JPH0132228B2 - - Google Patents
Info
- Publication number
- JPH0132228B2 JPH0132228B2 JP6097882A JP6097882A JPH0132228B2 JP H0132228 B2 JPH0132228 B2 JP H0132228B2 JP 6097882 A JP6097882 A JP 6097882A JP 6097882 A JP6097882 A JP 6097882A JP H0132228 B2 JPH0132228 B2 JP H0132228B2
- Authority
- JP
- Japan
- Prior art keywords
- compound
- general formula
- manufacturing
- formula
- zinc
- 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
- 150000001875 compounds Chemical class 0.000 claims description 29
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- 238000004519 manufacturing process Methods 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 15
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000002841 Lewis acid Substances 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims description 6
- 150000007517 lewis acids Chemical class 0.000 claims description 6
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 150000002825 nitriles Chemical class 0.000 claims description 5
- 235000005074 zinc chloride Nutrition 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 5
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 150000004756 silanes Chemical class 0.000 claims description 3
- 229940102001 zinc bromide Drugs 0.000 claims description 3
- NFDXQGNDWIPXQL-UHFFFAOYSA-N 1-cyclooctyldiazocane Chemical compound C1CCCCCCC1N1NCCCCCC1 NFDXQGNDWIPXQL-UHFFFAOYSA-N 0.000 claims description 2
- WADSJYLPJPTMLN-UHFFFAOYSA-N 3-(cycloundecen-1-yl)-1,2-diazacycloundec-2-ene Chemical compound C1CCCCCCCCC=C1C1=NNCCCCCCCC1 WADSJYLPJPTMLN-UHFFFAOYSA-N 0.000 claims description 2
- 229910015900 BF3 Inorganic materials 0.000 claims description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 2
- 239000012973 diazabicyclooctane Substances 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- BQZGVMWPHXIKEQ-UHFFFAOYSA-L iron(ii) iodide Chemical compound [Fe+2].[I-].[I-] BQZGVMWPHXIKEQ-UHFFFAOYSA-L 0.000 claims description 2
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 claims description 2
- 229910001623 magnesium bromide Inorganic materials 0.000 claims description 2
- 229910001509 metal bromide Inorganic materials 0.000 claims description 2
- 229910001510 metal chloride Inorganic materials 0.000 claims description 2
- 229910001512 metal fluoride Inorganic materials 0.000 claims description 2
- 229910001511 metal iodide Inorganic materials 0.000 claims description 2
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- YUOWTJMRMWQJDA-UHFFFAOYSA-J tin(iv) fluoride Chemical compound [F-].[F-].[F-].[F-].[Sn+4] YUOWTJMRMWQJDA-UHFFFAOYSA-J 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 2
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 claims 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 125000005119 alkyl cycloalkyl group Chemical group 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims 1
