CA2133652A1 - Liquid crystal compounds having prefluoroether terminal portions - Google Patents

Abstract

Fluorine-containing liquid crystal compounds are provided. The compounds comprise a fluorocarbon terminal portion having at least one catenary ether oxygen and a hydrocarbon terminal portion, the terminal portion being connected by a central core, the compounds having smectic mesophases or having latent smectic mesophases.

Description

`;"`` 2~336~2 ~`,j`'0~3/~2396 - P~/US93/~3925 . .
hIQ~ID CRY~TAL COMPo~NDi5 ~AVING RERFL~OROET~ER TERMINAL PO~IOiN5 FIELD OF ~E INV~NTION
This invention relates to fluorinated achiral smectic liquid crystal compounds. Th~se compounds and mixtures of liquid crystal materials containing these compounds are useful in a variety of electrooptical displays.
BAC~Ro~ND OF T~E INVEN~ION
Devices employing liquid crystals have found use in a variety of electrooptical applications, in particular those which require compact, 15 energy-efficient, voltage~controlled light valves, such as watch and calculator displays, and flat-panel displays as are found in portable computers and compact televisions.
Liquid crystal displays have a number of 20 unique characteristics, including low voltage and low power of operation, which make them the most pro~ising of the non-emissive el~ctrooptical display candidates currently available. However, slow response and insufficient nonlinearity can impose limitations for 25 many potential applications. The requirement for speed may become especially important in proportion to the number of elements which have to be addressed in a '.
device. T~is limits the poten~ial use of some types of liquid crystals. ~.
~he'modes of liquid crystal displays that are most extensively employed at the present are ~wisted nematic (TN), supertwisted birefringence effect (SBE), 1-and dynami~ scattering (DS), all employing nematic ~r nematic or chiral nematic (cholesteric) liquid 35 crystals. These:device~ are b~sed upon the dielec~ric ali~nment effects ~Freedericksz effe t) of the nematic and/or chiral nematic liquid crystal or mixtures of wo 93/~23g6 2 ~ 3 3 fi ~ Z PCT/US93/0~

nematic or chiral nematic liquid crystals upon application of an electric field. The average molecular long axis of the liquid crystal material ~ I
takes up a preferred orientation in the applied ~; -5 electric field, the orientation of which is dependent s on the sign of the dielectric anisotropy of the material or mixture, and this orientation relaxes upon removal of the applied electric field~ This reorientation and relaxation is slow,~ on the order of a 10 few milliseconds.
Although nematic and chiral~nematic liquid crystals are the most extensively employed, there are liquid crystal devices that employ~higher ordered smectic liquid crystals.; ~ -Devices employing~ materials with a smectic~A
mesophase are useful in device applications as described~in Crossland, et al. U.S. Patent NOB. , 4,411,494; 4,419,664; and 4,528,562; and F. J. Kahn ` (Appl~ Phys. Lett., vol. 22,;p. 111 (1973). These ;
20 devices are based on thç dielectria reorientation of~
the liquid crystals and~response~times~are on the order ~;~ of milliseconds.
Mixtures which exhibit a chiral smectic A~
mesophase are~useful ~in~à device as~described by 25 Lagerwall, et al.~;lst International~Symposium On FerroeIectric Liquid~Crystals, Bordeaux-Arcachon, France,~1987. Thése~mixtures~exhibit an electrooptic effect which is termed~a soft-mode ferroelectric effect ~ ;
~ a~d~lsub-microseco~d sw~tching; can~be~a~chieved.
-~ ~ 30 ~ Deviaes employing materials with a smectic C
mèsophase arè useful~i~n device~applications as described by Pelzl,;~et al. tKristall Technik.j vol. 14 p. 817 (~1979); Mo~ ryst. Liq. Cryst., vol. 53, p.;l67 : ~, ~,, . . , , , ;.
(lg79j; ~iquid Crystals~, vol. 2~, p.~ 21~(19$7)~; and 35~ iquid~Crystals,~vol.~2,~;p.~ 131~(1987~ The~e devices a~e;~based on the~die~lectri~ reorientation of the liquid cryqtals~a~d the~response times~are slow. ~

'~W093/22396 2 ~ 3 3 6 5 2 PCT/US93~03925 ~ 3 ~
A recent advance in the liquid crystal art ~as been the utilization of tilted chiral smectic liquid crystals, which are also termed ferroelectric~
liquid crystals, in devices which give microsecond 5 switching and bistable operation not possible in any of the devioe applications described above. Fe.rroelectric liquid crystals were discovered by R. B. M~yer, et al.
(J. Physique, vol~ 36, pp. 1-69, 1975). ~ high speed optical switchin~ phenomenon was discovered for the 10 ferroelectric liquid crystals by N. A. Clark, et al.
(Appl. Phys. Lett., vol. 36, p. 899 (1~80~ and UOS. :
Patent No. 4,367,924). :~
Fluorine-containing ferroelectric liquid crystal ma~erials have recently been developed. U.S.
15 Patent No. 4,886,619 (Janulis) discloses fluorine containing chiral smectic liquid crystal compounds which comprise a fluorocarbon terminal portion and a chiral hydrocarbon terminal portion with ~he terminal portions being connected by a central core. U.S.
20 Patent No. 5,082,587 (Janulis) discloses achiral fluorine-containing liquid crystal compounds which comprise a fluorocarbon terminal portion and a hydrocarbon or another fluorocarbon terminal portion, the terminal portions being connected by a central 25 core.
International Publication No. WO ~1/00897 ~Merck) discloses chiral or achiral ring compounds t whîch may be used as components of chiral, tilted, ! 1 , smec$ic liquid-crystalline phases with ferroelectric 30 properties. The compounds have the formula ~ .
Rl Al - A2 _Q~ H2 ) m~ ( CF2 ? n X

where Rl is an alkyl or per~luoroalkyl group with 1 to 35 12 ~arbon atoms, in which one or two non-adjacent C~2 or CF2 groups may be replaced by O-atoms, and/or -CO-, -COO-, CH=CH-, -C~-halogen-, CHCN~, ~OCOCH-halogen-, wO 93/2~396 ~ 3 6 5 2 PCT/US93/0 ~ `~`

or -COO-CHCN- groups or where Rl is X~(CF2)~-(CH2) m~Q~
and X is H or F; Al and A2 are mutually independently unsubstituted 1,4-phenylene groups or 1,4 phenylene groups substituted by one or two F atoms, whereby one 5 or two CH-groups may may be substituted by N; Q is -O-, -CQO-, -OCO- ox a single bond; m is 1 to 10; and n is 2 to 8, with the proviso that m is 3 to 10 if Q is -COO-or -O~O-~
The high spead switching of the ferroelectric 10 liquid crystals can be utilized in many applications:light valves, displays, printer heads, and the like.
In addition to the submicrosecond switching speeds, some ferroelectric device geometries exhibit bistable, threshold sensitive switching, making them candidates 15 for matrix addressed devices containing a large number of elements ~or passive displays of graphic and pictorial information, -a~ well as opti~al processing - :
applications.

20 8UMMARY OF ~RB XNV~NTION
The present invention provides fluorine-containing liquid crystal compounds comprisin~ an ,-aliphatic fluorocarbon terminal portion having at least one catenary ether oxygen an~ an aliphatic hydrocarbon 25 terminal portion, the terminal portions being connected :by a central core, the compounds having smectic mesopha~es or having latent smectic mesophases~
Compounds having latent smectic mesophases are those ;wh~ch by themselv~s do not exhibit a smectic mes~phase, 30 but when the compounds are in admixture with ~aid compounds having smectic mesophases~or other said ~; compounds having said latent smectic mesophases develop : smectic me~ophases, under appropriate conditions. The luorocarbon terminal por~ion can b~ represented by the 35 formula:-D(CxF2x03zCyF2y+l where x is 1 to:10, y is 1 to 10, z is 1 tQ 10 and D is~a ~covalent bond, .

~ ~1336~2 WO 93/22396 P~/US93/03925 ~ ~
1'-' -- 5 -- I .
O . ':;~

C CrH2r~ ~ ~~CrH2r~, --~CE~H2 ElttCr ' H2 r ~ ~, - CrH2 r-, 5 -C)SO2-, ~SO2-, ~52~CrH2r~ 1 ~CrH2r~1 -SO2~

O p 2p+1 10 -CrH2r-N-C- where r and r' are independently 1 to 20, s CpH2p+1 independently 1 to 10 for each (C~H29O), t is 1 t~ 6 and p is o to 4.
~5 In general, the compounds of this invention have a central core comprised of at least two rings independently selected from aromatic, heteroarom~tic, cycloaliphatic, or substituted aromatic, heteroaromatic, or cycloaliphatic rings~ connected one ~;
20 with another ~y a covalent bond or by groups selected from -COO-, -COS-, -HC=N-, -COSe-. Rings may be fused ` .
or non-fused. Heteroatoms within the heteroaromat~c -~
ring comprise at least one atom selected fxom N, O, or S. Non-adjacent methylene groups in cycloaliphatic 25 rings may be substituted by O or S atoms.
. The fluorine-containing liquid crystal compounds having fluor~carbon terminal portlons of the ~present invention are not optically active but are useful, for example, when used in mixtures with 30 optically active liquid crystal materials. These compounds have a numiber of desirable properties when. ~.
used in admixture:with~fluorinated ferroelectric liquid . crystals with per,fluoroaliphatic terminal portions such as those disclosed, f~r example, in U.S. Pat. No.
35 4,886,619 and U.S. Pat. No. 5,082,587. ~he compounds having per~luoroether:terminal ~ortions o~ the present invention possess lower temperature smectic A and C j-: phases than compounds having perfluoroaliphatic ~erminal por~ions without an ether linkage~having :: :

~` ~
W093/22396 2 13 3 6 5 % PCT/US93/~3 ~ `

substantially the same number of carbon atoms in the terminal portion.
The inclusion of the liquid crystal compounds of the invention in mixtures wîth fluorinated 5 ferroelectric liquid crystals with perfluoroaliphatic '~
terminal portions results in compositions with lower ~ ;
viscosity and faster switching tlme than with mixtures without the liquid crystal co~pounds of the inv~ntion.
The presence of the compounds having lO perfluoroether terminal portions increases the temperature range of the smectic C phase of the admixture. A device ~ontaining such admixture will ~unction only in the desired smectic C phase of ~he mixture. The compounds of the present invention having 15 per~luoroether terminal portions have lower transitions ~rom smectic C to higher order and, thus, act to prevent admixtures from going from smectic C to higher "
order until the admixture temperature is lower than that at which the compounds ha~ing perfluoroaliphatic 20 terminal portions would normally change to higher j~
order.
The Pluorine-containing liquid crystal compounds ha~ing perfluoroether terminal portions also have good chemical stability towards water, weak acids 25 and weak bases, do not undergo degradation during ,~
normal use in a liquid crystal display device, and ar photochemically stable, that is, they do not easily ~ -undergo photochemical reactions. These compounds, due to the novel ~luorocarbon terminal portion, have~
30 greatly enhanced smectogenic properties,-lower birefringences, and lower viscosities than their ~-;~ non-f}uori~e-containing analogues.
These ~luoxinated liquid crystal compounds haYing perfluoroether terminal portions and mixtures ~; 35 which contain them are useful in a vari-ty of elactrooptical displays, In particular, these ~luorinated materials~exhibit s~ectic mesophases, '^~" W093/2~3~ 3 3 ~ 5 2 PCT/US93/039~5 ~``
~ 7 ~
especially smectic A and C, and are useful in the formulation of smectic A (SmA), smectic C (SmC), chiral smectic A (Sm~ ), and chiral smectic C (SmC ) mixtures. I

S BRIEF DESC}~IP?ION OF THE DRAWINGE~ ¦
FIG. 1 shows comparative Smectic A and Smectic C phases for prior art liquid crystal materials and liquid crystal materials of the in~ention as determined by DSC.
FI&. 2 shows comparative Smectic A and Smectic ~ phases for prior art liquid crystal materials and liquid crystal materials of the invention as determined by optical microscopy.

DETAII.ED DE8CRIPTION OF THE INVENI~ION
The present invention relates to fluorine-containing liquid crystal compounds having p~rfluoroether terminal portions and mixtures derived therefrom which find use in smectic liquid crystal 20 display applications and the like. The liquid crystals of the present invention can be represented by ~he general formula I: .

R~MtaA~NtbB~ptc-D Rf (I) ~1 Ym Zn where M, N, and P are each independently ~;..
~:: 35 :

`
: ~ 40 ~ ~

, .. ........ .............. ......

WO 93/~2396 2133~5 ~ PCT/US93/03~
.

j~~, ` ~1, ., 3 5 ; :

a, b, and c ar~ each independently z ero or an integer of ~rom 1 to 3 with the proviso that the sum of a + b +
~40 ~ c be at least 2;

Lch A and B~are non-directionally ~nd indlependen~ly a covalent bond, C-O- ~ -C S-, -C-Se~
` 50 0 -~-1'e~ ( CH2CH2 ) k- where k: ls l to 4, ~ -CH=C~

~: :

.

