JPH0331699B2 - - Google Patents
Info
- Publication number
- JPH0331699B2 JPH0331699B2 JP4120982A JP4120982A JPH0331699B2 JP H0331699 B2 JPH0331699 B2 JP H0331699B2 JP 4120982 A JP4120982 A JP 4120982A JP 4120982 A JP4120982 A JP 4120982A JP H0331699 B2 JPH0331699 B2 JP H0331699B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- optically active
- compound represented
- reaction
- arethrolone
- 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- -1 ether compound Chemical class 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- BZKFMUIJRXWWQK-UHFFFAOYSA-N Cyclopentenone Chemical compound O=C1CCC=C1 BZKFMUIJRXWWQK-UHFFFAOYSA-N 0.000 claims 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 230000000749 insecticidal effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- OAMZXMDZZWGPMH-UHFFFAOYSA-N ethyl acetate;toluene Chemical compound CCOC(C)=O.CC1=CC=CC=C1 OAMZXMDZZWGPMH-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000002728 pyrethroid Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZCVAOQKBXKSDMS-AQYZNVCMSA-N (+)-trans-allethrin Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OC1C(C)=C(CC=C)C(=O)C1 ZCVAOQKBXKSDMS-AQYZNVCMSA-N 0.000 description 1
- JWWCLCNPTZHVLF-ZJDVBMNYSA-N (3as,4s,6r,6as)-6-[(4r)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyl-3a,4,6,6a-tetrahydrofuro[3,4-d][1,3]dioxol-4-ol Chemical compound O1C(C)(C)OC[C@@H]1[C@@H]1[C@@H]2OC(C)(C)O[C@@H]2[C@@H](O)O1 JWWCLCNPTZHVLF-ZJDVBMNYSA-N 0.000 description 1
- FMTFEIJHMMQUJI-NJAFHUGGSA-N 102130-98-3 Natural products CC=CCC1=C(C)[C@H](CC1=O)OC(=O)[C@@H]1[C@@H](C=C(C)C)C1(C)C FMTFEIJHMMQUJI-NJAFHUGGSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- OMIHGPLIXGGMJB-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]hepta-1,3,5-triene Chemical compound C1=CC=C2OC2=C1 OMIHGPLIXGGMJB-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229940024113 allethrin Drugs 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Saccharide Compounds (AREA)
Description
本発明は、ピレスロイド系殺虫化合物の重要な
中間体である光学活性アレスロロン（２−アリル
−３−メチル−２−シクロペンテン−１−オン）
の製法に関する。
アレスロロンはアレスリンに代表される種々の
ピレスロイド系殺虫化合物の重要なアルコール成
分であり、特にその（＋）−体はエステルとして
の殺虫活性が高いことが知られている。
従来、光学活性アレスロロンの製造方法につい
ては、dl−アレスロロンをコハク酸のハーフエ
ステルとして光学分割する方法（特開昭48−
75545号公報）、dl−アレスロロンをフタル酸の
ハーフエステルとして光学分割する方法（特開昭
49−124046号公報）、dl−アレスロロンより誘
導されるケトンを不斉還元する方法（特開昭54−
79252号公報）、dl−アレスロロンを光学活性な
