CN101735129A - 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
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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 have 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 a ubiquitous small molecule phenolic compound in the plant tissue, in the many physiological actions of plant, bringing into play important effect, as maturation of the blooming of the sprouting of the closing of pore, seed, plant, fruit etc., be the chemical substance of effect highly significant in the 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 protection cytolemma improves 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 toxic action, and environment there is not detrimentally affect yet, be that the agricultural plant of a class safety is regulated material, in the development of nutrition type seed treatment agent, have broad application prospects.
Thiourea derivative is a class purposes compound very widely, has desinsection, weeding, coordinate plant growth, anti-inflammatory, antimicrobial function, extensively is used as weedicide, plant-growth regulator, and treats diseases such as tuberculosis, diabetes, cancer.
In view of Whitfield's ointment and thiourea substances all have superior bioactive to plant, we design and have synthesized such Whitfield's ointment class thiocarbamide of deriving, and expect that they can promote the sprouting and the growth of seed, and farm crop are had drought resisting, heat resistanceheat resistant, disease-resistant effect.
Summary of the invention
The purpose of this invention is to provide a class and had the active N-phenyl-N ' of good biological-(2-acetoxy benzoyl) thiourea derivative.
Another object of the present invention provides the preparation method of a kind of N-phenyl-N '-(2-acetoxy benzoyl) thiourea derivative.
A further object of the invention provides 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 to introduced ester group in N-phenyl-N '-(2-acetoxy benzoyl) thiourea derivative, 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:
With acetone is solvent, and with N, dinethylformamide is a catalyzer, with acetylsalicylic acid and solid phosgene according to 1.0: 0.5～1.0: 2.0 mol ratio at 40～80 ℃ of following 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 1.0: 1.0～1.0: 2.0 mol ratio, normal-temperature reaction 0.5～2.0h obtains the own thiocyanic ester of intermediate 2-acetoxy benzoyl, does not separate;
Directly add aromatic amine according to acetyl salicylyl acid and aromatic amine with 1.0: 0.8～1.0: 1.0 mol ratio at last; 1.0: 0: 1.0: 0.9～1.0: 2.0: 1.5 mol ratio is in stirring at room reaction 0.5～2.0h; steam solvent; in reaction vessels, add the mixture of ice and water (inorganic salt that dissolving produces again; separate out organic product), suction filtration gets solid, oven dry after fully stirring; recrystallization obtains N-phenyl-N '-(2-acetoxy benzoyl) thiocarbamide.Its synthetic route is as follows:
The arylamine that the present invention adopts is aniline, o-toluidine, a monomethylaniline, 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, get 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 are 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 are i;
R=m-OH, product are j;
R=p-OH, product are k;
R=p-Cl, product are l.
The present invention uses that environmental protection, operability are good, the solid phosgene of safe ready is as chloride reagent, has synthesized this series material fast, efficiently with phase transfer catalysis process and one kettle way, and the solvent in the 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 100,10,1,0.1,0.01 and the solution of 0.001mg/L concentration respectively.Cultivate Semen Brassicae campestris with the solution that 10ml has prepared in the petri dish of diameter 10cm, make blank assay with distilled water, 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, calculates this compounds growth regulating-activity per-cent to the rape seedlings root under each concentration with following formula:
A＝(N-N
0)/N
0×100％
Wherein: A is the sample biological activity, and N is the growth length of rape seedling root in the solution, N
0Growth length for rape seedling root in the 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 in of dicotyledons Semen Brassicae campestris seedling root under the high density, but reduction along with concentration, compound shows promoter action to the growth regulating of root, this promoter action is the strongest when finite concentration, and promoter action is generally good than indolylacetic acid, and promoter action weakens again when concentration reduces again.For example, compound b has restraining effect consumingly to rape seedling root when high density, along with reducing of concentration, restraining effect gradually becomes promoter action, best to the promoter action of rape seedling root when concentration is 0.01mg/L, but concentration is when 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 rape seedlings root is respectively 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 an 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 good novel crop growth conditioning agent of a class, all kinds of dicotyledonous farm crop (are comprised rape, cotton, peanut, Sunflower Receptacle, potato, tobacco, all kinds of melons and fruits etc.) applied this series vegetable growth regulator after, 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
Acetylsalicylic acid and solid phosgene are placed flask according to the ratio of amount than 1.0: 1.0, add acetone and make solvent, drip N again, dinethylformamide is made catalyzer, at 60 ℃ of backflow 1.5h.After the cool to room temperature, more directly in flask the admixture quality be the ammonium thiocyanate of the porphyrize of 1.5 times of acetylsalicylic acid amounts, and add PEG-400 and make phase-transfer catalyst, stirring at room reaction 1h.The aniline that adds 0.9 times of acetylsalicylic acid amount at last to the flask the inside, stirring at room reaction 1h.After having reacted, at first on Rotary Evaporators, steam solvent acetone (recycling), in flask, add an amount of mixture of ice and water again; after fully stirring, suction filtration, oven dry; recrystallization obtains corresponding N-phenyl-N '-pure product of (2-acetoxy benzoyl) thiocarbamide.
