CN105693557A - Hydrogen fluoride urea and preparation method thereof - Google Patents
Hydrogen fluoride urea and preparation method thereof Download PDFInfo
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- CN105693557A CN105693557A CN201610003049.1A CN201610003049A CN105693557A CN 105693557 A CN105693557 A CN 105693557A CN 201610003049 A CN201610003049 A CN 201610003049A CN 105693557 A CN105693557 A CN 105693557A
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- carbamide
- hydrogen fluoride
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C273/02—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of urea, its salts, complexes or addition compounds
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Abstract
The invention discloses hydrogen fluoride urea and a preparation method thereof.The hydrogen fluoride urea has the molecular formula of CH4N2O.nHF, wherein n is larger than 0 and smaller than 6.The mass of hydrogen fluoride accounts for 25.0-62.4% of the total mass of hydrogen fluoride urea; by controlling the temperature in a reaction still to be -50 DEG C to -10 DEG C, adding anhydrous hydrogen fluoride according to the mass ratio of (1-5):3, controlling the temperature in the reaction still to be -15 DEG C to -30 DEG C, conducting stirring reaction for 20-40 minutes, and then conducting reaction for 2-4 hours at the room temperature to obtain hydrogen fluoride urea of different proportions.The production process is easy to operate, the reaction yield is high, and the prepared hydrogen fluoride urea is a fluorinating reagent stable to use in the daily environment and can be used as an intermediate in fluorinating reaction for fluorinating aliphatic hydrocarbon and small-molecular aromatic hydrocarbon; due to the fact that the hydrogen fluoride urea has certain acidity, the acidity of the system can not be decreased in the use process, metal catalysts can not be interfered with, and the high reaction activity is achieved in acid catalysis reaction.
Description
Technical field
The present invention relates to the fluorination reagent field in organic fluorine chemistry, more particularly to a kind of fluohydric acid gas carbamide and preparation method thereof。
Background technology
Since coming out from early 1930s freon, organic fluorine chemistry shows flourish trend always。Owing to the introducing of fluorine atom causes that organic and inorganic compound has the physics of uniqueness, chemical property and biological activity, thus in many sophisticated technologies (atomic energy industry, rocket, aerospace etc.) and some great industrial projects (chlorine industry, fuel cell project) and medicine, pesticide, all fluorochemical has been carried out research extensively and profoundly and application。
The method introducing fluorine atom in Organic substance is a lot, and it is different that selective fluorination replaces principle according to fluorine atom, is generally divided into electrochemical selective fluorination, electrophilic fluorination and nucleophilic fluorination: electrophilic fluorination and nucleophilic fluorination are respectively necessary for fluorine-containing electrophilic reagent and nucleopilic reagent。
Traditional fluorination reagent is fluorine gas, owing to fluorine gas is strong oxidizer, almost can react with all substances, and along with the phenomenon such as heat release and blast, thus dilute fluorine gas solution typically by noble gas so that fluorination reaction is easily controlled and improves fluoride selectivity, the fluorination reagent prepared at low temperatures by fluorine gas and sodium acetate, acetylating agent Fluorine monohydroxide salt, preparation containing18The saccharide aspect of F labelling has more research application, and HF is also the fluorination reagent that laboratory is conventional, but its highly volatile, and there is stronger corrosivity, therefore it is restricted in the application of laboratory。