Organoxysilane compounds having silyl-protected carboxyl groups and methods for producing the same

Abstract

To provide an organoxysilane compound having a carboxy group protected with a silyl group that, when used as a silane coupling agent, a surface treatment agent, a resin additive, a coating additive, an adhesive, etc., is inhibited from undergoing a silyl group elimination reaction, can impart rigidity, heat resistance, and high mechanical strength, and exhibits an excellent addition effect.SOLUTION: Provided is an organoxysilane compound having a carboxy group protected with a silyl group, represented by general formula (1) (where, R1 represents a C3-20, unsubstituted, secondary or tertiary hydrocarbon group, R2, R3, R5, and R6 each independently represent a C1-20 (un)substituted monovalent hydrocarbon group, R4 represents a hydrogen atom or a methyl group, and n indicates 0, 1, or 2).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an organoxysilane compound having a carboxy group protected by a silyl group, which is useful as a silane coupling agent, a surface treating agent, a resin additive, a paint additive, an adhesive, etc., and a method for producing the same.

Background Art

[0002] Organoxysilane compounds having a carboxy group are useful as silane coupling agents, surface treating agents, resin additives, paint additives, adhesives, etc. However, since there is a possibility of reaction between the carboxy group and the organoxysilyl group, compounds in which the carboxy group is protected are common.

[0003] Examples of such organoxysilane compounds having a protected carboxy group include an alkoxysilane compound having a carboxy group protected by a trimethylsilyl group described in Patent Document 1 and an organoxysilane compound having a carboxy group protected by a triisopropylsilyl group described in Patent Document 2.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, in the compound described in Patent Document 1, the protecting group of the carboxyl group is a trimethylsilyl group, which allows the trimethylsilyl group to be easily eliminated. As a result, the reaction between the carboxyl group and the organoxysilyl group proceeds, and the compound cannot exert sufficient effect when used as a silane coupling agent, surface treatment agent, resin additive, paint additive, adhesive, etc. Furthermore, although the compound described in Patent Document 2 is less prone to silyl group elimination compared to the compound described in Patent Document 1, its effect in suppressing the elimination reaction is not sufficient. Furthermore, in recent years, there has been a growing demand for rigidity, heat resistance, and high mechanical strength in resins or cured products used in optical and electronic materials. However, known organoxysilane compounds having carboxyl groups protected by silyl groups cannot provide satisfactory rigidity, heat resistance, or high mechanical strength.

[0006] The present invention has been made in view of the above circumstances, and aims to provide an organoxysilane compound having a silyl-protected carboxyl group and a method for producing the same, which, when used as a silane coupling agent, surface treatment agent, resin additive, paint additive, adhesive, etc., suppresses the elimination reaction of the silyl group, and can impart rigidity, heat resistance, and high mechanical strength, thereby exhibiting an excellent additive effect. [Means for solving the problem]

[0007] As a result of diligent research to achieve the above objective, the present inventors have discovered that when an organoxysilane compound having a carboxyl group protected by a specific silyl group is used as a silane coupling agent, surface treatment agent, resin additive, paint additive, adhesive, etc., the elimination reaction of the silyl group is suppressed, and rigidity, heat resistance, and high mechanical strength can be imparted, exhibiting excellent additive effects, and thus the present invention has been completed.

[0008] In other words, the present invention is 1. An organoxysilane compound having a carboxyl group protected by a silyl group represented by the following general formula (1), [ka] (In the formula, R 1 represents an unsubstituted secondary or tertiary hydrocarbon group having 3 to 20 carbon atoms, and R 2 , R 3 , R 5 and R 6 each independently represent a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R 4 represents a hydrogen atom or a methyl group, and n represents 0, 1 or 2.) 2. An organoxysilane compound having a carboxy group protected with a silyl group in which R 1 is an unsubstituted secondary hydrocarbon group having 3 to 20 carbon atoms, and R 2 and R 3 are unsubstituted secondary hydrocarbon groups having 3 to 20 carbon atoms, 3. An organoxysilane compound having a carboxy group protected with a silyl group in which R 1 is an unsubstituted tertiary hydrocarbon group having 4 to 20 carbon atoms, and R 2 and R 3 are unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, 4. An organoxysilane compound having a carboxy group protected with one or two silyl groups in which R 1 to R 3 are all isopropyl groups, 5. An organoxysilane compound having a carboxy group protected with one or three silyl groups in which R 1 is a tert-butyl group, and R 2 and R 3 are methyl groups, 6. A norbornene compound having a carboxy group protected with a silyl group represented by the following general formula (2) [Chemical formula] (In the formula, R 1 , R 2 , R 3 and R 4 represent the same meaning as described above.) and a compound represented by the following general formula (3) HSiR 5 n(OR 6 ) 3-n (3) (In the formula, R 5 , R 6 (And n have the same meaning as above.) A method for producing an organoxysilane compound having a silyl-protected carboxyl group of 1, by reacting a hydrogen silane compound shown in the presence of a platinum compound. To provide. [Effects of the Invention]

