13C NMR of α-haloketones

The carbon chemical shifts of several series of α-haloketones have been measured. Whereas the carbon carrying the halogens shows a regular downfield shift with increasing electronegativity of the substituents, the adjacent carbonyl carbon is shifted upfield by chlorine, bromine and iodine, and is little affected by fluorine substitution. The conformational implications of these results are discussed.     

The reaction of 4-alkyl-3-thiosemicarbazides with β-haloketones

The reactions of 4-alkyl-3-thiosemicarbazides with β-halophenones and o-halophenones gave 4,5-dihydro-N-alkyl-3-phenyl-1H-pyrazole-1-carbothioaraides and 3-phenyl-1H-indazoles, respectively.     

The reaction of α-haloketones with N-alkyl benzothiazolium salts

Phenacyl chloride ( 1a ) reacts with the 3-methylbenzothiazolium quaternary salt ( 2 ) to give 4-methyl-2-benzoyl-4H-1,4-benzothiazine ( 4a ). A mechanism is discussed. Secondary α-haloketones give benzothiazolines. Merocyanine dyes are formed by the reaction of 2 with carbanions. It is shown that 2 functions as a hydride ion abstractor in the formation of merocyanine dyes.     

Reactions of piroxicam with alkyl iodides

Alkylation of piroxicam with a homologous series of alkyl iodides gave reversibly formed O-alkyl products 1 as well as unexpected, irreversibly formed zwitterionic compounds 2 , alkylated on the pyridine nitrogen, and O,N-bis-alkyl products 3 . Proof of structure was accomplished by nmr and X-ray crystal analysis. Product distribution ratios were determined by hplc and are explained by the Hard-Soft Acid-Base principle.     

An efficient and convenient transformation of α-haloketones to α-hydroxyketones using cesium formate

A new safe and convenient transformation has been developed. In the presence of cesium formate in dry MeOH solution, α-haloketones underwent direct conversion reaction to afford α-hydroxyketone in excellent yields. Furthermore, this methodology can be extended and applied in 2-chloro-N-(1,3-diphenyl-1H-pyrazol-5-yl)acetamide, 2-chloro-N-(2,6-dimethylphen-yl)acetamide, 1-(bromomethylsulfonyl)benzene, and N-(bromomethyl)phthalimide to give the corresponding products in moderate to excellent yields.     

Reactions of atomic carbon with acyl chlorides

Reactions of arc-generated carbon atoms with acyl chlorides proceed by two distinct mechanistic pathways depending on the nature of the alkyl group in the substrate. Acetyl chloride affords vinyl chloride from the putative chloromethylcarbene produced by deoxygenation, whereas pivaloyl chloride gives t-butyl chloride as the predominant product via a chain reaction from the initially generated pivaloyl radical. When the alkyl group is isopropyl, both pathways are implicated.     

Reactions of α,β‐Enones with Diazo Compounds. Part 4

In this study, (E)‐ and (Z)‐enones carrying only a phenyl substituent at their C(β) atom were treaced with dimethyl diazomalonate in the presence of (acetylacetonato)copper(II). According to the configuration of the starting enones, the products were dioxole or dihydrofuran derivatives, significant heterocycles in natural products.     

Reactions of α,β‐Enones with Diazo Compounds,Part 3

Carbonyl ylides arising from ethyl acetodiazoacetate/dimethyl diazomalonate and α,β‐enones with mainly s‐cis conformations underwent disrotatory cyclization to produce dihydrofuran derivatives. This process proved to be sensitive to steric effects. The corresponding ylides arising from rather s‐trans α,β‐enals yielded dioxole derivatives. The mechanisms of the reactions are discussed.     

Reactions of β-sulfenyl α,β-unsaturated ketones with guanidine,Amidines, and diamines

β-Sulfenyl α, β-unsaturated ketones 1a-c reacted with guanidine or amidines to give pyrimidine derivatives 3 in 14-76% yields. Treatment of ketones 1 with diamines such as ethylenediamine and o -phenylenediamine afforded the seven-membered heterocycles, 2,3-dihydro-1,4-diazepine 5 and 2,3-benzo-1,4-diazepines 8a-c .     

Reactions of α,β-unsaturated ketones with cyanoacetamide

3-Aryl-1-phenyl-2-propen-1-ones Ia-f and aroylphenylacetylenes Va-d reacted under reflux for 3 hours with cyanoacetamide in the presence of sodium ethoxide to give the corresponding 4-aryl-3-cyano-6-phenyl-2-(1H)pyridones VI. However, when ketones Ia-e were refluxed with cyanoacetamide for one hour in the presence of sodium ethoxide or piperidine, they gave the corresponding 4-aryl-3-cyano-3,4-dihydro-6-phenyl-2-(1H)pyridones IIIa-e, which upon heating with selenium gave the corresponding 2-pyridones VI. The structures of the products are based on chemical and spectroscopic evidence.     

Absolute Konfiguration der enantiomeren α-CyclogeraniumsäUren, α-Cyclogeraniale, α-Jonone, γ-Jonone, α-und ϵ-Carotine

By chemical correlation with manool and ambrein the absolute configurations of the enantiomeric α-cyclogeranic acids, α-cyclogeranials, α-ionones and α- and ?-carotenes have been elucidated.     

Reactions of α,β‐Unsaturated Thioamides with Diazo Compounds

Several reactions of the α,β‐unsaturated thioamide 8 with diazo compounds 1a – 1d were investigated. The reactions with CH₂N₂ ( 1a ), diazocyclohexane ( 1b ), and phenyldiazomethane ( 1c ) proceeded via a 1,3‐dipolar cycloaddition of the diazo dipole at the C?C bond to give the corresponding 4,5‐dihydro‐1H‐pyrazole‐3‐carbothioamides 12a – 12c , i.e., the regioisomer which arose from the bond formation between the N‐terminus of the diazo compound and the C(α)‐atom of 8 . In the reaction of 1a with 8 , the initially formed cycloadduct, the 4,5‐dihydro‐3H‐pyrazole‐3‐carbothioamide 11a , was obtained after a short reaction time. In the case of 1c , two tautomers 12c and 12c ′ were formed, which, by derivatization with 2‐chlorobenzoyl chloride 14 , led to the crystalline products 15 and 15 ′. Their structures were established by X‐ray crystallography. From the reaction of 8 and ethyl diazoacetate ( 1d ), the opposite regioisomer 13 was formed. The monosubstituted thioamide 16 reacted with 1a to give the unstable 4,5‐dihydro‐1H‐pyrazole‐3‐carbothioamide 17 .     

Reactions of amides of arylphosphorous acids with acyl chlorides

Conclusions The reactions of amides of arylphosphorous acids with acyl chlorides take place with replacement of the amide group and formation of amides of carboxylic acids and the corresponding aryl chlorophosphates.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2131–2133, September, 1968.