O-F and the N-F reagent developed afterwards is two class fluorination reagents comparatively important in fluorination reaction, O-F reagent such as CF3COOF and CF3OF etc., N-F reagent such as N-fluorine two benzenesulfonimide (NSFI), diethylamine sulfur trifluoride (DAST) and double; two (2-methoxy ethyl) amino sulfur trifluoride (BAST) etc., wherein BAST is a kind of electrophilic fluorination reagent, fluorination process can introduce fluorine atom at the ortho position of carbonyl, reaction yield is high, and cost is low。The activity relatively fluorine gas of this two classes fluorination reagent is gentleer, but owing to many of which broadly falls into Strong oxdiative reagent, therefore application still suffers from certain limitation。Amine substance is combined the salt formed with fluohydric acid gas makes reactivity become gentle and be physically easier to perform, therefore novel fluorination reagent, as: triethylamine three (fluohydric acid gas) (Et3N-3HF), pyridine hydrogen fluoride salt (PPHF) becomes comparatively conventional fluorination reagent, wherein triethylamine three (fluohydric acid gas) is with its gentle and effective reactivity, good regioselectivity, less corrosivity and low price etc., there is the incomparable superioritys such as fluohydric acid gas, thus cause the great interest of organic chemists。What magazine " organic chemistry " the 29th volume the 9th phase in 2009 " triethylamine three (fluohydric acid gas) application in organic synthesis " was detailed describes reaction and the metal-organic synthesis etc. such as the nucleophilic substitution of triethylamine three (fluohydric acid gas), epoxy addition reaction, electrophilic addition reaction and desiliconization protection base; triethylamine three (fluohydric acid gas) after developing for 1980; it is widely used in various fields; but the use of triethylamine three (fluohydric acid gas) can reduce the acidity of system, and metallic catalyst may be produced interference。
Summary of the invention
For solving the problems referred to above, the invention provides a kind of novel nucleophilic fluorination reagent urea fluohydric acid gas and its preparation method。Technical scheme is as follows:
A kind of fluohydric acid gas carbamide, it is characterised in that: the molecular formula of described fluohydric acid gas carbamide is: CH4N2O nHF, wherein 0 < n < 6。
Further, the molecular formula of described fluohydric acid gas carbamide is: CH4N2O nHF, wherein 1≤n≤5。
Further, fluohydric acid gas mass percent in described fluohydric acid gas carbamide is 25.0%～62.4%。
A kind of preparation method of fluohydric acid gas carbamide, including being made by step:
1) in reactor, add anhydrous hydrogen fluoride, control reactor temperature between-40～-25 DEG C；
2) adding carbamide again in described reactor, control the speed that carbamide adds, make reactor temperature less than-15 DEG C, the mass ratio of described anhydrous hydrogen fluoride and carbamide is 1～5:3, stirring reaction 20～40min；
3) reactor being warming up to room temperature, at room temperature react 2～4h, gained is fluohydric acid gas carbamide。
Further, described carbamide is chemical pure carbamide, and described anhydrous hydrogen fluoride is industrial anhydrous hydrogen fluoride。
Further, described reactor is inner liner polytetrafluoroethylene reactor。
Further, described reactor is the stainless steel cauldron of the inner liner polytetrafluoroethylene of sandwich。
Reaction of the present invention is exothermic reaction, and one of primary raw material is anhydrous hydrogen fluoride, and hydrofluoric boiling point is relatively low, so temperature is the major influence factors of reaction success or failure, temperature height is unfavorable for that reaction carries out, and can make hydrofluoric volatilization aggravation simultaneously, instrument and operator are threatened；Temperature is too low, and response speed is slow, wastes big energy, increases cost simultaneously, so temperature is preferably more than-10 DEG C。
In reaction of the present invention, the productivity preparing fluohydric acid gas carbamide is also had impact by the dropping order of anhydrous hydrogen fluoride and carbamide, should be preferably added drop-wise in anhydrous hydrogen fluoride by carbamide。
