JPH0556327B2 - - Google Patents
Info
- Publication number
- JPH0556327B2 JPH0556327B2 JP59116253A JP11625384A JPH0556327B2 JP H0556327 B2 JPH0556327 B2 JP H0556327B2 JP 59116253 A JP59116253 A JP 59116253A JP 11625384 A JP11625384 A JP 11625384A JP H0556327 B2 JPH0556327 B2 JP H0556327B2
- Authority
- JP
- Japan
- Prior art keywords
- cyclopentenone
- acetoxy
- 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
- DHNDDRBMUVFQIZ-UHFFFAOYSA-N 4-hydroxycyclopent-2-en-1-one Chemical class OC1CC(=O)C=C1 DHNDDRBMUVFQIZ-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- BZKFMUIJRXWWQK-UHFFFAOYSA-N Cyclopentenone Chemical class O=C1CCC=C1 BZKFMUIJRXWWQK-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003905 agrochemical Substances 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- YZWFCEBQLPOTMV-UHFFFAOYSA-N (1-methyl-4-oxo-5-pentylcyclopent-2-en-1-yl) acetate Chemical compound CCCCCC1C(=O)C=CC1(C)OC(C)=O YZWFCEBQLPOTMV-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- KZYVOZABVXLALY-UHFFFAOYSA-N 4-hydroxy-3-methyl-2-prop-2-enylcyclopent-2-en-1-one Chemical compound CC1=C(CC=C)C(=O)CC1O KZYVOZABVXLALY-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- WGUKZZGKFOMLML-UHFFFAOYSA-N (1,5-dimethyl-4-oxocyclopent-2-en-1-yl) acetate Chemical compound CC1C(=O)C=CC1(C)OC(C)=O WGUKZZGKFOMLML-UHFFFAOYSA-N 0.000 description 1
- SJGDINJFWLOUAS-UHFFFAOYSA-N (1-methyl-4-oxo-5-pent-2-ynylcyclopent-2-en-1-yl) acetate Chemical compound CCC#CCC1C(=O)C=CC1(C)OC(C)=O SJGDINJFWLOUAS-UHFFFAOYSA-N 0.000 description 1
- RPCHZPHYUQVGCB-UHFFFAOYSA-N (1-methyl-4-oxo-5-prop-2-ynylcyclopent-2-en-1-yl) acetate Chemical compound CC(=O)OC1(C)C=CC(=O)C1CC#C RPCHZPHYUQVGCB-UHFFFAOYSA-N 0.000 description 1
- OEWQKLNLFPKGRZ-UHFFFAOYSA-N (1-methyl-4-oxo-5-propan-2-ylcyclopent-2-en-1-yl) acetate Chemical compound CC(C)C1C(=O)C=CC1(C)OC(C)=O OEWQKLNLFPKGRZ-UHFFFAOYSA-N 0.000 description 1
- IVQHFFYQGUAWAH-UHFFFAOYSA-N (1-methyl-4-oxo-5-propylcyclopent-2-en-1-yl) acetate Chemical compound CCCC1C(=O)C=CC1(C)OC(C)=O IVQHFFYQGUAWAH-UHFFFAOYSA-N 0.000 description 1
- DCRKYQWETCHGKF-UHFFFAOYSA-N (4-oxo-5-pent-2-ynylcyclopent-2-en-1-yl) acetate Chemical compound CCC#CCC1C(OC(C)=O)C=CC1=O DCRKYQWETCHGKF-UHFFFAOYSA-N 0.000 description 1
- PRQBBUZNXYNNJX-UHFFFAOYSA-N (4-oxo-5-pentylcyclopent-2-en-1-yl) acetate Chemical compound CCCCCC1C(OC(C)=O)C=CC1=O PRQBBUZNXYNNJX-UHFFFAOYSA-N 0.000 description 1
- JVHLTXYUBJWDSM-UHFFFAOYSA-N (4-oxo-5-prop-2-ynylcyclopent-2-en-1-yl) acetate Chemical compound CC(=O)OC1C=CC(=O)C1CC#C JVHLTXYUBJWDSM-UHFFFAOYSA-N 0.000 description 1
- FTXVWWGDBFIVRU-UHFFFAOYSA-N (4-oxo-5-propan-2-ylcyclopent-2-en-1-yl) acetate Chemical compound CC(C)C1C(OC(C)=O)C=CC1=O FTXVWWGDBFIVRU-UHFFFAOYSA-N 0.000 description 1
