Formic acid chloride

Lead formate separates from aqueous solution without water of crystallisation. It can therefore be used for the preparation of anhydrous formic acid. For this purpose, the powdered lead formate is placed in the inner tube of an ordinary jacketed cond ser, and there held loosely in position by plugs of glass-wool. The condenser is then clamped in an oblique position and the lower end fitted into a receiver closed with a calcium chloride tube. A current of dry hydrogen sulphide is passed down the inner tube of the condenser, whilst steam is passed through the jacket. The formic acid which is liberated... 

Mercuric chloride test. Add mercuric chloride solution to formic acid or a solution of formate and w arm. A white precipitate of mercurous chloride, insoluble in dil. HCl, is produced. Sometimes the reduction proceeds as far as metallic mercury, which appears as a grey precipitate. 

Pungent odour. Formic acid, acetic acid, acetyl chloride, acetic anhydride, benzoyl chloride, benzyl chloride, pyridine. Benzoquinone (when warmed with water). 

Into a 250 or 500 ml. round-bottomed flask provided with a reflux condenser place 46 g. (38 ml.) of A.R. formic acid (98/100 per cent.) and 37 g. (46 ml.) of n-butyl alcohol. Reflux for 24 hours. Wash the cold mixture with small volumes of saturated sodium chloride solution, then with saturated sodium bicarbonate solution in the presence of a httle... 

By passing a mixture of carbon monoxide and hydrogen chloride into the aromatic hydrocarbon in the presence of a mixture of cuprous chloride and aluminium chloride which acts as a catalyst (Gattermann - Koch reaction). The mixture of gases probably reacts as the equivalent of the unisolated acid chloride of formic acid (formyl chloride) ... 

Acetic acid, fp 16.635°C ((1), bp 117.87°C at 101.3 kPa (2), is a clear, colorless Hquid. Water is the chief impurity in acetic acid although other materials such as acetaldehyde, acetic anhydride, formic acid, biacetyl, methyl acetate, ethyl acetoacetate, iron, and mercury are also sometimes found. Water significantly lowers the freezing point of glacial acetic acid as do acetic anhydride and methyl acetate (3). The presence of acetaldehyde [75-07-0] or formic acid [64-18-6] is commonly revealed by permanganate tests biacetyl [431-03-8] and iron are indicated by color. Ethyl acetoacetate [141-97-9] may cause slight color in acetic acid and is often mistaken for formic acid because it reduces mercuric chloride to calomel. Traces of mercury provoke catastrophic corrosion of aluminum metal, often employed in shipping the acid. 

Aldehyde Synthesis. Formylation would be expected to take place when formyl chloride or formic anhydride reacts with an aromatic compound ia the presence of aluminum chloride or other Friedel-Crafts catalysts. However, the acid chloride and anhydride of formic acid are both too unstable to be of preparative iaterest. 

Intermediate formation of formyl chloride is not necessary since the actual alkylating agent, HCO", can be produced by protonation of carbon monoxide or its complexes. However, it is difficult to obtain an equimolar mixture of anhydrous hydrogen chloride and carbon monoxide. Suitable laboratory preparations involve the reaction of chlorosulfonic acid with formic acid or the reaction of ben2oyl chloride with formic acid ... 

In appHcations as hard surface cleaners of stainless steel boilers and process equipment, glycoHc acid and formic acid mixtures are particularly advantageous because of effective removal of operational and preoperational deposits, absence of chlorides, low corrosion, freedom from organic Hon precipitations, economy, and volatile decomposition products. Ammoniated glycoHc acid Hi mixture with citric acid shows exceUent dissolution of the oxides and salts and the corrosion rates are low. 

