EP0703885A1 - Synthese de triphenilenes substitues utiles pour les cristaux liquides en forme de disque - Google Patents

Synthese de triphenilenes substitues utiles pour les cristaux liquides en forme de disque

Info

Publication number
EP0703885A1
EP0703885A1 EP94917727A EP94917727A EP0703885A1 EP 0703885 A1 EP0703885 A1 EP 0703885A1 EP 94917727 A EP94917727 A EP 94917727A EP 94917727 A EP94917727 A EP 94917727A EP 0703885 A1 EP0703885 A1 EP 0703885A1
Authority
EP
European Patent Office
Prior art keywords
mol
dichloromethane
stirred
added
oxidising agent
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.)
Withdrawn
Application number
EP94917727A
Other languages
German (de)
English (en)
Inventor
Richard James Bushby
Andrew Neil Cammindge
Gareth Headdock
Ruth Carol Borner
Neville Boden
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.)
BTG International Ltd
Original Assignee
British Technology Group Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from GB939312091A external-priority patent/GB9312091D0/en
Priority claimed from GB9405795A external-priority patent/GB9405795D0/en
Application filed by British Technology Group Ltd filed Critical British Technology Group Ltd
Publication of EP0703885A1 publication Critical patent/EP0703885A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B37/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving either the formation of a carbon-to-carbon bond between two carbon atoms not directly linked already or the disconnection of two directly linked carbon atoms
    • C07B37/10—Cyclisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/14—Preparation of ethers by exchange of organic parts on the ether-oxygen for other organic parts, e.g. by trans-etherification
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/225—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/23—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D319/10—1,4-Dioxanes; Hydrogenated 1,4-dioxanes
    • C07D319/14—1,4-Dioxanes; Hydrogenated 1,4-dioxanes condensed with carbocyclic rings or ring systems
    • 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
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/40—Ortho- or ortho- and peri-condensed systems containing four condensed rings
    • C07C2603/42—Ortho- or ortho- and peri-condensed systems containing four condensed rings containing only six-membered rings
    • 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
    • C09K2019/328—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems containing a triphenylene ring system

