CN1193988C - Preparation of 2-aryl-5-(trifluoride) pyrrole-3-nitrile and its use and preparation of its intermediate thereof - Google Patents
Preparation of 2-aryl-5-(trifluoride) pyrrole-3-nitrile and its use and preparation of its intermediate thereof Download PDFInfo
- Publication number
- CN1193988C CN1193988C CN 03112978 CN03112978A CN1193988C CN 1193988 C CN1193988 C CN 1193988C CN 03112978 CN03112978 CN 03112978 CN 03112978 A CN03112978 A CN 03112978A CN 1193988 C CN1193988 C CN 1193988C
- Authority
- CN
- China
- Prior art keywords
- aryl
- nitrile
- trifluoromethyl
- formula
- compound
- 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
- Pyrrole Compounds (AREA)
Abstract
The present invention relates to a method for preparing 2-aryl-5-(trifluoromethyl)pyrrole-3-nitrile, the application thereof and a method for preparing an intermediate product of 2-aryl-5-(trifluoromethyl)pyrrole-3-nitrile. The method comprises: alpha-aryl amino acid reacts with at least one mole equivalent of trifluoroacetic acid and an acylchlorating reagent under the action of organic solvent to form a trifluoroacetyl derivative of alpha-aryl amino acid; the trifluoroacetyl derivative of the alpha-aryl amino acid reacts with at least one mole equivalent of 2-halogenated acrylonitrile under the action of alkali, organic solvent and an acylchlorating reagent or acid anhydride to form a 2-aryl-5-(trifluoromethyl)pyrrole-3-nitrile compound; or a trifluoroacetyl derivative of the alpha-aryl amino acid directly reacts with at least one mole equivalent of 2-halogenated acrylonitril under the action of alkali, organic solvent and an acylchlorating reagent or acid anhydride to form a 2-aryl-5-(trifluoromethyl)pyrrole-3-nitrile compound, wherein the alpha-aryl trifluoroacetyl amino acid compound is prepared by that alpha-aryl amino acid is treated with trifluoroacetylation by using at least one mole equivalent of trifluoroacetic acid and an acylchlorating reagent under the action of organic solvent.
Description
Technical field
The present invention relates to preparation method and its application and the intermediates preparation that is used to prepare 2-aryl-5-(trifluoromethyl) pyrroles-3-nitrile of 2-aryl-5-(trifluoromethyl) pyrroles-3-nitrile.
Background technology
Aryl-pyrrolidine nitrile and derivative thereof be effective insecticidal, kill mite and invertebrate poison, especially 2-aryl 5-(trifluoromethyl) pyrroles-3-nitrile and derivative high-efficiency broad spectrum thereof, as 4-bromo-2-(rubigan)-1-(ethoxymethyl)-5-(trifluoromethyl) pyrroles-3-nitrile, be bromothalonil (chlorfenapyr), rise the insecticidal/acaricidal agent of sending out by American Cyanamid Company and come into the market for many years.About the preparation of this compounds and relevant intermediate, existing many patented methods, but also undesirable aspect validity and economy.
Summary of the invention
The purpose of this invention is to provide from the acid of alpha-aromatic trifluoroacetamido the more efficient methods of preparation 2-aryl-5-(trifluoromethyl) pyrroles-3-nitrile compound.
Another object of the present invention provides from alpha-aromatic amino acid, the method for the more convenient economy of preparation alpha-aromatic trifluoroacetamido acid.
Further aim of the present invention is to describe the application of above-claimed cpd aspect the agent of production arylpyrrole insecticidal.
Technical solution of the present invention:
A kind of preparation has the method for 2-aryl-5-(trifluoromethyl) pyrroles-3-nitrile compound of structural formula II I feature
Wherein A is hydrogen, C
1-C
4The C that alkyl, aryl, halogenated aryl or aryl replace
1-C
4Alkyl; R and L are independently hydrogen or halogen, C separately
1-C
4Alkyl or C
1-C
4Alkoxyl group; This method comprises:
A. with the alpha-aromatic amino acid of structural formula I
A wherein, the definition of R and L is the same, reacts in the presence of organic solvent with the trifluoracetic acid and the chloride reagent of at least 1 molar equivalent, forms the amino acid whose trifluoroacetyl derivative of alpha-aromatic of formula (II),
B. the 2-propylene halide nitrile of formula (II) compound and at least 1 molar equivalent reacts in the presence of alkali and organic solvent and chloride reagent or acid anhydrides, forms 2-aryl-5-(trifluoromethyl) pyrroles-3-nitrile compound of formula (III) structure.When selecting acid anhydrides for use, A is a hydrogen.
