JPH0158195B2 - - Google Patents
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- Publication number
- JPH0158195B2 JPH0158195B2 JP56128040A JP12804081A JPH0158195B2 JP H0158195 B2 JPH0158195 B2 JP H0158195B2 JP 56128040 A JP56128040 A JP 56128040A JP 12804081 A JP12804081 A JP 12804081A JP H0158195 B2 JPH0158195 B2 JP H0158195B2
- Authority
- JP
- Japan
- Prior art keywords
- solution
- ether
- compound
- methyl
- added
- Prior art date
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- 238000006243 chemical reaction Methods 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 4
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 claims description 3
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 claims description 2
- 101150065749 Churc1 gene Proteins 0.000 claims description 2
- 102100038239 Protein Churchill Human genes 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 230000032050 esterification Effects 0.000 claims 1
- 238000005886 esterification reaction Methods 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 40
- 239000000243 solution Substances 0.000 description 34
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 16
- -1 otatyl Chemical group 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 5
- ZCJHPTKRISJQTN-JGVFFNPUSA-N nanaomycin A Chemical compound O=C1C2=C(O)C=CC=C2C(=O)C2=C1[C@H](C)O[C@@H](CC(O)=O)C2 ZCJHPTKRISJQTN-JGVFFNPUSA-N 0.000 description 5
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000010898 silica gel chromatography Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- ZCJHPTKRISJQTN-UHFFFAOYSA-N Nanaomycin A Natural products O=C1C2=C(O)C=CC=C2C(=O)C2=C1C(C)OC(CC(O)=O)C2 ZCJHPTKRISJQTN-UHFFFAOYSA-N 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- YXHKONLOYHBTNS-UHFFFAOYSA-N Diazomethane Chemical compound C=[N+]=[N-] YXHKONLOYHBTNS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- MCVVUJPXSBQTRZ-UHFFFAOYSA-N methyl but-2-enoate Chemical compound COC(=O)C=CC MCVVUJPXSBQTRZ-UHFFFAOYSA-N 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Chemical group CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-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
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical class Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003710 aryl alkyl group Chemical class 0.000 description 1
- SLUNEGLMXGHOLY-UHFFFAOYSA-N benzene;hexane Chemical compound CCCCCC.C1=CC=CC=C1 SLUNEGLMXGHOLY-UHFFFAOYSA-N 0.000 description 1
- 150000001793 charged compounds Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- OIKHZBFJHONJJB-UHFFFAOYSA-N dimethyl(phenyl)silicon Chemical compound C[Si](C)C1=CC=CC=C1 OIKHZBFJHONJJB-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 238000004262 preparative liquid chromatography Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- GRONZTPUWOOUFQ-UHFFFAOYSA-M sodium;methanol;hydroxide Chemical compound [OH-].[Na+].OC GRONZTPUWOOUFQ-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- BCNZYOJHNLTNEZ-UHFFFAOYSA-N tert-butyldimethylsilyl chloride Chemical compound CC(C)(C)[Si](C)(C)Cl BCNZYOJHNLTNEZ-UHFFFAOYSA-N 0.000 description 1
- AKQNYQDSIDKVJZ-UHFFFAOYSA-N triphenylsilane Chemical compound C1=CC=CC=C1[SiH](C=1C=CC=CC=1)C1=CC=CC=C1 AKQNYQDSIDKVJZ-UHFFFAOYSA-N 0.000 description 1
Description
【発明の詳細な説明】
本発明は、有機合成試薬などとして有用な一般
式
（式中、Ｒは水素原子、アルキル基を、R1，
R2，R3は同一または異なつてアルキル基、フエ
ニル基を示す。）
により表わされる２―シリル化―３―ブテン酸誘
導体の製造法に関する。Detailed Description of the Invention The present invention provides a general formula useful as an organic synthesis reagent, etc. (In the formula, R is a hydrogen atom, an alkyl group, R 1 ,
R 2 and R 3 are the same or different and represent an alkyl group or a phenyl group. ) The present invention relates to a method for producing a 2-silylated-3-butenoic acid derivative represented by:
上記の定義をより詳しく説明すると、アルキル
基とはメチル、エチル、プロピル、イソプロピ
ル、ブチル、第３級ブチル、ペンチル、ヘキシ
ル、オタチル、デシル、ドデシル、ペンタデシ
ル、オクタデシルなどを意味する。 To explain the above definition in more detail, the alkyl group means methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl, pentyl, hexyl, otatyl, decyl, dodecyl, pentadecyl, octadecyl, and the like.