[0009] The organoxysilane compounds having silyl-protected carboxyl groups according to the present invention suppress the elimination reaction of silyl groups, and can impart rigidity, heat resistance, and high mechanical strength, exhibiting excellent additive effects during use. Therefore, they are useful as silane coupling agents, surface treatment agents, resin additives, paint additives, adhesives, and the like. [Brief explanation of the drawing]

[0010] [Figure 1] This is the 1H-NMR spectrum of 5-methyl-5-triisopropylsiloxycarbonyl-2-norbornene obtained in Synthesis Example 1. [Figure 2] This is the IR spectrum of 5-methyl-5-triisopropylsiloxycarbonyl-2-norbornene obtained in Synthesis Example 1. [Figure 3] This is the 1H-NMR spectrum of 5-methyl-5-tert-butyldimethylsiloxycarbonyl-2-norbornene obtained in Synthesis Example 2. [Figure 4] This is the IR spectrum of 5-methyl-5-tert-butyldimethylsiloxycarbonyl-2-norbornene obtained in Synthesis Example 2. [Figure 5] This is the 1H-NMR spectrum of 2-methyl-2-triisopropylsiloxycarbonyl-5-trimethoxysilylnorbornane obtained in Example 1. [Figure 6] This is the IR spectrum of 2-methyl-2-triisopropylsiloxycarbonyl-5-trimethoxysilylnorbornane obtained in Example 1. [Figure 7] This is the 1H-NMR spectrum of 2-methyl-2-triisopropylsiloxycarbonyl-5-methyldimethoxysilylnorbornane obtained in Example 2. [Figure 8] This is the IR spectrum of 2-methyl-2-triisopropylsiloxycarbonyl-5-methyldimethoxysilylnorbornane obtained in Example 2. [Figure 9] This is the 1H-NMR spectrum of 2-methyl-2-triisopropylsiloxycarbonyl-5-triethoxysilylnorbornane obtained in Example 3. [Figure 10] This is the IR spectrum of 2-methyl-2-triisopropylsiloxycarbonyl-5-triethoxysilylnorbornane obtained in Example 3. [Figure 11] This is the 1H-NMR spectrum of 2-methyl-2-triisopropylsiloxycarbonyl-5-methyldiethoxysilylnorbornane obtained in Example 4. [Figure 12] This is the IR spectrum of 2-methyl-2-triisopropylsiloxycarbonyl-5-methyldiethoxysilylnorbornane obtained in Example 4. [Figure 13] This is the 1H-NMR spectrum of 2-methyl-2-tert-butyldimethylsiloxycarbonyl-5-methyldiethoxysilylnorbornane obtained in Example 5. [Figure 14] This is the IR spectrum of 2-methyl-2-tert-butyldimethylsiloxycarbonyl-5-methyldiethoxysilylnorbornane obtained in Example 5. [Modes for carrying out the invention]

[0011] The organoxysilane compound having a silyl-protected carboxyl group according to the present invention is a compound represented by the following general formula (1) (hereinafter referred to as "compound (1)").

[0012] [ka]

[0013] In the above general formula (1), R 1 This is an unsubstituted secondary or tertiary hydrocarbon group having 3 to 20 carbon atoms, preferably 3 to 10, more preferably 3 to 5 carbon atoms. R 1 Examples of secondary hydrocarbon groups include isopropyl, isobutyl, and sec-butyl groups, while examples of tertiary hydrocarbon groups include tert-butyl, tert-amyl, texyl, and cumyl groups. Among these, R 1 As a secondary hydrocarbon group, the isopropyl group is R 1 A tert-butyl group is more preferred as the tertiary hydrocarbon group.

