JPH0355459B2 - - Google Patents
Info
- Publication number
- JPH0355459B2 JPH0355459B2 JP14860982A JP14860982A JPH0355459B2 JP H0355459 B2 JPH0355459 B2 JP H0355459B2 JP 14860982 A JP14860982 A JP 14860982A JP 14860982 A JP14860982 A JP 14860982A JP H0355459 B2 JPH0355459 B2 JP H0355459B2
- Authority
- JP
- Japan
- Prior art keywords
- cyclopentenone
- hydroxy
- methyl
- group
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- BZKFMUIJRXWWQK-UHFFFAOYSA-N Cyclopentenone Chemical compound O=C1CCC=C1 BZKFMUIJRXWWQK-UHFFFAOYSA-N 0.000 claims description 12
- -1 cyanohexyl group Chemical group 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 6
- 235000011054 acetic acid Nutrition 0.000 description 5
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- HNNRFEWGWVQYNP-UHFFFAOYSA-N 4-hydroxy-4-methyl-5-prop-2-enylcyclopent-2-en-1-one Chemical compound CC1(O)C=CC(=O)C1CC=C HNNRFEWGWVQYNP-UHFFFAOYSA-N 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 235000019260 propionic acid Nutrition 0.000 description 3
- 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 3
- 239000002994 raw material Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 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 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- HCGSXRYUKLYOFD-UHFFFAOYSA-N (2-methyl-4-oxo-3-pentylcyclopent-2-en-1-yl) acetate Chemical compound CCCCCC1=C(C)C(OC(C)=O)CC1=O HCGSXRYUKLYOFD-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
- 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-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
- BZTCJPVCZOODFD-UHFFFAOYSA-N 4-hydroxy-4-methyl-5-phenylcyclopent-2-en-1-one Chemical compound CC1(O)C=CC(=O)C1C1=CC=CC=C1 BZTCJPVCZOODFD-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
- 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
- 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
- XTMOUGOROVDTGR-UHFFFAOYSA-N 4-hydroxy-5-phenylcyclopent-2-en-1-one Chemical compound OC1C=CC(=O)C1C1=CC=CC=C1 XTMOUGOROVDTGR-UHFFFAOYSA-N 0.000 description 1
- ONQGUUWSGZTDPO-UHFFFAOYSA-N 4-hydroxy-5-prop-2-enylcyclopent-2-en-1-one Chemical compound OC1C=CC(=O)C1CC=C ONQGUUWSGZTDPO-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
- QWWTUUWNBYWOPE-UHFFFAOYSA-N 5-(4-chlorophenyl)-4-hydroxy-4-methylcyclopent-2-en-1-one Chemical compound CC1(O)C=CC(=O)C1C1=CC=C(Cl)C=C1 QWWTUUWNBYWOPE-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
- LNGQOESWVQUPGX-UHFFFAOYSA-N 5-butyl-4-hydroxycyclopent-2-en-1-one Chemical compound CCCCC1C(O)C=CC1=O LNGQOESWVQUPGX-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
- YBYBHQDUFSBDDA-UHFFFAOYSA-N 5-ethyl-4-hydroxycyclopent-2-en-1-one Chemical compound CCC1C(O)C=CC1=O YBYBHQDUFSBDDA-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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- FKMJJDZYBRVQBZ-UHFFFAOYSA-N OC1C(C(C=C1)=O)C=C/CCC Chemical compound OC1C(C(C=C1)=O)C=C/CCC FKMJJDZYBRVQBZ-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
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 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
