JPH03258743A - Ether bond-containing compound, production thereof and insecticide - Google Patents
Ether bond-containing compound, production thereof and insecticideInfo
- Publication number
- JPH03258743A JPH03258743A JP5357990A JP5357990A JPH03258743A JP H03258743 A JPH03258743 A JP H03258743A JP 5357990 A JP5357990 A JP 5357990A JP 5357990 A JP5357990 A JP 5357990A JP H03258743 A JPH03258743 A JP H03258743A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- formulas
- tables
- compound shown
- same meanings
- 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
- 150000001875 compounds Chemical class 0.000 title claims abstract description 48
- 239000002917 insecticide Substances 0.000 title claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title description 13
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 5
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims description 15
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 239000004480 active ingredient Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 241000238631 Hexapoda Species 0.000 abstract description 3
- 241000254173 Coleoptera Species 0.000 abstract description 2
- 241000255925 Diptera Species 0.000 abstract description 2
- 241000255777 Lepidoptera Species 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- RIKKDQCPYLBOND-UHFFFAOYSA-N ethenyl(methyl)carbamic acid Chemical compound C=CN(C)C(O)=O RIKKDQCPYLBOND-UHFFFAOYSA-N 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 229910052736 halogen Inorganic materials 0.000 abstract 2
- 150000002367 halogens Chemical class 0.000 abstract 2
- 230000001276 controlling effect Effects 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000002904 solvent Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- -1 4-(2-ethylbutyl)phenoxypropionate Chemical compound 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 5
- 230000005764 inhibitory process Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000010898 silica gel chromatography Methods 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000032669 eclosion Effects 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- UKJWAHQMLOLAJT-UHFFFAOYSA-N 4-(2-ethylbutyl)phenol Chemical compound CCC(CC)CC1=CC=C(O)C=C1 UKJWAHQMLOLAJT-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-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
- 241000607479 Yersinia pestis Species 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- 230000003054 hormonal effect Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- OAAZUWWNSYWWHG-UHFFFAOYSA-N 1-phenoxypropan-1-ol Chemical compound CCC(O)OC1=CC=CC=C1 OAAZUWWNSYWWHG-UHFFFAOYSA-N 0.000 description 1
- SXERGJJQSKIUIC-UHFFFAOYSA-N 2-Phenoxypropionic acid Chemical compound OC(=O)C(C)OC1=CC=CC=C1 SXERGJJQSKIUIC-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 241000256054 Culex <genus> Species 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- YIIMEMSDCNDGTB-UHFFFAOYSA-N Dimethylcarbamoyl chloride Chemical compound CN(C)C(Cl)=O YIIMEMSDCNDGTB-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- KYOBUEXQQCIAJH-UHFFFAOYSA-N diethylcarbamodithioic acid trihydrate Chemical compound O.O.O.CCN(CC)C(S)=S KYOBUEXQQCIAJH-UHFFFAOYSA-N 0.000 description 1
- LMBWSYZSUOEYSN-UHFFFAOYSA-N diethyldithiocarbamic acid Chemical compound CCN(CC)C(S)=S LMBWSYZSUOEYSN-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229950004394 ditiocarb Drugs 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- WUDNUHPRLBTKOJ-UHFFFAOYSA-N ethyl isocyanate Chemical compound CCN=C=O WUDNUHPRLBTKOJ-UHFFFAOYSA-N 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 229930014550 juvenile hormone Natural products 0.000 description 1
- 239000002949 juvenile hormone Substances 0.000 description 1
- 150000003633 juvenile hormone derivatives Chemical class 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000012669 liquid formulation Substances 0.000 description 1
- 230000029052 metamorphosis Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000000384 rearing effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000004563 wettable powder Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は優れたジベニルホルモン活性を有する新規な化
合物、その製造方法および該化合物類を有効威分として
含有する殺虫剤に関するものである．
〔従来の技術〕
農業害虫及び衛生害虫の防除にあたり、多数の有機合威
薬剤が使用されているが残留毒性や環境汚染又抵抗害虫
の発生等種々の問題を抱えている．そのため近年は生物
の生産物質に着目した農薬開発が進められている．
〔発明が解決しようとする課題〕
本発明の目的は昆虫に特有の変態現象に係る幼若ホルモ
ン（ジベニルホルモン）に着目し、公知化学的に比し、
優れた効力を示し、しかも工業的に有利に製造できる化
合物を見い出すことである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel compound having excellent dibenyl hormone activity, a method for producing the same, and an insecticide containing the compound as an effective ingredient. [Prior Art] Many organic synthetic chemicals are used to control agricultural and sanitary pests, but they have various problems such as residual toxicity, environmental pollution, and the occurrence of resistant pests. Therefore, in recent years, pesticide development has been progressing with a focus on substances produced by living organisms. [Problems to be Solved by the Invention] The purpose of the present invention is to focus on juvenile hormone (dibenyl hormone) related to the metamorphosis phenomenon peculiar to insects, and to
The objective is to find a compound that exhibits excellent efficacy and can be produced industrially advantageously.
ｆＪ望［Ｉ８ｌ十一自怪汁
（式中、Ｒ，はＣ，−，アルキル基を、Ｒ！は低級アル
キル基を、Ａ．．Ｂはそれぞれ一〇一、−Ｓ−、一古＝
古一又は−＾−、（ｒ＋ 、ｒｔ 、ｒｓはそれぞれ水
素原子又は低級アルキル基を示す。）を、但し、Ａ，Ｂ
同時に一〇一又はーＳ一ではない。fJ Nozomi [I8l 11 Jikaijiru (in the formula, R, is C, -, an alkyl group, R! is a lower alkyl group, A..B is each 101, -S-, Ikko =
Furuichi or -^-, (r+, rt, and rs each represent a hydrogen atom or a lower alkyl group), provided that A, B
At the same time, it is not 101 or -S1.
Ｘは酸素原子又は硫黄原子を、
Ｙは低級アルヰレン基を、
ｍｅはそれぞれＯ又は１を示す。但し、ｍ，ｌは同時に
Ｏではない。）で表わされる化合物、その製造方法及び
該化合物類を有効底分として含有することを特徴とする
殺虫剤である。X represents an oxygen atom or a sulfur atom, Y represents a lower alkylene group, and me represents O or 1, respectively. However, m and l are not O at the same time. ), a method for producing the same, and an insecticide characterized by containing the compounds as an effective base component.
本発明化合物は優れたジベニルホルモン活性を有し、双
翅目、鱗翅目、鞘翅目等の昆虫にきわめて高い防除効力
を示す。The compound of the present invention has excellent dibenyl hormone activity and exhibits extremely high control efficacy against insects such as Diptera, Lepidoptera, and Coleoptera.
本発明化合物は下記反応式に従って製造することができ
る。The compound of the present invention can be produced according to the following reaction formula.
■ 製造方法（ａｌ
（式中、Ｈａｌはハロゲン原子を示す。）反応は有機溶
媒中、塩基の存在下Ｏ″Ｃから用いる溶媒の沸点まで、
好ましくは室温から７０℃の温度で１時間から１０数時
間行なわれる。■ Production method (al (in the formula, Hal represents a halogen atom)) The reaction is carried out in an organic solvent in the presence of a base from O''C to the boiling point of the solvent used.
Preferably, the heating is carried out at a temperature of room temperature to 70° C. for 1 hour to 10-odd hours.
有機溶媒としては、ＤＭＳＯ，ＤＭＦ，アセトニトリル
、ジメトキシエタン等が使用できる。As the organic solvent, DMSO, DMF, acetonitrile, dimethoxyethane, etc. can be used.
また、塩基としては、ビリジン、トリエチルアミン、炭
酸ナトリウム、水酸化カリウム等が使用できる。また、
あらかしめ水素化ナトリウム等で一般式〔Ｉ［］で表わ
される化合物のナトリウム塩を製造した後、一般式ＣＩ
ＩＩ）で表わされる化合物と反応させることも可能であ
る。Further, as the base, pyridine, triethylamine, sodium carbonate, potassium hydroxide, etc. can be used. Also,
After preparing the sodium salt of the compound represented by the general formula [I[] with sodium hydride etc.,
It is also possible to react with a compound represented by II).
■ 製造方法中＋（Ｘ＝Ｏ，Ｎ＝１）
（式中、Ｚはハロゲン原子又はヒドロキシ基を示す。）
反応は有機溶媒中、必要により縮合剤の存在下、室温か
ら用いる溶媒の沸点までの温度で数１０分から数１０時
間行なわれる。溶媒はベンゼン、エーテル等反応に不活
性な溶媒ならなんでも使用できる。また、一般式ＣＶ）
においてＢが酸素原子、即ち、アルコールの場合は〔Ｖ
〕自身を溶媒に使用することも可能である。■ In the manufacturing method + (X = O, N = 1) (In the formula, Z represents a halogen atom or a hydroxy group.)
The reaction is carried out in an organic solvent, if necessary in the presence of a condensing agent, at a temperature from room temperature to the boiling point of the solvent used, for several tens of minutes to several tens of hours. Any solvent can be used as long as it is inert to the reaction, such as benzene and ether. Also, general formula CV)
When B is an oxygen atom, that is, alcohol, [V
] It is also possible to use itself as a solvent.
■ 製造方法（Ｃ）（Ａ−０，Ｘ＝○）反応は有機溶媒
中、塩基の存在下、ｏ′ｃから用いる溶媒の沸点まで好
ましくは室温から８０″Ｃの温度で数１０分から数１０
時間行なわれる。用いる溶媒、塩基等は製造方法（ａ）
と同様のものが使用でき、さらに塩基としてビリジン、
トリエチルアくン等を用いた場合にはそれ自身を溶媒と
しても使用できる。■Production method (C) (A-0,
Time is done. The solvent, base, etc. used are according to manufacturing method (a)
can be used, and in addition pyridine as a base,
When triethylamine or the like is used, it can also be used as a solvent itself.
■ 製造方法（ｄ）（Ａ＝Ｏ、Ｂ＝ＮＨ，Ｘ＝Ｏ）反応
は有機溶媒中、塩基の存在下、Ｏ″Ｃから用いる溶媒の
沸点まで、好ましくは室温付近の温度で数ｌＯ分から数
時間反応させる．
■本発明化合物は下記反応式を適宜選択することによっ
ても製造することができる．いずれの方法で製造した場
合も、反応終了後は、通常の後処理を行うことにより、
百的物を得ることができる．
本発明化合物の構造はＩＲ，ＮＭＲ、元素分析等から決
定した．
尚、本発明化合物のうち、Ａ又はＢが
−で表わされる化合物の場合は、Ｅ体、Ｚ体の異性体が
存在する．
〔実施例〕
次に実施例を挙げ本発明を更に詳細に説明する。■ Production method (d) (A=O, B=NH, React for several hours. ■ The compound of the present invention can also be produced by appropriately selecting the reaction formula below. Regardless of which method is used, after the reaction is completed, by performing a normal post-treatment,
You can get a hundred things. The structure of the compound of the present invention was determined by IR, NMR, elemental analysis, etc. In addition, among the compounds of the present invention, in the case of a compound where A or B is represented by -, isomers such as E form and Z form exist. [Example] Next, the present invention will be explained in more detail by giving examples.
実施例ｌ
４−（２−エチルブチル）フェノヰシエチルＮ，Ｎ−エ
チルメチルカーバメート（化合物番号３）：
４−（２−エチルプチル）フェノール０．５ｇ（２．８
＋＋ｎｏｌ） 、２−クロロメチルＮ，Ｎ−エチルメチ
ノレカーバメート０．５１ｇ（３．１■−ｏ１） 、８
５％粉末ＫＯＨ０．２ ４ ｇ （３．Ｆ＋＋ｍｏｌ
）をＤＭＳＯ５一に加え、５０゜〜６０゜Ｃで一晩攪拌
した．反応液に水を加え、エーテルで抽出した．抽出液
を水洗し、無水Ｍ ｇ Ｓ Ｏ ａで乾燥した後、減圧
留去して、粗生底物０． ７ ９ ｇを得た．シリカゲ
ルクロマトグラフィー（展開溶媒：クロロホルム）で精
製し、目的物０．６９ｇ（収率８０％）を得た。Example l 4-(2-ethylbutyl)phenodiethyl N,N-ethylmethylcarbamate (compound number 3): 4-(2-ethylbutyl)phenol 0.5 g (2.8
++nol), 2-chloromethyl N,N-ethyl methylolecarbamate 0.51g (3.1■-o1), 8
5% powder KOH0.2 4 g (3.F++ mol
) was added to 5 volumes of DMSO and stirred at 50° to 60°C overnight. Water was added to the reaction solution and extracted with ether. The extract was washed with water, dried over anhydrous MgS O a, and then evaporated under reduced pressure to obtain 0.0% crude bottom material. 79 g was obtained. It was purified by silica gel chromatography (developing solvent: chloroform) to obtain 0.69 g (yield: 80%) of the target product.
