WO1994029243A1 - 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 Download PDF

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Publication number
WO1994029243A1
WO1994029243A1 PCT/GB1994/001263 GB9401263W WO9429243A1 WO 1994029243 A1 WO1994029243 A1 WO 1994029243A1 GB 9401263 W GB9401263 W GB 9401263W WO 9429243 A1 WO9429243 A1 WO 9429243A1
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Prior art keywords
mol
dichloromethane
stirred
added
oxidising agent
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PCT/GB1994/001263
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English (en)
Inventor
Richard James Bushby
Andrew Neil Cammindge
Gareth Headdock
Ruth Carol Borner
Neville Boden
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British Technology Group Limited
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Priority claimed from GB939312091A external-priority patent/GB9312091D0/en
Priority claimed from GB9405795A external-priority patent/GB9405795D0/en
Application filed by British Technology Group Limited filed Critical British Technology Group Limited
Priority to JP7501498A priority Critical patent/JPH09502164A/ja
Priority to EP94917727A priority patent/EP0703885A1/fr
Publication of WO1994029243A1 publication Critical patent/WO1994029243A1/fr

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    • 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
  • 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
  • triphenylene nucleus may be symmetrically or
  • 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 annul us of hydrocarbon chains forming an insulating sheath. Since Chandrasekhar's original paper [1] reporting the first synthesis of a discotic liquid crystal there has been an
  • 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 tri bromide. The resulting hexahydroxytriphenylene is then alkylated with hexyl bromide
  • chloranil/sulphuric acid mixture can be used to trimerize 1,2-dihexyloxybenzene directly to form HAT6, purification of the HAT6 involves repeated chromatography and repeated
  • 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
  • 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.
  • ferric chloride Another alternative oxidation reagent in these reactions is ferric chloride [8].
  • Bengs et al . 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-hexakishexadecyloxytriphenylene and have used a similar procedure for making mixed trimers in low but unspecified yield.
  • A, B, C, D, E and F are independently chosen from among hydrogen, halogen, alkyl,
  • 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 3 .
  • the oxidising agent may be accompanied by a base such as K 2 CO 3 preferably
  • a one-electron oxidant such as NOBF 4 can be employed or a one-electron oxidant can be employed in combination with a transition metal, for example NOBF 4 can be employed in combination with FeCl 3 .
  • the oxidative coupling is followed by workup with a reducing agent, for example an alcohol such as methanol 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
  • a stepwise procedure This involves oxidising the biphenyl (e.g. with 1-2 moles of FeCl 3 ), then adding the benzene derivative, then excess of the oxidising agent, followed by a reductive workup.
  • the compound may be substituted in one or both
  • the product is a dark green solid which is certainly an oxidised form of the triphenylene, most probably the radical cation salt 5. This is then filtered off and reduced on the filter pad with methanol.
  • Formaldehyde is liberated and hexamethoxytriphenylene thus obtained directly and virtually pure.
  • 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 III 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:-
  • 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 FeCl 3 /acid/CH 2 Cl 2 have failed. However for the trimerization of related acid-sensitive substrates, the reaction is successful, if an excess of an insoluble base (FeCl 3 /K 2 CO 3 /CH 2 Cl 2 ) is added to the reaction mixture.
  • an insoluble base FeCl 3 /K 2 CO 3 /CH 2 Cl 2
  • 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 isomers, allowing unsymmetrical derivatives to be prepared:
  • discotic liquid crystals Although applications of discotic liquid crystals have yet to be developed, they are likely to be based on building functionality into systems and particularly based on polymeric systems.
  • Polymeric materials have the advantages over their low molar mass counterparts of ease of processability, in particular, to make supramolecularly aligned fibres or films.
  • Cross-linking can impart elastomeric properties, opening up applications requiring
  • Polymeric materials are also more "tolerant" to incorporation of dopants into the hydrocarbon chain matrix, permitting doping to significantly higher concentrations and hence functionalisation of these materials as p- or n-type semiconductors by the incorporation of, respectively, oxidants or reductants into the hydrocarbon chain matrix as taught in European Patent 364185.
  • the oxidant or reductant could be replaced with a
  • 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.
  • 1,2-Dihexyloxybenzene (10 g, 0.036 mol) and 2-hexyloxyanisole (7.5 g, 0.036 mol) were added to a suspension of iron (III) chloride (35 g, 0.217 mol) in refluxing dichloromethane and concentrated sulphuric acid (0.5 ml) over 1 hour. The mixture was stirred for a further 1 hour under reflux and poured onto methanol (250 ml).
  • NMP N-methylpyrrolidone
  • 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 (MgSO 4 ) and the solvent removed in vacuo. Distillation of the residue
  • Diphenylphosphine (1.7 g, 9.2 mmol) was dissolved in dry THF (60 ml) and cooled in an ice bath under argon. Butyl lithium (2.5 M in hexanes, 5 ml, 12.5 mmol) was added over 10 minutes.
  • 1,2-Bis-((2-chloroethoxy)ethoxy)benzene 14 g, 0.043 mol was stirred in dichloromethane (200 ml) with solid potassium carbonate (80 g). Iron (III) chloride (30 g, 0.19 mol) was added and the mixture stirred for 1 hour. Methanol (50 ml) was added carefully and the solids filtered off and washed with dichloromethane. The filtrate was concentrated in vacuo and methanol (150 ml) added.
  • 2,3-dimethylanisole (1.5 g, 0.011 mol) were added to a stirred suspension of iron (III) chloride (2.71 g) in dichloromethane (15 ml). The mixture was stirred for 45 minutes, quenched with methanol, concentrated and left to stand overnight. The resulting solid was filtered and subjected to column chromatography (silica, dichloromethane) and recrystallised from ethanol to give 1,2-dimethyl-3-methoxy-6,7,10,11-tetrahexyloxytriphenylene as white needles (0.19 g, 31%).
  • 3,3',4,4'-Tetrahexyloxybiphenyl (0.3 g, 0.0005 mol) was dissolved in o-xylene (5 ml) and added to a stirred suspension of iron (III) chloride (1.85 g) in o-xylene (10 ml). The mixture was stirred for 2 hours then quenched with methanol (100 ml) and left to stand overnight. The resulting solid was subjected to column chromatography (silica, dichloromethane/petroleum ether 6:4) and recrystallised from ethanol to give 2,3-dimethyl-6,7,10,11-tetrahexyloxytriphenylene as white platelets (0.154 g, 43%).
  • 1,2-Dihexyloxy-4-iodobenzene (10 g, 0.025 mol) and iodobenzene (5 g, 0.025 mol) were added to copper powder (20 g) and heated to 250°C. After cooling the reaction mixture was extracted with dichloromethane (4 ⁇ 50 ml), filtered and concentrated in vacuo. Ethanol was then added to initiate crystallisation of unwanted symmetrical biphenyls which were then removed by filtration, the residue then being concentrated in vacuo again. This residue was then subjected to column chromatography (silica,
  • 1,2-dihexyloxybenzene (1.3 g, 0.0047 mol) were added to a stirred suspension of ferric chloride (1.82 g) in dichloromethane (15 ml) and stirred for 2 hours. The reaction mixture was then quenched with methanol (100 ml) and left to stand for 3 hours. The resulting solid was then subjected to column chromatography

