Effect of the X and Y substituents on the carbonyl bond in 4-YC<Subscript>6</Subscript>H<Subscript>4</Subscript>C(O)X compounds

Mechanistic aspects of the effect of the X and Y substituents (X = Me, H, CF₃, CN, Br, Cl, F, OH, NH₂; Y = H, NMe₂, NH₂, CN, NO₂) on the carbonyl bond in 4-YC₆H₄C(O)X compounds are discussed on the basis of the ¹³C and ¹⁷O NMR data.     

ESR spectroscopic study on the addition of PhCONHCHCO2Me radicals to alkenes and spin traps

Using ESR spectroscopy, the rate constants for the addition of PhCONHCHCO₂Me radicals to alkenes CH₂=CXY (X = Me, Y = Ph; X = H, Y = Ph; X = Me, Y = CO₂Me; X = H, Y = CO₂Me; X = H, Y = CN) and nitrosodurene were determined at 22 °C. It is shown that a linear dependence exists between the donor-acceptor properties of the substituents at the vinyl group and the rate constants for the addition.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 2124–2126, August, 1996.     

Protonation of 3-Arylpropynoic Acid Derivatives in Superacids

According to the ¹H and ¹³C NMR data, 3-arylpropynoic acids and their esters XC₆H _n -C≡C-CO₂R (R = H, Me, Et) having electron-withdrawing substituents in the benzene ring (X = NO₂, CN, COMe, CO₂Me) exist in HSO₃F at ?80 to 0°C as XC₆H _n -C≡C-C⁺(OH)OR ions. Derivatives with other substituents (X = H, F, Me, MeO) in HSO₃F or CF₃SO₃H above ?40°C undergo protonation at the acetylenic carbon atom neighboring to the acid group to give unstable vinyl-type XC₆H _n -C⁺=CH-CO₂R cations which are then transformed into mixtures of stereoisomeric (Z and E) fluorosulfonates or triflluoromethanesulfonates XC₆H _n -CY=CH-CO₂R (Y = OSO₂F, OSO₂CF₃), the E isomer prevailing.     

Reactions of Vinyl Type Carbocations Generated in Fluorosulfonic Acid with Benzene Derivatives. New Synthesis of Alkyl 3,3-Diarylpropenoates

Vinyl type carbocations ArC⁺=CHX [X = CO₂H, CO₂Alk, C≡N, P(O)(OAlk)₂] generated from alkyl 3-arylpropynoates and related compounds in fluorosulfonic acid at ?75 to ?20°C react with various benzene derivatives, following the mechanism of electrophilic substitution of hydrogen. A new procedure for the synthesis of alkyl 3,3-diarylpropenoates having various substituents in the aryl fragments has been developed on the basis of protonation of the triple bond in alkyl 3-arylpropynoates.     

Studies on the effect of opposite terminal groups in phenylpolyenic conjugative systems

Seven homologous series p-A=B-C₅H₄(CH=CH)_nX=Y (A=B: NO₂, X=Y: CHO, COMe, CN, NO₂; A=B: CN, X=Y: CHO, CN; A=B: H, X=Y: NO₂) were synthesized, the effect of opposite terminal groups in phenylpolyenic conjugative systems has been studied by means of UV, XPS, ¹³C NMR and quantum chemical calculation. The results show that: 1. There exists the effect of opposite terminal groups exists in phenylpolyenic and other aromatic conjugative systems-2. When A=B and X=Y are the same, the group (-X=Y) connected at polyenic chain is a terminal group, while the other is an opposite terminal group. When the two groups are different, the one with weaker conjugative power plays the role of the opposite terminal group. 3. The effect of opposite terminal groups increases successively in the order of CN, COMe, CHO, NO₂ and can be quantitatively described with substitute equivalent ΔNs. The λ_max of compound containing an opposite terminal group can be calculated by the homologous equation 10^?4 $ \tilde v = a + b/(1/2)^2 N'^{- S} a $, most of the calculated values are in agreement with experiment results.     

