JPS6243995B2 - - Google Patents
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- Publication number
- JPS6243995B2 JPS6243995B2 JP11815979A JP11815979A JPS6243995B2 JP S6243995 B2 JPS6243995 B2 JP S6243995B2 JP 11815979 A JP11815979 A JP 11815979A JP 11815979 A JP11815979 A JP 11815979A JP S6243995 B2 JPS6243995 B2 JP S6243995B2
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- JP
- Japan
- Prior art keywords
- general formula
- compound
- trichloropropyl
- imidazole
- 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.)
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Description
本発明はトリハロプロパン誘導体に関する。
本発明のトリハロプロパン誘導体は新規な化合
物であり、下記一般式〔１〕で表わされる。
〔式中R1はアルキル基またはフエニル基およびＸ
はハロゲン原子を示す。Ａはメチン（−CH＝）
または窒素原子（−Ｎ＝）を示す。Ｂは低級アル
キル基を置換基として有することのあるメチン
（−CH＝）を示す。〕
上記一般式〔１〕で表わされる本発明化合物
は、抗菌活性を有し、殊に各種の値物病原性真菌
類に対して優れた殺菌活性を示し、また薬害のお
それもほとんどなく、農園芸用殺菌剤として有用
である。
上記一般式〔１〕においてR1で示されるアル
キル基としては炭素数１〜10の直鎖状もしくは分
枝状アルキル基例えばメチル、エチル、プロピ
ル、イソプロピル、ブチル、イソブチル、tert−
ブチル、ペンチル、ヘキシル、ヘプチル、オクチ
ル、イソオクチル、ノニル、デシル基等を例示で
きる。Ｘで示されるハロゲン原子は、弗素、塩
素、臭素及び沃素原子のいずれであつてもよい。
また上記一般式〔１〕において
The present invention relates to trihalopropane derivatives. The trihalopropane derivative of the present invention is a novel compound and is represented by the following general formula [1]. [In the formula, R 1 is an alkyl group or a phenyl group and
indicates a halogen atom. A is methine (-CH=)
Or indicates a nitrogen atom (-N=). B represents methine (-CH=) which may have a lower alkyl group as a substituent. ] The compound of the present invention represented by the above general formula [1] has antibacterial activity, particularly exhibits excellent bactericidal activity against various pathogenic fungi, has little risk of phytotoxicity, and is suitable for agricultural purposes. Useful as a horticultural fungicide. In the above general formula [1], the alkyl group represented by R 1 is a linear or branched alkyl group having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-
Examples include butyl, pentyl, hexyl, heptyl, octyl, isooctyl, nonyl, and decyl groups. The halogen atom represented by X may be any of fluorine, chlorine, bromine, and iodine atoms. Also, in the above general formula [1]
【式】で表
わされる基は、例えばイミダゾリル、トリアゾリ
ル基等の窒素原子２〜３個をヘテロ原子として有
する５員の不飽和ヘテロ環基を意味し、之等各基
のうち、ヘテロ環構成原子として炭素原子を有す
る基は、該炭素原子上に低級アルキル基を置換基
として有していてもよい。
以下本発明化合物の代表例を示す。
Γ１−（１−メトキシ−３・３・３−トリフルオ
ロプロピル）イミダゾール
Γ１−（１−ｎ−デシルオキシ−３・３・３−ト
リクロロプロピル）イミダゾール
Γ１−（１−イソプロピルオキシ−３・３・３−
トリクロロプロピル）イミダゾール
Γ１−（１−ｎ−ブチルオキシ−３・３・３−ト
リクロロプロピル）イミダゾール
Γ１−（１−イソオクチルオキシ−３・３・３−
トリブロモプロピル）イミダゾール
Γ１−（１−フエノキシ−３・３・３−トリクロ
ロプロピル）イミダゾール
Γ１−（１−ｎ−ブチルオキシ−３・３・３−ト
リクロロプロピル）−２−メチル−イミダゾー
ル
Γ１−（１−ｎ−ブチルオキシ−３・３・３−ト
リクロロプロピル）−２・４−ジメチル−イミ
ダゾール
Γ１−（１−フエノキシ−３・３・３−トリクロ
ロプロピル）−２−エチル−イミダゾール
Γ１−（１−ｎ−ブチルオキシ−３・３・３−ト
リクロロプロピル）−２−メチル−イミダゾー
ル
Γ１−（１−メトキシ−３・３・３−トリクロロ
プロピル）−１・２・４−トリアゾール
Γ１−（１−ｎ−ブチルオキシ−３・３・３−ト
リクロロプロピル）−１・２・４−トリアゾー
ル
Γ１−（１−フエノキシ−３・３・３−トリクロ
ロプロピル）−１・２・４−トリアゾール
Γ１−（１−イソブチルオキシ−３・３・３−ト
リクロロプロピル）−３−エチル−１・２・４
−トリアゾール
本発明化合物は、例えば下記一般式
〔式中R1及びＸは上記に同じ〕
で表わされる３−アルコキシ（又はフエノキシ）
−１・１・１・３−テトラハロプロパンを原料と
して、これに適当な不活性溶媒中、脱酸剤の存在
下もしくは不存在下に一般式
〔式中Ａ及びＢは上記に同じ〕
で表わされる公知のヘテロ環化合物を反応させる
ことにより製造される。
上記一般式〔２〕で表わされる原料化合物は、
公知化合物であり、例えば次式に示すようにして
合成される〔M.Laevas、Ann、Chem.〔12〕、
７、697（1952）、P.Tarrant、E.C.Stump、J.O.