ラクトンとのアセタールとしたのち、分離、分解
し光学活性アレスロロンとする方法（特開昭54−
130556号公報）等が知られている。
しかしながら上記方法はいずれも多くの工程を
必要とすること、高価な試薬を用いなければなら
ないこと、繁雑な操作を必要とすること等、必ず
しも充分とは言い難い。
このような状況の下に、本発明者らは光学活性
アレスロロンの製造方法について鋭意研究した結
果、従来の経路とは全く異なる新規で有利な製法
を見出し、本発明を完成するに至つた。
すなわち本発明は式（）
で示される２−アリル−３−ヒドロキシ−３−メ
チル−４−シクロペンテン−１−オンと２，３：
５，６−ジ−Ｏ−イソプロピリデン−α−Ｄ−マ
ンノフラノースを作用させて、式（）
で示されるエーテル化合物に導き、次いで該生成
物から式（）
で示される光学活性なエーテル化合物を分離取得
した後、これを酸性条件下で加水分解することに
よる光学活性アレスロロンの製法を提供するもの
である。
以下、本発明を詳細に説明する。
本発明において原料として用いられる前記式
（）で示される化合物は以下に示す方法により
容易に合成することができる。
またもう一方の原料である２，３：５，６−ジ−
Ｏ−イソプロピリデン−α−Ｄ−マンノフラノー
スは、Ｄ−マンノースとアセトンからBer.，60，
232（1927）の方法に従つて容易に合成することが
できる。
式（）で示される化合物と２，３：５，６−
ジ−Ｏ−イソプロピリデン−α−Ｄ−マンノフラ
ノースとを反応させるに際しては、塩基性触媒の
存在下に溶媒を用いて実施される。この時、２，
３：５，６−ジ−Ｏ−イソプロピリデン−α−マ
ンノフラノースの使用量は原料の式（）で示さ
れる化合物に対し、１〜10倍モルの範囲であり、
使用される溶媒は例えばテトラヒドロフラン、ベ
ンゼン、エーテル、アセトン、ジオキサン等の反
応に不活性な溶媒の単独もしくは混合物が挙げら
れる。その使用量は特に制限はないが、原料の式
（）で示される化合物に対し0.5〜10重量倍が適
当である。
また、使用される塩基性触媒としては例えばナ
トリウム、カリウム、リチウム等のアルカリ金
属、あるいはこれらのアルコラート、水素化物、
アミド類等の金属塩、ピリジン、トリエチルアミ
ン等の第３級アミンが例示され、これらは単独あ
るいは２種以上の混合物として使用することがで
き、その使用量は原料の式（）で示される化合
物に対し1/500〜1/2重量倍の範囲である。
反応温度は−10〜150℃の範囲で任意であるが、
好ましくは０〜70℃の範囲である。また、反応時
間については特に制限はない。
かかる反応によつて中間体である式（）で示
されるエーテル化合物が容易にかつ好収率で得ら
れ、これを未精製のままで次の物理的な分離手段
に付することによつて、式（）で示される光学
活性なエーテル化合物を得ることができる。この
時、分離手段としては例えばカラムクロマトグラ
フイーなどの手段を挙げることができる。
カラムクロマトグラフイーに用いられる充填剤
はアルミナ、シリカゲル等通常のものがあげら
れ、これらは式（）で示される化合物に対し５
〜40倍重量使用される。流出溶媒としては、上記
ジアステレオマーの分離に適当な系、例えばトル
エン−酢酸エチル系クロロホルム、ベンゼン−エ
ーテル系等があげられる。
このようにして得られた式（）で示される光
学活性なエーテル化合物は、メタノール、エタノ
ール、ジオキサン、テトラヒドロフランなどの含
水溶媒中、酸触媒の存在下に加水分解することに
より、光学活性なアレスロロンを得ることができ
る。
該反応において使用される酸触媒は例えば硫
酸、塩酸、トルエンスルホン酸、酢酸等の通常の
酸が用いられる。また、反応温度は０〜100℃で
任意であるが、好ましくは10〜70℃の範囲であ
る。
反応時間については特に制限はない。
このようにして得られた光学活性なアレスロロ
ンは必要に応じ、たとえば、抽出、分液、濃縮、
蒸留等により容易に精製することができる。
以下実施例により本発明を説明する。
実施例
撹拌装置、温度計を装着した四ツ口フラスコに
２，３：５，６−ジ−Ｏ−イソプロピリデン−α
−Ｄ−マンノフラノース15ｇおよびテトラヒドロ
フラン15mlを加え、冷却下に水素化ナトリウム
（60％パラフイン懸濁品）0.2ｇを加え10〜15℃に
冷却する。次に２−アリル−３−ヒドロキシ−３
−メチル−４−シクロペンテン−１−オン2.9ｇ
を１時間を要し撹拌しながら滴下する。同温度で
さらに２時間撹拌した後室温にて２時間撹拌す
る。反応終了後、1N−塩酸水溶液にて、反応混
合物を中和した後テトラヒドロフランを留去す
る。残渣を酢酸エチルにて抽出後濃縮し、粗結晶
18ｇを得た。
次に上で得た粗結晶を、シリカゲル300ｇ、溶
媒トルエン−酢酸エチル（10／３）の系でクロマ
ト精製する。流出した目的の光学活性なエーテル
体をフラクシヨン１〜３に分割した。各フラクシ
ヨンの収量は以下のとうりであつた。
The present invention relates to optically active allethrone (2-allyl-3-methyl-2-cyclopenten-1-one), which is an important intermediate for pyrethroid insecticidal compounds.