A kind of preparation has the method for 2-aryl-5-(trifluoromethyl) pyrroles-3-nitrile compound of structural formula (III) feature
A wherein, the definition of R and L is the same, it is characterized in that having the compound of formula (II) structure
A wherein, the definition of R and L is the same, with the 2-propylene halide nitrile of at least 1 molar equivalent, reacts in the presence of alkali and organic solvent and chloride reagent or acid anhydrides, forms 2-aryl-5-(trifluoromethyl) pyrroles-3-nitrile compound of formula (III) structure.When selecting acid anhydrides for use, A is a hydrogen.
A kind of preparation has the method for the alpha-aromatic trifluoroacetamido acid compound of structural formula (II),
A wherein, the definition of R and L is the same, and this method feature is with the trifluoracetic acid of 1 molar equivalent and chloride reagent to make the alpha-aromatic amino acid trifluoroacetylation of formula (I) structure at least in the presence of organic solvent,
A wherein, the definition of R and L is the same.
A kind of application with 2-aryl 5-(trifluoromethyl) pyrroles-3-nitrile compound of structural formula (III) is characterized in that it is used to prepare formula (IV) aryl-pyrrole compound with Insecticiding-miticiding effect,
Wherein the definition of R and L is the same; X is a chlorine or bromine; R
1Be C
1-C
6Alkyl; This method is 2-aryl-5-(trifluoromethyl) pyrroles-3-nitrile compound with formula (III),
Wherein A is a hydrogen, the definition of R and L is the same, in the presence of solvent and acid binding agent, halogen with at least 1 molar equivalent carries out ring bromination or chlorination, form 2-aryl 4-halo-5-(trifluoromethyl) pyrroles-3-nitrile intermediate, further in the presence of the alkalimetal hydride of at least 1 molar equivalent, with monochloromethyl C
1-C
6The alkyl oxide reaction makes 2-aryl-4-halo-1-(alkoxy methyl)-5-(trifluoromethyl) pyrroles-3-nitrile compound of formula (IV).
The inventive method technology is simple, and cost is low, and yield height, its preparation method are compared more effective more economical with the traditional preparation process method, and wide application.
Embodiment
The present invention relates to prepare the method for 2-aryl-5-(trifluoromethyl) pyrroles-3-nitrile compound of following formula (III)
Wherein A is a hydrogen, C
1-C
4Alkyl, aryl, halogenated aryl, or the C of aryl replacement
1-C
4Alkyl; R and L are hydrogen or halogen independently separately, C
1-C
4Alkyl or C
1-C
4Alkoxyl group; This method comprises the alpha-aromatic amino acid with formula (I) structure
A wherein, the definition of R and L is the same, reacts in the presence of organic solvent with the trifluoracetic acid and the chloride reagent of at least 1 molar equivalent, makes the alpha-aromatic trifluoroacetamido acid intermediate of formula (II).
The 2-propylene halide nitrile of formula (II) compound and at least 1 molar equivalent reacts in the presence of alkali and organic solvent and chloride reagent or acid anhydrides, makes 2-aryl-5-(trifluoromethyl) pyrroles-3-nitrile compound of formula (III) structure.When selecting acid anhydrides for use, A is a hydrogen.
The present invention also provides the preparation method of the alpha-aromatic trifluoroacetamido acid of formula (II)
A wherein, the definition of R and L is the same.