A kind of fluohydric acid gas carbamide of the present invention; it is a kind of in surroundings, use stable fluorination reagent; can as the intermediate of fluorination reaction; for fluoride fat hydrocarbon and micromolecular aromatic hydrocarbon; and owing to fluohydric acid gas carbamide has certain acidity; the acidity of system will not be reduced during use, and without interference with metallic catalyst, therefore there is in acid catalyzed reaction higher reactivity。The method preparing fluohydric acid gas carbamide that the present invention adopts, the operation equipment of employing is simple, and reaction yield is high, and by-product and waste liquid, waste residue are less, and this reaction has the feature of environmental protection。
Detailed description of the invention
Embodiment 1
It is 200L at volume, sandwich, reflux condensing tube is fixed in the reactor upper end of inner liner polytetrafluoroethylene, the interlayer of described reactor is full of condensed fluid, described interlayer and condensing tube share a refrigeration machine, open refrigeration machine, 20kg anhydrous hydrogen fluoride it is slowly added in reactor, control reactor temperature and be-25 DEG C, 60kg carbamide it is slowly added to again in reactor, control reactor temperature and be-15 DEG C, continue stirring reaction 20min, close refrigeration machine, reactor temperature is made to be warming up to room temperature, at room temperature react 2h, obtaining fluorinated hydrogen mass percent is 39.8%, molecular formula is CH4N2The fluohydric acid gas carbamide of O HF。
Gained fluohydric acid gas carbamide is white solid, and productivity is 25.0%。
Embodiment 2
It is 200L at volume, sandwich, reflux condensing tube is fixed in the reactor upper end of inner liner polytetrafluoroethylene, the interlayer of described reactor is full of condensed fluid, described interlayer and condensing tube share a refrigeration machine, open refrigeration machine, 40kg anhydrous hydrogen fluoride it is slowly added in reactor, control reactor temperature and be-25 DEG C, 60kg carbamide it is slowly added to again in reactor, control reactor temperature and be-15 DEG C, continue stirring reaction 20min, close refrigeration machine, reactor temperature is made to be warming up to room temperature, at room temperature react 2h, obtaining fluorinated hydrogen mass percent is 39.8%, molecular formula is CH4N2The fluohydric acid gas carbamide of O 2HF。
Gained fluohydric acid gas carbamide is white solid, and productivity is 92.5%。
Embodiment 3
It is 200L at volume, sandwich, reflux condensing tube is fixed in the reactor upper end of inner liner polytetrafluoroethylene, the interlayer of described reactor is full of condensed fluid, described interlayer and condensing tube share a refrigeration machine, open refrigeration machine, 20kg anhydrous hydrogen fluoride it is slowly added in reactor, control reactor temperature and be-30 DEG C, 60kg carbamide it is slowly added to again in reactor, control reactor temperature and be-15 DEG C, continue stirring reaction 20min, close refrigeration machine, reactor temperature is made to be warming up to room temperature, at room temperature react 2.5h, obtaining fluorinated hydrogen mass percent is 45.4%, molecular formula is CH4N2The fluohydric acid gas carbamide of O 2.5HF。
Gained fluohydric acid gas carbamide is white solid, and productivity is 92.0%。
Embodiment 4
It is 200L at volume, sandwich, reflux condensing tube is fixed in the reactor upper end of inner liner polytetrafluoroethylene, the interlayer of described reactor is full of condensed fluid, described interlayer and condensing tube share a refrigeration machine, open refrigeration machine, 20kg anhydrous hydrogen fluoride it is slowly added in reactor, control reactor temperature and be-30 DEG C, 60kg carbamide it is slowly added to again in reactor, control reactor temperature and be-15 DEG C, continue stirring reaction 20min, close refrigeration machine, reactor temperature is made to be warming up to room temperature, at room temperature react 2.5h, obtaining fluorinated hydrogen mass percent is 49.8%, molecular formula is CH4N2The fluohydric acid gas carbamide of O 3HF。
