Other Aldehydes

Noth. The above method can be successfully applied only to dilute solutions of formaldehyde which are free in particular from other alfphatic aldehydes, since the latter, if present, would undergo a similar oxidation. Formaldehyde, if mixed with other aldehydes, should be estimated by quantitative addition of potassium cyanide for details, see advanced text-books of quantitative organic analysis. 

The reagent is attacked by oxidising agents with the formation of formaldehyde, hence it cannot be used for the detection of the latter (or of other aldehydes) in the presence of oxidising agents. 

Acetaldehyde (and other aldehydes containing at least one hydrogen atom in the a position) when treated with a small quantity of dilute sodium hydr oxide solution or other basic catalyst gives a good yield of aldol (p hydroxy-n-but3Taldehyde) (I), which readily loses water, either by heating the isolated aldol alone or with a trace of mineral acid, to form crotonaldehyde (II) ... 

Just as most other aldehydes do, furfural condenses with compounds possessing active methylene groups such as aUphatic carboxyUc esters and anhydrides, ketones, aldehydes, nitriles, and nitroparaffins. 

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). 

The reaction is very exothermic. The heat of reaction of propylene oxidation to acrolein is 340.8 kJ /mol (81.5 kcal/mol) the overall reactions generate approximately 837 kJ/mol (200 kcal/mol). The principal side reactions produce acryUc acid, acetaldehyde, acetic acid, carbon monoxide, and carbon dioxide. A variety of other aldehydes and acids are also formed in small amounts. Proprietary processes for acrolein manufacture have been described (25,26). 

Reaction with Other Aldehydes. Polyacrylamide reacts with glyoxal [107-22-2], C2H2O2, under mild alkaline conditions to yield a polymer with pendant aldehyde fiinctionahty. 

At high enough concentrations, PAN is a potent eye irritant and phytotoxin. On a smoggy day in the Los Angeles area, PAN concentrations are typically 5 to 10 ppb in the rest of the United States PAN concentrations are generally a fraction of a ppb. An important formation route for formaldehyde [50-00-0] HCHO, is reaction 9. However, o2onolysis of olefinic compounds and some other reactions of VOCs can produce HCHO and other aldehydes. 

Other Aldehydes. The higher aldehydes react with phenol in much the same manner as formaldehyde, although at much lower rates. 

In some cases, Bucherer s process is employed also, but strict control of reaction conditions is needed because the reactivity of formaldehyde is different from other aldehydes. DL-Alanine (212) is produced by either Strecker s or Bucherer s process from acetaldehyde. 

Amino resins are thermosetting polymers made by combining an aldehyde with a compound containing an amino (—NH2) group. Urea—formaldehyde (U/F) accounts for over 80% of amino resins melamine—formaldehyde accounts for most of the rest. Other aldehydes and other amino compounds are used to a very minor extent. The first commercially important amino resin appeared about 1930, or some 20 years after the introduction of phenol—formaldehyde resins and plastics (see Phenolic resins). 

Aldol additions of benzaldehyde with active methylene groups produce other aldehydes. 

Using a number of other aldehydes, more compHcated products result. Stmcture (2) was also found to react with alkynes in the presence of copper(I) chloride to give furans ... 

The butanals form the conventional aldehyde hydra2one, semicarba2one, and dimedone-type derivatives. In the absence of other aldehydes and ketones, -butyraldehyde can be deterrnined by addition of sodium bisulfite and the excess bisulfite deterrnined with iodine or thiosulfate (34). 

Urea—Other Aldehyde Reaction Products. Urea can also react with other aldehydes to form slow release nitrogen fertilizers. However, cost constraints associated with higher aldehydes have either precluded or limited broad commercial development of these products. Two exceptions are isobutyhdene diurea (IBDU), registered trademark of Vigoro Industries, and crotonyHdene diurea (CDU), registered trademark of Chisso-Asahi Fertilizer Co. 

Two aldehydes (qv) have made their mark in the field of disinfection, namely formaldehyde [50-00-0] and glutaraldehyde [111-30-8]. Other aldehydes do not match these compounds in activity (111,112). 

Paint and varnish manufacturing Resin manufacturing closed reaction vessel Varnish cooldng-open or closed vessels Solvent thinning Acrolein, other aldehydes and fatty acids (odors), phthalic anhydride (sublimed) Ketones, fatty acids, formic acids, acetic acid, glycerine, acrolein, other aldehydes, phenols and terpenes from tall oils, hydrogen sulfide, alkyl sulfide, butyl mercaptan, and thiofen (odors) Olefins, branched-chain aromatics and ketones (odors), solvents Exhaust systems with scrubbers and fume burners Exhaust system with scrubbers and fume burners close-fitting hoods required for open kettles Exhaust system with fume burners... 

Ethyl cthylcyanoacetate and ethyl propylcyanoacetate have been prepared by the same method in yields of 85 and 94%, respectively. Other aldehydes and ketones have been used under slightly different conditions to prepare other ethyl monoalkyl-cyanoacetates. ... 

Formaldehyde HCHO Acetylaldehyde CH3CHO Other aldehydes RCHO Acids... 

