Enantiomer separation of rac-2,2′-dihydroxy-1,1′-binaphthyl (BNO) by inclusion complexation with racemic or achiral ammonium salts and a novel transformation of a 1:1:1 racemic complex of BNO, Me4N·Cl and MeOH into a conglomerate complex in the solid state

The complete simultaneous and mutual enantiomer resolution of 2,2′-dihydroxy-1,1′-binaphthyl (BNO) and N-(3-chloro-2-hydroxypropyl)-N,N,N-trimethylammonium chloride, Me₃N⁺CH₂CH(OH)CH₂Cl·Cl⁻ into their enantiomers by inclusion complexation between their racemates in EtOH in the presence of a chiral seed crystal is reported. The enantiomer resolution of the rac-BNO was also accomplished easily by inclusion complexation with achiral ammonium salts, N-(2-hydroxyethyl)-N,N,N-trimethylammonium chloride, Me₃N⁺CH₂CH₂OH·Cl⁻ and tetramethylammonium chloride, Me₄N⁺·Cl⁻. Inclusion complexation of the rac-BNO with Me₃N⁺ CH₂CH₂OH·Cl⁻ gave only a 1:1 conglomerate inclusion complex but not a racemic complex. Recrystallization of the rac-BNO and an equimolar amount of Me₄N⁺·Cl⁻ from MeOH (7 ml) and MeOH (15 ml) gave a 1:1:1 racemic complex, BNO·Me₄N⁺·Cl⁻·MeOH and a 1:1 conglomerate complex, BNO·Me₄N⁺·Cl⁻, respectively. Novel transformation of the former racemate into the latter conglomerate occurred by heating or by exposure to MeOH vapor in the solid state.     

A new route to (±)-erythro-roccellic acid and chaetomellic anhydride C through functional rearrangement, promoted by n-propylamine or CH3ONa/CH3OH, of N-propyl-3-chloro-4-dichloromethyl-3-dodecylpyrrolidin-2-one

The rearrangement of a trichloro-pyrrolidin-2-one, prepared by the CuCl-TMEDA catalyzed atom transfer radical cyclization of N-alkyl-N-(3-chloro-2-propenyl)-2,2-dichloromyristamide, with n-propylamine or CH₃ONa/CH₃OH, is the key step of a new, short and inexpensive route to chaetomellic anhydride C and (±)-erythro-roccellic acid.     

Derivatives of 3-Deoxy-3-(N-Hydroxyamino)-D-Ribose

Abstract

A series of 3-(N-arylmethyl-N-hydroxyamino)-l,2-O-cyclopentylidene-3-deoxy-5-O-toluoyl-α-D-riboses has been prepared. The blocking groups used were chosen to allow an easy nucleosidation of these compounds to spin labelled analogs of natural nucleosides. The conformational behavior of the N-arylmethyl-N-hydroxyamino group has been studied using ³/_CH NMR coupling data and molecular mechanics computations. Upon spontaneous oxidation, these hydroxylamines led to the corresponding aminoxyl free radicals which were submitted to EPR spectroscopy and quantum mechanical computations at a semiempirical level (PM3).     

Synthesis and reactions of N-acetyl- and N-(2-chloroacetyl)-N-[(2E)-1-methylbut-2-en-1-yl]-2-iodoanilines

The reaction of N-(1-methylbut-2-en-1-yl)-2-iodaniline with Ac₂O or ClCH₂C(O)Cl results in a mixture of syn- and anti-atropisomers of N-acetyl- and N-chloroacetyl-N-(1-methylbut-2-en-1-yl)-2-iodaniline in a ratio of 1:1. Ozonolysis of the latter followed by reduction with dimethyl sulfide in CH₂Cl₂ gives rise to the atropisomers mixture of 2-[N-(chloroacetyl)-N-(2-iodophenyl)]aminopropanal in a ratio of 1:3. When heated in boiling benzene, the mixture of atropoisomeric aldehydes reacts with triphenylphosphine to afford a mixture of 2-[(N-acetyl)-N-(2-iodophenyl)]aminopropanal atropisomers in 1:3 ratio.     

