CN101735129B - N-phenyl-N'-(2-acetoxy benzoyl) thiourea derivative and preparation and application thereof - Google Patents
N-phenyl-N'-(2-acetoxy benzoyl) thiourea derivative and preparation and application thereof Download PDFInfo
- Publication number
- CN101735129B CN101735129B CN200910117631.0A CN200910117631A CN101735129B CN 101735129 B CN101735129 B CN 101735129B CN 200910117631 A CN200910117631 A CN 200910117631A CN 101735129 B CN101735129 B CN 101735129B
- Authority
- CN
- China
- Prior art keywords
- phenyl
- acetoxy benzoyl
- thiourea derivative
- stirring
- acetoxy
- 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 - Fee Related
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides an N-phenyl-N'-(2-acetoxy benzoyl) thiourea derivative. The serial compound is prepared by the following steps of: firstly, taking acetone as a solvent, taking an N,N-dimethyl formamide as a catalyst and reacting aspirin and solid phosgene to prepare an intermediate of acetylsalicylryl chloride; then, taking PEG-400 as a phase transfer catalyst, adding ammonium thiocyanate directly and reacting at normal temperature for 0.5-2.0h to obtain an intermediate of 2-acetoxy benzoyl isothiocyanate; and finally, adding aromatic amine, stirring at room temperature, reacting for 1.0-2.0h, distilling off the solvent, then adding an ice water mixture into a reaction vessel, leaching to obtain a solid after stirring fully, leaching, drying and recrystallizing to obtain N-phenyl-N'-(2-acetoxy benzoyl) thiourea. Biological activity experiments show that the serial compound has a superior promotion function to the growth of the root systems of dicotyledonous crops at a certain concentration, which has a very important actual meaning for reinforcing the lodging resistance capability, the drought resistance capability and the flood resistance capability of the crops.
Description
Technical field
The invention belongs to technical field of organic chemistry, relate to a class and there is good bioactive salicylic acid thiourea derivative, relate in particular to a kind of N-phenyl-N '-(2-acetoxy benzoyl) thiourea derivative and preparation method thereof.The present invention also relates to the N-phenyl-N '-application of (2-acetoxy benzoyl) thiourea derivative in the crop growth conditioning agent simultaneously.
Background technology
Whitfield's ointment is ubiquitous small molecule phenolic compound in plant tissue, in the many physiological actions of plant, play an important role, as maturation of the blooming of the sprouting of the closing of pore, seed, plant, fruit etc., it is the chemical substance of effect highly significant in agriculture production.The 1980s, scientist finds that Whitfield's ointment is a signal of interest molecule in the reaction of plant disease-resistant signal transduction.With bigcatkin willow acidleach kind or seed dressing, can effectively increase the plurality of enzymes activity of seed, the integrity of Cell protection film, improve the ability of crop opposing high temperature, freeze injury, saline and alkaline, arid, disease, increases output and raising quality; And animals and plants are not all had to toxic action, and environment is not had to detrimentally affect yet, be the agricultural plant Auto-regulator of a class safety, in the development of nutrition type seed treatment agent, have broad application prospects.
Thiourea derivative is class purposes compound very widely, has desinsection, weeding, coordinate plant growth, anti-inflammatory, antibiotic function, extensively is used as weedicide, plant-growth regulator, and the diseases such as treatment tuberculosis, diabetes, cancer.
In view of Whitfield's ointment and thiourea substances all have good biological activity to plant, we design and have synthesized the derivative class thiocarbamide of such Whitfield's ointment, and expect that they can promote sprouting and the growth of seed, and farm crop are had to drought resisting, heat resistanceheat resistant, disease-resistant effect.
Summary of the invention
The purpose of this invention is to provide N-phenyl-N ' that a class has the good biological activity-(2-acetoxy benzoyl) thiourea derivative.
Another object of the present invention is to provide the preparation method of a kind of N-phenyl-N '-(2-acetoxy benzoyl) thiourea derivative.
A further object of the invention is to provide the N-phenyl-N '-application of (2-acetoxy benzoyl) thiourea derivative in the crop growth conditioning agent.
(1) N-phenyl-N '-(2-acetoxy benzoyl) thiourea derivative
The structural formula of N-phenyl-N ' of the present invention-(2-acetoxy benzoyl) thiourea derivative is as follows:
R＝H、o-CH
3、o-CH
3、p-OCH
3、β-Naphthyl、p-NO
2、o-OCH
3、p-OCH
2CH
3、o-OH、m-OH、p-OH、p-Cl。
Owing in N-phenyl-N '-(2-acetoxy benzoyl) thiourea derivative, having introduced ester group, it is low that these compounds have a fusing point than similar thiourea compound, the advantage that solvability is good, and its biological activity also should be better than salicylic acid material and acylthioureas.
