JPH0692344B2 - Method for producing 2-cyclopentenone esters - Google Patents
Method for producing 2-cyclopentenone estersInfo
- Publication number
- JPH0692344B2 JPH0692344B2 JP57199588A JP19958882A JPH0692344B2 JP H0692344 B2 JPH0692344 B2 JP H0692344B2 JP 57199588 A JP57199588 A JP 57199588A JP 19958882 A JP19958882 A JP 19958882A JP H0692344 B2 JPH0692344 B2 JP H0692344B2
- Authority
- JP
- Japan
- Prior art keywords
- cyclopentenone
- hydroxy
- methyl
- reaction
- general formula
- 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 - Lifetime
Links
- BZKFMUIJRXWWQK-UHFFFAOYSA-N Cyclopentenone Chemical class O=C1CCC=C1 BZKFMUIJRXWWQK-UHFFFAOYSA-N 0.000 title claims description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- -1 2-cyclopentenone ester Chemical class 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 230000003287 optical effect Effects 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 9
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 8
- 235000011054 acetic acid Nutrition 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000000605 extraction Methods 0.000 description 4
- 235000019260 propionic acid Nutrition 0.000 description 4
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-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
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000001632 sodium acetate Substances 0.000 description 3
- 235000017281 sodium acetate Nutrition 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- JXKPEJDQGNYQSM-UHFFFAOYSA-M sodium propionate Chemical compound [Na+].CCC([O-])=O JXKPEJDQGNYQSM-UHFFFAOYSA-M 0.000 description 2
- 239000004324 sodium propionate Substances 0.000 description 2
- 235000010334 sodium propionate Nutrition 0.000 description 2
- 229960003212 sodium propionate Drugs 0.000 description 2
- XHFLOLLMZOTPSM-UHFFFAOYSA-M sodium;hydrogen carbonate;hydrate Chemical compound [OH-].[Na+].OC(O)=O XHFLOLLMZOTPSM-UHFFFAOYSA-M 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- WSXIDMLKPGJZCU-UHFFFAOYSA-N (2,3-dimethyl-4-oxocyclopent-2-en-1-yl) propanoate Chemical compound CCC(=O)OC1CC(=O)C(C)=C1C WSXIDMLKPGJZCU-UHFFFAOYSA-N 0.000 description 1
- MDFPPPIHFJPKRF-UHFFFAOYSA-N (2-methyl-4-oxo-3-prop-2-enylcyclopent-2-en-1-yl) acetate Chemical compound CC(=O)OC1CC(=O)C(CC=C)=C1C MDFPPPIHFJPKRF-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical class CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- KUZRPQHDPJDXAZ-UHFFFAOYSA-N 4-hydroxy-4,5-dimethylcyclopent-2-en-1-one Chemical compound CC1C(=O)C=CC1(C)O KUZRPQHDPJDXAZ-UHFFFAOYSA-N 0.000 description 1
- ZLKSWXWJGSKXGZ-AATRIKPKSA-N 4-hydroxy-4-methyl-5-[(e)-pent-1-enyl]cyclopent-2-en-1-one Chemical compound CCC\C=C\C1C(=O)C=CC1(C)O ZLKSWXWJGSKXGZ-AATRIKPKSA-N 0.000 description 1
- ZLKSWXWJGSKXGZ-WAYWQWQTSA-N 4-hydroxy-4-methyl-5-[(z)-pent-1-enyl]cyclopent-2-en-1-one Chemical compound CCC\C=C/C1C(=O)C=CC1(C)O ZLKSWXWJGSKXGZ-WAYWQWQTSA-N 0.000 description 1
- GRDMLYFTFVGTIH-UHFFFAOYSA-N 4-hydroxy-4-methyl-5-pent-2-ynylcyclopent-2-en-1-one Chemical compound CCC#CCC1C(=O)C=CC1(C)O GRDMLYFTFVGTIH-UHFFFAOYSA-N 0.000 description 1
- QSBOWRGBKFLEFP-UHFFFAOYSA-N 4-hydroxy-4-methyl-5-pentylcyclopent-2-en-1-one Chemical compound CCCCCC1C(=O)C=CC1(C)O QSBOWRGBKFLEFP-UHFFFAOYSA-N 0.000 description 1
- BLXRCUAXNAVKIQ-UHFFFAOYSA-N 4-hydroxy-4-methyl-5-prop-2-ynylcyclopent-2-en-1-one Chemical compound CC1(O)C=CC(=O)C1CC#C BLXRCUAXNAVKIQ-UHFFFAOYSA-N 0.000 description 1
