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CA2006037A1 - Liquid-crystal derivatives of nitogen-containing heterocyclic system as components of a liquid-crystal material and a liquid-crystal material - Google Patents

Liquid-crystal derivatives of nitogen-containing heterocyclic system as components of a liquid-crystal material and a liquid-crystal material

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Publication number
CA2006037A1
CA2006037A1 CA 2006037 CA2006037A CA2006037A1 CA 2006037 A1 CA2006037 A1 CA 2006037A1 CA 2006037 CA2006037 CA 2006037 CA 2006037 A CA2006037 A CA 2006037A CA 2006037 A1 CA2006037 A1 CA 2006037A1
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Prior art keywords
liquid
compound
formula
crystal material
material according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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CA 2006037
Other languages
French (fr)
Inventor
Boris M. Bolotin
Alexandr V. Ivaschenko
Natalva I. Smirnova
Natalya I. Korotkova
Assya I. Pavljuchenko
Mikhail F. Grebenkin
Irina F. Agafonova
Petr P. Dakhnov
Vladimir F. Petrov
Ljudmilia V. Krujuchkova
Ljudmila A. Karamysheva
Klavdia V. Roitman
Ruben K. Geivandov
Evgeny P. Pozhidaev
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Individual
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Individual
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Priority claimed from SU884617049A external-priority patent/RU1781214C/en
Priority claimed from SU884617051A external-priority patent/RU1775399C/en
Priority claimed from SU884617052A external-priority patent/SU1749219A1/en
Priority claimed from SU884617050A external-priority patent/SU1754714A1/en
Priority claimed from SU884617054A external-priority patent/SU1749218A1/en
Application filed by Individual filed Critical Individual
Publication of CA2006037A1 publication Critical patent/CA2006037A1/en
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
    • C07D213/30—Oxygen atoms
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    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/26—Radicals substituted by halogen atoms or nitro radicals
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    • C07D—HETEROCYCLIC COMPOUNDS
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    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
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    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/84—Nitriles
    • C07D213/85—Nitriles in position 3
    • C—CHEMISTRY; METALLURGY
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/12—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/12—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D215/14—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/20—Oxygen atoms
    • C07D215/22—Oxygen atoms attached in position 2 or 4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/48—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3441—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom
    • C09K19/3444—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom the heterocyclic ring being a six-membered aromatic ring containing one nitrogen atom, e.g. pyridine

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Liquid Crystal Substances (AREA)

Abstract

LIQUID-CRYSTAL MATERIAL

Abstract A liquid-crystal material is proposed, compris-ing at least two components, at least one of which is a liquid-crystal derivative of nitrogen-containing he terocyclic systems of the general formula R1-A1-Z-A2-R2, wherein R1 and R2 are jointly or independently -CnH2n+1, -CmH2m+1, CnH2n+1O-, CmH2m+1 , CH2=CH(CH2)k-, -CN, -N=C=S, Hal , at k = 0-3, l = 0-2, m.n. = 1-15;
Z is -CH2-CH2-, -CH=CH-, -C?C-, -COO-, a single bond, when A1 is , ;
A2 is , , , ;
when A2 is , , ;
A1 is , , ;
R is -CH3, -CN, -Cl, -F at l = 0-2. The content of said component is 1 to 50 wt. %.

Description

Z~)06~3~7 LIQUID-CRYSTAL DERIVA~I:VES 0~ NITROGEN-GON~AINING
HETER~CYCLIC SYS~EMS A.S COM~ONENTS 9F A ~IQUID
CRYS~A~ MATERIAL AND A ~I~UID-CRYSTA~ ~TERIA~

~ he present invention relates to a liquid-crys-tal mQteri~l u~ed in electro-optical de~ices.
The propo~ed invention will ~ind ~ide applicat-ion in electronic indus~ry for displ~ying alphanume-ric data, eOg~ i~ electronic watch~ and microcalcu~
lator3, There are pre~entl~r known in the art liquid-cryc tal oompounds~ 5-a1kyl-2-(4-cyanophenyl) pyridine ~ of the fo~mlla Alk-~--(~ C~

where Alk! ha~ing 2 to 7 carbon atoms, are components 15 of li~u~d-cry~tal materials (SU, A, 675800). ~ ~;
Al~o know~ in the art are 5-alkyl-2 (4-alkyl- or 4-alk~loxyphenyl)pyridines of the formula Al k~ (O) R e k -- / wher~n Al~, Alk', ~v ~ g.1 to 12 carbon atoms, are 20 Component~ of liquid-cr~tal material~ (GB9 A, ;~
2161808~.
Al~o known in the art ~re liquid-cry~tal com~
~ .
pound~ of 5-alkyl-2- [4~(trans-4-alkylcycl~he~

r ~ ~ ~
2(~ )37 phe~yl~-pyridine of the formula Alk~ ek ''~ wherein Alk~ Alk~, havi:ng ~ 6 hydrogen atomes (SU, A, 13026~4), are components of liquid-cry~tal materi-als.
Tha above compounds,are characterized by high ... .. .. . .
~ v~lue~ of anisotropy of dielectric perneability at a .. . . .
. low clari~ication temperatur~ ~n a narrow nematic ,. . . .. .
: phase interval. These propertie~ hinder t~e u~e of 10 the, liquid-ory~tal material~ comprisi~g these com-pounds in a wide range o~ working temperatures.
~ ,object of the present invention is to pro-d~.Ace a novel liquid-or~stal material~ based on li-.. . . . . . .
quid-crystal derivative~ of nitrogen-containing hete- . '' rooyclic 9y8tom9 having a high clarification tempera-ture, optical anisotropy and a wide nematic phase ,, : interval, which allow this material to be used i~ a wlds ra~g3 of oper~ting tem?erature~, ~
~ hi~ object i~ atta1ned due to the fact that ~. ~',, :~ 20 liquid-crystal material i~ proposed compri~ing at .
; '' le~st two component~, of which at least,one i~ a liquid-crystal derivative of Q nitrogen-containing heterocyclic ~y~tem of the general formu~a -,.
Rl_A1_z_A2~R2 (I) wherein R~ and R2 are to~ether or independently ~ H2n+1 7 ~~mH2mt~1 ~ CrlH2n+1 0 ~ -CmH2m+l ~
C~2DCH( CH2 )k--9 -C~9 -N=C=S, - H~l, (~> )1 CmH2m+1 at k ~ 0-3 1 ~ 0-2 m.nO ~ 1-15;
æ i~ -CH2-CX2-, wcH~cHW,~--c-, _coo~
or a single bond, .
when A~

R R
when A2 i9 ~1 --~ 7 -~- ' `;~

R is -CH3, ~ CN9 -F at 1 ~ 0-2 ,~.,, :, Given below are liquid-cry~tal deri~atives of nitrogen-.containi:llg heterocyclic ~y~tems of the 15 general ~ormula R1-Al-~Z-A2-R2 ,~1/ compri~ing the followi:ng compounds9 of which at lea~t on~ in¢lude~
the proposed liquid-crys.. al material. : :~

~3 ,.,'` .: ' '' '~.

,'~00~03 CnH2n+1 ~
N ~--C m H2 m ~1 CnH2n+1 0~ Cm H~m~l /III/

CmH2m+1~ ~\~ CnH2~ /IV/

- ':

CnH2n+1 0~ Cm H~tn+1 ~V/
Cl~
CnH2n+1 (~ /VI/
~`~ J~3~CInH2n7~1 CnH2n+1 ~)~_ /VII/
. ~ C~" 2m~1 Cn~2n+1 ~
/VIII/
~S --Cm 1~2~

Cnl2n+1 0~ cmH2r,,~ /IX/

C~H2n+1 C~~ O~nl H2 ~ /x/

F

2~)~)6()37 C~H2n+1 [~ _ /XI/
N ~) ~

CnH2n+1 0~ /XII/
s nH2n+l ~ /XII I/
~ C l~
~ ,.`.' CnH2n+1 ~ /XIV/
~J ~ OC~7 ~1~ n1 t 7 ' 1~0 `:: ` ~
. . .
CnH2n+1 O~ CI~ ~t ~ n7 + 1 /~v/
h O

CnH2n+1 ~ /XVI/ ~::
--N~ ~H~ .
HO , ~;;
CnH2n+1 l~ /XVII/
~N ~ Ct I

I CnH2n~ CH--c~(o)kc~7 lt~ ~1 / VIII/ ; ~

Cn~2n+1 ~ ~ /XIX/
~i\l CH2CH2~(0)k c~ll2m~

CnH2n+1 0~_C--C~--(0)1<CrnH2 2006~)3~7 CnH2n~ C ~ t~ H - m t 1 /XXI/ ~ .

Cn~2n+1~0~,~,~ Clnll~n1tl /X~II/
Cll~

CH2=CH(CH2 )k~ C,~1 ~2n1 tl /X~

CH2=CH(CH2)k-~?_~--(())k Cn1H2nltl /~XIV/

CnH2n+~ Cl~ =Clt., /.~xv/

~H2=CH(CH2)k~>--(CH2)kCH--C~2 /X~VI/

CH2=CH(CH2 )k-~ F fXXVII/

CnH2n+1 ~,~--C--C ~(~ t1 /XVIII/

nH~n+1 ~> C-C~>--()I~C~7H)"~ XIX/

n 2n~(~>~C--c~c--c~3~crrlll2~J ~
NC - ~--C--C--~ ~ Jk Cm ~ t l /X~I/

~nH2n~ >~ Cm Hz,~, t l /XXXII/
HO

Z0~6037 CnH2n+1~ C~ H2m-~ 1 /.~;III/ ~;
HO ~ :

CI1~2n~ cm ~ tl /~V~YIV/
HO

V/
110 ` : :~
Vn~2n+1~~ CN /X~YVI/ `.
H O

Cnn2n+1 ~>~~ C H2CH2~)--(0)1~ Ch CnH2n+1 ~)--CI~CH2~3- C~ t1 ;

VnH2n+l~cH2cH2~- C~ c 11~ t~

Vn~2n+1 t)k ~--~N /XL/
~H~

C H2 1 (~k~ Cl~ /XI.I/

CnH2n~1 ()k~ ~CN /XIII/ ~`

2~ 603~
- , CnH2n+1 ()k~N /XLIII/
C~3 Cn~2n+1 ~ (JI<~1~1H21~1 /XI.IV/
CH~

CnH2n+ 1 {~ ) k ~ m H ~ n~ 1 /X~V/

CnH2n+1 ()k-~ Cl11H~ mt1 /XLVI/

CnH2n+1 ( )k-~ ~~{~~ Cn1 ~n1~1 /X~VII/
~H3 CnH2n+1 ()k~Cr~ l /XI,~TIII/

CnH2n+l ()k-~ Cn~H~h~t1 /XLIX/
~H3 0~ o a c {~--c CnH2n+1 1~) /I,I/
N OOC ~ C~H2rn~1 CnX2n+1 ~ Ct~ /LII ) CnH2n+ 1 (~ 0 Cn ~ H~. In~1 /:L II I/

CnH2 n+ 1 ~ C(~--~>~ C H- CH 2{~--(O) k C ~ 1~ 2 . .. .. . .
; ,~ . . .
,., . . ~ . . . . .
'.' .::, ' ! . ' ' ' , ' .

ZO~ O3~

CnH2n~1 ~ CH2 - CH~ -~ (O)K C~H~mtl/LV/
CH~ :

CnH2~+1 ~ ~ ~ -CmH.~ VI/

Cn~2nt1 ~ ~ ~ -CN /LVTI/
~1 0 ' - :-..:

CnH2n~ ~ ~ CN /LVIII/ ; ;

: ~

The proposed compounds are characterized by high : : .
.. .. .
value~ of clarification temperature, optical aniso- ~:
tropy a~d wide nematic phase intervals, i,eO feature .
a rang~ o~ propertie~ needed for substa~ce~ to be ~: :
used as component3 of liquid-crystal m~terials. `~
It i~ advantageous that the liquid-cry~tal mate-rial of the liquid-crystal derivative of the nitro~
gen-containing heterocyclic ~y~tem o~ the formula /I/
i3 prov:Lded in an amou~t of 1 to 50 wt. ~0. ~ ~.

_ g _ ~-~
..:-'"-`;'"

-` X0060;~

The liquid-cry~tal mqterial ha~ing such a ratio of components is characterized by optimum pr~perties, Such liquid-cryst~l materialq wilI find applica+-ion in microcalcuiators, ~/~tches9 and outdoor electro--optical devices.

Ihe Eest ~mbodi~.ent of the Invention rhe compounds I, II, IIL, IV, V, VI, V-II~ IX, ~, XI, XIV, XV, XVI, X~JII synthesized by means of condens-atio~ of the ~lan~ich salts with 4-alkylcyclo'.lexanones, followed by cycling of a 1,~-dicarbonyl com?ound ui~h hydroxylami.ne hydrochlor1'de into a respective derivat-ive of tetrahydroquinoline; mhe com~ound ~II is ob-ta~ned by m~ans of successi~e reaction~ fro~ 2-~t4 -rlitrophe~yl)~6~-a'~yl-5,6,7,8-tetrahydroquinoline.
The c~mpound XIII is obtained b~- reacting 2-(4_brol~.o-phenyl)-6-~lkyl-5,~,7,8-t~trahydroquinolinQ ~!ith copper cyanide.
The cornpound VII is obtained by reacting an appropriate Mannich qalt with 4~(trans-4-al~ylc~-clo-hexyl)cyclohaxaIle, ~ollowed by desul~hurizat on o~the thiophene derivative.
~ he compound III is obtained by rneAns of con-densation of 2-~ethyl-6-alkyl-5,6,7~8-tetrahydroqui-no].ine with n-alkyl- or alkoxybenzaldehyde, ... . ..
~he co~pound XIX iq obt~ined ~y hydration of the cornpound ~VIII~

:; . : . - .... . . . .
,., :. : ~ . . . . .
:~ ,. ; ,: , .. .. .

