JPH0360811B2 - - Google Patents
Info
- Publication number
- JPH0360811B2 JPH0360811B2 JP7244881A JP7244881A JPH0360811B2 JP H0360811 B2 JPH0360811 B2 JP H0360811B2 JP 7244881 A JP7244881 A JP 7244881A JP 7244881 A JP7244881 A JP 7244881A JP H0360811 B2 JPH0360811 B2 JP H0360811B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- compound
- general formula
- methyl
- 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.)
- Expired
Links
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- 150000002170 ethers Chemical class 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000002350 geranyl group Chemical group [H]C([*])([H])/C([H])=C(C([H])([H])[H])/C([H])([H])C([H])([H])C([H])=C(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- -1 2-heptyl- 3-Methyl-4-methoxy-2-cyclopentenone Chemical compound 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-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
- BZKFMUIJRXWWQK-UHFFFAOYSA-N Cyclopentenone Chemical class O=C1CCC=C1 BZKFMUIJRXWWQK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- DHNDDRBMUVFQIZ-UHFFFAOYSA-N 4-hydroxycyclopent-2-en-1-one Chemical class 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
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- LOUPRKONTZGTKE-WZBLMQSHSA-N Quinine Chemical compound C([C@H]([C@H](C1)C=C)C2)C[N@@]1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-WZBLMQSHSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229960001755 resorcinol Drugs 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NOOLISFMXDJSKH-UTLUCORTSA-N (+)-Neomenthol Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@@H]1O NOOLISFMXDJSKH-UTLUCORTSA-N 0.000 description 1
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- IVGYSSJKFLEVIX-UHFFFAOYSA-N (-(E)-Pyrethrolone Natural products CC1=C(CC=CC=C)C(=O)CC1O IVGYSSJKFLEVIX-UHFFFAOYSA-N 0.000 description 1
- IVGYSSJKFLEVIX-SNAWJCMRSA-N (E)-pyrethrolone Chemical compound CC1=C(C\C=C\C=C)C(=O)CC1O IVGYSSJKFLEVIX-SNAWJCMRSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-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
- 235000007516 Chrysanthemum Nutrition 0.000 description 1
- 244000189548 Chrysanthemum x morifolium Species 0.000 description 1
- 235000001258 Cinchona calisaya Nutrition 0.000 description 1
- NOOLISFMXDJSKH-UHFFFAOYSA-N DL-menthol Natural products CC(C)C1CCC(C)CC1O NOOLISFMXDJSKH-UHFFFAOYSA-N 0.000 description 1
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 1
- 239000005792 Geraniol Substances 0.000 description 1
- GLZPCOQZEFWAFX-YFHOEESVSA-N Geraniol Natural products CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- HOPRXXXSABQWAV-UHFFFAOYSA-N anhydrous collidine Natural products CC1=CC=NC(C)=C1C HOPRXXXSABQWAV-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- WORJEOGGNQDSOE-UHFFFAOYSA-N chloroform;methanol Chemical compound OC.ClC(Cl)Cl WORJEOGGNQDSOE-UHFFFAOYSA-N 0.000 description 1
- 238000011097 chromatography purification Methods 0.000 description 1
- LOUPRKONTZGTKE-UHFFFAOYSA-N cinchonine Natural products C1C(C(C2)C=C)CCN2C1C(O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-UHFFFAOYSA-N 0.000 description 1
- UTBIMNXEDGNJFE-UHFFFAOYSA-N collidine Natural products CC1=CC=C(C)C(C)=N1 UTBIMNXEDGNJFE-UHFFFAOYSA-N 0.000 description 1