(2) preparation of N-phenyl-N '-(2-acetoxy benzoyl) thiourea derivative
N-phenyl-N ' of the present invention-(2-acetoxy benzoyl) thiourea derivative be prepared as follows step:
Take acetone as solvent, take DMF as catalyzer, by acetylsalicylic acid and solid phosgene according to the mol ratio of 1.0: 0.5～1.0: 2.0 at 40～80 ℃ of lower back flow reaction 0.5～2.0h, make intermediate acetyl bigcatkin willow acyl chlorides, do not separate;
Make phase-transfer catalyst with PEG-400 again, directly add ammonium thiocyanate according to acetyl salicylyl acid and ammonium thiocyanate with the mol ratio of 1.0: 1.0～1.0: 2.0, normal-temperature reaction 0.5～2.0h, obtain the own thiocyanic ester of intermediate 2-acetoxy benzoyl, do not separate;
Finally according to acetyl salicylyl acid and aromatic amine, with the mol ratio of 1.0: 0.8～1.0: 1.0, directly add aromatic amine; 1.0: the mol ratio of 0: 1.0: 0.9～1.0: 2.0: 1.5 is in stirring at room reaction 0.5～2.0h; steam solvent; in reaction vessels, add mixture of ice and water (to dissolve the inorganic salt that produce again; separate out organic product), after fully stirring, suction filtration obtains solid, dries; recrystallization, obtain N-phenyl-N '-(2-acetoxy benzoyl) thiocarbamide.Its synthetic route is as follows:
The arylamine that the present invention adopts is aniline, o-toluidine, m-toluidine, to monomethylaniline, beta-naphthylamine, p-Nitroaniline, ORTHO ANISIDINE, p-ethoxyaniline, ortho-aminophenol, a hydroxyanilines, para hydroxybenzene amine or p-Chlorobenzoic acid amide, corresponding product is as follows:
Work as R=H, obtain product a;
R=o-CH
3, product is b:;
R=m-CH
3, product is c;
R=p-OCH
3, product is d:;
R=β-Naphthyl, product is e;
R=p-NO
2, product is f;
R=o-OCH
3, product is g;
R=p-OCH
2cH
3, product is h;
R=o-OH, product is i;
R=m-OH, product is j;
R=p-OH, product is k;
R=p-Cl, product is l.
The present invention uses that environmental protection, operability are good, the solid phosgene of safe ready is as chloride reagent, with phase transfer catalysis process and one kettle way, has synthesized fast, efficiently this series material, and the solvent in reaction can reuse.
(3) N-phenyl-N '-bioactive research of (2-acetoxy benzoyl) thiourea derivative
The present invention adopts plate culture to study the growth regulating effect of this series compound to blue or green assorted No. 3 seedlings root of dicotyledons Semen Brassicae campestris.
This series compound is made into respectively to 100,10,1,0.1,0.01 and the solution of 0.001mg/L concentration.The solution prepared with 10ml is cultivated Semen Brassicae campestris in the petri dish of diameter 10cm, with distilled water, makes blank assay, and the indolylacetic acid solution of same concentrations is as standard control.Room temperature growth 4 days is also measured the growth length of rape root, with following formula, calculates this compounds growth regulating-activity per-cent to the Brassica Napus Seedling root system under each concentration:
A＝(N-N
0)/N
0×100％
Wherein: A is the sample biological activity, the growth length that N is Brassica Napus Seedling root in solution, N
0growth length for Brassica Napus Seedling root in distilled water.Calculation result is listed in table 1.As can be seen from Table 1, this compounds shows stronger inhibition activity to being grown under high density of dicotyledons Semen Brassicae campestris seedling root, but the reduction along with concentration, compound shows promoter action to the growth regulating of root, when finite concentration, this promoter action is the strongest, and promoter action is generally good than indolylacetic acid, when concentration reduces again, promoter action weakens again.For example, compound b has restraining effect consumingly to the Brassica Napus Seedling root when high density, along with reducing of concentration, restraining effect gradually becomes promoter action, best to the promoter action of Brassica Napus Seedling root when concentration is 0.01mg/L, but concentration is while diminishing again, and promoter action reduces again.In these compounds, the effect of d and j is the most outstanding, when concentration is 0.01mg/L, the growth regulating-activity per-cent A of Brassica Napus Seedling root system is respectively to 50.6% and 46.1%, and the A value of indolylacetic acid is 14.3%.Therefore, can be developed to a kind of new plant growth regulator fully.
The growth regulating-activity data of table 1 plant
Annotate: IAA is indolylacetic acid
Experimental results demonstrate, this series vegetable growth regulator is applicable to dicotyledonous farm crop, can make the dicotyledonous crops well developed root system, strengthened the lodging tolerance of dicotyledonous farm crop, drought-resistant ability, flood fighting waterlogging ability etc., therefore this series compound is the novel crops growth regulator that a class is good, all kinds of dicotyledonous farm crop (are comprised to rape, cotton, peanut, Sunflower Receptacle, potato, tobacco, all kinds of melons and fruits etc.) after having applied this series vegetable growth regulator, to make the situation of growth regulator not far better than applying this series vegetable growth regulator and applying indolylacetic acid for the growing state of crop root.