- 239000003814 drug Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- GTUVXOOHBUUGBH-UHFFFAOYSA-N furan;methanol Chemical class OC.C=1C=COC=1 GTUVXOOHBUUGBH-UHFFFAOYSA-N 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 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
- 239000012044 organic layer Substances 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- JXKPEJDQGNYQSM-UHFFFAOYSA-M sodium propionate Chemical compound [Na+].CCC([O-])=O JXKPEJDQGNYQSM-UHFFFAOYSA-M 0.000 description 1
- 239000004324 sodium propionate Substances 0.000 description 1
- 235000010334 sodium propionate Nutrition 0.000 description 1
- 229960003212 sodium propionate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 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
本発明は、一般式（）
（式中、R1は水素原子、アルキル基、アルケニ
ル基を、R2はアルキル基、アルケニル基、アル
キニル基、シクロアルキル基、アリール基、ω−
シアノヘキシル基を、Ｒは水素原子または低級ア
ルキル基を示す。）
で示されるシクロペンテノンエステルの製造方法
に関する。
上記一般式（）で示されるシクロペンテノン
エステルはそれ自身農薬およびその中間体として
有用であるばかりでなく、香料や医薬品の中間体
としても有用なものであり、例えば該化合物を亜
鉛末−酢酸にて還元すれば、アシロキシ基が水素
に置換されたシクロペンテノン誘導体とすること
ができ、この化合物は香料として極めて重要なも
のである。
かかるシクロペンテノンエステルは、下式に示
されるように
対応するアルコールのエステル化やハロゲン原子
の置換反応などによつて合成することが可能であ
るが、いずれの方法も原料自身が高価であり、工
業的製法としても難点があつて、満足し得るもの
ではない。
このようなことから、本発明者らは一般式
（）で示されるシクロペンテノンエステルの新
しい製造法について研究した結果、従来全く知ら
れていなかつた新規な反応によつて、好収率で目
的物を得る工業的に有利な方法を見出し、本発明
を完成するに至つた。
すなわち本発明は、一般式（）
（式中、R1およびR2は前記と同じ意味を有す
る。）
で示されるシクロペンテノンアルコールと低級脂
肪族カルボン酸類を作用させることを特徴とする
前記一般式（）で示されるシクロペンテノンエ
ステルの製造方法である。
かかる反応は、本発明者らによつてはじめて明
らかにされた新規な反応である。
この反応において、原料として用いられるシク
ロペンテノンアルコールは、たとえば次式に示さ
れるようにフランカルビノール類を転位させるこ
とにより容易に合成することができる。
（式中、R1およびR2は前記と同様の意味を有す
る。）
かかる一般式（）で示されるシクロペンテノ
ンアルコールとして、具体的には２−メチル−３
−ヒドロキシ−４−シクロペンテノン、２−エチ
ル−３−ヒドロキシ−４−シクロペンテノン、２
−ｎ−プロピル−３−ヒドロキシ−４−シクロペ
ンテノン、２−イソプロピル−３−ヒドロキシ−
４−シクロペンテノン、２−ｎ−ブチル−３−ヒ
ドロキシ−４−シクロペンテノン、２−ｎ−ペン
チル−３−ヒドロキシ−４−シクロペンテノン、
２−ｎ−ヘキシル−３−ヒドロキシ−４−シクロ
ペンテノン、２−ｎ−ヘプチル−３−ヒドロキシ
−４−シクロペンテノン、２−アリル−３−ヒド
ロキシ−４−シクロペンテノン、２−（２−シス
−ブチニル）−３−ヒドロキシ−４−シクロペン
テノン、２−（２−シス−ペンテニル）−３−ヒド
ロキシ−４−シクロペンテノン、２−（２−トラ
ンス−ペンテニル）−３−ヒドロキシ−４−シク
ロペンテノン、２−（２−シス−ヘキセニル）−３
−ヒドロキシ−４−シクロペンテノン、２−プロ
パルギル−３−ヒドロキシ−４−シクロペンテノ
ン、２−（２−ペンチニル）−３−ヒドロキシ−４
−シクロペンテノン、２−（ω−シアノヘキシル）
−３−ヒドロキシ−４−シクロペンテノン、２−
フエニル−３−ヒドロキシ−４−シクロペンテノ
ン、２−（α−メチルアリル）−３−ヒドロキシ−
４−シクロペンテノン、２−メチル−３−ヒドロ
キシ−３−メチル−４−シクロペンテノン、２−
エチル−３−ヒドロキシ−３−メチル−４−シク
ロペンテノン、２−ｎ−プロピル−３−ヒドロキ
シ−３−メチル−４−シクロペンテノン、２−ｎ
−ブチル−３−ヒドロキシ−３−メチル−４−シ
クロペンテノン、２−ｎ−ペンチル−３−ヒドロ
キシ−３−メチル−４−シクロペンテノン、２−
ｎ−ヘキシル−３−ヒドロキシ−３−メチル−４
−シクロペンテノン、２−ｎ−ヘプチル−３−ヒ
ドロキシ−３−メチル−４−シクロペンテノン、
２−アリル−３−ヒドロキシ−３−メチル−４−
シクロペンテノン、２−（２−シス−ブチニル）−
３−ヒドロキシ３−メチル−４−シクロペンテノ
ン、２−（２−シス−ペンテニル）−３−ヒドロキ
シ−３−メチル−４−シクロペンテノン、２−
（２−トランス−ペンテニル）−３−ヒドロキシ−
４−シクロペンテノン、２−（３−シス−ヘキセ
ニル）−３−ヒドロキシ−３−メチル−４−シク
ロペンテノン、２−フエニル−３−ヒドロキシ−
３−メチル−４−シクロペンテノン、２−ｐ−ク
ロロフエニル−３−ヒドロキシ−３−メチル−４
−シクロペンテノン、２−プロパルギル−３−ヒ
ドロキシ−３−メチル−４−シクロペンテノン、
２−（２−ペンチニル）−３−ヒドロキシ−３−メ
チル−４−シクロペンテノン、２−ｎ−ペンチル
−３−アリル−３−ヒドロキシ−４−シクロペン
テノン、２−（ω−シアノヘキシル）−３−ヒドロ
キシ−３−メチル−４−シクロペンテノンなどが
例示される。
また、もう一方の反応原料である低級脂肪族カ
ルボン酸類としてはギ酸、酢酸、プロピオン酸、
酪酸、吉草酸などのカルボン酸およびこれらの金
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）が挙
げられ、これらは単独もしくは混合物として用い
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。
一般式（）で示されるシクロペンテノンアル
コールと低級脂肪族カルボン酸類との反応は、溶
媒の存在もしくは非存在下に加熱することにより