Definitions

  • This invention relates to a method of synthesising pure (i.e. isomer-free) substituted, e.g. unsymmetrically substituted, triphenylenes and includes the compounds so made. Hitherto, such synthesis undesirably yielded isomers in plenty. These compounds, which form a good feedstock for polymerisation, may find application as discotic liquid crystals, which may be of low or high molar mass.
  • the method makes it possible to prepare polymeric discotic liquid crystals of defined structure because, without unsymmetrically substituted triphenylenes, homogeneous polymers of defined structure based on this nucleus cannot be made.
  • the method is also useful for liquid crystal systems of low molar mass in which the triphenylene nucleus may be symmetrically or unsymmetrically substituted. It allows these compounds to be made pure, cheaply and in large quantities.
  • Discotic liquid crystals based on the triphenylene nucleus show promise particularly because they form ordered hexagonal columnar phases, and triphenylene based polymers in particular are likely to be especially important.
  • Potential applications are likely to be based on building functionality into these systems to create conducting and/or photosensitive materials for use in xerography, laser printing, electronic photography, information storage, sensors (especially chemical sensors), etc.
  • hexaalkoxytriphenylenes are doped with an oxidant they are converted into semiconductors in which the preferred direction of conduction is along the columns of the hexagonal columnar phases, the aromatic core of the columns providing a conducting pathway with the annulus of hydrocarbon chains forming an insulating sheath.
  • Hexasubstituted triphenylenes are a widely synthesised class of discotic liquid crystals. Their synthesis traditionally involves the oxidative trimerization of 1 ,2-dimethoxybenzene (veratrole) 1 in 67% sulphuric acid using the quinone chloranil as oxidant [2,3]. This reaction is more or less limited to the production of hexamethoxytriphenylene 2 and if, for example, hexahexyloxytriphenylene (HAT6) 4 is required it is necessary to replace the alkoxy groups OMe; the methyls can be removed either by using hydrogen bromide/acetic acid or boron tribromide. The resulting hexahydroxytriphenylene is then alkylated with hexyl bromide
  • decompositio products Salts of this type are decomposed by reaction with nucleophiles such as water (which is in part the reason why such reactions are carried out in acidic solvents) and so the workup procedure is crucial to the outcome of the reaction.
  • nucleophiles such as water
  • Such a reductive workup can be achieved either by chemical or electrochemical methods [6]. If the reaction is carried out under carefully controlled conditions the radical cation salt 5 crystallises out on the anode surface (electrocrystallisation) .
  • electrochemical route is slow and the workup relatively tedious so that we have not succeeded in making more than ca. 1 g quantities at a time in this way and in most cases we do not regard it as a serious competitor to the "chloranil" route.
  • Another alternative oxidation reagent in these reactions is ferric chloride [8].
  • Bengs et si. have described a reaction procedure in which 1 ,2-bishexadecyloxybenzene was treated with ferric chloride in 70% sulphuric acid at 80°C followed by an ice/water workup to give a 20% yield of 2,3,6,7,10,11-hexakishexa- decylox triphenylene and have used a similar procedure for making mixed trimers in low but unspecified yield.
  • the oxidative coupling is performed in an organic solvent.
  • the oxidising agent can comprise a transition metal, such as Fe(III) or V or Cr, e.g. the compound FeCl ⁇ .
  • the oxidising agent may be accompanied by a base such as K2CO3 preferably insoluble in the organic solvent (preferably in excess, to mop up arising acid) or by not more than 1 weight % acid, such as H2SO4, and preferably at below 40°C (more preferably below 30°C) , e.g. 15-25°C.
  • a one-electron oxidant such as NOBF4 can be employed or a one-electron oxidant can be employed in combination with a transition metal, for example NOBF4 can be employed in combination with FeC ⁇ .
  • a reducing agent for example an alcohol such as ethanol or ethanol .
  • Methanol is an example of a mild reducing agent. If ferric chloride is used as the oxidising agent, methanol also has the function of dissolving ferrous iron Fe(II) while not being a solvent for the desired product, and when oxidised, it forms a volatile aldehyde.
  • the compound may be substituted in one or both
  • G and H are as previously defined and N and M are independently chosen from among hydrogen, halogen, alkyl, alkoxy, hydroxy, acyloxy and aryloxy.
  • This route to hexamethoxytriphenylene is both quicker and easier than any other route and has the advantage that it is easy to perform on a relatively large sale. It also has the advantage over the chloranil route that most 1,2-dialkoxybenzenes can be trimerized directly to give good yields.
  • the reaction can be performed using a variety of Fe* salts but in particular ferric chloride has been used.
  • This reaction can be used as a step towards preparing discotic liquid crystals of the hexaacyloxy type 6 by the following route:-
  • 7.TP6E02M Lyotropic discotic liquid crystals of the type shown in formula 7 can also be made as shown in the above scheme. Attempts to prepare these by trimerization of the corresponding benzene derivatives using FeC ⁇ /acid/D ⁇ C ⁇ have failed. However for the trimerization of related acid-sensitive substrates, the reaction is successful, if an excess of an insoluble base (FeCl3/. ⁇ 2C03/CH2Cl2 is added to the reaction mixture.
  • reaction conditions can be used to effect mixed trimerization reactions which, in favourable circumstances (e.g. as to product and reactant solubility) can be separated from positional iso ers, allowing unsym etrical derivatives to be prepared:
  • the electron acceptor A would be for example trinitrofluorenone, tetrachloro-p-benzoquinone or TCNQ-F4, in which case the direct transfer is induced photochemically, or cyanine or triphenylmethane cationic dyes, where the photoexcited state of the dye would act as the oxidant.
  • These doped materials are likely to have interesting photoconductivity and electroluminescence properties. The former would find applications in, for example, xerography, laser printing, electronic photography, i age/information storage, and the latter in large area displays, TV, etc.
  • the present invention provides within its scope not only the above described new method of synthesis, but also the new products of such a synthesis.
  • Hx n-hexyl unless otherwise indicated.
  • Veratrole (23 g, 0.166 mol) was added slowly to a well stirred suspension of iron (III) chloride (81 g, 0.5 mol) in dichloromethane (500 ml) and concentrated sulphuric acid (1.6 g). As the veratrole was added hydrogen chloride gas was given off and the temperature rose until the dichloromethane was refluxing (40°C). The reaction mixture was stirred for a further 2 hours and then filtered. Methanol was carefully added to the solid on the filter pad which changed colour from dark green to grey with copious washings. Heat and formaldehyde were liberated and it is advised that this step is performed in a well ventilated fume-cupboard.
  • Acetyl chloride 35 g, 0.45 mol was added to 2-hexyloxyphenol (65 g, 0.34 mol) with stirring over 1 hour and the mixture stirred for a further 24 hours.
  • Dichloromethane 200 ml was added and the solution washed with dilute potassium carbonate until the aqueous layer was basic.
  • the organic solution was dried MgSU4) and the solvent removed in vacuo. Distillation of the residue at 100-106°C/0.8 mm Hg afforded 2-hexyloxyphenyl acetate as a colourless oil (75 g, 94%).
  • Diphenylphosphine (1.7 g, 9.2 mmol) was dissolved in dry THF (60 ml) and cooled in an ice bath under argon. Butyllithium (2.5 M in hexanes, 5 ml, 12.5 mmol) was added over 10 minutes. Solid 2,7,10,11-tetrahexyloxy-3,6-dimethox triphenylene (1.7 g, 2.5 mmol) was added and the solution stirred at 50-60°C for 4 hours and at room temperature overnight. The mixture was poured onto dilute sulphuric acid and extracted with ethyl acetate (3 x 70 ml).
  • 1,3-Dimethoxybenzene (0.49 g, 0.0036 mol) and 3,3' ,4,4'-tetrahexyloxybiphenyl (0.5 g, 0.0009 mol) were added to a stirred suspension of iron (III) chloride (2.2 g, 0.0135 mol) in dichloromethane (30 ml).
  • the reaction was quenched with methanol after 50 minutes and left to stand overnight.
  • the crude solid product was filtered off and subjected to column chromatography (silica, ethyl acetate/petroleum ether 1:3). The product was collected and recrystallised from ethanol to give white needles (0.25 g, 42%).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Fats And Perfumes (AREA)

