DE2022470A1 - 1,3-diazoheterocycles from gamma-cyano-varboxylic acid - halides and hydrohalides - Google Patents

1,3-diazoheterocycles from gamma-cyano-varboxylic acid - halides and hydrohalides

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Publication number
DE2022470A1
DE2022470A1 DE19702022470 DE2022470A DE2022470A1 DE 2022470 A1 DE2022470 A1 DE 2022470A1 DE 19702022470 DE19702022470 DE 19702022470 DE 2022470 A DE2022470 A DE 2022470A DE 2022470 A1 DE2022470 A1 DE 2022470A1
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halogen
cyano
substituted
halides
acid
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DE19702022470
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German (de)
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Guenther Dipl-Chem Entenmann
Gerhard Dr Simchen
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Individual
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Individual
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/70—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings condensed with carbocyclic rings or ring systems
    • C07D239/72—Quinazolines; Hydrogenated quinazolines
    • C07D239/95—Quinazolines; Hydrogenated quinazolines with hetero atoms directly attached in positions 2 and 4

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

Halogen substd. 1,3-diazoheterocycles are prepd. from gamma-cyanocarboxylic acid halides and hydrohalides. Starting materials may be beta-cyanoisocyanates, beta-cyanoisothiocyanates or beta-aminonitriles and pref. beta-aminonitrile is reacted with reagents e.g. phosgene or thiophosgene and the mixture used as starting material without isolating intermediates.

Description

Verfahren zur Herstellung halogensubstituierter 1.3-Diaza-heterocyclen.Process for the preparation of halogen-substituted 1,3-diaza-heterocycles.

In der deutschen Patentanmeldung P1620389.7 vom 11.7.1960 wurde die Umsetzung von γ-cyansubstituierten Carbonsäuren mit Halogenierungsmitteln beschrieben.In the German patent application P1620389.7 of July 11, 1960 the Implementation of γ-cyano-substituted carboxylic acids with halogenating agents described.

tiit diesem latent wird ein Verfahren z'ir lierstellung halogensubstituierter Heterocyclen beansprucht, dadurch gekennzeichnet, daß man 1. eine γ-Cyancarbonsäure mit einem Halogenierungsmittel umsetzt, 2. eine γ-Cyancarbonsäure zunächst in das Carbonsäure-Halogenid überführt und dieses mit einer Halogenwasserstoffsäure cyclisiert.With this, a process for producing halogen-substituted substances becomes latent Claimed heterocycles, characterized in that 1. a γ-cyanocarboxylic acid reacts with a halogenating agent, 2. a γ-cyanocarboxylic acid first converted into the carboxylic acid halide and this with a hydrohalic acid cyclized.

In Weiterausbildung dieser Methode zur Synthese halogensubstituierter Heterocyclen wurde nun ein Darstellungsverfahren halogensubstituierter 1.3-Diazaheterocyclen gefunden, das dadurch gekennzeichnet ist, daß man -ß-Cyancarbamidsäurehalogenide und ß-Cyanthiocarbamidsäurehalogenide nit Halogenwasserstoff umsetzt. In a further development of this method for the synthesis of halogen-substituted heterocycles, a method for preparing halogen-substituted 1,3-diazaheterocycles has now been found, which is characterized in that -β-cyancarbamic acid halides and β-cyanthiocarbamic acid halides are reacted with hydrogen halide.

nierin bedeutet X ein Halogenatom, die Kohlenstoffatome Cα und Cß sind vorzugsweise Glieder eines aromatischen oder heteroaromatischen Kingsystems. So erhält man, wenn Cα und Cß Glieder eines benzolringes sind, 4-Halogenchinazolone-(2) und 4-Halogenchinazolinthione-(2). Bei diesem Verfahren sind die ß-Cyancarbamidsäurehalogenide und ß-Cyanthiocarbamidsäurehalogenide nur Zwischenprodukte, die in der kegel nicht isoliert werden. Als Ausgangssubstanzen dienen vielnehr die als deren Vors-tuSen anziisehenden-isocyanato- und ß-Isothiocyanatonitrile, die man mit Halogenwasserstoff zur Reaktion bringt. Nierin X denotes a halogen atom, the carbon atoms Cα and Cβ are preferably members of an aromatic or heteroaromatic king system. Thus, if Cα and Cß are members of a benzene ring, 4-haloquinazolones- (2) and 4-haloquinazolinthione- (2) are obtained. In this process, the ß-Cyancarbamidsäurehalogenide and ß-Cyanthiocarbamidsäurehalogenide are only intermediates, which are not isolated in the cone. The isocyanato- and ß-isothiocyanatonitriles, which are listed as precursors and are reacted with hydrogen halide, are used as starting substances.

Eine weitere Vereinfachung des Verfahrens besteht nun darin, daß man von ß-Aminonitrilen ausgeht und diese mit geeigneten Agentien wie z.b. phosgen oder 'hiophosgen dierekt in die Heterocyclen überführt. A further simplification of the process consists in starting from ß-aminonitriles and converting these directly into the heterocycles using suitable agents such as phosgene or 'hiophosgene.

Die Kohlenstoffatome Cα und Cß sind wiederum vorzugsweise glieder eines aromatischen oder heteroaromatischen Ringsystems.The carbon atoms Cα and Cβ are again preferably members an aromatic or heteroaromatic ring system.

sie Umsetzungen wurden in organischen Lösungsmitteln oder direkt bei Raumtemperatur oder erhöhter Temperatur durchgeführt.they were in organic solvents or directly during reactions Room temperature or elevated temperature carried out.