[0014] In the above general formula (1), R 2 , R 3 , R 5 and R 6 Each of these is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms. R 2 , R 3 , R 5 and R 6 The monovalent hydrocarbon group may be linear, branched, or cyclic. Specific examples include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, and n-icosyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, texyl, and 2-ethylhexyl; cyclic alkyl groups such as cyclopentyl and cyclohexyl; alkenyl groups such as vinyl, allyl, propenyl, 1-butenyl, and 1-pentenyl; aryl groups such as phenyl, tolyl, and xylyl; and aralkyl groups such as benzyl and phenethyl.

[0015] Among these, R 2 , R 3, R 5 and R 6 Preferred members include substituted or unsubstituted linear, branched, or cyclic alkyl groups, alkenyl groups, aryl groups, and aralkyl groups having 1 to 10 carbon atoms, and more preferably, from the viewpoint of ease of obtaining raw materials, unsubstituted linear or branched alkyl groups having 1 to 3 carbon atoms, with methyl, ethyl, and isopropyl groups being even more preferred. Furthermore, some or all of the hydrogen atoms of these monovalent hydrocarbon groups may be substituted with other substituents. Examples of such substituents include alkoxy groups with 1 to 3 carbon atoms, such as methoxy, ethoxy, and propoxy groups; halogen atoms, such as fluorine, chlorine, and bromine; aryl groups with 6 to 10 carbon atoms, such as phenyl and tolyl groups; aralkyl groups with 7 to 10 carbon atoms, such as benzyl and phenethyl groups; cyano, amino, ester, ether, carbonyl, acyl, and sulfide groups with 2 to 10 carbon atoms. One or more of these substituents may be used in combination. The substitution positions of these substituents are not particularly limited, nor is the number of substituents limited.

[0016] The above R 1 , R 2 and R 3 As for combinations, R 1 If is an unsubstituted secondary hydrocarbon group with 3 to 20 carbon atoms, R 2 and R 3 The preferred component is an unsubstituted secondary hydrocarbon group having 3 to 20 carbon atoms, and R 1 ~R 3 However, combinations of isopropyl groups are more preferable in all cases. On the other hand, R 1 If is an unsubstituted tertiary hydrocarbon group with 4 to 20 carbon atoms, R 2 and R 3 The preferred component is an unsubstituted primary hydrocarbon group having 1 to 20 carbon atoms, and R 1 However, with a tert-butyl group, R 2 and R 3 However, a combination of methyl groups is even more preferable. Such combinations allow for better suppression of the silyl group elimination reaction and control of the elimination reaction after use.

[0017] Specific examples of compound (1) include 2-tert-butyldimethylsiloxycarbonyl-5-trimethoxysilylnorbornane, 2-tert-butyldimethylsiloxycarbonyl-5-methyldimethoxysilylnorbornane, 2-tert-butyldimethylsiloxycarbonyl-5-dimethylmethoxysilylnorbornane, 2-tert-butyldimethylsiloxycarbonyl-5-triethoxysilylnorbornane, 2-tert-butyldimethylsiloxycarbonyl-5-methyldiethoxysilylnorbornane, and 2-tert-butyl Dimethylsiloxycarbonyl-5-dimethylethoxysilylnorbornane, 2-triisopropylsiloxycarbonyl-5-trimethoxysilylnorbornane, 2-triisopropylsiloxycarbonyl-5-methyldimethoxysilylnorbornane, 2-triisopropylsiloxycarbonyl-5-dimethylmethoxysilylnorbornane, 2-triisopropylsiloxycarbonyl-5-triethoxysilylnorbornane, 2-triisopropylsiloxycarbonyl-5-methyldiethoxysilylnorbornane, 2-triisopropylsiloxycarbonyl Xycarbonyl-5-dimethylethoxysilylnorbornane, 2-tert-butyldimethylsiloxycarbonyl-6-trimethoxysilylnorbornane, 2-tert-butyldimethylsiloxycarbonyl-6-methyldimethoxysilylnorbornane, 2-tert-butyldimethylsiloxycarbonyl-6-dimethylmethoxysilylnorbornane, 2-tert-butyldimethylsiloxycarbonyl-6-triethoxysilylnorbornane, 2-tert-butyldimethylsiloxycarbonyl-6-methyldiethoxysilylnorbornane , 2-tert-butyldimethylsiloxycarbonyl-6-dimethylethoxysilylnorbornane, 2-triisopropylsiloxycarbonyl-6-trimethoxysilylnorbornane, 2-triisopropylsiloxycarbonyl-6-methyldimethoxysilylnorbornane, 2-triisopropylsiloxycarbonyl-6-dimethylmethoxysilylnorbornane, 2-triisopropylsiloxycarbonyl-6-triethoxysilylnorbornane, 2-triisopropylsiloxycarbonyl-6-methyldiethoxysilylnorbornane,2-Triisopropylsiloxycarbonyl-6-dimethylethoxysilylnorbornane, 2-Methyl-2-tert-butyldimethylsiloxycarbonyl-5-trimethoxysilylnorbornane, 2-Methyl-2-tert-butyldimethylsiloxycarbonyl-5-methyldimethoxysilylnorbornane, 2-Methyl-2-tert-butyldimethylsiloxycarbonyl-5-dimethylmethoxysilylnorbornane, 2-Methyl-2-tert-butyldimethylsiloxycarbonyl-5-triethoxysilylnorbornane, 2-Methyl-2-te rt-butyldimethylsiloxycarbonyl-5-methyldiethoxysilylnorbornane, 2-methyl-2-tert-butyldimethylsiloxycarbonyl-5-dimethylethoxysilylnorbornane, 2-methyl-2-trisopropylsiloxycarbonyl-5-trimethoxysilylnorbornane, 2-methyl-2-trisopropylsiloxycarbonyl-5-methyldimethoxysilylnorbornane, 2-methyl-2-trisopropylsiloxycarbonyl-5-dimethylmethoxysilylnorbornane, 2-methyl-2-trisopropylsiloxycarbonyl -5-triethoxysilylnorbornane, 2-methyl-2-trisopropylsiloxycarbonyl-5-methyldiethoxysilylnorbornane, 2-methyl-2-trisopropylsiloxycarbonyl-5-dimethylethoxysilylnorbornane, 2-methyl-2-tert-butyldimethylsiloxycarbonyl-6-trimethoxysilylnorbornane, 2-methyl-2-tert-butyldimethylsiloxycarbonyl-6-methyldimethoxysilylnorbornane, 2-methyl-2-tert-butyldimethylsiloxycarbonyl-6-dimethylmethoxy Sisilylnorbornane, 2-methyl-2-tert-butyldimethylsiloxycarbonyl-6-triethoxysilylnorbornane, 2-methyl-2-tert-butyldimethylsiloxycarbonyl-6-methyldiethoxysilylnorbornane, 2-methyl-2-tert-butyldimethylsiloxycarbonyl-6-dimethylethoxysilylnorbornane, 2-methyl-2-trisopropylsiloxycarbonyl-6-trimethoxysilylnorbornane, 2-methyl-2-trisopropylsiloxycarbonyl-6-methyldimethoxysilylnorbornane,Examples include 2-methyl-2-trisopropylsiloxycarbonyl-6-dimethylmethoxysilylnorbornane, 2-methyl-2-trisopropylsiloxycarbonyl-6-triethoxysilylnorbornane, 2-methyl-2-trisopropylsiloxycarbonyl-6-methyldiethoxysilylnorbornane, and 2-methyl-2-trisopropylsiloxycarbonyl-6-dimethylethoxysilylnorbornane.

[0018] Next, a method for producing compound (1) of the present invention will be described. Compound (1) can be produced, for example, by reacting a norbornene compound having a silyl group protected by the following general formula (2) (hereinafter referred to as "compound (2)") with a hydrogensilane compound represented by the following general formula (3) (hereinafter referred to as "compound (3)") under a platinum catalyst.

[0019] [ka] (In the formula, R 1 ~R 4 (This expresses the same meaning as above.)

[0020] HSiR 5 n (OR 6 ) 3-n (3) (In the formula, R 5 , R 6 (And n have the same meaning as above.)

[0021] Specific examples of compound (2) include 5-tert-butyldimethylsiloxycarbonyl-2-norbornene, 5-triisopropylsiloxycarbonyl-2-norbornene, 5-methyl-5-tert-butyldimethylsiloxycarbonyl-2-norbornene, and 5-methyl-5-triisopropylsiloxycarbonyl-2-norbornene.

[0022] Specific examples of compound (3) include trimethoxysilane, methyldimethoxysilane, dimethylmethoxysilane, triethoxysilane, methyldiethoxysilane, and dimethylethoxysilane.

[0023] The mixing ratio of compound (2) and compound (3) is not particularly limited, but from the viewpoint of reactivity and productivity, 0.5 to 2.0 moles of compound (3) per mole of compound (2) is preferred, and 0.8 to 1.5 moles is more preferred.

[0024] Furthermore, a platinum compound is used as a catalyst in the reaction between compound (2) and compound (3). Examples of platinum compounds include chloroplatinic acid, an alcoholic solution of chloroplatinic acid, a toluene or xylene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex, tetrakistriphenylphosphine platinum, dichlorobistriphenylphosphine platinum, dichlorobisacetonitrile platinum, dichlorobisbenzonitrile platinum, dichlorocyclooctadiene platinum, and platinum-activated carbon.

[0025] The amount of platinum compound used is not particularly limited, but from the viewpoint of reactivity and productivity, 0.000001 to 0.2 moles per mole of compound (2) is preferred, and 0.00001 to 0.1 moles is more preferred.

[0026] The reaction temperature for the above reaction is not particularly limited, but is preferably 0 to 200°C, more preferably 20 to 150°C, and the reaction time is also not particularly limited, but is preferably 1 to 40 hours, more preferably 1 to 20 hours. The reaction atmosphere is preferably an inert gas atmosphere such as nitrogen or argon.

[0027] Although the above reaction proceeds without a solvent, a solvent may also be used. Examples of solvents include hydrocarbon solvents such as pentane, hexane, cyclohexane, heptane, isooctane, benzene, toluene, and xylene; ether solvents such as diethyl ether, tetrahydrofuran, and dioxane; ester solvents such as ethyl acetate and butyl acetate; aprotic polar solvents such as acetonitrile, N,N-dimethylformamide, and N-methylpyrrolidone; and chlorinated hydrocarbon solvents such as dichloromethane and chloroform. These solvents may be used individually or in combination of two or more.

[0028] The reaction solution obtained in the manner described above can be recovered by conventional methods such as distillation and removal of low-boiling compounds.

[0029] Compound (2) can be produced by a Diels-Alder reaction of a silyl (meth)acrylate compound represented by the following general formula (4) (hereinafter referred to as "compound (4)") with cyclopentadiene or dicyclopentadiene.

[0030] [ka] (In the formula, R 1 ~R 4 (This expresses the same meaning as above.)

[0031] The mixing ratio of compound (4) to cyclopentadiene or dicyclopentadiene is not particularly limited, but from the viewpoint of reactivity and productivity, it is preferable to use a ratio of 0.5 to 2.0 moles, particularly 0.8 to 1.5 moles, of cyclopentadiene per mole of compound (4).

[0032] The reaction temperature for the above reaction is not particularly limited, but is preferably 0 to 200°C, and more preferably 20 to 180°C. The reaction time is also not particularly limited, but is preferably 1 to 40 hours, and more preferably 1 to 20 hours. The reaction atmosphere is preferably an inert gas atmosphere such as nitrogen or argon.

[0033] Although the above reaction can proceed without a solvent, a solvent may also be used. Examples of solvents that can be used include hydrocarbon solvents such as pentane, hexane, cyclohexane, heptane, isooctane, benzene, toluene, and xylene; ether solvents such as diethyl ether, tetrahydrofuran, and dioxane; ester solvents such as ethyl acetate and butyl acetate; aprotic polar solvents such as acetonitrile, N,N-dimethylformamide, and N-methylpyrrolidone; and chlorinated hydrocarbon solvents such as dichloromethane and chloroform. These solvents may be used individually or in combination of two or more. [Examples]

[0034] The present invention will be specifically described below with reference to synthesis examples and embodiments, but the present invention is not limited to the embodiments described below.

[0035] [Synthesis Example 1] In a flask equipped with a stirrer, reflux apparatus, dropping funnel, and thermometer, 242.4 g (1.0 mol) of triisopropylsilyl methacrylate and 66.2 g (0.5 mol) of dicyclopentadiene were charged and heated to 160°C, where the mixture was stirred for 8 hours. The reaction mixture was distilled to obtain 208.0 g of a fraction with a boiling point of 127°C / 0.3 kPa.

