WO2006117800A2 - Nouveaux derives de 3, 4-propylenedioxythiophene comprenant des groupes fonctionnels pendants - Google Patents

Nouveaux derives de 3, 4-propylenedioxythiophene comprenant des groupes fonctionnels pendants Download PDF

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Publication number
WO2006117800A2
WO2006117800A2 PCT/IN2006/000063 IN2006000063W WO2006117800A2 WO 2006117800 A2 WO2006117800 A2 WO 2006117800A2 IN 2006000063 W IN2006000063 W IN 2006000063W WO 2006117800 A2 WO2006117800 A2 WO 2006117800A2
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Prior art keywords
radical
optionally substituted
valent
alkyl
malonic acid
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PCT/IN2006/000063
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English (en)
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WO2006117800A3 (fr
WO2006117800B1 (fr
Inventor
Anil Kumar
Sarada Prasad Mishra
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Indian Institute Of Technology Bombay
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Publication of WO2006117800A2 publication Critical patent/WO2006117800A2/fr
Publication of WO2006117800A3 publication Critical patent/WO2006117800A3/fr
Publication of WO2006117800B1 publication Critical patent/WO2006117800B1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems

Definitions

  • the invention relates to the syntheses of novel 3,4-propylenedioxythiophene monomers having pendant functional groups.
  • Intrinsically electronic conducting polymers owing to the considerable derealization of the ⁇ - electrons along the main chain exhibit non-linear optical properties and after oxidation or reduction are also good electrical conductors. These compounds have promising applications in data storage, optical signal processing, suppression of electromagnetic interference (EMI) and solar energy conversion, rechargeable batteries, light-emitting diodes, electrochromic windows and display panels, field-effect transistors, printed circuit boards, chemical and bio sensors and antistatic materials.
  • EMI electromagnetic interference
  • solar energy conversion rechargeable batteries
  • light-emitting diodes light-emitting diodes
  • electrochromic windows and display panels electrochromic windows and display panels
  • field-effect transistors printed circuit boards
  • chemical and bio sensors and antistatic materials chemical and bio sensors and antistatic materials.
  • poly(3,4-ethylenedioxythiophene) exhibit many interesting properties that include stability in oxidized and reduced states, low bandgap, high electrochromic contrast and rapid switching.
  • PEDT poly(3,4-ethylenedioxythiophene)
  • An overview of numerous poly(alkylenedioxythiophene) derivatives, in particular poly-3,4- (ethylene-1 ,2-dioxy)thiophene derivatives, their monomers, syntheses and applications are discussed in detail in Adv. Mater. 12, 2000, 481-494.
  • U.S. Pat. No. 5,111 ,327 described substituted 3, 4-alkylenedioxythiophenes and their conductive polymerization products.
  • the invention provides compounds of the formula I.
  • R is a n-valent linear or branched, optionally substituted, aliphatic C1 -Cn radical, an n-valent, optionally substituted, cycloaliphatic C3-Cn radical or an n-valent, optionally substituted, aromatic C6-Cn radical.
  • X is a n-valent linear or branched, optionally substituted, aliphatic CI -Cn radical, an n- valent, optionally substituted, cycloaliphatic C3-Cn radical or an n-valent, optionally substituted, aromatic C6-Cn radical (except benzylic or benzylic derivatives when R is a methyl group); -
