CN1760189A - Method for preparing N-alkoxy carbonyl, thiazolethioketone derivative,s and usage - Google Patents
Method for preparing N-alkoxy carbonyl, thiazolethioketone derivative,s and usage Download PDFInfo
- Publication number
- CN1760189A CN1760189A CN 200510061124 CN200510061124A CN1760189A CN 1760189 A CN1760189 A CN 1760189A CN 200510061124 CN200510061124 CN 200510061124 CN 200510061124 A CN200510061124 A CN 200510061124A CN 1760189 A CN1760189 A CN 1760189A
- Authority
- CN
- China
- Prior art keywords
- thiazole thione
- carbonyl oxygen
- thiazole
- hydrocarbon carbonyl
- thione derivative
- 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
Landscapes
- Thiazole And Isothizaole Compounds (AREA)
Abstract
A N-hydrocarbyloxycarbonyl-2-thiazolethione derivative is prepared through condensation reaction between 2-thiazolethione and chlorocarbonate in organic solvent under existence of acid capture, and post-treating. It can be used as the insecticide for red spider and the bactericide for gray mold, powdery mildew, etc.
Description
(1) technical field
The present invention relates to a kind of N-hydrocarbon carbonyl oxygen-2-thiazole thione derivative, preparation method and its usage.
(2) background technology
Heterogeneous ring compound has been the main flow of novel pesticide development, and in heterogeneous ring compound, again based on nitrogen heterocyclic ring.Thiazole compound is a development in recent years class more rapidly, and many commercial desinsections, sterilization, weedicide belong to such.For example, the sterilant lythidathion with interior absorption of the former industry of Japanese stone company exploitation has the stronger ability of killing for the various insects that traditional sterilant produced resistance; The triticonazole of SUMITOMO CHEMICAL chemical company exploitation in 1974 is a kind of systemic fungicide, and the formation that infect hypha on the spore is adhered in inhibition prevents rice blast.
The 2-thiazole thione is not only a useful organic intermediate, and itself has certain fungicidal activity.Simultaneously, existing document illustration N-replacement-2-thiazole thione derivative has extensive biological activity, is applied to medicine, pesticide field.For example, JP 9124647 has disclosed a class N-heterocyclic acyl-2-thiazole thione derivative and has had good fungicidal activity; WO 03031414 has disclosed a class N-substituted alkyl-2-thiazole thione derivative and has had anti-inflammatory activity.
Yet, the bibliographical information of the synthetic and bioactivity research of rarely found relevant N-hydrocarbon carbonyl oxygen-2-thiazole thione derivative.
(3) summary of the invention
The object of the invention is to provide a kind of N-hydrocarbon carbonyl oxygen-2-thiazole thione derivative, preparation method and its usage.
N-hydrocarbon carbonyl oxygen of the present invention-2-thiazole thione derivative is suc as formula shown in (I):
Wherein R represents C
1～C
10Alkyl group, cycloalkyl or haloalkyl, or C
6～C
10Aryl; It is one of following that R preferably represents: n-propyl, normal-butyl, isobutyl-, n-pentyl, isopentyl, cyclohexyl, 2-chloroethyl, more preferably represent normal-butyl or isopentyl or 2-chloroethyl; It is one of following that R also preferably represents: phenyl, benzyl, 3-aminomethyl phenyl, 2-chloro-phenyl-, more preferably represent benzyl or 2-chloro-phenyl-.
The preparation method of N-hydrocarbon carbonyl oxygen of the present invention-2-thiazole thione derivative, comprise the steps: suc as formula the thiazolidinethion-2 of (II) with suc as formula the chloro-formic ester of (III) under the acid binding agent effect, carry out condensation reaction at 0～10 ℃ in organic solvent, aftertreatment gets product;
Wherein R represents C
1～C
10Alkyl group, cycloalkyl or haloalkyl, or C
6～C
10Aryl.
Reaction equation is:
Described acid binding agent is preferably triethylamine or pyridine.
Described organic solvent is preferably trichloromethane, methylene dichloride or tetrahydrofuran (THF).
Described thiazolidinethion-2: chloro-formic ester: the molar ratio of acid binding agent is generally 1: 1.0～1.3: 1.2～2.0, and the consumption of organic solvent is generally 20～50 times of thiazolidinethion-2 quality;
Described condensation reaction time can be 1～20 hour.
