<1> is 1-6C alkyl, vinyl, cyclopropyl or chloromethyl; R<2> is 1-6C alkyl, vinyl, cyclopropyl, chloromethyl or group of formula II (R<4> and R<5> are H, halogen, -OCH3, -OCHF2, phenyl, etc.); R<3> is group of formula II; Q is pyrrolidinyl, piperidinyl, azepinyl, morpholino or piperazinyl; n is 3-7]. EXAMPLE:5-(1-Piperidinyl)pentyl-4-chlorophenyldimethylsilane. USE:An intermediate for the synthesis of physiologically active substances such as pharmaceuticals and agricultural chemicals. PREPARATION:The objective compound can be produced by reacting a com pound of formula III {X is halogen or -OR<6> [R<6> is (halo)alkyl, alkylsulfonyl or arylsulfonyl]} with pyrrolidine, piperidine, azepine, morpholine or (substituted) piperazine.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a novel organosilicon compound that has not been published in any literature and a method for producing the same, and particularly relates to a cyclic aminoalkylsilane useful as a synthetic intermediate, and a method for producing the same by reacting a silane in which an alkyl group having a terminal reactive group is bonded to a silicon atom with a cyclic amine.

(Prior art) A carbon atom containing 3 carbon atoms with silicon substituents and nitrogen substituents at both ends.
As the above-mentioned chain compounds, some compounds have been reported in the past.

CH3 CH.

[Latv, PSRZinat, Akad,
Vestis, Kim, Sev.

(31343 (1978) reference 1 C) 13 (Refer to Japanese Patent Application Laid-open No. 56-8394) C.I.

(See US Pat. No. 4,416,876) However, a compound in which the nitrogen substituent has a cyclic structure has not been known so far, and a method for its synthesis has not been reported. However, the necessity of such compounds was recognized as synthetic intermediates for producing useful substances.

(Structure of the Invention) As a result of intensive research into the synthesis of the above-mentioned novel compound cyclic aminoalkylsilane, the present inventors discovered that an alkyl group having a halogen, alkoxy group, or a sulfonate group as a substituent at the terminal has a silicon atom. The inventors discovered that the desired silane could be obtained in high yield by the reaction between the silane bonded to the silane and the cyclic amine compound, and after further study, the present invention was completed.

The first invention of this application has the following formula:
Represents a cyclopropyl group or a chloromethyl group, R2
is an alkyl group having 1 to 6 carbon atoms, a vinyl group, a cyclopropyl group, a chloromethyl group, or a formula (wherein R4 and R5 are independently a hydrogen atom, a halogen atom -0 (: R3 group, -OC liver group, -(represents an lcF3 group, a phenyl group, a halogen-substituted phenyl group, a phenoxy group, a halogen-substituted phenoxy group, a -CF3 group, or an alkyl group having 1 to 4 carbon atoms), R3 represents a group represented by the formula (in the formula, R4 and R6 are the same as above), and a represents a pyrrolidinyl group, piperidinyl group, azepinyl group, morpholino group, or piperazinyl group (provided that one or two of these groups (in the case of a piperazinyl group, the nitrogen atom at the 4th position may be substituted with a polmyl group or an ethoxycarbonyl group), and n is 3 to 3.
Represents the integer 7. The gist of this is a cyclic aminoalkylsilane represented by the following.

The second invention is an invention of a method for producing the above-mentioned cyclic aminoalkylsilane, comprising: - formula 2% formula % ([wherein R1 is an alkyl group having 1 to 6 carbon atoms, a vinyl group,
Represents a cyclopropyl group or a chloromethyl group, R2
is an alkyl group having 1 to 6 carbon atoms, a vinyl group, a cyclopropyl group, a chloromethyl group or a formula (wherein R4 and R5 are independently a hydrogen atom, a halogen atom -0C83 group, -0C14
F2 group, -0CF3 group, phenyl group, ]\loglog-substituted phenyl group, phenoxy group, halogen-substituted phenoxy group, -CF3 group, or an alkyl group having 1 to 4 carbon atoms. ), R3 represents a group represented by the formula (in the formula, R' and R' are the same as above), and X represents a halogen atom or a group represented by the formula -0R6 (in the formula, R6
is an alkyl group, a haloalkyl group, or an alkylsulfonyl group. ), and n represents an integer of 3 to 7. ] and pyrrolidine, piperidine, acevin, morpholinulin or piperazine (these compounds C may also be substituted with one or two methyl or carbonyl groups) or formyl or piperazine substituted with an ethoxycarbonyl group, expressed by the formula I■ R2-3i-(CHd-FV-Q [wherein R1, R2, R8, and n are the same as above, Q is a pyrrolidinyl group, a piperidinyl group, an azepinyl group, a morpholino group, or a piperazinyl group (however, these groups may be substituted with one or two methyl or carbonyl groups, and in the case of a piperazinyl group, a quaternary The nitrogen atom at position may be substituted with a formyl group or an ethoxycarbonyl group.

