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Ch 12 Alcohols and Thiols
Ch 12 Alcohols and Thiols

... • intermolecular forces of Carbonyls ...
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... Saponification • Base-catalyzed hydrolysis of ester. • “Saponification” means “soap-making.” • Soaps are made by heating NaOH with a fat (triester of glycerol) to produce the sodium salt of a fatty acid - a soap. • One example of a soap is sodium stearate, Na+ -OOC(CH2)16CH3. ...
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... Organic compounds in which an sp3 hybridized carbon is bonded to an electronegative atom or group can undergo two types of reactions. They can undergo substitution reactions, in which the electronegative atom or group is replaced by another atom or group. They can also undergo elimination reactions, ...
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... involves the addition of a solution of CrO3 in sulfuric acid (Jones' Reagent) to a solution of the compound being tested in acetone. This reagent oxidizes primary and secondary alcohols and all aldehydes (via its hydrate) with a distinctive color change (orange to green or blue-green) and it gives n ...
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Wolff rearrangement



The Wolff rearrangement is a reaction in organic chemistry in which an α-diazocarbonyl compound is converted into a ketene by loss of dinitrogen with accompanying 1,2-rearrangement. The Wolff rearrangement yields a ketene as an intermediate product, which can undergo nucleophilic attack with weakly acidic nucleophiles such as water, alcohols, and amines, to generate carboxylic acid derivatives or undergo [2+2] cycloaddition reactions to form four-membered rings. The mechanism of the Wolff rearrangement has been the subject of debate since its first use. No single mechanism sufficiently describes the reaction, and there are often competing concerted and carbene-mediated pathways; for simplicity, only the textbook, concerted mechanism is shown below. The reaction was discovered by Ludwig Wolff in 1902. The Wolff rearrangement has great synthetic utility due to the accessibility of α-diazocarbonyl compounds, variety of reactions from the ketene intermediate, and stereochemical retention of the migrating group. However, the Wolff rearrangement has limitations due to the highly reactive nature of α-diazocarbonyl compounds, which can undergo a variety of competing reactions.The Wolff rearrangement can be induced via thermolysis, photolysis, or transition metal catalysis. In this last case, the reaction is sensitive to the transition metal; silver (I) oxide or other Ag(I) catalysts work well and are generally used. The Wolff rearrangement has been used in many total syntheses; the most common use is trapping the ketene intermediate with nucleophiles to form carboxylic acid derivatives. The Arndt-Eistert homologation is a specific example of this use, wherein a carboxylic acid may be elongated by a methylene unit. Another common use is in ring-contraction methods; if the α-diazo ketone is cyclic, the Wolff rearrangement results in a ring-contracted product. The Wolff rearrangement works well in generating ring-strained systems, where other reactions may fail.
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