某些二烃基锡(IV)衍生物的穆斯堡尔谱和配位结构

合成了五个新的(β-甲氧羰基乙基)锡的衍生物,它们是R2Sn(acac)2(R≡CH3CCOCH2CH2),R2Sn(dbm)2,R2SnO,R2[1]Sn(dbm)2,[R1=CH3OCOCH(CH3)CH2)和R2[1]SnO.测定了这些化合物的1HNMR,IR和穆斯堡尔谱数据。比较了这些化合物与R2SnCl2,R2[1]SnCl2,(C8H17)2SnCl2和(C8H17)2Sn(OCOC11H23)2的有关结构数据。     

Acetylenic Peroxides Derived from 4,4'-Biphenyldicarboxylic Acids

Lithium peroxyacetylides were reacted with Paraform to obtain lithium peroxyalcoholates. The latter react with 4,4'-biphenyldicarboxylic and 2,2'-sulfonyl-4,4'-biphenyldicarboxylic dichlorides, yielding peroxy-containing esters. Lithium peroxyacetylides react with 4,4'-biphenyldicarboxylic and 2-methoxy- and 2,2'-sulfonyl-4,4'-biphenyldicarboxylic acids to form acetylenic biphenyldihydroxytetraperoxides.     

Mixed dialkyltin(IV) trifluoroacetates

Mixed dialkytin(IV) trifluoroacetates,Me EtSn(O₂CCF₃)₂,Et Pr ⁿ Sn(O₂CCF₃)₂ andPr ⁿ Bu ⁿ Sn(O₂CCF₃)₂ have been prepared by metathetical reactions of the corresponding dialkyltin(IV) chlorides with silver trifluoroacetate in CH₂Cl₂. They are monomeric in benzene and nonconducting inMeNO₂ andMeCN. Bidentate trifluoroacetate groups are indicated by their IR spectra.Mössbauer spectra confirmtrans-arrangement of theR-Sn-R moiety.¹H,¹⁹F NMR and mass spectra are also discussed.

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Gemischte Dialkylzinn(IV)-trifluoracetate

Zusammenfassung Die gemischten Dialkylzinn(IV)-trifluoroacetateMe EtSn(O₂CCF₃)₂,Et Pr ⁿ Sn(O₂CCF₃)₂ undPr ⁿ Bu ⁿ Sn(O₂CCF₃)₂ wurden über Metathese-Reaktionen der entsprechenden Dialkylzinn(IV)-chloride mit Silbertrifluoracetat in CH₂Cl₂ dargestellt. Sie sind monomer in Benzol und nichtleitend inMeNO₂ undMeCN. Die IR-Spektren zeigen zweizähnige Trifluoracetat-Gruppen an. DieMössbauer-Spektren bestätigen dietrans-Anordnung derR-Sn-R-Einheit. Die¹H-,¹⁹F-NMR und die Massenspektren werden ebenfalls diskutiert.

     

Synthesis of some novel heterocyclic dyes derived from pyrazole derivatives

Diazotized aryl amines were coupled with 3-substituted 5-amino pyrazoles to produce a series of novel 3-substituted 5-amino-4-arylazopyrazoles. Also, 3-substituted 5-amino-pyrazoles were diazotized and coupled with different phenols to give the corresponding novel 3-substituted 5-aryl azo pyrazoles. These dyes were characterized by elemental analysis and spectral data, applied to different types of fibres (wool, polyester and a blend of wool/polyester as disperse dyes) and their fastness properties were evaluated.     

Copolymers derived from rapeseed derivatives via ADMET and thiol-ene addition

Novel (co)polymers were synthesized from substances obtained from rapeseed via ADMET and thiol-ene additions. α,ω-Dienes derived from oleic and erucic acid were copolymerized with a ferulic acid derivative, a representative phenolic acid (p-hydroxycinnamic acid) present, for instance, in rapeseed cake. Copolymers with different ratios of these monomers were prepared via two different routes (ADMET and thiol-ene) and studied in detail. Both monomer and polymer synthesis were optimized in order to achieve high yielding synthetic procedures that meet the requirements of green chemistry. Some thermal properties of the resulting copolymer series were then studied and correlated to the co-monomer composition.     

Crown ethers derived from cyclodextrin: Interaction with triphenylmethane derivatives

Periodate oxidation followed by borohydride reduction of beta cyclodextrin results in crown ether type derivatives. The polyaldehyde obtained by periodate oxidation has been reduced to polyalcohol and converted to a permethylated derivative. These macrorings are much more flexible than beta cyclodextrin itself.The interaction of beta cyclodextrin (-CD), methylated beta cyclodextrin (DIMEB), polyalcohol and permethylated crown ethers derived from beta cyclodextrin with two triphenylmethane, derivatives and their triphenyltin analogues has been studied. On the basis of the changes in the UV spectra and the solubility enhancement it can be concluded that cyclodextrins (-CD and DIMEB) form complexes only with the triphenylmethane, derivatives. On the other hand the crown ethers prepared from -CD give complexes only with the triphenyltin derivatives.     