Embodiment
The preparation of embodiment 1, product a
By acetylsalicylic acid and solid phosgene, according to amount, the ratio than 1.0: 1.0 is placed in flask, adds acetone to make solvent, then drips DMF and make catalyzer, at 60 ℃ of backflow 1.5h.After cool to room temperature, then to admixture quality in flask, be directly the ammonium thiocyanate of the porphyrize of 1.5 times of acetylsalicylic acid amounts, and add PEG-400 to make phase-transfer catalyst, stirring at room reaction 1h.The most backward flask the inside adds the aniline of 0.9 times of acetylsalicylic acid amount, stirring at room reaction 1h.After having reacted, at first on Rotary Evaporators, steam solvent acetone (recycling), then add appropriate mixture of ice and water in flask; after fully stirring, suction filtration, dry; recrystallization, obtain corresponding N-phenyl-N '-(2-acetoxy benzoyl) thiocarbamide sterling.
The characterization data of product is as follows:
The a:EtOH recrystallization, white thread crystalline substance, productive rate 85.2%.m.p.95～96 ℃;
1h NMR, (CDCl
3, 400MHz) δ: 12.460 (s, 1H, CONH), 9.920 (s, 1H, CSNH), 8.080～7.256 (m, 9H, ArH), 2.549～2.542 (m, 3H, CH
3);
13c NMR (CDCl
3, 100MHz) δ: 21.253,123.861,124.006,124.044,126.780,126.909,128.891,131.406,134.439,137.487,148.332,164.191,168.245,178.023, IR (KBr, cm
-1) v:3359.853123.65, (NH), 1776.27 (OC=OCH
3), 1664.97 (NHC=OAr), 1248.46 (C=S); Anal.Calcd forC
16h
14n
2o
3s:C 61.13, and H 4.49, and N 8.91; Found C 61.20, H 4.51, and N 8.93.
The preparation of embodiment 2, product b
By acetylsalicylic acid and solid phosgene, according to amount, the ratio than 1.0: 1.0 is placed in flask, adds acetone to make solvent, then drips DMF and make catalyzer, at 60 ℃ of backflow 1.5h.After cool to room temperature, then to admixture quality in flask, be directly the ammonium thiocyanate of the porphyrize of 1.5 times of acetylsalicylic acid amounts, and add PEG-400 to make phase-transfer catalyst, stirring at room reaction 1.0h.The most backward flask the inside adds the o-toluidine of 0.9 times of acetylsalicylic acid amount, stirring at room reaction 1.0h.After having reacted, at first on Rotary Evaporators, steam solvent acetone (recycling), then add appropriate mixture of ice and water in flask; after fully stirring, suction filtration, dry; recrystallization, obtain corresponding N-phenyl-N '-(2-acetoxy benzoyl) thiocarbamide sterling.
The b:EtOH recrystallization, white thread crystalline substance, productive rate 87.2%, m.p.132～134 ℃;
1h NMR, (CDCl
3, 400MHz) δ: 12.143 (s, 1H, CONH), 10.010 (s, 1H, CSNH), 8.100～7.241 (m, 8H, ArH), 2.551 (m, 3H, O=CCH
3), 2.360 (m, 3H, ArCH
3);
13c NMR (CDCl
3, 100MHz) δ: 17.969,21.259,123.823,123.899,125.972,126.406,126.719,127.610,130.743,131.743,133.143,134.416,136.214,148.347,164.198,168.215,178.952; IR (KBr, cm
-1) v:3308.50,3211.16 (NH), 1760.66 (OC=OCH
3), 1672.50 (NHC=OAr), 1256.63 (C=S); Anal.Calcd for C
17h
16n
2o
3s:C 62.18, and H 4.91, and N 8.53; Found C 62.25, H 4.96, and N 8.50.
The preparation of embodiment 3, product c
By acetylsalicylic acid and solid phosgene, according to amount, the ratio than 1.0: 1.0 is placed in flask, adds acetone to make solvent, then drips DMF and make catalyzer, at 60 ℃ of backflow 1.5h.After cool to room temperature, then to admixture quality in flask, be directly the ammonium thiocyanate of the porphyrize of 1.5 times of acetylsalicylic acid amounts, and add PEG-400 to make phase-transfer catalyst, stirring at room reaction 1.0h.The most backward flask the inside adds the m-toluidine of 0.9 times of acetylsalicylic acid amount, stirring at room reaction 1.0h.After having reacted, at first on Rotary Evaporators, steam solvent acetone (recycling), then add appropriate mixture of ice and water in flask; after fully stirring, suction filtration, dry; recrystallization, obtain corresponding N-phenyl-N '-(2-acetoxy benzoyl) thiocarbamide sterling.
