JP3457022B2 - Adduct of silyl ester and epoxide and method for producing the same - Google Patents
Adduct of silyl ester and epoxide and method for producing the sameInfo
- Publication number
- JP3457022B2 JP3457022B2 JP05025293A JP5025293A JP3457022B2 JP 3457022 B2 JP3457022 B2 JP 3457022B2 JP 05025293 A JP05025293 A JP 05025293A JP 5025293 A JP5025293 A JP 5025293A JP 3457022 B2 JP3457022 B2 JP 3457022B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- alkyl
- substituted
- represented
- halogen atom
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- -1 silyl ester Chemical class 0.000 title claims description 27
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 150000002118 epoxides Chemical class 0.000 title description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- 125000003118 aryl group Chemical group 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000004593 Epoxy Substances 0.000 claims description 7
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 7
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 125000004104 aryloxy group Chemical group 0.000 claims description 5
- 150000003983 crown ethers Chemical class 0.000 claims description 5
- 150000004673 fluoride salts Chemical class 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims 6
- 125000005843 halogen group Chemical group 0.000 claims 6
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000011698 potassium fluoride Substances 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- VFFKJOXNCSJSAQ-UHFFFAOYSA-N trimethylsilyl benzoate Chemical compound C[Si](C)(C)OC(=O)C1=CC=CC=C1 VFFKJOXNCSJSAQ-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- WTXAYXHQTCVNGE-UHFFFAOYSA-N 1-phenyl-6-propan-2-ylidenecyclohexa-1,3-diene Chemical group CC(C)=C1CC=CC=C1C1=CC=CC=C1 WTXAYXHQTCVNGE-UHFFFAOYSA-N 0.000 description 1
- XQQZRZQVBFHBHL-UHFFFAOYSA-N 12-crown-4 Chemical compound C1COCCOCCOCCO1 XQQZRZQVBFHBHL-UHFFFAOYSA-N 0.000 description 1
- VFTFKUDGYRBSAL-UHFFFAOYSA-N 15-crown-5 Chemical compound C1COCCOCCOCCOCCO1 VFTFKUDGYRBSAL-UHFFFAOYSA-N 0.000 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- LKMJVFRMDSNFRT-UHFFFAOYSA-N 2-(methoxymethyl)oxirane Chemical compound COCC1CO1 LKMJVFRMDSNFRT-UHFFFAOYSA-N 0.000 description 1
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000005360 alkyl sulfoxide group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000005104 aryl silyl group Chemical group 0.000 description 1
- LNENVNGQOUBOIX-UHFFFAOYSA-N azidosilane Chemical class [SiH3]N=[N+]=[N-] LNENVNGQOUBOIX-UHFFFAOYSA-N 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 1
- YSSSPARMOAYJTE-UHFFFAOYSA-N dibenzo-18-crown-6 Chemical compound O1CCOCCOC2=CC=CC=C2OCCOCCOC2=CC=CC=C21 YSSSPARMOAYJTE-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical group 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- BABPEPRNSRIYFA-UHFFFAOYSA-N silyl trifluoromethanesulfonate Chemical compound FC(F)(F)S(=O)(=O)O[SiH3] BABPEPRNSRIYFA-UHFFFAOYSA-N 0.000 description 1
- XJRDFEPOYGNZTR-UHFFFAOYSA-N silylselanylsilane Chemical class [SiH3][Se][SiH3] XJRDFEPOYGNZTR-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- QHUNJMXHQHHWQP-UHFFFAOYSA-N trimethylsilyl acetate Chemical compound CC(=O)O[Si](C)(C)C QHUNJMXHQHHWQP-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明はシリルエステルとグリシ
ジルエーテル型エポキシドとの反応により得られるシリ
ルオキシ基およびアルキルないしアリールオキシ基を持
つエステル化合物およびその製造方法に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ester compound having a silyloxy group and an alkyl or aryloxy group obtained by reacting a silyl ester with a glycidyl ether type epoxide, and a process for producing the same.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】従来エ
ポキシドと種々のシリル化合物との反応が検討されてき
た。例えば、金属アルコキシドを触媒として、シリルア
ジドとエポキシドから、O−シリルアジドヒドリンが得
られている〔C. Blandy et. al., Tetrahedron Lett.,
24, 4189(1983)〕。また、トリフェニルホスフィンを触
媒として、シリルハライドがエポキシドに付加し、O −
シリルハロヒドリンを与えている〔G. C. Andrews et.
