Sodium hydride, reaction with

Sodium cyanoborohydride. reductive ami nation with, 931 Sodium cyclamate, LP50 of, 26 Sodium hydride, reaction with alcohols, 605... 

The sodium hydride reaction with water is pH limited and requires an additional reactant to force the reaction to completion. 

Acid-base reactions also include those in which the solvent itself functions as an acid or base. This can be shown as follows. Sodium hydride reacts with water to produce a basic solution,... 

Benzo[6]thiophene-2-carbaldehyde can be converted to 2-(l, 2 -epoxyethyl)-benzo[6]-thiophene by reaction with trimethylsulfoxonium iodide and sodium hydride or with diazomethane. However, the 3-carbaldehyde is reported to give the 3-acetyl derivative on treatment with diazomethane (Scheme 120) (70AHC(ll)177). 

Inorganic As(III) and As(V) were determined by atomic absorption spectrometry using the hydride technique. Total inorganic arsenic, As(III) + As(V), was measured after a prereduction reaction of As(V) to As(III) in acidic solution containing potassium iodide and ascorbic acid. For the selective hydride formation of As(III), samples were maintained at pH 5.0 during the hydride reaction (with 3% NaBH4, 1% NaOH) with a citrate-sodium hydroxide buffer solution (31). As(V) was determined by difference between total As and As(III). The detection limit of As(III) and As(V) was 0.1 nM. The selectivity of this method was checked by additions of As(III) and As(V) to lake water 95-100% recovery of As(III) and As(V) was found (32). 

At this point a common method of conversion of tertiary aliphatic nitro compounds into nitromethyl derivatives and, further, into aldehydes deserves mention (Komblum Erickson 1981). According to this method, the reagent NaCH2N02 is used. To prepare this reagent, sodium hydride reacts with nitromethane. Then a tertiary aliphatic nitro compound is introduced into the solution formed. Several organic solvents were probed. The reaction considered proceeds most effectively in DMSO. Komblum and Erickson (1981) attributed this feature to small amounts of NaCH2SOCH3 (sodium dimsyl) produced in DMSO at the expense of its reaction with sodium hydride. Sodium dimsyl acts as a powerful one-electron reducer that induces the following chain anion radical process ... 

Write equations for the reaction of a specific alcohol or phenol with sodium or sodium hydride or with an aqueous base (NaOH, KOH). 

Dialkoxyphosphoryl-substituted carbanions, usually generated by the reaction of methyl-substituted phosphonic acid dialkyl esters with sodium hydride, react with a variety of oxiranes to give substituted cyclopropanes in moderate to good yield. Whereas the reaction of A5-phos-phanes with oxiranes (see Section 1.2.2.1.) gives cyclopropanes under forcing reaction conditions (200 °C, 8 hours), the phosphoryl-substituted carbanions give cyclopropanes under relatively mild conditions by a similar reaction mechanism (Houben-Weyl, Vol4/3, p 138). 

NITROCARBOL (75-52-5) Forms explosive mixture with air (flash point 95°F/35°C). Thermally unstable. Shock, friction, pressure, or elevated temperature above 599°F/315°C can cause explosive decomposition, especially if confined. Violent reaction with strong oxidizers, alkyl metal halides, diethylaluminum bromide, formic acid, methylzinc iodide. Contact with acids, bases, acetone, aluminum powder, amines, bis(2-aminoethyl)amine, haolforms make this material more sensitive to explosion. Reacts, possibly violently, with ammonium hydroxide, calcium hydroxide, calcium hypochlorite, 1,2-diaminomethane, formaldehyde, hexamethylbenzene, hydrocarbons, hydroxides, lithium perchlorite, m-methyl aniline, nickel peroxide, nitric acid, metal oxides, potassium hydride, potassium hydroxide, sodium hydride. Mixtures with ammonia, aniline, diethylenetriamine, metal oxides, methyl amine, morpholine, phosphoric acid, silver nitrate form shock-sensitive compounds. Forms high-explosive compound with urea perchlorate. Mixtures with hydrocarbons and other combustible materials can cause fire and explosions. Attacks some plastics, rubber, and coatings. 

In the opinion of Drozd [57], special consideration should be given to isopropyl esters of acids. These esters are formed in the reaction of 2-bromopropane with sodium hydride [184]. With the help of this method isopropyl derivatives can be obtained for other classes of organic compounds ... 

Perhaps the most direct approach to 2,3-di-O-methyl tartrates is to treat the corresponding ester, such as lb, with a base like sodium hydride together with excess methyl iodide. Performed on a scale of up to one kilogram, this reaction provides in 66% yield diethyl (+ )-2,3-di-O-methyltartrate (569). Saponification of the diesters followed by anhydride formation with refluxing acetyl chloride furnishes 570, which is converted to 3,4-dimethoxy-thiopyrrolidone (571). This is the key intermediate for the synthesis of the antibiotic ani-somycin (572). The synthesis itself is not diastereoselective, and suffers from the tedious methodology required to introduce the correct acetoxy functionality present in 572 [183] (Scheme 126). 

Buono et al. [11, 13] described the preparation of menthyl phosphinites 2 from PhPCl2 and their separation into diastereoisomers. The subsequent reaction of (Sp)-phosphinite 2 with sodium hydride and with methyl iodide afforded the menthyl methylphenylphosphinite borane Rp)-6 with retention of configuration at phosphorus [24]. The palladium-catalyzed (Pd[PPh3]4) coupling reaction of the (5p)-2 with... 

The other method involved a two-step treatment, first with sodium hydride, then with acetyl chloride. The presence of about 3% DMSO in the methylol cellulose caused some problems, manifested by less than theoret al yield of acetate incorporation, but still materials with DS in acetyl of 0.2 to about 1 were prepared reproducibly under homogeneous reaction conditions. 

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