Used chloro-formic ester can be by alcohol or phenol and two (trichloromethyl) carbonic ether under the acid binding agent effect in the above-mentioned reaction, reacts to make in organic solvent.Its molar ratio is alcohol or phenol: two (trichloromethyl) carbonic ether: acid binding agent can be 3: 1: 3; Described organic solvent can be trichloromethane or methylene dichloride or toluene, and its consumption is generally alcohol or phenol quality 30～50 times; Acid binding agent can be triethylamine or pyridine or aqueous sodium hydroxide solution; Its temperature of reaction is 0～30 ℃, and its reaction times is 1.5～3.0 hours.Reaction equation is:
The R definition is the same in the formula.
Described N-hydrocarbon carbonyl oxygen-2-thiazole thione derivative is as the application of insectofungicide.Adopt the Potter spray method that the synthetic compound has been carried out the insecticidal activity assay of mythimna separata (Mythimna separata), adopt dipping plant method the synthetic compound to be carried out the insecticidal activity assay of black bean aphid (Aphis fabae) and red spider (Tetranychus urticae).The result shows, described N-hydrocarbon carbonyl oxygen-2-thiazole thione derivative does not have insecticidal activity to aphid, mythimna separata is had faint insecticidal activity, and red spider is had insecticidal activity preferably, especially when R=n-pentyl, benzyl or 2-chloro-phenyl-, compound to the inhibition activity of red spider all more than 75%.
Adopt toxic potato agar substratum (PDA) method that the synthetic compound has been carried out Pyricularia oryzae (Pyricularia oryzae), fusarium graminearum (Gibberella zeae), the fungicidal activity of Phytophthora capsici germ (Phytophthora capsici) and botrytis cinerea pers (Botrytis cinerea) is measured, adopt pot-culture method that compound has been carried out Sclerotinia sclerotiorum sterilization (Sclerotonia sclerotiorum) determination of activity, adopt potted plant stem and leaf of Wheat to preserve the spore method fungicidal activity that the synthetic compound has carried out wheat powdery mildew (Blumeria graminis) is measured.The result shows that described N-hydrocarbon carbonyl oxygen-2-thiazole thione derivative does not have the preventive effect effect substantially to fusarium graminearum, Phytophthora capsici germ, and Pyricularia oryzae, botrytis cinerea pers, Sclerotinia sclerotiorum, wheat powdery mildew are had different preventive effect effects.
(4) embodiment
The invention will be further described below in conjunction with embodiment, but protection scope of the present invention is not limited to this.
Synthesizing of the positive penta oxygen carbonyl of embodiment 1 N--2-thiazole thione
In the 250ml there-necked flask, add two (trichloromethyl) carbonic ethers of 19.8g (0.067mol) and 50ml methylene dichloride, slowly add Pentyl alcohol (0.2mol) under stirring.The ice bath cooling slowly drips the solution of triethylamine (0.2mol) and 10ml methylene dichloride down, and holding temperature is between 0～5 ℃.After dropwising, slowly heat up, stirred 2 hours down at 20 ℃.(3 * 50ml), anhydrous sodium sulfate drying filters, and concentrates, and decompression steams n-amyl chlorocarbonate to wash three times.Yield 85.6%.
Thiazolidinethion-2 (0.60g, 5mmol) and triethylamine (0.72g 7mmol) is dissolved in the 10ml methylene dichloride, stirs.The ice bath cooling drips above-mentioned n-amyl chlorocarbonate (6mmol) down.Dropwise, reacted 4 hours down at 0～10 ℃.Wash three times, anhydrous sodium sulfate drying filters, and concentrates.Resistates obtains the positive penta oxygen carbonyl of 0.98g yellow transparent buttery N--2-thiazole thione with column chromatography [V (sherwood oil): V (ethyl acetate)=1: 1] separation and purification.Yield is 84.0%.
This compound
1H NMR and IR are as described below:
1H NMR(CDCl
3)δ：0.92(t，3H，J＝4.5Hz，-CH
2CH
2CH
2CH
2CH
3)，1.32~1.76(m，6H，-CH
2(CH
2)
3CH
3)，3.33(t，2H，J＝4.5Hz，-SCH
2-)，4.27(t，2H，J＝4.3Hz，-OCH
2)，4.53(t，2H，J＝4.5Hz，-NCH
2-)；
IR v(cm
-1)：2956，2870，1753，1721，1466，1373，1245，1198，1144，1057，974，908，764；
Synthesizing of embodiment 2 N-isoamyl oxygen carbonyl-2-thiazole thiones
In the 250ml there-necked flask, add two (trichloromethyl) carbonic ethers of 19.8g (0.067mol) and 50ml trichloromethane, slowly add primary isoamyl alcohol (0.2mol) under stirring.The ice bath cooling slowly drips the solution of pyridine (0.2mol) and 10ml trichloromethane down, and holding temperature is between 0～5 ℃.After dropwising, slowly heat up, stirred 2 hours down at 25 ℃.(3 * 50ml), anhydrous sodium sulfate drying filters, and concentrates, and decompression steams isoamyl chlorocarbonate to wash three times.Yield 82.7%.