The present invention will be explained in detail below.

The cyclic aminoalkylsilane of the present invention has a general formula of 1% formula%. In the above formula, R1 represents an alkyl group having 1 to 6 carbon atoms, a vinyl group, a cyclopropyl group, or a chloromethyl group,
Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, 1so-propyl group, n-butyl group, 1so-butyl group, n-pentyl group, and n-hexyl group.

R2 is an alkyl group having 1 to 6 carbon atoms, a vinyl group, a cyclopropyl group, a chloromethyl group, or a formula (in the formula, R4, R5
are independently hydrogen atom, halogen atom -0CR, group, -0C
It represents an HF2 group, a -0CF3 group, a phenyl group, a halogen-substituted phenyl group, a phenoxy group, a halogen-substituted phenoxy group, a -CF3 group, or an alkyl group having 1 to 4 carbon atoms. ), which has 1 carbon number
Examples of the alkyl group in ~6 are the same as those for R1, and examples of the group represented by the formula include phenyl group, 4-fluorophenyl group, 3-fluorophenyl group, 4-chlorophenyl group, 3-chlorophenyl group, 4-bromophenyl group, 3,4-difluorophenyl group, 3,5-difluorophenyl group, 3.4-dichlorophenyl group, 3.5
-dichlorophenyl group, 4-methylphenyl group, 3-methylphenyl group, 4-ethylphenyl group, 4-propylphenyl group, 4-iso-propylphenyl group, 4-butylphenyl group, 4-t-butylphenyl group, 3゜4-
Dimethylphenyl group, 3,5-dimethylphenyl group, 4
-chloro-3-methylphenyl group, 3-chloro-4-methylphenyl group, 4-trifluoromethylphenyl group,
3-trifluoromethylphenyl group, 2-trifluoromethylphenyl group, 4-methoxyphenyl group, 3-methoxyphenyl group, 2-methoxyphenyl group, 4-ethoxyphenyl group, 4-n-propoxyphenyl group, 4- n
-butoxyphenyl group, 4-trifluoromethoxyphenyl group, 3-trifluoromethoxyphenyl group, 2-trifluoromethoxyphenyl group, 4-difluoromethoxyphenyl group, 4-(4-chlorophenyl)phenyl group, 4-phenoxy Examples include, but are not limited to, phenyl group, 4-(4-chlorophenoxy)phenyl group, and the like.

R3 represents a group represented by the formula (in the formula, R4 and R5 are the same as above), and examples thereof include the same groups as for R2.

Q is a pyrrolidinyl group, a piperidinyl group, an azepinyl group,
Morpholino group or piperazinyl group (however, these groups may be substituted with one or two methyl or carbonyl groups, and in the case of a piperazinyl group, a quaternary
The nitrogen atom at position may be substituted with a formyl group or an ethoxycarbonyl group. ), which includes 1-
piperidinyl group, 2-methyl-1-piperidinyl group, 3
-Methyl-1-piperidinyl group, 2,6-cymethyl-1
-piperidinyl group, 3,5-dimethyl-1-piperidinyl group, 1-pyrrolidinyl group, 3-methyl-1-pyrrolidinyl group, 1-azepinyl group, 4-morpholino group, 2,6
-dimethylmorpholino group, 1-piperazinyl group, 1-methyl-4-piperazinyl group, 1-formyl-4-piperazinyl group, 1-carboethoxy 4-piperazinyl group,
2-year-old xobi-lysin-1-yl group, 2-oxopiperidin-1-yl group, 2-oxoazepin-1-yl group,
Examples include 2,5-diketopiperazin-1-yl group and 2,3-dioxopiperazin-1-yl group.

n indicates the methylene chain length, which is an integer from 3 to 7.

Next, the method for producing the cyclic aminoalkylsilane of the present invention will be explained.

In the method of the present invention, it is used as a silane raw material represented by the general formula 2% formula %). R', R in the formula
2, R3, n are as explained above,
X represents a halogen atom, an alkoxy group, an alkylsulfonyloxy group, or an arylsulfonyloxy group, examples of which include chlorine, bromine, iodine, methanesulfonyloxy group, p-toluenesulfonyloxy group, trifluoromethanesulfonyloxy group, etc. be done.

As the silane represented by the formula 2, known ones or novel compounds discovered by the present inventors can be used.

In general formula 2, n=3 can be synthesized by reacting a known compound such as chloropropyldimethylchlorosilane, chloropropylmethyldichlorosilane or chloropropyltrichlorosilane with an alkyl or aryl metal compound.