- CABQWNWINVOVCX-UHFFFAOYSA-N (4-oxo-5-propylcyclopent-2-en-1-yl) acetate Chemical compound CCCC1C(OC(C)=O)C=CC1=O CABQWNWINVOVCX-UHFFFAOYSA-N 0.000 description 1
- XVWHCHBZTWDVME-UHFFFAOYSA-N (5-butyl-1-methyl-4-oxocyclopent-2-en-1-yl) acetate Chemical compound CCCCC1C(=O)C=CC1(C)OC(C)=O XVWHCHBZTWDVME-UHFFFAOYSA-N 0.000 description 1
- OYENHAWOTNTRKN-UHFFFAOYSA-N (5-butyl-4-oxocyclopent-2-en-1-yl) acetate Chemical compound CCCCC1C(OC(C)=O)C=CC1=O OYENHAWOTNTRKN-UHFFFAOYSA-N 0.000 description 1
- UIJZOKQESZSUNG-UHFFFAOYSA-N (5-cyclohexyl-1-methyl-4-oxocyclopent-2-en-1-yl) acetate Chemical compound CC(=O)OC1(C)C=CC(=O)C1C1CCCCC1 UIJZOKQESZSUNG-UHFFFAOYSA-N 0.000 description 1
- GRJDGUYCMRPIGB-UHFFFAOYSA-N (5-cyclohexyl-4-oxocyclopent-2-en-1-yl) acetate Chemical compound CC(=O)OC1C=CC(=O)C1C1CCCCC1 GRJDGUYCMRPIGB-UHFFFAOYSA-N 0.000 description 1
- FTIRZWQAZLGWPY-UHFFFAOYSA-N (5-ethyl-1-methyl-4-oxocyclopent-2-en-1-yl) acetate Chemical compound CCC1C(=O)C=CC1(C)OC(C)=O FTIRZWQAZLGWPY-UHFFFAOYSA-N 0.000 description 1
- QOTXSSHXFVIEJP-UHFFFAOYSA-N (5-ethyl-4-oxocyclopent-2-en-1-yl) acetate Chemical compound CCC1C(OC(C)=O)C=CC1=O QOTXSSHXFVIEJP-UHFFFAOYSA-N 0.000 description 1
- AAFVVZBALGKUGA-UHFFFAOYSA-N (5-heptyl-1-methyl-4-oxocyclopent-2-en-1-yl) acetate Chemical compound CCCCCCCC1C(=O)C=CC1(C)OC(C)=O AAFVVZBALGKUGA-UHFFFAOYSA-N 0.000 description 1
- KEGLYEDMMWHPBD-UHFFFAOYSA-N (5-heptyl-4-oxocyclopent-2-en-1-yl) acetate Chemical compound CCCCCCCC1C(OC(C)=O)C=CC1=O KEGLYEDMMWHPBD-UHFFFAOYSA-N 0.000 description 1
- GKIBQFVQGMRMBC-UHFFFAOYSA-N (5-hexyl-1-methyl-4-oxocyclopent-2-en-1-yl) acetate Chemical compound CCCCCCC1C(=O)C=CC1(C)OC(C)=O GKIBQFVQGMRMBC-UHFFFAOYSA-N 0.000 description 1
- WJFYBBHNEIVKEJ-UHFFFAOYSA-N (5-hexyl-4-oxocyclopent-2-en-1-yl) acetate Chemical compound CCCCCCC1C(OC(C)=O)C=CC1=O WJFYBBHNEIVKEJ-UHFFFAOYSA-N 0.000 description 1
- VOLPZMGMPABFJB-UHFFFAOYSA-N (5-methyl-4-oxocyclopent-2-en-1-yl) acetate Chemical compound CC1C(OC(C)=O)C=CC1=O VOLPZMGMPABFJB-UHFFFAOYSA-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
- KPXHHHHMZICWTO-UHFFFAOYSA-N 4-hydroxy-3-methyl-2-pentylcyclopent-2-en-1-one Chemical compound CCCCCC1=C(C)C(O)CC1=O KPXHHHHMZICWTO-UHFFFAOYSA-N 0.000 description 1
- XGXOHEQJGPZLBP-UHFFFAOYSA-N C(C)(=O)OC1(C(C(C=C1)=O)C=CCCC)C Chemical compound C(C)(=O)OC1(C(C(C=C1)=O)C=CCCC)C XGXOHEQJGPZLBP-UHFFFAOYSA-N 0.000 description 1
- 235000007516 Chrysanthemum Nutrition 0.000 description 1
- 244000189548 Chrysanthemum x morifolium Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- XGXOHEQJGPZLBP-SREVYHEPSA-N [1-methyl-4-oxo-5-[(z)-pent-1-enyl]cyclopent-2-en-1-yl] acetate Chemical compound CCC\C=C/C1C(=O)C=CC1(C)OC(C)=O XGXOHEQJGPZLBP-SREVYHEPSA-N 0.000 description 1
