CN1865209A - Fluorine-containing alcohols and process for production thereof - Google Patents

Fluorine-containing alcohols and process for production thereof Download PDF

Info

Publication number
CN1865209A
CN1865209A CN 200610081937 CN200610081937A CN1865209A CN 1865209 A CN1865209 A CN 1865209A CN 200610081937 CN200610081937 CN 200610081937 CN 200610081937 A CN200610081937 A CN 200610081937A CN 1865209 A CN1865209 A CN 1865209A
Authority
CN
China
Prior art keywords
compound
fluorine
cfhcf
ocf
formula
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
Application number
CN 200610081937
Other languages
Chinese (zh)
Inventor
古川丰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AGC Inc
Original Assignee
Asahi Glass Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Publication of CN1865209A publication Critical patent/CN1865209A/en
Pending legal-status Critical Current

Links

Abstract

Provided are novel fluorine-containing alcohols and a process for producing the same, specifically, fluorine -containing alcohols represented by the general formula: R<1>CY<1>HCY<2>Y<3>OQ<1>OH or HOQ<2>OCZ<1>Z<2>CZ<3>HR<2>CZ<4>HCZ<5>Z<6>OQ<2>OH (wherein R<1> is a fluorine-containing monovalent organic group or the like; R<2> is a fluorine-containing divalent organic group or the like; Y<1> to Y<3> and Z<1> to Z<6> are each fluoro; and Q<1> and Q<2> are each alkylene or the like), and a process for producing fluorine-containing alcohols having groups represented by the general formula: -CX<1>HCX<2>X<3>OQOH by reacting a compound having a group represented by the general formula: -CX<1>=CX<2>X<3> with a diol represented by the general formula: HOQOH in the presence of an alkali metal compound (wherein X<1>, X<2>, and X<3> are each fluoro; and Q is alkylene or the like).

