CN101058533A - Method of synthesizing fluoromethyl-1,1,1,3,3,3-hexafluoroisopropyl ether - Google Patents
Method of synthesizing fluoromethyl-1,1,1,3,3,3-hexafluoroisopropyl ether Download PDFInfo
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- CN101058533A CN101058533A CN 200610148706 CN200610148706A CN101058533A CN 101058533 A CN101058533 A CN 101058533A CN 200610148706 CN200610148706 CN 200610148706 CN 200610148706 A CN200610148706 A CN 200610148706A CN 101058533 A CN101058533 A CN 101058533A
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- isopropyl ether
- hexafluoro isopropyl
- hexafluoro
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Abstract
The invention discloses a synthesizing method of fluomethyl-1,1,1,3,3,3-hexafluoroisopropyl ether, which comprises the following steps: 1) reacting 1,1,1,3,3,3-hexafluorine-2-propanol and ,3,5-trioxymethylene or oligoformaldehyde and Lewis acid chloride to generate chloromethyl-1,1,1,3,3,3-hexafluoroisopropyl ether as intermediate and HOAlCl2 as by-product; adding 6N HCl to disintegrate to remove by-product HOAlCl2; 2) reacting chloromethyl-1,1,1,3,3,3-hexafluoroisopropyl ether and fluorination agent and solvent to produce the product; improving the selectivity of intermediate; removing by-product easily.
Description
Technical field
The present invention relates to methyl fluoride-1,1,1,3,3, the synthetic method of 3-hexafluoro isopropyl ether.
Background technology
Methyl fluoride-1,1,1,3,3,3-hexafluoro isopropyl ether, molecular formula (CF
3)
2CHOCH
2F is called for short Ultane.
In recent years, discover that fluoridizing ether material can perform well in sucking the narcotic field.These materials roughly have desflurane (CF
3CHFOCH
2F), isoflurane (CF
3CHClOCHF
2), isofluranum (HClFCCF
2OCHF
2) and methyl fluoride-1,1,1,3,3,3-hexafluoro isopropyl ether ((CF
3)
2CHOCH
2F) these are several.Methyl fluoride-1 wherein, 1,1,3,3,3-hexafluoro isopropyl ether (hereinafter to be referred as Ultane) has induced anesthesia and the characteristic fast of reviving, and also can reduce cerebral vascular resistance, CMR, brain oxygen-consumption, myocardium shrinkage function and blood pressure, pungency to respiratory tract is starkly lower than other suction narcotic, does not see its liver renal toxicity as yet.And this exactly is the modern character that narcotic needs most that sucks, and Ultane is subjected to paying close attention to widely and paying attention to as a kind of novel inhaling type narcotic in the world.
U.S. Pat 4250334 and US4469898 have described the technological line of producing Ultane, all mention with 1,1,1,3,3, and (molecular formula is (CF to 3-hexafluoro-2-propyl alcohol
3)
2CHOH is hereinafter to be referred as HFIP) as reaction raw materials.In the U.S. Pat 4469898, generate Ultane with formaldehyde and hydrogen fluoride, protonating agent, dehydrated reagent and fluorination reagent reaction by HFIP; U.S. Pat 4250334 has been described an other technological line, HFIP is joined in excessive Paraformaldehyde 96 and the hydrogen fluoride react, and comes the moisture that produces in the absorption reaction process with excessive sulfuric acid simultaneously.These two pieces of synthetic methods that United States Patent (USP) is described, because the existence of by product all needs product is carried out purifying, and these by products are difficult to be removed; Use extremely strong hydrogen fluoride reagent and the sulfuric acid of corrodibility that the protection against corrosion of equipment is had relatively high expectations in the production, improved the production cost of Ultane to a certain extent.
U.S. Pat 6469219 is mentioned direct fluorinated methyl hexafluoro isopropyl ether.Direct reaction need use extremely active BrF
3Reagent comes fluorinated methyl hexafluoro isopropyl ether.The BrF that in this reaction, needs 0.5～1mol
3Come to react with the methyl hexafluoro isopropyl ether of 0.67mol, temperature of reaction is controlled between 20～50 ℃.Directly fluoridize and under argon shield, directly to fluoridize with fluorine gas.U.S. Pat 5705710 is mentioned with methoxy propyl dintrile and strong active oxidation fluorizating agent bromine trifluoride and is synthesized Ultane.