- KROXSYKVAMTEBH-UHFFFAOYSA-N 4-hydroxy-4-methyl-5-propan-2-ylcyclopent-2-en-1-one Chemical compound CC(C)C1C(=O)C=CC1(C)O KROXSYKVAMTEBH-UHFFFAOYSA-N 0.000 description 1
- IKVJOBDPGRWXRL-UHFFFAOYSA-N 4-hydroxy-4-methyl-5-propylcyclopent-2-en-1-one Chemical compound CCCC1C(=O)C=CC1(C)O IKVJOBDPGRWXRL-UHFFFAOYSA-N 0.000 description 1
- FKMJJDZYBRVQBZ-SNAWJCMRSA-N 4-hydroxy-5-[(e)-pent-1-enyl]cyclopent-2-en-1-one Chemical compound CCC\C=C\C1C(O)C=CC1=O FKMJJDZYBRVQBZ-SNAWJCMRSA-N 0.000 description 1
- YBOSXQPPIAJHBR-UHFFFAOYSA-N 4-hydroxy-5-methylcyclopent-2-en-1-one Chemical compound CC1C(O)C=CC1=O YBOSXQPPIAJHBR-UHFFFAOYSA-N 0.000 description 1
- GBJLMAFSBULEHH-UHFFFAOYSA-N 4-hydroxy-5-pent-2-ynylcyclopent-2-en-1-one Chemical compound CCC#CCC1C(O)C=CC1=O GBJLMAFSBULEHH-UHFFFAOYSA-N 0.000 description 1
- PJVOCKSLNHMZQP-UHFFFAOYSA-N 4-hydroxy-5-pentylcyclopent-2-en-1-one Chemical compound CCCCCC1C(O)C=CC1=O PJVOCKSLNHMZQP-UHFFFAOYSA-N 0.000 description 1
- BFSFRKPXQRZGQB-UHFFFAOYSA-N 4-hydroxy-5-prop-2-ynylcyclopent-2-en-1-one Chemical compound OC1C=CC(=O)C1CC#C BFSFRKPXQRZGQB-UHFFFAOYSA-N 0.000 description 1
- DHZISXYGHCFXSZ-UHFFFAOYSA-N 4-hydroxy-5-propan-2-ylcyclopent-2-en-1-one Chemical compound CC(C)C1C(O)C=CC1=O DHZISXYGHCFXSZ-UHFFFAOYSA-N 0.000 description 1
- NDLFPIAPKCLHDQ-UHFFFAOYSA-N 4-hydroxy-5-propylcyclopent-2-en-1-one Chemical compound CCCC1C(O)C=CC1=O NDLFPIAPKCLHDQ-UHFFFAOYSA-N 0.000 description 1
- KIVXAZNNGZNKRO-UHFFFAOYSA-N 5-(cyclopenten-1-yl)-4-hydroxy-4-methylcyclopent-2-en-1-one Chemical compound CC1(O)C=CC(=O)C1C1=CCCC1 KIVXAZNNGZNKRO-UHFFFAOYSA-N 0.000 description 1
- JNXGEGVOTILFFE-UHFFFAOYSA-N 5-(cyclopenten-1-yl)-4-hydroxycyclopent-2-en-1-one Chemical compound OC1C=CC(=O)C1C1=CCCC1 JNXGEGVOTILFFE-UHFFFAOYSA-N 0.000 description 1
- VSAISQPJOKIOJC-UHFFFAOYSA-N 5-butyl-4-hydroxy-4-methylcyclopent-2-en-1-one Chemical compound CCCCC1C(=O)C=CC1(C)O VSAISQPJOKIOJC-UHFFFAOYSA-N 0.000 description 1
- YABVXKGXOSAVDV-UHFFFAOYSA-N 5-cyclohexyl-4-hydroxycyclopent-2-en-1-one Chemical compound OC1C=CC(=O)C1C1CCCCC1 YABVXKGXOSAVDV-UHFFFAOYSA-N 0.000 description 1
- VGTUXRVDBMHWBD-UHFFFAOYSA-N 5-ethyl-4-hydroxy-4-methylcyclopent-2-en-1-one Chemical compound CCC1C(=O)C=CC1(C)O VGTUXRVDBMHWBD-UHFFFAOYSA-N 0.000 description 1
- YVJWEFBXOALURR-UHFFFAOYSA-N 5-heptyl-4-hydroxy-4-methylcyclopent-2-en-1-one Chemical compound CCCCCCCC1C(=O)C=CC1(C)O YVJWEFBXOALURR-UHFFFAOYSA-N 0.000 description 1
- JOJDSFWDKMJLIB-UHFFFAOYSA-N 5-heptyl-4-hydroxycyclopent-2-en-1-one Chemical compound CCCCCCCC1C(O)C=CC1=O JOJDSFWDKMJLIB-UHFFFAOYSA-N 0.000 description 1
- CHKGQHDUAIYQOY-UHFFFAOYSA-N 5-hexyl-4-hydroxy-4-methylcyclopent-2-en-1-one Chemical compound CCCCCCC1C(=O)C=CC1(C)O CHKGQHDUAIYQOY-UHFFFAOYSA-N 0.000 description 1
- HGSCAIODYYGEOB-UHFFFAOYSA-N 5-hexyl-4-hydroxycyclopent-2-en-1-one Chemical compound CCCCCCC1C(O)C=CC1=O HGSCAIODYYGEOB-UHFFFAOYSA-N 0.000 description 1
- LSRSWQXATYYYAY-PLNGDYQASA-N CC\C=C/C1C(=O)C=CC1(C)O Chemical compound CC\C=C/C1C(=O)C=CC1(C)O LSRSWQXATYYYAY-PLNGDYQASA-N 0.000 description 1
- URJPBINEJUWLKI-UHFFFAOYSA-N OC1C(C(C=C1)=O)C=C/CC Chemical compound OC1C(C(C=C1)=O)C=C/CC URJPBINEJUWLKI-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical class CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 1
- 159000000021 acetate salts Chemical class 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 230000006340 racemization Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical class CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 本発明は、一般式（II） （式中、R1は水素原子、アルキル基またはアルケニル基