Tetrahydroharman, m.p. 179-80°, has been prepared by a number of workers by a modification of this reaction, viz., by the interaction of tryptamine (3-)5-aminoethylindole) with acetaldehyde or paraldehyde and Hahn et al. have obtained a series of derivatives of tetrahydronorharman by the use of other aldehydes and a-ketonic acids under biological conditions of pH and temperature, while Asahina and Osada, by the action of aromatic acid chlorides on the same amine, have prepared a series of amides from which the corresponding substituted dihydronorharmans have been made by effecting ring closure with phosphorus pentoxide in xylene solution. 

In 1883, Bottinger described the reaction of aniline and pyruvic acid to yield a methylquinolinecarboxylic acid. He found that the compound decarboxylated and resulted in a methylquinoline, but made no effort to determine the position of either the carboxylic acid or methyl group. Four years later, Doebner established the first product as 2-methylquinoline-4-carboxylic acid (8) and the second product as 2- methylquinoline (9). Under the reaction conditions (refluxing ethanol), pyruvic acid partially decarboxylates to provide the required acetaldehyde in situ. By adding other aldehydes at the beginning of the reaction, Doebner found he was able to synthesize a variety of 2-substituted quinolines. While the Doebner reaction is most commonly associated with the preparation of 2-aryl quinolines, in this primary communication Doebner reported the successful use of several alkyl aldehydes in the quinoline synthesis. 

A few other aldehydes have been used in the reaction, either under normal or pseudo-physiological conditions. Of these, glycolalde-hyde, 5-hydroxypentanal, phenylacetaldehyde, and benzalde-hyde condense readily, but hydroxy and methoxy derivatives of these aromatic aldehydes give the product in poor yield,presumably due to their instability, as evidenced by their tendency to undergo self-condensation in acid solution. Reaction with phthaldehydic acids, such as opianic acid, proceeded readily, whereas reaction with chloral did not occur,... 

Other aldehydes which have been used in the reaction are pro-panal, butanal, glycolaldehyde, 3-hydroxybutanal, and a number of phenylacetaldehydeand benzaldehyde derivatives. Whereas condensation of tryptophan with acetaldehyde takes place even at room temperature and pH 6.7, the reactions with chloral, chloroacetaldehyde, and crotonaldehyde fail entirely. 

The synthetic importance of the reaction is limited, because as a consequence of the disproportionation, the yield of the alcohol as well as the carboxylic acid is restricted to 50%. However good yields of alcohols can often be obtained when the reaction is carried out in the presence of equimolar amounts of formaldehyde. The formaldehyde is oxidized to formic acid and concomitantly reduces the other aldehyde to the desired alcohol. This variant is called the crossed Cannizzaro reaction. 

Instead of formaldehyde, other aldehydes or ketones may be used—aliphatic as well as aromatic recently methylene dihalides have been employed with success. The amine component is often employed as hydrochloride in addition to... 

The regioselectivity of this reaction is excellent (92 8), and the diastereomeric purity of 2 is estimated to be 93% de on the basis of the oxidation of 2 to (5)-2-cyclohexen-1-ol (93% ee). Similarly, the reaction of 2 with acetaldehyde provides (S.iS H- -cyclohexeny ethanol with an enantiomeric purity of 92% cc. Reactions of 2 with other aldehydes, however, have not yet been reported. 

Cyclohexenyl(diisopinocampheyl)borane (2), prepared by the hydroboration of 1,3-cy-clohexadiene with diisopinocampheylborane, reacts with acetaldehyde at — 78 "C to provide l-(2-cyclohexenyl)ethanol in 66% yield and 94% ee21. Reactions with other aldehydes, however. have not yet been reported. 

In contrast, transmetalation of the lithium enolate at —40 C by treatment with one equivalent of copper cyanide generated a species 10b (M = Cu ) that reacted with acetaldehyde to selectively provide a 25 75 mixture of diastereomers 11 and 12 (R = CH3) which are separable by chromatography on alumina. Other diastereomers were not observed. Similar transmetalation of 10a (M = Li0) with excess diethylaluminum chloride, followed by reaction with acetaldehyde, produced a mixture of the same two diastereomers, but with a reversed ratio (80 20). Similar results were obtained upon aldol additions to other aldehydes (see the following table)49. 

A subclass of lyases, involved in amino acid metabolism, utilizes pyridoxal 5-phosphate (PLP, 3-hydroxy-2-methyl-5-[(phosphonooxy)methyl]-4-pyridinecarbaldehyde) as a cofactor for imine/ enamine-type activation. These enzymes are not only an alternative to standard fermentation technology, but also offer a potential entry to nonnatural amino acids. Serine hydroxymethyl-tansferase (SHMT EC 2.1.2.1.) combines glycine as the donor with (tetrahydrofolate activated) formaldehyde to L-serine in an economic yield40, but will also accept a range of other aldehydes to provide /i-hydroxy-a-amino acids with a high degree of both absolute and relative stereochemical control in favor of the L-erythro isomers41. 

Phenolic oligomers are prepared by reacting phenol or substituted phenols with formaldehyde or other aldehydes. Depending on the reaction conditions (e.g., pH) and the ratio of phenol to formaldehyde, two types of phenolic resins are obtained. Novolacs are derived from an excess of phenol under neutral to acidic conditions, while reactions under basic conditions using an excess of formaldehyde result in resoles. 

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