al., Tetrahedron Lett., 22, 3803(1981)〕。塩基存在
下、シリルトリフラートがエポキシドに付加した後、酸
が脱離して、O −シリルアリルアルコールが得られてい
る〔Murata et. al., J. Am. Chem. Soc., 101, 2738
(1979)〕。さらに、ZnI2触媒を用いて、シリルセレニド
とエポキシドより同様の付加物が得られている〔N. Miy
oshi et. al., Chem. Lett., 909(1979)〕。2. Description of the Related Art Reactions between epoxides and various silyl compounds have hitherto been studied. For example, O-silyl azidohydrins have been obtained from silyl azides and epoxides using metal alkoxides as catalysts [C. Blandy et. Al., Tetrahedron Lett.,
24 , 4189 (1983)]. In addition, silyl halide is added to the epoxide by using triphenylphosphine as a catalyst,
Giving silylhalohydrin [GC Andrews et.
al., Tetrahedron Lett., 22 , 3803 (1981)]. After addition of silyl triflate to an epoxide in the presence of a base, the acid is eliminated to obtain O-silylallyl alcohol (Murata et. Al., J. Am. Chem. Soc., 101, 2738).
(1979)]. Furthermore, similar adducts have been obtained from silyl selenides and epoxides using ZnI 2 catalyst [N. Miy
oshi et. al., Chem. Lett., 909 (1979)].
【０００３】一方、本発明者らは、フッ化セシウムを触
媒とするアリールシリルエーテルによるグリシジルエー
テルの選択的な開環反応を見出し〔特開平１−233288号
公報、Y. Nambu, T. Endo, Tetrahedron Lett., 31(1
2), 1723(1990)〕、隣接ジオールの一方がアリール化、
他方がシリル化された付加物を得ている。しかし、本発
明に示すようなシリルエステルによるグリシジルエーテ
ル型エポキシドの開環反応の例はなく、従って、付加物
を得た例もみられない。On the other hand, the present inventors have found a selective ring-opening reaction of glycidyl ether with aryl silyl ether using cesium fluoride as a catalyst [JP-A-1-233288, Y. Nambu, T. Endo, Tetrahedron Lett., 31 (1
2), 1723 (1990)], one of the adjacent diols is arylated,
The other gives the silylated adduct. However, there is no example of a ring-opening reaction of a glycidyl ether type epoxide with a silyl ester as shown in the present invention, and therefore no example of obtaining an adduct is found.
【０００４】[0004]
【課題を解決するための手段】本発明者らは上記課題を
解決すべく鋭意研究の結果、本発明を完成した。The present inventors have completed the present invention as a result of earnest research to solve the above problems.
【０００５】即ち本発明は、一般式（Ｉ）That is, the present invention has the general formula (I)
【０００６】[0006]
【化４】 [Chemical 4]
【０００７】（式中、R1は置換または無置換のアリール
基もしくはアルキル基、R2は同一または異なったアルキ
ル基もしくはアリール基、 Rは置換または無置換のアリ
ール基もしくはアルキル基を示す。）で表されるシリル
オキシ基およびアルキルないしアリールオキシ基を持つ
エステル化合物を提供するものである。(In the formula, R 1 represents a substituted or unsubstituted aryl group or alkyl group, R 2 represents an identical or different alkyl group or aryl group, and R represents a substituted or unsubstituted aryl group or alkyl group.) The present invention provides an ester compound having a silyloxy group and an alkyl or aryloxy group represented by
【０００８】また本発明は、一般式（II）
R1COOSiR2 3 （II）
（式中、R1は置換または無置換のアリール基もしくはア
ルキル基、R2は同一または異なったアルキル基もしくは
アリール基を示す。）で表されるシリルエステルと、一
般式（ＩＩＩ）The present invention also provides a compound of the general formula (II) R 1 COOSiR 2 3 (II) (wherein R 1 is a substituted or unsubstituted aryl group or alkyl group, and R 2 is the same or different alkyl group or aryl group). And a silyl ester represented by the general formula (III)
【０００９】[0009]
【化５】 [Chemical 5]
【００１０】（式中、 Ｒは置換または無置換のアリー
ル基もしくはアルキル基を示す。）で表されるエポキシ
化合物を、フッ化物塩触媒の存在下に反応させることを
特徴とする、前記一般式（Ｉ）で表されるシリルオキシ
基およびアルキルないしアリールオキシ基を持つエステ
ル化合物の製造方法を提供するものである。(Wherein R represents a substituted or unsubstituted aryl group or alkyl group), the epoxy compound is reacted in the presence of a fluoride salt catalyst. The present invention provides a method for producing an ester compound having a silyloxy group and an alkyl or aryloxy group represented by (I).