Gained fluohydric acid gas carbamide is white solid, and productivity is 91.7%。
Embodiment 5
It is 200L at volume, sandwich, reflux condensing tube is fixed in the reactor upper end of inner liner polytetrafluoroethylene, the interlayer of described reactor is full of condensed fluid, described interlayer and condensing tube share a refrigeration machine, open refrigeration machine, 20kg anhydrous hydrogen fluoride it is slowly added in reactor, control reactor temperature and be-35 DEG C, 60kg carbamide it is slowly added to again in reactor, control reactor temperature and be-15 DEG C, continue stirring reaction 30min, close refrigeration machine, reactor temperature is made to be warming up to room temperature, at room temperature react 3h, obtaining fluorinated hydrogen mass percent is 53.8%, molecular formula is CH4N2The fluohydric acid gas carbamide of O 3.5HF。
Gained fluohydric acid gas carbamide is white solid, and productivity is 91.5%。
Embodiment 6
It is 200L at volume, sandwich, reflux condensing tube is fixed in the reactor upper end of inner liner polytetrafluoroethylene, the interlayer of described reactor is full of condensed fluid, described interlayer and condensing tube share a refrigeration machine, open refrigeration machine, 20kg anhydrous hydrogen fluoride it is slowly added in reactor, control reactor temperature and be-35 DEG C, 60kg carbamide it is slowly added to again in reactor, control reactor temperature and be-15 DEG C, continue stirring reaction 30min, close refrigeration machine, reactor temperature is made to be warming up to room temperature, at room temperature react 3h, obtaining fluorinated hydrogen mass percent is 56.5%, molecular formula is CH4N2The fluohydric acid gas carbamide of O 4HF。
Gained fluohydric acid gas carbamide is white solid, and productivity is 91.0%。
Embodiment 7
It is 200L at volume, sandwich, reflux condensing tube is fixed in the reactor upper end of inner liner polytetrafluoroethylene, the interlayer of described reactor is full of condensed fluid, described interlayer and condensing tube share a refrigeration machine, open refrigeration machine, 20kg anhydrous hydrogen fluoride it is slowly added in reactor, control reactor temperature and be-40 DEG C, 60kg carbamide it is slowly added to again in reactor, control reactor temperature and be-15 DEG C, continue stirring reaction 40min, close refrigeration machine, reactor temperature is made to be warming up to room temperature, at room temperature react 4h, obtaining fluorinated hydrogen mass percent is 59.5%, molecular formula is CH4N2The fluohydric acid gas carbamide of O 4.5HF。
Gained fluohydric acid gas carbamide is white solid, and productivity is 90.8%。
Embodiment 8
It is 200L at volume, sandwich, reflux condensing tube is fixed in the reactor upper end of inner liner polytetrafluoroethylene, the interlayer of described reactor is full of condensed fluid, described interlayer and condensing tube share a refrigeration machine, open refrigeration machine, 20kg anhydrous hydrogen fluoride it is slowly added in reactor, control reactor temperature and be-40 DEG C, 60kg carbamide it is slowly added to again in reactor, control reactor temperature and be-15 DEG C, continue stirring reaction 40min, close refrigeration machine, reactor temperature is made to be warming up to room temperature, at room temperature react 4h, obtaining fluorinated hydrogen mass percent is 62.4%, molecular formula is CH4N2The fluohydric acid gas carbamide of O 5HF。
Gained fluohydric acid gas carbamide is white solid, and productivity is 90.5%。
Claims (7)
1. a fluohydric acid gas carbamide, it is characterised in that: the molecular formula of described fluohydric acid gas carbamide is: CH4N2O nHF, wherein 0 < n < 6。
2. fluohydric acid gas carbamide according to claim 1, it is characterised in that: the molecular formula of described fluohydric acid gas carbamide is: CH4N2O nHF, wherein 1≤n≤5。