を、R2はアルキル基、アルケニル基またはアルキニル基
を、R3は水素原子または低級アルキル基をそれぞれ示
す。） で示される２−シクロペンテノンエステル類の製造法に
関し、更に詳しくは、一般式（Ｉ） （式中、R1およびR2は前記と同じ意味を有し、Ｒは−OH
または−OOCR′である。ここでＲ′は水素原子または低
級アルキル基である。） で示される４−シクロペンテノン類と低級脂肪族カルボ
ン酸を加熱下に反応させることからなる前記一般式（I
I）で示される２−シクロペンテノンエステル類の製造
方法である。DETAILED DESCRIPTION OF THE INVENTION The present invention has the general formula (II) (In the formula, R 1 represents a hydrogen atom, an alkyl group or an alkenyl group, R 2 represents an alkyl group, an alkenyl group or an alkynyl group, and R 3 represents a hydrogen atom or a lower alkyl group.) Regarding the method for producing the pentenone ester, more specifically, the general formula (I) (In the formula, R 1 and R 2 have the same meanings as described above, and R is —OH.
Or -OOCR '. Here, R'is a hydrogen atom or a lower alkyl group. ) A 4-cyclopentenone represented by the formula (I) and a lower aliphatic carboxylic acid are reacted under heating to give the above-mentioned general formula (I
It is a method for producing 2-cyclopentenone esters represented by I).
尚、本発明における上記２−シクロペンテノンエステル
類は僅かながら（＋）または（−）の施光性を有してお
り、従って正確にはｄ−またはｌ一体のいずれか一方が
少過剰である光学異性体混合物であるが、一般にその光
学純度は非常に低いため、以下の本文中ではこれを便宜
上ラセミ体と呼ぶことがある。The 2-cyclopentenone esters in the present invention have a slight (+) or (-) light-applying property, and therefore, to be exact, either one of d- and l is excessively small. Although it is a certain optical isomer mixture, its optical purity is generally very low, and hence it may be referred to as a racemate in the following text for convenience.
本発明者らは先に一般式（Ｉ）で示される光学活性な４
−シクロペンテノン類およびその製造方法について提案
しており、該化合物がそれぞれの光学活性体に応じて農
薬あるいは医薬用中間体として極めて重要なものである
ことを見出しているが、一定の用途、たとえば殺虫剤な
どの農薬用途を目的とする場合には、負の旋光性を有す
る４−シクロペンテノン類は有用であっても、その対称
体である正の旋光性を有する４−シクロペンテノン類は
その目的には有効でなく、従って、一般式（Ｉ）で示さ
れる４−シクロペンテノン類のうち有効に利用し得るの
は一方の光学活性体のみとなってその対称体は不用とな
り、化合物全体としての利用価値が低いという問題があ
る。The present inventors have previously described the optically active 4 represented by the general formula (I).
-Proposed cyclopentenones and a method for producing the same, and found that the compound is extremely important as an agricultural chemical or a pharmaceutical intermediate according to each optically active substance, but has certain uses, For example, for the purpose of agricultural chemicals such as insecticides, 4-cyclopentenones having negative optical activity are useful, but 4-cyclopentenone, which is a symmetrical body thereof, having positive optical activity. The groups are not effective for that purpose, and therefore, among the 4-cyclopentenones represented by the general formula (I), only one optically active substance can be effectively used, and the symmetric body becomes unnecessary. However, there is a problem that the utility value of the compound as a whole is low.
このようなことから、本発明者らは一般式（Ｉ）で示さ
れる４−シクロペンテノン類のうち不用となる他方の光
学活性体を有効に利用すべく検討の結果、光学活性な一
般式（Ｉ）で示される４−シクロペンテノン類を特定条
件下で反応させることにより、一般式（II）で示される
２−シクロペンテノンエステル類がラセミ体で得られる
ことを見出し、本発明に至った。From these facts, the present inventors have studied to effectively use the other optically active substance of the 4-cyclopentenones represented by the general formula (I), which is unnecessary, and as a result, have shown that the optically active general formula It was found that by reacting 4-cyclopentenones represented by (I) under specific conditions, 2-cyclopentenone esters represented by general formula (II) can be obtained in a racemic form, and the present invention provides I arrived.
