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Title:
PERFLUOROPOLYVINYL MODIFIED ARYL INTERMEDIATES AND MONOMERS
Document Type and Number:
WIPO Patent Application WO/2014/078173
Kind Code:
A1
Abstract:
A compound of formula (I) wherein Rf is -CF3, -C2F5, or -CF2CFXCF3; X is -F, or -OC3F7; Y is -H, -Cl, or -Br; R is -OH, -(CH2)nOH, -(OCH2CH2)mOH, -(CH2)n(OCH2CH2)mOH, -O-C(O)-R1, -(CH2)nO-C(O)-R1, -(OCH2CH2)mOC(O)-R1, -C(O)NHw(CH2CH2OH)2-w, -C≡N, C≡CH, or -C(O)R2; n is 1 to 10; m is 1 to 10; R1 is C1 to C10 alkyl; R2 is -H, C1 to C10 alkyl, -Cl, or -OCH2CH2OH; a is 1 to 5; b is 1 to 5; and w is 0, 1 or 2.

Inventors:
DRYSDALE, Neville, Everton (227 Welsh Tract Road, Newark, Delaware, 19702, US)
Application Number:
US2013/069020
Publication Date:
May 22, 2014
Filing Date:
November 08, 2013
Export Citation:
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Assignee:
E. I. DU PONT DE NEMOURS AND COMPANY (1007 Market Street, Wilmington, Delaware, 19898, US)
International Classes:
C07C65/21; C07C41/06; C07C43/205; C07C43/23; C07C45/71; C07C47/575; C07C49/84
Domestic Patent References:
WO2007149449A2
Foreign References:
US20120277460A1
EP0391390A1
EP0355025A2
US7531700B2
Other References:
FURIN, G. G. ET AL: "Reaction of 1,1,2-trifluoro-2-hexafluoro-2'- (heptafluoropropoxy)propoxyethylene with amines or alcohols", JOURNAL OF FLUORINE CHEMISTRY, vol. 106, no. 1, 2000, pages 13-24, XP002718135, ISSN: 0022-1139, DOI: 10.1016/S0022-1139(00)00290-6
Attorney, Agent or Firm:
BENJAMIN, Steven, C. (E. I. du Pont de Nemours and Company, Legal Patent Records CenterChestnut Run Plaza 721/2340,974 Centre Roa, PO Box 2915 Wilmington Delaware, 19805, US)
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Claims:
CLAIMS

What is claimed is:

1 . A compound of formula (I)

wherein

Rf is -CF3, -C2F5, or -CF2CFXCF3;

X is -F, or -OCsFy;

Y is -H, -CI, or -Br;

R is -OH, -(CH2)nOH, -(OCH2CH2)mOH,

-(CH2)n(OCH2CH2)mOH! -0-C(0)-R1 , -(CH2)nO-C(0)-R1 ,

-(OCH2CH2)mOC(0)-Rl , -C(0)NHw(CH2CH2OH)2-w. -C≡N, -C≡CH, or

-C(0)R2;

n is 1 to 1 0;

m is 1 to 1 0;

R^ is C-j to Gi g alkyl;

R2 is -H, Ci to C-so alkyl, -CI, or -OCH2CH2OH;

a is 1 to 5;

b is 1 to 5;

and w is 0, 1 or 2,

2. A compound of Claim 1 , wherein Rf is -CF3.

3. A compound of Claim 1 , wherein Rf is -C2F5.

4. A compound of Claim 1 , wherein Rf is -CF2CFXCF3 and X

-F.

5. A compound of Claim 1 , wherein Rf is -CF2CFXCF3 and X is -OC3F7.

8. A compound of Claim 1 , wherein R is -OH, -(CH2)nOH, -OCH2CH2)mOH, or -(CH2)n(QCH2CH2)mQH.

7. A compound of Claim 1 , wherein R is -C(0)-0-R^ or

-C(0)R2; n is 1 to 10; m is 1 to 10; R1 is Ci to C-j Q alkyl; and R2 is -H, Ci to C10 alkyl, -CI, or -OCH2CH2OH.

8. A compound of Claim 1 , wherein R is -C≡N, -C≡CH, or

-N02.

9. A compound of Claim 1 , wherein R is

-C(0)NHw(CH2CH2OH)2w and w is 0, 1 or 2.

10. A compound of Formula (!) wherein Y is H.

1 1 . A compound of Formula (!) wherein Y is CI.

12. A compound of Formula (I) wherein Y is Br.

13. A method for roducing compounds of Formula (XX)

wherein

Rf is -CF3, -C2F5, or -CF2CFXCF3;

X is -F, or -OCsFj;

Y is -H, -CI, or Br;

R6 is -OH, -(CH2)nOH, -(OCH2CH2)mOH, -0-C(0)-R1 ,

-(CH2)nO-C(0)-R1 , -(OCH2CH2)mOC(0)-R1 ;

-C(0)NHW(CH2CH20H)2-W, -C=N, -C=CH, -NO2, -C(0)R2, -C(0)-OR4; or -CH=CH2;

n is 1 to 10; m is 1 to 10;

is Ci to Ci o ai ;

R2 is -H, C-i to Ci o alkyi, -C!, or -OCH2CH2OH;

R4 is ~H, or Ci to C10 alkyi;

a is 1 to 5;

b is 1 to 5;

and w is 0, 1 or 2;

comprising contacting a compound of Formula (XXI)

wherein R7 is -OH, -(CH2)nQH, -(OCH2CH2)mOH, -0-C(0)-R1 , -(CH2)nO-C(0)-R1 , -(OCH2CH2)mOC(OVR1 ;

-C(0)NHw(CH2CH20H)2-w. -C≡N> -C≡CH. -N02, -C(G)R2, -CfO)-OR4; or -CH^Ch^;

n is 1 to 10;

m is 1 to 10;

is C-j to C10 alkyi;

R2 is -H, Ci to Ci 0 alkyi, -CI, or -OCH2CH2OH;

R4 is -H, or Ci to C<io alkyi;

a is 1 to 5; and

b is 1 to 5;

with one or more compounds of formuia(X!V) wherein Rf is -CF3, -C2 5, -CF2CFXCF3;

X is -F, or -OC3F7; and

Y is -H, -CI, or -Br in the presence of a base and a solvent.

14. A method of Claim 1 1 , wherein the solvent is tetrahydrofuran, carbon tetrachloride, or carbon tetrabromide.

15. A method of Claim 12, wherein the solvent is tetrahydrofuran.

18. A method of Ciaim 1 1 , wherein the base is potassium carbonate, sodium carbonate, orpotassium bicarbonate.

17. A method of Ciaim 14, wherein the base is potassium carbonate.

Description:
TITLE

PERFLUOROPOLYVI YL MODIFIED A YL INTERMEDIATES AND

MONOMERS

FIELD OF THE INVENTION

The present invention comprises aryi compounds having partialiy f!uorinated tails which can be useful as intermediates and starting materials for producing various water and oil repellents, soil resists, and surfactants.

BACKGROUND OF THE INVENTION

Water and oil repellents, soil resists, and surfactants compounds generally are prepared from linear perfluorinated alcohols. These alcohols are expensive and are prepared through several step synthesis. These alcohols are either then reacted to make final products or further synthesized into intermediates prior to making final products. New starting materials are needed that do not utilize linear perfluorinated alcohols.

U.S. Patent 7,531 ,700 teaches fiuorinated solvents having benzene rings with a) perfluorinated pendent alkyl groups, b) alkyl, alkoxy, or oxyaikyl groups and c) optionally halogen pendent groups useful for the manufacture of organic electronic devices. These solvents are non- reactive.

Patent Application VVO 2007/149449 teaches fiuoroalkoxystyrenes prepared by contacting fiuorinated olefin with a solution of hydroxysiyrene. These fiuoroalkoxystyrenes are useful in resins, elastomers, polymers or coatings.

What is needed are nonlinear compounds as starting materials and intermediates to produce compounds for water and oil repellents, soil resists, and surfactants compounds. The present invention meets this need.

SUMMARY OF THE INVENTION

The present invention comprises a compound of formula (I)

wherein

Rf is -CF3, -C2F5, -CF2CFXCF3;

X is -F, or -OC3F7;

Y is -H, -CI, or -Br;

R is -OH, -(CH 2 ) n OH, -(OCH 2 CH 2 ) m OH,

-{CH2)n(OCH 2 CH 2 ) m OH, -0-C(0)-Rl , -(CH 2 ) n O-C(0)-R ,

-{OCH 2 CH 2 ) m OC(0)~R 1 ) -C(0)NH w (CH 2 CH 2 OH)2. W! -C=N, -C=CH, (

-C(0)R 2 ;

n is 1 to 10;

m is 1 to 10;

R is C-j to C-i 0 aikyi;

R 2 is -H, Ci to Ci 0 alkyl, -CI, or -OCH 2 CH 2 OH;

a is 1 to 5;

b is 1 to 5;

and w is 0, 1 or 2,

The present invention also comprises a method of producing compounds of Formula XX)

wherein Rf is -CF3, -C2F5, or -CF2CFXCF3;

X is -F, or -OCsFy;

Y is -H, -CI, or -Br;

R6 is -OH, -(CH 2 ) n OH, -(0CH 2 CH 2 ) m 0H, -0-C(0)-R 1 , -(CH 2 ) n O-C(0)-R 1 , -(OCH 2 CH 2 ) m OC(0)-R 1 ;

-C(0)NH w (CH 2 CH 2 OH) 2 . w , -C≡N, -C=CH, -N0 2 , -C(0)R 2 , or

-C(0)-OR 4 ; -CH=CH 2 ;

n is 1 to 10;

m is 1 to 10;

R^ is C-j to C-j Q alkyl;

R 2 is -H, C-j to C-s o alkyl, -CI, or -0CH 2 CH 2 0H; R 3 is H c CH 3 ;