Synthesis and Characterisation of 1‐[9‐(H,Me3Si,Me3Ge,Me3Sn)9‐Fluorenyl]‐3,7,10‐trimethylgermatranes. The Crystal Structure Analysis of 1‐(9‐Fluorenyl)‐3,7,10‐trimethylgermatrane

The title compounds, viz. C₁₃H₈(R)Ge · (OCHMeCH₂)₃N ( 1 : R = H, 2 : R = Me₃Si; 3 : R = Me₃Ge) were prepared as mixtures of diastereomers by the reaction of N(CH₂CHMeOSnAlk₃)₃ ( 7 : Alk = Et; 8 : Alk = Bu) with C₁₃H₈(R)GeBr₃ ( 4 : R = H, 5 : R = Me₃Si; 6 : R = Me₃Ge), respectively. The synthesis of C₁₃H₈(Me₃Sn)Ge · (OCHMeCH₂)₃N ( 13 ) by the reaction of germatrane ( 1 ) with Me₃SnNMe₂ is reported. Identity and structures were established by elemental analyses, ¹H and ¹³C NMR spectroscopy and mass spectrometry. The crystal structure of 1 was determined by X‐ray diffraction methods.     

Addition of Benzodioxahalogenophosphoranes to the Carbonyl Group: New Phosphoranes and their Reactivity

Abstract

Halogenophosphoranes catPX₃ (X = C1, Br) (3), catPBr₂Y [Y = CHF₂CF₂CH₂(4), F(5), OCH=CBr₂ (6), CN (7), cat = C₆H₄O₂-o] react with aldehydes containing electron-withdrawing groups (CZ₃CHO, Z = C1, Br) in solvent to form the products of insertion in P-X bond. The structure of compounds (12–15) and their diastereomeric composition were determined by the NMR ¹H, ¹³C, and ³¹P spectroscopy. Phosphoranes (8–11) disproportionate to PX₃ and cat₂POCHXCZ₃ (X, 2 = Br, Br; C1, Br) (16, 17). Dibromophosphoranes (4–7) and monobromophosphorane (3) are also added to the carbonyl group of CZ₃CHO to form unsymmetric P(V) derivatives catPBr(OCHBrCZ₃)Y (18, 19) and (16, 17, 20–25). The thermal behaviour of compounds (18, 19) was investigated.     

H/D isotope effect on charge‐inverted hydrogen‐bonded systems: Systematic classification of three different types in H3XH…YH3 (X = C,Si, or Ge,and Y = B,Al, or Ga) with multicomponent calculation

Three different H/D isotope effect in nine H₃XH(D)^…YH₃ (X = C, Si, or Ge, and Y = B, Al, or Ga) hydrogen‐bonded (HB) systems are classified using MP2 level of multicomponent molecular orbital method, which can take account of the nuclear quantum nature of proton and deuteron. First, in the case of H₃CH(D)^…YH₃ (Y = B, Al, or Ge) HB systems, the deuterium (D) substitution induces the usual H/D geometrical isotope effect such as the contraction of covalent R(C? H(D)) bonds and the elongation of intermolecular R(H(D)^…Y) and R(C^…Y) distances. Second, in the case of H₃XH(D)^…YH₃ (X = Si or Ge, and Y = Al or Ge) HB systems, where H atom is negatively charged called as charge‐inverted hydrogen‐bonded (CIHB) systems, the D substitution leads to the contraction of intermolecular R(H(D)^…Y) and R(X^…Y) distances. Finally, in the case of H₃XH(D)^…BH₃ (X = Si or Ge) HB systems, these intermolecular R(H(D)^…Y) and R(X^…Y) distances also contract with the D substitution, in which the origin of the contraction is not the same as that in CIHB systems. The H/D isotope effect on interaction energies and spatial distribution of nuclear wavefunctions are also analyzed. © 2015 Wiley Periodicals, Inc.     

Mössbauer Studies of Radiation Effect on Pentacyano Complexes of Iron

Mössbauer and ir spectroscopies have been applied to the study of radiation effect on Fe¹¹X(CN)₃ (X=NO⁺, NH₃, H₂O, NO₂^?, SO₃⁼) and Fe¹¹¹X(CN)₃ (X=NH₁, H₂O, NO₂^?). Fe(II) complexes were not oxidized to Fe(III), whereas Fe(III) complexes were reduced to Fe(II). Na₂[FeNH₃(CN)₃]·H₂O was partially reduced at 7 hour irradiation, but [FeNO(CN)₂]⁼ was obtained at the longer irradiations due to the replacement of H by O produced by water radiolysis.     

