CN1962618A - 2,2,2-trifluoro-N-(2-chlorotoluene) imine acyl chloride and its 'one-pot' synthesis method - Google Patents
2,2,2-trifluoro-N-(2-chlorotoluene) imine acyl chloride and its 'one-pot' synthesis method Download PDFInfo
- Publication number
- CN1962618A CN1962618A CN 200610118160 CN200610118160A CN1962618A CN 1962618 A CN1962618 A CN 1962618A CN 200610118160 CN200610118160 CN 200610118160 CN 200610118160 A CN200610118160 A CN 200610118160A CN 1962618 A CN1962618 A CN 1962618A
- Authority
- CN
- China
- Prior art keywords
- solvent
- chloride
- acyl chloride
- liquid
- fluoro
- 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.)
- Pending
Links
Landscapes
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a synthesizing method of 2, 2, 2-trifluoro-N-(2-chlorotoluene) acylated chloride imino and synthesizing method, which comprises the following steps: 1. adopting carbon tetrachloride as solvent protected by nitrogen; adding triphenylphosphine and trimethylamine in the reacting container; reducing the temperature less than 10 Deg C in the icy bath and stirring; adding trifluoroacetic acid to stir 10-20 min; adding 2-benzenemethanol amino; setting the molar rate of triphenylphosphine, trimethylamine, trifluoroacetic acid and 2-benzenemethanol amino at 4-6:1-1.2:1:1-1.2; 2. heating to reflux for 3-24h; decompressing; evaporating the solvent; 3. adding ligroine; immersing; sucking; washing solid in the Brinell hopper through ligroine; 4. removing the solvent in the obtaining liquid; separating the liquid through neutral alumina column chromatography; adopting ligroine as eluent; obtaining the light yellow liquid as the product.
Description
Technical field:
The present invention relates to a kind of fluorine-containing imine acyl chloride and synthetic method thereof, particularly 2,2,2-three fluoro-N-(2-toluene(mono)chloride) imine acyl chloride and " one kettle way " synthetic method thereof.
Background technology:
All contain O at present a large amount of bioactive compoundss, heteroatomss such as N, and heterogeneous ring compound is the hugest class of number in organic compound, many materials that in physiological process, play an important role, base as nucleic acid, amino acid all includes heterocycle structure in VITAMIN and the alkaloid.People design as required some have the functional heterogeneous ring compound of special function and purposes, useful as drug, dyestuff, biosimulation material, organic conductor, engineering macromolecular material etc.
Imine acyl chloride is built soon as synthetic, because it has more active carbon chlorine key, plays important effect in synthesizing heterocyclic compounds.Chloromethyl on the phenyl ring also is more active reflecting point, for example: can connect a large amount of useful groups by grignard reaction.
On the other hand, in the pharmaceutical chemistry field, fluorine atom or a perfluoroalkyl are incorporated into and are considered to one of most effectual way that host compound is modified in the host molecule.Because the fluorine atom radius is little, has bigger electronegativity again, its formed C-F key bond energy is than big many of c h bond bond energy, the stability and the physiologically active of organofluorine compound have been increased significantly, fluorinated organic compound also has higher fat-soluble and hydrophobicity in addition, promote it to absorb in vivo and transmission speed, physiological action is changed.Have characteristics such as consumption is few, toxicity is low, drug effect is high, metabolic capacity is strong so a lot of fluorine-containing medicines and agricultural chemicals are relative on performance, this makes its proportion in the new pharmaceutical pesticide species more and more higher.
Summary of the invention:
The object of the present invention is to provide a kind of 2,2,2-three fluoro-N-(2-toluene(mono)chloride) imine acyl chloride and " one kettle way " synthetic method thereof.