- 150000002085 enols Chemical class 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- -1 enol silyl ethers Chemical class 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- YAPQBXQYLJRXSA-UHFFFAOYSA-N theobromine Chemical compound CN1C(=O)NC(=O)C2=C1N=CN2C YAPQBXQYLJRXSA-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- DRBJCTHMAXSQQA-UHFFFAOYSA-N 3-acetyloxan-2-one Chemical compound CC(=O)C1CCCOC1=O DRBJCTHMAXSQQA-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- BYPFEZZEUUWMEJ-UHFFFAOYSA-N Pentoxifylline Chemical compound O=C1N(CCCCC(=O)C)C(=O)N(C)C2=C1N(C)C=N2 BYPFEZZEUUWMEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 229960004559 theobromine Drugs 0.000 description 3
- ROCZJWMPGISRQB-UHFFFAOYSA-N 2,3-dihydrofuran-5-yloxy(trimethyl)silane Chemical compound C[Si](C)(C)OC1=CCCO1 ROCZJWMPGISRQB-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- JKTCBAGSMQIFNL-UHFFFAOYSA-N 2,3-dihydrofuran Chemical compound C1CC=CO1 JKTCBAGSMQIFNL-UHFFFAOYSA-N 0.000 description 1
- QGHNDAKWOGAJHS-UHFFFAOYSA-N 2-Phenylbutyrolactone Chemical compound O=C1OCCC1C1=CC=CC=C1 QGHNDAKWOGAJHS-UHFFFAOYSA-N 0.000 description 1
- FTXCTXYJXIABGR-UHFFFAOYSA-N 3,4-dihydro-2h-pyran-6-yloxy(trimethyl)silane Chemical compound C[Si](C)(C)OC1=CCCCO1 FTXCTXYJXIABGR-UHFFFAOYSA-N 0.000 description 1
- YWFCZBVEJWJGAQ-UHFFFAOYSA-N 3-(1-trimethylsilyloxyethyl)oxolan-2-one Chemical compound C[Si](C)(C)OC(C)C1CCOC1=O YWFCZBVEJWJGAQ-UHFFFAOYSA-N 0.000 description 1
- SPEHEHYVDRYEDX-UHFFFAOYSA-N 3-methyloxan-2-one Chemical compound CC1CCCOC1=O SPEHEHYVDRYEDX-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- JARXNQUBGBXALE-UHFFFAOYSA-N C(C)[SiH](CC)CC.Cl Chemical compound C(C)[SiH](CC)CC.Cl JARXNQUBGBXALE-UHFFFAOYSA-N 0.000 description 1
- NTIUZMQTVYPKIB-UHFFFAOYSA-N C[SiH](C)C1=CC=CC=C1.Cl Chemical compound C[SiH](C)C1=CC=CC=C1.Cl NTIUZMQTVYPKIB-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 238000005575 aldol reaction Methods 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000017531 blood circulation Effects 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 210000005259 peripheral blood Anatomy 0.000 description 1
- 239000011886 peripheral blood Substances 0.000 description 1
- SUSQOBVLVYHIEX-UHFFFAOYSA-N phenylacetonitrile Chemical compound N#CCC1=CC=CC=C1 SUSQOBVLVYHIEX-UHFFFAOYSA-N 0.000 description 1
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 description 1
- 229920006391 phthalonitrile polymer Polymers 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- WTMBDLOLJLGCEH-UHFFFAOYSA-N triethyl-[(5-methyl-3,4-dihydro-2h-pyran-6-yl)oxy]silane Chemical compound CC[Si](CC)(CC)OC1=C(C)CCCO1 WTMBDLOLJLGCEH-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Description
本発明は、エノールシリルエーテル類の製造方
法に関するものである。
本発明におけるエノールシリルエール類は、
一般式 ：
（式中、R1は水素、アルキル、シクロアルキ
ル、アルケニル、アラルキルまたはアリール基を
意味し、R2，R3，R4はそれぞれアルキル、シク
ロアルキルまたはアリール基を意味し、ｎは１〜
４の整数を意味する。）
で表わされる化合物（以下化合物と言う）であ
る。
エノールシリルエーテル類は、エノレートアニ
オンの前駆体あるいは等価体さらには炭素―炭素
二重結合とも見なすことが出来、例えば、塩基性
または酸性条件下でのハロゲン化アルキルによる
アルキル化反応、あるいは酸性条件下、ケトン、
アルデヒド、アセタール等とのアルドール反応、
さらには、カルベンとの反応による三員環形成反
応、酸塩化物によるアシル化反応等、広範な反応
に用いられ、有機合成化学上最も重要な合成中間
体の一つであり、医薬、農薬、香料、工業薬品そ
の他の有用物質の原料として価値が高い。
従来、これらエノールシリルエーテル類の製造
法としては、一般的にはケトン、アルデヒド、エ
ステル等に対し、リチウムジイソプロピルアミド
の様な強塩基を作用させた後、塩化シラン類を反
応させて得る方法（G.Stork，P.F.Hudrlik，J.
Am.Chem.Soc.，90，4462，4464（1968）．）と、
トリエチルアミンの様な弱塩基を用い、Ｎ，Ｎ―
ジメチルホルムアミドの様な極性溶媒中塩化シラ
ン類を反応させて得る方法（H.O.House他、J.
