CN1125719A - 2-tertiary butyl-1-aroyl-4-substituted thiosemicarbazide compound and its synthesis and application - Google Patents
2-tertiary butyl-1-aroyl-4-substituted thiosemicarbazide compound and its synthesis and application Download PDFInfo
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Abstract
The process for synthesizing 2-tert-butyl-1-aroyl-4-substituted semicarbazide (thiourea) compounds, which have strong activity to regulate insect growing and better activity to kill mite and suppress growth of plant, is disclosed.
Description
The invention relates to an insect growth regulator and a preparation method and application thereof.
The pesticide plays an important role in the development of national economy. The agricultural development today is not free from the use of pesticides, which has become one of the important means of plant protection.
Insecticides are the most used pesticides in developing countries. Agricultural pesticides have evolved through a process ranging from organochlorines, organophosphates, carbamates to pyrethroids. However, the frequent use of the above insecticides in large quantities causes the resistance of the pests to these conventional insecticides, and at the same time, these agents also cause damage to the natural enemy organisms growing in the same ecosystem as the pests and cause environmental pollution. To overcome these disadvantages, it is envisaged to synthesize an insecticide to control the insect endocrine system to interfere with the normal growth and development of the insect, which ultimately leads to killing of the insect, and such an insecticide is known as an insect growth regulator. Since the insect growth regulator has an excellent insecticidal mechanism, which is remarkably different from the conventional agricultural insecticides, it can selectively control pests without causing resistance and is harmless to both human and livestock and natural enemies, thereby maintaining normal natural ecology without causing environmental pollution. Insect growth regulators, known as third generation insecticides, have thus become the most desirable and effective means for controlling agricultural pests.
The development of insect growth regulators began in the seventies, but few products are commercially available so far, and for this reason, many foreign research institutes have transferred their research direction from the main variety of insect growth regulators, benzoylurea compounds, to its derivatives, hopefully to find more new varieties of insect growth regulators. For example, aromatic acyl (aryl) semicarbazide compounds are researched and developed by Dow company in America, and 1-aromatic acyl-4-aromatic semicarbazide compounds are found to have certain insect growth regulation activity but lower activity, so that industrial application is not obtained; paul, B.K. et al have conducted extensive studies on certain 1, 4-diarylacylamino (thio) ureas and found that these compounds have certain fungicidal and plant growth regulating activities, but no insect growth regulating activities, and in conclusion, scientists at home and abroad are still in the process of continuing research and development on such insect growth regulators.
The invention aims to develop a compound with strong biological activity, namely 2-tertiary butyl-1-aroyl-4-substituted amino (sulfur) urea, on the basis of previous work, which not only has strong insect growth regulating activity, but also has good acaricidal activity and plant growth inhibiting activity.
The idea of the invention is that: 1, 4-diarylamino (thio) urea compounds are used as basic skeletons, then a tert-butyl group with specific activity is introduced into a 2-position to form a brand new compound, namely 2-tert-butyl-1-aroyl-4-substituted amino (thio) urea compounds, and then biological activity tests are carried out on the compounds, and the results show that part of compounds not only have strong insect growth regulating activity, but also have good acaricidal and plant growth inhibiting activity.
The invention is also realized by providing a compound with the following structural general formula:
wherein: r is unsubstituted or substituted aryl, unsubstituted or substituted aroyl, substituted diphenyl ether group, heterocyclic substituent group;
X1-is oxygen or sulphur;
X2-is 0 to 3 identical or different halogen, alkyl, nitro, ether groups.
