Tris methyl derivatives reactions

Angier and Marsico followed the course of alkylation first. The 7-dimethylamino-5-methylmercapto derivative reacted with dimethyl sulfate in an alkaline medium to yield a mixture of the 2- and 3-methyl derivatives. The reaction of the 7-diraethylamino derivative with ethyl iodide in an alkaline medium led to a mixture of all three possible monoethyl derivatives. The position of the alkyl group in all these substances was defined by comparing the UV spectra with derivatives prepared by a straightforward synthesis. After reacting the mercuric salts with tri-0-benzoylribofuranosyl chloride, they demonstrated the ribose residue to be bound in position 2. The same structure was shown to be valid for the derivative prepared by Andrews and Barber. ... 

The vapor-phase pyrolysis of 4-hydroxy-1,2,3-triazole and its iV-methyl derivative affords methan-imine and its A-methyl analog. Analysis of the reaction path by the MNDO method shows the presence of two stable or metastable isomers, (liif)-4-hydroxy-l,2,3-triazole and its ketone protomer <89NJC551>. 4-Diazo-1,2,3-triazoles (122) thermolyze or photolyze in benzene to 4//-l,2,3-tri-azolylidenes (123) which convert benzene to 4-phenyl-1,2,3-triazoles and/or isomerize to a-diazo-nitriles (124). Intermediates (124) react with benzene via a carbene to give addition, ring expansion or substitution products (Scheme 17) <82TL5115>. The similar thermolysis of diazotriazoles in substituted benzene gives complex mixtures in which all of the components are sometimes impossible to isolate and identify <90AHC(48)65>. 

The chemical reactions of the cinnolinium-4-olates (233) are conveniently illustrated by considering specific reactions of the 2-methyl derivative (243) (Scheme 10). Compound 243 readily forms salts Ethanolic hydrogen chloride gives 2-methyl-4-hydroxycinnolinium chloride (239) and tri-ethyloxonium tetrafluoroborate gives 2-methyl-4-ethoxycinnolinium tetra-... 

Attempts to use basic reaction components other than 2,4-dialkoxy-pyrimidines met with varied success. Thus, the early attempt of Hilbert30 to react a-acetobromoglucose with 4-amino-2-methoxy-pyrimidine (19) failed. On the other hand, when 4-ethoxy-2(lI/)-pyrimidinone (20) or l-methyl-4-methoxy-2(li/)-pyrimidinone (21) was condensed with 2,3,5-tri-O-benzoyl-D-ribofuranosyl chloride, moderate yields were obtained of 3-/9-D-ribofuranosyluracil (22) and its 1-methyl derivative (23), respectively.31... 

This type of reaction was reported for tris(2-methoxyethyl)aminei and for the tetraamine tris(2-diethylaminoethyl)amine (Etetren). The latter was also obtained by alkylation of A, A-diethylethylenediamine with (C2H5)2NCH2CH2-Cl. 7 The corresponding methyl derivative tris(2-dimethylaminoethyl)amine (Mestren) was prepared by methylation of tris(2-aminoethyl)amine (tren). Similarly, methylation of tris(2-thiolethyl)amine was used to prepare tris(2-methylthioethyl)amine (D = SCHs). The method reported here (Sec. C) seems more efficient, in that it avoids the intermediate synthesis of N(CH2CH2-SH)a and is based on the reaction above with NaSCHs the sodium methyl-mercaptide is either prepared in advance or in situ by the reaction of CH3SH with NaOCHa. 

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