Org.Chem.，36，2361（1971）．）がある。しかし
ながら前者の場合には、リチウムジイソプロピル
アミドの様な高価な試薬を用いねばならず、工業
的には好ましいものではない。一方、後者の方法
では、ケトンあるいはアルデヒドのエノールシリ
ルエーテル類は合成出来るが、エステル類の場合
にはエノールシリルエーテル類は合成出来ない。
それ故、エステル類のエノールシリルエーテル化
を安価でかつ工業的に実施出来ることが望まれ
る。
従つて、本発明の目的はエステル類のうちラク
トン類につき、安価で工業的に容易なエノールシ
リルエーテル類の製造法を提供することにある。
本発明によるエノールシリルエーテル類を製造
するための方法は、
一般式：
（式中、R1は水素、アルキル、シクロアルキ
ル、アルケニル、アラルキルまたはアリール基を
意味し、ｎは１〜４の整数を意味する。）（以下化
合物という）
で表わされるラクトン類と、
一般式：R2R3R4Six
（式中、R2，R3，R4はそれぞれアルキル、シ
クロアルキルまたはアリール基を意味し、ｘはハ
ロゲン原子を意味する。）（以下化合物という）
で表わされるハロゲン化シラン類とを反応させる
ことからなる前記一般式で表わされるエノール
シリルエーテル類を得ることを特徴とするもので
ある。
そして本発明方法は、この化合物ととの反
応に際して、塩基性物質、ルイス酸およびニトリ
ル系溶媒を共存させることを特徴としている。
化合物および化合物はともに工業的に容易
に入手可能であり、この様な方法により化合物
を安価で収率よく製造することができる。
反応に際して共存される塩基性物質は、水素引
き抜き剤として、また副生する塩化水素の捕足剤
として働くが、リチウムジイソプロアミド等と比
較し、安価で操作性の良いものが好ましく、トリ
エチルアミン、トリブチルアミン、Ｎ，Ｎ―ジメ
チルアニリン、ピリジン、ジアザビシクロウンデ
セン、ジアザビシクロオクタン等の第三級アミン
類を好適なものとしてあげることが出来る。
ルイス酸としては、三弗化硼素、四弗化スズ等
の金属弗化物；三塩化アルミ、四塩化チタン、塩
化亜鉛等の金属塩化物；臭化亜鉛、臭化マグネシ
ウム等の金属臭化物；ヨウ化亜鉛、ヨウ化鉄等の
金属ヨウ化物を好適例として挙げることが出来
る。
ニトリル系溶媒としてはアセトニトリル、プロ
ピオニトリル、ブチロニトリル、イソブチロニト
リル、マロンジニトリル、アクリロニトリル、ベ
ンジルシアニド、ベンゾニトリル、フタロニトリ
ル等を好適例として挙げることが出来るが、価
格、取り扱い上等の点でアセトニトリルがとりわ
け好ましい。また、ニトリル系溶媒以外の溶媒を
併せて共存させることも可能であり、この際の溶
媒としては、ヘキサン、シクロヘキサン、ベンゼ
ン、トルエン等の炭化水素系溶媒；ジメチルエー
テル、ジエチルエーテル、テトラヒドロフラン、
ジオキサン等のエーテル系溶媒；クロロホルム、
塩化メチレン等のハロゲン系溶媒；Ｎ，Ｎ―ジメ
チルホルムアミド、Ｎ―メチルピロリドン等のア
ミド系溶媒を挙げることが出来る。また、化合物
および塩基性物質の使用量は化合物に対して
当量以上必要であり、過剰に用いても問題はない
が、通常1.0〜2.0当量用いれば十分である。更に
反応に使用するルイス酸の量は化合物に対して
過剰に用いてもよいが、当量以下で十分であり、
通常0.01〜1.0当量の間で使用するのが好ましい。
反応は、−70℃付近から100℃付近まで、いずれの
温度でも進行するが、最適温度は、用いる塩基性
物質、化合物、ルイス酸あるいは溶媒の種類に
より異なる。しかし、通常−50℃付近から50℃付
近の間で行うことが好ましい。
本発明方法によれば、この様にして目的化合物
、即ちエノールシリルエーテル類を収率良く得
ることができ、常法に従つて単離精製し得る。
この目的化合物は、既述の如く、医薬その他
の各種の化学品の合成中間体として有用であるか
ら、このものが直ちに次の反応に利用される場合
には、必ずしも単離することを要さない。例え
ば、この化合物は単離せずに、そのまま種々の
ケトン、アルデヒドまたは酸ハライド等との反応
に利用可能である。
尚、この化合物は、一般式においてR1が
水素である場合に、例えば酸ハライドで代表され
る。
一般式： R5COY
（式中、R5はR1と同様の基を意味し、Ｙはハ
ロゲンまたは水酸基の反応性誘導体を意味する。）
で表わされるカルボン酸誘導体と反応させること
により、各種のα―アシルラクトン類を製造する
ことができる。
更に、この様にして得られたα―アシルラクト
ン類は、テオブロミンまたはその塩と反応させる
ことにより、種々のオキソアルアルキルテオブロ
ミンまたはその誘導体を製造することができる。
オキソアルキルテオブロミンは、例えば１―（５
―オキソヘキシル）テオブロミンが、末梢血管中
の血行改善剤として、特に有効であるから、本発
明方法によつて得られるエノールシリルエーテル
の重要な応用品の１つであるが、この点について
の詳細は、別途特許出願されれた特開昭58―
162585号公報の明細書に記載されていることを付
記する。
以下、実施例と参考例により本発明を更に詳細
に説明するが、本発明はこれらによつて限定され
るものではない。
実施例 １
〔５―トリメチルシロキシ―２，３―ジヒドロ
フランの製造〕
窒素雰囲気下、トリエチルアミン30ｇの塩化亜
鉛1.0ｇを加えて室温で撹拌し、細かい懸濁液と
する。γ―ブチロラクトン17.2ｇ（化合物；R1
＝Ｈ，ｎ＝２）と塩化トリメチルシラン26.0ｇ
（化合物；R2＝R3＝R4＝CH3，ｘ＝Cl）のアセ
トニトリル（100ml）溶液を加え、室温で10時間
反応させる。反応液にベンゼン100mlを加えて沈
殿をロ別し、減圧下で溶媒を留去する。残渣を窒
素気流中減圧下で蒸留すると５―トリメチルシロ
キシ―２，３―ジヒドロフラン（化合物）が
28.4ｇ（bp.78〜80℃／50Torr）得られる。
実施例 ２
