JPH0119385B2 - - Google Patents
Info
- Publication number
- JPH0119385B2 JPH0119385B2 JP58121007A JP12100783A JPH0119385B2 JP H0119385 B2 JPH0119385 B2 JP H0119385B2 JP 58121007 A JP58121007 A JP 58121007A JP 12100783 A JP12100783 A JP 12100783A JP H0119385 B2 JPH0119385 B2 JP H0119385B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- alkyl group
- formula
- lower alkyl
- lower alkoxy
- 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
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 10
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 9
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 125000001153 fluoro group Chemical group F* 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 150000003558 thiocarbamic acid derivatives Chemical class 0.000 claims description 3
- 125000002490 anilino group Chemical class [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 150000002989 phenols Chemical class 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 27
- 150000001875 compounds Chemical class 0.000 description 21
- 230000002363 herbicidal effect Effects 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 241000196324 Embryophyta Species 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 239000004009 herbicide Substances 0.000 description 8
- 239000002689 soil Substances 0.000 description 8
- 241000209094 Oryza Species 0.000 description 7
- 235000007164 Oryza sativa Nutrition 0.000 description 7
- 235000009566 rice Nutrition 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000004480 active ingredient Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 244000068988 Glycine max Species 0.000 description 3
- 235000010469 Glycine max Nutrition 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 235000011181 potassium carbonates Nutrition 0.000 description 3
- -1 thiol carbamates Chemical class 0.000 description 3
- VLJSLTNSFSOYQR-UHFFFAOYSA-N 3-propan-2-ylphenol Chemical compound CC(C)C1=CC=CC(O)=C1 VLJSLTNSFSOYQR-UHFFFAOYSA-N 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-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
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 2
- 241001076438 Oxya japonica Species 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 241001148683 Zostera marina Species 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000887 hydrating effect Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 238000009333 weeding Methods 0.000 description 2
- CZEWVBLUMUTPKM-UHFFFAOYSA-N (3-methylphenyl)carbamothioic s-acid Chemical compound CC1=CC=CC(NC(S)=O)=C1 CZEWVBLUMUTPKM-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 241000254032 Acrididae Species 0.000 description 1
- 240000001592 Amaranthus caudatus Species 0.000 description 1