R4 is -H, or C-j to C-j Q alkyi;

a is 1 to 5;

b is 1 to 5;

and w is 0, 1 or 2;

comprising contacting a compound of Formula (XXI)

wherein

R7 is -OH, ~(CH 2 ) n OH, -(0CH 2 CH 2 ) m 0H,

-(CH 2 )n(OCH 2 CH 2 ) m OH ! -0-C(0)-R , -(CH 2 ) n O-C(0)-R 1 ,

(0CH 2 CH 2 ) m 0C(0)-R 1 ; -C(0)NH w (CH 2 CH 2 0H) 2 w , -C=N

-NO2, -C(0)R 2 , -C(0)-OR 4 , or -CH-CH 2 ;

n is 1 to 10;

m is 1 to 10;

R^ is C-j to C-j Q alkyl;

R 2 is -H, Ci to C-j 0 alkyl, -CI, or -0CH 2 CH 2 0H; R4 is -H, or C-j to C-J Q aSky!;

a is 1 to 5;

b is 1 to 5;

with one or more compounds of formula(XIV)

wherein

R f is -CF3, -C2F5, or -CF2CFXCF3;

X is -F, or -OC3F7; and

Y is -H, -CI, or -Br

in the presence of a base and a solvent.

DETAILED DESCRIPTION

Herein trademarks are shown in upper case.

The present invention provides a compound of formuia (I)

wherein

R f is -CF 3 , -C2F5, or -CF 2 CFXCF 3 ;

X is -F, or -OCsF ;

Y is -H, -CI, or -Br;

R is -OH, -(CH2) n OH, -(OCH 2 CH2)mOH,

-(CH2)n(OCH2CH2) m OH, -0-C(0)-R 1 , -(CH2) n O-C(0)-R 1 , - (OCH2CH2) m OC(0)-R 1 ; -C(0)NH w (CH2CH 2 OH)2. Wl -C=N, -C=CH, or

-C(0)R 2 ;

n is 1 to 10;

m is 1 to 10;

is C-j to Ci o alkyl;

R 2 is -H, Ci to Ci o aikyl, -CI, or -OCH2CH2OH;

R3 is H or CH3;

a is 1 to 5;

b is 1 to 5; and

w is 0, 1 or 2.

Compounds of the present invention include pendent groups (Rf-0-CFY~CF 2 0~) a and (R)b and wherein a is 1 to 5 and b is 1 to 5.

Compounds of the present invention may have 1 , 2, 3 ,4 or 5 pendent groups of Rf-Q-CFY-CF 2 0-, and 1 , 2, 3, 4, or 5 pendent groups of -R, and mixtures thereof, provided that the total number of pendent groups is less than or equal to 6. The Rf-0-CFY-CF20- and ~R groups may be ortho, para, or meta on the benzene ring or combinations thereof.

Preferred compounds of Formula (I) include those wherein R is ■■■■ OH, -(CH 2 ) n OH, ~(OGH 2 CH 2 ) m OH, and -(CH 2 )n(OCH2CH2) m OH, wherein each of m and n are independently 1 , 2, 3, 4 , 5, or 8. More preferred are compounds of Formula (I) wherein R is -OH, -(CH 2 )nOH, -

(OCH 2 CH2) m OH, and -(CH2) n (OCH 2 CH 2 ) m OH, wherein each of m and n are independently 1 , 2, or 3. Also preferred are those wherein Rf is -

CF3 or -C 2 F5 i and R is -OH, (CH 2 ) n OH, -(OCH 2 CH 2 ) m OH, and

-(CH 2 )n(OCH2CH2)mOH, wherein each of m and n are independently 1 ,

2, or 3.

Additional preferred compounds of Formula (I) are those wherein R is -0-C(0)-R 1 or -C(0)R 2 , wherein R 1 is an alky! of 1 , 2, 3, 4 , 5, or 8 carbons; and R 2 is H or an alkyl of 1 , 2, 3, 4 , 5, or 6 carbons. More preferred are compounds of Formula (I) wherein R is -0-C(0)-R^ or -C(0)R2, wherein is an alkyi of 1 , 2, or 3 carbons; and R2 is H or an aikyi of 1 , 2, or 3 carbons. Also preferred are those wherein Rf is -CF3 or

~ C 2 F 5, and R is -0-C(0)-R 1 or -C(0)R2, wherein R is an alky! of 1 , 2, or

3 carbons; and R2 is H or an aikyi of 1 , 2, or 3 carbons.

Also preferred are compounds of Formula (!) wherein R is -C≡N, or

-C≡CH. More preferred are compounds of Formula (I) wherein R is -C≡N or -C≡GH, and Rf is --CF3 or -C2F5 Other preferred compounds of

Formula (I) are those wherein R is -C(0)NH w (CH2CH20H)2-w wherein w is 0, 1 or 2. More preferred are compounds of Formula (!) wherein R is -C(0)NH W (CH2CH20H)2- W wherein w is 0, 1 or 2, and Rf is -CF3 or -

C2F5.

Compounds of Formula (I) can be produced in various ways.

