Heterocyclic and acyclic derivatives of F-N-isopropylacetimidoyl chloride

$\text{F}$-N-Isopropylacetimidoyl chloride, CF₃CClNCF(CF₃)₂, has been used as a precursor for a variety of heterocyclic and acyclic compounds. Reaction with azide ion yields a mixture of the imidoyl azide, CF₃(N₃)CNCF(CF₃)₂, and the 1,5-tetrazole, CF₃$\text{CNNN}$CF(CF₃)₂. Hexafluoropropylideniminolithium produces as a minor product the conjugated diimine, (CF₃)₂CNC(CF₃)NCF(CF₃)₂, from nucleophilic attack at the imidoyl chlorine and as a major product the triimine, (CF₃)₂CNC(CF₃)NC(CF₃)₂NC(CF₃)₂, from further attack at the isopropyl fluorine. A thio-amide, CF₃C(S)NHCH(CF₃)₂, and a Δ³-1,2,4-dithiazoline, $\text{SSC(CF}{}_3\text{)NC}$(CF₃)₂, are produced upon reaction of hyrogen sulfide with the imidoyl chloride. Pathways are proposed for each of the reactions.     

N-halogeno-compounds. Part 9 [1]. Azoxy- and azo-arenes derived from 4-(dichloroamino)tetrafluoropyridine; crystal structure of trans-2,3,5,6-tetrafluoro-4-(2,4,6-trimethylphenyl-onn-azoxy)pyridine

The nitrosoarenes ArNO (Ar = C₆H₅, 2-MeC₆H₄, 2,4,6- Me₃C₆H₂ and C₆F₅) have been condensed with 4-(dichloroamino)- tetrafluoropyridine to provide the azoxy-compounds py_FN$\text{N}\text{+}$($\text{N}\text{-}$)Ar (py_F = 2,3,5,6-tetrafluoro-4-pyridyl); de-oxygenation of the first three with triphenylphosphine or triethyl phosphite gave the corresponding azo-compounds, and the reverse reaction was achieved in the case of py_FNNC₆H₂Me₃-2,4,6 using peroxytrifluoroacetic acid. Thermolysis of 4-azidotetrafluoropyridine in the presence of pentafluoronitrosobenzene provided the perfluorinated azoxy-compound py_FN$\text{N}\text{+}$($\text{O}\text{-}$)C₆F₅. X-Ray methods have been used to determine the molecular geometry of py_FN$\text{N}\text{+}$($\text{O}\text{-}$)C₆H₂Me₃-2,4,6.     

WCl6/LiAlH4 Promoted transformation of imines into secondary and tertiary amines

The reaction of WCl₆/LiAlH₄ with imines, R′NCHR, gave tertiary amines, R′N(CH₂R)₂, and secondary amines, R′NHCHRCH₂R. Isotope labeling experiments revealed that the reaction involved two types of azatungstenacyclobutanes, $\text{WNR′CHRC}$HR and $\text{WCHRNR′C}$HR, produced from the reaction of an alkylidene tungsten intermediate with the imine CN double bond. Formation of these metallacyclobutanes is highly dependent on the solvent used.     

Cycloaddition of dimethylacetylene dicarboxylate to η2-coordinated trithiocarbonate

The reaction of the η²-trithiocarbonate complex [triphos)Ni(S₂CS)] (triphos  1,1,1,-tris(diphenylphosphinomethyl)ethane) with dimethylacetylene dicarboxylate gives the nickel(II) complex [(triphos)Ni(S₂$\text{CSCRCRCRC}$R)] (R  CO₂CH₃) containing as ligand unprecedented 2,2 dithiolato derivative of substituted thiapyran.     

The replacement of vinylic hydrogen by fluorine

In 3$\text{H}$, 4$\text{H}$-tetrafluoro-3-thiolen and 1$\text{H}$,2$\text{H}$-octafluorocyclohexene, the conversion of -CHCH- into -CHCF- by fluorination over KCoF₄ takes place by saturation to -CHFCHF- followed by dehydrofluorination, and not by direct replacement of a vinylic hydrogen.     

