CN102633725A - Synthetic method of N-heptafluorobutyrylimidazole - Google Patents
Synthetic method of N-heptafluorobutyrylimidazole Download PDFInfo
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- CN102633725A CN102633725A CN201210102625XA CN201210102625A CN102633725A CN 102633725 A CN102633725 A CN 102633725A CN 201210102625X A CN201210102625X A CN 201210102625XA CN 201210102625 A CN201210102625 A CN 201210102625A CN 102633725 A CN102633725 A CN 102633725A
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- imidazoles
- fluorine butyryl
- fluorine
- butyryl radicals
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Abstract
The invention relates to a preparation method of a key reagent for detecting food contaminant chloropropanol, and particularly relates to a synthetic method of N-heptafluorobutyrylimidazole (the registry number of CAS (chemical abstract service) is 32477-35-3). The method disclosed by the invention has the advantages of being short in synthetic route and total yield and is economic and convenient, and the product purity is high after the product is purified.
Description
Technical field
The present invention relates to the preparation method that a kind of contaminants in food propylene chlorohydrin detects key reagent, specifically
NThe compound method of-seven fluorine butyryl radicals imidazoles (heptafluoro-butyryl imidazole, CAS registration number 32477-35-3).
Background technology
NThe structural formula of-seven fluorine butyryl radicals imidazoles (heptafluoro-butyryl imidazole, CAS registration number 32477-35-3) is:
The detection method of propylene chlorohydrin pollutant is ripe in the food; Internationally recognized method is a stable isotope dilution mass spectrometry method; The People's Republic of China adopts this method; And drafted the detection method GB/T5009.191-2006 that has formulated propylene chlorohydrin compounds in the various food in 2006, in the detection of this pollutant, need use a critical derivatization reagent---
N-seven fluorine butyryl radicals imidazoles.At present this reagent is domestic can not produce, and only there is a few manufacturer in developed country such as America and Europe, the complete dependence on import of China; It costs an arm and a leg; Because China is the productive consumption big country of various food such as soy sauce, and a lot of food relates to the export trade, to the detection of the propylene chlorohydrin pollutant in the food; Not only be related to people's health, also be related to China Exports and national image.For this reason, China needs a certain amount of foreign exchange of cost to buy the detection that this derivatization reagent is used for this pollutant every year.Therefore, under the increasingly serious situation of food safety, more be necessary its research and development of domesticizing.
Up to the present,
NThe compound method of-seven fluorine butyryl radicals imidazoles is not seen bibliographical information.
Summary of the invention
The present invention provides
NIt is short that the compound method of-seven fluorine butyryl radicals imidazoles, the inventive method have synthetic route, and total recovery is higher, economical and convenient, the high advantage of product purified back purity.
Technical scheme of the present invention is achieved in that synthesis route is following:
In the following formula,
R
1=hydrogen, sodium, potassium
R
2=chlorine, bromine
R
3=C
1-C
4Alkyl.
The present invention specifically comprises following step:
(1): with initiator hyptafluorobutyric acid compound (II) is raw material, prepares compound seven fluorine butyryl halogen (III) through halogenated method; With compound seven fluorine butyryl halogen (III) and imidazoles (IV) prepared in reaction compound
N-seven fluorine butyryl radicals imidazoles (I);
(2): with initiator hyptafluorobutyric acid compound (II) is raw material, prepares compound seven fluorine butyryl halogen (III) through halogenated method; With compound seven fluorine butyryl halogen (III) and C
1-C
4The Fatty Alcohol(C12-C14 and C12-C18) esterification makes compound hyptafluorobutyric acid ester (V); Compound hyptafluorobutyric acid ester (V) makes with imidazoles (IV) reaction
N-seven fluorine butyl acyl imidazoles (I).
Technical scheme of the present invention is:
Step (a) is not with an organic solvent, or with an organic solvent carries out in the one or more combination solvent in methylene dichloride, trichloromethane, toluene, THF, acetone, ETHYLE ACETATE, the methyl acetate, catalyzer be triethylamine, pyridine,
N, NOne or more combination in the-N, the employed halide reagent of halogenating reaction are POCl3, phosphorus pentachloride, thionyl chloride, phosphorus tribromide, tribromo oxygen phosphorus, oxalyl chloride, solid phosgene and Tosyl chloride; Cooking halogenating agent with thionyl chloride can be without solvent, and aftertreatment is fairly simple, catalyzer a little
N, N-N gets final product, therefore, preferred thionyl chloride with
N, N-dimethyl-formyl.
