CN103214386B - New method for synthesizing amide compounds - Google Patents
New method for synthesizing amide compounds Download PDFInfo
- Publication number
- CN103214386B CN103214386B CN201210516266.2A CN201210516266A CN103214386B CN 103214386 B CN103214386 B CN 103214386B CN 201210516266 A CN201210516266 A CN 201210516266A CN 103214386 B CN103214386 B CN 103214386B
- Authority
- CN
- China
- Prior art keywords
- water
- ethanol
- add
- reaction
- acetonitrile
- 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 relates to a method for synthesizing amide compounds. A nitro compound and aldehyde (mole ratio is 1:1-1.6) are used as reaction substrates, zinc dust (mole ratio of the zinc dust to the nitro compound is 2-4:1) is used as a catalyst and a reducing agent, acetate or ammonium chloride (mole ratio of the acetate or the ammonium chloride to the nitro compound is 8-2:1) is used as a reaction medium, and methanol, ethanol, acetonitrile, water, methanol/water, ethanol/water and acetonitrile/water are respectively used as solvents. The nitro compound is reduced to synthesizing amide by a one-kettle way under 20-70 DED C for 0.5-5h by stirring. The method of the invention has advantages of short reaction line, simple operation, mild condition, green and environmental protection, and has important meanings on amide bond formation research in organic chemistry, synthesis research of peptide medicaments, and amide bond formation research in pesticide synthesis.
Description
Technical field
The present invention relates to the synthetic method of a compounds, specifically, relate to the synthetic method of amides, in particular, relate to the formation of amido linkage.
Background technology
The formation of amido linkage has had ripe method very early, but now people, still in unremitting effort, make great progress, and have found all kinds of catalyzer such as many metals, makes the formation of amido linkage more and more simpler, high efficiency.
Along with the proposition of Green Chemistry theory, give chemist with new direction, for the formation of amido linkage, green synthetic theory is also proposed, the present invention also meets green method.
Secondly, amides pesticide is the grow a lot agricultural chemicals of potentiality of a class tool, it relates to amides sterilant, acid amide fungicides and acetamide-group herbicides, and in the agricultural chemicals of other kind synthesizes, often also can relate to the formation of amido linkage, the research therefore forming for amido linkage is significant.
Finally, protein is the important substance of vital movement, in biological vital movement, plays an important role.If the chemical nature majority of enzyme is protein; Protein is the important component of living organism tissue; Mammals breathes the essential substance oxyphorase that starts shipment on oxygen therapy.Protein is mainly made up of amino acid, amino acid is by a series of reaction synthetic peptide, there is carboxyl and amino condensation reaction and generate amido linkage, peptide obtains having bioactive protein through a series of activation in biological tissue, therefore synthetic significant for peptide for the formation research of amido linkage.And peptide medicament development now rapidly, has broad prospects for the research of the diseases such as tumour, the formation research of amido linkage is also significant for this.
Summary of the invention
The object of this technology is to overcome the deficiency in traditional amido linkage formation method, and taking nitro-compound as substrate, with aldehyde compound, select suitable catalyzer, reaction medium and solvent, with gentle condition, simple operation, " one kettle way " obtains amides.
Concrete summary of the invention is as follows:
One,
(1) reaction formula:
Catalyzer: zinc powder (Zn);
Reaction medium: acetic acid (HOAc) or ammonium chloride (NH
4cl);
Temperature: 20-70 DEG C;
Organic solvent: methyl alcohol, ethanol, acetonitrile, water, methanol/water, ethanol/water, acetonitrile/water.
(2) operation steps:
1,, taking acetic acid as reaction medium, methyl alcohol (ethanol or acetonitrile or water) is solvent:
Take a certain amount of nitro-compound and be dissolved in ethanol (methyl alcohol, acetonitrile or water), water-bath temperature control stirring, add successively aldehyde, zinc powder, acetic acid, stirring reaction, TLC detection reaction process, question response finishes, the termination reaction that adds water, suction filtration, in filter cake, add ethyl acetate, filtrate is extracted with ethyl acetate, combined ethyl acetate, with saturated common salt washing, anhydrous sodium sulfate drying, concentrated, with ethyl acetate or ethanol or acetone recrystallization, suction filtration obtains solid.
