Miscellaneous Transformations

The hydroxy group in a MBH adduct has been oxidized with Jones reagent, affording doubly activated olefins that are highly reaetive. However, pyridi-nium chloroehromate on silica as an oxidant is much less effeetive in the oxidation of MBH adducts.Methyl 2-hydroxyalkylacrylates have also been converted into the corresponding keto eompounds by temporarily 

---

Only transformations in the longest linear sequence (LLS) are considered. The term skeleton constructions refers to C-C and C-O bond formations (notwithstanding redox reactions) that directly introduce native structural features of the bryostatins without further modification. The term other functional group manipulations refers to steps that indirectly introduce native structural elements, the interconversion of functional groups (e.g., the introduction and removal of auxiliaries) and miscellaneous transformations that do not involve skeleton construction... 

OILS, MISCELLANEOUS TRANSFORMER Electrical insulating oil, Insulating oil, Petroleum insulating oil NL 0 1 0 ... 

Oils, Miscellaneous Transformer — Fire Hazards Flash Point (deg. F) 295 OC Flammable Limits in Air (Ho) Data not available Fire Extinguishing Agents Dry chemical, foam, or carbon dioxide Fire Extinguishing Agents Not to be Used Water may be ineffective Special Hazards of... 

A number of other miscellaneous transformations of hetero-aromatic A-oxides have been reported. Of particular interest is the application189 of the photolysis of 2-cyanoquinoline 1-oxides to the synthesis of 1-aminocarbostyrils 2-cyano-4-methylquinoline 1-oxide is converted into the quinolinone by irradiation in dichloromethane solution in the presence of a secondary amine, and the conversion presumably takes place via the intermediate oxaziridine [Eq. (45)]. 

Part A Reactions with [bis(trifluoroacetoxy)iodo]benzene. Transformations of Alkynes. Transformations of Ketones. Phenolic Oxidation. Oxidation of Nitrogen Compounds. Transfomration of Sulfur Compounds. Miscellaneous Transformations. 

Miscellaneous Transformations Leading to Renewable Monomers, Solvents, and Specialty Chemicals... 

It appears worthwhile to discuss the reactions of longifolene in terms of the above four categories, even though some reactions of longifolene are known to lead to products of more than one type. In such cases, the reaction has been discussed under only one head or both the heads, depending on whether one pathway is dominant or not. Besides these four categories of reactions, some other pertinent transformations of longifolene and its derivatives are discussed under two additional heads (i) Conversions into other sesquiterpene skeletons, and (ii) Miscellaneous transformations. 

Miscellaneous Transformations. Cyanotrimethylsilane effects the transformation of acyl chlorides to acyl cyanides, a-chloro ethers and a-chloro thioethers to a-cyano ethers and a-cyano thioethers (eq 19), t-butyl chlorides to nitriles (eqs 20 and 21), 1,3,5-trisubstituted hexahydro-l,3,5-triazines to amino-acetonitriles, the cyanation of allylic carbonates and acetates (eqs 22 and 23), and the formation of aryl thiocyanates from aryl sulfonyl chlorides and sulfinates. The reagent has been used effectively in peptide synthesis and in a range of other synthetic applications. " ... 

Miscellaneous Transformations. The hypervalent iodine(III) reagent phenyliodine bis(trifluoroacetate) (PIFA) mediates the selective cyanation reaction of a wide range of electron-rich heteroaromatic compounds such as pyrroles, thiophenes, and indoles under mild conditions (eq 42). Nonactivated arylalkenes are effectively converted to tertiary benzylic nitriles in the presence of triflic acid and cyanotrimethylsilane (eq 43). ... 

Miscellaneous Transformations. Aromatic aldehydes and nitriles like acetonitrile or benzonitrile are converted by CIbSII to secondary amides, through a redox reaction (eq 3). When acrylonitrile is used instead, the product is an imino aldehyde (eq 4). 

Miscellaneous Transformations. 1,3-Propanediol can be converted to 3-chloro-l- (60%), 3-iodo-l- (68%), and 3-bromo-l-propanol (90%) or to 1,3-dibromopropane (85-95%). With imidoyl chlorides, 3-chloropropyl benzoates are produced. The title reagent has good solvent properties and finds use in the Wolff-Kishner reduction. Cyclohexenones and (1) give hydroxypropyl phenols under oxidative conditions (eq 5). ... 

---