Synthesen von Thiazolo‐ und [1,3]Thiazino[1,2,4]triazinonen

Abstract

Es werden die Synthesen der Thiazolo-und [1,31Thiazino[l,2,4]triazinone 3 -6 beschrieben. Die Darstellungen der Verbindungen 3 und 5 gelangen regiospezifisch mittels der Verbindungen 12 und 13. Syntheses of Thiazolo-and [1,3]Thiazinoll,2,41triazinonesThe syntheses of the thiazolo-and [1,3]thiazino[1,2,4]triazinones 3-6 are described. Preparations of compounds 3 and 5 were achieved regiospecifically by using the compounds 12 and 13.Die Arninotriazinone 1 und 2 sind gut bekannte Verbindungen rnit herbiziden Eigenschaften '). Wir haben die thiazolo-und [ 1,3]thiazinoanellierten Triazinone der Typen 3 -6 hergestellt und stellten fest, daR auch diese Verbindungen herbizid sind. Die wirksamsten Vertreter fanden wir in der Verbindungsklasse 3.Gemeinsarne Startrnaterialien der durchgefuhrten Triazinonsynthesen waren Glyoxylsauren und -ester (8, 9)*). Zur Darstellung von 3 und 4 wurden diese rnit Thiosemicarbazid zu den 3-Mercaptotriazinonen 73) und weiter mit 1,2-Dibromethan zu den Thiazolotriazinonen umgesetzt. Bei dieser Anellierung erhalt man in der Regel ein Gernisch der Regioisomeren 3 und 4, die sich jedoch saulenchrornatographisch leicht trennen lassen (Methode A)4'. Als Nachteil erwies sich, dalj die biologisch weniger aktiven lsomere 4 immer Hauptprodukte waren. Die Isomeren 3 entstanden nur als Nebenprodukte, oder -wie bei den Reaktionen der Methyl-und tert-Butyltriazinone 7a, bgar nicht.Regiospezifische Synthesen der Thiazolotriazinone 3 lieljen sich dann durch Umsetzungen der Glyoxylsauren 8 oder -ester 9 mit 2-Hydrazinothiazolin (12) (Methode B)') glatt realisieren. Analog konnten dann die [I ,3]Thiazinotriazinone 5 aus den Glyoxylsauren oder -estern mit 2-Hydrazino-5,6-dihydro-4H-l,3-thiazin (13) erhalten werden.Letzteres lien sich analog der Darstellung von 12@ durch Urnsetzung von Thiosemicarbazid rnit 3-Brompropylarnin-hydrobromid synthetisieren.Synthesen der ungesattigten Thiazolotriazinone 6 erfolgten auf folgendem Wege: Umsetzung der Glyoxylsauren 8 rnit Thiosemicarbazid zu den Sauren 10, Weiterreaktion rnit den entsprechenden a-Chlorcarbonylverbindungen zu den Thiazolhydrazinen 11 und schliel3lich Cyclisierung uber die gemischten Anhydride zu 6".

Transformation of a CuII Thiazolo‐1,2,4‐triazine Derivative from a Metastable Coordination Network to a Monomer in Solution and Vapor Conditions

“…1,2,4-triazine-3-thione and thiazolo-1,2,4-triazine derivatives, are targets because of the structural characteristics of the condensed donor sites (N, O, and S atoms) and their inhibitory activity against peroxidases containing Cu 2+ ions. [9,10] However, the coordination mode of these heterocyclic compounds is unclear for two reasons: (i) few structural characterizations of the coordination complexes have been carried out [11,12] and (ii) dynamic exchange reactions of the coordination site occur between the multiple donor species depending on the external conditions. [13][14][15] Therefore, we examined some model com-of 5a decreased according to the color change.…”

Synthesis of Rigidified eIF4E/eIF4G Inhibitor-1 (4EGI-1) Mimetic and Their in Vitro Characterization as Inhibitors of Protein–Protein Interaction

“…Clemmensen reduction of the ketones 45,46 was followed by intramolecular polyphosphoric acid-mediated acylation, 47 generating the corresponding α-tetralone derivatives 9a 45 and 9b 46 that were then α-brominated to the corresponding 2-bromo-6,7-dichloro-3,4-dihydronaphthalen-1(2H)-one, 10a, 46,48 and 2-bromo-5,6-dichloro-3,4-dihydronaphthalen-1(2H)-one, 10b. Hantzsch-type reaction 49 between thiosemicabazide and these α-bromoketones generated predominantly the corresponding hydrazines 11a and 11b in (18) in the presence of HF liq afforded 7,8-dichlorochroman-4-one (19) but in the presence of Eaton's reagent it yielded 5,6dichlorochroman-4-one (20). Because of excessive steric hindrance considerations, we shelved ketone 20 and carried α-bromination of 16 and 19 successfully by employing pyridinium bromide perbromide (PBPB).…”

“…Clemmensen reduction of the ketones , was followed by intramolecular polyphosphoric acid-mediated acylation, generating the corresponding α-tetralone derivatives 9a and 9b that were then α-brominated to the corresponding 2-bromo-6,7-dichloro-3,4-dihydronaphthalen-1­(2 H )-one, 10a , , and 2-bromo-5,6-dichloro-3,4-dihydronaphthalen-1­(2 H )-one, 10b . Hantzsch-type reaction between thiosemicabazide and these α-bromoketones generated predominantly the corresponding hydrazines 11a and 11b in moderate yields side-by-side with lesser amounts of the side-product amines 12a and 12b . Finally, condensation between 4,5-dihydronaphtho­[1,2- d ]­thiazol-2-yl)­hydrazines, 11a and 11b , with 2-( o -nitrophenyl)­pyruvic acid in the presence of 5% acetic acid afforded the isomeric mixture of the desired rigidified 1 mimetic, ( E / Z )- 13a (type P1) and ( E / Z )- 13b (type P2) in 35–40% yield.…”

α-Keto Acids: Acylating Agents in Organic Synthesis

“…Despite the unquestionable biochemical importance that has been attributed to α-keto acids 1 since the 19th century, the use of this class of compounds as starting materials in organic synthesis started to be considered around the 1930s and 1940s, mainly in esterification and condensation reactions. , Over the following years, until nowadays, several studies on the behavior of α-keto acid 1 in condensation and esterification reactions with N-, O-, and S-based nucleophiles have contributed to elucidate its reactivity as an electrophile in both carbonyl and carboxyl groups, in the construction of a wide range of structures. − …”