JPS625138B2 - - Google Patents
Info
- Publication number
- JPS625138B2 JPS625138B2 JP11361878A JP11361878A JPS625138B2 JP S625138 B2 JPS625138 B2 JP S625138B2 JP 11361878 A JP11361878 A JP 11361878A JP 11361878 A JP11361878 A JP 11361878A JP S625138 B2 JPS625138 B2 JP S625138B2
- Authority
- JP
- Japan
- Prior art keywords
- compound
- formula
- cyclic
- acid ester
- parts
- 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
- 125000004122 cyclic group Chemical group 0.000 claims description 8
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 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
- 150000001875 compounds Chemical class 0.000 description 28
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000009472 formulation Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- -1 Ethyl 2-nitrocyclohex-4-enecarboxylate Chemical compound 0.000 description 6
- 230000000844 anti-bacterial effect Effects 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 239000000417 fungicide Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 241000233679 Peronosporaceae Species 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229940125904 compound 1 Drugs 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 230000000855 fungicidal effect Effects 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 240000008067 Cucumis sativus Species 0.000 description 2
- 235000010799 Cucumis sativus var sativus Nutrition 0.000 description 2
- 238000005698 Diels-Alder reaction Methods 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- HOTCCRPFEOUSLL-ONEGZZNKSA-N ethyl (e)-3-nitroprop-2-enoate Chemical compound CCOC(=O)\C=C\[N+]([O-])=O HOTCCRPFEOUSLL-ONEGZZNKSA-N 0.000 description 2
- 230000000887 hydrating effect Effects 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000004563 wettable powder Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- FAQVSLROUMIXEI-UHFFFAOYSA-N 3-acetyloxybuta-1,3-dien-2-yl acetate Chemical compound C(C)(=O)OC(=C)C(=C)OC(C)=O FAQVSLROUMIXEI-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000223218 Fusarium Species 0.000 description 1
- LFZAGIJXANFPFN-UHFFFAOYSA-N N-[3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-thiophen-2-ylpropyl]acetamide Chemical compound C(C)(C)C1=NN=C(N1C1CCN(CC1)CCC(C=1SC=CC=1)NC(C)=O)C LFZAGIJXANFPFN-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Substances CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- NMQQBXHZBNUXGJ-UHFFFAOYSA-N buta-1,3-dienyl acetate Chemical compound CC(=O)OC=CC=C NMQQBXHZBNUXGJ-UHFFFAOYSA-N 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- JEYXDWBGAXACCZ-UHFFFAOYSA-N ethyl 5-acetyloxy-6-nitrocyclohex-3-ene-1-carboxylate Chemical compound C(C)OC(=O)C1CC=CC(C1[N+](=O)[O-])OC(C)=O JEYXDWBGAXACCZ-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000002337 glycosamines Chemical class 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 238000003898 horticulture Methods 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000009331 sowing Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
この発明は新規な環状β−ニトロカルボン酸エ
ステル誘導体に関するものである。
環状β−ニトロカルボン酸エステル誘導体とし
て、従来、５−エトキシカルボニル−６−ニトロ