~' ~ ;W093/22396 ~ ~ 3 ~ 6 5 2 PCT/US93/03925 _ g _ I
Il ~
-C-C-, -CH-N-, -CH2-O-, -C- or -O- ;
each X, Y, and Z are independently -H, -Cl, -F, -Br, 5 -I, -OH, -OCH3, -CH3, ~CF3, -OCF3 -CN, or -NO2;
each l, m, and n are independently zero or an integer of l ~o 4, o 10 D is a covalent bond, -C-O-CrH2r-, ~O-CrH2r-, ~o~c~H2sottcr~H~r~-~ ~CrH2r ' -OS02-, -SO2- ~ ~S02-CrH2r~ ~ ~CrH2r~N S2 CpH2p+
o -CrH2r-N-C- where r and r' are indapendently 1 to 20, CpH2p+ 1 s is independently 1 to 10 for each (C~H2SO), t is 1 to 6 and where r and r' are independently 1 to 20, and p is 0 to 4;
25 R is ~O~C~2q~OtwCq~2q~ C~2g~OtwCq~H2q~t~ 2q~R
O O
O~C~2q~R~ -C~O~C~2q~R~ or ~O~C~C~2q~~
whexe R' is -Cl, -F, -CF3, -NO2, -CN, ~H, o o ~O~C~Cq,H2q,+1, or ~C~O~Cq,H2q,+1 and q and q' are ind~pendently 1 to 20~ w is 1 to 10 and R can be : straight chain or branched; and Rflis ~(CXF2~O)zCyF2y+l where x is îndependently 1 to 1!0 for ~ach CXF2xO, y is 1 to 10 and z i l to 10.
A preferred class o~ compounds of the ~-in~ention have:a pyrimidine core and can be represented . 40 by the formula .

2133652 ~;
W093/223~6 .~ PCT/US93/03~3 .. ::

dH2d~ oCII2~Cx~72 j~0)z~yF2y or \>~ ~2(c~P2~o)zcy~2y+

.
;
where d is 5 to 10, x is independently 1 to 3 for each .
CxF2xo, y is 1 to 4 and z is 1 to 3.
Compounds of the present invention have birefringences typically in the range of 0.05-0.18 ,.i 5 depending on the ring systems present and the number of ~`
rings, suppressed nematic mesophases, i.e., exhibit no . ;~
or very small n~matic mesophase temperature ranges and enhanced smectic mesophases. Mixtures o~ the compounds of the inYention with oth~er li~uid cr~stal materials 10 can be formulated to provide ~esired transition temperatures and broad mesophase temperature ranges.
5uch mixtures preferably contain fluorine-containing chiral smectic liquid crystals as disclosed in U.S.
Pat. No. 4,886,619 (Janulis) and/or achiral 15 fluorine-containing liquid crystals as disclosed in U.S. Pat. No. 5,082,587. ;
The individual compounds of this invention which exhibit smectic A~behaviQr can be used in admixture with other materials in smectic A de~ice 20 applications (see~rossland, et al. U.S. Patent Nqs.
4,411,494, 4,419,664, and 4,528,562, and F. J0 Kahn ~`
(Appl. Phys. Lett., vol. ~2, p. 111 (1973). ~:
: The individual compounds of this invention which exhibit sme~tic ~ behavior can be used in . ~;
25 admixture with other materials in the sme~tic C
Freedericksz device;application described by Pelzl et al., (see Kristall Technik., vol. ~4, p. 817 (1979);
, `` ` 2~33~52 1 ` ` WO 93/223!~6 - Pcr!usg3/o392s Mol. Cryst. Liq. Cryst., vol. 531 p. 167 (1979); Liquid Crystals, VQl. 2, p. 21 (1987); and Liquid Crystals, vol~ 2, p. 131 (1987)). As pointed out in the studie~
of Pelzl, et al. the decay time in the smectic C phase ~.
5 is shorter than in the nematic phase of the same material and in some cases the rise times are shorter, making this type of device application preferential to utilizing nematics in the classical Freedericksz device mode for some applications. The rise and decay times lO ~or the materials examined by Pelzl, et a~. were on the order of 2-lO0 milliseconds for a 50~ change in the measured light intensity. For materials of the present invention, rise and decay times of less than 1 millisecond have been observed for an 80% change in the 15 light intensity. Rise and decay times of a few milliseconds for an 80% change in the light intensity have been observed in room temperature mixtures.
Devic~s utilizing materials of the present invention make practical the use o~ smectic C materials in place 20 of nematic materials i~ Freedericksæ type devices and significantly shorter rise and decay times are attainable. : -The compounds of this invention do not show chiral smectic (ferroelectric) liquid crystal behavior 25 by themselves since they are achiral. However, a preferred embodiment of this invention comprises mixtures which contain materials of this invention with at least one chiral (optically active) component. The broad smectic C mesophase ranges and lower temperature 30 smectic C mesophases of many of the materials of this inven~ion make them useful and desirable as components ~-: in the formulation of broad smectic C eutectics, which become ~ferroelectric,-or chiral smectic C, upon ~~
addition of a chiral additive. Those compounds of the ., 35 invention having multiple ether o~ygen atoms are capable of increasing the temperature range for broader eutectic ranges in:mixtures~ An ether oxygen link :;

W093/~2396 21331j j2 PCT/US93/039'.~

between the hydrocarbon termînal portion and the central core further increases the SmA to SmC ~~
transition temperature ~ j Other advantages of using the materials of ~ ¦ -5 this invention in the formulation of chiral smectic mixtures are the low bire~ringence and viscosity which can be obtained. The lower viscosity of these materials results in reduced response times or the ferroelectric switching for a given bulk polarization 10 value. The lower birefringence of these materials allows the fabricatio~ of devices with larger device spacings. These materials provide a reduced temperature dependence of the smectic interlayer spacing. This property provides a spontaneous 15 generation of a bookshelf layer structure which is ideal for a ferroelectric li~uid crystal device. Light transmission through a surface~stabilized ferroelectric device (as described in U.S. Patent No. 4,367,924) with ;
two polarizers is represented by the following 20 e~uation:

I = Io (sin2(4e)) (sin2(~nd/~)) .

where Io = transmission through parallel polarizers e = material tilt angle on = liquid crystal birefringence d = devic~ spacing ~i = wavelength of light used To maximize the transmission, both sin2(4e) and sin2(~nd/~) must be at maximum. This uccurs when each term equals one. The first term is a maximum when the tilt angle equals 22.5. This is a function of the liquid crystal and is constant for a given mate~ial at '.
35 a given temperakure~ The second term is maximum when ~nd =~/2.

,"``~,`,. ~ 33G52 ~
~; W093l22396 PCT/US93/03925 ~.

This demonstrates the criticality of the low birefringence of the materials of this invention~ Low birefringence allows a larger de~ice thickness, d for~a given wav~length of light. Thus, a larger device 5 spacing is possible while still maximizing ~: , tran~mission, allowing easier device construction. :
The fluorine-containing liquid crystal compounds havi~g per~luoroether terminal portions of the invention can be prepared by a process comprising 10 the steps of tl) mixing at least one compound represented by the formula R~MtaAtl tbB
Xl Ym with at least one compound represented by the formula :~

B''tPtC-D-Rf Zn or (2) mixing at least one compound represented by the 25 formula R~l taA~ .

Xl . :
with at least ane compound represented by the formula A''~ltbB~Itc-D-Rf ~m Zn where M, N, and P are each independently f j,~......

~ S

`' .

~ , ~ .
~ ~ ' W093/~Z396'~1 3 3 6 j ~ PCT/US93/03Y~

~

~ ' ~ ~ N ~

~ ~ N ~ ~ J

a, b, and c are each independently zero or an integer of from 1 to 3 with the proviso that the sum of a+b+~
be ~t least 2;

40 each A and B are nondirectionally and independently a covalent bond, -C-0-, -C-S-, -C-Se-, -C-~e-, -CH=N-, 1, ~: 45 0 -CH2-0-, DC~, or -0~ CH~CH23X- where k is 1 to 4, -~H=CH~, or -C-C~

`-` W O 93/22396 2 ~ 3 3 6 ~ ~ P~r/US93/03925 ~ - 15 -each A', A'', B', and B'' are independently -OH, -COOH, .-CH(CH2OH)2, -SH, -SeH, -TeH, -NH2, -COCl, -CHO, -OSO2CF3 or -CH2COOH with the proviso that A' can ent~r into an addition or condensation reaction with A'' and ¦ -5 B' can enter into an addition or condensation reaction ' :
with B'';

each X, Y, an~ Z are independently -H~ -Cl, -F, -OCH3, -OH, -CH3, -CF3, -OCF3, -NO2, -Br, -I, or -CN;
, , each 1, m, and n are independently zero:or an integer of 1 to 4;

R is ~O~c~2q~Otwcq~H2q~

tCqH2q OtWCg~H2q~+l/ ~CqH2q~R~ ~ ~0~~ 12q~R~ ~ , O ' O : ' -OgCgH2q-R', or -gOCgH2g-R', where R' is -H, -Cl, -F, -CF3, -NO2, -CN, ~OCCq,Hq,~lj O ~ : ~
or -~-O-C~2q+l and q and q' are independently 1 to 20;
o Il ~ is a covalent bon~ ~C~O~CrH2r~~ ~~CrH2r~~
~)tc8H2~ottcr~H2r~ CrH2r-, -OSO2-, -SO2-, ~S02~crH2r~~ ~CrH2r~N S2 35 ~ CpH2p+
O
~ 11 ' : i,.
: 40 -CH2)r-N-C- where r~ and r' are~
Cp~2p+1 : independently 1 to 20, s is independently 1. to 10 for 45 ea~h (~fl~2~)~ ~ is~1 to 6 and~p is 0 to , ~

:~ ` :
:: :

W093/22396 Z 133ii5 ~ PCTIUS93/03 Rf is -tCx~2xO)zCyF2y+l where x is indep~ndently 1 to 10 for ~,ach CXF2xo group, y is 1 to 10 and z is 1 to 10;
and allowing said A' and A'' or B' and B'' to react in ~ ;~
the pre~ence of suitable coupling agents, i.e., a 5 reagent which effects coupling.
Objects and advantages of this invention are ~`
further illustrated by the following examples, but the particular materials and amounts thereof recited in these examples, as well as other conditions and 10 details, should not be construed to unduly limit this invention.
In the following examples, all temperatures are in degrees Centigrade and all parts and percentages are by weight unless indicated otherwise. Commercially 15 available materials were chemically tr~nsformed by reaction pathways well-known to those skilled in the art and detailed in the examples. Chemical transformations were comprised of a~ylation, esterification, etherification, alkylation, and 20 combinations thereo~ using fluorine-containing and non-fluorine-containing reactants to provide the precursor compounds, which, in turn were caused to react together to yield tha achiral fluorine-containing liquid crystal compounds of this invention.
Compounds prepared in the various examples of this invention were characterized ~y their melting or boiling point and structures were conf.irmed by using at least one of the methods of analysis: chromatography, 13c_, lH_ and 19F-NMR, IR and MS spectroscopies.
Examples 1-35 describe procedures for preparing intermediate compounds `useful in preparing ,-the liquid crystal compounds of this invention.
Example~ 36-84 descri~e preparation of the liquid crystal compounds of this invention.
The 5-alkyl-2-(4 hydroxyphenyl)pyrimidines used in the examples were prepared using the method described by ~aschke, ~. and S~olle, R. in "Synthese ¦!~
` ` ``` wo g3~z~396 ~ 1 3 3 6 S 2 PCT/US93/03925 niedrigschmelzender Kristallin-Flussiger Hetercyclen;
5-n-Alkyl~-2-~4-n-alkanoyloxy-phenyl]pyrimidine~ Z.
Chem~, (l5), pp. 441-443 ~1~75).

Cell drainings derived from the electrochemical fluorination of methyl 3-methoxy-propanoate ~45 g, 55% perfluoro-3-methoxypropionyl fluoride) were chilled to -78C in a dry ice acetone 10 bath in a ~lask fitted wîth a -78C condenser, overhead stirrer, thermometer, and addition funnel. The exit line to the condenser was fitted with a drying tower.
~ver a period of 5 minutes, methanol ~6 g) was added to the rapidly stirred solution. The flask was warmed to~
15 0C and stirring was continued for one hour. At that time, the reaction mixture was allowed to warm to room tempera~ure and then was stirred for an additional two hours. Water (100 mL) was added and the reaction mixture was allowed to phase split. The lower 20 fluorochemical phase (4~ g) was washed again with wa~er (50 mL) to give 33 g o~ crude product. The crude product was added to a flask fitted with a 10~2 cm ~~
distillation column filled with steel helices and a distillation splitter. Polyphosphorlc acid t~ g) was 25 addeid to the di~tillation pot and the fluorochemical product was distilled. Two product cuts were obtained: ;
boiling at 80-84C (5.2 g, 64% methyl perfluoro~3-methoxypropanoate~, boiling at ~4-87C (6.5 g, 78%
m~thyl perfluoro-3-methoxypropanoate)j. The GC-mass 30 spectrum of the second product cut confirmed the identity of the m~jor peak as CF3OCF2CF2CO2CH3, methyl ~.
perfluoro-3-methoxypropanoate.
Sodium borohydride (5.0 g) was added to a flask fitted with a condenser~ overhead ~tirreir, ¦~
~5 thermomster, and addition funnel. The sodium borohydrid~i was slurried with 40 g of ~etraglyme. With good stirring, the methyl-perfluoro-3-methoxypropanoate :: :

;: :