2,, taking acetic acid as reaction medium, methanol/water (ethanol/water or acetonitrile/water) is solvent:
Take a certain amount of nitro-compound and be dissolved in methyl alcohol (ethanol, acetonitrile), add water to without solid and separate out, water-bath temperature control stirring, adds aldehyde, zinc powder, acetic acid, stirring reaction successively, TLC detection reaction process, question response finishes, and termination reaction adds water, suction filtration adds ethyl acetate in filter cake, and filtrate is extracted with ethyl acetate, combined ethyl acetate, with saturated common salt washing, anhydrous sodium sulfate drying, concentrated, with ethyl acetate or ethanol or acetone recrystallization, suction filtration obtains solid.
3, taking ammonium chloride as reaction medium:
Take a certain amount of nitro-compound and be dissolved in ethanol (methyl alcohol, acetonitrile), add ammonium chloride, add water to completely and dissolve without solid and separate out, water-bath temperature control stirring, then add successively aldehyde, zinc powder, stirring reaction, TLC detection reaction process, question response finishes, and termination reaction adds water, suction filtration adds ethyl acetate in filter cake, and filtrate is extracted with ethyl acetate, combined ethyl acetate, with saturated common salt washing, anhydrous sodium sulfate drying, concentrated, with ethyl acetate or ethanol or acetone recrystallization, suction filtration obtains solid.
Two
(1) reaction formula:
Catalyzer: zinc powder (Zn);
Reaction medium: acetic acid (HOAc) or ammonium chloride (NH
4cl);
Temperature: 20-70 DEG C;
Organic solvent: methyl alcohol, ethanol, acetonitrile, water, methanol/water, ethanol/water, acetonitrile/water.
(2) operation steps
1,, taking acetic acid as reaction medium, methyl alcohol (ethanol or acetonitrile or water) is solvent:
Take a certain amount of nitro-compound and be dissolved in ethanol (methyl alcohol, acetonitrile or water), water-bath temperature control stirring, add successively aldehyde, zinc powder, acetic acid, stirring reaction, TLC detection reaction process, question response finishes, the termination reaction that adds water, suction filtration, in filter cake, add ethyl acetate, filtrate is extracted with ethyl acetate, combined ethyl acetate, with saturated common salt washing, anhydrous sodium sulfate drying, concentrated, with ethyl acetate or ethanol or acetone recrystallization, suction filtration obtains solid.
2,, taking acetic acid as reaction medium, methanol/water (ethanol/water or acetonitrile/water) is solvent:
Take a certain amount of nitro-compound and be dissolved in methyl alcohol (ethanol, acetonitrile), add water to without solid and separate out, water-bath temperature control stirring, adds aldehyde, zinc powder, acetic acid, stirring reaction successively, TLC detection reaction process, question response finishes, and termination reaction adds water, suction filtration adds ethyl acetate in filter cake, and filtrate is extracted with ethyl acetate, combined ethyl acetate, with saturated common salt washing, anhydrous sodium sulfate drying, concentrated, with ethyl acetate or ethanol or acetone recrystallization, suction filtration obtains solid.
3, taking ammonium chloride as reaction medium:
Take a certain amount of nitro-compound and be dissolved in ethanol (methyl alcohol, acetonitrile), add ammonium chloride, add water to completely and dissolve without solid and separate out, water-bath temperature control stirring, then add successively aldehyde, zinc powder, stirring reaction, TLC detection reaction process, question response finishes, and termination reaction adds water, suction filtration adds ethyl acetate in filter cake, and filtrate is extracted with ethyl acetate, combined ethyl acetate, with saturated common salt washing, anhydrous sodium sulfate drying, concentrated, with ethyl acetate or ethanol or acetone recrystallization, suction filtration obtains solid.
Three
(1) reaction formula:
Catalyzer: zinc powder (Zn);
Reaction medium: acetic acid (HOAc) or ammonium chloride (NH
4cl);
Temperature: 20-70 DEG C;
Organic solvent: methyl alcohol, ethanol, acetonitrile, water, methanol/water, ethanol/water, acetonitrile/water.
(2) operation steps
1,, taking acetic acid as reaction medium, methyl alcohol (ethanol or acetonitrile or water) is solvent:
Taking a certain amount of nitro-compound is dissolved in ethanol (methyl alcohol, acetonitrile, water), water-bath temperature control stirring, adds aldehyde, zinc powder, acetic acid, stirring reaction successively, TLC detection reaction process, question response finishes, and termination reaction adds water, suction filtration adds ethyl acetate in filter cake, and filtrate is extracted with ethyl acetate, combined ethyl acetate, with saturated common salt washing, anhydrous sodium sulfate drying, concentrated, with ethyl acetate or ethanol or acetone recrystallization, suction filtration obtains solid.
