Preparation sodium derivative

The reaction of the anhydride 1 with the previously prepared sodium derivative of the phosphonate ester 73 (R = Me) gives a mixture of the benzoxazinone 74 and quinolinedione 75, the ratio and yields of which depend on the solvent used for the reaction. If the reactions of compounds 73 (R = Me, Et, CH2=CHCH2, PI1CH2) are carried out with the previously prepared sodium derivative of the anhydride 1, only compounds 75... 

A solvent of much greater versatility for the preparation of sodium derivatives of carbohydrates is liquid ammonia. Schmid and Becker (16) showed that the liquid ammonia technique could be used to prepare sodium derivatives of carbohydrates. Muskat prepared the sodium derivatives of sugars after removal of the liquid ammonia, the products were resuspended in an inert solvent and alkylated with methyl iodide. Potassium and lithium derivatives also were made by Muskat (17),... 

It is readily prepared by the action of metallic sodium on dry ethyl acetate. The reaction, which occurs only in the presence of a trace of ethanol, is complex, but may be considered (in effect) as a condensation of two molecules of ethyl acetate under the influence of sodium ethoxide, the sodium derivative of the enol form being thus obtained. Clearly, only a trace of ethanol is thus initially... 

Refractionation of the low-boiling impurities gives a further quantity of the acetoacetate, but if the initial distillation has been carefully conducted, the amount recovered is less than i g., and the refractionation is not worth while. If possible, complete the preparation in one day. If this is not possible, it is best to allow the cold crude sodium derivative (before acidification) to stand overnight, the flask being closed by a cork carrying a calcium chloride tube the yield will now fall to about 38 g. Alternatively, the crude ester may be allowed to remain overnight in contact with the sodium sulphate, but in this case the yield will fall to about 30 g. 

Mono and Di-iubstitution Derivatives. The enolic sodium derivative of ethyl acetoacetate (E) is prepared by mixing ethanolic solutions of the ester and of sodium ethoxide. It should not be prepared by the direct action of metallic sodium on the ester, as the reaction is slow and the nascent hydrogen evolved reduces some of the ester to ethyl p4iydroxy- butyrate, CH3CH(OH)CHjCOOEt. 

Crystalline derivatives, suitable for identification and characterisation are dealt with in Section IV, 114, but the preparation of the following, largely liquid, derivatives will be described in the following Sections. When phenols are dissolved in aqueous sodium hydroxide solution and shaken with acetic anhydride, they undergo rapid and almost quantitative acetylation if the temperature is kept low throughout the reaction. This is because phenols form readily soluble sodium derivatives, which react with acetic anhydride before the latter undergoes appreciable hydrolysis, for example ... 

Higher alkyl ethers are prepared by treating the sodium derivative of the phaiol (made by adding the phenol to a solution of sodium ethoxide in ethyl alcohol) with the alkyl iodide or bromide (Williamson synthesis), for example ... 

The preparation of the sodium derivative of the phenol may be avoided by heating the enol and alkyl halide in the presence of potassium carbonate and acetone, for example ... 

Organosodium compounds are prepared from sodium and other organometaUic compounds or active methylene compounds by reaction with organic haUdes, cleavage of ethers, or addition to unsaturated compounds. Some aromatic vinyl compounds and aHyUc compounds also give sodium derivatives. 

The sodium ethoxide catalyzed rearrangement of readily prepared thiazole derivatives provides a facile thiophene synthesis (Scheme 103) (76JPR343). 

A third synthesis which has resulted in the preparation of rieinine and a number of its derivatives is due to Schroeter, Seidler, Sulzbacher and Kanitz,i2 who foimd that cyanoacetyl chloride polymerises spontaneously to 6-chloro-2 4-dihydroxy-3-cyano-pyridine. The di-sodium derivative of this with methyl sulphate produces A -methyl-6-chloro-4-hydroxy-3-cyano-2-pyridone (6-chlororicininic acid), the mono-sodium derivative of which, with methyl bromide or sulphate, is converted into 6-chlororicinine and the latter is reduced by zinc and sulphuric acid to rieinine. A fourth synthesis, starting from 3-nitro-4-pyridone, is due to Reitmann. ... 

Shaw and McDowellhave prepared imidazolone derivatives by cyclization of a-acylamino amides. In a variation of this reaction the azlactone (30) was gradually converted to the hydroxamic acid (31) by methanolic hydroxylamine. Sodium methoxide and hydroxylamine readily gave the acyclic hydroxamic acid (32) which could be cyclized to 31 by dilute acid. Benzyloxyurea has been used in the sjrnthesis of pyrimidine hydroxamic acids (33) by reaction with /S-diketones followed by catalytic hydrogenation of the benzyl group. Protection... 

