JPH0324472B2 - - Google Patents
Info
- Publication number
- JPH0324472B2 JPH0324472B2 JP28873386A JP28873386A JPH0324472B2 JP H0324472 B2 JPH0324472 B2 JP H0324472B2 JP 28873386 A JP28873386 A JP 28873386A JP 28873386 A JP28873386 A JP 28873386A JP H0324472 B2 JPH0324472 B2 JP H0324472B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- formula
- general formula
- lower alkyl
- alkyl group
- 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
- 150000001875 compounds Chemical class 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000001188 haloalkyl group Chemical group 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- -1 methylenedioxy group Chemical group 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 2
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 2
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical group NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 claims 4
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 claims 1
- 230000002378 acidificating effect Effects 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 230000000895 acaricidal effect Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 241001454293 Tetranychus urticae Species 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- KWWTWICEMDMPRG-WCBMZHEXSA-N (4s,5s)-4-methyl-5-(4-methylphenyl)-4,5-dihydro-1,3-thiazol-2-amine Chemical compound C[C@@H]1NC(=N)S[C@H]1C1=CC=C(C)C=C1 KWWTWICEMDMPRG-WCBMZHEXSA-N 0.000 description 1
- 125000006705 (C5-C7) cycloalkyl group Chemical group 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- AZFNGPAYDKGCRB-XCPIVNJJSA-M [(1s,2s)-2-amino-1,2-diphenylethyl]-(4-methylphenyl)sulfonylazanide;chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene Chemical compound [Ru+]Cl.CC(C)C1=CC=C(C)C=C1.C1=CC(C)=CC=C1S(=O)(=O)[N-][C@@H](C=1C=CC=CC=1)[C@@H](N)C1=CC=CC=C1 AZFNGPAYDKGCRB-XCPIVNJJSA-M 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000392 cycloalkenyl group Chemical group 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 244000013123 dwarf bean Species 0.000 description 1
- 235000013601 eggs Nutrition 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000035784 germination Effects 0.000 description 1
- 235000021331 green beans Nutrition 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004304 potassium nitrite Substances 0.000 description 1
- 235000010289 potassium nitrite Nutrition 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Description
本発明は新規な化合物及びその製造法に関し、
詳しくは一般式（）
（式中、R1は低級アルキル基を、R2はハロゲ
ン原子、低級アルキル基、低級ハロアルキル基、
低級アルコキシ基もしくはメチレンジオキシ基で
置換されていてもよいフエニル基を示す。）で表
わされる化合物のトランス体及びその製造方法に
関するものである。
本発明化合物は農医薬中間体、特に優れた殺ダ
ニ活性を有する一般式（）
（式中、R1及びR2は前記と同じ意味を示し、
R3は置換基を有しもしくは有せざるC5〜7のシク
ロアルキル基、シクロアルケニル基、又は酸素原
子を有する複素環を、Ｙは酸素原子又は硫黄原子
を示す。）で表わされる化合物の中間前として有
用である。
本発明化合物は以下に示す方法により製造する
ことができる。
反応はベンゼン、トルエン、キシレン等の有機
溶媒中、50℃から用いる溶媒の沸点までの温度で
１時間から５時間行う。
亜硝酸塩との反応は酸の存在下、水溶液中で０
℃から還流条件で、１時間から10時間行う。
亜硝酸塩としては亜硝酸ソーダ、亜硝酸カリ等
が使用できる。酸としては酢酸、塩酸、硫酸等通
常の有機、無機の酸が使用できる。
次いで行う熱分解は法と同じ条件で行う。
，法いずれの方法で反応を行つた場合にも
反応終了後は通常の後処理を行うことにより目的
物を好収率で得ることができる。
尚、一般式（）又は（）で表わされる原料
化合物には互変異性体が考えられる。また、一般
式（）で表わされる原料化合物は、例えば下記
反応式に従つて製造することができる。
次に実施例を挙げ本発明化合物を更に詳細に説
明する。
実施例 １
トランス−４−メチル−５−（４−メチルフエ
ニル）−２−チアゾリドン（化合物番号３）：
トランス−２−アミノ−４−メチル−５−（４
−メチルフエニル）−２−チアゾリン9.6ｇを酢酸
7.6ｇ、水76mlの混合溶液の中に入れ、この液に、
０℃〜５℃に冷却下、水16mlに亜硝酸ソーダ3.6
ｇを溶解した液を撹拌下滴下し、２時間反応し
た。さらに反応完結のため、３時間50〜60℃に加
熱し、反応液を濾過、水洗、酢酸エチルで洗浄
後、ただちにトルエン140mlに入れ、３時間還流
した。
反応終了後、トルエンを減圧留去し、残渣をカ
ラムクロマトグラフイーで精製し目的物5.4ｇを
得た。 ｍ・ｐ 130〜132℃
実施例 ２
トランス−５−（４−クロロフエニル）−４−メ
チル−２−チアゾリドン（化合物番号２）：
トランス−５−（４−クロロフエニル）−４−メ
チル−２−ニトロソアミノ−２−チアゾリン3.0
ｇをトルエン60mlに入れ、２時間還流した。反応
