JPS58185572A

JPS58185572A - Triazole derivative and herbicide containing said derivative

Info

Publication number: JPS58185572A
Application number: JP6979182A
Authority: JP
Inventors: Katsumichi Aoki; 青木　勝道; Hideo Arahori; 荒堀　英雄; Takeo Watanabe; 渡辺　武雄; Masafumi Ootsuru; 大津留　雅史; Keigo Satake; 佐竹　慶吾; Hiroe Shinkawa; 新川　博恵; Shiro Yamazaki; 山崎　詞朗
Original assignee: Kureha Corp
Current assignee: Kureha Corp
Priority date: 1982-04-26
Filing date: 1982-04-26
Publication date: 1983-10-29
Also published as: JPH0360822B2

Abstract

NEW MATERIAL:A 1,2,4-triazole derivative of formula I (R1 is H or alkyl; m is 0,1 or 2; R2 is alkyl, alkoxyl, nitro or halogen; n is 1 or 2). USE:A herbicide capable of exhibiting particularly improved herbicidal activity against broad-leaved weeds, e.g. common purslane, fat hen or wild amaranth. PROCESS:A compound of formula II is reacted with a compound of formula IIIto give a compound of formula IV, which is then refluxed in a solution of 29% NH4OH (in an molar amount of 54.9 times of that of the compound of formula IV) and CH3OH to afford the compound of formula I .

Description

【発明の詳細な説明】本発明は、　一般式（１）（式中、Ｒ８は水素原子又はアルキル基を表わし、ｍＨ
Ｏ，１又は２を表わし、Ｒ１はアルキル基、アルコキシ
ル基、ニトロ基又はノへロゲ／原子倉表わし、ｎ　ｒｉ
ｌ又は２を表わす）で示される倉現なｊ、　２　、４−　）リアゾール誘導
体及びこれを有効成分とする除草剤に関する。Detailed Description of the Invention The present invention is based on the general formula (1) (wherein R8 represents a hydrogen atom or an alkyl group, and mH
represents O, 1 or 2, R1 represents an alkyl group, an alkoxyl group, a nitro group or a nitrogen/atomic chain, n ri
The present invention relates to a natural j, 2, 4-) lyazole derivative represented by (representing l or 2) and a herbicide containing the same as an active ingredient.

本発明者らは、種々研究を積み重ねた結果、上記一般式
（１）で表わされる１、２．４−）リアゾール誘導体が
優れた実用的除草効果を有することを発見し、本発明に
至った。As a result of various studies, the present inventors discovered that the 1,2,4-) lyazole derivative represented by the above general formula (1) has an excellent practical herbicidal effect, leading to the present invention. .

本発明の一般式（＋）の化合物（以下、本発明化合物と
略称する）は、イネ、小麦、トウモロコシ、棉等に楽４
！ｒを生ずることなく、種子発芽試験、土壌処理試験、
茎葉敗布処理試験等の除草試練で広＃ｉＷｉ物及びイネ
科ｍ物に対して除草活性を示し、特に広Ｊａｍ＜スベリ
ヒエ、シロザ、タネツケバナ、イヌビエ等）には優れ九
除菫活性金示す。その除草剤としての施用範囲は、水田
、畑地、果樹園等の奥耕地の地、花丹栽培への使用があ
げられる。The compound of the general formula (+) of the present invention (hereinafter abbreviated as the compound of the present invention) can be easily applied to rice, wheat, corn, cotton, etc.
! Seed germination test, soil treatment test, without causing r.
In weeding tests such as stem and leaf rot treatment tests, it has shown herbicidal activity against broad grasses and grasses, and is particularly effective against broad jams (purslane, whitewort, ash, grasshopper, etc.). The scope of its application as a herbicide includes use in paddy fields, upland fields, deep cultivated areas such as orchards, and for flower cultivation.

本発明化合物は、ジアゾニウム塩と馬尿酸との反応によ
り得られる４−フェニルヒドラゾノ−２−フェニルオキ
サゾリン−５−オン（１）ｔ、２９％ＮＨ４ＯＨ（５４
，９倍モル量）／メタノール溶液中、還流することによ
り合成され得る。The compound of the present invention is 4-phenylhydrazono-2-phenyloxazolin-5-one (1) obtained by the reaction of diazonium salt and hippuric acid, 29% NH4OH (54
, 9 times the molar amount)/methanol solution by refluxing.

