Synthesis Of Trans Research Articles

Synthesis of Tris(trifluoromethyl)nickelates(II)—Coping with “The C2F5 Problem”

Synthesis of Tris(trifluoromethyl)nickelates(II)—Coping with “The C2F5 Problem”

Synthesis of tris(2-hydroxyethyl)ammonium complex derivatives of glutaric acid and study of their stimulating effect on plant seeds

Synthesis of tris(2-hydroxyethyl)ammonium complex derivatives of glutaric acid and study of their stimulating effect on plant seeds

Synthesis of tris- and pentakis(tetra-armed cyclen) and their complexing properties towards silver(I) ions

Synthesis of tris- and pentakis(tetra-armed cyclen) and their complexing properties towards silver(I) ions

Synthesis of Tris[2‐(dimethylamino)ethyl]amine with Regiospecific Deuterium Labels

AbstractSimple synthetic routes to regioselectively deuterated tris[2‐(dimethylamino)ethyl]amine (Me6TREN) variants are described. Imine formation with formaldehyde‐d2 from tris(2‐aminoethyl)amine (TREN) and subsequent reductions with NaBD4 afforded N[CH2CH2N(CD3)2]3 or d18‐Me6TREN in 79 % yield. A trisubstitution protocol from 2‐bromo‐N,N‐dimethylacetamide and ammonium carbonate and subsequent reduction of the N(CH2CONMe2)3 intermediate by lithium aluminum deuteride has afforded N[CH2CD2N(CH3)2]3 or (d6‐arm)‐Me6TREN in three steps and 52 % overall yield. A similar protocol from 2‐bromo‐N,N‐dimethyl‐d2‐acetamide, obtained in two steps from d4‐acetic acid, with reduction of the N(CD2CONMe2)3 intermediate by lithium aluminum hydride has afforded N[CD2CH2N(CH3)2]3 or (d6‐cap)‐Me6TREN in four steps and 13 % overall yield from CD3COOD.

Tris(ortho-carboranyl)borane: An Isolable, Halogen-Free, Lewis Superacid.

The synthesis of tris(ortho-carboranyl)borane (BoCb3 ), a single site neutral Lewis superacid, in one pot from commercially available materials is achieved. The high fluoride ion affinity (FIA) confirms its classification as a Lewis superacid and the Gutmann-Beckett method as well as adducts with Lewis bases indicate stronger Lewis acidity over the widely used fluorinated aryl boranes. The electron withdrawing effect of ortho-carborane and lack of pi-delocalization of the LUMO rationalize the unusually high Lewis acidity. Catalytic studies indicate that BoCb3 is a superior catalyst for promoting C-F bond functionalization reactions than tris(pentafluorophenyl)borane [B(C6 F5 )3 ].

Tris(ortho‐carboranyl)borane: An Isolable, Halogen‐Free, Lewis Superacid

AbstractThe synthesis of tris(ortho‐carboranyl)borane (BoCb3), a single site neutral Lewis superacid, in one pot from commercially available materials is achieved. The high fluoride ion affinity (FIA) confirms its classification as a Lewis superacid and the Gutmann‐Beckett method as well as adducts with Lewis bases indicate stronger Lewis acidity over the widely used fluorinated aryl boranes. The electron withdrawing effect ofortho‐carborane and lack of pi‐delocalization of the LUMO rationalize the unusually high Lewis acidity. Catalytic studies indicate that BoCb3is a superior catalyst for promoting C−F bond functionalization reactions than tris(pentafluorophenyl)borane [B(C6F5)3].

Regioselective access to orthogonal Diels-Alder C60 bis-adducts and tris-heteroadducts via supramolecular mask strategy

The regioselective polyfunctionalization of highly symmetric spherical I h -C 60 is extremely challenging and usually leads to the formation of regioisomeric mixtures not amenable for high-pressure liquid chromatography (HPLC) purification. Here, we pioneer the use of tetragonal prismatic nanocapsules to perform selective Diels-Alder (DA) functionalization of encapsulated I h -C 60 using acenes. The supramolecular mask allows the regioselective synthesis of either e,e -bis-anthracene-C 60 (functionalization at 90°) or the synthesis of trans -1-bis-pentacene-C 60 (functionalization at 180°) by changing only the acene length. Moreover, the mask strategy allows one to obtain unprecedented equatorial hetero-tris-functionalized-C 60 adducts combining Diels-Alder with Bingel mask regiofunctionalization. Computational modeling provides crucial insights to rationalize the regioselective control exerted by the supramolecular mask on the successive DA cycloadditions. Molecular dynamics (MD) simulations revealed significant differences in the host-guest interactions and equilibrium established between the first-formed anthracene- and pentacene-based mono-adducts with the nanocapsule, which finally determine the observed orthogonal regioselectivity. • Orthogonal synthesis of Diels Alder bis-C 60 adducts via supramolecular masks • Acene-length-dependent isolation of e,e -bis-anthracene-C 60 and trans -1-bis-pentacene-C 60 • Equatorial hetero-tris-functionalized-C 60 adducts combining Diels-Alder with Bingel reactions • Computational modeling as key tool to rationalize the role of supramolecular masks Supramolecular masks can be used to prepare C 60 regioselectively. Pujals et al. use tetragonal prismatic nanocapsules to control the Diels-Alder reaction of encapsulated C 60 with acenes, achieving orthogonal switching from 90° ( e,e -bis-anthracene-C 60 ) to 180° ( trans -1-bis-pentacene-C 60 ) functionalization by enlarging the acene and providing access to equatorial tris-heteroadducts via Bingel cyclopropanation of encapsulated mono- or bis-Diels-Alder adducts.