Description

Fluorine-containing alcohol and preparation method thereof
The application is that international application no is PCT/JP2003/007771, and international filing date is national applications the dividing an application for the Chinese patent application of " fluorine-containing alcohol and preparation method thereof " that number be 03815064.6 title after the PCT international application on June 19th, 2003 enters China's stage.
Technical field
The present invention relates to novel fluorine-containing alcohol and preparation method thereof.
Background technology
The fluorochemicals that terminal portions possesses hydroxyl has R f(CF 2CF 2) nCH 2CH 2OH (R fThe expression Polyfluoroalkyl), the preparation method of this fluorochemicals has following method.
That is, make R by telomerization fI and CF 2=CF 2Reaction generates R f(CF 2CF 2) nI (n is the integer more than 1) makes this compound and ethene carry out addition again, generates R f(CF 2CF 2) nCH 2CH 2I uses then and is loaded with alkali-metal solid acid catalyst, generates R f(CF 2CF 2) nCH 2CH 2The method of OH (the Japanese Patent spy opens 2000-79345).
But, prepare R by telomerization f(CF 2CF 2) nDuring I, has the compound that above-mentioned carbonatoms (that is, the n in the aforementioned chemical formula) distributes owing to generate, by the R of this compound deriving f(CF 2CF 2) nCH 2CH 2OH also is the fluorochemicals with above-mentioned carbon number distribution.Therefore, obtain the fluorochemicals that terminal portions has hydroxyl and has specific carbonatoms, must after reaction, separate.
The present inventor thinks, eliminate the difficult point of the carbon number distribution in the above-mentioned telomerization, importantly uses glycol in reaction raw materials, has found terminal portions to have the new compound of hydroxyl based on this.That is, the purpose of this invention is to provide new fluorine-containing alcohol and preparation method thereof.
R 1CY 1HCY 2Y 3OQ 1OH formula 1
HOQ 2OCZ 1Z 2CZ 3HR 2CZ 4HCZ 5Z 6OQ 3OH
Formula 2
The implication of the symbol in formula 1 and the formula 2 is as described below.R 1: 1 valency organic radical, halogen atom or hydrogen atom; R 2: the divalent organic radical; Y 1, Y 2, Y 3: represent hydrogen atom or fluorine atom, R respectively independently 1When being not fluorine atom, Y 1, Y 2, Y 3In at least 1 be fluorine atom; Z 1, Z 2, Z 3, Z 4, Z 5, Z 6: represent hydrogen atom or fluorine atom, Z respectively independently 1, Z 2, Z 3In at least 1 be fluorine atom, and Z 4, Z 5, Z 6In at least 1 be fluorine atom; Q 1, Q 2, Q 3: represent the divalent organic radical respectively independently.
In addition, the invention provides the preparation method of the fluorine-containing alcohol (compound 5) of group with following formula 5 expressions, the feature of this method is in the presence of alkali metal compound, to make the compound (compound 3) of the group with following formula 3 expressions and glycol (compound 4) reaction of following formula 4 expressions.
-CX 1=CX 2X 3Formula 3
HOQOH formula 4
-CX 1HCX 2X 3OQOH formula 5
The implication of the symbol in formula 3, formula 4, the formula 5 is as described below.X 1, X 2, X 3: represent hydrogen atom or fluorine atom, X respectively independently 1, X 2, X 3In at least 1 be fluorine atom; Q:2 valency organic radical.
The best mode that carries out an invention
In the compound 1, R 1Be 1 valency organic radical, halogen atom or hydrogen atom.R 1Be preferably 1 valency alkyl or 1 valency halo alkyl, good especially for containing 1 valency halo alkyl of etheric oxygen atom.R 1Can be linear chain structure, also branched structure can be arranged, also can have ring structure.
Wherein, R 1Be preferably the fluoro alkyl, the good especially perfluoroalkyl that is replaced by fluorine atom for all hydrogen atoms of alkyl, especially good is the perfluoroalkyl that contains etheric oxygen atom.When containing etheric oxygen atom, this etheric oxygen atom preferably is present in terminal portions.