Thiazolidinethion-2 (0.60g, 5mmol) and triethylamine (0.82g 8mmol) is dissolved in the 15ml methylene dichloride, stirs.The ice bath cooling drips above-mentioned isoamyl chlorocarbonate (6mmol) down.Dropwise, reacted 10 hours down at 0～10 ℃.Wash three times, anhydrous sodium sulfate drying filters, and concentrates.Resistates obtains 0.99g yellow transparent buttery N-isoamyl oxygen carbonyl-2-thiazole thione with column chromatography [V (sherwood oil): V (ethyl acetate)=1: 1] separation and purification.Yield is 85.0%.
This compound
1H NMR and IR are as described below:
1H NMR(CDCl
3)δ：0.93(d，6H，J＝4.3Hz，2CH
3)，1.59~1.64(m，2H，-CH
2CH)，1.71~1.81(m，1H，-CH)，3.33(t，2H，J＝4.8Hz，-SCH
2-)，4.31(t，2H，J＝4.3Hz，-OCH
2)，4.53(t，2H，J＝4.8Hz，-NCH
2-)；
IR v(cm
-1)：2958，1751，1718，1465，1373，1245，1198，1058，994，764；
Synthesizing of the positive butoxy carbonyl of embodiment 3 N--2-thiazole thione
Pentyl alcohol is changed to propyl carbinol, and other makes butyl chloroformate with embodiment 1.Yield 88.3%.
Thiazolidinethion-2 (0.60g, 5mmol) and pyridine (0.56g 7mmol) is dissolved in the 10ml trichloromethane, stirs.The ice bath cooling drips above-mentioned butyl chloroformate (6mmol) down.Dropwise, reacted 3 hours down at 0～10 ℃.Wash three times, anhydrous sodium sulfate drying filters, and concentrates.Resistates obtains the positive butoxy carbonyl of 0.95g yellow transparent buttery N--2-thiazole thione with column chromatography [V (sherwood oil): V (ethyl acetate)=3: 1] separation and purification.Yield is 87.0%.
This compound
1H NMR and IR are as described below:
1H NMR(CDCl
3)δ：0.95(t，3H，J＝4.8Hz，-CH
2CH
2CH
2CH
3)，1.41~1.47(m，2H，-CH
2CH
2CH
2CH
3)，1.69~1.73(m，2H，-CH
2CH
2CH
2CH
3)，3.32(t，2H，J＝4.5Hz，-SCH
2-)，4.29(t，2H，J＝4.2Hz，-CH
2CH
2CH
2CH
3)，4.53(t，2H，J＝4.5Hz，-NCH
2-)；
IR v(cm
-1)：2959，1755，1724，1465，1373，1245，1199，1150，1059，997，950，765；
Synthesizing of embodiment 4 N-isobutyl boc-2-thiazole thione
Primary isoamyl alcohol is changed to isopropylcarbinol, and other makes isobutyl chlorocarbonate with embodiment 2.Yield 85.7%.
Thiazolidinethion-2 (0.60g, 5mmol) and pyridine (0.64g 8mmol) is dissolved in the 15ml tetrahydrofuran (THF), stirs.The ice bath cooling drips above-mentioned isobutyl chlorocarbonate (6mmol) down.Dropwise, reacted 6 hours down at 0～10 ℃.Wash three times, anhydrous sodium sulfate drying filters, and concentrates.Resistates obtains 1.03g yellow transparent buttery N-isobutyl boc-2-thiazole thione with column chromatography [V (sherwood oil): V (ethyl acetate)=3: 1] separation and purification.Yield is 94.0%.