行われる。
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、ヘキサン等の脂肪族
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な溶媒の単独または混合
物があげられる。その使用量については特に制限
されない。
また、反応成分である低級脂肪族カルボン酸を
溶媒として使用することもできる。
この反応において、低級脂肪族カルボン酸類の
使用量はシクロペンテノンアルコール（）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。
反応温度は０〜150℃であるが、好ましくは30
〜140℃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
れるシクロペンテノンエステルが容易に、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。
以下に実施例により本発明を説明する。
実施例 １
撹拌装置、温度計を装置した四ツ口フラスコ
に、２−アリル−３−ヒドロキシ−３−メチル−
４−シクロペンテノン15.2ｇ、酢酸45mlおよび酢
酸ナトリウム２ｇを加え、還流下に７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60mlおよび水40mlを加えて抽出処理する。
有機層を重曹水洗い、水洗したのち、トルエン
を留去する。濃縮残渣を蒸留して、４−アセトキ
シ−２−アリル−３−メチル−２−シクロペンテ
ノンを得た。
収量18.5ｇ（収率95.3％）
b.p.100〜110℃／0.1〜0.3mmHg
尚、上記実施例において、酢酸ナトリウム２ｇ
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に示すとおりであつた。
The present invention is based on the general formula () (In the formula, R 1 is a hydrogen atom, an alkyl group, an alkenyl group, and R 2 is an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, an ω-
R represents a cyanohexyl group, and R represents a hydrogen atom or a lower alkyl group. ) The present invention relates to a method for producing a cyclopentenone ester. The cyclopentenone ester represented by the above general formula () is not only useful itself as a pesticide and its intermediate, but also as an intermediate for fragrances and pharmaceuticals. When reduced with , it is possible to obtain a cyclopentenone derivative in which the acyloxy group is substituted with hydrogen, and this compound is extremely important as a fragrance. Such cyclopentenone ester is as shown in the formula below. Although it is possible to synthesize it by esterification of the corresponding alcohol or substitution reaction of halogen atoms, both methods require expensive raw materials and have drawbacks as an industrial method, but none of them are satisfactory. isn't it. Based on these facts, the present inventors researched a new method for producing cyclopentenone ester represented by the general formula (). As a result, the present inventors found that a new method for producing cyclopentenone ester represented by the general formula () was achieved. They have discovered an industrially advantageous method for obtaining a product and have completed the present invention. That is, the present invention provides general formula () (In the formula, R 1 and R 2 have the same meanings as above.) A cyclopentenone represented by the above general formula (), which is obtained by reacting a cyclopentenone alcohol represented by the formula with a lower aliphatic carboxylic acid. This is a method for producing ester. This reaction is a novel reaction revealed for the first time by the present inventors. In this reaction, cyclopentenone alcohol used as a raw material can be easily synthesized, for example, by rearranging furan carbinols as shown in the following formula. (In the formula, R 1 and R 2 have the same meanings as above.) Specifically, the cyclopentenone alcohol represented by the general formula () is 2-methyl-3
