GB2174396A - Cholesterol derivatives - Google Patents

Cholesterol derivatives Download PDF

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Publication number
GB2174396A
GB2174396A GB12237A GB8612237A GB2174396A GB 2174396 A GB2174396 A GB 2174396A GB 12237 A GB12237 A GB 12237A GB 8612237 A GB8612237 A GB 8612237A GB 2174396 A GB2174396 A GB 2174396A
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GB
United Kingdom
Prior art keywords
compound
lower alkyl
methylene
cholesterol derivatives
alkylene chain
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.)
Granted
Application number
GB12237A
Other versions
GB8612237D0 (en
GB2174396B (en
Inventor
Paul Joseph Shannon
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Armstrong World Industries Inc
Original Assignee
Armstrong World Industries Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Armstrong World Industries Inc filed Critical Armstrong World Industries Inc
Publication of GB8612237D0 publication Critical patent/GB8612237D0/en
Publication of GB2174396A publication Critical patent/GB2174396A/en
Application granted granted Critical
Publication of GB2174396B publication Critical patent/GB2174396B/en
Expired legal-status Critical Current

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Classifications

    • 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
    • C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J9/00—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of more than two carbon atoms, e.g. cholane, cholestane, coprostane
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F20/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F20/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • 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
    • C09K19/36—Steroidal liquid crystal compounds
    • 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
    • C09K19/38—Polymers
    • C09K19/3833—Polymers with mesogenic groups in the side chain
    • C09K19/3842—Polyvinyl derivatives
    • C09K19/3852—Poly(meth)acrylate derivatives
    • C09K19/3866—Poly(meth)acrylate derivatives containing steroid groups
    • 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
    • C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
    • C09K2019/0448—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the end chain group being a polymerizable end group, e.g. -Sp-P or acrylate

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Health & Medical Sciences (AREA)
  • Steroid Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Liquid Crystal Substances (AREA)

Abstract

Cholesterol derivatives, useful as intermediates in the manufacture of cholesteric liquid crystalline monomers, are of formula:- <IMAGE> where X1=Br, I, or a sulfonic acid ester, R2=an alkylene chain having from 3-14 methylene or lower alkyl- substituted methylene groups, and y=0 or 1.

Description

1 GB2174396A 1
SPECIFICATION
Cholesterol derivatives The present invention relates to compounds suitable as intermediates in the manufacture of momomeric liquid crystals which are in turn useful to prepare polymeric liquid crystalline materials.
In our co-pending Application No. 83.33323, Serial No. 2133406, from which the present application is divided, there are described and claimed certain photopolymerizable monomers which are useful to prepare polymeric films, among which are monomers having the structure 10 R 1 0 0 C -C-O-R 2-C 0 H Hy where R,= H or CH, R2=alkylene chain having from 3-14 methylene or lower alkyl-substituted methylene groups, and y= 1.
The present invention provides compounds which are useful as intermediates to prepare photopolymerizable monomers, including those of the parent application, said components having 35 the structure 0 Xl-R 2_ ' 11 ' -0-C III Hy where X,=Br, 1 or a suifonic acid ester, R2=an alkylene chain having from 3-14 methylene or lower alkyl-substituted methylene groups, and y=0 or 1.
in this specification, the symbol represents a single bond when y=l and a double bond 60 when y=0.
The cholesterol derivatives which may be used to practice the present invention are cholesterol (where y0) and 5,6-dihydrocholesterol (where y=l). Lower alkyl as used herein means an alkyl group comprising from 1-4 carbon atoms. 1 The compounds of the present invention may be prepared in surprisingly good yield by treating an o)-substituted-alkyl acid halide (1), which preferably is an w-bromoalkyl acid chloride, 65 2 GB2174396A with the appropriate cholesterol derivative (11) to produce the cholesteryl o)-substituted-alkyl ester (111) of the invention. Reaction of this compound with an alkali metal acrylate or methacrylate (N) in the presence of a radical inhibitor and an appropriate catalyst then yields a photopolymerizable acrylate or methacrylate ester (V). This sequence is illustrated by reference to the following 5 general reaction:
H 1 IS 11 X 1-R 2-C-X2 + H II I R 0 1 11 CH 2 =C-C-O-M + III R 1 0 0 1 11 11 CH 2z-C---0-R2-C- Y v 3 GB2174396A 3 5 r 10 0 11 X -R -C..io-c ' a.
1 2 1 i E III Hy In these reactions, R,=H or CH3; R,=an alkylene chain having from 3-14 methylene or lower alkyl substituted methylene groups; y=0 or 1; X,=Br, 1 or a sulfonic acid ester; X2=13r or Cl; M=Na or K. Examples of suitable sulfonic acid esters are CH,S03_; p-CH. 'C^SO,-; C'^SO,-; 25 and p-BrC^S03_. Preferably X, will be Br andX2will be Cl. Further, R2 Will preferably have from 4 to 14 carbon atoms in the alkylene chain.
The following example illustrates the invention.
EXAMPLE
A 0.1 mol quantity of cholesterol or 5,6-dihydrocholesterol, 0.12 mol of pyridine and 0.12 mol of co-bromoalkanoyl chloride is dissolved in 200-300 mi of a suitable solvent such as ethanol-free chloroform or ether/dichloromethane. The mixture is stirred at O'C for 2 hours and at ambient temperature for 16 hours, and is then diluted with 300 mi of solvent. The organic phase is washed with two 200-mi portions of 1N hydrochloric acid and then with water, after 35 which it is dried over magnesium sulphate. Upon concentrating the dried solution, the esters (111) are obtained and purified by recrystallization from a suitable solvent such as 1:1 ether-ethanol.
Representative compounds are illustrated in the following table:
40 45 45 0 Br- (CH H 50 2) n-C 0 Hy Hy 4 GB2174396A 4 Compound n y Yield (%) MP(.q Ilia 10 0 89 99-100 5 Illb 5 0 86 120-121 Ilic 3 0 86 87-90 Illd 3 1 91 92-93 Ille 10 1 87 65-67 10

