4-Nitrophenyl phenyl carbonate

Aminolysis of a series of aryl 2,4-dinitrophenyl carbonates by a series of quinuclidines gave linear Br0nsted-type plots, the magnitudes of their slopes confirming their mechanisms as concerted.40 A comparison41 of the aminolysis, by primary amines, of 4-nitrophenyl phenyl carbonate (31 X = O) with its thiono analogue (31 X = S) is discussed in the section Thioacids, Thioesters, Thiolactones, and Thiocarbonates below. 

Cleavage at the phosphorus-carbon bond in esters of (trichloromethyl)phosphonic acid under alkaline conditions has been known for many years and yields ethanol, phosphoric acid and chloroform, and a study of the kinetics has shown that as the concentration of alkali rises, CO, HCl and HCOOH are formed in increasing amounts, possibly through the sequence illustrated in Scheme 9. However, hydrolytic removal of the trichloromethyl group is possible in conditions other than alkaline. At pH 1-10, 4-nitrophenyl phenyl(trichloromethyl)phosphinate is cleaved at the P—C bond to the extent of90-100%, although this is accompanied by hydrolysis at the POC bonding with the liberation of small... 

Force-field calculations have shown that when there is a spacer between the two phenyl rings, such as in (2-nitrophenyl) phenyl thioether and 2-nitrobenzophenone, the distances between the nitrene nitrogen and the ortho carbon, where cyclization should occur in the hypothetical imido clusters, are much longer than in compound This explains why these substrates afforded the corresponding amines, with only trace amounts of the desired six-membered heterocycles being observable, when subjected to reaction conditions the same as those used for Eq. (12). ... 

Methyl pelargonate Methyl phenyl sulfone 2-(Methylsulfonyl) ethanol p-Nitrophenol m-Nitrophenyl phenyl sulfide o-Nitrophenyi phenyl sulfide p-Nitrophenyl phenyi suifide Phenyl disulfide Phenylthioglycolic acid Phthalamide. Propargyl alcohol Propylene carbonate 3-Sulfolene 4,4 -Thiobis (6-t-butyl-o-cresol) 4,4 -Thiodibenzenethiol 4,4 -Thiodi (2,6-di-t-butylphenol) 4,4 -Thiodi (2,6-dimethylphenol) 2,2 -Thiodi (4-t-octylphenol) Thiophenol Tribromomethyl phenylsulfone... 

In some cases acid amide formation was observed on attempted deprotonation at oxaziridine ring carbon. 2-r-Butyl-3-(4 -nitrophenyl)oxaziridine (67) was converted to the anion of acid amide (68) by sodium amide (69TL3887), while 2-(4 -nitrobenzoyl)-3-phenyl-oxaziridine (69) afforded the diacylimide (70) by addition of cyclohexylamine to its benzene solution at room temperature (67CB2593). 

However, in some cases azines can be converted to hydrazones by treatment with excess hydrazine and NaOH. Arylhydrazines, especially phenyl, p-nitrophenyl, and 2,4-dinitrophenyl, are used much more often and give the corresponding hydrazones with most aldehydes and ketones.Since these are usually solids, they make excellent derivatives and are commonly employed for this purpose. Cyclic hydrazones are also known, ° as are conjugated hydrazones. a-Hydroxy aldehydes and ketones and ot-dicarbonyl compounds give osazones, in which two adjacent carbons have carbon-nitrogen double bonds ... 

Deacylation of hydrophobic p-nitrophenyl alkanoates Hydroxamic acid and phenyl ester derivatives had alkyl or fluoroalkyl substituents. Rate effects depend on selectivity of binding of fluoro- and hydro-carbon derivatives Kunitake et ai, 1984... 