〔６―トリメチルシロキシ―２，３―ジヒドロ
―4H―ピランの製造〕
実施例１と同様にして、δ―バレロラクトン
20.0ｇ（化合物；R1＝Ｈ，ｎ＝３）を反応さ
せ、６―トリメチルシロキシ―２，３―ジヒドロ
―4H―ピラン（化合物）が30.5ｇ（bp.44〜45
℃／5Torr）得られる。
実施例 ３
〔５―ジメチル―ｔ―ブチルシロキシ―２，３
―ジヒドロフランの製造〕
実施例１と同様にして、塩化トリメチルシラン
のかわりに塩化ジメチル―ｔ―ブチルシラン（化
合物；R2＝R3＝CH3、R4＝ｔ―C4H5，Ｘ＝
Cl）を用いてγ―ブチロラクトン17.2ｇより５―
ジメチル―ｔ―ブチルシロキシ―２，３―ジヒド
ロフラン（化合物）が35.5ｇ（bp76〜78℃／
10Torr）得られる。
実施例 ４
〔５―メチル―６―トリエチルシロキシ―２，
３―ジヒドロ―4H―ピラン製造〕
窒素雰囲気下、トリエチルアミン30ｇに臭化亜
鉛1.5ｇを加えて室温で撹拌し、細かい懸濁液と
する。２―メチル―δ―バレロラクトン22.8ｇ
（化合物；R1＝CH3，ｎ＝３）と塩化トリエチ
ルシラン36.1ｇ（化合物；R2＝R3＝R4＝C2H5，
Ｘ＝Cl）のアセトニトリル（100ml）溶液を加え
室温で10時間反応させる。反応液にベンゼン100
mlを加えて沈殿をロ別し、減圧下で溶媒を留去す
る。残渣を窒素気流中減圧下で蒸留すると、５―
メチル―６―トリエチルシロキシ―２，３―ジヒ
ドロ―4H―ピラン（化合物）が38.8ｇ（bp.85
〜88℃／5Torr）得られる。
実施例 ５
〔４―ブチル―５―ジブチルフエニルシロキシ
―２，３―ジヒドロフランの製造〕
実施例４と同様にして、塩化トリエチルシラン
のかわりに塩化ジメチルフエニルシラン（化合物
；R2＝R3＝CH3，
The present invention relates to a method for producing enol silyl ethers. The enolsilyl ale in the present invention has the general formula: (In the formula, R 1 means hydrogen, alkyl, cycloalkyl, alkenyl, aralkyl or aryl group, R 2 , R 3 , R 4 each means alkyl, cycloalkyl or aryl group, n is 1-
means an integer of 4. ) (hereinafter referred to as a compound). Enol silyl ethers can be considered precursors or equivalents of enolate anions and even carbon-carbon double bonds, and can be used, for example, in alkylation reactions with alkyl halides under basic or acidic conditions, or under acidic conditions. lower, ketones;
Aldol reactions with aldehydes, acetals, etc.
Furthermore, it is used in a wide range of reactions such as three-membered ring formation reactions with carbenes and acylation reactions with acid chlorides, and is one of the most important synthetic intermediates in organic synthetic chemistry. Highly valuable as a raw material for fragrances, industrial chemicals, and other useful substances. Conventionally, the method for producing these enol silyl ethers is generally to react a strong base such as lithium diisopropylamide with a ketone, aldehyde, ester, etc., and then react with a chlorinated silane ( G. Stork, PFHudrlik, J.
Am.Chem.Soc., 90 , 4462, 4464 (1968). )and,
Using a weak base such as triethylamine, N,N-
A method in which chlorosilanes are reacted in a polar solvent such as dimethylformamide (HOHouse et al., J.
Org.Chem., 36 , 2361 (1971). ). However, in the former case, an expensive reagent such as lithium diisopropylamide must be used, which is not industrially preferable. On the other hand, in the latter method, enol silyl ethers of ketones or aldehydes can be synthesized, but enol silyl ethers cannot be synthesized in the case of esters.
