JPH0466550A - Production of optically active 2-cyclopentenones - Google Patents
Production of optically active 2-cyclopentenonesInfo
- Publication number
- JPH0466550A JPH0466550A JP17574190A JP17574190A JPH0466550A JP H0466550 A JPH0466550 A JP H0466550A JP 17574190 A JP17574190 A JP 17574190A JP 17574190 A JP17574190 A JP 17574190A JP H0466550 A JPH0466550 A JP H0466550A
- Authority
- JP
- Japan
- Prior art keywords
- optically active
- general formula
- cyclopentenones
- complex
- cyclopentenone
- 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.)
- Granted
Links
- BZKFMUIJRXWWQK-UHFFFAOYSA-N Cyclopentenone Chemical class O=C1CCC=C1 BZKFMUIJRXWWQK-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 230000003287 optical effect Effects 0.000 claims abstract description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 3
- 150000003892 tartrate salts Chemical class 0.000 claims abstract 8
- -1 respectively Chemical group 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical group 0.000 claims description 4
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 3
- 239000002994 raw material Substances 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 239000013543 active substance Substances 0.000 abstract description 2
- 125000001589 carboacyl group Chemical group 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- 150000003899 tartaric acid esters Chemical class 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 8
- 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
- 239000003208 petroleum Substances 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 230000009918 complex formation Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- DHNDDRBMUVFQIZ-UHFFFAOYSA-N 4-hydroxycyclopent-2-en-1-one Chemical compound OC1CC(=O)C=C1 DHNDDRBMUVFQIZ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000000068 chlorophenyl group Chemical group 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000001207 fluorophenyl group Chemical group 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-M 3-Methylbutanoic acid Natural products CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N Methyl 3-methylbutanoate Chemical compound COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-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
- FGKJLKRYENPLQH-UHFFFAOYSA-N alpha-isocaproic acid Natural products CC(C)CCC(O)=O FGKJLKRYENPLQH-UHFFFAOYSA-N 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
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloro-acetic acid Natural products OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 1
- 229960005215 dichloroacetic acid Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002168 ethanoic acid esters Chemical class 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- HNBDRPTVWVGKBR-UHFFFAOYSA-N methyl pentanoate Chemical compound CCCCC(=O)OC HNBDRPTVWVGKBR-UHFFFAOYSA-N 0.000 description 1
- LABTWGUMFABVFG-UHFFFAOYSA-N methyl propenyl ketone Chemical class CC=CC(C)=O LABTWGUMFABVFG-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229950010765 pivalate Drugs 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 150000003151 propanoic acid esters Chemical class 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〈従来技術〉
一般式（１）
し、＊印は不斉炭素原子であることを表す。）で示され
る光学活性２−シクロペンテノン類は、極めて貴重な生
理活性物質であるプロスタグランジン類製造の重要な原
料であるが、その製造は大変困難であり、従来より工業
的に容易に、かつ高光学純度で収率よく光学活性２−シ
クロペンテノンを製造する方法が強く望まれていた。と
りわけ−Ｃ式（＋）でＲが水素原子である化合物につい
ては、有効な分割方法が知られていなかった。[Detailed Description of the Invention] <Prior Art> General formula (1) where the * mark represents an asymmetric carbon atom. ) The optically active 2-cyclopentenones shown in There has been a strong desire for a method for producing optically active 2-cyclopentenone with high optical purity and good yield. In particular, no effective splitting method has been known for compounds in which R is a hydrogen atom in the -C formula (+).
〈発明が解決しようとする課題〉
このようなことから、本発明者は光学活性２シクロペン
テノン類を工業的に容易に、かつ高光学純度で収率よく
製造する方法について鋭意研究を行った結果、本発明を
完成するに至った。<Problem to be solved by the invention> In view of the above, the present inventor conducted extensive research on a method for industrially easily producing optically active 2-cyclopentenones with high optical purity and good yield. As a result, the present invention was completed.