C.29、1198（1964）、米国特許第2560219号及び
C.A.、46、1023（1952）〕。
〔式中R1及びＸは上記に同じ〕
即ち上記一般式〔４〕で表わされる化合物と一
般式〔５〕で表わされる化合物とを光射照するか
又はラジカル開始剤例えばベンゾイルパーオキサ
イド、アゾビスイソブチロニトリル等の存在下に
50〜100℃の温度下に加熱して反応させることに
より容易に収得できる。
上記一般式〔２〕で表わされる化合物と一般式
〔３〕で表わされる化合物との反応は、より具体
的には次の如くして行なわれる。即ち例えばアセ
トン、メチルエチルケトン等のケトン類、アセト
ニトリル等のニトリル類、ジグライム、テトラヒ
ドロフラン等のエーテル類、四塩化炭素、クロロ
ホルム、塩化メチレン等のハロゲン化炭化水素
類、ベンゼン、トルエン、キシレン等の芳香族炭
化水素類、メタノール、エタノール等のアルコー
ル類、ジメチルスルホキシド等の適当な不活性溶
媒中で、例えば炭酸カリウム、炭酸ナトリウム、
炭酸水素カリウム、炭酸水素ナトリウム、水酸化
カリウム、水酸化ナトリウム、トリエチルアミ
ン、ジメチルアニリン等、好ましくは炭酸カリウ
ム、炭酸ナトリウム、炭酸水素カリウム、炭酸水
素ナトリウム等の弱塩基性化合物を脱酸剤として
利用するか又は用いることなく、一般式〔２〕の
化合物と一般式〔３〕の化合物とを０〜100℃好
ましくは室温〜50℃下に１〜５時間通常１〜２時
間程度反応させることにより行なわれる。一般式
〔２〕の化合物に対する一般式〔３〕の化合物の
使用量は、脱酸剤を用いる場合は、通常等モル以
上好ましくは等モル〜２倍モル程度とし、また脱
酸剤を用いない場合は好ましくは２倍モル以上と
すればよい。また脱酸剤は通常一般式〔２〕の化
合物に対して等モル以上好ましくは等モル〜1.5
倍モル程度用いるのが適当である。
かくして一般式〔１〕で表わされる本発明のト
リハロプロパン誘導体を収得する。得られる化合
物は、反応終了後常法に従いカラムクロマトグラ
フイーや溶媒抽出法、再結晶法等により単離精製
できる。
以下本発明化合物の製造に用いる原料化合物の
製造例を参考例として挙げ、次いで本発明化合物
の製造例を実施例として挙げる。
参考例 １
四塩化炭素150mlにアゾビスイソブチロニトリ
ル300mgを加え還流する。滴下斗よりｎ−ブチ
ルビニルエーテル50ｇを少量づつ滴下し、更に１
時間還流後四塩化炭素を減圧下に除去し、減圧蒸
留する。２mmHg下に74〜75℃の留分として、３
−ｎ−ブチルオキシ−１・１・１・３−テトラク
ロロプロパン118ｇを得る。
実施例 １
３−ｎ−ブチルオキシ−１・１・１・３−テト
ラクロロプロパン5.08ｇをアセトン50mlに溶解
し、室温撹拌下にイミダゾール1.36ｇを加え、同
温度に更に２時間撹拌を続ける。反応終了後減圧
濃縮し残留物を四塩化炭素200mlに溶解し、不溶
部を除去し、水100mlで洗浄後無水硫酸マグネシ
ウムで乾燥し、四塩化炭素を減圧下に完全に除去
して、淡黄色油状の１−（１−ｎ−ブチルオキシ
−３・３・３−トリクロロプロピル）イミダゾー
ル3.8ｇを得る。
屈折率 ｎ１６ Ｄ＝1.5039
核磁気共鳴スペクトル分析（CDCl3溶媒、テト
ラメチルシラン内部標準薬、室温測定）
δ＝7.40ppm（ｓ、1H）
6.85ppm（ｓ、2H）
5.50ppm（ｔ、1H）
3.40ppm（ｍ、4H）
1.80〜1.00ppm（ｍ、7H）
実施例 ２〜８
上記実施例１と同様にしてR1および
が第１表記載のものである各化合物を得る。第１
表には得られた各化合物の物性（屈折率）を併記
する。
The group represented by [Formula] means a 5-membered unsaturated heterocyclic group having 2 to 3 nitrogen atoms as heteroatoms, such as an imidazolyl group or a triazolyl group; A group having a carbon atom as may have a lower alkyl group as a substituent on the carbon atom. Representative examples of the compounds of the present invention are shown below. Γ1-(1-methoxy-3,3,3-trifluoropropyl)imidazoleΓ1-(1-n-decyloxy-3,3,3-trichloropropyl)imidazoleΓ1-(1-isopropyloxy-3,3,3 −
trichloropropyl) imidazole Γ1-(1-n-butyloxy-3,3,3-trichloropropyl)imidazole Γ1-(1-isooctyloxy-3,3,3-
tribromopropyl) imidazole Γ1-(1-phenoxy-3,3,3-trichloropropyl)imidazole Γ1-(1-n-butyloxy-3,3,3-trichloropropyl)-2-methyl-imidazole Γ1-(1 -n-butyloxy-3,3,3-trichloropropyl)-2,4-dimethyl-imidazole Γ1-(1-phenoxy-3,3,3-trichloropropyl)-2-ethyl-imidazole Γ1-(1-n -butyloxy-3,3,3-trichloropropyl)-2-methyl-imidazole Γ1-(1-methoxy-3,3,3-trichloropropyl)-1,2,4-triazole Γ1-(1-n-butyloxy -3,3,3-trichloropropyl)-1,2,4-triazole Γ1-(1-phenoxy-3,3,3-trichloropropyl)-1,2,4-triazole Γ1-(1-isobutyloxy- 3,3,3-trichloropropyl)-3-ethyl-1,2,4
