Archives for Chemistry Experiments of C4H10O2

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Effect of Methyl Substitution on Conformation and Molecular Arrangement of BEDT-TTF Derivatives in the Crystalline Environment

Two methylated bis(ethylenedithio)tetrathiafulvalene (ET) derivatives, Me2ET and Me4ET were stereoselectively synthesized to examine the effect of methylation on conformations of dihydrodithiin rings and molecular arrangements in the crystalline state.Since the donating ability of Me2ET and Me4ET are similar to that of ET, the methylated ET derivatives are considered to be appropriate to investigate the “lattice pressure” effect on ET radical salts by changing the volume of donor molecules.The upper limit of an activation energy for the ring inversion of the dimethylated dihydrodithiin in solution was estimated to be 32 kJ mol-1 by 13C NMR spectroscopy.The X-ray structure analyses revealed that orientations of methyl groups are fixed to axial in Me2ET and to equatorial in Me4ET, accompanied by the change of molecular stacking.The “volume of a methyl group” was evaluated by comparing the molecular volumes of Me2ET and Me4ET with that of ET, and the effective volume for the axial methyl group turns out to be 15percent larger than that of the equatorial.The solid state 13C NMR (CP/MAS) spectra of ET and its derivatives showed that the chemical shifts of resonance lines reflect the conformations of dihydrodithiin rings in crystals.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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NMR determination of the absolute configuration of chiral 1,2- and 1,3-diols

Each of the chiral 1,2- and 1,3-diols examined was derivatized exclusively to a single diastereomeric acetal by the use of a new axially chiral reagent, 2?-methoxy-1,1?-binaphthalene-8-carbaldehyde (MBC). The absolute configuration of the original 1,2- and 1,3-diols was determined by the NOE correlation between the proton signals of the reagent moiety and those of the diol moiety in the acetals.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

Simple exploration of (S)-Propane-1,2-diol

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The regioselective and stereospecific substitution of unsymmetrical 1,2-diols using the 1,3,2lambda5-dioxaphospholane methodology

Stereo specific tosylate (-OTs) or azide (N3-) substitution at the C-4 stereocenter of a monosubstituted 1,3,2lambda5-dioxaphospholane (the equivalent of the C-2 stereocenter in an unsymmetrical 1,2-diol) is readily achieved by treatment with either P-toluenesulfonic acid (P-TsOH) in tetrahydrofuran solvent or P-TsOH/sodium azide in acetonitrile solvent, respectively.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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First enantiopure calix[6]aza-cryptand: Synthesis and chiral recognition properties towards neutral molecules

The synthesis of the first enantiopure calix[6]aza-cryptand was achieved in five steps from the known 1,3,5-tris-O-methylated calix[6]arene. A 1H NMR spectroscopic study has shown that the chiral tren cap constrains the calixarene core in a straight cone conformation ideal for host-guest chemistry applications. As a result, the tetra-protonated derivative displays remarkable host properties towards polar neutral molecules and enantioselective recognition processes have been evidenced with chiral guests.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

Properties and Exciting Facts About C3H8O2

Future efforts will undeniably focus on the diversification of the new catalytic transformations. These may comprise an expansion of the substrate scope from aromatic and heteroaromatic compounds to other hydrocarbons. Keep reading other articles of 4254-15-3! Synthetic Route of 4254-15-3

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Enhanced cooperative activation effect in the hydrolytic kinetic resolution of epoxides on [co(salen)] catalysts confined in nanocages

(Chemical Equation Presented) Being cagey: More than two chiral [Co-(salen)] catalyst molecules can be confined in one nanocage of SBA-16 by reducing the pore entrance size by silylation. The [Co(salen)]/SBA-16 catalysts with more than two [Co(salen)] complexes in each cage show a significantly enhanced cooperative activation effect and exhibit much higher activity than the homogeneous [Co(salen)] catalyst in the hydrolytic kinetic resolution of epoxides (see scheme).