  • R 11 is a n-valent linear or branched, optionally substituted, aliphatic C1 -Cn radical, an n- valent, optionally substituted, cycloaliphatic C3-Cn radical or an n-valent, optionally substituted, aromatic C6-Cn radical.
  • R" is hydrogen or is a n-valent linear or branched, optionally substituted, aliphatic C1 -Cn radical, an n-valent, optionally substituted, cycloaliphatic C3-Cn radical or an n-valent, optionally substituted, aromatic C6-Cn radical.
  • R" 1 is hydrogen or is a n-valent linear or branched, optionally substituted, aliphatic C1 -Cn radical, an n-valent, optionally substituted, cycloaliphatic C3-Cn radical or an n-valent, optionally substituted, aromatic C6-Cn radical.
  • R" 11 is hydrogen or is a n-valent linear or branched, optionally substituted, aliphatic C1 - Cn radical, an n-valent, optionally substituted, cycloaliphatic C3-Cn radical or an n-valent, optionally substituted, aromatic C6-Cn radical.
  • R is L or hydrogen or is a n-valent linear or branched, optionally substituted, aliphatic
  • CI-Cn radical an n-valent, optionally substituted, cycloaliphatic C3-Cn radical or an n-valent, optionally substituted, aromatic C6-Cn radical.
  • R is a n-valent linear or branched, optionally substituted, aliphatic C2-Cn radical, an n-valent, optionally substituted, cycloaliphatic C3-Cn radical or an n-valent, optionally substituted, aromatic C6-Cn radical.
  • the present invention has significant advantages over the previously known approach for the funcationalization of alkylenedioxythiophenes.
  • US 5,111 ,327 the synthesis of EDT-methanol, hydroxyl-PDT and their derivatives has been reported.
  • US 6,852,831 the synthesis and functionalization of hydroxyalkanol-PDT is reported.
  • the inherent disadvantages of these synthetic strategies are the necessity of the column purification as the product contains mixture of two dialkoxythiophene derivatives, making it unsuitable for scale-up. Furthermore, both the strategies give only one or two types of starting dialkoxythiophenes and hence have limited scope of fine tuning the structural features of the monomers.
  • the present invention provides a practical solution to both of these problems by providing only a single monomer (eliminating the need of separation of mixture) and also provides the ability to fine tune the structure of the starting monomers from highly hydrophobic to highly hydrophilic.
  • the present invention provides new routes (as per Scheme I, II, and III) for the easy syntheses of novel functional derivatives of 3,4-propylenedioxythiophene, compounds of the formula I.
  • Step A Reacting diethyl malonate with ethyl haloformate in dry organic solvent in presence of a base to produce the 2-ethoxycarbonyl-malonic acid diethyl ester
  • Step B Reacting 2-ethoxycarbonyl-malonic acid diethyl ester, obtained in step A, with aliphatic halides or aliphatic tosylate in organic solvents in presence of a base to produce alkyl 2- ethoxycarbonyl-malonic acid diethyl ester
  • Step C Reacting alkyl 2-ethoxycarbonyl-malonic acid diethyl ester, obtained in step B, with a reducing agent in organic solvent to produce alkyl triols of the formula Il
  • Step F Reacting diethyl malonate with allyl or propargyl halide in organic solvents in presence of a base to produce 2,2-diallyl malonic acid diethyl ester or 2,2-dipropargyl malonic acid diethyl ester, respectively