すなわち本発明は、前記した如く、一般式（１）で示さ
れる光学活性な４−シクロペンテノン類と低級脂肪族カ
ルボン酸を加熱し、ラセミ化を伴って転位させることに
より一般式（II）で示される２−シクロペンテノンエス
テル類をラセミ体として得る方法である。That is, according to the present invention, as described above, the optically active 4-cyclopentenones represented by the general formula (1) and the lower aliphatic carboxylic acid are heated and rearranged with racemization to thereby form the general formula (II). Is a method for obtaining 2-cyclopentenone esters represented by
本発明により得られる一般式（II）で示される２−シク
ロペンテノンエステル類は、たとえばこれを加水分解す
ることによりラセミ体の２−置換−４−ヒドロキシ−８
−メチル−２−シクロペンテノン類とすることができ、
このものはラセミ体のかたちで殺虫剤用途などに有効に
利用することができる。The 2-cyclopentenone esters represented by the general formula (II) obtained by the present invention are, for example, hydrolyzed to give racemic 2-substituted-4-hydroxy-8.
-Methyl-2-cyclopentenones,
This product can be effectively used in the form of racemate for insecticides and the like.
かくして、本発明によれば不用化合物として扱われてい
た一般式（Ｉ）で示される４−シクロペンテノン類のい
ずれか一方の光学活性体が、再利用可能な化合物に変換
されていることとなり、本発明のもたらす経済的意義は
極めて高い。Thus, according to the present invention, one of the optically active isomers of the 4-cyclopentenones represented by the general formula (I), which was treated as an unnecessary compound, is converted into a reusable compound. The economic significance of the present invention is extremely high.
本発明において、原料として用いられる４−シクロペン
テノン類としては、たとえば３−ヒドロキシ−２−メチ
ル−４−シクロペンテノン、８−ヒドロキシ−２−エチ
ル−４−シクロペンテノン、３−ヒドロキシ−２−ｎ−
プロピル−４−シクロペンテノン、３−ヒドロキシ−２
−イソプロピル−４−シクロペンテノン、３−シドロキ
シ−２−ｎ−ブチル−４−シクロペンテノン、３−ヒド
ロキシ−２−ｎ−ペンチル−４−シクロペンテノン、３
−ヒドロキシ−２−ｎ−ヘキシル−４−シクロペンテノ
ン、３−ヒドロキシ−２−ｎ−ヘプチル−４−シクロペ
ンテノン、３−ヒドロキシ−２−アリル−４−シクロペ
ンテノン、３−ヒドロキシ−２−（２−シス−ブテニ
ル）−４−シクロペンテノン、３−ヒドロキシ−２−
（ω−ブテニル）−４−シクロペンテノン、３−ヒドロ
キシ−２−（２−トランス−ペンテニル）−４−シクロ
ペンテノン、３−ヒドロキシ−２−（３−シス−ヘキセ
ニル）−４−シクロペンテノン、３−ヒドロキシ−２−
プロパルギル−４−シクロペンテノン、３−ヒドロキシ
−２−（２−ペンチニル）−４−シクロペンテノン、３
−ヒドロキシ−２−（α−メチルアリル）−４−シクロ
ペンテノン、３−ヒドロキシ−２−（１−シクロペンテ
ニル）−４−シクロペンテノン、３−ヒドロキシ−２−
シクロヘキシル−４−シクロペンテノン、３−ヒドロキ
シ−2,3−ジメチル−４−シクロペンテノン、３−ヒド
ロキシ−２−エチル−３−メチル−４−シクロペンテノ
ン、３−ヒドロキシ−２−ｎ−プロピル−３−メチル−
４−シクロペンテノン、３−ヒドロキシ−２−イゾプロ
ピル−３−メチル−４−シクロペンテノン、３−ヒドロ
キシ−２−ｎ−ブチル−３メチル−４−シクロペンテノ
ン、３−ヒドロキシ−２−ｎ−ペンチル−３−メチル−
４−シクロペンテノン、３−ヒドロキシ−２−ｎ−ヘキ
シル−３−メチル−４−シクロペンテノン、３−ヒドロ
キシ−２−ｎ−ヘプチル−３−メチル−４−シクロペン
テノン、３−ヒドロキシ−２−アリル−３−メチル−４
−シクロペンテノン、３−ヒドロキシ−２−（２−シス
−ブテニル）−３−メチル−４−シクロペンテノン、３
−ヒドロキシ−２−（ω−プテニル）−３−メチル−４
−シクロペンテノン、３−ヒドロキシ−２−（２−シス
−ペンテニル）−３−メチル−４−シクロペンテノン、
３−ヒドロキシ−２−（２−トランス−ペンテニル）−
３−メチル−４−シクロペンテノン、３−ヒドロキシ−
２−（３−シス−ヘキセニル）−３−メチル−４−シク
ロペンテノン、３−ヒドロキシ−２−プロパルギル−３
−メチル−４−シクロペンテノン、３−ヒドロキシ−２
−（２−ペンチニル）−３−メチル−４−シクロペンテ
ノン、３−ヒドロキシ−２−（α−メチルアリル）−３
−メチル−４−シクロペンテノン、３−ヒドロキシ−２
−（１−シクロペンテニル）−３−メチル−４−シクロ
ペンテノン、３−ヒドロキシ−２−シクロヘキシル−３
−メチル−４−シクロペンテノンおよびこれらの化合物
における３−位のヒドロキシル基がアセトキシ基または
プロピオニルオキシ基に置換された化合物が例示され
る。In the present invention, 4-cyclopentenones used as a raw material include, for example, 3-hydroxy-2-methyl-4-cyclopentenone, 8-hydroxy-2-ethyl-4-cyclopentenone, 3-hydroxy- 2-n-