The Synthesis of Tris(silyl)silanides Revisited. A Study of Reactivity and Stability

AbstractIn this contribution, we investigated the stability of (H3Si)3SiLi (2a) in the presence of tetramethylethylenediamine (TMEDA) and 1,2‐bis(diphenylphosphino)ethane (DPPE). Moreover, the synthesis to obtain tris(silyl)silanides with alternated counter ions by the base mediated desilylation approach was described. Additionally, metal‐metal exchange reactions of 2 a with MgBr2, ZnCl2, HgCl2 were examined. Subsequently, we reacted 2 a with 1.0 and 0.5 equivalents of ZnCl2[TMEDA] and could obtain the isolable zinc substituted silanides 5 a,b. Finally, we reacted 2 a with equimolar amounts of [(MesNacnac)MgI(OEt2)] and [(DippNacnac)MgI(OEt2)] and found the selective transmetalation to the corresponding magnesium substituted silanides 6 a,b in good yields. Interestingly, for compounds 5 a,b and 6 a,b the removal of the reaction solvents did not induce a degradation. For compound 6 a crystals suitable for X‐ray analysis could be grown, which represents the first structural characterization of an isolable perhydrogenated hypersilanide.

Heterodi-, -tri- and -tetrametallic Transition-Metal-Complexes

Complexes trans-[Pt(CCMc)2(PBu3)2)] (Mc = Fc = Fe(ƞ5-C5H4)(ƞ5-C5H5) (3), [1,2] Mc = Rc = Ru(ƞ5-C5H4)(ƞ5-C5H5) (4)) were synthesized by treatment of cis-[PtCl2(PBu3)2] with McCCH (Mc = Fc (1), Rc (2)). The synthesis of trans-[Pt(PR3)2(CCFc)(CCRʹ)] (R = Bu: Rʹ = H (7a), Rʹ = PPh2 (7b), Rʹ = Rc (7c); R = Ph: Rʹ = 4-C5H4N (8a), Rʹ = C6H4-4-CN (8b), Rʹ = 2,2ʹ-bipyridin-5-yl (8c), Rʹ = C6H4-4-CCH (8d)) was realized by the reaction of trans-[PtCl(PR3)2(CCFc)] (R = Bu (5), R = Ph (6)) with alkynes HCCRʹ. Treatment of 8a with [RuCl2(cymene)]2 (cymene = η6-1-Me-4-iPr-C6H4) or [Rh(η5-C5Me5)Cl2]2 and of 8c with [Mo(CO)4(2,5-norbornadiene)] or [Mn(CO)5Br] led to heterotrimetallic trans-[Pt(PPh3)2(CCFc)(CCRʹ-{M})] (Rʹ = 4-C5H4N: {M} = Ru(η6-cymene)Cl2 (10a), = Rh(η5-C5Me5)Cl2 (10b); Rʹ = 2,2ʹ-bipyridin-5-yl: {M} = Mo(CO)4 (11a), = Mn(CO)3Br (11b)). When 8b,c were reacted with [{[Ti](µ-σ,π-CCSiMe3)2}Cu(MeCN)][PF6] ([Ti] = Ti(η5-C5H4SiMe3)2) then heterotetrametallic trans-[Pt(PPh3)2(CCFc)(CCRʹ-{M})][PF6] ({M} = [Ti](µ-σ,π-CCSiMe3)2Cu: R’ = 2,2ʹ-bipyridin-5-yl (11c), Rʹ = -C6H4-4-CN (11d) were produced. Compounds 3, 4 and 7c were characterized by single-crystal X-ray diffraction studies establishing the trans arrangement at Pt. The electrochemical behaviour of all compounds was investigated by CV showing reversible redox events for Fc in 3, 7a,c, 8a−d, 10a,b, 11b,c in the range of E°1′ = -120 − -85 mV, while M feature irreversible redox processes between 745 and 1230 mV.