In the compound 1, Y 1, Y 2, Y 3Being preferably fluorine atom, preferably is fluorine atom all.In addition, Q 1Be preferably the divalent alkyl, good especially is alkylidene group.Q 1Be preferably-(CH 2) tThe group of-(t is the integer more than 1) expression is more preferably t and is 2～12 group, and good especially is that t is 2～6 group.
For making compound 1 synthetic easily, so compound 1 is preferably R ' CFHCF 2O (CH 2) mThe compound (compound 6) of OH (R ' for containing the fluorine-containing organic radical of 1 valency of carbonatoms 1～16 of etheric oxygen atom, m is 2～12 integer) expression.In the compound 6, R ' can be a linear chain structure, also branched structure can be arranged.When branched structure was arranged, a chain portion preferably was present in end, and this chain portion is preferably (CF 3) 2CF-.
Wherein, R ' is preferably the fluoro alkyl, the perfluoroalkyl that all hydrogen atoms of good especially is alkyl are replaced by fluorine atom, and especially good is the perfluoroalkyl that contains etheric oxygen atom.When containing etheric oxygen atom, this etheric oxygen atom preferably is present in terminal portions.
Object lesson as compound 1 can exemplify following compound.
H(CF 2) 2O(CH 2) 2OH、
H(CF 2) 2O(CH 2) 3OH、
H(CF 2) 2O(CH 2) 4OH、
H(CF 2) 2O(CH 2) 6OH、
CF 3CFHCF 2O(CH 2) 2OH、
CF 3CFHCF 2O(CH 2) 3OH、
CF 3CFHCF 2O(CH 2) 4OH、
CF 3CFHCF 2O(CH 2) 6OH、
C 2F 5CFHCF 2O(CH 2) 2OH。
C 2F 5CFHCF 2O(CH 2) 3OH、
C 2F 5CFHCF 2O(CH 2) 4OH、
C 2F 5CFHCF 2O(CH 2) 6OH、
C 3F 7CFHCF 2O(CH 2) 2OH、
C 3F 7CFHCF 2O(CH 2) 3OH、
C 3F 7CFHCF 2O(CH 2) 4OH、
C 3F 7CFHCF 2O(CH 2) 6OH。
C 5F 11CFHCF 2O(CH 2) 2OH、
C 5F 11CFHCF 2O(CH 2) 3OH、
C 5F 11CFHCF 2O(CH 2) 4OH、
C 5F 11CFHCF 2O(CH 2) 6OH、
C 7F 15CFHCF 2O(CH 2) 2OH、
C 7F 15CFHCF 2O(CH 2) 3OH、
C 7F 15CFHCF 2O(CH 2) 4OH、
C 7F 15CFHCF 2O(CH 2) 6OH。
C 3F 7OCFHCF 2O(CH 2) 2OH、
C 3F 7OCFHCF 2O(CH 2) 3OH、
C 3F 7OCFHCF 2O(CH 2) 4OH、
C 3F 7OCFHCF 2O(CH 2) 6OH、
C 4F 9OCFHCF 2OCH 2CH 2OH、
C 4F 9OCFHCF 2O(CH 2) 3OH、
C 4F 9OCFHCF 2O(CH 2) 4OH、
C 4F 9OCFHCF 2O(CH 2) 6OH、
C 5F 11OCFHCF 2O(CH 2) 2OH、
C 5F 11OCFHCF 2O(CH 2) 3OH、
C 5F 11OCFHCF 2O(CH 2) 4OH、
C 5F 11OCFHCF 2O(CH 2) 6OH、
C 6F 13OCFHCF 2O(CH 2) 2OH、
C 6F 13OCFHCF 2O(CH 2) 3OH、
C 6F 13OCFHCF 2O(CH 2) 4OH
C 6F 13OCFHCF 2O(CH 2) 6OH。
(CF 3) 2CFCF 2CFHCF 2O(CH 2) 2OH、
(CF 3) 2CFCF 2CFHCF 2O(CH 2) 3OH、
(CF 3) 2CFCF 2CFHCF 2O(CH 2) 4OH、
(CF 3) 2CFCF 2CFHCF 2O(CH 2) 6OH、
F[CF(CF 3)CF 2O]CFHCF 2O(CH 2) 2OH、
F[CF(CF 3)CF 2O]CFHCF 2O(CH 2) 4OH、
F[CF(CF 3)CF 2O] 2CFHCF 2O(CH 2) 2OH、
F[CF(CF 3)CF 2O] 2CFHCF 2O(CH 2) 4OH、
F[CF(CF 3)CF 2O] 3CFHCF 2O(CH 2) 2OH、
F[CF(CF 3)CF 2O] 3CFHCF 2O(CH 2) 4OH。
In the compound 2, R 2Be preferably divalent alkyl or divalent halo alkyl, good especially for containing the divalent halo alkyl of etheric oxygen atom.R 2Can be linear chain structure, also branched structure can be arranged, also can have ring structure.
Wherein, R 2Be preferably the fluoro alkyl, the good especially perfluoroalkyl that is replaced by fluorine atom for all hydrogen atoms of alkyl, especially good is the perfluoroalkyl that contains etheric oxygen atom.When containing etheric oxygen atom, this etheric oxygen atom preferably is present in terminal portions.
In the compound 2, Z 1, Z 2, Z 3, Z 4, Z 5, Z 6Being preferably fluorine atom, preferably is fluorine atom all.Q 2And Q 3Preferably and the Q in the aforesaid compound 1 1Identical.
For making compound 2 synthetic easily, so compound 2 is preferably R " [CFHCF 2O (CH 2) qOH] 2The compound (compound 7) of (R " be the fluorine-containing organic radical of the divalent that contains etheric oxygen atom of carbonatoms 1～16, q is 2～12 integer) expression.In the compound 7, R " can be linear chain structure, also branched structure can be arranged.When branched structure was arranged, a chain portion preferably was present in end, and this chain portion is preferably (CF 3) 2CF-.
Wherein, R " be preferably the fluoro alkyl, the good especially perfluoroalkyl that is replaced by fluorine atom for all hydrogen atoms of alkyl, especially good is the perfluoroalkyl that contains etheric oxygen atom.When containing etheric oxygen atom, this etheric oxygen atom preferably is present in terminal portions.
The object lesson of compound 2 can exemplify following compound.