The preparation method of the compound comprises the following steps: isocyanate (R-NCO) or isothiocyanate (R-NCS) is taken as a raw material, and is respectively subjected to condensation reaction with an intermediate N-tertiary butyl-N' -aroyl hydrazine in a solvent under the conditions of heating and stirring to prepare the target compound, namely the 2-tertiary butyl-1-aroyl-4-substituted amino (sulfur) urea compound, of the invention, wherein the reaction equations are shown as (1) and (2):
wherein:
(1) the starting isocyanate (R-NCO) can be synthesized according to the methods disclosed in U.S. Pat. No. 3,450,747, U.S. Pat. No. 3,584,028: for example, aromatic amides (or substituted aromatic amides) with oxalyl chloride (COCl)2The reaction produces aroyl (or substituted aroyl) isocyanate, and the reaction equation is as follows:
in this case, R in the formula is unsubstituted or substituted aroyl, and similarly, isocyanates in which R is an aryl group or a substituted aryl group, a substituted diphenyl ether group, or a heterocyclic substituent can be synthesized.
(2) The starting isothiocyanate (R-NCS) can be synthesized as disclosed in document j.indian chem.soc., 46(12), 1121 (1969): for example, aroyl: (Or substituted aroyl) chloride and potassium thiocyanide (KSCN) to prepare the isothiocyanate, wherein the reaction equation is as follows:
in this case, R in the formula is an aroyl group or a substituted aroyl group, and similarly, isothiocyanates in which R is an aryl group or a substituted aryl group, a substituted diphenylether group, or a heterocyclic substituent can be synthesized.
(3) Synthesis of intermediate N-tert-butyl-N' -aroylhydrazine
The catalyst is prepared by taking tert-butyl hydrazine hydrochloride and aroyl (or substituted aroyl) chloride as raw materials and reacting under the catalysis of alkali, and the reaction equation is as follows:wherein:
[1]the tert-butyl hydrochloride can be prepared according to the method disclosed in U.S. Pat. No. 4,435,600, i.e. tert-butyl alcohol and hydrazine hydrochloride are used as raw materials and are heated and reacted under the catalysis of acid, and the reaction equation is as follows:
[2]raw material aroyl chloride or substituted aroyl chloride is a commercial product, wherein a substituent group X is 0-3 same or different halogens, alkyls, nitryl and ether groups.
(4) The solvent can be one or mixture of hydrocarbons, toluene, benzene, acetonitrile, and dimethylformamide, and the solvent can be toluene, 1, 2-dichloroethane, and acetonitrile.
(5) The reaction temperature is controlled between 60 ℃ and 130 ℃, preferably in the range of 75 ℃ to 115 ℃, and is generally carried out at the reflux temperature of the solvent.
(6) The reaction time is preferably 3 to 5 hours.
The present invention will be further illustrated with reference to the following examples, which are not intended to limit the scope of the present invention.
Example 12 Synthesis of tert-butyl-1-benzoyl-4- (2-chlorobenzoyl) thiosemicarbazide, the reaction equation is as follows:
0.015mol of KSCN and 20ml of anhydrous acetonitrile are added into a 50ml dry three-neck flask with a thermometer and a stirring device, and 0.01mol of 2-chlorobenzoyl chloride is added dropwise at room temperature under stirring, and the dropwise addition is finished within 10 min. Heating at 80-85 deg.C for 10min to obtain orange red liquid. Cooling, filtering, decompressing and desolventizing the filtrate to obtain a crude orange red 2-chlorobenzoyl isothiocyanate product for later use.
