1-Alkylamino

If 2-amino-4,5-dimethylthiazole is treated under such conditions 2-alkylamino-4.5-dimethylthiazoles are formed (202). 

Acetamidothiazoles are reduced with LiAlH to 2-alkylamino-thiazoles in good yields (81, 130, 477, 478), (see also Section I.l.E). 

The condensation of a-haloketones with monosubstituted alkyl or aryl-selenoureas (25) leads to 2-alkylamino- (26. 27) or 2-arylaminOselana-zoles (28) while disubstituted selenoureas give 2-(dialkylamino) selenazoles (26. 27) (Table X-3a). 

Chromone, 2-alkylamino-5,8-dimethoxy-synthesis, 3, 717 Chromone, 2-amino-aromaticity, 3, 714 tautomerism, 3, 644... 

Thiazole, 2-acetylamino-4-methyl-alkylation, 6, 256 Thiazole, 2-acylamino-4-hydroxy-synthesis, 6, 297 Thiazole, 5-alkoxy-cleavage, 6, 289 synthesis, 6, 302 Thiazole, 2-alkyl-A7-alkylation, 6, 253 hydrogen exchange, 6, 276 methylation, 6, 253 quatemization, 6, 253-254 reactions, S, 88 Thiazole, 4-alkyl-A7-alkylation, 6, 253 methylation, 6, 253 quatemization, 6, 253-254 Thiazole, 5-alkyl-A7-alkylation, 6, 253 methylation, 6, 253 Thiazole, 2-alkylamino-tautomerism, 6, 248 Thiazole, 4-alkyl-2,5-dimethyl-quatemization, 6, 253-254 Thiazole, 2-alkylthio-reactions, S, 103 rearrangement, 5, 103 6, 291 Thiazole, 3-allyl-4-hydroxy-2-imino-synthesis, 6, 297 Thiazole, 2-allyloxy-rearrangement, 6, 289 Thiazole, 2-amino-diazo coupling, 6, 257 nitration, 6, 255... 

The synthesis of 5-aminothiazoles via the reaction of isocyanate derivatives with aminomalononitrile p-toluenesulfonate (AMNT) has been investigated. It was found that AMNT 12 reacted with alkyl and aryl isothiocyanates in l-methyl-2-pyrrolidine (NMP) to furnish 5-amino-2-(alkylamino)-4-cyanothiazoles (13a) and 5-amino-2-(arylamino)-4-cyanothiazoles (13b-c) in 44-81 % yields. " ... 

Alkylamino)- or 2-(arylamino)-3//-l, 3,4-benzotriazepin-5(4//)-ones 15 are obtained from 2-aminobenzoic acid hydrazide. Treatment with isothiocyanates yields the thiosemicarbazides 14, which readily cyclize under the influence of dieyclohexylcarbodiimide. Selected examples are given.357... 

Alkylamino)- and 2-(Arylamino)-3f/-l,3,4-benzotriazepin-5(4//)-ones 15 General Procedure 357... 

Alkylamino- 450 2-(N-Alkyl-benzylamino)- 247 5-Benzylamino- 451 2-Hydroxy-1,2-diphenyl- 422... 

Alkylamino-4-oxo-selenazolines, amino-imino tautomerism, spectroscopic studies, 261... 

The alkylamination of quinizarin (22) in the presence of copper salts has been studied by Matsuoka and co-workers.16 The reaction proceeds via oxidation by copper ion of 22 to quinizarinoquinone (29). 2-Alkylamino-quinizarin (25) was obtained in quantitative yield. The 1,2-ring-closure product (30) is obtained by the reaction of 22 with ethylenediamines in the presence of copper ions17 (Scheme 9). 

B. tris(2 -Alkylamino)borazine-Derived Poly Z -(alkylamino)borazines]... 

Oxidation of Aralkyl,iV -(2-benzimidazolyl)thioureas 294 with hydrogen peroxide, in the presence of sodium hydroxide, gives 2-alkylamino[l,2,4]thiadiazolo[2,3- ]benzimidazoles 139 (Equation 45) <1999JHC991>. 

The only preparation reported for 7-cyanoheptanal is that described by the submitters. The present procedure starting from 2-methoxycyclooctanone oxime is superior to modifications employing 2-alkylamino- or 2-ethylthiocyclooctanone oxime in the Beckmann cleavage step. 