-Triazole The compound of the present invention can be expressed, for example, by the following general formula: 3-alkoxy (or phenoxy) represented by [In the formula, R 1 and X are the same as above]
Using -1,1,1,3-tetrahalopropane as a raw material, the general formula [In the formula, A and B are the same as above] It is produced by reacting a known heterocyclic compound represented by the following formula. The raw material compound represented by the above general formula [2] is
It is a known compound, and can be synthesized, for example, as shown in the following formula [M. Laevas, Ann, Chem. [12],
7 , 697 (1952), P. Tarrant, ECStump, JO.
C. 29 , 1198 (1964), U.S. Patent No. 2,560,219 and
CA, 46 , 1023 (1952)]. [In the formula, R 1 and In the presence of bisisobutyronitrile etc.
It can be easily obtained by heating and reacting at a temperature of 50 to 100°C. More specifically, the reaction between the compound represented by the above general formula [2] and the compound represented by the general formula [3] is carried out as follows. For example, ketones such as acetone and methyl ethyl ketone, nitriles such as acetonitrile, ethers such as diglyme and tetrahydrofuran, halogenated hydrocarbons such as carbon tetrachloride, chloroform and methylene chloride, and aromatic carbons such as benzene, toluene and xylene. For example, potassium carbonate, sodium carbonate,
Potassium bicarbonate, sodium bicarbonate, potassium hydroxide, sodium hydroxide, triethylamine, dimethylaniline, etc., preferably weakly basic compounds such as potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate, etc. are used as deoxidizing agents. The reaction is carried out by reacting the compound of general formula [2] with the compound of general formula [3] at 0 to 100°C, preferably room temperature to 50°C, for 1 to 5 hours, usually for about 1 to 2 hours. It can be done. The amount of the compound of general formula [3] to be used of the compound of general formula [2], when using a deoxidizing agent, is usually equal to or more than the same mole, preferably about 1 to 2 times the mole, and when no deoxidizing agent is used. In this case, it is preferable to increase the amount by 2 times the mole or more. In addition, the deoxidizing agent is usually equal to or more than equimolar, preferably equimolar to 1.5 to the compound of general formula [2].
