JPH0243732B2 - SHINKINA ARUDEHIDOKAGOBUTSUOYOBISONOSEIZOHOHO - Google Patents
SHINKINA ARUDEHIDOKAGOBUTSUOYOBISONOSEIZOHOHOInfo
- Publication number
- JPH0243732B2 JPH0243732B2 JP8563680A JP8563680A JPH0243732B2 JP H0243732 B2 JPH0243732 B2 JP H0243732B2 JP 8563680 A JP8563680 A JP 8563680A JP 8563680 A JP8563680 A JP 8563680A JP H0243732 B2 JPH0243732 B2 JP H0243732B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- general formula
- compound represented
- compound
- represented
- 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
- -1 aldehyde compound Chemical class 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 5
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 238000000034 method Methods 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000000543 intermediate Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000006957 Michael reaction Methods 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
- 238000006243 chemical reaction Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- ZCVAOQKBXKSDMS-AQYZNVCMSA-N (+)-trans-allethrin Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OC1C(C)=C(CC=C)C(=O)C1 ZCVAOQKBXKSDMS-AQYZNVCMSA-N 0.000 description 2
- FMTFEIJHMMQUJI-NJAFHUGGSA-N 102130-98-3 Natural products CC=CCC1=C(C)[C@H](CC1=O)OC(=O)[C@@H]1[C@@H](C=C(C)C)C1(C)C FMTFEIJHMMQUJI-NJAFHUGGSA-N 0.000 description 2
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- AIJULSRZWUXGPQ-UHFFFAOYSA-N Methylglyoxal Chemical compound CC(=O)C=O AIJULSRZWUXGPQ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229940024113 allethrin Drugs 0.000 description 2
- OMNLPAKGAQSUGE-UHFFFAOYSA-N butane-2-thione Chemical compound CCC(C)=S OMNLPAKGAQSUGE-UHFFFAOYSA-N 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000000749 insecticidal effect Effects 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- HFEHLDPGIKPNKL-UHFFFAOYSA-N allyl iodide Chemical compound ICC=C HFEHLDPGIKPNKL-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は新規なアルデヒド化合物およびその製
造方法に関する。さらに詳しくは、農薬の有用な
中間体である下記一般式（）で示される新規な
アルデヒド化合物およびその製造方法に関する。
〔式中、R1は式
The present invention relates to a novel aldehyde compound and a method for producing the same. More specifically, the present invention relates to a novel aldehyde compound represented by the following general formula (), which is a useful intermediate for agricultural chemicals, and a method for producing the same. [In the formula, R 1 is the formula
【式】で示される基
（ここにR2は水素原子またはメチル基を表わす。）
を表わす。〕
有用な農薬として知られているアレスリンは、
1949年にM.S.Schechterにより発明され、そのす
ぐれた殺虫活性と低毒性のゆえに広く全世界で使
用されており、その合成法についても種々の検討
がなされている。
その中で、アレスリンのアルコール成分の合成
法についても種々の提案がなされており、その一