Propyl-4-cyclopentenone, 3-hydroxy-2
-Isopropyl-4-cyclopentenone, 3-Sidoxy-2-n-butyl-4-cyclopentenone, 3-hydroxy-2-n-pentyl-4-cyclopentenone, 3
-Hydroxy-2-n-hexyl-4-cyclopentenone, 3-hydroxy-2-n-heptyl-4-cyclopentenone, 3-hydroxy-2-allyl-4-cyclopentenone, 3-hydroxy-2 -(2-cis-Butenyl) -4-cyclopentenone, 3-hydroxy-2-
(Ω-butenyl) -4-cyclopentenone, 3-hydroxy-2- (2-trans-pentenyl) -4-cyclopentenone, 3-hydroxy-2- (3-cis-hexenyl) -4-cyclopen Tenon, 3-hydroxy-2-
Propargyl-4-cyclopentenone, 3-hydroxy-2- (2-pentynyl) -4-cyclopentenone, 3
-Hydroxy-2- (α-methylallyl) -4-cyclopentenone, 3-hydroxy-2- (1-cyclopentenyl) -4-cyclopentenone, 3-hydroxy-2-
Cyclohexyl-4-cyclopentenone, 3-hydroxy-2,3-dimethyl-4-cyclopentenone, 3-hydroxy-2-ethyl-3-methyl-4-cyclopentenone, 3-hydroxy-2-n- Propyl-3-methyl-
4-cyclopentenone, 3-hydroxy-2-isopropyl-3-methyl-4-cyclopentenone, 3-hydroxy-2-n-butyl-3methyl-4-cyclopentenone, 3-hydroxy-2-n -Pentyl-3-methyl-
4-cyclopentenone, 3-hydroxy-2-n-hexyl-3-methyl-4-cyclopentenone, 3-hydroxy-2-n-heptyl-3-methyl-4-cyclopentenone, 3-hydroxy- 2-allyl-3-methyl-4
-Cyclopentenone, 3-hydroxy-2- (2-cis-butenyl) -3-methyl-4-cyclopentenone, 3
-Hydroxy-2- (ω-ptenyl) -3-methyl-4
-Cyclopentenone, 3-hydroxy-2- (2-cis-pentenyl) -3-methyl-4-cyclopentenone,
3-hydroxy-2- (2-trans-pentenyl)-
3-methyl-4-cyclopentenone, 3-hydroxy-
2- (3-cis-hexenyl) -3-methyl-4-cyclopentenone, 3-hydroxy-2-propargyl-3
-Methyl-4-cyclopentenone, 3-hydroxy-2
-(2-Pentynyl) -3-methyl-4-cyclopentenone, 3-hydroxy-2- (α-methylallyl) -3
-Methyl-4-cyclopentenone, 3-hydroxy-2
-(1-Cyclopentenyl) -3-methyl-4-cyclopentenone, 3-hydroxy-2-cyclohexyl-3
Examples include -methyl-4-cyclopentenone and compounds in which the 3-position hydroxyl group in these compounds is substituted with an acetoxy group or a propionyloxy group.
また、もう一方の反応原料である低級脂肪族カルボン酸
としてはギ酸、酢酸、プロピオン酸、酪酸、吉草酸など
が例示され、かかるカルボン酸はその単独あるいはこれ
らの金属塩（たとえばリチウム塩、ナトリウム塩、カリ
ウム塩、カルシウム塩、銅塩、亜鉛塩、パラジウム塩、
鉛塩、スズ塩、マンガン塩など）、有機アミン塩（たと
えばトリメチルアミン塩、トリエチルアミン塩、ピリジ
ン塩、ピコリン塩など）と併用して用いられるが、特に
カルボン酸とその金属塩を併用するのが好ましい。Examples of the lower aliphatic carboxylic acid which is the other reaction raw material include formic acid, acetic acid, propionic acid, butyric acid, valeric acid and the like, and such carboxylic acid is a single metal salt thereof or a metal salt thereof (for example, lithium salt, sodium salt). , Potassium salt, calcium salt, copper salt, zinc salt, palladium salt,
It is used in combination with lead salts, tin salts, manganese salts, etc.) and organic amine salts (eg, trimethylamine salts, triethylamine salts, pyridine salts, picoline salts, etc.), but it is particularly preferable to use carboxylic acids and their metal salts in combination. .