- CDGVWSVDFAZHMV-AATRIKPKSA-N [4-oxo-5-[(e)-pent-1-enyl]cyclopent-2-en-1-yl] acetate Chemical compound CCC\C=C\C1C(OC(C)=O)C=CC1=O CDGVWSVDFAZHMV-AATRIKPKSA-N 0.000 description 1
- XAGQZBBSHHZJHW-UHFFFAOYSA-N [5-(cyclopenten-1-yl)-1-methyl-4-oxocyclopent-2-en-1-yl] acetate Chemical compound CC(=O)OC1(C)C=CC(=O)C1C1=CCCC1 XAGQZBBSHHZJHW-UHFFFAOYSA-N 0.000 description 1
- UQEAVMDLQXGWDD-UHFFFAOYSA-N [5-(cyclopenten-1-yl)-4-oxocyclopent-2-en-1-yl] acetate Chemical compound CC(=O)OC1C=CC(=O)C1C1=CCCC1 UQEAVMDLQXGWDD-UHFFFAOYSA-N 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 1
- 229940005991 chloric acid Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- -1 propionyloxy group Chemical group 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002728 pyrethroid Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000006462 rearrangement reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は、一般式（）
（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それぞれ示す。）
で示される４−ヒドロキシシクロペンテノン類の
製造法に関し、更に詳しくは、一般式（）
（式中、R′は水素原子または低級アルキル基
である。R1およびR2は前記と同じ意味を有す
る。）
で示されるdl−４−シクロペンテノン類（以下、
単に４−シクロペンテノン類と呼ぶ）を、水およ
び酸性物質の共存下に反応させることからなる前
記一般式（）で示される４−ヒドロキシシクロ
ペンテノン類の製造法である。
本発明により得られる一般式（）で示される
４−ヒドロキシシクロペンテノン類は農薬あるい
は医薬中間体として重要であるばかりでなく、香
料あるいはその中間体として有用な化合物であ
る。とくに、菊酸のエステルに導き、ピレスロイ
ド系殺虫剤として用いられるため、農薬用中間体
として重要な化合物である。
従来、かかる一般式（）で示される４−ヒド
ロキシシクロペンテノン類の合成法としては、数
多くの方法が知られているが、高価な原料を使
う、収率が悪い等工業的な製法としては決して満
足のいくものではなかつた。
このような状況下で、本発明者らは前記一般式
（）で示される４−ヒドロキシシクロペンテノ
ン類の製造法について研究した結果、従来全く知
られていない経路でかつ高純度、高収率で目的物
を得、しかも工業的に有利な方法を見い出した。
すなわち本発明は、前記一般式（）で示され
る４−シクロペンテノン類を水および酸性物質の
共存下に反応させることにより、一般式（）で
示される４−ヒドロキシシクロペンテノン類を得
る方法である。
尚、本発明に類似するものとして、シクロペン
テノン類の転位反応に関して
Tetrahedron，1979，35，135
Heterocycles，VOl19，No9，1735〜1744
（1982）
に記載の方法が知られている。しかしこれらはい
ずれもエステルからエステルへの転位であり、工
業的にも満足のいく方法ではなく、農薬としても
使用するためには、さらにエステル体の加水分解
を実施しなければならず、この加水分解の収率も
決して満足のいくものではなかつた。
しかるに、本発明者らが見い出した方法は４−
シクロペンテノン類から一気に４−ヒドロキシシ
クロペンテノン類を得るものであり、従来全く知
られていない新規な方法であるばかりでなく、収
率、純度の点で極めてすぐれたものであり、工業
的利用価値は計り知れないものがある。
以下に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４−シ
クロペンテノン類としては、たとえば３−アセト
キシ−２−メチル−４−シクロペンテノン、３−
アセトキシ−２−エチル−４−シクロペンテノ
ン、３−アセトキシ−２−ｎ−プロピル−４−シ
クロペンテノン、３−アセトキシ−２−イソ−プ
ロピル−４−シクロペンテノン、３−アセトキシ
−２−ｎ−ブチル−４−シクロペンテノン、３−
アセトキシ−２−ｎ−ペンチル−４−シクロペン
テノン、３−アセトキシ−２−ｎ−ヘキシル−４
−シクロペンテノン、３−アセトキシ−２−ｎ−
ヘプチル−４−シクロペンテノン、３−アセトキ
シ−２−アリル−４−シクロペンテノン、３−ア
セトキシ−２−（２−シス−ブチニル）−４−シク
ロペンテノン、３−アセトキシ−２−（ω−ブテ
ニル）−４−シクロペンテノン、３−アセトキシ
−２−（２−トランス−ペンテニル）−４−シクロ
ペンテノン、３−アセトキシ−２−（３−シス−
ヘキセニル）−４−シクロペンテノン、３−アセ
トキシ−２−プロパルギル−４−シクロペンテノ
ン、３−アセトキシ−２−（２−ペンチニル）−４
−シクロペンテノン、３−アセトキシ−２−（α
−メチルアリル）−４−シクロペンテノン、３−
アセトキシ−２−（１−シクロペンテニル）−４−
シクロペンテノン、３−アセトキシ−２−シクロ
ヘキシル−４−シクロペンテノン、３−アセトキ
シ−2.3−ジメチル−４−シクロペンテノン、３
−アセトキシ−２−エチル−３−メチル−４−シ
クロペンテノン、３−アセトキシ−２−ｎ−プロ
ピル−３−メチル−４−シクロペンテノン、３−
アセトキシ−２−イソプロピル−３−メチル−４
