WO2020174058A1 - Procédé d'obtention de quinoxaline - Google Patents

Procédé d'obtention de quinoxaline Download PDF

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Publication number
WO2020174058A1
WO2020174058A1 PCT/EP2020/055176 EP2020055176W WO2020174058A1 WO 2020174058 A1 WO2020174058 A1 WO 2020174058A1 EP 2020055176 W EP2020055176 W EP 2020055176W WO 2020174058 A1 WO2020174058 A1 WO 2020174058A1
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WO
WIPO (PCT)
Prior art keywords
reaction
solvent
phenylenediamine
reaction temperature
acetic acid
Prior art date
Application number
PCT/EP2020/055176
Other languages
German (de)
English (en)
Inventor
Miriam Margarethe UNTERLASS
Lukas P. LEUTGEB
Fabián Andrés AMAYA-GARCIA
Original Assignee
Technische Universität Wien
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 Technische Universität Wien filed Critical Technische Universität Wien
Priority to EP20712212.8A priority Critical patent/EP3931184A1/fr
Priority to KR1020217029374A priority patent/KR20210134668A/ko
Publication of WO2020174058A1 publication Critical patent/WO2020174058A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
    • C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
    • C07D241/40—Benzopyrazines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
    • C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
    • C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
    • C07D241/40—Benzopyrazines
    • C07D241/42—Benzopyrazines with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings

Definitions

  • the present invention relates to a new production process for quinoxalines. STATE OF THE ART
  • the present invention relates to the condensation according to synthesis route "A", that is to say of o-phenylenediamines with 1,2-diketones. These condensation reactions are typically carried out in ethanol or acetone as the solvent under reflux in the presence of a catalyst. Numerous catalysts are known for this purpose, including e.g. B.
  • the solvents tested were methanol, ethanol, THF, dichloromethane, acetonitrile, 1: 1 mixtures of THF or ethanol and water, and water alone, where I2 was added as a catalyst at 5 mol% in each case.
  • the aim of the invention was against this background to develop a rapid, inexpensive and environmentally friendly process for the preparation of quinoxalines, in particular aromatically substituted quinoxalines, from correspondingly substituted o-phenylenediamines.
  • the present invention achieves this aim by providing a process for the preparation of quinoxalines by condensation of optionally substituted o-phenylenediamine with a diketone according to the following reaction scheme: Scheme 4
  • Ri, R2 and R3 are each independently hydrogen or a monovalent, saturated, unsaturated or aromatic hydrocarbon radical having 1 to 20 carbon atoms, one or more carbon atoms optionally being replaced by heteroatoms, each independently selected from O, N, S, F, CI and Br are selected and n is an integer from 0 to 4;
  • radicals Ri and / or the radicals R2 and R3 are connected to one another and together with the atoms to which they are bonded form a saturated, unsaturated or aromatic ring and / or one Ri of two o-phenylenediamine molecules together for stand a chemical bond and thus form a diaminobenzidine;
  • condensation reaction is carried out in water as a solvent by heating the reactants under pressure to a reaction temperature> 100 ° C.
  • the process of the present invention is based on the surprising discovery by the inventors that o-phenylenediamines, although they are extremely unstable under the conditions prevailing in the inventive method and react within a few minutes, as will be shown in Comparative Example 1 later, nonetheless in good yields are condensable to the desired quinoxalines - even at temperatures above 200 ° C under high pressures, which is anything but gentle reaction conditions, and without the need for the addition of catalysts. It was also particularly surprising that aromatic diketones, such as. B. benzil and dimethoxybenzil, with which according to the prior art at room temperature only conversions of 10-30% were achieved even after 5 hours, the desired quinoxalines could be obtained within a very short time in yields of over 90%.
  • the yields were about the same as when using pure water the addition of acetic acid apparently had no effect on the stability of the diamine under hydrothermal conditions, but this showed a clear catalytic effect.
  • an aqueous solution of acetic acid more preferably an approximately 1 to approximately 10%, in particular an approximately 5%, aqueous solution of acetic acid is used as the aqueous solvent.
  • the reaction mixture is heated to a reaction temperature of at least 200 ° C., in particular to a reaction temperature of about 230 ° C., in order to ensure the fastest possible condensation reactions.
  • a reaction temperature of at least 200 ° C., in particular to a reaction temperature of about 230 ° C.
  • pressures between 20 and 30 bar were generally established.
  • the heating to the hydrothermal conditions is carried out using microwave radiation in the shortest possible time, specifically within just 2 minutes.
  • the high reaction temperature need only be maintained for a period of not more than 10 minutes, preferably not more than 5 minutes.
  • Ri and R2 are each aromatic radicals, which can sometimes be linked to one another, since the resulting quinoxalines could for the first time be produced in good yields within a short time using water as the sole solvent, and also conjugated aromatic systems which are valuable materials for the manufacture of optoelectronic components.
  • the o-phenylenediamine is used in dimeric form, ie one Ri of two o-phenylenediamine molecules together form a chemical bond that connects these molecules to form a dimer, ie a diaminobenzidine, which in particular has 3, Is 3'-diaminobenzidine.
  • dimeric quinoxalines with relatively high molecular weights have not previously been accessible in such a simple manner.
  • a further catalyst in addition to acetic acid, can nonetheless be added in order to further increase the conversion of the condensation reaction in the short reaction times according to the present invention, even if the reaction takes place in a short time even without such an additional catalyst and can be carried out with satisfactory yields.
  • the process according to the invention allows the desired quinoxalines to be synthesized in good yields within a few minutes of reaction time, without the need to add any catalyst.
  • the invention also relates to a new substance synthesized for the first time by the inventors, namely the dimeric quinoxaline as a product of the later Example 14, i.e. H. 2,2 ', 3,3'-tetrakis (4-methoxyphenyl) -6,6'-dichinoxaline or 6- (2,3-bis (4-methoxyphenyl) quinoxalin-6-yl) -2,3-bis ( 4-methoxyphenyl) quinoxaline of the following formula (14):
  • o-Phenylenediamine (64.9 mg, 0.6 mmol) was weighed together with 9,10-phenanthrene-quinone (124.9 mg, 0.6 mmol) into a glass microwave insert and mixed with 15 ml of dist. Water layered. A magnetic stir bar was added and the insert sealed and placed in a microwave reactor. The reaction mixture was heated to 230 ° C. over the course of 2 minutes with stirring and held at this temperature for 5 minutes. The reaction mixture was then cooled and the precipitated solid was filtered off. The product was washed with distilled water and dried overnight in a drying cabinet heated to 80 ° C. In this way, 127.9 mg (76.0% of theory) of the title compound were obtained.
  • o-Phenylenediamine (42.3 mg, 0.4 mmol) was weighed together with the respective diketone (0.4 mmol) in a glass microwave insert and poured into 2 ml of either dist. Suspended water or 5% acetic acid, after which the insert was sealed and placed in a microwave reactor. The reaction mixture was heated to 230 ° C. within 1-2 minutes and held at this temperature for 5, 10 and 30 minutes, respectively. The reaction mixture was then cooled and the precipitated solid was filtered off. The product was washed with distilled water and dried overnight in a drying cabinet heated to 80 ° C.
  • the title compound was determined using dist. Water as a solvent in a yield of 64% of theory. Th. After a reaction time of 5 min (Example 6a) and of 87% of theory. Th. After 30 min (Example 6b) and using 5% acetic acid as a solvent in a yield of 76% of theory. Th. After 5 min (Example 6c) and also from 87% of theory. Th. After 10 min (Example 6d) in each case as a yellow solid.
  • the title compound was determined using dist. Water as a solvent in a yield of 63% of theory. Th. After a reaction time of 5 min (Example 7a) and 86% of theory. Th. After 30 min (Example 7b) and using 5% acetic acid as a solvent in a yield of 74% of theory. Th. After 5 min (Example 7c) and from 84% of the theory. Th. Obtained after 10 min (Example 7d) in each case as a gray solid.
  • Example 8a The title compound was obtained using 5% acetic acid as a solvent in a yield of 76% of theory. Th. After a reaction time of 5 min (Example 8a) and of 86% of theory. Th. Obtained after 10 min (Example 8b) in each case as a yellow solid.
  • Example 9a The title compound was obtained using 5% acetic acid as a solvent in a yield of 69% of theory. Th. After a reaction time of 5 min (Example 9a) and 80% of theory. Th. After 10 min (Example 9b) in each case as a yellow solid.
  • the title compound was obtained using 5% acetic acid as a solvent in a yield of 71% of theory. Th. After a reaction time of 5 min (example 10a) and 80% d. Th. After 10 min (Example 10b) in each case as a yellow solid obtained.
  • the title compound was obtained using 5% acetic acid as the solvent in a yield of 84% of theory. Th. After a reaction time of 5 min (Example 11 a) and 97% of theory. Th. After 10 min (Example 1 1 b) he hold each as a white solid.
  • the title compound was obtained using 5% acetic acid as a solvent in a yield of 81% of theory. Th. After a reaction time of 5 min (Example 12a) and 93% of theory. Th. After 10 min (Example 12b) he holds each as a white solid.
  • the title compound was obtained using 5% acetic acid as a solvent in a yield of 82% of theory. Th. After a reaction time of 5 min (Example 13a) and 93% of theory. Th. After 10 min (Example 13b) in each case as a yellow solid obtained.
  • Example 15a The title compound was obtained using 5% acetic acid as a solvent in a yield of 83% of theory. Th. After a reaction time of 5 min (Example 15a) and 94% of theory. Th. After 10 min (Example 15b) in each case as a yellow solid obtained.
  • o-phenylenediamine was used alone, i.e. without a reaction partner, with 15 ml of distilled water. Water was added and the mixture was heated to 200 ° C. overnight in a steel autoclave. After drying in a high vacuum, an FT-IR-ATR spectrum was recorded. and compared with a spectrum of the starting material before heating, the two curves being superimposed.
  • Fig. 1 shows this comparison, the curve after exposure to hydrothermal conditions and those of the starting material are shown in bold. It can be seen that practically all of the characteristic bands had disappeared, which means that the o-phenylenediamine had reacted almost completely during the hydrothermal conditions.
  • a rapid NMR analysis showed, however, that not (or not only) the o-quinonediimine or 2,3-diaminophenazine shown in Scheme 2, but a large number of reaction products, had arisen.