  • Step G Reacting 2,2-diallyl malonic acid diethyl ester or 2,2-dipropargyl malonic acid diethyl ester, obtained in step F, with a reducing agent in organic solvent to produce 2,2-diallyl-1 ,3- propanediol or 2,2-dipropargyl-i ,3-propanediol, respectively
  • Step H Reacting the 2,2-diallyl-1 ,3-propanediol or 2,2-dipropargyl-1 ,3-propanediol, obtained in step G 1 with 3,4-dialkoxythiophene in dry organic solvent in presence of an acid as the catalyst to produce 3,3-diallyl-3,4-dihydro-2H-thieno[3,4-b][1 ,4]dioxepine or 3,3-dipropargyl-3,4-dihydro-
  • Step I Reacting diethyl malonate with allyl or propargyl halide in organic solvents in presence of a base to produce 2-allyl malonic acid diethyl ester or 2-propargyl malonic acid diethyl ester, respectively
  • Step J Reacting 2-allyl malonic acid diethyl ester or 2-propargyl malonic acid diethyl ester, obtained in step I, with alkyl halides or alkyl tosylate in polar solvents in presence of a base to produce 2-alkyl-2-allyl-malonic acid diethyl ester or 2-alkyl-2-propargyl-malonic acid diethyl ester, respectively
  • Step K Reacting 2-alkyl 2-allyl-malonic acid diethyl ester or 2-alkyl-2-propargyl-malonic acid diethyl ester, obtained in step J, with a reducing agent to produce 2-alkyl-2-allyl-1 ,3-propanediol or 2-alkyl-2-propargyl-1 ,3-propanediol, respectively
  • the base used in Step A, B, F, I, J are selected from: metal alkoxides in alcohol, NaOH, NaH, K 2 CO 3 , KOH, sodamide
  • the base used in Step E are selected from: metal alkoxides in alcohol, NaOH, NaH, K 2 CO 3 ,
  • the catalyst used in Step E is selected from: DABCO, DMAP, DBU, pyridine, or any other tertiary amine.
  • concentration of the catalyst used in step E can be varied upto 100 mol% but practical concentrations would be upto 2 mol%.
  • the aliphatic halide group used in Step B and J are selected from alkanyls, alkenyls or alkynyls.
  • Polar solvents for Step A-L are selected from: alcohols such as methanol and ethanol, ketones such as acetophenone, halogenated hydrocarbons such as methylene chloride, chloroform, tetrachloromethane and fluorohydrocarbons, esters such as ethyl acetate and butyl acetate, aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as pentane, hexane, heptane and cyclohexane, nitriles such as acetonitrile and benzonitrile, sulfoxides such as dimethylsulfoxide, sulfones such as dimethylsulfone, phenylmethylsulfone and sulfolan, liquid aliphatic amides such as methyl acetamide, dimethyl acetamide, dimethyl formamide, pyrrolidone, N-methyl-pyrrol
  • the alkyl group in alkyl halides or alkyl tosylates and alkane sultones used in Step E are chosen from linear or branched aliphatic or cycloaliphatic or aromatic or alkoxy groups, alkyl acetates, alkyl nitriles, alkanal, alkanone, alkyl carboxylates, alkyl sulfonates, alkyl phosphonates, alkyl amines, allyl, alkenyl, alkyl epoxides, alkyl amides, alkyl isocyanates, alkyl azides, alkyl thio ethers, alkyl anhydrides.
  • the key inventive feature lies in the combination of the steps indicated above and more particularly:
  • triethyl sodio-methanetricarboxylate (1 g, 3.94 mmol) was taken in a mixture of dry toluene and dry DMF (1 :1).
  • benzyl chloride (7.87 mmol) and heated at 90 0 C for 20 h.
  • the reaction mixture was then cooled and to this was added 15 mL of toluene.
  • the organic layer was washed first with water and then with brine solution. The organic layers were combined, dried over anhydrous Na 2 SO 4 and concentrated to get yellowish liquid.
  • the compound was extracted in ethyl acetate.
  • the organic layer was washed with water, dried over Na2SO4 and evaporated to get a sticky liquid.
  • LAH lithium aluminum hydride