一般式（）の化合物は、一般式
CH2＝CHCH2SiR1R2R3 （）
（式中、R1，R2，R3は前記と同義である。）
で表わされる化合物と、アート錯体形成化合物を
反応させ、ついでカルボン酸生成反応に付し、必
要に応じて、生成物をエステル化することにより
製造される。 The compound of general formula () is a compound represented by the general formula CH 2 =CHCH 2 SiR 1 R 2 R 3 () (wherein, R 1 , R 2 , and R 3 have the same meanings as above), and It is produced by reacting a complex-forming compound, then subjecting it to a carboxylic acid production reaction, and optionally esterifying the product.
ここで、アート錯体形成化合物とは、アルミニ
ウムなどの電子受容性の強い元素のアルキル化合
物（トリエチルアルミニウムなど）ならびにアル
カリ金属のアルキル化合物（第３級ブチルリチウ
ムなど）などである。 Here, the ate complex-forming compound includes an alkyl compound of a strong electron-accepting element such as aluminum (such as triethylaluminum) and an alkyl compound of an alkali metal (such as tertiary butyllithium).
この反応は、通常窒素気流下に反応不活性な溶
媒中、０℃以下、好ましくは−80℃から０℃で、
Ｎ，Ｎ，N′，N′―テトラメチルエチレンジアミ
ンなどを用いて進行する。 This reaction is usually carried out in a reaction-inert solvent under a nitrogen stream at 0°C or lower, preferably between -80°C and 0°C.
The process proceeds using N,N,N',N'-tetramethylethylenediamine, etc.
この反応により生成するアート錯体化合物は、
たとえば、一般式
（式中、R′は同一または異なつてアルキル基
を、R1，R2，R3は前記と同義である。）
で表わされる。 The ate complex compound produced by this reaction is
For example, the general expression (In the formula, R' is the same or different and represents an alkyl group, and R 1 , R 2 and R 3 are as defined above.)
一般式（）の化合物のカルボン酸生成反応は
通常、反応に不活性な溶媒中、０℃以下の温度で
二酸化炭素を吹き込むことによつて進行する。 The carboxylic acid production reaction of the compound of general formula () usually proceeds by blowing carbon dioxide into a solvent inert to the reaction at a temperature of 0° C. or lower.
得られたカルボン酸誘導体〔一般式（）の化
合物で、記号Ｒが水素原子を示す化合物〕は、そ
のまま、または酸クロライド、酸無水物などの反
応性誘導体に導き、エステル化剤（ジアゾアルカ
ン、アルコラート、アルカノール、または対応す
るアラルキル体など）と常法に従つて反応させる
と、目的とするエステル化合物が得られる。 The obtained carboxylic acid derivative [a compound of the general formula (), in which the symbol R represents a hydrogen atom] is used as it is or converted into a reactive derivative such as an acid chloride or an acid anhydride, and then treated with an esterifying agent (diazoalkane, diazoalkane, etc.). (alcolate, alkanol, or the corresponding aralkyl derivative) according to a conventional method, the desired ester compound is obtained.
本発明の化合物は、抗菌作用を有することが知
られているナナオマイシン類、フレノシン類の合
成中間体として極めて有用な一般式
（式中、Ｘは水素原子、低級アルキル基を、Ｚ
は低級アルキル基を示す。ここで、低級アルキル
基とは、メチル、エチル、プロピル、イソプロピ
ル、ブチル、第三級ブチルなどを意味する。）
で表わされる化合物を合成する試薬として特に有
用である。 The compound of the present invention has the general formula (In the formula, X is a hydrogen atom, a lower alkyl group, Z
represents a lower alkyl group. Here, the lower alkyl group means methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl, and the like. ) is particularly useful as a reagent for synthesizing the compound represented by
以下、実施例および参考例により本発明を具体
的に説明する。 The present invention will be specifically explained below using Examples and Reference Examples.