Reactions of F-propene and its dimer with sodium dialkyldithiocarbamate

Sodium dialkyldithiocarbamates readily attacked $\text{F}$-propene to give S-(1,1,2,3,3,3-hexafluoropropyl)-N,N-dialkyldithiocarbamates, CF₃CHFCF₂SC(S)-NR₂, and $\text{Z}$ and $\text{E}$-S-(1,2,3,3,3-pentafluoropropenyl)-N,N-dialkyldithiocarbamates, CF₃CFCFSC(S)NR₂. The pyrolysis of the former compound quantitatively gave the dialkylthiocarbamoyl fluorine, R₂NC(S)F, while the latter compound and sodium tetraphenylborate formed the corresponding 1,3-dithiolan-2-ylium tetraphenylborate. $\text{F}$-2-Methyl-2-pentene also reacted with sodium dialkyldithiocarbamate to give (CF₃)₂CHC[SC(S)NR₂]CFCF₃. The mechanism of this reaction is supposed to involve a 1,4-RSF-elimination.     

Nuclear magnetic resonance spectra of polyfluorobuta-1,3-dienes. Part II [1]. Variable temperature study of two 2-azabutadienes

The two perfluoro-azadienes CF₂N.CRCF₂ (R = CF₃ or CF₂Cl) show temperature dependent ¹⁹F n.m.r. spectra, with non-equivalent fluorine nuclei of the CF₂N portion at low temperatures, which coalesce due to inversion at the nitrogen at higher temperatures (ΔG3 = 60 kJ mol^?1). N.m.r. parameters have been obtained. One of the five-bond FF coupling constants is much larger ($\text{ca}$. 24 Hz) than the remainder (0·5–5·5 Hz), possibly due to ‘through-space’ coupling of fluorines in the $\text{cis}$-skew conformation.     

Syntheses of σ-cyclobut-1-en-3-onyl complexes by cycloaddition of ketenes to some transition metal alkynyl complexes

Reactions of ketenes (R¹R²CCO) with (η⁵-C₅H₅)Ni(PPh₃)CCR (I) and (η⁵-C₅H₅)Fe(CO)(L)CCR (III, L = CO and PPh₃) give σ-cyclobut-1-en-3-onyl complexes, {(η⁵-C₅H₅)Ni(PPh₃)$\text{CC(R)COC}$}R¹R² (VI) and (η⁵-C₅H₅)Fe(CO)(L)$\text{CC(R)COC}$R¹R² (IX)}, (2 + 2) cycloaddition products, in good yields. The σ-cyclobutenonyl complexes also can be prepared by the reaction of I and III with acyl chlorides in the presence of triethylamine.     

Cleavage of iron2-alkenyl and iron2-alkynyl bonds by mercury(II) chloride

Reactions of HgCl₂ with η⁵-C₅H₅Fe(CO)₂R (R  CH₂CHCH₂ and CH₂C(CH₃)CH₂) in THF at 25°C rapidly afford $\text{1}\text{1}$ adducts of the two reactants. These adducts were converted to the corresponding PF₆^? salts, [η⁵-C₅H₅Fe(CO)₂(η²-CH₂C(R)CH₂HgCl)]⁺ PF₆^? (R  H and CH₃), for characterization. Slower reactions with cleavage of the ironcarbon σ bond and elimination of the R group from η⁵-C₅H₅Fe(CO)₂R occur for R  CH₂CHC(CH₃)₂, CH₂CHCHC₆H₅, and CH₂CCC₆H₅. Both elimination and $\text{1}\text{1}$ adduct formation are observed when R  CH₂CHCHCH₃. The kinetics of the cleavage reactions are presented and possible mechanisms for both cleavage and $\text{1}\text{1}$ adduct formation are discussed.     

Etude de l''addition des organomagnesiens satures et benzyliques aux enynes conjugues, simples et fonctionnels

Saturated and benzylic organomagnesium compounds are shown to readily undergo addition reactions with the conjugated enynes H$\text{C}\text{4}$$\text{C}\text{3}$C$\text{H}\text{2}$$\text{C}\text{1}$HCH₂R′, with R′ = alkyl, OH, OC₄H₉, NHC₂₅, N(C₂H₅)₂, by refluxing for several hours in benzene or toluene.This reaction leads to both υ-acetylenic compounds (1,2-addition) and β-allenic compounds (1,4-addition).     