Claims (4)

  1. CLAIMS 1. A compound of the formula
    0 Xl-R 2-' 11 -01 Hy 1 30 E 1 where X,=Br, 1, or a suffonic acid ester, R2=an alkylene chain having from 3-14 methylene or lower alkyl-substituted methylene groups, and y=0 or 1.
  2. 2. A compound as claimed in claim 1, wherein R2 comprises from 4 to 14 methylene or 35 lower alkyl-substituted methylene groups.
  3. 3. A compound as claimed in claim 1 or claim 2, wherein X,=Br.
  4. 4. A compound as claimed in claim 1 specifically mentioned herein.
    Printed in the United Kingdom for Her Majesty's Stationery Office, Dd 8818935, 1986, 4235.
    Published at The Patent Office, 25 Southampton Buildings, London, WC2A 'I AY, from which copies may be obtained.
GB12237A 1982-12-15 1986-05-20 Cholesterol derivatives Expired GB2174396B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US45008882A 1982-12-15 1982-12-15

Publications (3)

Publication Number Publication Date
GB8612237D0 GB8612237D0 (en) 1986-06-25
GB2174396A true GB2174396A (en) 1986-11-05
GB2174396B GB2174396B (en) 1987-06-03

Family

ID=23786717

Family Applications (2)

Application Number Title Priority Date Filing Date
GB08333323A Expired GB2133406B (en) 1982-12-15 1983-12-14 Cholesteric liquid crystal compounds useful for preparing polymeric films
GB12237A Expired GB2174396B (en) 1982-12-15 1986-05-20 Cholesterol derivatives

Family Applications Before (1)

Application Number Title Priority Date Filing Date
GB08333323A Expired GB2133406B (en) 1982-12-15 1983-12-14 Cholesteric liquid crystal compounds useful for preparing polymeric films

Country Status (8)

Country Link
JP (1) JPS59110700A (en)
BE (1) BE897870A (en)
CA (1) CA1255653A (en)
DE (2) DE3347990C2 (en)
FR (1) FR2537976B1 (en)
GB (2) GB2133406B (en)
LU (1) LU85103A1 (en)
NL (1) NL190525C (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1214592A (en) * 1982-12-15 1986-11-25 Paul J. Shannon Polymeric liquid crystals
FR2572813A1 (en) * 1984-11-07 1986-05-09 Armstrong World Ind Inc PROCESS FOR PREPARING POLYMERIC LIQUID COATINGS HAVING MULTIPLE OPTICAL ANSWERS AND COATINGS THUS OBTAINED
US5629055A (en) * 1994-02-14 1997-05-13 Pulp And Paper Research Institute Of Canada Solidified liquid crystals of cellulose with optically variable properties
DE4441651A1 (en) * 1994-11-23 1996-04-25 Basf Ag Polymerisable material for coating and printing substrates
US7914700B2 (en) * 2006-03-31 2011-03-29 E. I. Du Pont De Nemours And Company Liquid crystal compositions and polymer networks derived therefrom
CN100389123C (en) * 2006-07-21 2008-05-21 中国科学院上海有机化学研究所 Synthesis of 26-bromo-16, 22-dioxy-cholesterol compounds

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3580864A (en) * 1969-04-30 1971-05-25 Westinghouse Electric Corp Cholesteric-phase liquid-crystal compositions stabilized against true-solid formation,using cholesteryl erucyl carbonate
CA980105A (en) * 1971-06-14 1975-12-23 Hoffmann-La Roche Limited Cholesteric liquid crystals containing materials
DE2622658A1 (en) * 1976-05-20 1977-12-01 Parker Research Robert High temp cholesteric liq crystal compsn - contg 3-chloropropionate and arom esters of cholesterol, which do not crystallise on standing at room temp

Also Published As

Publication number Publication date
LU85103A1 (en) 1984-04-02
FR2537976B1 (en) 1987-01-09
CA1255653A (en) 1989-06-13
JPH0116839B2 (en) 1989-03-27
FR2537976A1 (en) 1984-06-22
NL190525C (en) 1994-04-05
GB8612237D0 (en) 1986-06-25
GB8333323D0 (en) 1984-01-18
GB2174396B (en) 1987-06-03
DE3340953A1 (en) 1984-06-20
DE3340953C2 (en) 1986-10-23
NL190525B (en) 1993-11-01
BE897870A (en) 1984-01-16
GB2133406A (en) 1984-07-25
DE3347990C2 (en) 1987-01-08
NL8304276A (en) 1984-07-02
JPS59110700A (en) 1984-06-26
GB2133406B (en) 1987-06-10

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PE20 Patent expired after termination of 20 years

Effective date: 20031213