（−）ｎ（参考文献；ジャーナル・オン・ザ・アメリカン・ケミ
カル・ソサイーテイ、　７９　％　、　１９５６貞。(-)n (Reference: Journal on the American Chemical Society, 79%, 1956).

１９５７年）。また、式（曹）の化合物音アセト／中、
２９％ＮＨ，ＯＨ（１，３倍モル量）溶液と還流工作用
させ、次いで濃ｊ醸全用いることによっても合成できる
。後者の方法ハ、前者に比べてアンモニア水溶液及び溶
媒の１史用量が少くて、反応波処理がｄ易であるため有
利である。(1957). Also, the compound sound aceto/in the formula (sodium carbonate),
It can also be synthesized by refluxing with a 29% NH,OH (1.3 times the molar amount) solution and then using Kojjozen. The latter method is advantageous compared to the former because the amount of ammonia aqueous solution and solvent per cycle is smaller and the reaction wave treatment is easier.

本発明化合物の具体別とその理化学的性質ｔ−第１表に
下す。Specific details of the compounds of the present invention and their physical and chemical properties are shown in Table 1.

なお、第１表には各化合物番号に対応する礪遺式會示し
た。Note that Table 1 shows the formulas corresponding to each compound number.

６０次に本発明化合物の合成例を以下に示す。60 Next, a synthesis example of the compound of the present invention will be shown below.

会成例１：化合物番号３の合成Ｏ−メチル馬尿酸５，６ｆと酢酸ナトリウム（無水物）
Ｓ、Ｚｔを無水酢酸２４ｄ中、５０℃で３０分間、つい
で水冷下撹拌する。そこへ、別に３，４−キシリジン３
．２を食酢＃！１７−と３ｓ％塩酸４．９−の温合物に
とかし氷水冷却下、亜硝酸イソアルミル３．８８ｓｇｔ
滴下してｌ１ｉｌｉｊｉｌシた３、４−ジメチルフェニ
ルジアゾニウムクロリド溶＊を滴下する。滴下ＩＩＩｋ
３０分間攪拌し生成する黄色の結晶をＩａ取して、吸引
下水ついでアセトンで洗浄し中間原料１に得る。Synthesis Example 1: Synthesis of Compound No. 3 O-methyl hippuric acid 5,6f and sodium acetate (anhydride)
S and Zt were stirred in 24 d of acetic anhydride at 50° C. for 30 minutes and then cooled with water. There, separately 3,4-xylidine 3
．． 2 with vinegar #! 17- and 3s% hydrochloric acid 4.9- and cooled with ice water, 3.88 sgt of isoalumyl nitrite
Add dropwise 3,4-dimethylphenyldiazonium chloride solution*. Dripping IIIk
After stirring for 30 minutes, the resulting yellow crystals were collected as Ia, and washed under suction with water and then with acetone to obtain Intermediate Raw Material 1.

これをアセト／γ０−に分散し、２９Ｘアンモニア水溶
液５−を加えて２０分間還流する０次に３５％塩ａ１５
−會加えて１０分間還流して、反応混合物を室温までさ
ます。氷水３００−に上記反応混合豐ｔそそぎ、析出物
上濾取する。エタノールから再結晶して黄色結晶の目的
＠ｔ４た。（収量５、：Ｍ、収率６８％）。ｍ、ｐ、１
８８〜１９０℃；■Ｒ（第３図に示す）。Disperse this in acetate/γ0-, add 29X ammonia aqueous solution 5- and reflux for 20 minutes. Next, 35% salt a15
- Add and reflux for 10 minutes and allow the reaction mixture to cool to room temperature. Pour the reaction mixture into 300ml of ice water and filter the precipitate. Recrystallization from ethanol yielded yellow crystals @t4. (Yield 5:M, yield 68%). m, p, 1
88-190°C; ■R (as shown in Figure 3).