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

L'invention se rapporte à la synthèse de 3,4-propylènedioxythiophènes représentés par la formule (I) dans laquelle R représente un radical aliphatique en C1-Cn éventuellement substitué, et Y représente un groupe fonctionnel pendant. L'invention concerne en outre des procédés de préparation desdits composés.
PCT/IN2006/000063 2005-03-21 2006-02-23 Nouveaux derives de 3, 4-propylenedioxythiophene comprenant des groupes fonctionnels pendants WO2006117800A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IN302MU2005 2005-03-21
IN302/MUM/05 2005-03-21

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WO2006117800A2 true WO2006117800A2 (fr) 2006-11-09
WO2006117800A3 WO2006117800A3 (fr) 2007-02-22
WO2006117800B1 WO2006117800B1 (fr) 2007-04-05

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009094361A2 (fr) * 2008-01-21 2009-07-30 University Of Connecticut Polymères conjugués de 3,4-propylènedioxythiophène substitué, leur composition, leur procédé de fabrication et leur utilisation
US8513377B2 (en) 2011-03-02 2013-08-20 The University Of Connecticut Selenium-based monomers and conjugated polymers, methods of making, and use thereof
US8586702B2 (en) 2010-08-27 2013-11-19 University Of Delaware Substituted 3,4-propylenedioxythiophene monomers and 3,4-propylenedioxythiophene-based crosslinkers and polymers thereof
WO2014188090A1 (fr) * 2013-05-23 2014-11-27 Centre National De La Recherche Scientifique Materiau superoleophobe et/ou superhydrophobe, son procede de preparation et ses applications
US9680102B2 (en) 2010-03-25 2017-06-13 University Of Connecticut Formation of conjugated polymers for solid-state devices
US9944757B2 (en) 2012-07-23 2018-04-17 The University Of Connecticut Electrochromic copolymers from precursors, method of making, and use thereof
US10323178B2 (en) 2014-05-16 2019-06-18 The University Of Connecticut Color tuning of electrochromic devices using an organic dye

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
DATABASE CAPLUS [Online] MISHRA S.P. ET AL.: 'Synthesis and characterization of electrochromic polymers based of 3,4-propylenedioxythiophenes', XP003009469 Database accession no. (144:88621) & MACRO 2004, INTERNATIONAL CONFERENCE ON POLYMERS FOR ADVANCED TECHNOLOGIES, THIRUVANATHAPURAM, INDIA 15 December 2004 - 17 December 2004, pages OP.8/1 - OP.8/4 *
KROS A., NOLTE R.J.M., SOMMERDIJK N.A.J.M.: 'Poly(3,4-ethylenedioxythiophene)-based copolymers for biosensor applications' JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY vol. 40, no. 6, 2002, pages 738 - 747, XP002361455 *
MISHRA S.P. ET AL.: 'Synthesis and characterization of functionalized 3,4-propylenedioxythiophene and its derivatives' J. MATER. CHEM. vol. 14, 2004, pages 1896 - 1900, XP003009468 *
MISHRA S.P. ET AL.: 'Synthesis and characterization of monosubstituted and disubstituted poly(3,4-propylenedioxythiophene) derivatives with high electrochromic contrast in the visible region' JOURNAL OF POLYMER SCIENCE PART A: POLYMER CHEMISTRY vol. 43, no. 2, 2005, pages 419 - 428, XP003009467 *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009094361A2 (fr) * 2008-01-21 2009-07-30 University Of Connecticut Polymères conjugués de 3,4-propylènedioxythiophène substitué, leur composition, leur procédé de fabrication et leur utilisation
WO2009094361A3 (fr) * 2008-01-21 2009-10-29 University Of Connecticut Polymères conjugués de 3,4-propylènedioxythiophène substitué, leur composition, leur procédé de fabrication et leur utilisation
US7951902B2 (en) 2008-01-21 2011-05-31 The University Of Connecticut Conjugated polymers from substituted 3,4-propylenedioxythiophene, compositions, method of making, and use thereof
US9680102B2 (en) 2010-03-25 2017-06-13 University Of Connecticut Formation of conjugated polymers for solid-state devices
US8586702B2 (en) 2010-08-27 2013-11-19 University Of Delaware Substituted 3,4-propylenedioxythiophene monomers and 3,4-propylenedioxythiophene-based crosslinkers and polymers thereof
US8513377B2 (en) 2011-03-02 2013-08-20 The University Of Connecticut Selenium-based monomers and conjugated polymers, methods of making, and use thereof
US8822635B2 (en) 2011-03-02 2014-09-02 The University Of Connecticut Selenium-based monomers and conjugated polymers, methods of making, and use thereof
US9944757B2 (en) 2012-07-23 2018-04-17 The University Of Connecticut Electrochromic copolymers from precursors, method of making, and use thereof
WO2014188090A1 (fr) * 2013-05-23 2014-11-27 Centre National De La Recherche Scientifique Materiau superoleophobe et/ou superhydrophobe, son procede de preparation et ses applications
FR3005956A1 (fr) * 2013-05-23 2014-11-28 Centre Nat Rech Scient Materiau superoleophobe et/ou superhydrophobe, son procede de preparation et ses applications
US10323178B2 (en) 2014-05-16 2019-06-18 The University Of Connecticut Color tuning of electrochromic devices using an organic dye

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WO2006117800B1 (fr) 2007-04-05

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