〈課題を解決するだめの手段〉
即ち本発明は、一般式（１）で示される光学活性２−シ
クロペンテノン類と、−Ｅ式（ＩＩ）（式中、Ｒはハロ
ゲンで置換さねてい一ζもよい炭素数２−６の−ｊ′ル
カノイル基または水素原子を表１イ 尺
（式中、Ｒ，およびＲ７はそれぞれ低級アルキル基また
はＲ１とＲ２が結合して一緒ムこなったアルキレン基を
表し、Ｒｏはフェニル基、ハロゲン化フェニル基または
低級アルキルフェニル基を表し、率印は不斉炭素原子で
あることを表す。）で示さねる光学活性酒石酸誘導体と
が結合１−でなる光学活性シクロペンテノン錯体を分解
することを特徴とする一般式（１）で示される光学活性
２ｇ／クロベンラーノン類の製造法に関するもので」）
る。<Means for Solving the Problem> That is, the present invention provides optically active 2-cyclopentenones represented by general formula (1) and -E formula (II) (wherein R is not substituted with halogen). Table 1 shows the -j'lukanoyl group or hydrogen atom having 2 to 6 carbon atoms (wherein R and R7 are each a lower alkyl group or an alkylene group formed by bonding R1 and R2 together). group, Ro represents a phenyl group, a halogenated phenyl group, or a lower alkylphenyl group, and the index symbol represents an asymmetric carbon atom. This relates to a method for producing optically active 2g/clobenranones represented by general formula (1), which is characterized by decomposing an active cyclopentenone complex.
Ru.
尚、オ記一般式（＋）と一般式（ＩＩ）からなる光学活
性シクロペンテノン錯体は従来全く知られておらず、本
発明者が初めて見出した新規化合物である。Incidentally, the optically active cyclopentenone complex consisting of general formula (+) and general formula (II) has not been known at all, and is a new compound discovered for the first time by the present inventor.
また、上記一般式（Ｕ）で示される光学活性酒石酸誘導
体が一般式（Ｉｌｌ）
（式中、Ｒは前記と同し意味を表す。）で示される２−
シクロペンテノン類の光学活性体のいずれか一方のみを
選択的に取り込んで安定な錯体を形成することは従来よ
り全く知られていない。Further, the optically active tartaric acid derivative represented by the above general formula (U) is a 2-
It has not been known to form a stable complex by selectively incorporating only one of the optically active forms of cyclopentenones.
本発明において、原ネ４となる２−シクロペンテノン類
のうちＲがハロゲンで置換されていてもよい炭素数２〜
６のアルカノイル基を示ずエステル類は、Ｒが水素原子
である２−フクロベンテン４−オン−１−オールとハロ
ゲンで置換されていてもよい炭素数２へ−６のカルボン
酸の酸ハライド（例えは酸りＬ１ライド）を、塩基の存
在下に反応させるこ七により容易に！！８！造すること
ができる。In the present invention, among the 2-cyclopentenones serving as base element 4, R has 2 to 2 carbon atoms, which may be substituted with halogen.
The esters without an alkanoyl group of 6 are 2-fuclobenten-4-one-1-ol in which R is a hydrogen atom and the acid halide of a carboxylic acid having 2 to 6 carbon atoms which may be substituted with a halogen ( For example, acid L1 ride) can be easily reacted in the presence of a base! ! 8! can be built.
かかる２−７クロベンテンー４−オン−１−オルのエス
テル類としては、例えば酢酸エステル、プロピオン酸エ
ステル、ｎ−酪酸エステル、イソ酪酸エステル、ｎ−吉
草酸エステル、イソ吉草酸エステル、ピバリン酸エステ
ル、メチルエチル酢酸エステル、ｎ−カプロン酸エステ
ル、イソカプロン酸エステル、β−メチル占草酸エステ
ル、ｔｅｒ Ｌ−フチル酢酸エステル、ジエチル酢酸エ
ステル、メチル−ｎ−プロピル酢酸エステル、メチルイ
ソプロピル酢酸エステル、２−メチルブタン−２−カル
ボン酸エステル、クロル酢酸エステル、ブロム酢酸エス
テル、ジクロル酢酸エステル、β−クロルプロピオン酸
エステル、Ｔ−クロル酪酸エステル等が例示される。Such esters of 2-7 clobenten-4-one-1-ol include, for example, acetate, propionate, n-butyrate, isobutyrate, n-valerate, isovalerate, pivalate, Methyl ethyl acetate, n-caproic acid ester, isocaproic acid ester, β-methyl dianthyl acetate, ter L-phthyl acetate, diethyl acetate, methyl-n-propylacetate, methylisopropylacetate, 2-methylbutane- Examples include 2-carboxylic acid ester, chloroacetic acid ester, bromoacetic acid ester, dichloroacetic acid ester, β-chloropropionic acid ester, and T-chlorobutyric acid ester.