2,, taking acetic acid as reaction medium, methanol/water (ethanol/water or acetonitrile/water) is solvent:
Take a certain amount of nitro-compound and be dissolved in methyl alcohol (ethanol, acetonitrile), add water to without solid and separate out, water-bath temperature control stirring, adds aldehyde, zinc powder, acetic acid, stirring reaction successively, TLC detection reaction process, question response finishes, and termination reaction adds water, suction filtration adds ethyl acetate in filter cake, and filtrate is extracted with ethyl acetate, combined ethyl acetate, with saturated common salt washing, anhydrous sodium sulfate drying, concentrated, with ethyl acetate or ethanol or acetone recrystallization, suction filtration obtains solid.
3, taking ammonium chloride as reaction medium:
Take a certain amount of nitro-compound and be dissolved in ethanol (methyl alcohol, acetonitrile), add ammonium chloride, add water to completely and dissolve without solid and separate out, water-bath temperature control stirring, then add successively aldehyde, zinc powder, stirring reaction, TLC detection reaction process, question response finishes, and termination reaction adds water, suction filtration adds ethyl acetate in filter cake, and filtrate is extracted with ethyl acetate, combined ethyl acetate, with saturated common salt washing, anhydrous sodium sulfate drying, concentrated, with ethyl acetate or ethanol or acetone recrystallization, suction filtration obtains solid.
embodiment
With specific embodiment, technical scheme of the present invention is described below, but protection scope of the present invention is not limited to this:
Embodiment 1
Taking 2.0 g(14.6 mmol) para-nitrotoluene is dissolved in 25.0 mL ethanol, 35 DEG C of stirring in water bath, add successively 1.9 g(17.5 mmol) phenyl aldehyde, 3.8 g(58.3 mmol) zinc powder, 7.0 g(6.7 mL, 116.6mmol) acetic acid, stirring reaction 0.5 h, TLC detection reaction process, question response finishes, add 50 mL water termination reactions, suction filtration, filtrate extracts with 30 mL × 3 EtOAc, in filter cake, add 40 mL EtOAc, merge EtOAc, to washing with saturated common salt, anhydrous sodium sulfate drying, concentrated, with EtOAc or EtOH or acetone recrystallization, it is N-(4-aminomethyl phenyl) benzamide that suction filtration obtains white needles solid, fusing point 126-127 DEG C.
1HNMR(CDCl
3）δ:8.3-8.4(dd,2H),7.9(s,1H),7.66-7.68(d,2H),7.45-7.49(m,3H),
7.25-7.27(d,2H),2.4(s,3H)。
Embodiment 2
Taking 2.0 g(14.6 mmol) para-nitrotoluene is dissolved in 25.0 mL ethanol, add 0.78 g ammonium chloride, be placed in 35 DEG C of stirring in water bath, dripping distilled water to solid just dissolves, add successively 2.5 g(17.5 mmol) 4-chloro-benzaldehyde, 3.8 g(58.3 mmol) zinc powder, stirring reaction 0.5 h, add 50 mL water termination reactions, suction filtration, filtrate extracts with 30 mL × 3 EtOAc, in filter cake, add 40 mL EtOAc to dissolve, merge EtOAc, wash with saturated common salt, anhydrous sodium sulfate drying, concentrated, use EtOAc recrystallization, it is that N-(4-aminomethyl phenyl) is to chlorobenzamide that suction filtration obtains white solid, fusing point 165-166 DEG C.
1HNMR(CDCl
3）δ:8.3-8.4(d,2H),7.9(s,1H),7.64-7.66(d,2H),7.43-7.45(d,2H),7.26-7.28(d,2H),2.4(s,3H)。
Embodiment 3
Taking 2.0 g(14.6 mmol) para-nitrotoluene is dissolved in 25.0 mL ethanol, add 0.78 g ammonium chloride, be placed in 35 DEG C of stirring in water bath, dripping distilled water to solid just dissolves, add successively 2.14 g(17.5 mmol) p-Hydroxybenzaldehyde, 3.8 g(58.3 mmol) zinc powder, stirring reaction 0.5 h, add 50 mL water termination reactions, suction filtration, filtrate extracts with 30 mL × 3 EtOAc, in filter cake, add 40 mL EtOAc to dissolve, merge EtOAc, wash with saturated common salt, anhydrous sodium sulfate drying, concentrated, use EtOAc recrystallization, it is that N-(4-aminomethyl phenyl) is to chlorobenzamide that suction filtration obtains white solid, fusing point 95.0-95.5 DEG C.