Preferred specific examples of compounds of Formula (I) include, but are not limited to,

d

In one embodiment, compounds of the present invention of Formula (I), wherein R f is -CF 3 , ~C 2 F 5 , -CF 2 CFXCF 3 ; X is -F, or -OC3F7; Y is -H, -

CI, or ~Br and R is -OH, ~(CH 2 ) n OH, ~(OCH 2 CH 2 ) m OH, -C(0)~G-R 1 , -C(0)NH2, -C=N, -C=CH, or -C(G)R2, can be prepared by contacting variety of functiona!ized aryl rings of Formula (XIII)

wherein R 5 is -OH, -(CH2) N OH, -(OCH2CH2) M OH,

-(CH 2 )n(OCH 2 CH2) M OH ! -(CH 2 )n(OCH 2 CH2) M OH , -0-C(0)-R1 , -C(0)NH2, -C=N, -C=CH, or -C(0)R 2 ; n is 1 to 10; m is 1 to 1 0; R 1 is Ci to Ci o alkyi; R 2 is -H, Ci to Ci Q alkyL -CI, or -OCH 2 CH 2 OH; a is 1 to 5; and b is 1 to 5 with one or more perfluorovinyi ethers of formula (XIV)

wherein Rf is -CF3, -C2F5, or -CF2CFXCF3; X is -F, or -OC3F7; and Y is H, -CI, or -Br.

For compounds of Formula (XIV), when Rf is ~CF3, the compound is perfluoromethylvinyl ether of Formula (XV)

when Rf is -C2F5, the compound is a perfluorovinyi ethyl ether of Formula when Rf is -CF2CFXCF3 and X is -F, the compound is a

perf!uoropropy!viny! ether of Formula (XVI!)

and when Rf is -CF2CFXCF3 and X is -OC3F7, the compound is a perfluoropropylvinyl ether of Formula (XVISI)

(XVIII)

The reaction of the aryl compounds of Formula (Xill) with perfiuorovinyi ethers of Formula (XIV) can be completed in a solvent and a base. Suitable bases include those known to deprotonate the hydrogen of a phenol. Examples of such bases include, but are not limited to, potassium carbonate, sodium carbonate, and potassium bicarbonate. Examples of such bases include, but are not limited to, potassium carbonate, sodium carbonate, and potassium bicarbonate. Examples of suitable solvents include, but are not limited to, tetrahydrofuran, carbon tetrachloride, and carbon tetrabromide. In Formula (I), when

tetrahydrofuran is the solvent, then Y is -H. In Formula (I), when carbon tetrachloride is the solvent, then Y is -CI. In Formula (I), when carbon tetrabromide is the solvent, then Y is -Br. The reaction temperature can be complete between room temperature and solvent reflux temperatures. in one embodiment, the present invention relates to a compound of Formula (I), wherein Rf is -CF3, -C2F5, -CF2CFXCF3; X is -F, or -OC3F7;

Y is -H, -CI, or -Br and R is -OH, -(CH2) n OH, -(OCH2CH2) m OH, or

-{CH2)n(OCH2CH2) m OH; n is 0 to 10; m is 1 to 10. Compounds of this embodiment can be prepared by reacting compounds of Formula (XII!) wherein R is -OH, -(CH2) n OH, -(OCH2CH2) m OH, or

-(CH2)n(OCH2CH2)mOH; n is 1 to 10; m is 1 to 10 with one or more compounds of Formula (XIV) as defined above.

In a second embodiment, the present invention relates to a compound of Formula (I), wherein Rf is -CF3, -C2F5, -CF2CFXCF3; X is -

F, or -OC3F7; and Y is -H, -CI, or -Br and R is -C(0)-0-R 1 ; or -C(0)R 2 ; and n is 1 to 10; m is 1 to 10; R^ is C-j to C-j 0 a!kyl; R2 is -H, C-j to C-j g aikyi, -CI, or -OCH2CH2OH, and R 4 is -H, or C-j to C-j Q alkyl. Compounds of the second embodiment can be prepared by reacting compounds of Formula (XI II) wherein R is -C(0)-0-R ; or -C(0)R 2 : and n is 1 to 10; m is 1 to 10; R "5 is C-j to C-jQ aikyi; and R2 is -H, C-j to C-j g alkyl, -CI, or - OCH2CH2OH; with one or more compounds of Formula (XIV) as defined above.

In a third embodiment, the present invention relates to a compound of Formula (I), wherein Rf is -CF3, -C2F5, or -CF2CFXCF3; X is -F, or

-OC3F7; and Y is -H, -CI, or -Br and R is -C≡N, or -C≡CH. Compounds of the third embodiment can be prepared by reacting compounds of Formula (XII!) wherein R is -C≡N, or -C≡CH, with one or more compounds of Formula (XIV), as defined above.

In a fourth embodiment, the present invention relates to alcohol amide containing compounds of Formula (I), wherein Rf is -CF3, -C2F5, or -CF2CFXCF3; X is -F, or -OC3F7; and Y is -H, -CI, or -Br and R is

-C(0)NH W (CH2CH20H)2- wherein w is 0, 1 or 2. In this embodiment, the alcohol amide containing compounds of Formula (I) can be prepared by contacting a compound of Formula (!) wherein Rf is -CF3, --C2F5, -

CF2CFXCF3; X is -F, or -OC3F7; and Y is -H, -CI , or -Br and R is -C(0)R 2 and R2 is -CI , with ethanoi amine (wherein w is 1 ) or di(ethano!)amine (wherein w is 0). Compounds of Formuia (!) wherein R is -C(G)R2 and R^ is -CI can be prepared by contacting compounds of Formula (I) wherein R is -C(0)OH with thionyl chloride. Compounds of Formula (!) wherein R is -C(0)OH can be prepared by contacting compounds of Formula (I) wherein R is -C(G)R2 and R^ is -OCH2CH2OH with potassium hydroxide. Compounds of Formuia (I) wherein R is -C(0)R2 and R2 is -OCH2CH2OH can be prepared as defined above in the second embodiment.