終了後トルエンを減圧留去し残渣をカラムクロマ
トグラフイーで分離精製し目的物2.0ｇを得た。
m.p 150〜152℃
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。
The present invention relates to a novel compound and a method for producing the same,
For details, see the general formula () (In the formula, R 1 is a lower alkyl group, R 2 is a halogen atom, a lower alkyl group, a lower haloalkyl group,
Indicates a phenyl group optionally substituted with a lower alkoxy group or methylenedioxy group. ) and its production method. The compound of the present invention is an agricultural and pharmaceutical intermediate, and has the general formula () having particularly excellent acaricidal activity. (In the formula, R 1 and R 2 have the same meanings as above,
R3 represents a C5-7 cycloalkyl group, cycloalkenyl group, or a heterocycle having an oxygen atom, with or without a substituent, and Y represents an oxygen atom or a sulfur atom. ) is useful as an intermediate for compounds represented by The compound of the present invention can be produced by the method shown below. The reaction is carried out in an organic solvent such as benzene, toluene or xylene at a temperature from 50°C to the boiling point of the solvent used for 1 to 5 hours. The reaction with nitrite is 0 in aqueous solution in the presence of acid.
It is carried out for 1 to 10 hours under reflux conditions from °C. As the nitrite, sodium nitrite, potassium nitrite, etc. can be used. As the acid, common organic and inorganic acids such as acetic acid, hydrochloric acid, and sulfuric acid can be used. The subsequent thermal decomposition is carried out under the same conditions as in the method. When the reaction is carried out by either method, the desired product can be obtained in good yield by carrying out the usual post-treatment after the reaction is completed. Note that the raw material compound represented by the general formula () or () may have tautomers. Further, the raw material compound represented by the general formula () can be produced, for example, according to the following reaction formula. Next, the compounds of the present invention will be explained in more detail with reference to Examples. Example 1 Trans-4-methyl-5-(4-methylphenyl)-2-thiazolidone (Compound No. 3): trans-2-amino-4-methyl-5-(4
-methylphenyl)-2-thiazoline (9.6 g) in acetic acid
Put it in a mixed solution of 7.6g and 76ml of water, and add it to this solution.
Add 3.6 ml of sodium nitrite to 16 ml of water while cooling to 0°C to 5°C.
A solution containing g was added dropwise under stirring, and the mixture was reacted for 2 hours. Further, to complete the reaction, the mixture was heated at 50 to 60°C for 3 hours, and the reaction solution was filtered, washed with water, and washed with ethyl acetate, then immediately poured into 140 ml of toluene, and refluxed for 3 hours. After the reaction was completed, toluene was distilled off under reduced pressure, and the residue was purified by column chromatography to obtain 5.4 g of the target product. m・p 130-132°C Example 2 Trans-5-(4-chlorophenyl)-4-methyl-2-thiazolidone (compound number 2): trans-5-(4-chlorophenyl)-4-methyl-2-nitrosamino-2-thiazoline 3.0
g was added to 60 ml of toluene and refluxed for 2 hours. After the reaction was completed, toluene was distilled off under reduced pressure, and the residue was separated and purified by column chromatography to obtain 2.0 g of the target product.
mp 150-152°C Table 1 shows representative examples of the compounds of the present invention produced in the same manner, including the above examples.