The characterization data of product is as follows:
The c:EtOH recrystallization, white needle-like crystals, productive rate 81.5%, m.p.84～86 ℃;
1h NMR, (CDCl
3, 400MHz) δ: 12.40～12.403 (s, 1H, CONH), 9.892 (s, 1H, CSNH), 7.091～8.081 (m, 8H, ArH), 2.552～2.5555 (m, 3H, O=CCH
3), 2.395 (m, 3H, ArCH
3);
13c NMR (CDCl
3, 100MHz) δ: 21.261,21.390,121.178,123.884,124.135,124.615,126.780,127.755,128.723,131.421,134.408,137.449,138.935,148.393,164.191,168.253,177.977IR (KBr, cm
-1) v:3381.21 (NH), 1776.58 (OC=OCH
3), 1660.76 (NHC=OAr), 1281.31 (C=S); Anal.Calcd for C
17h
16n
2o
3s:C62.18, H 4.91, and N 8.53; Found C 62.14, H 4.90, and N 8.56.
The preparation of embodiment 4, product d
By acetylsalicylic acid and solid phosgene, according to amount, the ratio than 1.0: 1.0 is placed in flask, adds acetone to make solvent, then drips DMF and make catalyzer, at 60 ℃ of backflow 1.5h.After cool to room temperature, then to admixture quality in flask, be directly the ammonium thiocyanate of the porphyrize of 1.5 times of acetylsalicylic acid amounts, and add PEG-400 to make phase-transfer catalyst, stirring at room reaction 1.0h.The most backward flask the inside add 0.9 times of acetylsalicylic acid amount to monomethylaniline, stirring at room reaction 1.0h.After having reacted, at first on Rotary Evaporators, steam solvent acetone (recycling), then add appropriate mixture of ice and water in flask; after fully stirring, suction filtration, dry; recrystallization, obtain corresponding N-phenyl-N '-(2-acetoxy benzoyl) thiocarbamide sterling.
The characterization data of product is as follows:
The d:EtOH recrystallization, white needle-like crystals, productive rate 92.0%.m.p.141～143 ℃;
1h NMR, (CDCl
3, 400MHz) δ: 12.357 (s, 1H, CONH), 9.906 (s, 1H, CSNH), 8.074～7.210 (m, 8H, ArH), 2.554～2.527 (m, 3H, O=CCH
3), 2.366 (m, 3H, OCH
3);
13c NMR (CDCl
3, 100MHz) δ: 21.009,21.169,123.762,123.952,124.006,126.665,129.378,131.291,134.294,134.843,136.778,148.233,164.046,168.169,177.992; IR (KB r, cm
-1) v:3361.69 (NH), 1783.45 (OC=OCH
3), 1668.84 (NHC=OAr), 1246.46 (C=S); Anal.Calcd for C
17h
16n
2o
4s:C 59.29, H 4.68 N 8.13; Found C59.25, H 4.71, and N 8.19.
The preparation of embodiment 5, product e
By acetylsalicylic acid and solid phosgene, according to amount, the ratio than 1.0: 1.0 is placed in flask, adds acetone to make solvent, then drips DMF and make catalyzer, at 60 ℃ of backflow 1.5h.After cool to room temperature, then to admixture quality in flask, be directly the ammonium thiocyanate of the porphyrize of 1.5 times of acetylsalicylic acid amounts, and add PEG-400 to make phase-transfer catalyst, stirring at room reaction 1.0h.The most backward flask the inside adds the beta-naphthylamine of 0.9 times of acetylsalicylic acid amount, stirring at room reaction 1.0h.After having reacted, at first on Rotary Evaporators, steam solvent acetone (recycling), then add appropriate mixture of ice and water in flask; after fully stirring, suction filtration, dry; recrystallization, obtain corresponding N-phenyl-N '-(2-acetoxy benzoyl) thiocarbamide sterling.
The characterization data of product is as follows:
E:EtOH-DMF mixed solvent recrystallization, white crystal, productive rate 85.2%, m.p.161～163 ℃;
1h NMR, (CDCl
3, 400MHz) δ: 12.640 (s, 1H, CONH), 10.126 (s, 1H, CSNH), 8.162～7.246 (m, 11H, ArH), 2.569～2.565 (m, 3H, CH
3);
13c NMR (CDCl
3, 100MHz) δ: 21.314,121.605,123.739,123.891,125.217,126.414,126.787,126.978,127.946,128.388,128.609,131.543,133.395,134.126,134.523,148.438,164.404,168.245,179.676; IR (KBr, cm
-1) v:3313.61 (NH), 1753.87 (OC=OCH
3), 1672.60 (NHC=OAr), 1219.01 (C=S); Anal.Calcd for C
20h
16n
2o
3s:C 65.92, H 4.43 N7.69; Found C 65.98, H 4.39, and N 7.61.
The preparation of embodiment 6, product f
By acetylsalicylic acid and solid phosgene, according to amount, the ratio than 1.0: 1.0 is placed in flask, adds acetone to make solvent, then drips DMF and make catalyzer, at 60 ℃ of backflow 1.5h.After cool to room temperature, then to admixture quality in flask, be directly the ammonium thiocyanate of the porphyrize of 1.5 times of acetylsalicylic acid amounts, and add PEG-400 to make phase-transfer catalyst, stirring at room reaction 1.0h.The most backward flask the inside adds the p-Nitroaniline of 0.9 times of acetylsalicylic acid amount, stirring at room reaction 1.0h.After having reacted, at first on Rotary Evaporators, steam solvent acetone (recycling), then add appropriate mixture of ice and water in flask; after fully stirring, suction filtration, dry; recrystallization, obtain corresponding N-phenyl-N '-(2-acetoxy benzoyl) thiocarbamide sterling.
