JPH0564632B2 - - Google Patents
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- Publication number
- JPH0564632B2 JPH0564632B2 JP16936785A JP16936785A JPH0564632B2 JP H0564632 B2 JPH0564632 B2 JP H0564632B2 JP 16936785 A JP16936785 A JP 16936785A JP 16936785 A JP16936785 A JP 16936785A JP H0564632 B2 JPH0564632 B2 JP H0564632B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- group
- hydroxybutenolide
- compound
- present
- 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.)
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- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 8
- 239000003504 photosensitizing agent Substances 0.000 claims description 7
- -1 β-substituted-γ-hydroxybutenolide Chemical class 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 238000000034 method Methods 0.000 description 11
- JZQBAGOECGRTSA-UHFFFAOYSA-N 3-hydroxy-2h-furan-5-one Chemical class OC1=CC(=O)OC1 JZQBAGOECGRTSA-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 229930014626 natural product Natural products 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- IICCLYANAQEHCI-UHFFFAOYSA-N 4,5,6,7-tetrachloro-3',6'-dihydroxy-2',4',5',7'-tetraiodospiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound O1C(=O)C(C(=C(Cl)C(Cl)=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 IICCLYANAQEHCI-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 206010034972 Photosensitivity reaction Diseases 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229930187593 rose bengal Natural products 0.000 description 2
- 229940081623 rose bengal Drugs 0.000 description 2
- STRXNPAVPKGJQR-UHFFFAOYSA-N rose bengal A Natural products O1C(=O)C(C(=CC=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 STRXNPAVPKGJQR-UHFFFAOYSA-N 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical compound C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 description 2
- 125000004665 trialkylsilyl group Chemical group 0.000 description 2
- VOFXXOPWCBSPAA-UPXBXCCMSA-N (+)-Strigol Natural products O(/C=C/1\C(=O)O[C@H]2[C@@H]\1CC=1[C@H](O)CCC(C)(C)C2=1)[C@@H]1OC(=O)C(C)=C1 VOFXXOPWCBSPAA-UPXBXCCMSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- DNVMNEBSCNECGO-ZHOBSPGKSA-N 4-[2-[(1r,6r)-1,6-dimethyl-2-methylidenecyclohex-3-en-1-yl]ethyl]-2-hydroxy-2h-furan-5-one Chemical compound C[C@@H]1CC=CC(=C)[C@]1(C)CCC1=CC(O)OC1=O DNVMNEBSCNECGO-ZHOBSPGKSA-N 0.000 description 1