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
Acetylsalicylic acid and solid phosgene are placed flask according to the ratio of amount than 1.0: 1.0, add acetone and make solvent, drip N again, dinethylformamide is made catalyzer, at 60 ℃ of backflow 1.5h.After the cool to room temperature, more directly in flask the admixture quality be the ammonium thiocyanate of the porphyrize of 1.5 times of acetylsalicylic acid amounts, and add PEG-400 and make phase-transfer catalyst, stirring at room reaction 1.0h.The o-toluidine that adds 0.9 times of acetylsalicylic acid amount at last to the flask the inside, stirring at room reaction 1.0h.After having reacted, at first on Rotary Evaporators, steam solvent acetone (recycling), in flask, add an amount of mixture of ice and water again; after fully stirring, suction filtration, oven dry; recrystallization obtains corresponding N-phenyl-N '-pure product of (2-acetoxy benzoyl) thiocarbamide.
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
Acetylsalicylic acid and solid phosgene are placed flask according to the ratio of amount than 1.0: 1.0, add acetone and make solvent, drip N again, dinethylformamide is made catalyzer, at 60 ℃ of backflow 1.5h.After the cool to room temperature, more directly in flask the admixture quality be the ammonium thiocyanate of the porphyrize of 1.5 times of acetylsalicylic acid amounts, and add PEG-400 and make phase-transfer catalyst, stirring at room reaction 1.0h.At last to the flask the inside add 0.9 times of acetylsalicylic acid amount between monomethylaniline, stirring at room reaction 1.0h.After having reacted, at first on Rotary Evaporators, steam solvent acetone (recycling), in flask, add an amount of mixture of ice and water again; after fully stirring, suction filtration, oven dry; recrystallization obtains corresponding N-phenyl-N '-pure product of (2-acetoxy benzoyl) thiocarbamide.
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
Acetylsalicylic acid and solid phosgene are placed flask according to the ratio of amount than 1.0: 1.0, add acetone and make solvent, drip N again, dinethylformamide is made catalyzer, at 60 ℃ of backflow 1.5h.After the cool to room temperature, more directly in flask the admixture quality be the ammonium thiocyanate of the porphyrize of 1.5 times of acetylsalicylic acid amounts, and add PEG-400 and make phase-transfer catalyst, stirring at room reaction 1.0h.At last to the 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), in flask, add an amount of mixture of ice and water again; after fully stirring, suction filtration, oven dry; recrystallization obtains corresponding N-phenyl-N '-pure product of (2-acetoxy benzoyl) thiocarbamide.
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
Acetylsalicylic acid and solid phosgene are placed flask according to the ratio of amount than 1.0: 1.0, add acetone and make solvent, drip N again, dinethylformamide is made catalyzer, at 60 ℃ of backflow 1.5h.After the cool to room temperature, more directly in flask the admixture quality be the ammonium thiocyanate of the porphyrize of 1.5 times of acetylsalicylic acid amounts, and add PEG-400 and make phase-transfer catalyst, stirring at room reaction 1.0h.The beta-naphthylamine that adds 0.9 times of acetylsalicylic acid amount at last to the flask the inside, stirring at room reaction 1.0h.After having reacted, at first on Rotary Evaporators, steam solvent acetone (recycling), in flask, add an amount of mixture of ice and water again; after fully stirring, suction filtration, oven dry; recrystallization obtains corresponding N-phenyl-N '-pure product of (2-acetoxy benzoyl) thiocarbamide.