HO(CH 2) 2OCF 2CFH(CF 2) 2CFHCF 2O(CH 2) 2OH、
HO(CH 2) 3OCF 2CFH(CF 2) 2CFHCF 2O(CH 2) 3OH、
HO(CH 2) 4OCF 2CFH(CF 2) 2CFHCF 2O(CH 2) 4OH、
HO(CH 2) 6OCF 2CFH(CF 2) 2CFHCF 2O(CH 2) 6OH、
HOCH 2CH 2OCF 2CFH(CF 2) 3CFHCF 2OCH 2CH 2OH、
HO(CH 2C) 3OCF 2CFH(CF 2) 3CFHCF 2O(CH 2) 3OH、
HO(CH 2) 4OCF 2CFH(CF 2) 3CFHCF 2O(CH 2) 4OH、
HO(CH 2) 6OCF 2CFH(CF 2) 3CFHCF 2O(CH 2) 6OH。
HO(CH 2) 2OCF 2CFHO(CF 2) 2OCFHCF 2O(CH 2) 2OH、
HO(CH 2) 3OCF 2CFHO(CF 2) 2OCFHCF 2O(CH 2) 3OH、
HO(CH 2) 4OCF 2CFHO(CF 2) 2OCFHCF 2O(CH 2) 4OH、
HO(CH 2) 6OCF 2CFHO(CF 2) 2OCFHCF 2O(CH 2) 6OH、
HO(CH 2) 2OCF 2CFHO(CF 2) 3OCFHCF 2O(CH 2) 2OH、
HO(CH 2) 3OCF 2CFHO(CF 2) 3OCFHCF 2O(CH 2) 3OH、
HO(CH 2) 4OCF 2CFHO(CF 2) 3OCFHCF 2O(CH 2) 4OH、
HO(CH 2) 6OCF 2CFHO(CF 2) 3OCFHCF 2O(CH 2) 6OH、
HO(CH 2) 2OCF 2CFH[OCF 2CF(CF 3)]OCF 2(CF 2) 4CF 2O[CF(CF 3)CF 2O]CFHCF 2O(CH 2) 2OH。
HO(CH 2) 3OCF 2CFH[OCF 2CF(CF 3)]OCF 2(CF 2) 4CF 2O[CF(CF 3)CF 2O]CFHCF 2O(CH 2) 3OH、
HO(CH 2) 4OCF 2CFH[OCF 2CF(CF 3)]OCF 2(CF 2) 4CF 2O[CF(CF 3)CF 2O]CFHCF 2O(CH 2) 4OH、
HO(CH 2) 6OCF 2CFH[OCF 2CF(CF 3)]OCF 2(CF 2) 4CF 2O[CF(CF 3)CF 2O]CFHCF 2O(CH 2) 6OH。
In the compound 3, X 1, X 2, X 3Being preferably fluorine atom, preferably is fluorine atom all.Compound 3 can pass through J.Am.Chem.Soc, and the preparation method of records such as 75,4525 (1953) is synthetic.
Compound 3 is preferably the compound (compound 8) of following formula 8 expressions.
R[CX 1=CX 2X 3] pFormula 8
R:p valency organic radical, the integer of p:1～4, X 1, X 2, X 3: represent hydrogen atom or fluorine atom, X respectively independently 1, X 2, X 3In at least 1 be fluorine atom.
In the compound 8, R preferably and the R in the aforesaid compound 1 1Or the R in the aforesaid compound 2 2Identical.X 1, X 2, X 3Being preferably fluorine atom, preferably is fluorine atom all.P is preferably 1 or 2.
The object lesson of compound 3 can exemplify following compound.
CF 2＝CF 2、CF 3CF＝CF 2、C 2F 5CF＝CF 2、
C 3F 7CF＝CF 2、C 5F 11CF＝CF 2、
C 7F 15CF＝CF 2、C 3F 7OCF＝CF 2、
C 4F 9OCF＝CF 2、C 5F 11OCF＝CF 2、
C 6F 13OCF＝CF 2、(CF 3) 2CFCF 2CF＝CF 2、
F[CF(CF 3)CF 2O]CF＝CF 2、
F[CF(CF 3)CF 2O] 2CF＝CF 2、
F[CF(CF 3)CF 2O] 3CF＝CF 2。
CF 2＝CF(CF 2) 2CF＝CF 2、
CF 2＝CF(CF 2) 3CF＝CF 2、
CF 2＝CFO(CF 2) 2OCF＝CF 2、
CF 2＝CFO(CF 2) 3OCF＝CF 2、
CF 2＝CF[OCF 2CF(CF 3)]OCF 2(CF 2) 4CF 2
O[CF(CF 3)CF 2O]CF＝CF 2。
In the compound 4, Q preferably and the Q in the aforesaid compound 1 1Identical.
The object lesson of compound 4 is preferably HO (CH 2) 2OH, HO (CH 2) 3OH, HO (CH 2) 4OH, HO (CH 2) 6OH etc.
In the compound 5, X 1, X 2, X 3, Q is preferably identical with group in aforesaid compound 3 or the compound 4.
Compound 5 is preferably the compound (compound 9) of following formula 9 expressions.
R[CX 1HCX 2X 3OQOH] pFormula 9
R:p valency organic radical, X 1, X 2, X 3: represent hydrogen atom or fluorine atom, X respectively independently 1, X 2, X 3In at least 1 be fluorine atom, Q:2 valency organic radical, the integer of p:1～4.
In the compound 9, R, X 1, X 2, X 3, Q, p be preferably identical with the group in aforesaid compound 4 or the aforesaid compound 8.Compound 5 is preferably aforesaid compound 1 or aforesaid compound 2.
The alkali metal compound that is used for the reaction of compound 3 and compound 4 is preferably basic metal, alkalimetal hydride, alkali metal hydroxide, amination basic metal etc.Specifically can exemplify basic metal such as Na, K, Cs, alkali metal hydroxides such as NaOH, KOH, alkalimetal hydrides such as NaH, KH, NaNH 2, KNH 2Etc. amination basic metal.
In the above-mentioned reaction, the consumption of alkali metal compound is not particularly limited,, better uses O.01～1.0 times mole, consider speed of response especially, preferably use 0.05～0.5 times of mole corresponding to 1 mole compound 3.In this scope, use, can reduce the generation of by product, can react with suitable speed of response, so more satisfactory.