【００１１】上記一般式（Ｉ）〜(III) において、R1,
R2, R で示されるアルキル基としては、メチル基、エチ
ル基、ｔ−ブチル基等が挙げられる。アリール基として
は、フェニル基、フェニレン基、イソプロピリデンビフ
ェニル基、ナフチル基、ナフチレン基、また置換基とし
ては、メトキシ基、クロル基、ブロム基、ニトロ基など
が挙げられる。In the above general formulas (I) to (III), R 1 ,
Examples of the alkyl group represented by R 2 and R include a methyl group, an ethyl group and a t-butyl group. Examples of the aryl group include a phenyl group, a phenylene group, an isopropylidene biphenyl group, a naphthyl group, and a naphthylene group, and examples of the substituent include a methoxy group, a chloro group, a bromo group, and a nitro group.
【００１２】本発明に用いられる前記一般式（II）で表
されるシリルエステルのうち特にトリメチルシリル基を
持つものは、相当するカルボン酸と小過剰量のヘキサメ
チルジシラザンあるいはピリジン等の塩基存在下、トリ
メチルシリルクロリドとを反応させることにより容易に
得られる。Among the silyl esters represented by the general formula (II) used in the present invention, those having a trimethylsilyl group are particularly useful in the presence of a corresponding carboxylic acid and a small excess of a base such as hexamethyldisilazane or pyridine. , Easily obtained by reacting with trimethylsilyl chloride.
【００１３】本発明の製造方法においては、上記一般式
（II）で表されるシリルエステルと、一般式(III) で表
されるエポキシ化合物とを反応させる際にクラウンエー
テルを共存させると、より高収率で一般式（Ｉ）で表さ
れるエステル化合物が得られる。本反応に用いられるク
ラウンエーテルとしては、12−クラウン−４−エーテ
ル、15−クラウン−５−エーテル、18−クラウン−６−
エーテル、ジベンゾ−18−クラウン−６−エーテル等が
挙げられる。In the production method of the present invention, when a crown ether is allowed to coexist when the silyl ester represented by the general formula (II) is reacted with the epoxy compound represented by the general formula (III), The ester compound represented by the general formula (I) is obtained in high yield. As the crown ether used in this reaction, 12-crown-4-ether, 15-crown-5-ether, 18-crown-6-
Examples thereof include ether and dibenzo-18-crown-6-ether.