The characterization data of product is as follows:
F:EtOH-DMF mixed solvent recrystallization, thread light yellow crystal, productive rate 91.5%, m.p.163～165 ℃;
1h NMR, (CDCl
3, 400MHz) δ: 12.974 (s, 1H, CONH), 10.032 (s, 1H, CSNH), 8.304～7.265 (m, 8H, ArH), 2.555～2.530 (m, 3H, CH
3);
13c NMR (CDCl
3, 100MHz) δ: 21.253,123.091,123.518,123.960,124.600,126.932,131.535,134.865,143.157,145.123,148.400,164.511,168.062,177.863; IR (KBr, cm
-1) v:3376.72 (NH), 1772.58 (OC=OCH
3), 1670.58 (NHC=OAr), 1284.95 (C=S); Anal.Calcdfor C
16h
13n
3o
5s:C 53.48, and H 3.65, and N 11.69; Found C 53.44, H 3.61, and N 11.72.
The preparation of embodiment 7, product g
By acetylsalicylic acid and solid phosgene, according to amount, the ratio than 1.0: 1.0 is placed in flask, adds acetone to make solvent, then drips DMF and make catalyzer, at 60 ℃ of backflow 1.5h.After cool to room temperature, then to admixture quality in flask, be directly the ammonium thiocyanate of the porphyrize of 1.5 times of acetylsalicylic acid amounts, and add PEG-400 to make phase-transfer catalyst, stirring at room reaction 1.0h.The most backward flask the inside adds the ORTHO ANISIDINE of 0.9 times of acetylsalicylic acid amount, stirring at room reaction 1.0h.After having reacted, at first on Rotary Evaporators, steam solvent acetone (recycling), then add appropriate mixture of ice and water in flask; after fully stirring, suction filtration, dry; recrystallization, obtain corresponding N-phenyl-N '-(2-acetoxy benzoyl) thiocarbamide sterling.
The characterization data of product is as follows:
The g:EtOH recrystallization, white crystal, productive rate 88.7%, m.p.128～129 ℃;
1hNMR, (CDCl
3, 400MHz) δ: 12.135 (s, 1H, CONH), 10.002 (s, 1H, CSNH), 8.079～7.212 (m, 8H, ArH), 2.544～2.500 (m, 3H, O=CCH
3), 2.370～2.149 (m, 3H, OCH
3);
13c NMR (CDCl
3, 100MHz) δ: 17.923,21.192,123.762,123.846,125.911,126.345,126.650,127.549,130.689,131.337,133.082,134.347,136.176,148.286,164.160,168.161,178.884; IR (KBr, cm
-1) v:3307.91,3211.54 (NH), 1760.80 (OC=OCH
3), 1672.50 (NHC=OAr), 1257.52 (C=S); Anal.Calcd for C
17h
16n
2o
4s:C 59.29, H 4.68N8.13; Found C 59.21, H 4.73, and N 8.15.
The preparation of embodiment 8, product h
By acetylsalicylic acid and solid phosgene, according to amount, the ratio than 1.0: 1.0 is placed in flask, adds acetone to make solvent, then drips DMF and make catalyzer, at 60 ℃ of backflow 1.5h.After cool to room temperature, then to admixture quality in flask, be directly the ammonium thiocyanate of the porphyrize of 1.5 times of acetylsalicylic acid amounts, and add PEG-400 to make phase-transfer catalyst, stirring at room reaction 1.0h.The most backward flask the inside adds the p-ethoxyaniline of 0.9 times of acetylsalicylic acid amount, stirring at room reaction 1.0h.After having reacted, at first on Rotary Evaporators, steam solvent acetone (recycling), then add appropriate mixture of ice and water in flask; after fully stirring, suction filtration, dry; recrystallization, obtain corresponding N-phenyl-N '-(2-acetoxy benzoyl) thiocarbamide sterling.
The characterization data of product is as follows:
The h:EtOH recrystallization, white plates crystal, productive rate 84.3%, m.p.140～142 ℃;
1h NMR, (CDCl
3, 400MHz) δ: 12.282 (s, 1H, CONH), 9.896 (s, 1H, CSNH), 6.905～8.056 (m, 8H, ArH), 4.009～4.067 (m, 2H, OCH
2), 2.530～2.539 (m, 3H, O=CCH
3), 1.394～1.4358 (m, 3H, CH
2cH
3);
13c NMR (CDCl
3, 100MHz) δ: 14.676,21.131,63.549,114.464,123.724,124.013,125.522,126.604,130.232,131.230,134.225,148.248,157.507,164.054,168.131,178.015IR (KBr, cm
-1) v:3359.99 (NH), 1781.34 (OC=OCH
3), 1669.42 (NHC=OAr), 1286.73 (C=S); ; Anal.Calcd forC
18h
18n
2o
4s:C 60.32, and H 5.06, and N 7.82; Found C 60.32, H 5.01 N 7.80.