Alternatively in this fourth embodiment, alcohol amide containing compounds of Formula (i) can be prepared by contacting N, N- diethano!phenol amide with a perfiuorovinyl ether of Formula (XI I !) in a solvent and a base, such as potassium carbonate.

in a fifth embodiment, the present invention relates to a method of producing compounds of Formula (XX)

wherein

Rf is -CF3, -C2F5, or -CF2CFXCF3;

X is -F, or -OCsFj;

Y is -H, -CI, or -Br;

R 6 s ... QH, -(CH 2 )nOH, -(OCH 2 CH2;) m OH, -(CH2)n(OCH 2 CH2)mOH, -0-C(0)-R , -(CH 2 ) n O-C(0)- (OCH 2 CH 2 ) m OC(0)-Rl ; -C(0)NH w (CH 2 CH 2 OH)2.w. -C

-N0 2 , -C(0)R 2 , -C(0)-OR 4 ; or -CH-CH 2 ;

n is 1 to 10;

m is 1 to 10;

is C-j to C-j Q aikyl;

R2 is -H, Ci to Ci o aikyl, -CI, or -OCH 2 CH 2 OH;

R 3 is H or CHa;

R 4 is -H, or Ci to Cio aikyl;

a is 1 to 5;

b is 1 to 5;

and w is 0, 1 or 2;

comprising contacting a compound of Formula (XXI) wherein R? is -(CH 2 ) n OH, -(GCH 2 CH 2 ) m GH, -(CH 2 ) n (OCH 2 CH 2 ) m OH, -0-C(0)-R , -C(0)NH w (CH 2 CH 2 OH) 2 . w , -C=N, -C=CH, -N0 2 , -C(0)R 2 , -

C(0)-OR 4 or -CH=CH 2 ; n is 1 to 10; m is 1 to 10; R 1 is Ci to Cio aikyl;

R 2 is -H, Ci to Ci o alkyl, -CI, or -OCH 2 CH 2 OH; R 4 is -H, or Ci to Ci o aikyl; a is 1 to 5; b is 1 to 5; w is 0, 1 , or 2 with one or more compounds of formula (XIV)

wherein Rf is -CF3, -C2F5, or -CF 2 CFXCF3; X is -F, or -GC3F7; and Y is

H, -CI, or -Br in the presence a base and a solvent. Suitable bases include those known to deprotonate the hydrogen of a phenol. Examples of such bases include, but not limited to, potassium carbonate, sodium carbonate, and potassium bicarbonate. Examples of suitable solvents include, but not limited to, tetrah drofuran, carbon tetrachloride, and carbon tetrabromide.

Compounds of the present invention and as defined above, are useful, for example, as starting monomers and intermediates for 1 ) the preparation of poiyacryiate copolymers used for oil and water repellency, 2) as reactants for producing phosphate surfactants, and 3) in producing partially fluorinated urethanes useful for oil and water repellency as well as stain resistance to fibrous substrates. The compounds produced from the method of the present invention are not only useful as intermediates and starting materials for repellency compounds, but also include those compounds useful in the electronics displays, such as, for example, compounds of Formula (XX) wherein is -CH=CH2.

EXAMPLES

Materials

Perfiuorovinyi ethers 1 ,1 ,1 ,2,2,3, 3-heptafiuoro-3~((1 ,2,2- trifluorovinyl)oxy)propane and 1 ,1 ,1 ,2,2,3,3-heptafluoro-3-(1 ,1 ,1 ,2,3,3- bexafiuoro-3-(1 ,2,2trifIuorovinyioxy)propan-2-yioxy)propane are commercially available from E. I. du Pont de Nemours and Company, Wilmington, DE. Ail other reactants, unless otherwise specified, are available from Sigma-A!drich, St. Louis, MO.

Example 1

(4-(1 ,1 ,2-trif!uoro-2-(perfluoropropoxy)ethoxy)phenyi)methanoi

In the dry box, tetrahydrofuan (2000 mL) and 4- (hydroxymethyi)phenol (24.8 g, 0.20 mo!) were added to a round bottom flask equipped with a stirrer. Potassium carbonate (13.8 g, 0.10 mo!) was then added to the flask. 1 ,1 ,1 ,2,2,3,3-heptafluoro-3-((1 ,2,2- trifluorovinyl)oxy)propane (79.89 g, 0.30 mol) was then added via the addition funnel and the reaction was placed in an oil bath and heated to a gentle reflux overnight. The content was analyzed by proton N R to be (4-(1 ,1 ,2-trif!uoro-2-(perfluoropropoxy)ethoxy)phenyl)methanol. The potassium carbonate was removed via filtration and the resulting material concentrated via roto-evaporation. Vacuum distillation afforded the desired material, bp 89-92oC at 1 .00 torr, 87.65 yield).

