WO2001053287A2 - Derives de di (het) arylaminothiophene - Google Patents

Derives de di (het) arylaminothiophene Download PDF

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Publication number
WO2001053287A2
WO2001053287A2 PCT/DE2001/000005 DE0100005W WO0153287A2 WO 2001053287 A2 WO2001053287 A2 WO 2001053287A2 DE 0100005 W DE0100005 W DE 0100005W WO 0153287 A2 WO0153287 A2 WO 0153287A2
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WO
WIPO (PCT)
Prior art keywords
het
reaction
thiophene derivatives
derivatives according
aryl
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PCT/DE2001/000005
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German (de)
English (en)
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WO2001053287A3 (fr
Inventor
Horst Hartmann
Jörg Schumann
Andreas Kanitz
Wolfgang Rogler
Original Assignee
Siemens Aktiengesellschaft
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Publication of WO2001053287A2 publication Critical patent/WO2001053287A2/fr
Publication of WO2001053287A3 publication Critical patent/WO2001053287A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
    • C07D333/54—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
    • C07D333/56—Radicals substituted by oxygen atoms

Definitions

  • organic materials are required that are capable of electroluminescence. These can either be compounds of small molecular size (see, for example, US Pat. No. 4,539,507) that can be evaporated, or polymeric materials (see, for example, US Pat. No. 5,247,190) that can be processed by spin coating.
  • the invention therefore relates to new 5-substituted 2- (N, N-di (het) arylamino) thiophene derivatives of the general structure
  • R 10 has the same meaning as R 9 ; R has the following meaning: 0, CH-R 5 or
  • R 1 , R 2 , R 3 and R 4 are as defined above and R 5 has the meaning of R 1 .
  • the new di (het) arylaminothiophene derivatives are produced by means of a hetaryl ring closure reaction under mild conditions and without metal catalysts. These compounds can thus be produced in high purity, ie the efficiency of these materials, in particular the electroluminescence, is not impaired by impurities which are present in compounds produced by known processes, for example because of the catalyst used.
  • a further advantage of these materials is improved redox properties that can be adapted to the respective purpose, due to the variety of structural options that result from the construction principle described in more detail below.
  • This construction principle also enables the new materials to be easily in shape can be obtained from oligomer and polymer structures, ie that oligo- and poly-aminothiophene derivatives can be prepared.
  • R 1 , R 2 , R 3 , R 4 and R 5 have the meaning given above; if R 3 is R 9 , the compound II carries on the free bond a group -CH 2 -COX, where X is halogen, preferably Cl, Br or J;
  • R 6 has the meaning of R 2 and may further include a group -CH 2 X or -R 10 be -C0-CH 2 X, wherein R 10 and X are as defined above defi ⁇ ;
  • R 7 and R 8 are H, Ci- to Cio-alkyl or phenyl or together form a C 4 - to C ⁇ -alkylene group or a group -CH 2 -CH 2 -0-CH 2 -CH 2 -;
  • a " the anion of a Vilsmeier reagent.
  • the first step in the synthesis of the thiophene derivatives consists in the reaction of a secondary A ins I with a carboxylic acid halide II to a carboxamide (acid amide) III.
  • the reaction is carried out in a suitable solvent, preferably dioxane, at an elevated temperature, preferably in the range of the boiling point of the solvent, under an inert gas.
  • a suitable solvent preferably dioxane
  • the acid amide III is then converted into a thiocarboxamide (thioamide) IV in a second stage.
  • Lawesson reagent a reagent acting in a homogeneous phase for introducing sulfur into carbonyl compounds (see: Römpp Chemie-Lexikon ", 9th edition, page 2464) in a suitable solvent, preferably diglycol diethyl ether elevated temperature, preferably at approximately 100 ° C. Duration: several hours, generally approximately 6 hours, but sulfur can also be introduced in a heterogeneous phase, for example using phosphorus pentasulfide.
  • the thioamide IV is converted by a reaction of the Vilsmeier type (according to Liebscher) into a vinylogous thiocarboxamide V required for the hetaryl ring closure (see: * Org. Synth. ", Vol. 74 (1997) , Pages 257 to 263.
  • the thioamide IV is reacted with orthoformic acid ester and a secondary amine, the boiling point of which is above 100 ° C., preferably morpholine, the ethanol formed in the intermediate formation of formamide acetal being removed, for example by distillation - lation.