また、もう一方の原料である一般式（ＩＩ）で示される
光学活性酒石酸誘導体は、例えば特開昭５９２２４６９
号公報に記載の方法により容易に合成することができる
。In addition, the optically active tartaric acid derivative represented by the general formula (II), which is the other raw material, is disclosed in, for example, JP-A-5922469.
It can be easily synthesized by the method described in the publication.
尚、該一般式（ＩＩ）において、置換基Ｒ゛としテ具体
的にはクロロフェニル基、フロロフェニル基、ナフチル
基、トルイル基、エチルフェニル基などが例示される。In the general formula (II), specific examples of the substituent R' include a chlorophenyl group, a fluorophenyl group, a naphthyl group, a tolyl group, and an ethylphenyl group.
またＲ ＋ Ｒｚ としてはメチル基、エチル基、
プロピル基、ブチル基、ペンチル基等がそれぞれ例示さ
れ、さらにＲ１とＲ２が結合して一緒になったブチレン
基、ペンチレン基、ヘキシレン基等を形成した置換基な
どが例示される。Moreover, R + Rz includes a methyl group, an ethyl group,
Examples include a propyl group, a butyl group, a pentyl group, etc., and further examples include substituents in which R1 and R2 are combined to form a butylene group, a pentylene group, a hexylene group, etc.
光学活性シクロペンテノン錯体の製造は、２シクロペン
テノン類と光学活性酒石酸ｇ ＩＩ体とを有機溶媒中で
接触させて２−シクロペンテノン類の光学活性体のいず
れか一方と光学活性酒石酸誘導体とが結合してなる錯体
を析出させ、これを分離することにより行われる。The optically active cyclopentenone complex is produced by contacting 2-cyclopentenones and optically active tartaric acid g II form in an organic solvent, and then combining either one of the optically active forms of 2-cyclopentenones and an optically active tartaric acid derivative. It is carried out by precipitating a complex formed by bonding and separating it.
この反応において、２−シクロペンテノン類としてはラ
セミ体あるいはいずれか一方の光学活性体が過剰にある
光学活性混合物のいずれであってもよいが、−船釣には
ラセミ体が用いられる。In this reaction, the 2-cyclopentenone may be either a racemate or an optically active mixture containing an excess of one of the optically active forms, but the racemic form is used for boat fishing.
この反応における原料２−シクロペンテノン類の使用量
は、錯体を形成せしめようとする光学活性２−シクロペ
ンテノン類の原料エステル類中の含量に応して適宜選ば
れるが、通常は光学活性酒石酸誘導体に対して錯体を形
成せしめようとする光学活性２−シクロペンテノン類が
０．５〜２倍当量である。従って、原料２−シクロペン
テノン類としてラセミ体を使用する場合は、光学活性酒
石酸誘導体に対して１〜４倍当量である。The amount of the raw material 2-cyclopentenone used in this reaction is appropriately selected depending on the content of the optically active 2-cyclopentenone to form a complex in the raw material ester, but usually the optically active The optically active 2-cyclopentenone to form a complex with the tartaric acid derivative is 0.5 to 2 equivalents. Therefore, when a racemate is used as the raw material 2-cyclopentenone, it is used in an equivalent amount of 1 to 4 times the optically active tartaric acid derivative.
この錯体形成反応に使用される光学活性酒石酸誘導体と
しては、前記した如き置換基Ｒ′を有する化合物が使用
されるが、錯体形成能、収率、生成錯体の分解により得
られる光学活性２−シクロペンテノン類の光学純度等か
ら考えて、置換基Ｒがフェニル基、クロロフェニル基、
フロロフェニル基を有する光学活性酒石酸誘導体が好ま
しく使用される。また、Ｒ＋ Ｒ−としてはＲｏと
Ｒ２とが一緒になったブチレン基、ペンチレン基が、さ
らにＲが水素原子である２−シクロペンテノン類につい
ては特に、ＲＩ Ｒ２がともにエチル基であるものが
好ましく使用される。As the optically active tartaric acid derivative used in this complex-forming reaction, a compound having a substituent R' as described above is used. Considering the optical purity of pentenones, the substituent R is a phenyl group, a chlorophenyl group,
Optically active tartaric acid derivatives having a fluorophenyl group are preferably used. Furthermore, as R+ R-, there are butylene and pentylene groups in which Ro and R2 are combined, and for 2-cyclopentenones where R is a hydrogen atom, especially those where RI and R2 are both ethyl groups. Preferably used.