For achieving the above object, the reaction mechanism that the inventive method has adopted is:
According to above-mentioned reaction mechanism, the present invention adopts following technical scheme:
A kind of 2,2,2-three fluoro-N-(2-toluene(mono)chloride) imine acyl chloride is characterized in that the structure of this compound is:
The physical parameter of this compound:
Molecular formula: C
9H
6Cl2F
3N
Structural formula:
Chinese named: 2,2,2-three fluoro-N-(2-toluene(mono)chloride) imine acyl chloride
English name: N-(2-(chloromethyl) phenyl)-2,2,2-trifluoroacetimidoyl chloride
Molecular weight: 256.05
Outward appearance: weak yellow liquid
Proton nmr spectra (500MHz, CDCl
3): 7.494 (dd, 1H, J=1.5,7.5 Hz); 7.488～7.302 (m, 2H); 7.034 (dd, 1H, J=1.0,8.0Hz); 4.543 (s, 2H);
Carbon-13 nmr spectra (125MHz, CDCl
3): 142.5,134.4 (q, J
C-C-F=42.9Hz), 130.2,129.5,129.4,127.6,119.1,116.7 (q, J
C-F=276.0 Hz), 42.1;
Nucleus magnetic resonance fluorine spectrum (470MHz, CDCl
3, interior mark: CF
3Cl): δ=-75.65;
IR(neat)2964，1697，1488，1287，1210，1166，952，762cm
-1。
A kind of above-mentioned 2,2, the synthetic method of 2-three fluoro-N-(2-toluene(mono)chloride) imine acyl chloride, it is characterized in that this method has following steps: 1. under the nitrogen protection, with the tetracol phenixin is solvent, adds triphenylphosphine and triethylamine in reaction vessel, stirs under ice-water bath and reduces to below 10 ℃; Add trifluoroacetic acid again, stirred 10～20 minutes, add 2-amino-benzene methyl alcohol at last, the mol ratio of described four kinds of reactant triphenylphosphines, triethylamine, trifluoroacetic acid, 2-amino-benzene methyl alcohol is: 4～6: 1～1.2: 1: 1～1.2; 2. reflux is 3～24 hours, and reaction finishes, and decompression steams the solvent in the reaction soln, 3. adds sherwood oil then in reactor, soaks, and suction filtration is with the solid in the petroleum ether B; 4. the liquid that obtains is spun off solvent, the liquid that obtains neutral alumina column chromatography for separation, developping agent is a sherwood oil, gets weak yellow liquid and is 2,2,2-three fluoro-N-(2-toluene(mono)chloride) imine acyl chloride.
The present invention compared with prior art, have following conspicuous high-lighting characteristics and significance a bit: raw material of the present invention is easy to get, and operate very simply, one kettle way synthesizes.Productive rate reaches 51-63%, is fit to scale operation.
Embodiment:
Example 1: Synthetic 2,2,2-three fluoro-N-(2-toluene(mono)chloride) imine acyl chloride adopts following steps: 1. add triphenyl phosphorus 2.64 grams in 25 milliliters the flask with three necks,round bottom that reflux condensing tube is housed, 10 milliliters in tetracol phenixin, 0.28 milliliter of triethylamine, 0.13 milliliter of trifluoroacetic acid, ice bath stirred 10 minutes, add 2-amino-benzene methyl alcohol 0.21 gram, 2. oil bath slowly is heated to 60 ℃ of reactions and begins to cause, and has solid to generate, and the reheat reaction in 3 hours that refluxes finishes, decompression steams the solvent in the reaction soln, 3. in bottle, add sherwood oil then, soak suction filtration, with the solid in the petroleum ether B, filtrate spins off solvent; 4. the liquid that obtains neutral alumina column chromatography for separation, developping agent are sherwood oil, promptly obtain product 2,2,2-three fluoro-N-(2-toluene(mono)chloride) imine acyl chloride 0.274 gram.Productive rate is 63%.
Example 2: Synthetic 2,2,2-three fluoro-N-(2-toluene(mono)chloride) imine acyl chloride adopts following steps: 1. add triphenyl phosphorus 10.5 grams in 100 milliliters the flask with three necks,round bottom that reflux condensing tube is housed, 45 milliliters in tetracol phenixin, 1.12 milliliters of triethylamines, 0.5 milliliter of trifluoroacetic acid, ice bath stirred 15 minutes, add 2-amino-benzene methyl alcohol 0.824 gram, 2. oil bath slowly is heated to 60 ℃ of reactions and begins to cause, and has solid to generate, and the reheat reaction in 5 hours that refluxes finishes, decompression steams the solvent in the reaction soln, 3. in bottle, add sherwood oil then, soak suction filtration, with the solid in the petroleum ether B, filtrate spins off solvent; 4. the liquid that obtains neutral alumina column chromatography for separation, developping agent are sherwood oil, promptly obtain product 2,2,2-three fluoro-N-(2-toluene(mono)chloride) imine acyl chloride 0.973 gram.
Example 3: Synthetic 2,2,2-three fluoro-N-(2-toluene(mono)chloride) imine acyl chloride adopts following steps: 1. add triphenyl phosphorus 383 grams in 2 liters the flask with three necks,round bottom that reflux condensing tube is housed, 600 milliliters in tetracol phenixin, 60 milliliters of triethylamines, 25 milliliters of trifluoroacetic acids, ice bath stirred 20 minutes, add 2-amino-benzene methyl alcohol 43 grams, 2. oil bath slowly is heated to 60 ℃ of reactions and begins to cause, and has solid to generate, and the reheat reaction in 12 hours that refluxes finishes, decompression steams the solvent in the reaction soln, 3. in bottle, add sherwood oil then, soak suction filtration, with the solid in the petroleum ether B, filtrate spins off solvent; 4. the liquid that obtains neutral alumina column chromatography for separation, developping agent are sherwood oil, promptly obtain product 2,2,2-three fluoro-N-(2-toluene(mono)chloride) imine acyl chloride 45.6 grams.Productive rate is 51%.