This route is by the same Br of methoxy propyl dintrile that contains two itrile groups
3F reacts and makes Ultane.But final product has two, and one is Ultane, and another is a methyl hexafluoro isopropyl ether.Methyl hexafluoro isopropyl ether can be purified to come out or add again from reactant and be contained Br
3Be converted into Ultane in the reaction vessel of F; The reaction product Ultane then can obtain by the distillatory method.This reaction can be carried out under the condition that participates in without any need for solvent, and temperature of reaction neither be too harsh.But in the synthetic method of these two pieces of U.S. Pat 6469219 and US5705710, all use strong active oxidation fluorizating agent bromine trifluoride Br
3F, this reagent price comparison is expensive and have a certain risk.
Summary of the invention
The objective of the invention is: a kind of output height (at least 80%) is provided, and reaction process is simple, economic and practical, the synthetic method of the Ultane of non-corrosiveness, compliance with environmental protection requirements.
For achieving the above object, the technical scheme of employing is:
1) by HFIP, 1,3,5-trioxane or paraformaldehyde and chlorination Lewis acid generate intermediate chloromethyl-1,1,1,3,3,3-hexafluoro isopropyl ether and by product HOAlCl
2
HFIP and 1,3,5-trioxane or paraformaldehyde mol ratio are 1: 1 to 10: 1.
Chlorination Lewis acid and 1,3, the mol ratio of 5-trioxane or paraformaldehyde are 1: 1 to 8: 1.Wherein the chlorination Lewis acid is a kind of in phosphorus trichloride or the aluminum chloride.
Reaction system adds HFIP and chlorination Lewis acid by proportioning under 0 ℃ and agitation condition, after HCl gas is discharged ten minutes, add 1,3 by proportioning again, 5-trioxane or paraformaldehyde, continuation stirring reaction drip 6N hydrochloric acid decomposition by-products HOAlCl after about 8 hours
2, add deionized water then until solid dissolving, system layering, get underlying liquid and can get intermediate chloromethyl-1,1,1,3,3,3-hexafluoro isopropyl ether.
2) by intermediate chloromethyl-1,1,1,3,3,3-hexafluoro isopropyl ether is produced Ultane with fluorination reagent and solvent reaction again.
Fluorination reagent and chloromethyl-1,1,1,3,3, the mol ratio of 3-hexafluoro isopropyl ether is 1: 1 to 10: 1.Fluorination reagent is KF, NaF, KF
2H and NaF
2H, CaF
2In a kind of.
The solvent that is adopted is dimethyl sulfoxide (DMSO), N, a kind of in dinethylformamide, ethylene glycol, diethylene glycol dimethyl ether, polyoxyethylene glycol and the water.Temperature of reaction is 30～120 ℃, and is relevant with selected solvent; Reaction times is controlled at 1～10h.Add water sepn and extract Ultane.
The advantage of the technical solution used in the present invention is that cost of material is cheaper and is not with corrodibility, so neither be very high to equipment requirements.Reaction is carried out in two steps, and is easy and simple to handle, and reaction preference has obtained raising to a great extent simultaneously, and intermediate building-up reactions selectivity reaches more than 90%, and Ultane building-up reactions selectivity reaches more than 70%, and by product is also removed and handled than being easier to.
Embodiment
The first step reaction is thermopositive reaction in the technical scheme.When using 1,3, during the 5-trioxane, reaction is carried out relatively slowly, and process can obtain controlling more stably; And when using paraformaldehyde, reaction carries out relatively rapidly but exothermic phenomenon is come relatively more violently.So in the first step, the both can use theoretically, but need to decide according to particular case and requirement.And add the chlorination Lewis acid in reaction is to be used for activating 1,3 in the first step, 5-trioxane or paraformaldehyde, and use as a kind of chlorination group.
The HFIP (purity 99%) and 1,3 that in the first step reaction, adds, 5-trioxane or paraformaldehyde mol ratio are 1: 1 to 10: 1; Chlorination Lewis acid and 1,3, the mol ratio of 5-trioxane or paraformaldehyde are 1: 1 to 8: 1.Wherein the chlorination Lewis acid is a kind of in phosphorus trichloride or the aluminum chloride.
This reaction can be controlled under-20 ℃～50 ℃ temperature condition to be carried out.If for reaction can be carried out better, the temperature of the first step reaction can be controlled between 0～30 ℃.Between this section temperature, the speed of reaction is accelerated along with the raising of temperature.Reaction times then can be controlled in 5～20h.