Abstract

Les triphénylènes à substitution asymétrique nécessaires à la synthèse des cristaux liquides (en disque) sont obtenus en utilisant du chlorure de fer (III), contenu dans un solvant organique à température ambiante, pour réaliser la liaison oxydante de 1,2-dialkoxybenzènes et de 3,3',4,4'-tétra-alkoxybiphényles. Ceci est suivi d'un bilan réducteur. Le même protocole d'oxydo-réduction a prouvé son efficacité dans la trimérisation des 1,2-dialkoxybenzènes.
EP94917727A 1993-06-11 1994-06-13 Synthese de triphenilenes substitues utiles pour les cristaux liquides en forme de disque Withdrawn EP0703885A1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
GB939312091A GB9312091D0 (en) 1993-06-11 1993-06-11 Synthesis and applications of discostic liquid crystals based on triphenylene
GB9312091 1993-06-11
GB9405795 1994-03-23
GB9405795A GB9405795D0 (en) 1994-03-23 1994-03-23 Synthesis of asymmetrically substitute triphenylenes useful as discotic liquid crystals
PCT/GB1994/001263 WO1994029243A1 (fr) 1993-06-11 1994-06-13 Synthese de triphenilenes substitues utiles pour les cristaux liquides en forme de disque

Publications (1)

Publication Number Publication Date
EP0703885A1 true EP0703885A1 (fr) 1996-04-03

Family

ID=26303053

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94917727A Withdrawn EP0703885A1 (fr) 1993-06-11 1994-06-13 Synthese de triphenilenes substitues utiles pour les cristaux liquides en forme de disque

Country Status (5)

Country Link
EP (1) EP0703885A1 (fr)
JP (1) JPH09502164A (fr)
CN (1) CN1128985A (fr)
GB (1) GB2279072A (fr)
WO (1) WO1994029243A1 (fr)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9405793D0 (en) * 1994-03-23 1994-05-11 Cammidge Andrew N Functionalised discotic liquid crystals mesogens through structural modification of triphenylenes
JP4698421B2 (ja) * 2003-10-22 2011-06-08 大塚化学株式会社 ２，３，６，７，１０，１１−ヘキサヒドロキシトリフェニレンの製造方法
JP4444774B2 (ja) * 2004-03-19 2010-03-31 富士フイルム株式会社 光学異方性材料、液晶表示装置及びトリフェニレン化合物
JP2011201831A (ja) * 2010-03-26 2011-10-13 Ube Industries Ltd 〔２，３，６，７，１０，１１−ヘキサ（置換）オキシ〕−トリフェニレン化合物の製造方法
KR101298349B1 (ko) * 2011-01-04 2013-08-20 주식회사 두산 유기 화합물 및 이를 이용한 유기 전계 발광 소자
KR101274924B1 (ko) * 2011-01-04 2013-06-14 주식회사 두산 유기발광 화합물 및 이를 포함한 유기 전계발광 소자
CN102701921B (zh) * 2012-06-14 2014-05-14 四川师范大学 盘状液晶中间体2-羟基-3,6,7,10,11-五烷氧基苯并菲和直链烷基苯的合成方法
CN102757349B (zh) * 2012-06-21 2015-03-04 江苏和成显示科技股份有限公司 苯并菲衍生物及其应用
JP5878842B2 (ja) * 2012-08-06 2016-03-08 和光純薬工業株式会社 ２，３，６，７，１０，１１−ヘキサヒドロキシトリフェニレン類の製造方法
JPWO2017209297A1 (ja) * 2016-06-02 2019-04-18 国立大学法人名古屋大学 トリアリーレン化合物及びその製造方法
CN110600525B (zh) * 2019-09-29 2022-06-03 京东方科技集团股份有限公司 一种显示面板、显示装置及其显示方法
CN112409323A (zh) * 2020-11-20 2021-02-26 四川师范大学 一种类石墨烯共轭杂环苯并菲盘状液晶的制备方法及介晶性

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9429243A1 *

Also Published As

Publication number Publication date
CN1128985A (zh) 1996-08-14
JPH09502164A (ja) 1997-03-04
GB9411828D0 (en) 1994-08-03
GB2279072A (en) 1994-12-21
WO1994029243A1 (fr) 1994-12-22

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