1HNMR(CDCl
3）δ:13.4(s,1H),8.6(s,1H),7.3-7.4(m,2H),7.18-7.25(m,4H),7.0-7.1(d,1H),6.91-6.95(t,1H),3.08(s,3H)。
Embodiment 4
Taking 2.0 g(12.7 mmol) parachloronitrobenzene is dissolved in 15.0 mL ethanol, be placed in 35 DEG C of stirring in water bath, 10 mL add water, separate out without solid, add successively 1.6 g(15.3 mmol) phenyl aldehyde, 3.3 g(50.8 mmol) zinc powder, 1.5 g(25.4 mmol) HOAc, stirring reaction 0.5 h, add 50 mL water, suction filtration, filtrate extracts with 30 mL × 3 EtOAc, in filter cake, add 40 mL EtOAc to dissolve, merge EtOAc, wash with saturated common salt, anhydrous sodium sulfate drying, concentrated, use EtOAc recrystallization, it is N-(4-chloro-phenyl-) benzamide that suction filtration obtains white solid, fusing point 199-200 DEG C.
1HNMR(CDCl
3）δ:8.3-8.4(m,2H),7.9(s,1H),7.72-7.76(m,2H),7.44-7.50(m,5H)。
Embodiment 5
Taking 2.0 g(14.6 mmol) para-nitrotoluene is dissolved in 25.0 mL ethanol, be placed in 35 DEG C of stirring in water bath, add successively 2.2 g(17.5 mmol) p-Fluorobenzenecarboxaldehyde, 3.8 g(58.4 mmol) zinc powder, 1.8 g(29.2 mmol) HOAc, stirring reaction 0.5 h, add 50 mL water, suction filtration, filtrate extracts with 30 mL × 3 EtOAc, in filter cake, add 40 mL EtOAc to dissolve, merge EtOAc, wash with saturated common salt, anhydrous sodium sulfate drying, concentrated, use EtOAc recrystallization, it is that N-(4-aminomethyl phenyl) is to fluorobenzamide that suction filtration obtains white solid, fusing point 155-156 DEG C.1HNMR(CDCl3）δ:8.44-8.49(m,2H),7.9(s,1H),7.66-7.91(d,2H),7.28-7.31(d,2H),7.16-7.21(m,2H),2.45(s,3H)。
Embodiment 6
Taking 1.0 g(6.5 mmol) p-Nitromethoxybenzene is dissolved in 15.0 mL methyl alcohol, be placed in 35 DEG C of stirring in water bath, add successively 1.1 g(7.8 mmol) 4-chloro-benzaldehyde, 1.7 g(26.0 mmol) zinc powder, 0.78 g(13.0 mmol) HOAc, stirring reaction 0.5 h, add 30 mL water, suction filtration, filtrate extracts with 15 mL × 3 EtOAc, in filter cake, add 20 mL EtOAc to dissolve, merge EtOAc, wash with saturated common salt, anhydrous sodium sulfate drying, concentrated, use EtOAc recrystallization, it is that N-(4-p-methoxy-phenyl) is to chlorobenzamide that suction filtration obtains white solid, fusing point 187.2-187.3 DEG C.
1HNMR(CDCl
3）δ:8.32-8.36(m,2H),7.86(s,1H),7.70-7.74(m,2H),7.42-7.46(m,2H),6.94-6.99(m,2H),3.87(s,3H)。
Embodiment 7
Taking 2.0 g(10.3 mmol) ethyl p-nitrobenzoate is dissolved in 15.0 mL methyl alcohol, be placed in 35 DEG C of stirring in water bath, add 5 mL water, add successively 2.0 g(14.3 mmol) 4-chloro-benzaldehyde, 2.7 g(41.0 mmol) zinc powder, 1.2 g(20.5 mmol) HOAc, stirring reaction 0.5 h, add 40 mL water, suction filtration, filtrate extracts with 20 mL × 3 EtOAc, in filter cake, add 30 mL EtOAc to dissolve, merge EtOAc, wash with saturated common salt, anhydrous sodium sulfate drying, concentrated, use EtOAc recrystallization, it is that N-(4-acetyl oxygen carbonyl phenyl) is to chlorobenzamide that suction filtration obtains white solid, fusing point 199-200 DEG C.