−ビシクロ〔２・２・１〕−ヘプテン−(2)誘導体
は知られている〔日本化学会第29秋季年会予稿集
第705頁（1973）及び同第31秋季年会予稿集第518
頁（1974）〕。これらの化合物はデイールス・アル
ダー反応による生成物であり、シクロペンタジエ
ンとα・β−不飽和−β−ニトロカルボン酸エチ
ルエステルとの反応により製造されている。
本発明はこれらの化合物とは異つた、文献未載
の新規かつ有用な化合物を提供することを目的と
する。
本発明は一般式
（式中Ｘ、Ｙは水素原子、水酸基又はアセトキシ
基を示す）
で表わされる環状β−ニトロカルボン酸エステル
誘導体である。式中NO2基及びCOOC2H5基はそ
れぞれα配置の場合またはβ配置の場合があり、
また両者の関係もＥまたはＺ配置の場合が含まれ
る。ただしＥ体の方が安定であり、後述のように
抗菌性に優れ、かつ中間体としても有用である。
Ｅ体にはNO2基がα配置でCOOC2H5基がβ配置
の場合と、NO2基がβ配置でCOOC2H5基がα配
置の場合がある。Ｘ、Ｙはそれぞれ同一の原子ま
たは基であつてもよく、また立体配置も限定され
ない。
本発明の化合物に含まれる代表的な化合物とし
て次のものが挙げられる。
(1) 化合物１
エチル ２−ニトロシクロヘキサ−４−エン
カルボキシレート
式
沸点 86〜88℃／0.5mmHg
(2) 化合物２
エチル ３−アセトキシ−２−ニトロシクロ
ヘキサ−４−エン カルボキシレート
式
融点 75〜76℃
(3) 化合物３
エチル ３−ハイドロキシ−２−ニトロシク
ロヘキサ−４−エン カルボキシレート
式
沸点 132〜133℃／0.3mmHg
(4) 化合物４
エチル ３・６−ジアセトキシ−２−ニトロ
シクロヘキサ−４−エン カルボキシレート
式
融点 119〜120℃
本発明の化合物はデイールス・アルダー反応に
より合成することができる。その反応式の一例を
次に示す。
（式中Ｘ、Ｙは前記と同じものを示す）
上記反応式により生成する化合物は通常Ｅ体で
あるが、Ｚ体を生成するにはジエノフイルとして
Ｚ体のものを使用する。反応溶媒としては、ベン
ゼン、トルエン、キシレン、クロルベンゼン等の
芳香族系溶媒、塩化メチレン、クロロホルム、四
塩化炭素等の脂肪族ハロゲン化物等を使用するこ
とができる。反応温度は０〜150℃、好ましくは
20〜100℃であり、反応時間は２〜100時間、好ま
しくは５〜50時間である。
本発明の化合物は殺菌剤、特に農園芸用殺菌剤
として有用であり、稲馬鹿苗病、きゆうりべと病
等に卓効を奏する。また本発明化合物は近年、天
然より単離、構造決定された抗菌性物質として有
用なオリゾキシマイシン（Ｄ−２−〔（＋）−６−
アミノ−トランス−５−ヒドロキシ−１・３−シ
クロヘキサジエン−１−カルボキシ〕−プロピオ
ン酸）およびその類緑体、あるいはある種のアミ
ノ糖などを合成するための中間体としても有用で
ある。
次に本発明化合物の合成例を示す。
合成例 １
化合物１の合成
ブタジエン2.0ｇ（37ミリモル）を乾燥クロロ
ホルム30mlに溶解し、これに（Ｅ）−β−ニトロ
アクリル酸エチル4.5ｇ（31ミリモル）を加え、
封管中100℃に加熱し、35時間反応させた。反応
終了後クロロホルムを留去し、残液を蒸留するこ
とにより、沸点86〜88℃／0.5mmHgの黄色透明液
体5.3ｇ（収率86.5％）を得た。生成物の元素分
析値（C9H13NO4として）は次の通りであつた。
実測値（％） 計算値（％）
Ｃ： 54.01 54.26
Ｈ： 6.25 6.58
Ｎ： 6.82 7.03
合成例 ２
化合物２の合成
（Ｅ）−β−ニトロアクリル酸エチル4.0ｇ（25
ミリモル）とアセトキシブタジエン3.4ｇ（30ミ
リモル）を乾燥クロロホルム30mlに溶解し、封管
中100℃で25時間加熱した。反応終了後、クロロ
ホルムを留去し、残油をシリカゲルクロマトグラ
フイーで精製し、結晶化成分を得た。これをアル
コールにより再結晶して融点75〜76℃の無色柱状
結晶4.9ｇ（収率75.5％）を得た。生成物はNMR
により目的物と同定した。NMRスペクトルは第
１表に示す通りである。第１表中δに対応するプ
ロトンの位置は付記した式に番号で示す。
This invention relates to novel cyclic β-nitrocarboxylic acid ester derivatives. 5-ethoxycarbonyl-6-nitro-bicyclo[2.2.1]-heptene-(2) derivatives are conventionally known as cyclic β-nitrocarboxylic acid ester derivatives [29th Autumn Annual Meeting of the Chemical Society of Japan] Proceedings No. 705 (1973) and Proceedings of the 31st Autumn Annual Meeting No. 518
Page (1974)]. These compounds are products of the Diels-Alder reaction and are produced by the reaction of cyclopentadiene with ethyl .alpha..beta.-unsaturated-.beta.-nitrocarboxylic acid. The object of the present invention is to provide a new and useful compound that is different from these compounds and has not been described in any literature. The present invention is based on the general formula (In the formula, X and Y represent a hydrogen atom, a hydroxyl group, or an acetoxy group.) It is a cyclic β-nitrocarboxylic acid ester derivative represented by the following formula. In the formula, the NO 2 group and the COOC 2 H 5 group may each have an α configuration or a β configuration,
The relationship between the two also includes the case of E or Z arrangement. However, the E form is more stable, has excellent antibacterial properties as described below, and is also useful as an intermediate.