可成’ｆ’Ｊ２：化合切番号７の合成ｐ−メチル馬尿酸５．６ｔと酢酸ナトリウム（無水物）
５．２Ｆを無水酢酸２４−中、５０℃で３０分間、つい
で水冷下撹拌する。そこへ、別にアニソ７２．３４−を
酢酸１７−と３５％塩酸４．９−の混合物にとかし氷水
冷却下、亜ｂｓ酸イノアミル３．８８−１−Ｍ下して調
製し九フェニルンアゾニウムクロリド溶液を滴下する。Compound 'f'J2: Synthesis of compound number 7 p-methylhippuric acid 5.6t and sodium acetate (anhydride)
5.2F was stirred in 24-mL acetic anhydride at 50°C for 30 minutes, then under water cooling. Separately, aniso 72.34- was dissolved in a mixture of acetic acid 17- and 35% hydrochloric acid 4.9-, and under ice water cooling, 3.88-1 M of inoamyl bsite was prepared. Add the chloride solution dropwise.

滴下後３０分間攪拌し生成する黄色の結晶【ａ取して、
吸引下水ついでアセトンで洗浄し中間原料を得る。After dropping, stir for 30 minutes and generate yellow crystals [a]
The intermediate raw material is obtained by suctioning sewage and washing with acetone.

こｎｔアセトン７０−に分散し、２９％アンモニア水溶
液５ｗｔを加えて２０分間還流する。次に、３５％１＃
５−を加えて１０分間還流して、反応混合拗音室温まで
さます。氷水３００ｓｊに上記反応混合＃ＩＪをそそぎ
析出物を濾取する。エタノールから再結晶して白色結晶
の目的＠ｆ：４！４た。（収置４．８Ｆ、収＄　６７　
Ｘ）、　ｍ、　ｐ、　ｌｓ５−１５６℃；ＩＲ（第１図
に示す）。This was dispersed in 70% of acetone, 5 wt of a 29% ammonia aqueous solution was added, and the mixture was refluxed for 20 minutes. Then 35% 1#
Add 5- and reflux for 10 minutes, and allow the reaction mixture to cool to room temperature. Pour the above reaction mixture #IJ into 300 sj of ice water and collect the precipitate by filtration. Recrystallized from ethanol to obtain white crystals @f:4!4. (Location: 4.8F, storage: $67
X), m, p, ls5-156°C; IR (as shown in Figure 1).

ピ成例３；化酋物番号２３の合成ｐ−クロロ馬尿酸５．６ｆと酢酸ナトリウム（無水物）
ｓ、ｚｒを無水酢酸２４−中、５０℃で３０分間、つい
で水冷下撹拌する。そこへ、別にｍ−トルイジン２．７
２ｓｓｇｔ酢酸１フーと３５％塩＃４．９−の混合物に
とかし氷水冷却下、亜硝酸イソアミル３．８８ｍｔ滴下
してｌ１ｌｌｌｉｌｌｌｉｌした３−メチルフェニルジ
アゾニウムクロリド溶液１に滴下する０滴下後鉛分関攪
拌し生成する黄色の結晶ｔ−瀘濾取て、吸引下水ついで
アセトンで洗浄し中間原料を得る。Example 3: Synthesis of compound number 23 p-chlorohippuric acid 5.6f and sodium acetate (anhydride)
s and zr were stirred in 24-acetic anhydride at 50° C. for 30 minutes, then under water cooling. There, separately m-toluidine 2.7
Dissolve in a mixture of 2ssgt acetic acid 1 and 35% salt #4.9, add dropwise 3.88mt of isoamyl nitrite under cooling with ice water, and add dropwise to 1lllilllil 3-methylphenyldiazonium chloride solution 1. After 0 drops, stir with lead separation. The resulting yellow crystals are filtered through a T-filter, drained under suction, and then washed with acetone to obtain an intermediate raw material.

これをアセトン７０−に分散し、２９％アンモニア水溶
液Ｓ−を加えて２０分間還流する１次に３５％塩酸５−
を加えて１０分間還流して、反応混合物を室温までさま
す。氷水３００−に上記反応混合物をそそぎ析出物ｔＩ
ｌｌｌＩＩｉＬする。エタノールから再結晶して白色結
晶の目的物を得喪。（収量４．８ｆ、収率６５％）。ｍ
、　ｐ、　１４ｇ−１５０℃、　ＩＲ（第２３図に示す
）。Disperse this in acetone 70-, add 29% ammonia aqueous solution S-, and reflux for 20 minutes. Next, 35% hydrochloric acid 5-
was added and refluxed for 10 minutes, allowing the reaction mixture to cool to room temperature. Pour the above reaction mixture into 300ml of ice water to obtain precipitate tI.
IllIIiL. The desired product was obtained as white crystals by recrystallization from ethanol. (Yield 4.8f, yield 65%). m
, p, 14g-150°C, IR (shown in Figure 23).

