Herein, we report the transformation of bmonomethyl itaconate, an inexpensive and biorenewable alternative to petroleum feedstocks, to the high-value monomer amethylene-c,c-dimethyl-c-butyrolactone (Me 2 MBL) through a selective addition strategy. This strategy is also applied to the synthesis of a-methylene-c-butyrolactone (MBL, tulipalin A), a monomer that can be polymerized to give materials with desirable properties (high decomposition temperature, glass transition temperature, and refractive index). Subsequent polymerization of both Me 2 MBL and MBL through reversible addition-fragmentation chain-transfer polymerization generates well-defined poly(Me 2 MBL) and poly(MBL) (PMBL). Physical characterization of poly(Me 2 MBL) shows good physical properties comparable with known PMBL materials.

A new polymorph of aripiprazole has been discovered, making it the most polymorphic drug to date with twelve reported anhydrous forms, and a record-breaking ninth solved crystal structure. The new form was induced by seeding with crystals of the active metabolite dehydro-aripiprazole.

Renewable materials are a research necessity, with the creation of a sustainable chemical industry representing a grand challenge for the field of chemistry and materials science. On this basis, biorenewable resources are being transformed into degradable or recyclable high value polymers with a diverse array of applications. Itaconic acid (IA) is a notable biorenewable resource due to its low cost and large annual production. We report the synthesis of renewable thermosets and thermoplastics that are almost completely derived from IA. Using catalytic, solvent-free, and high yielding transformations from an itaconate source, we efficiently synthesized a saturated diol, a saturated diester, and an unsaturated diester. Subsequent binary step-growth polycondensation polymerizations between the diol and either diester generated polyesters with relatively high molar masses (>10 kg/mol). Ternary polymerizations of all three monomers in varying feed ratios produced polyesters with tunable amounts of unsaturated units along the backbone. Atom economies and low process mass intensities for these reactions reflect green processes. Thermoset materials were generated from these unsaturated terpolymers through thiol-ene click reactions with a potentially renewable cross-linker. We then established the tensile properties and molar mass between cross-links of these thermosets through mechanical testing and demonstrated hydrolytic stability under acidic and neutral conditions, but hydrolytic degradation under basic conditions. An α,ω-hydroxy terminated saturated polyester was prepared, functionalized with an atom transfer radical polymerization initiator, and then chain-extended with the α-methylene-γ-butyrolactone, which can be derived from IA, to give triblock polymers.

Crystal form exploration of dehydro-aripiprazole (dAPZ), the active metabolite of the antipsychotic drug aripiprazole (APZ), elucidated five polymorphs (I, II, III, IV, and V), two methanol solvates, and a monohydrate. The forms were characterized by thermal microscopy, differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA), single and powder X-ray diffraction (SCXRD and PXRD), and infrared spectroscopy. DSC analysis showed monotropic relationships among polymorphs I, II, III, and IV and enantiotropic relationships for the two form pairs I ↔ V and II ↔ V. Solvent-mediated conversion experiments indicated that Form V is the thermodynamically stable form in the temperature range 5−60 °C and Form I is the stable form at ≥70 °C, where a transition temperature lies between 60 and 70 °C. Two polymorphs of the methanol solvate (S MeOH 1 and S MeOH 2) were crystallized from methanol solutions in 1:1 dAPZ/methanol molar ratio. S MeOH 2 is the thermodynamically stable form of the two methanol solvates at ambient temperature. The monohydrate (S H 2 O ) was obtained by solvent-mediated conversion experiments of any of the methanol solvates in water. Single-crystal structure analysis of polymorphs I, II, V and the two methanol solvates showed the formation of dimeric structures with N−H•••OC (amide−amide) hydrogen-bonded homodimer synthons. In the case of S H 2 O , two water molecules are present between the units of the dimer, and each water molecule exhibits hydrogenbonding with one of the piperazine nitrogen atoms of a third dAPZ molecule. Analysis of the crystal structures and PXRD patterns for both the APZ and dAPZ nonsolvated polymorphs reveals that all the forms are distinct from one another. When solvates and hydrates were added to the comparison (a total of 18 crystalline forms of APZ and dAPZ), only S MeOH 2 of dAPZ was found to have an identical packing arrangement to the APZ methanol solvate. This study illustrates that despite the chemical structure similarity between dAPZ and APZthe differences being one CC double-bond vs a C−C single-bond and a molecular weight change of 2 Da out of 448the observed crystal packing arrangement in the polymorphs of the active metabolite differs significantly from those observed for the parent drug.

We report the cationic ring-opening homo- and copolymerization of the 7-membered exocyclic hemiacetal ester 7-methoxyoxepan-2-one (MOPO) to afford poly(7-methoxyoxepan-2-one) [poly(MOPO)] and its copolymers with isobutyl vinyl ether (IBVE).