W093/22396 PCT/US93/03g ~ ``.
13 '3 ~i S 2 ! . ~
. - 18 -(30.3 g) was added over a 30 minute period. The reaction mixture w~s heated at 90C for two hours. The , ;.
reaction mixture was cooled to room temperature and poured into water (40 g). After the addition of the 5 crude reaction product was complete, concentrated .;
sulfuric acid ~6.0 g) was added tQ`the water/product mi.xture. The water/product mixt~re was ret~rned to the flask and the product isolated by azeotropic distillation with water. A Barret trap was plac~d 10 between the flask and the condenser. The crude reaction mixture was heated so that the product/water would distill into the trap. In the trap, the azeotrope split into two layers and the upper water layer was recycled to the flask. A total of 27.2 g of 15 fluorochemical product was isolated from the trap.
Karl Fischer water analysis showed the product to be 5.46 weight percent water. The product was added to :
polyphosphoric acid (23 g) and heated at 60C for one hour. The resultant product was one-plate distilled 20 from the polyphosporic acid. The desired product (15.7 g) distilled at 96-100C. Analysis showed this .:~
material to be 0.1 weight percent water. F-NM~ showed thi~ material to contain the following: 91.1 mole% of the desir~d product, CF30CF2CF2CH2OH, l,1-dihydrohepta-25 fluoro-3-methoxypropanol, 6~0 mole% CF3CF2CH20H, and 1.2 mole% CF3CF2CF2CH2OH.
1,1-Dihydroheptafluoro-3-methoxypropanol (13.77 g, 0.0637 moles) and triethylamine ~9.75 mL, 0.0701 moles) w~re dissolved in methylene chloride (25 30 mL) in a 100 mL ~lask fitted wi~h a magnetic stir ~ar, ~.
low temperatur~ thermometer, ssptum, and a nitrogen $
bubbler. The contents of the flask were then cooled to ~20C and tri~lic anhydride (10.7 mL, 0.0637 moles) were added slowly via syringe to ~aintain the 35 tQmperature be}ow -15C. A~ter the addition was complet~, the reaction was allowed to warm to room temperature. The solution was transferred to a .~`i;~` ` ~13'~fiS2 W093/22396 P~T/VS93/03925 separatory funnel and washed twice with 30 mL 0.5 N HCl and once with 3 n ml water~ The r~sulting solution was finally distilled and 8.75 mL of material boiling at~
118-120C were collected. GC showed 69 area % of the 5 main component, 1,1-dihydroheptafluoro-3- methoxypropyl ,`
triflate.

EXA~PLE ~
Cell drainings derived from the 10 electrochemical fluorination of ethoxyethyl acetate (235 g, 17% per~luoro-2-ethoxyacetyl fluoridej were chilled to -78C in a dry ice acetone bath in a flask fitted with a -78C condenser, overhead stirrer, thermometer, and addition funnel. The exit line to the 15 conden~er was fitted with a drying tower. Over a period of 5 minutes, ~ethanol (12 g) was added to the rapidly stirred solution. The flask was warmed to 0C
and stirring was continued for one hour. At that time~
the reaction mixture was allowed to warm to room 20 temperature and then was stirred overnight. Then, concentrated ~ulfuric acid (6 mL) was added and the reaction mixture phase-split. The lower fluorochemical phase was split away from the upper sulfuric ;~
acid/methanol/HF phase. A total of 101 g of crude 25 product was isolated. GC showed this material to be 16 weight percent C~3CO2CH3 and 26 weight percent CF3CF2CF2CQ2C~3; gc/mas8 spectrum confirmed the identity o~ these p~aks. The crude product was added to a flask fitted with a 10.2 cm distillation column 30 filled with steel helices and a distillation splitter.
Four product c~ts were obtained: boiling at 65-70~C
(5.8 ~, 27% methyl perfluoro-2-ethoxyacetate), boiling ,-`
~; at 70-~75C (6.4 g, 34% methyl perfluoro-2-ethoxyacetate), boiling at~75-~0C (}6~ g, 36% methyl 35 perfluoro-2-ethoxyace~ate)/ boiling at 80-~2C (16.1 g, 4~4% methyl perfluoro2-~thoxyacetatej. The four product cuts were combined. The GC-mass spectrum of ~ ~3365~ ~
W0~3/22396 ~ PCT/US~3/03g~j :

- 20 - `
the blended product confirmed the identity of the major product peak as CF3CF20CF2C02CH3, methyl perfluoro- ¦

2-ethoxyacetate. ~ ' Sodium borohydride (5.6 g) was added to a ~ -`
5 flask fitted with a condenser, overhead stirrer, thermometer, and addition funnel. The sodium borohydride was slurried with tetraglyme (45 g). With good stirring, the methyl perfluoro-2-ethoxyacetate (45.1 g, 37~ methyl perfluoro-2-ethoxyacetate) wzs 10 added over a 30 minute period. The reaction mixture was he~ted at 90C for two hours. The reaction mixture was cooled to room temperature and poured into water (80 g). After the addition of the crude reaction product was complete, concPntrated sulfuric acid (7.2 15 g) was added to the water/product mixture. The water/product mixture was returned to the flas~ and the product isclated by azeotropic distillation with water.
A Barret trap was placed between the flask and the condenser. The crude reaction mixture was heated to 20 distill the product/water into the trap. ~n the trap, the azeotrope split into two layers and the upper water layer was recycled to the flask~ A total of 20.5 g of fluorochemical product was isolated from the trap. Gas chromatography (GC) showed the product to be 66 25 desired product, CF3CF20CF2CH20H, l,l-dihydro--heptafluoro-2-ethoxyethanol. The GC/mas~ spectrum showed ~his material to consist of 73.8%
CF3CF~OCF2CH20H, 5.8~ CF30CF2C~20H and 2.3%
F31CF20CF2 CF2cH20H ~
1,1-Dihydro-heptafluoro-2-ethoxyethanol mixture, as described above (19.6 g, 82% fluorochemical alcohols), was dissolved in methylene chloride (30 mL) and dried with silica gel (0.9 g, 100~200 mesh, 983 grade) and filtered. The methylene chloride solution 35 was placed in a fla~k fitted with a magnetic stirrer, thermometer, and addition funnel. Triethylamine (12.4 g) was added to the flask, and the internal temperature .

133652 ~
W~g3/22396 PCT/~S93/0392~ 1`

rose to A0C. The flask was cooled to 5OC in an ice bath, and then triflic anhydride (34.1 g) was added slowly so that the temperature did not exceed 10C. ~ ¦
The reaction mixture stirred overnight with warming to ¦
5 room temperature. Water (50 mL) and methylene chloride (20 mL) were added and the mixture allowed to phase split. The lower product phase was then washed with 3~ sulfuric acid (50 mL) and water (20 mL). The methylene chloride was then stripped off at atmospheric 10 pressure. The product cut distilled at a head t~imperature of 107-115C. A total of 10.4 g of product was obtained. ~'he GC/mass spectrum showed this material to consist of 75.7 area % CF3CF20CF2CH20S02CF3.
F-NMR showed this material to consist of the following 15 weight %: 87.0% CF3CF20CF2CH2OSO2CF3, 4.~6%
cF3cF2cF2cF2ocF2cH2oso2cF3~ 0-3% CF3CF2CF20CF2CH20S02 3 Example_3 Sodium borohydride (8.3 g) was added to a 20 flask fitted with a condenser, overhead s~irrer, therm~meter, and addition funnel. The sodium borohydride was slurried with tetraglyme ~100 g~. With -good~stirring, methyl perfluoro-2-(butoxyethoxy)acetate 100 g, prepared by fluorination and methanolysis of 25 butoxyethoxyethyl acetat:e) was added~over a 30 minute ; ~ period. The reaction mixture was~heated at 90C for two hours and theni cooled to 40C. Methanol~(18~g)~was added slowly. The reaction mix ure was heated at 50C
; florl30 minut~s, then water (160 g) was rapidly added.! I
30 A~ter the addition of the wa~er was complete, 3 ;;
concentrated sul~uric ac`id ~11 g) wa~added to the ~; water~product mixture.~ The~crude~product was washed~ ~ ~
with water ~160 g) to yield~95~g cruds product. ~The ~ ¦
crude pro~uct was distilled at 160 Pa (1.2 mm Hg) at a ; 35~head temperature of~ 51-60C ~o give 77.8 g of the desired product~ dihydroperfluoro-2-~(butoxyethoxy) than~

W093/~23 ~ ¦ 3 3 fi S 2 PCT/USg3/035~ ~:

1,1-Dihydro-perfluoro-2-(butoxyethoxy)-ethanol ~10 g) was dissolved in methylene chlaride (30 mL) and placed in a flask fitted with a magnetic ~ ~
stirrerl thermometer, and addition funnel. Triflic ~ ;
5 anhydride t8.1 g) was added to the flask. The flask was cooled to 5C in an ice bath, and then triethylamine ~2.~ g) was added slowly so that the temperature did not exceed 10C. The reaction mixture was stirred overnight with warming to room temperature.
10 Water (20 mL) and methylene chloride (10 mL) were added and the mixture was allowed to phase split. The lower product phase was then washed with:3% sulfuric acid ~20 mL) and water ~10 mL). The methylene chloride was then stripped off atmospherically. The product cut 15 dis~illed at a head temperature of 92-95C at 50 kPa (45 mm Hg). A total of 9.4 g of product was obtained.
GC/~ass spectrum showed this material to consist of 88 area % of the desired product, CF3(CF~)30CF2CF2OCF2CH2OSO2CF3, 1,1-dihydroperfluoro-2-(butoxyethoxy)ethyl triflate, and 10 area %CF3SO2N(C2Hs)2-~E~ .

4-Cyano-4'-hydroxybiphenyl was converted to 25 the corresponding amidine hydrochloride via the method of MoW~ Partridge and W.F. Short (J. Chem. Soc.(1947), p. 390). The amidine hydrochloride (10 g, 0.0402 moles) and 2-octyl-3-dimethylaminoacrolein ~8.5 g, . 0.0402 moles, prepared as described by Z.~Arnold, and 30 F. Sorm, Coll. Czech. Chem. Çommun., 23(1958) p? 452) : were then treated with 25~ s~dium metho~ide in methanol '.
t37 mL, 0.1608 moles3~ in 1 0 mL of absolute eth~nol.
The resulting mixture was heated:to reflux and refluxed 5overnight. Aftar cooling to room temperature, the : 35 solvent was removed under reduced pressure. Water tlO0 mL), ether ~100 mL) and acetic acid (10 mL) were then ;:~ added to the flask and the mixture was stirred until :

~`W093/22396 ~ 1 3 3 6 ~ 2 PCT/US93/~392~

- 23 - 1 :
the solids dissolved. The resulting layers were ¦ ~`
separated. The aqueous layer was extracted twice with ether (50 mL). The combined ether layers were washed~
three times with water (50 mL), and dried with 5 anhydrous magnesium sulfate. Finally, the solvent was removed under reduced pressure, and the resulting solid was recrystallized from hot acetonitrile to yield 5.38 g (37%) of the desired product, 5-octyl-2-(4'-hydroxybiphenyl)pyrimidine.
, 4-Benzyloxyphenol (10 g, 0.0499 moles) was slowly added to 60% sodlum hydride in mineral oil (2.8 g) suspended in 100 mL of dry dimethoxyethane. After 15 stirring the resulting solution for 30 minu~es at room temperature, it was cooled with a dry ice/acetone bath.
1,1-dihydroheptafluoro-2-ethoxyethyl triflate (18 g, Example 2) was then added slowly. When the addition was complete, the ice bath was re~oved, and the mixture 20 was stirred at room temperature overnight. The solvent was then removed under reduced pressure and water (200 mL~, and ether (150 m~) were added. When the solids had dissolved, the layers were separated~and the ;
aqueous layer was extracted twice wlth ethe~ (150 mL).
25 The combined ether layers were washed once with 1 N
sodium hydroxide (125 mL) and twice with water (150 mL), dried with anhydrous magnesium sulfate, and stripped to dryn~ss on a rotary ~vaporator. The resulting solid ~13 g) was dissolved in ethanol and 30 hydrogenated at 0O4 MPa (60 psi) in the presence of catalytic 10% palladium on carbon for l8 hours. When the hydrogenation was complete the catalyst was removed by filtration, and th~ solvent was~ removed on a rotary evaporator. The resulting solid (6.5 g3 was c 35 recrys~allized from petroleum ether to yield 4 g of 4-dihydroheptafluoro-2-ethoxyethoxy)phenol.

W0~3/2Z396 ~1 3 3 6 5 PCT/US93/03~

In this example, a compound was prepared in the same manner as that described in Example 5, except that 1,1-dihydroperfluoro-2-~butoxyethoxy)ethyl 5 triflate (28 g, 0.049 moles) was substituted for the 1,1-dihy~roheptafluoro-2-ethoxyethyl triflate, to provide 7.6 g of 4-(1,1-dihydropërfluoro-2-(butoxyethoxy)-ethoxy)phenol.

4'-Benzyloxy-4-hydroxybiphenyl (1.5 g, 0.0054 moles) was slowly added to 60% sodium hydride in mineral oil (0.3 g) suspended in dry dimethoxyethane (15 mL). After stirring the resulting solution for 20 15 minutes at room temperature, it was cooled with an ice bath. l,1-Dihydroh~ptaf}uoro-2-ethoxyethyl triflate (1.9 g, 0.0055 moles~ was then added slowly. When the addition was complete, the ice bath was removed, and :
~he mixture stirred at room temperature overnight. The 20 solvent was then removed under reduced pressure, and water (25 mL) and ethyl ether (25 mL) were added. When the solids had dissolved, the layers were separated and the aqu~ous layer was extracted three.times with ether t15 mL). The combined ether layers were washed three 25 times with water ~20 mL), dried with anhydrous magnesium sulfate, and solvent removed on a rotary evaporator. Th~ resulting solid was dissolved in tetrahydrofuran and hydrogenated at 0.4 MPa (60 psi) in the presence of catalytic 10% palladium on carbon for 30 18 hours. Wh'en the hydrogenation was complet2 the catalyst was removed by filtration, and the solvent was : removed on a rotary evaporator. The resulting solid was recrystallized from hexane to yield 1.2 g of 4'- j (l,l-dihydroheptafluoro-2~ethoxyethoxy)-4-35 hydroxybiphenyl.