In addition, the present invention has also described formula (IV) and has had production method by the aryl-pyrrole compound of Insecticiding-miticiding effect
Wherein the definition of R and L is the same; X is a chlorine or bromine; R
1Be C
1-C
6Alkyl; This method is 2-aryl-5-(trifluoromethyl) pyrroles-3-nitrile compound with formula (III)
Wherein A is a hydrogen, the definition of R and L is the same, in the presence of solvent and acid binding agent, halogen with at least 1 molar equivalent carries out ring bromination or chlorination, form 2-aryl-4 halos-5-(trifluoromethyl) pyrroles-3-nitrile intermediate, further in the presence of the alkalimetal hydride of at least 1 molar equivalent, with monochloromethyl C
1-C
6The alkyl oxide reaction makes 2-aryl-4-halo-1-(alkoxy methyl)-5-(trifluoromethyl) pyrroles-3-nitrile compound of formula (IV).
Method of the present invention can be illustrated with following equation I:
Equation I:
A wherein, R, the definition of L and X is the same.
It is trifluoroacetylation reagent (US5118816, CN1035669C etc.) that the method for the alpha-aromatic trifluoroacetamido acid of present known preparation formula (II) adopts trifluoroacetic anhydride (TFAA) or ethyltrifluoroacetate.U.S. Pat 5144041 has disclosed the method that is similar to 2-aryl-5-(trifluoromethyl) pyrroles 3-nitrile compound (wherein A is dehydrogenation some substituting group in addition) of formula III by the alpha-aromatic trifluoroacetamido acid that is similar to formula (II) (wherein A is dehydrogenation some substituting group in addition) in the presence of acid anhydrides, organic bases and solvent with 2-propylene halide nitrile prepared in reaction.
The present invention adopts the alpha-aromatic amino acid of formula (I) directly to carry out trifluoroacetylation with trifluoracetic acid and chloride reagent, and yield is good.Advantageously, method of the present invention does not need to adopt expensive trifluoroacetic anhydride (TFAA), does not adopt the relatively poor ethyltrifluoroacetate of yield yet, does not more need the existence of alkali.
The method according to this invention makes the alpha-aromatic amino acid of formula (I) and the trifluoracetic acid of at least 1 molar equivalent, and reaction forms the alpha-aromatic trifluoroacetamido acid of formula (II) in the presence of an amount of chloride reagent and solvent.After reaction is finished, to use such as extraction, filtering conventional process and isolate product, or be preferably, reaction product solution can be used in next step preparation of the production aryl-pyrrolidine nitrile shown in the aforesaid equation I.
Be applicable to that the chloride reagent in the inventive method is phosphorus trichloride, phosphorus tribromide, phosgene, superpalite, two (trichloromethyl) carbonic ether or sulfur oxychloride.
Be applicable to that the solvent in the inventive method comprises conventional inert organic solvents, for example: nitrile such as acetonitrile; Ether such as ether, tetrahydrofuran (THF), dioxan, ethylene glycol diethyl ether etc.; Halohydrocarbon such as methylene dichloride, 1, the 2-ethylene dichloride, chlorine is walked back and forth, 1, tetracol phenixin etc.; Carboxylic acid amides such as N, dinethylformamide, N-Methyl pyrrolidone etc.; Sulfoxide such as methyl-sulphoxide etc.; Aromatic hydrocarbons such as benzene, toluene, dimethylbenzene etc.; Halogenated aryl hydrocarbon such as chlorobenzene, dichlorobenzene etc.; Also can adopt excessive trifluoracetic acid and do not use other solvent in addition.
The alpha-aromatic trifluoroacetamido acid of formula of the present invention (II) and the 2-propylene halide nitrile of at least 1 molar equivalent, in the presence of alkali and organic solvent and chloride reagent or acid anhydrides, react, form 2-aryl-5-(trifluoromethyl) pyrroles-3-nitrile compound of formula (III) structure, yield is satisfactory.When selecting acid anhydrides for use, A is a hydrogen.
Be applicable to that the chloride reagent in the inventive method is phosphorus trichloride, phosphorus tribromide, phosgene, superpalite, two (trichloromethyl) carbonic ether or sulfur oxychloride; Acid anhydrides is aceticanhydride or trifluoroacetic anhydride (TFAA) etc.Be applicable to that the alkali in the inventive method is C
1-C
4Trialkylamine, pyridine, basic metal C
1-C
4Alkoxide or basic metal carbonic acid (hydrogen) salt, preferred triethylamine and pyridine.
