JPH069502A - Cyclohexenone compound and its production - Google Patents
Cyclohexenone compound and its productionInfo
- Publication number
- JPH069502A JPH069502A JP5085135A JP8513593A JPH069502A JP H069502 A JPH069502 A JP H069502A JP 5085135 A JP5085135 A JP 5085135A JP 8513593 A JP8513593 A JP 8513593A JP H069502 A JPH069502 A JP H069502A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- zinc
- formula
- general formula
- lower alkyl
- 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- -1 Cyclohexenone compound Chemical class 0.000 title abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 150000003752 zinc compounds Chemical class 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 239000011701 zinc Substances 0.000 abstract description 4
- ZUWDWMUSAHEJIZ-UHFFFAOYSA-N methyl 3-methoxy-2-methyl-4-oxocyclohex-2-ene-1-carboxylate Chemical compound COC(=O)C1CCC(=O)C(OC)=C1C ZUWDWMUSAHEJIZ-UHFFFAOYSA-N 0.000 abstract description 3
- 238000005580 one pot reaction Methods 0.000 abstract description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 abstract description 2
- JDLYKQWJXAQNNS-UHFFFAOYSA-L zinc;dibenzoate Chemical compound [Zn+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 JDLYKQWJXAQNNS-UHFFFAOYSA-L 0.000 abstract description 2
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract 1
- 239000003905 agrochemical Substances 0.000 abstract 1
- 229940079593 drug Drugs 0.000 abstract 1
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 abstract 1
- 239000011592 zinc chloride Substances 0.000 abstract 1
- 235000005074 zinc chloride Nutrition 0.000 abstract 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WDVLUEIBBKAGNQ-UHFFFAOYSA-N 1,4-dimethoxybutan-2-one Chemical compound COCCC(=O)COC WDVLUEIBBKAGNQ-UHFFFAOYSA-N 0.000 description 2
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 229910007340 Zn(OAc)2.2H2O Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical compound C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- BEAZKUGSCHFXIQ-UHFFFAOYSA-L zinc;diacetate;dihydrate Chemical compound O.O.[Zn+2].CC([O-])=O.CC([O-])=O BEAZKUGSCHFXIQ-UHFFFAOYSA-L 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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】農医薬の中間体として有用なシク
ロヘキセノン化合物及びその製造方法に関する。TECHNICAL FIELD The present invention relates to a cyclohexenone compound useful as an intermediate for agricultural medicine and a method for producing the same.
【０００２】[0002]
【従来の技術】本発明化合物の類似化合物として、J. C
hem. Soc., Perkin I, 602(1972)に次の記載がある。2. Description of the Related Art As a compound similar to the compound of the present invention, J. C.
hem. Soc., Perkin I, 602 (1972) has the following description.
【化３】 （式中ｒは低級アルキル基を示す。） 反応条件により（ａ）又は（ｂ）が合成される。又、ビ
ニルケトンの合成法としては、Synthetic Communicatio
n, 3(3), 205〜209(1973）にＣＨ3 ＯＣＨ2 ＣＨ2 ＣＯ
ＣＨ2 ＯＣＨ3 にＰ−トルエンスルホン酸を作用させ
て、ＣＨ2 ＝ＣＨＣＯＣＨ2 ＯＣＨ3 を合成した例が記
載されているが、収率は低い。[Chemical 3] (In the formula, r represents a lower alkyl group.) (A) or (b) is synthesized depending on the reaction conditions. The synthetic method of vinyl ketone is Synthetic Communicatio.
n, 3 (3), to 205~209 (1973) CH 3 OCH 2 CH 2 CO
The CH 2 OCH 3 is reacted with a P- toluenesulfonic acid, CH 2 = is an example obtained by combining the CHCOCH 2 OCH 3 is described, yields are low.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、一般式Ｒ4
ＯＣＨ2 ＣＨ2 ＣＯＣＨ2 ＯＲ1 で表される化合物と一
般式Ｒ2 ＣＯＣＨ2 ＣＯＯＲ3 で表される化合物より工
業的に有利に一般式〔Ｉ〕で表される化合物The present invention is based on the general formula R 4
A compound represented by the general formula [I] is industrially more advantageous than a compound represented by OCH 2 CH 2 COCH 2 OR 1 and a compound represented by the general formula R 2 COCH 2 COOR 3 .
【化４】 （式中、Ｒ1 、Ｒ2 、Ｒ3 およびＲ4 は前記と同じ意味
を示す。）を提供することである。[Chemical 4] (Wherein R 1 , R 2 , R 3 and R 4 have the same meanings as described above).
【０００４】[0004]
【課題を解決するための手段】本発明は、（１）一般式
〔Ｉ〕The present invention provides (1) general formula [I]
【化５】 （式中、Ｒ1 、Ｒ2 およびＲ3 は前記と同じ意味を示
す。）で表される化合物、[Chemical 5] (Wherein R 1 , R 2 and R 3 have the same meanings as described above),
【０００５】（２）一般式〔ＩＩ〕 Ｒ4 ＯＣＨ2 ＣＨ2 ＣＯＣＨ2 ＯＲ1 〔ＩＩ〕 で表される化合物と一般式〔ＩＩＩ〕 Ｒ2 ＣＯＣＨ2 ＣＯＯＲ3 〔ＩＩＩ〕 で表される化合物とを、触媒として亜鉛化合物の存在下
反応させることを特徴とする一般式〔Ｉ〕(2) A compound represented by the general formula [II] R 4 OCH 2 CH 2 COCH 2 OR 1 [II] and a compound represented by the general formula [III] R 2 COCH 2 COOR 3 [III] Is reacted in the presence of a zinc compound as a catalyst, the general formula [I]
【化６】 （式中、Ｒ1 、Ｒ2 、Ｒ3 およびＲ4 は前記と同じ意味
を示す。）で表される化合物の製造方法である。[Chemical 6] (Wherein R 1 , R 2 , R 3 and R 4 have the same meanings as described above).
【０００６】本発明化合物は、その製造法において触媒
として、ＺｎＣｌ2 ，Ｚｎ（ＮＯ3）2 ，ＺｎＯ，塩基
性炭酸亜鉛（３Ｚｎ（ＯＨ）2 ・２ＺｎＣＯ3 ）等の無
機亜鉛化合物、Ｚｎ（ＣＨ3 ＣＯＯ）2 ，安息香酸亜鉛
等の有機亜鉛化合物、およびＺｎ末、など亜鉛化合物
（これらは混合使用してもよい）を使用することにより
１ポットで、高収率で得られる。触媒の量としては、一
般式〔ＩＩ〕の化合物１モルに対し、0.０１〜１モル、
好ましくは0.１〜0.３モルである。溶媒としては、ベン
ゼン、トルエン、キシレン、メシチレン等が用いられ、
反応温度は８０℃以上それぞれの溶媒の沸点までであ
る。後処理は亜鉛化合物を除去する目的で、水洗または
酸、アルカリ処理を行う。The compound of the present invention is used as a catalyst in the production method thereof, as an inorganic zinc compound such as ZnCl 2 , Zn (NO 3 ) 2 , ZnO, basic zinc carbonate (3Zn (OH) 2 .2ZnCO 3 ), Zn (CH 3 COO) 2 , an organozinc compound such as zinc benzoate, and a zinc compound such as Zn powder (these may be used as a mixture) can be obtained in one pot with a high yield. The amount of the catalyst is 0.01 to 1 mol with respect to 1 mol of the compound of the general formula [II],
It is preferably 0.1 to 0.3 mol. As the solvent, benzene, toluene, xylene, mesitylene, etc. are used,
The reaction temperature is 80 ° C. or higher and up to the boiling point of each solvent. The post-treatment is washing with water or acid or alkali treatment for the purpose of removing the zinc compound.