実施例 １
窒素雰囲気下、−78℃に冷却したテトラヒドロ
フラン60ml中へ、２，1M第三級ブチルリチウム
のペンタン溶液12mlを加え、引き続いてＮ，Ｎ，
N′，N′―テトラメチルエチレンジアミン3.75ml
を加えた。これに、トリフエニルアリルシラン
6.00ｇを溶かしたテトラヒドロフラン溶液10mlを
加え、その後徐々に−30℃に昇温した。生成した
濃黄色溶液を再び−78℃に冷却した後、15％トリ
エチルアルミニウムのヘキサン溶液を溶液の黄色
が消失するまで加えた。反応溶液の温度を−78℃
に保ちつつ、乾燥二酸化炭素を吹きこみ続け、ゆ
つくりと０℃にまで昇温する。その後反応溶液を
氷―飽和塩化アンモニウム溶液にあける。５％塩
酸溶液を白色固体が完全に溶解するまで加え、溶
液を酸性にした後、エーテルで抽出した。エーテ
ル層を一つにして、飽和塩化アンモニウム水溶液
で洗浄し、無水硫酸ナトリウムで乾燥後、溶媒を
減圧下に除いた。残査をlH―NMRにより分析す
ると、２―トリフエニルシリル―３―ブテン酸、
４―トリフエニルシリル―３―ブテン酸およびト
リフエニルアリルシランが65：25：10の比率の混
合物であつた。塩化メチレンから再結晶すると、
２―トリフエニルシリル―３―ブテン酸1.98ｇが
得られた。母液をシリカゲルカラムクロマトに付
すと、さらに1.80ｇ得られた。収量4.33ｇ（63
％）。Example 1 Under a nitrogen atmosphere, 12 ml of a 2,1 M tertiary-butyllithium pentane solution was added to 60 ml of tetrahydrofuran cooled to -78°C, followed by N, N,
N′,N′-tetramethylethylenediamine 3.75ml
added. To this, triphenylallylsilane
10 ml of a tetrahydrofuran solution containing 6.00 g was added, and then the temperature was gradually raised to -30°C. After the resulting dark yellow solution was cooled again to −78° C., a 15% hexane solution of triethylaluminum was added until the yellow color of the solution disappeared. The temperature of the reaction solution is -78℃
While keeping the temperature at 0°C, continue blowing in dry carbon dioxide and slowly raise the temperature to 0°C. The reaction solution is then poured into ice-saturated ammonium chloride solution. A 5% hydrochloric acid solution was added until the white solid was completely dissolved to make the solution acidic, and then extracted with ether. The ether layers were combined, washed with a saturated aqueous ammonium chloride solution, dried over anhydrous sodium sulfate, and then the solvent was removed under reduced pressure. Analysis of the residue by lH-NMR revealed that 2-triphenylsilyl-3-butenoic acid,
The mixture was 4-triphenylsilyl-3-butenoic acid and triphenylallylsilane in a ratio of 65:25:10. When recrystallized from methylene chloride,
1.98 g of 2-triphenylsilyl-3-butenoic acid was obtained. When the mother liquor was subjected to silica gel column chromatography, an additional 1.80 g was obtained. Yield 4.33g (63
%).
これをエーテル中ジアゾメタンでメチル化し、
生成物をベンゼン―ヘキサンから再結晶すると、
純品の２―トリフエニルシリル―３―ブテン酸メ
チル3.24ｇが得られた。融点96〜97℃、収率45％
（トリフエニルシランに対して）。 This was methylated with diazomethane in ether,
When the product is recrystallized from benzene-hexane,
3.24 g of pure methyl 2-triphenylsilyl-3-butenoate was obtained. Melting point 96-97℃, yield 45%
(for triphenylsilane).
1H―NMR〔重クロロホルム中、δ（ppm）〕：
3.33（ｓ，3H），3.80（ｄ，1H，Ｊ＝10Hz），4.80
〜5.10（ｍ，2H），6.08（at，1H，Ｊ＝10，18Hz），
7.2〜7.7（ｍ，15H）。 1H -NMR [in deuterated chloroform, δ (ppm)]:
3.33 (s, 3H), 3.80 (d, 1H, J=10Hz), 4.80
~5.10 (m, 2H), 6.08 (at, 1H, J=10, 18Hz),
7.2-7.7 (m, 15H).
赤外スペクトル（臭化カリウム法、cm-1）：
1715（vs）。 Infrared spectrum (potassium bromide method, cm -1 ):
1715 (vs).