一般式（Ｉ）で示される光学活性な４−シクロペンテノ
ン類と低級脂肪族カルボン酸との反応は溶媒の存在もし
くは非存在下に加熱することによりわれる。The reaction between the optically active 4-cyclopentenones represented by the general formula (I) and the lower aliphatic carboxylic acid is carried out by heating in the presence or absence of a solvent.
この反応において溶媒を使用する場合、その溶媒として
はたとえばテトラヒドロフラン、エチルエーテル、アセ
トン、メチルエチルケトン、トルエン、ベンゼン、クロ
ルベンゼン、ジクロルメタン、ジクロルエタン、クロロ
ホルム、四塩化炭素、ジメチルホルムアミド、ジメチル
スルホキシド等の脂肪族もしくは芳香族炭化水素、エー
テル、ハロゲン化炭化水素等の反応に不活性な溶媒の単
独または混合物があげられる。When a solvent is used in this reaction, the solvent is, for example, tetrahydrofuran, ethyl ether, acetone, methyl ethyl ketone, toluene, benzene, chlorobenzene, dichloromethane, dichloroethane, chloroform, carbon tetrachloride, dimethylformamide, dimethylsulfoxide, or the like. Solvents such as aromatic hydrocarbons, ethers and halogenated hydrocarbons, which are inert to the reaction, may be used alone or as a mixture.
その使用量については特に制限されない。また、反応成
分である低脂肪族カルボン酸を溶媒として使用すること
もできる。The amount used is not particularly limited. Further, a low-aliphatic carboxylic acid which is a reaction component can also be used as a solvent.
この反応において、低級脂肪族カルボン酸の使用量は、
光学活性な４−シクロペンテノン類に対して１当量以上
必要であり、好ましくは２当量以上である。In this reaction, the amount of lower aliphatic carboxylic acid used is
It is necessary to be 1 equivalent or more, and preferably 2 equivalents or more, with respect to the optically active 4-cyclopentenones.
反応温度は50〜160℃の範囲で任意であるが、好ましく
は60〜140℃の範囲である。The reaction temperature is arbitrary in the range of 50 to 160 ° C, but is preferably in the range of 60 to 140 ° C.
反応時間については特に制限はない。このような反応に
よって、一般式（II）で示されるラセミ体のシクロペン
テノンエステル類が容易に、かつ好収率で得られ、これ
らは通常の分離手段、たとえば抽出、分液、濃縮、蒸留
等により反応混合物から容易に単離することができる。The reaction time is not particularly limited. By such a reaction, racemic cyclopentenone esters represented by the general formula (II) can be obtained easily and in good yield, which can be obtained by a conventional separation means such as extraction, separation, concentration and distillation. Can be easily isolated from the reaction mixture.
以下、実施例により本発明を説明する。Hereinafter, the present invention will be described with reference to examples.
実施例１ 撹拌装置、温度計を装着した四ッ口フラスコにｄ−２−
アリル−３−ヒドロキシ−３−メチル−４−シクロペン
テノン3.8g〔旋光度α▲〕20 D▼＋22.5゜（Ｃ＝1,クロ
ロホルム）〕、酢酸20mおよび酢酸ナトリウム0.4gを
加え、還流下に７時間撹拌する。Example 1 d-2- in a four-necked flask equipped with a stirrer and a thermometer
Allyl-3-hydroxy-3-methyl-4-cyclopentenone 3.8 g [optical rotation α ▲] 20 D ▼ + 22.5 ° (C = 1, chloroform)], acetic acid 20 m and sodium acetate 0.4 g are added and refluxed. Stir down for 7 hours.
反応終了後、減圧にて酢酸を留去し、残渣にトルエン20
mおよび水10mを加えて抽出処理する。After the reaction was completed, acetic acid was distilled off under reduced pressure, and toluene was added to the residue.
m and 10 m of water are added for extraction.
有機層を重曹水洗い、水洗いしたのちトルエンを留去す
る。濃縮残渣をカラムクロマト精製して４−アセトキシ
−２−アリル−３−メチル−２−シクロペンテノン3.65
g（収率94％）を得た。The organic layer is washed with sodium bicarbonate water, washed with water, and then toluene is distilled off. The concentrated residue was purified by column chromatography to give 4-acetoxy-2-allyl-3-methyl-2-cyclopentenone 3.65.
g (94% yield) was obtained.