The preparation of embodiment 9, product i
By acetylsalicylic acid and solid phosgene, according to amount, the ratio than 1.0: 1.0 is placed in flask, adds acetone to make solvent, then drips DMF and make catalyzer, at 60 ℃ of backflow 1.0h.After cool to room temperature, then to admixture quality in flask, be directly the ammonium thiocyanate of the porphyrize of 1.5 times of acetylsalicylic acid amounts, and add PEG-400 to make phase-transfer catalyst, stirring at room reaction 1.0h.The most backward flask the inside adds the ortho-aminophenol of 0.9 times of acetylsalicylic acid amount, stirring at room reaction 0.5h～2.0h.After having reacted, at first on Rotary Evaporators, steam solvent acetone (recycling), then add appropriate mixture of ice and water in flask; after fully stirring, suction filtration, dry; recrystallization, obtain corresponding N-phenyl-N '-(2-acetoxy benzoyl) thiocarbamide sterling.
The characterization data of product is as follows:
I:EtOH-H
2o mixed solvent recrystallization, white trichite, productive rate 92.1%, m.p.177～179 ℃;
1h NMR, (CDCl
3, 400MHz) δ: 12.512 (s, 1H, CONH), 10.071 (s, 1H, CSNH), 8.108～7.015 (m, 8H, ArH), 6.455 (s, 1H, OH), 2.559 (m, 3H, CH
3);
13c NMR (CDCl
3, 100MHz) δ: 21.299,120.241,121.636,123.518,123.937,125.210,125.728,126.879,129.157,131.573,134.766,148.642,149.642,164.633,168.039,177.161; IR (KBr, cm
-1) v:3437.14 (OH), 3357.33 (NH), 1778.10 (OC=OCH
3), 1651.06 (NHC=OAr), 1246.40 (C=S); Anal.Calcd for C
16h
14n
2o
4s:C 58.17, and H 4.27, and N 8.48; Found C58.10, H 4.21, and N 8.43.
The preparation of embodiment 10, product j
By acetylsalicylic acid and solid phosgene, according to amount, the ratio than 1.0: 1.0 is placed in flask, adds acetone to make solvent, then drips DMF and make catalyzer, at 60 ℃ of backflow 1.5h.After cool to room temperature, then to admixture quality in flask, be directly the ammonium thiocyanate of the porphyrize of 1.5 times of acetylsalicylic acid amounts, and add PEG-400 to make phase-transfer catalyst, stirring at room reaction 1.0h.The most backward flask the inside add 0.9 times of acetylsalicylic acid amount between hydroxyanilines, stirring at room reaction 1.0h.After having reacted, at first on Rotary Evaporators, steam solvent acetone (recycling), then add appropriate mixture of ice and water in flask; after fully stirring, suction filtration, dry; recrystallization, obtain corresponding N-phenyl-N '-(2-acetoxy benzoyl) thiocarbamide sterling.
The characterization data of product is as follows:
J:EtOH-H
2o mixed solvent recrystallization, white bulk crystals, productive rate 84.3%, m.p.122～123 ℃;
1h NMR (CDCl
3, 400MHz) δ: 12.461 (s, 1H, CONH), 9.890 (s, 1H, CSNH), 8.056～6.724 (m, 8H, ArH), 5.518 (s, 1H, OH), 2.540 (m, 3H, O=CCH
3);
13c NMR (CDCl
3, 100MHz) δ: 21.245,110.921,114.038,116.118,123.853,123.945,126.818,129.889,131.322,134.500,138.485,148.301,155.922,164.305,168.474,177.687; IR (KBr, cm
-1) v:3318.78 (OH), 3361.92 (NH), 1782.22 (OC=OCH
3), 1669.42 (NHC=OAr), 1205.43 (C=S); Anal.Calcd for C
16h
14n
2o
4s:C 58.17, and H 4.27, and N 8.48; Found C 58.09, H 4.22, and N 8.45.
The preparation of embodiment 11, product k
By acetylsalicylic acid and solid phosgene, according to amount, the ratio than 1.0: 1.0 is placed in flask, adds acetone to make solvent, then drips DMF and make catalyzer, at 60 ℃ of backflow 1.5h.After cool to room temperature, then to admixture quality in flask, be directly the ammonium thiocyanate of the porphyrize of 1.5 times of acetylsalicylic acid amounts, and add PEG-400 to make phase-transfer catalyst, stirring at room reaction 1.0h.The most backward flask the inside add 0.9 times of acetylsalicylic acid amount between hydroxyanilines, stirring at room reaction 1.0h.After having reacted, at first on Rotary Evaporators, steam solvent acetone (recycling), then add appropriate mixture of ice and water in flask; after fully stirring, suction filtration, dry; recrystallization, obtain corresponding N-phenyl-N '-(2-acetoxy benzoyl) thiocarbamide sterling.