【０００７】[0007]
【実施例】次に実施例を挙げて、本発明を具体的に説明
する。 実施例１ ２−メトキシ−４−メトキシカルボニル−３−メチル−
２−シクロヘキセン−１−オンEXAMPLES Next, the present invention will be specifically described with reference to examples. Example 1 2-Methoxy-4-methoxycarbonyl-3-methyl-
2-cyclohexen-1-one
【化７】 トルエン８０ml中に１，４−ジメトキシ−２−ブタノン
１2.８ｇ、アセト酢酸メチル１５ｇ、ＺｎＣｌ2 2.３ｇ
を仕込み、２４時間還流を行なった。反応終了後酢酸エ
チル１００mlを加え、さらに１０％塩酸処理、水洗、乾
燥後、溶媒を留去し、得られたオイル状物をカラムクロ
マトグラフィーにより分離精製することにより目的物１
4.５ｇを得た。ｎD 27=1. ４９０２[Chemical 7] 12.8 g of 1,4-dimethoxy-2-butanone, 15 g of methyl acetoacetate, 2.3 g of ZnCl 2 in 80 ml of toluene.
Was charged and refluxed for 24 hours. After completion of the reaction, 100 ml of ethyl acetate was added, and the mixture was further treated with 10% hydrochloric acid, washed with water and dried, and then the solvent was distilled off.
Obtained 4.5 g. n D 27 = 1.4902
【０００８】実施例２ 上記ＺｎＣｌ2 を３Ｚｎ（ＯＨ）2 ・２ＺｎＣＯ3 に代
える以外は同一な操作を行ない、目的物１3.７ｇを得
た。Example 2 The same operation was carried out except that the above ZnCl 2 was replaced by 3Zn (OH) 2 .2ZnCO 3 to obtain 13.7 g of the desired product.
【０００９】実施例３ ２−メトキシ−４−メトキシカルボニル−３−メチル−
２−シクロヘキセン−１−オンExample 3 2-Methoxy-4-methoxycarbonyl-3-methyl-
2-cyclohexen-1-one
【化８】 キシレン２４ｌに１，４−ジメトキシ−２−ブタノン
６．３７ｋｇ、アセト酢酸メチル７．２０ｋｇ、ＺｎＣ
ｌ2 １．４ｋｇ、Ｚｎ（ＯＡｃ）2 ・２Ｈ2 Ｏ１．２ｋ
ｇを仕込み、７時間還流を行った。反応終了後酢酸エチ
ル３ｌを加え、さらに１０％塩酸処理、水洗、乾燥後、
溶媒を留去し、得られたオイル状物１２．３ｋｇを蒸留
し、目的物 ６．２ｋｇ（１３２〜１３６℃／３ｍｍＨ
ｇ）を得た。[Chemical 8] Xylene 24l in 1,4-dimethoxy-2-butanone 6.37 kg, methyl acetoacetate 7.20 kg, ZnC
l 2 1.4 kg, Zn (OAc) 2 .2H 2 O 1.2 k
g was charged and the mixture was refluxed for 7 hours. After completion of the reaction, 3 l of ethyl acetate was added, and the mixture was further treated with 10% hydrochloric acid, washed with water and dried,
The solvent was distilled off, and 12.3 kg of the obtained oily substance was distilled to obtain 6.2 kg of the desired product (132 to 136 ° C./3 mmH
g) was obtained.
【００１０】[0010]
【発明の効果】本発明の化合物は、例えば、特願平３−
３５６８２９に開示された工程を経れば、ＷＯ９１／０
０２６０、特願平３−１９３５９５に示された除草剤の
中間体となる。本発明化合物は農医薬中間体として有用
であり、特定の触媒を用いることにより１ポットで高収
率で得られる。The compound of the present invention can be used, for example, in Japanese Patent Application No.
After the steps disclosed in 356829, WO 91/0
0260, an intermediate of the herbicide shown in Japanese Patent Application No. 3-193595. The compound of the present invention is useful as an agricultural and pharmaceutical intermediate, and can be obtained in a high yield in one pot by using a specific catalyst.