Be applicable to that the solvent in the inventive method comprises conventional inert organic solvents, for example nitrile such as acetonitrile; Ether such as ether, tetrahydrofuran (THF), dioxan, ethylene glycol diethyl ether etc.; Halohydrocarbon such as methylene dichloride, 1,2-ethylene dichloride, chloroform, 1, tetracol phenixin etc.; Carboxylic acid amides such as N, dinethylformamide, N-Methyl pyrrolidone etc.; Sulfoxide such as methyl-sulphoxide etc.; Aromatic hydrocarbons such as benzene, toluene, dimethylbenzene etc.; Halogenated aryl hydrocarbon such as chlorobenzene, dichlorobenzene etc.Be preferably organic polar solvent, preferred acetonitrile, N, dinethylformamide etc.
Above-claimed cpd with the inventive method preparation is the acaricidal intermediate of arylpyrrole insecticidal of production formula (IV).Method of the present invention comprises the production of a kind of effective insecticidal miticide 4-bromo-2-(rubigan)-1-(alkoxy methyl)-5-(trifluoromethyl) pyrroles-3-nitrile.
For the ease of to further understanding of the present invention, the embodiment that provides has below done more detailed description to it.These embodiment are not to be used for limiting scope of the present invention or implementation principle for narration only.Term 1HNMR is meant the 1H nuclear magnetic resonance spectrum, and EIMS is meant the electron ionization mass spectrum, and HPLC is meant high pressure liquid chromatography.
Embodiment 1
The preparation of α-(rubigan)-N-(trifluoroacetyl group) glycine
With α-(rubigan) glycine (5.6g, 0.03mol) mixture in acetonitrile uses trifluoracetic acid (4.8g successively, 0.042mol) and phosphorus trichloride (1.8g, 0.013mol) handle, under reflux temperature, stirred 5-6 hour, use the HPLC trace analysis, transform fully to α-(rubigan) glycine.With reaction mixture cooling and vacuum concentration, obtain the light yellow solid resistates.This solid residue water/toluene mixture is carried out stir process, filter after drying and obtain the Powdered title product of slightly yellowish white solid 5.2g (productive rate 61.6%), mp:170-172 ℃.
1H?NMR(DMSO，6)：5.49(d，J＝7.4，1H，C-H)，7.43(m，4H，Ar-H)，10.12(bs，1H，COO-H)，13.2(bs，1H，N-H)。
Embodiment 2
The preparation of α-(rubigan)-N-(trifluoroacetyl group) glycine
With also using superpalite (3.6g with embodiment 1 described essentially identical method, 0.018mol) replace wherein phosphorus trichloride as chloride reagent, obtain the Powdered title product of faint yellow solid 5.9g (productive rate 69.8%), mp:177-170 ℃.
Embodiment 3
The preparation of α-(rubigan)-N-(trifluoroacetyl group) glycine
With (3.6g, 0.03mol) replacement phosphorus trichloride wherein can obtain the Powdered title product of pale solid 5.5g (productive rate 65.1%), mp:177-171 ℃ as chloride reagent with embodiment 1 described essentially identical method and with sulfur oxychloride.
Embodiment 4
The preparation of α-(rubigan)-N-(trifluoroacetyl group) sarkosine
With α-(rubigan) sarkosine (6.0g, 0.03mol) mixture in toluene uses trifluoracetic acid (4.8g successively, 0.042mol) and phosphorus trichloride (2.0g, 0.014mol) handle, under reflux temperature, stirred 5-6 hour, use the HPLC trace analysis, transform fully to α-(rubigan) sarkosine.With reaction mixture cooling and vacuum concentration, obtain solid residue.This solid residue is heavily steamed twice with toluene, and washing obtains orange solids shape title product 8.0g (productive rate 90.2%), mp:115-117 ℃.
