Formic acid sources

OSP OSP, acetic or formic acid, source of copper or other metals. 0.5-1.0... 

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]. 

Formic acid behaves differently. The expected octadienyl formate is not formed. The reaction of butadiene carried out in formic acid and triethylamine affords 1,7-octadiene (41) as the major product and 1,6-octadiene as a minor product[41-43], Formic acid is a hydride source. It is known that the Pd hydride formed from palladium formate attacks the substituted side of tt-allylpalladium to form the terminal alkene[44] (see Section 2.8). The reductive dimerization of isoprene in formic acid in the presence of Et3N using tri(i)-tolyl)phosphine at room temperature afforded a mixture of dimers in 87% yield, which contained 71% of the head-to-tail dimers 42a and 42b. The mixture was treated with concentrated HCl to give an easily separable chloro derivative 43. By this means, a- and d-citronellol (44 and 45) were pre-pared[45]. 

J-unsaturated ester is formed from a terminal alkyne by the reaction of alkyl formate and oxalate. The linear a, /J-unsaturated ester 5 is obtained from the terminal alkyne using dppb as a ligand by the reaction of alkyl formate under CO pressure. On the other hand, a branehed ester, t-butyl atropate (6), is obtained exclusively by the carbonylation of phenylacetylene in t-BuOH even by using dppb[10]. Reaction of alkynes and oxalate under CO pressure also gives linear a, /J-unsaturated esters 7 and dialkynes. The use of dppb is essen-tial[l 1]. Carbonylation of 1-octyne in the presence of oxalic acid or formic acid using PhiP-dppb (2 I) and Pd on carbon affords the branched q, /J-unsatu-rated acid 8 as the main product. Formic acid is regarded as a source of H and OH in the carboxylic acids[l2]. 

A sample of the protein, horse heart myoglobin, was dissolved in acidified aqueous acetonitrile (1% formic acid in HjO/CHjCN, 1 1 v/v) at a concentration of 20 pmol/1. This sample was injected into a flow of the same solvent passing at 5 pl/min into the electrospray source to give the mass spectrum of protonated molecular ions [M + nH] shown in (a). The measured ra/z values are given in the table (b), along with the number of protons (charges n) associated with each. The mean relative molecular mass (RMM) is 16,951,09 0.3 Da. Finally, the transformed spectrum, corresponding to the true relative molecular mass, is shown in (c) the observed value is close to that calculated (16,951.4), an error of only 0.002%. 

Olefins are carbonylated in concentrated sulfuric acid at moderate temperatures (0—40°C) and low pressures with formic acid, which serves as the source of carbon monoxide (Koch-Haaf reaction) (187). Liquid hydrogen fluoride, preferably in the presence of boron trifluoride, is an equally good catalyst and solvent system (see Carboxylic acids). 

Carboxylic acids having 6—24 carbon atoms are commonly known as fatty acids. Shorter-chain acids, such as formic, acetic, and propionic acid, are not classified as fatty acids and are produced synthetically from petroleum sources (see Acetic acid Formic acid and derivatives Oxo process). Fatty acids are produced primarily from natural fats and oils through a series of unit operations. Clay bleaching and acid washing are sometimes also included with the above operations in the manufacture of fatty acids for the removal of impurities prior to subsequent processing. 

Formaldehyde is a gas with a boiling point of -21 °C. It is usually supplied as a stabilised aqueous solution ( 40% formaldehyde) known as formalin. When formalin is used as the source of the aldehyde, impurities present generally include water, methanol, formic acid, methylal, methyl formate and carbon dioxide. The first three of these impurities interfere with polymerisation reactions and need to be removed as much as possible. In commercial polymerisation the low polymers trioxane and paraformaldehyde are convenient sources of formaldehyde since they can be obtained in a greater state of purity. 

When a photosynthetic organism is omitted, the addition of a photosensitizer is necessary. The methods use light energy to promote the transfer of an electron from a photosensitizer to NAD(P) via an electron transport reagent [6g]. Recently, carbon dioxide cvas reduced to formic acid with FDH from Saccharomyces cerevisiae in the presence of methylviologen (MV ) as a mediator, zinc tetrakis(4-methylpyridyl) porphyrin (ZnTMPyP) as a photosensitizer, and triethanolamine (TEOA) as a hydrogen source (Figure 8.8) [6h]. 

The molecular mass of the protein was redetermined by infusing a 5-10 pmolp.l solution of the protein in 50% aqueous acetonitrile containing 0.2% formic acid at a flow rate of 6 p,lmin into an electrospray source. The scan rate employed on the mass spectrometer was from m/z 60 to m/z 1800 in 12 s. This is a relatively slow scan speed which will lead to a more precise molecular weight determination. Scan speeds of this order may be, and indeed should be, utilized for infusion experiments if sufficient sample is available but it is unlikely to be feasible when chromatographic separations, particularly those involving capillary columns, are employed because of the restriction imposed by the chromatographic peak width (see Section 3.5.2.1 above). 

Rice C, Ha RI, Masel RI, Waszczuk P, Wieckowski A, Barnard T. 2002. Direct formic acid fuel cells. J Power Sources 111 83-89. 

Other Gas Reactions. Several other reactive gases or vapours were examined but found to be unsatisfactory. No ester formation ( 1745 cm"1) was found when oxidatized films were exposed to acetic acid or formic acid vapour. Alcohol/carboxylic acid reactions in the solid state have often been suggested as the source of ester products, but not substantiated (4,5). Gaseous ammonia reacted with carboxylic acid groups to give absorptions at 1550 cm"1 [-C(=0)-0 ] and 1300 cm"1 (NHi +). However, these absorptions were very broad and the method inferior to acid measurement by SF. Although N20 did not react with oxidized polyolefins, the reaction of N02 with oxi-... 

Figure 21. Electrochemical production of formic acid (HCOOH) and CO. Source third Carbon Dioxide Utilisation Summit. DNV GL.

Online LC-ESI-TOF-MS experiments are carried out in a very similar fashion to the off-line NPS-HPLC separations described above, with a few notable exceptions. Firstly, 0.3% (v/v) formic acid is added to each mobile phase to counteract the ionization suppression induced by TFA. Because of the formic acid UV detection must be carried out at 280 nm (as opposed to 214 nm). To aid in normalization between runs 1 jag of Bovine insulin (MW = 5734 Da) is added to each chromatofocusing fraction prior to injection onto the column. Finally, the flow is split postcolumn directing 200 JlL/min into the ion source and the remaining 300 JlL/min through the UV detector and fraction collection. 

Cobalt porphyrin derivatives were also reported129 to be active for electrochemical reduction of C02 to formic acid at an amalgamated Pt electrode. More recently, Becker et al have reported130 that Ag2+ and Pd2+ metalloporphyrins acted as homogeneous catalysts for C02 reduction in dry CH2C12 oxalic acid and H2 (its source was not clear) were produced, but no CO was detected. 

Catalysis and Synthesis in the Laboratory. Research on the practical applications of catalysis was not matched in the laboratory. We began a study of metal and non-metal catalyzed reactions early in our sonochemistry program. Our first project was to develop a convenient method of hydrogenating a wide range of olefins. We chose formic acid as our hydrogen source and found it to be effective. For example, with continuous irradiation, palladium catalyzed hydrogenations of olefins are complete in one hour(44). 

Apart from the Meerwin-Ponndorf-Verley (MPV) reaction,16 18catalytic asymmetric transfer hydrogenation has remained quite primitive,111,112 with successful examples of reduction of activated olefins, using alcohols or formic acid as hydrogen source, being reported only recently.113,114... 

Indigo is considered as one of the most important dyes. Its preparations are usually analysed by HPLC with UV-Vis [46,60] or APCI MS detection. [61,62] Separation of the colouring components of indigo extracted with DMSO is usually performed with the use of a Cl 8 column. Spectrophotometric detection of blue indigotin is performed at 617 nm, red indirubin at 540 nm, and brown isoindigo at 365 and 490 nm. As mobile phases, mixtures of methanol or acetonitrile and water with the addition of TFA or formic acid are used to ensure compatibility with the requirements of the APCI source. 

A novel approach to purine synthesis involves the use of ADC compounds as a source of one nitrogen atom in the five-membered ring.148 150 Treatment of 6-amino-l,3-dimethyluracil (94, R = H) with DEAZD gives the 5-substitution product (95, R = H). The N—N bond is cleaved by Raney nickel or formic acid, and ring closure to 1,3-dimethyluric acid is simply effected by heating.148 Whether the initial adduct is formed by a substitution... 

The methylation of secondary amines works better than for primary amines because there is no competition between the formation of mono- or dimethylated products. The best results for the microwave-enhanced conditions were obtained when the molar ratios of substrate/formaldehyde/formic acid were 1 1 1, so that the amount of radioactive waste produced is minimal. The reaction can be carried out in neat form if the substrate is reasonably miscible with formic acid/aldehyde or in DM SO solution if not. Again the reaction is rapid - it is complete within 2 min at 120 W microwave irradiation compared to longer than 4 h under reflux. The reaction mechanism and source of label is ascertained by alternatively labeling the formaldehyde and formic acid with deuterium. The results indicate that formaldehyde contri-... 

The reaction of biphenyl with formic acid and K2S208 in a mixture of GF3C02H and GH2G12, using Pd(OCOCF3)2 as a catalyst, gives hydroxyl-biphenylcarboxylic acid in 45% yield (Equation (76)).101 The hydroxylation and carboxylation proceeds on one molecule. This reaction is applied to the palladium-catalyzed carboxylation of benzenes using formic acid as a carbonyl source. 

An interesting catalytic ruthenium system, Ru(7/5-C5Ar4OH)(CO)2H based on substituted cyclopentadienyl ligands was discovered by Shvo and coworkers [95— 98]. This operates in a similar fashion to the Noyori system of Scheme 3.12, but transfers hydride from the ruthenium and proton from the hydroxyl group on the ring in an outer-sphere hydrogenation mechanism. The source of hydrogen can be H2 or formic acid. Casey and coworkers have recently shown, on the basis of kinetic isotope effects, that the transfer of H+ and TT equivalents to the ketone for the Shvo system and the Noyori system (Scheme 3.12) is a concerted process [99, 100]. 

A variety of ketones were hydrogenated using Shvo s catalyst at 100 °C using excess formic acid rather than H2 as the source of hydrogen [74], Excellent yields (> 90%) of alcohols were generally obtained in 6 h or less, with total turnovers in the range of 6000-8000. The unsaturated 16-electron Ru complex that results after hydrogen is delivered to the substrate is proposed to react with for-... 

---