Concerning the manufacturing method. Allethrone is an important alcohol component of various pyrethroid insecticidal compounds represented by allethrin, and its (+)-isomer is known to have particularly high insecticidal activity as an ester. Conventionally, the method for producing optically active arethrolone has been a method in which dl-arethrolone is optically resolved as a half ester of succinic acid (Japanese Unexamined Patent Application Publication No. 1973-1972).
75545), a method for optically resolving dl-arethrolone as a half ester of phthalic acid (Japanese Unexamined Patent Publication No. 75545),
49-124046), a method for asymmetric reduction of ketones derived from dl-arethrolone (Japanese Patent Application Laid-open No. 1983-
79252), a method in which dl-allethrone is made into an acetal with an optically active lactone, and then separated and decomposed to produce optically active allethrone (Japanese Patent Application Laid-open No. 1987-
130556) etc. are known. However, all of the above methods require many steps, require the use of expensive reagents, and require complicated operations, so they are not necessarily sufficient. Under these circumstances, the present inventors conducted intensive research on the method for producing optically active allethrone, and as a result, discovered a new and advantageous method for producing optically active allethrone, which is completely different from the conventional route, and completed the present invention. That is, the present invention is based on the formula () 2-allyl-3-hydroxy-3-methyl-4-cyclopenten-1-one and 2,3:
By acting with 5,6-di-O-isopropylidene-α-D-mannofuranose, the formula () Then, from this product, the formula () is obtained. The present invention provides a method for producing optically active allethrone by separating and obtaining an optically active ether compound represented by the formula and then hydrolyzing it under acidic conditions. The present invention will be explained in detail below. The compound represented by the formula () used as a raw material in the present invention can be easily synthesized by the method shown below. Also, the other raw material, 2,3:5,6-di-
O-isopropylidene-α-D-mannofuranose is obtained from D-mannose and acetone, Ber., 60 ,
232 (1927). A compound represented by formula () and 2,3:5,6-
The reaction with di-O-isopropylidene-α-D-mannofuranose is carried out using a solvent in the presence of a basic catalyst. At this time, 2,
3: The amount of 5,6-di-O-isopropylidene-α-mannofuranose used is in the range of 1 to 10 times the mole of the compound represented by the raw material formula (),
Examples of the solvent used include tetrahydrofuran, benzene, ether, acetone, dioxane, and other solvents inert to the reaction, either alone or as a mixture. The amount used is not particularly limited, but it is suitably 0.5 to 10 times the weight of the compound represented by the formula () as a raw material. In addition, the basic catalysts used include, for example, alkali metals such as sodium, potassium, and lithium, or their alcoholates, hydrides,
Examples include metal salts such as amides, tertiary amines such as pyridine and triethylamine, and these can be used alone or as a mixture of two or more, and the amount used depends on the compound represented by the formula () of the raw material. It is in the range of 1/500 to 1/2 times the weight. The reaction temperature is arbitrary in the range of -10 to 150°C, but
Preferably it is in the range of 0 to 70°C. Moreover, there is no particular restriction on the reaction time. Through such a reaction, the intermediate ether compound represented by the formula () can be easily obtained in a good yield, and by subjecting this unpurified to the next physical separation means, An optically active ether compound represented by the formula () can be obtained. At this time, examples of separation means include column chromatography. Typical packing materials used in column chromatography include alumina and silica gel, which have a 5%
~40 times the weight used. Examples of the effluent solvent include systems suitable for separating the above diastereomers, such as toluene-ethyl acetate, chloroform, benzene-ether, and the like. The optically active ether compound represented by the formula () thus obtained is hydrolyzed in a water-containing solvent such as methanol, ethanol, dioxane, or tetrahydrofuran in the presence of an acid catalyst to form optically active arethrolone. Obtainable. As the acid catalyst used in this reaction, common acids such as sulfuric acid, hydrochloric acid, toluenesulfonic acid, and acetic acid are used. Further, the reaction temperature is arbitrary in the range of 0 to 100°C, but preferably in the range of 10 to 70°C. There is no particular restriction on the reaction time. The optically active arethrolone thus obtained can be extracted, separated, concentrated,
It can be easily purified by distillation or the like. The present invention will be explained below with reference to Examples. Example 2,3:5,6-di-O-isopropylidene-α was placed in a four-necked flask equipped with a stirrer and a thermometer.
