Formaldehyde mechanism

A new mechanism, called the methane-formaldehyde mechanism, has been put forward for the transformation of the equilibrium mixture of methanol and dimethyl ether, that is, for the formation of the first C-C bond.643 This, actually, is a modification of the carbocation mechanism that suggested the formation of ethanol by methanol attaching to the incipient carbocation CH3+ from surface methoxy.460,462 This mechanism (Scheme 3.3) is consistent with experimental observations and indicates that methane is not a byproduct and ethanol is the initial product in the first C-C bond formation. Trimethyloxonium ion, proposed to be an intermediate in the formation of ethyl methyl ether,447 was proposed to be excluded as an intermediate for the C-C bond formation.641 The suggested role of impurities in methanol as the reason for ethylene formation is highly speculative and unsubstantiated. 

The rate of reaction is relatively slow under neutral conditions but is readily enhanced in the presence of either acid or base. That is, the reaction can be either acid catalyzed or base catalyzed, allowing the equihbrium to be achieved much more rapidly. Consider the base-catalyzed hydration of formaldehyde (Mechanism 20.3). 

Now consider the acid-catalyzed hydration of formaldehyde (Mechanism 20.4). 

In the proposal for the methane-formaldehyde mechanism, methane and formaldehyde are formed from the surface methoxy intermediates and react to form ethanol [83-86]. Tajima et al. [83] used theoretical calculations to indicate that CHyHCHO are also potential reaction intermediates, van Santen with Blaszkowski [86] have theoretically found a transition state for hydride transfer between methanol and surface methoxy to form methane and potentially formaldehyde. Because methane is very slow to react, almost all conventional experimental and theoretical studies have supposed methane to be independent of the first C-C bond... 

Storch D G and Kushner M J 1993 Destruction mechanisms for formaldehyde in atmospheric pressure low temperature plasmas J. Appl. Phys. 73 51-5... 

Method A. Cool a solution of the nitrate-free dichloride, prepared from or equivalent to 5 0 g. of palladium or platinum, in 50 ml. of water and 5 ml. of concentrated hydrochloric acid in a freezing mixture, and treat it with 50 ml. of formahn (40 per cent, formaldehyde) and 11 g. of the carrier (charcoal or asbestos). Stir the mixture mechanically and add a solution of 50 g. of potassium hydroxide in 50 ml. of water, keeping the temperature below 5°. When the addition is complete, raise the temperature to 60° for 15 minutes. Wash the catalyst thoroughly by decantation with water and finally with dilute acetic acid, collect on a suction filter, and wash with hot water until free from chloride or alkali. Dry at 100° and store in a desiccator. 

C. Palladium on carbon catalyst (5 per cent. Pd). Suspend 41-5 g. of nitric acid - washed activated carbon in 600 ml. of water in a 2-litre beaker and heat to 80°. Add a solution of 4 1 g. of anhydrous palladium chloride (1) in 10 ml. of concentrated hydrochloric acid and 25 ml. of water (prepared as in A), followed by 4 ml. of 37 per cent, formaldehyde solution. Stir the suspension mechanically, render it alkaUne to litmus with 30 per cent, sodium hydroxide solution and continue the stirring for a further 5 minutes. Filter off the catalyst on a Buchner funnel, wash it ten times with 125 ml. portions of water, and dry and store as in B. The yield is 46 g. 

In a 500 ml. three-necked flask, fitted with a reflux condenser and mechanical stirrer, place 121 g. (126-5 ml.) of dimethylaniline, 45 g. of 40 per cent, formaldehyde solution and 0 -5 g. of sulphanilic acid. Heat the mixture under reflux with vigorous stirring for 8 hours. No visible change in the reaction mixture occurs. After 8 hours, remove a test portion of the pale yellow emulsion with a pipette or dropper and allow it to cool. The oil should solidify completely and upon boiling it should not smell appreciably of dimethylaniline if this is not the case, heat for a longer period. When the reaction is complete, steam distil (Fig. II, 41, i) the mixture until no more formaldehyde and dimethylaniline passes over only a few drops of dimethylaniline should distil. As soon as the distillate is free from dimethylaniline, pour the residue into excess of cold water when the base immediately solidifies. Decant the water and wash the crystalline solid thoroughly with water to remove the residual formaldehyde. Finally melt the solid under water and allow it to solidify. A hard yellowish-white crystalline cake of crude base, m,p. 80-90°, is obtained in almost quantitative yield. RecrystaUise from 250 ml. of alcohol the recovery of pure pp -tetramethyldiaminodiphenylmethane, m.p. 89-90°, is about 90 per cent. 