)6()3~7 The compound XX is obtained by bromination of the double bond of the compound XVIII, followed by treatment of the reaction mixture with alkali.
The compound~ ~XI and XXII are synthe3ized by condensation of 1-akryl-4-substituted benzenes with corresponding enainine into 3,6-disubstituted 3,4-di- :
hydro-?-N-piperidine-2H-pyr~nes9 the latter bein~
then converted i~tG pyridine derivatives by reacting them with hydroxylamine hydrochloride.
The compounds ~XIII, X~IY, XXVII sre obtalned by reacting n-substituted phenyllithium Ylith pyridine, ~:
followed by al~ylation of the corresponding alkenyl bromide, ~ he compounds ~V, X.YVI are obtained by re~cting a respective m~gnesium-or~anic derivative with 2 -iodine phenyl)-5-substituted ?yridine.
The compounds XXVIII are obt~ined by reacting alkylacetylenes with 2-t4-iodopheny~ alkylpyridine in the prese~ce of a cataly~t. he compounds X~
.XXX, ~I are synthesized from 2-iodo-5-bromopyri-di~es by means of successive conversions.
~ he compounds X~XII, XgXIII, YYY~IV, ~X~ XXVI
are ~ynthesized by condensation of 1-akryloyl-2,4--disubstituted benzoyls with enamine, followed by .. . - - .... -25 treatment o~ the respective pyrane with hydro~yl hyd- :.-rochloride, followed by treatment of the respective pyrane ~ith hydro~yl hydrochloride and hydroly~i~ of : :

--. 2 ~ 3~

2-alkoxy group in 2,5-disubstituted pyridine derivat-ive .
The com~ounds XXXVII and ~VIII are synthesized from a respective derivative of 2-meth~vl-pyridine and substituted benzaldehydes, ~ollowed by hydrogenation of the double bond.
The co~pounds Xl and XII are o~tained from res-pective pyridine derivative with ethylene bond in po-sition 2 by its oxidation to 5-substituted pycolic acid with sub3equent conversion of the carbo~yl group into a nitr'c one.
The co~?ounds XIII and X1III are obtained b~
condensatio~ of acetylic derivatives with cyanacet-amide, by substituting 2-oxy group ~ith chloride and it~ reduction with 5 % Pd/C.
The com~ounds XLIV to XLI~, LTV, LV, 1VI, LVII, LVIII are obtained by condensation of respective ena-mi~es ~nd vinyl ketone~ with subsequent treatment of the prod`uct of reaction with hydro~yl h,ydrochloride, The compounds ~, 1I are obtained by acylating 6-alkyl-5,6,7,8-tetrahydroquinol-2-ine.
The eompound3 1III are obtained by substituting 2-oxy groups with bromine, the latter being then re-.
placed by an alkoxy group or a cyano group 1II.
The liquid-cry~tai material, according to the invention, is prepared by mixing at least two liquid--crysta1 components, one o~ which9 accordi~g to the 2()06~)37 , , inventio~ a derivative of a nitrogen-containing heterocyclic sy3tem of formula /I/ tsken in an amount o* 1 - 50 wt, %. The mixing is effected while heating the mixture until an i~otropic phase appears; then the mixture i9 cooled.
~ he other component of the liquid-crystal materi-al m~y be any compone~t selected from the following class: derivatives of diphenylm cyclohexane, dioxanes, pyramidine, alkyl ~alkoxy) phenyl eRters of alkyl (alkoxy) benzoic acids and trans-cyclohexane carbo~y-lic acids, alkylphenyl esters of 4-(trans-4-alkylcyc-lohexyl) benzoic acid, 4-(trans-4-qlkylcyclohexyl) phenyl esters o~ trans-4-alkylcyclohexane carboxylic acid, 1,2-diphenylethane, 1-cyclohe~yl-2-phenyl 15 ethane. ;
The amount a~d ratio of the components in the mixture are selected in accordance with the preset propertieis of the liquid-crystal material.
. .
Given below are examples of specific embodiments of the proposed invention discloqing the method of preparation and propertieq o~ derivatives of nitrogen- ~`
-containing heterocyclic systems of formulas /I/ to /LVIII/, as well as the method of preparation and .
properties of the liquid-crystal material.

- 13 ~

~00~037 E~ample 1 Preparation of 2-(4-heptylphenyl)-6-pentyl-5,6,7, 8-tetrahydroquinone II a.
A mixture of 0~1 mole of 1-(3-dimethylaminopropy-onyl)-4-heptyl benzene hydrochloride and 0.2 mole of 4-amylcyclohexanone i3 heated at a temperature of 160 - 170 C for 1 hr. ~he mixture is cooled and pour-ed into 100 ml of H20. The mi~ture is acidified with 5 % hydrochloric acid, extr~cted with benzene, thè
latter is dried over Na2S04, filtered through SiO2, 5/40, h - 2 cm, and evacuated in vacuum, Added to the residue are 0.4 mole o~ NH20H HCl, 100 ml of etha-nol and 50 ml of water, Th~ reaction mixture is boil-ed for 8 hrs, leached to pH 9 and e~tracted with benzene. ~he benzene is washed with 'Nater (2 x 50 rl), dried over Na2S04 and filtered through SiO2, L 5/40 h = 2 cm, The benzene i~ distilled of~. The residue is recrystallized ~rom alcohol. 0.68 g (21 ~) of .. . , ..
2-(4-heptylphenyl)-6-pe~tyl-5,6,7,8-tetrahydroquino-line is isolated.
Other 2-(4- aIkyl~henyl)-6- alk~l-5,6,7,8-tetra-hydroquinolines II (b-i) whose prnpertie~, approxi-mate ~ormula and elementary analysis data are shown in Table 1.
The comparative analysis data on the phase tran-sition temperature3 o~ the II (b-i) compound and the prior art pyridine derivatives are given in Table 2.

-- ZIID06~3~7 ~ . r~ ~ 0 0 ~^ ~ O O ~ ~
~D O a~ O O O O O -r~
: ~ ~ D L~
c~ 0 ~ a~ 0 0 0 ~ LS~ L~ L~ Lr, Lr~ L~'~ Lr`~ L~
a~ c~ v c;~ 0 0 0 0 0 0 0 0 ~ .~, .~ ~ ~ ~; ~ ~ ~; ~ ~ ~ ~; , ~ ~ a~ ~ ~ u~ Lr~ ~ ~ t-- ~ , ~ ~ r~ ~o~ ~ ~ , ,,~", ,~ ~ ~ ,~ ~
5~ ~ ~ ~ o Lr~ ~, C5~ ~ ~_ P~ O ~ 1 N ~J N C~J (~, ~ : ' ¢q-, ~v ~ v ~ v ~ v v ~''-,, -_ ,=~ ,~
.,.~
I
+ . L~r~0 ~ OLr~
~. o ~ . ~ . . . .,.- `
~ . ~ O ~ ~CJ~ O O O . :~`, ' C~ ~^. , ~
I a~ ~ ~"~ ,,,,,,", ~?J ~ I ~ ~ co cr. 0 o~ ~ 0 ~
' V ' ~ L~ Ll~ Lr~ U~ L~ Lr~ L.~ Lr~ ,~ -~z . ~ ~ C) 0 0 , a) , 0 , ,i ' .: .

O ~D ,' .''`' ~; ", 1, ' ~ V I' '~
E~ o L~ ~ ~ ,~ .

~ t- Lf~ , I ~ ~O I I I C~l ~ ~ ~ C~J ' ~ ~Q V ~ 0 ~ ~ 0 ~ ,.
:~ .
., ~ ~ . ...
C~ o ~ CU
E~ o~ U~ N ~ C~
.~ .
~ ~ ~ L~ ~ Lr~ Lf~ 50~ ' ~
~ :

H 0 ~ ~ '~

ZOObO~'7 T a b l e 2 CnH2n~c~ n~ Cn~2n+rO~_C"~H2n~1 _ _ . . .. ._ n m TC N~ TS_N, TN_~, Com-d n m TC_N, TS_ C _ C _ C C
a 5 7 37 76 b 3 3 53 - 59 c 3 5 55.4 - 66 d 3 2 70 ~ 4lX
5 5 33 30.7~ - e 5 5 43 72.7 73.6 5 7 10 38.5 7 5 31 46.5 - f 7 5 24 82 g 7 7 ~2 fl4 h 7 9 33 83 i 5 9 21 73.5 ~ monotropic transition.
: The total yield ~or formula /II/ is 20 - 25 ~0.
All novel compounds of formula /II/ at room tempera~
ture are in the form o~ a white powder.
~he structure of ~ormula /II/ compou~ds ha~ been determined by means of P~R-spectroscopy.
From ~able 2 it is clear that the clarification ~-temperature of II (a-i) is higher than the clari~i-cation temperature3 of the prior art analog3 in the row of pyridine derivatlves, - 16 ~

-~:

E~mple 2 ~-;
Prepsration of 2-(4-alkoxyphenyl)-6-alkyl-5,6,7, 8-tetrahydroquinoline III~
The compound~ of ~ormula /III/ are prepared qimi-larly to those of formula /II/ by reacting 4-alkylcyc-lohexanone3 with chlorohydrate 1-(3-dimethylaminopro-, `~
pyonyl)-4-alko~ybenzene, followed by condens~tion o, -the 1,5-dicarbonyl derivative with hydroxylamine h~d-roc~loride with a total yield of 20 - 25 ~.
The propertie3 of the compound III (a-h) and the elementary analysis data are given in Table 3.
The comparative data on the phase transition tem-peratures of the compounds III (a-h) and their ana-"~
log3 in the pyridine row are given ln Table 4.
~he examples given in Table 5 illustrate the use of the claimed compounds II and III as components of liquld-cry3tal m~terials prepared u3ing the method3 described above. ~ `
The compositions in the examples are given in per cent by weight.
From examples 3 - 20 it follows that the com-pounds of formula~ /II/, /III~ provide high clarifi-. . .
cation temperature~ for liquid-crystal materials and wide nematic phase interYals~ These materials can be used in general purpoQe electron-optical indicators.

z0~603~
~ ~ , ~ ~ ~D L~ \ N Lr~ L~
a ) 1 Q) X CT~ o~

~ ~ L~
C~ N C~
C) ~t'; N ~ N ~; OJ N N N
I C:) V C~) ~ CO ~ C) ) C~) C~
., Ic~ I
:: Cl I
~ ~ O O O O O O O _~

rJ~ ~ ~\ ~ N L~
O N ~ r~ ~ ~' ~ N
V i ~ V V V
~) O ~

~ ~ ~ c~
"~ ~r~ I ~ ; o \J ~ i N ~ ' ~I N ~ ~, V ! ~ 3 ~

1 3 L.~ cr~ N i N C~
c~ . o a~
O
`':

~; H . .
I I I I I I e~' N 1 1 V ~i 3 C.

~;
N ~~ ~ L~ Lr~
V C~ ~ L'~ CC r~i ~ 3 ~~.
~ ^ ~ : .

_ O L~ D L'~ ~ O ~ Lr~

O ':
~ ¦ H ~ t`~ L'~ L~ C~ ~ ~

X , ~
~' ~,..' :: -;, ,' ,' Z~06037J ~:
. .
:
b l e ~

~nH2n+~ C~ 21 1+1 CllH2n+1 ~> /ITI/

~ . _ . . . .. _ . _ . . . _ _ . ... _ _ .
rl TC-N' S~ /LII/ r m TG ;~ rr~
C-S S-l C C-S
C ~`C ~C ~ ' :
.. .... . .. . . .. _ . _ _ _ .
72 - c 3 6 8~
5~.5 - 6~ d 5 5 ~7,2 - -- :
~' 5 21 ,3 6~.,- e 5 ~ Q5 - ^,^4 5 G 6 s 7 3 9 3 - ^
h 7 l C ~Q,~1 C' : ' ' '`.? O S i t i O~ ; '~e r.~ C ~
_ . . _. ~
3 ~. .
;
C3~7 O~ 20 -15~

' 1~ I .
~ 11 O ~ Cl~ 32 .

~ ) O C 5 H ~ h ) 5 C3H7-O~ OC~HS 16 : :

- 19 - ~ :

~0~603~

Tabl e 5 ( c ollt inue d ) _.. _ . ...... _....... . _ _ .... _ _ . _ . . .
C3H7-O--~ OC 11~ 12 5 1, \`~' (~(~ C Y~5 1 ~

V,,~ C~ 5 3 7 ~ C~ 2~ ~17~'.. 3 C 5H1 1--~ri~ ' 3`) G ~ C~ e) 3 7 C) ~) V C . j 5~-1 1 O--Vl O ~ OC2 j~ ~ 1 3 ~6i13 O~--C HS 1~

C 3 L~7 -- O --@~ 1 3 1 5 ~ ~ 2 . 2 C 5H1 1 -O~C IY 1 7 ';

OC5H~

2Q_ ~ :

:
~s.ble 5 (cont~nu~d) = ., _ . . ,, . . , _ . .... . . .

, ~. . , :

~ Dc,~H13 (~

C~ 10 C~ 5 ~3;-7~0~ c3~17 20 ~;

t 1 0 \~ ~/--C 3 ~ 7 i O

5~ 1 '~ C ~ -- C ~ ~, .3 . !~ t -~ 5~ N 18 :
C - "1 1 - 0'~

, / C7X1~ C~>--C,-l C3H7 0-C2,~ v~1~5 8 C3H7 0 C,H,I~-OC~,H9 8 C5H11 0 ~ >-C,Hs 15 -- 2..1 --~)6~

~ bl e 5 ( c ont inue d ) .. . . . .

_ _ . . . . ..

~ 3H7 ~ C -~ ~3 '1 0 C4E 9~0~\~_ C5 ", ~ 1 0 C ~ H7 C5;i~ cy 8 -~1 a~ .3 7 ~ C ~ 1 2 C3r;7 C~ OC~H~ c) 8 C5H11 r\ ~C/ 20 ~ , , . . ~
C5~ ()C~H 3- 10 C5E~ O~\/~Ci~ 5 - 22 - :; ~

: ~:..' ~0603~
. . .

~b 1 e 5 ( c on~ inue d ) .. . . _ _ . . . ..

- - -1 1 0 ~ ~>- C 3 H 7 1 0 5X11 0~ Cj H 10 r~ 1 3 ~ 8 5 11 \,' \~ 12 CsH~ c) 10 C7E~15~ -C

C3"7-~ ~C~
~' 7'~ 8 Cq ;~ ~ 0 ~>-<~-CI~ ~
C 5H1 1 0--(~--~>{> C5 1~ 1 l 1 0 3H7 - O ~- O C4 115 1 0 5H11 O ~ C2 H3 5 F

3~
~ab le 5 ( c ont inue d ) _ _ _ _ . ~ . . .

9 5 11 C,~)~CN 8 -14~1OV~

~7~;15 C~ CN 12 C ~ ( I ! Cj) 1 5 C ~ OC~ 2) 1 5 C 6~-1 3 - C~ ' 1 0 . ;~

, ~ , C3-'7~ C~ 10 .,,~,"
: -; . ~

C3'~;7-0-~C~ c3il7 8 C 5 ~ 0- ~ C2 ,~

C3~7-O-~coo~_c~ 5 C3H70~ Cl~ 8 -10~96.3 ~ ~

C5H11 ~(O~~ CN 12 ~ ~ ;
,~

- 24~

~s.ble 5 ( c ont inue d ) . . ~

~ , . . . _ . ..... . . . . .. .

~ S ~ c ) 1 0 7 15 O~ C~, H,~ 0 7H15 0--CC;~ CN 8 r\
C3~17 ~,~ C3 11l1 7 5 1~ 15 3 7 0 ~J\--\~O C~ li 1 5 1' Q~> C~ll s (llk) lo 3 7 0~ C 1~ ) 10 ~ I ; I
11 c5Hl1 ~> $--c~ 5 -12~105.2 5 11 O~ Cl~ 5 C4~9-Co>--~- CN 5 ~0(~03~
Table 5 (cotl.t~nued) 5 11 0~OC,~;I lO

5 1 1 0~~ i) C ~ ) 1 5 CC, ,- ~ ) 15 ~ 3~ c~ , 10 C~ C3i~'7 C5~1 1 @~> ~;~ 5 5^1, O (~

C5--7~ >~O-Cj-,4 3 7 O~--OC6H1 12 C 5H1 1 {o)~--Cl~ 1 0 -14 ~10 C7H15~ Cl`l ..

