Pyrimidine reactions. VIII. Methiodides formed from some dimethylaminopyrimidines

1965 ◽  
Vol 18 (2) ◽  
pp. 199 ◽  
Author(s):  
DJ Brown ◽  
T Teitei
Keyword(s):  
Nitrogen Atom ◽  
Methyl Iodide ◽  
Hydrogen Sulphide ◽  
Aqueous Ethanol ◽  
Alkaline Degradation ◽  
Dimethylamino Group ◽  
Nucleoside Synthesis ◽  
Sodium Hydrogen ◽  
Quaternary Compounds

4.Dimethylaminopyrimidine and its 2-chloro-, 2-dimethylamino-, 6-chloro-, 6-methylthio-, and 6-dimethylamino-derivatives are quaternized by methyl iodide at N 1. The structures of the resulting methiodides are proven by alkaline degradation to known oxopyrimidines. 4-Dimethylamino-2-(and 6-)methoxypyrimidine and 2-dimethylamino-4-methoxypyrimidine all undergo quaternization on a nuclear nitrogen atom followed by spontaneous loss of methyl iodide to yield oxopyrimidines (cf. the so-called Johnson and Hilbert nucleoside synthesis). The unique lability of the dimethylamino group in these quaternary compounds is exemplified in the con- version of 2-dimethylamino-1,6-dihydro-1,3-dimethyl-6-oxopyrimidinium iodide into 1,3-dimethyluracil by mere dissolution in water or aqueous ethanol, and by the reaction of 2,4-bisdimethylamino-I-methylpyrimidinium iodide with ethanolic sodium hydrogen sulphide to give 4-dimethylamino-1,2-dihydro-1-methyl-2-thio- pyrimidine.

Levallorphan methyl iodide (SR 58002), a potent narcotic antagonist with peripheral selectivity superior to that of other quaternary compounds

Life Sciences ◽  
1983 ◽  
Vol 33 ◽  
pp. 477-480 ◽  
Author(s):  
M. Dragonetti ◽  
A. Bianchetti ◽  
R. Sacilotto ◽  
A. Giudice ◽  
N. Ferrarese ◽  
...  
Keyword(s):  
Methyl Iodide ◽  
Narcotic Antagonist ◽  
Quaternary Compounds

Reactions of phenyldimethylsilyllithium with β-N,N-dimethylaminoenones: A convenient synthesis of β-dimethyl(phenyl)silylacrylic acid and its derivatives

2004 ◽  
Vol 82 (2) ◽  
pp. 325-332 ◽  
Author(s):  
Ian Fleming ◽  
Elena Marangon ◽  
Chiara Roni ◽  
Matthew G Russell ◽  
Sandra Taliansky Chamudis
Keyword(s):  
Key Words ◽  
Methyl Iodide ◽  
Carbonyl Compounds ◽  
Conjugate Addition ◽  
Brief Treatment ◽  
Dimethylamino Group ◽  
Convenient Synthesis ◽  
Work Up

Phenyldimethylsilyllithium reacted with 5,5-dimethyl-3-(N,N-dimethylamino)cyclohex-2-enone (7), 3-(E)-N,N-dimethylaminopropenal (11), and 4-N,N-dimethylaminobut-3-en-2-one (13) to give the corresponding β-silyl-α,β-unsaturated carbonyl compounds 8, 12, and 14, in which the dimethylamino group has been displaced by the phenyldimethylsilyl group. Phenyldimethylsilyllithium reacted with ethyl β-N,N-dimethylaminopropenoate (15) by conjugate addition, but, in contrast to the ketones 7 and 13 and the aldehyde 11, the intermediate enolate 16 was C-protonated in the aqueous work-up to give ethyl 3-N,N-dimethylamino-3-dimethyl(phenyl)silylpropanoate (17). When the enolate 16 was instead given a mysteriously brief treatment with methyl iodide before work-up, the product was ethyl 3-(E)-dimethy(phenyl)silylpropenoate (18). Phenyllithium and methyllithium also added conjugatively to ethyl β-N,N-dimethylaminoacrylate (15) but, in contrast to the silyl case, the intermediate enolate 22 reacted unexceptionally with methyl iodide to give the products 25 and 26 of stereoselective C-methylation. This synthesis of the ester 18 was used to synthesize the Oppolzer sultam derivative 30.Key words: conjugate addition, elimination, substitution, silyllithium, silylenone.