また、２−シクロペンテン−４−オン−１−オールのエ
ステル類としては、効率よく錯体を形成し、収率的にも
良好なものとして、前記した如き２−シクロペンテン−
４−オン−１−オールのエステル類のうちでも、特に酢
酸エステル類、プロピオン酸エステルが好ましく使用さ
れる。In addition, as esters of 2-cyclopenten-4-one-1-ol, 2-cyclopenten-4-one-1-ol, such as those described above, can be used as esters that form complexes efficiently and have good yields.
Among the esters of 4-one-1-ol, acetic acid esters and propionic acid esters are particularly preferably used.
この錯体形成反応に使用される有機溶媒としては、エチ
ルエーテル、ヘンゼン、トルエン、アセトニトリル、酢
酸エチル、四塩化炭素、クロロホルム、ジクロルメタン
、ジクロルエタン、ヘキサン、石油エーテル、リグロイ
ン等の反応に不活性な溶媒の単独あるいはそれらの混合
溶媒等が例示される。Organic solvents used in this complex formation reaction include ethyl ether, Hensen, toluene, acetonitrile, ethyl acetate, carbon tetrachloride, chloroform, dichloromethane, dichloroethane, hexane, petroleum ether, ligroin, and other inert solvents. Examples include a single solvent or a mixed solvent thereof.
反応温度は一２０°Ｃ〜使用溶媒の沸点の範囲で任意で
あるが、通常Ｏ〜８０°Ｃの範囲である。The reaction temperature is arbitrary within the range of -20°C to the boiling point of the solvent used, but is usually in the range of 0 to 80°C.
このような方法により、２−シクロペンテノン類と光学
活性酒石酸誘導体とを有機溶媒中で接触せしめると、原
料２−シクロペンテノン類中のいずれか一方の光学活性
体と光学活性酒石酸誘導体とが容易に結合して包接錯体
を生成する。When 2-cyclopentenones and optically active tartaric acid derivatives are brought into contact with each other in an organic solvent by such a method, one of the optically active substances in the raw material 2-cyclopentenones and the optically active tartaric acid derivative are combined. It easily binds to form inclusion complexes.
この反応液を冷却するか、反応液にヘキサン、石油エー
テルのような錯体不溶性の溶媒を加えると錯体が結晶と
して析出し、これを分離することにより、目的とする光
学活性２−シクロペンテノン類と光学活性酒石酸誘導体
とが結合した錯体を光学純度よく、かつ高収率で得るこ
とができ、必要ならばさらに上記したような方法で再結
晶等を行うことにより精製することができる。When this reaction solution is cooled or a complex-insoluble solvent such as hexane or petroleum ether is added to the reaction solution, the complex precipitates as crystals, and by separating this, the desired optically active 2-cyclopentenone can be obtained. and an optically active tartaric acid derivative can be obtained with good optical purity and in high yield, and if necessary, it can be further purified by recrystallization or the like using the method described above.
かくして得られた光学活性ソクロペンテノン錯体を４９
解することにより、光学活性２−シクロペンテノン類を
得ることができる。The optically active socropentenone complex thus obtained was
By understanding this, optically active 2-cyclopentenones can be obtained.
この分解方法とＬ７ては、例えば錯体を減圧下に加ＰＩ
たり、カラムクロマトグラフィーで処理することにより
行なわれる。In this decomposition method and L7, for example, the complex is subjected to PI under reduced pressure.
This can be done by treatment with column chromatography or column chromatography.
滅Ｈ−下に加熱する方法において、減圧の程度および温
度はそれぞれの条件で適宜選ばれるが、般ｔこば】〜］
、００ｍｍＨｇ程度の圧力下で、光学活性な２−シクロ
ペンテノン類が留出し２てくる温度である。In the method of heating under reduced pressure, the degree of pressure reduction and temperature are selected as appropriate depending on the respective conditions, but in general.
This is the temperature at which optically active 2-cyclopentenones are distilled out under a pressure of about ,00 mmHg.
また、カラムクロマ１−グラフィーでの展開溶媒は先に
例示した反応溶媒を含め、必要に応１．て１種または２
１１以上を適宜選択することができる。In addition, the developing solvent for column chromatography may include the reaction solvent exemplified above, and as necessary. Type 1 or 2
11 or more can be selected as appropriate.
