Reactions Catalyzed by Potassium Fluoride. II. The Conversion of Adipic Acid to Cyclopentanone

Rand, Leon; Wagner, Walter; Warner, Peter; Kováč, L.

doi:10.1021/jo01050a504

Cited by 45 publications

(61 citation statements)

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“…[15] For the transformation of adipic acid into cyclopentanone in the presence of different amounts of potassium fluoride as base, similar observations as those reported above were again made when the reaction was performed using different amounts of barium hydroxide. The low conversion at stoichiometric amounts of base contrasted the good yield (81%) obtained when using only 5 mol-% of potassium fluoride, although in this case the reaction rate was slower.…”

Section: Introductionsupporting

confidence: 77%

“…Chem. 2005, 979-988 www.eurjoc.org 1 adipic acid -60 [7] 2 adipic acid 290-300 -88-98 [8] 3 barium 430 -84 [8] adipate 4 adipic acid Ba(OH) 2 87 [5] (1.7 wt.-%) 5 adipic acid 285-295 Ba(OH) 2 80 [10] (5 wt.-%) 6 adipic acid 290-295 Ba(OH) 2 Ͼ95 [4] (4 mol-%) 7 adipic acid 270-280 U(NO 3 ) 4 85 [4] (4 mol-%) 8 adipic acid 270-280 FeSO 4 90 [4] (4 mol-%) 9 adipic acid 250-280 KF 81 [15] (5 mol-%) 10 adipic acid 350 NaOH 84 [45] (10 mol-%) [a] 11 adipic acid 250…”

Section: Synopsis and Scope Of The Ketonic Decarboxylationmentioning

confidence: 99%

“…For instance, when reacting dimethyl octanedioate in the presence of alumina, cycloheptanone is obtained in a regular yield of 29% (Table 8, entry 6) as opposed to 69% in the case of cyclopentanone (Table 6, entry 8). At the [45] (5 mol-%) 6 3 -tert-butyl 350 Na 2 CO 3 83 [45] (5 mol-%) 7 2,2-dimethyl 225 [a] Na 3 PO 4 77 [46] (23 mol-%) 8 2,2-dimethyl 225 [a] Na 2 B 4 O 7 80 [47] (19 mol-%) 9 2,2,5,5-tetramethyl 320-340 KF anhydrous 52 [15] (45 mol-%) 10 2,2,5,5-tetramethyl 320-330 BaO 72 [15] (15 mol-%)…”

Section: Synopsis and Scope Of The Ketonic Decarboxylationmentioning

confidence: 99%

“…Scheme 3. Mechanism proposed by Rand et al [15] for the ketonic decarboxylation of adipic acid to give cyclopentanone; this process involves deprotonation, decarboxylation, and nucleophilic attack on the non-dissociated carboxylic acid group…”

Section: Introductionmentioning

confidence: 99%

“…[15] This cyclisation cannot be explained by the mechanism involving a β-keto acid intermediate. [17] Scheme 4.…”

Section: Introductionmentioning

confidence: 99%

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Ketonization of Carboxylic Acids by Decarboxylation: Mechanism and Scope

2005

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In the ketonic decarboxylation process, a ketone is formed from two moles of carboxylic acid; water and carbon dioxide are produced as side‐products. At present, the mechanism of this reaction remains under debate; it has been proposed as a radical mechanism, a mechanism involving a ‐keto acid as intermediate, or a concerted mechanism. This paper demonstrates that the latter mechanism is the most likely one and that weak bases may play the role of promoters. Different processes are reviewed for the syntheses of the following ketones: symmetrical ketones, such as acetone or 3‐pentanone, cyclic ketones, such as cyclopentanone (parent compound and substituted derivatives), fatty ketones, and some unsymmetrical ketones. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

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Section: Introductionsupporting

confidence: 77%

Section: Synopsis and Scope Of The Ketonic Decarboxylationmentioning

confidence: 99%

Section: Synopsis and Scope Of The Ketonic Decarboxylationmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

“…[15] This cyclisation cannot be explained by the mechanism involving a β-keto acid intermediate. [17] Scheme 4.…”

Section: Introductionmentioning

confidence: 99%

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Ketonization of Carboxylic Acids by Decarboxylation: Mechanism and Scope

2005

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TheDieckmann Condensation (Including theThorpe‐Ziegler Condensation)

Schaefer

Bloomfield

2011

Organic Reactions

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The Dieckman condensation is an acetoacetic ester condensation in which a dicarboxylic ester is cyclized to a beta‐ketonic ester through the action of a base. The dicarboxylic ester must have at least one alpha‐hydrogen atom and the carbalkoxy groups must be situated that cyclization will result in a 4‐membered ring or larger ring. Discovery and development of the reaction are generally credited to Dieckmann, who found that heating an adipic or a pimelic ester with sodium and a trace alcohol led to cyclization with formation of a cyclopentanone or a cyclohexanone. The Dieckmann condensation has proved useful for the preparation of a variety of carbocyclic and heterocyclic ketones and has been extended to the synthesis of 7 and 8‐membered rings.

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Preparation of Ketones

1971

Compendium of Organic Synthetic Methods

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Reactions Catalyzed by Potassium Fluoride. II. The Conversion of Adipic Acid to Cyclopentanone

Cited by 45 publications

References 0 publications

Ketonization of Carboxylic Acids by Decarboxylation: Mechanism and Scope

Ketonization of Carboxylic Acids by Decarboxylation: Mechanism and Scope

TheDieckmann Condensation (Including theThorpe‐Ziegler Condensation)

Preparation of Ketones

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