Mononuclear, dinuclear, and hexanuclear goldI complexes with (aza-15-crown-5)dithiocarbamate

The reactions of sodium (aza-15-crown-5)dithiocarbamate with [AuClL] precursors lead to mono-, di-, or hexanuclear derivatives depending on L. The homoleptic hexanuclear gold(I) cluster [Au6(S2CNC10H20O4)6] is formed by displacement of the chloride and isocyanide ligands in [AuCl(CN(2,6-Me2C6H3))]. X-ray diffraction studies show a novel geometry in gold cluster chemistry where the six gold atoms display a cyclohexane-like geometry in a chair conformation with Au-Au-Au angles of 117.028(9) degrees, two short gold-gold distances of 2.9289(5) A, and bidentate bridging dithiocarbamate ligands. The molecular structure shows a crown of gold atoms surrounded by crown ethers. This derivative luminesces at 569 nm at room temperature in the solid state. A dinuclear isomer [Au2(S2CNC10H20O4)2] had been reported previously and was obtained by reaction with [AuCl(SMe2)]. The mechanism to obtain the hexanuclear derivative involves a mononuclear intermediate [Au(S2CNC10H20O4)(CNR)] for which the X-ray structure shows a short gold-gold distance of 3.565 A with the two molecules in an anti configuration. Phosphine gold(I) mononuclear derivatives [Au(S2CNC10H20O4)(PR3)] (R = Me, Ph, both characterized by X-ray diffraction) and dinuclear diphosphine derivatives [{Au(S2CNC10H20O4)}2(mu-P-P)] (P-P = dppm, bis(diphenylphosphinomethane); dppp, 1,3-bis(diphenylphosphinopropane); and dppf, 1,1'-bis(diphenylphosphinoferrocene)) are also reported. In the mononuclear complexes, the molecular structure confirms that the dithiocarbamato ligand is mainly acting as monodentate, with a second longer Au-S distance of 3.197 (PMe3), 2.944(4) (PPh3), and 2.968 A (CNR). Three phosphine complexes are emissive at 562 (PMe3), 528 (PPh3), and 605 nm (dppm), at 77 K. X-ray diffraction studies of the dppm derivative show gold-gold intramolecular contacts of 3.0972(9) A (3.2265(10) A for a second independent molecule) and basically monodentate coordination of the dithiocarbamato ligands. All the complexes extract sodium and potassium salts from aqueous solutions. The diphosphine derivatives are noticeably better extractors than the monophosphino derivatives, mainly for potassium salts.     

Multiple-stage mass spectrometry analysis of bisphenol A diglycidyl ether, bisphenol F diglycidyl ether and their derivatives

The fragmentation of bisphenol A diglycidyl ether (BADGE), bisphenol F diglycidyl ether (BFDGE) and their derivatives was studied by electrospray ionization tandem mass spectrometry. Multiple-stage mass spectrometry and accurate mass measurements were combined to establish the fragmentation pathways. BADGEs and BFDGEs tend to form ammonium adducts under electrospray conditions which fragmented easily. The fragmentation of [M+NH(4)](+) for BADGEs started with the cleavage of the phenyl-alkyl bond, which was followed by the α-cleavage of the ether group to generate the characteristic product ions at m/z 135, [C(9)H(11)O](+), and m/z 107, [C(7)H(7)O](+). The fragmentation of the BFDGE isomer mixtures was studied by on-line reversed-phase liquid chromatography coupled to multiple-stage mass spectrometry (LC/MS(n)). Information obtained from product ion spectra for each BFDGE isomer and its comparison with the fragmentation pathway of BADGE allowed each isomer and the chromatographic elution order to be identified.     

Solvatochromic analysis of some N-nitroso oxime derivatives--Taft and Catalan approach

Some novel N-nitroso oxime derivatives were synthesized and characterized by (1)H, (13)C, (1)H-(1)H and (1)H-(13)C COSY NMR spectra. The spectra of all these N-nitroso oximes reveal the presence of two isomers labelled as E (-NOH group is anti to N-N=O moiety) and Z (-NOH group is syn to N-N=O moiety) in solution and the coupling constants ruled out the possibility of normal chair conformation. From the theoretical studies and coupling constant values it was found that both E (major) and Z (minor) isomers of N-nitroso oximes exist as an equilibrium mixture of CA and boat conformation (B(1)) and this was also supported by DFT calculation. The photophysical properties of these oxime derivatives were studied and the observed lower fluorescence quantum yield may be due to an increase in the non-radiative deactivation rate constant. This is attributed due to the presence of non-chair conformation of N-nitroso oxime derivatives.     

Influence of carrier ligand NH hydrogen bonding to the O6 and phosphate group of guanine nucleotides in platinum complexes with a single guanine ligand

Coordinated N,N',N"-trimethyldiethylenetriamine (Me3dien) has several possible configurations: two have mirror symmetry (R,S configurations at the terminal nitrogens) and the terminal N-Me's anti or syn with respect to the central N-Me (anti-(R,S) and syn-(R,S) isomers, respectively), and two are nonsymmetrical (R,R and S,S configurations at terminal nitrogens, rac denotes a 1:1 mixture of the two isomers). For each configuration, two Me3dienPtG atropisomers can be formed (anti or syn orientation of central N-Me and G 06, G = guanine derivative), and these can be observed since the terminal N-Me's decrease the rate of G rotation about the Pt-N7 bond. In symmetrical syn-(R,S)-Me3dienPtG derivatives with G = 9-EtG and 3'-GMP, the anti rotamer, which can form O6-NH H-bonds, was slightly favored over the syn rotamer but never more than 2:1. This anti rotamer is also favored by lower steric repulsion between the terminal N-Me's and G O6; thus, the contribution of O6-NH H-bonding to the stability of the anti rotamer could be rather small. With G = 5'-GMP, an O6-NH H-bond in the anti rotamer and a phosphate-NH H-bond in the syn rotamer can form. Only the syn rotamer was detected in solution, indicating that NH H-bonds to 5'-phosphate are far more important than to O6, particularly since steric factors favor the anti rotamer. Interconversion between rotamers was faster for syn-(R,S)- than for rac-Me3dien derivatives. This appears to be determined by a smaller steric impediment to G rotation of two "quasi equatorial" N-Me's, both on one side of the platinum coordination plane (syn-(R,S) isomer), than one "quasi equatorial" and one "quasi axial" N-Me on either side of the coordination plane (rac isomer).     

Mononuclear (nitrido)iron(V) and (oxo)iron(IV) complexes via photolysis of [(cyclam-acetato)FeIII(N3)]+ and ozonolysis of [(cyclam-acetato)FeIII(O3SCF3)]+ in water/acetone mixtures

