141-53-7 sodium formate

Sodium acetate CH3COONa Sodium succinate (CHaCOONa), Sodium benzoate CeHjCOONa Sodium formate HCOONa i Sodium oxalate fCOONa) J Sodium salicylate HOCeH COONa... 

Chloroform and iodoform give also sodium formate in this reaction CHCI3 -h 4NaOH = HCOONa -h 3NaCl -f zH O. A portion of the solution, before the addition of the HNO3, should therefore be tested for formic acid (Tests, p. 350) ensure however that the solution is neutralised where necessary during these tests. 

The sodium formate is sparingly soluble in ethyl alcohol and therefore separates out. The residual ethyl formate is catalytically decomposed in the presence of sodium ethoxide at the boUing point of the ethyl alcohol, t.e., by refluxing the mixture ... 

The distillate weighs about 110 g. and contains methyl formate and methylal. If it is placed in a flask provided with a reflux condenser and a solution of 25 g. of sodium hydroxide in 40 ml. of water is added, the methyl formate is liydrolysed to sodium formate and the methylal separates on the surface. The latter may be removed, dried with anhydrous calcium chloride and distilled about 30 g. of methylal, b.p. 37-42°, are obtained. If the aqueous layer is evaporated to diyness, about 25 g. of sodium formate are isolated. 

Footnote 1 - The byproducts of the first step are Dimeth-oxymethane and Sodium Formate. 

In the reaction of Q,/3-unsaturated ketones and esters, sometimes simple Michael-type addition (insertion and hydrogenolysis, or hydroarylation, and hydroalkenylation) of alkenes is observed[53,54]. For example, a simple addition product 56 to methyl vinyl ketone was obtained by the reaction of the heteroaromatic iodide 55[S5]. The corresponding bromide affords the usual insertion-elimination product. Saturated ketones are obtained cleanly by hydroarylation of o,/3l-unsaturated ketones with aryl halides in the presence of sodium formate, which hydrogenolyses the R—Pd—I intermediate to R— Pd—H[56]. Intramolecular hydroarylation is a useful reaction. The diiodide 57 reacts smoothly with sodium formate to give a model compound for the afla-toxin 58. (see Section 1.1.6)[57]. Use of triethylammonium formate and BU4NCI gives better results. 

The alkenyloxirane 126 in excess reacts with aryl and alkenyl halides or triflates in the presence of sodium formate to afford the allylic alcohol 127[104], Similarly, the reaction of the alkenyloxetane 128 gives the homo-allylic alcohol 130[105]. These reactions can be explained by insertion of the double bond in the Ar—Pd bond, followed by ring opening (or /3-eliraination) to form the allylic or homoallylic alkoxypalladium 129, which is converted into the allylic 127 or homoallylic alcohol 130 by the reaction of formate. The 3-alkenamide 132 was obtained by the reaction of the 4-alkenyl-2-azetizinone 131 with aryl iodide and sodium formate [106]. 

Formate is an excellent hydride source for the hydrogenolysis of aryl halides[682]. Ammonium or triethylammonium formate[683] and sodium formate are mostly used[684,685]. Dechlorination of the chloroarene 806 is carried out with ammonium formate using Pd charcoal as a catalyst[686]. By the treatment of 2,4,6-trichloroamline with formate, the chlorine atom at the /iiara-position is preferentially removed[687]. The dehalogenation of 2,4-diha-loestrogene is achieved with formic acid, KI, and ascorbic acid[688]. 

The reaction of formate salts with mineral acids such as sulfuric acid is the oldest iadustrial process for the production of formic acid, and it stiU has importance ia the 1990s. Sodium formate [141-53-7] and calcium formate [544-17-2] are available iadustriaHy from the production of pentaerythritol and other polyhydric alcohols and of disodium dithionite (23). The acidolysis is technically straightforward, but the unavoidable production of sodium sulfate is a clear disadvantage of this route. 

Formates. lron(Il) formate dihydrate [13266-734], Fe(HC02)2 2H20, is a green salt which can be prepared from iron(Il) sulfate and sodium formate in an inert atmosphere. The compound is slightly soluble in water and fairly resistant to air oxidation. The anhydrous salt [3047-594] is known. 

Many industrial processes have been employed for the manufacture of oxahc acid since it was first synthesized. The following processes are in use worldwide oxidation of carbohydrates, the ethylene glycol process, the propylene process, the diaLkyl oxalate process, and the sodium formate process. 