-Hydroxy-4-cyclopentenone, 2-ethyl-3-hydroxy-4-cyclopentenone, 2
-n-propyl-3-hydroxy-4-cyclopentenone, 2-isopropyl-3-hydroxy-
4-cyclopentenone, 2-n-butyl-3-hydroxy-4-cyclopentenone, 2-n-pentyl-3-hydroxy-4-cyclopentenone,
2-n-hexyl-3-hydroxy-4-cyclopentenone, 2-n-heptyl-3-hydroxy-4-cyclopentenone, 2-allyl-3-hydroxy-4-cyclopentenone, 2-(2 -cis-butynyl)-3-hydroxy-4-cyclopentenone, 2-(2-cis-pentenyl)-3-hydroxy-4-cyclopentenone, 2-(2-trans-pentenyl)-3-hydroxy- 4-cyclopentenone, 2-(2-cis-hexenyl)-3
-Hydroxy-4-cyclopentenone, 2-propargyl-3-hydroxy-4-cyclopentenone, 2-(2-pentynyl)-3-hydroxy-4
-cyclopentenone, 2-(ω-cyanohexyl)
-3-hydroxy-4-cyclopentenone, 2-
Phenyl-3-hydroxy-4-cyclopentenone, 2-(α-methylallyl)-3-hydroxy-
4-cyclopentenone, 2-methyl-3-hydroxy-3-methyl-4-cyclopentenone, 2-
Ethyl-3-hydroxy-3-methyl-4-cyclopentenone, 2-n-propyl-3-hydroxy-3-methyl-4-cyclopentenone, 2-n
-Butyl-3-hydroxy-3-methyl-4-cyclopentenone, 2-n-pentyl-3-hydroxy-3-methyl-4-cyclopentenone, 2-
n-hexyl-3-hydroxy-3-methyl-4
-cyclopentenone, 2-n-heptyl-3-hydroxy-3-methyl-4-cyclopentenone,
2-allyl-3-hydroxy-3-methyl-4-
Cyclopentenone, 2-(2-cis-butynyl)-
3-hydroxy 3-methyl-4-cyclopentenone, 2-(2-cis-pentenyl)-3-hydroxy-3-methyl-4-cyclopentenone, 2-
(2-trans-pentenyl)-3-hydroxy-
4-cyclopentenone, 2-(3-cis-hexenyl)-3-hydroxy-3-methyl-4-cyclopentenone, 2-phenyl-3-hydroxy-
3-Methyl-4-cyclopentenone, 2-p-chlorophenyl-3-hydroxy-3-methyl-4
-cyclopentenone, 2-propargyl-3-hydroxy-3-methyl-4-cyclopentenone,
2-(2-pentynyl)-3-hydroxy-3-methyl-4-cyclopentenone, 2-n-pentyl-3-allyl-3-hydroxy-4-cyclopentenone, 2-(ω-cyanohexyl) -3-hydroxy-3-methyl-4-cyclopentenone and the like are exemplified. In addition, lower aliphatic carboxylic acids, which are the other raw materials for the reaction, include formic acid, acetic acid, propionic acid,
Carboxylic acids such as butyric acid and valeric acid, their metal salts (e.g. lithium salts, sodium salts, potassium salts, calcium salts, copper salts, zinc salts, palladium salts, lead salts, tin salts, manganese salts, etc.), organic amine salts (For example, trimethylamine salt, triethylamine salt, pyridine salt, picoline salt, etc.), and these may be used alone or as a mixture, but it is particularly preferable to use a carboxylic acid and its metal salt in combination. The reaction between the cyclopentenone alcohol represented by the general formula () and lower aliphatic carboxylic acids is carried out by heating in the presence or absence of a solvent. In this reaction, when a solvent is used, examples of the solvent include aliphatic or Examples include solvents that are inert to the reaction, such as aromatic hydrocarbons, ethers, and halogenated hydrocarbons, either alone or as a mixture. There is no particular restriction on the amount used. Moreover, lower aliphatic carboxylic acid, which is a reaction component, can also be used as a solvent. In this reaction, the amount of lower aliphatic carboxylic acids used is 1 equivalent or more, preferably 2 equivalents or more, relative to the cyclopentenone alcohol (). The reaction temperature is 0 to 150°C, preferably 30°C.
