Preparation of ketones by direct reaction of grignard reagents with acid chlorides in tetrahydrofuran

Sato, Fumie; Inoue, Masanori; Oguro, Kaoru; Satô, Masao

doi:10.1016/s0040-4039(01)86573-4

Cited by 79 publications

(31 citation statements)

References 9 publications

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“…36 However, the synthesis of symmetric ketones directly from organometallic reagents and acid chlorides or esters often proceeds in low yield because of the possibility of subsequent addition of the organometallic reagent to the in situ generated ketone to form a tertiary alcohol. 37 We have optimized a complementary method for the preparation of symmetric aryl ketones which simply involves the addition of an aryllithium to DMC as shown in Scheme 2.…”

Section: Scheme1mentioning

confidence: 99%

Expedient Synthesis of Symmetric Aryl Ketones and of Ambient-Temperature Molten Salts of Imidazole

Lucas

Mehdi

et al. 2000

Synthesis

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A short procedure for the synthesis of 2,2-di(3-thienyl)-1,3-dioxolan is described. The route developed is convenient (only two synthetic and one chromatographic steps are required) and efficient (66% overall yield from 3-bromothiophene). This compound was transformed into the ketone, cyclopenta [2,1-b:3',4'-b']dithiophen-4-one by a known process. Optimized syntheses of symmetric aryl ketones, 1-alkyl-3-methylimidazolium and 1-alkyl-2-methyl-3-methylimidazolium liquid salts are also reported.Electrochemical capacitors are energy conversion devices which consist of two active electrode materials that are in contact with an appropriate electrolyte. 1 First, electronically conducting polymers such as polythiophene derivatives, have recently received some attention as electrode materials due to their potentially high power densities which originate from fast redox switching (e.g. fast ionic transport). 2 Second, conventional liquid solvent-salt and polymer-salt were used as electrolyte (to insure ionic conduction between the two polymer electrodes) in these capacitors. 2 Thiophene derivatives are among the most widely investigated model compounds for electrically conducting material since they give rise to polymers which may be both p-and n-type doped. 2-7 Within this family of polymers, poly(cyclopenta[2,1-b:3',4'-b']dithiophen-4-one, (CDT) 5, introduced by Lambert and Ferraris, 8 stands out for its electrochemical properties, high stability in the conducting state and propensity to multiple redox cycling, making it a stable p-and n-dopable conductor suitable for application as supercapacitors composites as we have recently shown. 9 Roncali et al. have also reported that the polymer obtained from the 1,3-dioxolane derivative of the title compound 5 displayed similar electrochemical properties. 10 Since, many of the precursors of small band gap conducting polymers are substituted-4-methylidene derivatives of 5, 4,9-16 ketone 5 is an important intermediate in the synthesis of a variety of low band gap conducting polymers. 17On the other hand, room-temperature ionic liquids have also attracted interest as solvents for synthesis and catalysis applications, which have recently been reviewed. 18 These liquid salts can replace classic organic solvents which may be volatile and/or hazardous. Much of the progress realized to date render these room-temperature molten salts more stable, chemically and thermally. These liquids are entirely composed of ions and in this state, they resemble the ionic melts which are generally produced by heating normal metallic salts such as sodium chloride to high temperature (e.g. NaCl to over 800°C). Some other useful features of these ionic liquid systems include the greater solubilities of organic species, the prevalence of high coulombic forces resulting in the absence of any significant vapor pressure and the availability of air and moisture stable, water immiscible ionic liquids (e.g. imidazolium salts of PF 6 -or BF 4 -). Such systems are able media for the development of completely nove...

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Section: Scheme1mentioning

confidence: 99%

Expedient Synthesis of Symmetric Aryl Ketones and of Ambient-Temperature Molten Salts of Imidazole

Lucas

Mehdi

et al. 2000

Synthesis

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“…1 The reaction of acid chlorides with Grignard reagents gives ketones, but yields are low to moderate due to the formation of the corresponding tertiary alcohols. 2 To overcome these drawbacks the reaction of in situ formed acyl triphenylphosphonium ions from acid chlorides and Bu3P with Grignard reagents has been developed, but the separation of Bu 3 P is tedious. 3 Alternatively, the coupling of acid chlorides with terminal alkynes 4 or organostannanes 5 in the presence of palladium catalyst and alkynyldimethylaluminum reagents, 6 derived from Et3N-catalyzed alumination of terminal alkynes, leads to the aromatic ketones or ynones at reflux temperature.…”

Section: Methodsmentioning

confidence: 99%

6-Methyl-2,4-pyrimidyl Diesters. A Highly Efficient Acylating Agent for the Synthesis of Unsymmetrical Ketones

Lee¹

2010

Bulletin of the Korean Chemical Society

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“…Nevertheless, ketones can be obtained when the reactivity of the substrate i is increased (e.g. X = Cl) [2] [3]. Another method for favoring ketone formation is based on the survival of the addition product ii prior to hydrolysis iii R ' iv In many cases, application of one or the other of these two methods is successful.…”

Section: Synthesis Of (E)-1-propenyl Ketones From Carboxylic Esters Andmentioning

confidence: 99%

“…Another method for favoring ketone formation is based on the survival of the addition product ii prior to hydrolysis iii R ' iv In many cases, application of one or the other of these two methods is successful. However, the highly reactive allylic Grignard reagents are known to give predominantly the tertiary alcohol iv even with acid chlorides at -78" [2] (method 1: activation of substrate) and the procedures that take advantage of the stabilization of intermediate ii (method 2) are not appropriate for highly substituted systems.…”

Section: Synthesis Of (E)-1-propenyl Ketones From Carboxylic Esters Andmentioning

confidence: 99%

Synthesis of (E)‐1‐Propenyl Ketones from Carboxylic Esters and Carboxamides by Use of Mixed Organolithium‐Magnesium Reagents. Synthesis of α‐Damascone, β‐Damascone, and β‐Damascenone

Fehr

Galindo

1986

Helvetica Chimica Acta

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The novel reagents formed by combination of allylmagnesium chloride and a strong non-nucleophilic lithium base (LiNR,) convert non-or slowly enolizable carboxylic esters or carboxamides into 2-propenyl ketones which are protected from further reaction by their in situ conversion into enolates. This modified Grignard reaction is applied to efficient syntheses of a -damascone, 8-damascone, B-damascenone, and various other (E)-1-propenyl ketones.

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Preparation of ketones by direct reaction of grignard reagents with acid chlorides in tetrahydrofuran

Cited by 79 publications

References 9 publications

Expedient Synthesis of Symmetric Aryl Ketones and of Ambient-Temperature Molten Salts of Imidazole

Expedient Synthesis of Symmetric Aryl Ketones and of Ambient-Temperature Molten Salts of Imidazole

6-Methyl-2,4-pyrimidyl Diesters. A Highly Efficient Acylating Agent for the Synthesis of Unsymmetrical Ketones

Synthesis of (E)‐1‐Propenyl Ketones from Carboxylic Esters and Carboxamides by Use of Mixed Organolithium‐Magnesium Reagents. Synthesis of α‐Damascone, β‐Damascone, and β‐Damascenone

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