実施例 ２
窒素気流下、−78℃に冷却したテトラヒドロフ
ラン５ml中へ、2.1M第三級ブチルリウムのペン
タン溶液0.72mlおよびＮ，Ｎ，N′，N′―テトラ
メチルエチレンジアミン0.23mlを加え、さらにア
リルジメチルフエニルシラン176mlを加えた。１
時間かけて反応溶液の温度を徐々に−30℃にまで
昇温した後、再び−78℃に冷却し15％トリエチル
アルミニウムのヘキサン溶液を反応溶液の黄色が
消失するまで加えた。引き続き、乾燥二酸化炭素
を反応溶液に吹きこみ、０℃まで徐々に昇温し
た。反応混合物を氷―飽和塩化アルミニウム溶液
にあけ、すばやくエーテルで抽出し、無水硫酸マ
グネシウムで乾燥後、ジアゾメタンを溶かしたエ
ーテル溶液を加え、メチル化した。ベンゼンを展
開液としてシリカゲルカラムに付すと、純品の２
―ジメチルフエニルシリル―３―ブテン酸メチル
142mgが無色油状物として得られた。収率61％。Example 2 Under a nitrogen stream, 0.72 ml of a 2.1 M tertiary butylurium pentane solution and 0.23 ml of N,N,N',N'-tetramethylethylenediamine were added to 5 ml of tetrahydrofuran cooled to -78°C, and allyl 176 ml of dimethylphenylsilane was added. 1
The temperature of the reaction solution was gradually raised to -30°C over time, then cooled again to -78°C, and a 15% hexane solution of triethylaluminum was added until the yellow color of the reaction solution disappeared. Subsequently, dry carbon dioxide was blown into the reaction solution, and the temperature was gradually raised to 0°C. The reaction mixture was poured into ice-saturated aluminum chloride solution, quickly extracted with ether, dried over anhydrous magnesium sulfate, and then methylated by adding an ether solution containing diazomethane. When applied to a silica gel column using benzene as a developing solution, pure 2
-Methyl dimethylphenylsilyl-3-butenoate
142 mg was obtained as a colorless oil. Yield 61%.
1H―NMR〔重クロロホルム中、δ（ppm）〕：
0.38（ｓ，6H），3.10（ｄ，1H，Ｊ＝10Hz），3.48
（ｓ，1H），4.64〜5.00（ｍ，2H），5.95（ｄ，ｔ，
1H，Ｊ＝10，17Hz），7.24〜7.50（ｍ，5H）。 1H -NMR [in deuterated chloroform, δ (ppm)]:
0.38 (s, 6H), 3.10 (d, 1H, J=10Hz), 3.48
(s, 1H), 4.64-5.00 (m, 2H), 5.95 (d, t,
1H, J=10, 17Hz), 7.24-7.50 (m, 5H).
赤外スペクトル（液膜法、cm-1）：1720，1630。 Infrared spectrum (liquid film method, cm -1 ): 1720, 1630.
参考例１ 一般式（）の化合物の調製例
(i) 窒素気流下、３―アセチル―５―メトキシ―
１，４―ナフトキノン230mg（1.0mmol）およ
び２―トリフエニルシリル―３―ブテン酸メチ
ル257mg（1.1mmol）の塩化メチレン溶液30ml
を−78℃に冷却し、攪拌しながら、塩化第二錫
140μlを加えた。生成した濃紫色溶液を約１時
間かけて−30℃に昇温させ、この温度で１時間
保つと、次第に黄褐色に変化した。水を加え
て、エーテルにて繰返し抽出後、エーテル層を
水および飽和食塩水にて洗浄し、無水硫酸マグ
ネシウムですばやく乾燥した。Reference Example 1 Preparation example of compound of general formula () (i) Under nitrogen flow, 3-acetyl-5-methoxy-
A solution of 230 mg (1.0 mmol) of 1,4-naphthoquinone and 257 mg (1.1 mmol) of methyl 2-triphenylsilyl-3-butenoate in 30 ml of methylene chloride.
Cool to -78°C and add stannic chloride while stirring.
140μl was added. The resulting deep purple solution was heated to -30°C over about 1 hour, and when kept at this temperature for 1 hour, it gradually turned yellowish brown. After adding water and repeatedly extracting with ether, the ether layer was washed with water and saturated brine, and quickly dried over anhydrous magnesium sulfate.
エーテルを減圧下留去すると、残査として４
―（３―アセチル―４―ヒドロキシ―５―メト
キシ―１―オキソ―１，２―ジヒドロ―２―ナ
フチル）―２―ブテン酸メチルが定量的に得ら
れた。 When the ether is distilled off under reduced pressure, 4 is left as a residue.