~ X0~6~37 ;,, T~b1 e 5 ( C Ont 1nUe d ) S 1 ' ~/(~ C5 11 ~1I C) 5 7 15 O~ C;~ ) 15 3 7 O~C2H5 10 3H7 O ~--0~ 5 C5~1~WC~ , 3 C5E11-O~/~}C ~5 C 5~1 1 O~-~>--C~ ~5 3 7 O /\~ ~>{} C3l17 C5~11~Q~)~> c 7H~S (lla) C3~l7~ C5H~ C) 10 - 2 7 ~

- Z70~603~o~
Tsble 5 (continued) . . _ O~~ i) C~o h~ ) 6 ~17 .1~ .8 ~ ~
.:, ~_o~" (I)li~J 6 ~:

~(/~-OC~ c) 6 '~':'' :',' C~ d) 7 ~..;

~ G - - 1 3 ( ~

~>--' i0'~12~ ) 5 ~:;
`''~ ''" :'';

OCj-17 ('''9) ~ ~

~ OC5~

C 3H7 - O--~ CN 3 ' ~

_ 28 - :-Z~)6~)3'~
,~ ` -';; ' ~abl e 5 ( c ont inue d ) .
2 3 4- ~ ~~~
___ __ _ _ .

5f~ ~ Cl~l 12 C3H7-0~ C, i-l 7 3 7 0 ~ O C3~77 10 5H1~ \~ Cl~ 3 ~7 0~ \~'C,-c~7 tO

3 7 l ~ 6 - I 9 T 1 O 5 .

3~ cj h ~ c) 0~ ~C~h5 (1~l d) ~ ~> C7 ~ lS ( ~

0~-~--C ? H l s ( 1 l 1 ~ ) :

:' ', ,',.: ' , ' ' :, i , ! . . . , ~
'.''' ' : , ~ ' ,;''" .,' ~ ' , ' , '' ' ' ~: 037 .

Table 5 (continued) .. . _.. .. .. . _ .......

__ .
511 ~ 5jl19 (~ ) 6 C7H15~ cy1~

CN 3 ;

C7Hl~

C3~7-0-(~C~ 0 C5E~ Cl~ 8 .
4 Hg O~ -~)_ cly 8 ~ ~:

V 5H1 1 0 ~ ~ G
C~ ~ 5 -5~111.3 7H1 5- CO~ - CN ~ `
''~' ; 2~0~037 ~able 5 ~co~ ued) _ . _ 0~ > o c ", " ( 111 11)2 0 C ~ ~r,, O u~(~ O C6 1l ~ 7 ( 1_l c ) 2 0 O C ~ l7 ~ 5 C ~ 0 0--O C ~ 1 3 C 6 -1 ~ ~ \ ~ r .1 ~ O ~ ~

r~ J;-/\~\/~ C>-C3l~7 10 C ~> O Cj î

F C~ 7 - ' i 1 1 3 ~ 2 !. IC7~ >-C~ '~

0~ CS H 11 .i!,.: -,, , . . ' `s Tablé 5 (co~ltlnued) : :
____ __ t 7 l5~-Cst" (Il') 25 3 7 0 (~ ~ 15 3 7 ( >~3 ~14i 5 C 3H7- 0~>_ C~ C~`~ 8 ~ ;:

1 7 C 5~ 2 5 -2 3 i ,~-, 8 `: ~;

C3 -70~c~ 1 o ' 5H1 ~ O CS 11 C3HI-0~ 8 `

(~3H7-0~ 3C",Hg 12 IC 5H1 1 O- ~>-(,~ Cl\~

3 7 0~ C2H5 10 ~:

C5~ ?~czH5 22 o~
Ta~le 5 ( c ont inue d ) .. . . .

.. . .. . .

1~ C~ 0~ 8 -2~.65,1 C7 -~15 ~0~ Cl l 12 C5~ C5 H 1 ( ~

C5--? C~-C(~ O- C~,7 8 C 5--1 1 O - coo O- C~
5 -1 1 0 C(~ a 0--C5 111, C -C-~C~JIS 20 .

C4 ~9 ~J~_~--CN 3 C5 11 O ~-C~ 2 5X1 I O~)~) O ~'t 5 C5~1 ~-O--~_(~)~C, H~ 5 C5~ O_~ )--C H 18 9 5 1 f ~ ~> Cl`l 3C -2C~55.2 ..... .. . . . . .. .

~0~3t7 Table 5 (continued) _ _ . . . . . _ 5r'1 1 ~- CN 8 ;

C 3F;7 0- ~\~ ' N 1 0 (~4~9 0~~\ ~)~ i`~ 7 C~ '17~ \~Ci`l 15 C 3 7 (~ _ ~--O Cj- rl ?, C~i3-0-C'~ )~c~
3 ~ CJ ~ ~ 1 O

5H1 1 \~/'~ C2 ~ S 9 C5;11 C~ ,N 8 -27~60.5 7 1 5 \. / ~ ,N 1 5 ~:

' 1 ~ ' ' I ;

~ 5H~ 5 ~

C4H9-GCOO~_o~llg 10 .,",,,,.~

- 34 - :~ ;

2~6~37 Table 5 (continued) . _ , , . ~ .
5 11 O ~ C5~ 10 C5H11 O -C~0 ~ 0c~s 10 3 7 O ~ ~ s . 20 5 11 O ~ ~ C2~s 5 5 11 ~ ~ ~ ~ -C~H~ 10 C5H11 G~c5 ~1t 11 Example 21 .. . . .. . . . .
Preparation of 2-[4-(tran~-4-alkylcyclohexyl)--phenyl~-6-alkyl-5,6,7,8-tetrahydroquinoline~ IV.
21.1~.The compound~ of formula ~IV! are prepared ~imi-larly to the compound~ of formula /II/ by reacting 4--alkylcyclohexanone~ with 1-(3-dimethylaminopropyonyl)--4-(tran3-4-alkylcyclohexoyl)benzene hydrochloride, .. . . . .
foliowed by condensation of 1,5-dicarbonyl derlvative with hydroxylamine hydrochloride with a yield of 25 -30 %. The propertie~ of the compound IV and the ele-... . . . . i . .. . .
mentary analy~is data are ~iven in Table 6.
Table 7 presents e~amples of compositions and :~
. - 35 -~603~
T a b l ~ 6 m 2m+1 ~) {~VJ;~--C n l~2 ,l ~ l / IV/

/_V/ ~ m~ _ ~, T~_J, Foun~ Ap~ro m.ate Cal^ul~tec, ~' C X C '~i .
a 5 3116 203 86.33 10-21 C29~1N R6.29 10.2 '2 3 5132 1?6 86.2t 10.3 C29X~ 85.29 10.-'~
c 3 3108 22~ 86.~ 9-S7 C27~37N36.3~ 9.93 d ~ 3100 203 85.36 10.11 C26~35~ 85.3~ 10."9 e 3 292 201 85.31 9 .3t C25~35I~ 86.37 9 ,7~
. . '-:
I' 9. `., 1 ~ 7 .
.
:.oO Con~?ositio~ ~it, ~;0 '~'e.~ti^
~I~.G~e i~t~
o, C 3 X7--~\~ C 1~ 2 o , 5 T 5 C 5H1 1 -(~ CN :~

C4~I9-~} C00~- C2~ 2~ ~ `
. ' 6 13 O ~~OC2Hs 15 2H5 ~3--(~C3~ /C) 10 23 C3H7~0~)--CI`1 17 -23-93 . 5 - 36 - - :
.:

a Z~)6~3 ~abl e 7 ( c ont inue d ) ~ .. .. _ _ ..
i~, l 2 3 4 . C5H11 ~C~ 23 3 7 ~0~5 16 C3H7-O~ OC ~9 12 5H1 1 0~ ~ 3 ~ 7 ( I ~ ~) 2 2 C5~11 0~{--> C3H 10 C5'~ O-~rN 10 -~a.s3.?

C3'~'7-O~c,~ 15 7 15 0~CN 23 C3~7 C~-- rn~ OC~115 8 C5~I11-0 C~gC3~7 6 , : C3~7-0~t~ , C5H~ CI`J ;~

C2}~5-O~}C3~7 (I~e) 5 ~ ~-1`1 :: , _ 3 7 _ 6(~3~
~able 7 (continued) ,,, ,, , ,, _, , ~ ., ,, , ,, _ , ~
C5H~ 3H~ ) 5 C5H~ > _ C3~1 8 ~: .

~5'~ 8 -31~9~.2 5 11 '~ C.'`l i 2 ~4X9~}` o{~>- Cj~

C 5 i1 1 ~C} ~

C3H7-~} C, H~ OC,~,H~ 8 5H11 ~ 4Y--~oC~H~

3 7 0 ~ ~ 5 :

-C3H~ c) 10 C3H7{~Cyl~g ~ d) 10 C2Hs~ ~ c3 ~ v æ) 1 0 - 3~ - :

- 2i[~603~7 Table 7 ( c ont inue d ) _ _ ... . ., .. , .~ _ _ _ . _ _ ~

.. . . ..
C 5H1 1 C}~CN 5 ~4Hg O~>-~CIJ 5 26 C5H11~(~C,~ 5 -26~106.7 C3;~70~ C~ 7 C 5-~1 1 ~ ~ C~l 3 C 5~1 1 ~ C 1`1 8 C 7;~15 ~>-~ CIY 1 2 C ~H11 CO)~-c~ l 5 C3H7-O~ C2 H5 20 ~ ,_ .. ...
G 5H1 1 ~<~ Q 5 C2H5 O~> ~C H (- ) 10 C5El 1 O~ C~ g) 5 ;;

3~ 3~C41lg (l-Vd) 5 - 39~

~j, ., , . ~ . . . . ; , .. . . . . .. . . . , . ,. , ... . -0~6~3 3 `
i~ !
., Table 7 (continued) ,1 . _ , .~ l 2 3 4 ,, . . . _ ~ _ . _ . _ . . .. _ .. . . . _ . .
3 7 o~3--~5 11 1 1 ( I V Q) 5 ~ ~ ~ 10 27 C5H11~O~X~ cl~ ;7 -24~115.2 C7H15 CG"~ C~ 1 O

C4~9{o)~)-C,~' 7 C3~7~0~~C() ~ c~7 8 C5~ O~ 2l~5 20 -~rC ~ ~:

C5~11-\~ C,~7 (IY~) 5 , ~ 1 3 7 O~J~O~ S l~ (_ Q) 5 C3H7-O~_~} C3~7 (l~ C) 5 C3~7{}~C~IIg (l~/d) 2~603~

~able 7 ( c ont inlle d ) . . . ~

C2H5 0~7 (~e) 10 C3H7- r C51t,l l o C5n11-~c?l 7 -28s115~6 G3H7-0~/~--CN 8 C 5 11 0 ~>

C 6;~13--~O)~ C~; l C3~7-(~~C,~ C,~ 5 C 5 ~1 1 O4~G~- C~ 8 ; ~
~; `'' . ' ~ "
cS~ ~C2H~

5H11 ~ ~>~(~ 4 C3~7~ J~ c2Hs ( ~v ~ ) 4 - 41 ~

~06~37 Table 7 (continued) , .
C3H7~ ~C3H7 (1~ C) 5 !'~

C3~7-<~ C4~3 (Ivd) 5 C3~ ~c;~t~ ) 4 C2~'5~ (- ) 5 Ca~5 ~ b1113 (Il~f) 4 C5~ 3 (1~ 1,) 4 `

29 c3~70 ~--<~CI`J 8 ~il1a.3 C 4Hg O~ C i J 1 2 C 6H1 3~ C~ C~ ~ ~13 1 5 C6~13~ OC9H~q 11 -C3H7-0--(~--C2 H5 5 5 11 ~ ~> 4 ;~OO~iO3~

Table 7 ( c ont inue d ) .. . ... ...

.

C5H11~ C~Hj(IY h) C5E~ 3~

C3~7_<~C~ (IY,~) 6 ~
,,.~ -:
C3H7~ H7(l~1 C) 9 -:
`-C31~7~

3H7 C~) ~ CS~ ) 5 C2H5~ ~C2~(IY ~

C3H7-0~ 13 -18*63.8 5H11 0--~CI~ 17 C3H7 O COO--~--C3H~

C3H7 O--C00--~ OC2 H5 15 ; ~-Z00603~7 ,.,~, , Table j ( c ont inue d ) .
2 ~ 4 a3~7_0~ ~C3~7 (~ ) 3-I7 ~ G~ H 5 ~r11 (~ )~C,i~, 10 ~5U11-O~ 7 . :~

31 C -;~ 1 -0--~ Cl'l 13 -2~3~6'' . 6 C7il 5-0-~1`1 17 5 1 1 0--C~ O ~ (~ 7 ~

CD~.3 0 COO~_OC3H7 ~

a3.,7~ (~CSHl~ (- ) 1 C~.~9- O ,COO (~>- CN 1 O

C3H7-0~ C2H5 25 C5F~ Cl'l 5 ZO [)~iO3~7 Table 7 (continued) 3 . ~

C5~11 0-C~ C~H7 9 C 5H1 1 -0~ 28~11 0 ,8 C7X15-0-(~) ~N

Cs~ O~-~cs 3 C 3X7 - O~ F 8 3 7 0~>--C? 1 1 ~ 2 5 `

`'7~15 C~H1 5~ ~(~C~ H7 ( C9~9_<~)_(~[~C~-Hl1 (Ivl11) 4 1 0H2 ~ 7 ~ 15 ( i l~
;, C7Ht 5 ~ 0 5 - 45~

20~)6()~7 Table 7 (continued) C5H11 (~}~(~C7H,5 (IY~) 4 C 3X7 - ~3~>~ ( -C51~ 0~

C9~19 (~)~)_ Clo H, ( - ~ -propertie~ of the liquid-crystal materials including the novel compounds o~ formula /IV/.
The e~ample~ o~ the liquid-cry~tal materials given i~ Table 7 show that the usè of the novel mate-rials of the formula /IV/ as components o~ liquid--crystal materials give~ the latter high upper li-mits of the nematic phase interval and wide ranges of this phase making it possible to use the liquid--crystal materials in general-purpose electron-optic-al devices, Example 33 Preparation of 6-alkyl-2-[4-ttran3-4-alkyl-3--methylcyclohe~yl)phe~yl¦ -5,6,7,8-tetrahydroquino-line~ V.