This compound
1H NMR and IR are as described below:
1H NMR(CDCl
3)δ：0.99(d，6H，J＝4.3Hz，2CH
3)，2.01~2.07(m，1H，-CH)，3.34(t，2H，J＝4.8Hz，-SCH
2-)，4.06(d，2H，J＝4.0Hz，-OCH
2-)，4.55(t，2H，J＝4.8Hz，-NCH
2-)；
IR v(cm
-1)：2961，1755，1723，1469，1371，1245，1199，1144，1057，995，862，765；
Synthesizing of positive third oxygen carbonyl of embodiment 5 N--2-thiazole thione
In the 250ml there-necked flask, add two (trichloromethyl) carbonic ethers of 19.8g (0.067mol) and 50ml trichloromethane, slowly add n-propyl alcohol (0.2mol) under stirring.The ice bath cooling slowly drips the solution of triethylamine (0.2mol) and 10ml trichloromethane down, and holding temperature is between 0～5 ℃.After dropwising, slowly heat up, stirred 2 hours down at 20 ℃.(3 * 50ml), anhydrous sodium sulfate drying filters, and concentrates, and decompression steams the chloroformic acid n-propyl to wash three times.Yield 87.0%.
Thiazolidinethion-2 (0.60g, 5mmol) and triethylamine (0.72g 7mmol) is dissolved in the 15ml trichloromethane, stirs.The ice bath cooling drips above-mentioned chloroformic acid n-propyl (6mmol) down.Dropwise, reacted 9 hours down at 0～10 ℃.Wash three times, anhydrous sodium sulfate drying filters, and concentrates.Resistates obtains positive third oxygen carbonyl of 0.89g yellow transparent buttery N--2-thiazole thione with column chromatography [V (sherwood oil): V (ethyl acetate)=2: 1] separation and purification.Yield is 87.0%.
This compound
1H NMR and IR are as described below:
1H NMR(CDCl
3)δ：1.00(t，3H，J＝4.8Hz，-CH
2CH
2CH
3)，1.71~1.80(m，2H，-CH
2CH
2CH
3)，3.34(t，2H，J＝4.8Hz，-SCH
2-)，4.24(t，2H，J＝4.0Hz，-CH
2CH
2CH
3)，4.54(t，2H，J＝4.8Hz，-NCH
2-)；
IR v(cm
-1)：2967，1755，1723，1468，1372，1244，1198，1141，1058，993，956，764；
Synthesizing of embodiment 6 N-(2-chloroethyl) oxygen carbonyl-2-thiazole thione
N-propyl alcohol is changed to chloroethanol, and other makes chloroformic acid (2-chloroethyl) ester with embodiment 7.Yield 80.9%.
Thiazolidinethion-2 (0.60g, 5mmol) and pyridine (0.64g 8mmol) is dissolved in the 15ml trichloromethane, stirs.The ice bath cooling drips above-mentioned chloroformic acid (2-chloroethyl) ester (6mmol) down.Dropwise, 0～10 ℃ of reaction 2 hours.Wash three times, anhydrous sodium sulfate drying filters, and concentrates.Resistates obtains 1.07g golden transparent buttery N-(2-chloroethyl) oxygen carbonyl-2-thiazole thione with column chromatography [V (sherwood oil): V (ethyl acetate)=1: 1] separation and purification.Yield is 95.0%.
This compound
1H NMR and IR are as described below:
1H NMR(CDCl
3)δ：3.37(t，2H，J＝4.5Hz，-SCH
2-)，3.79(t，2H，J＝4.3Hz，-CH
2CH
2Cl)，4.52(t，2H，J＝3.5Hz，-CH
2CH
2Cl)，4.58(t，2H，J＝4.5Hz，-NCH
2-)；
IR v(cm
-1)：2953，1752，1438，1375，1243，1196，1143，1055，1006，917，761，664；
Synthesizing of embodiment 7 N-hexamethylene oxygen carbonyl-2-thiazole thiones
Primary isoamyl alcohol is changed to hexalin, and other makes cyclohexyl chloroformate with embodiment 2.Yield 80.7%.
The solvent trichloromethane is changed to tetrahydrofuran (THF), and other obtains 1.13g golden transparent buttery N-hexamethylene oxygen carbonyl-2-thiazole thione with embodiment 7.Yield is 92.0%.