Die erhaltenen Halogen-1.3-diazaheterocyclen sind äußerst reaktionsfähige Verbindungen. So läßt sich beispielsweise das Halogenatom durch nucleophile Agentien leicht austauschen.The halogen-1,3-diazaheterocycles obtained are extremely reactive Links. For example, the halogen atom can be removed by nucleophilic agents easily exchange.

Beispiele Nr. X Y Z Bezeichnung Schmp. Ausb.Examples No. XYZ designation m.p. yield.

1 0 Cl H 4-Chlorochinazolon-(2) 213 86 % 2 0 Cl Hr 4-Chlor-6-bromchinazolon-(2) >3500 85 o 3 O Br H 4-Bromchinazolon-(2) 331° 92 % 4 S Cl H 4-Chlorchinazolinthion-(2) 296° 95 % Darstellung der Chinazolone und Chinazolinthione aus o-Cyanphenylisocyanaten bzw. o-Cyanphenylsenfölen.1 0 Cl H 4-chloroquinazolone- (2) 213 86% 2 0 Cl Hr 4-chloro-6-bromoquinazolone- (2) > 3500 85 o 3 O Br H 4-bromoquinazolone- (2) 331 ° 92% 4 S Cl H 4-chloroquinazolinthione- (2) 296 ° 95% Preparation of the quinazolones and quinazolinethiones from o-cyanophenyl isocyanates or o-cyanophenyl mustard oils.

0,01 Mol o-Cyanphenylisocyanat bzw. o-Cyanphenylsenföl werden in 50 ccm Dibutyläther gelöst, HCl eingeleitet und 7 Stunden auf 70-80 °C erhitzt. Das ausgefallene Produkt wird abgesaugt, 5 Stunden i.Vak, beJ 100 °C getrocknet und aus Chlorbenzol oder Brombenzol umkristallisiert.(Beispiel Nr. 1-4.) Darstellung der Chinazolone aus o-Aminobenzonitrilen.0.01 mol of o-cyanophenyl isocyanate or o-cyanophenyl mustard oil are used in 50 ccm of dibutyl ether dissolved, HCl introduced and heated to 70-80 ° C for 7 hours. That The precipitated product is filtered off with suction, dried in vacuo at 100 ° C. for 5 hours and dried recrystallized from chlorobenzene or bromobenzene. (Example No. 1-4.) Illustration the quinazolones from o-aminobenzonitriles.

0,01 Mol o-Aminobenzonitril-hydrochlorid werden in 50 ccm Dibutyläther suspendiert und bei 110 °C mit Phosgen umgesetzt, bis kein HCl mehr entsteht. Dann wird 7 Stunden bei 70 °C HCl eingeleitet. Aufarbeitung wie oben.0.01 mol of o-aminobenzonitrile hydrochloride are dissolved in 50 cc of dibutyl ether suspended and reacted with phosgene at 110 ° C. until no more HCl is formed. then HCl is passed in at 70 ° C. for 7 hours. Work up as above.

(Beispiel Nr. 1).(Example No. 1).

Claims (3)

Anspruchclaim 1. Verfahren zur erstellung von halogensubstituierten 1 .3-Diazaheterocyclen in Weiterausbildung des Verfahrens zur nerstellung halogensubstituierter Heterocyclen nach Patentanmeldung P1620389.7, dadurch gekennzeichnet, daß man γ-Cyancarbonsäurehalogenide mit Halogenwasserstoffen umsetzt.1. Process for the preparation of halogen-substituted 1 .3-diazaheterocycles in further training of the process for the preparation of halogen-substituted heterocycles according to patent application P1620389.7, characterized in that γ-cyanocarboxylic acid halides Reacts with hydrogen halides. 2. Verfahren zur Herstellung von halogensubstituierten 1.3-Diazaheterocyclen, dadurch gekennzeichnet, daß man p-Cyanisocyanate und p-Cyanisothiocyanate mit lIalogenwasserstoffen umsetzt.2. Process for the preparation of halogen-substituted 1,3-diazaheterocycles, characterized in that p-cyano isocyanates and p-cyano isothiocyanates with halogenated hydrogen implements. 3. Verfahren zur herstellung von halogensubstituierten 1.3-Diazaheterocyclen, dadurch gekennzeichnet, daß man ß-Aminonitrile mit geeigneten Agentien,wie Phosgen oder Thiophosgen ohne Isolierung von Zwischenprodukten umsetzt.3. Process for the preparation of halogen-substituted 1,3-diazaheterocycles, characterized in that ß-aminonitriles with suitable agents such as phosgene or thiophosgene without isolation of intermediates.
DE19702022470 1970-05-08 1970-05-08 1,3-diazoheterocycles from gamma-cyano-varboxylic acid - halides and hydrohalides Pending DE2022470A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4395550A (en) * 1979-07-05 1983-07-26 Sandoz Ltd. Tetrahydro-2(1H)-quinazolinones and cyclohexene nitriles

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4395550A (en) * 1979-07-05 1983-07-26 Sandoz Ltd. Tetrahydro-2(1H)-quinazolinones and cyclohexene nitriles

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