~ .

: : .

W093/2~396 ~ 1 3 3 6 ~ 2 PCT/US93/~39~5 - 25 - -:
EXAMPLE 8 . .
In this example, a compound was prepared in :-~he same manner as that described in Example 7, utilizing 0.3 g of 60% sodium hydride in mineral oil, 5 15 m~ of dimethoxyethane, l.o g (o.on36 moles) of 4'- '.
benzyloxy-4-hydroxybiphenyl, except that l,l-dihydroperfluoro-2-(butoxyethoxy)ethyl triflate t2.3 g, 0.0040 moles) was substituted for the 1,1- :
dihydroheptafluoro-2-ethoxyethyl triflate, to provide lO 1~0 g of 4'-(l,1-dihydroperfluoro-2-(butoxyethoxy)-ethoxy)-4-hydroxybiphenyl.

6-Benzyloxy-2-napthol ~2.5 g, o.o1o moles) ``
15 was slowly added to 60% sodium hydride in mineral oil (0.7 g) suspended in dry dimethoxyethane (25 mL).
~fter stirring the resulting solution for 20 minutes at room temperature, it was cooled with an ice bath. 1,1- -Dihydroheptafluoro-2-ethoxyethyl triflate (3.8 g, 0.011 20 moles) was then added slowly~ When the addition was `,.
complete, the ice bath was removed and the mixture was stirred at room temperature overnight. The solvent wa~
then removed under reduced pressure and water (30 mL) and ether ~30 mL) were a~ded. When the solids had 25 dissolved, the layers were separated and the aqueous layer was extracted twice with ether (25 mL). The c~mbined ~ther layers were washed three times with water (20 mL), dried with anhydrous magnesium sulfate ', and stripped to dryness on a rotary evaporator. The '-30 resulting solid was dissolved in tetrahydrofuran and hydrogenated at 0~4 MPa (60 psi~ in the~presence of ~.-catalytic 10% palladium on carbon for 18 hours. When i-the hydroge~ation was complste the cataly~t was removed by filtration, and the solvent was removed on a rotary ~: : 35 evaporator. ~he resulting solid was recrystallized from hexane to yield 1.28 g of 6~ dihydrohepta- -fluoro-2-ethoxyethoxy)-2-hydroxynapthalene.

W093/2~396 '), 13 3 6 5 Z PCr/U593/03~.
- 26 - :

` In this example, a compound was prepared in the same manner as that described in Example 9, except that l,1-dihydroperfluoro-2-(butoxyethoxy)ethyl 5 triflate (6.2 g, 0.010 moles) was substituted for the 1,1-dihydroheptafluoro-2-ethoxyethyl triflate, to provide 2.5 g of 6-~ dihydroperfluoro-2-(butoxyethoxy)ethoxy)-2-hydroxynapthalene~

Sodium hydride ~0.39 g of 80% suspension in mineral oil) was added to dimethyl formamide ~5 mL) in a three-necked flask under an inert atmosphere. Methyl hydroxybenzoate (1.96 g, 0.129 moles) was dissol~ed in 15 a mi~ture of toluene (10 mL) and dimethyl formamide ~5 mL). The methyl hydroxybenzoate solution was added to the sodium hydride over a period of 15 minutes. The reaction was allowed to stir at room temperature for one hour. l,1-Dihydroheptafluoro-2-ethoxyethyl 20 tri~late (4.5 g, 0.129 moles) was then added and the flask was heated to 116C for one hour. The reaction : mixture was cooled to room temperature and poured into ~-water (25 mL). The upper product phase was split off and rewashed with additional water (25 mL). The crude 25 product solution was then stripped at 26.7 Pa (0.2 mm Hg) until the pot temperature reached 120C. The produ~t was th~n distilled at 4 Pa (0.03 mm Hg~. The product (3.7 g3 distilled at 100-105C head temperature and consi5ted of a white low melting solid. GC-mass 30 spectxum ~howed~the~material to consist of 89~ o~ the product, ~ethyl 4-(2,2-difluoro-2-pentafluoro-~ ~ithoxye~hoxy)benzoate, with a molecular weight of 350, : 5% of a material with a molecular weight of 430, and 6%
` of the starting methyl~ hydroxybenzoate. The infrared 35 ~pectrum wa~ consistent with the desired ~tructure.
Subsequently, the methyl 4-(2,2-difluoro-2 pentafluo~oethoxyethoxy)benzoate (3.3 g3 was heated at W~93~22396 ~1 3'3fi52 ~CT/US93/03925 reflux with 10% KOH (20 mL) for 2 hours. The ~ ~;
hydrolysis reaction was then cooled to room temperature, and acidified with 98% sulfuric acid (1.75 g). The fluorinated benzoic acid precipitated, was ~- :
5 isolated by filtration and washed twice with water (10 mL). The crude acid was then stirred with ethanol (50 mL) and filtered. The cake was washed with an additional 25 mL of ethanol. The materi~l was dried in a vacuum o~en at room temperature and 26.7 Pa (O.2 mm 10 Hg). The desired 4-(1,1-dihydroheptafluoro~2-ethoxyethoxy)benæoic acid (2.7 g) was isolated. ~-EXAMPLE .2 Sodium (1.15 g, 50 mmoles) was reacted with 15 anhydrous ethanol (200 mL~ under a nitrogen atmosphere.
2,3-dicyanohydro~uinone ~.01 g, 50 mmoles) in anhydrous ethanol (50 mL) was added dr~pwise to the ethoxide solution. Upon completion of the addition, potassium iodide (O.5 g) in 5 mL water was added. This 20 ~olution was brought to reflux and octyl bromide ~9.66 g, 50 mmoles) was added dropwise. The rèaction was then refluxed under nitrogen atmosphere for one day.
The mixture was acidified with O.SN aqueous HCl and the solvents were r~moved under reduced pressure. The 25 crude reaction mixture was flash chromatographed using silica gel and methylene chloride as eluent. The appropriate fractions containing the ~esired product, 2,3-dicyano-4~octyloxyph~nol, were combined and the solvent removed under reduced pressure on a rotary 30 evaporator. The crude product was recrystallized from ethanol/water ko give 4.5 g 2,3 dicyano-4-octyloxyphenol. . ¦

E~PLE 13 2,3-Difluoro-4-oc~yloxyphenol was prepared as described in Reiffenrath, V. et al., I'New Liquid W093/2239~ 1 336S~ PCT/US93/03~ ~

Crystalline Compounds With Negative Dielectric Anisotrophy" Li~uid Crystals, 5, (1989~, pp. ~59-170.

Example_14 t ~
1,1-Dihydroperfluo~o~2-(2-hexyloxyethoxy)- .-ethyl triflate (c6Fl3oc2F4o~2cH2oso2cF3~ bp 90 3.0 mm Hg) was prepared from methyl perfluoro~2-(hexyloxyethoxy)ethanoate and 1,1-dihydroperfluoro~2-(~ hexyloxyethoxy)ethanol (bp 80-35-C at 3.5 mm Hg) as 10 described in Example 3.

ExamPle 15 1,1-Dihydroperfluoro-4-(4-butoxybutoxy)butyl triflate (C4FgOC4F80C3F6CH20S02CF3~ bp 76-80 C at 0.1 mm 15 Hg) was prepared from methyl perfluoro-4-(4-b~toxybut~xy) butanoate and l,l-dihydroperfluoro-4-(4 butoxybutoxy)but~nol (bp 87-100-C at 3 mm Hg) as describ~d in Example 3.

20 Exam~le 16 1,1-Dihydroperfluoro-2-(2~ methoxyethoxy)-ethoxy~ ethyl triflate (CF30(C2F4~)2CF2CH20S02CF3~ b 73C at 15 mm Hg) was prepared from methyl perfluoro-2-(2-(2-methoxyethoxy)ethoxy) ethanoate and 1~ dihydro-25 perfluoro-2-(2-(2 methoxyethoxy)ethoxy) ethanol (bp 72-75-C at 15 mm Hg) as described in Example 3.
, Exam~le 17 ~ Dihydroperfluoro-~-(butoxy)propyl 30 triflate (C4FgOC2F4CH20S02CF3t bp 73qC at 15 mm Hg) was prepared from methyl perfluoro-3 (butoxy) propanoate and 1,1-dihydroperfluoro-f3-(butoxy) propanol (~p ~0C
at 15 mm Hg) as deicri~ed in Example 3.

35 Exa~ ~e 18 1,1-Dihydroperfluoro-4-(butoxy)butyl triflate (C4F90C3F6~H~OSO~CF3, bp 57-63C at 2.5 mm Hg) was .

` ` ` i `~
,,.`.. ;~,``,., 213~52 ~.,' W093/~39~ PC~/US93/03925 j:`

- 29 - .
prepared from methyl perfluoro-4-tbutoxy)butanoate and 1,1-dihydroperfluoro-4-(butoxy~butanol as described in Example 3.

5 Exam~le 19 .
l,l-Dihydroperfluoro-3-(hexyloxy)propyl triflate (C6F130C2F4CH20S02CF3, bp 65-67C at 0.1 mm Hg) was prepared from methyl perfluoro-3-(hexyloxy) ~.
propanoate and l,l-dihydroperfluoro-3-(hexyloxy) 10 propanol as described in Example 3.

Ex~mPle ~0 1,1-Dihydroperfluoro-3 ~octyloxy)propyl triflate (C8FlgOC2F4CH20S02CF3t bp 56 C at 1 mm Hg) was 15 prepared from methyl perfluoro-3-(octy~oxy~ propanoate and 1,1-dihydroper~luoro-3-(octyloxy) propanol as described in Example 3.

Exam~le 21 1,1-Dihydroper~luoro-3-(decyloxy)propyl triflate (C1~F2l0c2F4cH20s02cF3~ bp 130 14 was prepared from methyl perfluoro-3-(decyloxy) propanoate and 1,1-dihydroperfluoro-3-~decyloxy~
propanol as described in Example 3.

~3~ . .
1,1-Dihydroperfluoro-3~(n~.opentoxy~propyl triflate ((~F3)3CCF20C2F4CH20S02CF3) was prepar~d from '.
methyl perfluoro-3-(neopentoxy) propanoate and 1,1-30 dihydroperPluoro-3 (neopentoxy) propanol as described in Example 3.

7,:
Example 23 Ethylene carbonate (l.Og, 11.6 mmol) was 35 added to a stirred solution of 1,1-dihydroperfluoro-2-(2 butoxyethoxyjethanol (5.0g, 11.6 mmol) and potassiumhydroxide ~7 mg,:0.12 mmol) in tetraglyme ~2 ml). The W093/22396 PCT/US93/03 ~ `

2 ~33 6~ ~ - 30 -solution was heated to lOO'C for 6 hours and then at ambient temperature for 10 hours. The product was distilled from the reaction mixture to give 3.66g of 2-[l,1-dihydroperfluoro-2-(2-butoxyethoxy)ethoxy] ethanol S (bp 52 C at 0.8 mm Hg) as a clear o~. Alcohol (3.66g, ~.
7.7 mmol) was then added to a s~ir~e`~ solution of 4-N,N
dimethylaminopyridine (90 mg, O.a~mol), triethylamine (~.1 ml, 15.4mmol) and p tolue ~ ulfonyl chloride (l.~lg, 8.5 mmol) in dichloromethane (20 ml). The 10 solution was stirred under a nitrogen atmosphere for 10 hours a~d was then filtered through a pad of silica gel (20 g) (washed through with 100 ml of 4:1 hexane/ethyl acetate). The filtrate was concentrated to give the desired product, 2~ dihydroperfluoro-2~(2-15 butoxyethoxy)athoxy] ethyl-p-toluenesulfonate C~9~4~2~2~0sO~-r~3 2~ :

as a slightly browned oil.

25 ~a~ Q-~
2-(1,1-Dihydroperfluorooctyloxy)ethanol (C7F15CH20CH2CH20H~ was prepared by heating 1,1 dihydroperfluorooctanol (141.9 g), ethylene carbonate (51.7 g) and triethylamine (36.7 g) under reflux in an 30 inert atmosphare ~bath temperature 100C) for 36 hours~
At that time, gas chromatography showed a mixture of 816%l of the desired product, 4% starting alcohol, and 6%
diadduct, with the balance being volatile impurities.
Aqueous acidic workup with Freon 113 as the extraction 35 solvent gave crude product. Vacuum distillati4n at aspirator pressure yi~lded forefractions containing 90%
product, 68O1 g, and a center cut of 99% purity, 41.8 g-:;~

'`" W093/22~9621336S2 PCT/US93!03925 `-~ o " .
- 31 - J, .
_xample 25 ¦
2-(1,1-Dihydroperfluorohexyloxy)ethanol (C5FllCH20CH2CH20H) was prepared as described in Example 24 except l,1-dihydroperfluorohexanol was 5 substitut~d for the l,l-dihydro-perfluorooctanol.

ExamPle 26 2-(2-(1,1-Dihydroperfluorooctyloxy)-ethoxy)ethanol (C7Fl5CH20CH2CH20C~2CH20H) was prepared by 10 heating 2-(1,1-dihydroperfluorooctyloxy)ethanol (53 g) (Example 24), ethylene car~onate (46.4 g) and `' triethylamine (33.8 g) undar inert atmosphere. The mixture was heated at reflux for S days. Aqueous acidic workup with Freon 113 as the extraction solvent 15 gave crude product. The product was distilled (kugelrohr) to give ~3.63 g of the desired product.

Example 27 l-Bromo-2-(1,1 dihydroperfluorooctyloxy)- ;
20 ethane (C7F1sCH20CH2CH2Br) was prepared as described in Ha~ack and Auchter, JACS 107 5238 ~1985). A ~o ml flask ~itted with magnetic stirring, inert atmosphere, the~mometer, and septum inlet was charged with triphenylphosphine (6.22 g) and acetonitrile (25 ml).
25 The flask was chilled in an ice-salt bath to a solution temperature of -3C and bromine, 3.76 g, was added by ga~tight syringe over 15 minutes, maintaining a solution tempera~ure of less than SC. After an ¦additional 5 minutes, the bath ~as removed and 2-(1,1 30 dihydroperfluorooctyloxy)2thanol (~xample 2~) (lo.0 g) was added by syringe over about 7 minutes. Af~er one ~ ;
hour, the reaction was worked up in water, dichloromethane as the extraction solvent, dried and solvent removed to yield a mixture of product and 35 triphenylphosphin~ oxide byproduct. Tritura~ion with Freon 113 yielded crude product as a colorless oil, ~rom which separated a small amount of the wog3/~239 ~ 1 3 3 6 PCT/US93/039L~

tr.iphenylphosphine oxide byproduct. Filtration gave 11.65 g product (11.42 g theoretical yield). No l:
further purification was carried out.

5 ~a~æle 28 ~ Dihydroperfluor.o~xyl 2-bromoethyl ether, ~,. . .
(C5F11CH20CH2CH2Br) was prepared as in Example 27, except 2-(1,1-dihydroperfluorohexyloxy)ethanol was substituted for the 2-(l,l~dihydroperfluoroocytloxy)-}0 ethanol.

ExamPle 29 1-Bromo-2-(2-(1,1-dihydroperfluorooctyloxy)-ethoxy)ethane (C7F1sC~20CH2CH20CH2CH2Br) was prepared as 15 in Example 27 except 2-(2-(1,1-dihydroperfluoro-octyloxy)-ethoxy3ethanol was substituted for the 2-(1,1-dihydroperfluorooctyloxy)ethanol.

In a one-liter flask, 30 g (0.09 moles) of 2-benzyloxytrimethinium perchloroate (prepared according to the procedure of A. Holy and Z. Arnold, Collection Czecho~lov. Chem. Commun., 38 (lg73) 1372~, 15.6 g ~0.09 mo}es) para-hydroxybenzamidlne hydrochloride, 25 82.5 ml (0.36 moles) of 25% sodium methoxide in methanol, and 500 ml o~ ethanol were combined. The mixture was h~ated to reflux overnight, and then cooled -~
~o room temperature. Then, 75 ml of acetic acid and 30Q ml of water was added to the flask, resulting in 30 the precipitation of the product. The product was collected by filtration, washed with water and air dried. The yield of 5-benzyloxy-2-(4- ,.-hydroxyphenyl)pyrimidine was 23.0~ g (32%).

35 ExamPle 31 In a one-liter flask, 16.5 g (0.05 moles) of 2~benzyloxytrlmethinium perchloroate (prepared :

~ wo93/2~396 2~365~ PCT/US93/03~25 according to the procedure of A. Holy and Z. Arnold, Collection Czechoslov. Chem. Commun., 38 (1973) 1372), ¦
12.3 g (0.05 moles) 4'-hydroxyphenylbenzamidine ~ }
hydrochloride, 45 ml (0.20 moles) of 25% sodium 5 methoxide in methanol, nd 300 ml of methanol were combined. The mixture.was heated to reflux overnight, and then cooled to roo~ temperature. To the ~lask were ;;
added 300 ml of water, which resulted in precipitate formation. Most of the methanol was removed under 10 vacuum on a rotary evaporator. The solid was collected by filtration. The cake was dissolved in 95C water and the hot solution was acidified with concentrated hydrochloric acid to precipitate the product. The product was collected by filtration from the hot 15 mixture, washed with warm watPr, and air dried. The yield of 5-benzyloxy-2-(4'-hydroxybiphenyl)pyrimidine was 11.97 g (68%).

Exam~le 32 5-Benzyloxy-2-(4-hydroxyphenyl)pyrimidine (18 g, 0.0647 moles, Example 30) wa~ dissolved in 150 ml of N,N-dimethylformamide in a 500 ml flask, a~d 1.7 g of dry sodium hydride was added. After stirring the mixture for 15 minutes, 36.5 g (0.0647 moles) of 1,1-25 dihydroperflu~ro-2-(butoxyethoxy)ethyltri~'late was added and the mixture was heated to 95~C for 1 hour~
Upon cooling to room temperature, an equal volume of water was added. The resulting solid was collected by filt~ation. The solid was then slurried in boi~ing 30 methanol, cooled to room temperature, and again collected by filtration. The solid was hydrogenat~d on '.
a Parr Hydxogenator with catalytic 10~ palladium on carbon in tetrahydrofuran under ~13.7 kPa hydrogen pr~ssure for about 18 hours. When the hydrogenation 35 was complete, the cat~lyst was removed by filtration : and th~ solvent was r~moved on a ro~ary evaporator to yield 25.62 g (66% yield) of 5-hydroxy-2-(4-~1,1-W093/22396 213365 2 PCT!US93103 dihydroperfluro-2-(butoxyethoxy)-ethoxy~phenyl)-pyrimidine.
.` ' Y
Example 33 5-Hydroxy-2-(4-(l~ ,dihydroperfluro-2-(butoxy)ethoxy)phenyl) pyrimidine was prepared as described in Example 32 except that 1,1-dihydro-per~luro-2-(butoxy)ethyltriflate was~substituted for 1,l~dihydroperfluoro-2-(butoxyethoxy)ethyl~riflate, xample 34 5-Benzyloxy-2-(4-hydroxyphenyl)pyrimidine (2 g, 0.0072 moles~ Example 30) was dissolved in 15 ml of N,N-dimethylformamide in a 50 ml flask and 0.2 g of dry 15 sodium hydride was added. A~ter stirring the mixture ~: for 15 minutes, 1.39 g (0.0072 moles) of octylbromide was added and the mixture was heated to 100C for 2 hours. Upon cooling to room temperature, 15 ml of water was added. The resulting solid was collected by 20 filtration and the.solid was then slurried in ~oiling - , methanol, cooled to room temperature, and again :~
collected by filtration. Th solid waæ hydrogenated on a Parr Hydrogenator with catalytic~10% palladium on : carbon in tetrahydrofuran under 413.7 kPa hydrogen 25 pressure for about 18 hours. When the hydrogenation was complete, the catalyst was removed by filtration, : and the solvent was removed on a rotary evaporator to yield 1.62 g (75% yield) of 5-hydroxy-2-~4-~octyloxy)-phenyl)pyrimidine.
: J
ExamPle 35 5: ydroxy 2-(4'~ dihydroperfluro-2~
butoxyethoxy)ethoxy).~biphenyl)pyrimidine~was prepared~ ¦
` : as described in Example~32;except tha~ 5-benzyloxy-2-35 (4'-hydXo~ybiphenyl)pyrimidine~(Example~3`1) was ~ ' substituted for~5-benæyloxy-2-(:4-hydroxyphenyl)-pyrimidine. ;

21336S2 f~~ W093/22396 ! PCT/US93/03925 ~
,:, ., - 35 - :-Example 36 A 100 mL 3-neck flask fitted with a magnetic stir bar, septum, ~topper, and water cooled condenser~
connected to a nitrogen bubbler was charged with dry ¦;
5 sodium hydride (0.8 g, 0.0345 moles), toluene (20 mL), `,:
and dimethyl formamide (20 mL). With vigcrous stirring, ~-hexyl-2-(4-hydroxyphenyl)pyrimidine (5.9 g, 0~023 moles) was added slowly to control the hydrogen evolution. The resulting mixture was stirred at room 10 temperature for 30 minutes. Then, l,l-dihydrohepta-fluoro-3-methoxypropyl triflate (8 g, 0.023 moles, prepared in Example 1) was added and~the solution was heated to reflux. After 1 hour, the reac~ion mixture ~:~
was allowed to cool to room temperature~ The contents 15 of the flask were poured into a separatory funnel ~:.
containing water (50 mL). The resulting layers were ~ ~
separated and the aqueous layer was extracted twice :
with toluen~ (~O mL). The combined organic layers were then washed three times with water, dried with 20 anhydrous sodium sul~ate, and filtered. After solvent remo~al on a rotary evaporator, a brown oil resulted.
This oil was chromatographed on silica gel (125 g), eluting with chloroform. Care was taken to separate the product ~rom a yellow impurity which ~luted off the 25 column just before and overlapping with the desired product~ A pale yellow semisolid (li~uid crystalline at room temperature) rasulted. The yield of this desired product, 5-hexyl-2-~4-(1,1-dihydro- '.
heptafluoro-3- methoxypropoxy~phenyl)pyrimidine, 30 ~ompound 1, Table 1, was 2.8 g.

ExamPle 3~
A 100 mL 3-ne.ck flask fitted with a magnetic "
s~ir bar, septum, stopper, and water cooled condenser 35 connected to a nitrogen bu~bl r was charged with 60%
sodium hydride/mineral oil ~1.6 g, 0.04 moles~, toluene (25 mL), and dimethyl formamide (25 mL). With vigorou~
.

~:

~_ ~- ?.`
WO 93/22396?,.~3'3 6S ~ P~US93J03g"J' `.

stirring, 5-octyl-2-(4-hydroxyphenyl)pyrimidine (7.6 g, 0.0~67 moles) was added slowly to control the hydrogen evolution. The resulting mixtur@ was stirred at roo~
temperature for 30 minutes. Theh, 1,1-dihydrohepta-5 fluoro-2-ethoxyethyl triflate~ 9.3 g, 0.0267 moles, prepared a~ in Example 2) ~a~ added and the solution was heated to reflux. After 1 hour, the reaction mixture was cooled to room temperature. The contents o~ the ~lask were poured into a s~paratory funnel 10 containing water (50 mL). The resulting layers were separated, and the aqueous layer was extracted twice with toluene (20 mL). The combined organic layers were then washed three times with water, trèated with silica . gel (5 g) ~or one hour and filtered. After solvent 15 removal on a rotary evaporator, a light brown oil resulted. This oil was chromatographed on silica gel (125 g), eluting with chloroform. A pale yellow semisolid (liquid crystalline at room temperature) resulted. The yield of the desired product, 20 5~octyl-2-(4-(1,1-dihydroheptafluoro-2-ethcxyethoxy)phenyl)pyrimidine, Compound 2, Table 1, was 6.4 g.

Example 38 : 25 ~ A 100 mL 3-neGk flask fitted with a ~agnetic stir bar, septum, stopper, and water cooled condenser connected to a nitrogen bubbler was charged with 60~
sodium hydride/mineral oil (0.8 g,: 0.0~ moles), toluene (lS mL), and dimethyl formamide (15 mL). Wit~ vigoro4s ; 30 stirring, 5-octyl-2-(4-hydroxyphenyl)pyrimidine (3076 g, 0.0132 moles) was added slowly to control the hydr~g~n ~volution. The resulting mixture was stirred ; :at room temper~ture for 30 minutes. Then, 1,1- '~
:ihydroperfluoro-2-(butoxyethoxy)ethyl:triflate (7.~7 ;~ ~35 g, ~0.0132 moles, prepared as in~Example~3~ was added and the solution:was:heated to reflux. After 1 hour, the reaction mixture was cooled to room tempPrature~

`
:

~"~ 21 3~6S2 ~, ~; W093/22396 f` PCT/US93/03~2 The contents of the flask were poured into a separatory funnel containing water (50 mL3. The resulting layers were separated and the aqueous layer was extracted twice with toluene (20 mL). The combined organic 5 layers were then washed three times with water, treated `-with silica gel t5 g) for one hour, and filtered.
After solvent removal on rotary evaporator, a light brown oil resulted. This oil was chromatographed on silica gel (125 g), eluting with chloroform. A pale lO yellow semisolid (liquid crystalline at room temperature) resulted. The yield of the desired product, 5-octyl~2-(4-(1,1-dihydroperfluoro-2~
butoxyethoxy)ethoxy)phenyl)pyrimidine, Compound 3, Table l, was 4.7 g.
Exam~fe 39 Product was prepared as in ~xample 38 except 0.585 g sodium hydride, 80% dispersion in oil an~ 11.0 g l,l~dihydroperfluoro-2-butoxyethoxyethyl triflate 20 were used and 5.0 g 5-hexyl-2-(~-hydroxyphenyl)-pyximidin~ was substituted for the 5-octyl-2-(4-hydroxy-phenyl)- pyrimidine. The resulting product, 5-hexy1-2-(4-(1,1-dihydroperfluoro-2-(2-butoxyethoxy)~ ethoxy3phenyl)pyrimidine, is 25 Compound 4, Table 1.
'.