This compound
1H NMR and IR are as described below:
1H NMR(CDCl
3)δ：1.40~1.95(m，10H，-(CH
2)
5-)，3.37(t，2H，J＝4.5Hz，-SCH
2-)，4.59(t，2H，J＝4.5Hz，-NCH
2-)，4.94(m，1H，-OCH)；
IR v(cm
-1)：2935，2859，1751，1693，1475，1451，1424，1369，1304，1276，1244，1199，1175，1061，1011，934，769；
Synthesizing of embodiment 8 N-carbobenzoxy-(Cbz)-2-thiazole thione
In the 250ml there-necked flask, add two (trichloromethyl) carbonic ethers of 19.8g (0.067mol) and 50ml trichloromethane, slowly add benzylalcohol (0.2mol) under stirring.The ice bath cooling slowly drips the solution of pyridine (0.2mol) and 10ml trichloromethane down, and holding temperature is between 0～5 ℃.After dropwising, slowly heat up, stirred 3 hours down at 30 ℃.(3 * 50ml), anhydrous sodium sulfate drying filters, and concentrates, and decompression steams chloroformic acid benzyl ester to wash three times.Yield 81.7%.
Thiazolidinethion-2 (0.60g, 5mmol) and pyridine (0.56g 7mmol) is dissolved in the 10ml trichloromethane, stirs.The ice bath cooling drips above-mentioned chloroformic acid benzyl ester (6mmol) down.Dropwise, reacted 15 hours down at 0～10 ℃.Wash three times, anhydrous sodium sulfate drying filters, and concentrates.Resistates obtains 1.03g xanchromatic circle with ethyl alcohol recrystallization, i.e. N-carbobenzoxy-(Cbz)-2-thiazole thione.Fusing point 72-75 ℃, yield is 81.5%.
This compound
1H NMR and IR are as described below:
1H NMR(CDCl
3)δ：3.28(t，2H，J＝4.5Hz，-SCH
2-)，4.52(t，2H，J＝4.7Hz，-NCH
2-)，5.30(s，2H，-OCH
2)，7.26~7.44(m，5H，-Ph)；
IR v(cm
-1)：1749，1374，1263，1247，1204，1155，1056，1002，913，762，733；
Synthesizing of embodiment 9 N-carbobenzoxy-2-thiazole thione
In the 250ml there-necked flask, add two (trichloromethyl) carbonic ethers of 19.8g (0.067mol) and 50ml toluene, stir slowly add down phenol (50mL, 0.2mol).The ice bath cooling slowly drips the aqueous sodium hydroxide solution of 80 grams 10% down, and holding temperature is between 0～5 ℃.After dropwising, slowly heat up, stirred 2 hours down at 30 ℃.Separating funnel divides oil-yielding stratum, and anhydrous sodium sulfate drying filters, and concentrates, and decompression steams phenyl chloroformate.Yield 88.4%.
Thiazolidinethion-2 (0.60g, 5mmol) and triethylamine (0.72g 7mmol) is dissolved in the 10ml trichloromethane, stirs.The ice bath cooling drips above-mentioned phenyl chloroformate (6mmol) down.Dropwise, reacted 12 hours down at 0～10 ℃.Wash three times, anhydrous sodium sulfate drying filters, and concentrates.Resistates obtains the 1.15g yellow crystals with the normal hexane recrystallization, i.e. N-carbobenzoxy-2-thiazole thione.Fusing point: 113～114 ℃.Yield is 96.0%.
This compound
1H NMR and IR are as described below:
1H NMR(CDCl
3)δ：3.37(t，2H，J＝4.8Hz，-SCH
2-)，4.66(t，2H，J＝4.8Hz，-NCH
2-)，7.20~7.42(m，5H，-Ph)；
IR v(cm
-1)：1765，1591，1488，1373，1301，1270，1255，1187，1161，1125，1051，900，759，746；
Toluene oxygen carbonyl-2-thiazole thione is synthetic between embodiment 10 N-
In the 250ml there-necked flask, add two (trichloromethyl) carbonic ethers of 19.8g (0.067mol) and 50ml toluene, slowly add m-cresol (0.2mol) under stirring.The ice bath cooling slowly drips the aqueous sodium hydroxide solution of 80 grams 10% down, and holding temperature is between 0～5 ℃.After dropwising, slowly heat up, stirred 3 hours down at 30 ℃.Separating funnel divides oil-yielding stratum, and anhydrous sodium sulfate drying filters, and concentrates, and decompression steams the chloroformic acid m-tolyl ester.Yield 80.0%.
Thiazolidinethion-2 (0.60g, 5mmol) and triethylamine (0.72g 7mmol) is dissolved in the 10ml tetrahydrofuran (THF), stirs.The ice bath cooling drips above-mentioned chloroformic acid m-tolyl ester (6mmol) down.Dropwise, reacted 16 hours down at 0～10 ℃.Wash three times, anhydrous sodium sulfate drying filters, and concentrates.Resistates obtains the 1.10g yellow crystals with the dehydrated alcohol recrystallization, i.e. toluene oxygen carbonyl-2-thiazole thione between N-.Fusing point: 121～122 ℃.Yield is 87.0%.