In the above-mentioned reaction, preparation has the compound of the group of 1 formula, 5 expressions, and when promptly preparing compound 1, the consumption of compound 4 is preferably 1～5 times of mole corresponding to 1 mole compound 3, and good especially is 2～4 times of moles.Preparation has the compound of the group of 2 formulas, 5 expressions, and when promptly preparing compound 2, the consumption of compound 4 is preferably 2～10 times of moles corresponding to 1 mole compound 3, and good especially is 4～8 times of moles.In this scope, react, be easy to generate the hydroxyl of a side of having only compound 4 and the resultant of reaction of compound 3, so more satisfactory.
The temperature of above-mentioned reaction is preferably 0～150 ℃, and good especially is 40～120 ℃.In this scope, react, can suitable speed of response react, and the polyreaction of compound 3 is not only arranged, so more satisfactory.
In addition, this reaction can be used solvent, also can be without solvent, but preferably use solvent.This solvent is preferably the solvent of solvent, the dissolved compound 5 of dissolved compound 4, the solvent of non-activity in fact in above-mentioned reaction.This solvent is preferably ether, nitrile compound etc.Specifically can exemplify ether, glyme, two  alkane, tetrahydrofuran (THF), acetonitrile, propionitrile, good especially is two  alkane, tetrahydrofuran (THF) or acetonitrile.
Consumption to solvent is not particularly limited, and considers speed of response and productivity, and being preferably the compound 5 that makes as resultant is the amount of 1～60 quality %, and good especially is, and to make compound 5 be the amount of 3～50 quality %.
In addition, because the under high pressure easy initiated polymerization of compound 3, so, in above-mentioned reaction, preferably use polymerization retarder in order to prevent the generation of polyreaction.This polymerization retarder can just join in the reactive system before adding raw material, also can join in the reactive system with raw material.This polymerization retarder is not particularly limited, can exemplifies limonene, firpene, cymene (シ メ Application), terpinene etc.
Among the present invention, the mechanism that generates compound 5 is inferred as follows.
That is, alkali metal compound makes glycol (compound 4) change alkoxide cpd into, and addition reaction takes place for this alkoxide cpd and compound 3, and its metal part is replaced by hydrogen atom again, has just generated compound 5.Use under the situation of glycol, even a hydroxyl reacts, another hydroxyl also can be residual, so can make fluorine-containing alcohol.
Utilize the present invention can synthesize new fluorine-containing alcohol.This fluorine-containing alcohol is useful as the intermediate of washing composition, all cpds.For example, make the reaction of compound 1 and vinylformic acid and the fluorinated acrylate that obtains is useful as the raw material and the water and oil repellent agent of UV cured resin.In addition, when compound 2 is the copolymer composition use of resin as polycondensations such as urethane, can carry out modification to the surface of this resin.
In addition, compound 3 as the raw material of fluorine-containing alcohol of the present invention can adopt Adv.Synth.Catal.2001, and 343, the direct fluorination method of No.2 record is synthetic, owing to directly fluoridize and can select the structure of raw material, the fluorine-containing alcohol that obtains can have various structures.
Embodiment
Below, exemplify embodiments of the invention and be specifically described, but the present invention is not limited to this.
[example 1]
In the stainless steel reaction vessel of internal volume 50mL, add 1 of 30g, the C of 4-two  alkane, 10g 3F 7OCF=CF 2, 4.67g HO (CH 2) 2Airtight behind the KOH of OH and 0.55g, while stir in 70 ℃ of reactions 8 hours.Then, add 50mL water and make reaction solution be divided into 2 layers, again organic layer is distilled, obtain the CF of 10.9g as resultant 3CF 2CF 2OCFHCF 2OCH 2CH 2OH and C 3F 7OCFHCF 2OCH 2CH 2OCF 2CFHOC 3F 7In this resultant the former: the latter's ratio is 75: 25 (mol ratio).
To CF 3CF 2CF 2OCFHCF 2OCH 2CH 2The measurement result of OH is as described below.
IR(neat)：3395，1342，1236，1199，1153，1102，985cm -1、
1H-NMR(CDCl 3)δ：1.84(t，J＝6.3Hz，3H，OH)，3.86～3.94(m，2H，CH 2OH)，4.15(t，J＝4.6Hz，2H，CF 2OCH 2)，5.95(d，t，53.5Hz，2.9Hz，1H，CFHCF 2)、
19F-NMR(CDCl 3)δ：-81.4(t，J＝6.4Hz，3F，CF 3)，-84.88and-86.99(ABquartet，J＝145.1Hz，2F，CF 2OCFH)，-89.00and-89.84(ABquartet，J＝144.0Hz，2F，CF 2OCH 2)，-129.50～-129.60(m，2F，CF 2CF 3)，-144.0(d，quintet，J＝53.5Hz，6.4Hz，1F，CFH)。
[example 2]
In the stainless steel reaction vessel of internal volume 50mL, add 1 of 30g, the C of 4-two  alkane, 10g 3F 7OCF=CF 2, 13.55g HO (CH 2) 4Airtight behind the KOH of OH and 0.55g, while stir in 70 ℃ of reactions 8 hours.Then, add 50mL water and make reaction solution be divided into 2 layers, again organic layer is distilled, obtain the CF of 12.8g as resultant 3CF 2CF 2OCFHCF 2O (CH 2) 4OH and C 3F 7OCFHCF 2O (CH 2) 4OCF 2CFHOC 3F 7In this resultant the former: the latter's ratio is 94: 6 (mol ratio).
To CF 3CF 2CF 2OCFHCF 2O (CH 2) 4The measurement result of OH is as described below.
IR(neat)：3349，2951，1341，1237，1199，1153，987cm -1、
1H-NMR(CDCl 3)δ：1.39(s，1H，OH)，1.60～1.73(m，2H，CH 2CH 2OH)，1.73～1.86(m，2H，CF 2OCH 2CH 2)，3.63～3.76(m，2H，CH 2OH)，4.03(t，J＝6.3Hz，2H，CF 2OCH 2)，5.86(d，t，53.7Hz，2.8Hz，1H，CFHCF 2)、
19F-NMR(CDCl 3)δ：-81.4(t，J＝7.5z，3F，CF 3)，-84.86and-86.96(ABquartet，J＝145.0Hz，2F，CF 2OCFH)，-89.30and-89.94(ABquartet，J＝144.0Hz，2F，CF 2OCH 2)，-129.5～-129.6(m，2F，CF 2CF 3)，-144.2(d，quintet，J＝53.7Hz，8.6Hz，1F，CFH)。
[example 3]
In the stainless steel reaction vessel of internal volume 50mL, add 1 of 30g, the C of 4-two  alkane, 10g 3F 7OCF=CF 2, 5.72g HOCH 2CH 2CH 2Airtight behind the KOH of OH and 0.55g, while stir in 70 ℃ of reactions 8 hours.Then, add 50mL water and make reaction solution be divided into 2 layers, again organic layer is distilled, obtain the CF of 11.6g as resultant 3CF 2CF 2OCFHCF 2OCH 2CH 2CH 2OH and C 3F 7OCFHCF 2OCH 2CH 2CH 2OCF 2CFHOC 3F 7In this resultant the former: the latter's ratio is 89: 11 (mol ratio).
To CF 3CF 2CF 2OCFHCF 2OCH 2CH 2CH 2The measurement result of OH is as described below.
IR(neat)：3356，1342，1236，1199，1153，1098，987cm -1、
1H-NMR(CDCl 3)δ：1.58(s，1H，OH)，1.93(quintet，J＝6.1Hz，2H，CH 2CH 2CH 2)，3.76(t，J＝6.0Hz，2H，CH 2OH)，4.14(t，J＝6.1Hz，2H，CF 2OCH 2)，5.87(d，t，53.5Hz，2.9Hz，1H，CFHCF 2)、
19F-NMR(CDCl 3)δ：-81.4(t，J＝7.5z，3F，CF 3)，-84.88and-87.02(ABquartet，J＝148.0Hz，2F，CF 2OCFH)，-89.36and-90.05(ABquartet，J＝146.1Hz，2F，CF 2OCH 2)，-129.54～-129.64(m，2F，CF 2CF 3)，-144.2(d，quintet，J＝53.5Hz，8.1Hz，1F，CFH)。
[example 4]
In the stainless steel reaction vessel of internal volume 50mL, add 1 of 30g, the C of 4-two  alkane, 10g 3F 7OCF=CF 2, 8.88g HO (CH 2) 6Airtight behind the KOH of OH and 0.55g, while stir in 70 ℃ of reactions 8 hours.Then, add 50mL water and make reaction solution be divided into 2 layers, again organic layer is distilled, obtain the CF of 13.0g as resultant 3CF 2CF 2OCFHCF 2O (CH 2) 6OH and C 3F 7OCFHCF 2O (CH 2) 6OCF 2CFHOC 3F 7In this resultant the former: the latter's ratio is 87: 13 (mol ratio).
To CF 3CF 2CF 2OCFHCF 2O (CH 2) 6The measurement result of OH is as described below.
IR(neat)：3351，2942，1341，1237，1199，1154，1092，988cm -1、
1H-NMR(CDCl 3)δ：1.32～1.48(5H，OH，CH 2CH 2CH 2CH 2CH 2CH 2)，1.52～1.75(m，4H，CH 2CH 2CH 2CH 2CH 2CH 2)，3.65(t，J＝6.5Hz，2H，CH 2OH)，3.98(t，J＝6.5Hz，2H，CF 2OCH 2)，5.85(d，t，54.1Hz，2.9Hz，1H，CFHCF 2)、
19F-NMR(CDCl 3)δ：-81.3(t，J＝6.4Hz，3F，CF 3)，-84.71and-86.86(ABquartet，J＝146.1Hz，2F，CF 2OCFH)，-89.06and-89.85(ABquartet，J＝144.0Hz，2F，CF 2OCH 2)，-129.38～-129.50(m，2F，CF 2CF 3)，-144.1(d，J＝54.1Hz，1F，CFH)。
[example 5]
In the stainless steel reaction vessel of internal volume 50mL, add 1 of 30g, the CF of 4-two  alkane, 10g 2=CFO (CF 2) 2OCF=CF 2, 12.26g HO (CH 2) 4Airtight behind the KOH of OH and 0.55g, while stir in 70 ℃ of reactions 8 hours.Then, add 50mL water and make reaction solution be divided into 2 layers, again organic layer is distilled, obtain the HO (CH of 13.2g as resultant 2) 4OCF 2HCFO (CF 2) 2OCFHCF 2O (CH 2) 4OH.
To HO (CH 2) 4OCF 2HCFO (CF 2) 2OCFHCF 2O (CH 2) 4The measurement result of OH is as described below.
IR(neat)：3349，2951，1341，1237，1199，1153，987cm -1、
1H-NMR(CDCl 3)δ：1.39(s，2H，OH)，1.60～1.73(m，4H，CH 2CH 2OH)，1.73～1.86(m，4H，CF 2OCH 2CH 2)，3.63～3.76(m，4H，CH 2OH)，4.03(t，J＝6.3Hz，4H，CF 2OCH 2)，5.86(d，t，53.7Hz，2.8Hz，2H，CFHCF 2)、
19F-NMR(CDCl 3)δ：-84.86and-86.96(ABquartet，J＝145.0Hz，4F，CF 2OCFH)，-89.30and-89.94(ABquartet，J＝144.0Hz，4F，CF 2OCH 2)，-144.2(d，quintet，J＝53.7Hz，8.6Hz，2F，CFH)。

Claims (3)

1. fluorine-containing alcohol is characterized in that, by following formula 2 expressions,
HOQ 2OCZ 1Z 2CZ 3HR 2CZ 4HCZ 5Z 6OQ 3OH
Formula 2
The implication of the symbol in the formula 2 is as described below, R 2: the divalent perfluoroalkyl that contains etheric oxygen atom; Z 1, Z 2, Z 3, Z 4, Z 5, Z 6: represent hydrogen atom or fluorine atom, Z respectively independently 1, Z 2, Z 3In at least 1 be fluorine atom, and Z 4, Z 5, Z 6In at least 1 be fluorine atom; Q 2, Q 3: difference is expression-(CH independently 2) t-, t is 2～6 integer.
2. the preparation method of the described fluorine-containing alcohol of claim 1 is characterized in that, in the presence of alkali metal compound, makes the compound of following formula 8 expressions and the glycol reaction of following formula 4 expressions,
R[CX 1=CX 2X 3] pFormula 8
HOQOH ... formula 4
The implication of the symbol in formula 8, the formula 4 is as described below, R: contain the divalent perfluoroalkyl of etheric oxygen atom, the integer of p:1～4, X 1, X 2, X 3: represent hydrogen atom or fluorine atom, X respectively independently 1, X 2, X 3In at least 1 be fluorine atom; Q:-(CH 2) t-, t is 2～6 integer.
3. the preparation method of fluorine-containing alcohol as claimed in claim 2, its feature is that also the p in the aforementioned formula 8 is 2.
CN 200610081937 2002-06-27 2003-06-19 Fluorine-containing alcohols and process for production thereof Pending CN1865209A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2002188062 2002-06-27
JP2002188062 2002-06-27
JP2002195905 2002-07-04

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
CN 03815064 Division CN1665768A (en) 2002-06-27 2003-06-19 Fluorine-containing alcohol and method for its production

Publications (1)

Publication Number Publication Date
CN1865209A true CN1865209A (en) 2006-11-22

Family

ID=37424379

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 200610081937 Pending CN1865209A (en) 2002-06-27 2003-06-19 Fluorine-containing alcohols and process for production thereof

Country Status (1)

Country Link
CN (1) CN1865209A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106748670A (en) * 2016-12-19 2017-05-31 衢州氟硅技术研究院 A kind of ether-containing key fluorine alcohol and preparation method thereof
CN109312031A (en) * 2016-06-17 2019-02-05 默克专利股份有限公司 Fluoropolymer

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109312031A (en) * 2016-06-17 2019-02-05 默克专利股份有限公司 Fluoropolymer
CN109312031B (en) * 2016-06-17 2021-04-09 默克专利股份有限公司 Fluorine-containing polymer
CN106748670A (en) * 2016-12-19 2017-05-31 衢州氟硅技术研究院 A kind of ether-containing key fluorine alcohol and preparation method thereof
CN106748670B (en) * 2016-12-19 2020-11-17 衢州氟硅技术研究院 Ether bond-containing fluoroalcohol and preparation method thereof

Similar Documents

Publication Publication Date Title
CN1031063C (en) Process for preparing peroxide perfluoropolyethers
CN1665768A (en) Fluorine-containing alcohol and method for its production
CN1274661C (en) Fluorine compounds and water and oil-repellant compositions
CN1974511A (en) Process for producing organic compounds
CN1930195A (en) Curable composition and process for producing cured fluorochemical
CN1240658C (en) Process for prepn. of fluorinated ketones
CN1025327C (en) Process for production of aromatic hydroxycarboxylic acid
CN1914147A (en) Adamantane derivative and process for producing the same
CN1242979C (en) Process for producing fluorinated ester compound
CN1064952C (en) New substituted 2,2-dimethyl-omega-phenoxyalkanoic acids and esters, process for their preparation and pharmaceutical compositions containing them
CN1212314C (en) Process for producing fluorosulfonyl fluoride compound
CN1167662C (en) Process for producing vic-dichloro acid fluoride
CN1726182A (en) Fluorinated adamantane derivatives
CN1865209A (en) Fluorine-containing alcohols and process for production thereof
CN1196666C (en) Process for preparation of fluorinated acyl fluorides and fluorinated vinyl ethers
CN1209331C (en) Process for preparing unsaturated compounds by pyrolysis
CN1028096C (en) Method of preparing methanol
CN1466562A (en) Process for producing acyl fluoride and carboxylic acid salt
CN1816509A (en) Method for producing 1,3-propanediol
CN1747923A (en) Process for producing perfluorodiacyl fluorinated compounds
CN1675191A (en) Ultraviolet transmitting fluoropolymer and pellicle comprising said polymer
CN1876784A (en) Fluorinated lubricants
CN1665769A (en) Fluorine-containing unsaturated compound and method for its production
CN1580045A (en) Process for large-scale preparation of 2-vinyl pyridine
CN1095825C (en) Process for preparation of alkyl halodifluoroacetates

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