But the by product HOAlCl that in the first step reaction, generates
2But to chloromethyl-1,1,1,3,3,3-hexafluoro isopropyl ether has certain toxicity, can cause chloromethyl-1,1,1,3,3, the degraded of 3-hexafluoro isopropyl ether.Particularly the chlorion in the product can be as a kind of Lewis acid, thereby causes chloromethyl-1,1,1,3,3,3-hexafluoro isopropyl ether and methyl fluoride-1,1,1,3,3, the degraded of 3-hexafluoro isopropyl ether.So, preferably remove the HOAlCl that produces by the first step
2Thereby, make intermediate and product be unlikely the generation DeR.The method of removing is also very simple, uses simple precipitation just can make HOAlCl
2Separate the HOAlCl after the recovery with system
2Can produce the required raw material chlorination Lewis acid of reaction by further reaction again.From system, remove HOAlCl in fact
2Also have kind of a better method, make its decomposition by adding acid exactly, for example in reaction system, add HCl and just can make HOAlCl
2Decompose.Also have document to mention can to use the excessive KF of 1mol or other excessive alkali fluoride metals of 1mol come in and HOAlCl
2
The chloromethyl-1,1,1,3,3 that the first step reaction produces, 3-hexafluoro isopropyl ether intermediate carry out the reaction of second step with fluorination reagent again and produce Ultane.Fluorination reagent and chloromethyl-1,1,1,3,3, the mol ratio of 3-hexafluoro isopropyl ether is 1: 1 to 10: 1.The fluorination reagent range of choice is also very wide, can be from such as KF
2H, CaF
2, NaF, KF, NaF
2Select a kind of in the alkali fluoride metals such as H.
The second step reaction needed is carried out in a kind of solvent.These solvents are dimethyl sulfoxide (DMSO), N, a kind of in dinethylformamide, ethylene glycol, diethylene glycol dimethyl ether, polyoxyethylene glycol and the water.Reaction generally is controlled under 30～120 ℃ of these temperature of reaction to be carried out, but the differing temps of selecting along with solvent also has a very big rangeability.For example, be solvent with ethylene glycol, temperature can be controlled at 60～95 ℃.And if use other solvents, temperature of reaction then needs higher.Controlled 1～the 10h that is made as of the time of this fluoridation.
Also need at last the Ultane that reaction generates is separated, separation can be used the distillatory method, for example dodges anxious distillation.Using more method now is to add entry Ultane is separated from mixture in product.Reason is that Ultane is water insoluble and other materials or solvent in the reaction are all water-soluble, adds to leave standstill after the entry to produce layering, and lower floor is a Ultane, and the upper strata is other water-soluble materials, has so just played the isolating effect of separating funnel that is similar to.
Embodiment 1
Adopt the glass reaction still of the 50L of a band lower discharge port, its subsidiary cover mechanical stirring device, a thermopair, an inner coil pipe and a refrigerant condenser.Add phosphorus trichloride 3556g (25.86mol), add HFIP 4345g (48.28mol) while stirring after system is dropped to 0 ℃, continue to stir light, add 1,3 then, 5-trioxane 2327g (25.86mol) up to HCl gas row.Temperature can rise to some extent, to about 8 ℃, but can fall back 0 ℃ immediately again, continues stirring reaction 8 hours.Begin slowly to drip the HCl 4L of 6N subsequently, reaction is thermopositive reaction, so temperature can rise to some extent, maintains 45 ℃.Add the 5L deionized water and stirring subsequently, be divided into two-layerly up to the whole dissolution system of solid significantly, take out underlying liquid and can obtain product chloromethyl-1,1,1,3,3,3-hexafluoro isopropyl ether.
Embodiment 2
Adopt the glass reaction still of a 50L, its subsidiary cover mechanical stirring device, a thermopair and constant temperature jacket.Chloromethyl-1,1,1,3,3,3-hexafluoro isopropyl ether 7031g (32.48mol) is dissolved in and continues in the 16L dimethyl sulfoxide (DMSO) to stir, and adds NaF 1364g (32.48mol) in the time of stirring it is fluoridized, and is warmed up to 30 ℃ of afterreaction 1h then.Add the 5L deionized water and stirring again, up to solution obviously be divided into two-layer after, take out underlying liquid and can obtain the product Ultane.