- 235000009328 Amaranthus caudatus Nutrition 0.000 description 1
- 235000006890 Chamerion angustifolium subsp angustifolium Nutrition 0.000 description 1
- 235000002278 Chamerion angustifolium subsp circumvagum Nutrition 0.000 description 1
- 244000287353 Crassocephalum crepidioides Species 0.000 description 1
- 241000219146 Gossypium Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 241000254158 Lampyridae Species 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 231100000674 Phytotoxicity Toxicity 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000004659 dithiocarbamates Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- ZHTSFQWDLLBQNR-UHFFFAOYSA-N methyl(phenyl)carbamothioic s-acid Chemical compound SC(=O)N(C)C1=CC=CC=C1 ZHTSFQWDLLBQNR-UHFFFAOYSA-N 0.000 description 1
- WAZUROKOCYSLSU-UHFFFAOYSA-N n-methyl-n-(3-methylphenyl)carbamothioyl chloride Chemical compound ClC(=S)N(C)C1=CC=CC(C)=C1 WAZUROKOCYSLSU-UHFFFAOYSA-N 0.000 description 1
- 230000001069 nematicidal effect Effects 0.000 description 1
- QYNCNBOIYOQMIF-UHFFFAOYSA-N o-(3-propan-2-ylphenyl) n-methyl-n-(3-methylphenyl)carbamothioate Chemical compound CC(C)C1=CC=CC(OC(=S)N(C)C=2C=C(C)C=CC=2)=C1 QYNCNBOIYOQMIF-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 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
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 238000009331 sowing Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000004563 wettable powder Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
本発明はチオカーバメート誘導体およびその製
造法に関する。
従来、特定のＯ―アリール Ｎ―アリールチオ
カーバメート系化合物が医薬として抗菌作用およ
び殺線虫作用を有することは周知である。また一
般にカーバメート、チオールカーバメートおよび
ジチオカーバメート系化合物が除草活性を有する
ことは公知である。また特開昭48−49925号公報
では特定のアリール Ｎ―アリールカーバメート
系化合物が除草剤として使用し得ることが開示さ
れている。しかしながら、Ｏ―アリール Ｎ―ア
リールチオカーバメート系化合物が有効な除草剤
として使用し得ることは知られてない。
本発明者らは、Ｏ―アリール Ｎ―アリールチ
オカーバメート誘導体で、十分な除草効果を有
し、かつ、高度の選択性を有する化合物を開発す
べく鋭意研究を重ねた結果、本発明化合物が各種
雑草に対して優れた除草活性を示すことを見い出
し、本発明を完成した。
すなわち、本発明は、一般式（）：
（式中、R1は３位置換の炭素数２以上の低級
アルキル基または４位置換のトリフルオロメチル
基、R2は低級アルキル基、R3およびR4は各々水
素原子、ハロゲン原子、低級アルキル基、低級ア
ルコキシ基またはトリフルオロメチル基を示す。
R3とR4は互いに同一または相異なる。ただし、
R3とR4がいずれも水素原子以外の場合、R3とR4
のいずれかがフツ素原子または低級アルコキシ基
として４位に結合することはない。）で表される
チオカーバメート誘導体（以下、本発明化合物と
いう。）およびその製造法を提供するものである。
本発明化合物は文献未記載の新規化合物であ
り、その有用な生理活性も知られていない。
本発明化合物を有効成分として含有する除草剤
は特に湛水下の水田において、ノビエを始めとす
る多くの雑草に対して極めて優れた除草活性を示
すとともに、移植水稲には実質的に無害であり、
水田用除草剤として好適である。また、畑地土壌
処理により、イネ科雑草と広葉作物の間に優れた
選択除草効果を示し、畑地用除草剤としても適用
性を有することが認められた。
前記一般式（）で表される本発明化合物は、
下記反応式に従つて製造することができる。
（式中、R1は３位置換の炭素数２以上の低級
アルキル基または４位置換のトリフルオロメチル
基、R2は低級アルキル基、R3およびR4は各々水
素原子、ハロゲン原子、低級アルキル基、低級ア
ルコキシ基またはトリフルオロメチル基を示す。
R3とR4は互いに同一または相異なる。ただし、
R3とR4がいずれも水素原子以外の場合、R3とR4
のいずれかがフツ素原子または低級アルコキシ基
として４位に結合することはない。Halはハロゲ
ン原子を示す。）
上記の反応は、脱ハロゲン化水素剤の存在下、
さらに反応溶媒の存在下あるいは不存在下に、通
常、０℃から150℃の反応温度で進行し、反応時
間は数分ないし48時間程度である。
