Miscellaneous Carbonyl Derivatives

Miscellaneous Carbonyl Derivatives Carboxylic Acid Halides (d in ppm, J in Hz)... 

Miscellaneous Cyclizations of Carbonyl Derivatives to Form Benzothiophenes 906... 

Thioxo-1,2,4-dithiazolidines can be obtained from thioxo-l,2,4-thiadiazolidines by Dimroth rearrangement (Scheme 47) or reversibly by addition and elimination of acetone (Scheme 22). 1,2,4-Dithiazole type products are also obtained from thiocarbonyl isothiocyanates (154) by reaction with CI2 <84CHEC-I(6)897>, PhMgBr, Sj, or CS2. Other routes include reactions of carbonyl isothiocyanates and thiocarbonyl isocyanates with P4S10 or Sg <84Chec-I(6)897> and sulfonyl isocyanates with dialkyl thioketenes. Phenylisothiocyanate heated with N,C-disubstituted oxaziridines affords 3,5-diimino-l,2,4-dithiazolidines (226, 227). Other miscellaneous syntheses of 1,2,4-dithiazoline derivatives include cyclization of A7-thioacyl hexafluoroacetonimine to 5,5-bis(trifluoromethyl)-... 

Miscellaneous derivatives are hydrolyzed back to the starting carbonyl compounds. Hienylhydtazones of ketones are converted into the parent ketones tqion treatment with manganese dioxide.Tosylhydra-zones react with molybdenyl chloride or tungsten tetrafluoride to give both aldehydes and ketones. Sodium peroxide converts aldoximes into carboxylic acids. 

Miscellaneous Uses. Substituted derivatives of (1), e.g. (7), react with a,p-unsaturated carbonyl systems in a highly stereose-... 

Miscellaneous. The barriers to pyramidal inversion of a series of acyl phosphines (55) [RCOP(CHMe2)2] have been measured. Electron-withdrawing substituents in R facilitate the inversion whereas electron-donating groups hinder it because of the increase or decrease of interaction of the phosphorus lone-pair with the carbonyl group. The Hammett p constant for the inversion of phosphines has been determined using substituent constants derived from the inversion of 1-aryl-2,2-dimethylaziridines. The pyramidal inversion barriers for phosphines and arsines have been reviewed. ... 

Takeoka et al. (24) reported in 1986 that there were 52 volatiles present in kiwifruit, including 11 carbonyls, 9 alcohols, 16 esters, 11 hydrocarbons and one miscellaneous components. They suggested that peak no. 2 was tetrachloromethane which was derived from the solvent used in the extraction. It is possible that the presence of toluene (peak 12), p-xylene (peak 20), m-xylene (peak... 

Miscellaneous Systems Other systems have been described [li,m] ferrocene/ carbon tetrachloride (a trichloromethyl radical is formed), ferrocene/carbon tetrabromide, metal carbonyl/onium salts (e.g., the [cyclopentadienyl Fe (CO)2]2/ diaryliodonium hexafluorophosphate combination where a phenyl radical is generated), benzene chromium tricarbonyl/halide derivative, and so on. 

There are several studies investigating the flavor composition of smoked products that gives the products their characteristic flavors. The main components responsible for the smoke flavor are phenol derivatives. In addition to the flavoring compounds arising from wood pyrolysis, flavoring compounds derived from plants are also present. The soluble fraction mostly contains fatty adds and fatty esters, in addition to acids, alcohols, carbonyls, esters, furans, lactones, furans, and many miscellaneous compounds [108]. The phenolic fraction of traditional kiln-smoked Bacon contains phenols, furfuryl alcohol, and cyclotene while different compounds, such as 2,4,5-trimethyl-3(2//)-furanone, have been isolated from cooked Oscar Mayer bacon [109],... 

Miscellaneous Reactions. In addition to the key reactions above, DDQ has been used for the oxidative removal of chromium, iron, and manganese from their complexes with arenes and for the oxidative formation of imidazoles and thiadia-zoles from acyclic precursors. Catal)ftic amounts of DDQ also offer a mild method for the oxidative regeneration of carbonyl compounds from acetals, which contrasts with their formation from diazo compounds on treatment with DDQ and methanol in nonpolar solvents. DDQ also provides effective catalysis for the tetrahydropyranylation of alcohols. Furthermore, the oxidation of chiral esters or amides of arylacetic acid by DDQ in acetic acid provides a mild procedure for the synthesis of chiral a-acetoxy derivatives, although the diastereoselectivity achieved so far is only 65-67%. ... 

Miscellaneous Reactions. Trimethylsilyldiazomethane converts acid- and base-sensitive maleic anhydride derivatives into the corresponding bis(methyl esters) (eq 70). Terminal silyl enol ethers are conveniently prepared from aldehydes by first treating the carbonyl compound with TMSC(Li)N2, followed sequentially by methanol and Rh2(OAc)4 (eq 71). The method works well with base-sensitive substrates and is superior to the attempted regioselective deprotonation/O-silylation of the corresponding methyl ketone. ... 

C. Miscellaneous Chromium, Molybdenum, and Tungsten Carbonyl Anions Other Than Cyclopentadienyl Derivatives... 

Several studies have investigated empirically the flux of chemicals within snow or between snow and the atmosphere (Guimbaud et al., 2002 Albert and Shultz, 2002 Herbert et al., 2006). In particular, measured concentration gradients within the atmospheric boundary layer or within the snow pack have been used to calculate a chemical s flux into or out of the snow pack. This approach has resulted in miscellaneous parameterizations to calculate fluxes of, for example, carbonyl compounds and NO c species from the snow pack as a result of photochemical processes in snow (Domind and Shepson, 2002 Hutterli et al., 1999 Guimbaud et al., 2002 Grannas et al., 2002). However, flux measurements can only be used to derive kinetic transport parameters, such as diffusivities and mass transport coefficients, if the chemicals involved are reasonably persistent and do not undergo rapid conversions within the snow pack. For example, measurements of the flux of carbonyl compounds out of snow are more likely to reflect the kinetics of formation in the snow pack than the kinetics of snow-air gas exchange. As a result, there is a very limited number of experimental studies that provide quantitative information on the rate of chemical transport in snow. 

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