Conventionally, there was no known synthesis method for compounds with n = 4 to 7, and they were new compounds, but the present inventors induced chloromethylsilane into a Grignard reagent, and
It was discovered that this can be synthesized by reacting it with a bromochloro compound in the presence of a coupling catalyst. (Patent pending) Silane, which has a chloromethyl group and a hydroxyalkyl group bonded to a silicon atom, was a new compound with no known synthesis method. As a result of the discovery of a method (patent pending), a raw material silane having a tetramethyl group can now be obtained by halogenating or sulfonating the hydroxyl group of this silane raw material using known methods.

The other raw material, the cyclic amine compound, is pyrrolidine, piperidine, azepine, morpholine, or piperazine (however, these compounds may be substituted with one or two methyl or carbonyl groups), or formyl or ethoxy. Piperazine substituted with a carbonyl group includes pyrrolidine, 2-methylpyrrolidine, 3-methylpyrrolidine, piperidine, 2-methylpiperidine, 3-methylbiperazine, 4-methylpiperidine, 2,6-dimethylpiperidine, 3.5-dimethylpiperidine, azepine, morpholine, 2,6-dimethylmorpholine, piperazine, 2-methylbiperazine, 1
-Methylbiperazine, 1-formylpiperazine, 1-ethoxycarbonylbiverazine, 2-pyrrolidinone, 2-
Examples include piperidinone and 2-azepinone.

In the method of the present invention, the silane compound represented by the above-mentioned general formula 2 is reacted with a cyclic amine compound, and this reaction can be carried out under normal nucleophilic substitution conditions. That is, the following solvents are used alone or in combination, and the reaction is carried out in this solvent at room temperature to 150°C, preferably 50 to 100°C. As a solvent, methanol, ethanol, 1so-propanol, acetone, methyl ethyl ketone, benzene, toluene, xylene, diethyl ether, tetrahydrofuran, ],
]3-dimethoxyethane N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphortriamide ()IMPA), and the like.

The reaction proceeds under these conditions, but a catalyst can be used to accelerate the reaction. Examples of the catalyst include sodium iodide, potassium iodide, tetra-n-butylammonium hydrogen sulfate, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydride, potassium hydride, and the like.

The compound of the present invention synthesized as described above can be easily isolated by methods commonly used in the field of organic synthetic chemistry. That is, after dilution with water or saline, hexane, benzene, toluene, ethyl acetate, ethyl ether,
By extracting with an organic solvent that does not mix with water, such as n-butyl alcohol, and distilling off the solvent under reduced pressure, if necessary, the target compound can be isolated by distillation under reduced pressure or chromatography. Can be isolated.

The cyclic aminoalkylsilane of the present invention is a new compound, and can be used as an intermediate for the production of other useful substances, such as an intermediate for the synthesis of physiologically active substances such as pharmaceuticals and agricultural chemicals, and for the synthesis of building blocks thereof. It is useful as an intermediate for Additionally, these compounds themselves are useful as antioxidants, surface treatment agents, adhesion promoters, and biological control agents.

According to the production method of the present invention, a cyclic aminoalkylsilane, which is a novel compound, can be obtained in high yield.

Next, examples of the present invention will be given. Further, the synthesis of the raw material silane used in this example will be shown in a reference example. In the spectral data in the examples below, S represents a singlet, d represents a doublet, t represents a triplet, m represents a multiplet, and dod represents a doublet.

Reference example 1 25.9 g of 3-bromopropyldimethylchlorosilane (
A 100mf2T liver solution containing 120,1J mol) was cooled to 5°C, and 60mρ of a 20molar TI (F solution of p-chlorophenylmagnesium bromide) was added dropwise thereto over 1 hour. It was kept at ℃.

The reaction became a black solution that produced a single slurry. A dilute hydrochloric acid solution of ammonium chloride was added to this, the organic layer was separated, dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain a slightly viscous colorless liquid. When this is distilled under reduced pressure, 3-bromopropyl-4-chlorophenyldimethylsilane 29. Og (yield 83%) was obtained. The analysis results of this silane were as follows.

Mass spectrum m/e 276 (M”-CHll, 251.255.25
3.189.169 (base) Nuclear magnetic resonance spectrum (δ+ ppm) 0.29 [6H, sl, 0
．． 85 (2H, ml, 1..83 (2H, m)
, 3.37 (2H, t.