Example 2

(4-(1 ,1 ,2-trifiuoro-2-(1 ,1 ,2,3,3,3-hexafiuoro-2- (perfluoropropoxy)propoxy)ethoxy)pheny!)methanoi

In the dry box, tetrahydrofuan (50 mL) and 4-(hydroxymethyl)pheno (0.82 g, 0.005 mol) were added to a round bottom flask equipped with a stirrer. Potassium carbonate (0.345 g, 0.0025 mol) was then added to the flask. 1 ,1 ,1 ,2,2,3,3-Heptafluoro-3-(1 ,1 ,1 ,2,3,3-hexafluoro-3- (1 ,2,2trifiuorovinyloxy)propan-2-yloxy)propane (3.24 g, 0.0075 mol) was then added via the addition funnel and the reaction was placed in an oil bath and heated to a gentle reflux over 2 days. The content was analyzed by proton NMR and shown to be (4-(1 ,1 ,2-trifiuoro-2-(1 ,1 ,2,3,3,3- hexafluoro-2-

(perfluoropropoxy)propoxy)ethoxy)pheny!)methanol. Example 3

2-(2-(1 ,1 ,2-inflLioro-2-(pernuoropropoxy)ethoxy)phenoxy)ethanol

In the dry box, tetrahydrofuan (2000 mL) and

2-(hydroxyethoxy)phenol (30.8 g, 0.20 mo!) were added to a round bottom flask equipped with a stirrer. Potassium carbonate (13.8 g, 0.10 moi) was then added to the flask. 1 ,1 ,1 ,2,2,3,3-heptafluoro-3-((1 ,2,2- trifiuoroviny!)oxy)propane (79.89 g, 0.30 mo!) was then added via the addition funnel and the reaction was placed in an oil bath and heated to a gentle reflux overnight. The content was analyzed by proton NMR to be 2- (2-(1 ,1 ,2-trifluoro-2-(perfluoropropoxy)ethoxy)phenoxy)ethanol. The potassium carbonate was removed via filtration and the resulting material concentrated via roto-evaporation. Vacuum distillation afforded the desired material, bp 96-97oC at 1 .0 -1 .2 torr, 94.86 yield).

Example 4

2-(2-(1 ,1 ,2-trifluoro-2-(1 ,1 ,2,3,3,3-hexafluoro-2- (perfluoropropoxy)propoxy)ethoxy)phenoxy)ethanol

In the dry box, tetrahydrofuan (50 mL) and 2-(hydroxyethoxy)pheno! (0.77 g, 0.005 moi) were added to a round bottom flask equipped with a stirrer. Potassium carbonate (0.345 g, 0.0025 moi) was then added to the flask. 1 , 1 ,1 , 2,2,3, 3-Heptaf!uoro-3-(1 , 1 ,1 , 2,3, 3-hexafiuoro-3-

(1 ,2,2trifiuorovinyIoxy)propan-2-yIoxy)propane (3.24 g, 0.0075 moi)was then added via the addition funnel and the reaction was placed in an oil bath and heated to a gentle reflux overnight. The content was analyzed by proton NMR and shown to be 2-(2-(1 ,1 ,2-trif!uoro~2-(1 ,1 ,2,3,3,3- hexafIuoro-2-(perfiuoropropoxy)propoxy)ethoxy)phenoxy)ethano l.

Example 5

2-hydroxyethyi 4-(1 ,1 ,2-trifluoro-2-(1 ,1 ,2,3,3,3-hexafl

(perfluoropropoxy)propoxy)ethoxy)benzoate

In the dry box, tetrahydrofuan (50 mL) and 2-hydroxyethyi 4- hydroxybenzoate (0.91 g, 0.005 moi) were added to a round bottom flask equipped with a stirrer. Potassium carbonate (0.345 g, 0.0025 moi) was then added to the flask. 1 ,1 ,1 ,2,2,3,3-Heptafluoro-3-(1 ,1 ,1 ,2,3,3- hexafIuoro-3-(1 ,2,2-trifluorovinyloxy)propan-2-y!oxy)propane (3.24 g, 0.0075 moi) was then added via the addition funnel and the reaction was

18 placed in an oi! bath and heated to a gentle reflux overnight. The content was analyzed by proton NMR and shown to be 2-hydroxyethy! 4-(1 ,1 ,2- trif!uoro-2-(1 ,1 ,2,3,3,3-hexafluoro-2~

(perfluoropropoxy)propoxy)ethoxy)benzoate.