Therefore, it is desired that enol silyl etherification of esters can be carried out at low cost and industrially. Therefore, an object of the present invention is to provide an inexpensive and industrially easy method for producing enol silyl ethers for lactones among esters. The method for producing enol silyl ethers according to the present invention has the general formula: (In the formula, R 1 means hydrogen, alkyl, cycloalkyl, alkenyl, aralkyl, or aryl group, and n means an integer of 1 to 4.) (hereinafter referred to as a compound) Lactones represented by the general formula : R 2 R 3 R 4 Six (wherein R 2 , R 3 , R 4 each means an alkyl, cycloalkyl or aryl group, and x means a halogen atom) (hereinafter referred to as a compound) The method is characterized in that enol silyl ethers represented by the above general formula are obtained by reacting with halogenated silanes. The method of the present invention is characterized in that a basic substance, a Lewis acid, and a nitrile solvent are allowed to coexist during the reaction with this compound. Both the compound and the compound are easily available industrially, and the compound can be produced at low cost and with good yield by such a method. The basic substance coexisting during the reaction acts as a hydrogen abstracting agent and as a trapping agent for by-produced hydrogen chloride, but it is preferable to use one that is cheaper and easier to handle than lithium diisoproamide, etc., and triethylamine, triethylamine, Suitable examples include tertiary amines such as tributylamine, N,N-dimethylaniline, pyridine, diazabicycloundecene, and diazabicyclooctane. Lewis acids include metal fluorides such as boron trifluoride and tin tetrafluoride; metal chlorides such as aluminum trichloride, titanium tetrachloride, and zinc chloride; metal bromides such as zinc bromide and magnesium bromide; iodide. Preferred examples include metal iodides such as zinc and iron iodide. Preferred examples of nitrile solvents include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, malondinitrile, acrylonitrile, benzyl cyanide, benzonitrile, phthalonitrile, etc. However, due to price, handling, etc. In this respect, acetonitrile is particularly preferred. In addition, it is also possible to coexist solvents other than nitrile solvents, and examples of solvents in this case include hydrocarbon solvents such as hexane, cyclohexane, benzene, and toluene; dimethyl ether, diethyl ether, tetrahydrofuran,
Ether solvents such as dioxane; chloroform,
Examples include halogen solvents such as methylene chloride; amide solvents such as N,N-dimethylformamide and N-methylpyrrolidone. Further, the amount of the compound and the basic substance to be used is required to be equivalent to or more than the amount of the compound, and although there is no problem even if it is used in excess, it is usually sufficient to use 1.0 to 2.0 equivalents. Furthermore, the amount of Lewis acid used in the reaction may be in excess of the compound, but an equivalent amount or less is sufficient,
It is usually preferable to use between 0.01 and 1.0 equivalents.
The reaction proceeds at any temperature from around -70°C to around 100°C, but the optimum temperature varies depending on the type of basic substance, compound, Lewis acid, or solvent used. However, it is usually preferable to carry out the heating between around -50°C and around 50°C. According to the method of the present invention, the target compound, ie, enol silyl ethers, can be obtained in good yield in this manner, and can be isolated and purified according to conventional methods. As mentioned above, this target compound is useful as a synthetic intermediate for pharmaceuticals and various other chemical products, so it is not necessarily necessary to isolate it if it is to be used immediately in the next reaction. do not have. For example, this compound can be used as it is for reactions with various ketones, aldehydes, acid halides, etc., without being isolated. This compound is represented by, for example, an acid halide when R 1 is hydrogen in the general formula. By reacting with a carboxylic acid derivative represented by the general formula: R 5 COY (in the formula, R 5 means the same group as R 1 , and Y means a reactive derivative of halogen or hydroxyl group), various α-acyl lactones can be produced. Further, by reacting the α-acyl lactones thus obtained with theobromine or a salt thereof, various oxoalkyltheobromines or derivatives thereof can be produced.
Oxoalkyltheobromine is, for example, 1-(5
-Oxohexyl) theobromine is particularly effective as an agent for improving blood circulation in peripheral blood vessels, so it is one of the important applications of the enolsilyl ether obtained by the method of the present invention. is a patent application filed separately in 1982.
It is additionally noted that it is stated in the specification of Publication No. 162585. EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples and Reference Examples, but the present invention is not limited thereto. Example 1 [Production of 5-trimethylsiloxy-2,3-dihydrofuran] Under a nitrogen atmosphere, 30 g of triethylamine and 1.0 g of zinc chloride are added and stirred at room temperature to form a fine suspension. γ-butyrolactone 17.2g (compound; R 1
=H, n=2) and trimethylsilane chloride 26.0g
A solution of (compound; R 2 = R 3 = R 4 = CH 3 , x = Cl) in acetonitrile (100 ml) was added, and the mixture was allowed to react at room temperature for 10 hours. Add 100 ml of benzene to the reaction solution, filter out the precipitate, and evaporate the solvent under reduced pressure. Distilling the residue under reduced pressure in a nitrogen stream yields 5-trimethylsiloxy-2,3-dihydrofuran (compound).