A 29Si, 13C and 1H NMR study of the interaction of various halotrimethylsilanes and trimethylsilyl triflate with dimethyl formamide and acetonitrile,a comment on the nucleophile induced racemisation of halosilanes

The ²⁹Si, ¹³C and ¹H NMR spectra of $\text{1}\text{1}$ mixtures of Me₃SiI and Me₃SiOSO₂CF₃ with DMF in CD₂Cl₂ show signals that are consistent with the formation of Me₃SiO$\text{C}\text{+}$H(NMe₂)X^? but not with penta- or hexa-coordinate silicon species. The spectra of a $\text{1}\text{1}$ mixture of Me₃SiBr and DMF show a rapidly exchanging, equilibrium mixture of Me₃SiO$\text{C}\text{+}$H(NMe₂)Br^? and starting materials. No strong evidence for salt formation between DMF and Me₃SiCl was obtained. The spectra of Me₃SiX (X = I, Br, Cl, OSO₂CF₃) in CD₃CN indicate that neither adduct formation nor extra coordination at silicon is significant.     

Inorganic Syntheses,Volume XXI : edited by J.P. Fackler,Jr., Wiley-Interscience,New York, 1982, xvii + 215 pages, £29.25.

The 1/1 reaction of Et₂Zn with N-t-butyliminopropanone (t-BuNC(H)C(Me)O) leads to quantitative formation of dinuclear [EtZ$\text{n(Et)(t-Bu)NC(H)=C(Me)O}$]₂ via ethyl transfer within the unstable Et₂Zn(t-BuNC(H)?C(Me)O) complex. An X-ray structure determination has shown the product to have a dinuclear structure involving a N,O-chelate bonded [Et(t-Bu)NC(H)C(Me)O]^? mono-anionic ligand and a central four membered Zn₂O₂ ring formed by intermolecular ZnO coordination. Hydrolysis of this zinc complex gives a quantitative yield of N-t-butyl-N-ethylamino propanone, which upon reaction with Et₂Zn reforms the dinuclear zinc complex.     

Carbon-13-nuclear magnetic resonance spectra of 5-coordinate tris-olefin complexes of rhodium(I)

Studies of the ¹³C N.M.R. spectra of the series RhX[P(Ch₂CH₂CHCH₂)₃] and RhX[P(CH₂CH₂CH₂CHCH₂)₃] where x  Cl or Br have revealed that (a) the J(¹⁰³Rh-¹³C) (olefin) for the complexes studied is only $\text{1}\text{2}$ ? $\text{1}\text{3}$ that found for square-planar complexes, and (b) the fluxional character in the olefinic carbons observed for the compounds RhX[P(CH₂CH₂CHCH₂)₃] is related to the partial rotation of the olefin about the rhodium-olefin bond.     

Magnesium ion mediated protonation of imines in acetonitrile

Addition of magnesium perchlorate to a solution of imine PhCHN-C₄H₉ ($\text{1}$) and diimine PhCHN(CH₂)₃NCHPh ($\text{4}$), in acetonitrile, results in the formation of the corresponding iminium salts due to traces of water present in the solvent. This conclusion is based upon infrared spectra of solutions of imines, iminium salts, deuterated iminium salts and mixtures of imines and magnesium perchlorate in acetonitrile, containing varying amounts of water. The results suggest that magnesium ion catalyzed reactions of imines in CH₃CN involve iminium intermediates.     

Cyclometallation reactions of N-(benzylidene)benzylamines with palladium compounds

The cyclometallation of p-RC₆H₄CHNCH₂C₆H₂, (R = H, Cl, NO₂) by PdX₂ (X = Cl, AcO) has been studied.In every case the cyclometallation occurs with formation of a five-membered ring containing the methine group. The structure of these compounds [$\text{PdX(}\text{p}\text{-RC}{}_6\text{H}{}_3\text{CHN}$CH₂C₆H₅)]₂, derived from ¹H NMR spectra, are different from those reported previously. Reaction of these compounds with PEt₃ gives the compounds [PdX(p-RC₆H₃CHNCH₂C₆H₅)(PEt₃)₂] but with an excess of PPh₃ only the complexes [$\text{PdX(}\text{p}\text{-RC}{}_6\text{H}{}_3\text{CHN}$CH₂C₆H₅)(PPh₃)] are formed.     