This compound
1H NMR and IR are as described below:
1H NMR(CDCl
3)δ：2.36(s，3H，-CH
3)，3.38(t，2H，J＝4.5Hz，-SCH
2-)，4.66(t，2H，J＝4.5Hz，-NCH
2-)，6.99~7.29(m，4H，-Ph)；
IR v(cm
-1)：1758，1608，1485，1369，1284，1263，1225，1195，1145，1051，999，938，809，774，754，689；
Synthesizing of the adjacent chlorobenzene oxygen of embodiment 11 N-carbonyl-2-thiazole thione
M-cresol is changed to ortho chloro phenol, and other makes the adjacent chlorobenzene ester of chloroformic acid with embodiment 12.Yield 81.5%.
Thiazolidinethion-2 (0.60g, 5mmol) and triethylamine (0.72g 7mmol) is dissolved in the 10ml trichloromethane, stirs.The ice bath cooling drips the adjacent chlorobenzene ester (6mmol) of above-mentioned chloroformic acid down.Dropwise, reacted 12 hours down at 0～10 ℃.Wash three times, anhydrous sodium sulfate drying filters, and concentrates.Resistates obtains the 1.12g yellow crystals with the dehydrated alcohol recrystallization, i.e. the adjacent chlorobenzene oxygen of N-carbonyl-2-thiazole thione.Fusing point: 109～111 ℃.Yield is 82.0%.
This compound
1H NMR and IR are as described below:
1H NMR(CDCl
3)δ：3.42(t，2H，J＝4.5Hz，-SCH
2-)，4.75(t，2H，J＝4.5Hz，-NCH
2-)，7.22~7.48(m，4H，-Ph)；
IR v(cm
-1)：1770，1475，1376，1296，1273，1252，1197，1119，1059，901，765，746，740；
The test of embodiment 12 fungicidal activities
Adopt toxic potato agar substratum (PDA) method that the fungicidal activity that embodiment 1～11 synthetic compound has carried out Pyricularia oryzae (Pyricularia oryzae), fusarium graminearum (Gibberella zeae), Phytophthora capsici germ (Phytophthora capsici) and botrytis cinerea pers (Botrytiscinerea) is measured, general sieve concentration is 25ppm; Adopt potted plant toxic potato agar substratum (PDA) method that the fungicidal activity that the synthetic compound has carried out Sclerotinia sclerotiorum (Sclerotoniasclerotiorum) is measured, general sieve concentration is 500ppm; Adopt potted plant stem and leaf of Wheat to preserve the spore method fungicidal activity that the synthetic compound has carried out wheat powdery mildew (Blumeria graminis) is measured, general sieve concentration is 500ppm.Test result sees Table 1.
Table 1 N-hydrocarbon carbonyl oxygen-2-thiazole thione derivative is to the restraining effect of germ
| The embodiment title | Compound/R | Gibberellic hypha | The phytophthora root rot bacterium | Pyricularia oryzae | Ash arrhizus bacteria | The sclerotium germ | The white powder germ |
| Inhibiting rate (%) | Inhibiting rate (%) | Inhibiting rate (%) | Inhibiting rate (%) | Preventive effect (%) | Preventive effect (%) | ||
| Embodiment 6 | The 2-chloroethyl | 6.5 | 0 | 17.5 | 21.9 | 40.0 | 56.0 |
| Embodiment 5 | N-propyl | 0 | 0 | 28.1 | 29.2 | 12.5 | 22.0 |
| Embodiment 3 | Normal-butyl | 0 | 0 | 17.5 | 21.9 | 17.6 | 17.3 |
| Embodiment 4 | Isobutyl- | 0 | 0 | 21.1 | 11.7 | 28.5 | 12.5 |
| Embodiment 1 | N-pentyl | 0 | 0 | 38.6 | 27.7 | 11.5 | 22.0 |
| Embodiment 2 | Isopentyl | 7.5 | 0 | 52.6 | 51.1 | 32.0 | 20.0 |
| Embodiment 7 | Cyclohexyl | 0 | 0 | 48.0 | 33.5 | 7.5 | 0 |
| Embodiment 9 | Phenyl | 5.0 | 0 | 14.0 | 11.7 | 22.0 | 17.0 |
| Embodiment 8 | Benzyl | 0 | 0 | 52.6 | 30.7 | 18.5 | 7.5 |
| Embodiment 10 | Between tolyl | 0 | 0 | 0 | 0 | 12.0 | 0 |
| Embodiment 11 | Chloro-O-Phenyl | 12.5 | 0 | 28.0 | 12.6 | 37.0 | 28.0 |
| - | Blank | 0 | 0 | 0 | 0 | 0 | 0 |
The test of embodiment 13 insecticidal activities
Adopt the Potter spray method that embodiment 1～11 synthetic compound has been carried out the insecticidal activity assay of mythimna separata (Mythimna separata), working concentration is 1000mg/L; Adopt dipping plant method that the synthetic compound has been carried out the insecticidal activity assay of black bean aphid (Aphis fabae) and red spider (Tetranychusurticae), working concentration is 500mg/L.Test result sees Table 2.