Pallada‐ and platinacycle complexes of phosphorus ylides; synthesis,X‐ray characterization,theoretical and electrochemical studies and application of Pd(II) complexes as catalyst in Suzuki‐Miyaura coupling reaction

The new unsymmetrical phosphonium salts [Ph₂PCH₂PPh₂CH₂C(O)C₆H₄R]Br (R= m ‐Br ( S ₁ ) and p ‐CN ( S ₂ )) were synthesized in the reaction of 1,1‐bis(diphenylphosphino)methane (dppm) and BrCH₂C(O)C₆H₄R (R= m ‐Br and p ‐CN) ketones, respectively. Further treatment with NEt₃ gave the α‐keto stabilized phosphorus ylides Ph₂PCH₂PPh₂C(H)C(O)C₆H₄R (R= m ‐Br ( Y ₁ ) and p ‐CN ( Y ₂ )). These ligands were reacted with [MCl₂(cod)] (M= Pd and Pt; cod= 1,5‐cyclooctadiene) to give the pallada‐ and platinacycle complexes [MCl₂(Ph₂PCH₂PPh₂C(H)C(O)C₆H₄R)] (M= Pd, R= m ‐Br ( 3 ); R= p ‐CN ( 4 ) and M= Pt, R= m ‐Br ( 5 ); R= p ‐CN ( 6 )). Cyclic voltammetry, elemental analysis, IR and NMR (¹H, ¹³C and ³¹P) spectroscopic methods were used for characterization of the obtained compounds. Further, the structure of complexes 3 and 4 were characterized crystallographically. Palladacycles 3 and 4 were proved to be excellent catalysts for the Suzuki‐Miyaura coupling reactions of various aryl chlorides and arylboronic acids in mixed DMF/H₂O media. Also, the bonding situations between two interacted fragments [PtCl₂] and Y ₁ and Y ₂ ligands in platinacycles 5 and 6 were investigated based on DFT method by using NBO, EDA and ETS‐NOCV analysis.     

Phase-transfer Tsuji—Trost allylation of CH-acids with the assistance of palladium complexes with bidentate P<Superscript>III</Superscript>—N—P<Superscript>III</Superscript> ligands

The Tsuji—Trost allylation of CH acids, in particular, those of the YCH₂CO₂Et type (Y = CO₂Et, C(O)Me, CN), with allylic acetates in the K₂CO₃—DMF system in the presence of palladium catalysts with ligands RN(PPh₂)₂ (R = Ph, Prⁱ, c-C₆H₁₁) is accomplished.     

Protonation versus Oxonium Salt Formation: Basicity and Stability Tuning of Cyanoborate Anions

Anhydrous H[BH₂(CN)₂] crystallizes from acidic aqueous solutions of the dicyanodihydridoborate anion. The formation of H[BH₂(CN)₂] is surprising as the protonation of nitriles requires strongly acidic and anhydrous conditions but it can be rationalized based on theoretical data. In contrast, [BX(CN)₃]⁻ (X=H, F) gives the expected oxonium salts (H₃O)[BX(CN)₃] while (H₃O)[BF₂(CN)₂]/H[BF₂(CN)₂] is unstable. H[BH₂(CN)₂] forms chains via N−H⋅⋅⋅N bonds in the solid state and melts at 54 °C. Solutions of H[BH₂(CN)₂] in the room‐temperature ionic liquid [EMIm][BH₂(CN)₂] contain the [(NC)H₂BCN−H⋅⋅⋅NCBH₂(CN)]⁻ anion and are unusually stable, which enabled the study of selected spectroscopic and physical properties. [(NC)H₂BCN−H⋅⋅⋅NCBH₂(CN)]⁻ slowly gives H₂ and [(NC)H₂BCN−BH(CN)₂]⁻. The latter compound is a source of the free Lewis acid BH(CN)₂, as shown by the generation of [BHF(CN)₂]⁻ and BH(CN)₂⋅py.     

Studies on phosphatidylserine by tandem quadrupole and multiple stage quadrupole ion-trap mass spectrometry with electrospray ionization: Structural characterization and the fragmentation processes