Step (b) is with carrying out in compound seven fluorine butyryl halogen (III) and the one or more combination solvent of imidazoles in organic solvent dichloromethane, trichloromethane, toluene, THF, acetone, ETHYLE ACETATE, methyl acetate; Catalyzer is the one or more combination reaction in triethylamine, pyridine, the 4-dimethyl amine yl pyridines, makes compound
N-seven fluorine butyryl radicals imidazoles (I); Doing solvent and triethylamine with methylene dichloride, to do the catalyzer yield high, and quality is good, therefore, and preferred methylene dichloride and triethylamine.
Step (c) is with compound seven fluorine butyryl halogen (III) and C
1-C
4Carry out under the one or more combination solvent of Fatty Alcohol(C12-C14 and C12-C18) in organic solvent dichloromethane, trichloromethane, toluene, THF, acetone, ETHYLE ACETATE, methyl acetate; Catalyzer is the one or more combination reaction in triethylamine, pyridine, the 4-dimethyl amine yl pyridines, makes compound hyptafluorobutyric acid ester (V); Because alcohol toxicity is smaller, and doing solvent and triethylamine with methylene dichloride, to do the catalyzer yield high, and quality is good, and therefore, preferred absolute ethyl alcohol is done solvent and triethylamine at methylene dichloride and done under the catalyzer condition and react.
Step (d) is with carrying out in compound hyptafluorobutyric acid ester (V) and the one or more combination solvent of imidazoles in organic solvent dichloromethane, trichloromethane, toluene, THF, acetone; Catalyzer is the one or more combination reaction in triethylamine, pyridine, the 4-dimethyl amine yl pyridines, makes compound
N-seven fluorine butyryl radicals imidazoles (I); Doing solvent and triethylamine with methylene dichloride, to do the catalyzer yield high, and quality is good, therefore, and preferred methylene dichloride and triethylamine.
Preparing method of the present invention further specifies as follows: among the present invention, yield is higher, and reaction conditions is gentle, the preferred synthetic route of good product quality:
Embodiment
Below with instance the present invention is illustrated, these instances are intended to set forth optimum implementation of the present invention, those skilled in the art is according to case of the present invention, the various changes of carrying out in conjunction with the knowledge of this area are also within scope of the present invention; Following instance does not limit the present invention, utilizes similar method can make other compound of the present invention.
Embodiment
1. prepare compound seven fluorine butyryl chlorides (VII)
50 milliliters of hyptafluorobutyric acids are added in 500 milliliters of three-necked bottles, drip to Dropwise 5 wherein
N, N-N adds 80 milliliters of thionyl chlorides, is heated to back flow reaction 2 hours, and observe no gas and produce the back stopped reaction, the thin out yellow of liquid, cut below 50 ℃, yield 94.5% are collected in air distillation.
2. preparation compound
N-seven fluorine butyryl radicals imidazoles (I)
40 gram imidazoles are joined in 2 liters of three-necked bottles, and dress TM and drying tube add 700 milliliters of exsiccant methylene dichloride and 100 milliliters of exsiccant triethylamines on the three-necked bottle, stir to make the imidazoles dissolving; Slowly be warming up to 40 ℃, drip 150 grams, seven fluorine butyryl chlorides (VI), temperature is controlled at below 60 ℃, after dropwising; 55-60 ℃ was reacted 3.5 hours, then reaction solution gently was poured in 200 ml waters, obtained dichloromethane layer; Water layer is used dichloromethane extraction, merges organic layer, and saturated nacl aqueous solution washs once; Anhydrous magnesium sulfate drying behind the elimination siccative, steams under the condition of normal pressure and removes methylene dichloride.When no longer including the liquid outflow, obtain weak yellow liquid, be with the oil pump underpressure distillation
N-seven fluorine butyryl radicals imidazoles, yield 80%.
N-seven fluorine butyryl radicals glyoxaline structures conclusive evidence data are following:
Hydrogen spectrum: instrument: Bruker AV-600, solvent: CDCl3, δ: 7.20 (1H), 7.61 (1H), 8.28 (1H)
Mass spectrum: instrument: Tianjin, island GCMS-QP5050A EI-MS (70eV): 264 [M]+, 197 [M-CF2]+, 68 [M-COC3F7]+.
Claims (6)
1.
NThe compound method of-seven fluorine butyryl radicals imidazoles, it comprises the steps:
In the following formula,
R
1=hydrogen, sodium, potassium
R
2=chlorine, bromine
R
3=C
1-C
4Alkyl.
2. according to claim 1
NThe compound method of-seven fluorine butyryl radicals imidazoles has 2 kinds, and it comprises following step:
(1): with initiator hyptafluorobutyric acid compound (II) is raw material, prepares compound seven fluorine butyryl halogen (III) through halogenated method; With compound seven fluorine butyryl halogen (III) and imidazoles (IV) prepared in reaction compound
N-seven fluorine butyryl radicals imidazoles (I);
(2): with initiator hyptafluorobutyric acid compound (II) is raw material, prepares compound seven fluorine butyryl halogen (III) through halogenated method; With compound seven fluorine butyryl halogen (III) and C
1-C
4The Fatty Alcohol(C12-C14 and C12-C18) esterification makes compound hyptafluorobutyric acid ester (V); Compound hyptafluorobutyric acid ester (V) makes with imidazoles (IV) reaction
N-seven fluorine butyryl radicals imidazoles (I).