次に実施例の若干會あげるが、担体（稀釈剤）及び助剤
、その混合比及び有効成分は広い範囲で変更し得るもの
である。Next, some examples will be given, but the carrier (diluent), the auxiliary agent, the mixing ratio thereof, and the active ingredient can be varied within a wide range.

実施列ｌ：水相剤化合物Ａ　１　　　　　　　　　　　　５０ｓリグニン
スルホン酸塩　　　　　　　　　　　５部アルキルスル
ホン鈑塩　　　　　　　　　　３８１１珪噛土　　　　
　　　　　　　　　　　　４２部金混合粉砕し水和剤と
し、水で稀釈して使用する。Implementation row 1: Water phase agent compound A 1 50s lignin sulfonate 5 parts alkyl sulfone sheet salt 3811 siliceous clay
42 parts of gold are mixed and ground to make a wettable powder, diluted with water, and used.

実施例２：乳剤化合物Ａ７　　　　　　　　　　　２５部キシレン　　
　　　　　　　　　　　６５部ポリオキ７エチレンアル
キル了りルエーテル　　　１０％を均一混合し乳剤とし
、水で稀釈し７て使用する。Example 2: Emulsion compound A7 25 parts xylene
65 parts of polyoxygenate and 10% of ethylene alkyl ether are uniformly mixed to form an emulsion, diluted with water and used.

実施例３：粒剤化貧＠Ａ３　　　　　　　　　　８部ベントナイト　　　　　　　　　　　　　４０部クレー
　　　　　　　　　　　　　　４５部リグニンスルホン
鈑基塩　　　　　　　　　７部を均一に混合し、艷に水
１に加えて騨合せ、押出式造粒懺で粒状に加工乾燥して
粒剤とする。Example 3: Granulation poor@A3 8 parts bentonite 40 parts clay 45 parts lignin sulfone base salt 7 parts were mixed uniformly, added to 1 part water in a tank, mixed, and processed into granules using an extrusion type granulator. Dry to make granules.

次に本発明化合物の有効性を証するため若干の賦−例を
示す。Next, some examples will be shown to demonstrate the effectiveness of the compounds of the present invention.

ブラフ　／　−（８５０Ｘ！１０Ｘ２００％　）に土壌
ｔツｋｂ畑地状とし、試験植物の種子の一定量を播種し
覆土した後、本発明化合物が、アール当りｌ５ｏｔ相当
量になるようＫＩＩＩｉＬ次稀釈液を土壌表面に均一に
＆布し、温室内にて育生管理した。処［１２５日債に次
の基準にて評価した。Bluff / - (850X! 10X 200%) was made into a field with 100% of soil, and after sowing a certain amount of seeds of the test plant and covering with soil, the KIIIiL next dilution solution was added so that the compound of the present invention was in an amount equivalent to 150% per area. It was spread evenly on the soil surface and grown in a greenhouse. [125-day bonds were evaluated based on the following criteria.

評４ＩＡ基準Ｏ殺草効果なし１　２０％の殺草効果２　　４０％　　　＃３　　６０％の！８箪効果４　　　　８０％　　　　＃５　　１００％　　　Ｍ上記試験の給米を第２表に示す。Evaluation 4IA standards O No herbicide effect 1 20% weed killing effect 2 40% # 3.60%! 8 箪 effect 4 80% # 5 100% M Table 2 shows the rice supply for the above test.

第　　　２　　　表ｆ：、−例２：植物発生始期処理の除皐効果試験試験例
１と同様操作により播棟し、慣物が１〜２頻期に達した
ときに有効成分アール当り５０ｆ相当量の水懸濁ａｔ茎
茎葉上土壌表面均一に散布し、温室内にて育生管理した
。処理２５日恢に試験例１と同様に調査した。上記試験
の結果を第３表に示す。Table 2 f: -Example 2: Test on the effect of removing saplings during treatment at the beginning of plant development.When the seedlings were sown in the same manner as in Test Example 1, and when the habitual matter reached the 1st to 2nd period, an amount equivalent to 50f per active ingredient R was applied. A water suspension of the mixture was sprayed uniformly on the soil surface on the stems, leaves, and grown in a greenhouse. The same investigation as in Test Example 1 was conducted 25 days after the treatment. The results of the above test are shown in Table 3.