28.4g (bp.78-80°C/50Torr) is obtained. Example 2 [Production of 6-trimethylsiloxy-2,3-dihydro-4H-pyran] In the same manner as in Example 1, δ-valerolactone
20.0g (compound; R 1 = H, n = 3) was reacted, and 30.5g (bp. 44-45
℃/5Torr) is obtained. Example 3 [5-dimethyl-t-butylsiloxy-2,3
-Production of dihydrofuran] In the same manner as in Example 1, dimethyl chloride-t-butylsilane (compound; R 2 = R 3 = CH 3 , R 4 = t-C 4 H 5 , X =
5- from 17.2 g of γ-butyrolactone using
35.5g of dimethyl-t-butylsiloxy-2,3-dihydrofuran (compound) (bp76-78℃/
10Torr) obtained. Example 4 [5-methyl-6-triethylsiloxy-2,
Production of 3-dihydro-4H-pyran] Under a nitrogen atmosphere, add 1.5 g of zinc bromide to 30 g of triethylamine and stir at room temperature to form a fine suspension. 2-methyl-δ-valerolactone 22.8g
(compound; R 1 = CH 3 , n = 3) and 36.1 g of triethylsilane chloride (compound; R 2 = R 3 = R 4 = C 2 H 5 ,
Add a solution of X=Cl) in acetonitrile (100 ml) and react at room temperature for 10 hours. Benzene 100% in the reaction solution
ml, filter out the precipitate, and evaporate the solvent under reduced pressure. Distilling the residue under reduced pressure in a nitrogen stream yields 5-
Methyl-6-triethylsiloxy-2,3-dihydro-4H-pyran (compound) is 38.8g (bp.85
~88℃/5Torr) is obtained. Example 5 [Production of 4-butyl-5-dibutylphenylsiloxy-2,3-dihydrofuran] In the same manner as in Example 4, dimethylphenylsilane chloride (compound; R 2 = R 3 = CH3 ,
窒素雰囲気下、２―フエニル―γ―ブチロラク
トン16.2ｇ（化合物；
Under a nitrogen atmosphere, 16.2 g of 2-phenyl-γ-butyrolactone (compound;
窒素雰囲気下、トリエチルアミン15ｇに塩化亜
鉛0.5ｇを加えて室温で撹拌し、細かい懸濁液と
する。γ―ブチロラクトン8.6ｇと塩化トリメチ
ルシラン13.0ｇのアセトニトリル（50ml）溶液を
加え、室温で10時間反応させ実施例１の５―トリ
メチルシロキシ―２，３―ジヒドロフラン（化合
物）を生成させる。反応液を−30℃に冷却し、
アセトアルデヒド5.0ｇを加えた後ゆつくりと昇
温し、約５時間後室温となつたところ５％炭酸水
素ナトリウム溶液にあける。塩化メチレンを加え
て分液した後、有機層を無水硫酸ナトリウムで乾
燥する。無機塩をロ別し、溶媒を留去後、減圧下
蒸留すると２―（1′―トリメチルシロキシエチ
ル）―γ―ブチロラクトンが12.1ｇ（bp.90〜96
℃／20Torr）得られる。
参考例 ２
〔α―アセチル―δ―バレロラクトンの製造〕
窒素雰囲気下、トリエチルアミン222ｇに塩化
亜鉛５ｇを加えて室温で撹拌し、細かい懸濁液と
する。δ―バレロラクトン100ｇと塩化トリメチ
ルシラン120ｇのアセトニトリル（400ml）溶液を
加え室温で10時間反応させ、実施例２の６―トリ
メチルシロキシ―２，３―ジヒドロ―4H―ピラ
ン（化合物）を生成させる。更に同温度で塩化
アセチル86ｇをゆつくりと加え、１時間撹拌す
る。反応液に水を加え酢酸エチルにより分液抽出
する。有機層の溶媒を留去後、残渣を減圧下蒸留
するとα―アセチル―δ―バレロラクトンが114
ｇ（bp.135〜140℃／4Torr）得られる。
参考例 ３
〔１―（５―オキソヘキシル）テオブロミンの
製造〕
テオブロミン3.80ｇ（0.02モル）と参考例２で
得られたα―アセチル―δ―バレロラクトン4.26
ｇ（0.03モル）をヘキサメチルホスホトリアミド
20mlに加え、水素化ナトリウム96mg（0.002モル）
を加えて、180〜190で２時間加熱撹拌する。ヘキ
サメチルホスホルトリアミドを減圧下に留去し、
残渣に塩化メチレンおよび５％水酸化ナトリウム
水溶液を加えて分液し、未反応のテオブロミンを
除去する。有機層を活性炭で処理した後、減圧下
に濃縮し、得られた粗結晶をｉ―プロパノールよ
り再結晶して、１―（５―オキソヘキシル）テオ
ブロミンの白色粉末を4.45ｇを得た。
Under a nitrogen atmosphere, add 0.5 g of zinc chloride to 15 g of triethylamine and stir at room temperature to form a fine suspension. A solution of 8.6 g of γ-butyrolactone and 13.0 g of trimethylsilane chloride in acetonitrile (50 ml) was added and reacted at room temperature for 10 hours to produce 5-trimethylsiloxy-2,3-dihydrofuran (compound) of Example 1. Cool the reaction solution to -30°C,
After adding 5.0 g of acetaldehyde, the temperature was slowly raised, and when it reached room temperature after about 5 hours, it was poured into a 5% sodium hydrogen carbonate solution. After adding methylene chloride and separating the layers, the organic layer is dried over anhydrous sodium sulfate. After filtering off the inorganic salts and distilling off the solvent, 12.1g of 2-(1'-trimethylsiloxyethyl)-γ-butyrolactone (bp.90-96
