Jones reagent chromium

Mild acid then cleaves off the silyl protecting group. The alcohol at position 17 is then oxidized with Jones reagent (chromium trioxide in acetone) to afford 14a-hydroxyestrone 3-methyl ether (32-5). 

Jacobsen reaction 19, 611 Japp-Klingemann cleavage 7,406 19,28,185 Jones reagent (chromium trioxide-sulfuric acid-acetone) 2, 289 12, 335... 

When a solution of chromic and sulfuric acids in water is added at 0-20° to an alcohol or formate dissolved in acetone, a rapid oxidation takes place with the separation of the green chromium III reduction product as a separate layer. This system is commonly known as Jones reagent. The rate of oxidation is so fast that it is often possible to run the reaction as a titration to an... 

A variety of chromium (VI) oxidizing systems have been developed which allow for the oxidation of a wide range of sensitive compounds. One of the most widely used chromium (VI) reagents is the Jones reagent (/), whose use is detailed in the procedure. A related system employs acetic acid as the solvent, and an example of this reagent is also given. 

Various experimental conditions have been used for oxidations of alcohols by Cr(VI) on a laboratory scale, and several examples are shown in Scheme 12.1. Entry 1 is an example of oxidation of a primary alcohol to an aldehyde. The propanal is distilled from the reaction mixture as oxidation proceeds, which minimizes overoxidation. For secondary alcohols, oxidation can be done by addition of an acidic aqueous solution containing chromic acid (known as Jones reagent) to an acetone solution of the alcohol. Oxidation normally occurs rapidly, and overoxidation is minimal. In acetone solution, the reduced chromium salts precipitate and the reaction solution can be decanted. Entries 2 to 4 in Scheme 12.1 are examples of this method. 

Jones reagent is prepared by dissolving chromium oxide (C1O3) (23.5 g) in coned sulfuric acid (21 mL) with cooling and then diluting with distilled water to give a total volume of 175 mL.4... 

Primary alcohols are readUy oxidised to carboxylic acids with common oxidising agents such as potassium permanganate (KMn04) in neutral, acidic or alkaline media or by potassium dichromate (K2Cr207) and chromium trioxide (CrOg) in acidic media (Jones reagent). 

Jones reagent was prepared by the method in Fieser and Fieser Dissolve 13.36 g of chromium trioxide in 11.5 nt of coned sulfuric acid, and carefully dilute this cooled solution (0 C) with water to 50 ml. 

All of the usual chromium-based oxidation reagents that have been used for the oxidation of cyclobutanols to cyclobutanones, for example, chromium(VI) oxide (Jones reagent),302 pyri-dinium chlorochromate,304 pyridinium dichromate,307 and chromium(YI) oxide/pyridine (Collins),303 are reported to do so without any serious problems. Alternatively, tetrapropylam-monium perruthenate in the presence of A-methylmorpholine A -oxide. oxalyl chloride in the presence of triethylamine in dimethyl sulfoxide (Swern),158,309,310 or phenyl dichlorophos-phate in the presence of triethylamine and dimethyl sulfoxide in dichloromethane (Pfitzner-Moffatt),308 can be used. The Pfitzner-Moffatt oxidation procedure is found to be more convenient than the Swern oxidation procedure, especially with respect to the strict temperature control that is necessary to achieve good yields in the latter, e.g. oxidation of 1 to give 2.308... 

Many other reagents and procedures have been developed for oxidizing alcohols. Some are simply modifications of the procedures we have seen. For example, the Collins reagent is a complex of chromium trioxide and pyridine, the original version of PCC. The Jones reagent is a milder form of chromic acid a solution of diluted chromic acid in acetone. 

Chromium salts may precipitate upon addition of the Jones reagent. A minimal amount of water may be added to dissolve them. 

The chromium trioxide-pyridine complex is a highly selective oxidant for alcoholic groups [28]. A mechanism similar to that discussed above seems possible, the selectivity being due to lowered reactivity of chromium trioxide in the pyridine complex. The remarkably smooth and selective oxidation of alcohols by chromium trioxide-sulphuric acid (Jones reagent) in acetone solution [2g] has not been explained. 

Chromium trioxide [chromium(VI) oxide, chromic add, or chromic anhydride], Cr03 (dark red crystals, mp 195 °C), is one of the most powerful and universal oxidants. It is applied in solutions in acetic acid, dilute sulfuric acid, a mixture of acetic acid and dilute sulfuric acid, dilute sulfuric acid and acetone (Jones reagent), acetic anhydride and acetic acid (Fieser reagent) [535], water, water and ether [536,537,535], dichloromethane [539],... 

The main applications of oxidation with chromium trioxide are transformations of primary alcohols into aldehydes [184, 537, 538, 543, 570, 571, 572, 573] or, rarely, into carboxylic acids [184, 574], and of secondary alcohols into ketones [406, 536, 542, 543, 575, 576, 577, 578, 579, 580, 581, 582, 583, 584]. Jones reagent is especially successful for such oxidations. It is prepared by diluting with water a solution of 267 g of chromium trioxide in a mixture of 230 mL of concentrated sulfuric acid and 400 mL of water to 1 L to form an 8 N CrOj solution [565, 572, 579, 581, 585, 556]. Other oxidations with chromic oxide include the cleavage of carbon-carbon bonds to give carbonyl compounds or carboxylic acids [482, 566, 567, 569, 580, 587, 555], the conversion of sulfides into sulfoxides [541] and sulfones [559], and the transformation of alkyl silyl ethers into ketones or carboxylic acids [590]. 

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