scholarly journals THE REACTIONS OF ACTIVE NITROGEN WITH HYDROGEN SULPHIDE AND CARBON DISULPHIDE

1960 ◽  
Vol 38 (3) ◽  
pp. 334-342 ◽  
Author(s):  
R. A. Westbury ◽  
C. A. Winkler
Keyword(s):  
Nitrogen Atom ◽  
Hydrogen Sulphide ◽  
Temperature Effects ◽  
Carbon Disulphide ◽  
Third Body ◽  
Active Nitrogen

The destruction of either hydrogen sulphide or carbon disulphide by active nitrogen appears to be minimal at some temperature in the range 200–250 °C. Both reactions yield large amounts of polymer.It is postulated that the main reactions involve destruction of the reactant as it acts as a third body for recombination of nitrogen atoms. As the temperature is increased, dissociation of the nitrogen atom – reactant complex apparently increases. To account for the observed temperature effects, it is assumed that reactions also occur to regenerate reactant.

THE STRUCTURE OF AMINOPYRINE SALTS

1965 ◽  
Vol 43 (12) ◽  
pp. 3322-3329 ◽  
Author(s):  
Denys Cook
Keyword(s):  
Hydrogen Bond ◽  
Nitrogen Atom ◽  
Infrared Spectra ◽  
Dimethylamino Group ◽  
Complex Anions ◽  
Normal Formula

The infrared spectra of aminopyrine salts can be interpreted on the basis of protonation of the 4-dimethylamino group nitrogen atom. In the hydrohalides the normal [Formula: see text] hydrogen bond occurs, but in salts with complex anions an intramolecular [Formula: see text] hydrogen bond is probable, though an intermolecular one between the same partners cannot be ruled out.

N,N′,N′-Trimethylethylendiamin-substituierte Phosphor(III)-Verbindungen und deren Oxidation zu Derivaten mit tetra- und pentakoordiniertem Phosphor / N,N′,N′-Trim ethylethylenediamine-Substituted Phosphorus(III) Com pounds and their Oxidation to Derivatives with Four-and Five-Coordinated Phosphorus

1992 ◽  
Vol 47 (2) ◽  
pp. 275-283 ◽  
Author(s):  
Thomas Kaukorat ◽  
Reinhard Schmutzler
Keyword(s):  
Mass Spectrometry ◽  
Nmr Spectroscopy ◽  
Nitrogen Atom ◽  
Phosphorus Atom ◽  
Phosphorus Compounds ◽  
Trivalent Phosphorus ◽  
Reaction Products ◽  
Acceptor Interaction ◽  
Dimethylamino Group ◽  
Donor Acceptor

A study was made of the intramolecular donor-acceptor interaction in N,N′,N′-trimethylethylenediamine- substituted phosphorus compounds, involving λ3-, λ4- and λ5-phosphorus atoms, as a function of the nature of the substituents at phosphorus. The reaction of N-trimethylsilyl-N,N′,N′-trimethylethylenediamine (1) with (PriO)2PCl furnished the acyclic, trimethylethylenediamine-substituted phosphorus(III) compound 4. There is no NMR spectroscopic evidence for an intramolecular donor-acceptor interaction between the phosphorus atom and the nitrogen atom of the dimethylamino group in 4. The oxidation of the trivalent phosphorus atom in 4 and in the related compound 5 by sulfur, selenium, tetrachloroo- benzoquinone, and hexafluoroacetone led to the corresponding λ4P compounds 6 - 9 and to the λ5P compounds 10 and 11. No intramolecular donor-acceptor interaction could be detected in any of these products. There was no reaction between 5 and elemental tellurium. The reaction products were characterized by NMR spectroscopy, mass spectrometry, and by elemental analysis.

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