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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Asymmetric, catalytic, and direct self-aldol reaction of acetaldehyde catalyzed by diarylprolinol

(Chemical Equation Presented) An asymmetric, catalytic, and direct self-aldol reaction of acetaldehyde was catalyzed by diarylprolinol in NMP, affording the trimer acetal, which was generated by the reaction of the self-aldol product with another acetaldehyde molecule in a moderate yield with good enantioselectivity. Acetal is the synthetic equivalent of the self-aldol product, which can be converted into other synthetically useful compounds in one pot without compromising the enantioselectivity.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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Experiments Directed Towards the Synthesis of Anthracyclinones. XVI Tin(IV)- and Titanium(IV)-Mediated Cyclizations of ortho-Allyl-Substituted Homochiral Hydroxyanthraquinone Dioxolans

Tin(IV) chloride and titanium(IV) chloride mediated cyclizations of the ortho-allyl-substituted homochiral hydroxyanthraquinone acetals (7)-(10), prepared by optimized reductive Claisen rearrangements, have afforded monochloro and dichloro tetracyclic products, the stereochemistry of which has been assigned by using n.m.r. techniques.An SN2-like process in which the dioxolan ring is maintained as an ion pair intermediate is favoured when either tin(IV) chloride or titanium(IV) chloride is used at -78 deg.Thereafter the direction of addition of chloride at C9 is largely governed by the orientation of this ion pair.An alternative path which probably involves a free oxocarbenium ion predominates at higher temperatures.An adjacent methoxy group on the anthraquinone lowers the stereoselectivity at both C7 and C9, possibly by bidentate coordination of the Lewis acid involving the quinone carbonyl, the methoxy oxygen and the acetal oxygens.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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Efficient general synthesis of 1,2- and 1,3-Diols in high enantiomeric excess via the intramolecular asymmetric reduction of the corresponding ketoalkyl diisopinocampheylborinate intermediates

The first successful asymmetric reduction of unhindered aliphatic ketones with B-chlorodiisopinocampheylborane is reported. In contrast to the reduction in high ee of aralkyl ketones, such as acetophenone, with the reagent, the reduction of unhindered dialkyl ketones, such as 3-methyl-2-butanone, provides only poor ee. However, treatment of alpha- and beta-hydroxyketones with one equiv of diisopnocampheylborane or B-chlorodiisopinocampheylborane rapidly produces the corresponding ketoalkyl diisopinocampheylborinate intermediates, which then undergo facile intramolecular reduction. This reaction sequence, followed by oxidative workup, provides a general synthesis of 1,2- and 1,3-diols in 84?99% enantiomeric excess.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

Properties and Exciting Facts About (S)-Propane-1,2-diol

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PROCESS FOR THE PRODUCTION OF ALKANEDIOL DERIVATIVES

The present invention provides a process for producing an alkanediol derivative represented by the general formula (II) from an ester compound represented by the general formula (I), safely without giving rise to racemization.The present invention lies in a process for producing an alcohol derivative represented by the following general formula (II):(wherein R2and R3are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; X is a hydrogen atom or a protecting group for hydroxyl group; and n is 0 or 1), which process comprises reducing an ester compound represented by the following general formula (I):(wherein R1is an alkyl group having 1 to 4 carbon atoms; and R2, R3, X and n have the same definitions as given above) with sodium borohydride in a mixed solvent of at least one kind of solvent selected from the group consisting of aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons and a primary alcohol.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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Chirality driven metallic versus semiconducting behavior in a complete series of radical cation salts based on dimethyl-ethylenedithio- tetrathiafulvalene (DM-EDT-TTF)

Enantiopure (S,S) and (R,R) dimethyl-ethylenedithio-tetrathiafulvalene (DM-EDT-TTF) 1 donors are synthesized by cross coupling followed by decarboxylation reactions. In the solid state the methyl groups are arranged in axial positions within sofa-type conformation for the six-membered rings. Crystalline radical cation salts formulated as [(S,S)-1]2PF 6, [(R,R)-1]2PF6, and [(rac)-1] 2PF6 are obtained by electrocrystallization. When the experiment is conducted with enantioenriched mixtures both enantiopure and racemic phases are obtained. The monoclinic enantiopure salts, containing four independent donors in the unit cell, show semiconducting behavior supported by band structure calculations of extended Hueckel type. The racemic salt contains only one independent donor in the mixed valence oxidation state +0.5. Under ambient pressure the racemic material is metallic down to 120 K, while an applied pressure of 11.5 kbar completely suppresses the metal-insulator transition. Band structure calculations yield an open Fermi surface, typical for a pseudo-one-dimensional metal, with unperfected nesting, thus ruling out the possibility of charge or spin density modulations to be at the origin of the transition. Raman spectroscopy measurements, in agreement with structural analysis at 100 K, show no indication of low-temperature charge ordering in the racemic material at ambient pressure, thus suggesting Mott-type charge localization for the observed metal-insulator transition.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate