Synthesis of Functionalized o‐, m‐, and p‐Terphenyl Derivatives by Consecutive Cross‐Coupling Reactions of Triazene‐Substituted Arylboronic Esters

Triazene‐substituted arylboronic esters were prepared readily from the corresponding aryl magnesium derivatives and shown to function as a new class of donor–acceptor‐substituted coupling reagents. The selective functionalization of these aromatic derivatives led to a wide variety of terphenyl derivatives in which the original bifunctional unit (often further substituted with another functional group) formed the central aromatic ring. The functionalized terphenyl derivatives were formed in two efficient cross‐coupling steps from the triazene‐substituted boronic esters: Suzuki cross‐coupling with an aryl halide was followed by BF₃?OEt₂‐induced palladium‐catalyzed coupling of the diazonium salt generated in situ from the triazene with an arylboronic acid.     

New fluorinated polysiloxanes containing an ester function in the spacer. I. Synthesis and characterization

Unsaturated perfluoroalkyl esters derived from undecylenic acid: CH₂?CH? (CH₂)₈? COO? CH₂? CH₂? R_F (with R_F?C₆F₁₃, 2a and R_F?C₈F₁₇, 2b ) and C₈F₁₇? (CH₂)₁₀? COO? CH₂? CH?CH₂, 2c were prepared with excellent yields. Their hydrosilylation by methylhydrodimethylsiloxane copolymers of various Si? H contents gives new fluorinated polysiloxanes which were examined by ¹H- and ¹³C-NMR, GPC, differential scanning calorimetry, and optical polarizing microscopy. Polymers derived from compounds 2a and 2b exhibit mesomorphic structures. © 1994 John Wiley & Sons, Inc.     

Recent syntheses and reactions of cyclic imidic esters

Δ²-Oxazolines and 4H-5,6-dihydrooxazines are readily obtainable from carboxylic acids and 2- or 3-amino alcohols by gas-phase dehydration, and 4H-dihydrooxazines can also be obtained by condensation of N-(hydroxymethyl) carboxamides with olefins. These cyclic imidic esters undergo reactions in which the ring is cleaved; these reactions include a new type of polymerization. The behavior of alkyl groups in position 2 and the cyclodditions in the 2,3-position also have been studied. Reactions in side chains on position 2 and addition experiments on the sulfur analogues of the cyclic imidic esters are also reported. A table shows the principal infrared bands of substituted Δ²-oxazolines.     

Identification of cis/trans isomers of methyl ester and oxazoline derivatives of unsaturated fatty acids using GC–FTIR–MS

Identification of cis/trans isomers of unsaturated fatty acids cannot usually be achieved by GC-MS (gas chromatography-mass spectrometry) without reference substances. In this study a GC-FTIR-MS system (gas chromatography-Fourier transform-mass spectrometry) was used to identify fatty acid methyl esters (FAMEs) and differentiate between the cis/trans isomers. Besides methyl esters, 2-alkenyl-4,4-dimethyloxazoline derivatives (DMOX), which have been used to locate double bond positions of unsaturated fatty acids, were examined with respect to their suitability for cis/trans differentiation. A combined GC-FTIR-MS system with a wide band (4000–550 cm^?1) mercury cadmium telluride (MCT) detector was used in series and parallel to identify 31 reference unsaturated fatty acids, including 7 pairs of cis/trans isomers. Serum samples of healthy persons and commercially available fish oil were analyzed as examples of complex mixtures. Using splitless injection the detection limit for the less sensitive IR detector was 25 ng/μl in case of the weak cis and trans bands. In the FTIR spectra cis/trans isomers were identified by analysis of bands arising from C? H out-of-plane (oop) bending: for both the FAME and DMOX derivatives cis-1,2-disubstituted double bonds give a strong band near 720 cm^?1 and the corresponding trans isomers near 967 cm^?1. cis Isomers could be identified further by a band at 3012 cm^?1. With the combined data of the GC-FTIR-MS system it is now possible to identify polyunsaturated fatty acids with regard to the discrimination of cis/trans isomers.     