In the E form, there are cases in which the NO 2 group is in the α configuration and the COOC 2 H 5 group is in the β configuration, and there are cases in which the NO 2 group is in the β configuration and the COOC 2 H 5 group is in the α configuration. X and Y may each be the same atom or group, and the steric configuration is not limited. Representative compounds included in the compounds of the present invention include the following. (1) Compound 1 Ethyl 2-nitrocyclohex-4-enecarboxylate Formula Boiling point 86-88℃/0.5mmHg (2) Compound 2 Ethyl 3-acetoxy-2-nitrocyclohex-4-ene carboxylate Formula Melting point 75-76℃ (3) Compound 3 Ethyl 3-hydroxy-2-nitrocyclohex-4-ene carboxylate Formula Boiling point 132-133℃/0.3mmHg (4) Compound 4 Ethyl 3,6-diacetoxy-2-nitrocyclohex-4-ene carboxylate Formula Melting point: 119-120°C The compound of the present invention can be synthesized by Diels-Alder reaction. An example of the reaction formula is shown below. (In the formula, X and Y are the same as above.) The compound produced by the above reaction formula is usually the E-form, but to produce the Z-form, a Z-form is used as the dienophile. As the reaction solvent, aromatic solvents such as benzene, toluene, xylene, and chlorobenzene, aliphatic halides such as methylene chloride, chloroform, and carbon tetrachloride, and the like can be used. The reaction temperature is 0-150℃, preferably
The temperature is 20 to 100°C, and the reaction time is 2 to 100 hours, preferably 5 to 50 hours. The compound of the present invention is useful as a fungicide, particularly as a fungicide for agriculture and horticulture, and is highly effective against rice blight, downy mildew, and the like. In addition, the compound of the present invention has been recently isolated from nature and whose structure has been determined, oryzoximycin (D-2-[(+)-6-
It is also useful as an intermediate for synthesizing amino-trans-5-hydroxy-1,3-cyclohexadiene-1-carboxy]-propionic acid) and its green derivatives, or certain amino sugars. Next, a synthesis example of the compound of the present invention will be shown. Synthesis Example 1 Synthesis of Compound 1 2.0 g (37 mmol) of butadiene was dissolved in 30 ml of dry chloroform, and 4.5 g (31 mmol) of ethyl (E)-β-nitroacrylate was added thereto.
The mixture was heated to 100°C in a sealed tube and allowed to react for 35 hours. After the reaction was completed, chloroform was distilled off and the residual liquid was distilled to obtain 5.3 g (yield: 86.5%) of a yellow transparent liquid with a boiling point of 86-88°C/0.5 mmHg. The elemental analysis value (as C9H13NO4 ) of the product was as follows. Actual value (%) Calculated value (%) C: 54.01 54.26 H: 6.25 6.58 N: 6.82 7.03 Synthesis example 2 Synthesis of compound 2 (E)-β-Ethyl nitroacrylate 4.0 g (25
3.4 g (30 mmol) of acetoxybutadiene were dissolved in 30 ml of dry chloroform and heated in a sealed tube at 100° C. for 25 hours. After the reaction was completed, chloroform was distilled off, and the residual oil was purified by silica gel chromatography to obtain a crystallized component. This was recrystallized from alcohol to obtain 4.9 g (yield: 75.5%) of colorless columnar crystals with a melting point of 75-76°C. The product is NMR
It was identified as the target object. The NMR spectrum is shown in Table 1. The position of the proton corresponding to δ in Table 1 is indicated by a number in the appended formula.