【００１４】一般式（II）で表されるシリルエステルと
一般式(III) で表されるエポキシ化合物との付加反応
は、一般式(III) で表されるエポキシ化合物に対して、
１〜５倍モルの一般式（II）で表されるシリルエステル
を反応させ、触媒としてフッ化テトラアルキルアンモニ
ウム、フッ化セシウム、フッ化カリウム等のフッ化物塩
を、一般式(III) で表されるエポキシ化合物に対して
0.1〜10 mol％用いるのが好ましい。反応温度は０℃〜
150℃の範囲が好ましく、無溶媒または芳香族炭化水
素、アルキルエーテル、脂環式エーテル、アルキルアミ
ド、アルキルスルホキシド等の溶媒中あるいはクラウン
エーテルの共存下で反応させる。特に好ましくは、一般
式(III) で表されるエポキシ化合物に対して１〜２倍モ
ルの一般式（II）で表されるシリルエステルを用い、２
〜５ mol％のCsF およびクラウンエーテルを加えて80℃
〜 150℃に加熱すると、無溶媒中、高収率で一般式
（Ｉ）で表されるエステル化合物が得られる。10分〜３
時間で十分反応は進行するが、好ましくは１時間が適当
である。The addition reaction between the silyl ester represented by the general formula (II) and the epoxy compound represented by the general formula (III) is carried out by adding the epoxy compound represented by the general formula (III) to
The silyl ester represented by the general formula (II) is reacted in an amount of 1 to 5 times, and a fluoride salt such as tetraalkylammonium fluoride, cesium fluoride or potassium fluoride is represented by the general formula (III) as a catalyst. For epoxy compounds
It is preferable to use 0.1-10 mol%. Reaction temperature is 0 ℃
The temperature is preferably 150 ° C., and the reaction is carried out without solvent or in a solvent such as an aromatic hydrocarbon, an alkyl ether, an alicyclic ether, an alkylamide and an alkyl sulfoxide, or in the presence of a crown ether. Particularly preferably, 1 to 2 moles of the silyl ester represented by the general formula (II) is used with respect to the epoxy compound represented by the general formula (III).
Add ~ 5 mol% CsF and crown ether to 80 ℃
When heated to ˜150 ° C., the ester compound represented by the general formula (I) can be obtained in high yield in the absence of solvent. 10 minutes to 3
The reaction proceeds sufficiently with time, but preferably 1 hour is appropriate.
【００１５】[0015]
【発明の効果】本発明によれば、グリシジルエーテルを
原料とし、合成中間体として有用な、一般式（Ｉ）で表
されるシリルオキシ基を有する化合物が容易に得られ
る。さらにエステル型エポキシ樹脂製造の基本反応とし
て有用性が期待できる。INDUSTRIAL APPLICABILITY According to the present invention, a compound having a silyloxy group represented by the general formula (I), which is useful as a synthetic intermediate, can be easily obtained from glycidyl ether as a raw material. Further, it can be expected to be useful as a basic reaction for producing an ester type epoxy resin.
【００１６】[0016]
【実施例】以下、実施例により本発明を更に詳細に説明
するが、本発明はこれらの実施例に限定されるものでは
ない。尚、以下の実施例における構造式中、Phはフェニ
ル基、Meはメチル基、n-Buはｎ−ブチル基を示す。EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples. In the following structural formulas, Ph represents a phenyl group, Me represents a methyl group, and n-Bu represents an n-butyl group.
【００１７】実施例１
二方コックを装着した反応容器に CsF 0.30g(2mmol) 、
18−クラウン−６−エーテル0.53ｇ(2mmol) を計り取
り、加熱減圧乾燥した後、窒素気流下、フェニルグリシ
ジルエーテル11.4ｇ(0.1mol)、トリメチルシリルベンゾ
エート23.4ｇ(0.1mol)を加え、軽く脱気後密栓する。さ
らに内容物をよく攪拌しながら 130℃で２時間加熱す
る。反応後、マグネシウムシリケート上で触媒を濾別し
た後、減圧蒸留により、下記式 (IV) で表されるβ付加
体であるトリメチルシリルオキシ基を持つエステル化合
物（α付加体を10％含む）20.9ｇ(60mmol)を得た。Example 1 0.30 g (2 mmol) of CsF was added to a reaction vessel equipped with a two-way cock,
After measuring 0.53 g (2 mmol) of 18-crown-6-ether and heating and drying under reduced pressure, 11.4 g (0.1 mol) of phenyl glycidyl ether and 23.4 g (0.1 mol) of trimethylsilyl benzoate were added under a nitrogen stream and degassed lightly. Then plug tightly. Further, the contents are heated at 130 ° C for 2 hours while stirring well. After the reaction, the catalyst was filtered off on magnesium silicate, and then distilled under reduced pressure to obtain 20.9 g of an ester compound (containing 10% of α-adduct) having a trimethylsilyloxy group, which is a β-adduct represented by the following formula (IV). (60 mmol) was obtained.
【００１８】[0018]
【化６】 [Chemical 6]
【００１９】沸点：210〜220 ℃／0.3mmHg
ＩＲ：1725 cm-1（エステル)1
Ｈ−ＮＭＲ(CDCl3) ：0.18(s,9H,OSiCH3), 3.9〜4.3
(m,5H,CH2-CH(O-)-CH2),6.8〜7.6(m,8H,Ar), 8.0〜8.1
(m,2H,Ar)
実施例２
触媒として KF 0.12g(2mmol)、18−クラウン−６−エー
テル0.53g(2mmol)を用いて 120℃で１時間反応させる以
外は実施例１と同様に反応させた後、減圧蒸留により、
30.6ｇ(88mmol)の上記式 (IV) で表されるトリメチルシ
リルオキシ基を持つエステル化合物（α付加体４％を含
む）を得た。Boiling point: 210 to 220 ° C./0.3 mmHg IR: 1725 cm -1 (ester) 1 H-NMR (CDCl 3 ): 0.18 (s, 9H, OSiCH 3 ), 3.9 to 4.3
(m, 5H, CH 2 -CH (O -) - CH 2), 6.8~7.6 (m, 8H, Ar), 8.0~8.1
(m, 2H, Ar) Example 2 Reaction was performed in the same manner as in Example 1 except that KF 0.12 g (2 mmol) and 18-crown-6-ether 0.53 g (2 mmol) were used as catalysts and reacted at 120 ° C. for 1 hour. Then, by vacuum distillation,
30.6 g (88 mmol) of an ester compound having a trimethylsilyloxy group represented by the above formula (IV) (including 4% of α-adduct) was obtained.
【００２０】実施例３
触媒として Bu4NF（１Ｍテトラヒドロフラン溶液）2.0m
l(2mmol)を用いて 130℃で１時間反応させる以外は実施
例１と同様に反応させた後、減圧蒸留により33.0g(95mm
ol) の上記式 (IV) で表されるトリメチルシリルオキシ
基を持つエステル化合物（α付加体42％を含む）を得
た。Example 3 As catalyst, Bu 4 NF (1M tetrahydrofuran solution) 2.0 m
After reacting in the same manner as in Example 1 except that 1 (2 mmol) was reacted at 130 ° C. for 1 hour, 33.0 g (95 mm
ol) having an ester compound having a trimethylsilyloxy group represented by the above formula (IV) (including 42% of α-adduct).
【００２１】実施例４
触媒としてKF及び18−クラウン−６−エーテルを各２mm
ol用い、実施例２と同様にして、メチルグリシジルエー
テル 8.8ｇ(0.1mol)とトリメチルシリルベンゾエート2
3.4ｇ(0.1mol)を 130℃で１時間反応させ、減圧蒸留に
より、29.8ｇ(92mmol) の下記式（Ｖ）で表されるトリ
メチルシリルオキシ基を持つエステル化合物( α付加体
31％を含む）を得た。Example 4 2 mm each of KF and 18-crown-6-ether as catalysts
was used in the same manner as in Example 2 except that 8.8 g (0.1 mol) of methyl glycidyl ether and trimethylsilyl benzoate 2 were used.
After reacting 3.4 g (0.1 mol) at 130 ° C. for 1 hour, 29.8 g (92 mmol) of an ester compound having a trimethylsilyloxy group represented by the following formula (V) (α-adduct) was obtained by vacuum distillation.
(Including 31%).
【００２２】[0022]
【化７】 [Chemical 7]
【００２３】沸点：135〜140 ℃／0.06mmHg
ＩＲ：1723 cm-1（エステル)1
Ｈ−ＮＭＲ(CDCl3) ：0.18(s,9H,OSiCH3), 3.36(s,3H,
OCH3),3.4〜4.5(m,5H,CH2-CH(O-)-CH2), 7.2〜7.6(m,3
H,Ar),8.0〜8.1(m,2H,Ar)
実施例５
触媒としてKF及び18−クラウン−６−エーテルを各２mm
ol用い、実施例２と同様にして、ｎ−ブチルグリシジル
エーテル13.0ｇ(0.1mol)とトリメチルシリルアセテート
13.2ｇ(0.1mol)を130℃で１時間反応させ、減圧蒸留に
より、21.5ｇ(82mmol) の下記式 (VI) で表されるトリ
メチルシリルオキシ基を持つエステル化合物（α付加体
34％を含む）を得た。Boiling point: 135-140 ° C./0.06 mmHg IR: 1723 cm -1 (ester) 1 H-NMR (CDCl 3 ): 0.18 (s, 9H, OSiCH 3 ), 3.36 (s, 3H,
OCH 3 ), 3.4 to 4.5 (m, 5H, CH 2 -CH (O-)-CH 2 ), 7.2 to 7.6 (m, 3
H, Ar), 8.0 to 8.1 (m, 2H, Ar) Example 5 2 mm each of KF and 18-crown-6-ether as catalysts
was used in the same manner as in Example 2, except that 13.0 g (0.1 mol) of n-butyl glycidyl ether and trimethylsilyl acetate were used.
After reacting 13.2 g (0.1 mol) at 130 ° C. for 1 hour and distilling under reduced pressure, 21.5 g (82 mmol) of an ester compound (α-adduct having a trimethylsilyloxy group represented by the following formula (VI):
(Including 34%).
【００２４】[0024]
【化８】 [Chemical 8]
【００２５】沸点：95〜100 ℃／0.06mmHg
ＩＲ：1745 cm-1（エステル)1
Ｈ−ＮＭＲ(CDCl3) ：0.14(s,9H,OSiCH3), 0.8〜1.0
(m,3H,CH3),1.2〜1.7(m,4H,CH2CH2), 1.93(s,3H,CH3CO
O),3.4〜４．１（ｍ，５Ｈ，ＣＨ２−ＣＨ（Ｏ−）−Ｃ
Ｈ２）Boiling point: 95-100 ° C./0.06 mmHg IR: 1745 cm -1 (ester) 1 H-NMR (CDCl 3 ): 0.14 (s, 9H, OSiCH 3 ), 0.8-1.0
(m, 3H, CH 3 ), 1.2 to 1.7 (m, 4H, CH 2 CH 2 ), 1.93 (s, 3H, CH 3 CO
O), 3.4~4.1 (m, 5H , CH 2 -CH (O -) - C
H 2 )
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 Ｉｎｄｉａｎ Ｊｏｕｒｎａｌ ｏｆ Ｃｈｅｍｉｓｔｒｙ，Ｖｏｌ．10，Ｎ ｏ．１（1972）ｐ．106−ｐ．108 Ｃｈｅｍ．Ｊ．Ｃｈｉｎ．Ｕｎｉ ｖ．，Ｖｏｌ．３，Ｎｏ．４（1982) ｐ．482−ｐ．488 (58)調査した分野(Int.Cl.7，ＤＢ名) C07F 7/18 ─────────────────────────────────────────────────── ─── Continued Front Page (56) References Indian Journal of Chemistry, Vol. 10, No. 1 (1972) p. 106-p. 108 Chem. J. Chin. Uni v. , Vol. 3, No. 4 (1982) p. 482-p. 488 (58) Fields surveyed (Int.Cl. 7 , DB name) C07F 7/18
Claims (3)
基から選ばれる少なくとも１種の置換基で置換されてい
るかまたは無置換のアリール基もしくはアルキル基、R2
は同一または異なったアルキル基もしくはアリール基、
Rは、アルコキシ基、ハロゲン原子及びニトロ基から選
ばれる少なくとも１種の置換基で置換されているかまた
は無置換のアリール基もしくはアルキル基を示す。但
し、R 1 がメチル基である場合を除く。）で表されるシリ
ルオキシ基およびアルキルないしアリールオキシ基を持
つエステル化合物。1. A compound represented by the general formula (I): (In the formula, R 1 represents an alkoxy group, a halogen atom and a nitro group.
Substituted with at least one substituent selected from the group
Luke or unsubstituted aryl group or alkyl group, R 2
Are the same or different alkyl groups or aryl groups,
R is selected from an alkoxy group, a halogen atom and a nitro group.
It represents an aryl or alkyl group which is substituted or unsubstituted with at least one substituent . However
Except when R 1 is a methyl group. And an ester compound having a silyloxy group and an alkyl or aryloxy group.
基から選ばれる少なくとも１種の置換基で置換されてい
るかまたは無置換のアリール基もしくはアルキル基、R2
は同一または異なったアルキル基もしくはアリール基を
示す。）で表されるシリルエステルと、一般式（III) 【化２】 （式中、 Rは、アルコキシ基、ハロゲン原子及びニトロ
基から選ばれる少なくとも１種の置換基で置換されてい
るかまたは無置換のアリール基もしくはアルキル基を示
す。）で表されるエポキシ化合物を、フッ化物塩触媒の
存在下に反応させることを特徴とする、一般式（Ｉ）で
表されるシリルオキシ基およびアルキルないしアリール
オキシ基を持つエステル化合物の製造方法。【化３】 （式中、R 1 は、アルコキシ基、ハロゲン原子及びニトロ
基から選ばれる少なくとも１種の置換基で置換されてい
るかまたは無置換のアリール基もしくはアルキル基、R 2
は同一または異なったアルキル基もしくはアリール基、
Rは、アルコキシ基、ハロゲン原子及びニトロ基から選
ばれる少なくとも１種の置換基で置換されているかまた
は無置換のアリール基もしくはアルキル基を示す。） 2. A compound represented by the general formula (II) R 1 COOSiR 2 3 (II) (wherein R 1 is an alkoxy group, a halogen atom or a nitro group).
Substituted with at least one substituent selected from the group
Luke or unsubstituted aryl group or alkyl group, R 2
Are the same or different alkyl groups or aryl groups. ) And a silyl ester represented by the general formula (III): (In the formula, R represents an alkoxy group, a halogen atom and a nitro group.
Substituted with at least one substituent selected from the group
Shows a Luke or unsubstituted aryl group or an alkyl group. ), An epoxy compound represented by the formula (I) is reacted in the presence of a fluoride salt catalyst.
A method for producing an ester compound having a silyloxy group and an alkyl or aryloxy group represented . [Chemical 3] (In the formula, R 1 represents an alkoxy group, a halogen atom and a nitro group.
Substituted with at least one substituent selected from the group
Or an unsubstituted aryl or alkyl group, R 2
Are the same or different alkyl groups or aryl groups,
R is selected from an alkoxy group, a halogen atom and a nitro group.
Substituted with at least one substituent
Represents an unsubstituted aryl group or alkyl group. )
ることを特徴とする請求項２記載の製造方法。3. The method according to claim 2, wherein the reaction is carried out in the presence of crown ether.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05025293A JP3457022B2 (en) | 1993-03-11 | 1993-03-11 | Adduct of silyl ester and epoxide and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05025293A JP3457022B2 (en) | 1993-03-11 | 1993-03-11 | Adduct of silyl ester and epoxide and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06263774A JPH06263774A (en) | 1994-09-20 |
| JP3457022B2 true JP3457022B2 (en) | 2003-10-14 |
Family
ID=12853795
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP05025293A Expired - Lifetime JP3457022B2 (en) | 1993-03-11 | 1993-03-11 | Adduct of silyl ester and epoxide and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3457022B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5589796B2 (en) * | 2009-11-27 | 2014-09-17 | 宇部興産株式会社 | Non-aqueous electrolyte, electrochemical device using the same, and trialkylsilyloxy group-containing compound used therefor |
-
1993
- 1993-03-11 JP JP05025293A patent/JP3457022B2/en not_active Expired - Lifetime
Non-Patent Citations (2)
| Title |
|---|
| Ｃｈｅｍ．Ｊ．Ｃｈｉｎ．Ｕｎｉｖ．，Ｖｏｌ．３，Ｎｏ．４（１９８２）ｐ．４８２−ｐ．４８８ |
| Ｉｎｄｉａｎ Ｊｏｕｒｎａｌ ｏｆ Ｃｈｅｍｉｓｔｒｙ，Ｖｏｌ．１０，Ｎｏ．１（１９７２）ｐ．１０６−ｐ．１０８ |
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| Publication number | Publication date |
|---|---|
| JPH06263774A (en) | 1994-09-20 |
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