Sodium, reaction with phenol

The reaction between 3,5 dinitrobenzoyl chloride and compounds containing the OH, NHj, or NH groups is very rapid, and therefore is particularly suitable for identification purposes cf. pp. 335, 338, 381). It is usual to have sodium hydroxide present during the reaction with phenols and amino-acids, but this is not necessary with alcohols if they are dry. 

Mono-substitution occurs most readily in the stepwise replacement of the halogen substituents of 2,4,6-trichloro-s-triazine with aqueous methanol and sodium bicarbonate (30°, 30 min), the monomethoxy derivative (324) is obtained on heating (65°, 30 min), the disubstitu-ted derivative is formed and on brief heating (65°) with the more basic sodium carbonate or methanolic sodium hydroxide (25°, 3 hr) complete methoxylation (320) occurs. Ethanolic ethoxide (25°, 1 hr) or sodium carbonate (35°) is sufficient to give complete ethoxy-dechlorination. The corresponding phenoxy derivatives are obtained on treatment with one (0°), two (15°, 1 hr), or three equivalents (25-70°, 3 hr) of various sodium phenoxides in aqueous acetone. The stepwise reaction with phenols, alcohols, or thiols proceeds in better yield in organic solvents (acetone or chloroform) with collidine or 2,6-lutidine as acid acceptors than in aqueous sodium bicarbonate. ... 

Imidazolides of aromatic sulfonic acids react much more slowly in alcoholysis reactions than the carboxylic acid imidazolides. Although the reaction with phenols is quantitative when a melt is heated to 100 °C for several hours, with alcohols under these conditions only very slight alcoholysis is observed. In the presence of 0.05 equivalents (catalytic amount) of sodium ethoxide, imidazole sodium, of NaNH2, however, imidazolides of sulfonic acids react with alcohols almost quantitatively and exothermically at room temperature in a very short time to form sulfonic acid esters (sulfonates). (If the ratio of sulfonic acid imidazolide to alcoholate is 1 2, ethers are formed see Chapter 17). The mechanism of catalysis by base corresponds to that operative in the synthesis of carboxylic esters by the imidazolide method. Because of the more pronounced nucleophilic character of alkoxide ions, sulfonates can also be prepared in good yield by alcoholysis of their imidazolides in the presence of hydroxide ions i.e., with alcoholic sodium hydroxide. 45 Examples of syntheses of sulfonates are presented below. 

Bromide ion reacts with a dilute solution of sodium / -1 o 1 uc nc sulfo nc h 1 o ra -mide (chloramine-T) and is oxidized to bromine which readily reacts with phenol red at pH 4.5 to 4.7. The bromination reaction with phenol red produces a color that ranges from red to violet, depending on the concentration of bromide ion. An acetate buffer solution is used to maintain the pH between 4.5 and 4.7. The presence of high concentration of chloride ions in the sample may seriously interfere in the test. In such cases, the addition of chloride to the pH buffer solution or the dilution of the sample may reduce such interference effect. Remove free chlorine in the sample by adding Na C solution. In addition, the presence of oxidizing and reducing agents in the sample may interfere in the test. 

Since the l,2-bis(dichlorophosphino)alkanes made by this new process are reactive intermediates they have a variety of potential uses. Compound 1 has been converted to the 1,2-bis (dime thoxyphosphino)ethane and used for making metal carbonyl complexes . There also is a report on the conversion to 1,2-bis-(dimethylphosphino)ethane and 1,2-bis(diethylphosphino)ethaneZ. The tetra-sodium salt of ethylenediphosphinetetraacetic acid has been made using intermediate lL2. The reactions with phenols and cyclic aliphatic alcohols also have been reported—. 

The final construction step utilized the modified von Pechmann conditions previously described (zinc carbonate/sodium bicarbonate) to fuse phenol (94) to the activated vinyl bromide (72), thereby affording aflatoxin Mj (13). The route discussed above also presents a formal total synthesis of aflatoxin M2 (14), since this is able to be prepared76 through the controlled catalytic hydrogenation of aflatoxin Mj (13). It should also be possible to apply this technology in a synthesis of aflatoxin GMt (15), by the use of a suitable substrate [possibly ( )] in the von Pechmann reaction with phenol (94). 

The reaction catalyzed by asparaginase (glutami-nase) is shown in Table 2. The ammonia released is used to monitor enzyme activity. It can be detected spectrophotometrically by the classical color analytical reaction with phenol and sodium hypochlorite, or... 

Ammonium ion is one of the inorganic species most frequently determined by UV-visible spectrophotometry. It is freed by the Kjeldahl method from organic matter and can be spectrophotometrically determined by reaction with phenol and hypochlorite in the presence of nitroprusside ion, with which it yields a blue compound (indophenol) with an absorbance maximum at 625 nm. Another alternative, especially avoiding the use of phenol, is by measuring the absorbance at 660 nm of an indophenol blue derivative generated by the reaction of ammonium ion with sodium salicylate in the presence of hypochlorite ion. These procedures are routinely used for the determination of ammonium ion with autoanalyzers. 

Urea gives a yellow color with / -dimethylaminobenzaldehyde (6), a positive biuret reaction (p. 271), a color reaction with sodium nitroprusside in alkaline media in the presence of ammonium persulfate (red color) (7), a color reaction with phenol and sodium hypochlorite (8), a very sensitive reaction with phenylhydrazine and aniline (9), and a reaction with xanthydrol (10). 

When reacted with sodium hydroxide, phenol forms a salt (sodium phenoxide) plus water. The reaction of sodium metal with phenol produces sodium phenoxide and hydrogen gas. 

Silver oxide or silver carbonate is the catalyst most commonly used for the condensation of acetylglycosyl halides with alcohols or phenols. Except in the case of the lower aliphatic alcohols, the aglycone is dissolved in a dry solvent, which is often an organic base to promote the forward reaction. With phenols, but not alcohols, the use of sodium or potassium hydroxide Reftrtnees p. 15a... 

Sodium carbonate solution [cf. Section 5, p. 330). Note that phenols (except those containing acidic groups, e.., nitrophenols) give no reaction with sodium carbonate solution. 

Reaction of phenol with 1 2 epoxypropane in aqueous sodium hydroxide at 150°C gives a single product C9H12O2 m 90% yield Suggest a rea sonable structure for this compound... 

The reaction with sodium sulfite or bisulfite (5,11) to yield sodium-P-sulfopropionamide [19298-89-6] (C3H7N04S-Na) is very useful since it can be used as a scavenger for acrylamide monomer. The reaction proceeds very rapidly even at room temperature, and the product has low toxicity. Reactions with phosphines and phosphine oxides have been studied (12), and the products are potentially useful because of thek fire retardant properties. Reactions with sulfide and dithiocarbamates proceed readily but have no appHcations (5). However, the reaction with mercaptide ions has been used for analytical purposes (13)). Water reacts with the amide group (5) to form hydrolysis products, and other hydroxy compounds, such as alcohols and phenols, react readily to form ether compounds. Primary aUphatic alcohols are the most reactive and the reactions are compHcated by partial hydrolysis of the amide groups by any water present. 

Carbonates ate manufactured by essentially the same method as chloroformates except that more alcohol is required in addition to longer reaction times and higher temperatures. The products are neutralized, washed, and distilled. Corrosion-resistant equipment similar to that described for the manufacture of chloroformates is requited. Diaryl carbonates are prepared from phosgene and two equivalents of the sodium phenolates or with phenols and various... 

Available Chlorine Test. The chlorine germicidal equivalent concentration test is a practical-type test. It is called a capacity test. Under practical conditions of use, a container of disinfectant might receive many soiled, contaminated instniments or other items to be disinfected. Eventually, the capacity of the disinfectant to serve its function would be overloaded due to reaction with the accumulated organic matter and organisms. The chlorine germicidal equivalent concentration test compares the load of a culture of bacteria that a concentration of a disinfectant will absorb and still kill bacteria, as compared to standard concentrations of sodium hypochlorite tested similarly. In the test, 10 successive additions of the test culture are added to each of 3 concentrations of the hypochlorite. One min after each addition a sample is transferred to the subculture medium and the next addition is made 1.5 min after the previous one. The disinfectant is then evaluated in a manner similar to the phenol coefficient test. For equivalence, the disinfectant must yield the same number of negative tubes as one of the chlorine standards. 

With Phenols. The 2-hydroxylethyl aryl ethers are prepared from the reaction of ethylene oxide with phenols at elevated temperatures and pressures (78,79). 2-Phenoxyethyl alcohol is a perfume fixative. The water-soluble alkylphenol ethers of the higher poly(ethylene glycol)s are important surface-active agents. They are made by adding ethylene oxide to the alkylphenol at ca 200°C and 200—250 kPa (>2 atm), using sodium acetate or... 

The quaternary fraction of pot curare, after the removal of some neoprotocuridine, was separated into a portion salted out by sodium bicarbonate, and a portion not so precipitated. The latter was fractionated on a plan described in the original, the most active product obtained being an amorphous iodide with a paralysing dose of 1- 5 mg. per kilo frog. This iodide was phenolic, gave the Millon reaction, but no strychnine-like reaction with bichromate and sulphuric acid. No crystalline product could be isolated, but on complete methylation certain of the fractions yielded crystalline methiodides as follows —... 

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