[0036] The mass spectrum of the obtained fraction, 1 1H-NMR and IR spectra were measured. These results confirmed that the obtained compound is 5-methyl-5-triisopropylsiloxycarbonyl-2-norbornene (hereinafter referred to as "norbornene A"). [Mass Spectrum] m / z 308,265,243,199,171,69 [ 1 [H-NMR spectrum (deuterated chloroform solvent)] This is shown in the chart in Figure 1. [IR spectrum] This is shown in the chart in Figure 2.

[0037] [Synthesis Example 2] 200.4 g (1.0 mol) of tert-butyldimethylsilyl methacrylate and 66.2 g (0.5 mol) of dicyclopentadiene were charged into a flask equipped with a stirrer, reflux apparatus, dropping funnel, and thermometer. The mixture was heated to 160°C and stirred at that temperature for 4 hours. The reaction mixture was distilled to obtain 192.1 g of a fraction with a boiling point of 103°C / 0.4 kPa.

[0038] The mass spectrum of the obtained fraction, 1 1H-NMR and IR spectra were measured. These results confirmed that the obtained compound is 5-methyl-5-tert-butyldimethylsiloxycarbonyl-2-norbornene (hereinafter referred to as "norbornene B"). [Mass Spectrum] m / z 266,201,185,143,69,66 [ 1 [H-NMR spectrum (deuterated chloroform solvent)] This is shown in the chart in Figure 3. [IR spectrum] This is shown in the chart in Figure 4.

[0039] [Example 1] In a flask equipped with a stirrer, reflux apparatus, dropping funnel, and thermometer, 30.9 g (0.1 mol) of norbornene A obtained in Synthesis Example 1 and 0.07 g of a 3% by mass toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex were charged and heated to 60°C. After the internal temperature stabilized, 12.2 g (0.1 mol) of trimethoxysilane was added dropwise over 2 hours at 60-70°C, and the mixture was stirred at that temperature for 2 hours. The reaction mixture was distilled to obtain 22.4 g of a fraction with a boiling point of 155-165°C / 0.08 kPa.

[0040] The mass spectrum of the obtained fraction, 1 1H-NMR and IR spectra were measured. These results confirmed that the obtained compound is 2-methyl-2-triisopropylsiloxycarbonyl-5-trimethoxysilylnorbornane. [Mass Spectrum] m / z 415,387,251,199,121,91 [ 1 [H-NMR spectrum (deuterated chloroform solvent)] This is shown in the chart in Figure 5. [IR spectrum] This is shown in the chart in Figure 6.

[0041] [Example 2] In a flask equipped with a stirrer, reflux apparatus, dropping funnel, and thermometer, 30.9 g (0.1 mol) of norbornene A obtained in Synthesis Example 1 and 0.07 g of a 3% by mass toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex were charged and heated to 60°C. After the internal temperature stabilized, 10.6 g (0.1 mol) of methyldimethoxysilane was added dropwise over 2 hours at 60-70°C, and the mixture was stirred at that temperature for 2 hours. The reaction mixture was distilled to obtain 31.5 g of a fraction with a boiling point of 154-160°C / 0.1 kPa.

[0042] The mass spectrum of the obtained fraction, 1 1H-NMR and IR spectra were measured. These results confirmed that the obtained compound is 2-methyl-2-triisopropylsiloxycarbonyl-5-methyldimethoxysilylnorbornane. [Mass Spectrum] m / z 399,371,249,199,105,75 [ 1 [H-NMR spectrum (deuterated chloroform solvent)] This is shown in the chart in Figure 7. [IR spectrum] This is shown in the chart in Figure 8.

[0043] [Example 3] In a flask equipped with a stirrer, reflux apparatus, dropping funnel, and thermometer, 61.7 g (0.2 mol) of norbornene A obtained in Synthesis Example 1 and 0.13 g of a 3% by mass toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex were charged and heated to 60°C. After the internal temperature stabilized, 32.9 g (0.2 mol) of triethoxysilane was added dropwise over 2 hours at 60-70°C, and the mixture was stirred at that temperature for 2 hours. The reaction mixture was distilled to obtain 57.3 g of a fraction with a boiling point of 143-155°C / 0.03 kPa.

[0044] The mass spectrum of the obtained fraction, 1 1H-NMR and IR spectra were measured. These results confirmed that the compound obtained was 2-methyl-2-triisopropylsiloxycarbonyl-5-triethoxysilylnorbornane. [Mass Spectrum] m / z 457,429,225,199,163,119 [ 1 [H-NMR spectrum (deuterated chloroform solvent)] This is shown in the chart in Figure 9. [IR spectrum] This is shown in the chart in Figure 10.

[0045] [Example 4] In a flask equipped with a stirrer, reflux apparatus, dropping funnel, and thermometer, 30.9 g (0.1 mol) of norbornene A obtained in Synthesis Example 1 and 0.07 g of a 3% by mass toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex were charged and heated to 60°C. After the internal temperature stabilized, 13.4 g (0.1 mol) of methyldiethoxysilane was added dropwise over 2 hours at 60-70°C, and the mixture was stirred at that temperature for 2 hours. The reaction mixture was distilled to obtain 36.1 g of a fraction with a boiling point of 164-175°C / 0.1 kPa.

[0046] The mass spectrum of the obtained fraction, 11H-NMR and IR spectra were measured. These results confirmed that the obtained compound is 2-methyl-2-triisopropylsiloxycarbonyl-5-methyldiethoxysilylnorbornane. [Mass Spectrum] m / z 427,399,375,263,199,133 [ 1 [H-NMR spectrum (deuterated chloroform solvent)] This is shown in the chart in Figure 11. [IR spectrum] This is shown in the chart in Figure 12.

[0047] [Example 5] In a flask equipped with a stirrer, reflux apparatus, dropping funnel, and thermometer, 53.3 g (0.2 mol) of norbornene B obtained in Synthesis Example 2 and 0.13 g of a 3% by mass toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex were charged and heated to 60°C. After the internal temperature stabilized, 26.9 g (0.2 mol) of methyldiethoxysilane was added dropwise over 2 hours at 60-70°C, and the mixture was stirred at that temperature for 2 hours. The reaction mixture was distilled to obtain 67.7 g of a fraction with a boiling point of 145-153°C / 0.06 kPa.

[0048] The mass spectrum of the obtained fraction, 1 1H-NMR and IR spectra were measured. These results confirmed that the obtained compound is 2-methyl-2-tert-butyldimethylsiloxycarbonyl-5-methyldiethoxysilylnorbornane. [Mass Spectrum] m / z 385,207,163,143,133,77 [ 1 [H-NMR spectrum (deuterated chloroform solvent)] This is shown in the chart in Figure 13. [IR spectrum] This is shown in the chart in Figure 14.

Claims

1. An organoxysilane compound having a carboxyl group protected by a silyl group, as shown in the following general formula (1). 【Chemistry 1】 (In the formula, R 1 R represents an unsubstituted secondary or tertiary hydrocarbon group having 3 to 20 carbon atoms. 2 , R 3 , R 5 and R 6 Each of these independently represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R 4 (where n represents a hydrogen atom or a methyl group, and n represents 0, 1, or 2.)

2. The above R 1 is a secondary hydrocarbon group having 3 to 20 carbon atoms without substitution, and the above R 2 and R 3 are secondary hydrocarbon groups having 3 to 20 carbon atoms without substitution. The organoxysilane compound having a carboxy group protected with the silyl group according to Claim 1.

3. The aforementioned R 1 However, it is an unsubstituted tertiary hydrocarbon group having 4 to 20 carbon atoms, and the R 2 and R 3 However, the organoxysilane compound having a carboxyl group protected by a silyl group according to claim 1, which is an unsubstituted primary hydrocarbon group having 1 to 20 carbon atoms.

4. The aforementioned R 1 ~R 3 However, the organoxysilane compound having a silyl-protected carboxyl group according to claim 1 or 2, all of which are isopropyl groups.

5. The aforementioned R 1 However, it is a tert-butyl group, and the R 2 and R 3 However, an organoxysilane compound having a carboxyl group protected by a silyl group according to claim 1 or 3, which is a methyl group.

6. The following general formula (2) 【Chemistry 2】 (In the formula, R 1 , R 2 , R 3 and R 4 (This expresses the same meaning as above.) Norbornene compounds having a carboxyl group protected by a silyl group as shown below, and the following general formula (3) HSiR 5 n (OR 6 ) 3-n (3) (In the formula, R 5 , R 6 (And n have the same meaning as above.) A method for producing an organoxysilane compound having a silyl group protected by a carboxyl group, according to claim 1, comprising reacting a hydrogensilane compound represented by in the presence of a platinum compound.

Images