Embodiment 3
Adopt an exsiccant 250ml round-bottomed flask, its subsidiary a tetrafluoro stirring rod, a thermometer and a refrigerator.Open refrigerator and carry out freezingly, in flask, add aluminum chloride 18.6g (0139mol), HFIP31.2g (0.186mol), logical N after making system temperature drop to 0 ℃
2Bubbling ten minutes is driven away and is unfavorable for reacting the HCl gas that carries out in the system.Add paraformaldehyde 4.18g (0.034mol) then, close freezingly, allow it freely rise to and begin after the room temperature to stir.Behind the reaction 12h, drip 6N HCl 50ml, can pour into behind the adding 50ml deionized water after dropwising and carry out layering in the separating funnel, can obtain product chloromethyl-1,1,1,3,3,3-hexafluoro isopropyl ether after the taking-up bottom clear liquor.
Embodiment 4
Adopt an exsiccant 250ml round-bottomed flask, its subsidiary magnetic stirring apparatus, thermometer, a ball shape prolong and a refrigerator.Open refrigerator spherical condensation tube is carried out freeze cycle, subsequently chloromethyl-1,1,1,3,3, add flask after 3-hexafluoro isopropyl ether 11g (0.05mol) dissolves in 50ml ethylene glycol, add 17.7g (0.3mol) KF again, opening magnetic agitation after being warmed up to 60 ℃ reacts.Stir behind the 4h add the 150ml deionized water in the system after, pour into and carry out layering in the separating funnel, can obtain the product Ultane after the taking-up bottom clear liquor.
Embodiment 5
In an exsiccant 100ml round-bottomed flask, add phosphorus trichloride 56.5g (0.41mol), add HFIP 86g (0.51mol) among then the flask that phosphorus trichloride is housed being placed ice bath, discharge the HCl gas that produces, stir, after ten minutes, add 1,3,5-trioxane 4.63g (0.051mol) continues to stir and reacts.React after 20 hours, add prolong and reflux, circulatory mediator is selected the mixed condensing agent of ice and acetone.Begin to drip 6N 30ml hydrochloric acid then under the ice bath environment, the hydrolysis that dropwises the back polyoxymethylene also comes to an end.Take out product subsequently and in system, add the 50ml deionized water, can the layering discharging obtain intermediate product chloromethyl-1,1,1,3,3,3-hexafluoro isopropyl ether.
Embodiment 6
At ambient temperature, add chloromethyl-1,1,1,3,3,3-hexafluoro isopropyl ether 2.16g (0.01mol) and 10ml polyoxyethylene glycol, KF
2H 7.8g (0.1mol), the alcohol that adopts-20 ℃ add prolong and reflux as circulatory mediator.Lowering the temperature behind the reaction 10h down at 120 ℃, adding the 30ml deionized water after dropping to room temperature, can the layering discharging obtain the product Ultane.
Above embodiment can adopt NMR (Nuclear Magnetic Resonance) spectrum and two kinds of methods of gas chromatographic analysis to come product is characterized.NMR (Nuclear Magnetic Resonance) spectrum is used in the qualitative analysis of reaction mixture.Proton nmr spectra with the nuclear magnetic resonance spectrometer of Varian 300 or the 400MHz record.Carbon-13 nmr spectra is 75 or the 100MHz record.Chemical shift adopts ppm as unit, and its metering then is that benchmark is recorded (TMS, chemical shift is 0.00) to low script holder with the tetramethylsilane.Upright 9790 gas-chromatographies of good fortune are used in the quantitative analysis of reaction mixture.Analytical results shows: reaction preference of the present invention has obtained raising to a great extent, and intermediate building-up reactions selectivity reaches more than 90%, and Ultane building-up reactions selectivity reaches more than 70%.
Claims (8)
1. methyl fluoride-1,1,1,3,3, the synthetic method of 3-hexafluoro isopropyl ether is characterized in that:
1) by 1,1,1,3,3,3-hexafluoro-2-propyl alcohol, 1,3,5-trioxane or paraformaldehyde, chlorination Lewis acid generate intermediate chloromethyl-1,1,1,3,3,3-hexafluoro isopropyl ether and by product HOAlCl
2
2) by intermediate chloromethyl-1,1,1,3,3,3-hexafluoro isopropyl ether and fluorination reagent, solvent reaction are produced methyl fluoride-1,1,1,3,3,3-hexafluoro isopropyl ether.
2. according to claim 1 described methyl fluoride-1,1,1,3,3, the synthetic method of 3-hexafluoro isopropyl ether is characterized in that: 1,1,1,3,3, and 3-hexafluoro-2-propyl alcohol and 1,3, the mol ratio of 5-trioxane or paraformaldehyde is 1: 1 to 10: 1.