- GJMUCSXZXBCQRZ-UHFFFAOYSA-N geraniin Natural products Oc1cc(cc(O)c1O)C(=O)OC2OC3COC(=O)c4cc(O)c(O)c(O)c4c5cc(C(=O)C67OC3C(O6)C2OC(=O)c8cc(O)c(O)c9OC%10(O)C(C(=CC(=O)C%10(O)O)C7=O)c89)c(O)c(O)c5O GJMUCSXZXBCQRZ-UHFFFAOYSA-N 0.000 description 1
- 229930194078 geranin Natural products 0.000 description 1
- 229940113087 geraniol Drugs 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229960000443 hydrochloric acid Drugs 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229940041616 menthol Drugs 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 229960000948 quinine Drugs 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- GFYHSKONPJXCDE-UHFFFAOYSA-N sym-collidine Natural products CC1=CN=C(C)C(C)=C1 GFYHSKONPJXCDE-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Furan Compounds (AREA)
- 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（）
（式中、R1は水素原子、アルキル基またはア
ルケニル基を示し、R2はアルキル基、アルケニ
ル基、アリール基またはアルアルキル基を示し、
Ａはヒドロキシル基で置換されたアルキル基、ヒ
ドロキシル基で置換されたアリール基、ゲラニル
基またはメンチル基を示す。）
で示されるシクロペンテノン類のエーテル誘導体
に関する。
前記一般式（）で示される新規なシクロペン
テノン類のエーテル誘導体は、農薬あるいはその
中間体として価値あるばかりでなく、香料あるい
はこれらの中間体等としても有用なものである。
本発明化合物の類縁体として、２−ヘプチル−
３−メチル−４−メトキシ−２−シクロペンテノ
ン〔Tetrahedron，Vol.36，No.５，661（1980）〕
やピレスロロンメチルエーテル〔J.C.S.，239
（1944）〕などが知られており、たとえば前者の化
合物は
なる方法で製造することが記載されている。
しかしながら、上記文献には４位がメトキシ基
以外の化合物については全く記載がなく、前記一
般式（）化合物は３−ヒドロキシ−４−シクロ
ペンテノン類を原料として本発明者によつてはじ
めて合成された新規な化合物である。
しかも本発明化合物は公知化合物に比較して、
例えば、２−アリル−３−メチル−４−（２−ヒ
ドロキシエトキシ）−２−シクロペンテノン、２
−（２−シスペンテニル）−３−メチル−４−（２
−ヒドロキシエトキシ）−２−シクロペンテノン、
２−アリル−３−メチル−４−（３−ヒドロキシ
フエノキシ）−２−シクロペンテノン等の置換基
Ａがヒドロキシアルキル基や水酸基を有するアリ
ール基を示す場合には菊酸のエステルとすること
によつて新しいタイプの農薬として用いられるば
かりでなく、２−アリル−３−メチル−４−ゲラ
ニルオキシ−２−シクロペンテノン、３−メチル
−２−ｎ−ペンチル−４−ゲラニルオキシ−２−
シクロペンテノン、２−アリル−３−メチル−４
−ｌ−メンチルオキシ−２−シクロペンテノン等
のＡがゲラニン基やメンチル基を示す場合には優
れた芳香を有する香料もしくはその中間体とな
り、極めて価値ある化合物である。
本発明に係る一般式（）で示されるシクロペ
ンテノン類のエーテル誘導体は、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３−ヒドロキシ−４−シクロペンテノ
ン類と水酸基を有する化合物を反応させることに
より、容易にしかも極めて好収率で製造すること
ができる。
かかる反応は本発明者によつてはじめて明らか
にされた新規な方法であり、この反応において原
料として用いられる一般式（）化合物は、たと
えば次式に示されるようにフランカルビノーノ類
を転位させることにより容易に得ることができ
る。
また、もう一方の原料である水酸基を有する化
合物としては、たとえばエチレングリコール、
１、３−プロパンジオール、ゲラニオール、ｌ−
メントール、カテコール、レゾルシン、ハイドロ
キノンなどが挙げられる。
本発明に係る一般式（）化合物において、置
換基Ａはこれらの水酸基を有する有機化合物の
OH残基である。
一般式（）で示される３−ヒドロキシ−４−
シクロペンテノン類と水酸基を有する有機化合物
との反応は、溶媒の存在もしくは非存在下に触媒
を用いて反応させることにより実施される。
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水、ジオキサン、テトラヒ
ドロフラン、アセトン、メチルエチルケトン、
DMF、DMSO、ベンゼン、トルエン、クロロホ
ルム、ジクロルメタン、メチルエーテル、酢酸メ
チル等の脂肪族もしくは芳香族炭化水素、エーテ
ル、エステル、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。あ
るいは過剰量の水酸基を有する有機化合物を溶媒
として用いてもよい。
触媒としては、たとえばトルエンスルホン酸、
ベンセンスルホン酸、メタンスルホン酸、塩酸、
硫酸、リン酸、酢酸等の通常の酸性触媒、炭酸カ
リ、炭酸水素ナトリウム、トリエチルアミン、ピ
リジン、コリジン、キニーネ、ナトリウムメチラ
ート、ナトリウムエチラート、ナトリウム、カリ
ウム、リチウム等の金属もしくはこれらの水素化
物等の通常の塩基、金属の硝酸塩、硫酸塩、塩化
物、リン酸塩、酸化物類あるいは有機第４級アン
モニウム塩が例示される。これらは単独あるいは
２種以上の混合物として使用される。
触媒の使用量は特に制限されないが、通常原料
の一般式（）化合物に対して1/500〜1/2重量倍
である。
反応温度は０〜200℃で任意であるが、好まし
くは10〜160℃の範囲であり、反応時間について
も特に制限されない。
このような反応によつて、本発明化合物である
一般式（）で示されるシクロペンテノン類のエ
ーテル誘導体が容易に、かつ好収率で得られる。
以下、実施例により本発明を説明する。
実施例 １
２−アリル−３−メチル−４−（３−ヒドロキ
シルフエノキシ）−２−シクロペンテノンの製
造
撹拌装置、温度計を装着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0.1モル、これに対して５
倍重量部のレゾルシン、1/2倍重量部のテトラヒ
ドロフランおよび1/10倍重量部のトリエチルアミ
ンを加え、50〜80℃にて２時間撹拌する。
反応終了後、反応混合物にトルエンと水を加
え、分離した有機層はさらに５％炭酸ナトリウム
水溶液で洗浄する。得られた有機層からトルエン