~26)06(~3~7 These compoundq are prepared similarly to the compounds II by reacting 4-alkylcyclohexanones with 1-(3-dimethylsminopropyollyl)-4-(4-al~yl-3-methylcyclo-hexyl)be~zene hydrochlor:ide, followed by conde~sation ~:
5 of 1.5-dicarbonate deri~ative with hydro~ylamine hyd- .
rochloride with a yield of 17 - 20 %. ~hu-~, 6-propyl--2-~4-tran~- 4-alkyl-3-methylCyClOheXyl) phenyl]--5,6,7,8-tetrahydroquinoline has ~C N = 59 C;
~N-I ~ 155 C.
Found, %: C 86.30; H 1 0.41 . C30H43N. ~ :~
Calculated, %: C 86 ,27; H 10. 38 . . ~ ~-Example 34 ; ~
Preparstion of 2 -alkyl-6-(t rans-4-alkylcyclo- :~ :
he~yl)-5,6,7,8-tetrahydroquinoline~ VII.
34~. 2-thienyl-6-(trans-4-amylcyclohe~yl)- `;~`
-5,6,7,8-tetrahydroquinol~ne. ~ .
This compound i~ obtained in a similar way by -~
reacting 4-(trans-4-amylcyclnhexyl)cyclohe~anone with .. . . . .
2-(3-dimethylaminopropyonyl)-thiophene hydrochloride, :~
.. . ........ ... . . ....... . . . . .
followed by conden~ation o~ 1,5-dicarbonyl comp~und with hydro~ylamine hydrochl~ride with a yield of `
15 %. T~elt c 149 C (from alcohol).
.
-34.2 2-butyl-6-(trans-4-amylcycloheæyl)-5,6,7, 8-tetrahydroquinoline VII.
A mixture of 0.01 mole of 2- ~ enyl-6-(trans-4-.. . . ...................... .. .
-~n~lcyclohexyl)-5,6,7,8-tetrahydroquinoline9 1 g of `

~ )603~
.

Ni/Re and 30 ml of ethanlol are heated with boiling to complete de~ulphurization. ~he reaction mixture i9 ~iltered, the alcohol i~ di~tilled o~f and the resi-due is cleaned, u~ing ch:romatography in a column of Al203 of the ~econd degr~e of activity ~eluent hexane:
ben~ene - 1:1). Tmelt - 33 C; TI-N = 20 C ( alcohol).
Found, ~: C 84.27; H 11.60. C24H39N.
C~lculated, %: C 84.39; H 11.51.

E~ample 35 Preparation of 6-alkyl-2-(5-alkyl-thien-2-yl)--5,6,7,8-tetrahydroquinoline ~III.
6-Amyl-2-(5-propyl-thien-2-yl~-5,6,7,8-tetra-hydroquinoline ~III i~ prepared similarly to II by re- `
acting 4-alkylcyclohe2anone with 2-(3-dimethylamino-~ .
propyonyl)-5-propylthi~phene hydrochloride, follo~-ed by condensation o~ the obtained 1,5-dicarboxyl de-rivative with hydro~ylamine hydrochloride with a yield of 17 %. Tmelt ~ 34.4 C (from alcohol).
~ound, ~: C 75.68; H 8.21. ~ 28NS.
Calculated, %: C 75.74; H 8.12.

E~ample 36 Preparation of 6-alkyl-2-(4t~koxy-3-fluorophenyl)--5,6,7,8-tetrahydroquinolines I~.
6-Heptyl-2-(4-decyloxy -3-fluorophenyl)-5,6,7,8--tetrahydroquinoline.

',"7 ''' ;'. ",' . ' ' ' . '~ ' ~' . '' . ' ' : ' .

xo~

!

The compound i8 prepared ~imilarly to II by re- ~;
acting 4-heptylcyclohexanone and 1-(3-dimethylamino-propyonyl~3-fluoro-4-decy~loxybenzene hydrochloride, Pollowed by condensation of 1!5-dicarbonyl deri~ative with hydroxylamine hydrochloride with a yield o~ 31 (from alcohol)- ~C-SA= 49~ C; ~SA-I 8 Found, %: C 79.81; H 10.00. C32H48NF0.
Calculated, %: C 79.78; H 10O04.

Example 37 Preparation of 6-alkyl-2-(4-alkoxy-2-fluorophe- ;`
nyl)-5,6,7,8-tetrahydroquinoline ~
.
6-Amy1-2-(4-methoxy-2-fluorophenyl)-5,6,7,8--tetrahydroquinoline X~
The compound is prepared similarly to the com-pound II by reacting 4-amylcyclohexanone with 1-(3--dimethyl~minopropyonyl)-2-fluoro-4 -me thoxybenzenc hydrochloride, followed by condens~tior ~f the obtain-ed 1~5-dicarbonyl derivative with hydr~ylamine hyd-rochloride with a yield of 11 %. TC = 65 C; ~ -~
20 TI_N - 55 C (from ~lcohol). ;
ound~ % C 76-94; H 8-07. C21H26N~o.
Calculated, %: C 77.03; H 8.00.
": ~
Example 38 Preparatio~ of 6-alkyl-2-(4-fluorophenyl~-5,6,7, 8-tetrahydroquinoline XI.
; ,`, ' , - 49 - ~
'~',.''.

)6~7 ~';

6-Heptyl-2-(4-fluorophenyl)-5,6,738-tetrahydro-quinoline ~
~ he compound is prepared similarly to II by re-acting 4-heptylcyclohexano.ne with 1-(3-dimethylami.no-5 propyonyl)-4-Iluorobenzene hydrochloride~ followed by condensation of the obts.ined 1,5-dicarbonyl deri-vative with hydroæylamine hydrochloride ~ith a yield of 30% . TC = 6 3 C;
~I~N = 50C (from alcohol).

IO~'ound, ~: C 81.24; H 8.55. C22H28N~, Calculated, io: C 81.19; H 8.67.

Example 39 Preparation o:E 6-alkyl-2-(4-isothiocyanophenyl)- -, 5,6,7,8-tetrahydroquinoline XII.
I5 39.1. 6-Pentyl-2-(4-nitrophenyl)-5,6,7,8-tetra-hydroquinoline . ' This compound is prepared similarly to II by re-acting 4-pentylcyclohexanone with 1-(3-dimethylamino-I ~ , propyonyl)-4-nitrobenzene hydrochloride, ~ollowed by 20 condensation OI 1,5-dicarbonyl derivative with hydro-xylami.ne hydrochloride with a yield ot -15"~o and ~mel~ = 87 89C ( from alcohol) .
~ ound, ~0: C 73, 98; H 7 . 51 . C20H24N202 .
Calculated, ,'0: C 74. 05; H 7 . 46 ~

,'',!:`, ' . ., ~ ' :- , . . . : '. .

Z O ~ ~3 ~

39.2. 6-Pentyl-2-(4-aminophenyl)-5,6,7,8-tetra-hydroquinoline.
A mixture o~` 3S ml o~ ethanol, 0.005 mole o~
6-pentyI-2-(4-nitrophenyl)-5,6~7,8-tetrahydroquino-5 line, 1 g of Ni/Re, 2 ml of hydrazine hydrate and 0~1 g of NaOH is boiled in a flask with a reflux con- ~ -denser until the starting i~ubstance (39.1) is no longer present in the chromatogram. The reaction mixture is filtered, the alcohol is distilled off and -IO the residue is recrystallized from hexane. ~he amino derivative is isolated with a yield of 72~ and ~melt = 82-830c.

~ound, ;;~ C 81.66; H 9-02- C20H26N2-Calculated, ~v: C 81.59; H 8.90.
. ':, I539.3. 6-Pentyl-2-(4-isothiocyanophenyl)-5,6,778--tetrahydroquinoline XII.
0.01 mole of 6 pentyl-2-(4-aminophenyl)-5,6,7,8- ~-~
-tetrahydroquinoline (39.2) is dissolved in 5 ml of absolute benzene, 0.01 mole Qf CS2 and 1,5 ml of .
20 Et3N are added and left for a ~eek. After that the reaction mas~ is diluted wi-th absolute ether and the precipitate is filtered out~ ~he residue is transfer-,.":

)t)6(~37 red into a three-neck ~lask equipped with a s-tirrer, a thermometer and a dropping ~unnel operating wi~h a counterflow, 20 ml of absolute chloro~orm are put into the flask and 1,5 ml of Et3N are added at a tem-5 perature o~ 0C; then 1,5 ml of ethylchloro~ormia~eare added. ~he reaction mixture is s~irred for 10 m~
at 0C; then it i3 stirred at room temperature for 10 mn. ~he chloroform layer is washed with 1V~o HCl and water a~d, after drying above Na2S04~ is ~iltered IO through SiO2, ~ 5/40 (h = 2 cm). ~he mother liquor i~ boiled down in vacuum. ~he re~idue is recrystalliz-ed from hexane~ ~he 6-pentyl 2-(4-isothiocyanophenyl)-5,6,7,8-tetrahydroquinoline is isolated with 50 yield and with transition temperature3: ~C ~ = 92C;
I5 ~S_N a 104C; ~N-I = 115.3C.

~ ound, ~70: a 75-08; H 7-16- C21H24N2S-Calculated, ~0: C 74.96; H 70190 Example 40 Preparation o~ 6-alkyl-2-(4-cyanophenyl~-5,6,7,8-20 -tetrahydroquinoline XIII.

40.1~ 6-Heptyl-2-(4-bromophenyl)-5,6,7,8-tetra-hydroquinoline.
~ hi~ compound is prepared similarly .tc /II/ ~rom ~-heptylcyclohexanone and 1-(3-dimethylaminopropyonyl)-4-bromoben-~ 52 _ .... . .

~0~160;~7 . - . . . . .
zene hydrochloride, followed by condensation of 1,5-dicarbo-- . . ..
nyl derivative with hydro~ylamine hydrochloride with a yield of 23 %. Prepared in a similar way are bromine derivatives whose properties, approxim~te formula and elementary anqlysis dat~ are given in T~ble 8.
~ a b l e 8 CnH2n+1 ~ - ~ - B

.. . . .............................. . .
Com- n Yield, T~el~,Found, % Approximate Calculated, ~ound % ol ~ formula C C H C H -~
40.1 a 3 35 116 65.38 6.04 C18~20BrN 65.46 6.18 b 4 30 9~ 66.31 6.26 C19H22BrN 66.28 6.4~, c 5 26 1û8 67.18 7.01 C20H24BrN 67.04 6.75 d 6 18 87 67.59 7.03 C21X26Br~ 67.74 7.04 e 7 23 95 68.36 7.21 C22~28BrN 68.39 7~3 f 8 30 88 69.7 7-46 C23~303r~ 69.72 7.55 40.2. 6~eptyl-2-(4-cyanophenyl)-5,6,7,8-tetrahydroqui- -noline 1~III e/.
- A mixture of 0.01 mole of 6-heptyl-2-(4-bromophenyl)-. .
-5,~,7,8-tetrahydroquinoline? 0.006 mole of Cu2CN2 and 5 ml of N-methylpyrrolidone are boiled with stirring fo~ 4 hrs. -The mi~ture is cooled, diluted with 20 ml of an aqueous solu- -.. . ... .. .
tion of NH OH and is stirred at room temperature for 3 hrs.
~he rèsidue is ~iltered, washed with water and dissoived in ... .. . . . . . . .. . . . . . . . . . ....
benzene. The benzene solution is dried by means of Na2S04 and is filtered through a layer of SiO2, h = 2 cm~ ~ 5/40, ~he ` ;~0~603 ;~

benzene i~ distilled of~ and the re9idue i~ recrystallized ... . .. . . .
from ethsnol. 1.88 g (57 ~) of the.t.arget product is isolated.
.
The XIII (a to f) compounds are prepared in a ~imilar way.
Their properties are, an ap~roximate formula and elementqry analysis data are shown in Table 9.
r a b l e 9 CnH2~+1 ~ N

.
Com- n Yield, TC ~ TN .~ ~ound, ~o Approxi- Calculated~ ~
pound % -l -l _ - m~te .. _ ..
~C C C H formula C H
.. .. . ~ .. .. _ .
XIII a 3 64 102 97,~82.4 7.11 C19~ 0~2 82.57 7.29 b 4 59 84 89 82-76 7-83 C20H22N2 82-72 7-64 c 5 61 96.2 98 82-79 8-01 C21H24N2 82-85 7-95 d 6 67 69 97.3 82.69 8.34 C22H26N2 82.~7 8.23 ^ e 7 57 67 98.1 83.08 8.5 23 28 2 E 8 64 65.9 93.8 83.11 8.67 C24H30N2 83~24 8.73 ~ monotropic transition.

The comparative data on the phase.transition tempera-tures and nematic phase intervals ~ TN for the prior art 5--alkyl-2-(4-cyanophenyl) pyridines and the nov~l 6-alkyl-2--(4-cyanophenyl)-5,6,7,8,tetrahydroquinolines /~III/ are .
given in Table 10.
~rom Table 10 it is evident that the clarification tem-peratures TN ~ o:E the derivatives XIIIa f are much lower than -~
tho~e o~ the pyridine analogs9 while the nematic pha~e inter- .
. .
val i9 much wider.

~able 11 ~hows the compo~itions and properties of the liquid-crystal materials comprising the novel compound3 of the general formula /XIII/. ..
As is clear from Table 11, the use of novel compounds of the formula /XIII/ aæ .~ :
components of liquid-cry~tal materiali~ provide~ .
high clarification tèmperaturès for the~e mate- ;. .
rial~, which is necessary when they are u~ed I0 i.n general-purpose electron-optical devices. , ~.

Example 51 ,,.:
Preparation of 6-alkyl-2-(2-hydroxy-4~
-alkyloxyphenyl)-5,6,7,8-tetrahydruquinoline.
This compound is prepared similarly to II by I5 reacting 4-heptylcyclohexanone with chlorohydrate 1-(3-dimeth~laminopropyo.nyl~ hydroxy-4-.nonyl-oxybe~zene, followed by co~den~ation of 1~5- :~
dicarbonyl compound with hydroxylamine hydrochlo-ride with a yield of 15~o. ~C S = 73C;
20 ~SB-SA = 89 C; TSA_I = 164 C (from alcohol).

- 55 - :~

.- 2~0~iO;~7 i .
~ a b l e 10 nH2n~1 ~)~Ci~ C H2 10~ /~;III/

,. _ .... ,_. .
Tc_N ~ T ~~ TN, n TC~ ~ T~ ` TN, C C C C C ' ' C

a ~ 43.4 43,8 0.4 ~ 3 102 97.6~ _a,4 ~ 4 32.3 26.5''-5.~ ~v 4 84 83 5 c 5 33.6 ~3~5 9.9 c 5 96.2 38 1.8 d 6 29 32.5 3,5 d 6 69 97.3 18.3 e 7 3C,9 47 1~.1 e 7 67 98.1 31.1 8 39.5 ~3 ~3,5 f 8 65.9 93.8 17.
monotro?ic ~,ronsi t ion.

Table 11 5;~0~t:3 t:~le co,~ositians a~i. ?ro?e-tie~ o~ the liquid-cr~stal l.~teriols co.-~prisin~; t~e -.ovel compo.lnds of the gene~al forr.ul~
nl a b 1 e 11 I~o.Composition .~t, ~ ernatic phase i t e r-~ a l, _ _ 41 ~3H/~ -cll (Xlll Q) 20 _7s92.5 Cl~l (Xlll C) 30 - :;:
. ` .~'.

