Glycol, oxidative functionalization

Replacement of the carbamate function by an amide seems to be compatible with meprobamate-like activity in a compound formally derived from a 1,2-glycol. Oxidation of the commercially available aldehyde, 22, under controlled conditions affords the corresponding acid (23). This is then converted to its amide (24) via the acid chloride. Epoxidation by means of perphthalic acid affords oxanamide (25). ... 

Oxidative cleavage of the olefin is accomplished by the method of ijemieux-Johnson.12 The process begins with dihydroxylation of the double bond using osmium tetroxide (see Chapter 3)T leading to a cis diol and osmium(VI) oxide. The added periodate has two functions first, it reoxidizes the osmium(VI) species to os-mium(VIII), but it also cleaves the glycol oxidatively to an aldehyde. This is the reason for utilizing several equivalents of periodate. The periodate is in turn reduced from the +VH to the +V oxidation state. 

Hydroxyapatite (CajQ(P04)g(0H)2) has also attracted considerable interest as a catalyst support. In these materials, wherein Ca sites are surrounded by P04 tetrahedra, the introduction of transition metal cations such as Pd into the apatite framework can generate stable monomeric phosphate complexes that are efficient for aerobic selox catalysis [99]. Carbon-derived supports have also been utihzed for this chemistry, and are particularly interesting because of the ease of precious metal recovery from spent catalysts simply by combustion of the support. Carbon nanotubes (CNTs) have received considerable attention in this latter regard because of their superior gas adsorption capacity. Palladium nanoparticles anchored on multiwalled carbon nanotubes (MWCNTs) and single-walled carbon nanotubes (SWCNTs) show better selectivity and activity for aerobic selox of benzyl and cinnamyl alcohols [100, 101] compared to activated carbon. Interestingly, Pd supported on MWCNTs showed higher selectivity toward benzaldehyde, whereas activated carbon was found to be a better support in cinnamyl alcohol oxidation. Functionalized polyethylene glycol (PEG) has also been employed successfully as a water-soluble, low-cost, recoverable, non-toxic, and non-volatile support with which to anchor nanoparticulate Pd for selox catalysis of benzyl/cinnamyl alcohols and 2-octanol [102-104]. 

The achiral triene chain of (a//-rrans-)-3-demethyl-famesic ester as well as its (6-cis-)-isoiner cyclize in the presence of acids to give the decalol derivative with four chirai centres whose relative configuration is well defined (P.A. Stadler, 1957 A. Escherunoser, 1959 W.S. Johnson, 1968, 1976). A monocyclic diene is formed as an intermediate (G. Stork, 1955). With more complicated 1,5-polyenes, such as squalene, oily mixtures of various cycliz-ation products are obtained. The 18,19-glycol of squalene 2,3-oxide, however, cyclized in modest yield with picric acid catalysis to give a complex tetracyclic natural product with nine chiral centres. Picric acid acts as a protic acid of medium strength whose conjugated base is non-nucleophilic. Such acids activate oxygen functions selectively (K.B. Sharpless, 1970). 

Regioselectivity of C—C double bond formation can also be achieved in the reductiv or oxidative elimination of two functional groups from adjacent carbon atoms. Well estab llshed methods in synthesis include the reductive cleavage of cyclic thionocarbonates derivec from glycols (E.J. Corey, 1968 C W. Hartmann, 1972), the reduction of epoxides with Zn/Nal or of dihalides with metals, organometallic compounds, or Nal/acetone (seep.lS6f), and the oxidative decarboxylation of 1,2-dicarboxylic acids (C.A. Grob, 1958 S. Masamune, 1966 R.A. Sheldon, 1972) or their r-butyl peresters (E.N. Cain, 1969). 

Materials that typify thermoresponsive behavior are polyethylene—poly (ethylene glycol) copolymers that are used to functionalize the surfaces of polyethylene films (smart surfaces) (20). When the copolymer is immersed in water, the poly(ethylene glycol) functionaUties at the surfaces have solvation behavior similar to poly(ethylene glycol) itself. The abiUty to design a smart surface in these cases is based on the observed behavior of inverse temperature-dependent solubiUty of poly(alkene oxide)s in water. The behavior is used to produce surface-modified polymers that reversibly change their hydrophilicity and solvation with changes in temperatures. Similar behaviors have been observed as a function of changes in pH (21—24). 

Nickel peroxide is a solid, insoluble oxidant prepared by reaction of nickel (II) salts with hypochlorite or ozone in aqueous alkaline solution. This reagent when used in nonpolar medium is similar to, but more reactive than, activated manganese dioxide in selectively oxidizing allylic or acetylenic alcohols. It also reacts rapidly with amines, phenols, hydrazones and sulfides so that selective oxidation of allylic alcohols in the presence of these functionalities may not be possible. In basic media the oxidizing power of nickel peroxide is increased and saturated primary alcohols can be oxidized directly to carboxylic acids. In the presence of ammonia at —20°, primary allylic alcohols give amides while at elevated temperatures nitriles are formed. At elevated temperatures efficient cleavage of a-glycols, a-ketols... 

The reaction occurs at approximately 80-130°C using the proper catalyst. Many catalysts have been tried for this reaction, and there is an indication that the best catalyst types are those of the tertiary amine and quaternary ammonium functionalized resins. This route produces ethylene glycol of a high purity and avoids selectivity problems associated with the hydrolysis of ethylene oxide. 

A final class of multifunctional initiators is based on the use a (muUi)functional polymer and a low molecular weight redox agent. Radicals on the polymer chain arc generated from the polymer bound functionality by a redox reaction. Ideally, no free initiating species are formed. The best known of this class are the polyol-redox and related systems. Polymers containing hydroxy or glycol and related functionality are subject to one electron oxidation by species such as ceric ions or periodate (Scheme 7.23).266,267 Substrates such as cellulose,... 

Poly(tetramethylene oxide) polyols (see Scheme 4.4) are a special class of polyethers syndiesized via acid-catalyzed ring-opening polymerization of tetrahy-drofuran. Although less susceptible to side reactions, the synthesis of these C4 ethers is less flexible in terms of product composition and structure. Thus, because of diis syndietic route, only two-functional glycols are available and copolymers are not readily available. Molecular weights of commercial C4 glycols range up to about 3000 g/m. 

Propylene glycol, i.e., 1,2-propanediol (1,2-PDO), is an important commodity chemical. It is used as biodegradable functional fluids and as precursors for the syntheses of unsaturated polyester resins and pharmaceuticals (9-10). Propylene glycol is currently produced from petroleum-derived propylene via oxidation to propylene oxide and subsequent hydrolysis (9, 11). However, the rising cost of propylene provides an incentive to find a substitute to propylene for this... 

In our ongoing efforts to develop oxidation catalysts that are functional in water as environmentally berrign solvent, we synthesized a water-soluble pentadentate salen ligand with polyethylene glycol side chairts (8). After coordination of copper(II) ions to the salen ligand, a dinuclear copper(II) complex is obtained that is soluble in water, methanol and mixtures of both solvents. The aerobic oxidation of 3,5-di-tert.-butylcatechol (DTBC) into 3,5-di-terr.-butylqitinone (DTBQ) was used as a model reaction to determine the catalytically active species and initial data on its catalytic activity in 80% methanol. 

Acetic acid appears to function both as an accelerator for the oxidation and an inhibitor of the rearrangement to glycolic acid. 

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