Mortality ratio is being the A level more than 90%, is the B level between 70～90%, is the C level between 50～70%, is the D level between 0～50%.
Table 2 N-hydrocarbon carbonyl oxygen-2-thiazole thione derivative is to the killing action of insect
| The embodiment title | Compound/R | Mythimna separata | Aphid | Red spider | |||
| Mortality ratio (%) | The virulence rank | Mortality ratio (%) | The virulence rank | Mortality ratio (%) | The virulence rank | ||
| Embodiment 6 | The 2-chloroethyl | 22.0 | 0 | 8.89 | D | ||
| Embodiment 5 | N-propyl | 5.0 | D | 0 | 0 | ||
| Embodiment 3 | Normal-butyl | 0 | 0 | 72.58 | B | ||
| Embodiment 4 | Isobutyl- | 8.70 | D | 0 | 56.63 | C | |
| Embodiment 1 | N-pentyl | 5.30 | D | 0 | 50.0 | C | |
| Embodiment 2 | Isopentyl | 16.70 | D | 0 | 75.0 | B | |
| Embodiment 7 | Cyclohexyl | 9.57 | D | 0 | 43.24 | D | |
| Embodiment 9 | Phenyl | 13.5 | 0 | 0 | |||
| Embodiment 8 | Benzyl | 21.0 | 0 | 77.17 | B | ||
| Embodiment 10 | Between tolyl | 0 | 0 | 54.37 | C | ||
| Embodiment 11 | Chloro-O-Phenyl | 25.2 | 0 | 78.75 | B | ||
| - | Blank | 0 | 0 | 0 | |||
Claims (10)
1, a kind of N-hydrocarbon carbonyl oxygen-2-thiazole thione derivative suc as formula (I):
Wherein R represents C
1～C
10Alkyl group, cycloalkyl or haloalkyl, or C
6～C
10Aryl.
2, N-hydrocarbon carbonyl oxygen as claimed in claim 1-2-thiazole thione derivative is characterized in that described R representative is one of following: n-propyl, normal-butyl, isobutyl-, n-pentyl, isopentyl, cyclohexyl, 2-chloroethyl.
3, N-hydrocarbon carbonyl oxygen as claimed in claim 2-2-thiazole thione derivative is characterized in that described R represents normal-butyl or isopentyl or 2-chloroethyl.
4, N-hydrocarbon carbonyl oxygen as claimed in claim 1-2-thiazole thione derivative is characterized in that described R representative is one of following: phenyl, benzyl, 3-aminomethyl phenyl, 2-chloro-phenyl-.
5, N-hydrocarbon carbonyl oxygen as claimed in claim 4-2-thiazole thione derivative is characterized in that described R represents benzyl or 2-chloro-phenyl-.
6, the preparation method of the described N-hydrocarbon carbonyl oxygen of a kind of claim 1-2-thiazole thione derivative, comprise the steps: suc as formula the thiazolidinethion-2 of (II) with suc as formula the chloro-formic ester of (III) under the acid binding agent effect, carry out condensation reaction at 0～10 ℃ in organic solvent, aftertreatment gets product;
Wherein R represents C
1～C
10Alkyl group, cycloalkyl or haloalkyl, or C
6～C
10Aryl.
7, preparation method as claimed in claim 6 is characterized in that described acid binding agent is triethylamine or pyridine.
8, preparation method as claimed in claim 6 is characterized in that described organic solvent is trichloromethane, methylene dichloride or tetrahydrofuran (THF).
9, as the described preparation method of one of claim 6～8, it is characterized in that described thiazolidinethion-2: chloro-formic ester: the molar ratio of acid binding agent is 1: 1.0～1.3: 1.2～2.0, and the consumption of organic solvent is 20～50 times of thiazolidinethion-2 quality; Described condensation reaction time is 1～20 hour.