The reactions of cyclotriphosphazene with 2-(2-hydroxyethylamino)ethanol. Spectroscopic studies of the derived products

Abstract

The reactions of cyclotriphosphazene (1) with 2-(2-hydroxyethylamino)-ethanol (2) were investigated. 2-(2-hydroxyethylamino)-ethanol (2) is a tri-functional reagent consisting of both aliphatic hydroxyl and the secondary amino groups and its nucleophilic substitution reactions with cylotriphosphazene can lead to different product types; open chain, spiro, ansa, bridged and their mixtures. The reactions with one, two and three equimolar ratios of 2-(2-hydroxyethylamino)-ethanol, in the presence of NaH at 0–10?°C and at room temperature gave the following cyclotriphosphazene derivatives: one mono-spiro, N₃P₃Cl₄[O–(CH₂)₂–NH–(CH₂)₂–O] (3, 1:1, r.t.); its isomer mono-ansa (5, 1:1, r.t.); one dispiro, N₃P₃Cl₂[O–(CH₂)₂–NH–(CH₂)₂–O]₂ (4, 1:1, r.t.); its isomer spiro-ansa (6, 1:2, r.t.); and one single-bridged compound with spiro substituted units, N₃P₃Cl₃[O–(CH₂)₂–NH–(CH₂)₂–O]₃N₃P₃Cl₃ (7, 1:3, at 0–10?°C); as well as single-, N₃P₃Cl₅[O–(CH₂)₂–NH–(CH₂)₂–O]N₃P₃Cl₅ (8, 1:2, r.t.), double-, N₃P₃Cl₄[O–(CH₂)₂–NH–(CH₂)₂–O]₂N₃P₃Cl₄ (9, 1:2, r.t.), and tri-bridged, N₃P₃Cl₃[O–(CH₂)₂–NH–(CH₂)₂–O]₃N₃P₃Cl₃ (10, 1:3, at 0–10?°C) derivatives. Triple-bridged derivative is the major product in this system. The structures of the novel-derived compounds were characterized by TLC-MS, FT-IR, elemental analysis, ¹H, and ³¹P NMR spectral.     

Synthesis of haloconduritols from an endo-cycloadduct of furan and vinylene carbonate

A method for preparing haloconduritols having a conduritol-A construction is described. A mixture of endo- and exo-cycloadduct derivatives prepared from the Diels-Alder reaction of furan and vinylene carbonate was converted into diacetate derivatives by hydrolysis (K₂CO₃/MeOH) followed by acetylation (Ac₂O/pyridine). Boron trihalide (BBr₃ or BCl₃)-assisted ring-opening of the endo-diacetate in CH₂Cl₂ at −78°C gave (1α,2α,3β,6β)-6-halogeno-4-cyclohexene-1,2,3-triol 1,2-diacetate from which the corresponding triacetate was prepared by acetylation (AcCl). trans-Esterification of the triacetate (MeOH/HCl) afforded (1α,2α,3β,6β)-6-halogeno-4-cyclohexene-1,2,3-triol (X=Br or Cl). BF₃-Assisted ring-opening of the endo-diacetate in CH₂Cl₂ gave (1α,2α,3β,6β)-6-chloro-4-cyclohexene-1,2,3-triol 1,2-diacetate by means of halogen exchange.     

Synthesis,spectroscopy, electrochemistry and in situ spectroelectrochemistry of partly halogenated coumarin phthalonitrile and corresponding metal-free,cobalt and zinc phthalocyanines