を留去して２−アリル−３−メチル−４−（３−
ヒドロキシフエノキシ）−２−シクロペンテノン
を95％の収率で得た。
クロロホルム−メタノール（5/2＝Ｖ／Ｖ）で
クロマト精製すれば純品を与える。
20 D1.5707
実施例 ２〜８
実施例１に準じてシクロペンテノン類のエーテ
ル誘導体を製造した結果を表−１に示す。
尚、表における触媒、溶媒、OH含有化合物の
使用量はいずれもそれぞれの反応における原料一
般式（）化合物に対する重量倍で示した。
また、目的一般式（）化合物における置換基
R1、R2は原料一般式（）化合物と同じである。
【表】DETAILED DESCRIPTION OF THE INVENTION The present invention relates to 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, an aryl group or an aralkyl group,
A represents an alkyl group substituted with a hydroxyl group, an aryl group substituted with a hydroxyl group, a geranyl group or a menthyl group. ) Regarding ether derivatives of cyclopentenones. The novel ether derivatives of cyclopentenones represented by the general formula () are not only valuable as agricultural chemicals or intermediates thereof, but also useful as fragrances or intermediates thereof. As an analog of the compound of the present invention, 2-heptyl-
3-Methyl-4-methoxy-2-cyclopentenone [Tetrahedron, Vol. 36, No. 5, 661 (1980)]
and pyrethrolone methyl ether [JCS, 239
(1944)], for example, the former compound is It is described that it is manufactured by the following method. However, the above literature does not contain any description of compounds having a 4-position other than a methoxy group, and the compound of the general formula () was synthesized for the first time by the present inventor using 3-hydroxy-4-cyclopentenones as a raw material. It is a new compound. Moreover, compared to known compounds, the compound of the present invention has
For example, 2-allyl-3-methyl-4-(2-hydroxyethoxy)-2-cyclopentenone, 2
-(2-cispentenyl)-3-methyl-4-(2
-hydroxyethoxy)-2-cyclopentenone,
When substituent A such as 2-allyl-3-methyl-4-(3-hydroxyphenoxy)-2-cyclopentenone represents a hydroxyalkyl group or an aryl group having a hydroxyl group, it is an ester of chrysanthemum acid. In addition to being used as a new type of pesticide, 2-allyl-3-methyl-4-geranyloxy-2-cyclopentenone, 3-methyl-2-n-pentyl-4-geranyloxy-2 −
Cyclopentenone, 2-allyl-3-methyl-4
When A in -l-menthyloxy-2-cyclopentenone and the like represents a geranin group or a menthyl group, it becomes a fragrance having an excellent aroma or an intermediate thereof, and is an extremely valuable compound. The ether derivative of cyclopentenones represented by the general formula () according to the present invention has the general formula () (In the formula, R 1 and R 2 have the same meanings as above.) By reacting the 3-hydroxy-4-cyclopentenone represented by the formula with a compound having a hydroxyl group, it is possible to easily and with an extremely good yield. can be manufactured. This reaction is a novel method revealed for the first time by the present inventor, and the compound of general formula () used as a raw material in this reaction can be used to rearrange furan carbino compounds as shown in the following formula, for example. can be easily obtained. In addition, as the other raw material, a compound having a hydroxyl group, for example, ethylene glycol,
1,3-propanediol, geraniol, l-
Examples include menthol, catechol, resorcinol, and hydroquinone. In the compound of general formula () according to the present invention, substituent A is an organic compound having these hydroxyl groups.