1HNMR(CDCl3）δ:8.37-8.39(d,2H),8.16-8.19(d,2H),7.96(s,1H),7.84-7.87(d,2H),7.46-7.48(d,2H),4.395-4.449(m,2H),1.41-1.45(t,3H)。
Embodiment 8
Taking 2.0 g(12.0 mmol) p-nitroacetophenone is dissolved in 25.0 mL methyl alcohol, be placed in 35 DEG C of stirring in water bath, add successively 1.8 g(16.8 mmol) phenyl aldehyde, 3.1 g(48.0 mmol) zinc powder, 1.4 g(24.0 mmol) HOAc, stirring reaction 0.5 h, add 50 mL water, suction filtration, filtrate extracts with 30 mL × 3 EtOAc, in filter cake, add 30 mL EtOAc to dissolve, merge EtOAc, wash with saturated common salt, anhydrous sodium sulfate drying, concentrated, use EtOAc recrystallization, it is that N-(4-acetyl oxygen carbonyl phenyl) is to chlorobenzamide that suction filtration obtains white solid, fusing point 180-181 DEG C.
1HNMR(CDCl3）δ:8.40-8.44(m,2H),8.07-8.11(m,2H),7.98(s,1H),7.89-7.92(m,2H),7.50-7.53(m,3H),2.66(s,3H)。
Embodiment 9
Taking 1.0 g(6.5 mmol) p-Nitromethoxybenzene is dissolved in 15.0 mL acetonitriles, be placed in 35 DEG C of stirring in water bath, add 5 mL water, add successively 0.56 g(7.8 mmol) butyraldehyde, 1.7 g(26.0 mmol) zinc powder, 0.78 g(13.0 mmol) HOAc, stirring reaction 0.5 h, add 30 mL water, suction filtration, filtrate extracts with 30 mL × 3 EtOAc, in filter cake, add 30 mL EtOAc to dissolve, merge EtOAc, wash with saturated common salt, anhydrous sodium sulfate drying, concentrated, use EtOAc recrystallization, it is that N-(4-acetyl oxygen carbonyl phenyl) is to chlorobenzamide that suction filtration obtains white solid, fusing point 87-88 DEG C.
1HNMR(CDCl
3）δ:7.48-7.52(d,2H),7.23(s,1H),6.95-7.00(d,2H),3.83(s,3H),2.33-2.45(m,2H),1.7-1.8(m,2H),0.9-1.0(t,3H)。
Claims (5)
1. taking nitro-compound and aldehyde as a synthetic method for starting raw material synthesizing amide, it is characterized in that nitro-compound one step obtains acid amides, synthetic route is as follows:
Adopt zinc powder as reductive agent and catalyzer, and the amount of substance of zinc powder and nitro-compound is than being 2-4:1, using acetic acid or ammonium chloride as reaction medium, and acetic acid or ammonium chloride with the amount of substance of nitro-compound than being 1-2:1.
2. synthetic method according to claim 1, is characterized in that zinc powder and the amount of substance ratio of nitro-compound are 4:1.
3. synthetic method according to claim 1, is characterized in that acetic acid or ammonium chloride and the amount of substance ratio of nitro-compound are 2:1.
4. synthetic method according to claim 1, is characterized in that temperature of reaction is 20-70 DEG C, reaction conditions gentleness.