XA~fPLE 40 A S0 mL flask was charged with 60~ sodium hydride in mineral oil (0.2 g, 0.004 moles), toluene !
` 30 ~io mLj, N,N-dimethylformamide (10 mL) and 5-octyl- .
2-(4'-hydroxybiphenyl)pyrimidine (0.00277 moles, prepared a~ ln Example 4)~under an atmosphere of dry nitrogen. The mixture was stirreid at room tPmperature for 1.5 hours. l,1-Dihydrohept fluoro 2-ethoxyethyl 35 triflate (0.96 g, 0.00277 moles) was then added, and the mi~ture was~heated to 100C for 1.5 hours. After cooling t~ room temperature, the contents of the flask :: :

W093~2396 PCT~US93/03g~
~335~ - 38 - I -were poured into a separatory funnel oontaining water ~60 mL) and toluene (20 mL). The layers were separated and the aqueous layer was extracted twice with 20 mL Qf toluene. The combined organic~;ayers were washed three 5 times with 30 mL of water, dr;~:èd with anhydrous sodium `
sulfate, and filtered. The~olvent was removed under reduced pressure. The resulting brown solid ~as recrystallized from ethanol, and~then flash chromatographed on silica gel, eluting with chloroform 10 to yield 0.58 g of white solid, 5-ootyl-2-(4'-(1,1-dihydroheptafluoro-2-ethoxyethoxy)biphenyl)-pyrimidine (Compound 5, Table 1).
' 5-Octyl-2-(4'-(1,1-dihydroperfluoro-2-(2-butoxyethoxy)ethoxybiphenyl)pyrimidine was prepared as ;~ described in Example 40,;except that 1,1-dihydro-perfluoro-2-(2-l-butoxyethoxy)ethyl~triflate ~1.6 g, 0.00277 moies) was used in place of~l;,l_dihydrohepta-20 fluoro-2-ethoxyethyl triflate, to yield~0.4 g of 5- ~ ~, octyl-2-(4'-(l,1-dihydroperfluoro-2-(2-butoxyethoxy)-ethoxybiphenyl)pyrimidine (Compound 6,;Table l).

E~AMPLE 42 4-Decyloxyben~zoic acid (0.45 g, 0.0016 moles) and 4-(1,1-dihydrohepta~fluoro-2-ethoxy-ethoxy)phenol (0.5 ~g,~ 0.0016 moles,~prepared~as~in Example 5) were~
dissolved in dichloromethane (25 mL). 1,3-di ~ clohexy?carbodilmide~0.3s g,~0.0017 moles~ was 30 add~d to the reaction mixture, followed by 4-(N,N-dimethylamino)pyridine (0.0~ g, 0~.0004 moles). The resultant mixture`~was sti~red at~room temperature under ~-nitrogen for~18~hours. The precipitated~urea was ; removed from~the;;~product solution~by~filtration,~ and 35 the~fil~rate~w~s~concentrated~on a rotary evaporator at reduced~pressure~ The~crude solid~was; purif ied~by~
recrystal}ization~from~ethanol,~followed~by flash 2133~52 ` W093/2239~ PCT/US93/03925 1 :

~ 39 ~
chromatography on silica gel, eluting with chloroform, to yield 0.12 g of the desired product, Compound 7, in Table 1. ~ t i ~.
In Examples ~3-S3l Compounds 8-20 of Table 1, respectively, were prepared as in Example 42, except the precursor compounds indicated ~elow were substituted for the 4-decyloxybenzoic acid and the 4-10 (ljl-dihydroheptafluoro-2-ethoxyethoxy)phenol.
Example 43, compound 8, was prepared from 3-chloro-4-octyloxybenzoic acid and 4 (1,1-dihydroheptafluoro-2-ethoxy2thoxy~phenol (Example 5).
Example 44, compound 9, was prepared from 3-15 chloro-4-octyloxybenzoic acid and 4-~
dihydroperfluoro-2~(butoxyethoxy)ethoxy)phenol (Example 6). .
Example 45, compound 10, was prepared from 6-~4~methylhexyloxy)nicotinic aci~ and 4 20 dihydroheptafluoro-2-ethoxyethoxy)phenol (~xample 5~
This product was liquid at room temperature, thus it was not recrystallizad, and was simply purified by chromatography.
Example 46, compound ll, was prepared from 6-25 (4 methylhexyloxy)nicotinic acid and 4-(1,1-dihydroperfluoro-2-~2-butoxyethoxy)ethoxy)phenol (Example 6). This product was liquid at room ~emperatur~, thus it was not recrystallized, and was simply purlfied by chromatography. ~ :
Example 47, compound 12, was prepared from octyloxybenzoic acid and 6-(1,1-dihydroheptafluoro-2- ~;
ethoxy@thoxy) 2-hydroxynapthalene (Example 9~ .
Example 48, compound 13, was prepared from ~r decyloxybenzoic acid and 6-(1,1-dihydroheptafluoro-2-35 ethoxyethoxy)-2-hydroxynapthalene (Example 9).

:~ ' W093/~23~6 2~33~S2 PCT/US93/03~

Example 49, compound 14, was prepared from decyloxybenzoic acid and 6-(1,1-dihydroperfluoro-2-(2- ¦
butoxyethoxy)ethoxy)-2-hydroxynapthalene (Example 10)~.
Example 50, compound 15;~ was prepared from 5 octyloxybenzoic acid and 4'~ dihydroheptafluoro-2-ethoxyethoxy)-4-hydroxybiphen~i (Example 7).
Example 51, cbmpound 16, was prepared from .~
decyloxybenzoic acid and 4'-(1,1-dihydroheptafluoro-2- .
ethoxyethoxy)-4-hydroxy~iphenyl (Example 7).
:
Example 52, compound 17, was prepared from decyloxybenzoic acid and 4'-(1,1-dihydroprefluoro-2-(2-butoxyethoxy)ethoxy)-4-hydroxybiphenyl (~xample 8).
Example 53, compound 18, was prepared from 4-(1,1-dihydroheptafluoro-2-ethoxyethoxy)benzoic acidj `:
15 (Example 11) and hydroquinone mono-trans-4- -~
pentylcyclohexanecarboxylate.
"
E%AMPLE 54 2,3-Dicyano-4-octyloxyphenol (0.8 g, 0.0030 20 mole, Example 12), l,1-dihydroheptafluor~-2- ethoxy-ethoxy)benzoic acid (1.0 g, 0.0030 mole, Example 11) ,:
and dichloromethane (50 mL) were placed into a 100 mL
round bottom flask under a dry nitrogen a~mosphere. .
1,3-Dicyclohexylcarbodiimide ~0.64 g, 0.0031 mole) and ~!
Z5 a few crystals of 4-(NIN-dimethylamino)pyridine were : -added~with stirring. Stirring was continued for ~four hours at room temperature. The resulting mixture was - ;, ~
then f iltexed to remove precipitated urea that had ~ t 'i'' formed. In a separatory funnel, th~ clear filtrate was ~!
30 washed with dilute hydrochloric acid, dilute potassium carb~nate and water. After drying with anhydrous magne~ium sulfate, the solution was again filtered and ~.
: the~s~lvent was removed on a rotary e~aporator to yield j ;
a white solid.: The solid was then flash 35:~chromatographed~on silica gel ~80 g)~, eluting with dichlorometha~e~to isolate the;desired product, 2/;3-dicyano-4-octyloxyphenyl- 4-(1,1-dihydrohepta-: ~

~..; ~ e~

~ W0~3/~96 2 1 3 3 6 5 2 PCT/US93/03925 `

- 41 - j fluoroethylethoxy)benzoate, Compound 19, Table 1.

2,3-Difluoro-4-octyloxyphenol (o.s2 g, 0.0036 5 mole, Example 13), 4-(.1,1-dihydrohepta-fluoroethyl-ethyoxy)~enzoic acid (1.2 g, 0.0036 mole, Example 11) and di.chloromethane (60 mL) were placed into a 100 mL
round bottom flask under a dry nitrogen atmosphere.
1,3~Dicyclohexylcarbodiimide (0.77 g, 0~0037 mole~ and 10 a few crystals of 4-(N,N-dimethyl-amino)pyridine were added wi~h stirring. Stirring was continued for four hours at room temperature. T~e resulti~g mixture was then filtered to remove precipitated urea that had formed. In a separatory funnel, the clear filtrate was 15 washed with dilute hydrochloric acid, dilute potassium carbonate and water. After drying with anhydrous magne~ium sulfate, the solution was again ~iltered and the solvent was removed on a rotary evaporator to yield a white solid. The solid was then flash 20 chromatographed on silica gel (80 g), eluting with dichloromathana to isolate the desired product, 2,3-difluoro-4-octyloxyphenyl 4-(1,1-dihydrohepta-fluoroethoxyethoxy)benzoate (1.2 g), Compound 20, Table 1.
~5 ~ .
COMP~ATIVE EXAMPLES 1-5 In Comparative Example 1, Compound C1, Table 1, was prepared using the procedure used to prepare Compound 7, except 4~ -dihydroperfluorobutoxy)pheno!l 30 was used in place of 4~ dihydroheptafluoro-2-ethoxyethoxy)phenol.
In comparative Example ~, CQmpound C2, Table 1, was prepared using the procedure used to prepare Compound 10, except 4-(1,1-dihydrohepta~.uorobutoxy)- 3' ' 35 phenol w~ used in place of 4-(l,lodihydrohepta-fluoro-2-ethoxyethoxy)phenol.

i"''~.'` ~ `
wo 93/223962 13 3 6S ~ PCT/U~93/03,~ ~

In Comparative Example 3, Compound C3, Table -`
1, was prepared using the procedure used to prepare ¦~
Compound 13, except 6-(1,1-dihydroperfluorobutoxy)--2-naphthol was used in place of~ 6-(1,1-dihydrohepta-S fluoro-2-ethoxyethoxy)-2-hyd~Pxynaphthalene. i "
In Comparative ~E~ample 4, Compound C4, Table ..
1, was prepared using the procedure of Example 37 except l,l-dihydroperfluorobutyl triflate was substituted for 1,1-dihydroheptafluoro-2-ethoxyethyl 10 triflate.
In Comparative Example 5, Compound C5, Table 1, was prepared using the ~rocedure of ~xample 37 except l,l-dihydroperfluorohexyl trifla~e was substituted for 1,1-dihydroheptafluoro-2-ethoxyethyl -lS triflate. l;

':`

.:
;

,1. -t :` ' :

:

~133~52 WO 93/22396 ~ PCr/US$~3/03925 Compound Structure S 1 ~cN ~30~2C~cP20c~3 C~\~}2C~2CP2C1~3 C H[ 7{ \)~ 2~2~P2clF2~c4E~ 9 ,.

4 C6~13~OE~2~CP2C~720C4~9 N

C 8H ~--~2CEI 2oc~ 2G 3 ~;
i.
~ !

.

WO 93/22396 ` PCI`/US~3/03 23336SS~ _ 44 _ 6 C~1~17~ 2CE20Ci'2CP2oC,,P9 7 C,~2l0--~O
C~6}2c~p2oc~2c~3 , C~ ' ;
~=\ ~ ' . ' 8 C8H ,~O~ ~ /=\ `;
~ ~~2~2~ 3 C~

9 C~ CF2OCF2CP2OC~F9 3xcE~2cEl 2ocE~ 2cE7 ~ r ;
~' ~ : : ., ..
: ~ .
, , ' ` :

``'` W 0 93/223~6 2133~ ri~r/US93/03925 - 45 - .

:
CEI3C~ 3 ~o~acJ~ocp2~F2oc~p~ .

1: `

/=\
2 C8E3~17=~
\~2CE1 20C~2C~ 3 ' .

O :
3 ~oH21~7~
~=~2C~P2oCE72c~3 : ` 7`'"

4 C~0H21~{~ ' O~p C~20CP~E720C~
i , ~ 15 15 Ct~7~ ~ 2C~3cx F~c~3 ~ ~

: ~:

t ; ~ .

' ~

336S?~ -46-16 C~3CF30CE2CF3 1.

17 < i ~ ; OCI{3~0CF~CF~OC4F~

18 C ~0 ~ / OCEI~CF~OCr7~OE~

19 ca~ }12CF~ CF3 ~ CN

C,~l~O~-OCEI2C~20C~2C~3 ~7 F

r.;
. ` `WO !~3/~2396 J~ b ~ 2 PCI`/US93J03925 .
:

21~
o~OCH2CF 2~F 2~F 3 o C2 ~H1CHaC~ ~N~o~ 2cP~p2cp3 10 C3 CIO~u~
2CE~2C~2C~3 i:

.

C4 ~C~H17~ \)~}~ z~3~7 ~

C5 C"HI7{~ _ OCH*5E~

'.'`
~: ~ `The compounds of Table 1 were evalllated for transition temperatures by optical~ observation of ~ ~ ;
20 mterial phase changes using a I,inkam rMH60û hot stag~ I
and a Zei~;s ~polarizing mic:roscope. ~ The transition emperatures (C), upon cooling from the lsotropic wog3/2239~,1336S2' PCr/US93Jû3S ~ `
-- 48 -- ~
state (I) to the crystalline state (K), are set forth , :
in Table 2 TP~BLE 2 __ _ _ __ . _ _ - . `~
Compound to SmC to SmE to M to X ~ ~
No. I to S~_ . . _ . ..
~ 83-_ _ ~ 1 ..
_ 67 26 7 74 47 _ -5 ~
_ , . . _ _ _ 4 60 22 -15 I :
__ . _ _ , ~00 151 66 64 ., . _ . _ _ ~ _ _. _ _ __ . ~ ; ,.
7 72 . 8 ~3 3 _ _ _ _ 37 . 7 ~
. , l C1 _ 87 61 _ 42 .
_ 8 --65 _ 37-- _ _ ` ' _ . _ . . _ _ _ _ . . _ ,;., ~virtual 2 2 SmA at 6 , . on rapid cooling) _ . . _ _ .
_ _. 43 30 C2 27 ~ <-43 . _ _ . _ _ . .:
20_ 12__ 131 62 50 _ _ __ 36 . ..
13 128 8~ . _ 44 :
.___ __ C3 137 91 _ _ ~ . 44 ~ _ ~ _ 4 148 _ 97 _51 ~4 , .
222 _145 _ _ 105 85 . . I :
l , 16 186 136 121 105 _ ~, ;

7 189 _ __158 ~_ 92 ~.. .
18 1~9 _ 113 ~ _ . 9? ~ _ 83_ _ 19 ~ _ _ 1 0 6 1 :.
~ _ 63 _- ~ == ~ __ = _ ~ _ As can 3: e in comparillg Compound 7 to Compound C1, Compound 10 to Compound C:~ and Compound 13 .