Embodiment 5
The preparation of 2-(rubigan)-5-(trifluoromethyl) pyrroles-3-nitrile
Successively with phosphorus trichloride (1.7g, 0.012mol), the 2-chloroacrylonitrile (2.2g, 0.024mol) and triethylamine (ca.6ml) be added drop-wise to that α-(5.6g is in acetonitrile solution 0.02mol) for (rubigan)-N-(trifluoroacetyl group) glycine.After being added dropwise to complete, reaction mixture heating under the reflux temperature about 4 hours, is used the HPLC trace analysis, complete to α-(rubigan)-N-(trifluoroacetyl group) glycine reactant.Reaction is complete to be cooled to room temperature and to topple in the entry solid collected by filtration, dry white crystal shape title product 5.1g (productive rate 94.3%), mp:236-239 ℃ of getting.
EIMS(m/z，％)：272(M+2，32)，270(M，100)，250(25)，215(29)；
1HNMR(DMSO，δin?ppm)：7.30(s，1H，pyrrole-H)，7.65(d，J＝8.5Hz，2H，Ar-H)，7.80(d，J＝8.5，2H，Ar-H)，13.4(s，1H，N-H)
Embodiment 6
The preparation of α-(rubigan)-5-(trifluoromethyl) pyrroles-3-nitrile
With with embodiment 5 described essentially identical methods and with aceticanhydride or trifluoroacetic anhydride (TFAA) replacement chloride reagent wherein, can obtain solid powdery title product.
Embodiment 7
The preparation of 4-bromo-2-(rubigan)-5-(trifluoromethyl) pyrroles-3-nitrile
With bromine (9.6g, 0.06mol) slowly join 2-(rubigan)-5-(trifluoromethyl) pyrroles-3-nitrile (11.0g, 0.04mol), sodium bicarbonate (4.0g, 0.045mol) and the mixture of chloroform in, reaction mixture is heated under reflux temperature, and with the HPLC trace analysis to 2-(rubigan)-5-(trifluoromethyl) pyrroles-complete bromination of 3-nitrile, need about 4 hours.Solid and extremely neutral with massive laundering is filtered, collected to the complete room temperature that is cooled to of reaction, dry white or faint yellow solid shape title product 12.8g (productive rate 91.6%), the mp: greater than 240 ℃ (decomposition) of getting.
EIMS(m/z，％)：352(M+4，24)，350(M+2，100)，348(M，80)，269(10)，251(32)，249(100)，242(9)，214(16)；
1H?NMR(DMSO，δin?ppm)：7.64(d，J＝8.0Hz，2H，Ar-H)，7.78(d，J＝8.1Hz，2H，Ar-H)，13.4(bs，1H，N-H)。
Embodiment 8
The preparation of 4-bromo-2-(rubigan)-1-(ethoxyl methyl)-5-(trifluoromethyl) pyrroles-3-nitrile
With sodium hydride (60%, 1.3g, (10.5g 0.03mol) in the mixture of dry tetrahydrofuran, stirred under the room temperature 1 hour 0.033mol) slowly to join 4-bromo-2-(rubigan)-5-(trifluoromethyl) pyrroles-3-nitrile.(4.3g 0.045mol), after being added dropwise to complete, under the reflux temperature is heating reaction mixture about 4 hours to drip chloromethyl ether in above-mentioned reaction mixture.Reaction is finished and to be cooled to room temperature, adds the shrend reaction of going out, standing demix, organic layer decompression precipitation recovery solvent, resistates adds water and stirs, filter collection solid, dry the white or Powdered title product of faint yellow solid (12.0g, it is 95.3% that HPLC analyzes content, yield 93.5%), mp:90-91 ℃.
ELMS(m/z，％)：408(M+2，15)，406(M，10)，363(12)，361(9)，350(10)，328(13)，327(9)，326(10)，247(22)，59(100)；
1H?NMR(CDCl
3，δin?ppm)：1.17(t，3H，J＝7.0)，3.40(q，2H，J＝7.0)，5.20(s)，7.50(m，4H，Ar-H)。
Claims (8)
1, a kind of preparation has the method for 2-aryl-5-(trifluoromethyl) pyrroles-3-nitrile compound of structural formula II I feature
Wherein A is hydrogen, C
1-C
4The C that alkyl, aryl, halogenated aryl or aryl replace
1-C
4Alkyl; R and L are independently hydrogen or halogen, C separately
1-C
4Alkyl or C
1-C
4Alkoxyl group; This method comprises:
A. with the alpha-aromatic amino acid of structural formula I
A wherein, the definition of R and L is the same, reacts in the presence of organic solvent with the trifluoracetic acid and the chloride reagent of at least 1 molar equivalent, forms the amino acid whose trifluoroacetyl derivative of alpha-aromatic of formula (II),
B. the 2-propylene halide nitrile of formula (II) compound and at least 1 molar equivalent reacts in the presence of alkali and organic solvent and chloride reagent or acid anhydrides, forms 2-aryl-5-(trifluoromethyl) pyrroles-3-nitrile compound of formula (III) structure.