3. according to claim 2
NThe compound method of-seven fluorine butyryl radicals imidazoles; Wherein step (a) is not with an organic solvent; Or with an organic solvent carry out in the one or more combination solvent in methylene dichloride, trichloromethane, toluene, THF, acetone, ETHYLE ACETATE, the methyl acetate, catalyzer be triethylamine, pyridine,
N, NOne or more combination in the-N, the employed halide reagent of halogenating reaction are POCl3, phosphorus pentachloride, thionyl chloride, phosphorus tribromide, tribromo oxygen phosphorus, oxalyl chloride, solid phosgene and Tosyl chloride.
4. according to claim 2
NThe compound method of-seven fluorine butyryl radicals imidazoles; Wherein step (b) is with carrying out in compound seven fluorine butyryl halogen (III) and the one or more combination solvent of imidazoles in organic solvent dichloromethane, trichloromethane, toluene, THF, acetone, ETHYLE ACETATE, methyl acetate; Catalyzer is the one or more combination reaction in triethylamine, pyridine, the 4-dimethyl amine yl pyridines, makes compound
N-seven fluorine butyryl radicals imidazoles (I).
5. according to claim 2
NThe compound method of-seven fluorine butyryl radicals imidazoles, wherein step (c) is with compound seven fluorine butyryl halogen (III) and C
1-C
4Carry out under the one or more combination solvent of Fatty Alcohol(C12-C14 and C12-C18) in organic solvent dichloromethane, trichloromethane, toluene, THF, acetone, ETHYLE ACETATE, methyl acetate; Catalyzer is the one or more combination reaction in triethylamine, pyridine, the 4-dimethyl amine yl pyridines, makes compound hyptafluorobutyric acid ester (V).
6. according to claim 2
NThe compound method of-seven fluorine butyryl radicals imidazoles; Wherein step (d) is with carrying out in compound hyptafluorobutyric acid ester (V) and the one or more combination solvent of imidazoles in organic solvent dichloromethane, trichloromethane, toluene, THF, acetone; Catalyzer is the one or more combination reaction in triethylamine, pyridine, the 4-dimethyl amine yl pyridines, makes compound
N-seven fluorine butyryl radicals imidazoles (I).
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108276272A (en) * | 2018-03-23 | 2018-07-13 | 武汉大学 | A method of preparing seven fluorine isobutyryl chlorides by seven fluoro- 2- halogenated alkanes |
| CN111103277A (en) * | 2020-01-21 | 2020-05-05 | 滁州学院 | Chloropropanol sensitive gas sensor, preparation method thereof, detection device containing sensor and detection method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0583375B1 (en) * | 1988-12-15 | 1996-09-04 | E.I. Du Pont De Nemours And Company | Preparation of n-acylimidazoles |
| CN101508675A (en) * | 2009-03-26 | 2009-08-19 | 浙江工业大学 | Novel disulfonic acid type alkyl imidazole ionic liquid, preparation and uses thereof |
| CN101781253A (en) * | 2009-01-16 | 2010-07-21 | 南京理工大学 | Method for preparing gemini ionic liquid with fluorous biphasic property |
-
2012
- 2012-04-10 CN CN201210102625XA patent/CN102633725A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0583375B1 (en) * | 1988-12-15 | 1996-09-04 | E.I. Du Pont De Nemours And Company | Preparation of n-acylimidazoles |
| CN101781253A (en) * | 2009-01-16 | 2010-07-21 | 南京理工大学 | Method for preparing gemini ionic liquid with fluorous biphasic property |
| CN101508675A (en) * | 2009-03-26 | 2009-08-19 | 浙江工业大学 | Novel disulfonic acid type alkyl imidazole ionic liquid, preparation and uses thereof |
Non-Patent Citations (1)
| Title |
|---|
| 张宝华，等: "咪唑酰胺化衍生物的制备与性能", 《上海大学学报（自然科学版）》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108276272A (en) * | 2018-03-23 | 2018-07-13 | 武汉大学 | A method of preparing seven fluorine isobutyryl chlorides by seven fluoro- 2- halogenated alkanes |
| CN111103277A (en) * | 2020-01-21 | 2020-05-05 | 滁州学院 | Chloropropanol sensitive gas sensor, preparation method thereof, detection device containing sensor and detection method |
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Application publication date: 20120815 |