Oxidation. Maleic and fumaric acids are oxidized in aqueous solution by ozone [10028-15-6] (qv) (85). Products of the reaction include glyoxyhc acid [298-12-4], oxalic acid [144-62-7], and formic acid [64-18-6], Catalytic oxidation of aqueous maleic acid occurs with hydrogen peroxide [7722-84-1] in the presence of sodium tungstate(VI) [13472-45-2] (86) and sodium molybdate(VI) [7631-95-0] (87). Both catalyst systems avoid formation of tartaric acid [133-37-9] and produce i j -epoxysuccinic acid [16533-72-5] at pH values above 5. The reaction of maleic anhydride and hydrogen peroxide in an inert solvent (methylene chloride [75-09-2]) gives permaleic acid [4565-24-6], HOOC—CH=CH—CO H (88) which is useful in Baeyer-ViUiger reactions. Both maleate and fumarate [142-42-7] are hydroxylated to tartaric acid using an osmium tetroxide [20816-12-0]/io 2LX.e [15454-31 -6] catalyst system (89). 

The rate of stripping or the stripabiUty on cataly2ed urethane and epoxy resin finishes can be increased by adding formic acid, acetic acid, and phenol. Sodium hydroxide, potassium hydroxide, and trisodium phosphate [10101-89-0] may be added to the formula to increase the stripabiUty on enamel and latex paints. Other activators include oleic acid [112-80-17, trichloroacetic acid [76-85-9], ammonia, triethanolamine [102-71-6], and monoethyl amine. Methylene chloride-type removers are unique in their abiUty to accept cosolvents and activators that allow the solution to be neutral, alkaline, or acidic. This abihty gready expands the number of coatings that can be removed with methylene chloride removers. 

Uses ndReactions. Dihydromyrcene is used primarily for manufacture of dihydromyrcenol (25), but there are no known uses for the pseudocitroneUene. Dihydromyrcene can be catalyticaUy hydrated to dihydromyrcenol by a variety of methods (103). Reaction takes place at the more reactive tri-substituted double bond. Reaction of dihydromyrcene with formic acid gives a mixture of the alcohol and the formate ester and hydrolysis of the mixture with base yields dihydromyrcenol (104). The mixture of the alcohol and its formate ester is also a commercially avaUable product known as Dimyrcetol. Sulfuric acid is reported to have advantages over formic acid and hydrogen chloride in that it is less compUcated and gives a higher yield of dihydromyrcenol (105). 

Oxidation of vinyl chloride with ozone [10028-15-6] in either the Hquid or the gas phase gives formic acid and formyl chloride. The ozone reaction with vinyl chloride can be used to remove it from gas streams in vinyl chloride production plants. 

The alkanoic acids, with the exception of formic acid, undergo typical reactions of the carboxyl group. Formic acid has reducing properties and does not form an acid chloride or an anhydride. The hydrocarbon chain of alkanoic acids undergoes the usual reactions of hydrocarbons except that the carboxyl group exerts considerable influence on the site and ease of reaction. The alkenoic acids in which the double bond is not conjugated with the carboxyl group show typical reactions of internal olefins. All three types of reactions are industrially important. 

Chlorine dioxide produced from the methanol reductant processes contains carbon dioxide and small amounts of formic acid. For this reason, sulfur dioxide and chloride-based chlorine dioxide processes are stih used for sodium chlorite production. This problem has been addressed by recycling a portion of the vapor from methanol-based generators so that formic acid further reacts to carbon dioxide ... 

At 180°C, reaction with water results in formic acid, methyl chloride, methanol, hydrochloric acid, and some carbon monoxide. 

Methylene chloride is easily reduced to methyl chloride and methane by alkaU metal ammonium compounds in Hquid ammonia. When the vapor is contacted with reduced nickel at 200°C in the presence of excess hydrogen, hydrogen chloride and elementary carbon are produced. Heating with alcohoHc ammonia at 100—125°C results in hexamethylenetetramine, (CH2) N4, a heterocycHc compound with aqueous ammonia at 200°C, hydrogen chloride, formic acid, and methylamine are produced. 

Chloroform and water at 0°C form six-sided crystals of a hydrate, CHCl I8H2O [67922-19-41which decompose at 1.6°C. Chloroform does not decompose appreciably when in prolonged contact with water at ordinary temperature and in the absence of air. However, on prolonged heating with water at 225°C, decomposition to formic acid, carbon monoxide, and hydrogen chloride occurs. A similar hydrolysis takes place when chloroform is decomposed at elevated temperature by potassium hydroxide. 

Hydrogen cyanide, as the nitrile of formic acid [64-18-6] CH2O2, undergoes many of the typical nitrile reactions. For example, it can be hydrolyzed to formic acid by aqueous sulfuric acid (4) it can be hydrogenated to methylamine [74-89-5], CH N (5) and it can be converted to phenylformamidine [618-39-3], CyHgN2, using aniline and hydrogen chloride (6). 

The direct formation of dipyrimidin-5-yl sulfides occurs on treatment of appropriate 5-unsubstituted pyrimidine substrates with sulfur mono- or di-chloride. Thus, reaction of uracil (83 R = H) with sulfur monochloride in boiling formic acid gives diuracil-5-yl sulfide in good yield sulfur dichloride gives a poor yield. Simple derivatives of uracil and barbituric acid undergo similar reactions but not cytosine, isocytosine, 2,4-bismethylthiopyrimidine or pyrimidine-4,6-dione (59). The mechanism is unknown (72AJC2275). 

Acid moieties include formic acid itself, formates and orthoesters, formamide, DMF dimethyl acetal and ethyl diethoxyacetate, acids, acid chlorides and anhydrides, the last including a rare [3,4-oxalate esters, 2-acyl or 2-ethoxycar-bonyl derivatives e.g. 180) are formed. 

This group was developed for protection of the 5 -OH group in nucleosides. The derivative is prepared from the corresponding triaiylmethyl chloride, and is cleaved by reductive cleavage (Zn/AcOH) of the phenacyl ether to the p-hydroxyphenyl-diphenylmethyl ether followed by acidic hydrolysis with formic acid. ... 

It has been recrystd from H2O (fine needles) and is freely soluble in boiling H2O. Crysts also from H2O by addition of acetone. Purified by chromatography on Dowex 1 (in formate form), eluting with 0.25M formic acid. It was then adsorbed onto charcoal (which had been boiled for 15min with M HCI, washed free of chloride and dried at 100°), and recovered by stirring three times with isoamyl alcohol/H20 (1 9 v/v). The aqueous layer from the combined extracts was evaporated to dryness under reduced pressure, and the product was crystallised twice from hot H2O. [Morrison and Doherty Biochem J19 433 7967]. It has A-max 259nm (e 15,400) in H2O at pH 7.0. [Alberty et al. J Biol Chem 193 425 7957 Martell and Schwarzenbach Heh Chim Acta 39 653 7956]. The acridinium salt has m 208° [Baddiley and Todd J Chem Soc 648 1947 Pettit Synthetic Nucleotides, van Nostrand-Reinhold, NY, Vol 1 252 1972 NMR Sarma et al. J Am Chem Soc 96 7337 1974 Norton et al. J Am Chem Soc 98 1007 1976 IR of diNa salt Miles Biochem Biophys Acta 27 324 1958],... 

The stereoselective reactions in Scheme 2.10 include one example that is completely stereoselective (entry 3), one that is highly stereoselective (entry 6), and others in which the stereoselectivity is modest to low (entries 1,2,4, 5, and 7). The addition of formic acid to norbomene (entry 3) produces only the exo ester. Reduction of 4-r-butylcyclohexanone (entry 6) is typical of the reduction of unhindered cyclohexanones in that the major diastereomer produced has an equatorial hydroxyl group. Certain other reducing agents, particularly sterically bulky ones, exhibit the opposite stereoselectivity and favor the formation of the diastereomer having an axial hydroxyl groi. The alkylation of 4-t-butylpiperidine with benzyl chloride (entry 7) provides only a slight excess of one diastereomer over the other. 

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