3. fluohydric acid gas carbamide according to claim 1, it is characterised in that: fluohydric acid gas mass percent in described fluohydric acid gas carbamide is 25.0%～62.4%。
4. the preparation method of a kind of fluohydric acid gas carbamide according to claim 1, including being made by step:
1) in reactor, add anhydrous hydrogen fluoride, control reactor temperature between-40～-25 DEG C；
2) adding carbamide again in described reactor, control the speed that carbamide adds, make reactor temperature less than-15 DEG C, the mass ratio of described anhydrous hydrogen fluoride and carbamide is 1～5:3, stirring reaction 20～40min；
3) reactor being warming up to room temperature, at room temperature react 2～4h, gained is fluohydric acid gas carbamide。
5. the preparation method of fluohydric acid gas carbamide according to claim 4, it is characterised in that: described carbamide is chemical pure carbamide, and described anhydrous hydrogen fluoride is industrial anhydrous hydrogen fluoride。
6. the preparation method of fluohydric acid gas carbamide according to claim 4, it is characterised in that: described reactor is the reactor of inner liner polytetrafluoroethylene。
7. the preparation method of fluohydric acid gas carbamide according to claim 4, it is characterised in that: described reactor is the stainless steel cauldron of the inner liner polytetrafluoroethylene of sandwich。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201610003049.1A CN105693557A (en) | 2016-01-04 | 2016-01-04 | Hydrogen fluoride urea and preparation method thereof |
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| CN201610003049.1A CN105693557A (en) | 2016-01-04 | 2016-01-04 | Hydrogen fluoride urea and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108689886A (en) * | 2018-06-22 | 2018-10-23 | 湖北卓熙氟化股份有限公司 | A kind of preparation method of fluorination urea hydrogen |
| CN110382459A (en) * | 2017-02-23 | 2019-10-25 | 溴化合物有限公司 | Liquid urea hydrohalide |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1370827A (en) * | 1963-07-19 | 1964-08-28 | France Etat | Obtaining organic hydrofluoric acid association complexes which can be used as reactive solvent media |
| US3156707A (en) * | 1962-05-17 | 1964-11-10 | Petro Tex Chem Corp | Oxidation of aliphatic hydrocarbons |
| US4466893A (en) * | 1981-01-15 | 1984-08-21 | Halliburton Company | Method of preparing and using and composition for acidizing subterranean formations |
| CN1384049A (en) * | 2001-05-08 | 2002-12-11 | 皮姆－因维斯特科学生产食品股份公司 | Preparation of nitrogen trifluoride |
| US20090240043A1 (en) * | 2005-01-07 | 2009-09-24 | Alnylam Pharmaceuticals, Inc. | RNAi MODULATION OF RSV AND THERAPEUTIC USES THEREOF |
-
2016
- 2016-01-04 CN CN201610003049.1A patent/CN105693557A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3156707A (en) * | 1962-05-17 | 1964-11-10 | Petro Tex Chem Corp | Oxidation of aliphatic hydrocarbons |
| FR1370827A (en) * | 1963-07-19 | 1964-08-28 | France Etat | Obtaining organic hydrofluoric acid association complexes which can be used as reactive solvent media |
| US4466893A (en) * | 1981-01-15 | 1984-08-21 | Halliburton Company | Method of preparing and using and composition for acidizing subterranean formations |
| CN1384049A (en) * | 2001-05-08 | 2002-12-11 | 皮姆－因维斯特科学生产食品股份公司 | Preparation of nitrogen trifluoride |
| US20090240043A1 (en) * | 2005-01-07 | 2009-09-24 | Alnylam Pharmaceuticals, Inc. | RNAi MODULATION OF RSV AND THERAPEUTIC USES THEREOF |
Non-Patent Citations (1)
| Title |
|---|
| F. RAMONDO等: ""Study of the hydrogen-bonded (NH2CONH2)(H2O)2 and (NH2CONH2)(HF)2 complexes and of the interaction of H2O with metal cations and anions"", 《JOURNAL OF MOLECULAR STRUCTURE (THEOCHEM)》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110382459A (en) * | 2017-02-23 | 2019-10-25 | 溴化合物有限公司 | Liquid urea hydrohalide |
| CN108689886A (en) * | 2018-06-22 | 2018-10-23 | 湖北卓熙氟化股份有限公司 | A kind of preparation method of fluorination urea hydrogen |
| CN108689886B (en) * | 2018-06-22 | 2021-06-15 | 湖北卓熙氟化股份有限公司 | Preparation method of hydrogen fluoride urea |
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