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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.
PCT/GB1994/001263 1993-06-11 1994-06-13 Synthese de triphenilenes substitues utiles pour les cristaux liquides en forme de disque WO1994029243A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP7501498A JPH09502164A (ja) 1993-06-11 1994-06-13 ディスコチック液晶として有用な置換トリフェニレンの合成
EP94917727A EP0703885A1 (fr) 1993-06-11 1994-06-13 Synthese de triphenilenes substitues utiles pour les cristaux liquides en forme de disque

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB9312091.3 1993-06-11
GB939312091A GB9312091D0 (en) 1993-06-11 1993-06-11 Synthesis and applications of discostic liquid crystals based on triphenylene
GB9405795.7 1994-03-23
GB9405795A GB9405795D0 (en) 1994-03-23 1994-03-23 Synthesis of asymmetrically substitute triphenylenes useful as discotic liquid crystals

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WO1994029243A1 true WO1994029243A1 (fr) 1994-12-22

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

Cited By (3)

* Cited by examiner, † Cited by third party
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WO2012093852A2 (fr) * 2011-01-04 2012-07-12 주식회사 두산 Composé électroluminescent organique et dispositif électroluminescent organique comprenant ledit composé
WO2012093861A2 (fr) * 2011-01-04 2012-07-12 주식회사 두산 Composé organique électroluminescent et dispositif organique électroluminescent utilisant celui-ci
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

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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
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

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BENGS H ET AL: "Induction of a nematic columnar phase in a discotic hexagonal ordered phase forming system", LIQ. CRYST. (LICRE6,02678292);91; VOL.10 (2); PP.161-8, UNIV. MAINZ;INST. ORG. CHEM.; MAINZ; 6500; FED. REP. GER. (DE) *
BODEN N ET AL: "A quick-and-easy route to unsymmetrically substituted derivatives of triphenylene: preparation of polymeric discotic liquid crystals", J. CHEM. SOC., CHEM. COMMUN. (JCCCAT,00224936);94; (4); PP.465-6, LEEDS UNIV.;SCH. CHEM.; LEEDS; LS2 9JT; UK (GB) *
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012093852A2 (fr) * 2011-01-04 2012-07-12 주식회사 두산 Composé électroluminescent organique et dispositif électroluminescent organique comprenant ledit composé
WO2012093861A2 (fr) * 2011-01-04 2012-07-12 주식회사 두산 Composé organique électroluminescent et dispositif organique électroluminescent utilisant celui-ci
WO2012093852A3 (fr) * 2011-01-04 2012-11-29 주식회사 두산 Composé électroluminescent organique et dispositif électroluminescent organique comprenant ledit composé
WO2012093861A3 (fr) * 2011-01-04 2013-01-24 주식회사 두산 Composé organique électroluminescent et dispositif organique électroluminescent utilisant celui-ci
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

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CN1128985A (zh) 1996-08-14
JPH09502164A (ja) 1997-03-04
GB9411828D0 (en) 1994-08-03
GB2279072A (en) 1994-12-21
EP0703885A1 (fr) 1996-04-03

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