J=7.3Hzl, 7.34 (2H,d, J=
8.3Hzl, 7.40 f2H,d, J=8.
3Hz) Reference Example 2 Reference Example 1 except that a Grignard reagent derived from bromobenzene, p-bromofluorobenzene, 0-bromoanisole, m-bromoanisole, or p-bromoanisole was used instead of p-chlorophenylmagnesium bromide. By reacting in the same manner as - formula R''-5i-(CHz)iBr (R3 is the same as above) CHz, R3 is a phenyl group, 4-fluorophenyl group, 2-methoxyphenyl group, 3- A silane having a methoxyphenyl group or a 4-me xyphenyl group was synthesized.

Reference Example 3 3-Chloropropylmethyl dichloride was prepared at 9220° C., and a 2.0 mol T liver solution of p-chlorophenylmagnesium bromide at 53 m° C. was added dropwise thereto over 1 hour. During this time, the temperature of the reaction solution was maintained at 5 to 20°C.

The reaction became a black solution that produced a single slurry. After concentrating the reaction solution under reduced pressure, 300ml of hexane was added to the residue.
2 was added, stirred, and filtered. The solvent was distilled off from this filtrate to obtain 3-chloropropyl-4-chlorophenylmethylchlorosilane.

This was dissolved again in dry THF100+++Q, and while cooling, 20 molar concentration of vinylmagnesium bromide was added to THF.
The reaction was carried out using liver solution 53mj2 under the same conditions as above. A dilute hydrochloric acid solution of ammonium chloride was added to the resulting reaction solution, the organic layer was separated, dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain a slightly viscous colorless liquid.

When this was separated by silica gel column chromatography, 6.8 g of 4-chlorophenyl-3-chloropropylvinylmethylsilane (yield: 62%) was obtained. The analysis results of this silane were as follows.

Mass spectrum m/e 216 fM”-CaH61, 201,189,183
(Basel Reference Example 4 Using a Grignard reagent derived from bromobenzene or p-bromofluorobenzene instead of p-chlorophenylmagnesium bromide, and using ethylmagnesium bromide or cyclopropylmagnesium bromide instead of vinylmagnesium bromide. In the same manner as in Reference Example 3, in the formula R2-3i- (β for CH2h (R2 and R3 are the same as above), R2 is an ethyl group or cyclopropyl group, and R3 is a phenyl group or 4-fluorophenyl group. Silanes having each group were synthesized.

Example 1 4-chlorophenyl-3-bromopropyldimethylsilane obtained in Reference Example 12. Og (6,86 mlJ mol)
was dissolved in a mixed solvent of THFIDm and HMPA, 1.14 g (6.86 mmol) of potassium iodide and 1.17 g (13.7 mmol) of piperidine were added, and the mixture was stirred under a nitrogen atmosphere.

When reacting for 2 hours under reflux, the internal temperature will be 70°C to 80°C.
It rose to After cooling, add 50 nl of ethyl acetate and 50 m of water.
℃, the organic layer was separated, washed three times with 50 mβ water, dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain a pale yellow oil. This was separated by silica gel column chromatography to obtain 1.83 g (yield: 90%) of 3-(1-piperishell)propyl-4-chlorophenyldimethylsilane as a colorless oil. The analysis results of this silane were as follows.

Mass spectrum Kawa/e 295 (M”l, 189.169.155.98
(basel nuclear magnetic resonance spectrum (δ+ ppm
10,238 (6H,S), 0.670 (2H
,ml, 1.419 f2H,m+, 1.54
(6H, ml, 2.252 (2H, t, J: 8.3Hz
l, 2.321 (4H, ml, 7.31 (2H, d,
J=8.3Hz), 7.33 f2H,d, J=
8.3Hz Example 2 Using the silanes synthesized in Reference Examples 1 to 4, the reaction was carried out in the same manner as in Example 1, and R', R2, R3, Q shown in Table 1 was obtained. A compound having the following was synthesized. The mass spectra of these compounds were as shown in Table 1.

Table 1 Reference Example 5 Chloromethyldimethylchlorosilane 50g (350mm!
A solution of 150 mR1i2 (1 molar) in dry THF was cooled to 5°C and added with a 2.0 molar concentration of Grignard reagent derived from 4-fluoro-1-bromobenzene in THF.
175 mJ2 of the solution was added dropwise over 1 hour. During this time, the temperature of the reaction solution was maintained at 5 to 20°C. After maintaining the same temperature for an additional hour, 150 mβ of a diluted hydrochloric acid solution of ammonium chloride was added and stirred to separate the layers. The organic layer was then dried over anhydrous sodium sulfate, and the solvent was distilled off to give a colorless oil. When this was distilled under reduced pressure, 4-fluorophenylchloromethyldimethylsilane was obtained as a fraction with a boiling point of 75°C. The analysis results of this silane were as follows.

Mass spectrum rn/e 202 (M'l, 187.173.159.15
3 (basel nuclear magnetic resonance spectrum (δ+ pp
m) 0,432 f6H,sl, 2.946 f
2H,s), 7.092 (2H,dodl,
7.54 (2H, dad) Reference Example 6 Instead of 4-fluorophenylmagnesium bromide,
Using a phenyl Grignard reagent with different substituents on the phenyl group, in the same manner as in Reference Example 5, - formula (:3 R"-3i-CHaCI2 (R3 is the same as above) H3, R3 is a phenyl group, 3-fluorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group,
2-methoxyphenyl group, 3-methoxyphenyl group, 4
-methoxyphenyl group, 3-tolyl group, 4-tolyl group,
3,5-difluorophenyl group, 3,4-dichlorophenyl group, 3,5-dichlorophenyl group, 3-chloro-4
Compounds having -methylphenyl group, 4-chloro-3-methylphenyl group, 4-tert-butylphenyl group, or 4-trifluoromethylphenyl group were synthesized.

Reference example 7 Magnesium metal 2. 50 mρT liver suspension of Jog (98,'l) and 20 g of 4-fluorophenylchloromethyldimethylsilane obtained in Reference Example 5 (9
(8.7 mmol) was prepared from (4-fluorophenyldimethylsilyl).Separately, 15.5 g (98.7 mmol) of 1-bromo-3-di4ropropane
In 50 mfl HF solution, 100 mg of lithium chloride and 100 mg of cupric chloride were dissolved with thorough stirring.
While heating to 0 to 50°C and stirring, the Grignard reagent solution prepared earlier was added dropwise over 30 minutes. After keeping this at the same temperature for another 2 hours, after cooling, a dilute hydrochloric acid solution of ammonium chloride was added, and ethyl acetate 50n+4
Extracted twice with 2. The extract was dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the resulting residue was distilled under reduced pressure to obtain 4-fluorophenyl-4-chlorobutyldimethylsilane 17 as a fraction at 120°C (4 mmHg).
．． +g (yield 72%) was obtained. The analysis results of this silane were as follows.

Mass spectrum m/e 229 (M”-CTo), 188.173,153 (
base) nuclear magnetic resonance spectrum (δ, ppm 1
0, 269 (6H,s), 0. 737 (2
H, ml, 1.44 (2H, ml, 1.78
(2H.

m), 3. 52 (211, t, J=Fy.
4), 7. [15 (2H, dod), 7.
46 (211.

dodl Reference Example 8 -1i19 Formula R"- Si-(CHz)icβ (
R3 is the same as above. ) H3, R3 is a phenyl group, 3-fluorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group,
2-methoxyphenyl group, 3-methoxyphenyl group, 4
-methoxyphenyl group, 3-tolyl group, 4-tolyl group,
3,5-difluorophenyl group, 3,4-dichlorophenyl group, 3,5-dichlorophenyl group, 3-chloro-4
Compounds having a -methylphenyl group, a 4-ri-4-3-methylphenyl group, a 4-tert-butylphenyl group, or a 4-trifluoromethylphenyl group were synthesized.

Reference example 9 4-chlorophenylchloromethylmethylchlorosilane 2
A solution of 0 g (84,5 i) of 10On+J2T was cooled to 5°C and added with 4 drops of a 2.0M T)IF solution of cyclopropylmagnesium bromide.
was added dropwise over 1 hour. During this time, the temperature of the reaction solution was
It was kept at 0°C. The reaction became a black solution that produced a single slurry. A dilute hydrochloric acid solution of ammonium chloride was added to the resulting reaction solution under cooling, the organic layer was separated, dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain a slightly viscous colorless liquid. This was separated by silica gel column chromatography to obtain 17.9 g (yield: 86%) of 4-chlorophenylchloromethylcycloprobylmedylsilane.

Using this, the same reaction as in Reference Example 7 was carried out to synthesize 4-chlorophenyl-4-chlorobutylcyclopropylmethylsilane. (Yield 68%) The analysis results of this silane were as follows.

Mass spectrum m/e 271 (M”-C:H,), 245.230.2
15.195 (bl Nuclear Magnetic Resonance Spectrum (CDC)
j23. δ, ppm)-0,23flH,m), 0
．． 13 (3H, s), 0.23 (2H, m),
0.66 (2H.

m), 0.77 (2H, ml, 1.50 (2H, ml,
1.80 (2H, m), '3.53 (2H, t; J = 6
．． 3Hz), 7.34 (2H, d; J=8.3)
, 7.48 (2H, d: J=8.31 Reference Example 10 In the same manner as Reference Example 9, =III formula R"5i-qcu2hcI2 (R2, R" are the same as above) ■, R2 is ethyl , a vinyl group or a cyclopropyl group, and a compound having a phenyl group, a 4-fluorophenyl group, or a 4-chlorophenyl group as R3 was synthesized.