ｂ・p100〜110℃/0.1〜0.8mmHg 旋光度α▲〕20 D▼−1.8゜（Ｃ＝1,クロロホルム） 尚、上記実施例において、酢酸ナトリウム0.4gの代わり
に表−１に示す酢酸塩を使用する以外は全く同様に反応
させ、処理した結果、目的化合物の収率は表−１に示す
とおりであった。b · p 100 to 110 ° C./0.1 to 0.8 mmHg Optical rotation α ▲] 20 D ▼ −1.8 ° (C = 1, chloroform) In the above example, the acetate salt shown in Table 1 was used instead of 0.4 g of sodium acetate. The reaction and treatment were carried out in exactly the same manner except that was used, and the yield of the target compound was as shown in Table 1.
実施例２ ｄ−２−アリル−３−ヒドロキシ−３−メチル−４−シ
クロペンテノンにかえてｌ−２−アリル−３−ヒドロキ
シ−３−メチル−４−シクロペンテノン8.8g〔旋光度α
▲〕20 D▼−23.9゜（Ｃ＝1,クロロホルム）〕を使用す
る以外は実施例１と同様に反応、後処理し、さらにカラ
ムクロマト精製（トルエン：酢酸エチル＝10:1）して４
−アセトキシ−２−アリル−３−メチル−２−シクロペ
ンテノン3.53g（収率91％）を得た。 Example 2 d-2-allyl-3-hydroxy-3-methyl-4-cyclopentenone was replaced with l-2-allyl-3-hydroxy-3-methyl-4-cyclopentenone 8.8 g [optical rotation α
▲] 20 D ▼ −23.9 ° (C = 1, chloroform)] except that the reaction and post-treatment were carried out in the same manner as in Example 1, and column chromatography purification (toluene: ethyl acetate = 10: 1) was performed to obtain 4
3.53 g (yield 91%) of -acetoxy-2-allyl-3-methyl-2-cyclopentenone was obtained.
旋光度：α▲〕20 D▼＋2.4゜（Ｃ＝1,クロロホルム） 実施例８ 実焼例１で用いたと同様のフラスコにｌ−３−アセトキ
シ−２−アリル−３−メチル−４−シクロペンテノン3.
88g〔旋光度α▲〕20 D▼−93.6゜（Ｃ＝1,クロロホル
ム）〕、プロピオン酸30mおよびプロピオン酸ナトリ
ウム1.5gを仕込み、110〜120℃にて６時間撹拌する。Optical rotation: α ▲] 20 D ▼ + 2.4 ° (C = 1, chloroform) Example 8 1-3-acetoxy-2-allyl-3-methyl-4-in a flask similar to that used in the actual baking example 1. Cyclopentenone 3.
88 g [optical rotation α ▲] 20 D -93.6 ° (C = 1, chloroform)], 30 m of propionic acid and 1.5 g of sodium propionate are charged and stirred at 110 to 120 ° C for 6 hours.
反応終了後、減圧にてプロピオン酸を留去し、残渣にト
ルエン30m、水20mを加えて抽出処理する。以下、実
施例２に準じて後処理して２−アリル−４−プロピオニ
ルオキシ−３−メチル−２−シクロペンテノン3.1g（収
率80％）を得た。After completion of the reaction, propionic acid is distilled off under reduced pressure, and 30 m of toluene and 20 m of water are added to the residue for extraction treatment. Then, post-treatment was carried out according to Example 2 to obtain 3.1 g of 2-allyl-4-propionyloxy-3-methyl-2-cyclopentenone (yield 80%).
旋光度：α▲〕20 D▼−1.1゜（Ｃ＝1,クロロホルム） 実施例４ 撹拌装置、温度計を装着した四ッ口フラスコにｌ−３−
アセトキシ−２−アリル−３−メチル−４−シクロペン
テノン3.88g〔旋光度α▲〕20 D▼−93.6゜（Ｃ＝1,クロ
ロホルム）〕酢酸30mおよび酢酸ナトリウム1gを仕込
み、還流下に５時間撹拌する。反応終了後、減圧にて酢
酸を留去し、残渣にトルエン80mおよび水20mを加
え、抽出処理する。有機層を重曹水洗いしたのち、トル
エンを留去する。濃縮残渣をカラムクロマト精製して４
−アセトキシ−２−アリル−３−メチル−２−シクロペ
ンテノン3.18g（収率82％）を得た。Optical rotation: α ▲] 20 D ▼ -1.1 ° (C = 1, chloroform) Example 4 In a four-necked flask equipped with a stirrer and a thermometer, 1-3-
Acetoxy-2-allyl-3-methyl-4-cyclopentenone 3.88 g [optical rotation α ▲] 20 D ▼ -93.6 ° (C = 1, chloroform)] Acetic acid 30 m and sodium acetate 1 g were charged, and the mixture was refluxed at 5 Stir for hours. After completion of the reaction, acetic acid is distilled off under reduced pressure, and toluene (80 m) and water (20 m) are added to the residue for extraction. After washing the organic layer with sodium bicarbonate water, the toluene is distilled off. Purify the concentrated residue by column chromatography
3.18 g (yield 82%) of -acetoxy-2-allyl-3-methyl-2-cyclopentenone was obtained.