Methyl -(3-acetyl-4-hydroxy-5-methoxy-1-oxo-1,2-dihydro-2-naphthyl)-2-butenoate was obtained quantitatively.
1H―NMR（重クロロホルム中、δ（ppm）〕：
2.12（ｓ，3H），2.20〜2.60（ｍ，2H），3.60（ｓ，
3H），3.8（1H），3.85（ｓ，3H），2.59（ｄ，1H，
Ｊ＝16Hz），6.64（ｄ，ｔ，1H，Ｊ＝８，16Hz）
(ii) 窒素雰気下、３―ブチリル―５―メトキシ―
１，４―ナフトキノン258mg（1.0mmol）およ
び２―ジメチルフエニルシリル―３―ブテン酸
メチル257mg（1.1mmol）の塩化メチレン溶液
30mlを−78℃に冷却し、塩化第二錫140μlを滴
下した。このとき黄色溶液は濃紫色となつた。 1H -NMR (in deuterated chloroform, δ (ppm)):
2.12 (s, 3H), 2.20~2.60 (m, 2H), 3.60 (s,
3H), 3.8 (1H), 3.85 (s, 3H), 2.59 (d, 1H,
J = 16Hz), 6.64 (d, t, 1H, J = 8, 16Hz) (ii) 3-butyryl-5-methoxy under nitrogen atmosphere
Methylene chloride solution of 258 mg (1.0 mmol) of 1,4-naphthoquinone and 257 mg (1.1 mmol) of methyl 2-dimethylphenylsilyl-3-butenoate
30 ml was cooled to -78°C, and 140 μl of stannic chloride was added dropwise. At this time, the yellow solution turned deep purple.
反応溶液の温度を徐々に昇温させ、−30℃で
１時間攪拌すると、反応溶液は黄褐色となつ
た。水を加えて、エーテルにて抽出後、エーテ
ル層を常法にて水洗・乾燥処理し、エーテルを
減圧下留去すると、残査として４―（３―ブチ
リル―４―ヒドロキシ―５―メトキシ―１―オ
キソ―１，２―ジヒドロ―２―ナフチル）―２
―ブテン酸メチルが定量的に得られた。 The temperature of the reaction solution was gradually raised and stirred at -30°C for 1 hour, and the reaction solution turned yellowish brown. After adding water and extracting with ether, the ether layer is washed with water and dried in a conventional manner, and the ether is distilled off under reduced pressure, leaving a residue of 4-(3-butyryl-4-hydroxy-5-methoxy- 1-oxo-1,2-dihydro-2-naphthyl)-2
-Methyl butenoate was obtained quantitatively.
1H―NMR〔重クロロホルム中、δ（ppm）〕：
0.97（ｔ，3H，Ｊ＝７Hz），2.70（sex，2H，Ｊ
＝７Hz），2.20〜2.70（ｍ，4H），3.64（ｓ，
3H），3.92（ｓ，3H），3.60〜3.90（1H），5.65
（ｄ，1H，Ｊ＝16Hz），6.73（ｄ，ｔ，1H，Ｊ
＝８，16Hz），17.05（ｓ，1H）
参考例２ ナナオマイシンＡの調製例
(i) 上記参考例(i)にて得られた４―（３―アセチ
ル―４―ヒドロキシ―５―メトキシ―１―オキ
ソ―１，２―ジヒドロ―２―ナフチル）―２―
ブテン酸メチルに窒素雰囲気下、第三級ブチル
ジメチルシリルクロライド378mg、イミダゾー
ル408mgおよびジメチルホルムアミド２mlを加
え、一夜室温にて攪拌後、水を加え、エーテル
にて抽出した。 1H -NMR [in deuterated chloroform, δ (ppm)]:
0.97 (t, 3H, J = 7Hz), 2.70 (sex, 2H, J
=7Hz), 2.20-2.70 (m, 4H), 3.64 (s,
3H), 3.92 (s, 3H), 3.60-3.90 (1H), 5.65
(d, 1H, J = 16Hz), 6.73 (d, t, 1H, J
= 8, 16Hz), 17.05 (s, 1H) Reference Example 2 Preparation Example of Nanaomycin A (i) 4-(3-acetyl-4-hydroxy-5-methoxy- obtained in Reference Example (i) above) 1-oxo-1,2-dihydro-2-naphthyl)-2-
378 mg of tertiary butyldimethylsilyl chloride, 408 mg of imidazole and 2 ml of dimethylformamide were added to methyl butenoate under a nitrogen atmosphere, and after stirring at room temperature overnight, water was added and extracted with ether.