脱ハロゲン化水素剤としては、水酸化ナトリウ
ム、水酸化カリウム等の水酸化アルカリ、水酸化
カルシウム等の水酸化アルカリ土類、炭酸ナトリ
ウム、炭酸カリウム、炭酸水素ナトリウム、炭酸
水素カリウム等の炭酸アルカリ塩、水素化ナトリ
ウム等の水素化金属、トリエチルアミン、ジメチ
ルアニリン、ピリジン等の第三級アミン等を挙げ
ることができる。反応式(2)においては、原料のア
ニリン誘導体を脱ハロゲン化水素剤として使用で
きる。
反応溶媒としては、水およびメタノール、エタ
ノール、イソプロパノール等のアルコール類、ア
セトン、メチルエチルケトン等のケトン類、ベン
ゼン、トルエン、キシレン等の芳香族炭化水素
類、エチルエーテル、テトラヒドロフラン、ジオ
キサン等のエーテル類、クロロベンゼン、クロロ
ホルム、四塩化炭素、ジクロロエタン等のハロゲ
ン化炭化水素類、ジメチルホルムアミド、ジメチ
ルスルホキシド等の極性溶媒等が用いられる。
次に本発明化合物の製造法を具体的に説明す
る。
実施例 １
Ｏ―３―イソプロピルフエニル Ｎ―メチル―
Ｎ―（３―メチルフエニル）チオカーバメート
の製造法（本発明化合物No.３）
Ｎ―メチル―Ｎ―（３―メチルフエニル）チオ
カルバモイルクロライド2.00ｇ，３―イソプロピ
ルフエノール1.36ｇおよび無水炭酸カリウム1.38
ｇをメチルエチルケトン50mlに添加し、15時間加
熱還流した。反応混合物を室温まで冷却した後、
冷水中に注ぎ、生成物をベンゼンで抽出した。ベ
ンゼン溶液を10％水酸化ナトリウム水溶液、水、
飽和塩化ナトリウム水溶液の順で洗い、無水硫酸
マグネシウムで乾燥した後、減圧下でベンゼンを
留去した。残留物をカラムクロマトグラフイー
（シリカゲル、ベンゼン／ヘキサン＝１／１（Ｖ／
Ｖ）展開）で精製して、Ｏ―３―イソプロピルフ
エニル Ｎ―メチル―Ｎ―（３―メチルフエニ
ル）チオカーバメート2.32ｇ（収率78％）を得
た。このものの一部をエタノールより再結晶し、
融点48〜49.5℃の無色結晶を得た。
実施例 ２
Ｏ―３―tert―ブチルフエニル Ｎ―メチル―
Ｎ―フエニルチオカーバメートの製造法（本発
明化合物No.４）
Ｎ―メチルアニリン1.07ｇおよび無水炭酸カリ
ウム1.38ｇをアセトン20mlに添加し、室温で攪拌
しながら、Ｏ―３―tert―ブチルフエニル クロ
ルチオホルメイト2.29ｇをアセトン20mlに溶解し
て加えた。このまま30分間攪拌した後、２時間加
熱還流した。反応混合物を室温まで冷却した後、
冷水中に注ぎ、生成物をベンゼンで抽出した。ベ
ンゼン溶液を希塩酸，水，飽和塩化ナトリウム水
溶液の順で洗い、無水硫酸マグネシウムで乾燥し
た後、減圧下でベンゼンを留去した。残留物をカ
ラムクロマトグラフイー（シリカゲル、ベンゼ
ン／ヘキサン＝１／１（Ｖ／Ｖ）展開）で精製し
てＯ―３―tert―ブチルフエニル。
Ｎ―メチル―Ｎ―フエニルチオカーバメート
1.77ｇ（収率77％）を得た。このものの一部をヘ
キサンより再結晶し、融点78.5〜79℃の無色結晶
を得た。
次に前記一般式（）で示される本発明化合物
の代表例とその物性を下記第１表に示す。本発明
化合物は、この具体例の化合物に限定されるもの
ではない。
本発明化合物は、各種雑草に対して優れた除草
活性を示し、しかも水稲、大豆、ワタ等の作物に
対して薬害を与えないので除草剤の有効成分とし
て好適である。すなわち、本発明化合物の作用特
The present invention relates to thiocarbamate derivatives and methods for producing the same. It has been well known that certain O-aryl N-arylthiocarbamate compounds have antibacterial and nematicidal effects as pharmaceuticals. Furthermore, it is generally known that carbamates, thiol carbamates and dithiocarbamate compounds have herbicidal activity. Furthermore, JP-A-48-49925 discloses that certain aryl N-aryl carbamate compounds can be used as herbicides. However, it is not known that O-aryl N-arylthiocarbamate compounds can be used as effective herbicides. The present inventors have conducted extensive research to develop O-aryl N-arylthiocarbamate derivatives that have sufficient herbicidal effects and a high degree of selectivity. It was discovered that this product exhibits excellent herbicidal activity against weeds, and the present invention was completed. That is, the present invention provides general formula (): (In the formula, R 1 is a lower alkyl group substituted at the 3-position and having 2 or more carbon atoms or a trifluoromethyl group substituted at the 4-position, R 2 is a lower alkyl group, R 3 and R 4 are each a hydrogen atom, a halogen atom, a lower Indicates an alkyl group, lower alkoxy group or trifluoromethyl group.
R 3 and R 4 are the same or different from each other. however,
If R 3 and R 4 are both other than hydrogen atoms, R 3 and R 4
Neither of them is bonded to the 4-position as a fluorine atom or a lower alkoxy group. ) (hereinafter referred to as the compound of the present invention) and a method for producing the same. The compound of the present invention is a novel compound that has not been described in any literature, and its useful physiological activity is also unknown. The herbicide containing the compound of the present invention as an active ingredient exhibits extremely excellent herbicidal activity against many weeds including field weed, especially in flooded rice fields, and is virtually harmless to transplanted paddy rice. ,
Suitable as a herbicide for paddy fields. In addition, when treated with upland soil, it showed an excellent selective weeding effect between grass weeds and broad-leaved crops, and was recognized to have applicability as a herbicide for upland fields. The compound of the present invention represented by the general formula () is
It can be produced according to the reaction formula below. (In the formula, R 1 is a lower alkyl group substituted at the 3-position and having 2 or more carbon atoms or a trifluoromethyl group substituted at the 4-position, R 2 is a lower alkyl group, R 3 and R 4 are each a hydrogen atom, a halogen atom, a lower Indicates an alkyl group, lower alkoxy group or trifluoromethyl group.
R 3 and R 4 are the same or different from each other. however,
If R 3 and R 4 are both other than hydrogen atoms, R 3 and R 4
Neither of them is bonded to the 4-position as a fluorine atom or a lower alkoxy group. Hal indicates a halogen atom. ) The above reaction is carried out in the presence of a dehydrohalogenating agent,
Further, the reaction usually proceeds in the presence or absence of a reaction solvent at a reaction temperature of 0°C to 150°C, and the reaction time is about several minutes to 48 hours. Examples of dehydrohalogenation agents include alkali hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth hydroxides such as calcium hydroxide, and alkali carbonates such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate. , metal hydrides such as sodium hydride, and tertiary amines such as triethylamine, dimethylaniline, and pyridine. In reaction formula (2), the aniline derivative as a raw material can be used as a dehydrohalogenating agent. Reaction solvents include water, alcohols such as methanol, ethanol, and isopropanol, ketones such as acetone and methyl ethyl ketone, aromatic hydrocarbons such as benzene, toluene, and xylene, ethers such as ethyl ether, tetrahydrofuran, and dioxane, and chlorobenzene. , halogenated hydrocarbons such as chloroform, carbon tetrachloride, and dichloroethane, and polar solvents such as dimethylformamide and dimethyl sulfoxide. Next, the method for producing the compound of the present invention will be specifically explained. Example 1 O-3-isopropylphenyl N-methyl-
Method for producing N-(3-methylphenyl)thiocarbamate (invention compound No. 3) 2.00 g of N-methyl-N-(3-methylphenyl)thiocarbamoyl chloride, 1.36 g of 3-isopropylphenol, and 1.38 g of anhydrous potassium carbonate.
g was added to 50 ml of methyl ethyl ketone and heated under reflux for 15 hours. After cooling the reaction mixture to room temperature,
Poured into cold water and extracted the product with benzene. Benzene solution, 10% sodium hydroxide solution, water,
After washing with saturated aqueous sodium chloride solution and drying over anhydrous magnesium sulfate, benzene was distilled off under reduced pressure. The residue was subjected to column chromatography (silica gel, benzene/hexane = 1/1 (V/
V) Development) to obtain 2.32 g (yield 78%) of O-3-isopropylphenyl N-methyl-N-(3-methylphenyl)thiocarbamate. A part of this substance was recrystallized from ethanol,
Colorless crystals with a melting point of 48-49.5°C were obtained. Example 2 O-3-tert-butylphenyl N-methyl-
Method for producing N-phenyl thiocarbamate (inventive compound No. 4) 1.07 g of N-methylaniline and 1.38 g of anhydrous potassium carbonate were added to 20 ml of acetone, and while stirring at room temperature, O-3-tert-butylphenyl chloride was added. 2.29 g of ruthioformate was dissolved in 20 ml of acetone and added. After stirring as it was for 30 minutes, the mixture was heated under reflux for 2 hours. After cooling the reaction mixture to room temperature,