In this study, the preparation of novel 7-hydroxy-3-(2-chloro-4-fluorophenyl)coumarin (1), the ligand, 7-(3,4-dicyanophenoxy)-3-(2-chloro-4-fluorophenyl)coumarin (2), metal-free phthalocyanine 3 and metallophthalocyanine complexes 4 and 5 (MPcs, M = Co, Zn), β-substituted with 7-oxo-3-(2-chloro-4-fluorophenyl)coumarin functional group was achieved. By the reaction of 7-hydroxy-3-(2-chloro-4-fluorophenyl)coumarin (1) with 1,2-dicyano-4-nitrobenzen in dry DMF as the solvent in the presence of K₂CO₃ as the base, the 7-(3,4-dicyanophenoxy)-3-(2-chloro-4-fluorophenyl)coumarin (2) was synthesized. Compound 2 reacted with Co(CH₃COO)₂·4H₂O in 2-N,N-dimethylaminoethanol to furnish a novel coumarin containing cobalt(II) phthalocyanine 4. The cyclotetramerization of 2 with Zn(CH₃COO)₂·2H₂O in 2-N,N-dimethylaminoethanol gave the novel coumarin containing Zn(II)phthalocyanine 5; while tetramerization without any metal salts in 2-N,N-dimethylaminoethanol gave the metal-free phthalocyanine 3. The structures of obtained compounds were confirmed by elemental analysis, UV–Vis, IR, MALDI-TOF mass and ¹H NMR spectra. The cyclic and differential pulse voltammetry, and in situ spectroelectrochemistry of 7-oxo-3-(2-chloro-4-fuorophenyl)coumarin substituted phthalocyanines 3, 4 and 5 allowed us to identify metal- and phthalocyanine ring-based redox processes of the complexes.     

Stereoselective synthesis of 2-aryl-4-en-1-ols,promising synthons for the preparation of oxygen heterocycles

Reactions of arylacetic acids with N-methoxymethanamine afford corresponding Weinreb amides which at alkenylation with methallyl and prenyl bromides in the presence of (Me₃Si)₂N^–Na⁺ form unsaturated amides ArCHRCONMe(OMe) (R = CH₂CMe=CH₂, CH₂C=CMe₂). Amides readily react with BuLi and BnMgCl to give ketones ArCHRCOR' (R' = Bu, Bn). A stereoselective reduction of the latter with LiBH(s-Bu)₃ leads to a quantitative formation of syn-isomers of 2-aryl-4-en-1-ols.     

Infrared chemiluminescence in the reactions of 0.45 eV hydrogen atoms with Cl2, SCl2 and PCl3

Infrared chemiluminescence from HCl has been observed in “arrested relaxation” experiments to yield vibrational and rotational distributions from the reactions $\text{H}$+Cl₂, SCl₂ and PCl₃, where $\text{H}$ denotes hydrogen atoms with translational energy of 0.45 eV. The following relative populations were determined: N_v-1: N_v-2: N_v-3: N_v-4: N_v-5: N_v-6 = 0.89:1.00:0.84:0.47:0.26:0.11 for $\text{H}$+Cl₂: N_v-1: N_v-2: N_v-3: N_v-4: N_v-5: N_v-6 = 0.80:1.00:0.72:0.48:0.24:0.10 for $\text{H}$+SCl₂: N_v-1: N_v-2: N_v-3: N_v-4: N_v-5 = 0.79:1.00:0.88:0.36:0.14 for H+PCl₃. In all three reaction systems the chemiluminescence was attributed to the primary chlorine abstraction. Comparison with the results of the thermal processes (0.04 eV hydrogen atoms) led to the following conclusions: for H+Cl₂ the excess of translational energy is transformed into translational product energy and rotational energy of the molecule HCl; for H+SCl₂ the excess of translational energy is transformed mainly into translational energy of the products and perhaps internal energy of SCl; for H+PCl₃ the excess of translational energy allows the observation of the primary abstraction reaction, which could in earlier experiments at 300 K not be separated from secondary chemiluminescent processes. Bimodal rotational distributions were confirmed for several vibrational states of HCl formed in the systems $\text{H}$+Cl₂, and $\text{H}$+SCl₂. Bimodal rotational distributions were also detected in the chemiluminescent reaction H(0.04 eV)+CH₃SCl → HCl(v ? 5)+CH₃S.     

Amidine derivatives of α-arylglycines from N-(1-aryl-2,2,2-trichloroethyl)amides of arenesulfonic acids and secondary amines

The interaction of N-(1-aryl-2,2,2-trichloroethyl)amides of arenesulfonic acids with secondary amines or their salts in the presence of inorganic bases involves the formation of chloroaziridine intermediates. Depending upon the solvent and reagent ratio, the reaction results in N-[1-dialkylamino-2-chloro-2-arylethylidene]-, N-[2-dialkylamino-1-chloro-2-arylethylidene]-, N-[1,2-bis(dialkylamino)-2-arylethylidene]-, and N-(1,2-dioxo-2-arylethene)amides of arenesulfonic acids.     