2, preparation according to claim 1 has 2-aryl-5-(trifluoromethyl) pyrroles-3-nitrile compound method of structural formula (III) feature, the 2-propylene halide nitrile that it is characterized in that described formula (II) compound and at least 1 molar equivalent, when reacting in the presence of alkali and organic solvent and acid anhydrides, the A in the structural formula (II) should be hydrogen.
3, a kind of preparation has the method for 2-aryl-5-(trifluoromethyl) pyrroles-3-nitrile compound of structural formula (III) feature
A wherein, identical in the definition of R and L and the claim 1 is characterized in that and will have the compound of formula (II) structure
A wherein, the definition of R and L is the same, with the 2-propylene halide nitrile of at least 1 molar equivalent, reacts in the presence of alkali and organic solvent and chloride reagent or acid anhydrides, forms 2-aryl-5-(trifluoromethyl) pyrroles-3-nitrile compound of formula (III) structure.
4, preparation according to claim 3 has 2-aryl-5-(trifluoromethyl) pyrroles-3-nitrile compound method of structural formula (III) feature, the 2-propylene halide nitrile that it is characterized in that described formula (II) compound and at least 1 molar equivalent, when reacting in the presence of alkali and organic solvent and acid anhydrides, the A in the structural formula (II) should be hydrogen.
5, have the method for 2-aryl-5-(trifluoromethyl) pyrroles-3-nitrile compound of structural formula (III) feature according to claim 1 or 3 described preparations, described chloride reagent is phosphorus trichloride, phosphorus tribromide, phosgene, superpalite, two (trichloromethyl) carbonic ether or sulfur oxychloride; Described acid anhydrides is aceticanhydride or trifluoroacetic anhydride (TFAA).
6, have the method for 2-aryl-5-(trifluoromethyl) pyrroles-3-nitrile compound of structural formula (III) feature according to claim 1 or 3 described preparations, it is characterized in that described alkali is C
1-C
4Trialkylamine, pyridine, basic metal C
1-C
4Alkoxide or alkaline carbonate or supercarbonate, preferred triethylamine and pyridine.
7, a kind of preparation has the method for the alpha-aromatic trifluoroacetamido acid compound of structural formula (II),
A wherein, identical in the definition of R and L and the claim 1, this method feature is with the trifluoracetic acid of 1 molar equivalent and chloride reagent to make the alpha-aromatic amino acid trifluoroacetylation of formula (I) structure at least in the presence of organic solvent,
A wherein, the definition of R and L is the same.
