O. D. Gupta

Reactions of trifluoroamine oxide: a new method for selective fluorination of 1,3-diketones and β-ketoesters

Fluorination of 1,3-diketones and β-ketoesters with trifluoroamine oxide in the presence of tetrabutylammonium hydroxide (TBAH) provides a one step route to mono- and difluoro-products selectively fluorinated at the α-position in good yields.

(Trifluoromethyl)sulfenyl, (trifluoromethyl)sulfinyl, and (trifluoromethyl)sulfonyl derivatives of heterocyclic amines

Synthese des composes N-trifluoromethanesulfenyles par action du chlorure de trifluoromethanesulfenyl sur les heterocycles suivants: piperazine(A), tetraaza-1,4,8,11cyclotetradecane(B), hexamethylcyclotrisilazane(C), octamethylcyclotetrasilazane, triaza-1,8,10bora-9decaline, triaza-1,4,8cycloundecane et tetraaza-1,4,7,10cyclododecane; synthese des composes N-trifluoromethanesulfinyles par reaction de CF 3 S(O)Cl et des composes A, B et C; synthese des composes N-trifluorosulfonyles par reaction de CF 3 SO 2 Cl et des composes A et B

CARBONYL DIFLUORIDE : REACTIONS WITH METAL-PHOSPHINE COMPLEXES

Abstract Nickel complexes of the composition [Ni(L) n ]X 2 [L = bis(diphenylphosphino)methane (dpm), 1,2-bis(diphenylphosphino)ethane (dpe) and 1,3-bis(diphenylphosphino)propane (dpp), X = Cl − , Br − and I − , n = 1, 2] were allowed to react with carbonyl difluoride under homogeneous and heterogeneous conditions at ambient temperature or above. The dpm ligands of [Ni(dpm)]X 2 and [Ni(dpm) 2 ]X 2 were oxidatively fluorinated to the phosphorane but the complexes of the composition [Ni(dpe)]X 2 and [Ni(dpp)]X 2 did not react with carbonyl difluoride under any conditions tried. The 1:2 complexes [Ni(dpe) 2 ]X 2 and [Ni(dpp) 2 ]X 2 reacted with carbonyl difluoride at 25 °C in CH 2 Cl 2 to form fluorinated phosphoranes and the 1:1 complexes [Ni(dpe)]X 2 and [Ni(dpp)]X 2 , respectively. Carbonyl difluoride was found to react with the neutral complexes [Ni(dpp) 2 ] and [Ni(dpe) 2 ] to give the stoichiometric amounts of oxidatively fluorinated phosphoranes.

Reactions of tetracyclic tetraaminophosphoranes with dichloroperfluoro cyclic and acyclic alkenes and halo compounds

Abstract Cyclenphosphorane was reacted with 1,2-dichlorotetrafluorocyclobutene-1, 1,2-dichlorohexafluorocyclopentene-1, 1,2-dichlorooctafluorocyclohexene-1, iodopentafluorobenzene, 2-iodo-1,1,1-trifluoroethane, and 2,3-dichlorohexafluorobutene-2 in the presence of triethylamine at room temperature in tetrahydrofuran to form monochlorotetrafluorocyclobutenylcyclenphosphorane, monochlorohexafluorocyclopentenylcyclenphosphorane, monochlorooctafluorocyclohexenylcyclenphosphorane, pentafluorophenylcyclenphosphorane, 1,1,1-trifluoroethylcyclenphosphorane, and 2-chlorohexafluorobut-2-enylcyclenphosphorane in 70–80% yields, respectively. Cyclamphosphine oxide reacted with dichloroperfluorocyclic alkenes in the presence of triethylamine in chloroform to form N-(chlorotetrafluorocyclobutenyl)cyclamphosphine oxide, N-(chlorohexafluorocyclo-pentyl)cyclamphosphine oxide and N-(chlorooctafluorocyclohexenyl)-cyclamphosphine oxide in ∼50% yields, respectively. These moisture sensitive cyclamphosphine oxide derivatives are stable and are soluble in CHCl 3 , CH 3 CN and DMSO.

1,7-Di­hydro-1,4,7,10-tetra­aza­cyclo­­dodecane­phosphine oxide iodide

The title compound, C8H18N4OP+·I− or [H2cyclenPO][I], contains a five-coordinate P atom arranged in a slightly distorted trigonal bipyramid. The asymmetric unit contains half the cyclen moiety of the H~2~cyclenPO unit and two distinct iodide positions. The full molecule can be symmetry generated around the P atom using the symmetry code 1 \over 3 + x − y, 2 \over 3 − y, 5 \over 3 − z. The P—N bond length in the equatorial plane is 1.656 (5) A and the apical P—N interaction is much longer, 1.891 (4) A. The cyclen moieties are linked together via N—H⋯O hydrogen bonds and form a spiral chain along [001]. Crystallographically, there are two distinct anion sites, both in special positions, one of them with partial occupancy. One anion site may participate in an extremely weak hydrogen bond, linking the cyclen spiral chains into a pseudo-hexagonal three-dimensional array.

Macrocylic Amines — Precursors to some colorful chemistry

Abstract The interactions of macrocyclic amines with cyclic polyfluorinated olefins provide a route to a rather large new family of one, two, three or four substituted derivatives that are stable to hydrolysis and that have surprising thermal properties. Additionally, these materials are precursors to metal and nonmetal compounds, some of which are highly colored and which show an interesting chemistry in their own right. X-ray crystal structures are most useful in confirming these new macrocycles.

Novel reactions of trifluoroamine oxide with organic and inorganic substrates

Abstract The chemistry of trifluoroamine oxide has remained largely ignored since its initial synthesis more than twenty years ago [1,2]. A review of the chemistry and physical characteristics of trifluoroamine oxide has recently been published [3], indicating that its reported chemistry has been largely limited to its Lewis base behavior and Lewis acid catalyzed addition reactions. We find that trifluoroamine oxide reacts readily with, for example, a variety of amines to form the corresponding N-fluoro and N-nitroso derivatives in good yields. Oxidative fluorination of non-halogenated phosphines occurs under mild conditions to give R 3 PF 2 , and treatment of phosphites with ONF 3 yields three fluorinated products, i.e., RF, (RO) 2 P(O)F and (RO) 3 PF 2 . A number of metals including Ga, Sn and Sb are rapidly to GaF 3 , SnF 4 and SbF 5 , While WF 6 is obtained from the reaction between ONF 3 and W(CO) 6 . The synthesis of many new or previously difficult to obtain materials has been achieved, and their physical and chemical characteristics, including stability and synthetic utility, are described.

Carbonyl difluoride: a versatile fluorinating reagent

Carbonyl difluoride is a readily accessible reagent for introducing fluorine into molecules by oxidative addition to the central atom or by displacement of hydrogen from P–H, N–H, or C–H bonds.