Reaction of the monoanionic, pentacoordinate ligand lithium 1,4,8,11-tetraazacyclotetradecane-1-acetate, Li(cyclam-acetate), with FeCl3 yields, upon addition of KPF6, [(cyclam-acetato)FeCl]PF6 (1) as a red microcrystalline solid. Addition of excess NaN3 prior to addition of KPF6 yields the azide derivative [(cyclam-acetato)FeN3]PF6 (2a) as orange microcrystals. The X-ray crystal structure of the azide derivative has been determined as the tetraphenylborate salt (2b). Reaction of 1 with silver triflate yields [(cyclam-acetato)Fe(O3SCF3)]PF6 (3), which partially dissociates triflate in nondried solvents to yield a mixture of triflate and aqua bound species. Each of the iron(III) derivatives is low-spin (d5, S = 1/2) as determined by variable-temperature magnetic susceptibility measurements, M?ssbauer and EPR spectroscopy. The low-spin iron(II) (d6, S = 0) complexes 1red and 2ared have been prepared by electrochemical and chemical methods and have been characterized by M?ssbauer spectroscopy. Photolysis of 2a at 419 nm in frozen acetonitrile yields a nearly colorless species in approximately 80% conversion with an isomer shift delta = -0.04 mm/s and a quadrupole splitting delta EQ = -1.67 mm/s. A spin-Hamiltonian analysis of the magnetic M?ssbauer spectra is consistent with an FeV ion (d3, S = 3/2). The proposed [(cyclam-acetato)FeV=N]+ results from the photooxidation of 2a via heterolytic N-N cleavage of coordinated azide. Photolysis of 2a in acetonitrile solution at -35 degrees C (300 nm) or 20 degrees C (Hg immersion lamp) results primarily in photoreduction via homolytic Fe-Nazide cleavage yielding FeII (d,6 S = 0) with an isomer shift delta = 0.56 mm/s and quadrupole splitting delta EQ = 0.54 mm/s. A minor product containing high-valent iron is suggested by M?ssbauer spectroscopy and is proposed to originate from [((cyclam-acetato)Fe)2(mu-N)]2+ with a mixed-valent (FeIV(mu-N)FeIII))4+S = 1/2 core. Exposure of 3 to a stream of oxygen/ozone at low temperatures (-80 degrees C) in acetone/water results in a single oxidized product with an isomer shift delta = 0.01 mm/s and quadrupole splitting delta EQ = 1.37 mm/s. A spin-Hamiltonian analysis of the magnetic M?ssbauer yields parameters similar to those of compound II of horseradish peroxidase which are consistent with an FeIV=O monomeric complex (S = 1).     

Intramolecular amine-induced [1,3]-sigmatropic rearrangement in the reactions of aminophosphinites or phosphites with elemental sulfur or selenium

Ether- and thioether-functionalized cyclodiphosphazanes cis-[tBuNP(OCH2CH2EMe)]2 (E = O, 1; E = S, 2) react with 2 equiv of elemental sulfur or selenium to produce dichalcogenides cis-[tBuNP(E)(OCH2CH2EMe)]2 (4-6), whereas the similar reaction of amine-functionalized cyclodiphosphazane cis-[tBuNP(OCH2CH2NMe2)]2 (3) with elemental chalcogen results in the formation of thio- or selenophosphates trans-[tBuNP(O)(ECH2CH2NMe2)]2 (E = S, 7; E = Se, 8) through [1,3]-sigmatropic rearrangement. The X-ray crystal structure of 8 confirms the rearranged product as the trans isomer with a planar P2N2 ring. The equimolar reaction of P(OCH2CH2OMe)3 (9) with elemental sulfur or selenium produces the simple sulfide and selenide E=P(OCH2CH2OMe)3 (E = S, 11; E = Se, 12) derivatives, respectively. In contrast, the reaction between P(OCH2CH2NMe2)3 (10) and S or Se furnishes the rearranged products (13 and 14). The rearrangement reaction was monitored by (31)PNMR spectroscopy, which confirms the formation of selenophosphinic acid as the first step of the rearrangement. The [1,3]-sigmatropic rearrangement presumably takes place through chalcogen-nitrogen interactions.     

Electron impact induced fragmentation of 4-alkyl derivatives of 2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane and the corresponding 1-oxides, 1-sulfides and 1-selenides

The electron impact fragmentations of several derivatives of 2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane have been examined by means of high resolution and metastable ion analysis. The principal fragmentation route for bicyclophosphites, phosphates and phosphorothionates involves a loss of formaldehyde, followed by a loss of the PO₂X and HPO₂X groups (X = -, O, S). The behaviour of phosphoroselenates is quite different, due partly to the favoured loss of selenium from the molecular ion before further fragmentation. Fragmentation through C? O bond breaking and a rearranged molecular ion is dependent on the exocyclic chalcogen atom (-, O, S, Se) on phosphorus. The reactions have been rationalized in terms of 1- and 4-substitutions.     

On triazoles. XII. The carbamoylation and thiocarbamoylation of 5-amino-1,2,4-triazoles

The reaction of 5-amino-3-R-1H-1,2,4-triazoles 1 with isocyanates 2 (X = O) and isothiocyanates 2 (X = S) was studied. It was stated that with isocyanates 3a (X = O) type ring-carbamoylated products were formed which did not rearrange to the corresponding exo-carbamoylated derivatives 6a (X = O). On the other hand the thiocarbamoylation of derivatives 1 provided at mild conditions lead to derivatives 3a (X = S) which could be rearranged by heating to derivatives 6a (X = S). In one case the isomeric 4a (X = S) type derivative was also isolated. The comparison of the ir, uv, pmr and cmr spectra of the isomers isolated with the corresponding spectra of the carbamoylated and thiocarbamoylated 3,5-diamino-1,2,4-triazole derivatives helped to prove unequivocally the isomeric and tautomeric structure of compounds obtained giving a possibility to correct many confusions in the literature.     

Diastereoselective reduction of cyclopropenylcarbinol: new access to anti-cyclopropylcarbinol derivatives

[reaction: see text] Cyclopropenylcarbinol derivatives are regio- and diastereoselectively reduced with LiAlH(4) in Et(2)O into trans-cyclopropylcarbinols as a single isomer. The regioselectivity of the hydroalumination reaction on the cyclopropenyl ring has been mapped out by deuterium labeling experiments.     

G3(MP2) study of the C3H6O+* isomers fragmented from 1,4-dioxane+*

The fragmentation process of ionized 1,4-dioxane and the reactions between the C3H6O+* ions, one of the major fragments, and various reactants (including acetonitrile, formaldehyde, ethylene, and propene) have been studied experimentally with mass spectrometry. In the present work, G3(MP2) calculations were carried out to investigate these processes theoretically. In agreement with experiment, isomers CH3OCHCH2+* (1) and *CH2CH2OCH2+ (2) were found to be the C3H6O+* ions fragmented from ionized 1,4-dioxane, with 2 being the major product. The mechanisms of the formation of 1 and 2 were successfully established. In addition, the characteristic reactivities, as well as the corresponding reaction mechanisms, of both isomers were rationalized with the aid of calculations. Finally, a minor reaction between isomer 2 and propene was identified, and the presence of the product of this reaction was found to be useful in explaining the aforementioned mass spectrometric data.     

Selective preparation of oxygen-rich [60]fullerene derivatives by stepwise addition of tert-butylperoxy radical and further functionalization of the fullerene mixed peroxides

tert-Butylperoxy radicals add to C(60) selectively to form multi-adducts C(60)(O)(m)(OO(t)Bu)(n) (m = 0, n = 2, 4, 6; m = 1, n = 0, 2, 4, 6) in moderate yields under various conditions. Visible light irradiation favors epoxide formation. High concentration of tert-butylperoxy radicals mainly produces the hexa-homoadduct C(60)(OO(t)Bu)(6) 6; low concentration and long reaction time favor the epoxy-containing C(60)(O)(OO(t)Bu)(4) 7. The reaction can be stopped at the bis-adducts with limited TBHP. A stepwise addition mechanism is discussed involving mono-, allyl-, and cyclopentadienyl C(60) radical intermediates. m-CPBA reacts with the 1,4-bis-adduct to form C(60)(O)(OO(t)Bu)(2) and C(60)(O)(3)(OO(t)Bu)(2). The C-O bond of the epoxy ring in 7 can be cleaved with HNO(3) and CF(3)COOH. Nucleophilic addition of NaOMe to 7 follows the S(N)1 and extended S(N)2' mechanism, from which four products are isolated with the general formula C(60)(O)(a)(OH)(b)(OMe)(c)(OO(t)Bu)(d). Visible light irradiation of the hexa-adduct 6 results in partial cleavage of both the C-O and O-O bonds of peroxide moieties and formation of the cage-opened compound C(60)(O)(O)(2)(OO(t)Bu)(4). All the fullerene derivatives are characterized by spectroscopic data. A single-crystal structure has been obtained for an isomer of C(60)(O)(OH)(2)(OMe)(4)(OO(t)Bu)(2).     

Structure and intramolecular hydrogen bonds in Bis(trifluoromethylsulfonylamino)methane and N-[(trifluoromethylsulfonyl)aminomethyl]acetamide

Bis(trifluoromethylsulfonylamino)methane in an inert medium exists as an equilibrium mixture of monomeric forms with various types of intramolecular hydrogen bonds, whose population depends on the polarity of the medium. The energetically most favorable form is a symmetrical form containing two N-H...O=S bonds. Less stable are the isomer with two N-H...F-C bonds and the unsymmetrical isomer with two different hydrogen bonds. N-[(Trifluoromethylsulfonyl)aminomethyl]acetamide contains one intramolecular intramolecular N-H...O=C hydrogen bond and preserves ability for self-association.     

Conformational changes of 2,11-dithia[3.3]metacyclophane. A new look using VT NMR and calculation

The conformational changes of 2,11-dithia[3.3]metacyclophane are reexamined utilizing VT NMR data and calculations (ab initio, semiempirical, density functional, and molecular mechanics) to show that the syn to syn' inversion that occurs with exchange of the benzylic hydrogens proceeds most easily through bridge wobbles of the anti isomers and that the critical barrier is the conversion of the syn - chair - chair isomer to the anti-chair-chair isomer, barrier (found) = 9.3-9.6 kcal/mol, barrier (calc) = 10.3 kcal/mol, such that when this conversion is slow on the NMR time scale, the benzylic hydrogens no longer exchange, and the syn-chair-chair isomer becomes frozen. The syn-boat-chair isomer, however, can continue to invert to the anti-boat-chair isomer until lower temperatures, and thus, the benzylic hydrogens continue to exchange for this isomer. Thus, while bridge wobbles of the syn isomers have the largest barriers, bridge wobbles of the anti isomers have the smallest barriers, and so the barriers of the syn-to-anti conversions play a much greater role than previously determined.     

The structural and stereogenic properties of pentaerythritoxy-bridged cyclotriphosphazene derivatives: spiro-spiro, spiro-ansa and ansa-ansa isomers

Reactions of pentaerythritol with hexachlorocyclotriphosphazene, N3P3Cl6, and gem-disubstituted cyclotriphosphazene derivatives, N3P3Cl4R2 [R = Ph, NHBu(t) or (OCH2CF2CF2CH2O)0.5] gave a series of pentaerythritol-bridged derivatives linked spiro-spiro, spiro-ansa and ansa-ansa. The structures and stereogenic properties of the products were characterised by X-ray crystallography and 31P NMR spectroscopy on addition of the chiral solvating agent, (S)-(+)-2,2,2-trifluoro-1-(9-anthryl)ethanol. Molecules with spiro-spiro and spiro-ansa bridged gem-disubstituted cyclophosphazenes [R = Ph, NHBu(t) or (OCH2CF2CF2CH2O)0.5] are found to be chiral and exist as racemates. Molecules with ansa-ansa bridged cyclophosphazenes [R = Cl or (OCH2CF2CF2CH2O)0.5] have been characterised for the first time and are shown to have meso configurations. Analysis of crystal structure data shows that the six-membered chair form of the spiro rings and the eight-membered boat-chair form of the ansa rings in the bridged compounds are similar to analogous spiro and ansa exocyclic ring conformations of 1,3-propanedioxy-derivatives of cyclophosphazenes.     

Characterization of the Potent Insulin Mimetic Agent Bis(maltolato)oxovanadium(IV) (BMOV) in Solution by EPR Spectroscopy

Bis(maltolato)oxovanadium(IV) (abbreviated BMOV or VO(ma)(2)) has been characterized by electron paramagnetic resonance (EPR) spectroscopy in CH(2)Cl(2), H(2)O, MeOH, and pyridine at both room and low temperatures. Spin Hamiltonian parameters for mono- and bis(maltolato)oxovanadium(IV) complexes [VO(ma)](+) (=[VO(ma)(H(2)O)(n)()](+), n = 2 or 3) and VO(ma)(2) (Hma = 3-hydroxy-2-methyl-4-pyrone, maltol) have been obtained by computer simulation (SOPHE). Configurations of solvated vanadyl/maltol complexes, VO(ma)(2)S, in solution (S = solvent) are proposed on the basis of a comparison of their hyperfine coupling constants with those obtained for related vanadium(IV) compounds in the literature. Whereas at room temperature pyridine coordinates to VO(ma)(2) in a position cis to the oxo ligand (cis isomer), in H(2)O or in MeOH solvated and unsolvated cis and trans adducts of VO(ma)(2) are all formed, with the cis isomer dominant. As expected, the coordinating ability was found to be in the order py > H(2)O approximately MeOH > CH(2)Cl(2). In aqueous solutions at room temperature and neutral pH, cis- and trans-VO(ma)(2)(H(2)O) complexes are present as major and minor components, respectively.     

Relaxivity and water exchange studies of a cationic macrocyclic gadolinium(III) complex

We conducted relaxometric and water exchange studies of the cationic [Gd((S,S,S,S)-THP)(H2O)]3+ complex (THP 1,4,7,10-tetrakis(2-hydroxy-propyl)-1,4,7,10-tetraazacyclododecane). While the NMRD profiles obtained are typical for DOTA-like complexes (DOTA = 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetate), variable-temperature 7O NMR investigations revealed a relatively high water exchange rate (k(298)(ex) = 1.89 x 10(7) s(-1)). These results differ from those reported for other cationic tetraamide macrocyclic Gd(III) complexes, which exhibit characteristically low exchange rates. Since the low exchange rates are attributed partially to the geometry of the M isomer (square antiprismatic) in the tetraamide derivatives, the atypical water exchange rate observed in [Gd((S,S,S,S)-THP-(H2O)]3+ may result from a twisted square antiprismatic structure in this complex and from the relatively high steric strain at the water coordination site as a result of the presence of methyl groups at the alpha-position with respect to the Gd(III)-bound O atoms of THP.     

Superior Z→E and E→Z photoswitching dynamics of dihydrodibenzodiazocine, a bridged azobenzene, by S1(nπ*) excitation at λ = 387 and 490 nm

The ultrafast Z→E and E→Z photoisomerisation dynamics of 5,6-dihydrodibenzo[c,g][1,2]diazocine (1), the parent compound of a class of bridged azobenzene-based photochromic molecular switches with a severely constrained eight-membered heterocyclic ring as central unit, have been studied by femtosecond time-resolved spectroscopy in n-hexane as solvent and by quantum chemical calculations. The diazocine contrasts with azobenzene (AB) in that its Z rather than E isomer is the energetically more stable form. Moreover, it stands out compared to AB for the spectrally well separated S(1)(nπ*) absorption bands of its two isomers. The Z isomer absorbs at around λ = 404 nm, the E form has its absorption maximum around λ = 490 nm. The observed transient spectra following S(1)(nπ*) photoexcitation show ultrafast excited-state decays with time constants τ(1) = 70 fs for the Z and <50 fs for the E isomer reflecting very fast departures of the excited wave packets from the S(1) Franck-Condon regions and τ(2) = 270 fs (320 fs) related to the Z→E (resp. E→Z) isomerisations. Slower transient absorption changes on the time scale of τ(3) = 5 ps are due to vibrational cooling of the reaction products. The results show that the unique steric constraints in the diazocine do not hinder, but accelerate the molecular isomerisation dynamics and increase the photoswitching efficiencies, contrary to chemical intuition. The observed isomerisation times and quantum yields are rationalised on the basis of CASPT2//CASSCF calculations by a S(1)/S(0) conical intersection seam at a CNNC dihedral angle of ≈96° involving twisting and torsion of the central CNNC moiety. With improved photochromism, high quantum yields, short reaction times and good photostability, diazocine 1 and its derivatives constitute outstanding candidates for photoswitchable molecular tweezers and other applications.     

Chemistry of the diazeniumdiolates. 3. Photoreactivity

We have found O(2)-substituted diazeniumdiolates, compounds of structure R(2)N-N(O)=NOR' that are under development for various possible pharmaceutical uses, to be rather photosensitive. With R = ethyl and R' = methyl, benzyl, or 2-nitrobenzyl, the observed product distributions suggest that two primary pathways are operative. A minor pathway involves the extrusion of nitrous oxide (N(2)O) with simultaneous generation of R(2)N(*) and R'O(*), which may then form amines, aldehydes, and alcohols. The major reaction pathway is an interesting photochemical cleavage of the N=N bond to form a nitrosamine (R(2)NN=O) and an oxygen-substituted nitrene (R'ON). The intermediacy of the O-nitrene was inferred from the production of abundant oxime, via rearrangement of the O-nitrene to a C-nitroso compound (R'ON --> O=NR'), and subsequent tautomerization to the more stable oxime. Involvement of the O-nitrene was confirmed by trapping with 2,3-dimethyl-2-butene to form the aziridine and with oxygen to generate the nitrate ester. 2-Nitro substitution on the benzyl derivative had surprisingly little effect on the reaction course. For each compound examined, minor amounts of nitric oxide (NO), presumably produced by secondary photolysis of the nitrosamine, were observed. Time-resolved infrared experiments provided additional support for the above reaction pathways and confirmed that the nitrosamine is a primary photoproduct. We have also found that the relative contributions of the reaction pathways can be altered in certain derivatives. For example, when R' = 2,4-dinitrophenyl, the contribution of the nitrosamine/O-nitrene-forming pathway was diminished. Pharmacological implications of these results are discussed.     

Phosphorinane and Enol Rings in One Molecule. Evidence for Reciprocal Stabilization of Half-Chair Conformations

Abstract.

The X-ray crystal structure of 2-(2′,4′-dioxo-3′-pentyl)-5,5-dimethyl-2-oxo-1,3,2-dioxaphosphorinane (2) reveals significant half-chair distortion of the axially oriented cisenol ring. The molecule also undergoes in-plane deformations. R(O...O) = 2.410 Å in the enol moiety indicates a very strong hydrogen bonding. The enol content, δ_OH and thermodynamic parameters for the axial-equatorial conformational and keto-enol equilibriums were obtained from ¹H, ³¹P NMR and IR measurements in comparison with the planar 4,6-dimethyl isomer (1) containing equatorially oriented enol ring. The X-ray single crystal structure of 5,5-dimethyl-2-(methoxycarbonyl-3′-oxo-2′-butyl)-2-oxo-1,3,2-dioxaphosphorinane (3) reveals the unusual half-chair conformation of the dioxaphosphorinane cycle disposed a trans-enol ring substituent. ¹H, ³¹P NMR and IR solution data support the same structure displays a strong conformational preference while the minor forms are chair conformers with an axial or equatorial cis-enol ring.     

Mass spectra of isomeric monothiopyrophosphates

The main fragmentation patterns of the phosphorus-containing moiety of bis(5,5-dimethyl-2-oxo-1,3,2-dioxaphosphorinanyl) sulphide, 3, and its isomer P-oxo-P'-thiono-bis(5,5-dimethyl-1,3,2-dioxaphosphorinanyl) oxide, 4, are presented. Isotope studies with ¹⁸O, ³⁶S, ³⁴S and ²H indicate that compound 3 undergoes an extensive isomerization prior to fragmentation. The mechanism of this isomerization must involve interaction of at least two molecules, as shown by isotope scrambling experiments.