Epoxide alcohol

In general, one can use a variety of oxidation techniques to form derivatives of dienes and higher polyenes for their analysis however, the information obtained with conjugated systems is muddled by the complexity of products. Also, it is obvious that since the oxidized derivatives contain different functionalities, e.g. epoxides, alcohols, acids etc., the analytical techniques employed should also be variable (see also Scheme 2). 

A broad range of olefins, acetals, epoxides, alcohols, and chlorides were demonstrated effective alternative starting materials. Cobalt and rhodium carbonyls and bimetallic complexes were shown to catalyze the domino hydro-... 

REACTIONS WITH ALCOHOLS, PHENOLS AND EPOXIDES Alcohols... 

The synthesis of the Y zeolite-encapsulated manganese complex of the salen ligand has been reported recently [51]. It was found to have catalytic activity in the oxidation of cyclohexene, styrene, and stilbene with PhlO. Typically, 1 Mn(salen) is present per 15 supercages, resulting in catalytic turn-overs in the order of 60. The reactions investigated with the respective product yields are given in Scheme 5. Typical oxidation products are epoxides, alcohols and aldehydes. In comparison to the homogeneous case encapsulation seems to lower the reaction rate. From cyclohexene the expected oxidation product cyclohexene oxide is present in excess and is formed on the Mn(salen) site. 2-cyclohexene-l-ol is probably formed on residual Mn cations via a radical mechanism. 

The molybdenum-hydroperoxide complex (Step 3) reacts with the olefin in the rate-determining step to give the epoxide, alcohol, and molybdenum catalyst. This mechanism explains the first-order kinetic dependence on olefin, hydroperoxide, and catalyst, the enhanced reaction rate with increasing substitution of electron-donating groups around the double bond, and the stereochemistry of the reaction. 

Both undergo oxidation with epoxide and aldehyde formation, but the former gives an epoxidation/alcohol oxidation ratio of 3, whereas the latter gives an epoxidation/alcohol oxidation ratio of only 0.2. That this difference is due to the steric requirements inside the pores of the catalyst is demonstrated by the fact that the relative rates of epoxidation and alcohol oxidation of the same molecules on a large-pore Ti02/Si02 catalyst are almost the same (Tatsumi et al., 1993). 

The reaction accommodates halides, esters, ethers, nitriles, cyclopropanes, epoxides, alcohols and nitio groups. Even carbohydrates can be used.492-494 However, vinylic halides afford aldehydes and ketones... 

Dunach, Inesi and others also investigated the electrochemical synthesis of cyclic carbonates from C02 with epoxides, alcohols and glycols [66]. In this regard, Yang et al. [67] reported the use of pure room temperature ionic liquids (ILs) as reaction media in the electrochemical activation of C02 for the synthesis of cyclic carbonate from epoxide, under mild conditions. C02-saturated IL (BMIMBF4) solutions were also used for the electrochemical carboxylation of activated olefins [68]. Monocarboxylic acids were obtained in moderate yield (35-55%), and the IL was recycled five times. 

Fe(TPP)]jO Cycloalkanes + 02 Epoxides, alcohols, acids, ketones Solvent benzene X, = 350-440 nm TN 10 -103 (4233 for 1,5-dimethylcycloocta-1,5-diene) selective conversion of cyclooctane, 1-methylcyclooctane, and 1,5-dimethylcycloocta-1,5-diene to the corresponding epoxides [253]... 

It is common knowledge [41,120,121] that hydroxylating enzymatic systems, cytochrome P-450 and analogs, in particular, have the prospect of a broad field of practical application. For example, they can be used in the synthesis of various medical preparations, detoxication of living organisms and development of highly selective process techniques for the production of epoxides, alcohols and ketones. 

The most common types of compounds with oxygen-containing functional groups are epoxides, alcohols, phenols, ethers, aldehydes, ketones, and carboxylic acids. The functional groups characteristic of these compounds are illustrated by the examples of oxygen-containing compounds shown in Figure 1.15. 

Give an example compound of each of the following epoxides, alcohols, phenols, ethers, aldehydes, ketones, and carboxylic acids. 

Kishimoto Y, Ogawa I (2004) Amine-catalyzed, one-pot coproduction of dialkyl carbonates and 1, 2-diols from epoxides, alcohols, and carbon dioxide. Ind Eng Chem Res 43(26) 8155-8162... 

Several methods of condensation were used and each of them consisted of binding the perfluorinated chain to a molecule which exhibited two hydroxy groups or a forerunner of the diol (e.g. epoxide-alcohol or diepoxide). 

The deracemization of a number of pharmaceutically valuable building blocks has been carried out by biocatalytic processes. This includes epoxides, alcohols, amines and acids. DKR involves the combination of an enantioselective transformation with an in situ racemisation process such that, in principle, both enantiomers of the starting material can be converted to the product in high yield and ee. The racemization step can be catalysed either enzymatically by racemases, or non-enzymatically by transition metals. 

Li[Et3BH] (Superhydride) (lithium triethylborohydride) Tetrahydrofuran -78 to RT ester —> alcohol ketone —> alcohol aldehyde —> alcohol alkyl halide —> alkane epoxide —> alcohol... 

---