It is appropriate to use about double the molar amount. In this way, the trihalopropane derivative of the present invention represented by general formula [1] is obtained. After completion of the reaction, the resulting compound can be isolated and purified by column chromatography, solvent extraction, recrystallization, etc. in accordance with conventional methods. Hereinafter, production examples of raw material compounds used for production of the compounds of the present invention will be listed as reference examples, and then production examples of the compounds of the present invention will be listed as examples. Reference Example 1 Add 300 mg of azobisisobutyronitrile to 150 ml of carbon tetrachloride and reflux. Add 50 g of n-butyl vinyl ether little by little from the dropping funnel, and add 1
After refluxing for a period of time, carbon tetrachloride is removed under reduced pressure and distilled under reduced pressure. 3 as a fraction of 74-75℃ under 2mmHg
118 g of -n-butyloxy-1,1,1,3-tetrachloropropane are obtained. Example 1 5.08 g of 3-n-butyloxy-1,1,1,3-tetrachloropropane is dissolved in 50 ml of acetone, 1.36 g of imidazole is added while stirring at room temperature, and stirring is continued for an additional 2 hours at the same temperature. After the reaction was completed, the residue was concentrated under reduced pressure, dissolved in 200 ml of carbon tetrachloride, the insoluble portion was removed, washed with 100 ml of water, and dried over anhydrous magnesium sulfate. Carbon tetrachloride was completely removed under reduced pressure, leaving a pale yellow color. 3.8 g of oily 1-(1-n-butyloxy-3,3,3-trichloropropyl)imidazole are obtained. Refractive index n 16 D = 1.5039 Nuclear magnetic resonance spectroscopy (CDCl 3 solvent, tetramethylsilane internal standard, room temperature measurement) δ = 7.40ppm (s, 1H) 6.85ppm (s, 2H) 5.50ppm (t, 1H) 3.40ppm (m, 4H) 1.80-1.00ppm (m, 7H) Examples 2-8 R 1 and Each compound is obtained as listed in Table 1. 1st
The table also shows the physical properties (refractive index) of each compound obtained.
【表】【table】
【表】
＜抗菌試験＞
本発明化合物（実施例１及び５）の夫々100mg
をアセトン５mlに溶解し、展着剤２滴を加えた水
95mlに混合して、濃度1000ppmの供試液を作成
する。
各供試液をイネ葉（品種コシヒカリ）に充分に
散布し、散布24時間後に、稲イモチ病菌胞子懸濁
液（100倍で１視野に30個程度）を噴霧接種し、
24時間湿室に保つ。その後25℃で育成し、接種７
日後に最上展開葉の病斑数を調べる。また同様に
して本発明化合物を含有しないアセトン水を撒布
試験した無処理葉の病斑数を計数し、之等の値よ
り防除価（％）を算出した結果は下記第２表の通
りであつた。[Table] <Antibacterial test> 100 mg each of the compounds of the present invention (Examples 1 and 5)
Dissolve it in 5 ml of acetone and add 2 drops of a spreading agent to water.
Mix 95ml to create a test solution with a concentration of 1000ppm. Each test solution was thoroughly sprayed on rice leaves (variety Koshihikari), and 24 hours after spraying, a suspension of rice blast fungus spores (approximately 30 per field of view at 100x magnification) was inoculated by spraying.
Keep in a moist room for 24 hours. After that, grow at 25℃ and inoculate 7
After a day, check the number of lesions on the topmost leaf. Similarly, the number of lesions on untreated leaves that were tested by spraying acetone water that does not contain the compound of the present invention was counted, and the control value (%) was calculated from these values.The results are shown in Table 2 below. Ta.
Claims (1)
はハロゲン原子を示す。Ａはメチン（−CH＝）
または窒素原子（−Ｎ＝）を示す。 Ｂは低級アルキル基を置換基として有すること
のあるメチン（−CH＝）を示す。〕 で表わされることを特徴とするトリハロプロパン
誘導体。[Claims] 1. General formula [In the formula, R 1 is an alkyl group or a phenyl group and
indicates a halogen atom. A is methine (-CH=)
Or indicates a nitrogen atom (-N=). B represents methine (-CH=) which may have a lower alkyl group as a substituent. ] A trihalopropane derivative characterized by the following.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11815979A JPS5643274A (en) | 1979-09-13 | 1979-09-13 | Trihalopropane derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11815979A JPS5643274A (en) | 1979-09-13 | 1979-09-13 | Trihalopropane derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5643274A JPS5643274A (en) | 1981-04-21 |
| JPS6243995B2 true JPS6243995B2 (en) | 1987-09-17 |
Family
ID=14729554
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11815979A Granted JPS5643274A (en) | 1979-09-13 | 1979-09-13 | Trihalopropane derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5643274A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU583057B2 (en) * | 1984-10-04 | 1989-04-20 | Imperial Chemical Industries Plc | 1,1-bis (phenyl)-2-(tetrazolyl) propanol derivatives as insecticides |
| US5616166A (en) * | 1993-12-28 | 1997-04-01 | Kawasaki Steel Corporation | Tapping method for blast furnace |
-
1979
- 1979-09-13 JP JP11815979A patent/JPS5643274A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5643274A (en) | 1981-04-21 |
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