Application of biphasic reaction procedure using ferric chloride dissolved in an imidazolium salt and benzotrifluoride (FeIm-BTF procedure) to aza-Prins cyclization reaction

Aza-Prins cyclization reaction of N-tosyl-3-butenylamine with aliphatic and aromatic aldehydes was performed using a combination of FeCl₃ and 1-butyl-3-methylimidazolium hexafluorophosphate (BmimPF₆) or 1-butyl-3-methylimidazolium tetrachloroferrate (BmimFeCl₄) in benzotrifluoride (BTF). The desired N-tosyl-4-chloro-2-substituted piperidines were obtained from aliphatic aldehydes in comparable yields to those for the previously reported reactions in which FeCl₃ was used in CH₂Cl₂. On the other hand, significant progress for the piperidine synthesis from aromatic aldehydes has been achieved, particularly when BmimFeCl₄ was used with FeCl₃ in BTF.     

Metal complexes of tetradentate and pentadentate N-o-hydroxybenzamido-meso-tetraphenylporphyrin ligand: M(N-NCO(o-OH)C6H4-tpp) (M = Zn2+, Ni2+, Cu2+) and M′(N-NCO(o-O) C6H4-tpp) (M′ = Mn3+) (tpp = 5, 10, 15, 20-tetraphenylporphyrinate)

The crystal structures of N-o-hydroxybenzimido-meso-tetraphenylporphyrinatozinc(II) toluene solvate [Zn(N-NCO(o-OH)C₆H₄-tpp)·C₆H₅CH₃; 4·C₆H₅CH₃], N-o-hydroxybenzimido-meso-tetraphenylporphyrinatonickel(II) chloroform solvate [Ni(N-NCO(o-OH)C₆H₄-tpp)·0.6CHCl₃; 5·0.6 CHCl₃], N-o-hydroxybenzimido-meso-tetraphenylporphyrinatocopper(II) toluene solvate [Cu(N-NCO(o-OH)C₆H₄-tpp)·C₆H₅CH₃; 6·C₆H₅CH₃] and N-o-oxido-benzimido-meso-tetraphenylporphyrinato(-κ⁴,N¹,N²,N³,N⁵,κO²) manganese (III) methylene chloride·methanol solvate [Mn(N-NCO(o-O)C₆H₄-tpp)·CH₂Cl₂·MeOH; 8·CH₂Cl₂·MeOH] were established. The coordination sphere around Zn²⁺ ion in 4·C₆H₅CH₃, (or Ni²⁺ ion in 5·0.6 CHCl₃ or Cu²⁺ ion in 6·C₆H₅CH₃) is a distorted square planar (DSP) whereas for Mn³⁺ in 8·CH₂Cl₂·MeOH, it is a distorted trigonal bipyramid (DTBP) with O(1), N(1) and N(3) lying in the equatorial plane for 8·CH₂Cl₂·MeOH. The g value of 8.27 measured from the parallel polarization of X-band EPR spectra at 293 K is consistent with the high-spin mononuclear manganese(III) (S = 2) in 8. The magnitude of axial (D) zero-field splitting (ZFS) for the mononuclear Mn(III) in 8 was determined approximately as 3.0 cm^?1 by the paramagnetic susceptibility measurements and conventional EPR spectroscopy.     

Unexpected Knoevenagel self-condensation reaction of tetronic acid: synthesis of a new class of organic heterocyclic salts

A new class of pyridinium, quinolinium, isoquinolinum, and N-methylimidazolium-3-(2,5-dihydro-5-oxofuran-3-yl)-4-hydroxyfuran-2(5H)-one salts have been prepared in high yields by reacting pyridine, quinoline, isoquinoline, N-methylimidazole, 1,4-diazabicyclo[2.2.2]octane, and their derivatives with tetronic acid in CH₂Cl₂.     

Anion-Radical Salts of 7,7,8,8-Tetracyanoquinodimethane (TCNQ) with Cations Based on Amino-Chloropyridines

Anion-radical salts of 7,7,8,8-tetracyanoquinodimethane (TCNQ) with N-methyl-2-amino-5-chloropyridinium and N-methyl-2-chloro-3-aminopyridinium cations of simple and complex compositions were synthesized and studied. The salt (N?CH₃?2?Cl₃NH₂?Py)(TCNQ) is electrically conducting and thermally stable up to 340°C. This enables use of this anion-radical salt in electronics of organic materials.

