97467-19-1

Upstream product

• 1817-57-8 4-phenyl-3-butyne-2-one 
• 93-91-4 1-phenylbutan-1,3-dione 

Downstream Products

• 57626-33-2 2-bromo-1-phenyl-1,3-butanedione 

Relevant academic research and scientific papers

TsNBr2mediated oxidative functionalization of alkynes

A new approach has been developed for oxidative transformation of alkynes by controlled manipulation of TsNBr2mediated process. Alkynes could be readily converted to ketones and α-bromoketones via an oxybromination–debromination sequence. When alkynes are treated successively with TsNBr2, KI and Na2SO3in a mixture of acetone and water at room temperature, corresponding ketones were obtained. On the other hand, treatment of alkynes with TsNBr2and Na2SO3in a mixture of ethyl acetate, acetone and water at room temperature could produce corresponding α-bromoketones. 1-Bromoalkynes could also be synthesized from corresponding alkynes within a very short time using TsNBr2at room temperature. In all cases, excellent yields of corresponding products are obtained.

Divergent synthesis of α,α-dihaloamides through α,α-dihalogenation of β-oxo amides by using N-halosuccinimides

An efficient and divergent one-pot synthesis of α,α- dihaloamides from readily available β-oxo amides based on the selection of reaction conditions is reported. α,α-Dihalo-β-oxo amides were produced by treating β-oxo amides with N-chlorosuccinimide (NCS) or N-bromosuccinimide (NBS) in water at room temperature, whereas α,α-dihaloacetamides were synthesized by subjecting β-oxo amides to NCS or NBS in ethanol under reflux. A divergent synthesis of α,α-dihalo-β-oxo amides and α,α-dihaloacetamides has been developed from readily available β-oxo amides. Upon treatment with N-halosuccinimides in water at room temperature, α,α-dihalo-β- oxo amides were produced, whereas dihaloacetamides were synthesized by treatment of β-oxo amides with N-halosuccinimides in ethanol under reflux. Copyright

Trihaloisocyanuric acids as convenient reagents for regioselective halogenation of β-dicarbonyl compounds

The reaction of β-dicarbonyl compounds (β-ketoesters and β-diketones) with 0.34 mol equiv of trichloro- and tribromoisocyanuric acids produced regioselectively the corresponding α-monohalo β-dicarbonyl compound. On the other hand, utilization of 0.68 mol equiv of the trihaloisocyanuric acid produced the α,α-dihalo β-dicarbonyl compound.

Conversion of nucleophilic halides to electrophilic halides: Efficient and selective halogenation of azinones, amides, and carbonyl compounds using metal halide/lead tetraacetate

AlCl3/Pb(OAc)4 and ZnBr2/Pb(OAc) 4 are efficient electrophilic N- and α-C-halogenating agents. A variety of azinones, amides and carbonyl compounds were chemoselectively and regioselectively N-, or α-C-halogenated in good to excellent yield using AlCl3/Pb(OAc)4 and ZnBr2/Pb(OAc)4 in acetonitrile. Georg Thieme Verlag Stuttgart.

Reactions of Carbonyl-Conjugated Alkynes with N-Bromosuccinimide and N-Iodosuccinimide in DMF/H2O and Methanol/Sulfuric Acid: Syntheses of Dihalo Diketones, Dihalo Ketoesters, and Dihalo Acetals

The following terminal, carbonyl-conjugated alkynes were reacted with N- bromosuccinimide (NBS) and N-iodosuccinimide (NIS) in MeOH/H2SO4 to give dibromo and diiodo acetals in the indicated yields: 3-butyn-2-one, 1: NBS (75%), NIS (95%); 1-phenyl-1-propyn-l-one, 2: NBS (90%), NIS (40%); 1-hexyn-3-one, 3: NBS (90%), NIS (70%); methyl propiolate, 4: NBS (20%, not isolated), NIS (95%). 4,4-Dimethyl-l-pentyn-3-one (5) gave only a trace of dibromo acetal and no diiodo acetal; tribromide and tetrabromide were the major products. NBS and NIS reactions required, respectively, 20% and 33 wt % of H2SO4. The reaction was unsuccessful with internal alkynes 4-phenyl-3-butyn-2-one and 3-hexyn-2-one which gave only complex mixtures of products. Alkyne 2 gave a significant yield of acetal-ketal in addition to the dihalo acetals. Both the dibromo acetal- ketal and diiodo acetal-ketal were isolated, but only the former could be hydrolyzed to the dibromo acetal. Internal, carbonyl-conjugated alkynes reacted with NBS and NIS in H2O/DMF (40:60) to give the following products in the indicated yields: 4-phenyl-3-butyn-2-one (6): 1-phenyl-3,3- dibromo-1,3-butanedione (17, 70%), 1-phenyl-3,3-diiodo-1,3-butanedione (21, 95%); 3-hexyn-2-one (7): 3,3-dibromo-2,4-hexanedione (18, 80%), 3,3-diiodo-2,4-hexanedione (22, 95%); methyl 3- phenyl-2-propynoate (8): methyl 2,2-dibromo-3-keto-3-phenylpropanoate (19, 43%), methyl 2,2- diiodo-3-keto-3-phenylpropanoate (23, 95%); methyl 2-pentynoate (9): methyl 2,2-dibromo-3- ketopentanoate (20, 80%), methyl 2,2-diiodo-3-ketopentanoate (24, 95%). All reactions, except for 6 and 8 with NBS, required H2-SO4. The terminal, carbonyl-conjugated alkyne, 3-butyn-2-one, did not give products, possibly because of oxidation of the intermediate aldehyde by NBS and NIS. Mechanisms involving electrophilic attack by halogen on the triple bond and an acid-catalyzed mechanism are discussed.

Regioselective Synthesis of Dihydrofurans from 2,2-Dibromo 1,3-Diones and Olefins Using Copper

2,2-Dibromo 1,3-diones reacted with copper powder and olefin to give 2,3-dihydrofuran derivatives in a highly regioselective fashion.Acetylenes and 1,3-dienes also reacted with 2,2-dibromo 1,3-diones and copper to afford furan derivatives and 2-vinyl-2,3-