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
Acetylsalicylic acid and solid phosgene are placed flask according to the ratio of amount than 1.0: 1.0, add acetone and make solvent, drip N again, dinethylformamide is made catalyzer, at 60 ℃ of backflow 1.5h.After the cool to room temperature, more directly in flask the admixture quality be the ammonium thiocyanate of the porphyrize of 1.5 times of acetylsalicylic acid amounts, and add PEG-400 and make phase-transfer catalyst, stirring at room reaction 1.0h.The p-Nitroaniline that adds 0.9 times of acetylsalicylic acid amount at last to the flask the inside, stirring at room reaction 1.0h.After having reacted, at first on Rotary Evaporators, steam solvent acetone (recycling), in flask, add an amount of mixture of ice and water again; after fully stirring, suction filtration, oven dry; recrystallization obtains corresponding N-phenyl-N '-pure product of (2-acetoxy benzoyl) thiocarbamide.
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
Acetylsalicylic acid and solid phosgene are placed flask according to the ratio of amount than 1.0: 1.0, add acetone and make solvent, drip N again, dinethylformamide is made catalyzer, at 60 ℃ of backflow 1.5h.After the cool to room temperature, more directly in flask the admixture quality be the ammonium thiocyanate of the porphyrize of 1.5 times of acetylsalicylic acid amounts, and add PEG-400 and make phase-transfer catalyst, stirring at room reaction 1.0h.The ORTHO ANISIDINE that adds 0.9 times of acetylsalicylic acid amount at last to the flask the inside, stirring at room reaction 1.0h.After having reacted, at first on Rotary Evaporators, steam solvent acetone (recycling), in flask, add an amount of mixture of ice and water again; after fully stirring, suction filtration, oven dry; recrystallization obtains corresponding N-phenyl-N '-pure product of (2-acetoxy benzoyl) thiocarbamide.
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
Acetylsalicylic acid and solid phosgene are placed flask according to the ratio of amount than 1.0: 1.0, add acetone and make solvent, drip N again, dinethylformamide is made catalyzer, at 60 ℃ of backflow 1.5h.After the cool to room temperature, more directly in flask the admixture quality be the ammonium thiocyanate of the porphyrize of 1.5 times of acetylsalicylic acid amounts, and add PEG-400 and make phase-transfer catalyst, stirring at room reaction 1.0h.The p-ethoxyaniline that adds 0.9 times of acetylsalicylic acid amount at last to the flask the inside, stirring at room reaction 1.0h.After having reacted, at first on Rotary Evaporators, steam solvent acetone (recycling), in flask, add an amount of mixture of ice and water again; after fully stirring, suction filtration, oven dry; recrystallization obtains corresponding N-phenyl-N '-pure product of (2-acetoxy benzoyl) thiocarbamide.
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
Acetylsalicylic acid and solid phosgene are placed flask according to the ratio of amount than 1.0: 1.0, add acetone and make solvent, drip N again, dinethylformamide is made catalyzer, at 60 ℃ of backflow 1.0h.After the cool to room temperature, more directly in flask the admixture quality be the ammonium thiocyanate of the porphyrize of 1.5 times of acetylsalicylic acid amounts, and add PEG-400 and make phase-transfer catalyst, stirring at room reaction 1.0h.The ortho-aminophenol that adds 0.9 times of acetylsalicylic acid amount at last to the flask the inside, stirring at room reaction 0.5h～2.0h.After having reacted, at first on Rotary Evaporators, steam solvent acetone (recycling), in flask, add an amount of mixture of ice and water again; after fully stirring, suction filtration, oven dry; recrystallization obtains corresponding N-phenyl-N '-pure product of (2-acetoxy benzoyl) thiocarbamide.
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
Acetylsalicylic acid and solid phosgene are placed flask according to the ratio of amount than 1.0: 1.0, add acetone and make solvent, drip N again, dinethylformamide is made catalyzer, at 60 ℃ of backflow 1.5h.After the cool to room temperature, more directly in flask the admixture quality be the ammonium thiocyanate of the porphyrize of 1.5 times of acetylsalicylic acid amounts, and add PEG-400 and make phase-transfer catalyst, stirring at room reaction 1.0h.At last to the 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), in flask, add an amount of mixture of ice and water again; after fully stirring, suction filtration, oven dry; recrystallization obtains corresponding N-phenyl-N '-pure product of (2-acetoxy benzoyl) thiocarbamide.
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
Acetylsalicylic acid and solid phosgene are placed flask according to the ratio of amount than 1.0: 1.0, add acetone and make solvent, drip N again, dinethylformamide is made catalyzer, at 60 ℃ of backflow 1.5h.After the cool to room temperature, more directly in flask the admixture quality be the ammonium thiocyanate of the porphyrize of 1.5 times of acetylsalicylic acid amounts, and add PEG-400 and make phase-transfer catalyst, stirring at room reaction 1.0h.At last to the 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), in flask, add an amount of mixture of ice and water again; after fully stirring, suction filtration, oven dry; recrystallization obtains corresponding N-phenyl-N '-pure product of (2-acetoxy benzoyl) thiocarbamide.