The characterization data of product is as follows:
K:EtOH-H
2o mixed solvent recrystallization, white needle-like crystals, productive rate 80.3%, m.p.145～146 ℃;
1h NMR (CDCl
3, 400MHz) δ: 12.258 (s, 1H, CONH), 9.903 (s, 1H, CSNH), 8.069～6.833 (m, 8H, ArH), 5.321 (s, 1H, OH), 2.547 (m, 3H, O=CCH
3);
13c NMR (CDCl
3, 100MHz) δ: 21.276,115.668,123.876,124.036,126.063,126.810,130.415,131.360,134.462,148.332,154.466,164.252,168.413,178.449; IR (KBr, cm
-1) v:3237.77 (OH), 3365.10 (NH), 1776.44 (OC=OCH
3), 1688.55 (NHC=OAr), 1278.57 (C=S); Anal.Calcd for C
16h
14n
2o
4s:C 58.17, and H 4.27, N8.48; Found C 58.20, H 4.21, and N 8.46.
The preparation of embodiment 12, product l
By acetylsalicylic acid and solid phosgene, according to amount, the ratio than 1.0: 1.0 is placed in flask, adds acetone to make solvent, then drips DMF and make catalyzer, at 60 ℃ of backflow 1.5h.After cool to room temperature, then to admixture quality in flask, be directly the ammonium thiocyanate of the porphyrize of 1.5 times of acetylsalicylic acid amounts, and add PEG-400 to make phase-transfer catalyst, stirring at room reaction 1.0h.The most backward flask the inside adds the p-Chlorobenzoic acid amide of 0.9 times of acetylsalicylic acid amount, stirring at room reaction 1.0h.After having reacted, at first on Rotary Evaporators, steam solvent acetone (recycling), then add appropriate mixture of ice and water in flask; after fully stirring, suction filtration, dry; recrystallization, obtain corresponding N-phenyl-N '-(2-acetoxy benzoyl) thiocarbamide sterling.
The characterization data of product is as follows:
The l:EtOH recrystallization, white trichite, productive rate 89.8%, m.p.99～100 ℃;
1h NMR, (CDCl
3, 400MHz) δ: 12.532 (s, 1H, CONH), 9.943 (s, 1H, CSNH), 8.075～7.247 (m, 8H, ArH), 2.544～2.533 (m, 3H, O=CCH
3);
13c NMR (CDCl
3, 100MHz) δ: 21.238,122.047,123.792,123.876,123.952,126.803,126.886,129.828,131.421,134.385,134.568,138.577,148.332,164.282,168.161,178.061; IR (KBr, cm
-1) v:3383.14 (NH), 1777.08 (OC=OCH
3), 1667.89 (NHC=OAr), 1247.12 (C=S); Anal.Calcd for C
16h
13clN
2o
3s:C 55.09, and H 3.76, and N 8.03; FoundC 55.02, and H 3.78, and N 8.07.
Claims (5)
1.N-phenyl-N '-(2-acetoxy benzoyl) thiourea derivative, its structure is as follows:
Wherein R=H, p-OCH
3, p-OCH
2cH
3, o-OH, m-OH or p-OH.
2. the preparation method of N-phenyl-N '-(2-acetoxy benzoyl) thiourea derivative as claimed in claim 1 comprises the following steps:
Take acetone as solvent, take DMF as catalyzer, by acetylsalicylic acid and solid phosgene according to the mol ratio of 1.0: 0.5～1.0: 2.0 at 40～80 ℃ of lower back flow reaction 0.5～2.0h, make intermediate acetyl bigcatkin willow acyl chlorides;
Make phase-transfer catalyst with PEG-400 again, directly add ammonium thiocyanate according to acetyl salicylyl acid and ammonium thiocyanate with the mol ratio of 1.0: 1.0～1.0: 2.0, normal-temperature reaction 0.5～2.0h, obtain intermediate 2-acetoxy benzoyl lsothiocyanates, do not separate;
Finally according to acetyl salicylyl acid and arylamine, with the mol ratio of 1.0: 0.8～1.0: 1.0, directly add arylamine, stirring at room reaction 0.5～2.0h, steam solvent, add mixture of ice and water again in reaction vessels, after fully stirring, suction filtration obtains solid, dry, recrystallization, obtain N-phenyl-N '-(2-acetoxy benzoyl) thiourea derivative;
Described arylamine is any in aniline, p-ethoxyaniline, ortho-aminophenol, a hydroxyanilines, para hydroxybenzene amine.
3. the preparation method of N-phenyl-N '-(2-acetoxy benzoyl) thiourea derivative as claimed in claim 2, it is characterized in that: described catalyst n, the consumption of dinethylformamide is 1.2～1.4% of solid phosgene quality.
4. the preparation method of N-phenyl-N '-(2-acetoxy benzoyl) thiourea derivative as claimed in claim 2, it is characterized in that: the consumption of described phase-transfer catalyst PEG-400 is 0.2～0.5% of ammonium thiocyanate quality.
