Elimination reactions forming carbon-oxygen double bonds with

The tetrahedral addition product that is formed first is similar to a hemiacetal, but with an NH group in place of one of the oxygens. These addition products are normally not stable. They eliminate water to form a product with a carbon-nitrogen double bond. With primary amines, the products are called imines. Imines are like carbonyl compounds, except that the O is replaced by NR. They are important intermediates in some biochemical reactions, particularly in binding carbonyl compounds to the free amino groups that are present in most enzymes. 

In contrast with the kinds of E2 reactions considered so far, this elimination furnishes a carbon-oxygen instead of a carbon-carbon double bond. The Cr(IV) species formed undergoes a redox reaction with itself to Cr(III) and Cr(V) the latter may function as an oxidizing agent independently. Eventually, all Cr(VI) is reduced to Cr(III). 

Many addition-elimination reactions at carbonyl centers involve a nucleophilic attack on the carbonyl carbon, followed by an elimination that restores the double bond. We first explore addition followed by 1,2-elimination, one of many types of reactions referred to as condensations. Strictly speaking, a condensation occurs when two large molecules combine to create a more complex molecule with the loss of a small molecule, such as water or an alcohol. Therefore, a condensation is a form of substitution. We will also examine condensation reactions that form polymers (see Chapter 13). One of the more complex condensations is the formation of an imine or enamine from a carbonyl and an amine. In both of these cases an oxygen is replaced by a nitrogen with loss of water (Eq 10.105 and 10.106). 

Probably the most popular carbon-carbon double-bond-forming reaction involving sulphur proceeds via the elimination of a sulphur-oxygen species. This is illustrated by a synthesis of 1,5-unsaturated dicarbonyl compounds (236) which proceeds by phenylthioalkylation of enolates (236a), using the phenyl-thioalkene (237), followed by ozonolysis and elimination of the sulphoxide moiety to provide the double bond. An alternative method for double-bond formation is shown in the preparation of alkenes R CH=CHR by reductive cleavage of the sulphide (238) with titanium salts, and demonstrates the versatility of sulphur in such double-bond formations. In the latter example... 

Elimination reactions of primary alcohols occurs by an E2 mechanism in an acid-cataly2ed reaction. First, the acid protonates the oxygen of a primary alcohol to give a primary alkyl oxonium ion. Then, water is lost by an E2 mechanism because a primary carbocation is too unstable to form in an El process. This concerted step resembles the reaction of primary alkyl hahdes with a base. The proton of the alkyl oxonium ion is deprotonated by a Lewis base, which is water in the dehydration of alcohols. The electron pair in the C—H bond moves to form a carbon-carbon double bond, and the electron pair of the C—O bond is retained by the oxygen atom. The reaction with ethanol illustrates the process. In both the El process and the E2 dehydration reaction, the acid serves only as a catalyst. It is regenerated in the last step of the reaction. 

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