Synthesis of some novel sulfonyl ester derivatives derived from d-mannitol

The preparation of sulfonate-derivatives of d-mannitol i.e. 1,2:3,4-di-O-isopropylidene-3,4-di-O-p-toluenesulfonate-d-mannitol (3a), 1,2:3,4-di-O-isopropylidene-3,4-di-O-methanesulfonate-d-mannitol (3b), and 1, 2:3,4-di-O-isopropylidene-3,4-di-O-trifluoromethanesulfonate-d-mannitol (3c) is described. Full characterization and methodologies of these sulfonate-d-mannitol derivatives have been described as well.     

Nitroxide and anion radicals derived from isatogen and related indole derivatives

Neutral indolic nitroxides were obtained by oxidation of 1-hydroxyindoles with lead dioxide. Anion indolic nitroxides were obtained by reduction of indoline-N-oxides in DMSO/t-BuOK (reducing agent being the CH₃SOCH₂^? anion). In both cases an a^N of about 6 gauss was found. This value, which differs from values previously reported, is justified in the course of the work. Some other anion radicals derived from bi-indolic derivatives are also reported and their structures discussed on the basis of MO calculations or by comparison with analogous examples.     

Epoxyperoxides from Reaction of Allylic Peroxides with Potassium Alkylperoxylates

Addition of potassium hydroxide to a THF solution of an alkyl hydroperoxide and an allylic peroxide having an electron-poor double bond yielded the formation of epoxyperoxide. Such a heterocycle was generated via the. Michael addition of the peroxylate to the activated double bond of the unsaturated peroxide followed by an SNI at the O-O bond.     

Heterocycles derived from the condensation of 1,3-propanediamine with phthalic acid derivatives

The condensation of phthalic anhydride with 1,3-propanediamine afforded N-(o-carboxybenzoyl)-1,3-propanediamine (I) which by intravolecular cyclization was transformed into 2,3,4,6-b-tetrahydropyrimido[2,1-a]isoindol-6-one (II) rather than the benzodiazonine (III). An intermediate in the condensation is proposed. The reaction of 1,3-propanediamine with dimethyl phthalate also did not afford III, but rather a more complex product, dibenzo[c,l]-1,6,10,15-tetraazacyclooctadecane-5,11,16,22-tetraone (IX). Reaction of 1,3-propanediamine with phthaloyl chloride gave 6,13-propanodibenz[c,h]-1,6-diazecine-5,7,12,14-tetrone (XII). Spectroscopic data of the heterocycles obtained and chemical properties of II are given.     

Stable organogels derived from triazines functionalized with chiral α-amino acid derivatives

Triazines functionalized with three stereogenic α-amino-acidic appendages having at least one amide or hydroxamate function give highly stable organogels in haloalkanes and aromatic solvents, and their gelating ability depends on both structural and stereochemical properties.     

Proline derivatives incorporating hydrophobic long-chain derived from natural and synthetic fatty acids

The α-hydrophobic long chain-α-amino esters are prepared by α-hydroxylation of a series of fatty acid esters [derived from oleic acid (OA), linoleic acid (LA), arachidonic acid (ARA) and docosahexaenoic acid (DHA)] followed by Mitsunobu reaction and hydrazinolysis of the phthalimide. These amino esters are mixed with aldehydes and electrophilic alkenes to give very good chemical yields and diastereoselectivities of prolinate derivatives incorporating a hydrophobic long chain at the α-position. This multicomponent 1,3-dipolar cycloaddition (1,3-DC) takes place at room temperature. The synthesis of the homologue hydrophobic chain of OA is performed by its oxidation to aldehyde/racemic N-tert-butylsulfinyl imine/Neff reaction. Final 1,3-DC with benzaldehyde and N-methylmaleimide affords homologue prolinate derivative in good yield.     

Synthesis and biological evaluation of hydrazone and pyrazoline derivatives derived from androstenedione

Research on Chemical Intermediates - Here, two series of 17-hydrazone derivatives and D-fused pyrazoline derivatives possessing various aromatic heterocycle structures from androstenedione were...     

Synthesis and anticancer activity of geldanamycin derivatives derived from biosynthetically generated metabolites

A new series of geldanamycin derivatives were synthesized using a semi-synthetic approach involving genetically engineered biosynthetic intermediates. These analogues were then evaluated for anti-proliferation activity in human cancer cell lines, SK-Br3 and SK-Ov3. Most of the synthesized compounds exhibited potent in vitro anti-proliferation activity toward both cell lines. Such compounds potently inhibited the expression of the Hsp90 client protein ErbB2.     

Unexpected Novel Pheophytin Peroxides from the Leaves of Biden pilosa

Two new pheophytins, bidenphytins A ( 1 ) and B ( 2 ), with peroxide functionalities on ring E, were isolated from Biden pilosa Linn . var. radiata Sch . Bip ., a popular Taiwanese folk medicine. Also isolated were the following six known compounds: pheophytin a ( 3 ), (13²R)‐13²‐hydroxypheophytin a ( 4 ), (13²S)‐13²‐hydroxypheophytin a ( 5 ), (13²R)‐13²‐hydroxypheophytin b ( 6 ), (13²S)‐13²‐hydroxypheophytin b ( 7 ), and aristophyll‐C ( 8 ). Their structures were elucidated by spectroscopic methods (UV, IR, 1D‐ and 2D‐NMR) and by mass spectrometry (HR‐FAB‐MS). Possible biosynthetic pathways for 1 and 2 are proposed.