~140℃ range. There is no particular restriction on the reaction time. Through such a reaction, the cyclopentenone ester represented by the general formula () can be easily obtained in good yield, and these can be reacted by ordinary separation means such as extraction, separation, concentration, distillation, etc. Can be easily isolated from mixtures. The present invention will be explained below with reference to Examples. Example 1 2-allyl-3-hydroxy-3-methyl- was added to a four-necked flask equipped with a stirrer and a thermometer.
Add 15.2 g of 4-cyclopentenone, 45 ml of acetic acid and 2 g of sodium acetate, and stir under reflux for 7 hours. After the reaction is completed, acetic acid is distilled off under reduced pressure, and 60 ml of toluene and 40 ml of water are added to the residue for extraction. After washing the organic layer with sodium bicarbonate and water, toluene is distilled off. The concentrated residue was distilled to obtain 4-acetoxy-2-allyl-3-methyl-2-cyclopentenone. Yield 18.5g (yield 95.3%) bp100-110℃/0.1-0.3mmHg In the above example, 2g of sodium acetate
The reaction and treatment were carried out in exactly the same manner except that the acetate shown in Table 1 was used instead of , and the yield of the target compound was as shown in Table 1.
【表】
実施例 ２〜９
実施例１における２−アリル−３−ヒドロキシ
−３−メチル−４−シクロペンテノンに代えて表
−２に記載のシクロペンテノンアルコールを用い
る以外は実施例１と同様に反応させ、処理した結
果を表−２に示す。[Table] Examples 2 to 9 Same as Example 1 except that cyclopentenone alcohol listed in Table 2 was used in place of 2-allyl-3-hydroxy-3-methyl-4-cyclopentenone in Example 1. The results of the same reaction and treatment are shown in Table 2.
【表】
実施例 10
実施例１で用いたと同様のフラスコに２−アリ
ル−３−ヒドロキシ−３−メチル−４−シクロペ
ンテノン15.2ｇ、プロピオン酸60mlおよびプロピ
オン酸ナトリウム３ｇを仕込み、120〜130℃にて
８時間撹拌する。
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60mlおよび水40mlを加えて抽出処
理する。以下、実施例１と同様に処理して２−ア
リル−４−プロピオニルオキシ−３−メチル−２
−シクロペンテノンを得た。
収量19.7ｇ（収率94.7％）
b.p.115〜120℃／0.1〜0.2mmHg
実施例 11〜13
実施例10における２−アリル−３−ヒドロキシ
−３−メチル−４−シクロペンテノンに代えて表
−３に記載のシクロペンテノンアルコールを用い
る以外は実施例10と同様に反応させ、処理した結
果を表−３に示す。[Table] Example 10 A flask similar to that used in Example 1 was charged with 15.2 g of 2-allyl-3-hydroxy-3-methyl-4-cyclopentenone, 60 ml of propionic acid, and 3 g of sodium propionate. Stir at ℃ for 8 hours. After the reaction, propionic acid was distilled off under reduced pressure.
Add 60 ml of toluene and 40 ml of water to the residue for extraction. Hereinafter, 2-allyl-4-propionyloxy-3-methyl-2 was treated in the same manner as in Example 1.
- Cyclopentenone was obtained. Yield 19.7g (yield 94.7%) bp115-120℃/0.1-0.2mmHg Examples 11-13 Table 3 in place of 2-allyl-3-hydroxy-3-methyl-4-cyclopentenone in Example 10 The reaction was carried out in the same manner as in Example 10 except that the cyclopentenone alcohol described in Example 10 was used, and the results are shown in Table 3.
