2-Dimethylamino-4-nitrophenyl

The phosphoramidic chloride (11) has been employed to phosphorylate phenols and alcohols, including carbohydrates.16 Other activity in phosphorylation chemistry has been mostly concentrated in two main areas. In the first of these, Japanese workers have continued their studies on the use of 2-substituted-4-nitrophenyl-phosphoric acids. The 7V-protonated form of the 2-dimethylamino-compound (12 R = Me) is a better phosphorylating agent than the corresponding 2-diethylamino-compound. The reaction of (12) with hydroxy-amines results in selective O-phos-... 

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. 

Reagents. NaCl (Spectrum Chemical Co.) was fired 4 h at 550 °C in a muffle furnace to remove trace organic contaminants. Acetonitrile (HPLC grade J. T. Baker), dichloromethane (Burdick and Jackson), 5-dimethylamino-l-naphthalenesulfonyl chloride (dansyl chloride Aldrich), O-p-nitrobenzyl-N,N -diisopropylisourea (PNBDI Regis), and N-succinimidyl-p-nitrophenyl acetate (SNPA Regis) were used as purchased. 

The application of hydroxysuccinimide, 4-nitrophenyl, or other types of active esters together with 4-(dimethylamino)pyridine as a catalyst (Scheme 11) is a possibly complementary procedure to existing popular methods leading to depsipeptides. Nevertheless, this approach, in spite of its simplicity and mildness, has so far found limited application. 

An octa(dimethylaminopropyl)calixresorcin[4]arene [243 R = CH2CONH(CH2)3 NMe2] is a primitive artificial esterase for 4-nitrophenyl esters of various carboxylic acids. The overall mechanism is thought to involve complexation of substrate with the arene in its neutral form followed by intracomplex reaction of a dimethylamino function... 

Carboxylic acids, acyl chlorides, and sulfonyl chlorides used for deri-vatization of 4-aminophenylalanine and >-4-am i n op h e ny I a I a n i n e are as follows 5-hydantoinacetic acid, / ran, v - 4 - co t i n i n ec a r b o xy I i c acid, isonicotinic acid, 3-pyridinepropionic acid, 4-hydroxyphenylacetic acid, 2-butynoic acid, 2-pyrazinecarboxylic acid, cyclopropanecarboxylic acid, 3-hydroxy-2-qui-noxaline carboxylic acid, 5-bromovaleric acid, propargyl chloroformate, 3,4-dimethoxybenzoyl chloride, 2-thiophenesulfonyl chloride, 3-thiophene-carboxylic acid, 2-thiophenecarboxylic acid, 2-methylbutyric acid, 2-thio-pheneacetyl chloride, benzoic acid, furylacrylic acid, 4-nitrophenyl acetic acid, 2,5-dimethoxyphenylacetic acid, p-toluenesulfonyl chloride, 4-(di-methylamino)phenylacetic acid, 3-indolepropionic acid, phenoxyacetic acid, 3-(dimethylamino)benzoic acid, cyclohexanecarboxylic acid, naphtha-lenesulfonyl chloride, 4-bromophenylacetic acid, 4-bromobenzoic acid, 2-phenoxybutyric acid, 3,4-dichlorophenylacetic acid, (l-naphthoxy)acetic acid. 

Photooxidation of parathion also occurred on leaf surfaces (18), together with isomerization and other reactions. Fenitro-thion (j),O-dimethyl 0-3-methyl-4-nitrophenyl phosphorothionate) and other phosphorothionate insecticides behaved similarly (19). Some pesticides do not require external reagents for photodegradation on surfaces carbamate insecticides such as carbaryl (1-naphthyl li-methylcarbamate), aminocarb (4-dimethylamino-3-methylphenyl li-methylcarbamate), and mexacarbate (4-dimethylamino-... 

In order to evaluate the potential hazards chemical insecticides pose to forest environments, it is essential that adequate and reliable research data be generated on their environmental chemistry (distribution, persistence, movement, metabolic degradation, toxicity, fate, etc.). This paper gives a brief account of some laboratory and field research activities carried out at the Forest Pest Management Institute, Canadian Forestry Service to meet this requirement. Using two chemical insecticides which are extensively used now in forest insect control programs in Canada Viz aminocarb [Trade name, Matacil 4-dimethylamino-m-tolyl N-methylcarbamate] and fenitrothion [0,0-dimethyl 0-(3-methyl-4-nitrophenyl) phosphorothioate], studies conducted at the Institute to elucidate the environmental behavior and fate of forestry insecticides in general will be discussed. 

Jiang has expanded the Carreira method of alkyne addition to aldehydes to include other ligands and Zn(II) salts (Eq. 13) [17]. Thus use of stoichiometric quantities of Zn(II) difluoromethane sulfonate salt and (lS,2S)-3-(tert-butyldi-methylsilyloxy)-2-N,N-dimethylamino-l-(p-nitrophenyl)propane-l-ol (3) in the addition reaction can afford propargylic alcohols in high ee. Difluoromethanesul-fonic acid is prepared from 3,3,4-,4-tetrafluoro[1.2]oxathietane the amino alcohol has been used in the synthesis of chloramphenicol and is also readily accessible. Application of a combination of this same amino alcohol ligand with Zn(OTf)2 has also been shown to afford products in high yield and ee in addition reactions (Eq. 14) [18]. 

The presence of amino substituents in the 2- or 5-position activates the oxazole ring (4-aminooxazoles are unknown). Thus 2-amino-3-aryloxazoles yield the derivatives (127 X = Cl or Br) on halogenation, and nitration of 2-dimethylamino-4-phenyloxazole afforded 2-dimethylamino-5-nitro-4-(4-nitrophenyl)oxazole, the sole example of direct nitration of the oxazole ring. 5-Dialkylamino-2-phenyloxazoles react with trifluoroacetic anhydride to form the ketones (128) and they couple with arene diazonium fluoroborates the products (129) readily rearrange to 1,2,4-triazoles (130) in DMSO solution. 

The direct entry of a nitro group into the oxazole ring (1,3-oxazole) (exclusively at position 5) has only been reported twice [163, 164], Thus, 2-dimethylamino-4-(4-nitrophenyl)-5-nitrooxazole was isolated when 2-dimethylamino-4-phenyloxazole was heated [163] (Scheme 17). 

The reaction of 1-diethylaminoprop-l-yne with 4-nitrophenyl isocyanide at 25 °C for 12 days produced 2-dimethylamino-3-methyl-AT-(4-nitrophenyl)cyclopropenimine (2) in 34% yield. 

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