Add 15 g of -D-mannofuranose and 15 ml of tetrahydrofuran, and while cooling, add 0.2 g of sodium hydride (60% paraffin suspension) and cool to 10-15°C. Then 2-allyl-3-hydroxy-3
-Methyl-4-cyclopenten-1-one 2.9g
was added dropwise while stirring for 1 hour. The mixture was further stirred at the same temperature for 2 hours, and then at room temperature for 2 hours. After the reaction is completed, the reaction mixture is neutralized with a 1N aqueous hydrochloric acid solution, and then tetrahydrofuran is distilled off. The residue was extracted with ethyl acetate and concentrated to obtain crude crystals.
Obtained 18g. Next, the crude crystals obtained above are purified by chromatography using 300 g of silica gel and a solvent of toluene-ethyl acetate (10/3). The objective optically active ether which flowed out was divided into fractions 1 to 3. The yield of each fraction was as follows.
【表】
次にフラクシヨン１で得た抽状物2.0ｇをエタ
ノール10c.c.に溶解し、1N−塩酸水２mlを加え、
20〜40℃にて２時間撹拌する。
反応終了後、1N−NaOH水溶液にて中和し、
メチルイソブチルケトン10ml、水10mlを加え抽出
する。水層はさらにメチルイソブチルケトン10ml
にて２回抽出する。
有機層を併せ濃縮し、さらにカラムクロマトグラ
フイーにて精製して（＋）−アレスロロン0.74ｇ
を得た。光学純度を測定するとその（＋）体過剰
率は93.0％であつた。
（過剰率の測定はAgric.Biol.Chem.，41(10)，
2003（1977）による。）
同様にフラクシヨン２および３についても加水
分解し、以下の結果を得た。[Table] Next, dissolve 2.0 g of the extract obtained in fraction 1 in 10 c.c. of ethanol, add 2 ml of 1N hydrochloric acid,
Stir for 2 hours at 20-40°C. After the reaction is completed, neutralize with 1N-NaOH aqueous solution,
Add 10ml of methyl isobutyl ketone and 10ml of water and extract. Add 10ml of methyl isobutyl ketone to the aqueous layer.
Extract twice. The organic layers were combined and concentrated, and further purified by column chromatography to obtain 0.74 g of (+)-arethrolone.
I got it. When the optical purity was measured, the (+) excess was found to be 93.0%. (Measurement of excess rate can be found in Agric.Biol.Chem., 41 (10),
According to 2003 (1977). ) Fractions 2 and 3 were similarly hydrolyzed, and the following results were obtained.
Claims (1)
４−シクロペンテン−１−オンに２，３：５，６
−ジ−Ｏ−イソプロピリデン−α−Ｄ−マンノフ
ラノースを作用させて式 で示されるエーテル化合物に導き、次いで該生成
物から式 で示される光学活性なエーテル化合物を分離取得
した後、これを酸性条件下で加水分解することを
特徴とする光学活性アレスロロンの製法。[Claims] 1 2-allyl-3-hydroxy-3-methyl-
2,3:5,6 to 4-cyclopenten-1-one
-di-O-isopropylidene-α-D-mannofuranose to form the formula and then from this product the formula A method for producing optically active arethrolone, which comprises separating and obtaining an optically active ether compound represented by the formula, and then hydrolyzing it under acidic conditions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4120982A JPS58157798A (en) | 1982-03-15 | 1982-03-15 | Preparation of optically active allethrolone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4120982A JPS58157798A (en) | 1982-03-15 | 1982-03-15 | Preparation of optically active allethrolone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58157798A JPS58157798A (en) | 1983-09-19 |
| JPH0331699B2 true JPH0331699B2 (en) | 1991-05-08 |
Family
ID=12602010
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4120982A Granted JPS58157798A (en) | 1982-03-15 | 1982-03-15 | Preparation of optically active allethrolone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58157798A (en) |
-
1982
- 1982-03-15 JP JP4120982A patent/JPS58157798A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58157798A (en) | 1983-09-19 |
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