Abstract

L'invention concerne un procédé pour obtenir des quinoxalines par condensation de o-phénylènediamine éventuellement substituée avec une dicétone selon le schéma réactionnel (schéma 4) suivant, dans lequel : R1, R2 et R3 sont respectivement indépendamment de l'hydrogène ou un radical hydrocarbure monovalent, saturé, insaturé ou aromatique possédant 1 à 20 atomes de carbone, un ou plusieurs atomes de carbone étant éventuellement remplacés par des hétéroatomes, qui sont choisis chacun indépendamment de O, N, S, F, CI et Br, et n étant un nombre entier de 0 à 4, éventuellement deux radicaux R1 et/ou les radicaux R2 et R3 étant reliés l'un à l'autre et formant conjointement avec les atomes auxquels ils sont liés un cycle saturé, insaturé ou aromatique et/ou un R1 respectif de deux molécules d'o-phénylènediamine représentant conjointement une liaison chimique et formant donc une diaminobenzidine; et la réaction de condensation étant effectuée dans l'eau en tant que solvant par chauffage des produits de départ sous pression à une température de réaction > 100 °C.
PCT/EP2020/055176 2019-02-27 2020-02-27 Procédé d'obtention de quinoxaline WO2020174058A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP20712212.8A EP3931184A1 (fr) 2019-02-27 2020-02-27 Procédé d'obtention de quinoxaline
KR1020217029374A KR20210134668A (ko) 2019-02-27 2020-02-27 퀴녹살린의 제조 방법

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ATA76/2019A AT522210B1 (de) 2019-02-27 2019-02-27 Herstellungsverfahren für Chinoxaline
ATA76/2019 2019-02-27

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EP (1) EP3931184A1 (fr)
KR (1) KR20210134668A (fr)
AT (1) AT522210B1 (fr)
WO (1) WO2020174058A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113087674A (zh) * 2021-04-17 2021-07-09 河南大学 可见光诱导铁催化条件下合成喹喔啉类化合物的方法

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WO2005123737A2 (fr) * 2004-06-14 2005-12-29 Arizona Board Of Regents On Behalf Of The University Of Arizona Materiaux de transport de charge, procedes de fabrication et procedes d'utilisation
WO2010126006A1 (fr) * 2009-04-30 2010-11-04 日立化成工業株式会社 Composition de résine photosensible, élément photosensible utilisant la composition, procédé de formation d'un motif de réserve et procédé de production d'une carte de circuits imprimés
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113087674A (zh) * 2021-04-17 2021-07-09 河南大学 可见光诱导铁催化条件下合成喹喔啉类化合物的方法
CN113087674B (zh) * 2021-04-17 2022-06-17 河南大学 可见光诱导光敏剂催化条件下合成喹喔啉类化合物的方法

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AT522210A1 (de) 2020-09-15
AT522210B1 (de) 2024-04-15
KR20210134668A (ko) 2021-11-10
EP3931184A1 (fr) 2022-01-05

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