Claims (2)
1. one kind 2,2,2-three fluoro-N-(2-toluene(mono)chloride) imine acyl chloride is characterized in that the structure of this compound is:
2. one kind synthetic according to claim 12,2, the synthetic method of 2-three fluoro-N-(2-vinyl benzene) imine acyl chloride, it is characterized in that this method has following steps: 1. under the nitrogen protection, with the tetracol phenixin is solvent, in reaction vessel, add triphenylphosphine and triethylamine, under ice-water bath, stir and reduce to below 10 ℃; Add trifluoroacetic acid again, stirred 10～20 minutes, add 2-amino-benzene methyl alcohol at last, the mol ratio of described four kinds of reactant triphenylphosphines, triethylamine, trifluoroacetic acid, 2-amino-benzene methyl alcohol is: 4～6: 1～1.2: 1: 1～1.2; 2. reflux is 3～24 hours, and reaction finishes, and decompression steams the solvent in the reaction soln, 3. adds sherwood oil then in reactor, soaks, and suction filtration is with the solid in the petroleum ether B; 4. the liquid that obtains is spun off solvent, the liquid that obtains neutral alumina column chromatography for separation, developping agent is a sherwood oil, gets weak yellow liquid and is 2,2,2-three fluoro-N-(2-toluene(mono)chloride) imine acyl chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610118160 CN1962618A (en) | 2006-11-09 | 2006-11-09 | 2,2,2-trifluoro-N-(2-chlorotoluene) imine acyl chloride and its 'one-pot' synthesis method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610118160 CN1962618A (en) | 2006-11-09 | 2006-11-09 | 2,2,2-trifluoro-N-(2-chlorotoluene) imine acyl chloride and its 'one-pot' synthesis method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1962618A true CN1962618A (en) | 2007-05-16 |
Family
ID=38081866
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200610118160 Pending CN1962618A (en) | 2006-11-09 | 2006-11-09 | 2,2,2-trifluoro-N-(2-chlorotoluene) imine acyl chloride and its 'one-pot' synthesis method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1962618A (en) |
-
2006
- 2006-11-09 CN CN 200610118160 patent/CN1962618A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR20070037335A (en) | Process for preparing 5-methyl-2-furfural | |
| CN111233666A (en) | Method for efficiently synthesizing trifluoromethyl compound, trifluoromethyl compound and application | |
| CN1962618A (en) | 2,2,2-trifluoro-N-(2-chlorotoluene) imine acyl chloride and its 'one-pot' synthesis method | |
| CN114195818B (en) | 4-arylthio coumarin compound and preparation method thereof | |
| CN108148021A (en) | 2- imines (3H) furane derivative or thiophene derivant and its synthesis | |
| CN109574961A (en) | The method for preparing Suo Feibuwei intermediate | |
| CN101016274A (en) | 5-Chloro-2-difluoromethylbenzoxazole and synthesis method thereof | |
| CN100357269C (en) | 2,2-difluoro-N-O-bromo methyl phenyl imine acyl chloride and its synthesis method | |
| CN105254530B (en) | A kind of synthetic method containing amphene base Schiff class compound | |
| CN100465166C (en) | 5-Methyl-2-difluoromethyl benzoxazole and synthesis method thereof | |
| CN110294708B (en) | Preparation method of trifluoroethylselenophenanthridine and 3, 4-dihydroisoquinoline derivatives | |
| CN103254194B (en) | Preparation method of 8-thiaxanthine compound | |
| US6437154B1 (en) | Process for the preparation of 10-deacetylbaccatin III | |
| CN107365264B (en) | Preparation method of sulfonamide compound | |
| CN101016273A (en) | 5-Chloro-2-difluorobromomethylbenzoxazole and synthesis method thereof | |
| CN1869006A (en) | 2,2,2-trifluoro-N-(4-methoxy-2-methyl benzene) imine acyl chloride and its synthesis method | |
| CN1927818A (en) | N-(2-methyl-4-nitrophenyl)-2,2,2-trifluoro-acetimidoyl chloride and preparation method thereof | |
| CN1927834A (en) | 6-Fluoro-2-trifluoromethylindole and preparation method thereof | |
| CN101096352A (en) | 2,2,2-trifluoro-N-(4-methoxyl-2-bromine toluene) imines acyl chlorides and method for synthesizing the same | |
| US6872840B1 (en) | Synthesis of 8-membered carbocyclic compound having diexomethylene groups | |
| CN1869005A (en) | 2,2-difluoro-N-O-tolyl imineacyl chloride and its synthesis method | |
| CN1927821A (en) | N-(4-methoxy-2-methylphenyl)-2,2,3,3,4,4,4-heptafluoro-butyrimidoyl chloride and preparation method thereof | |
| CN101104581A (en) | Fluorine-containing alpha, beta-unsaturated ketone and synthetic method thereof | |
| CN108727189B (en) | Dinaphthol polyether chain is isolation base chiral molecular tweezer compound and its preparation and application | |
| CN101016276A (en) | 5-nitro-2-difluoromethylbenzimidazole and synthesis method 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 | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |