Dimorpholino

Imidazoline, 4,5-dimorpholino-mass spectra, 5, 361 2-Imidazoline, 1,2-diphenyl-... 

Pyrazino[2,3-d]pyridazine, 3,4-dihydro-dehydrogenation, 3, 348 Pyrazino[2,3-d]pyridazine, 5,8-dimorpholino-reactions... 

Pyridazine, 4-amino-5-formyl-3,6-dimorpholino-synthesis, 3, 346 Pyridazine, 4-amino-3-halo-reaction with potassium amide, 3, 29 Pyridazine, aryl-synthesis, 3, 28 Pyridazine, arylthio-synthesis, 3, 27 Pyridazine, 3-azido-... 

Pyrido[3,4-d]pyridazine, 1,4-dimorpholino-biological activity, 3, 261 Pyrido[4,3-c]pyridazine, dihydro-NMR, 3, 234 UV spectra, 3, 236... 

The oxidation of phenol in alcoholic media by a morpholine complex of Cu(II) (as a model for tyrosinase) to give 4,5-dimorpholino-orr/jo-benzoquinone in 64 %... 

Evidently, stable nitrile oxides can be investigated by spectral and X-ray methods using ordinary procedures. As examples, X-ray diffraction studies of o-sulfamoylbenzonitrile oxides (20), 5-methyl-2-(methylsulfonyl)-3-thiophene-carbonitrile oxide (21), (),( >-diphenylacrylonitrile oxide (22), and (dimorpholino-phosphoryl) carbonitrile oxide (23) can be cited. It should be underlined that structures of the latter compounds differ from those of classical stable 0,0 -disubstituted arylcarbonitrile oxides and tert-alkylcarbonitrile oxides. Therefore, not only purely steric shielding of the CNO group but also electrostatic or donor-acceptor interactions between the atoms of the latter and adjacent polar substituents (21, 23) and also electron delocalization in it-systems (20, 22) enhance the stability of nitrile oxide. 

Fields et al. found one example of an alkene, 1,1-dimorpholino-ethylene, which did not give the expected cycloaddition product, the 12,12-dimorpholino-6,ll-dihydro-6,ll-ethanoacridizinium ion (10). They conjectured that the l-(2-pyridyl)-2-morpholinonaphthalene (12) isolated had been formed via the expected adduct (10) which had undergone loss of morpholine to form the enamine (11) which could undergo ring opening (via a retro-quaternization reaction) followed by loss of a proton to yield (12). 

Bis-[morpholinioyliden]-ethan-dibromid liefert mit Amidinen 4,5-Dimorpholino-4,5-dihydro-imidazole, die durch Kochen in Trichlomiethan mit Ammoniumchlorid als Katalysator unter Bildung von 5-Morpholino-imidazolen Morpholin abspalten135. 

Bei den (Dichlor-methyl)-l,2,4-oxadiazolen fuhrt die Einwirkung von Morpholin unter dop-pelter Substitution zu den (Dimorpholino-methyl)-l, 2,4-oxadiazolen270. 

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

Die Reaktion von Dichlormethan mit sekundaren Aminen fuhrt zu N,N-Acetalen des Formaldehyds. Mit Dimethylamin entsteht (selbst noch bei 0°) Bis-[dimethylamind -methan in 50% Ausbeute neben anderen Produkten1. In guten Ausbeuten bilden sich analoge N,N-Acetale bei der Umsetzung von Dichlormethan mit cyclischen Aminen in Methanol untcr erhohtem Druck bei 30° z. B. Bis-[3-methyl-piperidino]-methan in 71 % Ausbeute Oder Dimorpholino-methan in 54% Ausbeute2 (vgl. a.Bd. E14a/3) ... 

Die Umsetzung von 3,4-Dinitro-l-methyl-pyrrol mit eincm UberschuB an sekundaren Aminen wie Piperidin oder Morpholin ergibt 2,3-Dipiperidino(b7.w. Dimorpholino)-l-me-thyl-4-nitro-2,3-dihydro-pyrrol (85 bzw. 87%)z. 

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. 

Similarly,both Meinert and Gambaretto, with their respective co-workers [80, 172, 175], have invoked this mechanism to explain the formation of partially fluorinated products in ECF reactions of the amines, tripropylamine, AT-methyl-morpholine, and a series of a,co-dimorpholino- and dipiperidino-alkanes. The selective order in which the hydrogens were substituted in these molecules was said to be consistent with that expected for the mechanism in that carbon atoms nearest to oxygen (in the morpholine rings), where the electron density is greatest, were the first to react, and those nearest to the quaternised nitrogen the last, not in a random order as might be expected in a radical mechanism. 

Dimethyl-3,4-dinitrothiophene undergoes a different type of reaction with cyclic secondary amines. The product from the reaction with morpholine, obtained in nearly quantitative yield, has been identified as 2,5-dimethyl-rrans-2,3-dimorpholino-4-nitro-2,3-dihydrothiophene. Most notable in this reaction is the high stereospecificity. The reaction probably proceeds through initial reversible addition of a molecule of morpholine to the 2,3-double bond (Scheme 139) <80JCS(P2)1764). 

The reaction of the diamino compound (107) under several different nitration conditions led to the formation of 5-nitroamino-8-aminopyrazino[2,3-d]pyridazine exclusively (68JHC53). 5,8-Dimorpholino substituted pyrazino[2,3-d]pyridazines are known to react with Grignard reagents to give 3-substituted 3,4-dihydro derivatives (75CPB1488). The dimorpholino heterocycles are also known to react photochemically with alcohols and cyclic ethers in the presence of photosensitizers to give 3-substituted 3,4-dihydro derivatives (Scheme 3) (75CPB1500). 

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

Dimorpholino-acetyl)-1-fluoro-E14a/3. 550f. (2 Br 2NR2) 4-(3,3-Dimorpholino-l-nilromethyl-ally])-l-fluoro- E15/2. 2188 (R,N)2C = CH2 +... 

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