エーテル層を常法にて水洗・乾燥処理後、シ
リカゲルカラムクロマト（溶離液：塩化メチレ
ン）に付し、対応する１―第三級ブチルジメチ
ルシリルオキシ化合物322mgを得た。無色針状
晶。融点107〜109℃。収率73％。 The ether layer was washed with water and dried in a conventional manner, and then subjected to silica gel column chromatography (eluent: methylene chloride) to obtain 322 mg of the corresponding 1-tert-butyldimethylsilyloxy compound. Colorless needles. Melting point 107-109℃. Yield 73%.
1H―NMR〔重クロロホルム中、δ（ppm）〕：
0.16（ｓ，6H），1.10（ｓ，9H），2.58（ｓ，3H），
3.68（ｓ，3H），3.72（ｄ，2H，Ｊ＝６Hz），
4.02（ｓ，3H），5.68（ｄ，1H，Ｊ＝16Hz），
6.80（ｄ，1H，Ｊ＝８Hz），6.93（ｄ，ｔ，1H，
Ｊ＝６，16Hz），7.32（ｔ，1H，Ｊ＝８Hz），
7.62（ｄ，1H，Ｊ＝８Hz），9.45（ｓ，1H）。 1H -NMR [in deuterated chloroform, δ (ppm)]:
0.16 (s, 6H), 1.10 (s, 9H), 2.58 (s, 3H),
3.68 (s, 3H), 3.72 (d, 2H, J=6Hz),
4.02 (s, 3H), 5.68 (d, 1H, J=16Hz),
6.80 (d, 1H, J=8Hz), 6.93 (d, t, 1H,
J = 6, 16Hz), 7.32 (t, 1H, J = 8Hz),
7.62 (d, 1H, J=8Hz), 9.45 (s, 1H).
赤外スペクトル（液膜法、cm-1）：3360（br，
ｓ），1725（vs），1690（vs）
質量スペクトル（ｍ／ｅ）：444（分子イオン
ピーク）
(ii) この１―第三級ブチルジメチルシリルオキシ
化合物127mg（0.27mmol）のメタノール溶液に
水素化ホウ素ナトリウム38mgを加え、室温で１
時間攪拌した。飽和塩化アンモニウム溶液を加
えたのち、エーテルにて抽出し、エーテル層を
常法にて処理した。 Infrared spectrum (liquid film method, cm -1 ): 3360 (br,
s), 1725 (vs), 1690 (vs) Mass spectrum (m/e): 444 (molecular ion peak) (ii) Hydrogen was added to a methanol solution of 127 mg (0.27 mmol) of this 1-tertiary butyldimethylsilyloxy compound. Add 38 mg of sodium borochloride and stir at room temperature.
Stir for hours. After adding a saturated ammonium chloride solution, extraction was performed with ether, and the ether layer was treated in a conventional manner.
エーテルを減圧下留去後、残査をシリカゲル
カラムクロマト（展開液：塩化メチレン）に付
すと、４―〔１―第三級ブチルメチルシリルオ
キシ―４―ヒドロキシ―３―（１―ヒドロキシ
エチル）―５―メトキシ―２―ナフチル〕―２
―ブテン酸メチル120mgが得られた。収率94％。 After distilling off the ether under reduced pressure, the residue was subjected to silica gel column chromatography (developing solution: methylene chloride) to obtain 4-[1-tert-butylmethylsilyloxy-4-hydroxy-3-(1-hydroxyethyl). -5-methoxy-2-naphthyl]-2
-120 mg of methyl butenoate was obtained. Yield 94%.