Claims (2)
低級アルキル基を示す。）で表される化合物。1. A compound represented by the general formula [I]: (Wherein R 1 , R 2 and R 3 are the same or different and each represents a lower alkyl group).
4 は低級アルキル基を示す。）で表される化合物とを、
触媒として亜鉛化合物の存在下反応させることを特徴と
する一般式〔Ｉ〕 【化２】 （式中、Ｒ1 、Ｒ2 およびＲ3 は前記と同じ意味を示
す。）で表される化合物の製造方法。2. A compound represented by the general formula [II] R 4 OCH 2 CH 2 COCH 2 OR 1 [II] and a general formula [III] R 2 COCH 2 COOR 3 [III] (wherein R 1 , R 2 and R 3 have the same meanings as described above, and R
4 represents a lower alkyl group. ) And a compound represented by
The compound of the general formula [I] is characterized by reacting in the presence of a zinc compound as a catalyst. (In the formula, R 1 , R 2 and R 3 have the same meanings as described above.) A method for producing the compound represented by the formula.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5085135A JPH069502A (en) | 1992-03-27 | 1993-03-22 | Cyclohexenone compound and its production |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4-101836 | 1992-03-27 | ||
| JP10183692 | 1992-03-27 | ||
| JP5085135A JPH069502A (en) | 1992-03-27 | 1993-03-22 | Cyclohexenone compound and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH069502A true JPH069502A (en) | 1994-01-18 |
Family
ID=26426162
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5085135A Pending JPH069502A (en) | 1992-03-27 | 1993-03-22 | Cyclohexenone compound and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH069502A (en) |
-
1993
- 1993-03-22 JP JP5085135A patent/JPH069502A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI662032B (en) | Method of producing thiamethoxam | |
| EP0606065B1 (en) | Method for the preparation of biphenyl derivatives | |
| CN108358868B (en) | Preparation method of 2-substituted benzothiazole compounds | |
| JPH069502A (en) | Cyclohexenone compound and its production | |
| JPH0136462B2 (en) | ||
| JPH05286889A (en) | Production of arylacetic acid and its alkali metal salt | |
| CH626347A5 (en) | Process for the preparation of 4-hydroxy-2-quinolinone-3-carboxylic esters | |
| WO1993020037A1 (en) | Cyclohexenone compound and production thereof | |
| JP4397990B2 (en) | Purification method of 3-alkylflavanonol derivatives | |
| CN116375570B (en) | A method for preparing dimethyl curcumin | |
| JP4759722B2 (en) | Process for producing aromatic carboxylic acid ester having a substituent | |
| KR950005737B1 (en) | Separation of monocomponents from ginkgoride mixtures | |
| CN111269172B (en) | Preparation method of polysubstituted piperidine compound | |
| JPH05170730A (en) | New intermediate compound and its production | |
| JP4948030B2 (en) | Method for producing fluorine-containing alcohol derivative | |
| JPH07206816A (en) | Preparation of 2,4,5-tribromopyrrole-3-carbonitrile | |
| JP3278957B2 (en) | Method for producing 3-allylphenols | |
| JP2706554B2 (en) | 4-trifluoromethylaniline derivative and method for producing the same | |
| JPS61118348A (en) | Manufacture of hydroxymethylenealkoxyacetic acid ester | |
| RU2237662C1 (en) | Method for preparing 1-acetyl-2-imidazolidone | |
| EP0675111A2 (en) | Process for the preparation of 6-hydroxymethyl-quinolines | |
| JPS606938B2 (en) | Method for producing 3-acylazopropionic acid ester | |
| JPH0841005A (en) | Production of 4-fluoroalkoxycynnamonitrile compound | |
| JP3953141B2 (en) | Process for producing 5-methyl-1,4-benzodioxan-6-carboxylic acids and novel intermediates thereof | |
| JPH0548226B2 (en) |