℃/20Torr) is obtained. Reference Example 2 [Production of α-acetyl-δ-valerolactone] Under a nitrogen atmosphere, add 5 g of zinc chloride to 222 g of triethylamine and stir at room temperature to form a fine suspension. A solution of 100 g of δ-valerolactone and 120 g of trimethylsilane chloride in acetonitrile (400 ml) is added and reacted at room temperature for 10 hours to produce 6-trimethylsiloxy-2,3-dihydro-4H-pyran (compound) of Example 2. Furthermore, 86 g of acetyl chloride was slowly added at the same temperature, and the mixture was stirred for 1 hour. Water was added to the reaction solution, and the mixture was separated and extracted with ethyl acetate. After distilling off the solvent in the organic layer, the residue was distilled under reduced pressure to obtain α-acetyl-δ-valerolactone.
g (bp.135-140°C/4 Torr). Reference Example 3 [Production of 1-(5-oxohexyl)theobromine] 3.80 g (0.02 mol) of theobromine and 4.26 g of α-acetyl-δ-valerolactone obtained in Reference Example 2
g (0.03 mol) of hexamethylphosphotriamide
20ml plus 96mg (0.002mol) of sodium hydride
Add and heat and stir at 180-190 for 2 hours. Hexamethylphosphortriamide was distilled off under reduced pressure,
Methylene chloride and a 5% aqueous sodium hydroxide solution are added to the residue to separate the layers, and unreacted theobromine is removed. After treating the organic layer with activated carbon, it was concentrated under reduced pressure, and the obtained crude crystals were recrystallized from i-propanol to obtain 4.45 g of white powder of 1-(5-oxohexyl)theobromine.
Claims (1)
アルケニル、アラルキルまたはアリール基を意味
し、ｎは１〜４の整数を意味する。） で表わされるラクトン類と、 一般式 ：R2R3R4Six （式中、R2，R3，R4はそれぞれアルキル、シ
クロアルキルまたはアリール基を意味し、ｘはハ
ロゲン原子を意味する。） で表わされるハロゲン化シラン類とを、塩基性物
質、ルイス酸およびニトリル系溶媒の存在下で反
応させることからなる。 一般式 ： （式中の符号は全て前記と同じ。） で表わされるエノールシリルエーテル類の製造方
法。 ２ 塩基性物質が、トリエチルアミン、トリブチ
ルアミン、Ｎ，Ｎ―ジメチルアニリン、ピリジ
ン、ジアザビシクロウンデセン、ジアザビシクロ
オクタン等の三級アミン類である特許請求の範囲
第１項記載の製造方法。 ３ ルイス酸が三弗化硼素、四弗化スズ等の金属
弗化物；三塩化アルミニウム、四塩化チタン、塩
化亜鉛等の金属塩化物；臭化亜鉛、臭化マグネシ
ウム等の金属臭化物；ヨウ化亜鉛、ヨウ化鉄等の
金属ヨウ化物である特許請求の範囲第１または２
項記載の製造方法。 ４ ニトリル系溶媒がアセトニトリル、プロピオ
ニトリル、ベンゾニトリル等である特許請求の範
囲第１，２または３項記載の製造方法。 ５ 一般式の化合物におけるＸが塩素である特
許請求の範囲第１，２，３または４項記載の製造
方法。[Claims] 1. General formula: (In the formula, R 1 is hydrogen, alkylcycloalkyl,
It means an alkenyl, aralkyl or aryl group, and n means an integer of 1 to 4. ) and the general formula: R 2 R 3 R 4 Six (wherein R 2 , R 3 , and R 4 each represent an alkyl, cycloalkyl, or aryl group, and x represents a halogen atom). ) is reacted with a halogenated silane represented by the following formula in the presence of a basic substance, a Lewis acid, and a nitrile solvent. General formula: (All symbols in the formula are the same as above.) A method for producing an enol silyl ether represented by: 2. The manufacturing method according to claim 1, wherein the basic substance is a tertiary amine such as triethylamine, tributylamine, N,N-dimethylaniline, pyridine, diazabicycloundecene, or diazabicyclooctane. 3 Lewis acids include metal fluorides such as boron trifluoride and tin tetrafluoride; metal chlorides such as aluminum trichloride, titanium tetrachloride, and zinc chloride; metal bromides such as zinc bromide and magnesium bromide; zinc iodide , Claim 1 or 2 is a metal iodide such as iron iodide.
