JPS6023675B2 - Method for producing α-siloxy-α-cyanocarboxylic acid ester - Google Patents
Method for producing α-siloxy-α-cyanocarboxylic acid esterInfo
- Publication number
- JPS6023675B2 JPS6023675B2 JP51109447A JP10944776A JPS6023675B2 JP S6023675 B2 JPS6023675 B2 JP S6023675B2 JP 51109447 A JP51109447 A JP 51109447A JP 10944776 A JP10944776 A JP 10944776A JP S6023675 B2 JPS6023675 B2 JP S6023675B2
- Authority
- JP
- Japan
- Prior art keywords
- acid ester
- siloxy
- producing
- reaction
- cyanocarboxylic
- 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
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- LCHWKMAWSZDQRD-UHFFFAOYSA-N silylformonitrile Chemical compound [SiH3]C#N LCHWKMAWSZDQRD-UHFFFAOYSA-N 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 5
- 239000011968 lewis acid catalyst Substances 0.000 claims description 3
- LEIMLDGFXIOXMT-UHFFFAOYSA-N trimethylsilyl cyanide Chemical group C[Si](C)(C)C#N LEIMLDGFXIOXMT-UHFFFAOYSA-N 0.000 claims description 2
- -1 cyanocarboxylic acid ester Chemical class 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 4
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 4
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- ILPVOWZUBFRIAX-UHFFFAOYSA-N propyl 2-oxopropanoate Chemical compound CCCOC(=O)C(C)=O ILPVOWZUBFRIAX-UHFFFAOYSA-N 0.000 description 3
- LNRVTEQEGXVMEF-UHFFFAOYSA-N 2-hydroxy-2-methylpropanedioic acid Chemical compound OC(=O)C(O)(C)C(O)=O LNRVTEQEGXVMEF-UHFFFAOYSA-N 0.000 description 2
- UYWQUFXKFGHYNT-UHFFFAOYSA-N Benzylformate Chemical compound O=COCC1=CC=CC=C1 UYWQUFXKFGHYNT-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 229910052987 metal hydride Inorganic materials 0.000 description 2
- 150000004681 metal hydrides Chemical class 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229940102001 zinc bromide Drugs 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- NLPHDTMWKOYKFS-UHFFFAOYSA-N (5-methyl-2-propan-2-ylcyclohexyl) 2-oxopropanoate Chemical compound CC(C)C1CCC(C)CC1OC(=O)C(C)=O NLPHDTMWKOYKFS-UHFFFAOYSA-N 0.000 description 1
- YIWGJFPJRAEKMK-UHFFFAOYSA-N 1-(2H-benzotriazol-5-yl)-3-methyl-8-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carbonyl]-1,3,8-triazaspiro[4.5]decane-2,4-dione Chemical compound CN1C(=O)N(c2ccc3n[nH]nc3c2)C2(CCN(CC2)C(=O)c2cnc(NCc3cccc(OC(F)(F)F)c3)nc2)C1=O YIWGJFPJRAEKMK-UHFFFAOYSA-N 0.000 description 1
- AFHZHGQGROJXQB-UHFFFAOYSA-N 2-(3-chlorophenyl)-2-oxoacetic acid Chemical compound OC(=O)C(=O)C1=CC=CC(Cl)=C1 AFHZHGQGROJXQB-UHFFFAOYSA-N 0.000 description 1
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 1
- WFERWTFFEKELDJ-UHFFFAOYSA-N 2-methylpropyl 2-oxopropanoate Chemical compound CC(C)COC(=O)C(C)=O WFERWTFFEKELDJ-UHFFFAOYSA-N 0.000 description 1
- TYEYBOSBBBHJIV-UHFFFAOYSA-M 2-oxobutanoate Chemical compound CCC(=O)C([O-])=O TYEYBOSBBBHJIV-UHFFFAOYSA-M 0.000 description 1