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
Acetylsalicylic acid and solid phosgene are placed flask according to the ratio of amount than 1.0: 1.0, add acetone and make solvent, drip N again, dinethylformamide is made catalyzer, at 60 ℃ of backflow 1.5h.After the cool to room temperature, more directly in flask the admixture quality be the ammonium thiocyanate of the porphyrize of 1.5 times of acetylsalicylic acid amounts, and add PEG-400 and make phase-transfer catalyst, stirring at room reaction 1.0h.The p-Chlorobenzoic acid amide that adds 0.9 times of acetylsalicylic acid amount at last to the flask the inside, stirring at room reaction 1.0h.After having reacted, at first on Rotary Evaporators, steam solvent acetone (recycling), in flask, add an amount of mixture of ice and water again; after fully stirring, suction filtration, oven dry; recrystallization obtains corresponding N-phenyl-N '-pure product of (2-acetoxy benzoyl) thiocarbamide.
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 (6)
1.N-phenyl-N '-(2-acetoxy benzoyl) thiourea derivative, its structure is as follows:
Wherein R=H, o-CH
3, m-CH
3, p-OCH
3, β-Naphthyl, p-NO
2, o-OCH
3, p-OCH
2CH
3, o-OH, m-OH, p-OH or p-Cl.
2. the preparation method of N-phenyl-N '-(2-acetoxy benzoyl) thiourea derivative according to claim 1 may further comprise the steps:
With acetone is solvent, and with N, dinethylformamide is a catalyzer, with acetylsalicylic acid and solid phosgene according to 1.0: 0.5～1.0: 2.0 mol ratio at 40～80 ℃ of following 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 1.0: 1.0～1.0: 2.0 mol ratio; normal-temperature reaction 0.5～2.0h obtains intermediate 2-acetoxy benzoyl lsothiocyanates, does not separate.
Directly add aromatic amine according to acetyl salicylyl acid and aromatic amine with 1.0: 0.8～1.0: 1.0 mol ratio at last; stirring at room reaction 0.5～2.0h; steam solvent; in reaction vessels, add mixture of ice and water again; suction filtration gets solid after fully stirring; oven dry, recrystallization obtains N-phenyl-N '-(2-acetoxy benzoyl) thiocarbamide.
3. as the preparation method of N-phenyl-N '-(2-acetoxy benzoyl) thiourea derivative as described in the claim 2, it is characterized in that: described arylamine is aniline, o-toluidine, a monomethylaniline, any in monomethylaniline, beta-naphthylamine, p-Nitroaniline, ORTHO ANISIDINE, p-ethoxyaniline, ortho-aminophenol, a hydroxyanilines, para hydroxybenzene amine, the p-Chlorobenzoic acid amide.
4. as the preparation method of N-phenyl-N '-(2-acetoxy benzoyl) thiourea derivative as described in the claim 2, it is characterized in that: described catalyst n, the consumption of dinethylformamide are 1.2～1.4% of solid phosgene quality.
5. as the preparation method of N-phenyl-N '-(2-acetoxy benzoyl) thiourea derivative as described in the claim 2, it is characterized in that: the consumption of described phase-transfer catalyst PEG-400 is 0.2～0.5% of an ammonium thiocyanate quality.
According to claim 1 N-phenyl-N '-(2-acetoxy benzoyl) thiourea derivative as the application of crop growth conditioning agent.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102093274A (en) * | 2010-12-23 | 2011-06-15 | 西北师范大学 | Chalcone-containing acylthiourea compounds and preparation method and use thereof |
| CN102101846A (en) * | 2010-12-06 | 2011-06-22 | 张家港田由新材料科技有限公司 | Preparation method of thiazole thiourea derivatives |
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| 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 |
| CN110911749A (en) * | 2019-12-03 | 2020-03-24 | 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 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102101846A (en) * | 2010-12-06 | 2011-06-22 | 张家港田由新材料科技有限公司 | 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 |
| CN102207455A (en) * | 2011-04-02 | 2011-10-05 | 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 |
| CN110911749A (en) * | 2019-12-03 | 2020-03-24 | 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 |
| 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 |
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