Primary alcohols ketones

It will also reduce acid chlorides, acid anhydrides and aldehydes to primary alcohols, ketones to secondary alcohols, and amides to the corresponding amines R-CONHi -> R CHiNH. Nitro-hydrocarbons if aromatic are... 

Zinc chloride was used as a catalyst in the Friedel Crafts benzylation of benzenes in the presence of polar solvents, such as primary alcohols, ketones, and water.639 Friedel-Crafts catalysis has also been carried out using a supported zinc chloride reagent. Mesoporous silicas with zinc chloride incorporated have been synthesized with a high level of available catalyst. Variation in reaction conditions and relation of catalytic activity to pore size and volume were studied.640 Other supported catalytic systems include a zinc bromide catalyst that is fast, efficient, selective, and reusable in the /wa-bromination of aromatic substrates.641... 

You learned earlier that primary alcohols are oxidized to aldehydes, and secondary alcohols are oxidized to ketones. You can think of the reduction of aldehydes and ketones as the reverse of these reactions. Aldehydes can be reduced to produce primary alcohols. Ketones can be reduced to produce secondary alcohols. 

Aldehydes Primary Alcohols Ketones Secondary Alcohols... 

Acid Catalyst. Camphorsulfonic acid (CS A) has been used extensively in synthetic organic chemistry as an acid catalyst. It has particularly been used in protecting group chemistry. For example, hydroxyl groups can be protected as tetrahydropyranyl (THP) ethers using dihydropyran and a catalytic amount of CSA (eq 1). Both 1,2- and 1,3-diols can be selectively protected by reaction with orthoesters in the presence of camphorsulfonic acid to form the corresponding cyclic orthoester (eq 2) This method of protection is particularly useful in that reduction of the orthoester with Diisobutylaluminum Hydride forms the monoacetal, which allows for preferential protection of a secondary alcohol in the presence of a primary alcohol. Ketones have also been protected using catalytic CSA (eq 3). ... 

Alkynes give alkenes and alkanes. Aldehydes give primary alcohols. Ketones give secondary alcohols. 4.46 a. +2CH3CH2OH... 

Aldehydes, acyl chlorides, esters, and carboxylic acids are reduced by hydride ion to primary alcohols ketones are reduced to secondary alcohols and amides are reduced to amines. 

Reduction of aldehydes generates primary alcohols ketones are formed by reducing secondary alcohols. This is usually an enzymatic readion. For example, benzyl alcohol arises from benzaldehyde (see Section 8.2.2.1.2). 

This definition of an oxidation-reduction relation allows us to relate alcohols to aldehydes and ketones. Addition of two hydrogen atoms to the double bond of a carbonyl group constitutes reduction to the corresponding alcohol. Aldehydes give primary alcohols ketones give secondary alcohols. The reverse process, removal of hydrogen to furnish carbonyl compounds, is an example of oxidation. Together, these processes are referred to as redox reactions. 

COMPOUNDS primary alcohols ketones yield secondary alcohols. 

The slow oxidation of primary alcohols, particularly MeOH, is utilized for the oxidation of allylic or secondary alcohols with allyl methyl carbonate without forming carbonates of the alcohols to be oxidized. Allyl methyl carbonate (564) forms 7r-allylpalladium methoxide, then exchange of the methoxide with a secondary or allylic alcohol 563 present in the reaction medium takes place to form the 7r-allylpalladium alkoxide 565, which undergoes elimination of j3-hydrogen to give the ketone or aldehyde 566. The lactol 567 was oxidized selectively with diallyl carbonate to the lactone 568 without attacking the secondary alcohol in the synthesis of echinosporin[360]. 

The most obvious way to reduce an aldehyde or a ketone to an alcohol is by hydro genation of the carbon-oxygen double bond Like the hydrogenation of alkenes the reac tion IS exothermic but exceedingly slow m the absence of a catalyst Finely divided metals such as platinum palladium nickel and ruthenium are effective catalysts for the hydrogenation of aldehydes and ketones Aldehydes yield primary alcohols... 

Secondary alcohols are oxidized to ketones by the same reagents that oxidize primary alcohols... 

To the synthetic chemist the most important of the reactions m Table 17 1 are the last two the oxidation of primary alcohols to aldehydes and secondary alcohols to ketones Indeed when combined with reactions that yield alcohols the oxidation methods are so versatile that it will not be necessary to introduce any new methods for preparing aide hydes and ketones in this chapter A few examples will illustrate this point... 

Reduction to alcohols (Section 15 2) Aide hydes are reduced to primary alcohols and ketones are reduced to secondary alcohols by a variety of reducing agents Catalytic hydrogenation over a metal catalyst and reduction with sodium borohydride or lithium aluminum hydride are general methods... 

With aldehydes, primary alcohols readily form acetals, RCH(OR )2. Acetone also forms acetals (often called ketals), (CH2)2C(OR)2, in an exothermic reaction, but the equiUbrium concentration is small at ambient temperature. However, the methyl acetal of acetone, 2,2-dimethoxypropane [77-76-9] was once made commercially by reaction with methanol at low temperature for use as a gasoline additive (5). Isopropenyl methyl ether [116-11-OJ, useful as a hydroxyl blocking agent in urethane and epoxy polymer chemistry (6), is obtained in good yield by thermal pyrolysis of 2,2-dimethoxypropane. With other primary, secondary, and tertiary alcohols, the equiUbrium is progressively less favorable to the formation of ketals, in that order. However, acetals of acetone with other primary and secondary alcohols, and of other ketones, can be made from 2,2-dimethoxypropane by transacetalation procedures (7,8). Because they hydroly2e extensively, ketals of primary and especially secondary alcohols are effective water scavengers. 

Because di-/ fZ-alkyl peroxides are less susceptible to radical-induced decompositions, they are safer and more efficient radical generators than primary or secondary dialkyl peroxides. They are the preferred dialkyl peroxides for generating free radicals for commercial appHcations. Without reactive substrates present, di-/ fZ-alkyl peroxides decompose to generate alcohols, ketones, hydrocarbons, and minor amounts of ethers, epoxides, and carbon monoxide. Photolysis of di-/ fZ-butyl peroxide generates / fZ-butoxy radicals at low temperatures (75), whereas thermolysis at high temperatures generates methyl radicals by P-scission (44). 

Secondary alcohols are oxidized at room temperature to ketones in high yields by HOCl generated in situ from aqueous NaOCl and acetic acid (109,110). Selective oxidation in the presence of a primary alcohol is possible. In methanol, aldehydes are oxidized to methyl esters (110). Under the proper conditions, alcohols can be esterified with HOCl forming isolable alkyl hypochlorites. 

The various Grignard reagents react with a variety of aldehydes and ketones to yield primary alcohols (yield, 27 6%), secondary alcohols (yield, 13 1-71 1%), and tertiary alcohols (yield, 24 9-81 7%) Products of the reactions with acetone are given in Table 4... 

The type of alcohol produced depends on the carbonyl compound. Substituents present on the car bonyl group of an aldehyde or ketone stay there—they become substituents on the carbon that bears the hydroxyl group in the product. Thus as shown in Table 14.3 (following page), formaldehyde reacts with Grignard reagents to yield primary alcohols, aldehydes yield secondary alcohols, and ketones yield tertiary alcohols. 

PCC (Section 15.10) Abbreviation for pyridinium chlorochro-mate CjHjNIT ClCr03. When used in an anhydrous medium, PCC oxidizes primary alcohols to aldehydes and secondary alcohols to ketones. 

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