-- 56 -- .

- Z~D~)6~);~7' Tabls 11 (continued) -4 9 0 ~--~ Oc~H~, 2 5 `' 6~13 O ~,00 -~--O C ~ '; 1 5 3 7 C~ 10 47 ,~ 10 -~*90-OJ_ ~--C N ( ~

C ~ 0/~ ( X lll C ) ? 1 ~ (~ Cl\ 20 3~ 7 O~ COO -~ c, fl7 15 C~,:.3 (~ C00 ~ OC~ H, 10 5 1 3 0 C~O~ oc2 ~ 1 5 C 5X1 1 0--(~ C, Hs 5 C5H11 ~ ~CN 10 43 C3H7-O~(~)_ C~ 17 -7~68 .2 C 5H1 1 -O--~ CI~

- 20~6~37 Table 11 (continued) ..... . ...
C3H7~ 0-(~--C,H~ 10 C4H9-~C(~--~ OC~H, 10 ~6~13~ ~r~~>-OC_.y, 1o 5 11 ~ 10 3H7 O-~ C, H -7 1 5 C\ (~ 10 ~ ;

3 7 O~ CI~ (Xill ~) 10 44 C4r.9-C~3 ~CI~ (Xlll ~) 5 -22;~
0~ CN ~XIil d) 5 7~15-O~3_CN (~

8 17 O~)~CN (xlilf) 5 C3H7~ H5 20 _ ~8~

: ;20~)6C~37 T~b l e 11 ( c ont inue d ) . . ~

3H7 C~- C~ H4--(~- C~ ~ - 1 0 c4H9-O ~ )-CI~! 10 5H~ ~C~`~ 8 5 1 1 0 C~ 7 5- 11 O-~-~{> c~ 5 C-;~ 0~/~- V~ ; 8 ~3X7 0--~--J'i^~H' 12 C ri 0~ ) 3 - 2 7 ~ 6 8, 2 O~ C.~ li d) 2 rO
5 11 ~

C7~I1 5 - CcJ )--~--Cj~ 1 5 C 3H7 - ~ 0 C2 1t 5 1 0 ~ 59 --- ;20 [)60;~7 ~able 11 (co~tinued) . . .

C4H~ Coo--C~OC H ~ 10 C5;.1 1 0 ~> NC5 10 c3;~_-O-~ y,s 20 5 11 ~ ~ ~3 5 C~LI1-O~ >_C~ 5 ,~

~6 (~7;~ 3 -32~65.9 ~tJ ~--Cil ( C3~7-0-~-C~ 7 '~
C5~-11-O~ -CN

'!l' C7~ 2 C 6H1 3 ~ CO~ 0 C~ H l 3 ` 5 C3~7-O--C2~ G2~15 C6H13 O~>--C,l 119 8 ~60~

i Z00~3~
~able 11 (continued) . _ ......

. _. _ . .. . . .. . . .

C3H7 0 (~ )~- C;~ 3 3 7 0 (~>-G)O~ C3~7 3 3 7 0~ --O--C,'~ 12 C3X7 O--C~ ~' ~S 10 C5~1 1 ~C~ '~1 9 5 1 1 0 C~ O C . ~ - l O

7 7 1 5 ~ 32 ~2 .9 C5nl1- ~-~-CN 30 C3Y7-~ CI~' 7 ' I 3 7 0 (~ - ~ 15 C 5H1 1 -O-C~ 1~ 4~)- CN 1 0 C5H1 1 O~ce 5 3H7 0--(~>~ C3 l~ 7 2 0 06 03 ~
Tabl e 11 ( c ont inue d ) C3H7-O~-~}C3H7 10 ~4~9~ COG ~-C~`I 10 C r~ C~X~~~ C~ 4 4a C3H?~3~ Ll~ ( Xl~ ,l) 10 -8~92.2 ''.'"'"~
0~_~C~ 51 O~J--(~ CN ( ~ d) `~

. :
C 3H7 - O~--C~ .iS 30 `~

Ç 5 1 1 ~ C2 1~ ~ 1 0 3H7 O~ C. i 1~ 1 0 :~

C 5H1 1 ~>~--~ C~ ~ 7 1 0 ;' ~
- 62_ `~

20~603~7 Table 11 (continued) ~= . . . , , _.,, _ _ 2 3 . 4 ..... ..... . .

49 C3~7-O--~ ~ClY ( Xlll Q) 8 -~101 C.--9 ~ CN (Xl~

C ~ _C~ 11 C) 10 ~ ' c - 0 ~ d) O~J ~ 8 c - 0~ CN (X~ ) 7 C ~ C~ - C~H~ 20 C~:--7{}~_o~ 11 5 C -- O ~- OC 1~12g 5 , C ;~ {}/~ C~ ~ 7 1 0 3 7 ( \~0 C3 ~7 - 63 - .

f~2,~ "~ .~, , , - " ",~ ' ' ', -~, - ,, , , ' , . .. , , ,,~ " ~ ,: ., .. '' . , ' .

2~ )3~7 Table 1 1 ( c ont inue d ) .. .. ~
3 7 O~Chl (X~ 3~106.7 0~ ~CN ( 5 O~,~

C6H13 O~ ~ Cl`l ~XIil d) 11 . `,'' ~ '~'.

C7;~15 C~ CN

C8H17~ ~C~ (XIIl.r) C3H7-~C2Hs 20 C3H7 0~)-dC2~

C 5H11 O~C; C~ 117 3~7-O--(~>~C3H7 10 - 6~- :

20 06 03~ !

Found~ ~: C 80.18; H lQ.01, C31H~7N02.
Calculated, %: C 79.95; H 10.17.
~ able 12 shows the composition and proper~iea Or the li~uid-cry~tal materials compri~ing the novel com-pound of ~ormula /~IV/.

E~ample 53 Preparation of 6-alkyl-2-(2-hydrozy~4-alkyl-- ;
phenyl)-5,6?7,8-tetrahydroqui~oline XV.
6-Pentyl-2-(2-hydroxy-4-methyiphenyl)-10 5,6,7,8-tetrahydroquinolineO
Thi~ compound is prepared similarly to II by re-acting 4-pentylcyclohexanone with 1-(3-dimethylamino-propyonyl)-2-hydroxy-4-methylbenzene hydrochloride, followed by conden3ation of 1,5-dicarbonyl compound with hydro~ylamine hydrochloride with a yield Or 16 ~. ~ C S = 88 C; T ~ ~ = 120.1 C; TS I ~ 136.2 C.
~ ound, %: C 81.65; H 8.81. C21H27N0.
Calculated, %: C 8t.65; H 8.79.
Table 13 shows the compo~ition and properties of the liquid-crystal materials comprising the novel compou~d of formula /XV/.

2006~3'7 T a b l e 12 No, Composition wt. 5~ Nematic phase int e rval, -- . . ., , _ _ C

52 C3H7--~--C~ 20 -1 5;63 .8 C5H11 O~ 3Z

--(O~ OC,3 ~119 ( ~
11 0 ~ `,'~.'`.:' , . . . : ~
C3H7-O~>_ OC, Hs 16 ; ~ ~

. ~ ~. ..
C3H7-O~--0C4H~3 12 C 5H1 1 ~ C~ ~ 5 1 0 ~ -5H1 1 -~>~ CN 5 ; ~:

-- 6~6 _ ~ 1)06~3~
,~, , .~
T a b l e 13 . ~
No. Compo~ition wt, % Nematic phase int e rval, 54 ~3~ - ~ CN 20 -17~65 r3 C5H11~ C~ 30 ~ ~ ~ C H3 ( X ~ ) ' 3H7 O C0~ OC2l1s 17 C5H11- ~ ~~ ~ _0C~Hs 6H~ 2HS

E~ample 55 .. .
.. , . - .
- Preparation of 6-alkyl-2-(4-bromo-2-hydroæyphe-nyl)-5,6,7,8-tetrahydroquinolines XVI.
6-Heptyl-2-(4-bromo-2-hydroxyphenyl)-5,6,7,8-tet-rahydroquinoline.
.. . .
~ his compou~d i~ prepared similarly to II by re-acting 4-heptylcyclohe~anone with 1-(3-dimethylamino-propyonyl)-2-hydroxy-4-bromobenzene hydrochloride, followcd by cond~nsatiDn Df 1,5-dicarbonyl cDmpound with hydroxylami~c h~drochlDrid~ with a ,.. , ",, . ~ - . , . , :

,~,;,, .: . . , ..... . .

20~)603~
~ield o~ 11 yo (from alcDh~l). The other /~VI/ (b, c) compounds are prepared in the same way The phase transition temperatures for /XVI/ (a-c) are given in Table 14.
T a b l e 14 C n~2n+ 1 0~/~_,~ 6 l~o Com- ~ield,T~_s, TS_I~ Found~ /o Approxim~te Calculated, %
po~nd ,'J .' formula --X~I C C C ~ C H ;~

a 7 11 94 143 65.51 7.12 C22H28BrN0 65.67 7.Q1 -~
b 3 10 133 128.4X65.71 6.05 C18H20BrN0 65.~5 5.1 c 5 15 108 141 64.2 6.17 C20H24BrN0 64.17 6.~6 The other lerivatives of fo~mula /~VI/ are pre~ared in a similar manner, qhen Hal = I or ~, mple 56 ;~

~ reparation of 6-alkyl-2-(4-cyano-2-hydro~yphenyl)--5,6,7,8-tetrahydroquinolines /~VII/. -~
6-~:eptyl-2~(4-cyano-2-hydroxyphenyl)-5,6,7,8-te~ahydro- ~-~
quinoline /XVII a/.
A mixture of 0.01 mole of XVI, 0.012 mole of CuC~ and 10 ml of N~methylpyrrolldone i3 boiled till di3appearance of the initial XVI, The reaGtion ma33 i9 cooled, poured onto 50 ml of 25 ~ ammonia, stirred for 1 hr and e~tracted with methylene chloride. The organic layer is washed with water, filtered through SiO2 ~ 5/40 (h = 3 cm) and boiled down The residue i~ recry~tallized from hexane and alcohol.

_ 68_ ~i '' .: '.

~11()60~

The other ~VII (b-c) compounds are prepared in a simil~r manner. The yield and phase transition temperature~ are.shown in Table 15.
T a b l e 15 CnH2n+1 O~ J~ c~ ( X~
~0 , _ _ Com- ~'ield, ~C-~ TN_I9 Found, ~a : A~pro~imate Calculated, ~,0 pound ~3 ~ -- formula ------XVII C C C H C
a 7 77 102 139.5 79.3 8.11 C23H28N20 79, 7 b 3 81 135 145 78,11 6.75 C1gH20N20 78,0~ 6.89 c 5 79 109 14~ 78.9 7.61 C21~24N20 78.72 7,5~

~ able 16 presents comp~rative data on the phase trPnsi-tio~ temperature~ of the compounds ~III and ~VII.
T a b l e 16 Cmnd n TC-N' TN-I' TN. Com- n TC-N, TN_I~ TN' AIII C C C XVII - C C C
a 3 102 97.6 -4.4 b 3 135 145 10 c 5 96.2 98 1.8 c 5 109 141 32 :
: ~ ~ 7 67 98.1 31.1 a 7 102 139.5 37,5 ; Table 17 shows the-compo3ition and pr~pertieq o~ the liquid-cry3t~1 materials comprising the novel compound~ of formula /XVII/ a-c.

:. :. ~ ; . . . . . .
.:.. .: . . . - - , . . . -2~ 137 -T a b i e 17 No. Composition wt,% Nematic ;~
ph~se int e rval, __ ._ .__ ~ . .,.""". ~ __ , C
1 2 3 4 `
.. _ _ . . ... _ -- ... _ . . ..

0~ ~CN 20 -S~l15.1 C5H11 ~ Y~I ~) 30 ~`NJ-~C~I , C4Hg--O~ -~ Hs 6H13 ~V0~ 0~_115 15 ~ :
~. .

3H7 ~(~ C_ H5 10 .~ . ;-:

0~--~ C~ (Xl/ll g) 10 -6~101 .3 ~ .
110 , .

0~ CN ( _ C) 1 5``~;
H 0 `
7 15 ~ ~ C N 2 0 ~J ' ' `

3 7 0 C00-~--OC,~5 15 C4Hg-O--~,00~ 0 C2115 _ 70 _ . Z~)6037 Table 17 (continued) .. . .. . . .. . _ 6 13 0 (~ OC~ 1ls 15 1 1 0 ~--(~ C, ~1; 5 C 5TT1 1 - (~)~

53 C3H7- O ~ CN 17 -6 t73 .7 C5H11- O - ~ C~ 20 3 7 0 CC0 ~ ~_C~HT

C4H9~ ~ C00- ~ - a~ 7 10 C6H13 0 ~-~--OC,H5 10 , ~,, 5 11 ~ ~ ~ 10 3H7 O ~ ~ C~ H, 3 C7H15`O_~--C~ 10 3 7 0~ ~> ( X ~ ) 10 HO

., ., . . - . .. . . . .

03'^~

Tabl e 17 ( c ont inue d ) _ ~ . _. _ - . _ 5Hl ' Q~ Yh c ) 7 -2 0~ 94 . 5 H0 ;

7H1 5~ ( X ~ ) 7 1~0 3 7 ~_ c~ ( X Yll ~) '' ~ ' . ', C3P;7~ ~ C2 H; 20 3H7 0--C2 H 4 ~ C2 ~ ~ 1 0 4 9 O~) (~C~l 10 I`~ . . ........... .

C5H11 O~>--C2H~ 8 :

C5H1 1 0-~o~)~) C~ 7 C 5H1 1 0--~ O--C?, H7 ; ~
C 5H1 1 0 ~ C2 H5 8 ~ :

O (~) C2 H 5 12 , : "

-- 72 _ ~ Z0~)6~)37 T~bl~ 17 (continued) ,,, ....____ _ . ----- - :
3 ~2 6 *70 . 7 ~0 0~ CN ~ X~

11 C~ ~ 10 CIH1 5-C~ 1 15 3 7 O~-O~.H5 10 4 9 0 ~OC~Ils 10 5 11 'O (~ IYCS 10 C 3H7 - O~ C2 1~5 2 0 C5H11 ~>~>--Crl 5 C5H11 O ~CN 9 C5H11 0 (~ CN

3 -32~67.3 T~ble 17 (continued) . _ _ . .. . . . ..

. _ . , . . _ _ . . _ . .
3 7 O ~ CN 7 CSH11-O~ CN 8 C7H1 5~~ 2 C6H1 3~C)~ OC~ 3 C 3H7 O C2 ~ O

6 13 O ~ 8 3 7 a O_CO~--(~C3~7 3 3 7 0 ~ C~O ~C3~l 3 3 7 O O COO~ C3 H7 12 3 7 O C2 H4 ~- O C2 ~5 1 O

C 5H1 1 -0_~ ~0--~

5 11 C} 2H~ ~OC2H5 10 63 C7H15 0~ ~CIY ( XYII Q) 1 -32~63.4 HO :

~;~. ., . ! . ~ , .. . . . . .

200603~

~able 17 (continued) 2 .3 4 C 5H1 1 ~ G~ 30 3 . 7 ~)~

, 3 7 O~)_ C2H5 1 5 C5~ aC'H~ CIY 10 , C 5H1 1 ~ O~ C~ 5 C 3~7 a~_C~ H7 8 C3~;7 O~ ~ C` C '~ 10 C~ g- O COO~- C~ 10 5 11 a<~ o C5H1~ ~

3 7 ~ ( ~ ) 10 ~6*11 3, 6 l~

C5H11 ~] ~--CIY (XVII C) 10 HD `

C7H1 5~CN (Xl~ll a) 20 t lO ' . ' - 7 5 ~

oo~

Table 17 (continued) 2 ... 3 .,. . ~

3H7 O_~ C' ~5 30 C 5H1 1 0~_ C~ H~ 1 0 C H O~ ~ C H ~

5 11 O~)~ C~ 3 1 10 53 7 O~) (X~'~l g) 16 -3~123.3 liO ~ `:

C 5H1 1 -O~ ( X ~' ll C) 1 7 : . ~

, H ~ :

O~ CN ( 1~ ) 17 ~ ;

C3H7-O~ C2~s~ 20 C 3H7 - O~ C2 ~5 5 C 3H7 - O~ C4 ~ 9 S

5 1 1 O ~)~' C 3 H1 1 0 3 7 O~ O C3 H1 -- 76 _ ~ ' ~ ' " ',, ., . ', ' ., . : .

ZO~ 37 .,.

~, ;
Table 17 show~ that the u~e of the novel com-.
pound~ of formula /XVII/ a~ components of liquid-crys-t~l materials provide~ a wide nematic pha~e interval for the~e materials.
. .
E~ample 66 Preparation of 6-alkyl-2-~-alkyl or alko~ysty-rene~-5,6,7,8-tetrahydroquinolines XVIII.
66.1. 2-Methyl-6-pentyl-5,6,7,8-tetrahydroqui-noline.
.. .. .. . .
2-Methyl-6-pentyl-5,6,7,8-tetrahydroquinoline is prepared ~imilarly to the preparation of II. 1 mole of 4-pentylcyclohexanone and 0.3 mole of 1-dimethyl-aminobutanone-3 are heated in a nitrogen stream at 120 130 C durin~ 8 - 10 hrs. The ~tarting sub-~tance i~ di~tilled off. The residue is dis~olved in alcohol ~150 m}), O.6 mole of hydroxylamine hydro-chloride i9 added ~nd the mixture i9 boiled for 6 hrs.
The reaction mi~ture iq diluted with water, le~ched ~nd extracted with benzene. The benzene extract i9 filtered through SiO2~ L 5/40 (h = 3 cm), the ~ol~ent '1~ ''I ~.;

- '~ .~ ' ";~

.~ :
is distilled of~ and the residue is distilled off in YaCUU~- Tboil = 208/-1 ~m Hg.
66.2~ 6-Pentyl-2-(4-buto~ystyrene)-5,6,798--tetr~hydroquinoline ~VIII a.
3 5 0.01 mole of 2-methyl-6-pentyl-5,6,7l8_tetrahyd-roqui~oli~e, 0.014 mole of 4-buto~ybenzaldehyde and 10 ml of acetic anhydride are boiled for 30 hrs in a nitrogen stream. The benzaldehyde is diqtilled off, the re~idue i9 leached and e~tracted with benzene.
~he benæene e~tract is pa~sed through SiO2, L 5/40 (h = 3 cm), the solvent i9 di3tilled off and the re-sidue is recrysta;lized from alcohol. TC N ~ 120 C;

TN I = 138.5 C.
~ound, %: C 82.88; H 9,26. C26H35~0.
Calculated, ~0: C ~2.71; H 9.34.
4-Substitut~d derivatives of styryl comprising Br, Cl, CN, CnH2n~1 groups wera prepared in a simi-lar way.

E~ample 67 Preparation of 1-(4-alkyl or 4-alko~yphenyl)-2-(6-alkyl-5,6,7,8-tetrahydroquinolyl-2)-ethane XIX.

- 78 _ X006tl3~

6701 1 -(4 -butoxyphenyl)-2-(6-pentyl-5 9 6,7 9 8--tetrahydroquinolyl-2)-eth~ne.
A 901ution containing 30 ml of ethyl alcohol and 2 g of 2-(4-buto5cy~tyrene)-6-pentyl-5,6,7,8-tetrahyd-5 roquinoline~ XVIII a i9 placed into an s.utoclave, 2 gof Ni/Re are added9 and the mixture is hydrogenerated at 9. hydrogen pressure of 10 atm at a temperature of 25 30 C until the hydrogen i~ absorbed completely.
The catalyst i3 filtered out, washed ~ith ethyl alco-10 hol, the ~olvent is distilled off and the residue i9recry~tallized from hexane. The derivative XI~ a i9 isolatedo ~C-N ~ 42-6 C; q~l-N ~ 29-2 C-~ ound, %: C 82.19; N 9.91. C26H37N0.Calculated, %: C 82.27; X 9.83, E~:ample 68 .. . .
Preparation of 2-~2-(4-alkyl- or alko~yphenyl) ;~-e~nyl]-6-alkyl-5,6,7,8-tetrahydroquinoline XX.
prep~ration o~ 2-~2-(4-buto~yphenyl)ethynyl -6- ;
-pe~thyl-5,6,7,8-tetrahydroquinoline X~ a.
.. . .................... . .... . ............... . .: , .. :
0.03 mole of 2-(4-butogystyrene)-6-pentyl-5,6,7, 8-tetrahydroquinoline is dissolved in 21 ml of glaci-al acetic acid and a 90lution o~ 0.03 mole of Br2 in `~
3 ml o~ aceti¢ acid i~ added dropwise. ~he mix~ure i~ boiled for 40 mn, cooled down and poured into 100 ml of water. The mixture is e~tracted with ben- ;-.. . . . _ . .......... . . .. . -,:,. ~ .
zene and chromatographed from the starting substance ~t 20~6~37 ..
on A1203 of the second clegree of activity (eluent ~-~l he~ane : benzene = 2:1). The solvent i~ distilled of~ -and the residue of unpurified c~ ~ or ~ -bromosubsti-tuted?-5,6,7,8 tetrahydroquin~line is placed into an alcohol 901ution of ~OH (0.03 mole of KOH in 25 ml of alcohol) and the reaction mixture i9 boiled for 2 hrsO
The mixture i~ diluted with water, extracted with ben-zene, the benzene extract i~ filtered through S102, L 5/40 (h - 3 cm), boiled o~f and recry9tallized from alcohol until a constant melting point i~ reached.
The compound ~g a is isolated with a yield of 11 ~.
Tc_N ~ 110.5 C; TN I = 124 C, Found9 %: C 83.21; H 8~70. C26H33NO.
Calculated, %: C 83.15; H 8.86.

Example 69 Preparation of 5-al~yl-2-[4-(4-alkyl-3-methyl-cyclohe~yl) phenyl]pyridine ~
5-Propyl-2-[444~entyl-3-methylcyclohexyl)phenyl]--pyridine ~X a~ .,. . .
0.03 mole of 1-acryloyl-4-~pe~tyl-3-methylcyclo-h~xyl)benzene is mi~ed with 0~03 mole of 1-(~ -pro-pylethylenyl) piperidine in 10 ml of absolute ethanol at a temperature of O - 10 C, and the mixture is stirred ~or 2 hrs at room temperature. 90 ml of ethyl alcohol~ 0.09 mole of hydroxylamine hydrochloride 9 10 ml of water and 5 ml of concentrated hydrochl~ric -- 80 _ `
J
~cid are added to the mi~ture, which is then boiled for 8 hr~ 2~3 of the ~olvent are di~tilled of~, 150 ml of water are added to the re~idue and the mixture is leached to pH~ 8 with an aqueous solution o~ caustic soda. ~he iso]ated product i9 extracted with benzene, the benzen~ layer is washed with water, dried over Na2S04 and is filtered through SiO2 9 L 5/40 (h = 3 cm). The solvent is distilled off. The - residue is recrystalli3ed from acetone and he~ane.
Other compound9 XXI (b-c) are prepared in a simi-lar way.
The phase transition temperaturea o~ the com~
,. . ............................................... ..
pounds XXI (a-e) are shown in Table ~8.
Table 19 shows the composition and properties of tiquid-cry~tal materi&ls comprising no~el com-pounds of formula /X2I/.
~ he u~e of the compound~ of formula /X~I/ as components of liquid~crystal materials gives the latter low bottom limits o~ the nematic phase inter~
val, which is necessary for using the~e materiQls in . ~
outdoor electric optical devices, ' `,',~ ' ,~':

- 8? ~

,L,6~t^~, ~D~DNa~~D
N Nt-- O C--o~ Q) ~ O OO~Oa~
~ _, Q~ . ~
O ~ 0~N t-- :
-! r-l V C) ' u~

E~ ~
::
r; t--C~ ~Lf~ L~
C ~ ~ ~ ~ ~ `~
:~ 4 ~ O N N N N N
¢ q~ C~

N ~ 0 0 Cr~
. .. , . . '.
O O O~ O ~

~:1 ~ Dr~ N
~ CJ~ t- 0 O~
O L~
~ ~ 0 0 c~ 0 a: ' a~ 0 o~D ~ O
rr ~ N ~~ d-~ ~ ': .. ' .. ~ N
H ~ o U~
~iO~ ~ 0 .
~ ~;
., . ~ ~o~ O , .~ ..
z; U~ Ir~ ~ N d-V C~ V ~ ~
~ . .o _ Ir~t'~ ~ L~ . U~
~ V C~ V V V
,, ., ~ ~U~ U~ $ I
~X X V N
. (~U~N N a ~

V C~V V N V

. ~
. ~ H ~ ~ 0 V ~
.

-- 82 ~ -.

i.~; .i . ~ i ,.~ . ... . .

. ,.,1 ~ 2~fà037 . T a b 1 e 19 :.
.
. . . _ . .
. No, Composition wt . ~ Nemat ic phase , i n t e rt~a l, ,. _ . . . _ _ C3X7~V~;~CN 20 _25~56.3 C 5~ CN ~:

C 4H9- 0--CO O ~ OC. !l; 2 5 . .

C6~13~O-COO~OC~5 1 5 ; ~

3H7 ~\j/~C~ H; 10 ~ .

~ .~``'"
:
~".`~

~ ' - 83~

;~()06~37 , --Example 71 Preparation of 2-[4-(4-alkyl- 3-methylcyclohe~yl) phenyl]-5-(trans-4-alkylcyclohe~yl)pyridines ~
Preparation of 2-[4-(4-pentyl-3-methylcyclohe~yl) phenyl]-5-(tran~-4-ethylcyclohexyl)pyridine ~II a~
This compound is prepared similarly to ~2I
(Example 70) by reacting 1-acryloyl-4-(4-pentyl-3--methylcyclohe~yl)benzene with 1[~-(trans-4-ethylcyc- ;
lohexyl~ethylenyl] piperidine, followed by treatment of 3-(trans-4-ethylcyclohe~yl)-6-[4-(4-pentyl-3-methyl-cyclohexyl)phenyl]~3,4-dihydro-2-N- piperidine-2H--pyrane with an ethanol solution o~ hydro~ylamine hydrochloride.
The phase transition temperatures of the c.om-pounds XXII (a-c) are given in ~able 20.
1'able 21 shows the composition and properties o~ the liquid-crystal materials comprising the novel compound~ of formula /~XII/.
The use of the compounds of formula /.Y~ s ; 20 component~ of liquid-crystal materials gives the latter low bottom limits of the nematic phase inter~
'~ val, which i3 necessary for using these material3 in outdoor electric optical devices.

,::A~-";, ": ,, ~,, , ::, ,:.,, . "- . ,; ,;, . , ", ~006~
~ . ~
o ~ ~ o o o ~ ~

N ~ 1~ 11`\ t-r-l . C~
~I ~ C~ ~ ~ 0 ,C~ . ~ ' ~ x`l X-t x~
¢ ~ ~ V ;' ~' . a~
I T ~ X O O O
~ ~ ~,,.r~\ ~;t :"
~ h C~ ! 0 0 a) ~ ~^ I "''`-''' ~ ~ t- O (~
~J ~ '`~;
~ l 0 ~ E~aOv N
i~: ~Z;
~U~ C\ ~ t~

~ O ~ ~

~. C ~ C) C \ ;

C~
O
~ H
v'~qq , ,' :. .

- 85 - :

:` ~o()~o~
~'~I ......

~ T a b l e 21 . .
i~oO Co~position wt, ~ ~ematic -.
pr.~e int e r~ral, 3 7 O ~ CN 20 -25~79.3 C~H3- 0 ~ _~ 16 5H11 O ~ ~ 22 -i ~ -C~j 7 ~5~ G~ ~c, H~ 25 5 1 1 ,0~3(~/} C~ ~5 . 10 C 11,~, :
~2ample 73 2-~4-t'~rans~4-slkylcyclohexyl)phenyll-5-~lkeny'pyri-dines X~III, 2-[4-(Trans-4-heptylcyclohe~yl)pheny~-5-(but-3-e~pyridine.
.. A solution of 0.08 mole of 4-(trans-4-heptylcyclohe~yl) bromobenzene in 30 ml of benzene i~ added drop~ise in an argon stream to 0.08 mole o~ 15% ~olution of butyl lithium in hex~ne and stirred for 2 to 3 hours. ~he precipitate is filtered off and dissolved in 103 ml of diethyl ether. o.o6 mole o~ pyridine is added drop~Nise to the above solution Qt 0C and the reQction mass is ~tirred at room temperature for - 86 _ : ~-,, , . - .
:.... . . .
i''.. ; ' ' ' " . ' , : . ~

ZO ~ 6 03 ;

3 hours~ ~hen the mixture is cooled to -5C and a solution of 0.06 mole of 1-bromobutene-3 in 100 ml .
~ he reaction mas~ is ,stirred for 2 hours at 5 room temperature, 300 ml of water is decomposed.
~he organic layer is isolated, ~iltered through SiO2 ~ 5/40 (h = 3 cm), the solvent is removed and the residue iæ recrystallized from acetone. ~`
The compound XXIII a is isolated.
IO The analogs of XXIII are prepared in a similar way. ~he phase tra,nsition temperaturs for XXIII
a are given in ~able 22. ;; ~' Example 74 Preparation of 2-(4-alkyl- or alko~yphenyl)-I5 5-alkenyl pyridineæ XXIV. ,~ ' 5-~Prop-2-eno)2-(~-pe~tylphenyl) pyridine. ~' 'rhiæ compound i~ prepared similarly to XXIII
by reacting 4-pentylphenyllithium with pyridine 9 ~`- "
followed by treatment wi-th 1-bromopr~pene-2. ; ', ~1ound, 'i~o: C 86.06; H 8.87. C19H23N.
Calculated, ~0: C 85,99; H 8.74.
' 'I 5-tbut-3-eno)-2-(4-decyloxy-3-fluorophenyl) '~,~
pyridine is prepared i~ a similar wa~.
~C-N = 40OC; -~N-I = 42OCo ;

- 87 ~

j ";~ " ~ ~ ~ " ,~ ~ ! , ,, . , . , ~ , . ~ , ~0(3~ 3 . , I
U~ ~ ~ '~ O ~
'I:i a) . ~ o o~ o :~ a~ ~i .~'. . ~1 ~ ~ ~~ ~ N
... 1:o~6 c~ ~ ~ ~ N
. ~ r-l ~ o o ~'~ ~ . , ~ ~D~D ~ \D ~D
E~ ~ V 0 ~00 C~ 0 0 0 . . ~
.
r-l O~
, O :~ ~J ~1 ~ ~ (~ ~, ~
5~ ~ ~ X ~ ~ ~ ~: X
, ~ ~ ~ u~ e- a~ ~ CO
_ Pt O ~ ~ N (~.i Ix~l ~ a~ o ~ C~ O
_ ~ X cr~ ~ ' ~ ~ . .
~ .~
~ ~ ~ 0 + ~ r~
s~ O ~
~U ~ V 0 0 0 0 0 0 0 ' .~ ~ ~ D N ~ --! 1_~
. ~ ~ ~D ~D ~ ~ ~D
E~ o ~ ~ ~,_ ~ ,_ ,_ [~ ~; 0.~\ 0. + CO
~ l O t~ ~ ~ ~
~ ~1~ O~) 0 0 ~ 0 ~ C-.~ ., 'I ~ ~q ~ ~ 0 N V V O 0 t-- 0 ~ 0 0 . _ ~ o ~ . ~ N

~) .IC~J
~, ., i:r , ~_ +
1 ~ . ~
1~ ~ ~ x~ x ~ ~ v vc~
:: . ~ ~ ~ N
~d H
. ~3 ' O O P':

.. J."; .'. ' '!.

,:' " -." ` : , ' . .; ' :

-~ ;20~)6~ 7 `
~`
~ Example 75 ~
: , Preparation of 5-alkyl-2-(4-alkenylphenyl)pyri-dines XXV.

75.l. 2-(4-Vinylphenyl)-5-pentylpyridine XXV a.
¦ 5 10 mmole of 2-(4-iodophenyl)-5-pentylpyridine, 0.1 mole o~ PdCl2(PPh3)2 dissolved in 5 ml of tetrahydroquinoline are placed i~ an argon stream into a ~lask provided with a magnatic stirrer, a dropping funnel, and a re~l~x condenser~ ~he funnel I0 is used for dropping a solution of 15 mmole o~
CH2=CH-MgBr in 15 ml o~ tetrahydrofurane. ~he `
mixute is stirred at room temperature for 4 hrs.
The exce~sive Gringnard reagent is decomposed with methanol and e~tracted with ether. ~he ether I5 solution is dried with MgS04, ~iltered through Al203 (f = 3 cm) and the solvent is distilled off.
~he final compound is isolated by recrystallization from ethanol.
~C S = 60C; ~S I = 54.7C (yield 38~/o).

- .
~ound, ~0: C 86022: H 8.39. Cl8H2lN.
Calculated, 70: C 86.01; H 8.42.

- 89 - -~

'" ' :' ' 20~

,!

In a ~imilar way, with a yield of 40 %, there i9 prepared 5-pentyl-2-(4-pent-4-en)phenyl pyridine, S-I = 17 C0 Found, %: C 86.12; H 9.19 C21H27N.
Calculated, %: C 85.95; ~ 9.27.

E~ample 76 Preparation of 5-~en~1-2-L4-~Xenylphenyl)] pyri-dine XXVI.
The flask equipped with a magnetic stirrer9 a dropping funnel and a reflux condenser is filled in an argon stream with 10 mmole of 2-(~-iodophenyl)-5--(prop-2-en) pyridine (~C S = 62 C; TS I = 85.1 C) and 0.1 mmole of PdCl2(PPh3)2 in 5 ml of tetrahydro-~uran . . 15 mmole of CH~=CH-C~2MgBr in 15 ml of tetrahydrofura~ i~ gradually added dropwise to the reaction mi~ture. ~he decompo3ition and i~olation of the final compound are effected similarly to the preparation of XX~.
Found, %: C 86.90; ~ 7 19. C~7~17N.
Calculated, %: C 86.77; ~ 7.82.

E~ample 77 Preparation of 2-t4-fluorophenyl)-5-alkenyl py-ridines XXVII.
.. . .. . . .. ..
77.1. 2-(4-Fluorophenyl)-5-(prop-2-en) pyri-dine.

_ 90 --~ Z~06~37 This compound i~ prepared similarly to XXIII.
Tc = 17 C.
~ ound, %: C 78.96; H 5~60. C14H12FN.
C~lculated, ~o: C 78.85; H 5.67.
77.2. 2-(4-~luorophenyl)-5-(but-3-en) pyridine is prepared in a similar way. Tc = 18 C (~rom alcohol), ~ ound, ~0: C 79.38; H 6.31. C15~14FN.
Calculated, %: C 79.27; H 6.21.
. . .
Example 78 Preparation ol 2-(4-ethynylphenyl)-5 alkylpyrl-dine XXVIII a.
! A flask provided with a reflux condenser i~
filled with a mixture of 10 mmole of 2-(4-iodophenyl)~
15 -5-pentylpyridine, 30 ml of chloroform, 20 mm~le of Et3N, 0.1 mmole of CuI, 0.1 mmole of PdC12(PPh3)2s 15 mmole of CH--CC5H11, which is b~iled for ~ hrs. ' !
Then the mi~ture is filtered and diluted with water;
the organic layer of Na2S04 is dried and boiled down.
~he residue i~ recrystallized from alcohol. The com-pound X~VIII a is i olated with a yield of 40 %. -TC-S = 35 C, Ts_I = 44.6 C.
~ound, %: C 86.60; H 9.01. C23H29N.
Calculated, %: C 86.47; H 9.15.
In a ~imilar way, there i9 prepared 2-[(4-hept--1-unyl~ph~nyl]-5-heptylpyridine X~VIII b.

_ g1 ~
~' ;~ 6~)37 . ~

TC S = ~7 C; ~S I 3 66.5 C (from ~lcohol).
Found, %: C 86.55; H 9.41. C25H33N.
Calculated, %: C 86.40; H 9.57.

E~ample 79 Preparation o~ 1-(5 alkylpyrid-2-yl)-2-(4-alkyl-or alkoxyphenyl)-acetylene /XXIX/.
1-(5-pentylpyrid-2-yl)-2-(4-butoxyphenyl)acety-le~e XXIX a.
79.1. 1-(5-bromopyrid-2-yl)-2-(4~butoxyphenyl) acetylene.
This compound i~ prepared similarly to XXVIII a by reacting ?-iodo-5-bromopyridine with 1-ethynyl-4--butoxybenzene in the presence of Et3N~ CùI, PdCl2(PPh3)2 With 50 ~ yield.
1-(Bromopyrid-2-yl)-2~(pentylphenyl)acetylene is prep~red in ~ ~imil~r manner.
Tc a 103 C (from alcohol); 1-(5-bromopyrid-2--yl)-2-~4-propylphenyl)acetylene; ~c = 102 - 104 C
(from alcohol).
79.2~ 1-(5-pentylpyrid-2-yl)-2-(4-butoxyphenyl) acetylene /XXIX a/.
The compound i~ obt~ined by reacting 1-(5-bromo-pyrid-2-yl)-2-(4-buto2yphenyl)acetylene with C5H11MgBr in tetrahydrofur2n with ~ yield of 20 %.
TC-N = 75 C; ~N-I = 78 C, Z~6~3 ' Found9 %: C 82,36; H 8.49. C22H27N0 Calculated, ~0: C 82.20; H 8.47.
1-(5-Heptylpyrid-2--yl)-2-(4-ethoxyphenyl) acety-lene ~ i3 prepared in a similar Isnner.
~c~ 84-5 C; 9~1~ N = 76.5 C.
~ound, ~0: C 82.30; H 8.44. C22H27N0.
Calculated, ~0: C 82.20; H 8,47. ; -1-(5-Propylpyrid-2-yl)-2-(4~*~xyphenyl)~cetylene X2IX c.
~C = 101 C; ~ N ~ 89 C (from alcohol). ~ ;
Found, %: C 81 .34; H 8,44, C1 8H1gN0.
Calculated, ~0: C 81.48; H 8,47.
1-(5-Pentylpyrid-2-yl)-2-(4-methoxyphenyl)acety-lene ~IX d ~ith ~c = 51,5 C; TI_N = 50 C.
Found, 5~0: C 81,60; ~ 7,88, C1CgH21NC~
Calculated, %: a 81.68; H 7.58.
1-/5-Trans-(4-ethylcyclohe~cyl) pyrid-2-yl/-2-(4--buto~cyphenyl) acetylene XgIX e ~7ith G N = 130 C;
TN I = 207 C .
Found~ %: C 82,91; H 8,52, C25H31N0.
Calculated, ~0: C 83.06; H 8.64.
. .
Example 80 Preparation of 2,5-bis(4-R-phenylethynyl)pyri-dine~ XXX.
2,5-biq-(4~Propylphenylethynyl)pyridine XX~3 a.
~his compound i~ prepared ~imilarly to XXI~ by ~ )O~ 3~7 ,~

reacting 2,5-dibromopyridine with HC ~ C ~ (O)kCnH2n+1 in the pre~ence of CuI
and PdCl2(PPh3)2 with a 40 % yield. TC S = 139 C;
S N = 144 C; ~N I = 237 C (from acetone).
Found, %: C 89.34; H 7.02, C27H25N.
Calculated, ~: C 89.21; H 6.93.

i E~ample 81 Preparation of 1-(5 cyanopyrid-2-yl)-2-(~-alkyl-or alko~yphenyl) acetylene X~
1-(5-Cyanopyrid-2-yl)-2-(4-alkyl- or alko~yphenyl) acetylene XXXI.
81,l. 1-(5-Cyanopyrid-2-yl)-2-(4-amylphenyl)--acetylene XXXI a.
A mixture of 0.01 mole of 1-~5-bromopyrid-2-yl)--2-(4-amylphenyl) acetylene, 0.011 mole of CUCN, 15 ml of N-methylpyrolydone were heated with boiling until the initial substance disappears. ~he decompo-sition and isolation are èffected 3imilarly to XIII.
~C N ~ 95 C; TN I ~ 101 C.
Found? ~t C 83.16; .I 6.75. C19H18N2.
Calcul~ed, %: C 83.18; H 6.61.

E~ample 82 ~-.. , , , ... , :
Preparation of 2-(4-alko~y-2-hydroxyphenyl)-5--alkylpyridine~ XXXII.
2-(4-Nonyloxy-2-hydro~yphenyl)-5-nonylp~ridine ~ 94 ~

~0~36~3'~7 X~XII a.
0.01 mole of 1-acryioyl-2,4-dinonylo~ybenzene i3 mi~ed at 0 C with 0.1 mole of 1-(~ -nonylethylenyl/
piperidine snd the mixture is kept for 4 hrs, 'I'he reaction mi~ture i9 diluted with 100 ml of ethyl alcohol, 10 ml of water, and 0.03 mole of hydro-xylamine hydrochloride is added to the reaction mixture and the latter is boiled ~or 8 hrs. 2/3 of volume of the solvent is distilled off, the residue is diluted with 100 ml of water, leached to pH 8 and e~tracted with benzene, 'I~he benzene fsolution i9 filtered thrcfugh a layer of SiO2, Tf 5/40 (h - 3 cm~, 0.005 mole of AlCl3 iæ
added and kept for 24 hrs. The reaction mass is pour-d into icy water, the organic layer is icolated,washed with water, 10 % solution of sof~ium bicarbo-.. . ................ . . ...................... . .
nate, with water, dried over Na2S04, and the solvent is filtered and diqtilled off. The residue i9 rfeCryS-tallized from alcohol. Ihe final compound is isolat-ed with 15 % yield. TC ~A = 44 C; TSA I = 104 C. -~
F'ound, %: C 79.18; H 10,22. C22H45N02.
Calculated7 %: C 79.22; H 10.32.
I~ a ~imilar fffvay, there is prepared 2-(4-buto~y--2-hydroxyphenyl)-5-heptylpyridine ~XII b with ~C-SA ~ 53 C; ~`SA-I = 100 C.
Found, ~O C 7?.41; H 9-30- C22H31N2a Calculated, %:C 77. 38; H 9a10.
- '35 -~. `

In a similar way, there i9 prepared 2-(4-hexyl-oxy-2-hydro~yphenyl)-5-hsptylpyridine ~g,~II e with i!~
~C-SA = 46 C 9 TSA I = 9~ C
Foun~,' %: C 78.25; H 9~43D C24H35N0 Calculated, ~: C 78.00; ~ 9.55.
"~
Example 83 Preparation of 2-(4-alkyl-2-hydroxyphenyl)-5--alkylpyridine~ ~XXIII.
2-(4-Methyl-2~hydroxyphenyl)-5-pentylpyridine X~XIII a.
. ~his compound i~ prepared sim1larly to E~ample 82 by reacting 1-t~ -pentylethylenyl)piperidine with 1-acroyl-2-metho~y-4-methylbenzene, ~ollowed by con-de~ation with hydro~ylamine hydrochloride ~nd de-alkylation o~ the methoxy group in the 2-(4-methyl-. . . . .. ~.. .. .
-2-m~thoxyphenyl)-5-pentylpyridine obtained, ~c ~ 67.4 C (from alcohol)~ :
F.ound~ C 79.76; H 8.35. C17H2~NO.
Calcul~ted, %: -C 79.96; H 8.29~ ~

Example 84 ~ .
Preparation of 2 (4-a1kyl- or alko~y-2-hydro~y- ~;
phenyl)-5-(tran~-4-alkylcyclohe~yl?pyridine XX~IV.
2-(4-Etho~y-2-hydro~yphenyl)-5-(tranq-4-butyl-cyclohe:cyl)pyridine X~IV a.
Th:L~ com~ound i~ prepared similarly to XX~

: ~ ~

~.

~`
21)~)Ei0~'7 ;.

by reacting 1~akryloyl-2,4-diethoxybenzene with 1- [~ (tran~-4 alkylcyclohe~syl)ethylenylJ piperidine, TC S ~ 119 ~C; TS~ 219 C; TN_I 3 231 ~C (from slCohol).
Found, %: C 78.22; H 8.70. C23H31~02.
Calculated, % C 78.15; H 8.83.
, . . .
2-(4-Methyl-2-hydro~yphenyl)~5-(tra~s-4~ethyl-cyclohexyljpyridine ~IV b is prepared in a qimilar manner. q`C S ~ 125,6C; TS N n 145 C; I~ 183,1 C
(from alcohol).
Found, %: C 80.32; H 9.88. C20H29N0o Calculate d, %: C 80.21; H 9.76.