かかる分解処理により、目的とする一般式（■）で示さ
れる光学活性２−シクロペンテノン類を光学純度よく、
好収率で得ることができる。Through this decomposition treatment, the desired optically active 2-cyclopentenone represented by the general formula (■) can be obtained with high optical purity.
It can be obtained in good yield.
また、かかる分解処理により回収される光学活性酒石酸
誘導体は４・要ならば再結晶等により精製のうえ、再使
用することができる。Furthermore, the optically active tartaric acid derivative recovered by such decomposition treatment can be reused after being purified by recrystallization or the like if necessary.
向、本発明の方法乙こおいては、原料光学活性酒石酸誘
導体の光学配位ｊｚ応して錯体を形成する２−シクロペ
ンテノン類の光学活性体が定まるため、原料光学活性酒
石酸誘導体の光字配位を使い分けることにより、ｔＨ体
分解後の２−シクロペンテノン類の光学活性体としてＳ
−配付、Ｒ配位の任意のものを得ることができる。In the method B of the present invention, the optical coordination of the optically active tartaric acid derivative as a starting material determines the optically active form of the 2-cyclopentenone that forms the complex. By properly using the symmetrical coordination, S
-distribution, any R configuration can be obtained.
従って、この反応を利用することにより、原料２−シク
ロペンテノン類とし７てラセミ体あるいはいずれか一方
の光学活性体が光学的に過剰にある光学活性混合物を使
用した場合には、錯体形成反応後の錯体を分離した反応
液（例えば錯体濾別後の濾液）中に錯体形成に使用され
たとは逆の光字配位を有する２−シクロペンテノン類が
反応残とＵ２て光学的に過剰鼠存在吏ることになるため
、例えば濾液を濃縮し、その残渣を減圧下に加熱茅留し
て該エステル類を回収し、これを先に使用し７たとは逆
の光字配位を有する光学活性酒石酸誘導体を用いて前述
したと同様の条件で接触処理することにより錯体を形成
せしめ、これを分解することにより先に得られたとは逆
の光学配位を有する２ンクロくンテノン類を得ることが
できる。Therefore, by utilizing this reaction, when a racemate or an optically active mixture containing an optically excess amount of either one of the optically active forms is used as the raw material 2-cyclopentenone, the complex formation reaction can be performed. In the reaction solution from which the complex was separated (e.g., the filtrate after complex filtration), 2-cyclopentenones having an optical configuration opposite to that used for complex formation are present in an optical excess of the reaction residue and U2. For example, the filtrate is concentrated, and the residue is heated and distilled under reduced pressure to recover the esters, which are used earlier and have an optical configuration opposite to that of 7. A complex is formed by contact treatment using an optically active tartaric acid derivative under the same conditions as described above, and this is decomposed to obtain a 2-unitenonene having an optical configuration opposite to that obtained previously. be able to.
〈発明の効果〉
かくして、本発明の方法により一般式（１）で示される
光学活性２−シクロベンう−ノン類を工業的に容易に、
し７かも高光学純度で収率よく製造することができる。<Effects of the Invention> Thus, optically active 2-cyclobenones represented by general formula (1) can be easily produced industrially by the method of the present invention.
7 can also be produced with high optical purity and good yield.
〈実施例〉 以下、実施例により本発明を説明する。<Example> The present invention will be explained below with reference to Examples.
参考例
ラセミ体の２−フクロペンテン−４−オン−１オール９
．８ｇをトルエン５０ｍ１ に熔解したン容液に、塩化
アセチル１．１．７ｇとピリジン１５．９ｇを加え、室
温で１２時間放置した後、水５０ｍ１を加えて分液し、
有機層を分離した。この有機層を水洗し、無水硫酸寸ト
リウＪ、で乾燥した後減圧版留して沸点９５°Ｃ（１０
／ｍｍＨｇ）を有するラセミ体の４−アセトキツ−２−
ノクロベンテノンが１２．６ｇ得られた。Reference example Racemic 2-fucropenten-4-one-1ol 9
．． 8 g of toluene was dissolved in 50 ml of toluene, 1.1.7 g of acetyl chloride and 15.9 g of pyridine were added, and after standing at room temperature for 12 hours, 50 ml of water was added to separate the liquid.