Manufacturing method described in section. 4. The manufacturing method according to claim 1, 2 or 3, wherein the nitrile solvent is acetonitrile, propionitrile, benzonitrile or the like. 5. The manufacturing method according to claim 1, 2, 3 or 4, wherein X in the compound of the general formula is chlorine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6097882A JPS58180493A (en) | 1982-04-14 | 1982-04-14 | Preparation of enol silyl ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6097882A JPS58180493A (en) | 1982-04-14 | 1982-04-14 | Preparation of enol silyl ether |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58180493A JPS58180493A (en) | 1983-10-21 |
| JPH0132228B2 true JPH0132228B2 (en) | 1989-06-29 |
Family
ID=13158021
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6097882A Granted JPS58180493A (en) | 1982-04-14 | 1982-04-14 | Preparation of enol silyl ether |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58180493A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2646425C (en) | 2006-03-21 | 2014-11-04 | The Governors Of The University Of Alberta | Novel poly(ethylene oxide)-block-poly(ester) block copolymers |
-
1982
- 1982-04-14 JP JP6097882A patent/JPS58180493A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58180493A (en) | 1983-10-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2341054B1 (en) | Process for the synthesis of HMG-CoA reductase inhibitors | |
| JP4659309B2 (en) | Process for producing 5-hydroxy-3-oxopentanoic acid derivative | |
| US4845257A (en) | 4-halogeno-2-oxyimino-3-oxobutyric acids and derivatives | |
| JPH0132228B2 (en) | ||
| JPH0214358B2 (en) | ||
| JP4176201B2 (en) | Method for producing 5-halogeno-2-substituted pyridine | |
| JP3946521B2 (en) | Method for producing simvastatin | |
| RU2027704C1 (en) | Method of synthesis of 6-fluoro-1,2-benzisothiazole, ortho-substituted phenacyl-derivative, and a method of its synthesis | |
| JP2000095730A (en) | Production of halogenated phenylmalonic ester | |
| JP3998925B2 (en) | Method for producing 3,3,3-trifluoro-2-hydroxypropionic acid derivative | |
| US20190010124A1 (en) | Method for synthesizing enaniomerically pure n-(pyridin-4-yl)-2-hydroxy-alkylamide derivatives | |
| JP2579547B2 (en) | Preparation of alkoxycarbonyl compounds | |
| JPH09316071A (en) | Production of carbapenem antibiotic intermediate | |
| JP2943972B2 (en) | Production of β-γ unsaturated ketones | |
| JP3855686B2 (en) | 3,3-dialkoxy-2-hydroxyimino derivative and process for producing the same | |
| JP3719736B2 (en) | Method for producing pyrazolones | |
| JP2001048826A (en) | Production of 1-phenyl-1,3-butanedione | |
| JP2603869B2 (en) | Process for producing 3-oxo-5-hexenoic acid esters | |
| JP3819473B2 (en) | 4,4-Bishalomethyl-3-oxoalkanecarboxylic acid derivative and method for producing 3-cyclopropyl-3-oxopropionic acid derivative using the same | |
| JP3758707B2 (en) | (-)-Trans-coumaucine production method and novel intermediate | |
| KR20000021998A (en) | Process for preparing simvastatin and intermediate compound thereof | |
| JP3517936B2 (en) | Method for producing 1,3-dioxolan | |
| JPH0713065B2 (en) | Method for producing furfuryl alcohol | |
| JPH11279169A (en) | Production of 3-isochromanones | |
| JP2004010527A (en) | Method for producing 2,4,5-trifluorobenzoylacetic acid alkyl ester |