E2ample 85 Preparation o~ 2-(4-bromo-2-hydroxyphenyl)-5 15 -alkylpyridine~
2-(4-Bromo-2-hydro~yphenyl)-5_heptylpyridine~
~X~V a.
~ hi~ compound is prepared ~imilarly to XXgII by reacting 1~ heptylethylenyl)piperidine and 20 1-akryloyl-4-bromo-2-metho~ybenzene. ~C S - 66 C;
3 I Y ?~ c. . -Found, ~0: C 61.95; H 6.42 . C1 8H22BrN0.
Calculated, %: C 62.07; H 6.37.

2-(4-Fluoro- or iodo-2-hydro:l~yphenyl)-5-alkyl-.
25 pyridines can be prepared in the same way.
- 9'1 _ ' 20~6Q3~

~!
;~
E~ample 86 ~, Preparation of 2-(4 cyano-2-hydro~yphenyl);5-alkylpyridine~ XX~VIo 2-(4-Cyano-2-hydro~yphenyl)-5-alkylpyridlne~
XX~VI ~.
. .
Thi3 compound is prepared 3imilarly to XVII by re~cting 2 t4-bromo-2-hydro~yphenyl)-5-heptylpyridine with Cu~N in N-methylpyrrolidoneO ~c ~ 83 C (~rom alcohol), -~
Found, %: C 77.35; H 7.65. C19H22N20.
Calculated, ~: C 77.52; H 7.53.

Example 87 Prepar~tion of 1- [5-(trans-4-alkylcyclohexyl)-A -pyrid-2-yl ~-2~(4-a1kyl- or alcoxyphenyl)ethane 15 X~VII.
t-[5-(Tr~ns-4-ethylcyclohy~yl)-pyrid-2-yl]-2 -butoxyphenyl)ethane.
8? . t. 1--~5-(Tran~-4-ethylcyclohe~yl)-pyrid-2- ;
~yl]-2-(4-butoxyphenyl)ethylene.
A mi~ture of 0.1 mole of 2-methyl-~_(4-ethylcyc-lohe~yl)pyridine9 50 ml of acetic anhydride ~nd Q.12 mole of 4-buto~ybenzaldehyde i9 boiled ~r . . .. .. .. . . .... _ . .. .....
48 hrs, ~he acetic anhydride i~ dlstilled off, The re-sidue i~ diluted with 250 ml of water, leached to pH 8 and extrscted with benzene. The benzene e~tr~ct i~ filtered through SiO2, L 5/40 (h _ 3 cm) and boll~ -- Z00603~
~, ~' . :.
~ ed o~f. The residue i~ recrystallized fram acetone.
h - -A Pinal product i9 i~olated ~with a yield of 25 %.
C S = 90 C; TS_N - 114 C; TN_I 3 1~ [5-(Trans-4-butylcyclohexyl )-pyrid-2-yl]_2-(4-, , ~ .. . .
5 -butoxyphenyl )ethylene with TC S = 78 C; ~S N a - 171 C, TN I ~ 243 C is prep~red in a similar way.
87.2. 1-[5-(Tran~-4-ethylcyclohexyl)-pyrid-2--yl~-2-~4-butoxyphenyl)ethane XXXVII a.
0.01 mole of compound 8?.1 in 50 ml of ethyl alcohol is hydroge~ated at hydrogen pre3sure of 10 atm and a temperature of 30 C till complete ab-~orbtion of the hydrogen. The mixture is ~iltered and the filtrate is boiled o~f~ The re~idue i~ recrys-tallized ~rom alcohol, XX~VII a is isolated with a yield of 60 ~0 with TC-s ~ 4~ C; TS-N ~ 61 C;
TN_I ~ 93 C0 Found, %: C 82.26; H 9.58. C25H35N0.
Calculated, %- C 82.14, H 9.65.
(Tran~-4-butylcyclohe~yl)-pyrid-2-yl~-2--(4-but~yphenyl) ethane ~XXVII b i~ prepared in a similar way. Tc_S = 41C; ~S-I = 119C (XXX~II b).
'Found, ~: C 82.51; H 9.97. C27H39NOo Calculated, ~: C 82.39; H 9,98.

~9 ~C) E)6~)37 E~ample 88 1-[5-(Tra~-4-alkylcyclohe~yl)-pyrid-2_yl]_2 rans-4-slkylcyclohe~yl)phenyl]sthane XXXVIII.
1-[5-(Tran~q-4-ethylc:yclohe~yl)-pyrid-2-yi~-2-[4-~tran~q-4-propylcyclohe~yl)phenyl]ethane XX~VIII.
88.1. 1~[5-(Trans-4 ethylcyclohexyl)-pyrid_2_ -Yl -2-[4-~ra~s-4-propylcyclohe~yl)phenyl]athyle~e~
A mi~ture of 0.1 mole o~ 2~methyl-5_(4_ethylcyc-lohexyl)pyridine, 0.1 mole o~ 4-(4-propylcyclohe~yl) benz~ldehyde and 50 ml of scetic aldehyde is boiled for 30 hr~. ~he acetic aldehyde i9 di3tilled off in vacuum. The residue i3 leached and extracted with benzene. The solvent i~q distilled off and the residue i9 recrystallized fro.n acetone. Compound 88.1 i~q iqo- `;
lated with ~ yield of 25 % and a melting point of 250 C.
~ ound, %: C 86.71; H 10.07. C30H41N.
Calculated, %: C 86.68; H 9.94.
88.2, 1-[5-(Tranq-4-ethylcyclohexyl)-pyrid-2--yl]-2-L4-~ran3-4-propylcyclohe~yl)phenyl ethane , ~XXVIII.
Thi~ compound i3 prepared similarly to 87 .? by ` `
hydrogenating an ethylene derivstire. TC-N ~ 140 C;
TN_I ~ 196 C.
Found, ~: C 86.31; H 10.27. C30H43N.
Calculated, %: ~ 86.27; H 10.38. ~ -- 1 00 ~

Z006(~7 . .

~cample 89 r 2-{4-l 2-(~rans-4-propylcyclohe~cyl)ethyl]phenyl} -5--(trans-4- ethylcyclohexy:L)pyridine ~IX a.
~his compound is prepared imilarly to Example 70 by reacting 1 [-~ (tran3-4-ethylcyclohe2yl)ethylen-yl piperidine and respective vinyl ketone, followed by cylization with hydroxylamine hydro&hloride.
TC-S = 9 g C; Ts_N = 161 C; TN I 3 262 C
Found, %: C 86,51; H 10024. C30H43N.
Calculated, ~0: C 86.27; H 10.38.
.
2-{41 2-(~rans-4-propylcyclohe~:yl)ethyl] phenyl} - 5 --(tr~ns-4-butylcyclohexyl)pyridine .~ b was prepared in a similar way, TC S ~ 74 C;
S-N ~ 212 C; TN I ' 268 C
t5 Found, %: C 86.40; H 10.45. C32H47N.
Calculated, %: C 86.23; H 10.63.

Ef~icienoy of the Invention ~he liquid-crystal material ba~ed on novel li-quid-cry3tal derivative3 of nitrogen-cont~ining heterocyclic 3ystems having a high value of the clari-fication temperature, a wide nematic pha3e interval .
can be used in a wide range of operating temperatures.

Claims (21)

1. Liquid-crystal derivatives of nitrogen-con-taining heterocyclic systems of the general formula R1-A1-Z-A2-R2, wherein X1 and R2 are jointly or inde-pendently -CnH2n+1, -CmH2m+1, CnH2n+1O-, CmH2m+1O?
CH2=CH(CH2)k-, -CN, -N=C=S, -Hal, at k = 0-3, l = 0-2, m.n. = 1-15;
Z is -CH2-CH2-, -CH=CH-, -C?C-, or a single bond, when A1 is , ;
A2 is , , , ;
when A2 is , , ;
A1 is , , ;
R is -CH3, -CN, -Cl, -F at l = 0-2 as a component for a liquid-crystal material.
2. A liquid-crystal material according to Claim 1, which comprises said compound of formula ;
3. A liquid-crystal material according to Claim 1, which comprises said compound of formula
4. A liquid-crystal material according to Claim 1, which comprises said compound of formula
5. A liquid-crystal material according to Claim 1, which comprises said compound of formula
6. A liquid-crystal material according to Claim 1, which comprises said compound of formula
7. A liquid-crystal material according to Claim 1, which comprises said compound of formula
8. A liquid-crystal material according to Claim 1, which comprises said compound of formula
9. A liquid-crystal material according to Claim 1, which comprises said compound of formula
10. A liquid-crystal material according to Claim 1, which comprises said compound of formula
11. A liquid-crystal material according to Claim 1, which comprises said compound of formula
12. A liquid-crystal material according to Claim 1, which comprises said compound of formula
13. A liquid-crystal material according to Claim 1, which comprises said compound of formula
14. A liquid-crystal material according to Claim 1, which comprises said compound of formula
15. A liquid-crystal material according to Claim 1, which comprises said compound of formula
16. A liquid-crystal material according to Claim 1, which comprises said compound of formula
17. A liquid-crystal material according to Claim 1, which comprises said compound of formula
18. A liquid-crystal material according to Claim 1, which comprises said compound of formula
19. A liquid-crystal material according to Claim 1, which comprises said compound of formula
20. A liquid-crystal material according to Claim 1, which comprises said compound of formula
21. A liquid-crystal material according to Claim 1, which comprises said compound of formula 2?. A liquid-crystal material according to Claim 1, which comprises said compound of formula 23. A liquid-crystal material according to Claim 1, which comprises said compound of formula 24. A liquid-crystal material according to Claim 1, which comprises said compound of formula 25. A liquid-crystal material according to Claim 1, which comprises said compound of formula 26. A liquid-crystal material according to Claim 1, which comprises said compound of formula 27. A liquid-crystal material according to Claim 1, which comprises said compound of formula 28. A liquid-crystal material according to Claim 1, which comprises said compound of formula 29. A liquid-crystal material according to Claim 1, which comprises said compound of formula 30. A liquid-crystal material according to Claim 1, which comprises said compound of formula 31. A liquid-crystal material according to Claim 1, which comprises said compound of formula 32. A liquid-crystal material according to Claim 1, which comprises said compound of formula 33. A liquid-crystal material according to Claim 1, which comprises said compound of formula 34. A liquid-crystal material according to Claim 1, which comprises said compound of formula 35. A liquid-crystal material according to Claim 1, which comprises said compound of formula 36. A liquid-crystal material according to Claim 1, which comprises said compound of formula 37. A liquid-crystal material according to Claim 1, which comprises said compound of formula 38. A liquid-crystal material according to Claim 1, which comprises said compound of formula 39. A liquid-crystal material according to Claim 1, which comprises said compound of formula 40. A liquid-crystal material according to Claim 1, which comprises said compound of formula 41. A liquid-crystal material according to Claim 1, which comprises said compound of formula 42. A liquid-crystal material according to Claim 1, which comprises said compound of formula 43. A liquid-crystal material according to Claim 1, which comprises said compound of formula 44. A liquid-crystal material according to Claim 1, which comprises said compound of formula 45. A liquid-crystal material according to Claim 1, which comprises said compound of formula 46. A liquid-crystal material according to Claim 1, which comprises said compound of formula 47. A liquid-crystal material according to Claim 1, which comprises said compound of formula 48. A liquid-crystal material according to Claim 1, which comprises said compound of formula 49. A liquid-crystal material according to Claim 1, which comprises said compound of formula 50. A liquid-crystal material according to Claim 1, which comprises said compound of formula 51. A liquid-crystal material according to Claim 1, which comprises said compound of formula 52. A liquid-crystal material seconding to Claim 1, which comprises said compound of formula 53. A liquid-crystal material according to Claim 1, which comprises said compound of formula 54. A liquid-crystal material according to Claim 1, which comprises said compound of formula 55. A liquid-crystal material according to Claim 1, which comprises said compound of formula 56. A liquid-crystal material according to Claim 1, which comprises said compound of formula 57. A liquid-crystal material according to Claim 1, which comprises said compound of formula 58. A liquid-crystal material according to claim 1, which comprises said compound of formula 59. A liquid-crystal material according to Claim 1, in which the content of said liquid-crystal deri-vative of the nitrogen-containing heterocyclic system is 1 to 50 wt. %.
CA 2006037 1988-12-19 1989-12-19 Liquid-crystal derivatives of nitogen-containing heterocyclic system as components of a liquid-crystal material and a liquid-crystal material Abandoned CA2006037A1 (en)

Applications Claiming Priority (12)

Application Number Priority Date Filing Date Title
SU4617047 1988-12-19
SU4617051 1988-12-19
SU884617049A RU1781214C (en) 1988-12-19 1988-12-19 2-[4-(4-trans-alkyl-3-methylcyclohexyl)-phenyl] 5-(4-trans-alkylcyclohexyl) pyridines as the components of a liquid-crystal material, and liquid-crystal material for electrolytic devices
SU4617047 1988-12-19
SU884617051A RU1775399C (en) 1988-12-19 1988-12-19 Heterocyclic compounds containing oxy-group as components of liquid-crystalline material, and liquid-crystalline material for electrooptical apparatuses
SU4617050 1988-12-19
SU4617052 1988-12-19
SU884617052A SU1749219A1 (en) 1988-12-19 1988-12-19 Pyridine derivatives as components of liquid-crystalline material for electric-optic devices
SU4617049 1988-12-19
SU884617050A SU1754714A1 (en) 1988-12-19 1988-12-19 5-(4-trans-alkylcyclohexyl)pyridine derivatives as liquid crystal material components and liquid crystal material for device in electric optics
SU884617054A SU1749218A1 (en) 1988-12-19 1988-12-19 2-[4-(4-trans-alkyl-3-methylcyclohexyl)-phenyl]-5- alkylpyridines as components of liquid-crystalline material and liquid- crystalline material for electric-optic devices
SU4617054 1988-12-19

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* Cited by examiner, † Cited by third party
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US8202878B2 (en) 2006-11-29 2012-06-19 Abbott Laboratories Inhibitors of diacylglycerol O-acyltransferase type 1 enzyme

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DE69522986T2 (en) * 1994-03-25 2002-04-04 Canon K.K., Tokio/Tokyo Mesomorphic compound, liquid crystal composition containing it, liquid crystal device, apparatus and display device using this composition
GB9412709D0 (en) * 1994-06-29 1994-08-17 Secr Defence Novel chiral cyclohexyl compounds
GB2339779A (en) * 1998-07-17 2000-02-09 Secr Defence 2,6 Quinoline Derivitives
US7465802B2 (en) * 2006-12-13 2008-12-16 Fu Jen Catholic University Facile synthesis of a series of liquid crystalline 2-(4′-alkylphenyl)-5-cyanopyridines

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8202878B2 (en) 2006-11-29 2012-06-19 Abbott Laboratories Inhibitors of diacylglycerol O-acyltransferase type 1 enzyme
US8586594B2 (en) 2006-11-29 2013-11-19 Abbvie Inc. Inhibitors of diacylglycerol O-acyltransferase type 1 enzyme

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