−シクロペンテノン、３−アセトキシ−２−ｎ−
ブチル−３−メチル−４−シクロペンテノン、３
−アセトキシ−２−ｎ−ペンチル−３−メチル−
４−シクロペンテノン、３−アセトキシ−２−ｎ
−ヘキシル−３−メチル−４−シクロペンテノ
ン、３−アセトキシ−２−ｎ−ヘプチル−３−メ
チル−４−シクロペンテノン、３−アセトキシ−
２−アリル−３−メチル−４−シクロペンテノ
ン、３−アセトキシ−２−（２−シス−ブチニル）
−３−メチル−４−シクロペンテノン、３−アセ
トキシ−２−（ω−ブチニル）−３−メチル−４−
シクロペンテノン、３−アセトキシ−２−（２−
シス−ペンテニル）−３−メチル−４−シクロペ
ンテノン、３−アセトキシ−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−アセトキシ−２−（８−シス−ヘキセ
ニル）−３−メチル−４−シクロペンテノン、３
−アセトキシ−２−プロパルギル−３−メチル−
４−シクロペンテノン、３−アセトキシ−２−
（２−ペンチニル）−３−メチル−４−シクロペン
テノン、３−アセトキシ−２−（α−メチルアリ
ル）−３−メチル−４−シクロペンテノン、３−
アセトキシ−２−（１−シクロペンテニル）−３−
メチル−４−シクロペンテノン、３−アセトキシ
−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
のアセトキシ基がプロピオニルオキシ基、ホルミ
ル基、ブテノイルオキシ基などのアシルオキシル
基に置換された化合物が例示される。
この反応で用いられる酸性物質としては塩酸、
硫酸、硝酸、リン酸、塩素酸、ポリリン酸、ホウ
酸、トルエンスルホン酸、メタンスルホン酸、酢
酸等の通常の無機酸、有機酸が例示され、その使
用量は原料である一般式（）で示される４−シ
クロペンテノン類に対して0.1〜100倍モル、好ま
しくは0.5〜50倍モルの範囲である。
また、水の使用量は原料４−シクロペンテノン
類に対して一般的には等モル以上であるが、酸性
物質として有機カルボン酸を用いる場合は３倍モ
ル以上、特に５倍モル以上であることが好まし
い。上限については何ら制限的でないが一般には
20モル倍である。
この反応において、上記水は溶媒としても利用
することができ、その他必要に応じてテトラヒド
ロフラン、ジオキサン、アセトン、ベンゼン、ト
ルエン、ジメチルスルホキシド、ジメチルホルム
アミド、ヘキサン、ジエチルエーテル、ジクロル
メタン、クロロマルム等の脂肪族もしくは芳香族
炭化水素、エーテル、ケトン、ハロゲン化炭化水
素などの反応に不活性な溶媒の単独または混合物
を溶媒として用いることができる。
反応温度は−10〜130℃の範囲で任意であるが、
好ましくは０℃〜110℃の範囲である。
反応時間については特に制限はない。
このような反応によつて、一般式（）で示さ
れる４−ヒドロキシシクロペンテノン類が容易
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。
以下、実施例により本発明を説明する。
実施例 １
撹拌装置、温度計を装着した四ツ口フラスコに
20％硫酸10mlを仕込み、内温を30〜50℃に調節し
ながらdl−３−アセトキシ−２−アリル−３−メ
チル−４−シクロペンテノン２ｇを１時間にて加
える。滴下終了後、同温度にて３時間保温する。
反応終了後、食塩３ｇを加え、メチルイソブチ
ルケトン20mlにて３回抽出する。有機層は、飽和
食塩水にて水洗いしたのちメチルイソブチルケト
ンを留去する。濃縮残渣をカラムクロマト精製し
て２−アリル−４−ヒドロキシ−３−メチル−２
−シクロペンテノン1.27ｇ（収率84％）を得た。
尚、上記実施例において、20％硫酸10mlの代わ
りに表−１に示す酸性物質の水溶液10mlを用いる
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に示すとおりであつた。
The present invention is based on the general formula () (In the formula, R 1 represents a hydrogen atom, an alkyl group, or an alkenyl group, and R 2 represents an alkyl group, an alkenyl group, or an alkynyl group, respectively.) is the general formula () (In the formula, R' is a hydrogen atom or a lower alkyl group. R 1 and R 2 have the same meanings as above.)
This is a method for producing 4-hydroxycyclopentenones represented by the general formula (), which comprises reacting 4-cyclopentenones (simply referred to as 4-cyclopentenones) in the presence of water and an acidic substance. The 4-hydroxycyclopentenones represented by the general formula () obtained by the present invention are not only important as agricultural chemicals or pharmaceutical intermediates, but also compounds useful as perfumes or intermediates thereof. In particular, it is an important compound as an intermediate for agricultural chemicals because it is converted into an ester of chrysanthemum acid and is used as a pyrethroid