【表】【table】
【表】
次に本発明化合物を用い製造される一般式
（）で表わされる化合物群の代表例及びそれら
の殺ダニ活性を示す。
試験例１ ナミハダニに対する効力
２寸鉢に播種したインゲンの発芽後７〜10日を
経過した第１本葉上に、有機燐剤抵抗性のナミハ
ダニの雌成虫を30頭接種したのち、乳剤の処方に
従い、製造した薬剤を化合物濃度が500，125ppm
になるように水で希釈して散布した。散布３日後
に殺虫率を求めるとともに、成虫を除去し、この
３日間に産寸された卵に関し、成虫まで発育し得
たか否かを11日目に調査し、殺ダニ有効度を求め
た。結果は次の通りである。[Table] Next, representative examples of the compound group represented by the general formula () produced using the compound of the present invention and their acaricidal activities are shown. Test Example 1 Efficacy against two-spotted spider mites Thirty female adult two-spotted spider mites resistant to organic phosphorus agents were inoculated onto the first true leaves of green beans sown in 2-inch pots 7 to 10 days after germination, and then the emulsion was formulated. The compound concentration of the drug manufactured according to the
It was diluted with water and sprayed. Three days after spraying, the insecticidal rate was determined, and the adults were removed, and on the 11th day, whether or not the eggs produced during these three days were able to develop to adulthood was determined to determine the degree of acaricidal effectiveness. The results are as follows.
【表】【table】
Claims (1)
原子、低級アルキル基、低級ハロアルキル基、低
級アルコキシ基もしくはメチレンジオキシ基で置
換されていてもよいフエニル基を示す。）で表わ
される化合物のトランス体。 ２ 一般式 （式中R1は低級アルキル基を、R2はハロゲン
原子、低級アルキル基、低級ハロアルキル基、低
級アルコキシ基もしくはメチレンジオキシ基で置
換されていてもよいフエニル基を示す。）で表わ
される化合物のトランス体を加熱分解することを
特徴とする一般式 （式中R1及びR2は前記と同じ意味を示す。） で表わされる化合物のトランス体の製造方法。 ３ 一般式 （式中R1は低級アルキル基を、R2はハロゲン
原子、低級アルキル基、低級ハロアルキル基、低
級アルコキシ基もしくはメチレンジオキシ基で置
換されていてもよいフエニル基を示す。）で表わ
される化合物のトランス体を酸性下亜硝酸塩と反
応させ、ついで加熱分解することを特徴とする 一般式 （式中R1及びR2は前記と同じ意味を示す。） で表わされる化合物のトランス体の製造方法。[Claims] 1. General formula (In the formula, R 1 represents a lower alkyl group, and R 2 represents a phenyl group optionally substituted with a halogen atom, a lower alkyl group, a lower haloalkyl group, a lower alkoxy group, or a methylenedioxy group.) trans form. 2 General formula (In the formula, R 1 represents a lower alkyl group, and R 2 represents a phenyl group optionally substituted with a halogen atom, a lower alkyl group, a lower haloalkyl group, a lower alkoxy group, or a methylenedioxy group.) A general formula characterized by the thermal decomposition of the trans isomer of (In the formula, R 1 and R 2 have the same meanings as above.) A method for producing a trans isomer of a compound represented by the following. 3 General formula (In the formula, R 1 represents a lower alkyl group, and R 2 represents a phenyl group optionally substituted with a halogen atom, a lower alkyl group, a lower haloalkyl group, a lower alkoxy group, or a methylenedioxy group.) A general formula characterized by reacting the trans isomer with nitrite under acidic conditions and then thermally decomposing it. (In the formula, R 1 and R 2 have the same meanings as above.) A method for producing a trans isomer of a compound represented by the following.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28873386A JPS62270569A (en) | 1986-12-05 | 1986-12-05 | Thiazolidone derivative and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28873386A JPS62270569A (en) | 1986-12-05 | 1986-12-05 | Thiazolidone derivative and production thereof |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12677880A Division JPS5750982A (en) | 1980-09-12 | 1980-09-12 | Thiazolidine derivative, its preparation and acaricide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62270569A JPS62270569A (en) | 1987-11-24 |
| JPH0324472B2 true JPH0324472B2 (en) | 1991-04-03 |
Family
ID=17733983
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28873386A Granted JPS62270569A (en) | 1986-12-05 | 1986-12-05 | Thiazolidone derivative and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62270569A (en) |
-
1986
- 1986-12-05 JP JP28873386A patent/JPS62270569A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62270569A (en) | 1987-11-24 |
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