The crude 2-chlorobenzoyl isothiocyanate obtained by the above reaction and 20ml of anhydrous acetonitrile were charged in a 50ml dry three-necked flask equipped with a thermometer and a reflux condenser. Adding 0.01mol of N-tert-butyl-N' -benzoyl hydrazine at room temperature for several times while stirring, and heating to 80-85 deg.C for reflux reaction for 0.5 hr. After cooling and standing overnight, a large amount of yellow precipitate precipitated out from the flask. Filtration is carried out, the filter cake is initially taken with 30ml of 50% NaHCO3After washing the solution, it was washed neutral with water to give 1.84g of a yellow solid, mp: 144.7-145.3 ℃ and the reaction yield is 47.1 percent. MS, 139(100) [ M + -C12H16N3OS]，141(30.4)[M++2-C12H16N3OS，105(91.7)[M+-C12H15C1N3OS]，77(39.5)[M+-C13H15C1N3O2S]，111(39.6)[M+-C13H16N3O2S]，113(14.1)[M++2-C13H16N3O2S]，57(7.8)[M+-C15H11C1N3O2S]Elemental analysis C% H% N%
Theoretical value: 58.535.1710.78
Measured value: 58.335.0110.80
Example 22 Synthesis of tert-butyl-1-benzoyl-4- (4-chlorobenzoyl) thiosemicarbazide, the reaction equation is as follows:
the preparation method is the same as example 1, wherein the raw material 2-chlorobenzoyl chloride is changed to 4-chlorobenzoyl chloride, the yield is 36%, mp: 155.2-156.0 ℃, Rf (C2H5OC2H5) ═ 0.78, IR: v 3220cm-1, 1660, 1590, 1500, 1390, 1200, 850. elemental analysis Cl%
Theoretical value: 9.11
Measured value: 9.15
Example 32 Tert-ButyleneSynthesis of 1- (2, 4-dichlorobenzoyl) -4- (2-chlorobenzoyl) semicarbazide, the reaction equation is as follows:
1g (0.0064mol) of 2-chlorobenzamide and 15ml of 1, 2-dichloroethane dehydrated and dried by a 4A molecular sieve are added into a 25ml dry three-neck flask provided with a thermometer and a reflux condenser, 1.06g (0.0084mol) of oxalyl chloride is dripped into the solution at 30 ℃ under continuous stirring, the solid suspended in the solvent gradually disappears, and the reaction solution becomes clear and a large amount of HCl gas is released. The reaction solution is refluxed for 3hr at about 80 ℃. Cooling, vacuum distilling to recover about 70% solvent, and using residual liquid (solution A) for next reaction.
1.68g (0.0064mol) of N-tert-butyl-N' -2, 4-dichlorobenzoylhydrazine are added to 10ml of 1, 2-dichloroethane, the temperature is raised to 80 ℃ with continuous stirring, and the solution A is added dropwise over 15 min. Then reacting at 75-80 deg.C for 0.5hr to obtain white solid. After further reaction for 3hr, cooling and filtering to obtain 2.41g of crude product, yield: 85 percent. And then, carrying out column chromatography treatment to obtain a pure product, mp: 167.1-167.5 ℃, TLC: rf (C2H5OC2H5) ═ 0.71, MS: 57(100) [ M + -C15H9C13N3O3], 139(80.0) [ M + -C12H14C12N3O2], 141(27.9) [ M + -C12H14C12N3O2+2], 154(28.9) [ M + C12H13C12N2O2], 111(37.8) [ M + -C13H14C12N3O3], 113(10.2) [ M + C13H14C12N3O3+2], 172(42.6) [ M + -C12H15C1N3O2], 174(24.0) [ M + C12H15C1N3O2+2], 176(6.2) [ M + -C12H15C1N3O2+4]. Elemental analysis C% H% N%
Theoretical value: 51.524.069.49
Measured value: 51.424.049.48
Example 42 Synthesis of tert-butyl-1- (4-nitrobenzoyl) -4- (2, 5-dichlorobenzoyl) semicarbazide, the reaction equation for which is as follows:the preparation method is the same as example 3, wherein the raw material 2-chlorobenzamide is changed into 2, 5-dichlorobenzamide, the reaction yield is 80%, mp: 185.6-186.2 ℃.
Example 52-tert-butyl-1- (4-chlorobenzoic acid)Synthesis of acyl) -4- (4-chlorophenyl) semicarbazide, the reaction equation is as follows:
to a 25ml dry three-necked flask equipped with a thermometer and a reflux condenser, 0.91g (0.007mol) of 4-chloroaniline and 15ml of toluene dehydrated and dried by 4A molecular sieve were added, and 1.08g (0.0084mol) of oxalyl chloride was added dropwise to the solution at 30 ℃ while stirring, whereby a large amount of white solid was precipitated in the flask. Heating the reaction solution, refluxing and reacting for 5 hr. Cooling, filtering to remove insoluble substances, and removing unreacted oxalyl chloride and solvent from the filtrate through rotary evaporation to obtain the 4-chlorophenyl isocyanate for later use.