Attempts to prepare hydroxybiphenyl derivative 19 by treatment of tetranitro derivative 18 with sodium benzaldoxime led to a mixture of the required phenol 19 and dibenzofuran 20 (Eq. 5) (82JCS(P1)2299). 

The acid was prepared in considerable quantities by the following rather complicated series of reactions. When ethyl yS-iodopropionate and the sodium derivative of ethyl cyanacetate are allowed to interact in... 

In an initial step, the sodium derivative of ethyl (3-benzoylphenyl)cyanoecetate is prepared as follows (3-benzoylphenyl)acetonitrile (170 g) is dissolved in ethyl carbonate (900 g). There is added, over a period of 2 hours, a sodium ethoxide solution [prepared from sodium (17.7 g) and anhydrous ethanol (400 cc)], the reaction mixture being heated at... 

Then, ethyl methyl(3-benzoylphenyl)cyanoacetate employed as an intermediate material is prepared as follows The sodium derivative of ethyl (3-benzoylphenyl)cyanoacetate (131 g) is dissolved in anhydrous ethanol (2 liters). Methyl iodide (236 g) is added and the mixture is heated under reflux for 22 hours, and then concentrated to dryness under reduced pressure (10 mm Hg). The residue is taken up in methylene chloride (900 cc) and water (500 cc) and acidified with 4N hydrochloric acid (10 cc). The methylene chloride solution is decanted, washed with water (400 cc) and dried over anhydrous sodium sulfate. The methylene chloride solution is filtered through a column containing alumina (1,500 g). Elution is effected with methylene chloride (6 liters), and the solvent is evaporated under reduced pressure (10 mm Hg) to give ethyl methyl(3-benzoylphenyl)cyano-acetate (48 g) in the form of an oil. 

The sodium derivative of the 2-trifluoromethylphenothiazine was prepared from 26.7 g (0.1 mol) of 2-trifluoromethylphenothiazine and 2.3 g (0.1 g atom) of sodium in 500 ml of liquid ammonia. After the reaction was completed, the ammonia was driven off and 500 ml of dry toluene were added. A solution of 25 g (0.09 mol) of N-(3-chloropropyl)-N -[2-(1,3-dioxanyl)-ethyl] -piperazine In 200 ml of toluene was added drop by drop to this solution which was then refluxed with stirring for 1B hours. After cooling, the precipitate which had formed was filtered and the filtrate was washed with water, dried and concentrated in vacuo. 33 g of brown oil, the N-3-(2-trifluoromethyl-10-phenothiazinyl)-propyl-N -2-[2-(1,3-dioxanyl)] -ethyl-piperazine, were obtained. 

Reduction and preparation of derivatives Concentrate the aqueous mixture to 0.5 ml. Add 20 mg of sodium borohydride dissolved in 0.5 ml of ion exchange water. Let this solution stand at room temperature for 1 hour. Destroy the excess sodium borohydride by adding acetic acid until gas evolution stops. Evaporate the solution to dryness. Add 5 ml of methanol and evaporate again to dryness. 

The colorless tris(0-ethyl dithiocarbonato)arsenic(III) and yellow antimony(III) complexes have been prepared from the corresponding metal trichlorides using this procedure. Tris-(alkyl trithiocarbonato)-, tris(0,0 -dialkyldithiophosphato)-, and other tris(0-alkyl dithiocarbonato)indium(III) complexes can undoubtedly be prepared from the potassium or sodium derivatives of the ligands using this procedure. 

High antiscorbutic power is also reported to be shown by a derivative of L-ascorbic acid in which the enolic hydroxyl group at C2 is replaced by an amino group. 3,4-Isopropylidene-L-threonic acid (LX), prepared from 5,6-isopropylidene-L-ascorbic acid, is converted into the 2-acetyl-3,4-isopropylidene-L-threonyl chloride (LXI) and this is then allowed to react with the sodium derivative of ethyl malonate. 

This is a widely used preparation route towards metal chalcogenolates since the alkali compounds, mainly lithium and sodium derivatives, react with halogen complexes of almost any metal. The chalcogenols in the presence of a base can be used to scavenge the hydrogen halide. 

In a Vilsmeier-Haack-Amold reaction, A/,Ar-disubstituted amino-methylenemalonates (329) were prepared in good yields from the sodium derivative of diethyl malonate or from diethyl malonate in the presence of triethylamine in benzene or toluene at a temperature below 20°C with imidoyl chlorides, which were prepared in situ from N./V-disubstituted formamides and phosphoryl chloride (63BRP917436). Instead of diethyl malonate, diethyl ethoxymagnesiummalonate could also be used (63 BRP917436). 

Dimethylethynyl carbinol has usually been prepared by the addition of acetylene to the sodium derivative of acetone,3 4 5 6 7>8 but potassium metal9 and sodium ethoxide10 have also been used. The above method is based upon that described by Sung Wou-seng.3 A more recent method uses potassium hydroxide, calcium carbide, and acetone.11... 

A detailed study of the formation of n-octyl ethers under solidrliquid two-phase conditions in the absence of an added solvent has been reported [10], Potassium alkoxides tend to produce higher yields of the ethers than do the corresponding sodium derivatives, but octene is the major product in the reaction of 1-bromooctane with potassium t-butoxide. High temperatures also tend to promote the preferential formation of octene and slightly higher yields of the ethers are obtained using n-octyl tosylate in preference to n-octyl bromide. p-Fluorinated acetals have been prepared either under basic catalytic liquidrliquid or solidrliquid conditions from the fluori-nated alcohol and dichloromethane [11] with displacement of the fluorine atoms. 

Besides solvation, a solvent can also participate in entrainment of ion-radical transformations. The reaction between tertiary aliphatic nitro compounds and the sodium derivative of nitromethane, NaCH2N02, is an example (Kornblum and Erickson 1981). To prepare NaCHjNOj, nitromethane is treated with sodium hydride. Then a tertiary aliphatic nitro compound is introduced into the solution formed. Several organic solvents were probed and CHjSOjCHj (DMSO) turned out to be the most effective. Kornblum and Erickson (1981) attributed this result to the formation of small amounts of NaCH2SOCH3 (sodium dimsyl) that was produced from DMSO as a result of its reaction with sodium hydride. Sodium dimsyl acts as a powerful one-electron reducer that induces the following chain anion-radical process ... 

Nickel boride, formed in situ from sodium borohydride and nickel chloride, has been used to prepare dihydro derivatives from thiothymine 385 <2001JME1853> and thiobarbituric acid derivatives 388 <2002J(P1)2520>. With 4-thiothymine derivatives, an isomeric mixture of 3,4- and 3,6-dihydro derivatives 386 and 387 was obtained <2001JME1853>, but with 2-thiobarbiturates, clean reduction at the 2-position was able to be achieved <2002J(P1)2520>. 

Two series of complex iridium salts corresponding to the hexammino-and diacido-iridium salts have been prepared containing ethylene-diamine. These have the same general characteristics as the ammino-salts. Both series have been resolved into optically active isomers, the dinitrito-series by means of d- and 1-bromo-camphor sulphonic acid, and the triethylenediamino-series by d- and 1-nitro-camphor. Attempts have been made to prepare etliylenediamino-derivatives containing tetravalent iridium. Thus, sodium hexaehloro-iridate, [IrCl6]Na2, reacts with ethylenediamine, but the products are syrupy and cannot be purified. Derivatives of trivalent iridium, however, have been prepared. These are crystalline and fairly easily purified. The... 

Electrolysis ol the fused alkali hydroxide.—At the time of Davy s discovery the dynamo had not been invented, and the electric current derived from batteries was far too costly for the production of sodium on a manufacturing scale. In modern works, where cheap electrical energy is available, modifications of Davy s original process—electrolysis of fused sodium hydroxide—are used for preparing sodium industrially —e.g. H. Y. Castner s electrolytic process (1890).a Potassium can also be made by H. Y. Castner s process. 

The first report on this approach was on the synthesis of [Nb2Xe(THT)3] (X = Cl, Br, I) by McCarley and Maas, using a one-electron procedure (equation 50). The soluble Nblfl adducts formed were easily separated from the sodium derivative and isolated in high yields (60-70%). The tantalum analogues [Ta2Xe(THT)3] (10 X = C1, Br) were similarly prepared, but from TaXs.581... 

Ethyl diacetylacetate has been prepared by Claisen from the sodium derivative of acetylacetone and ethyl chloroformate.1 It has also been prepared from the sodium derivative of ethyl acetoacetate and acetyl chloride,2,3,4 and from ethyl acetoacetate and acetyl chloride in the presence of magnesium.5... 

---