  • the imid chloride (Vilsmeier reagent) required for the Vilsmeier-Arnold reaction is prepared from a substituted forma id, preferably dimethylformamide, and a suitable acid chloride, in particular phosphorus oxychloride and oxalyl chloride.
  • the vinylogous thiocarboxamide V is converted into a thienyl (het) aryl ketone VII, ie a 2-, by reaction with an ⁇ -haloacyl compound VI in a suitable solvent, preferably acetic anhydride, dimethylformamide or tetrahydrofuran.
  • a suitable solvent preferably acetic anhydride, dimethylformamide or tetrahydrofuran.
  • This is done by a primary S-alkylation and a subsequent cyclization (ring closure reaction) and aro atization.
  • the cyclization can be accelerated by adding a deprotonating agent, preferably triethylar ⁇ in.
  • the compound VII serves for the production of further thiophene derivatives according to the invention.
  • this compound is firstly reacted with a phosphonic acid ester of type VIII - corresponding to a Wittig-Horner reaction (see: * Römpp Chemie-Lexikon ", 9th edition, pages 5056 and 1856) -, conjugated compounds of type IX, ie thienyl-1,2-di (het) aryl-ethylene can be obtained, the compounds VIII being prepared by a Michaelis-Arbusov reaction (see: ⁇ Römpp Chemie-Lexikon ", 9th edition, page 2771).
  • the compounds VII can also be subjected to a McMurry reaction in which carbonyl compounds are converted to alkenes (see: ⁇ J. Org. Chem. ", Vol. 54 (1989), pages 3748 to 3749) result in di eres of type X, ie 1, 2-dithienyl-1, 2-di (het) aryl-ethylene, or also corresponding polymers.
  • thiophene derivatives of type IX are reacted in an appropriate solvent, preferably toluene, dimethylformamide, tetrahydrofuran and N-methylpyrrolidone or a mixture of these solvents, in an equimolar ratio, in the presence of a strong one Base, preferably potassium tert-butoxide, for the deprotonation of phosphonic acid ester VIII.
  • a strong one Base preferably potassium tert-butoxide
  • Thiophene derivatives of type X are produced using a freshly prepared Ti catalyst and a Zn-Cu coupling agent, preferably in dimethoxyethane under reflux. After the reaction has ended, the catalyst is separated off and the reaction product is precipitated and isolated in a suitable manner, preferably using methanol.
  • n each represents an integer from 2 to 100.
  • 2-phenylacetic acid diphenyl amide (mp: 71-72 ° C.) is produced from diphenylamine and 2-phenylacetyl chloride.
  • 0.5 mol of the respective carboxamide III are suspended in 1.5 ml of DMF in a 2 1 beaker. 1.25 mol of P0C1 3 are added dropwise to this suspension in such a way that the temperature of the reaction mixture is between 50 and 60 ° C .; if necessary, cooling is carried out using an ice bath. A complete solution is formed in the course of the reaction and is kept at 60 ° C. for 30 minutes after the POCl 3 ⁇ addition, and the mixture is then cooled. A mixture of 0.5 mol of 70% perchloric acid and methanol is then carefully added to the reaction solution to decompose the excess Vilsmeier reagent. The amount of methanol used should be about twice the volume of the reaction solution. The chlorovinyliminium salt formed during the reaction precipitates out in the form of the perchlorate on cooling. The yield is at least 85% in each case.
  • 1-chloro-l-diphenylamino-propen-3-yl-dimethyliminium perchlorate (mp: 178-180 ° C.) is produced from acetic acid-diphenylamide and POCI3 in DMF.
  • 2-phenylthioacetic acid diphenylamide (mp: 142-144 ° C.) is produced from 2-phenylacetic acid diphenylamide and the Lawesson reagent.
  • 3-morpholino-2-phenylthio-acrylic acid diphenylamide (mp: 182 ° C.) is produced from 2-phenylthioacetic acid diphenylamide in the presence of triethyl orthoformate and morpholine, and 3-morpholino-2-phenylthioacrylic acid N- phenyl-N-1-naphthylamide (mp: 185 ° C) from 2-phenylthioacetic acid-N-phenyl-Nl-naphthylamide in the presence of triethyl orthoformate and morpholine.
  • a monofunctional vinylogous thioamide and a monofunctional acyl halide are added in succession, in the present case first 0.01 mol 3-morpholino-2-phenylthioacrylic acid diphenylamide and after 30 min 0.01 mol P enacyl bromide. After a further 30 minutes, 0.1 mol of triethylamine is added and after a further 15 minutes the mixture is allowed to cool, the polymeric thiophene derivative formed precipitating. Further processing is carried out in the manner described above.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