Support for the above view comes from NMR studies of the binding of phenyl and nitrophenyl acetates to a-CD (Komiyama and Hirai, 1980). These indicate that the nitro groups are located in the CD cavity and that the acetoxyl groups of the esters are held outside, more or less close to the secondary hydroxyls of the CD. It was calculated that the distance between the ester carbonyl carbon and the secondary hydroxyls decreases as p-nitro > phenyl > m-nitrophenyl, consistent with the observed order of rate acceleration (Komiyama and Bender, 1984). 

T. M. Kitson, The Action of Cytoplasmic Aldehyde Dehydrogenase on Methyl p-Nitro-phenyl Carbonate and p-Nitrophenyl Dimethylcarbamate , Biochem. J. 1989, 257, 579-584 T. M. Kitson, K. E. Kitson, A Comparison of Nitrophenyl Esters and Lactones as Substrates of Cytosolic Aldehyde Dehydrogenase , Biochem. J. 1996, 316, 225-232 T. M. Kitson, K. E. Kitson, Studies of the Esterase Activity of Cytosolic Aldehyde Dehydrogenase with Resorufin Acetate as Substrate , Biochem. J. 1997, 322, 701-708. 

Unsubstituted cycloamyloses have been used to catalyze a number of reactions in addition to acyl group transfer. Brass and Bender (8) showed that cycloamyloses promoted phenol release from diphenyl and bis(p-nitro-phenyl) carbonates and from diphenyl and bis(m-nitrophenyl)methyl phos-phonates. Breslow and Campbell (10,11) showed that the reaction of anisole with HOCL in aqueous solution is catalyzed by cyclohexaamylose and cycloheptaamylose. Anisole is bound by the cyclodextrins and is chlorinated exclusively in the para position while bound. Cycloheptaamylose has been used to promote regiospecific alkylation followed by the highly selective oxidation shown in reaction (3) (95). In addition cycloheptaamylose effec-... 

Kinetic studies of the reaction of Z-phenyl cyclopropanecarboxylates (1) with X-benzylamines (2) in acetonitrile at 55 °C have been carried out. The reaction proceeds by a stepwise mechanism in which the rate-determining step is the breakdown of the zwitterionic tetrahedral intermediate, T, with a hydrogen-bonded four-centre type transition state (3). The results of studies of the aminolysis reactions of ethyl Z-phenyl carbonates (4) with benzylamines (2) in acetonitrile at 25 °C were consistent with a four- (5) and a six-centred transition state (6) for the uncatalysed and catalysed path, respectively. The neutral hydrolysis of p-nitrophenyl trifluoroacetate in acetonitrile solvent has been studied by varying the molarities of water from 1.0 to 5.0 at 25 °C. The reaction was found to be third order in water. The kinetic solvent isotope effect was (A h2o/ D2o) = 2.90 0.12. Proton inventories at each molarity of water studied were consistent with an eight-membered cyclic transition state (7) model. 

Brydon and Roberts- added hemolyzed blood to unhemolyzed plasma, analyzed the specimens for a variety of constituents and then compared the values with those in the unhemolyzed plasma (B28). The following procedures were considered unaffected by hemolysis (up to 1 g/100 ml hemoglobin) urea (diacetyl monoxime) carbon dioxide content (phe-nolphthalein complex) iron binding capacity cholesterol (ferric chloride) creatinine (alkaline picrate) uric acid (phosphotungstate reduction) alkaline phosphatase (4-nitrophenyl phosphate) 5 -nucleotidase (adenosine monophosphate-nickel) and tartrate-labile acid phosphatase (phenyl phosphate). In Table 2 are shown those assays where increases were observed. The hemolysis used in these studies was equivalent to that produced by the breakdown of about 15 X 10 erythrocytes. In the bromocresol green albumin method it has been reported that for every 100 mg of hemoglobin/100 ml serum, the apparent albumin concentration is increased by 100 mg/100 ml (D12). Hemolysis releases some amino acids, such as histidine, into the plasma (Alb). 