1H―NMR（重クロロホルム中、δ（ppm）〕：
0.12（ｓ，3H），0.15（ｓ，3H），1.08（ｓ，9H），
1.62（ｄ，3H，Ｊ＝７Hz），3.68（ｓ，3H），
3.75（ｄ，2H，Ｊ＝６Hz），4.06（ｓ，3H），
4.97（ｍ，1H），5.70（ｄ，1H，Ｊ＝16Hz），
6.82（ｄ，1H，Ｊ＝８Hz），7.08（ｄ，ｔ，1H，
Ｊ＝６，16Hz），7.27（ｔ，1H，Ｊ＝８Hz），
7.65（ｄ，1H，Ｊ＝８Hz），9.75（ｓ，1H）
(iii) このようにして得られた化合物60mgをメタノ
ールに溶解し、室温で攪拌下ナトリウムメトキ
シド溶液（26％水酸化ナトリウムメタノール溶
液として）0.1mlを加える。１時間攪拌後、飽
和塩化アンモニウム溶液を加え、エーテルにて
抽出した。エーテル層を常法処理後、シリカゲ
ルカラムクロマトを行うと、５―第三級ブチル
ジメチルシリルオキシ―10―ヒドロキシ―９―
メトキシ―１―メチル―３，４―ジヒドロ―
1H―ナフト〔２，３―ｃ〕ピラン―３―イル
酢酸メチル57mgが２種のジアステレオマー混合
物として得られた。収率94％。 1H -NMR (in deuterated chloroform, δ (ppm)):
0.12 (s, 3H), 0.15 (s, 3H), 1.08 (s, 9H),
1.62 (d, 3H, J=7Hz), 3.68 (s, 3H),
3.75 (d, 2H, J=6Hz), 4.06 (s, 3H),
4.97 (m, 1H), 5.70 (d, 1H, J=16Hz),
6.82 (d, 1H, J=8Hz), 7.08 (d, t, 1H,
J = 6, 16Hz), 7.27 (t, 1H, J = 8Hz),
7.65 (d, 1H, J = 8 Hz), 9.75 (s, 1H) (iii) Dissolve 60 mg of the compound thus obtained in methanol, and add a sodium methoxide solution (26% sodium hydroxide methanol) under stirring at room temperature. (as a solution) add 0.1ml. After stirring for 1 hour, saturated ammonium chloride solution was added, and the mixture was extracted with ether. After the ether layer was treated in a conventional manner and subjected to silica gel column chromatography, 5-tert-butyldimethylsilyloxy-10-hydroxy-9-
Methoxy-1-methyl-3,4-dihydro-
57 mg of methyl 1H-naphtho[2,3-c]pyran-3-yl acetate was obtained as a mixture of two diastereomers. Yield 94%.
1H―NMR〔重クロロホルム中、δ（ppm）〕：
〜0.1（ｓ，6H），1.1（ｓ，9H），1.60（ｄ，3H，
Ｊ＝７Hz），2.2〜3.2（ｍ），3.70（ｓ，3H），3.73
（ｓ，3H），4.00（ｓ，3H），3.5〜4.4（ｍ，1H），
5.2（ｍ，1H），6.70（ｄ，1H，Ｊ＝８Hz），7.20
（ｄ，1H，Ｊ＝８Hz），7.60（ｄ，1H，Ｊ＝８
Hz），9.25（ｓ，1H），9.32（ｓ，1H）
(iv) このようにして得られた混合物57mg
（0.12mmol）のアセトニトリル溶液２mlへ、硝
酸第二セリウムアンモニウム170mgを水１mlに
溶解した液を加え、室温で５分間攪拌後、水を
加え、エーテルにて抽出した。エーテル層を常
法にて処理した後、プレパラテイブ液体クロマ
ト（展開液：塩化メチレン）により２種のジア
ステレオマーを分離すると、Ｏ―メチルナナオ
マイシンＡメチルエステル18mgが黄色結晶とし
て得られた。収率46％。融点142〜143℃（メタ
ノールから再結晶）。 1H -NMR [in deuterated chloroform, δ (ppm)]:
~0.1 (s, 6H), 1.1 (s, 9H), 1.60 (d, 3H,
J=7Hz), 2.2-3.2 (m), 3.70 (s, 3H), 3.73
(s, 3H), 4.00 (s, 3H), 3.5~4.4 (m, 1H),
5.2 (m, 1H), 6.70 (d, 1H, J=8Hz), 7.20
(d, 1H, J=8Hz), 7.60 (d, 1H, J=8
Hz), 9.25 (s, 1H), 9.32 (s, 1H) (iv) 57 mg of the mixture thus obtained
A solution of 170 mg of ceric ammonium nitrate dissolved in 1 ml of water was added to 2 ml of an acetonitrile solution of (0.12 mmol), and after stirring at room temperature for 5 minutes, water was added and extracted with ether. After treating the ether layer in a conventional manner, two diastereomers were separated using preparative liquid chromatography (developing solution: methylene chloride) to obtain 18 mg of O-methyl nanaomycin A methyl ester as yellow crystals. Yield 46%. Melting point 142-143°C (recrystallized from methanol).