部は実際の製造に取り入れられているものもあ
る。しかしこれらは収率、操作それに環境問題等
の点で必ずしも工業的に満足できるものではな
い。
例えば今日工業的に実施されているアレスロロ
ンの合成方法は、M.S.Schechterらによつて初め
て行なわれた方法を若干改良したもので以下の工
程よりなる。
しかし、該方法においては、化合物(4)からアレ
スロロン(5)に至る最終工程が低収率であること、
化合物(3)から化合物(4)を合成する際に用いるメチ
ルグリオサザール(6)の合成が容易でなく、かつ高
価である事などの欠点があげられ工業的には、必
ずしも満足いく方法ではない。
また、マイケル反応を利用したアレスロロンの
合成法としては、R.H.Schlessingerらの方法があ
げられ本方法は、メチルチオアセトン(7)とケテン
チオアセタールモノオキシド(8)を原料としたもの
で以下の工程よりなる。
しかしこのSchlessingerらの方法も工業的方法
としては次の様な大きな問題点を有している。
マイケル反応の後に、立体的に混み入つたケ
トンのα位にアリル基を導入するため、反応性
が高く、かつ高価なアリルアイオダイドを用い
ている。（化合物(9)→(10)の工程）
化合物(11)からアレスロロン(5)に至る反応で、
工業的に使用するには、危険度が大きくかつ取
扱いが容易でないｔ−ブトキシカリウムを用い
ている。
従つて、本方法も工業的な製法としては、必ず
しも満足できる方法ではない。
このような背景の下に本発明者らは、殺虫化合
物の中間体として使用されるシクロペンテノロン
類、特に式（）
で示されるシクロペンテノロン化合物の製法につ
き鋭意検討した結果、新規でしかも極めて有利に
これを製造し得る方法を見い出し、これに基づき
その重要な中間体、およびその製造方法に種々の
検討を加え本発明を完成した。
即ち、本発明は前記一般式（）で示される新
規なアルデヒド化合物およびその製造方法として
一般式（）
（式中、R1は前述と同じ意味を表わし、R3は
炭素数３以下のアルキル基を表わす。）
で示されるアセタール化合物を水の存在下、酸と
反応させることを特徴とする前記一般式（）で
示される新規なアルデヒド化合物の製造方法を提
供するものである。
一般式（）で示される本発明化合物は、塩基
で処理することにより、容易に且つ収率よく農薬
の有用な中間体である前記式（）で示されるシ
クロペンテノロン化合物に導くことができ、極め
て有用な中間体である。
また一般式（）で示されるアセタール化合物
は新規物であり、例えば一般式（）
（式中、R1は前述と同じ意味を有する。）で示
される化合物を塩基の存在下、式（）
CH3−CH＝CH−NO2 （）
で示されるニトロオレフインと反応させ、一般式
（）
で示されるニトロ化合物に導き、次いでこれを塩
基で処理後、炭素数３以下の低級アルコール中で
酸と処理することにより、容易に得ることができ
る。
一般式（）で示される本発明化合物におい
て、R1の具体例としては、例えばフエニル基、
ｐ−トリル基などが挙げられる。
一般式（）で示される本発明化合物の製造に
際しては一般式（）で示されるアセタール化合
物を水の存在下で、塩酸、硫酸などの鉱酸類ある
いは酢酸などの低級脂肪酸などのような酸と反応
させ水解することにより収率よく目的のアルデヒ
ド化合物を得ることができる。
溶媒は特に必要としないが、ベンゼン、トルエ
ン、ヘキサン、テトラヒドロフラン、メタノー
ル、エタノールなどの溶媒を混合して用いること
ができる。
反応温度は特に限定されるものではないが−60
℃〜60℃の範囲、好ましくは−30℃〜30℃の範囲
で行なうことができる。反応時間は用いる溶媒、
反応温度、酸などによつて異なるが多くは５分〜
３時間で行なうことができる。
一般式（）で示される本発明化合物を経て前
述のような方法によりシクロペンテノロン化合物
へ導く方法においては、マイケル反応の前にプロ
パルギル基を導入することができるため、プロパ
ルギル基の導入が極めて容易に行なえるという利
点を有している。
さらに一般式（）で示される化合物を塩基で
処理して最終目的物である式（）で示されるシ
クロペンテノロン化合物を合成する工程では、ナ
トリウムエチラートのような汎用な塩基でも収率
よく目的物が得られ、R.H.Schlessingerらの方法
に比し、工業的な製法として有利であり、また該
閉環反応工程の収率がよいこと、およびメチルグ
リオキザールを用いないこと等、今日工業的に行
なわれているM.S.Schechterらの方法と比べても
優れた点が多い。
以上述べたように本発明は、農薬の製造に極め
て有用な新規な中間体、およびその製造方法に関
するものであり、これらの工業生産にとつて、工
程数の削減、操作の容易さ、収率の良さなど、そ
の寄与するところは非常に大きい。
次に、本発明をより明確にするために、以下の
実施例で詳細に説明するが、本発明がこれらに限
定されるものではないことはいうまでもない。
実施例
３−アセチル−１，１−ジメトキシ−２−メチ
ル−３−ｐ−トルエンスホニルヘキサ−５−イン
1.38ｇを1N−HCl水20mlに仕込み、55℃で１時
間かきまぜた。エーテル抽出後、エーテル層を水
洗い、食塩水洗いを行なつて硫酸マグネシウムで
乾燥した。
溶媒留去後、シリカゲルカラムクロマトグラフ
イーを行ない、３−アセチル−２−メチル−３−
ｐ−トルエンスルホニル−ヘキサ−５−イル−１
−アール0.57ｇを得た。収率47.4％
NMRデータ（δ値、TMS標準、CCl4）
1.10，1.30（dd，Ｊ＝７Hz，3H）；2.30（ｓ，
3H）、2.34（ｓ，3H）；３〜3.3（ｍ，2H）；3.3
〜3.5（ｍ，1H）；7.3〜7.7（4H）；9.4（ｄ，
1H）Group represented by [Formula] (where R 2 represents a hydrogen atom or a methyl group)
represents. ] Allethrin is known as a useful pesticide.