The organic layer was separated. This organic layer was washed with water, dried over anhydrous sulfuric acid, and then distilled under reduced pressure with a boiling point of 95°C (10
Racemic 4-acetox-2- with /mmHg)
12.6 g of noclobentenone was obtained.
実施例】
（４ｆぐ トランス）−α、α、α゛ α゛ −テトラ
フェニル−１，４−ジオキガスピロＣ４，５）デカン−
２，３−ジメタツール（１） ６．８６ｇ （１３，６
ｍ＋＋＋ｏ１） とラセミ体のアセトキノ−２−ンクロ
ペンテノン（２） １．９ｇ（１３，６ｍｍｏｌ）をヘ
ンゼン７ｍｌにカロ熱ン容解し、次に石油エーテル４．
５ｍｌを加え２０°Ｃにて４時間放置した。析出した（
２体の（１）〕 ・ （ｒ体の［２））＝２・１の包
接錯体を濾取した。さらにこの結晶をヘンゼンー石油エ
ーテル２：１の混合溶液から再結晶し、２．０４ｇの包
接錯体を得た。Examples] (4fg trans)-α, α, α゛ α゛ -tetraphenyl-1,4-diokigaspiroC4,5)decane-
2,3-dimethatol (1) 6.86g (13,6
1.9 g (13.6 mmol) of racemic acetoquinol-2-enclopentenone (2) were dissolved in 7 ml of Hensen's carotherm, and then 4.0 g of petroleum ether was dissolved.
5 ml was added and left at 20°C for 4 hours. Precipitated (
An inclusion complex of two bodies (1)] and (r body [2))=2·1 was collected by filtration. Further, these crystals were recrystallized from a mixed solution of Hensen-petroleum ether 2:1 to obtain 2.04 g of an inclusion complex.
（Ｃα） Ｐ＝−７１° （ｃ−０，２、ＣｌｌＣｌ
）次に、上記包接錯体を減圧下に加熱し、版留するとＮ
−４−アセＩ・キノ−２−ノクロベンテノンが０．３８
ｇ （収率２０り得られた。(Cα) P=-71° (c-0,2, CllCl
) Next, the above inclusion complex is heated under reduced pressure and distilled to produce N.
-4-aceI・quino-2-noclobentenone is 0.38
g (yield: 20 g).
〔α ］ ］Ｐ＝−９６．５ （ｃ・０４２．
メタノール）光学純度 ９７χｅｅ
実施例２
（４Ｒ−１−ランス）−２，２−ジメチル−αα、α
α −テトラフェニル−１，３−ジオキソラン−４，５
−ジメタツール（３） １０．７３ｇ （２１，７ｍｍ
ｏｌ＞ とラセミ体の４−ヒドロキノ−２−シクロペン
テノン（４） ４．２６ｇ（４３，５ｍｍｏｌ）をエー
テル８０ｍに溶解し、次に石油エーテル２５＋ｎ ｌを
加え、室温で４時間放置すると、〔２体の（３）］：（
ｆ体の（４）］＝１：１の包接錯体がプリズム結晶とし
て得られた。この結晶をさらにエーテル：石油エーテル
−４：１の混合溶液で再結晶すると、包接錯体１．９７
ｇが得られた。この錯体を５ｍＩＩＩＨｇで加熱蕉留す
ると、ｆ−４−ヒドロキシ−２−シクロペンテノン０．
３２ｇが得られた。（収率７．５χ）〔α ］ 二５
＝−４２° （ｃ＝０．１． メタノール）光学純度
５８χｅｅ[α] ]P=-96.5 (c・042.
Methanol) Optical purity 97χee Example 2 (4R-1-lance)-2,2-dimethyl-αα,α
α-tetraphenyl-1,3-dioxolane-4,5
-Dimeta tool (3) 10.73g (21.7mm
ol> and racemic 4-hydroquino-2-cyclopentenone (4) 4.26 g (43.5 mmol) were dissolved in 80 ml of ether, then 25+nl of petroleum ether was added and left at room temperature for 4 hours. Two (3)]:(
An inclusion complex of f-isomer (4)]=1:1 was obtained as a prism crystal. When this crystal is further recrystallized from a mixed solution of ether:petroleum ether-4:1, an inclusion complex of 1.97
g was obtained. When this complex was heated and distilled at 5mIIIHg, 0.0% of f-4-hydroxy-2-cyclopentenone.