旋光度α▲〕20 D▼−0.9゜（Ｃ＝1,クロロホルム） 実施例５〜９ 光学活性な４−シクロペンテノン類として、表−２にす
化合物を用いる以外は実施例４と同様に反応させ、処理
した結果を表−２に示す。Optical rotation α ▲] 20 D ▼ -0.9 ° (C = 1, chloroform) Examples 5 to 9 The same as Example 4 except that the compounds shown in Table 2 were used as the optically active 4-cyclopentenones. The results of the reaction and treatment are shown in Table-2.
実施例10〜14 光学活性な４−シクロペンテノン類として、表−３に示
す化合物を用いる以外は実施例１と同様に反応させ、処
理した結果を表−３に示す。Examples 10 to 14 As the optically active 4-cyclopentenones, the reaction and treatment were carried out in the same manner as in Example 1 except that the compounds shown in Table 3 were used.
実施例15 実施例１で用いたと同様のフラスコにプロピオン酸20m
およびプロピオン酸ナトリウム1.5gを仕込み、100℃
に加熱する。次にｌ−３−アセトキシ−2,3−ジメチル
−４−シクロペンテノン〔旋光度α▲〕20 D▼−19.6゜
（Ｃ＝1,クロロホルム）〕3.36gを１時間を要して滴下
する。さらに同温度にて６時間保持する。以下、実施例
３に準じて後処理し、2,3−ジメチル−４−プロピオニ
ルオキシ−２−シクロペンテノン3.02g（収率83％）を
得た。Example 15 A flask similar to that used in Example 1 was charged with 20 m of propionic acid.
And charged with 1.5g of sodium propionate, 100 ℃
Heat to. Next, 3.36 g of 1-3-acetoxy-2,3-dimethyl-4-cyclopentenone [optical rotation α ▲] 20 D ▼ -19.6 ° (C = 1, chloroform)] was added dropwise over 1 hour. . Further, the temperature is maintained for 6 hours. Then, post-treatment was carried out according to Example 3 to obtain 3.02 g (yield 83%) of 2,3-dimethyl-4-propionyloxy-2-cyclopentenone.
旋光度α▲〕20 D▼−0.6゜（Ｃ＝1,クロロホルム） Optical rotation α ▲] 20 D ▼ -0.6 ° (C = 1, chloroform)
Claims (1)
水素原子または低級アルキル基である。R1は水素原子、
アルキル基、またはアルケニル基を、R2はアルキル基、
アルケニル基またはアルキニル基をそれぞれ示す。） で示される光学活性な４−シクロペンテノン類と低級脂
肪族カルボン酸を加熱下に反応させることを特徴とする
一般式 （式中、R1およびR2は前記と同じ意味を有し、R3は水素
原子または低級アルキル基を示す。） で示される２−シクロペンテノンエステル類の製造法1. A general formula (In the formula, R represents —OH or —OOCR ′, where R ′ is a hydrogen atom or a lower alkyl group. R 1 is a hydrogen atom,
An alkyl group or an alkenyl group, R 2 is an alkyl group,
An alkenyl group or an alkynyl group is shown, respectively. ) An optically active 4-cyclopentenone represented by the following formula and a lower aliphatic carboxylic acid are reacted under heating (In the formula, R 1 and R 2 have the same meanings as described above, and R 3 represents a hydrogen atom or a lower alkyl group.) A method for producing a 2-cyclopentenone ester
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57199588A JPH0692344B2 (en) | 1982-11-12 | 1982-11-12 | Method for producing 2-cyclopentenone esters |
| US06/523,602 US4535182A (en) | 1982-08-26 | 1983-08-16 | Process for preparing 2-cyclopentenone esters |
| DE8383108390T DE3361426D1 (en) | 1982-08-26 | 1983-08-25 | Process for preparing 2-cyclopentenone esters |
| EP83108390A EP0102066B1 (en) | 1982-08-26 | 1983-08-25 | Process for preparing 2-cyclopentenone esters |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57199588A JPH0692344B2 (en) | 1982-11-12 | 1982-11-12 | Method for producing 2-cyclopentenone esters |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5988443A JPS5988443A (en) | 1984-05-22 |
| JPH0692344B2 true JPH0692344B2 (en) | 1994-11-16 |
Family
ID=16410337
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57199588A Expired - Lifetime JPH0692344B2 (en) | 1982-08-26 | 1982-11-12 | Method for producing 2-cyclopentenone esters |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0692344B2 (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0355459A (en) * | 1989-07-21 | 1991-03-11 | Koufu Nippon Denki Kk | Louver mechanism |
| JPH046697A (en) * | 1990-04-24 | 1992-01-10 | Ube Ind Ltd | Static information storage element |
-
1982
- 1982-11-12 JP JP57199588A patent/JPH0692344B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5988443A (en) | 1984-05-22 |
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