30239-74-8

Upstream product

• 69379-35-7 2-bromo-2-ethyl-1-phenylbutan-1-one 
• 201230-82-2 carbon monoxide 
• 557-20-0 diethylzinc 
• 98-88-4 benzoyl chloride 
• 50417-71-5 (benzoyl)PdI(triphenylphosphine)2 
• 97-94-9 triethyl borane 
• 97-93-8 triethylaluminum 
• 96-10-6 diethylaluminium chloride 
• 592-02-9 diethylcadmium 
• 18365-11-2 ethyl copper 
• 2633-75-2 ethylzinc chloride 
• 90824-75-2 EtMnI 
• 627-44-1 diethylmercury 
• 597-64-8 tetraethyltin 

Downstream Products

• 20577-41-7 (E,Z)-2-Ethyl-1-phenyl-2-buten-1-on 
• 106596-80-9 Acetat des 3-Benzoyl-pentanol-⁽³⁾ 
• 30272-58-3 (E) 2-ethyl-1-phenyl-2-buten-1-one 
• 30248-91-0 (Z) 2-ethyl-1-phenyl-2-buten-1-one 

Relevant academic research and scientific papers

Reactions of PhCOPdX(PPh3)2 (X=I, Cl) with alkylmetals under carbon monoxide; formation of α-diketones and α-hydroxyketones under stoichiometric and catalytic conditions

The reactions of PhCOPdX(PPh3)2 (Ia: X=I; Ib: X=Cl) with alkylmetals under carbon monoxide have been investigated.The reactivity of ethylmetals toward Ia was found to decrease in the order: Et2M (M=Zn, Cd, Hg) ca.EtZnCl ca.EtCu > EtmgBr ca.EtMnI ca.Et3Al > Et2AlCl > Et3B ca.Et4Sn (no reaction).In these reactions, the simple coupling product, PhCOEt (II) and /or the carbonylative coupling products IIIa-IIIc (IIIa: PhCOCOEt; IIIb: PhCEt(OH)COEt; IIIc PhCOCEt2(OH)) were formed depending on the nature of the ethylmetal.Et2Hg and Et3Al gave exclusively II.EtMgBr, EtCu, and EtZnCl gave both of II and III.EtMnI and Et2M (M=Zn, Cd) selectively gave III.The use of Ar2Zn (AR=Ph, p-Tol) in place of Et2Zn gave decreased yields of the carbonylative coupling products.The palladium complex Ib showed almost the same reactivity toward Et2Zn as Ia.Further to this palladium-catalyzed carbonylation reactions of PhCOCl with alkylmetals were examined.The reaction with Et2Zn catalyzed by PdCl2(PR3)2 (R=Ph, p-FC6H4) afforded III (mainly IIIb and IIIc, about 200percent/Pd).The combination of Pd(PPh3)4 and Et3Al more effactively afforded III (mainly acyloin-type reduced products, about 900percent/Pd).

REACTIONS OF ACYL ANIONS GENERATED FROM ACID CHLORIDES AND DIIODOSAMARIUM

Acid chlorides react with SmI2 to give α-diketones.Various experiments show that the initially formed acyl radical is rapidly transformed into an acyl anion which is thus generated by quite an unusual route.This species acylates acid chlorides, aldehydes and ketones in situ to give α-diketones and α-diketols.There are some limitations to this acyl anion chemistry but the reactions are realized with a good efficiency at room temperature in THF solution.