10, the described N-hydrocarbon carbonyl oxygen of claim 1-2-thiazole thione derivative is as the application of insectofungicide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510061124 CN1760189A (en) | 2005-10-14 | 2005-10-14 | Method for preparing N-alkoxy carbonyl, thiazolethioketone derivative,s and usage |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510061124 CN1760189A (en) | 2005-10-14 | 2005-10-14 | Method for preparing N-alkoxy carbonyl, thiazolethioketone derivative,s and usage |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1760189A true CN1760189A (en) | 2006-04-19 |
Family
ID=36706435
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200510061124 Pending CN1760189A (en) | 2005-10-14 | 2005-10-14 | Method for preparing N-alkoxy carbonyl, thiazolethioketone derivative,s and usage |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1760189A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109265452A (en) * | 2018-08-21 | 2019-01-25 | 华南农业大学 | A kind of substituted-phenyl furans -2-mercaptothiazoline first ketone compounds and its preparation method and application |
| CN110283070A (en) * | 2019-06-28 | 2019-09-27 | 浙江禾本科技有限公司 | A kind of n-propyl chloroformate microreactor synthesis technology |
-
2005
- 2005-10-14 CN CN 200510061124 patent/CN1760189A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109265452A (en) * | 2018-08-21 | 2019-01-25 | 华南农业大学 | A kind of substituted-phenyl furans -2-mercaptothiazoline first ketone compounds and its preparation method and application |
| CN109265452B (en) * | 2018-08-21 | 2021-08-03 | 华南农业大学 | Substituted phenyl furan-2-mercaptothiazoline ketone compounds and preparation method and application thereof |
| CN110283070A (en) * | 2019-06-28 | 2019-09-27 | 浙江禾本科技有限公司 | A kind of n-propyl chloroformate microreactor synthesis technology |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1270593A (en) | Pyrimidin-4-one and pyrimidin-4-thione as fungicide | |
| CN1382127A (en) | Pyrazolecarboxamide and pyrazolethioamide as fungioide | |
| CN1293083C (en) | Siliconated phenyl amides derivatives useful as microbiocide | |
| CN1785993A (en) | Preparation method of non natural isocumarin and its 3,4-dihydro derivative and use thereof | |
| CN1207739A (en) | 1,2,3-thiadiazole carboxylic acid (thio) esters and use thereof as pest control agent or as microbicide | |
| CN1113062C (en) | Dihydrofuran carboxamides | |
| CN1708496A (en) | Cyclopropyl-thienyl-carboxamide as fungicides | |
| CN1760189A (en) | Method for preparing N-alkoxy carbonyl, thiazolethioketone derivative,s and usage | |
| CN1452458A (en) | Herbicidal 5-benzyloxymethyl-1,2,-isoxazoline derivs | |
| CN1024316C (en) | Imidazole fungicides | |
| CN1789253A (en) | Benzothiazole derivatives synthesis and sterilization property thereof | |
| CN1880307A (en) | 2,4-dichlor phenoxyacetic amide pyrimidine derivative and its preparation method and agricultural composition | |
| CN1654456A (en) | Pyrazole-containing bishydrazide compound and its preparation method and use | |
| CN1035254C (en) | Substituted thiophenecarboxamides | |
| CN1654457A (en) | Pyrazole-containing semicarbazide compound and its preparation method and use | |
| CN1223584C (en) | Pyrrolecarboxamides for use as fungicides | |
| CN1709875A (en) | Pyrazole diacylhydrazine compound, and its preparing method and use | |
| CN1644579A (en) | N-alkoxide oxo-2-triazolidone derivative, its preparation and use | |
| CN1785981A (en) | N-substituted phenyl-2-oxo-1, 3-thiazolidine-3-formamide derirative, preparation method and its use | |
| CN1234681C (en) | Amino acid derivatives and their use as pesticides | |
| CN1644582A (en) | Pyrazole contained diheterocyclic compound, its preparation and use | |
| CN1216871C (en) | Pyridazinyl ketone derivative having insect growth regulation activity and its preparation method | |
| CN1155590C (en) | Chromone compounds with antineoplastic activity and its open-loop products and preparing process | |
| CN1785983A (en) | Benzo [1,2,3] thiadiazole derivative its synthesis method and use | |
| CN1760188A (en) | N-acyl-2 oxo-1,3-derivatives of thiazolidine, preparation method and usage |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |