Formic reaction with

The desired pyridylamine was obtained in 69 % overall yield by monomethylation of 2-(aminomethyl)pyridine following a literature procedure (Scheme 4.14). First amine 4.48 was converted into formamide 4.49, through reaction with the in situ prepared mixed anhydride of acetic acid and formic acid. Reduction of 4.49 with borane dimethyl sulfide complex produced diamine 4.50. This compound could be used successfully in the Mannich reaction with 4.39, affording crude 4.51 in 92 % yield (Scheme 4.15). Analogous to 4.44, 4.51 also coordinates to copper(II) in water, as indicated by a shift of the UV-absorption maximum from 296 nm to 308 nm. 

My early work with acyl fluorides also involved formyl fluoride, ITCOF, the only stable acyl halide of formic acid, which was first made in 1933 by Nyesmeyanov, who did not, however, pursue its chemistry. 1 developed its use as a formylating agent and also explored formyla-tion reactions with CO and HF, catalyzed by BF3. 

Alkynes undergo stoichiometric oxidative reactions with Pd(II). A useful reaction is oxidative carboiiyiation. Two types of the oxidative carbonyla-tion of alkynes are known. The first is a synthesis of the alkynic carbox-ylates 524 by oxidative carbonylation of terminal alkynes using PdCN and CuCh in the presence of a base[469], Dropwise addition of alkynes is recommended as a preparative-scale procedure of this reation in order to minimize the oxidative dimerization of alkynes as a competitive reaction[470]. Also efficient carbonylation of terminal alkynes using PdCU, CuCI and LiCi under CO-O2 (1 I) was reported[471]. The reaction has been applied to the synthesis of the carbapenem intermediate 525[472], The steroidal acetylenic ester 526 formed by this reaction undergoes the hydroarylalion of the triple bond (see Chapter 4, Section 1) with aryl iodide and formic acid to give the lactone 527(473],... 

The protected nucleoside-3-phosphoramidite monomer units such as 671 are used in the solid-phase oligonucleotide synthesis. In the 60mer synthesis, 104 allylic protective groups are removed in almost 100% overall yield by the single Pd-catalyze reaction with formic acid and BuNH2[432], N,(9-protection of uridine derivatives was carried out under pha.se-transfer conditions[433]. 

Methanol can be converted to a dye after oxidation to formaldehyde and subsequent reaction with chromatropic acid [148-25-4]. The dye formed can be deterruined photometrically. However, gc methods are more convenient. Ammonium formate [540-69-2] is converted thermally to formic acid and ammonia. The latter is trapped by formaldehyde, which makes it possible to titrate the residual acid by conventional methods. The water content can be determined by standard Kad Eischer titration. In order to determine iron, it has to be reduced to the iron(II) form and converted to its bipyridyl complex. This compound is red and can be determined photometrically. Contamination with iron and impurities with polymeric hydrocyanic acid are mainly responsible for the color number of the merchandized formamide (<20 APHA). Hydrocyanic acid is detected by converting it to a blue dye that is analyzed and deterruined photometrically. 

Attempts to use acetic-formic anhydride with Friedel-Crafts catalysts resulted only in acetylation. However, using anhydrous HF as a catalyst, a small amount of aldehyde is also formed in accordance with the fact that acetic—formic anhydride gives both acetyl and formyl fluoride with HF. By continuous removal of the low boiling HCOF, the reaction can be shifted to the formation of this compound (118). 

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. 

Catalytic oxidation of isobutyraldehyde with air at 30—50°C gives isobutyric acid [79-31-2] ia 95% yield (5). Certain enzymes, such as horseradish peroxidase, cataly2e the reaction of isobutyraldehyde with molecular oxygen to form triplet-state acetone and formic acid with simultaneous chemiluminescence (6). 

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

Acetals. Acetal resins (qv) are polymers of formaldehyde and are usually called polyoxymethylene [9002-81-7]. Acetal homopolymer was developed at Du Pont (8). The commercial development of acetal resins required a pure monomer. The monomer is rigorously purified to remove water, formic acid, metals, and methanol, which act as chain-transfer or reaction-terminating agents. The purified formaldehyde is polymerized to form the acetal homopolymer the polymer end groups are stabilized by reaction with acetic anhydride to form acetate end groups (9). 

H. Reaction with Formic and Trichloroacetic Acids Enamines derived from aldehydes have been treated with formic acid under the conditions of the Leuckart-Wallach reaction 141) to give saturated tertiary amines 142). The enamine (98) reacts vigorously with formic acid at room temperature to give N-isobutyl morpholine (204). 

The reaction has been applied to more complex enamines 13) and to dienamines 19). The reduction may be rationalized by initial protonation at the enamine carbon and subsequent decarboxylation of formate ion and addition of the hydride ion to the iminium cation. This mechanism has been given support by the reaction of the enamine (205) with deuterated formic acid 143) to give the corresponding amines. The formation of 206 on reaction with DCOOH clearly indicates that protonation at the enamine carbon is the initial step. 

The remaining major method for the reduction of the C=N+ functionality is the reaction with formic acid. The first report was that of Luke , who found (95) that thermal cleavage of l,l-dimethyl-2-methylenepyrrolidinium formate was accompanied by reduction. Lukes then explored the generality... 

Hydrazinotriazine 749 was prepared by the condensation of the respective quinone with thiosemicarbazide followed by sequential cyclization, chlorination with phosphorus oxychloride, and reaction with hydrazine (88JHC1139). Cyclocondensation of 749 with formic acid or carbon disulfide gave triazolotriazines 750 (88JHC1139) (Scheme 156). 

Formaldehyde, benzaldehyde and aniline react violently with 90% performic acid (Ref 1). An unspecified organic compd was added to the acid, and soon after the initial vigorous reaction had subsided, the mixt expld violently (Ref 3). Reaction with aikenes is vigorously exothermic, and adequate cooling is necessary. Reactions with performic acid can be more safely accomplished by the slow addition of hydrogen peroxide to a soln of the compd in formic acid (Ref 4)... 

Fluorenylamine, 40,5 Formaldehyde, reaction with diethyl malonate to form diethyl bis-(hydroxymethyl)malonate, 40,27 Formamide, condensation with 4,4-dimethoxy-2-butanone to give 4-methylpyrimidine, 43, 77 Formic acid, and hydrogen peroxide, with indcne, 41, 53... 

Thionyl fluoride, as by-product in sulfur tetrafluoride reactions, 41, 105 toxidty of, 41,105 Thiophene-2-OL, 43, 55 2(5H)-Thiophenone, 43, 55 Thiosemicarbazide, in synthesis of 1,2,4 triazole, 40, 99 reaction with formic acid to yield l-formyl-3-thiosemicarbazide, 40,99... 

Carbon monoxide, CO, is produced when carbon or organic compounds burn in a limited supply of air, as happens in cigarettes and badly tuned automobile engines. It is produced commercially as synthesis gas by the re-forming reaction (Section 14.3). Carbon monoxide is the formal anhydride of formic acid, HCOOH, and the gas can be produced in the laboratory by the dehydration of formic acid with hot, concentrated sulfuric acid ... 

In its reactions SsO shows properties typical for both sulfur homocycles and sulfoxides. With elemental chlorine SOCI2 and S2CI2 are formed, with bromine SOBr2 and S2Br2 are obtained. Water decomposes SsO to H2S and SO2 besides elemental sulfur while cyanide ions expectedly produce thiocyanate. The reaction with iodide in the presence of formic acid is used for the iodometric determination of the oxygen content [70] ... 

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