~ 093/22396 21336S2 rCT/US93/03925 . - 49 -to Compound C3, the compounds o~ the present invention having perfluoroether terminal portions have lower transition temperatures for I to SmA than do similar~ ¦
compounds not having the ether group in ~he perfluoro 5 terminal portion.
That the compounds of the present invention have lower transition temperatures, particularly with regard to the Smectic A and Smectic C mesophases, is further shown in FIGS. ~ and 2 where the phases were 10 determined using DSC and optical microscopy, respectively.

In FIG. 1:
A is the Smectic A phase for Compound C4, 15 A' is the Smectic C phase for Compound C4, B is the Smectic A phase for Compound 2, B' is the Smectic C phase for Compound 2, C is the Smectic A phase for Compound C5, C' is the Smectic C phase for Compound~C5, 2~ D is the Smectic A phase for Compound 3, and D' is th~ Smectic C phase for Compound 3.

In FIG. 2:
E is the Smectic A phase for Compound C4, 25 E' is the Smectic C phase for Compound C4, F is the Smectic A phase for Compound 2, F' is the Smectic C phase for Compound 2, G is the Smectic A phase for Compound C5, t G' is the Smectic C phase for Compound C5, 30 H is the Sme~tic A phase for Compound 3, and H' is ~he Smectic C phase ~or Compound 3.

r ~AM~LE 56 ~ND COMPARATIVE EXAMPLE C6 In Example 56, a liquid crystal mixture was -~
35 prepared containing W093~223~ PCT/US93/03 ~
~,~336~ !

5 parts C8H~ 2c~2oc~9 -, 1.67 parts C8HI7 = ~K~l~c7~ls `1.67 parts C~al9 ~ cx~H2C

, .

25 1.66 parts C~oH~ C7Fls The mixture was evaluated for transition temperatures , ~ by~optical obse~vation of material phase changes using 30 a Linkam T~H~00 hot stage and a Zelss polarizing microscope. The results are set forth in Table 3.
In Comparative Example:6, a mixture was pr~ipared as in Example 5~6 except thei liquid crystal : material having the perfluoroether terminal portion was 1.
35 omitted. The mixture was evaluated for transîtion kemparatures as in Example 56,i The results are set ~orth in Table 3.~

i W O 93/223962 1 ~ ~ 6 ~ 2 P~r/US93/03925 - 51 - j Transition Temperatures (C) ¦
Example I to SmA SmA to SmC SmC to K
56 89 5g 23 C6 1~1 84 69 As can be seen from the data in Table 3, addition of the liquid crystal material having the perfluoroether terminal portion significan~ly lowered the transition 10 temperatures.

~ .
Product was prepared as described in Example 38 except l,1-dihydroperfluoro-2-(2~hexyloxyethoxy)ethyl 15 triflate (Example 14) was substituted for the 1,1-dihydroperfluoro-z~(2-butoxy~thoxy)ethyl triflate. The product was purified by chromatography and then recrystallized from ethanol at -20'C to give a white powder, 5-octyl-2-(~-(1,1-dihydroperfluoro-2-(2- -20 hexyloxyethoxy)ethoxy)phenyl pyrimidine, Compound 21, Table 4.

Example 58 Product wa~ prepared as describ~d in Example ~5 38 ~xcept 5-decyl-2-(4-hydroxyphenyl)pyrimidine was su~stitutad for the S-octyl-2-(4-hydroxyphenyl)pyrimidine : : and 1,l-dihydroperfluoro-2-(2-hexyloxyethoxy)ethyl ~: tr:iflate tExample 1~) was substituted for the 1,1 dihydroperfluoro-2i~(2-butoxyethoxy)ethyl triflate, The 30 product was purified by chromatography and then recrystallized from ethanol at -~o'C to give a whit~
powder, 5-D~cyl-2-(4-(1,1-dihydroperfluoro~2~(2 he~yloxyethoxy~ethoxy)phenyl pyrimidine, Compound 22, ble 4.

: ~

:~ ;:` :
`: :

::

W093/~396 3 65 2 PCT/US93/03~_J`

Example 59 .
Product was prepared as described in Example 38 ¦ ;:
except 1,1-dihydroperfluo~o-4-(4-butoxybutoxy)butyl -~ l tri~late (Example 15) ~s~;suk-stituted for the 1,1- li 5 dihydroperfluoro-2-(2-bùtoxyethoxy)ethyl ~riflate. The product was purified by chromatography and then recryst~lliæed and filtered from ethanol at -78C to give a white pearlescent paste at room temperature, 5-octyl-2-(4~ dihydroperfluoro-4-(4-butoxybutoxy)butoxy)phenyl 10 pyrimidine, Compound 23, Tab~e 4.

xample 60 Product was prepared as described in Example 38 except 5-decyl--2-~4-hydroxyphenyl)pyrimidine was 15 substituted for the 5-octyl-2-(4~hydro,xyphenyl)pyrimidine and 1,1-dihydroper~luoro-4-(4-butoxybutoxy)butyl triflate (Example lS) was substituted for the 1,1-dihydroper~luoroo2-(2-butoxyethoxy)ethyl triflate. The product was p~rified by chromatography and then 20 recrystallized and filtered ~rom ethanol a~ -78 C to give a white pearlescent paste at room temperature, 5-decyl-2-(4-(1,1-dihydroper~luoro-4~(4 butoxybutoxy)butoxy~phenyl pyrimidine, Compound 24, Ta~le 4.

25 ~xample _61 Product was prepared as described in Example 38 except l,l-*ihydroperfluoro-2-(2(2-methoxyethoxy)-ethoxy)ethyl tri~late (Example 16) was substituted for the l,l-dihydroper~luoro-2-t2-butoxyethoxy)ethyl 30 triflate. The product was purified by chromatography and '.
then re~ry~tallized and filtered from e~hanol at -78'C to ~.!j;, give a white p~arlescent pa~te at room temperature, 5- , octyl-2~(4~ }-dihydroperfluoro-4-(2-(2- ¦
methoxy~thoxy)ethoxy)ethoxy)phenyl pyrimldine, Compound 35 25, ~able 4.

2133~i~;2 r ExamE~le 62 Product was prepared as describPd in Example 38 except 5-decyl-2-(4-hydroxyphenyl)pyrimidine was substituted for the 5-octyl-2-(4-hydroxyphenyl)pyrimidine 5 and l,l-dihydroperfluoro-2-(2-(2- .' methoxyethoxy)ethoxy)ethyl triflate (Example 16~ was substituted for the l,1-dihydroperfluoro-2-(2-butoxyethoxy)ethyl triflate. The product was purified by chromatography and then recrystallized and filtered from 10 ethanol at -78'C to give a white pearlescent paste at room temperature, 5-decyl-2~ dihydroperf~uoro-2-(2-(2-methoxyethoxy)ethoxy)ethoxy)phenyl pyrimidine, Compound ~6~ Table 4.

15 ExamPle 63 ~ roduct was prepared as described in Example 38 except 1,1-dihydroperfluoro-3-(butoxy)propyl triflate (Example 17) was subætituted for the l,l-dihydroperfluoro-2-(2-butoxyethoxy)ethyl triflate. The 20 product was purified by chro~atography and then recrystallized from ethanol at -15 C to give a white aolid, 5-octyl-2 (4-~1,1-dihydroperfluoro-3-~butoxy)propoxy)phenyl pyrimidine, Compound 27, Table 4.

25 E~ample 64 Product was prepared as de~cribed in Example 38 except 5~decyl-2~(4-hydroxyphenyl)pyrimidine was substituted for the 5-o~tyl-2-(4-hydroxyphenyl~pyrimidine -' and l,l-dihydroperfluoro-3-(butoxy)propyl triflate , '~
(Example 17~ was substituted for the ~
dihydroperf~uoro-3-~butoxy)propyl triflate. The product was purified ~y chromatograp~y and then~recrystallizad ~ ^
from ethanoI at -15-C to give a white solid, 5-decyl-2-(4-(1,1-dihydroperflusro-3-(butoxy)propoxy)ph~nyl 35 pyrimidine, Compound 28, Tabls 4.

i ~ :

Wo93~22396~ ~ 3 6s 2 PCT/US93/0 Example 65 Product was prepared as described in Example 38 except 1,1-dihydroperfluoro-4-(butoxy)butyl triflate~
(Example 18) was substituted ~for the 1,1-5 dihydroperfluoro-2-(2-butox~e~hoxy3ethyl triflate. The product was purified by chromatography and then recrystallized and filte~èd from Pthanol at -15C to give a white paste, 5-octyl-2-(4-(~,1-dihydroperfluoro-4-(butoxy)butoxy)phenyl pyrimidine, Compound 29, Table 4.
Example 66 Product was prepared as described in ~xample 38 except 5-decyl-2-(4-hydroxyphenyl)pyrimidine was substituted for the 5-octyl-2-(4-hydr~xyphenyl)pyrimidine 15 and l,1-dihydroperfluoro-4-(butoxy)butyl triflate (Example 18) was substituted for the l,1-dihydroperfluoro-3-(butoxy)propyl triflate. The pro~uct was purified by chxomatography and then recrystalliæed from ethanol a~ -15'C to qive a white solid, 5-decyl 2-(4-(1,1-dihydroperfluoro-4-~butoxy)butoxy)phenyl pyrimidine, Compound 30, Table 4.

Exam~le 67 Product was prepared as described in Example 38 25 except 1,1-dihydroperfluoro-3-(hexyloxy)propyl tri~late ~Example 19) was substituted for the 1,1-dihydroperfluoro~2-~2-butoxyethoxy)ethyl triflate. The prod~ct was purified by chromatography and then recrystallized and filtered from ethanol a~ -15 C to ~iv~
30 a white solid, 5~octyl-2-(4-(1,1-dihydroperfluoro-3 ~, (hexyloxy)propoxy)phenyl pyrimidine, Compound 31, Table .

' 1-Exam~le 68 Product was prepared as described in Example 38 except 5-decyl-2-(4-hydroxyphenyl)pyrimidine was substituted for the 5-~ctyl-2-(4-hydroxyphenyl)pyrimidine ,..... ~. 2I336~2 '~` W093/~2396 PCT/US93/~3g25 and l,1--dihydroperfluoro-3-(hexyloxy)propyl triflate (Example 19) was,substi~uted for the l,1-dihydro-perfluoro-3-(~utoxy)propyl triflate. The product was~ ~
purified by chromatography and then recrys~allized from ~.
5 ethanol at -15-C to give a white solid, 5-decyl-2-~4 (l,1-dihydroperfluoro-3-(hexyloxy)propoxy)phenyl pyrimidine, Compound 32, Table 4.

ExamPle 69 Product was prepared as described in Example 38 except 1,1-dihydroperfluoro-3-(octyloxy)propyl triflate (Example 20) was substituted for the l,1-dihydro-perfluoro-2-(2-butoxyethoxy)ethyl triflate. The product was purified by chromatography and then recrystallized 15 and filtered from ethanol at room temperature to give a white solid, 5-octyl-2-(4-~1,1-dihydroperfluoro-3-(octyloxy)propoxy)phenyl pyrimidine, Compound 33, Table 4. ', 20 Exam~le 70 Product was prepared as described in Example 38 except 1,1-dihydroper~luoro-3-(decyloxy)propyl triflate (Example 21) was substituted for the l,1-~ihydro-perfluoro-2-(2-butoxyethoxy)ethyl trifla~e. The product ~: 2S~ was purified by chromatography and then recrystallized ~`~ and filtered from~e~hanol at room temperature to give a white solid, 5 octyl-2-~4-(1,1-dihydroperfluoro-3- 3 (octyloxy)propoxy)phenyl pyrimidi~e, Compound 34, Ta~le ~:

: Product was prepared as described in Example 38 except:l,1-dihydroperfluoro-3-~(neopentoxy)propyl triflate (, (E~ample 22~ was substituted ~or the 1,1-dihydro-35 perfluoro-2-(2-butoxyethoxy)ethyl triflate. The product was p~rified by chromatography and then recrystallized and ~iltered from ethanol at~-l5~C to give a whi~e solid, W0~3/2~396 ~33~5~ PCT/US93/03~ `

. - 56 5-octyl-2-(4-(1,1-dihydroperfluoro-3-(neopentoxy)-propoxy)phenyl pyrimidinP, Compound 35, Table 4.
A, ~ .
ExamPle 72 ~ . j S Product was prepared as described in Example 38 ~xcspt 2~ dihydroperflùoro-2-(2-~utoxyethoxy)ethoxy]-ethyl-p-toluenesulfonate (Example 23) was subs~ituted for the l,1-dihydroperfluoro-2-(2-butoxyethoxy)ethyl triflate. The product was purified by chromatography a~d 10 then recrystallized and filtered from ethanol at room temperature to giYe a white solid, 5~octyl-2-(4-(2-t~
dihydroper~luoro-2-(2-butoxyethoxy)ethoxy]ethoxy)phenyl pyrimidine, Compound 36, Table 4.

15 ~rEæ~
Product was prepared as described in Example 38 exc~pt 1-bromo-2-(1,1-dihydroperfluorooctyloxy)ethane (Example 27) was substituted for the 1,1-dihydro-perfluoro-2-(2-butoxyethoxy)èthyl triflate. The product 20 was purified by chromatography and then recrystallized from ethanol at room temperature to give a white solid, 5-octyl-2-(4-(1,1-dihydroperfluorooctyloxy)ethoxy)phenyl pyrimidine, Compound 37, Table 4.
.
25 ExamPle 74 Product was prepared as described in Example 38 except 1-bromo-2-(1,1-dihydroper~luorohexyloxy)ethane (Example 283 was substituted for the 1,1-dihydro-perf~uoro 2-(2-butoxyethoxy)ethyl triflate. The product 30 was purified by chromatography and then recrystallized from ethanol at room temperature to give a white solid, ?, S-octyl-~-(4-(2-(I,l-dihydroperfluorohexyloxy)- ', ethoxy)phenyl pyrimidine, Compound 38, Table ~.

xa~ _s Product was prepared as described in Example 38 except 1-h~omo-~-(2-(l,l dihydroperfluorooctyloxy)-~ .. ! ",` ` 2 1 3 3 6 5 2 .~?, WO 93/22396 PCT~US93/03925 ethoxy)ethane (Example 29) was substituted for the 1,1-dihydroperfluoro-2-(2-butoxyethoxy)ethyl triflate. The product was purified by chromatography and then recrystallized and filtered from ethanol at -15 C to give 5 a white solid, 5-octyl-2-(4-(2-(2-(1,1-dihydroperfluoro- '-octyloxy)ethoxy)ethoxy)phenyl pyrimidine, Compound 39, Table 4.

Example 76 5-Hydroxy-2-(4-(1,1-dihydroperfluoro-2-(butoxyethoxy)ethoxy)phenyl) pyrimidine (10 g, 0.0166 mol, Example 32) was dissolved in 150 mL of NjN-dimethylformamide and slowly treated with 0.5 g dry sodium hydride. After 15 minutes stirring, 1-bromodecane (3.67 g, 0.0166 mol) was added and the mixture was heated to 100C for 2 hours. Upon cooling to room temperature, 150 mL water was added and a solid~:precipitated. The solid was~collected by filtration, recrystallized from : ethanol and chromatographed on 150 g silica gel (chloro~orm), to yield 4.0 g, Compound 40, Table 4.

Examples 77-81 In Examples 77-81, Compound~ 40:-44 of Table 1 were prepared as in Example 76, except that the precursor 25 compounds indi~aked below were substituted for the~5-hydroxy-2-(4~ -dihydroperfluoro-2-~butoxyethoxy) ethoxy)phenyl)pyrimidine and l-bromodecane.
Example 77, Compound 41 was prep~red from 5- ¦
hydroxy-2-(4-(1,~1-dihydroperfluoro 2-~(butoxyethoxy)~
30 eth~xy)phenylipyrimidine (Example 32) and l-bromooctane.
Example~78, ~Compound 42 was prepared from 5 : ~ ~ hydroxy-2~- ~ 4:~ dihydroperfluoro-2-(~utoxy)ethoxy)- . 7 :~ phenyl) pyrîmidine~Example;33-)~and~1-bromooctane.~ i-: Example 79, Compound 43 was prepared from 5- !
35 hydroxy-2~-(4-(octyloxy)phenyl)pyrimidin:e (Example 34) and dihydroperfluro-2-(butoxy~.~thyltriflate.

~r~ '.q . ~ ' W093~3~6 PCT/US93/03~
~ ~3 - 58 - ! ~
Example 80, Compound 44 was prepared from 5-hydroxy-2-(4-(octyloxy)phenyl)pyrimidine (Example 34) and 1,1-dihydroperfluro-2-(butoxyethoxy)ethyltriflate.
Example 81, Compound 45 was prepared from 5-5 hydroxy-2-(4'-(1,1-dihydroperfluoro-Z-(butoxye~hoxy3-athoxy)bisphenol)pyrimidine (Example 35) and 1-bromo-2-(butoxyethoxy)ethane.

Compound Structure -.

S 2l C,H~7- ~ ~ 2CP20C21~0Cs~l3 2~ C10~21 ~ / ~ 2~P~OC2P~OC

.: . .

0 23 ~R}~ 2C3~ toc~9 CIoH2l~ocN2c3~6oc~Roc4Er9 ' .

~$w093t~396 2I336S2 PCI/USg3tO39~5 !~
- 59 - .

Compound Structure ;

N
C~~ /) 0~2C~2~0C2P~)2o~3 ~, ., .
~ .

. .
~N
2 6 ~)~2C~2(0C2F~)20CP3 :

,, 27 ~N ~
C8E3[1~ /)~1~C~C4F9 : :

j.
~ ` li, j.

28 ~2Cz~4~F9 .:
:~; 15 ~ ~9 ~ ~2C~C41'9 ~

WO 93/2~g6 P~/US93/û3~5 ` `
?.~33~

.
Compound Structure ", , C10~321~ /,=~ "/~ 0C~C3F60C4F9 31 C8Kl7~ / ~ C~F40C6F,3 32 ~N~\~ F4oc6l~l3 .` ` . ~.

CgE~,7~, ~ ~2C~F4oc8Fl7 ;~.
` ~ $;
J
`` ~ ' ~ l' ~;~

'~ W~93/~396 2133~ PCr/US93/03925 I:

~ .
Compound Structure . ,~ ,' C8Hl7~ /> ~r ~2C2~4C1~21 C~71"~ ~ U2C2~ 2c~3 . `.
,` ~

36 ~N~ 2~CEI2C~2C2E~ s : ., ', ,.
~ O , 1~
37 ~N
C8HI7~ /~ /~OC2B4O~LC7 ., C~l7~}~C~H40(~I2C~lt7ll ~

, ~ . . j ,; ~ : .

:

`

.. C, !' ,` ~ . ,` . ' .
WO 93/223~6 PCI/US93/03~
2 ~ 3'~6S2 - 62 _ _. _ _ Compound Structure 7~/~OC2H4~2 CI"H2'0~{~2CF20cP2Ci'20C~P, 41 C H7~{ ~)~2~P2~P2cp2oc~ps , , , 42 C3H~ = 2CI~2OC4Fg , 43 ~ 2C~24F9 ~' .

;` W093/223~ PCT~US93~03925 ~.
1` .~.
- 63 1 :

Compound structure ~HI70~N~ 2c~ 2c~2oc~9 r~

:...
'`.

c~o~ ~ oa4~_ ~ ~ ~S~o~ 4~5 :, ' ', The compounds of Table 4 were evaluated for transition temperatures by optical observation of material pyhase changes using a Link~m TMH600 hot s~age and Zeiss polarizing microscope. The transition ~`
10 temperatures (C), upon cooling from the iso~ropic state (I) to the crystalline state (K), are set forth in Table 5.
, .

^, ., ;.
'i`

',:
` , : ~ ' WO ~3/22396 PCr/US93/03 ?,~336~ h .- ~ - ~ .
Compound I to SmAto SmC to ~ to K
; _. ._ . , ~-1 21 _9 _ 52_ ____ 23_ 22 65 50 ___ 18 ; --_ _ _ __ _ _ _ , ..
23 103 53 ___ -11 _ . _ _ 24 94 60 .___ 13 I . . . ::

. _ .

I _ _ . _ ~0 1 27 82 47~ ___ 7 _8_ 67 55 ___ 28 29104 _57 ___ 9 3088 61 __ 16 '_ 1 3188 52 ___ 15 1 32 ` 73 _ 55 ~ _48 33 95 ___ _ __ ~0 34 98 ___ ___ 94 _ _ _ _ ~2_ 48 ___ 24 36 109 ___ __ 3 ~ ~ _ _ . ~ __ _37 _ 132_ ___ ___ 69 _ . 38 123 ___ ___ _ 74 _ I _ _ . _ _ 39 ~ ___ __ 48 1 ~ ~ _ _ 87_ 74 ___ 24 41 94 81 ___ 45 ~ ___ _ _ _ 2542 96 78 ___ 46 l~
43 ___ ___ ___ 88 . 1-!~ ~ ~ --- -- . -- : ~
44 94 _ -_ ___ 73 _ ~ ~ -1~2 107 84 ~1 ~
I . _ _-- ~ _ ~ ~ ;, -Various modifications and alt~rations oî this invention will become apparent to those sk~illed in the art without departing from the scope of the invention.

Claims (19)

What is claimed is:

1. Fluorine-containing liquid crystal compounds comprising a fluorocarbon terminal portion having at least one catenary ether oxygen and a hydrocarbon terminal portion, the terminal portions being connected by a central core, the compounds having smectic mesophases or having latent smectic mesophases.

2. Compounds of claim 1 wherein said fluorocarbon terminal portion can be represented by the formula -D(CxF2xO)zCyF2y+1 where x is independently 1 to 10 for each CxF2xO group, y is 1 to 10, z is 1 to 10 and D is a covalent bond, , -OCrH2r-, -O?CsH2sO?tCr'H2r'-, -CrH2r-, -OSO2-, -SO2-, -SO2-CrH2r-, , where r and r' are independently 1 to 20, s is independently 1 to 10 for each (CxH2sO), t is 1 to 6 and p is 0 to 4.

3. Achiral fluorine-containing liquid crystal compounds according to claim q wherein said compounds can be represented by the general formula I:
(I) where M, N, and P are each independently WO 93/22396 PCT/US93/03???

, , , , , , , , , , a, b, and c are each independently zero or an integer of from 1 to 3 with the proviso that the sum of a + b +
c be at least 2;

each A and B are non-directionally and independently a covalent bond, , , , -(CH2CH2)k- where k is 1 to 4, -CH=CH-, -C?C-, -CH=N-, -CH2-O-, or -O- ;
each X, Y, and Z are independently -H, -Cl, -F, -Br, -I, -OH, -OCH3, -CF3, -OCF3, -CH3, -CN, or -NO2;

each l, m, and n are independently zero or an integer of 1 to 4, D is , -O-CrH2r-, -O?CsH2sO?tCr,H2R,-, -CrH2r-, -OSO2-, -SO2-, -SO2-CrH2r-, , where r and r' are independently 1 to 20 and where r and and r' are independently 1 to 20, s is independently 1 to 10 for each (CsH2sO), t is 1 to 6 and p is 0 to 4;
R is -O?CqH2q-O?wCq,H2q'+1, ?CqH2q-O?wCq,H2q'+1' -CqH2q-R', -O-CqH2q-R', , or , where R' is -Cl, -F, -CF3, -NO2, -CN, -H, , or and q and q' are independently 1 to 20, w is 1 to 10 and R can be straight chain or branched; and Rf is ?CxF2xO)zCyF2y+1 where x is independently 1 to 10 for each CxF2xO group, y is 1 to 10 and z is 1 to 10.

4. A compound according to claim 1 wherein said compound can be represented by the formula or where d is 5 to 10, x is independently 1 to 3 for each CxF2xO group, y is 1 to 4 and z is 1 to 3.

5. A compound according to claim 1 wherein said compound can be represented by the formula where t is 6, 8 or 10.

6. A compound according to claim 1 wherein said compound can be represented by the formula where t is 6, 8 or 10.

7. A compound according to claim 1 wherein said compound can be represented by the formula where t is 6, 8 or 10.

8. A compound according to claim 1 wherein said compound can be represented by the formula

9. A compound according to claim 1 wherein said compound can be represented by the formula where t is 6, 8 or 10.

10. A compound according to claim 1 wherein said compound can be represented by the formula where t is 6, 8 or 10.

11. A compound according to claim 1 wherein said compound can be represented by the formula

12. A compound according to claim 1 wherein said compound can be represented by the formula

13. A compound according to claim 1 wherein said compound can be represented by the formula where t is 6, 8 or 10.

14. A compound according to claim 1 wherein said compound can be represented by the formula where t is 6, 8 or 10.

15. Compounds of claim 1 wherein said fluorocarbon terminal portion can be represented by the formula -D(CxF2xO)zCyF2y+1 where x is independently 1 to 10 for each CxF2xO group, y is 1 to 10, z is 1 to 10 and D is a covalent bond, , -O-CrH2r-, -O?CsH2sO?tCr'H2r'-, -CrH2r-, -OSO2-, -SO2-, -SO2-CrH2r-, , where r and r' are independently 1 to 20, s is independently 1 to 10 for each (CsH2sO), t is 1 to 6 and p is 0 to 4.

16. A compound according to claim 3 wherein Rf is -CF2OCF2CF2OC4F9.

17. Liquid crystal mixtures comprising at least one compound according to claim 1 and at least one chiral liquid crystal compound, said chiral liquid crystal compound being present in an amount sufficient to provide the mixture with ferroelectric properties.

18. A liquid crystal display device containing said compound of claim 1 wherein said compound has a smectic mesophase.

19. Fluorochemical amidine compounds represented by the formula .