3. according to claim 1 described methyl fluoride-1,1,1,3,3, the synthetic method of 3-hexafluoro isopropyl ether is characterized in that: described chlorination Lewis acid and 1,3, the mol ratio of 5-trioxane or paraformaldehyde are 1: 1 to 8: 1.
4. according to claim 1 or 3 described methyl fluorides-1,1,1,3,3, the synthetic method of 3-hexafluoro isopropyl ether is characterized in that: described chlorination Lewis acid is a kind of in phosphorus trichloride or the aluminum chloride.
5. according to claim 1 described methyl fluoride-1,1,1,3,3, the synthetic method of 3-hexafluoro isopropyl ether, it is characterized in that: described step 1) synthetic method is: reaction system adds 1,1,1 by proportioning under 0 ℃ and agitation condition, 3,3,3-hexafluoro-2-propyl alcohol and chlorination Lewis acid, after HCl gas is discharged ten minutes, add 1,3 again, 5-trioxane or paraformaldehyde, continuation stirring reaction drip 6N hydrochloric acid decomposition by-products HOAlCl after 8 hours
2, add deionized water then until solid dissolving, system layering, get underlying liquid and can get intermediate chloromethyl-1,1,1,3,3,3-hexafluoro isopropyl ether.
6. according to claim 1 described methyl fluoride-1,1,1,3,3, the synthetic method of 3-hexafluoro isopropyl ether is characterized in that: in step 2) described in fluorination reagent and chloromethyl-1,1,1,3,3, the mol ratio of 3-hexafluoro isopropyl ether is 1: 1 to 10: 1.
7. according to claim 1 described methyl fluoride-1,1,1,3,3, the synthetic method of 3-hexafluoro isopropyl ether is characterized in that: fluorination reagent described step 2) is KF, NaF, KF
2H and NaF
2H, CaF
2In a kind of.
8. according to claim 1 described methyl fluoride-1,1,1,3,3, the synthetic method of 3-hexafluoro isopropyl ether, it is characterized in that: solvent described step 2) is dimethyl sulfoxide (DMSO), N, a kind of in dinethylformamide, ethylene glycol, diethylene glycol dimethyl ether, polyoxyethylene glycol and the water.
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| CN 200610148706 CN101058533A (en) | 2006-12-30 | 2006-12-30 | Method of synthesizing fluoromethyl-1,1,1,3,3,3-hexafluoroisopropyl ether |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010000136A1 (en) * | 2008-07-02 | 2010-01-07 | 鲁南制药集团股份有限公司 | Method of synthesizing sevoflurane |
| WO2010054540A1 (en) * | 2008-11-17 | 2010-05-20 | 江苏恒瑞医药股份有限公司 | A method for preparing chloromethyl-1,1,1,3,3,3- hexafluoroisopropyl ether |
| CN102010334A (en) * | 2010-10-25 | 2011-04-13 | 江苏梅兰化工有限公司 | Method for preparing fluorine-containing acrylate |
| CN103934020A (en) * | 2013-01-22 | 2014-07-23 | 福建博特化学品有限责任公司 | Use of octa-substituted guazatine as synthesis catalyst of fluoromethyl hexafluoro isopropyl ether and catalytic synthesis method |
-
2006
- 2006-12-30 CN CN 200610148706 patent/CN101058533A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010000136A1 (en) * | 2008-07-02 | 2010-01-07 | 鲁南制药集团股份有限公司 | Method of synthesizing sevoflurane |
| WO2010054540A1 (en) * | 2008-11-17 | 2010-05-20 | 江苏恒瑞医药股份有限公司 | A method for preparing chloromethyl-1,1,1,3,3,3- hexafluoroisopropyl ether |
| CN102010334A (en) * | 2010-10-25 | 2011-04-13 | 江苏梅兰化工有限公司 | Method for preparing fluorine-containing acrylate |
| CN102010334B (en) * | 2010-10-25 | 2013-08-14 | 江苏梅兰化工有限公司 | Method for preparing fluorine-containing acrylate |
| CN103934020A (en) * | 2013-01-22 | 2014-07-23 | 福建博特化学品有限责任公司 | Use of octa-substituted guazatine as synthesis catalyst of fluoromethyl hexafluoro isopropyl ether and catalytic synthesis method |
| CN103934020B (en) * | 2013-01-22 | 2016-03-30 | 福建海西联合药业有限公司 | Eight Guanoctines replaced are as the application of the synthetic catalyst of methyl fluoride hexafluoroisopropyl ether and process for catalytic synthesis |
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