【表】
実施例 14
実施例１で用いたと同様にフラスコに、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18.2ｇおよび酢酸55mlを仕込
み、15時間、加熱撹拌する。
反応終了後、減圧にて酢酸を留去し、残渣にト
ルエン80mlと水50mlを加えて抽出処理する。
以下実施例１に準じて後処理し、２−ｎ−ペン
チル−３−メチル４−アセトキシ−２−シクロペ
ンテノン20.6ｇ（収率92％）を得た。b.p.125〜
135℃／0.2〜0.5mmHg[Table] Example 14 In the same flask as used in Example 1, 3-hydroxy-2-n-pentyl-3-methyl-4-
Charge 18.2 g of cyclopentenone and 55 ml of acetic acid, and heat and stir for 15 hours. After the reaction is completed, acetic acid is distilled off under reduced pressure, and 80 ml of toluene and 50 ml of water are added to the residue for extraction. Thereafter, post-treatment was performed according to Example 1 to obtain 20.6 g (yield: 92%) of 2-n-pentyl-3-methyl 4-acetoxy-2-cyclopentenone. bp125〜
135℃/0.2~0.5mmHg
Claims (1)
ル基を、R2はアルキル基、アルケニル基、アル
キニル基、シクロアルキル基、アリール基、ω−
シアノヘキシル基をそれぞれ示す。） で示されるシクロペンテノンアルコールと低級脂
肪族カルホン酸類を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、
Ｒは水素原子または低級アルキル基を示す。） で示されるシクロペンテノンエステルの製造方
法。[Claims] 1. General formula (In the formula, R 1 is a hydrogen atom, an alkyl group, an alkenyl group, and R 2 is an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, an ω-
Each represents a cyanohexyl group. ) A general formula characterized by reacting cyclopentenone alcohol and lower aliphatic carbonic acids (wherein R 1 and R 2 have the same meanings as above,
R represents a hydrogen atom or a lower alkyl group. ) A method for producing a cyclopentenone ester.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14860982A JPS5939852A (en) | 1982-08-26 | 1982-08-26 | Preparation of cyclopentenone ester |
| 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 |
|---|---|---|---|
| JP14860982A JPS5939852A (en) | 1982-08-26 | 1982-08-26 | Preparation of cyclopentenone ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5939852A JPS5939852A (en) | 1984-03-05 |
| JPH0355459B2 true JPH0355459B2 (en) | 1991-08-23 |
Family
ID=15456599
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14860982A Granted JPS5939852A (en) | 1982-08-26 | 1982-08-26 | Preparation of cyclopentenone ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5939852A (en) |
-
1982
- 1982-08-26 JP JP14860982A patent/JPS5939852A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5939852A (en) | 1984-03-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4376061B2 (en) | Alkenone production | |
| JPH0355459B2 (en) | ||
| JP3823385B2 (en) | Process for producing 2,4,5-trifluoro-3-iodobenzoic acid and esters thereof | |
| JP2000080082A (en) | Production of 5-halogeno-2-substituted pyridine | |
| JP3477631B2 (en) | Purification method of 1,3-bis (3-aminopropyl) -1,1,3,3-tetraorganodisiloxane | |
| JP2743198B2 (en) | Cyclopentanes | |
| JPH046697B2 (en) | ||
| JP4018816B2 (en) | Cycloheptenone derivative and method for producing the same, and method for producing cycloheptimidazole derivative using the same | |
| US6096894A (en) | Production method of 2-(p-alkylphenyl)pyridine compound | |
| JP2653138B2 (en) | Haloallylfuran carbinols and their preparation | |
| JP3272340B2 (en) | Method for producing 1-[(cyclopent-3-en-1-yl) methyl] -5-ethyl-6- (3,5-dimethylbenzoyl) -2,4-pyrimidinedione | |
| JPS6254416B2 (en) | ||
| JPH027305B2 (en) | ||
| JPH0267250A (en) | Production of 2,2-difluoro-3-hydroxycarboxylic acid derivative | |
| JPS6313982B2 (en) | ||
| JPH07247267A (en) | Production of phenyl ethers | |
| JPH06340630A (en) | Production of 2-chloro-pyridinemethanol | |
| JPS6227054B2 (en) | ||
| JP3494465B2 (en) | Method for producing optically active α-amino acid derivative | |
| KR100343551B1 (en) | Process for preparing 4-alkoxycarbonyl-5-chloropyrazole derivatives | |
| JP2893890B2 (en) | Method for producing carbonyl compound having bromodifluoromethyl group at β-position | |
| JPH0372054B2 (en) | ||
| JPH041736B2 (en) | ||
| JPS6350340B2 (en) | ||
| JPS6126555B2 (en) |