実施例２
プロビル４−（２−エチルブチル）フェノキシブロピオ
ネート（化合物番号２０）：ブロパノール１０ｄに４−
（２−エチルブチＪレ）フェノキシプロピオン酸０．８
４ｇ（３．４麟−Ｏｌ）、触媒量のバラトルエンスルホ
ン酸１水塩を加え、３時間還流煮沸した．反応液に水を
加え、エーテルで抽出し、水で洗浄、無水Ｍ ｇ Ｓ
Ｏ ４で乾燥後、減圧留去して粗生底物０． ９ ７
ｇを得た．シリカゲルクロマトグラフィー（展開触媒：
ヘキサン：酢酸エチル−〇二１）で精製し、百的物０．
８６ｇ（収率８６％）を得た．
実施例３
４−（２−エチルブチル）フエノキシエチルＮ，Ｎ−ジ
メチルカーバメート（化合物番号６）：ピリジン１０Ｍ
１に４−（２−エチルプチル）フェノールとプロモブロ
バノールとから合威した４−（２−エチルブチル）ファ
ノキシブ口バノール０。６７ｇ（２．８−■ｏｌ）とＮ
，Ｎ−ジメチルカルバモイルクロリド０− ３ ４ ｇ
（３． ２ｓｎｏｌ）を加え６０”−７０℃で一晩攪
拌した．反応液に水を加え、エーテルで抽出し、ＩＮ−
Ｈｃｌ、水の順に洗浄し、無水Ｍ ｇ Ｓ Ｏ ａで乾
燥した，溶媒を減圧留去して得られた粗生威物０． ６
７ ｇをシリカゲルクロマトグラフィ−（展開溶媒：
へキサン：酢酸エチル＝８ ７ ２）で精製し、目的物
０．１１ｇ（収率１３％）を得、フェノキシプロパノー
ルを０． ３ ２ ｇ回収した。Example 2 Probyl 4-(2-ethylbutyl)phenoxypropionate (Compound No. 20): 4-(2-ethylbutyl)phenoxypropionate in propanol 10d
(2-ethylbutylene)phenoxypropionic acid 0.8
4 g (3.4 in-Ol) and a catalytic amount of balatoluenesulfonic acid monohydrate were added, and the mixture was boiled under reflux for 3 hours. Water was added to the reaction solution, extracted with ether, washed with water, and anhydrous M g S
After drying with O 4 , distillation was carried out under reduced pressure to obtain 0.0% of the crude bottom material. 9 7
I got g. Silica gel chromatography (developing catalyst:
Hexane: Ethyl acetate - Purified with 021), 100% 0.
86g (yield: 86%) was obtained. Example 3 4-(2-ethylbutyl)phenoxyethyl N,N-dimethylcarbamate (Compound No. 6): Pyridine 10M
1, 0.67 g (2.8-OL) of 4-(2-ethylbutyl)fanoxibubanol, which was synthesized from 4-(2-ethylbutyl)phenol and promobrobanol, and N
, N-dimethylcarbamoyl chloride 0-34 g
(3.2 snol) was added and stirred overnight at 60"-70°C. Water was added to the reaction solution, extracted with ether, and IN-
The crude product obtained by washing with HCl and water in this order and drying with anhydrous MgS O a and distilling off the solvent under reduced pressure was obtained. 6
7 g was subjected to silica gel chromatography (developing solvent:
Purification with hexane:ethyl acetate = 8 7 2) yielded 0.11 g (yield 13%) of the target product, and 0.1 g of phenoxypropanol. 32g was collected.
実施例４
４−（２−エチルブチル）フェノキシエチルＮ一エチル
カーバメート（化合物番号１）；４−（２−エチルブチ
ル）フェノキシエタノール０． ３ ５ ｇ （ １．
６ｍｍｏｌ） 、エチルイソシアネートｏ．１ ２ｇ
（１．７ｍｍｏｌ） 、トリエチルアミン１滴を、エ
ーテル５１ｄに加え、室温で２時間攪拌した。Example 4 4-(2-ethylbutyl)phenoxyethyl N-ethylcarbamate (compound number 1); 4-(2-ethylbutyl)phenoxyethanol 0. 35 g (1.
6 mmol), ethyl isocyanate o. 1 2g
(1.7 mmol) and 1 drop of triethylamine were added to Ether 51d and stirred at room temperature for 2 hours.
反応液を水洗し、無水ＭｇＳ○４で乾燥した後、減圧留
去して、粗生底物０．５ｇを得た．これをカラムクラマ
トグラフィー（展開溶媒：へ牛サン：酢酸エチル＝１７
３）で精製し、目的物０． ４ ４ ｇ（収率９５％）
を得た。The reaction solution was washed with water, dried over anhydrous MgSO4, and then evaporated under reduced pressure to obtain 0.5 g of crude raw bottom. This was subjected to column chromatography (developing solvent: hexasan: ethyl acetate = 17
3), and the target product was purified by 0. 4 4 g (yield 95%)
I got it.
実施例５
イソブロビルＮ− （４− （２−エチルブチル）フェ
ノキシエチル〕メチルカーバメート（化合物番号１１）
：
ベンゼン５＋ｄに５３％水素化ナトリウム０．０９％（
２． ０ ｓ＋ｓｏｌ）を懸濁し、イソブロビルＮ−
Ｃ４−（２−エチルブチル）フエノキシエチル〕カーバ
メート０．５ｇ（１．６開ｏ１）を加えた。発砲終了後
、ヨウ化メチル０． ２ ５ ｇ （ １． Ｅｌ＋ｍ
ｏｌ）を加え、５０゜−６０゜Ｃで一晩攪拌した。反応
液に水を加え、エーテルで抽出した。抽出液を水で洗浄
！、 鉦ｙｋＭ ｙ Ｓ （’）， ’Ｆ斂慢した一熔
媒を滅圧留去して粗生底物０． ４ ４ ｇを得た。こ
れをシリカゲルクロマトグラフィー（展開溶媒：ヘキサ
ン：酢酸エチル＝８ ： ２）で精製し、目的物０．２
０ｇ（収率３８％）を得た。Example 5 Isobrovir N-(4-(2-ethylbutyl)phenoxyethyl)methylcarbamate (Compound No. 11)
: 53% sodium hydride 0.09% (
2. 0 s+sol) and isobrovir N-
0.5 g (1.6 ml) of C4-(2-ethylbutyl)phenoxyethyl]carbamate was added. After firing, methyl iodide 0. 2 5 g (1. El+m
ol) was added thereto, and the mixture was stirred at 50°-60°C overnight. Water was added to the reaction solution, and the mixture was extracted with ether. Wash the extract with water! , ykM y S ('), 'FThe evaporated molten medium was distilled off under reduced pressure to obtain 0.0% crude bottom material. 44 g was obtained. This was purified by silica gel chromatography (developing solvent: hexane: ethyl acetate = 8:2) to obtain 0.2
0 g (yield 38%) was obtained.
実施例６
４一不オベンチルフェノキシエチル Ｎ， Ｎ−ジエチ
ルジチオカーバメート（化合物番号４６）：
４−ネオベンチルフェノールとジプロモエタンとから合
威した４−ネオペンチルフェノキシエチルブロミド０．
６ｇ（２．２■園。■）のＤＭＦ熔液５一にソジウム、
ジエチルジチオカーバメート３水塩０． ７ ５ ｇ
（３． ３ｓｍｏｌ）のＤＭＦ溶液２−を、氷．冷下加
えた後、室温で５時間撹拌した。反応液に水を加え、ヘ
キサンで抽出し、無水ＭｇＳ○４で乾燥した。ヘキサン
を減圧留去して粗生威物０．６９ｇを得、これをシリカ
ゲルカラムクロマトグラフィ−（展開溶媒：ベンゼン：
ヘキサン＝４＝６）で精製し、目的物０．６７ｇ（収率
８９％）を得た。Example 6 4-Unbentylphenoxyethyl N,N-diethyldithiocarbamate (Compound No. 46): 4-Neopentylphenoxyethyl bromide synthesized from 4-neobentylphenol and dipromoethane.
Sodium in 6 g (2.2 ■) of DMF solution 51,
Diethyldithiocarbamate trihydrate 0. 7 5 g
(3.3 smol) of DMF solution 2- was placed on ice. After the addition under cooling, the mixture was stirred at room temperature for 5 hours. Water was added to the reaction solution, extracted with hexane, and dried over anhydrous MgSO4. Hexane was distilled off under reduced pressure to obtain 0.69 g of crude product, which was subjected to silica gel column chromatography (developing solvent: benzene:
Purification was performed using hexane (4=6) to obtain 0.67 g (yield: 89%) of the target product.
上記実施例を含め、同様に製造した本発明化合物の代表
例を第１表に示す。Table 1 shows representative examples of the compounds of the present invention produced in the same manner as in the above examples.
〔課題を解決するための手段一殺虫剤〕本発明の殺虫剤
は、一般式（ｒ）で表わされる化合物を有効威分として
含有するものであり、有効威分化合物の純品のままでも
使用できるが、通常、一般の農薬のとり得る形態、即ち
、永和剤粉剤、乳剤、フロアブル等の形態で使用される
。[Means for Solving the Problem - Insecticide] The insecticide of the present invention contains a compound represented by the general formula (r) as an active ingredient, and can be used as a pure product of the effective ingredient. However, it is usually used in the form that common agricultural chemicals can take, such as permanent powder, emulsion, flowable, etc.
添加剤及び担体としては、固型剤を目的とする場合は、
大豆粉、小麦粉等の植物性粉末、珪藻土、燐灰石、石膏
、タルク、バイロフィライト、クレイ等の鉱物性微粉末
が使用される。As additives and carriers, if the purpose is to use solid agents,
Vegetable powders such as soybean flour and wheat flour, and fine mineral powders such as diatomaceous earth, apatite, gypsum, talc, birophyllite, and clay are used.
液体の剤型を目的とする場合はケロシン、鉱油、石油、
ソルベントナフサ、キシレン、シクロヘキサン、シクロ
ヘキサノン、ジメチル水ルムアくド、ジメチルスルホキ
シド、アルコール、アセトン、水等を溶剤として使用す
る。これらの製剤において、均一なかつ安定な形態をす
るために必要ならば界面活性剤を添加することもできる
．このようにして得られた永和剤、乳剤、フロアプル等
は、水で所定の濃度に希釈して懸濁液あるいは乳濁液と
して、粉剤、粒剤はそのまま、植物に散布する方法で使
用される。For liquid formulations, use kerosene, mineral oil, petroleum,
Solvent naphtha, xylene, cyclohexane, cyclohexanone, dimethyl hydroxide, dimethyl sulfoxide, alcohol, acetone, water, etc. are used as the solvent. In these preparations, a surfactant may be added if necessary to obtain a uniform and stable form. Permanent agents, emulsions, floor pulls, etc. obtained in this way are diluted with water to a predetermined concentration to form a suspension or emulsion, and powders and granules are used as they are by spraying them on plants. .
［実施例一殺虫剤］
次に製剤の実施例を示すが、添加する担体、界面活性剤
等はこれらの実施例に限定されるものではない。[Example 1 Insecticide] Next, examples of formulations will be shown, but the carrier, surfactant, etc. to be added are not limited to these examples.
実施例７ 乳 剤
本発明化合物 ＩＯ部アルキルフ
ェニルボルオキシエチレン ５部ジメチルホルムアミド
３５部キシレン
５０部以上を混合溶解し、使用に際し水で希釈して
乳濁液として散布する。Example 7 Emulsion Compound of the present invention IO parts Alkylphenylboroxyethylene 5 parts Dimethylformamide 35 parts Xylene
Mix and dissolve 50 parts or more, dilute with water before use, and spray as an emulsion.
実施例８ 水和剤
本発明化合物 ２０部高級アルコ
ール硫酸エステル ５部クレイ
７４部ホワイトカーボン
１部以上を混合して微粉に粉砕し、使用に際
し水で希釈して懸濁液として散布する．
実施例９ 粉 剤
本発明化合物 ５部タルク
９１部シリカ
３部アルキルフエニルボルオキシエチ
レン １部以上を混合溶解し、使用に際してはそのまま
散布する。Example 8 Wettable powder Compound of the present invention 20 parts Higher alcohol sulfate ester 5 parts Clay
74 part white carbon
Mix one or more parts, grind into a fine powder, dilute with water and spray as a suspension before use. Example 9 Powder Compound of the present invention 5 parts Talc
91 parts silica
Mix and dissolve 3 parts or more of 1 part or more of alkyl phenylboroxyethylene and spray as is before use.
次に試験例を挙げ、本発明化合物の殺虫活性を示す．
試験例ｌ
アカイエカの最終齢幼虫２０匹を水１００ｄに取り、サ
ンプル化合物の各濃度のエタノール溶液を１０μｌ投与
した。２８゜Ｃで約一週間飼育した後、羽化阻害率を求
めた。対照区として、エタノール１０μｌを投与し、そ
の１０回の羽化阻害率の平均１１７％を用いて修正羽化
阻害率０を求めた。Next, test examples will be given to demonstrate the insecticidal activity of the compounds of the present invention. Test Example 1 Twenty final instar Culex Culex mosquito larvae were taken in 100 d of water, and 10 μl of an ethanol solution of each concentration of sample compound was administered. After rearing at 28°C for about one week, the inhibition rate of emergence was determined. As a control group, 10 μl of ethanol was administered, and a corrected eclosion inhibition rate of 0 was determined using the average of 117% of the eclosion inhibition rates obtained over 10 times.
各濃度の修正羽化阻害率よりｐｒｏｂｉｔ変換法を用い
て、サンプル化合物の半数羽化阻害濃度の逆対数値、Ｐ
ｌｓ。を算出した。結果を第２表に示す．
＊）Using the probit conversion method from the corrected eclosion inhibition rate of each concentration, the inverse logarithm of the half eclosion inhibition concentration of the sample compound, P
ls. was calculated. The results are shown in Table 2. *)
Claims (6)
は低級アルキル基を、Ａ、Ｂはそれぞれ−Ｏ−、−Ｓ−
、▲数式、化学式、表等があります▼又は▲数式、化学
式、表等があります▼、（ｒ＿１、ｒ＿２、ｒ＿３はそ
れぞれ水素原子又は低級アルキル基を示す。）を、但し
、Ａ、Ｂ同時に−Ｏ−又は−Ｓ−ではない。 Ｘは酸素原子又は硫黄原子を、 Ｙは低級アルキレン基を、 ｍｌはそれぞれ０又は１を示す、但し、ｍ、ｌは同時に
０ではない。）で表わされる化合物。(1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1 is a C_3_-_8 alkyl group, R_2
represents a lower alkyl group, and A and B represent -O- and -S-, respectively.
, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ , (r_1, r_2, r_3 each represent a hydrogen atom or a lower alkyl group.) However, A and B are simultaneously − Not O- or -S-. X represents an oxygen atom or a sulfur atom, Y represents a lower alkylene group, and ml represents 0 or 1, respectively, provided that m and l are not 0 at the same time. ).
る化合物と一般式 ▲数式、化学式、表等があります▼ （式中、Ｒ＿２、Ａ、Ｂ、Ｘ、Ｙ、ｍ及びｌは前記と同
じ意味を示し、Ｈａｌはハロゲン原子を示す。）で表わ
される化合物とを反応させることを特徴とする一般式 ▲数式、化学式、表等があります▼ （式中、Ｒ＿１、Ｒ＿２、Ａ、Ｂ、Ｘ、Ｙ、ｍ及びｌは
前記と同じ意味を示す。）で表わされる化合物の製造方
法。(2) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1 has the same meaning as above.) Compounds and general formulas ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1 has the same meaning as above.) R_2, A, B, X, Y, m and l have the same meanings as above, and Hal represents a halogen atom. A method for producing a compound represented by ▼ (wherein R_1, R_2, A, B, X, Y, m and l have the same meanings as above).
し、Ｚはハロゲン原子、又はヒドロキシ基を示す。）で
表わされる化合物と一般式 Ｈ−Ｂ−Ｒ＿２ （式中、Ｂ及びＲ＿２は前記と同じ意味を示す。）で表
わされる化合物とを反応させることを特徴とする一般式 ▲数式、化学式、表等があります▼ （式中、Ｒ＿１、Ｒ＿２、Ａ、Ｂ、Ｙ及びｍは前記と同
じ意味を示す。）で表わされる化合物の製造方法。(3) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1, Y, , A, and m have the same meanings as above, and Z represents a halogen atom or a hydroxyl group.) A general formula that is characterized by reacting a compound with a compound represented by the general formula H-B-R_2 (in the formula, B and R_2 have the same meanings as above) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ A method for producing a compound represented by the formula (wherein R_1, R_2, A, B, Y and m have the same meanings as above).
）。で表わされる化合物とを反応させることを特徴とす
る一般式 ▲数式、化学式、表等があります▼ （式中、Ｒ＿１、Ｒ＿２、Ｂ、Ｙ及びｌは前記と同じ意
味を示す）。で表わされる化合物の製造方法。(4) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 and Y have the same meanings as above). There are compounds and general formulas represented by ▲mathematical formulas, chemical formulas, tables, etc.▼ (in the formulas, R, B, l, and Hal have the same meanings as above). There are general formulas ▲mathematical formulas, chemical formulas, tables, etc.▼ that are characterized by reacting with the compound represented by (in the formula, R_1, R_2, B, Y, and l have the same meanings as above). A method for producing a compound represented by
２は前記と同じ意味を示す。）で表わされる化合物とを
反応させることを特徴とする一般式▲数式、化学式、表
等があります▼ （式中、Ｒ＿１、Ｒ＿２及びＹは前記と同じ意味を示す
。）で表わされる化合物の製造方法。(5) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 and Y have the same meanings as above). A compound represented by the general formula R_2NCO (wherein R_
2 has the same meaning as above. ) Production of a compound represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (wherein R_1, R_2 and Y have the same meanings as above) Method.
前記と同じ意味を示す。）で表わされる化合物の１種又
は２種以上を有効成分として含有することを特徴とする
殺虫剤。(6) A type of compound represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1, R_2, A, B, X, Y, m and l have the same meanings as above.) Or an insecticide characterized by containing two or more types as active ingredients.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5357990A JPH03258743A (en) | 1990-03-07 | 1990-03-07 | Ether bond-containing compound, production thereof and insecticide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5357990A JPH03258743A (en) | 1990-03-07 | 1990-03-07 | Ether bond-containing compound, production thereof and insecticide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03258743A true JPH03258743A (en) | 1991-11-19 |
Family
ID=12946748
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5357990A Pending JPH03258743A (en) | 1990-03-07 | 1990-03-07 | Ether bond-containing compound, production thereof and insecticide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03258743A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000003596A1 (en) * | 1998-07-18 | 2000-01-27 | Bayer Aktiengesellschaft | Utilization of substituted o-alkyl-carbamates for combating animal pests |
-
1990
- 1990-03-07 JP JP5357990A patent/JPH03258743A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000003596A1 (en) * | 1998-07-18 | 2000-01-27 | Bayer Aktiengesellschaft | Utilization of substituted o-alkyl-carbamates for combating animal pests |
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