Invented by MS Schechter in 1949, it is widely used throughout the world due to its excellent insecticidal activity and low toxicity, and various studies have been conducted on its synthesis methods. Among these, various proposals have been made regarding methods for synthesizing the alcohol component of allethrin, some of which have been incorporated into actual production. However, these methods are not necessarily industrially satisfactory in terms of yield, operation, environmental problems, etc. For example, the method for synthesizing allethrone that is currently practiced industrially is a slight improvement on the method first carried out by MS Schechter et al., and consists of the following steps. However, in this method, the final step from compound (4) to arethrolone (5) has a low yield;
There are drawbacks such as the difficulty and high cost of synthesizing methylglyosazar (6) used in the synthesis of compound (4) from compound (3), and this method is not necessarily satisfactory industrially. do not have. In addition, as a method for synthesizing arethrolone using the Michael reaction, there is a method by RH Schlessinger et al. This method uses methylthioacetone (7) and ketene thioacetal monooxide (8) as raw materials and consists of the following steps. . However, the method of Schlessinger et al. also has the following major problems as an industrial method. After the Michael reaction, allyl iodide, which is highly reactive and expensive, is used to introduce an allyl group into the α-position of the sterically crowded ketone. (Process of compound (9) → (10)) In the reaction from compound (11) to arethrolone (5),
For industrial use, potassium t-butoxy is used, which is highly dangerous and difficult to handle. Therefore, this method is not necessarily satisfactory as an industrial manufacturing method. Against this background, the present inventors investigated cyclopentenolones used as intermediates for insecticidal compounds, particularly those of the formula () As a result of intensive research into the method for producing the cyclopentenolone compound shown in Completed the invention. That is, the present invention provides a novel aldehyde compound represented by the general formula () and a method for producing the same. (In the formula, R 1 represents the same meaning as above, and R 3 represents an alkyl group having 3 or less carbon atoms.) The present invention provides a method for producing a novel aldehyde compound represented by formula (). The compound of the present invention represented by the general formula () can be easily and efficiently converted into a cyclopentenolone compound represented by the formula (), which is a useful intermediate for agricultural chemicals, by treatment with a base, It is an extremely useful intermediate. Furthermore, the acetal compound represented by the general formula () is a new product, for example, the acetal compound represented by the general formula () (wherein, R 1 has the same meaning as above) is reacted with a nitroolefin represented by the formula () CH 3 −CH=CH−NO 2 () in the presence of a base, and the compound represented by the general formula () It can be easily obtained by leading to a nitro compound represented by , then treating this with a base, and then treating it with an acid in a lower alcohol having 3 or less carbon atoms. In the compound of the present invention represented by the general formula (), specific examples of R 1 include, for example, a phenyl group,
Examples include p-tolyl group. When producing the compound of the present invention represented by the general formula (), an acetal compound represented by the general formula () is reacted with an acid such as a mineral acid such as hydrochloric acid or sulfuric acid or a lower fatty acid such as acetic acid in the presence of water. The desired aldehyde compound can be obtained in good yield by hydrolysis. Although a solvent is not particularly required, a mixture of solvents such as benzene, toluene, hexane, tetrahydrofuran, methanol, and ethanol can be used. The reaction temperature is not particularly limited, but −60
It can be carried out in the range of .degree. C. to 60.degree. C., preferably in the range of -30.degree. C. to 30.degree. The reaction time depends on the solvent used,
It varies depending on the reaction temperature, acid, etc., but in most cases it takes 5 minutes or more.
It can be done in 3 hours. In the method of leading to a cyclopentenolone compound by the method described above via the compound of the present invention represented by the general formula (), a propargyl group can be introduced before the Michael reaction, so it is extremely easy to introduce a propargyl group. It has the advantage of being able to be used in many ways. Furthermore, in the process of treating the compound represented by the general formula () with a base to synthesize the final target compound, a cyclopentenolone compound represented by the formula (), a general-purpose base such as sodium ethylate can be used with good yield. It is advantageous as an industrial production method compared to the method of RH Schlessinger et al., and it is not used industrially today because the yield of the ring-closing reaction step is good and methylglyoxal is not used. It has many advantages compared to the method of MSSchechter et al. As described above, the present invention relates to a novel intermediate extremely useful in the production of agricultural chemicals, and a method for producing the same, and is useful for the industrial production of these products by reducing the number of steps, ease of operation, and yield. Its contribution, such as the merits of this technology, is enormous. EXAMPLES Next, in order to make the present invention more clear, the present invention will be explained in detail using the following examples, but it goes without saying that the present invention is not limited thereto. Example 3-acetyl-1,1-dimethoxy-2-methyl-3-p-toluenesphonylhex-5-yne
1.38g was added to 20ml of 1N-HCl water and stirred at 55°C for 1 hour. After the ether extraction, the ether layer was washed with water, brine, and dried over magnesium sulfate. After distilling off the solvent, silica gel column chromatography was performed to obtain 3-acetyl-2-methyl-3-
p-Toluenesulfonyl-hex-5-yl-1
-0.57g of Earl was obtained. Yield 47.4% NMR data (δ value, TMS standard, CCl 4 ) 1.10, 1.30 (dd, J=7Hz, 3H); 2.30 (s,
3H), 2.34 (s, 3H); 3-3.3 (m, 2H); 3.3
~3.5 (m, 1H); 7.3 ~ 7.7 (4H); 9.4 (d,
1H)
Claims (1)
を表わす。〕 で示されるアルデヒド化合物。 ２ 一般式 〔式中、R1は式【式】で示される基 （ここにR2は水素原子またはメチル基を表わす。）
を表わし、R3は炭素数３以下のアルキル基を表
わす。〕で示されるアセタール化合物を水の存在
下酸と反応させることを特徴とする一般式 〔式中、R1は前述と同じ意味を有する。〕 で示されるアルデヒド化合物の製造方法。[Claims] 1. General formula [Wherein, R 1 is a group represented by the formula [Formula] (R 2 represents a hydrogen atom or a methyl group.)
represents. ] An aldehyde compound represented by 2 General formula [Wherein, R 1 is a group represented by the formula [Formula] (R 2 represents a hydrogen atom or a methyl group.)
, and R 3 represents an alkyl group having 3 or less carbon atoms. A general formula characterized by reacting an acetal compound represented by ] with an acid in the presence of water. [In the formula, R 1 has the same meaning as above. ] A method for producing an aldehyde compound represented by
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8563680A JPH0243732B2 (en) | 1980-06-23 | 1980-06-23 | SHINKINA ARUDEHIDOKAGOBUTSUOYOBISONOSEIZOHOHO |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8563680A JPH0243732B2 (en) | 1980-06-23 | 1980-06-23 | SHINKINA ARUDEHIDOKAGOBUTSUOYOBISONOSEIZOHOHO |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5711957A JPS5711957A (en) | 1982-01-21 |
| JPH0243732B2 true JPH0243732B2 (en) | 1990-10-01 |
Family
ID=13864312
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8563680A Expired - Lifetime JPH0243732B2 (en) | 1980-06-23 | 1980-06-23 | SHINKINA ARUDEHIDOKAGOBUTSUOYOBISONOSEIZOHOHO |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0243732B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0665091U (en) * | 1993-02-23 | 1994-09-13 | 火 明 葉 | Automatic vehicle stop sign device |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6887619B2 (en) | 2002-04-22 | 2005-05-03 | Quallion Llc | Cross-linked polysiloxanes |
-
1980
- 1980-06-23 JP JP8563680A patent/JPH0243732B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0665091U (en) * | 1993-02-23 | 1994-09-13 | 火 明 葉 | Automatic vehicle stop sign device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5711957A (en) | 1982-01-21 |
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