Carbamoyl Halides Research Articles

Double Addition vs. Ring Closure: Systematic Reactivity Study of CO(NCO)2 and CO(NCS)2 towards Hydrogen Halides

Reactions between carbonyl diisocyanate or isothiocyanate and hydrogen halide gases as stereotypical nucleophiles show two different reaction pathways. The diisocyanate adds nucleophiles to form carbamoyl halides, whereas the isothiocyanate undergoes ring closure forming thiadiazines. These reactions indicate the significant influence of the chalcogen atom on the reaction products as well as their stability and characteristics. More information can be found in the Research Article by F. Tambornino and co-workers (DOI: 10.1002/chem.202203983). Artwork by Janina Ill.

Enantioselective Synthesis of α-Alkenylated γ-Lactam Enabled by Ni-Catalyzed 1,4-Arylcarbamoylation of 1,3-Dienes

Enantioselective Synthesis of α-Alkenylated γ-Lactam Enabled by Ni-Catalyzed 1,4-Arylcarbamoylation of 1,3-Dienes

ChemInform Abstract: Influence of Sulfur for Oxygen Substitution in the Solvolytic Reactions of Chloroformate Esters and Related Compounds

AbstractReview: 88 refs.

Influence of sulfur for oxygen substitution in the solvolytic reactions of chloroformate esters and related compounds.

The replacement of oxygen within a chloroformate ester (ROCOCl) by sulfur can lead to a chlorothioformate (RSCOCl), a chlorothionoformate (ROCSCl), or a chlorodithioformate (RSCSCl). Phenyl chloroformate (PhOCOCl) reacts over the full range of solvents usually included in Grunwald-Winstein equation studies of solvolysis by an addition-elimination (A-E) pathway. At the other extreme, phenyl chlorodithioformate (PhSCSCl) reacts across the range by an ionization pathway. The phenyl chlorothioformate (PhSCOCl) and phenyl chlorothionoformate (PhOCSCl) react at remarkably similar rates in a given solvent and there is a dichotomy of behavior with the A-E pathway favored in solvents such as ethanol-water and the ionization mechanism favored in aqueous solvents rich in fluoroalcohol. Alkyl esters behave similarly but with increased tendency to ionization as the alkyl group goes from 1° to 2° to 3°. N,N-Disubstituted carbamoyl halides favor the ionization pathway as do also the considerably faster reacting thiocarbamoyl chlorides. The tendency towards ionization increases as, within the three contributing structures of the resonance hybrid for the formed cation, the atoms carrying positive charge (other than the central carbon) change from oxygen to sulfur to nitrogen, consistent with the relative stabilities of species with positive charge on these atoms.

ChemInform Abstract: An Improved One‐Pot Cost‐Effective Synthesis of N,N‐Disubstituted Carbamoyl Halides and Derivatives.

ChemInform Abstract: An Improved One‐Pot Cost‐Effective Synthesis of N,N‐Disubstituted Carbamoyl Halides and Derivatives.

Development of an Improved Method for Conversion of Thiuram Disulfides into N,N-Dialkylcarbamoyl Halides and Derivatives

A convenient procedure for preparing N,N-disubstituted carbamoyl halides is reported. It consists of two steps: (1) reaction of carbon disulfide and a secondary amine in the presence of a polar organic solvent and oxygen to produce the corresponding tetraalkyl thiuram disulfides and (2) reaction of tetraalkyl thiuram disulfide with a halide in the presence of an aprotic organic solvent to produce the corresponding N,N-disubstituted carbamoyl halide.

An improved one-pot cost-effective synthesis of N,N-disubstituted carbamoyl halides and derivatives

A convenient one-pot procedure is reported for preparing N,N-disubstituted carbamoyl chlorides by using chlorocarbonylsulfenyl chloride as a carbonylating agent. It comprises the reaction of secondary amines with chlorocarbonylsulfenyl chloride in the presence of an aprotic organic solvent to produce the corresponding N,N-disubstituted carbamoyl halides. Insertion of the carbonyl group without using phosgene is the novelty of this method.

Carbamoyllithiums. A Novel Method for Generation by Lithium-Tellurium Exchange Reaction

Abstract Reaction of Te-butyl carbamotelluroates with butyllithium at low temperatures resulted in efficient transmetallation to give corresponding carbamoyllithiums. A convenient one-pot procedure for nucleophilic carbamoylation using carbamoyl halides has been developed as an application of this reaction.

ChemInform Abstract: Syntheses of N‐Trifluoromethyl‐N‐nitroso‐amide, ‐sulfonamide, ‐carbamate and ‐urea Derivatives.

AbstractGemäß den Formelgleichungen werden ausgehend vom Tri‐ ?uornitrosomethan (I) über die Intermediärstufe (II) die N‐Trifluormethyl‐N‐nitroso‐Derivate (IV), (V), (VIII) und (X) hergestellt.

アミド，スルホンアミド，カルバミド酸エステル，および尿素のＮ‐トリフルオロメチル‐Ｎ‐ニトロソ誘導体の合成

N-Trifluoromethyl-N-nitrosobenzenesulfonamide and its derivatives bearing electron-donating or electron-withdrawing groups on the benzene rings were synthesized by the reaction of trifluoronitrosomethane with hydroxylamine at low temperature, followed by treatment with a base in the presence of arenesulfonyl halides. N-Trifluoromethyl-N-nitrosomethanesulfonamide was also synthesized.On the other hand, the use of acid halides or acid anhydrides, haloformates, and carbamoyl halides instead of the sulfonyl halides afforded N-trifluoromethyl-N-nitroso-amide, -carbamate, and -urea derivatives, respectively.

Synthesis of n-trifluoromethyl-n-nitrosamine derivatives

N-Trifluoromethy-N-nitroso-sulfonamide, -amide, -carbamate, and -urea derivatives were synthesized by the reaction of trifluoronitrosomethane with hydroxylamine at low temperature, followed by treatment with a base in the presence of arene- or alkane-sulfonyl halides, acid halides, acid anhydrides, haloformates, or carbamoyl halides.

Low-temperature fluorination of aliphatic isocyanates and carbamoyl halides

Low-temperature fluorination of aliphatic isocyanates and carbamoyl halides