Synthesis of well-defined multifunctionalized polystyrenes with benzyl bromide moieties by a novel iterative divergent approach

Well-defined chain-end-functionalized polystyrenes with two, four, eight, sixteen, and thirty-two benzyl bromide moieties were synthesized by the methodology based on a novel iterative divergent approach. In this methodology, the entire iterative synthetic sequence involves only two sets of the reactions: a coupling reaction of the terminal benzyl bromide moieties with the functionalized anion prepared from 1,1-bis(3-tert-butyldimethylsilyloxymethylphenyl)ethylene and sec-BuLi and a transformation reaction of the introduced tert-butyldimethylsilyloxymethyl groups into bromomethyl functions by treatment with LiBr-(CH₃)₃SiCl. The iteration started with chain-end-functionalized polystyrene with one benzyl bromide moiety and could be repeated five times. All iterations proceeded quantitatively to afford chain-end-functionalized polystyrenes with a definite number of benzyl bromide moieties up to thirty-two.     

Synthesis of novel well-defined chain-end-functionalized polystyrenes with dendritic chiral ephedrine moieties and their applications as highly enantioselective diethylzinc addition to N-diphenylphosphinoyl arylimines

A series of novel well-defined chain-end-functionalized polystyrenes having 2, 4, 8, and 16 chiral ephedrine moieties dendritically distributed at their hyperbranched chain-ends were quantitatively synthesized. Their well-defined architectures were fully confirmed by elemental analysis, FTIR, SEC as well as by ¹H and ¹³C NMR spectroscopies. These polymers were precisely controlled in the molecular weight and molecular weight distribution as well as well-defined in chain-end-functionalities. These dendritic chiral polymers serve as highly enantioselective chiral ligands in the enantioselective addition of diethylzinc to a series of N-diphenylphosphinoyl arylimines. Among them, chiral dendrimer having eight ephedrine moieties at the chain-ends afforded the corresponding enantiomerically enriched phosphinoylamides in good to high yields with enantioselectivities up to 93% ee. The obtained enantioselectivities are comparable with those obtained by using N-benzylephedrine and its corresponding copolymer as chiral ligands.     

Synthesis and characterization of new polystyrenes containing tributyltin moieties linked to the aromatic ring through a methylenic spacer

Novel polymeric derivatives bearing tributyltin carboxylate moieties in the side chain were synthesized. The coordination at tin in solution and in the solid state was investigated by both Sn‐NMR and FT‐IR: the metal atom appears completely tetracoordinated in chloroform solution, while in the solid state all polymeric products exhibit both tetra‐ and pentacoordination at tin, the latter increasing with the amount of tin containing units. No evidence of tin leaching by hydrolysis of the organometallic ester was observed for these materials. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5372–5383, 2004     

Synthesis of multicyclic and grafted polystyrenes

Well‐defined multicyclic polystyrenes are prepared in two steps. The first step is the preparation of a cyclic difunctional polystyrene by the reaction of α,ω‐dilithiopolystyrene chains with 1,3‐bis(phenylethenyl)benzene. Then, this product is covalently grafted to poly(chloromethylstyrene) chains leading to the formation of a high molar mass product containing linear and cyclic parts. As a model reaction and to optimize the previous reaction, a study of coupling of the linear difunctional model polystyrene with poly(chloromethylstyrene) is performed leading to grafted polystyrene. The grafted products are analyzed by size‐exclusion chromatography, matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry, and liquid chromatography at the exclusion‐adsorption transition point. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2723–2730, 2001     

Synthesis and characterization of a novel well-defined comb-like ionomer

A novel well-defined comb-like ionomer with cations was synthesized by the combination of living anionic polymerization and atom transfer radical polymerization (ATRP). The synthetic approach involves the coupling reaction of polystyrene (PS) backbone bearing 1,1-diphenylethene (DPE) pendant groups with living polystyryllithium (PSLi), subsequent amine functionalization of the resulting 1,1-diphenylmethyl anions with 3-dimethylaminopropyl chloride (DMAPC), and quaternization of tertiary amino groups with hydrochloric acid. The comb-like ionomer was characterized by ¹H NMR, IR, GPC measurements and end-group titrition.     

Question of the complexation of tetrachlorostannane with benzyl chloride

Conclusion The condensation of PhCH₂Cl with the liberation of HCl catalyzed by SnCl₄, occurs in the PhCH₂Cl-SnCl₄. system. The proposal of the existence of a cis-octahedral complex, 2PhCH₂Cl· SnCl₄, was proved erroneous.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2336–2337, October, 1987.     

(Cholestanyloxycarbonyl)benzyl esters as peptide substituents: Conformational properties of fully protected oligo-L-lysines with C-terminal (cholestanyloxycarbonyl)benzyl and benzyl ester moieties

This study involves L-lysine oligo peptides, protected at the N-terminus by the Nps and at the ε-amino functions by Boc groups. Two series were prepared from dimer to octamer, one containing the p-[(cholestan-3β-yloxy)carbonyl]benzyl, the other one the benzyl ester group at the C-terminus. Conformational analyses were performed by IR absorption. The occurrence of the intermolecular β-structure in the solid state and in CH₂Cl₂ solution was demonstrated for the highest oligomers. The relative stabilities of the self-associated species were determined by adding a variety of polar solvents to the CH₂Cl₂ solutions. The cholestanyl-containing peptides have a lower propensity to self-aggregate than the benzyl-ester analogues. Self-aggregation and decreasing solubility run in parallel. It was also directly shown that soluble urea derivatives may disrupt intermolecular H-bonds in CH₂Cl₂, a point of practical interest, particularly in solid-phase peptide synthesis.     

Synthesis of difunctional polystyrenes and their incorporation in block copolymers with bisphenol a polycarbonate

Block polymers of polystyrene and bisphenol A polycarbonate have been prepared and their bulk viscosities studied as functions of both shear stress and polystyrene block length. The polystyrene blocks were α,ω-diacid chlorides prepared from the reaction of “living” polystyrenes with diacid chlorides. These reactions were studied in order to discover the most effective way of preparing the polystyrene diacid chlorides. The polystyrene diacid chlorides are best prepared by reaction of disodiopolystyrene with phosgene. The flow properties of the block copolymers depend on the composition of the polymers but do not depend on the length of the polystyrene blocks.     

Kinetics and mechanism of benzyl chloride reaction with zinc in dimethylacetamide

Oxidative dissolution of zinc in the system of benzyl chloride-dimethylacetamide was investigated. The reaction stereochemistry as well as intermediates and reaction products formed were studied. The kinetic and thermodynamic parameters of the process were measured. The process was shown to follow the Langmuir-Hinshelwood mechanism with the formation of benzyl radicals and mono-solvated organozinc compound on the zinc surface. The components of mixture are adsorbed at various sites of the zinc surface, while recombination and the isomerization of the benzyl radicals occurs in solution.     

Synthesis of a well-defined polybromostyrene by living radical polymerization with a nitroxyl radical

Radical polymerization of p-bromostyrene was investigated with benzoyl peroxide (BPO) as an initiator in the presence of 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl (MTEMPO). The polymerization was performed in bulk for 3.5 h at 95°C and then continued for another 48 h at 125°C to afford the corresponding polybromostyrene with a narrow molecular weight distribution in high yield. ¹H NMR study revealed that the polymer obtained had BPO and MTEMPO moieties at its head and tail, respectively. It was confirmed that the polymerization proceeded in accordance with living mechanism, because the molecular weight linearly increased with an increase of the conversion, and it was directly proportional to the reciprocal of the initial concentration of BPO. Furthermore, the polystyrene obtained in the present study could quantitatively act as the initiator for the polymerization of p-bromostyrene in the living radical manner to afford the corresponding block copolymer, and vice versa. © 1996 John Wiley & Sons, Inc.     

Synthesis and self-assembly of a heteroarm star amphiphile with 12 alternating arms and a well-defined core

We report on a stepwise synthesis of a heteroarm starlike amphiphile containing 12 alternating arms (six polystyrene and six poly(acrylic acid)) connected to a hexabiphenyl aromatic core. The synthesis does not involve polymerization, and only commercially available precursors are used. Most importantly, this amphiphile undergoes self-assembly into spherical and wormlike cylindrical micelles in aqueous and methanol solutions, and forms reverse 1D micellar structures in chloroform. This remarkable morphological diversity of the reported amphiphile 1 is believed to be a direct consequence of its well-defined molecular architecture.     

NQR spectra of Cl35 in complexes of stannic chloride with monochlorodimethyl ether and benzyl chloride

Conclusions The NQR spectra of Cl³⁵ of complexes (1:2) of stannic chloride with monochlorodimethyl ether and benzyl chloride were investigated. Both complexes have an octahedral structure with a cis-arrangement of the donor molecules.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1634–1635, July, 1970.     

Synthesis of functional polymers with acetal-monosaccharide moieties

The polycondensation of methyl α-D-mannopyranoside ( 1 ) with 1,n-bis(formylphenoxy)alkanes ( 2 ), using acidic catalysts, leads to the formation of linear polymers and macrocyclic compounds. The structure of the polymer and macrocycles was determined by ¹H, ¹³C NMR spectroscopy and ESI-MS analysis.     

Synthesis of a new palladium salt using N‐benzyl DABCO chloride and its application in Suzuki reaction

A palladium catalyst was synthesized using N‐benzyl DABCO chloride and palladium chloride. The structure of this catalyst was characterized and then the catalyst was used in Suzuki cross‐ coupling reaction of different aryl halides with arylboronic acids. All substrates afforded the corresponding products in good to high yields in the presence of low amounts of the catalyst. Under the heating conditions employed, cheaper and more available aryl chlorides gave relatively high yields in the Suzuki reaction. Copyright © 2012 John Wiley & Sons, Ltd.     

Reaction of benzyl chloride with propylene and trifluoropropene under metallocomplex initiation conditions

The reactions of benzyl chloride with propylene and 3,3,3-trifluoropropene in the presence of Fe(CO)₅ ` + DMF were studied. With propylene, the reaction stops at the addition stage with the simultaneous formation of dibenzyl. In the case of 3,3,3-trifluoropropene, a telomerization takes place, whereby the second growing radical C₆H₅CH₂CH₂CH(CF₃)CH₂HCF₃ practically completely isomerizes with a 1,5-migration into the radical C₆H₅HCH₂CH(CF₃)CH₂CH₂CF₃. To confirm the structure of the isolated compounds, chromato-mass-spectrometry and¹³C NMR were used.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1384–1388, June, 1991.