As claimed in claim 1 N-phenyl-N '-(2-acetoxy benzoyl) thiourea derivative as the application of crop growth conditioning agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910117631.0A CN101735129B (en) | 2009-12-03 | 2009-12-03 | N-phenyl-N'-(2-acetoxy benzoyl) thiourea derivative and preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910117631.0A CN101735129B (en) | 2009-12-03 | 2009-12-03 | N-phenyl-N'-(2-acetoxy benzoyl) thiourea derivative and preparation and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101735129A CN101735129A (en) | 2010-06-16 |
| CN101735129B true CN101735129B (en) | 2014-01-01 |
Family
ID=42459212
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910117631.0A Expired - Fee Related CN101735129B (en) | 2009-12-03 | 2009-12-03 | N-phenyl-N'-(2-acetoxy benzoyl) thiourea derivative and preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101735129B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102101846B (en) * | 2010-12-06 | 2012-07-18 | 周玉莲 | Preparation method of thiazole thiourea derivatives |
| CN102093274A (en) * | 2010-12-23 | 2011-06-15 | 西北师范大学 | Chalcone-containing acylthiourea compounds and preparation method and use thereof |
| CN102207455B (en) * | 2011-04-02 | 2013-08-14 | 朱丽君 | An open hole identification method for anions F -, ac - and H2PO4- |
| CN105384641A (en) * | 2015-10-26 | 2016-03-09 | 安徽广信农化股份有限公司 | Wastewater treatment process for paranitrobenzoyl chloride |
| CN108863876A (en) * | 2018-09-12 | 2018-11-23 | 中国农业大学 | A kind of thiourea and preparation method and application with gibberellin function |
| CN110911749B (en) * | 2019-12-03 | 2023-02-03 | 珠海市赛纬电子材料股份有限公司 | High-voltage lithium ion battery electrolyte, additive and preparation method of additive |
-
2009
- 2009-12-03 CN CN200910117631.0A patent/CN101735129B/en not_active Expired - Fee Related
Non-Patent Citations (3)
| Title |
|---|
| JP特开昭51-121515 1976.10.23 |
| STN.CAS RN：298206-56-1.《Registry》.2000, * |
| 魏太保等.N-芳基2N’-邻硝基苯甲酰基硫脲衍生物的合成及其生物活性研究.《西北师范大学学报(自然科学版)》.2004,第40卷(第1期),45-47、50. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101735129A (en) | 2010-06-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101735129B (en) | N-phenyl-N'-(2-acetoxy benzoyl) thiourea derivative and preparation and application thereof | |
| CN102408364B (en) | Method for preparing paratoluensulfonyl chloride | |
| CN112876384A (en) | Synthesis process and application of diflubenzuron | |
| CN101544633B (en) | Synthesis technology for methyl thiadiazole formamide | |
| US10674723B2 (en) | 1,8-bis(Schiff base)-p-menthane derivatives as well as preparation method and applications thereof | |
| CN108640871B (en) | Fluorine-containing pyridine piperazine urea compound and application thereof | |
| CN103044287A (en) | Synthetic method for diaryl urea compound | |
| CN114249692B (en) | 2-imidazole benzamide active compound for preventing and treating wheat take-all and wheat stem basal rot | |
| CN100551238C (en) | Thio-ether type compounds plant growth regulator | |
| CN112479934A (en) | Synthesis method of methyl amino chloroformate | |
| CN103044336B (en) | Acylthiourea compound, preparation method and application thereof | |
| CN105777618B (en) | A kind of methyl α-naphthyl acetate pyridine ethyl ester type compound and purposes | |
| RU2219771C2 (en) | Agent for presowing treatment of cucumber seeds | |
| JPS61210075A (en) | Dihydrotriazole and herbicide | |
| RU2810585C1 (en) | Use of 2-chloro-n-(4-cyano-3-cyanomethyl-1h-pyrazol-5-yl)acetamide as a 2,4-d antidote in sunflower | |
| RU2196772C1 (en) | 6-methyl-8-methoxymethyl-3-phenylisoxazolo-[3',4':4,5]-thieno[2,3-b]pyridine eliciting growth regulating and antistress activity | |
| US3959301A (en) | Algicidol 2-chloro-5-tolyl-1,3,4-thiadiazoles | |
| RU2156242C1 (en) | 3,5-disubstituted 2,4-triazinones-6 having growth- regulating activity | |
| US3210178A (en) | Compositions for the selective combating of monocotyledonous seeds in cultures of useful plants | |
| US3903153A (en) | Dithiocarbamate hydrochloride salts and their manufacture | |
| SU578867A3 (en) | Method of preparing diuretan derivatives | |
| JPS58185572A (en) | Triazole derivative and herbicide containing said derivative | |
| US3916010A (en) | 1-Alkanoyloxy-haloethyl urea | |
| RU2015138C1 (en) | N-[(1-hydroxymethyl-2-hydroxy-2-n-nitrophenyl)ethyl]-amides showing growth-regulating activity | |
| CN106212487B (en) | A kind of application of 1,2,4- triazole derivatives of the structure of benzopyrazines containing methoxyl group as fungicide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140101 Termination date: 20141203 |
|
| EXPY | Termination of patent right or utility model |