Under acidic conditions, furfuryl alcohol polymerizes to black polymers, which eventually become crosslinked and insoluble in the reaction medium. The reaction can be very violent and extreme care must be taken when furfuryl alcohol is mixed with any strong Lewis acid or Brn nstad acid. Copolymer resins are formed with phenoHc compounds, formaldehyde and/or other aldehydes. In dilute aqueous acid, the predominant reaction is a ring opening hydrolysis to form levulinic acid [123-76-2] (52). In acidic alcohoHc media, levulinic esters are formed. The mechanism for this unusual reaction in which the hydroxymethyl group of furfuryl alcohol is converted to the terminal methyl group of levulinic acid has recendy been elucidated (53). 

Uses. Furfuryl alcohol is widely used as a monomer in manufacturing furfuryl alcohol resins, and as a reactive solvent in a variety of synthetic resins and appHcations. Resins derived from furfuryl alcohol are the most important appHcation for furfuryl alcohol in both utihty and volume. The final cross-linked products display outstanding chemical, thermal, and mechanical properties. They are also heat-stable and remarkably resistant to acids, alkaUes, and solvents. Many commercial resins of various compositions and properties have been prepared by polymerization of furfuryl alcohol and other co-reactants such as furfural, formaldehyde, glyoxal, resorcinol, phenoHc compounds and urea. In 1992, domestic furfuryl alcohol consumption was estimated at 47 million pounds (38). 

Positive-Tone Photoresists based on Dissolution Inhibition by Diazonaphthoquinones. The intrinsic limitations of bis-azide—cycHzed mbber resist systems led the semiconductor industry to shift to a class of imaging materials based on diazonaphthoquinone (DNQ) photosensitizers. Both the chemistry and the imaging mechanism of these resists (Fig. 10) differ in fundamental ways from those described thus far (23). The DNQ acts as a dissolution inhibitor for the matrix resin, a low molecular weight condensation product of formaldehyde and cresol isomers known as novolac (24). The phenoHc stmcture renders the novolac polymer weakly acidic, and readily soluble in aqueous alkaline solutions. In admixture with an appropriate DNQ the polymer s dissolution rate is sharply decreased. Photolysis causes the DNQ to undergo a multistep reaction sequence, ultimately forming a base-soluble carboxyHc acid which does not inhibit film dissolution. Immersion of a pattemwise-exposed film of the resist in an aqueous solution of hydroxide ion leads to rapid dissolution of the exposed areas and only very slow dissolution of unexposed regions. In contrast with crosslinking resists, the film solubiHty is controUed by chemical and polarity differences rather than molecular size. 

Homopolymer. Formaldehyde polymerises by both anionic and cationic mechanisms. Strong acids are needed to initiate cationic polymerisation. Anionic polymerisation, which can be initiated by relatively weak bases (eg, pyridine), can be represented by the following equations Initiation... 

Urea.—Forma.IdehydeResins. Cellular urea—formaldehyde resins can be prepared in the following manner an aqueous solution containing surfactant and catalyst is made into a low density, fine-celled foam by dispersing air into it mechanically. A second aqueous solution consisting of partially cured urea—formaldehyde resin is then mixed into the foam by mechanical agitation. The catalyst in the initial foam causes the dispersed resin to cure in the cellular state. The resultant hardened foam is dried at elevated temperatures. Densities as low as 8 kg/m can be obtained by this method (117). 

Formaldehyde is classified as a probable human carcinogen by the International Agency for Research on Cancer (lARC) and as a suspected human carcinogen by the American Conference of Governmental Industrial Hygienists (ACGIH). This is based on limited human evidence and on sufficient evidence in experimental animals (136). Lifetime inhalation studies with rodents have shown nasal cancer at formaldehyde concentrations that overwhelmed cellular defense mechanisms, ie, 6 to 15 ppm. No nasal cancer was seen at 2 ppm or lower levels (137). 

Methane oxidations occur only by intermediate and high temperature mechanisms and have been reported not to support cool flames (104,105). However, others have reported that cool flames do occur in methane oxidation, even at temperatures >400 ° C (93,94,106,107). Since methyl radicals caimot participate in reactions 23 or 24, some other mechanism must be operative to achieve the quenching observed in methane cool flames. It has been proposed that the interaction of formaldehyde and its products with radicals decreases their concentrations and inhibits the whole oxidation process (93). 