32g was obtained. (Yield 7.5χ) [α] 25
=-42° (c=0.1.methanol) Optical purity 58χee
Claims (4)
〜６のアルカノイル基または水素原子を表し、＊印は不
斉炭素原子であることを表す、）で示される光学活性２
−シクロペンテノン類と、一般式（II） ▲数式、化学式、表等があります▼（II） （式中、Ｒ＿１およびＲ＿２はそれぞれ低級アルキル基
またはＲ＿１とＲ＿２が結合して一緒になったアルキレ
ン基を表し、Ｒ＾１はフェニル基、ハロゲン化フェニル
基または低級アルキルフェニル基を表し、＊印は不斉炭
素原子であることを表す。） で示される光学活性酒石酸誘導体とが結合してなる光学
活性シクロペンテノン錯体を分解することを特徴とする
一般式（ I ）で示される光学活性２−シクロペンテノ
ン類の製造法。(1) General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R has 2 carbon atoms which may be substituted with halogen.
-6 represents an alkanoyl group or a hydrogen atom, * indicates an asymmetric carbon atom) Optical activity 2
-Cyclopentenones and general formula (II) ▲Mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R_1 and R_2 are lower alkyl groups, respectively, or alkylene formed by bonding R_1 and R_2 together. R^1 represents a phenyl group, a halogenated phenyl group, or a lower alkylphenyl group, and the * mark represents an asymmetric carbon atom.) A method for producing optically active 2-cyclopentenones represented by general formula (I), which comprises decomposing an optically active cyclopentenone complex.
示される光学活性酒石酸誘導体とを接触させて、一般式
（ I ）で示される光学活性２−シクロペンテノン類と
一般式（II）で示される光学活性酒石酸誘導体とが結合
してなる光学活性シクロペンテノン錯体を得、ついでこ
れを分解することを特徴とする一般式（ I ）で示され
る光学活性２−シクロペンテノン類の製造法。(2) General formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(m) (In the formula, R represents the same meaning as above.) 2-cyclopentenones represented by the general formula (II) ) is brought into contact with an optically active tartaric acid derivative represented by the general formula (I), and an optically active tartaric acid derivative represented by the general formula (II) is bonded to an optically active 2-cyclopentenone represented by the general formula (I). A method for producing optically active 2-cyclopentenones represented by general formula (I), which comprises obtaining an active cyclopentenone complex and then decomposing it.
類と、一般式（II）で示される光学活性酒石酸誘導体と
を接触させることを特徴とする一般式（ I ）で示され
る光学活性２−シクロペンテノン類と一般式（II）で示
される光学活性酒石酸誘導体とが結合してなる光学活性
シクロペンテノン錯体の製造法。(3) Optical activity represented by general formula (I) characterized by contacting 2-cyclopentenones represented by general formula (III) with an optically active tartaric acid derivative represented by general formula (II) A method for producing an optically active cyclopentenone complex formed by bonding 2-cyclopentenones and an optically active tartaric acid derivative represented by general formula (II).
ンテノン類と一般式（II）で示される光学活性酒石酸誘
導体とが結合してなる光学活性シクロペンテノン錯体。(4) An optically active cyclopentenone complex formed by bonding an optically active 2-cyclopentenone represented by the general formula (I) and an optically active tartaric acid derivative represented by the general formula (II).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17574190A JP2905931B2 (en) | 1990-07-03 | 1990-07-03 | Process for producing optically active 2-cyclopentenones |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17574190A JP2905931B2 (en) | 1990-07-03 | 1990-07-03 | Process for producing optically active 2-cyclopentenones |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0466550A true JPH0466550A (en) | 1992-03-02 |
| JP2905931B2 JP2905931B2 (en) | 1999-06-14 |
Family
ID=16001442
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17574190A Expired - Fee Related JP2905931B2 (en) | 1990-07-03 | 1990-07-03 | Process for producing optically active 2-cyclopentenones |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2905931B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5395977A (en) * | 1992-03-13 | 1995-03-07 | Sumitomo Chemical Company, Ltd. | Process for producing optical active 4-hydroxy-2-cyclopentenone |
-
1990
- 1990-07-03 JP JP17574190A patent/JP2905931B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5395977A (en) * | 1992-03-13 | 1995-03-07 | Sumitomo Chemical Company, Ltd. | Process for producing optical active 4-hydroxy-2-cyclopentenone |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2905931B2 (en) | 1999-06-14 |
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