Example 3 2.0 g (8, i7 mmol) of 4-fluorophenyl-4-chlorobutyldimedylsilane obtained in Reference Example 7
was dissolved in a mixed solvent of 10 mβ of THF and 5 m of HMPA, and 1.36 g (8.17 mmol) of potassium iodide and 1.39 g (16.34 mmol) of piperidine were added, followed by stirring under a nitrogen atmosphere.

When this is reacted for 2 hours under reflux, the internal temperature rises from 70°C to 80°C. After cooling, ethyl acetate 50mf2,
After adding 50 mf2 of water and separating the organic layer, an additional 50 mf2 of water was added and the organic layer was separated.
After washing with mf2 water three times, drying over anhydrous sodium sulfate, and evaporating the solvent, a pale yellow oil was obtained. This was separated by silica gel column chromatography to give a colorless oily 4-(1-piperidinyl)butyl-4-
2.10 g of fluorophenyldimethylsilane (yield: 88
%) was obtained. The analysis results of this product were as follows.

Mass spectrum m/e 293 fM”), 278.153.1.39.9
8 (basel nuclear magnetic resonance spectrum (δ+ pp
m 10, 222 (6H, sl, 0.72 (2
H, ml, 1.28 (2H, m), 1.41
(2H.

ml, 1.55 (6H, ml, 2.22 f
2H, m), 2.31 (4H, mlExample 4 Using the compounds synthesized in Reference Examples 7 to 10 and changing the type of cyclic amine, synthesis was performed in the same manner as in Example 3, -
Compounds having the groups shown in Table 2 as R', R'', R3, and Q in the formula % were synthesized. The analysis results of these compounds were also listed in Table 2.

Table 2 Example 5 0.802 g (8.09 mmol) of piperidin-2-one was added to T 11 F20m+f2. [HMPA] was dissolved in a mixed solvent at Om°C to form a homogeneous solution. While cooling on ice, 0.324 g of sodium hydride was added and stirred. In addition to this, 2°Og of 4-chlorophenyl-4-chlorobutyldimethylsilane synthesized in Reference Example 8 (8,
06 mmol) was added and the mixture was heated to reflux. After 6 hours of reaction, after cooling, add 50mf2 of water and 50mf2 of ethyl acetate.
J2 was added and distributed. The organic layer was further washed twice with 50 nl of water, dried over anhydrous sodium sulfate, and the solvent was evaporated to give a pale brown oil. This was separated by silica gel column chromatography and chloroform:
When the fraction eluted with ethyl acetate=IO:I is concentrated, 4
-(2-year-old xobiperidin-1-yl)butyl-4-chlorophenyldimethylsilane 2.15g (yield 82%)
was gotten. The analysis results of this silane were as follows.

Mass spectrum m/e 324 (M”), 309.295.281.266
, 252.202.169 (base) 154.11
3 Nuclear magnetic resonance spectrum (δ, ppm) 0.228 [
6H, sl, 0.735 (2H, ml, 1.
27 f2H, ml, 1.52 (21-I.

m), 1.733 (4t(,ml, 2.33
(2H, m), 3.175 (2H, m),
3.289i2H,t, J・7.8Hzl, 7.31(
2H, d, J・7.8), 7.39 (2H, d.

J=7.81 Also, instead of 2-piperidinone, 2-pyrrolidinone,
A reaction was carried out in the same manner as above using 2-azepinone to synthesize a compound in which R1 and R2 are a methyl group, R3 is a 4-chlorophenyl group, and O shown in Table 3. .

Table 3 Reference Example 11 Using 4-chlorophenylchloromethyldimethylsilane obtained in Reference Example 6, 1-bromo-3 in Reference Example 7
- Using 1-bromo-4-chlorobutane in place of chloropropane, the reaction was carried out in the same manner as in Reference Example 7 to synthesize 4-chlorophenyl-5-tritetrapentyldimethylsilane. (Yield 71%) The analysis results of this silane were as follows.

Mass spectrum m/e 274 (M”), 259.204.189.16
9 (basel nuclear magnetic resonance spectrum (δ, ppm
) 0, 257 (6H, sl, 0.74], (
211,m), 1.339 (2t(,ml,
1.440 (2H, ml, 1.753 (2H, m
), 3.501 (2H, t, J=6.9Hz)
, 7.34 (2H, d, J・8.3) , 7.40
(2H, d, J・83) Also, using the various silanes having a chloromethyl group synthesized in Reference Examples 5 and 6, formula R3-5t- (cH2hcρ TR3 is the same as above) is prepared in the same manner as above.