Other Nitrogen Compounds. The basis of the sophisticated nitrogen compounds Hsted in Table 10 is the reaction of formaldehyde with amino compounds. A significant amount of Hterature details investigation of the mechanism of action, particularly whether or not the antimicrobial activity depends on decomposition to formaldehyde (40—42). These compounds tend to have substantial water solubiUty and are more effective against bacteria than fungi and yeasts. Key markets for these compounds are metalworking fluids, cosmetics, and in-can preservation of paints (see Alkanolamines Amines, fatty amines). 

However, a second mole of alcohol or hemiformal caimot be added at the ordinary pH of such solutions. The equiUbrium constant for hemiformal formation depends on the nature of the R group of the alcohol. Using nmr spectroscopy, a group of alcohols including phenol has been examined in solution with formaldehyde (15,16). The spectra indicated the degree of hemiformal formation in the order of >methanol > benzyl alcohol >phenol. Hemiformal formation provides the mechanism of stabilization methanol is much more effective than phenol in this regard. 

Alkaline catalysts are also effective in the polymeri2ation—depolymeri2ation of methylene glycol. The mechanism of the formaldehyde addition to the phenolate is still not completely understood. The most likely mechanism involves the contribution of phenol hemiformals (10) (5). 

Optimum mechanical piopeities of the fibers are developed provided the precursor novolak filaments ate less than 25 ]lni in diameter to ensure sufficient diffusion of the formaldehyde and catalyst into the fiber. The individual fibers are generally elliptical in cross section. Diameters range from 14 to 33 )J.m (0.2—1.0 tex or 2—10 den) and fiber lengths ate 1—100 mm. Tensile strength is 0.11—0.15 N /tex (1.3—1.8 g/den) and elongation is in the 30—60% range. Elastic recovery is as high as 96%. 

Ca.ta.lysis, The mechanism of hydrogen abstraction from alcohols to form aldehydes (qv) over silver has been elucidated (11). Silver is the principal catalyst for the production of formaldehyde (qv), the U.S. production of which was 4 x 10 metric tons in 1993. The catalytic oxidation of... 

Once in the soil solution, urea—formaldehyde reaction products are converted to plant available nitrogen through either microbial decomposition or hydrolysis. Microbial decomposition is the primary mechanism. The carbon in the methylene urea polymers is the site of microbial activity. Environmental factors that affect soil microbial activity also affect the nitrogen availabiUty of UF products. These factors include soil temperature, moisture, pH, and aeration or oxygen availabiUty. 

Nail hardeners have been based on various proteia cross-linking agents. Only formaldehyde is widely used commercially. Contact with skin and inhalation must be avoided to preclude sensiti2ation and other adverse reactions. The popularity of products of this type is decreasiag because the polymers used ia nail elongators can be used to coat nails to iacrease the mechanical strength. 

A number of disinfectants apparentiy owe their activity to formaldehyde, although there is argument on whether some of them function by other mechanisms. In this category, the dmg with the longest history is hexamethylenetetramine (hexamine, urotropin) [100-97-0] which is a condensation product of formaldehyde and ammonia that breaks down by acid hydrolysis to produce formaldehyde. Hexamine was first used for urinary tract antisepsis. Other antimicrobials that are adducts of formaldehyde and amines have been made others are based on methylolate derivations of nitroalkanes. The apphcations of these compounds are widespread, including inactivation of bacterial endotoxin preservation of cosmetics, metal working fluids, and latex paint and use in spin finishes, textile impregnation, and secondary oil recovery (117). 

Mechanistic aspects of the action of folate-requiring enzymes involve one-carbon unit transfer at the oxidation level of formaldehyde, formate and methyl (78ACR314, 8OMI2I6OO) and are exemplified in pyrimidine and purine biosynthesis. A more complex mechanism has to be suggested for the methyl transfer from 5-methyl-THF (322) to homocysteine, since this transmethylation reaction is cobalamine-dependent to form methionine in E. coli. 

It is stated that in time the acidity (up to 2,5 units) of 0,1-1,0 M HMTA aqueous solutions changes maximally at 1°C, in comparatively to other temperatures (11, 16, 21°C). When the temperature arises the change of HMTA aqueous solutions pH values decreases in time. Formaldehyde and ammonium ions (end products of HMTA hydrolysis) have been fixed only in more diluted solutions (0,10 and 0,25M). The concentration of NH in them in some times is higher than H2C=0 concentration that is caused by oxidation of the last one to a formic acid, being accompanied by the change of the system platinum electrode potential. It is stated that concentration NH in solutions does not exceed 5% from HMTA general content. The conclusion the mechanism of HMTA destruction in H,0 to depend essentially on its concentration and temperature has been made. 

---