第　　３　　表Table 3

【図面の簡単な説明】第１図は出汁物番号１、第２図は化付づ番号２、第３図
は化合物番号３、第４図は化合物番号４、第５図は化合
物番号５、第６図は化合物番号６、第７図は化合物番号
７、第８図は化合物番号８、第９図は化合物番号９、第
１０図は化合物番号１０．１５１１図は化付物番号１１
、渠１２図は化合物番号１２、第１３図は化合物番号１
３、第１４図１１化合物４１偏１４、第１５図は化合脅
番号１５、第１６図は化合＃爵号１６、第１７図は化合
物番号１７、第１８図は化合物番号１８、第１９図は化
合物袖号１９、第２０図は化合物番号２０、第２１図は
化合物番号２１．第２２図は化合物番号２２、第２３図
は化合物番号２３、第２４図は化合ｖＪ番号２４、第２
５図は化合物番号２５、第２６図は化合物番号２６、第
２７図は化合物番号２７、第２８図は化合＊ＩＩ号２８
、第２９図は化合物番号２９、第３０図は化合物番号３
０．第３１図は化合物番号３１．４３２図は化合物番号
３２、第３３を示す図である。出−人　　　　（１１Ｏ，Ｈｈ；シ―°１代理人弁理士
　宮　　１１１　　広　　豊代理人弁理七　川　　目　
　我　雄第１図第２図第３図第４図第５図第６１１第７図Ｉ８関第９１１第１／　Ｅ第１２図第１６１ｉ！ａ第１７図第１８図第１９　ＩＩＩ第２０園第２１図第２２図第２３図第２４図第２５！％ｉ第２６１１第２７１１[Brief explanation of the drawings] Figure 1 is soup stock number 1, Figure 2 is number 2, Figure 3 is compound number 3, Figure 4 is compound number 4, Figure 5 is compound number 5, Figure 6 is compound number 6, Figure 7 is compound number 7, Figure 8 is compound number 8, Figure 9 is compound number 9, Figure 10 is compound number 10.1511 Figure is compound number 11.
, Figure 12 shows compound number 12, and Figure 13 shows compound number 1.
3, Fig. 14 11 Compound 41 Part 14, Fig. 15 shows compound number 15, Fig. 16 shows compound number 16, Fig. 17 shows compound number 17, Fig. 18 shows compound number 18, and Fig. 19 shows compound number 16. Compound number 19 is shown in Figure 20, compound number 20 is shown in Figure 21, and compound number 21 is shown in Figure 21. Figure 22 shows compound number 22, Figure 23 shows compound number 23, Figure 24 shows compound vJ number 24,
Figure 5 shows compound number 25, Figure 26 shows compound number 26, Figure 27 shows compound number 27, and Figure 28 shows compound *II number 28.
, Figure 29 shows compound number 29, Figure 30 shows compound number 3.
0. Figure 31 shows compound number 31. Figure 32 shows compound numbers 32 and 33. Representative (11O, Hh; Sea °1 Patent Attorney Miya 111 Yutaka Hiro Representative Patent Attorney Nanakawa Me
I male Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 611 Figure 7 I8 Seki No. 911 1/E Figure 12 Figure 161i! a Fig. 17 Fig. 18 Fig. 19 III Fig. 20 Fig. 21 Fig. 22 Fig. 23 Fig. 24 Fig. 25! %i 2611th 2711th

Claims

【特許請求の範囲】（１１一般式（式中、Ｒ１＃−ｔ／ｊＣ素原子又はアルキル基を表わ
し、ｍ１ｊＯ，１又は２を表わし、Ｒ２はアルキル基、
アルコキシル基、ニトロ基又はハロゲン原子ｔ−表わし
、ｎ　Ｆ′１１又は２に−表わす）で示される１、２．
４−）リアゾール−４体。（２）一般式（式中、ＲＩ＋ｒｘＪＩＪ及びｎは前記と同義である）で示される１、２．４−トリアゾール誘導体を有効成分
とする除草剤。[Claims] (11 general formula (wherein R1 #-t/j represents a elementary atom or an alkyl group, m1jO represents 1 or 2, R2 is an alkyl group,
1,2.
4-) Riazole-4 bodies. (2) A herbicide containing a 1,2,4-triazole derivative represented by the general formula (wherein RI+rxJIJ and n have the same meanings as above) as an active ingredient.