Abstract

L'invention concerne de nouveaux dérivés de 2-(N,N-di(het)arylamino)-thiophène de structure (I), dans laquelle R?1, R2 et R3¿ sont indépendamment l'un de l'autre chacun un système (het)aryle monofonctionnel; R1 peut en outre être un système (het)arylène bifonctionnel; R3 peut en outre signifier H ou hormis lorsque R1 est un système (het)arylène bifonctionnel désigner un groupement R9, R9 représentant une liaison chimique ou un système (het)arylène bifonctionnel; R4 a la signification de R2 ou désigne un des groupements suivants: (a), (b), (c), (d), (e) ou (f), R10 ayant la même signification que R9; R représente O, CH-R5 ou la formule (II), R5 ayant la signification de R1.
PCT/DE2001/000005 2000-01-20 2001-01-04 Derives de di (het) arylaminothiophene WO2001053287A2 (fr)

Applications Claiming Priority (2)

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DE10002423.8 2000-01-20
DE10002423 2000-01-20

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WO2001053287A2 true WO2001053287A2 (fr) 2001-07-26
WO2001053287A3 WO2001053287A3 (fr) 2001-12-06

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7026490B2 (en) 2001-02-09 2006-04-11 Osram Opto Semiconductors Gmbh Amorphous organic 1,3,2-dioxaborine luminophores, method for the production and use thereof
CN105566285A (zh) * 2016-03-23 2016-05-11 厦门大学 一种由乙酰丙酸制备5-甲基噻吩-2-硫醇的方法
DE102022116865A1 (de) 2022-07-06 2024-01-11 PhoSuMa Photonic & Sustainable Materials Heteroaromatische ketone und ihre verwendung in der radikalischen und kationischen polymerisation

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0120673A2 (fr) * 1983-03-25 1984-10-03 EASTMAN KODAK COMPANY (a New Jersey corporation) Dispositifs organiques électroluminescents ayant des rendements du pouvoir de conversion
EP0466094A2 (fr) * 1990-07-10 1992-01-15 Canon Kabushiki Kaisha Elément électrophotographique photosensible
EP0866110A1 (fr) * 1997-03-17 1998-09-23 Toyo Ink Manufacturing Co., Ltd. Substance émettant de la lumière pour dispositif organique électroluminescent et dispositif organique électroluminescent

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01241561A (ja) * 1988-03-23 1989-09-26 Fuji Electric Co Ltd 電子写真用感光体

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0120673A2 (fr) * 1983-03-25 1984-10-03 EASTMAN KODAK COMPANY (a New Jersey corporation) Dispositifs organiques électroluminescents ayant des rendements du pouvoir de conversion
EP0466094A2 (fr) * 1990-07-10 1992-01-15 Canon Kabushiki Kaisha Elément électrophotographique photosensible
EP0866110A1 (fr) * 1997-03-17 1998-09-23 Toyo Ink Manufacturing Co., Ltd. Substance émettant de la lumière pour dispositif organique électroluminescent et dispositif organique électroluminescent

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 13, no. 000 (P-979), 20. Dezember 1989 (1989-12-20) -& JP 01 241561 A (FUJI ELECTRIC CO LTD), 26. September 1989 (1989-09-26) *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7026490B2 (en) 2001-02-09 2006-04-11 Osram Opto Semiconductors Gmbh Amorphous organic 1,3,2-dioxaborine luminophores, method for the production and use thereof
CN105566285A (zh) * 2016-03-23 2016-05-11 厦门大学 一种由乙酰丙酸制备5-甲基噻吩-2-硫醇的方法
CN105566285B (zh) * 2016-03-23 2018-01-09 厦门大学 一种由乙酰丙酸制备5‑甲基噻吩‑2‑硫醇的方法
DE102022116865A1 (de) 2022-07-06 2024-01-11 PhoSuMa Photonic & Sustainable Materials Heteroaromatische ketone und ihre verwendung in der radikalischen und kationischen polymerisation
WO2024008805A1 (fr) 2022-07-06 2024-01-11 Phosuma Photonic & Sustainable Materials Gmbh Cetones hétéroaromatiques et leur utilisation dans la polymerisation radicalaire et cationique

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