【表】
合成例 ３
化合物３の合成
（Ｅ）−β−ニトロアクリル酸エチル4.0ｇ（25
ミリモル）とハイドロキシブタジエン3.4ｇ（30
ミリモル）とを乾燥ベンゼン40mlに溶解し、室温
で２昼夜反応させた。ベンゼンを留去し残液を蒸
留することにより沸点132〜133℃／0.3mmHgの淡
横色液体5.4ｇ（収率94.6％）を得た。生成物の
元素分析値（C9H13NO5として）は次の通りであ
る。
実測値（％） 計算値（％）
Ｃ： 50.56 50.23
Ｈ： 6.27 6.09
Ｎ： 6.58 6.51
合成例 ４
化合物４の合成
ジアセトキシブタジエン1.0ｇ（5.9ミリモル）
と（Ｅ）−β−ニトロアクリル酸エチル1.0ｇ
（6.9ミリモル）とを乾燥ベンゼンにとかし、６時
間、加熱還流させた。反応終了後ベンゼンを留去
し融点119〜120℃の無色結晶1.7ｇ（収率91.5
％）を得た。生成物の原素分析値（C13H17NO8と
して）は次の通りである。
実測値（％） 計算値（％）
Ｃ： 49.76 49.52
Ｈ： 5.50 5.44
Ｎ： 4.47 4.44
本発明の化合物を殺菌剤として使用するには、
各種助剤、例えば希釈剤、溶剤、界面活性剤等と
配合し、水和剤、粉剤、乳剤等の形態に製剤化し
て使用する。次に配合例を挙げて説明するが、本
発明化合物は、前記化合物１〜４ならびに他の化
合物もそれぞれ各配合例に適用可能であり、また
配合例もこれらに限定されず、それぞれの殺菌効
果を奏する範囲で変更可能である。本発明化合物
相互の併用はもちろん、他の殺菌剤との併用も可
能であり、さらに他の薬剤、例えば、殺草剤、殺
虫剤との併用も可能である。以下の配合例はそれ
ぞれ重量部で示す。
配合例 １
水和剤
化合物３ 20部、珪藻士 35部、クレー 35
部、ホワイトカーボン ５部、ポリオキシエチレ
ンアルキルフエニルエーテル ３部、リグニンス
ルホン酸ナトリウム ２部を混合粉砕して水和剤
とする。使用法は水に懸濁して噴霧するか、直接
種子等に粉衣して使用する。
配合例 ２
粉 剤
化合物１ ３部、タルク 47部、クレー 47
部、ホワイトカーボン ３部を混合紛砕して粉剤
とする。使用に際してはそのまま散布する。
配合例 ３
乳 剤
化合物４ 20部、キシレン 70部、ポリオキシ
エチレンアルキルフエニルエーテルとアルキルア
リールスルホネートとの１：１混合物 10部を混
合溶解させ乳剤とする。使用法は水で希釈し散布
液として使用する。
次に本発明化合物の殺菌効果を示す試験例を挙
げる。
試験例 １
稲馬鹿苗病防除効果試験
農家の圃場で馬鹿苗病（Gibberella
fuzikuroi）に自然感染した罹病稲種子に、化合
物１〜４を配合例１に準じて調整した水和剤を、
種子重量当り各化合物重量が0.2％、0.1％になる
ように粉衣し、稚苗育箱に種子100粒を藩種し、
室温30〜35℃、湿度90％に10日間放置して育苗
し、その後は湿播内に15日間置き、罹病率を調査
した。結果は第２表に示す通りである。表中罹病
苗率は次式により示される。
罹病苗率＝罹病苗数／調査苗数×100
なお比較のために、比較化合物
式
ならびに無処理区のデータを併記する。[Table] Synthesis Example 3 Synthesis of Compound 3 (E)-β-Nitroacrylate ethyl 4.0g (25
mmol) and 3.4 g (30
mmol) was dissolved in 40 ml of dry benzene and reacted at room temperature for two days and nights. By distilling off the benzene and distilling the residual liquid, 5.4 g (yield: 94.6%) of a pale yellow liquid with a boiling point of 132-133°C/0.3 mmHg was obtained. The elemental analysis of the product (as C 9 H 13 NO 5 ) is as follows. Actual value (%) Calculated value (%) C: 50.56 50.23 H: 6.27 6.09 N: 6.58 6.51 Synthesis example 4 Synthesis of compound 4 Diacetoxybutadiene 1.0g (5.9 mmol)
and ethyl (E)-β-nitroacrylate 1.0 g
(6.9 mmol) was dissolved in dry benzene and heated to reflux for 6 hours. After the reaction, benzene was distilled off to give 1.7 g of colorless crystals with a melting point of 119-120°C (yield: 91.5
%) was obtained. The elemental analysis value (as C 13 H 17 NO 8 ) of the product is as follows. Actual value (%) Calculated value (%) C: 49.76 49.52 H: 5.50 5.44 N: 4.47 4.44 To use the compound of the present invention as a fungicide,
It is used by blending it with various auxiliary agents, such as diluents, solvents, surfactants, etc., and formulating it in the form of wettable powders, powders, emulsions, etc. Next, the compound of the present invention can be applied to each of the above-mentioned compounds 1 to 4 as well as other compounds, and the formulation examples are not limited to these, and each compound has a bactericidal effect. It can be changed within the range of performance. The compounds of the present invention can be used not only with each other, but also with other fungicides, and further with other drugs such as herbicides and insecticides. The following formulation examples are each shown in parts by weight. Formulation example 1 Wettable powder Compound 3 20 parts, Diatomist 35 parts, Clay 35
1 part, 5 parts of white carbon, 3 parts of polyoxyethylene alkyl phenyl ether, and 2 parts of sodium ligninsulfonate are mixed and ground to prepare a wettable powder. It can be used by suspending it in water and spraying it, or by coating seeds directly with powder. Formulation example 2 Powder Compound 1 3 parts, talc 47 parts, clay 47
1 part and 3 parts of white carbon are mixed and ground to make a powder. When using, spray as is. Formulation Example 3 Emulsion 20 parts of Compound 4, 70 parts of xylene, and 10 parts of a 1:1 mixture of polyoxyethylene alkyl phenyl ether and alkylaryl sulfonate are mixed and dissolved to form an emulsion. How to use: Dilute with water and use as a spray solution. Next, a test example showing the bactericidal effect of the compound of the present invention will be given. Test example 1 Gibberella disease control effect test
A hydrating powder containing Compounds 1 to 4 prepared according to Formulation Example 1 was applied to diseased rice seeds naturally infected with P. fuzikuroi.
Coat the seeds so that the weight of each compound is 0.2% or 0.1%, and sow 100 seeds in a nursery box.
Seedlings were grown at a room temperature of 30 to 35°C and humidity of 90% for 10 days, and then placed in a wet sowing for 15 days to investigate morbidity. The results are shown in Table 2. The diseased seedling rate in the table is shown by the following formula. Rate of diseased seedlings = Number of diseased seedlings / Number of surveyed seedlings x 100 For comparison, the comparative compound formula Also include data for untreated areas.
【表】
試験例 ２
キユウリベト病防除効果試験
100cm2の角鉢に植えた双葉期のキユウリ（品
種：相模半白）に、化合物１〜４を配合例１に準
じて調整した水和剤を、第３表の所定濃度で１ポ
ツト当り30ml散布する。この場合、１区は５ポツ
トである。散布後、顕微鏡１視野20個／×150の
べと病の分生胞子懸濁液を葉の裏面に付着するよ
うに接種し、21℃の湿室に２昼夜放置し、その後
温室に置いて、処理10日後の発病率を調べた。結
果を３区平均値で第３表に示す。この場合発病葉
率は次式で示される。
発病葉率＝発病葉数／調査葉数×100
なお比較のために試験例１の比較化合物と無散
布区のデータを併記する。[Table] Test Example 2 Test for the control effect of cucumber downy mildew A hydrating powder containing Compounds 1 to 4 prepared according to Formulation Example 1 was applied to a cucumber at the futaba stage (variety: Sagami Hanshiro) planted in a 100 cm square pot. Spray 30ml per pot at the specified concentration shown in Table 3. In this case, the 1st district has 5 pots. After spraying, a suspension of downy mildew conidia (20/×150 per field of view under a microscope) was inoculated onto the underside of the leaves, left in a humid room at 21°C for 2 days and nights, and then placed in a greenhouse. The disease attack rate was investigated 10 days after treatment. The results are shown in Table 3 as the average values for the three wards. In this case, the diseased leaf rate is expressed by the following formula. Rate of diseased leaves = number of diseased leaves / number of investigated leaves x 100 For comparison, data for the comparative compound of Test Example 1 and the non-sprayed area are also shown.
【表】
以上の結果から本発明の化合物の殺菌効果は極
めて顕著であることがわかる。
以上本発明を説明したが、本発明は新規な化合
物であり、それ自体殺菌剤として有用であるとと
もに、さらに強力な抗菌性物質その他の化合物製
造の中間体としても有用である。[Table] From the above results, it can be seen that the bactericidal effect of the compound of the present invention is extremely remarkable. As described above, the present invention is a novel compound, which is useful as a bactericidal agent in itself, and is also useful as an intermediate for producing more powerful antibacterial substances and other compounds.
Claims (1)
基を示す） で表わされる環状β−ニトロカルボン酸エステル
誘導体。 ２ 式 で表わされる特許請求の範囲第１項の還状β−ニ
トロカルボン酸エステル誘導体。 ３ 式 で表わされる特許請求の範囲第１項の環状β−ニ
トロカルボン酸エステル誘導体。 ４ 式 で表わされる特許請求の範囲第１項の環状β−ニ
トロカルボン酸エステル誘導体。 ５ 式 で表わされる特許請求の範囲第１項の環状β−ニ
トロカルボン酸エステル誘導体。[Claims] 1. General formula A cyclic β-nitrocarboxylic acid ester derivative represented by (wherein X and Y represent a hydrogen atom, a hydroxyl group, or an acetoxy group). 2 formulas A cyclic β-nitrocarboxylic acid ester derivative according to claim 1, which is represented by: 3 formulas A cyclic β-nitrocarboxylic acid ester derivative according to claim 1, which is represented by: 4 formula A cyclic β-nitrocarboxylic acid ester derivative according to claim 1, which is represented by: 5 formula A cyclic β-nitrocarboxylic acid ester derivative according to claim 1, which is represented by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11361878A JPS5540627A (en) | 1978-09-18 | 1978-09-18 | Cyclic beta-nitrocarboxylic acid ester derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11361878A JPS5540627A (en) | 1978-09-18 | 1978-09-18 | Cyclic beta-nitrocarboxylic acid ester derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5540627A JPS5540627A (en) | 1980-03-22 |
| JPS625138B2 true JPS625138B2 (en) | 1987-02-03 |
Family
ID=14616769
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11361878A Granted JPS5540627A (en) | 1978-09-18 | 1978-09-18 | Cyclic beta-nitrocarboxylic acid ester derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5540627A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02112638U (en) * | 1989-02-22 | 1990-09-10 | ||
| JPH04153137A (en) * | 1990-10-15 | 1992-05-26 | Canon Inc | Sheet supply device |
-
1978
- 1978-09-18 JP JP11361878A patent/JPS5540627A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02112638U (en) * | 1989-02-22 | 1990-09-10 | ||
| JPH04153137A (en) * | 1990-10-15 | 1992-05-26 | Canon Inc | Sheet supply device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5540627A (en) | 1980-03-22 |
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