     

Synthesis, structure, and biological evaluation of C-2 sulfonamido pyrimidine nucleosides

The C-2 sulfonamido pyrimidine nucleosides were prepared by opening the 2,2′- or 2,3′-bond in anhydronucleosides under nucleophilic attack of sulfonamide anions. Reaction of the sodium salt of p-toluenesulfonamide or 2-(aminosulfonyl)-N,N-dimethylnicotinamide with 2,2′-anhydro-1-(β-d-arabinofuranosyl)cytosine gave the C-2 sulfonamido derivatives in excellent yields. Ring opening of the less reactive 2,2′-anhydrouridine and 2,3′-anhydrothymidine could be accomplished with DBU/CH₃CN activation of p-toluenesulfonamide, giving moderate yields for C-2 sulfonamido derivatives. The action of acetic acid or ZnBr₂/CH₂Cl₂ on 5-methyl-N²-tosyl-1-(2-deoxy-5-O-trityl-β-d-threo-pentofuranosyl)isocytosine led to the cleavage of both the protection group and the nucleoside bond, yielding 5-methyl-N²-tosylisocytosine as the major product. Structures of the prepared C-2 sulfonamido nucleosides were confirmed by the 1D and 2D NMR experiments, and X-ray structural analysis of 4-imino-N²-tosylamino-1-(β-d-arabinofuranosyl)pyrimidine. Both methods confirmed β-configuration and anti-conformation of the 2-sulfonamido nucleosides. The investigated compounds displayed moderate inhibition of tumor cell growth in vitro, as determined by the MTT assay using six different human tumor cell lines.     

Selective synthesis of bis[1,2]dithiolo[1,4]thiazines from 4-isopropylamino-5-chloro-1,2-dithiole-3-ones

Reaction of 4-isopropylamino-5-chloro-1,2-dithiole-3-ones 3 and S₂Cl₂ in acetonitrile gave selectively 3-oxo-bis[1,2]dithiolo[1,4]thiazine-5-thiones 1 by the addition of triethylamine and bis[1,2]dithiolo[1,4]thiazine-3,5-diones 5 under the action of formic acid. 3,5-Diones 5 were also obtained by intramolecular cyclization of N,N-bis(5-chloro-3-oxo[1,2]dithiol-4-yl)amines 6 with S₂Cl₂ in the presence of Et₃N.     

Gold(III) adducts of 2-vinyl- and 2-ethylpyridine and cyclometallated derivatives of 2-vinylpyridine: Crystal structure of the cyclometallated derivative [Au(k-C,N-CH2CH(Cl)-C5H4N)(PPh3)Cl][PF6]

Reaction of Na[AuCl₄] with 2-vinylpyridine (vinpy) and 2-ethylpyridine (etpy) affords the N-bonded adducts Au(Rpy)Cl₃ (R = CH₂CH, vinpy; CH₃CH₂, etpy). Cationic adducts, [Au(vinpy)₂Cl][X]₂ (X = BF₄, PF₆) and [Au(etpy)₂Cl₂][BF₄], were also obtained by reaction of Au(Rpy)Cl₃ with Rpy (1:1) and excess NaBF₄ or KPF₆. Thermal activation of Au(vinpy)Cl₃ in water gives the five-membered cycloaurated derivative [Au(k²-C,N-CH₂CH(Cl)-C₅H₄N)Cl₂] formally resulting through a trans nucleophilic addition of a chloride onto the CC bond. No cyclometallated derivatives are obtained by reactions of Au(etpy)Cl₃. An X-ray crystal structure determination on the PPh₃ derivative [Au(k²-C,N-CH₂CH(Cl)-C₅H₄N)(PPh₃)Cl][PF₆] was carried out.     

