Sodium metal reaction with amines

Sodium cyanide in DMF at 120 °C has been used for the decarboxylation of 1-substituted-4-oxoquinoline-3-carboxylic acids <94TL(35)8303>. Quinoline Reissert adducts have been epoxidized at the 3,4-bond. Its reaction with amine nucleophiles gave regiospecifically substituted 1,2,3,4-tetrahydroquinolines <95H(41)897>. Successive Claissen rearrangements of 2-(8-quinolinoxymethyl)-3-(8-quinolinoxy)-l-propene gave a product which shows excellent ability to extract heavy metal ions <95TL(36)5567>. An Eschenmoser approach has been used in a facile synthesis of monofunctional and difunctional A -substituted-4-alkylidenequinolines (54) (Scheme 39) <95S(St)56>. 

Very recently, Garst and coworkers 100) have provided a means to suppress the cyclization of (l-methyl-5-hexenyl)sodium with t-butyl amine101 . t-Butyl amine is a sufficiently reactive proton donor to compete successfully with the anion cyclization 138 - cis/trans-139 and the intramolecular 1,4-proton transfer 138 -> 142, leaving 1-heptene 140 as well as cis- and tra -l, 2-dimethylcyclopentane cis,trans-141 formation through radical cyclization only. For sodium metal reactions excess t-butyl amine-nearly eliminates cis,trans-141 suggesting that radical cyclization is negligible. For the Na + N" reaction, 2-heptenes 143 are eliminated by added t-butyl amine, but the yields of cis,trans-141 are merely diminished. As expected, the cis/trans... 

NITRATO de ZIRCONIO (Spanish) (13746-89-9) A powerful oxidizer. Violent reaction with reducing agents, combustible materials, powdered metals, organic substances, acetic anhydride, tert-butylhydroperoxide, metal cyanides, thiocyanates, sodium acetylide. Incompatible with amines, ammonium hexacyanoferrate(II), boranes, cyanides, citric acid, esters, hydrazinium perchlorate, isopropyl chlorocarbonate, nitrosyl perchlorate, organic azides, organic bases, sodium thiosulfate, sulfamic acid. Incompatible with esters, many other substances. Attacks metals. 

A base is any material that produces hydroxide ions when it is dissolved in water. The words alkaline, basic, and caustic are often used synonymously. Common bases include sodium hydroxide (lye), potassium hydroxide (potash lye), and calcium hydroxide (slaked lime). The concepts of strong versus weak bases, and concentrated versus dilute bases are exactly analogous to those for acids. Strong bases such as sodium hydroxide dissociate completely while weak bases such as the amines dissociate only partially. As with acids, bases can be either inorganic or organic. Typical reactions of bases include neutralization of acids, reaction with metals, and reaction with salts ... 

Subsequently, Julia, Uguen and Callipolitis104 105 used both lithium metal in ethyl-amine and sodium amalgam in ethanol to effect reductive cleavages of j8-hydroxysulphones or of allylic sulphones. The latter reaction is part of a synthetic sequence for the construction of alkenes that has been used with some considerable success... 

Among the most important indirect methods of analysis which employ redox reactions are the bromination procedures for the determination of aromatic amines, phenols, and other compounds which undergo stoichiometric bromine substitution or addition. Bromine may be liberated quantitatively by the acidification of a bromate-bromide solution mixed with the sample. The excess, unreacted bromine can then be determined by reaction with iodide ions to liberate iodine, followed by titration of the iodine with sodium thiosulphate. An interesting extension of the bromination method employs 8-hydroxyquinoline (oxine) to effect a separation of a metal by solvent extraction or precipitation. The metal-oxine complex can then be determined by bromine substitution. 

Angeli pioneered the concept of nucleophilic amine nitration by A-nitrating aniline with ethyl nitrate in the presence of potassium or sodium metal. In this reaction a complex anion... 

These reactions of lead metal and lead alloys with alkyl esters are conducted at elevated temperatures (usually above 80 °C) and at elevated pressure (autogenous pressure of RX), and in the presence of a suitable catalyst, such as ethers, amines, iodides, dependent on the particular system involved. Despite the large number of systems which have been investigated, none has been found to be as economical for the commercial production of tetramethyllead and tetraethyllead as the sodium-lead alloy reaction, with the possible exception of the electrolytic process developed by Nalco Chemical Company for tetramethyllead. Electrolytic processes are discussed in Section 6. 

Ozonolysis of vinylpyrazine in methanol at — 30° furnishes pyrazine aldehyde in 73% yield.196 Vinylpyrazine undergoes a variety of addition reactions and pyrazylethyl derivatives of amines, ketones, ethyl phenyl acetate, phenylacetonitrile, and acetamide have been obtained.197-199 2-(2-Pyrazylethyl)cyclohexanone (42) has been prepared both by the condensation of vinylpyrazine with cyclohexanone in the presence of sodium metal and by interaction of vinylpyrazine with the pyrrolidine enamine of cyclohexanone followed by hydrolysis.200... 

The reactivities of alkyl halides are in the sequence RI > RBr > RCl and MeX > EtX > PrX. Benzyl hahde reactions with tin do not require catalysts (equation 2). For less reactive halides, the catalysts and promoters employed include metals (sodium, magnesium, zinc, or copper), Lewis bases (amines, triorganophosphines and -stibines, alcohols, or ethers), iodides, and onium salts (R4MX). The use of tin-sodimn alloys can result in tri- or tetraorganotin products. Electrochemical synthesis has also been reported, e.g. the formation of R2SnX2 from the oxidation of anodic tin by RX in benzene solution and the formation of ILtSn from RI (R = Me or NCCH2CH2) and cathodic tin. 

Reacts with water or steam to produce heat. Violent reaction with bases (e.g., sodium hydroxide, potassium hydroxide, calcium hydroxide), alkali metals (e.g., sodium, potassium), amines (e.g., dimethylamine, triethylamine), lithium, pyridine. To fight fire, use alcohol foam. Incompatible with cations. When heated to decomposition (above 150°C) it emits acrid smoke and irritating fumes. See also ANHYDRIDES. 

Metals commonly utilized include the alkali metals, mainly lithium, sodium and potassium, and also calcium, zinc, magnesium, tin and iron. Alkali metals and calcium have been used in liquid ammonia," in low molecular weight aliphatic amines," in hexamethylphosphoramide, in ether or in THF containing crown ethers, or in very dilute solutions in polyethers such as 1,2-dimethoxyethane (DME)." Reactions with metal solutions in liquid ammonia often use a cosolvent, such as ether, THF or DME, to increase solubility of the organic substrate in the reaction mixture. These same metals, as well as zinc and magnesium, have been used as suspensions in various solvents including ether, toluene, xylene, etc. 

In the past 10 years other reductants of the C— Hg bond have been used, mainly thiols and sodium amalgam. Reduction with hydrogen sulfide, sodium dithionite, metals,alcohols, alkaline aqueous bases, aromatic amines, Wilkinson s catalyst and electrochemical reductions have also been described. Organomercurials react with thiols by free radical substitutions with an 5h2 mechanism (Scheme 34). The reaction between PhSH and A -hexenylmercury chloride initiated by light or AIBN gives a mixture of 1-hexene and methylcyclopentane. ... 

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