Air-stable aryl derivatives of pentafluoroorthotellurate.

We report on two different sets of air-stable derivatives of pentafluoroorthotellurate containing fluorinated and non-fluorinated aryl groups. The acid cis-PhTeF4OH was obtained in gram scale and further transformed to Ag[cis-PhTeF4O], which was used as a cis-PhTeF4O transfer reagent to obtain [PPh4][cis-PhTeF4O]. Furthermore, the synthesis of trans-(C6F5)2TeF3OH was achieved by a selective hydrolysis of trans-(C6F5)2TeF4 in the presence of KF and subsequent protonation by aHF. Quantum-chemical calculations show a higher acidity and robustness against fluoride abstraction for trans-(C6F5)2TeF3OH compared to cis-PhTeF4OH.

Synthesis of trans- methyl ferulate bearing an oxadiazole ether as potential activators for controlling plant virus

A series of new ferulic acid derivatives bearing an oxadiazole ether was synthesized by introducing a structure of oxadiazole into trans-ferulic acid via an ether linkage. The synthesized target compounds were evaluated in vivo for their anti-TMV (tobacco mosaic virus) activity, which indicated that some synthesized compounds displayed strong activity for controlling TMV. For protective activity, compounds 6f and 6h had the most activities of 65% and 69.8% at 500 mg L-1, respectively. Compounds 6a, 6b, 6e, 6f and 6h showed > 60% curative activities at 500 mg L-1. Preliminary proteomics analysis showed that compound 6h could regulate the phenylpropanoid biosynthesis pathway and chloroplast function. These results indicated that synthesized novel ferulic acid derivatives could be used for controlling TMV.

Synthesis of tris(3-pyridyl)aluminate ligand and its unexpected stability against hydrolysis: revealing cooperativity effects in heterobimetallic pyridyl aluminates.

We report the elusive metallic anion [EtAl(3-py)3]- (3-py = 3-pyridyl) (1), the first member of the anionic tris(3-pyridyl) family. Unexpectedly, the lithium complex 1Li shows substantial protic stability against water and alcohols, unlike related tris(2-pyridyl)aluminate analogues. This stability appears to be related to the inability of the [EtAl(3-py)3]- anion to chelate Li+, which precludes a decomposition pathway involving Li/Al cooperativity.

Synthesis of Tris(arylphosphite)-ligated Cobalt(0) Complexes [Co2(CO)6{P(OAr)3}2], and their Reactivity towards Phenylacetylene and Diphenylacetylene

The dinuclear complexes [Co2(CO)6{P(OAr)3}2] (1a, Ar = Ph; 1b, Ar = o-Tol) were prepared and reacted with PhC≡CH and PhC≡CPh to yield dimetallatetrahedranes [{(ArO)3P}(OC)2Co-Co(μ-RC≡CPh)(CO)2{P(OAr)3}] (3a, Ar = Ph, R = H; 3b, Ar = o-Tol, R = H; 3c, Ar = Ph, R = Ph; 3d, Ar = o-Tol, R = Ph). The main reaction of diphenylacetylene was accompanied by a side reaction, leading to the dissociation of a P(OAr)3 ligand for the formation of mono(phosphite) complexes [{(ArO)3P}(OC)2Co-Co(μ-PhC≡CPh)(CO)3] (2b, R = Ph; 2d, R = o-Tol). The crystal structures of 1b, 3a, and 3d were determined along with that of the mono(phosphite) complex [{(PhO)3P}(OC)2Co-Co(μ-PhC≡CPh)(CO)3] 2b.

Synthesis, Thermal, and Optical Properties of Tris(5‐aryl‐1,3,4‐oxadiazol‐2‐yl)‐1,3,5‐triazines, New Star‐Shaped Fluorescent Discotic Liquid Crystals

The synthesis of tris(aryloxadiazolyl)triazines (TOTs), C 3‐symmetrical star‐shaped mesogenes with a 1,3,5‐triazine center, 5‐phenyl‐1,3,4‐oxadiazole arms, and various peripheral alkoxy side chains is reported. Threefold Huisgen reaction on a central triazine tricarboxylic acid and suitable aryltetrazoles yields the title compounds. Selected analogues with a benzene center are included in this study and allow for an evaluation of the impact of the central unit on the physical properties. Thermal (differential scanning calorimetry, DSC; polarization optical microscopy, POM), optical (UV/Vis, fluorescence), electric (time of flight, TOF), and structural (single crystal; wide‐angle X‐ray scattering, WAXS) properties of these compounds were investigated. The modification of alkoxy chain length and substitution pattern allows for a tuning of the physical properties. TOTs emit blue to yellow light, depending on conjugation length, donor–acceptor substitution, and solvent polarity, whereas concentration quenches and aggregation enhances the emission. The width of the mesophases is typically around ΔT=100–150 K but can even exceed 220 K. Polarization optical microscopy and X‐ray diffraction on oriented filaments reveal that TOTs are highly ordered liquid crystals (LCs) with long‐range hexagonal columnar structure.

Microwave-induced new synthesis of trans and cis 3-phenylthio-4-carboethoxy β-lactams

Microwave-induced new synthesis of trans and cis 3-phenylthio-4-carboethoxy β-lactams

Glycosylated zinc phthalocyanine-gold nanoparticle conjugates for photodynamic therapy: Effect of nanoparticle shape

In this work, we report on the synthesis of tris-[(2,2,7,7-tetramethyltetrahydro-3aH-bis([1,3]dioxolo)[4,5-b:4′,5′-d]pyran-5-yl)methoxy)-2-(4-benzo[d]thiazol-2-ylphenoxyphthalocyaninato] zinc(II) (complex 3) and its linkage to gold nanoparticles (AuNPs) of different shapes through S-Au/N-Au self-assembly. The conjugates of complex 3 (with both gold nanorods (AuNR) and nanospheres (AuNS)), displayed decreased fluorescence quantum yield with corresponding improved triplet and singlet quantum yields compared to complex 3 alone, however 3-AuNR showed improved properties than 3-AuNS. Complex 3 showed relatively low in vitro dark cytotoxicity against the epithelial breast cancer cells with cell survival ≥ 85% at concentration ≤ 160 μg/mL but afforded reduced photodynamic therapy activity which may be due to aggregation. 3-AuNR afforded superior PDT activity with <50% viable cells at concentration ≥ 40 μg/mL in comparison to 3-AuNS with <50% viable cells at concentration ≥ 80 μg/mL. The superior activity of 3-AuNR is attributed to the photothermal therapy effect since nanorods absorb more light at 680 nm than nanospheres.

Synthesis, crystal structures and magnetic properties of two iron (II) tris(pyridyl)phosphine selenides complexes

ABSTRACTWe reported the synthesis of tris(pyridyl)phosphine selenide (TppSe) and tris(4-methylpyridin-2-yl)phosphine selenide (MeTppSe), which were prepared by a simple and straightforward one-pot method with red phosphorus in a KOH/DMSO suspension, and treatment of resulted phosphines with selenium in hot toluene. These compounds were characterized by mass spectroscopy, 1H, 13C and 31P NMR spectroscopies and the structure of MeTppSe was characterised by a single-crystal X-ray diffraction. Furthermore, The reactions of selenides with Fe(ClO4)2·6H2O afforded two new iron(II) mononuclear metal complexes [Fe(TppSe)2][ClO4]2·3DMF (1) and [Fe(MeTppSe)2][ClO4]2·2DMF (2). Detailed structural analyses and magnetic susceptibility measurements confirm no spin transition from low-spin to the high-spin state between 2 and 300 K in two iron(II) complexes.

Synthesis of Trans- andcis-2-acetyl-3-phenyl-3,3a,4,5-tetrahydro-2H-benzo[g] Indazoles: Evaluation as Inhibitors of β-hematin Formation

Several trans- and cis-2-acetyl-3-(substituted-phenyl)-3,3a,4,5-tetrahydro-2 H-benzo[ g]indazole derivatives have been synthesised via the condensation of the appropriate exocyclic α,β-unsaturated ketones with hydrazine in hot acetic acid, to obtain diastereomeric mixtures of N-acetylated isomers. Structure elucidation was based on their spectral data and the trans–cis stereochemistry using of NOE and NOESY experiments. Biological testing of these derivatives as inhibitors of β-hematin formation was carried out.

Solvent-free synthesis of tris(4-hydroxybutyl acrylate) phosphate in the presence of 1-methylimidazole

In this paper, we present the synthesis of tris(4-hydroxybutyl acrylate) phosphate using 1-methylimidazole as acid scavenger for hydrochloric acid by-product, when an ionic liquid is formed. The synthesis was performed in the absence of any organic solvent. The yield is 83% for ester. The phosphate was characterized by 1H–31P NMR and FTIR. The obtained phosphate is appropriate monomer for UV curing in the presence of photoinitiator. The obtained polymer was characterized by thermal analysis and LOI. The results showed good thermal stability and flame retardancy of UV-cured polymer.

学生実験教材としてのトリス(オキサラト)鉄(III) : 錯体の合成とその青写真への応用

学生実験教材としてのトリス(オキサラト)鉄(III) : 錯体の合成とその青写真への応用