Adding 1.13g (0.005mol) of N-tert-butyl-N' - (4-chlorobenzoyl) hydrazine and 10ml of toluene into a 25ml dry three-neck flask provided with a thermometer and a reflux condenser, heating and stirring, dropwise adding the prepared 4-chlorophenyl isocyanate, precipitating a large amount of white solid in the flask, continuously reacting at 75-80 ℃ for 3hr, cooling, and filtering to obtain a crude product. After recrystallization of the crude product from 1, 2-dichloroethane, 0.62g of a white solid is obtained, mp: 249.4-250.8 ℃, TLC: rf (CH2C12) ═ 0.71, yield: 32.6 percent. IR: v-3120 cm-1, 1680, 1595, 1550, 1470, 1380, 1200, 850, 830. Elemental analysis Cl%
Theoretical value: 18.68
Measured value: 18.69
Example 62 Synthesis of tert-butyl-1- (4-fluorobenzoyl) -4- (3-methylphenyl) semicarbazide, the reaction equation is as follows:
the preparation method is the same as example 5, wherein 4-chloroaniline is changed to 3-methylaniline, the reaction yield is 35%, mp: 225.1-226.3 ℃.
Example 72-tert-butyl-1- (4-methylbenzoyl) -4- [ 4' -a, a, a-trifluoromethylphenoxyphenyl]The synthesis of semicarbazide, the reaction equation is as follows:
adding 1.2g of oxalyl chloride in 15ml of toluene solution into a dry 50ml three-neck flask provided with a stirrer and a thermometer, dropwise adding 1.8g of 4-amino-4 ' -trifluoromethyl diphenyl ether in 15ml of toluene solution under stirring and ice bath cooling, continuing stirring at room temperature for 1 hour after the addition is finished, then heating the oil bath to 110 ℃, keeping the temperature for 3 hours, changing the solution from brown red to earthy yellow, stirring at room temperature for 0.5 hour, gradually precipitating solids in the process, filtering, distilling the filtrate under reduced pressure to remove unreacted oxalyl chloride to obtain 4- (4 ' -trifluoromethylphenoxy) phenyl isocyanate, and dissolving the 4- (4 ' -trifluoromethylphenoxy) phenyl isocyanate in 10ml of toluene for standby.
A50 ml dry three-necked flask equipped with a thermometer and a condenser was charged with 1.5g N-tert-butyl-N '- (4-methylbenzoyl) hydrazine and 15ml toluene, 10ml of a toluene solution of previously prepared 4- (4' -trifluoromethylphenoxy) phenylisocyanate was added dropwise with heating and stirring, and the reaction was carried out at 110 ℃ for 0.5 hour to precipitate a white solid during the reaction. After further reaction for 3 hours, the reaction mixture was cooled, filtered and washed with toluene to give 1.4g of a product. mp: 244.3-245.5 ℃, yield: 40 percent. IR: v is 3140cm-1, 1680, 1595, 1555, 1520, 1475, 1380, 1250, 1200, 860. Elemental analysis C% H% N%
Theoretical value: 64.465.208.67
Measured value: 64.405.268.65
Example 82-tert-butyl-1- (4-methoxybenzoyl) -4- [ 4' -a, a, a-trifluoromethylphenoxyphenyl]The synthesis of semicarbazide, the reaction equation is as follows:
the preparation method is the same as example 7, wherein the raw material N-tert-butyl-N '- (4-methylbenzoyl) hydrazine is changed to N-tert-butyl-N' - (4-methoxybenzoyl) hydrazine, the reaction yield is 36%, mp: 243.4-243.9 ℃.
Example synthesis of 92-tert-butyl-1-benzoyl-4- (3-chloro-4-fluorophenyl) semicarbazide, the reaction equation is as follows:the preparation method is the same as example 5, wherein the raw material 4-chloroaniline is changed into 3-chloro-4-fluoroaniline, and the mixture is reacted and collectedRate 24.7%, mp: 234.4-235.0 ℃, TLC: rf (CH2C12) ═ 0.63, IR: v is 3140cm-, 1680, 1600, 1550, 1520, 1470, 1380, 1200, 830, 800, 740.
