Preparation of highly branched poly(vinyl acetate) by transfer to allylic carbonate comonomers

Copolymerization of vinyl acetate with allyl carbonates that contain isopropyl groups yields highly branched poly(vinyl acetates).     

High-throughput purification of combinatorial libraries I: a high-throughput purification system using an accelerated retention window approach

We have developed a high-throughput purification system to purify combinatorial libraries at a 50-100-mg scale with a throughput of 250 samples/instrument/day. We applied an accelerated retention window method to shorten the purification time and targeted one fraction per injection to simplify data tracking, lower QC workload, and simplify the postpurification processing. First, we determined the accurate retention time and peak height for all compounds using an eight-channel parallel LC/UV/MS system, and calculated the specific preparative HPLC conditions for individual compounds. The preparative HPLC conditions include the compound-specific gradient segment for individual compounds with a fixed gradient slope and the compound-specific UV or ELSD threshold for triggering a fraction collection device. A unique solvent composition or solvent strength was programmed for each compound in the preparative HPLC in order to elute all compounds at the same target time. Considering the possible deviation of the predicted retention time, a 1-min window around the target time was set to collect peaks above a threshold based on UV or ELSD detection. Dual column preparative instruments were used to maximize throughput. We have purified more than 500 000 druglike compounds using this system in the past 3 years. We report various components of this high-throughput purification system and some of our purification results.     

Migratory-insertion reactions involving the thiocarbonyl ligand. dihapto-thioacyl complexes from the rearrangement of arylthiocarbonyl complexes of osmium(II). Structure of Os(η2-CSR)(η1-O2CCF3)(CO)(PPh3)2

Reaction of HgR₂ with OsHCl(CS)(PPh₃)₃ yields red, five-coordinate, OsRCl-(CS)(PPh₃)₂ (R = p-tolyl). From this have been derived the compounds OsRX(CS)(PPh₃)₂ with X = Br, I, S₂CNEt₂, O₂CMe, O₂CCF₃. These compounds add an additional ligand, MeCN, CO or CNR to form colourless, six coordinate arylthiocarbonyl complexes, which undergo migratory-insertion reactions to form red, dihapto-thioacyl complexes. The crystal structure of a representative example, Os(η²-CSR)(η¹-O₂CCF₃)(CO)PPh₃)₂ has been determined. The red equant crystals are orthorhombic, space group P2₁2₁2₁, a 11.584(1), b 19.184(2), c 18.90(1) Å, V 4199 ų, Z  4. The structure was solved by conventional heavy-atom methods and refined by full-matrix least-squares employing anisotropic thermal parameters for all non-hydrogen atoms except the carbon atoms of the triphenylphosphines. The final R factor is 0.057 for 2868 observed reflections.The coordination geometry in the monomeric complex is that of an octahedron distorted by the constraints of the ligands. The triphenyl phosphine ligands are mutually trans; the equatorial plane contains carbonyl, monohapto-trifluoroacetate, and dihapto-thioacyl ligands. Bond distances and angles are OsP 2.405, 2.407(4) Å; POsP 173.9(1)°; OsCO 1.83(2) Å; Os-O (trifluoroacetate) 2.206(11) Å; OsC (thioacyl) 1.91(2); OsS 2.513(6); CS 1.72 Å. The CS bond length implies a reduction in bond order from 2.0 to approx. 1.5 upon coordination to the metal.The η²-thioacyl ligand in Os(η²-CSR)Cl(CNR)(PPh³)₂ is methylated with methyl triflate and further reaction with LiCl produces the thiocarbene complex OsCl₂(C[SMe]R)(CNR)(PPh₃)₂.     

Generation and reactivity of bis(2,6-diethylphenyl)germanium(II)

The title intermediate ($\text{3a}$) is produced on photolysis of hexakis(2,6-diethyl-phenyl)cyclotrigermane ($\text{1}$) or bis(2,6-diethylphenyl)bis(trimethylsilyl)germane ($\text{4}$) as evidenced by trapping experiments, and thermally dimerizes to tetrakis(2,6-diethyl-phenyl)digermene ($\text{2a}$). Diarylgermylenes such as $\text{3a}$ do not form stable triethylamine adducts (e.g. $\text{5a}$) as has been previously reported.     

Thermal analysis of Vectran® fibers and films

Vectra^® liquid crystalline polymers (LCP's) were introduced as commercial products in the mid-1980's. The first of these (Vectra A130) was a wholly aromatic thermotropic copolyester ofp-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid. Vectra A130 is a thermotropic LCP that can be melt spun into filaments that on heat treatment are characterized by high strength and high modulus. Vectra resin can also be extruded into films. In the fiber or film form this material is commercially known as Vectran^®. Heat treatment enhances the tensile strength of Vectran fiber variants. Because of this, the elucidation of the physical transformations taking place in the internal structure of the material during heating has always been an important subject. Several thermal techniques are used to indicate clearly that what is observed as a glass transition is unlike the conventional glass transition in typical semicrystalline polymers. There is also an indication of the presence of multiple states of mesophase aggregation that collapse into a single state when taken to high enough temperatures.     

Molecular weights of backbones in graft copolymers

Copolymerization of a monomer X with an existing polymer yields a copolymer contaminated by poly-X homopolymer and ungrafted polymer. Measurements on the pure copolymer can yield only the molecular weights of the cumulative backbone portion and of the cumulative graft portion. However, if the grafts can be isolated, then the molecular weights of their individual chains may be determined also. Since it is not isolatable, the backbone is not amenable to similar treatment. Equations are derived for the molecular weights (of any average) of individual backbone chains; they are expressed in terms of the following experimentally accessible quantities: (i) molecular weight of original polymer; (ii) molecular weight of ungrafted portion: and (iii) fraction by weight of the original polymer which remains ungrafted. The procedure is thus the analogue, applied to the backbone, of chemical isolation applied to the grafts. The treatment has been examined for copolymers prepared by grafting acrylic acid to nylon-6 by mutual irradiation.