) CH3, R3 is a phenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 3-chlorophenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group,
4-methoxyphenyl group, 3-tolyl group, 4-tolyl group, 3,5-difluorophenyl group, 3,4-dichlorophenyl group, 3,5-dichlorophenyl group, 3-chloro-
4-methylphenyl group, 4-chloro-3-methylphenyl group, 4. - tert-butylphenyl group or 4-
A silane containing a trifluoromethylphenyl group was synthesized.

Reference Example 12 In the same manner as in Reference Example 7, 4-chlorophenyl- 5-Chloropendelcyclopropylmethylsilane was synthesized. (Yield 81%) The analysis results of this silane were as follows.

Mass spectrum m/e 285 (M”-CH,l, 259.230.215
(b) Nuclear magnetic resonance spectrum (CDcf2., +5.
ppm1-0.24 (IH, m), 0.23 (
3H,s), 0.65 f2H,ml, 0.7
6 (2H.

m), 1.42 (4H, m), 1.76 (
2H, q, J=8.3Hz), 3.51 (2H
,t.

J=6.8Hz), 7.34 (2H,d, J=8
．． 3Hzl, 7.47 (2H,d, J=8.3
Hz) In the same manner as above, in the formula R''-3i-(CH□hC flood (R2 and R3 are the same as above), R2 is an ethyl group, vinyl group or cyclopropyl group, R3 is a phenyl group, A silane having a 4-fluorophenyl group or a 4-chlorophenyl group was synthesized.

Example 6 Using 4-chlorophenyl-5-chloropendeldimethylsilane synthesized in Reference Example 11, 5-(1-piperidinyl)pendel-4-chlorophenyldimethylsilane was synthesized in the same manner as in Example 3. (Yield 79%) The analysis results of this silane were as follows.

Mass spectrum m/e 323 (M”l, 308.1.69.1.55.
98 (basel nuclear magnetic resonance spectrum (δ, pp
m) 0.230 (6H, s), 0.717 (2H, ml
, 1.330 (4H, nl, 1.46 (4H, ml,
1.58 (4H, ml, 2.26 (2H, m
l, 2.36 f4H, ml.

7, 32 (2H, d, J=8.3t(z), 7
．． 39 f2H, d, J = 8.3 Hzl In addition, using the various silanes synthesized in the reference examples and changing the type of cyclic amine, in the same manner as above, - formula % formula %) Table 4, R' shown in Table 5 or Table 6
, R2, R3, and Q were synthesized.

Example 7 A Grignard reagent was prepared by slowly dropping 5-trimethylsilyloxy-1-promopencune into a 20 m DEG C. dry THF suspension of 0.5 g (20.6 ml J+L) of metallic magnesium. Separately, 4-chlorophenylchloromethylmethylchlorosilane 4.93g
A solution of +20.6 ml of dry THF dissolved in 20 ml of dry THF was cooled to 5°C, and while stirring, the Grignard reagent solution prepared earlier was added dropwise over 30 minutes. During this time, the temperature of the reaction solution was maintained at 5 to 20°C. 30 more
After keeping the temperature at the same temperature for a minute, add 30m℃ of diluted hydrochloric acid solution of ammonium chloride (stir).
The extract was dried over anhydrous sodium sulfate, and the solvent was distilled off to give a colorless oil. This oil was separated by silica gel column chromatography to obtain 4.4 g of 5-hydroxypentyl-4-chlorophenylchloromethylmethylsilane as a pure product. (Yield 83%) 5-hydroxypendel-4-chlorophenylchloromethylmethylsilane 2 obtained as above
g (7.82 mmol) was dissolved in 10 mC dry THF. This was cooled on ice, and 0.7 l.ethylamine was added.
9 g (7.82 mmol) of methanesulfonyl chloride was added over 10 minutes while stirring. After keeping under the same conditions for a further 15 hours, 5 nl of HMPA, 0.79 g of triethylamine
F7.82 milJ mol), and morpholine 0.70 g
(8,0 milJ mol) was added and heated under reflux for 1 hour. The reaction solution was allowed to cool, and 50ml of ethyl acetate was added. Diluted with 2 and heated to 50m℃
Washed three times with water. The organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off, and the resulting pale yellow oil was separated by silica gel column chromatography.
1.9 g (yield 75%) of (4-morpholino)pentyl-4-chlorophenylchloromethylmethylsilane was obtained. The analysis results of this silane were as follows.

Mass spectrum m/e 359 (M"1,344,310,281..195,
156.155.125.100 (basel nuclear magnetic resonance spectrum (δ+ ppm1 (1,383
(31(,s), 0.916 (21L m),
1.34 (4H, m), 1.46 +21(.

m), 2.28 (2H, t, J□6.8Hz),
2.402 (4N, m), 2.951 (21
Ls) , 3.70 (21L t, ,, h4.41
(z), 7.33 (211, d, J 8.3l-1
z).