Aminolysis of P-trichloro-N-dichlorophosphorylmonophosphazene and the crystal structure of 1-(dichlorophosphinyl)-2-chloro-2,2-bis(diisopropylamino)phosphazene

The reactions of Cl₃PN P(O)Cl₂ ( 1 ) with primary and secondary amines have been studied. The following monophosphazenes, (RRN)₃PN P(O)(NRR)₂, and bis(phosphinoyl)amines, [(RRN)₂P(O)]₂NH were isolated: NRR = NHCH₂Ph, Net₂, NH(CH₂)₂CH₃ groups for monophosphazenes, and Net₂, NH(CH₂)₂CH₃ for phosphinoyl amines. The unexpected geminal phosphazene, Cl(RRN)₂PN P(O)Cl₂, {RRN = N[CH(CH₃)₂]₂}, was also obtained in moderate yield. The spectral data (IR, ¹H, ¹³C, and ³¹P NMR, and MS) are presented. The structure of 1-(dichlorophosphinyl)-2-chloro-2,2-bis(diisopropylamino)phosphazene ( 5 ) was determined by X-ray crystallography. The basicities of these and related compounds in nonaqueous nitrobenzene solution were obtained by potentiometric titration.     

<Emphasis Type="Italic">N</Emphasis>-allyl and <Emphasis Type="Italic">N</Emphasis>-propargyl trifluoromethanesulfonimides. Theoretical analysis

Tautomers of N-allyl- and N-propargyl-substituted trifluoromethanesulfonimides (CF₃SO₂)₂NR (R = CH₂CH=CH₂, Z/E-CH=CHMe, CH₂C≡CH, CH=CH=CH₂, C≡CCH₂) were calculated by the DFT (B3LYP, wB97XD, PBE1PBE), MP2, and CBS-QB3 methods. The results were compared with the theoretical data for the corresponding amines and amides NHRR¹ (R¹ = H, CF₃SO₂). It was shown that there is no conjugation between the nitrogen atom and C=C bond and that conjugation exists with the C≡C bond with electron density displacement toward the nitrogen atom. The calculations of anions derived from N-allyl- and N-propargyl-trifluoromethanesulfonimides revealed the possibility of their rearrangement with elimination of trifluoromethanesulfinate anion and formation of its H-complex with N-(prop-2-en-1-ylidene)trifluoromethanesulfonamide or N-(prop-2-yn-1-ylidene)trifluoromethanesulfonamide.     

The reactions of non-gem-hexanedioxytetrachlorocyclotriphosphazene with 2-(2-hydroxyethyl)thiophene,benzyl alcohol and 1,1,3,3-tetramethylguanidine. Spectroscopic studies of the derived products

Abstract

Reactions of non-gem-hexanedioxytetrachlorocyclotriphosphazene (1) with monofunctional nucleophilic reagents, 2-(2-hydroxyethyl)thiophene (2), benzyl alcohol (3) and 1,1,3,3-tetramethylguanidine (4) were investigated. The reactions, using an excess of NaH, in THF solutions, under refluxing conditions and with 1:2?mole ratios allow the synthesis of the following novel cyclotriphosphazene derivatives: 2,4-dichloro-2,4-(hexane-1,6-dioxy)-6,6-[2-(2-ethoxy)hiophene]-cyclotriphosphazatriene, N₃P₃Cl₂[O(CH₂)₆O-(C₆H₈OS)₂] (5); 2,4-(hexane-1,6-dioxy)-2,4,6,6-[2-(2-ethoxy) thiophene]-cyclotriphosphazatriene, N₃P₃[O(CH₂)₆O-(C₆H₈OS)₄] (6); 2,4-dichloro-2,4-(hexane-1,6-dioxy)-6,6-(methoxybenzene)-cyclotriphosphazatriene, N₃P₃Cl₂[O(CH₂)₆O-(C₆H₅CH₂O)₂] (7); 2,4-(hexane-1,6-dioxy)-2,4,6,6-(methoxybenzene)-cyclotriphosphazatriene, N₃P₃[O(CH₂)₆O-(C₆H₅CH₂O)₄] (8); and 2,4-dichloro-2,4-(hexane-1,6-dioxy)-6,6-(1,1,3,3-tetramethyguanidine)-cyclotriphosphazatriene, N₃P₃Cl₂[O(CH₂)₆O-HN-CN₂(CH₃)₄] (9). The structures of the synthesized compounds (5–9) have been characterized by elemental analysis, TLC-MS, ¹H, ¹³C and ³¹P {+¹H} and {?¹H} NMR spectral data.