Phenol, 3-chloro-4-nitro

It is reported that an industrial explosion was initiated by charging potassium hydroxide in place of potassium carbonate to the chloro-nitro compound in the sulfoxide [1], Dry potassium carbonate is a useful base for nucleophilic displacement of chlorine in such systems, reaction being controlled by addition of the nucleophile. The carbonate is not soluble in DMSO and possesses no significant nucleophilic activity itself. Hydroxides have, to create phenoxide salts as the first product. These are better nucleophiles than their progenitor, and also base-destabilised nitro compounds. Result heat and probable loss of control. As it nears its boiling point DMSO also becomes susceptible to exothermic breakdown, initially to methanethiol and formaldehyde. Methanethiolate is an even better nucleophile than a phenoxide and also a fairly proficient reducer of nitro-groups, while formaldehyde condenses with phenols under base catalysis in a reaction which has itself caused many an industrial runaway and explosion. There is thus a choice of routes to disaster. Industrial scale nucleophilic substitution on chloro-nitroaromatics has previously demonstrated considerable hazard in presence of water or hydroxide, even in solvents not themselves prone to exothermic decomposition [2],... 

Dipolar compounds such as those with chloro, nitro, and nitrile substituents are more strongly retained on cyano columns, compared to amino or diol [14]. Also, cyanopropyl silica can exhibit acidic or basic character, depending on the mobile phase used. It was shown that a complete reversal of elution order was obtained for phenol and anihne when MTBE and chloroform were used as the mobile phases, because phenol eluted first in the MTBE solvent and second in the chloroform solvent [9],... 

The complexes ML2, where M = Co, Cu, Ni, Zn HL = 2-hydroxy-5-(chloro/ nitro)-benzaldehyde[4-(3-methyl-3-mesitylcyclobutyl)-l,3-thiazol-2-yl]hydra-zone, give IR spectra indicating chelation of L through azomethine N and phenolate O atoms.509 Coordination of the 5-(2 -carboxyphenylazo)-8-hydro-xyquinoline to Co, Ni, Cu or U022+ via CN, N=N, COOH and OH was shown by IR spectroscopy.510 IR data for M(II) (=Co, Ni, Cu, Zn) complexes of A -salicyloyl-A"-/)-hydroxythiobenzohydrazide and related ligands show coordination by thiolato S, enolic O and two hydrazine N atoms.511... 

In another study, the bio degradability of the ozonation transformation products of chloro-, nitro- and amino-phenols were studied (Adams et al.,... 

When cresylic acid (or cresol, C 6 H 4 (CH 3 )OH.) is acted upon by nitric acid it produces a series of nitro compounds very similar to those formed by nitric acids on phenol, such as soditrm di-nitro-cresylate, known in the arts as victoria yellow. Naphthol, a phenol-like body obtained from naphthalene, under the same conditions, produces sodium di-nitro- naphthalic acid, C 10 H 6 (NO 2 ) 2 0. The explosive known as "roburite" contains chloro-nitro-naphthalene, and romit, a Swedish explosive, nitro-naphthalene. 

Unfortunately, a vast portion of the WO works reported in the literature deals with the non-catalyzed oxidation kinetics for single compounds. In a review by Matatov-Meytal and Sheintuch , it was found that pure compounds such as phenol, benzene, dichlorobenzene, and acetic acid obey a first-order rate law with respect to the substrates and mainly half order with respect to the oxygen concentration. A thorough kinetic investigation in an isothermal, differentially operated fixed bed reactor with the oxygen pre-saturated aqueous solutions has revealed that the catalytic oxidation of acetic acid, phenol, chloro-phenol, and nitro-phenol can be well expressed by means of the Langmuir-Hinshelwood kinetic formulation ° , namely... 

Guaiacol, bromoxynil, ioxynil, trichlorosyringol, o-chloiovanillin, dinoseb, and 11 chloro-, nitro- and methyl-substituted phenols were baseline resolved on a Cjg column using a 24-min 33/64 — 75/25 (90/10 acetonitrile/methanol with 0.015% TFA)/water (0.05% TFA) gradient. The monitored wavelength was changed from 280 to 230 nm at 7.8 min. Peak shapes woe uniformly excellent. Detection limits were <20 ng injected for each analyte. With a preextraction process described in the paper, overall detection limits were reported as 0.1 pg/L [932],... 

Phenol, 4-cyano-Phenol, 3-nitro-Phenol, 2-methyl-Phenol, 3-chloro-Phenol, 4-bromo-Phenol, 2-methyl-4,6-dinitro-Phenol, 2,6-dibromo-4-cyano-(3,5-Dibromo-4-hydroxybenzonitrile) Phenol, 4-tert-butyl-Phenol, 2,4,6-tribromo-Phenol, 2-sec-butyl-4,6-dinitro-Phenol, 2-tert-butyl-4,6-dinitro-Phenol, pentachloro-... 

Alkoxyl tion. The nucleophilic replacement of an aromatic halogen atom by an alkoxy group is an important process, especially for production of methoxy-containing iatermediates. Alkoxylation is preferred to alkylation of the phenol wherever possible, and typically iavolves the iateraction of a chloro compound, activated by a nitro group, with the appropriate alcohol ia the presence of alkaU. Careful control of alkaU concentration and temperature are essential, and formation of by-product azoxy compounds is avoided by passiag air through the reaction mixture (21). 

A subsequent study, using clearly homogeneous conditions, of the dedeutera-tion of [2-2H]-4-nitro-, -chloro-, and -methyl-phenols by aqueous sulphuric acid showed that the rate coefficients clearly increased with increasing acidity (Table 120) and plots of log rate coefficient versus the acidity function — H0 were linear,... 

Brightener structures of only moderate molecular size are of interest for white grounds in the transfer printing of polyester fabrics. Derivatives of 6-acetamidoquinoxaline with an electron-donating substituent (X) in the 2-position (11.48) were prepared by converting quinoxalin-2-one to 2-chloro-6-nitroquinoxaline and condensation with amines (X = RNH), alcohols (X = RO) or phenols (X = PhO), followed by reduction and acetylation (Scheme 11.19). The nitro intermediates (11.49) are also of interest as low-energy disperse dyes for polyester [61]. 

The hydrochloride of 3-amino-4-hydrazinopyridine 65 was prepared by reaction of the 4-chloro-3-nitropyridine derivative with ethoxycarbonyl-hydrazine in phenol to give the hydrochloride of ethyl 3-(3-nitro-4-pyridyl)carbazate 64 (R2 = OEt), which on successive heating in concentrated hydrochloric acid and hydrogenation over Pd/C gave 65. Its reaction with phenylacetic acid or with phenoxyacetic acid gave the hydrochloride... 

Alkyl-, nitro- and chloro-phenols 5-Dimethylaminonaphthalene-l -sulfonyl chloride 94... 

Puig et al. [450] determined ng/1 levels of priority methyl-, nitro-, and chloro-phenols in river water samples by an automated on-line SPE technique, followed by liquid chromatography-mass spectrometry (LC-MS) using atmospheric pressure chemical ionization (APCI) and ion spray interfaces. 

Phenols, particularly the highly chloro-or nitro-substituted variety, are an important group of organic contaminants which, at typical ambient pH, can be present in groundwater predominantly as phenolate anions. Ulibarri et al. [154] studied the adsorption capacity of 2,4,6-trinitrophenol (TNP) on Mg/Al LDHs and their calcined products. The adsorption of TNP on LDHs by anionic exchange is dramatically affected by the identity of the interlayer anion and LDH chlorides have an adsorption capacity of more than 4 times that of LDH carbonates. However, calcined LDH carbonates are more effective adsorbents than those derived by calcination of LDH chloride samples. This possibly reflects the higher surface area of the former species. 

Photooxidation of chlorobenzene in air containing nitric oxide in a Pyrex glass vessel and a quartz vessel gave 3-chloronitrobenzene, 2-chloro-6-nitrophenol, 2-chloro-4-nitrophenol, 4-chloro-2-nitro-phenol, 4-nitrophenol, 3-chloro-4-nitrophenol, 3-chloro-6-nitrophenol, and 3-chloro-2-nitrophenol (Kanno and Nojima, 1979). A carbon dioxide yield of 18.5% was achieved when chlorobenzene adsorbed on silica gel was irradiated with light (A. >290 nm) for 17 h. The sunlight irradiation of chlorobenzene (20 g) in a 100-mL borosilicate glass-stoppered Erlenmeyer flask for 28 d yielded 1,060 ppm monochlorobiphenyl (Uyeta et al., 1976). 

Photolytic. The UV photolysis (7, = 300 nm) of bifenox in various solvents was studied by Ruzo et al. (1980). In water, 2,4-dichloro-3 -(carboxymethyl)-4 -hydroxydiphenyl ether and 2,4-di-chloro-3 -(carboxymethyl)-4 -aminodiphenyl ether were identifled. In cyclohexane, 2,4-dichloro-4 -nitrodiphenyl ether and methyl formate were the major products. In methanol, a dichloro-methoxy phenol was identified. Photodegradation occurred via reductive dechlorination, de-carboxymethylation, nitro group reduction, and cleavage of the ether linkage (Ruzo et al., 1980). 

Those degradation products which have been identified in our investigations are 1-naphthol from carbaryl, 2,4-D acid and 2,4-dichlorophenol from 2,4-D ester, 2-chloro-2, 6 -diethylacetanilide from alachlor, o,o,oe-trifluro-2-nitro-6-amino-N,N-dipropyl-p-tolu-idine and o,o,o-trifluro-2,6-diamino-N,N-dipropyl-p-toluidine from trifluralin, and a variety of phenols and acids from the degradation of the aromatic solvents used in the formulation of the liquid pesticides as emulsifiable concentrates (41,42). 

The presence of nitro, carboalkoxy, carboxyl, chloro, formyl, alkyl, and acyl groups does not interfere with the reaction. A single alkoxy group also does not interfere, but if two or more are present, the yields are markedly decreased. The reaction is inhibited by the presence of unhindered, basic nitrogen substituents, by the phenolic group, and probably by the thiol group. 

The 4- and 6-positions of pyrrolo[2,3-3]pyridines can be substituted via palladium-catalyzed cross-coupling reactions with the 4- or 6-halo-substituted derivatives (Scheme 3) <2001SL609>. Nucleophilic displacement of the 4-substituent of 6-chloro-4-nitro- and 4,6-dichloro-pyrrolo[2,3-/ ]pyridines takes place with phenols. Protection of the pyrrole nitrogen with a /3-trimethylsilylethoxymethyl (SEM) group affords good yields of the aryl ethers (Equation 3) <2006TL2069>. 

Weak Medium 300 1 15 Alcohols, phenols, and intermolecular hydroxyl to carbonyl bonding <100° 10 100-300 50 1.2- Diols, a- and most /3-hydroxy ketones o-chloro and oal-koxy phenols 1.3- Diols some /3-hydroxy ketones /3-hydroxy amino compounds /3-hydroxy nitro compounds... 

The best yields are obtained with phenols bearing electron-withdrawing substituents such as nitro, chloro, trifluoromethyl, or ammonium. The deactivating effect of these groups protects the aromatic nucleus from attack by any intermediates.227... 

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