Valeraldehydes

It IS hard to find a class of compounds in which the common names of its members have influenced organic nomenclature more than carboxylic acids Not only are the common names of carboxylic acids themselves abundant and widely used but the names of many other compounds are derived from them Benzene took its name from benzoic acid and propane from propionic acid not the other way around The name butane comes from butyric acid present m rancid butter The common names of most aldehydes are derived from the common names of carboxylic acids—valeraldehyde from valeric acid for exam pie Many carboxylic acids are better known by common names than by their systematic ones and the framers of the lUPAC rules have taken a liberal view toward accepting these common names as permissible alternatives to the systematic ones Table 19 1 lists both common and systematic names for a number of important carboxylic acids... 

The principal valeraldehyde derivatives, -amyl and 2-methylbutyl alcohols, are used predominandy to make ziac diamyldithiophosphate lube oil additives (see Amyl alcohols Lubrication and lubricants), which are employed primarily in automotive antiwear appHcations. Similady, the / -valerate and 2-methylbutyrate esters of pentaerythritol and trimethylolpropane are used ia aeromotive synlube formulations and as refrigerant lubricants. 

Prior to 1975, reaction of mixed butenes with syn gas required high temperatures (160—180°C) and high pressures 20—40 MPa (3000—6000 psi), in the presence of a cobalt catalyst system, to produce / -valeraldehyde and 2-methylbutyraldehyde. Even after commercialization of the low pressure 0x0 process in 1975, a practical process was not available for amyl alcohols because of low hydroformylation rates of internal bonds of isomeric butenes (91,94). More recent developments in catalysts have made low pressure 0x0 process technology commercially viable for production of low cost / -valeraldehyde, 2-methylbutyraldehyde, and isovaleraldehyde, and the corresponding alcohols in pure form. The producers are Union Carbide Chemicals and Plastic Company Inc., BASF, Hoechst AG, and BP Chemicals. 

Union Carbide Chemicals and Plastics Company Inc. is the only producer of C-5 oxo derived alcohols (148,150) in the United States. About 75% of the 30,000 t of valeraldehyde and 2-methylbutyraldehyde produced by the oxo process was converted to the isomeric mixture of primary amyl alcohols in 1988 (150). The primary amyl alcohol mixture was available in tank car quantities for 1.02/kg in 1991. The Dow Chemical Company appears to have stopped commercial production of / fZ-amyl alcohol (151). 

The demand for amyl alcohols is expected to remain unchanged until 1993. Competition from other alcohols and limited appHcations limit growth in markets for amyl alcohols. U.S. demand was predicted to grow from 29 x 10 t in 1983 to 32 x Kf t by 1990 (152). In Europe, amyl alcohols account for over 80% of the demand for valeraldehyde (17,000 t in 1984). BASE and Hoechst AG produce both / -valeraldehyde and 2-methylbutyraldehyde from butenes by the oxo process (149). The demand for C-5 in Europe is also predicted not to grow substantially (150). Amyl alcohols are growing at a much lower rate than other oxo alcohols as shown in Table 7. 

Dimethylhutane Dtisopropyl 23 C(3Hi4 1-Pentanal Valeraldehyde 117 CsHioO... 

C5H10O VALERALDEHYDE -229.987 3.9652E-01 3.5518E-05 -108.28 259 C6H12 4-METHYL-l- -46.656 4,4313E-01 4.6863E-05 90.04... 

In the absence of base, the trimer can rearrange to iso-tripiperidein, a product of self-condensation.10,17 Tn the presence of base, however, a-tripiperidein is stable for over a year. In solution, tripiperidein readily detrimcnzes to the monomer, which is in equilibrium with S-amino-valeraldehyde [Pentanal, 5-amino-].8... 

Analogous to terminal alkenes, the reaction of 123 with valeraldehyde and cyclohexanone under radical-based conditions allowed for the preparation of the corresponding functional polysilanes 126 (Reaction 90). The efficiency of Si-H bond replacement was 80-85%... 

METHYL-1-BUTENE VALERALDEHYDE METHYL N-PROPYL KETONE METHYL ISOPROPYL KETONE DIETHYL KETONE... 

The RCH/RP process converts propylene to n- and Lo-butyraldehydes (or butenes to valeraldehydes) in the presence [HRh(CO)(TPPTS)] (with TPPTS = tris[sodium-m-sulfonatophcnvl phosphine as water soluble ligand) according to Equation 5.1. 

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