8, preparation according to claim 7 has the method for the alpha-aromatic trifluoroacetamido acid compound of structural formula (II), and wherein chloride reagent is phosphorus trichloride, phosphorus tribromide, phosgene, superpalite, two (trichloromethyl) carbonic ether or sulfur oxychloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03112978 CN1193988C (en) | 2003-03-14 | 2003-03-14 | Preparation of 2-aryl-5-(trifluoride) pyrrole-3-nitrile and its use and preparation of its intermediate thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03112978 CN1193988C (en) | 2003-03-14 | 2003-03-14 | Preparation of 2-aryl-5-(trifluoride) pyrrole-3-nitrile and its use and preparation of its intermediate thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1439634A CN1439634A (en) | 2003-09-03 |
| CN1193988C true CN1193988C (en) | 2005-03-23 |
Family
ID=27796933
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03112978 Expired - Fee Related CN1193988C (en) | 2003-03-14 | 2003-03-14 | Preparation of 2-aryl-5-(trifluoride) pyrrole-3-nitrile and its use and preparation of its intermediate thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1193988C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112608268A (en) * | 2020-12-22 | 2021-04-06 | 李通 | Method for producing chlorfenapyr intermediate pyrrole by using solvent DMF to replace acetonitrile |
| CN114524758A (en) * | 2022-01-12 | 2022-05-24 | 山东潍坊双星农药有限公司 | Novel synthesis process of chlorfenapyr |
| CN114573494B (en) * | 2022-04-14 | 2024-03-15 | 山东潍坊双星农药有限公司 | Preparation method of chlorfenapyr |
| CN118772034A (en) * | 2024-09-12 | 2024-10-15 | 山东亿嘉农化有限公司 | A preparation process of 2-p-chlorophenyl-5-(trifluoromethyl)pyrrole-3-carbonitrile |
-
2003
- 2003-03-14 CN CN 03112978 patent/CN1193988C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1439634A (en) | 2003-09-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1649827A (en) | Process for preparing highly functionalized gamma-butyrolactams and gamma-amino acids | |
| CN1561341A (en) | Hydrolysis of [R(R*,R*)]-2-(4-fluorophenyl)-beta,delta-dihydroxy-5-(1-methylethyl)-3-phenyl-4-[(phenylamino) carbonyl]-1H-pyrrole-1-heptanoic acid esters with calcium hydroxide | |
| CN1942439A (en) | Process for the production of atorvastatin calcium in amorphous form | |
| CN87101731A (en) | Carbostyril carboxylic acid derivatives that replaces on No. 8 positions and preparation method thereof | |
| CN1193988C (en) | Preparation of 2-aryl-5-(trifluoride) pyrrole-3-nitrile and its use and preparation of its intermediate thereof | |
| CN1884263A (en) | Pregabalin intermediate and process for preparing same | |
| CN1282645C (en) | Process for preparing 3-hydroxy-N,1,6-trialkyl-4-oxo-1,4-dihydropyridine-2-carboxamide | |
| CN1259517A (en) | Method for preparing 2,5-diamino-4,6-dichloropyrimidine | |
| CN1225634A (en) | Synthesis of indolylmaleimides | |
| CN1106798A (en) | Alkoxymethylation of pyrroles | |
| CN1131864C (en) | Chemical synthesis of morpholine derivatives | |
| JP4451938B2 (en) | Process for producing 2-aryl-5- (perfluoroalkyl) pyrrole compound from N- (perfluoroalkylmethyl) arylimidoyl chloride compound | |
| CN1930164A (en) | Process for the preparation of n-([1,2,4]triazolopyrimidin-2-yl)aryl sulfonamides | |
| CN1172805A (en) | Process for preparation of unsymmetrical 4, 6-bis (aryloxy) pyrimidine compounds | |
| CN101074208A (en) | Production of indole derivative | |
| CN1278253A (en) | Process for producing substituted alkylamines or salts thereof | |
| CN1768057A (en) | Process for preparing a polymorph of rosiglitazone maleate | |
| CN1846696A (en) | Method for producing enantiomer-free n-methyl-n- [(1s)-1-phenyl- 2-((3s)- 3-hydroxypyrrolidine- 1-yl)ethyl]- 2,2-diphenyl acetamide | |
| CN101061090A (en) | Process for producing alpha, alpha-difluoroamine | |
| CN1578760A (en) | Process for producing(2-nitrophenyl)acetonitrile derivative and intermediate therefor | |
| CN1198821C (en) | Process for preparation of sulfonamide derivs. and crystals thereof | |
| CN1184194C (en) | Method for producing n-butyryl-4-amino-3-methyl-methyl benzoate and the novel compound n-(4-bromine-2-methylphenyl)-butanamide | |
| CN1178919C (en) | Synthesis of intermediates useful in preparing tricyclic compounds | |
| CN1107148A (en) | Method for the preparation of 2-perflouoroalkyl-3-oxazolin-5-one | |
| CN1832931A (en) | A process for the preparation of phenyltetrazole derivatives |
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 | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20050323 Termination date: 20100314 |