- 241000192125 Firmicutes Species 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- ARGBKKMNXCMJSK-UHFFFAOYSA-N Strigol Natural products CC1C=C(OC=C2/C3CC4=C(C3OC2=O)C(C)(C)CCC4O)OC1=O ARGBKKMNXCMJSK-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229930002875 chlorophyll Natural products 0.000 description 1
- 235000019804 chlorophyll Nutrition 0.000 description 1
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- YQGOJNYOYNNSMM-UHFFFAOYSA-N eosin Chemical compound [Na+].OC(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C(O)=C(Br)C=C21 YQGOJNYOYNNSMM-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- FGJIDQWRRLDGDB-GMKZXUHWSA-N manoalide Natural products CC(=CCCC1=CC[C@@H](O[C@H]1O)C2=CC(=O)O[C@H]2O)CCC3=C(C)CCCC3(C)C FGJIDQWRRLDGDB-GMKZXUHWSA-N 0.000 description 1
- FGJIDQWRRLDGDB-CPIXEKRISA-N manoalide Chemical compound C=1([C@@H](O[C@H](CC=1)C=1[C@@H](OC(=O)C=1)O)O)CC\C=C(/C)CCC1=C(C)CCCC1(C)C FGJIDQWRRLDGDB-CPIXEKRISA-N 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000007226 seed germination Effects 0.000 description 1
- 229930002368 sesterterpene Natural products 0.000 description 1
- 150000002653 sesterterpene derivatives Chemical class 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- VOFXXOPWCBSPAA-KCNJUGRMSA-N strigol Chemical compound O1C(=O)C(C)=C[C@@H]1O\C=C/1C(=O)O[C@@H]2C(C(C)(C)CC[C@@H]3O)=C3C[C@@H]2\1 VOFXXOPWCBSPAA-KCNJUGRMSA-N 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Furan Compounds (AREA)
Description
【発明の詳細な説明】
本発明は置換された２−トリアルキルシリルフ
ラン化合物を光増感酸素酸化することにより、置
換されたγ−ヒドロキシブテノライド化合物を製
造する方法に関する。
γ−ヒドロキシブテノライド部分はストリゴー
ル（strigol）、マノアライド（manoalide）など、
種々の生物学的活性天然物分子中に存在し、その
部分の形成方法が天然物合成上極めて重要なステ
ツプとなつているが、効率的な合成法は確立され
ていない。
すなわち、本発明は、溶媒及び光増感剤の存在
下で、光照射しながら、
一般式〔〕又は〔〕
【式】又は【式】
（式中Ｒは低級アルキル基を、基〓Ｙは有機置
換基をそれぞれ示す）で表わされる２−トリアル
キルシリルフラン化合物に酸素を作用させること
を特徴とする
一般式〔〕又は〔〕
【式】又は【式】
（式中基〓Ｙは有機置換基を示す）で表わされ
るα又はβ−置換−γ−ヒドロキシブテノライド
の製造法である。
上記一般式〔〕又は〔〕において、Ｒとし
ては例えばメチル基、エチル基、プロピル基、ブ
チル基などの低級アルキル基が挙げられる。
また基〓Ｙとしては、例えば
【式】
【式】【式】
【式】【式】
【式】【式】
（ここでR1は基【式】
を、R2は基【式】を、R3は基
【式】を、R4は基−CH2−Ｏ−CH3をそ
れぞれ示す。）などが挙げられる。
一般式〔〕又は〔〕で表わされる２−トリ
アルキルシリルフラン化合物は、例えば
Tetrahedron Lett.，24，5835（1983），同文献，
25，4451（1984）及びChemistry Lett，479
（1975）に記載された方法で合成又はそこで得ら
れた化合物から誘導される。
本発明の方法においては、一般式に溶媒を用い
光増感剤の存在下で、光照射しながら、２−トリ
アルキルシリルフラン化合物に酸素を作用させて
行なわれる。溶媒は極性、無極性のいずれでもよ
いが、通常例えばメタノール、エタノール、ジク
ロロメタン、クロロホルム、エーテルなどを好ん
で使用することができる。光増感剤としては、例
えばローズベンガル（rose Bengal）、テトラフ
エニルポルフイン、メチレンブルー、クロロフイ
ル、エオシンなどが挙げられ、これらは触媒とし
て働き、その添加量は出発原料に対して0.01〜10
重量％である。
本発明方法における光照射は可視光線を用いて
行なわれ、光源に、例えばヨウ素・ハロゲンラン
プ、タングステンランプ、蛍光燈などが使用でき
る。
本発明の方法においては、一般式〔〕又は
〔〕で表わされる２−トリアルキルシリルフラ
ン化合物の側鎖（基〓Ｙ）によつて反応性が異な
る。すなわち、側鎖に二重結合を含むか否かによ
り、次のように反応条件が異なる。
【表】
このような条件の下に反応して得られた本発明
の生成物をカラムクロマトグラフイーなどで精製
することができる。
本発明方法によると、次式〔〕
において、とくに３−位又は４−位にトリ−及び
テトラー置換オレフインを含む置換基を有するフ
ラン化合物でも、光増感酸素酸化することにより
次式〔〕
において、α−位又はβ−位にトリー及びテトラ
−置換オレフインを含む置換基を有するγ−ヒド
ロキシブテノライドを位置特異的に生成させるこ
とができる特徴がある。
本発明の反応機構は明らかでないが、上記式
〔〕への一重項酸素の１，４−付加反応（上記
式ではC2とC5）によつて生じる次式〔〕で表
わされる化合物において、C2に結合したトリア
ルキルシリル基が、
酸素原子に極めて速やかに転位し、その後水に
よつて水素原子に置き代つた結果、上記式〔〕
で示されるγ−ヒドロキシブテノライドを与える
ものと推定される。つまり、トリアルキルシリル
基が一重項酸素の上記１，４−付加反応を促進す
ると共に式〔〕の化合物から式〔〕の化合物
への効率のよい変換に寄与するため、側鎖につい
ているオレフイン部への一重項酸素による反応よ
りむしろフラン環の選択的酸化を生じさせると思
われる。
本発明によると、出発原料として、３−位又は
４−位に置換基を有する２−トリアルキルシリル
フラン化合物を用いて、簡単かつ高収率でα又は
β−置換−γ−ヒドロキシブテノライドを製造す
ることができる。
こうして得たα又はβ−置換−γ−ヒドロキシ
ブテノライドはそれ自体での生物学的活性を示す
が、本発明の方法は、抗炎症作用並びにグラム陽
性菌に対し、強い抗菌活性作用を有するセスター
テルペン、マノアライドや、種の発芽促進作用を
有する天然物、ストリゴールの製造工程に利用す
ることができる。
次に実施例を例示して、本発明を説明する。
実施例１ （条件Ａ法）
下記第１表に記載の出発化合物No.１の２−トリ
メチルシリルフラン化合物59.9mg（0.21mmol）
のジクロロメタン３ml溶液に光増感剤としてテト
ラフエニルポルフイン0.7mgを加え、−78℃で、１
分間に15mlの割合で酸素を通じながら、300Wの
ヨウ素・ハロゲンランプ（理工科学産業社製、光
化学反応用）にて７分間光照射した。反応混合物
を室温にもどし、溶媒を減圧下に留去後、得られ
た粗生成物をシリカゲルカラムクロマトグラフイ
ー（流出溶媒：ヘキサン／エーテル３／１〜１／
１）により精製し、融点87〜88℃を有する生成物
No.１のγ−ヒドロキシブテノライド48mgを得た。
収率は94％であつた。
実施例２ （条件Ｂ法）
下記第１表に記載の出発化合物No.２の２−トリ
メチルシリルフラン化合物47mg（0.16mmol）の
無水メタノール２ml溶液に光増感剤としてローズ
ベンガル0.7mgを加え、−78℃で、１分間に2.5ml
の割合で酵素を通じながら、300Wのヨウ素・ハ
ロゲンランプにて、亜硝酸ナトリウムのフイルタ
ーを通して、攪拌下で15分間光照射した。反応混
合物を室温にもどし、溶媒を減圧下に留去後、得
られた粗生成物をシリカゲルカラムクロマトグラ
フイー（流出溶媒：ヘキサン／エーテル10／１〜
５／１）により精製し、油状物の生成物No.２のγ
−ヒドロキシブテノライド38mgを得た。収率は93
％であつた。
実施例 ３〜７
実施例１（条件Ａ法）又は実施例２（条件Ｂ法）
と全く同じ条件下に下記第１表記載の出発化合物
No.３〜７に光増感剤を添加、酸素を通じながら、
光照射し、生成物No.３〜７のγ−ヒドロキシブテ
ノライドを得た。
なお、生成物は赤外線（IR）吸収スペクトル、
核磁気共鳴（1H−NMR）吸収スペクトル及び
質量（Mass）スペクトルにてその構造を確認し
た。
以上の結果を第１表に示す。
【表】
【表】 DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing substituted γ-hydroxybutenolide compounds by photosensitized oxygen oxidation of substituted 2-trialkylsilylfuran compounds. The γ-hydroxybutenolide moiety includes strigol, manoalide, etc.
It exists in various biologically active natural product molecules, and the method for forming that moiety is an extremely important step in the synthesis of natural products, but an efficient synthesis method has not been established. That is, in the present invention, in the presence of a solvent and a photosensitizer, while irradiating with light, the general formula A 2-trialkylsilylfuran compound represented by the general formula [] or [] [formula] or [formula] (in which the group 〓Y is an organic substituent) This is a method for producing α- or β-substituted-γ-hydroxybutenolide represented by (indicating a group). In the above general formula [] or [], examples of R include lower alkyl groups such as methyl group, ethyl group, propyl group, and butyl group. In addition, as the group Y, for example, [formula] [formula] [formula] [formula] [formula] [formula] [formula] (where R 1 is the group [formula], R 2 is the group [formula], R 3 represents a group [formula], R 4 represents a group -CH 2 -O-CH 3 , and the like. The 2-trialkylsilylfuran compound represented by the general formula [] or [] is, for example,
Tetrahedron Lett., 24 , 5835 (1983),
25, 4451 (1984) and Chemistry Lett, 479
(1975) or derived from compounds obtained therein. In the method of the present invention, the 2-trialkylsilylfuran compound is exposed to oxygen in the presence of a photosensitizer using a solvent and irradiated with light. The solvent may be polar or non-polar, but methanol, ethanol, dichloromethane, chloroform, ether, etc. are usually preferably used. Examples of photosensitizers include rose Bengal, tetraphenylporphin, methylene blue, chlorophyll, eosin, etc. These act as catalysts, and the amount added is 0.01 to 10% relative to the starting material.
Weight%. Light irradiation in the method of the present invention is carried out using visible light, and examples of light sources that can be used include iodine-halogen lamps, tungsten lamps, and fluorescent lamps. In the method of the present invention, the reactivity differs depending on the side chain (group 〓Y) of the 2-trialkylsilylfuran compound represented by the general formula [] or []. That is, the reaction conditions differ as follows depending on whether the side chain contains a double bond or not. [Table] The product of the present invention obtained by reaction under such conditions can be purified by column chromatography or the like. According to the method of the present invention, the following formula [] In particular, even furan compounds having substituents including tri- and tetra-substituted olefins at the 3-position or 4-position can be converted to the following formula [] by photosensitized oxygen oxidation. The method has the feature that γ-hydroxybutenolide having a substituent including tri- and tetra-substituted olefins at the α-position or β-position can be produced positionally specifically. Although the reaction mechanism of the present invention is not clear, in the compound represented by the following formula [] produced by the 1,4-addition reaction of singlet oxygen to the above formula [] (C2 and C5 in the above formula), C2 is The bonded trialkylsilyl group is As a result of extremely rapid rearrangement into oxygen atoms and subsequent replacement by hydrogen atoms with water, the above formula []
It is estimated that it gives the γ-hydroxybutenolide shown in In other words, since the trialkylsilyl group promotes the above-mentioned 1,4-addition reaction of singlet oxygen and contributes to efficient conversion of the compound of formula [] to the compound of formula [], the olefin moiety attached to the side chain This appears to result in selective oxidation of the furan ring rather than reaction with singlet oxygen to . According to the present invention, α- or β-substituted-γ-hydroxybutenolide can be easily and in high yield using a 2-trialkylsilylfuran compound having a substituent at the 3- or 4-position as a starting material. can be manufactured. Although the α- or β-substituted-γ-hydroxybutenolide thus obtained exhibits biological activity by itself, the method of the present invention has anti-inflammatory activity and strong antibacterial activity against Gram-positive bacteria. It can be used in the production process of sesterterpenes, manoalides, and strigols, which are natural products that promote seed germination. Next, the present invention will be described by way of examples. Example 1 (Condition A method) 59.9 mg (0.21 mmol) of the 2-trimethylsilylfuran compound of starting compound No. 1 listed in Table 1 below.
Add 0.7 mg of tetraphenylporphine as a photosensitizer to 3 ml of dichloromethane solution of
Light was irradiated for 7 minutes using a 300W iodine/halogen lamp (manufactured by Riko Kagaku Sangyo Co., Ltd., for photochemical reactions) while passing oxygen at a rate of 15 ml per minute. After returning the reaction mixture to room temperature and distilling off the solvent under reduced pressure, the obtained crude product was subjected to silica gel column chromatography (eluent solvent: hexane/ether 3/1 to 1/
Product purified by 1) and having a melting point of 87-88°C
48 mg of No. 1 γ-hydroxybutenolide was obtained.