Example 102 Synthesis of tert-butyl-1-benzoyl-4- (2, 3, 4-trifluorophenyl) semicarbazide, the reaction equation of which is as follows:
the preparation method is the same as example 5, wherein the raw material of 4-chloroaniline is changed into 2, 3, 4-trifluoroaniline, the reaction yield is 23.7%, and the mp: 235.3-235.8 ℃, TLC: rf (CH2C12) 0.67, IR: v 3120cm-, 1680, 1585, 1550, 1520, 1470, 1380, 1200, 850, 740.
Example 11 synthesis of N-tert-butyl-N' - (4-methoxybenzoyl) hydrazine the reaction equation is as follows:
into a 250ml three-necked flask with stirring and refluxing apparatus, 22.5g (0.18mol) of N-t-butylhydrazine hydrochloride and 150ml of CH2Cl2 were charged, 14.4g of 50% NaOH solution was added dropwise with stirring, and after 15min, the reaction mixture was cooled to 5 ℃ while 10.23g (0.06mol) of 4-methoxybenzoyl chloride and 4.8g of 50% NaOH solution were added dropwise over 1.5 hr. After addition was complete, the reaction mixture was warmed to room temperature and stirring was continued for 1 hr. Washing the ether layer with 1M NaOH aqueous solution and 5% NaCl solution, extracting the product with 15% hydrochloric acid solution, and neutralizing the water phase with 6M NaOH to obtain crude product. The crude product was reconstituted with hexane to give 10.1g of white flocculent crystals, mp: 127.1-128.5 ℃, yield 76%, TLC: rf (C2H50C2H5) ═ 0.51.
As can be seen from the above examples, the 2-tert-butyl-1-aroyl-4-substituted amino (thio) ureas (abbreviated as "compounds") of the present invention can be readily synthesized by those skilled in the art according to the methods disclosed and described in the present invention.
The compounds synthesized according to the method of the present invention, when used as insect growth regulators, can be tested for biological activity as described below.
The biological activity test method comprises the following steps:
subject: shanghai local fruit fly.
Weighing 1.3g of agar, adding the agar into 200ml of water, heating and boiling, adding 13g of sucrose, stirring uniformly, cooling to 60 ℃, adding 17g of corn flour and 1.4g of standard yeast powder, stirring uniformly, and dropwise adding a plurality of drops of preservative propionic acid to obtain the culture medium for testing.
Weighing 11.4mg of a compound to be detected, pouring the compound into a glass bottle, adding 0.5-1.0 ml of edible soybean oil, heating the mixture at a low temperature for 5min under vigorous stirring, adding 114 g of prepared culture medium after the compound is completely dissolved in the soybean oil, and continuing to vigorously stir to enable the compound to be uniformly dispersed into the culture medium. This medium was then evenly distributed into 10 glass vials, and 50 newly produced fly eggs were spotted into each vial. Standing at certain temperature and humidity for ten days to allow the emergence of new fruit fly. The percentage difference between egg and newly born fruit fly numbers was the complete kill rate, and each data tested was compared to the test blank, and the results of some of the compounds were as follows.
Average complete kill ratio of Compound (%)Average complete kill ratio (%) of the compounds of the tables average complete kill ratio (%)
When the compound of the present invention is used as a plant growth inhibitor, the compound can be prepared into a dimethyl sulfoxide (DMSO) solution with a concentration of 100ppm for a plant growth inhibition activity test, and the test results of some compounds are as follows:
compound cockspur grass, sorghum, cucumber, radish and small goosegrass
A/B A/B A/B A/B A/B A/B
0/85 100/100 0/0 100/100 95/95 0/0
55/0 85/90 0/0 75/70 85/60 0/00/50 80/80 0/0 80/90 75/84 0/00/40 75/70 0/0 70/75 75/70 0/060/0 90/95 0/0 85/95 80/80 0/0
50/085/900/085/8080/700/0 Note: A/B A refers to activity on leaf surface; b refers to activity on roots.