7,43 (2N, d, J・8.3Hz) Also, in the same manner as above except that the cyclic amine was changed, a silane having the group shown in Table 7 in Formula 1 above (however, n = 5) was synthesized.

Table 7 Example 8 Using the compound synthesized in Reference Example 12 and in the same manner as in Example 5, a silane (n-5) having the group shown in Table 8 in Formula 1 was synthesized.

Table 8 Example 9 Using a method similar to that shown in Reference Examples 5 to 12 or Examples 3 to 8, silanes having the values and groups of n shown in Tables 9 to 11 in formula 1 are prepared. was synthesized.

Claims (1)

[Claims] 1. General formula 1 ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1 represents an alkyl group having 1 to 6 carbon atoms, a vinyl group, a cyclopropyl group, or a chloromethyl group. ,R
^2 is an alkyl group with 1 to 6 carbon atoms, a vinyl group, a cyclopropyl group, a chloromethyl group, or a formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^4 and R^5 are independently hydrogen atoms , halogen atom -OCH_3 group, -OCHF_2 group, -OCF_3 group, phenyl group, phenyl group substituted with halogen, phenoxy group, phenoxy group substituted with halogen, -CF
Represents _3 group or an alkyl group having 1 to 4 carbon atoms. ), R^3 represents a group represented by the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (in the formula, R^4 and R^5 are the same as above), Q represents a group represented by pyrrolidinyl group, piperidinyl group, azepinyl group, morpholino group or piperazinyl group (however, these groups may be substituted with one or two methyl or carbonyl groups, and in the case of a piperazinyl group, the nitrogen at the 4th position (the atom may be substituted with a formyl group or an ethoxycarbonyl group), and n represents an integer of 3 to 7. ] A cyclic aminoalkylsilane represented by: 2. General formula 2 ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1 represents an alkyl group having 1 to 6 carbon atoms, a vinyl group, a cyclopropyl group, or a chloromethyl group, and R
^2 is an alkyl group with 1 to 6 carbon atoms, a vinyl group, a cyclopropyl group, a chloromethyl group, or a formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^4 and R^5 are independently hydrogen atoms , halogen atom -OCH_3 group, -OCHF_2 group, -OCF_3 group, phenyl group, phenyl group substituted with halogen, phenoxy group, phenoxy group substituted with halogen, -CF
Represents _3 group or an alkyl group having 1 to 4 carbon atoms. ), R^3 represents a group represented by the formula ▲ Numerical formula, chemical formula, table, etc. ▼ (in the formula, R^4 and R^5 are the same as above), and X represents a halogen It represents an atom or a group represented by the formula -OR^6 (wherein R^6 represents an alkyl group, a haloalkyl group, an alkylsulfonyl group or an arylsulfonyl group), and n represents an integer of 3 to 7. ] and pyrrolidine, piperidine, azepine, morpholine or piperazine (however, these compounds may be substituted with one or two methyl groups or carbonyl groups), or formyl group or ethoxycarbonyl group General formula 1 ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R^1, R^2, R^3, n are the same as above, Q
is a pyrrolidinyl group, piperidinyl group, azepinyl group, morpholino group or piperazinyl group (however, these groups may be substituted with one or two methyl groups or carbonyl groups, and in the case of a piperazinyl group, the 4th position may have a nitrogen atom substituted with a formyl group or an ethoxycarbonyl group). ] A method for producing a cyclic aminoalkylsilane. 3. The cyclic aminoalkylsilane according to claim 1, wherein the compound represented by the general formula 1 is 5-(1-piperidinyl)pentyl-4-chlorophenyldimethylsilane. 4. The cyclic aminoalkylsilane according to claim 1, wherein the compound represented by the general formula 1 is 5-(1-piperidinyl)pentyl-4-chlorophenylchloromethylmethylsilane. 5. The cyclic aminoalkylsilane according to claim 1, wherein the compound represented by the general formula 1 is 6-(1-piperidinyl)hexyl-4-chlorophenyldimethylsilane. 6. The cyclic aminoalkylsilane according to claim 1, wherein the compound represented by the general formula 1 is 4-(1-piperidinyl)butyl-4-chlorophenyldimethylsilane. 7. The cyclic aminoalkylsilane according to claim 1, wherein the compound represented by the general formula 1 is 5-(1-pyrrolidinyl)pentyl-4-chlorophenyldimethylsilane. 8. The cyclic aminoalkylsilane according to claim 1, wherein the compound represented by the general formula 1 is 5-(1-morpholino)pentyl-4-chlorophenylchloromethylmethylsilane.