Poured into cold water and extracted the product with benzene. The benzene solution was washed with dilute hydrochloric acid, water, and a saturated aqueous sodium chloride solution in this order, dried over anhydrous magnesium sulfate, and then benzene was distilled off under reduced pressure. The residue was purified by column chromatography (silica gel, developed with benzene/hexane = 1/1 (V/V)) to obtain O-3-tert-butylphenyl. N-methyl-N-phenylthiocarbamate
1.77g (yield 77%) was obtained. A part of this product was recrystallized from hexane to obtain colorless crystals with a melting point of 78.5-79°C. Next, representative examples of the compounds of the present invention represented by the general formula () and their physical properties are shown in Table 1 below. The compounds of the present invention are not limited to the compounds of this specific example. The compound of the present invention exhibits excellent herbicidal activity against various weeds and does not cause any phytotoxicity to crops such as paddy rice, soybeans, and cotton, and is thus suitable as an active ingredient in herbicides. That is, the action characteristics of the compound of the present invention
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】
性として、作物に薬害を与えることなく、雑草を
枯殺するか、あるいは生長を停止、もしくは著し
く生長を抑制遅延させることによつて、作物との
生育競合を失わせることがあげられる。
本発明化合物は、特に湛水下の水田においてノ
ビエをはじめとしてタマガヤツリ、コナギ、キカ
シグサ、ホタルイ等の多くの雑草に対して50〜
500ｇ／10aの有効成分量で極めて優れた除草活
性を示すことが認められた。一方、稚苗水稲に対
する安全性も極めて高く1000ｇ／10aの有効成分
量でも全く影響は認められず、水田用除草剤とし
ての特性が極めて優れている。
さらに本発明化合物を、畑地作物である大豆等
の一般広葉作物の播種後に土壌処理剤として使用
すると、作物に薬害を与えることなく、ノビエ、
メヒシバ、エノコログサ等のイネ科雑草を有効に
防除することができ、畑地用除草剤として適用性
を有することが認められた。
次に本発明化合物の除草効果を使用例によつて
説明する。使用例中、「部」は重量部である。
使用例 １
湛水条件下における除草効果試験
本発明化合物10部を担体材料としてジークライ
ト〔商品名、国峰工業(株)製〕87.3部、界面活性剤
としてネオペレツクス〔商品名、花王アトラス(株)
製〕1.35部およびソルポール800A〔商品名、東邦
化学工業(株)製〕1.35部と共に混合粉砕して10％水
和剤を得た。
次に、直径９cmの磁製ポツトに水田土壌を入
れ、水を加えて代かき後、土壌表層に雑草種子を
播き２葉期の水稲苗（品種、日本晴）を１cmの深
さに２本２株植えとした。翌日２cmの湛水を行な
い、上述の如くして得た各本発明化合物の水和剤
の所定葉量をポツト当り10mlの水に希釈して水面
に滴下処理した。その後、温室に静置し、薬液処
理３週間後に除草効果および水稲に及ぼした影響
を調査した。
評価は６段階で表示したが、具体的には下記の
通りである。その結果は第２表および第３表に示
した。[Table] The ability to eliminate growth competition with crops by killing weeds, stopping their growth, or significantly inhibiting and delaying their growth without causing chemical damage to crops. . The compound of the present invention is particularly effective against many weeds such as wild grass, Japanese grasshopper, Japanese grasshopper, Japanese fireweed, and firefly, especially in flooded rice fields.
It was observed that an extremely excellent herbicidal activity was exhibited at an active ingredient amount of 500g/10a. On the other hand, it is extremely safe for young paddy rice seedlings, with no effects observed even at an active ingredient amount of 1000g/10a, and has extremely excellent properties as a herbicide for paddy fields. Furthermore, when the compound of the present invention is used as a soil treatment agent after sowing general broad-leaved crops such as soybeans, which are upland crops, it will not cause chemical damage to crops,
It was found that it can effectively control grass weeds such as grasshopper and foxtail grass, and has applicability as a herbicide for upland fields. Next, the herbicidal effects of the compounds of the present invention will be explained using usage examples. In the usage examples, "parts" are parts by weight. Usage example 1 Herbicidal effect test under submerged conditions 10 parts of the compound of the present invention as a carrier material, 87.3 parts of Siegrite [trade name, manufactured by Kunimine Kogyo Co., Ltd.], and as a surfactant, Neopellex [trade name, manufactured by Kao Atlas Co., Ltd.]
The mixture was mixed and ground with 1.35 parts of Solpol 800A (trade name, manufactured by Toho Chemical Industries, Ltd.) to obtain a 10% hydrating powder. Next, put paddy soil in a porcelain pot with a diameter of 9 cm, add water, and after puddling, weed seeds are sown on the soil surface layer, and two paddy rice seedlings (variety, Nipponbare) at the two-leaf stage are planted at a depth of 1 cm. I planted it. The next day, the pots were flooded with water to a depth of 2 cm, and a predetermined amount of the wettable powder of each of the compounds of the present invention obtained as described above was diluted with 10 ml of water per pot and dropped onto the water surface. Thereafter, the plants were left in a greenhouse, and three weeks after the chemical solution treatment, the herbicidal effect and the effect on paddy rice were investigated. The evaluation was displayed on a 6-level scale, and the specific details are as follows. The results are shown in Tables 2 and 3.
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】
使用例 ２
畑土壌表面処理による除草効果試験
直径12cmの磁製ポツトに畑土壌を入れ、数種の
植物種子を播き、１cm覆土した。前記使用例１の
如くして得た本発明化合物の水和剤の所定薬量を
ポツト当り10mlの水に希釈したものを土壌表面に
噴霧し、その後温室内に静置して適時散水した。
薬液処理３週間後に除草効果および大豆、ワタに
及ぼした影響を調査し、使用例１に準じて評価し
た。その結果は第４表に示した。[Table] Usage Example 2 Weeding effect test by field soil surface treatment Field soil was put into a porcelain pot with a diameter of 12 cm, seeds of several types of plants were sown, and the pot was covered with 1 cm of soil. A predetermined amount of the hydrating powder of the compound of the present invention obtained as in Use Example 1 was diluted in 10 ml of water per pot and sprayed onto the soil surface, and then left standing in a greenhouse and watered at appropriate times.
Three weeks after the chemical solution treatment, the herbicidal effect and the effect on soybeans and cotton were investigated and evaluated according to Use Example 1. The results are shown in Table 4.
【表】【table】
Claims (1)
アルキル基または４位置換のトリフルオロメチル
基を示し、R2は低級アルキル基を示し、R3およ
びR4は各々水素原子、ハロゲン原子、低級アル
キル基、低級アルコキシ基またはトリフルオロメ
チル基を示す。ただし、R3とR4は互いに同一ま
たは相異なる。R3とR4がいずれも水素原子以外
の場合、R3とR4のいずれかがフツ素原子または
低級アルコキシ基として４位に結合することはな
い。） で表されるチオカーバメート誘導体。 ２ 一般式（）： （式中、Ｘは水素原子またはハロチオカルボニ
ル基を示し、R1は３位置換の炭素数２以上の低
級アルキル基または４位置換のトリフルオロメチ
ル基を示す。） で表されるフエノール誘導体を 一般式（）： （式中、Ｙは（）式のＸが水素原子のときハ
ロチオカルボニル基、（）式のＸがハロチオカ
ルボニル基のとき水素原子を示し、R2は低級ア
ルキル基を示し、R3およびR4は各々水素原子、
ハロゲン原子、低級アルキル基、低級アルコキシ
基またはトリフルオロメチル基を示す。ただし、
R3とR4は互いに同一または相異なる。R3とR4が
いずれも水素原子以外の場合、R3とR4のいずれ
かがフツ素原子または低級アルコキシ基として４
位に結合することはない。） で表されるアニリン誘導体と反応させることを特
徴とする。 一般式（）： （式中、R1は３位置換の炭素数２以上の低級
アルキル基または４位置換のトリフルオロメチル
基、R2は低級アルキル基、R3およびR4は各々水
素原子、ハロゲン原子、低級アルキル基、低級ア
ルコキシ基またはトリフルオロメチル基を示す。
R3とR4は互いに同一または相異なる。ただし、
R3とR4がいずれも水素原子以外の場合、R3とR4
のいずれかがフツ素原子または低級アルコキシ基
として４位に結合することはない。） で表されるチオカーバメート誘導体の製造法。[Claims] 1 General formula (): (In the formula, R 1 represents a lower alkyl group having 2 or more carbon atoms substituted at the 3-position or a trifluoromethyl group substituted at the 4-position, R 2 represents a lower alkyl group, R 3 and R 4 each represent a hydrogen atom, Indicates a halogen atom, lower alkyl group, lower alkoxy group, or trifluoromethyl group. However, R 3 and R 4 are the same or different from each other. If R 3 and R 4 are both other than hydrogen atoms, R 3 and R 4 is not bonded to the 4-position as a fluorine atom or a lower alkoxy group.) A thiocarbamate derivative represented by: 2 General formula (): Phenol derivative represented by General formula (): (In the formula, Y represents a halothiocarbonyl group when X in formula () is a hydrogen atom, a hydrogen atom when X in formula () is a halothiocarbonyl group, R 2 represents a lower alkyl group, R 3 and R 4 is each a hydrogen atom,
Represents a halogen atom, lower alkyl group, lower alkoxy group or trifluoromethyl group. however,
R 3 and R 4 are the same or different from each other. When both R 3 and R 4 are other than hydrogen atoms, either R 3 or R 4 is 4 as a fluorine atom or a lower alkoxy group.
It is not connected to the position. ) It is characterized by reacting with an aniline derivative represented by General formula (): (In the formula, R 1 is a lower alkyl group substituted at the 3-position and having 2 or more carbon atoms or a trifluoromethyl group substituted at the 4-position, R 2 is a lower alkyl group, R 3 and R 4 are each a hydrogen atom, a halogen atom, a lower Indicates an alkyl group, lower alkoxy group or trifluoromethyl group.
R 3 and R 4 are the same or different from each other. however,
If R 3 and R 4 are both other than hydrogen atoms, R 3 and R 4
Neither of them is bonded to the 4-position as a fluorine atom or a lower alkoxy group. ) A method for producing a thiocarbamate derivative represented by
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12100783A JPS6013753A (en) | 1983-07-05 | 1983-07-05 | Thiocarbamate derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12100783A JPS6013753A (en) | 1983-07-05 | 1983-07-05 | Thiocarbamate derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6013753A JPS6013753A (en) | 1985-01-24 |
| JPH0119385B2 true JPH0119385B2 (en) | 1989-04-11 |
Family
ID=14800477
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12100783A Granted JPS6013753A (en) | 1983-07-05 | 1983-07-05 | Thiocarbamate derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6013753A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4849925A (en) * | 1971-10-26 | 1973-07-14 | ||
| JPS57176952A (en) * | 1981-04-03 | 1982-10-30 | Hoechst Ag | Thiocarbamic acid esters and manufacture |
-
1983
- 1983-07-05 JP JP12100783A patent/JPS6013753A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4849925A (en) * | 1971-10-26 | 1973-07-14 | ||
| JPS57176952A (en) * | 1981-04-03 | 1982-10-30 | Hoechst Ag | Thiocarbamic acid esters and manufacture |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6013753A (en) | 1985-01-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2860367B2 (en) | Heterocyclic compound, process for producing the same, and herbicide containing the same as active ingredient | |
| JPH0119385B2 (en) | ||
| JPH0434538B2 (en) | ||
| JPS6221344B2 (en) | ||
| JP2696252B2 (en) | Cyclohexanecarboxylic acid derivatives and herbicides and plant growth regulators containing the same | |
| JPS59216874A (en) | Carbamate derivative | |
| JPS6318922B2 (en) | ||
| JPS6061563A (en) | Thiocarbamate derivative | |
| JPS591697B2 (en) | Method for producing cyclohexane derivatives | |
| JPS6130671B2 (en) | ||
| JP2984775B2 (en) | Triazole derivatives, herbicide compositions for paddy fields and methods of using the same | |
| JPS59170068A (en) | Carbamate derivative | |
| JPH01175961A (en) | Hexahydrophthalanilide acid derivative, production thereof and herbicide comprising said derivative and active ingredient | |
| JPS6318921B2 (en) | ||
| JPS6356201B2 (en) | ||
| JPH01102070A (en) | Carbamoyltriazole derivative, its production, and herbicide containing the same as an active ingredient | |
| JPH0273047A (en) | Hexahydrophthalic acid anilide derivative, preparation thereof and herbicide containing said derivative as active ingredient | |
| JPS6147832B2 (en) | ||
| JPS6130670B2 (en) | ||
| JPS6234002B2 (en) | ||
| JPH0272145A (en) | Hexahydrophthalic acid anilide derivative, production thereof and herbicide containing said derivative as active ingredient | |
| JPS6237035B2 (en) | ||
| JPS625431B2 (en) | ||
| JPS60112756A (en) | Trifluoromethanesulfanilide derivative, production thereof and herbicide containing the same as active constituent | |
| JPS63264583A (en) | Pyridyl-2-oxy-phenoxypropionic acid derivative |