1H―NMR〔重クロロホルム中、δ（ppm）〕：
1.54（ｄ，3H，Ｊ＝７Hz），2.12〜2.28（ddd，
2H，Ｊ＝２，11，19Hz），2.60〜2.92（ｄ，2H，
Ｊ＝６Hz；dd，1H，Ｊ＝３，19Hz），3.73（ｓ，
3H），4.00（ｓ，3H），4.16〜4.46（ｍ，1H），
4.85〜5.10（ｍ，1H），7.20〜7.36（ｍ，1H），
7.50〜7.80（ｍ，2H）
赤外スペクトル（液膜法、cm-1）：1735（vs），
1655（vs），1585（vs）
質量スペクトル（20eV、相対強度）：330
（M+、80），257（100），256（85），241（43）
(v) このようにして得られたＯ―メチルナナオマ
イシンＡメチルエステルを、たとえば、テトラ
ヘドロン・レターズ、第21巻4469〜4472ページ
（1980年）に記載の方法に準じて反応処理する
と、融点171〜174℃のナナオマイシンＡが得ら
れた。これは、NMRデータからもナナオマイ
シンＡであることが確認できた。 1H -NMR [in deuterated chloroform, δ (ppm)]:
1.54 (d, 3H, J=7Hz), 2.12~2.28 (ddd,
2H, J=2, 11, 19Hz), 2.60~2.92 (d, 2H,
J = 6Hz; dd, 1H, J = 3, 19Hz), 3.73 (s,
3H), 4.00 (s, 3H), 4.16-4.46 (m, 1H),
4.85-5.10 (m, 1H), 7.20-7.36 (m, 1H),
7.50-7.80 (m, 2H) Infrared spectrum (liquid film method, cm -1 ): 1735 (vs),
1655 (vs), 1585 (vs) Mass spectrum (20eV, relative intensity): 330
(M + , 80), 257 (100), 256 (85), 241 (43) (v) The O-methylnanaomycin A methyl ester thus obtained is described, for example, in Tetrahedron Letters, No. 21 When the reaction was carried out according to the method described in Vol. 4469-4472 (1980), nanaomycin A with a melting point of 171-174°C was obtained. This was confirmed to be nanaomycin A from NMR data.
Claims (1)
ルキル基、フエニル基を示す。） で表わされる化合物とアート錯体形成化合物であ
るトリエチルアルミニウムおよび第３級ブチルリ
チウムを反応させ、ついで０℃以下の温度でカル
ボン酸生成反応に付し、必要に応じて生成物をエ
ステル化することを特徴とする一般式 （式中、Ｒは水素原子、アルキル基を、R1，
R2，R3は前記と同義である。） で表わされる２―シリル化―３―ブテン酸誘導体
の製造法。[Claims] 1. A compound represented by the general formula CH 2 =CHCH 2 SiR 1 R 2 R 3 (wherein R 1 , R 2 , and R 3 are the same or different and represent an alkyl group or a phenyl group) and triethylaluminum and tertiary butyllithium, which are ate complex-forming compounds, and then subjected to a carboxylic acid production reaction at a temperature of 0° C. or lower, and optionally esterification of the product. formula (In the formula, R is a hydrogen atom, an alkyl group, R 1 ,
R 2 and R 3 have the same meanings as above. ) A method for producing a 2-silylated-3-butenoic acid derivative represented by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56128040A JPS5849390A (en) | 1981-08-14 | 1981-08-14 | Silylated butenoic acid derivative and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56128040A JPS5849390A (en) | 1981-08-14 | 1981-08-14 | Silylated butenoic acid derivative and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5849390A JPS5849390A (en) | 1983-03-23 |
| JPH0158195B2 true JPH0158195B2 (en) | 1989-12-11 |
Family
ID=14975019
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56128040A Granted JPS5849390A (en) | 1981-08-14 | 1981-08-14 | Silylated butenoic acid derivative and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5849390A (en) |
-
1981
- 1981-08-14 JP JP56128040A patent/JPS5849390A/en active Granted
Non-Patent Citations (2)
| Title |
|---|
| .J.AM.CHEM.SOC=1977 * |
| J.ORGANOMETAL.CHEM=1975 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5849390A (en) | 1983-03-23 |
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