Example 8

1 -ethynyI-3-(1 ,1 ,2-trifluoro-2-(1 ,1 ,2,3,3,3-hexafluoro-2- (perfluoropropoxy)propoxy)ethoxy)benzene

In the dry box, tetrahydrofuan (50 mL) and 3-ethynylphenol (0.59 g, 0.005 mol) were added to a round bottom flask eguipped with a stirrer. Potassium carbonate (0.345 g, 0.0025 mo!) was then added to the flask. 1 ,1 ,1 ,2,2,3,3-Heptafluoro-3-(1 ,1 ,1 ,2,3,3-hexaf!uoro-3- (1 ,2,2trifluorovinyloxy)propan-2-yloxy)propane (3.24 g, 0.0075 mol) was then added via the addition funne! and the reaction was placed in an oii bath and heated to a gentle reflux overnight. The content was analyzed by proton NMR and shown to be 1 ~ethynyl-3~(1 ,1 ,2-trif!uoro-2-(1 ,1 ,2,3,3,3- hexafluoro-2-(perf!uoropropoxy)propoxy)ethoxy)benzene.

Example 7

4-(1 ,1 ,2-trifluoro-2-(1 ,1 ,2,3,3,3-hexafluoro-2- (perfluoropropoxy)propoxy)ethoxy)benzaidehyde

in the dry box, tetrahydrofuan (25 mL) and 4-hydroxybenzaidehyde (0.61 g, 0.005 mol) were added to a round bottom flask equipped with a stirrer. Potassium carbonate (0.175 g, 0.00126 mol) was then added to the flask. 1 ,1 ,1 ,2,2,3,3-Heptafluoro-3-(1 ,1 ,1 ,2,3,3-hexafluoro-3- (1 ,2,2trifluorovinyloxy)propan-2-yloxy)propane (3.24 g, 0.0075 mol) was then added via the addition funnel and the reaction was placed in an oil bath and heated to a gentle reflux for two hours. The content was analyzed by proton NMR and shown to be 1 -ethynyl-3-(1 ,1 ,2-trifiuoro-2- (1 ,1 ,2,3,3,3-hexafluoro-2-(perfluoropropoxy)propoxy)ethoxy)benze ne.

Example 8

1 -(4-(1 ,1 ,2-trifiuoro-2-(perfluoropropoxy)ethoxy)pheny!)ethanone

In the dry box, tetrahydrofuan (50 mL) and 1 -(4- hydroxyphenyl)ethanone (0.68 g, 0.005 mol) were added to a round bottom flask equipped with a stirrer. Potassium carbonate (0.175 g, 0.00126 mol) was then added to the flask. 1 ,1 ,1 ,2,2,3,3-heptafiuoro-3- ((1 ,2,2-trifluorovinyl)oxy)propane (1 .99 g, 0.0075 mol) was then added via the addition funnel and the reaction was placed in an oil bath and heated to a gentle reflux for 5.5 hours. The content was analyzed by proton NMR and shown to be 1 -ethynyl-3-(1 ,1 ,2-trifluoro-2-(1 ,1 ,2,3,3, 3-hexaf!uoro-2- (perfluoropropoxy)propoxy)ethoxy)benzene.

Example 9

-(4-(2-chioro-1 ,1 ,2~trifluoro-2-(perfluoropropoxy)eihoxy)phenyl)ethanone

In the dry box, tetrahydrofuan (25 mL), dimethyl formamide (10.0 mL) and 1 -(4-hydroxyphenyl)ethanone (0.68 g, 0.005 mol) were added to a round bottom flask equipped with a stirrer. Potassium carbonate (0.175 g, 0.00126 mol) was then added to the flask, 1 ,1 ,1 ,2,2,3,3- heptafiuoro-3-((1 ,2,2-trifluoroviny!)oxy)propane (1 .99 g, 0.0075 mol) was then added via the addition funnel and the reaction was placed in an oil bath and heated to a gentle reflux for six hours. The content was analyzed by proton NMR and shown to be 1 -(4-(2-chloro-1 ,1 ,2-trifiuoro-2- (perfluoropropoxy)ethoxy)phenyl)ethanone. Example 10

1 -(4-(1 ,1 ,2-trifluoro-2-(1 ,1 ,2,3,3,3-hexafluoro-2-

(perfluoropropoxy)propoxy)ethoxy)phenyl)ethanone

In the dry box, tetrahydrofuan (25 mL) and 1 -(4- hydroxypheny!)ethanone (0.68 g, 0.005 mo!) were added to a round bottom flask equipped with a stirrer. Potassium carbonate (0.175 g, 0.00128 mo!) was then added to the flask. 1 ,1 , 1 ,2,2,3, 3-Heptafiuoro-3- (1 ,1 ,1 ,2,3,3-hexafiuoro-3-(1 ,2,2trifluorovinyioxy)propan-2-yloxy)propane (3.24 g, 0.0075 mo!) was then added via the addition funnel and the reaction was placed in an oil bath and heated to a gentle reflux for 5.5 hours. The content was analyzed by proton NMR and shown to be 1 -(4- (1 ,1 ,2-trif!uoro-2-(1 ,1 ,2,3,3,3~hexaf!uoro-2~

(perfluoropropoxy)propoxy)ethoxy)phenyl)ethanone.