Effenberger, E Gutterer, B. Jager, J. Stereoselective synthesis of (IR)- and (lR,25)-l-aryl-2-alkylamino alcohols from (R)-cyanohydrins. Tetrahedron Asymmetry 1997, 8,459 67. 

In another approach, 2-(alkylamino)alcohol is employed as starting material for aziridine syntheses with the aid of dihalogenophosphoranes (70BCJ1185). Intramolecular transformation of 3-azidopropyloxirane 73 results in a simultaneous formation of a condensed aziridino[l,2-a]pyrrol-idine system (Scheme 39). The azide group is first transformed into imino-phosphorane 74, the nucleophilic N atom cleaves the oxirane to form betaine 75 [as in the Mitsunobu reaction (81S1)], and the phosphorus is shifted from N to O and then eliminated as phosphane oxide under simultaneous cyclization to bicyclic 76 (89JA7500). 

The mechanism of the acid-catalyzed decomposition of 1-alkyltriazolines has been studied <93JOC2097>. The hydrolytic decomposition of these triazolines in aqueous buffers leads predominantly to 1-alkylaziridines with lesser amounts of 2-(alkylamino)ethanol, alkylamines, and acetaldehyde. The rate of hydrolysis of 1-alkyltriazolines is about twice as fast as that of the analogous acyclic 1,3,3-trialkyltriazenes and varies in the order t-butyl > isopropyl > ethyl > butyl > methyl > propyl > benzyl <92JOC6448>. The proposed mechanism, involving rate-limiting formation of a 2-(alkylamino)ethyldiazonium ion, is shown in Scheme 65. A theoretical study ab initio calculation) of the acid-induced decomposition of 4,5-dihydro-l,2,3-triazolines has also been reported <91JA7893>. 

Treatment of 2-amino-5-nitrothiobenzamide with iV,iV-dimethylformamide dimethyl acetal gives 2-amino-iV-((dimethylamino)methylene)-5-nitrobenzothioamide 191 in excellent yield <2004TL5913>. Cycloaddition reaction of 191 with DMAD results in formation of dimethyl 2-(2-amino-5-nitrophenyl)-4-(dimethylamino)-4//-l,3-thiazine-5,6-dicarboxylate 192 in low yield when R = H. This is caused by cycloreversion of thiazine 192 to give dimethyl 2-((dimethylamino)methylene)-3-thioxosuccinate 193 and 2-amino-5-nitrobenzonitrile 194 (Scheme 19). When W((dimethylamino)methylene)-2-(alkylamino)-5-nitrothiobenzamides 191 (R = Me, Bn) are reacted with DMAD, the expected 4//-l,3-thiazine-5,6-dicarboxylates 195 are produced as stable compounds. 

Heterocycle Amine Methoda % Yield of 2-alkylamino productb... 

Dimethyl-3-(2-oxo-2-phenyl-ethyl--bromid lagert sich beim Kochen mit Triethylamin in Acetonitril in 2-(2-Imino-5-phenyl-2,3-dihydro-oxazol-3-yl)-4,6-dimethyl-pyrimidin um. Aus diesem werden durch Kochen in Alkoholen mit 4-Methyl-benzolsulfonsaure als Katalysator 2-Alkoxy-l-(4,6-dimethyl-2-pyrimidyl)-4-phenyl-imidazole oder durch Erhitzen mit primaren oder sekundaren Aminen ebenfalls in Gegenwart von 4-Methyl-benzolsulfonsaure 2-Alkylamino-l-(4,6-dimcthyl-2-pyrimidyl)-4-phe-nyl-imidazole erhalten374 ... 

Die Hydrolyse von l-Alkyl-2,l,3-benzothia(selena)diazolium-pikraten liefert die leicht zersetz-lichen 2-Alkylamino-aniline in sehr guter Ausbeute (s. a. S. 224), die als Rohprodukte in 98%iger Ameisensaure aufgenommen und umgesetzt werden225. 

Mit Palladium auf Aktivkohle ist es moglich, sowohl die Reduktion von 2-Alkylamino-l-ni-troso-naphthalinen als auch die Oxidation nach der Zugabe des Aldehyds in einem Arbeitsgang durchzufiihren. (2-Amino-l-nitro-naphthaline lassen sich auf diese Weise mit Aldehyden cy-clisieren) z. B.175 ... 

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