It is an OH residue. 3-hydroxy-4- represented by general formula ()
The reaction between cyclopentenones and an organic compound having a hydroxyl group is carried out using a catalyst in the presence or absence of a solvent. In this reaction, when a solvent is used, examples of the solvent include water, dioxane, tetrahydrofuran, acetone, methyl ethyl ketone,
Examples include DMF, DMSO, benzene, toluene, chloroform, dichloromethane, methyl ether, aliphatic or aromatic hydrocarbons such as methyl acetate, ethers, esters, halogenated hydrocarbons, and other solvents inert to the reaction, either alone or in mixtures. . Alternatively, an organic compound having an excessive amount of hydroxyl groups may be used as a solvent. Examples of catalysts include toluenesulfonic acid,
Benzene sulfonic acid, methanesulfonic acid, hydrochloric acid,
Common acidic catalysts such as sulfuric acid, phosphoric acid, and acetic acid, potassium carbonate, sodium hydrogen carbonate, triethylamine, pyridine, collidine, quinine, sodium methylate, sodium ethylate, metals such as sodium, potassium, and lithium, or their hydrides, etc. Examples include common bases, metal nitrates, sulfates, chlorides, phosphates, oxides, and organic quaternary ammonium salts. These may be used alone or as a mixture of two or more. The amount of catalyst used is not particularly limited, but is usually 1/500 to 1/2 times the weight of the compound of general formula () as a raw material. The reaction temperature is arbitrary in the range of 0 to 200°C, but preferably in the range of 10 to 160°C, and the reaction time is not particularly limited either. Through such a reaction, the ether derivative of the cyclopentenone represented by the general formula (), which is a compound of the present invention, can be easily obtained in a good yield. The present invention will be explained below with reference to Examples. Example 1 Production of 2-allyl-3-methyl-4-(3-hydroxylphenoxy)-2-cyclopentenone 2-allyl-3-hydroxy was added to a four-necked flask equipped with a stirrer and a thermometer. -3-methyl-
0.1 mole of 4-cyclopentenone, for which 5
Double parts by weight of resorcin, 1/2 parts by weight of tetrahydrofuran and 1/10 parts by weight of triethylamine are added, and the mixture is stirred at 50 to 80°C for 2 hours. After the reaction is completed, toluene and water are added to the reaction mixture, and the separated organic layer is further washed with a 5% aqueous sodium carbonate solution. Toluene was distilled off from the obtained organic layer to give 2-allyl-3-methyl-4-(3-
Hydroxyphenoxy)-2-cyclopentenone was obtained with a yield of 95%. Chromatographic purification with chloroform-methanol (5/2=V/V) gives a pure product. 20 D 1.5707 Examples 2 to 8 Table 1 shows the results of producing ether derivatives of cyclopentenones according to Example 1. In addition, the amounts of the catalyst, solvent, and OH-containing compound used in the table are all shown in weight times the starting material general formula () compound in each reaction. Also, substituents in the target general formula () compound
R 1 and R 2 are the same as those of the raw material general formula () compound. 【table】
Claims (1)
ルケニル基を示し、R2はアルキル基、アルケニ
ル基、アリール基またはアルアルキル基を示し、
Ａはヒドロキシル基で置換されたアルキル基、ヒ
ドロキシル基で置換されたアリール基、ゲラニル
基またはメンチル基を示す。） で示されるシクロペンテノン類のエーテル誘導
体。[Claims] 1. 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, an aryl group or an aralkyl group,
A represents an alkyl group substituted with a hydroxyl group, an aryl group substituted with a hydroxyl group, a geranyl group or a menthyl group. ) Ether derivatives of cyclopentenones.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7244881A JPS57188541A (en) | 1981-05-13 | 1981-05-13 | Ether derivative of cyclopentenone compound |
| US06/377,050 US4665174A (en) | 1981-05-12 | 1982-05-11 | Production of cyclopentenone derivatives |
| GB8213799A GB2100254B (en) | 1981-05-12 | 1982-05-12 | Cyclopentenone derivatives and their production |
| FR8208298A FR2509291B1 (en) | 1981-05-12 | 1982-05-12 | CYCLOPENTENONE DERIVATIVES AND THEIR MANUFACTURING METHOD |
| DE19823217904 DE3217904A1 (en) | 1981-05-12 | 1982-05-12 | CYCLOPENTENONE DERIVATIVES AND METHOD FOR THE PRODUCTION THEREOF |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7244881A JPS57188541A (en) | 1981-05-13 | 1981-05-13 | Ether derivative of cyclopentenone compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57188541A JPS57188541A (en) | 1982-11-19 |
| JPH0360811B2 true JPH0360811B2 (en) | 1991-09-17 |
Family
ID=13489577
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7244881A Granted JPS57188541A (en) | 1981-05-12 | 1981-05-13 | Ether derivative of cyclopentenone compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57188541A (en) |
-
1981
- 1981-05-13 JP JP7244881A patent/JPS57188541A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57188541A (en) | 1982-11-19 |
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