When the compound of the present invention is used as an acaricide to perform acaricidal activity test, the compound can be prepared into dimethyl sulfoxide (DMSO) solutions with concentrations of 1000ppm, 500ppm and 250ppm respectively, and the test results of some compounds are as follows: compound 1000ppm 500ppm 250ppm10086
40.3
98.1 81.4
98.7 40.0
100 95.2 75.0100 94.2 75.0
100 94.7100 42.1
94.7 94.6 60.0100 100100 100In addition, according to the synthesis method disclosed by the invention and the method provided by the embodiment, the following compounds can be prepared: 2-tert-butyl-1- (2, 4-dichlorobenzoyl) -4- (2-chlorobenzoyl) thiosemicarbazide 2-tert-butyl-1-benzoyl-4- (4-chlorobenzoyl) thiosemicarbazide 2-tert-butyl-1- (4-chlorobenzoyl) -4- (4-chlorobenzoyl) thiosemicarbazide 2-tert-butyl-1- (2, 4-dichlorobenzoyl) -4- (4-chlorobenzoyl) thiosemicarbazide 2-tert-butyl-1- (4-chlorobenzoyl) -4- (2-chlorobenzoyl) semicarbazide 2-tert-butyl-1- (2, 4-dichlorobenzoyl) -1-benzoyl-4- (4-chlorobenzoyl) semicarbazide 2-tert-butyl-1- (4-methylbenzoyl) -4- (4-chlorobenzoyl) semicarbazide 2-tert-butyl-1- (3-methylbenzoyl) -4- (4-chlorobenzoyl) semicarbazide 2-tert-butyl-1- (4-methoxybenzoyl) -4- (4-chlorobenzoyl) semicarbazide 2-tert-butyl-1- (4-nitrobenzoyl) -4- (4-chlorobenzoyl) semicarbazide 2-tert-butyl-1- (4-bromobenzoyl) -4- (4-chlorobenzoyl) semicarbazide 2-tert-butyl-1- (2, 4-Dichlorobenzoyl) -4- (4-chlorobenzoyl) semicarbazide 2-tert-butyl-1-benzoyl-4- (3-methyl-2-pyridyl) semicarbazide 2-tert-butyl-1-benzoyl-4- (5-methyl-2-pyridyl) semicarbazide 2-tert-butyl-1- (4-chlorobenzoyl) -4- (3-methyl-2-pyridyl) semicarbazide 2-tert-butyl-1- (4-chlorobenzoyl) -4- (5-methyl-2-pyridyl) semicarbazide 2-tert-butyl-1- (4-chlorobenzoyl) -4- (4-methoxy-6-methyl-1, 3, 5-triazinyl) semicarbazide 2-tert-butyl-1- (4-methylbenzene)Formyl) -4- (4-methoxy-6-methyl-1, 3, 5-triazinyl) semicarbazide 2-tert-butyl-1- (4-methoxybenzoyl) -4- (4-methoxy-6-methyl-1, 3, 5-triazinyl) semicarbazide 2-tert-butyl-1- (4-chlorobenzoyl) -4- (4, 6-dimethoxypyrimidin-2-yl) semicarbazide 2-tert-butyl-1- (4-methoxybenzoyl) -4- (4, 6-dimethoxypyrimidin-2-yl) semicarbazide 2-tert-butyl-1- (4-nitrobenzoyl) -4- (4, 6-Dimethoxypyrimidin-2-yl) semicarbazide 2-tert-butyl-1-benzoyl-4- (4-chlorophenyl) semicarbazide 2-tert-butyl-1- (4-chlorobenzoyl) -4- (4-chlorophenyl) semicarbazide 2-tert-butyl-1- (2, 4-dichlorobenzoyl) -4- (4-chlorophenyl) semicarbazide 2-tert-butyl-1-benzoyl-4- (2, 3-dichlorophenyl) semicarbazide 