- QHKABHOOEWYVLI-UHFFFAOYSA-N 3-methyl-2-oxobutanoic acid Chemical compound CC(C)C(=O)C(O)=O QHKABHOOEWYVLI-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- LCTONWCANYUPML-UHFFFAOYSA-M Pyruvate Chemical compound CC(=O)C([O-])=O LCTONWCANYUPML-UHFFFAOYSA-M 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229930013930 alkaloid Natural products 0.000 description 1
- 229940063656 aluminum chloride Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- ODHZQMBYSQUZCW-UHFFFAOYSA-N butyl 2-oxobutanoate Chemical compound CCCCOC(=O)C(=O)CC ODHZQMBYSQUZCW-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- VZGXHAYBPVPUAO-UHFFFAOYSA-N cyclohexyl 2-oxopentanoate Chemical compound CCCC(=O)C(=O)OC1CCCCC1 VZGXHAYBPVPUAO-UHFFFAOYSA-N 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- LFAGQMCIGQNPJG-UHFFFAOYSA-N silver cyanide Chemical compound [Ag+].N#[C-] LFAGQMCIGQNPJG-UHFFFAOYSA-N 0.000 description 1
- 229940098221 silver cyanide Drugs 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- PUGUQINMNYINPK-UHFFFAOYSA-N tert-butyl 4-(2-chloroacetyl)piperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(C(=O)CCl)CC1 PUGUQINMNYINPK-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 229960001939 zinc chloride Drugs 0.000 description 1
Description
【発明の詳細な説明】
本発明はＱ−シロキシーＱ−シアノカルボン酸ヱステル
を製造する方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing Q-siloxy Q-cyanocarboxylic acid esters.
更に詳しくは、ルイス酸触媒存在下Ｑ−ケトカルボン酸
ェステルとシアノシランとを反応させＱーシロキシ−Ｑ
ーシアノカルボン酸ェステルを製造する方法に関するも
のである。本発明の方法で製造されるＱーシロキシ−Ｑ
−シアノカルボン酸ェステルは一般式（式中、ＲＩは水
素、アルキル基又はアリール基であり、Ｒ２〜Ｒ５はア
ルキル基又はアリール基である。More specifically, Q-ketocarboxylic acid ester and cyanosilane are reacted in the presence of a Lewis acid catalyst to form Q-siloxy-Q.
-This invention relates to a method for producing a cyanocarboxylic acid ester. Q-siloxy-Q produced by the method of the present invention
-Cyanocarboxylic acid ester has the general formula (where RI is hydrogen, an alkyl group, or an aryl group, and R2 to R5 are an alkyl group or an aryl group.
）で表わされる化合物であるがこのものはＱーケト酸ェ
ステルの０−シリルシアンヒドリンである。従って、金
属水素化物で還元することにより対応するアミノグリコ
ールに導くことができる〔関連する参考文献：Ｄ．Ａ．
ＥＶａｍ、Ｇ．Ｌ．Ｃａｍｏｌｌａｎｄ Ｌ．Ｋ．Ｔｍ
ｅｓ船ｌｅ、Ｊ．Ｃせｇ．Ｃｈｅｍ．、３９、９１４（
１９７４）〕他、同じく金属水素化物あるいはグリニャ
ール試薬との反応により対応するＱーオキシケトンに誘
導することもできる。〔関連する参考文献：Ｄ．Ａ．Ｅ
ｖａｎｓ、Ｊ．Ｍ．Ｈｏｆｆｍａｎ、Ｌ．Ｋ．Ｔｒ雌Ｓ
ｄａｌｅ、Ｊ，Ａｍｅｒ，Ｃｈｅｍ，Ｓｏｏ、９５・５
８２２（１９７３）；Ｄ．Ａ．Ｅｖａｎｓ、Ｊ．Ｍ．Ｈ
ｏｆｆｍａｎ、ｉｂｊｄ．、数入１灘３（１９７６）〕
ので、これらの合成中間体として重要な化合物である。
このようにして得られるアミノグリコール、Ｑーオキシ
ケトンはテルベン、アルカロイド又は糠議導体の合成に
重要な役割を果している。更にＱ−シロキシ−Ｑ−シア
ノカルポン酸ェステルは水あるいはメタノールとの反応
により脱シリル化して対応するＱーオキシーＱーシアノ
カルボン酸ェステルを定量的に与えるが、更に加水分解
することによりＱ−オキシジカルボン酸に譲導すること
ができる。実際、メチルタルトロン酸（イソリンゴ酸）
はＱーオキシーＱーシアノプロピオン酸ェステルの加水
分解によって合成されている〔日．Ｐｏｍｍｅｒｅｈｎ
ｅ、Ａｒｃｈ、Ｐｈａｒｍ．、２３７、１６１（１８９
９）；Ａ．Ｊ．ｍｔｅｅ、技ｒ．、３９１８５６（１９
０６）参照〕。従来、Ｑーシロキシーはーシアノカルボ
ン酸ェステルはＱ−ケト酸ェステルに青酸を付加させて
得られるシアンヒドリンとクロロシランとの脱塩化水素
反応による方法〔Ｋ．Ｃ．ＦｒｉｓｃｈａＭＭ．Ｗｏｌ
ｆ、Ｊ．０ｒｇ．Ｃｈｅｍへ１隻 ６５７（１９５３）
〕によつて合成されていた。) is a Q-keto acid ester O-silylcyanhydrin. Therefore, reduction with metal hydrides can lead to the corresponding aminoglycols [Related references: D. A.
EVam, G. L. Camolland L. K. Tm
es ship le, J. C seg. Chem. , 39, 914 (
(1974)] and can also be derived into the corresponding Q-oxyketone by reaction with metal hydrides or Grignard reagents. [Related references: D. A. E
vans, J. M. Hoffman, L. K. Tr female S
dale, J, Amer, Chem, Soo, 95.5
822 (1973);D. A. Evans, J. M. H
offman, ibjd. , Kazuiri 1 Nada 3 (1976)]
Therefore, it is an important compound as a synthetic intermediate.
The aminoglycol and Q-oxyketone thus obtained play an important role in the synthesis of terbenes, alkaloids or rice bran conductors. Furthermore, Q-siloxy-Q-cyanocarboxylic acid ester is desilylated by reaction with water or methanol to give the corresponding Q-oxy-Q-cyanocarboxylic acid ester quantitatively, but it can be further hydrolyzed to yield Q-oxydicarboxylic acid. can be guided. In fact, methyltartronic acid (isomalic acid)
is synthesized by hydrolysis of Q-oxy-Q-cyanopropionic acid ester [J. Pommerehn
e, Arch, Pharm. , 237, 161 (189
9);A. J. mtee, technique r. , 391856 (19
See 06)]. Conventionally, Q-siloxy-cyanocarboxylic acid ester has been produced by a dehydrochlorination reaction between cyanohydrin obtained by adding hydrocyanic acid to Q-keto acid ester and chlorosilane [K. C. FrischaMM. Wol
f, J. 0rg. 1 ship to Chem 657 (1953)
] was synthesized by.
しかるに、この方法は所望化合物の収率が低く、更には
青酸が猛毒であるので取扱いに十分注意を払う必要があ
るなどの欠点を有している。本発明は従来法の斯様な欠
点を改善し安全且つ高収率でＱーシロキシーＱーシアノ
カルボン酸ヱステルを製造する新規な方法である。However, this method has drawbacks such as a low yield of the desired compound and furthermore, the hydrocyanic acid is highly toxic and must be handled with great care. The present invention is a novel method for producing Q-siloxy Q-cyanocarboxylic acid esters safely and in high yields by overcoming these drawbacks of the conventional methods.
本発明によればＱ−ケトカルボン酸ェステルと１〜１．
２当量のシアノシラン並びに触媒量のルイス酸を混合し
無溶媒又は不活性溶媒中で損拝することによりＱーシロ
キシ−Ｑーシアノカルポン酸ェステルを高収率で製造す
ることができる。本発明で用いるシアノシランは例えば
ハロゲン化シランとシアン化銀との反応、ハロゲン化シ
ランとシアン化カリウムの反応により容易に製造するこ
とができる。本発明において使用し得るシアノシランの
ケイ素上の置換基Ｒ３、Ｒ４及びＲ５としてはアルキル
基、アリール基の組合せを広く抱含するが、入手の容易
さの点でシアノトリメチルシランが最も好ましい。又、
本発明のもう一つの原料であるＱ−ケト酸ェステルとし
てはグリオキシル酸メチル、グリオキシル酸エチル、ピ
ルビン酸プロピル、ピルビン酸ィソブチル、ピルピン酸
メンチル、ピルビン酸ボルニル、エチルグリオキシル酸
ブチル、プロピルグリオキシル酸シクロヘキシル、ィソ
プロピルグリオキシル酸ペンジル又はｔープチルグリオ
キシル酸フヱニルの如き脂肪族Ｑーケトカルボン酸ェス
テル又はペンゾィルギ酸エチル、ベンゾィルギ酸メンチ
ル、Ｑ−ナフチルグリオキシル酸プロピル、ｐートリル
グリオキシル酸ィソプロピル「ｍ−クロルフェニルグリ
オキシル酸フェニル、０一アニシルグリオキシル酸ペン
ジル、ｐ−ジメチルァミノフェニルグリオキシル酸シク
ロヘキシルの如き芳香族Ｑ−ケト酸ェステル等を広範に
例示することができる。According to the present invention, Q-ketocarboxylic acid ester and 1 to 1.
Q-siloxy-Q-cyanocarboxylic acid ester can be produced in high yield by mixing 2 equivalents of cyanosilane and a catalytic amount of Lewis acid and stirring the mixture without a solvent or in an inert solvent. The cyanosilane used in the present invention can be easily produced by, for example, a reaction between a halogenated silane and silver cyanide, or a reaction between a halogenated silane and potassium cyanide. Substituents R3, R4 and R5 on the silicon of the cyanosilane that can be used in the present invention include a wide range of combinations of alkyl groups and aryl groups, but cyanotrimethylsilane is most preferred in terms of easy availability. or,
Q-keto acid esters that are another raw material of the present invention include methyl glyoxylate, ethyl glyoxylate, propyl pyruvate, isobutyl pyruvate, menthyl pyruvate, bornyl pyruvate, butyl ethylglyoxylate, cyclohexyl propylglyoxylate, Aliphatic Q-ketocarboxylic acid esters such as pendyl isopropylglyoxylate or phenyl t-butylglyoxylate or ethyl penzoylformate, menthyl benzylformate, propyl Q-naphthylglyoxylate, isopropyl p-tolylglyoxylate, m-chlorophenylglyoxylate A wide range of examples include aromatic Q-keto acid esters such as phenyl, pendyl 1-anisylglyoxylate, and cyclohexyl p-dimethylaminophenylglyoxylate.
本発明の反応は室温で充分進行するが反応時間を短縮す
るために加溢してもさしつかえない。The reaction of the present invention proceeds satisfactorily at room temperature, but may be overflowed to shorten the reaction time.
また本反応は無溶媒で円滑に進行するがｎーヘキサン、
エーテル、塩化メチレン又はテトラヒドロフラン等の不
活性溶媒中で行ってもさしつかえない。本発明を実施す
るにあたり使用し得るルイス酸触媒としてはョウ化亜鉛
、臭化亜鉛、塩化亜鉛、塩化アルミニウム、臭化アルミ
ニウム、アルコキシ塩化アルミニウム、アルコキシアル
ミニム、アルコキシ臭化アルミニウム、三フッ化ホウ素
エーテル鍔体、四塩化スズ、四塩化チタン又はアルコキ
シ塩化チタン等を広範に例示することができる。In addition, this reaction proceeds smoothly without solvent, but n-hexane,
It may also be carried out in an inert solvent such as ether, methylene chloride or tetrahydrofuran. Lewis acid catalysts that can be used in carrying out the present invention include zinc bromide, zinc bromide, zinc chloride, aluminum chloride, aluminum bromide, alkoxyaluminum chloride, alkoxyaluminum, alkoxyaluminum bromide, and boron trifluoride. A wide range of examples include ether flange, tin tetrachloride, titanium tetrachloride, and alkoxy titanium chloride.
本反応は水を嫌うので無水条件下で行うのが望ましい。
本発明の方法では副生物を伴わないので反応混合物に含
まれるルイス酸を櫨過などで除去すれば純度の高い所望
生成物を得ることができそのまま次の反応に用いること
ができるが、更に高純度のＱ−シロキシーＱーシアノカ
ルボン酸ェステルを必要とする際には減圧蒸留を行えば
目的を達することができる。Since this reaction dislikes water, it is preferable to conduct it under anhydrous conditions.