Although the preparation has been repeated, there have been no other reports of the type of reaction, (described in 1923) in which carbazole in the presence of excess potassium hydroxide and nitrobenzene at only 50°C gave a good yield of 9-(4-nitrophenyl)-carbazole, presumably via an adduct such as 43 subsequently oxidized by excess nitrobenzene and/or air. More recent examples of N-arylation of carbazoles have involved copper catalysis in reaction of aryl halides with carbazoles. Thus, copper bronze and potassium carbonate heated with the carbazole and the appropriate aromatic halide have produced 9-(4-methoxyphenyl)- and 9-(2-tolyl)carbazoles 9-(4-phenylphenyl)carbazole, l,4-di(carbazol-9-yl)benzene, 4,4 -di(carbazol-9-yl)biphenyl, and 9-(2-pyridyl)- and 9-(2-quinolyl)carbazoles 9-[2-(2-phenylphenyl)phenyl]- and 9-[2-(4-methylphenyl)phenyl] carbazoles 9-(3-bromo-6-nitrophenyl)-, 9-[3-(carbazol-9-yl]-, 9-(2-nitrophenyl)-, 9-(4-methyl-2-nitrophenyl)-, 9-(4-methoxycarbonyl)-l-nitro-, and l-nitro-9-(4-tolyl)carbazoles 9-(2-methoxycarbonylphenyl)carbazole 9-[2- 2-... 

Wang resin bound 4-nitrophenyl carbonate is a convenient intermediate for the attachment of amines to polystyrene as carbamates (see Experimental Procedure 14.2). Aliphatic amines [82-87], ammonia [88], and amino acids [89] react exothermically with this support, whereas anilines generally require catalysis and/or long reaction times (Entry 3, Table 14.7). For the immobilization of anilines as carbamates, Wang resin derived chloroformate [90-92] generally leads to better results than resin-bound 4-nitrophenyl carbonates. Amidines also react with polystyrene-bound 4-nitrophenyl carbonates to yield /V-alkoxycarbonyl amidines (Section 3.9 [93-95]). Support-bound alkoxycarbonyl hydrazines can be prepared by treating polystyrene-bound phenyl carbonates with hydrazine [96-98]. 

The rates and mechanisms of hydrolysis and transesterification of phenyl benzoate in aqueous ethanolic KOH solution were determined by non-linear least-squares regression.4 Kinetic studies of the transesterification of a series of 4-nitrophenyl 3- and 4-substituted benzoates by 4-chlorophenol in DMF in the presence of potassium carbonate at various temperatures were reported.5... 

Diphenyl-diacetylene is the parent hydi ocarhon of indigo blue, and the dye itself can be prepared by means of tliis reaction, starting with o-nitro-phenyl-propiolic acid. By loss of carbon dioxide the acid becomes o-nitro-phenyl-acetylene, the copper derivative of which passes to di-ortho-nitrophenyl-diacety-lene ... 

The a-(p-nitrophenyl)-a-ethyl-glutarimide starting material can be prepared as follows 217 g of a-phenyl-a-ethyl-glutarimide are dissolved in 800 g of concentrated sulfuric acid with subsequent cooling to about -10°C and nitration is carried out at -10°C to +10°C by slow addition of a mixed acid consisting of 110 g of concentrated sulfuric acid and 110 g of 63% nitric acid. The nitration solution is stirred into ice, the separated nitro compound taken up in methylene or ethylene chloride, the solution washed with water and sodium carbonate solution until neutral and the solvent evaporated under vacuum. The residue is crystallized from methanol or ethyl acetate, whereby a yellowish crystal powder of MP 128-136°C is obtained in a yield of about 85% which consists for the most part of a-(p-nitrophenyl)-a-ethyl-glutarimide. By recrystallization from methanol the pure p-nitrophenyl compound is obtained of MP 137-139°C. From the residues of the mother liquors a small quantity of the isomeric a-(o-nitrophenyl)-a-ethyl-glutarimide of MP 170-172°C can be obtained. 

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