The sodium formate process is comprised of six steps (/) the manufacture of sodium formate from carbon monoxide and sodium hydroxide, (2) manufacture of sodium oxalate by thermal dehydrogenation of sodium formate at 360°C, (J) manufacture of calcium oxalate (slurry), (4) recovery of sodium hydroxide, (5) decomposition of calcium oxalate where gypsum is produced as a by-product, and (6) purification of cmde oxahc acid. This process is no longer economical in the leading industrial countries. UBE Industries (Japan), for instance, once employed this process, but has been operating the newest diaLkyl oxalate process since 1978. The sodium formate process is, however, still used in China. 

Typical specifications of the powder are as follows sodium methylate, 97.5% sodium hydroxide, 0.5% sodium carbonate, 0.4% sodium formate, 0.3% and free methanol, 0.5%. 

At room temperature, Htde reaction occurs between carbon dioxide and sodium, but burning sodium reacts vigorously. Under controUed conditions, sodium formate or oxalate may be obtained (8,16). On impact, sodium is reported to react explosively with soHd carbon dioxide. In addition to the carbide-forrning reaction, carbon monoxide reacts with sodium at 250—340°C to yield sodium carbonyl, (NaCO) (39,40). Above 1100°C, the temperature of the DeviHe process, carbon monoxide and sodium do not react. Sodium reacts with nitrous oxide to form sodium oxide and bums in nitric oxide to form a mixture of nitrite and hyponitrite. At low temperature, Hquid nitrogen pentoxide reacts with sodium to produce nitrogen dioxide and sodium nitrate. 

Dithionites. Although the free-dithionous acid, H2S2O4, has never been isolated, the salts of the acid, in particular zinc [7779-86-4] and sodium dithionite [7775-14-6] have been prepared and are widely used as industrial reducing agents. The dithionite salts can be prepared by the reaction of sodium formate with sodium hydroxide and sulfur dioxide or by the reduction of sulfites, bisulfites, and sulfur dioxide with metallic substances such as zinc, iron, or zinc or sodium amalgams, or by electrolytic reduction (147). 

No reaction takes place below 500°C when sodium cyanide and sodium hydroxide are heated in the absence of water and oxygen. Above 500°C, sodium carbonate, sodium cyanamide [19981-17-0] sodium oxide, and hydrogen are produced. In the presence of small amounts of water at 500°C decomposition occurs with the formation of ammonia and sodium formate, and the latter is converted into sodium carbonate and hydrogen by the caustic soda. In the presence of excess oxygen, sodium carbonate, nitrogen, and water are produced (53). 

Examples are given of common operations such as absorption of ammonia to make fertihzers and of carbon dioxide to make soda ash. Also of recoveiy of phosphine from offgases of phosphorous plants recoveiy of HE oxidation, halogenation, and hydrogenation of various organics hydration of olefins to alcohols oxo reaction for higher aldehydes and alcohols ozonolysis of oleic acid absorption of carbon monoxide to make sodium formate alkylation of acetic acid with isobutylene to make teti-h ty acetate, absorption of olefins to make various products HCl and HBr plus higher alcohols to make alkyl hahdes and so on. 

Palladium catalysts have been prepared by fusion of palladium chloride in sodium nitrate to give palladium oxide by reduction of palladium salts by alkaline formaldehyde or sodium formate, by hydrazine and by the reduction of palladium salts with hydrogen.The metal has been prepared in the form of palladium black, and in colloidal form in water containing a protective material, as well as upon supports. The supports commonly used are asbestos, barium carbonate, ... 

Sodium formate (anhydrous) [141-53-7J M 68.0, m 253°, d 1.92. A saturated aqueous solution at 90° (0.8mL water/g) was filtered and allowed to cool slowly. (The final temperature was above 30° to prevent formation of the hydrate.) After two such crystns the crystals were dried in an oven at 130°, then under high vacuum. [Westrum, Chang and Levitin J Phys Chem 64 1553 I960-, Roecker and Meyer J Am Chem Soc 108 4066 1986.] The salt has also been recrystd twice from ImM DTPA (diethylenetriaminepentaacetic acid which was recrystd 4x from MilliQ water and dried in a vac), then twice from water [Bielski and Thomas J Am Chem Soc 109 7761 1987]. 

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