Since the method of the present invention does not produce by-products, the desired product with high purity can be obtained by removing the Lewis acid contained in the reaction mixture by filtration, etc., and can be used as it is in the next reaction. When a pure Q-siloxy Q-cyanocarboxylic acid ester is required, vacuum distillation can be used to achieve the purpose.
以下、実施例により本発明を更に詳細に説明する。Hereinafter, the present invention will be explained in more detail with reference to Examples.
実施例 １
チッ素置換した反応容器に３か９（１モル％）のョウ化
亜鉛と１．３０夕（０．０１モル）のピルビン酸プロピ
ルを入れ更に１．１９夕（０．０１２モル）のシア／ト
リメチルシランを加え室温で１幼時間燈拝した。Example 1 3 or 9 (1 mol %) of zinc iodide and 1.30 mol (0.01 mol) of propyl pyruvate were placed in a nitrogen-substituted reaction vessel, and then 1.19 mol (0.012 mol) of propyl pyruvate was added. ) of Cia/trimethylsilane was added and allowed to stand at room temperature for 1 hour.
反応終了後、反応混合物に２０の‘のペンタンを加えて
析出したョウ化亜鉛を猿過した。櫨液をロータリ−ェバ
ポレーターで濃縮し、更に減圧蒸留したところ沸点１０
９℃／２１脚Ｈｇを有するＱ−トリメチルシロキシ−Ｑ
ーシアノプロピオン酸プロピル２．２０夕（収率９６％
）が得られた。実施例 ２〜８
実施例１と同様にして以下第１表の結果を得た。After the reaction was completed, 20 ml of pentane was added to the reaction mixture to filter out the precipitated zinc iodide. When the oak liquor was concentrated using a rotary evaporator and further distilled under reduced pressure, the boiling point was 10.
Q-trimethylsiloxy-Q with 9°C/21 leg Hg
-Propyl cyanopropionate 2.20 hours (yield 96%)
)was gotten. Examples 2 to 8 The results shown in Table 1 below were obtained in the same manner as in Example 1.
聡 糠Satoshi Bran
Claims (1)
とシアノシランとを反応させることを特徴とするα−シ
ロキシ−α−シアノカルボン酸エステルの製造方法。 ２ 反応を無水の条件下で行うことから成る特許請求の
範囲第１項に記載の方法。 ３ シアノシランがシアノトリメチルシランである特許
請求の範囲第１又は２項に記載の方法。[Scope of Claims] 1. A method for producing an α-siloxy-α-cyanocarboxylic acid ester, which comprises reacting an α-ketocarboxylic acid ester and a cyanosilane in the presence of a Lewis acid catalyst. 2. A process according to claim 1, which comprises carrying out the reaction under anhydrous conditions. 3. The method according to claim 1 or 2, wherein the cyanosilane is cyanotrimethylsilane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP51109447A JPS6023675B2 (en) | 1976-09-14 | 1976-09-14 | Method for producing α-siloxy-α-cyanocarboxylic acid ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP51109447A JPS6023675B2 (en) | 1976-09-14 | 1976-09-14 | Method for producing α-siloxy-α-cyanocarboxylic acid ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5334729A JPS5334729A (en) | 1978-03-31 |
| JPS6023675B2 true JPS6023675B2 (en) | 1985-06-08 |
Family
ID=14510459
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP51109447A Expired JPS6023675B2 (en) | 1976-09-14 | 1976-09-14 | Method for producing α-siloxy-α-cyanocarboxylic acid ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6023675B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5303311B2 (en) * | 2009-02-26 | 2013-10-02 | 国立大学法人東京工業大学 | Process for producing optically active fluorinated alkynylated product |
| JP5585979B2 (en) * | 2009-11-12 | 2014-09-10 | 国立大学法人北海道大学 | Optically active cyanohydrin compounds and method for producing the same |
-
1976
- 1976-09-14 JP JP51109447A patent/JPS6023675B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5334729A (en) | 1978-03-31 |
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