insecticide. Many methods have been known for synthesizing 4-hydroxycyclopentenones represented by the general formula (), but none of them are suitable for industrial production due to the use of expensive raw materials or poor yields. It was never satisfying. Under these circumstances, the present inventors conducted research on a method for producing 4-hydroxycyclopentenones represented by the general formula () and found that they were produced using a route that was completely unknown in the past, with high purity, and high yield. We have found a method that allows us to obtain the desired product and is also industrially advantageous. That is, the present invention provides a method for obtaining 4-hydroxycyclopentenones represented by the general formula () by reacting 4-cyclopentenones represented by the general formula () in the presence of water and an acidic substance. It is. Incidentally, as something similar to the present invention, regarding the rearrangement reaction of cyclopentenones, Tetrahedron, 1979, 35 , 135 Heterocycles, VOl 19, No 9, 1735-1744
(1982) is known. However, these are all rearrangements from ester to ester, and these are not industrially satisfactory methods.In order to use them as agricultural chemicals, the ester must be further hydrolyzed, and this hydrolyzed The yield of decomposition was also not satisfactory. However, the method discovered by the present inventors is 4-
This method obtains 4-hydroxycyclopentenones from cyclopentenones at once, and is not only a new method that was completely unknown until now, but also extremely superior in terms of yield and purity, making it suitable for industrial use. Its utility value is immeasurable. The present invention will be explained in detail below. In the present invention, examples of 4-cyclopentenones used as raw materials include 3-acetoxy-2-methyl-4-cyclopentenone, 3-
Acetoxy-2-ethyl-4-cyclopentenone, 3-acetoxy-2-n-propyl-4-cyclopentenone, 3-acetoxy-2-iso-propyl-4-cyclopentenone, 3-acetoxy-2- n-butyl-4-cyclopentenone, 3-
Acetoxy-2-n-pentyl-4-cyclopentenone, 3-acetoxy-2-n-hexyl-4
-cyclopentenone, 3-acetoxy-2-n-
Heptyl-4-cyclopentenone, 3-acetoxy-2-allyl-4-cyclopentenone, 3-acetoxy-2-(2-cis-butynyl)-4-cyclopentenone, 3-acetoxy-2-(ω -butenyl)-4-cyclopentenone, 3-acetoxy-2-(2-trans-pentenyl)-4-cyclopentenone, 3-acetoxy-2-(3-cis-
hexenyl)-4-cyclopentenone, 3-acetoxy-2-propargyl-4-cyclopentenone, 3-acetoxy-2-(2-pentynyl)-4
-cyclopentenone, 3-acetoxy-2-(α
-methylallyl)-4-cyclopentenone, 3-
Acetoxy-2-(1-cyclopentenyl)-4-
Cyclopentenone, 3-acetoxy-2-cyclohexyl-4-cyclopentenone, 3-acetoxy-2.3-dimethyl-4-cyclopentenone, 3
-acetoxy-2-ethyl-3-methyl-4-cyclopentenone, 3-acetoxy-2-n-propyl-3-methyl-4-cyclopentenone, 3-
Acetoxy-2-isopropyl-3-methyl-4
-cyclopentenone, 3-acetoxy-2-n-
Butyl-3-methyl-4-cyclopentenone, 3
-acetoxy-2-n-pentyl-3-methyl-
4-cyclopentenone, 3-acetoxy-2-n
-hexyl-3-methyl-4-cyclopentenone, 3-acetoxy-2-n-heptyl-3-methyl-4-cyclopentenone, 3-acetoxy-
2-allyl-3-methyl-4-cyclopentenone, 3-acetoxy-2-(2-cis-butynyl)
-3-Methyl-4-cyclopentenone, 3-acetoxy-2-(ω-butynyl)-3-methyl-4-
Cyclopentenone, 3-acetoxy-2-(2-
cis-pentenyl)-3-methyl-4-cyclopentenone, 3-acetoxy-2-(2-trans-pentenyl)-3-methyl-4-cyclopentenone, 3-acetoxy-2-(8-cis- hexenyl)-3-methyl-4-cyclopentenone, 3
-acetoxy-2-propargyl-3-methyl-
4-cyclopentenone, 3-acetoxy-2-
(2-pentynyl)-3-methyl-4-cyclopentenone, 3-acetoxy-2-(α-methylallyl)-3-methyl-4-cyclopentenone, 3-
Acetoxy-2-(1-cyclopentenyl)-3-
Methyl-4-cyclopentenone, 3-acetoxy-2-cyclohexyl-3-methyl-4-cyclopentenone, and the acetoxy group at the 3-position in these compounds is an acyloxyl group such as a propionyloxy group, a formyl group, or a butenoyloxy group. Examples include compounds substituted with groups. The acidic substances used in this reaction are hydrochloric acid,
Common inorganic acids and organic acids such as sulfuric acid, nitric acid, phosphoric acid, chloric acid, polyphosphoric acid, boric acid, toluenesulfonic acid, methanesulfonic acid, and acetic acid are exemplified, and the amount used is based on the general formula () of the raw material. The amount is in the range of 0.1 to 100 times, preferably 0.5 to 50 times, by mole relative to the indicated 4-cyclopentenone. In addition, the amount of water used is generally at least equimolar to the raw material 4-cyclopentenone, but when using an organic carboxylic acid as the acidic substance, it is at least 3 times the mole, especially at least 5 times the mole. It is preferable. There is no restriction on the upper limit, but in general
20 moles. In this reaction, the above water can also be used as a solvent, and if necessary, aliphatic or Solvents inert to the reaction, such as aromatic hydrocarbons, ethers, ketones, and halogenated hydrocarbons, may be used alone or in mixtures as the solvent. The reaction temperature is arbitrary in the range of -10 to 130°C, but
Preferably it is in the range of 0°C to 110°C. There is no particular restriction on the reaction time. Through such a reaction, 4-hydroxycyclopentenones represented by the general formula () can be easily obtained in good yields, and these can be separated by conventional separation means such as extraction, separation, concentration, and distillation. It can be easily isolated from the reaction mixture by et al. The present invention will be explained below with reference to Examples. Example 1 In a four-necked flask equipped with a stirrer and a thermometer.
Pour 10 ml of 20% sulfuric acid, and add 2 g of dl-3-acetoxy-2-allyl-3-methyl-4-cyclopentenone over 1 hour while adjusting the internal temperature to 30-50°C. After finishing dropping, keep warm at the same temperature for 3 hours. After the reaction is complete, add 3 g of common salt and extract 3 times with 20 ml of methyl isobutyl ketone. The organic layer is washed with saturated brine, and then methyl isobutyl ketone is distilled off. The concentrated residue was purified by column chromatography to obtain 2-allyl-4-hydroxy-3-methyl-2
- 1.27 g (yield 84%) of cyclopentenone was obtained. In addition, in the above example, the yield of the target compound was as shown in Table 1. It was hot.
【表】
実施例 ２
実施例１で用いたと同様のフラスコに３−アセ
トキシ−２−ｎ−ペンチル−３−メチル−４−シ
クロペンテノン2.24ｇ、テトラヒドロフラン
（THF）10mlおよび20％硫酸10mlを仕込み、30〜
50℃にて６時間撹拌する。
反応終了後、実施例１に準じて後処理、精製し
て４−ヒドロキシ−２−ｎ−ペンチル３−メチル
−２−シクロペンテノン（収率1.5585％）を得
た。
実施例 ３
３−アセトキシ−２−アリル−３−メチル−４
−シクロペンテノンに代えて３−アセトキシ−２
−アリル−４−シクロペンテノン1.8ｇ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＝
５：４）して２−アリル−４−ヒドロキシ−２−
シクロペンテノン1.15ｇ（収率83.5％）を得た。
実施例 ４
３−アセトキシ−２−アリル−３−メチル−４
−シクロペンテノンに代えて２−アリル−３−プ
ロピオニルオキシ−３−メチル−４−シクロペン
テノン2.08ｇを使用する以外は実施例１と同様に
反応、後処理、精製して２−アリル−４−ヒドロ
キシ３−メチル−２−シクロペンテノン1.26ｇ
（83％）を得た。
実施例 ５
実施例１で用いたと同様のフラスコに10％塩酸
水10mlおよびジオキサン10mlを仕込み、内温40〜
50℃にて２−アリル−３−アセトキシ−３−メチ
ル−４−シクロペンテノン1.94ｇを２時間にて加
える。その後同温度で３時間撹拌する。
以下、実施例１に準じて後処理し、２−アリル
−３−メチル−４−ヒドロキシ−２−シクロペン
テノン1.28ｇ（収率84.5％）を得た。
また、ジオキサンに代えてテトラヒドロフラン
を用いて同様に行つたところ目的物1.29ｇ（収率
85％）を得た。
実施例 ６〜９
４−シクロペンテノン類として、表２に示す化
合物を用い、表−２に示す条件以外は実施例１と
同様に反応させ、処理した結果を表−２に示す。[Table] Example 2 A flask similar to that used in Example 1 was charged with 2.24 g of 3-acetoxy-2-n-pentyl-3-methyl-4-cyclopentenone, 10 ml of tetrahydrofuran (THF), and 10 ml of 20% sulfuric acid. , 30～
Stir at 50°C for 6 hours. After the reaction was completed, the product was post-treated and purified according to Example 1 to obtain 4-hydroxy-2-n-pentyl 3-methyl-2-cyclopentenone (yield: 1.5585%). Example 3 3-acetoxy-2-allyl-3-methyl-4
-3-acetoxy-2 instead of cyclopentenone
The reaction and post-treatment were carried out in the same manner as in Example 1, except that 1.8 g of -allyl-4-cyclopentenone was used, and further column chromatography purification (toluene; ethyl acetate =
5:4) and 2-allyl-4-hydroxy-2-
1.15 g (yield 83.5%) of cyclopentenone was obtained. Example 4 3-acetoxy-2-allyl-3-methyl-4
-2-allyl- 4-hydroxy 3-methyl-2-cyclopentenone 1.26g
(83%). Example 5 A flask similar to that used in Example 1 was charged with 10 ml of 10% hydrochloric acid and 10 ml of dioxane, and the internal temperature was 40~40.
At 50 DEG C., 1.94 g of 2-allyl-3-acetoxy-3-methyl-4-cyclopentenone is added over a period of 2 hours. Thereafter, the mixture was stirred at the same temperature for 3 hours. Thereafter, post-treatment was performed according to Example 1 to obtain 1.28 g (yield: 84.5%) of 2-allyl-3-methyl-4-hydroxy-2-cyclopentenone. When the same procedure was carried out using tetrahydrofuran instead of dioxane, the desired product was 1.29 g (yield:
85%). Examples 6 to 9 The compounds shown in Table 2 were used as 4-cyclopentenones, and the reaction was carried out in the same manner as in Example 1 except for the conditions shown in Table 2. The results of the treatment are shown in Table 2.
【表】
＊ 本例のみ反応条件は実施例５に準じる。
実施例 10
実施例１で用いたと同様の装置に３−アセトキ
シ−２−アリル−３−メチル−４−シクロペンテ
ノン3.0ｇ、水10ｇおよび酢酸５ｇを仕込み、還
流下に、10時間撹拌する。反応終了後、反応液を
減圧下に濃縮し、メチルイソブチルケトン60mlに
て３回抽出する。抽出有機層をあわせ、水洗のの
ち、硫酸マグネシウムにて乾燥する。
有機層を減圧濃縮し、さらにカラムクロマトグ
ラフイーにて精製して、２−アリル−４−ヒドロ
キシ−３−メチル−２−シクロペンテノン1.95ｇ
（収率83％）を得た。[Table] *The reaction conditions for this example were the same as in Example 5.
Example 10 Into the same apparatus as used in Example 1, 3.0 g of 3-acetoxy-2-allyl-3-methyl-4-cyclopentenone, 10 g of water and 5 g of acetic acid were charged, and the mixture was stirred under reflux for 10 hours. After the reaction is completed, the reaction solution is concentrated under reduced pressure and extracted three times with 60 ml of methyl isobutyl ketone. The extracted organic layers are combined, washed with water, and then dried over magnesium sulfate. The organic layer was concentrated under reduced pressure and further purified by column chromatography to obtain 1.95 g of 2-allyl-4-hydroxy-3-methyl-2-cyclopentenone.
(yield 83%).
Claims (1)
を、R1は水素原子またはアルキル基を、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dl−４−シクロペンテノン類を、水お
よび酸性物質の共存下に反応させることを特徴と
する一般式 （式中、R1およびびR2は前記と同じ意味を有
する。） で示される４−ヒドロキシシクロペンテノン類の
製造法。[Claims] 1. General formula (In the formula, R′ represents a hydrogen atom or a lower alkyl group, R 1 represents a hydrogen atom or an alkyl group, and R 2 represents an alkyl group, an alkenyl group, or an alkynyl group, respectively.) A general formula characterized by reacting tenones in the coexistence of water and an acidic substance. (In the formula, R 1 and R 2 have the same meanings as above.) A method for producing 4-hydroxycyclopentenones represented by the following.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59116253A JPS60258138A (en) | 1984-06-05 | 1984-06-05 | Preparation of 4-hydroxycyclopentenone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59116253A JPS60258138A (en) | 1984-06-05 | 1984-06-05 | Preparation of 4-hydroxycyclopentenone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60258138A JPS60258138A (en) | 1985-12-20 |
| JPH0556327B2 true JPH0556327B2 (en) | 1993-08-19 |
Family
ID=14682545
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59116253A Granted JPS60258138A (en) | 1984-06-05 | 1984-06-05 | Preparation of 4-hydroxycyclopentenone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60258138A (en) |
-
1984
- 1984-06-05 JP JP59116253A patent/JPS60258138A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60258138A (en) | 1985-12-20 |
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