The yield was 94%. Example 2 (Condition B method) To a 2 ml solution of anhydrous methanol containing 47 mg (0.16 mmol) of the 2-trimethylsilylfuran compound of starting compound No. 2 listed in Table 1 below, 0.7 mg of rose bengal was added as a photosensitizer, and - 2.5ml per minute at 78℃
While passing the enzyme through the enzyme at a ratio of 200 to 3000, the mixture was irradiated with light for 15 minutes under stirring using a 300W iodine/halogen lamp through a sodium nitrite filter. The reaction mixture was returned to room temperature, the solvent was distilled off under reduced pressure, and the resulting crude product was subjected to silica gel column chromatography (eluent solvent: hexane/ether 10/1~
5/1), and the γ of oily product No. 2 was purified by
-38 mg of hydroxybutenolide was obtained. Yield is 93
It was %. Examples 3 to 7 Example 1 (Condition A method) or Example 2 (Condition B method)
The starting compounds listed in Table 1 below under exactly the same conditions as
Add photosensitizer to No. 3 to 7, pass oxygen,
Light irradiation was performed to obtain γ-hydroxybutenolides of products Nos. 3 to 7. The product has an infrared (IR) absorption spectrum,
Its structure was confirmed by nuclear magnetic resonance (1H-NMR) absorption spectrum and mass spectrum. The above results are shown in Table 1. [Table] [Table]
Claims (1)
ら、 一般式〔〕又は〔〕 【式】又は【式】 〔式中Ｒは炭素数１−４の低級アルキル基を、
基〓Ｙは、【式】 【式】【式】 【式】【式】 【式】又は 【式】（ここで、R1は基 【式】を、R2は基 【式】を、R3は基【式】 を、R4は基−CH2−Ｏ−CH3を示す）をそれぞ
れ示す〕で表わされる２−トリアルキルシリルフ
ラン化合物に酸素を作用させることを特徴とする 一般式〔〕又は〔〕 【式】又は【式】 〔式中基〓Ｙは、【式】 【式】【式】 【式】【式】 【式】又は 【式】（ここで、R1は基 【式】を、R2は基 【式】を、R3は基【式】 を、R4は基−CH2−Ｏ−CH3を示す）を示す〕
で表わされるα又はβ−置換−γ−ヒドロキシブ
テノライドの製造法。[Claims] 1. In the presence of a solvent and a photosensitizer, while irradiating with light, a compound of the general formula [] or [] [Formula] or [Formula] [wherein R is lower alkyl having 1 to 4 carbon atoms] The base,
Group Y is [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] or [Formula] (where R 1 is the group [Formula], R 2 is the group [Formula], R 3 represents a group [Formula] and R 4 represents a group -CH 2 -O-CH 3 ), respectively]. ] or [] [Formula] or [Formula] [In the formula, Y is [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] or [Formula] (where R 1 is a group [ [Formula], R 2 represents a group [Formula], R 3 represents a group [Formula], R 4 represents a group -CH 2 -O-CH 3 )]
A method for producing α- or β-substituted-γ-hydroxybutenolide represented by
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16936785A JPS6229581A (en) | 1985-07-30 | 1985-07-30 | Production of alpha or beta-substituted-gamma-hydroxybutenolide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16936785A JPS6229581A (en) | 1985-07-30 | 1985-07-30 | Production of alpha or beta-substituted-gamma-hydroxybutenolide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6229581A JPS6229581A (en) | 1987-02-07 |
| JPH0564632B2 true JPH0564632B2 (en) | 1993-09-16 |
Family
ID=15885269
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16936785A Granted JPS6229581A (en) | 1985-07-30 | 1985-07-30 | Production of alpha or beta-substituted-gamma-hydroxybutenolide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6229581A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5082954A (en) * | 1987-06-08 | 1992-01-21 | Allergan, Inc. | Intermediates and processes for preparing 4-substituted 2-5(H)-furanones as anti-inflammatory agents |
-
1985
- 1985-07-30 JP JP16936785A patent/JPS6229581A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6229581A (en) | 1987-02-07 |
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