2.3- Dimorpholino-3-phenyl

Dimorpholino-phenyl-methan und analoge Aminale reagieren mit Phenyl-ethin in Gegen-wart von Kupfer(I)-halogeniden, vermutlich iiber eine kupferorganische Zwischenstufe, zu l,3-Diphenyl-3-morpholino-propin bzw. analogen Produkten2. 

Dichlor- -diphosphonsaure-diathylester 571 Dichlor- -diphosphonsaure-diisopropylester 571 Dimorpholino-phenyl- 396 Dinitro-phenyl- 584... 

Dimorpholino-methylj-3- (4-meihoxy-phenyl)-1,2,4-oxadiazoh 90% Schmp. 124-125°... 

Ethane 2,2-Dimorpholino-l-(4-fluoro-phenyl)-1-0X0- E14a/3, 550f. (Ar-CO- CIIBr2 + HNR2)... 

Die N,N-Acetaie von 4,5-Dioxo-4,5-dihydro-l H-pyrazolen, wie 4,4-Dimorpholino-3-methyl-5-oxo-l-phenyl-4,5-dihydro-l H-pyrazol, werden durch Natriumdithionit beim Erhitzen in waB-rigem Ethanol in 80%iger Ausbeute zu 5-Hydroxy-4-morpholino-l H-pyrazolen reduziert1062 z.B. ... 

On addition of methyllithium in tetrahydrofuran/diethyl ether, pyrido[3,4-r/]pyridazine gives a 1 1 mixture of the two isomeric 1,2- and 4,3-addition compounds, i.e. 1-methyl-1,2-dihydropy-rido[3,4-r/]pyridazine (10) and 4-methyl-3,4-dihydropyrido[3,4-<7]pyridazine (11), which are readily oxidized by air to yield the fully aromatic systems (see Section 7.2.1.5.1.3).6 129 If the pyridazine ring is deactivated by amino substituents as in l,4-dimorpholino-7-phenylpyri-do[3,4-r/ pyridazine or its 5-methyl derivative, addition of organometallics such as benzyllithi-um, benzylmagnesium chloride or rcrt-butylmagnesium bromide occurs at the pyridine ring and yields 5-alkyl-5-methyl-l,4-dimorpholino-7-phenyl-5,6-dihydropyrido[3,4-d]pyridazines 12.119... 

Method A To a stirred solution of 4-substituted 5.8-dimorpholino-2-phenyl-3,4-dihydropynmido[4.5-rf]-pyridazine 1 (R1 = morpholino 1.5 mmol) or 4,8-disubstituted 5-niorpholino-2-phenyl-3,4-dihydropyrim-ido[4,5-<7]pyridazine 1 (R1 morpholino 2 mmol) in benzene (100 mL) was added a solution of DDQ (1.7 mmol or 2.2 mmol) in benzene (50 mL) at rt. After 0.5-1 h the mixture was purified by column chromatography (silica gel). The crude products were recryslallized from Et2(), petroleum ether or MeOH. 

In a smiliar manner, organolithium compounds also react with 5,8-dimorpholino-2-phenyl-pyrimido[4,5-cf]pyridazine.62... 

Photochemical addition of alcohols or ethers also leads to 4-substituted 5,8-dimorpholino-2-phenyl-3,4-dihydropyrimido[4,5-i/]pyridazines, e.g. 6.63... 

Dimorpholino-2-phenylpyrazino[2,3-rf]pyridazine (3) reacts with Grignard reagents to form 2-substituted 5,8-dimorpholino-3-phenyl-l,2-dihydropyrazino[2,3-tf]pyridazines 4.62... 

Under photochemical conditions, the reaction of methanol ordioxane with 3 yields 2-substituted 5,8-dimorpholino-3-phenyl-l, 2-dihydropyrazino[2,3-t/]pyridazines of type 4 in 55 and 40% yield, respectively.63... 

The oxidation of 4-benzyl-5,7-dimorpholino-2-phenyl-3,4-dihydropyrimido[4,5-t/]pyrimidine (l R1 = Bn) with potassium hexacyanoferrate(III) proceeds under oxidative elimination to give 2,4-dimorpholino-7-phenylpyrimido[4,5-<7]pyrimidine (2). Under the same conditions, the 4-ethyl analog (1, R1 = Et) gives 5-ethyl-2,4-dimorpholino-7-phenylpyrimido[4,5-[Pg.383]

The reaction of Grignard reagents with 2,4-dimorpholino-7-phenylpyrimido[4,5-r7]pyrimidine (8) leads to 4-substituted 5,7-dimorpholino-2-phenyl-3,4-dihydropyrimido[4,5-photochemical conditions, 2,4-dimorpholino-7-phenylpyrimido[4,5- f]pyrimidine (8) reacts with methanol or acetone to give the corresponding 3,4-dihydro derivative 10.63... 

Dimorpholino-2-phenyl-l,3,5-thiadiazinium Perchlorate (2) Typical Procedure 100... 

Dimorpholino-2-phenyl-l,3,5-oxadiazinium perchlorate (1 4.28 g, 10 mmol) was added to a stirred saturated solution of H2S in MeCN (40 mL) at 0 °C. After dropwise addition of Et3N (1.01 g, 10 mmol), the resultant mixture was allowed to stand at rt for 15 min. The solution was then acidified with HOAc to precipitate the product and after 1 h it was filtered by suction and recrystallized yield 2.4-2.6 g (54-60%) mp 284 °C. 

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