The Synthesis of Novel Methotrexate-like Compounds

Summary. Methotrexate (MTX) is a folate antagonist used in treatment of several chronic inflammatory and neoplastic conditions. In this study, new MTX-like compounds that may-be potential anticancer agents were synthesized and their structures were determined by IR, UV, GC-MS, ¹H NMR, and ¹³C NMR spectra. Also, in this study, a series structurally related to MTX or folate analogous compounds were evaluated whether they have inhibitory properties on the dihydrofolate reductase activity (DHFR).     

TiCl4-promoted addition of nucleophiles to open chain α-amidoalkylphenyl sulfones

Linear α-amidoalkylphenyl sulfones are converted into the corresponding N-acyliminium ions by treatment with TiCl₄ at low temperature and then made to react with different nucleophiles such as allyltrimethylsilane, silyl ketene acetal, anisole and thiophene.     

Synthesis of α1-(Cbz-aminoalkyl)-α2-(hydroxyalkyl)phosphinic esters

A synthesis of α₁-(Cbz-aminoalkyl)-α₂-(hydroxyalkyl)phosphinic esters was achieved by the 1,2-addition of the appropriate aldehyde to Cbz-protected phosphinic analogues of amino acid esters in the presence of at least three equivalents of trimethylsilyl chloride and NEt₃. The complete deprotection of the product esters could be achieved in one step using 35% HBr in acetic acid.     

Cathodic reduction of SO2 in the presence of organic dihalides

The reaction of the electrolytically generated SO ₂ ^– anion radical with 1,-dihalides is used for the synthesis of sulfur containing heterocycles like oxathiolane-, oxathiane-, thiane- and thiepane-oxides. 1,2-Dihalides are reductively deblocked to give olefines.

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Kathodische Reduktion von SO₂ in Gegenwart organischer Dihalogenide

Zusammenfassung Die Reaktion des elektrolytisch erzeugten SO ₂ ^– -Anionradikals mit 1,-Dihalogeniden führt zu schwefelhaltigen Heterocyclen wie Oxathiolan-, Oxathian-, Thian- und Thiepanoxiden. 1,2-Dihalogenide geben durch reduktive Eliminierung Olefine.

     

The influence of micellization ofn-decylamine on its basicity and reactivity toward carboxylic acid esters

Micellization ofn-decylamine in aqueous solution leads to substantial decrease in its pK _a, and increase in its reactivity in the nucleophilic substitution ofp-nitrophenylic esters of carboxylic acids (up to 70 times compared to ethylamine which forms no micelles). The influence of cetylpyridinium bromide on the acid-base properties ofn-decylamine and its reactivity was investigated. It was found that the reaction withn-decylamine can be accelerated or retarded depending on the hydrophobicity of the esters. The quantitative characteristics of the mieellar catalytic processes were estimated.Translated fromIzvestiya Akademii Nauk Seriya Khimicheskaya, No. 2, pp. 366–370, February, 1996.     

Preparation,characterization, and mesophase formation of esters of ethylcellulose and methylcellulose

A range of mixed ether-esters of cellulose was prepared from partially substituted ethylcellulose and methylcellulose. The ¹³C-NMR analysis of ethylcellulose with a DS of 2.5 indicated that the hydroxyl groups at carbon six of anhydroglucose units were completely substituted. Acetylation of the ethylcellulose under different conditions yielded (acetyl) (ethyl) cellulose (AEC) samples with acetyl degree of substitution ranging from 0 to 0.5. Fully substituted (propionyl) (ethyl) cellulose (PEC) and (acetyl) (methyl) cellulose (AMC) were also prepared. Chiral nematic liquid crystals were formed in these mixed ester/ethers of cellulose in concentrated solutions of acidic solvents. The critical concentration for the phase separation of the cellulosic solutions depended on the nature of the substituent, the degree of substitution, and the solvent at a given temperature. Methylcellulose solutions in trifluoroacetic acid and dichloroacetic acid form chiral nematic liquid crystals with a left-handed helicoidal structure. The acetylated methyl cellulose samples did not show the reversal of handedness with increasing acetyl content that was previously observed for the corresponding ethylcellulose samples. © 1994 John Wiley & Sons, Inc.