Low-energy CAD product-ion spectra of various molecular species of phosphatidylserine (PS) in the forms of [M−H]⁻ and [M−2H+Alk]⁻ in the negative-ion mode, as well as in the forms of [M+H]⁺, [M+Alk]⁺, [M−H+2Alk]⁺, and [M−2H+3Alk]⁺ (where Alk=Li, Na) in the positive-ion mode contain rich fragment ions that are applicable for structural determination. Following CAD, the [M−H]⁻ ion of PS undergoes dissociation to eliminate the serine moiety (loss of C₃H₅NO₂) to give a [M−H−87]⁻ ion, which equals to the [M−H]⁻ ion of a phoshatidic acid (PA) and give rise to a MS³-spectrum that is identical to the MS²-spectrum of PA. The major fragmentation process for the [M−2H+Alk]⁻ ion of PS arises from primary loss of 87 to give rise to a [M−2H+Alk−87]⁻ ion, followed by loss of fatty acid substituents as acids (R_xCO₂H, x=1,2) or as alkali salts (e. g., R_xCO₂Li, x=1,2). These fragmentations result in a greater abundance of [M−2H+Alk−87−R₂CO₂H]⁻ than [M−2H+Alk−87−R₁CO₂H]⁻ and a greater abundance of [M−2H+Alk−87−R₂CO₂Li]⁻ than [M−2H+Alk−87−R₁CO₂Li]⁻; while further dissociation of the [M−2H+Alk−87−R_{2(or 1)}CO₂Li]⁻ ions gives a preferential formation of the carboxylate anion at sn-1 (R₁CO₂⁻) over that at sn-2 (R₂CO₂⁻). Other major fragmentation process arises from differential loss of the fatty acid substituents as ketenes (loss of R_x′CH=CO, x=1,2). This results in a more prominent [M−2H+Alk−R₂′CH=CO]⁻ ion than [M−2H+Alk−R₁′CH=CO]⁻ ion. Ions informative for structural characterization of PS are of low abundance in the MS²-spectra of both the [M+H]⁺ and the [M+Alk]⁺ ions, but are abundant in the MS³-spectra. The MS²-spectrum of the [M+Alk]⁺ ion contains a unique ion corresponding to internal loss of a phosphate group probably via the fragmentation processes involving rearrangement steps. The [M−H+2Alk]⁺ ion of PS yields a major [M−H+2Alk−87]⁺ ion, which is equivalent to an alkali adduct ion of a monoalkali salt of PA and gives rise to a greater abundance of [M−H+2Alk−87−R₁CO₂H]⁺ than [M−H+2Alk−87−R₂CO₂H]⁺. Similarly, the [M−2H+3Alk]⁺ ion of PS also yields a prominent [M−2H+3Alk−87]⁺ ion, which undergoes consecutive dissociation processes that involve differential losses of the two fatty acyl substituents. Because all of the above tandem mass spectra contain several sets of ion pairs involving differential losses of the fatty acid substituents as ketenes or as free fatty acids, the identities of the fatty acyl substituents and their positions on the glycerol backbone can be easily assigned by the drastic differences in the abundances of the ions in each pair.     

Synthesis and reactivity of new methylallylpalladium(II) complexes with bidentate 2-(methylthio-N-benzylidene)anilines

This work describes the synthesis, characterisation and reactivity of new methylallyl Pd(II) complexes that contain bidentate 2-(methylthio-N-benzylidene)anilines as ligands. The reaction of the binuclear complex [(η³-Me-allyl)Pd(μ-Cl)₂] with AgBF₄ causes the total abstraction of the chloride bridges, with the subsequent formation of an intermediary fragment of Pd(II). This fragment in turn reacts with neutral bidentate 2-(methylthio-N-benzylidene)anilines to give cationic complexes of Pd(II) of general formula [(η³-Me-allyl)Pd(η²-S,N-MeSC₆H₄NCHC₆H₄(X)Y)]BF₄ [X=H, Y=H (1); X=F, Y=H (2); X=Me, Y=H (3); X=H, Y=Cl (4); X=H, Y=Me₂N (5); X=H, Y=NO₂ (6)]. The new complexes were characterised by means of elemental analysis, IR, NMR [¹H, ¹⁹F{¹H}, ¹³C{¹H}, ³¹P{¹H}, Dept, ¹H-¹H-COSY, HSQC, HMBC] and mass spectroscopies. The reaction of the Pd(II) complexes with nucleophiles such as NaI, (EtO)₂PS₂K, KCN, KSCN or NaH lead to the deco-ordination of the bidentate ligands to give dimeric or polymeric complexes of Pd(II). The reactivity pattern observed is discussed by a theoretical analysis based on Fukui functions.     

STUDIES ON THE BACTERIAL ACTIVITY OF COBALT(III) COMPLEXES. PART III. COBALT(III) CARBOXYLATE COMPLEXES

Abstract

Cobalt(III) complexes of the type [Co(en)₂(chel)]X.nH₂O where en = ethylenediamine, chel = phthalato = C₆H₄CO₂)^2? ₂, maleato = (O₂CCH = CHCO₂)^2?, succinato = (O₂CCH₂CH₂CO₂)^2?, homophthalato = (O₂CC₆H₄(CH₂)CO₂)^2?, citraconato = (O₂CC(CH₃) = CHCO₂)^2?, itaconato = (CH₂ = C(CO₂)CH₂CO₂)^2?, X = NO^? ₃, Br^?, (O₂CC₆H₄CO₂H)^?, (O₂CHC = CHCO₂H)^?, (O₂C(CH₂)₂CO₂H)^?, (O₂CC₆H₄(CH₂)CO₂H)^?, (O₂CHC = C(CH₂)-CO₂H)^?, and (O₂C-CH₂?C(= CH₂)-CO₂H)^?, [Co(en)₂(malonato)]X.2H₂O (where malonato = (O₂CCH₂CO₂)^2?, X = Cl^?, Br^?, and NO^? ₃) and [Co(en)₂CO₃]Cl.2H₂O have been investigated for their bacterial activity against Escherichia coli B growing on EMB agar and in minimal glucose media both in lag and log phases. Among the most active are where chel = phthalato and homophthalato. The effects are distinct from those known for compounds of Pt, e.g., cis?[Pt(NH₃)₂Cl₂] and rhodium, e.g., trans?[Rh(C₅H₅N)₄,Cl₂].6H₂O. Antagonisms are reported.     

Monometallic,homo- and hetero-bimetallic complexes based on redox active tris(3,5-dimethylpyrazolyl)boratomolybdenum and tungsten nitrosyls. Part V.Para-substituent effects on the reduction potentials of arylamide complexes

Summary Two series of complexes having the formula [M{HB(3,5-Me₂C₃N₂H)₃}(NO)Cl(NHC₆H₄Z-p)]; in which M=Mo and Z=F, Cl, Br, OMe, SMe, CN, CO₂Me or NO₂ and M=W and Z=Br, OMe, CN, CO₂Me or NO₂, have been prepared. The reduction potentials of these new complexes were measured by cyclic voltammetry and, in combination with previously reported data for related species and for [Mo{HB(3,5-Me₂C₃N₂H)₃} (NO)I-(NHC₆H₄Z-p], were used to determine reaction constants for the reduction of [M{HB(3,5-Me₂C₃N₂H)₃}(NO)X(NHC₆H₄Z)]M=Mo and X=I or Cl; M=W, X=Cl.Part IV. N. Al Obaidi, M. Chaudhury, D. Clague, C. J. Jones, J. C. Pearson, J. A. McCleverty and S. S. Salam, submitted toJ. Chem. Soc., Dalton Trans., Paper 6/869.     

Intramolecular Interactions of Phosphor-Containing Groups with an Aromatic Fragment in Different Conformations

Abstract

Geometrical and electronic structure of conformers was studied by optical spectroscopy and quantum chemistry methods. The interaction mechanism of phosphor-containing groups with an aromatic fragment in YC₆H₄PX₂ (Y = H, Cl, Me, OMe, NMe₂, C(O)OR; × = Alk, OAlk, NAlk₂, Cl) and YC₆H₄P(Z)X₂ (Y = H, C1, Me, OMe, NMe₂; × = Alk, OAlk, NAlk₂, F, C1; Z = O, S) compounds is discussed. In case of bisector conformation (A), where the benzene ring plane coincides with a XPX-angle bisectrix, ll-acceptor action of phosphorus-containing groups increases with X varying in a series: Alk <NAlk₂ ≈ OAlk ≤ F4 << C1. These properties are displayed in ground and excited states of molecules, and are determined by interaction of PX₂ and P(Z)X₂ vacant group orbitals antisymmetric with respect to bisector plane with aromatic fragment π-orbitals. For phosphorchloride groups [sgrave]-π-conjugation dominates and the d-π-conjugation contribution is small. π-acceptor effect for P(0)X₂is weaker than for PX₂ and P(S)X₂ groups (especially in excited states) which is due to competitive transfer of electron density from oxygen to PX₂ fragment. In case of the gonal conformation (B) where benzene ring and bisector plane of PX₂ fragment are perpendicular, π-donor effect of PAlk₂ group is found to be 2–4 times weaker than for NAlk₂. According to quantum-chemical calculations with the MNDO method ArPX₂ the stabilization of conformer B for ArPX₂ increases in a series X: C1 <C=N <F <H <CH₃; and for ArP(0)X₂ the main conformation is (A).     

Vinyliden-Übergangsmetallkomplexe: II. Die Protonierung der Vinyliden-Komplexe C5H5Rh(CCHR)(PPri3) und ihre stufenweise Umwandlung in Vinyl- und α-Halogenalkyl-Rhodiumverbindungen

The protonation ofC₅H₅Rh(CCH₂)(PPrⁱ₃) (I) by CF₃CO₂H, HCl and HI gives the vinylrhodium compounds C₅H₅Rh(CHCH₂)(PPrⁱ₃)X (II-IV). The reaction of III (X = Cl) and IV (X = I) with a second molecule of HCl leads to the formation of the α-chloroethyl complexes C₅H₅Rh(CHClCH₃)(PPrⁱ₃)X (VII, VIII). The stereochemistry of these products allows us to propose a mechanism for HCl addition to the CC double bond of the vinyl ligand. C₅H₅Rh(CCHPh)(PPrⁱ₃) (XII) reacts with CF₃CO₂H and HI to give the kinetically preferred compounds C₅H₅Rh(Z-CHCHPh)(PPrⁱ₃)X (XIVa, XVa) of which XIVa (X = CF₃CO₂) in4bpolar solvents rearranges smoothly to form the thermodynamically more stable E isomer C₅H₅Rh(E-CHCHPh)(PPrⁱ₃)OCOCF₃ (XIVb). C₅H₅Rh(E-CHCHPh)(PPrⁱ₃)I (XVb) is obtained from XIVb and NaI. The protonation reactions of C₅H₅Rh(CCHMe)(PPrⁱ₃) (XIII) with CF₃CO₂H, HCl and HI always produce mixtures of isomers of the complexes C₅H₅Rh(CHCHMe)(PPrⁱ₃)X (XVI-XVIII). The ratio of Z to E isomers (≈ 62/38) is not dependent on the anion X and is also not influenced by the polarity of the solvent.     

Mono‐ and heterodi‐nuclear complexes of aluminium: synthesis,characterization and antifungal activity

Some new types of mononuclear derivatives, AlL(1–4)L(1–4)H ( 1a–1d ) of aluminium were synthesized by the reaction of Al(OPrⁱ)₃ and LH₂ [XC(NYOH)CHC(R)OH], X = CH₃, Y = (CH₂)₂, R = CH₃(L1H₂); X = C₆H₅, Y = (CH₂)₂, R = CH₃(L2H₂); X = CH₃, Y = (CH₂)₃, R = CH₃(L3H₂); X = C₆H₅, Y = (CH₂)₃, R = CH₃(L4H₂) in 1:2 molar ratio in refluxing benzene. Reactions of AlL(1–4)L(1–4)H with hexamethyldisilazane in 2:1 molar ratio yielded some new ligand bridged heterodinuclear derivatives AlL(1–4)L(1–4)SiMe₃ ( 2a – 2d ). All these newly synthesized derivatives were characterized by elemental analysis and molecular weight measurements. Tentative structures were proposed on the basis of IR and NMR spectra (¹H, ¹³C, 27 Al and ²⁹Si) and FAB‐mass studies. Schiff base ligands and their mono‐ and heterodi‐nuclear derivatives with aluminium have been screened for fungicidal activities. These compounds showed significant antifungal activity against Aspergillus niger and A. flavus. Copyright © 2007 John Wiley & Sons, Ltd.     

Formation of substituted pyrazolines in the reaction of C,N-diphenylnitrilimine with a zwitterion derived from triisopropylphosphine and ethyl 2-cyanoacrylate

The reaction of C,N-diphenylnitrilimine with a P-zwitterion derived from Prⁱ ₃P and H₂C=C(CN)CO₂Et afforded the first representative of 2-pyrazolines containing the phosphonium group and products of the addition of nitrilimine to Prⁱ ₃P and H₂C=C(CN)CO₂Et. The reaction of the P-zwitterion with C-4-nitrophenyl-N-phenylnitrilimine gave rise to a condensation product of one Prⁱ ₃P molecule and two nitrilimine molecules. The three-dimensional structures of the compounds synthesized were established by X-ray diffraction analysis.