Synthesis of well‐defined,soluble poly(3‐alkyl‐4‐benzamide) by chain‐growth condensation polymerization

Well‐defined poly(3‐alkyl‐4‐benzamide) was synthesized by means of chain‐growth condensation polymerization of phenyl 3‐octyl‐4‐(4‐octyloxybenzyl(OOB)amino)benzoate ( 1c ) from initiator 2 , followed by removal of the OOB groups on amide nitrogen of poly 1c . Polymerization of 1c with phenyl 4‐(trifluoromethyl)benzoate ( 2b ) in the presence of 1,1,1,3,3,3‐hexamethyldisilazide (LiHMDS) and LiCl in THF at ?10 °C gave poly 1c with a narrow molecular weight distribution (M_w/M_n ≤ 1.08) and a well‐defined molecular weight (M_n = 4480–12,700) determined by the feed ratio of monomer to initiator (from 10 to 30). The OOB groups of poly 1c were removed with H₂SO₄ to give the corresponding N‐unsubstituted poly(p‐benzamide) (poly 1c′ ) with low polydispersity. The solublity of poly 1c′ in polar organic solvents was dramatically higher than that of poly(p‐benzamide), demonstrating that introduction of an alkyl group on the aromatic ring is very effective for improving the solubility of poly(p‐benzamide). © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 360–365     

Color centers in irradiated MgF2

Abstract

Color centers in rutile-structured MgF₂ single crystals irradiated at 20K/360K by reactor neutrons are investigated spectroscopically at LNT. Four different types of the F-F vacancy bond in MgF₂ are possibly identified to the observed absorption bands as due to the F₂ centers; instead of previous assignments, the 300nm band to the F₂(D_2h), the 325nm band to the F₂(C₁), the 355nm band to the F₂(C_2v), and the 400nm band to the F₂(C_2h) centers.     

Aryl-β-C-glucosidation using glucal boronate: application to the synthesis of tri-O-methylnorbergenin

Novel aryl-β-C-glucosidation method using glucal boronate was developed. This protocol can offer several advantages including use of non-toxic, easily handling glucal boronate as a crystalline solid and storable at room temperature for several months. Tri-O-methylnorbergenin (8,10-di-O-methylbergenin), an anti-HIV active bergenin derivative, was concisely synthesized by application of the aryl-β-C-glucosidation method.     

Preparation of Metallaiminophosphoranes and Their Reactivity

Treatment of [Cp*(CO) 2 M{P(NHPh)(OMe) 2 }]PF 6 (M = Fe and Ru) with NaNH 2 gives metallaiminophosphoranes, Cp*(CO) 2 M{P(NPh)(OMe) 2 }. The x-ray structures and reactivity of the complexes are reported.     

Vinyl Polymerization. 418. Polymerization of Vinyl Monomer Initiated by Betaine-Type Polymers in Aqueous Solution

Abstract

Three kinds of betaine-type polymers, which are macromolecular amphoteric electrolytes, were found to be able to polymerize vinyl monomers in aqueous solution through a radical mechanism without any further initiator. Betain-type polymers form hydrophobic areas (HA) in water. Vinyl polymerization commenced in the HA. The effect of the pH of the aqueous solution on polymerization was investigated.     

Synthesis and Polymerization of N-(L-Menthylcarboxylatomethyl)maleimide

A new type of optically active N-(L-menthylcarboxylatomethyl)maleimide (MGMI) was synthesized from maleic anhydride, glycine, and L-menthol. Radical homopolymerization of MGMI was performed at 50°C for 24 h to give optically active polymer having [α]_D = -57°. Radical copolymerizations of MGMI (M ₁) were performed with styrene (ST, M ₂), methyl methacrylate (MMA, M ₂) in benzene at 50°C. From the results, the monomer reactivity ratios (r ₁, r ₂) and the Alfrey-Price Q, e values were determined as follows: r ₁ = 0.16, r ₂ = 0.006 for the MGMI-ST system; r ₁ = 0.15, r ₂ = 1.65 for the MGMI-MMA system, and Q ₁ = 0.72, e ₁ = 1.59 calculated from the MGMI-MMA system. Anionic homopolymerizations of MGMI were also carried out. Chiroptical properties of the polymers were investigated.     

Vinyl Polymerization. 431. Vinyl Polymerizations Initiated by Block and Random Poly(Styrene-co-Sodium Methacrylate)

Abstract

The polymerization of some kinds of vinyl monomer was found to occur without an ordinary initiator in aqueous solutions of AB-type block or random copolymers of sodium methacrylate with styrene as a so-called “uncatalyzed polymerization.” Although the spin trapping technique showed that the initiation mechanism by the block copolymer was the same as that by the random copolymer, the initiating ability of the block copolymer was lower than that of the random copolymer. Such results are attributable to the difference in the incorporating ability of monomer into the micelles formed by the block copolymer and into the hydrophobic areas formed by the random copolymer.     

Asymmetric Induction Copolymerization of Optically Active N-(1-Menthyl Carboxylatomethyl) Citraconimide with Methyl Methacrylate

Copolymerization of an optically active N-(1-menthyl carboxylatomethyl)citraconimide (MCMCI) was carried out with methyl methacrylate (MMA) with azobisisobutyronitrile as the initiator in benzene at 50°C. All the copolymers obtained were optically active. After the removal of the optically active menthyl group, the hydrolyzed poly(MCMCI-co-MMA)'s still showed optical activity. The asymmetric induction to the copolymer main chain and the mechanism are discussed based on the measurements of optical rotatory dispersion and circular dichroism of the original and hydrolyzed copolymers.     

Vinyl Polymerization. 439. Vinyl Polymerization Initiated by Poly(Ethylene Glycol] Diglycolic Acid or its Sodium Salt

Abstract

The polymerization of some kinds of vinyl monomer was found to occur in aqueous solutions of poly(ethylene glycol) diglycolic acid (PEG Acid) or sodium poly(ethylene glycol) diglycolate (PEG Acid Na) through radical mechanisms without any further initiator, as a so-called “uncatalyzed polymerization.” Although the initiating radical species for PEG Acid was determined to be the same as that for PEG Acid Na by means of the spin-trapping technique, the initiating ability of PEG Acid was higher than that of PEG Acid Na. These results are assumed to be attributable to the difference in the initiation mechanisms of the two systems and in the incorporating abilities of monomer into the hydrophobic areas formed by PEG Acid and PEG Acid Na.