Example 1 1

methyl 4-(1 , 1 ,2-trif!uoro-2-(1 ,1 ,2,3,3,3-hexafluoro-2- (perfluoropropoxy)propoxy)ethoxy)benzoate

In the dry box, THF (500mL) and methyl 4-hydroxybenzoate (28.8 g, 0.175 mo!) were added to an oven dry RB flask equipped with a stirrer, Potassium carbonate (12.00 g, 0.087 mo!) was then added. 1 ,1 ,1 ,2,2,3,3- Heptafluoro-3-(1 ,1 ,1 ,2,3,3-hexafluoro-3-(1 ,2,2trif!uorovinyioxy)propan-2- y!oxy)propane (94.5 g, 0.219 mo!) was then added via the addition funnel and the reaction allowed to stir at room temperature. The reaction mixture was heated to a gentle reflux, oi! temperature about 80°C, under nitrogen overnight. An aliquot was withdrawn and concentrated under vacuum and analyzed via proton NMR that showed the complete conversion to the desired materia!. The cooled reaction mixture was then filtered through silica gel and then concentrated at reduced pressure, resulting in 101 .52 g (99.33%) yield of the desired material. Example 12

Water (500.0 mL) and potassium hydroxide were added to a round bottom flask equipped with a stirrer. Methyl 4-(1 ,1 ,2-trifiuoro-2- (1 ,1 ,2,3,3,3-hexafluoro~2-(perfluoropropoxy)propoxy)ethoxy)benzo ate (50.0 g, 0.0858 mol), as prepared in Example 1 1 , was then added via the addition funnel and the reaction was placed in an oil bath and heated to a gentle reflux overnight. The flask was allowed to cool before acidifying with concentrated HCi, down to ph~1 .0. The precipitate was filtered and dried overnight. The solids were analyzed by proton NMR to be 4-(1 , 1 ,2- trif!uoro-2-(1 ,1 ,2,3,3,3-hexafiuoro-2-

(perfluoropropoxy)propoxy)ethoxy)benzoic acid.

Example 13

4-(1 ,1 ,2-trifluoro-2-(1 ,1 ,2,3,3,3-hexafluoro-2- (perfluoropropoxy)propoxy)ethoxy)benzoyl chloride

4-(1 ,1 ,2-trifluoro-2-(1 ,1 ,2,3,3,3-hexafluoro-2-

(perfluoropropoxy)propoxy)ethoxy)benzoic acid (52.00 g, 0.0912 mol) as prepared in Example 12 and thionyl chloride (385 g, 3.09 mol) were place in an oven dried RB flask equipped with a stirrer, reflux condenser and under nitrogen. The reaction was placed in an oil bath and heated to a gentle reflux overnight. The content was analyzed by proton NMR and shown to be 4-(1 ,1 ,2-trifluoro-2-(1 , 1 ,2,3,3,3-hexafIuoro-2- (perfluoropropoxy)propoxy)ethoxy)benzoyi chloride.

Example 14

N,N-bis(2-hydroxyethyl)-4-(1 ,1 ,2-trifiuoro-2-(1 ,1 ,2,3,3,3-hexafluoro-2- (perfluoropropoxy)propoxy)ethoxy)benzamide

in the dry box, tetrahydrofuan (50 mL) and diethanoi amine (0.714 g, 0.0068 mol) were added to a round bottom flask equipped with a stirrer, 4-(1 ,1 ,2-trifluoro-2-(1 ,1 ,2,3,3,3-hexafluoro-2-

(perfluoropropoxy)propoxy)ethoxy)benzoyl chloride (2.00 g, 0.0034 mol) as prepared in Example 13 was then added and the reaction was stirred for one hour. The content was analyzed by proton NMR and shown to be N,N-bis(2-hydroxyethyl)-4-(1 ,1 ,2-trifluoro-2-(1 ,1 ,2,3,3,3-hexafluoro-2- (perfluoropropoxy)propoxy)ethoxy)benzamide.

Example 15

1 -(1 ,1 ,2-trifluoro-2-(1 ,1 ,2,3,3,3-hexafluoro-2-

(perfluoropropoxy)propoxy)ethoxy)-4-vinyl benzene

In the dry box, THF (50mL) and 4-vinylphenoi (5.00 g of a 10% solution in propylene glycol) were added to an oven dry RB flask equipped with a stirrer, Potassium carbonate (0.35 g, 0.0025 mo!) was then added. 1 ,1 ,1 ,2,2,3,3-Heptafluoro-3-(1 ,1 ,1 ,2,3,3-hexafiuoro-3- (1 ,2,2thfluoroviny1oxy)propan-2-y1oxy)propane (2.70 g, 0.00825 mol) was then added via the addition funnel and the reaction allowed to stir at room temperature. The reaction mixture was heated to a gentle reflux under nitrogen overnight. An aliquot was withdrawn and concentrated under vacuum and analyzed via proton NMR which showed the complete conversion to be 1 -(1 ,1 ,2-trifluoro-2-(1 ,1 ,2,3,3,3~hexafluoro~2- (perfluoropropoxy)propoxy)ethoxy)-4-vinyibenzene. The cooled reaction mixture was then concentrated at reduced pressure taken up in methylene chloride washed with water (-25 mL) separated, then dried over anhydrous sodium sulfate. The separated organic phase was then concentrated at reduced pressure and then column chromatograph on silica gel obtaining 1 .15 g (about 50.0%) of the theoretical yield) of product.