Cobalt metallocycles: IV. Ring opening of cobaltacyclopentadienes by addition of SiH,SH,NH and CH to the diene moiety

Cobaltacyclopentadiene complexes, (η⁵-C₅H₅)(PPh₃)($\text{CoCR}{}^1\text{CR}{}^2\text{CR}{}^2\text{C}$R¹) (R¹, R² =; Ph, Me, CO₂Me), reacted with RH (RH: triethylsilane, thiocresol, dimethyl- and ethylene-thiourea, pyrrole, thiophene) to give diene complexes, (η⁵-C₅H₅)(η⁴-HCR¹CR²CR²CR¹R)Co, or uncomplexed, highly substituted butadiene derivatives, HCR¹CR²CR²CR¹R. The reaction with thiourea proceeded catalytically in the presence of excess of diphenylacetylene although turn-over of the catalyst was small.     

Four-membered chelate aminoalkenyl complexes of platinum(II). Synthesis,carbonylation and oxidation to aminoacidato complexes

Amination of Pt^II-allene complexes of the type cis[PtCl₂(Me₂CCCHR)(PPh₃)] gives the new four-membered C, N chelate aminoalkenyl complexes [$\text{PtC(CMe}{}_2\text{)CHRN}$Me₂(PPh₃)Cl]. These undergo ready insertion of carbon monoxide into the CPt σ-bond; the resulting acyl complexes are oxidized by hydrogen peroxide to aminoacidato complexes, and the free unsaturated β-aminoacids can be recovered in good yield by ligand displacement.     

Reactivite d'alcynes fluores vis-a-vis de methylthiolates [(η5-C5H5)M(SMe)(CO)3] et d'hydrures [(η5-C5H5)MH(CO)3] de molybdene et de tungstene

The electron deficient acetylene, hexafluorobut-2-yne, reacts with molybdenum and tungsten methanethiolate derivatives (prepared in situ) to give vinyl and three-, five-, or six-membered heterocyclic derivatives: [Cp(OC)- $\text{MoC(O)C(CF}{}_3\text{)C(CF}{}_3\text{)C(O)S}$Me], [Cp(OC)₂$\text{MC(CF}{}_3\text{)C(CF}{}_3\text{)C(CF}{}_3\text{)C(O)S}$Me], [CpW(CO)₃C(CF₃C(CF₃)SMe], [CpW{η³-$\text{C(CF}{}_3\text{)C(CF}{}_3\text{)C(SMe)OC}$(O)}-(CO)₂]. These reactions contrast with those of trifluoropropyne where no organometallic species are obtained. On heating or irradiation with CF₃CCCF₃ [CpMH(CO)₃] gives known bridged species and in the presence of dimethyl disulphide the vinyl derivative [CpM(CO)₃C(CF₃)C(CF₃)H]and an isomer of undetermined structure.     

Some reactions of 1,2,3,4,7,7-hexafluorobicyclo[2,2,1]hepta-2,5-diene: Thermolysis and attack by methoxide ion and by bistrifluoromethyl nitroxide

1,2,3,4,7,7-Hexafluorobicyclo[2,2,1]hepta-2,5-diene gave 1,2,3,4-tetrafluorebenzene in at least 73% yield when heated to 450°C in a sealed tube; the CF₂ bridge appeared, in part, as octafluorocyclobutane. Nucleophilic attack by sodium methoxide- methanol on the diene occurred exclusively at the CFCF bond, causing the formation of 1,2,4,7,7-pentafluoro-3-methoxybicyclo- [2,2,1]hepta-2,5-diene and a 1,4,5,6,7,7-hexafluoro-5-methoxybicyclo [2,2,1]hept-2-ene thought, on the basis of ¹⁹F nmr data, to be the 6-$\text{endo}$-F,5-$\text{exo}$-MeO isomer. Radical attack on 1,2,3,- 4,7,7-hexafluorobicyclo[2,2,1]hepta-2,5-diene by bistrifluoromethyl nitroxide took place at both olefinic sites, with a $\text{ca}$. 10:1 preference for the CFCF linkage; all three geometrical isomers of 5,6-bis(bistrifluoromethylamino-oxy)-1,4,5,6,7,7- hexafluorobicyclo[2,2,1]hept-2-ene were formed.