5. synthetic method according to claim 1, is characterized in that solvent is selected from methyl alcohol, ethanol, acetonitrile, methanol/water, ethanol/water and acetonitrile/water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210516266.2A CN103214386B (en) | 2012-12-06 | 2012-12-06 | New method for synthesizing amide compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210516266.2A CN103214386B (en) | 2012-12-06 | 2012-12-06 | New method for synthesizing amide compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103214386A CN103214386A (en) | 2013-07-24 |
| CN103214386B true CN103214386B (en) | 2014-08-13 |
Family
ID=48812606
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210516266.2A Expired - Fee Related CN103214386B (en) | 2012-12-06 | 2012-12-06 | New method for synthesizing amide compounds |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103214386B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107652200B (en) * | 2017-09-07 | 2019-06-14 | 陕西科技大学 | A method of N- aryl Zhong Fang amide is synthesized using aryl hydrazine |
| CN112300020B (en) * | 2019-11-28 | 2023-04-25 | 陕西师范大学 | Method for synthesizing amide derivative by vanadium catalysis |
-
2012
- 2012-12-06 CN CN201210516266.2A patent/CN103214386B/en not_active Expired - Fee Related
Non-Patent Citations (6)
| Title |
|---|
| Chemische Lichtwirkungen;Giacomo Ciamocian et al.;《Berichte der deutschen chemischen Gesellschaft》;19050228;第38卷(第1期);第1176-1184页 * |
| Electron transfer reactions. Reaction of nitrones with potassium;KONDAA SHOKA et al.;《CAN. J. CHEM.》;19871231;第65卷;第2039-2049页 * |
| Giacomo Ciamocian et al..Chemische Lichtwirkungen.《Berichte der deutschen chemischen Gesellschaft》.1905,第38卷(第1期),第1176-1184页. |
| J. CASTELLS et al..OXIDATIVE BENZOIN REACTIONS.《Tetrahedron》.1982,第38卷(第3期),第337-346页. |
| KONDAA SHOKA et al..Electron transfer reactions. Reaction of nitrones with potassium.《CAN. J. CHEM.》.1987,第65卷第2039-2049页. |
| OXIDATIVE BENZOIN REACTIONS;J. CASTELLS et al.;《Tetrahedron》;19821231;第38卷(第3期);第337-346页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103214386A (en) | 2013-07-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8394961B2 (en) | Method for the preparation of dabigatran | |
| CN103232431B (en) | Dihalogenated pyrazole amide compound and its use | |
| CN102020633B (en) | Method for preparing 1-(3,5- dichloropyridine-2-yl)-pyrazolecarboxamide compounds | |
| CN103788083A (en) | Method for preparing herbicide topramezone | |
| CN103214386B (en) | New method for synthesizing amide compounds | |
| CN108689950B (en) | [ (6-substituted-pyrimidin-4-yloxy) phenyl ] -3-methoxyacrylate methyl ester | |
| RU2649000C2 (en) | Method of producing some 2-(pyridin-3-yl)thiazoles | |
| JPH08134048A (en) | Production of oxazolines | |
| CN104292166B (en) | The chloro-2-cyano group of 4--N, N-dimethyl-5-p-methylphenyl imidazoles-1-sulphonamide synthetic method | |
| CN105198801A (en) | N-(4-chloro-3-picolyl)-2-(3-methylbenzamide) benzamide as well as preparation method and application thereof | |
| CN103059010A (en) | 1,4-benzoxazinone-1,2,3-triazole compound having antifungal activity, and its preparation method | |
| EP4232442A1 (en) | A process for the preparation of chlorantraniliprole | |
| CN107935929A (en) | 3 trifluoromethyl 1H pyrazoles of a kind of 1 methyl, 4 amide derivatives and preparation method and application | |
| JP5192637B2 (en) | Difluorobenzo- [1,3] -dioxole | |
| CN104086345B (en) | A kind of Pt nanowires catalyzes and synthesizes the method for amides | |
| JP3870647B2 (en) | Process for producing optically active α-hydroxy ketones | |
| JP2575823B2 (en) | Method for producing α-aminoacetonitrile hydrochlorides | |
| KR101339757B1 (en) | Process for the preparation of 2-aminoazoles using metal catalyst, oxidant and acid | |
| JP2692923B2 (en) | Process for producing imidazolidone derivative | |
| CN106977493A (en) | A kind of thiophene derivant and its synthetic method | |
| KR102051523B1 (en) | Synthetic method of tetrahydroisoquinoline derivatives | |
| CN107739322B (en) | Synthetic method of sulfonamide compound | |
| US20230312508A1 (en) | Improved process for preparation of anthranilamides | |
| CN106220633A (en) | 1,2,4 triazole derivatives of a kind of chloride benzopyrazines structure are as the application of antibacterial | |
| CN105777713A (en) | N-(2-pyridyl)-2-(2,4-dimethyl parazole formamido) benzamide as well as preparation thereof and use thereof |
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: 20140813 Termination date: 20141206 |
|
| EXPY | Termination of patent right or utility model |