2-tert-butyl-1- (4-chlorobenzoyl) -4- (2, 3-dichlorophenyl) semicarbazide 2-tert-butyl-1- (2, 4-dichlorobenzoyl) -4- (2, 3-dichlorophenyl) semicarbazide 2-tert-butyl-1-benzoyl-4- (2, 6-dichlorophenyl) semicarbazide 2-tert-butyl-1- (4-chlorobenzoyl) -4- (2, 6-dichlorophenyl) semicarbazide 2-tert-butyl-1- (2, 4-dichlorobenzoyl) -4- (2, 6-dichlorophenyl) semicarbazide2-tert-butyl-1-benzoyl-4- (2, 4, 6-trichlorophenyl) semicarbazide 2-tert-butyl-1- (4-chlorobenzoyl) -4- (2, 4, 6-trichlorophenyl) semicarbazide 2-tert-butyl-1- (2, 4-dichlorobenzoyl) -4- (2, 4, 6-trichlorophenyl) semicarbazide 2-tert-butyl-1-benzoyl-4- (2, 4, 5-trichlorophenyl) semicarbazide 2-tert-butyl-1- (4-chlorobenzoyl) -4- (2, 4, 5-trichlorophenyl) semicarbazide 2-tert-butyl-1- (2, 4-dichlorobenzoyl) -4- (2, 4, 5-trichlorophenyl) semicarbazide 2-tert-butyl-1-benzoyl-4- (3-chloro-4-fluorophenyl) semicarbazide 2-tert-butyl-1- (4-chlorobenzoyl) -4- (3-chloro-4-fluorophenyl) semicarbazide 2-tert-butyl-1- (2, 4-chlorobenzoyl) -4- (3-chloro-4-fluorophenyl) semicarbazide 2-tert-butyl-1-benzoyl-4- (2, 3, 4-trifluorophenyl) semicarbazide 2-tert-butyl-1- (4-chlorobenzoyl) -4- (2, 3, 4-trifluorophenyl) semicarbazide 2-tert-butyl-1- (2, 4-Dichlorobenzoyl) -4- (2, 3, 4-trifluorophenyl) semicarbazide 2-tert-butyl-1- (4-chlorobenzoyl) -4- [ 4' -a, a, a-trifluoromethylphenoxyphenyl]Semicarbazide 2-tert-butyl-1-benzoyl-4- [ 4' -a, a, a-trifluoromethylphenoxyphenyl]Semicarbazide 2-tert-butyl-1- (4-chlorobenzoyl) -4- [ 4' -a, a, a-trifluoromethylphenoxyphenyl]Semicarbazide 2-tert-butyl-1- (3-methylbenzoyl) -4- [ 4' -a, a, a-trifluoromethylphenoxyphenyl]Semicarbazide 2-tert-butyl-1- (4-methoxybenzoyl) -4- [ 4' -a, a, a-trifluoromethylphenoxyphenyl]Semicarbazide 2-tert-butyl-1- (4-methylbenzoyl) -4- [4 '-a, a, a-trifluoromethyl-2' -chlorophenoxyphenyl]Semicarbazide 2-tert-butyl-1- (4-methylbenzoyl) -4- [4 '-a, a, a-trifluoromethyl-2' -chlorophenoxyphenyl]Semicarbazide 2-tert-butyl-1- (4-methoxybenzoyl) -4- [4 '-a, a, a-trifluoromethyl-2' -chlorophenoxyphenyl]Semicarbazide 2-tert-butyl-1- (4-bromobenzoyl) -4- [4 '-a, a, a-trifluoromethyl-2' -chlorophenoxyphenyl]Semicarbazide
Claims (3)
1. A2-tert-butyl-1-aroyl-4-substituted amino (thio) urea compound has the following structural general formula:
wherein: r is unsubstituted or substituted aryl, unsubstituted or substituted aroyl, substituted diphenyl ether group, heterocyclic substituent group;
X1-is oxygen or sulphur;
X2-is 0 to 3 identical or different halogen, alkyl, nitro, ether groups.
2. A synthetic method of 2-tert-butyl-1-aroyl-4-substituted amino (thio) urea compounds is characterized in that: isocyanate (R-NCO) or isothiocyanate (R-NCS) is taken as a raw material, and is respectively condensed with N-tertiary butyl-N' -aroyl (or substituted aroyl) hydrazine in a solvent under the heating and stirring conditions to prepare the compound of the invention, and the reaction equation is as follows:
wherein: r is unsubstituted or substituted aryl, unsubstituted or substituted aroyl, substituted diphenyl ether group and heterocyclic substituent group; x2Is 0 to 3 identical or different halogen, alkyl, nitro, ether groups.
The solvent can be one or mixture of hydrocarbons, toluene, benzene, acetonitrile, and dimethylformamide, and the solvent can be toluene, 1, 2-dichloroethane, and acetonitrile.
The reaction temperature is controlled between 60 ℃ and 130 ℃, preferably in the range of 75 ℃ to 115 ℃, and is generally carried out at the reflux temperature of the solvent.
The reaction time is preferably 3 to 5 hours.
3. The application of 2-tert-butyl-1-aroyl-4-substituted amino (thio) urea compounds is characterized in that the compounds not only have strong insect growth regulating activity, but also have acaricidal activity and plant growth inhibiting activity.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 95111757 CN1125719A (en) | 1995-09-12 | 1995-09-12 | 2-tertiary butyl-1-aroyl-4-substituted thiosemicarbazide compound and its synthesis and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 95111757 CN1125719A (en) | 1995-09-12 | 1995-09-12 | 2-tertiary butyl-1-aroyl-4-substituted thiosemicarbazide compound and its synthesis and application |
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| Publication Number | Publication Date |
|---|---|
| CN1125719A true CN1125719A (en) | 1996-07-03 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 95111757 Pending CN1125719A (en) | 1995-09-12 | 1995-09-12 | 2-tertiary butyl-1-aroyl-4-substituted thiosemicarbazide compound and its synthesis and application |
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| Country | Link |
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| CN (1) | CN1125719A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105392562A (en) * | 2013-07-25 | 2016-03-09 | 昭和电工株式会社 | Reaction accelerator, urethane compound using same, thiourethane compound, and production method for amide compound or urea compound |
| US20200290959A1 (en) * | 2017-11-20 | 2020-09-17 | Purdue Research Foundation | Cellulose synthase inhibitors as a new class of herbicide and non-gmo crops that are resistant to the herbicide |
| US11497213B2 (en) * | 2018-09-04 | 2022-11-15 | Purdue Research Foundation | Synergistic effect of isoxaben and cellulosin as a herbicide |
| US11938121B2 (en) | 2020-04-15 | 2024-03-26 | Purdue Research Foundation | Treatment of infections and biofilm formation using a cellulose synthase inhibitor |
-
1995
- 1995-09-12 CN CN 95111757 patent/CN1125719A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105392562A (en) * | 2013-07-25 | 2016-03-09 | 昭和电工株式会社 | Reaction accelerator, urethane compound using same, thiourethane compound, and production method for amide compound or urea compound |
| US9656952B2 (en) | 2013-07-25 | 2017-05-23 | Showa Denko K.K. | Reaction accelerator and method of producing urethane compound, thiourethane compound, amide compound, or urea compound using same |
| US20200290959A1 (en) * | 2017-11-20 | 2020-09-17 | Purdue Research Foundation | Cellulose synthase inhibitors as a new class of herbicide and non-gmo crops that are resistant to the herbicide |
| US11497213B2 (en) * | 2018-09-04 | 2022-11-15 | Purdue Research Foundation | Synergistic effect of isoxaben and cellulosin as a herbicide |
| US11805780B2 (en) | 2018-09-04 | 2023-11-07 | Purdue Research Foundation | Synergistic effect of isoxaben and cellulosin as an herbicide |
| US11938121B2 (en) | 2020-04-15 | 2024-03-26 | Purdue Research Foundation | Treatment of infections and biofilm formation using a cellulose synthase inhibitor |
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