Functionalization and crosslinking reactions of ethyl-α-hydroxymethylacrylate

Ethyl-α-hydroxymethylacrylate (EHMA) was esterified with hexanoyl chloride in 80% yield. The homopolymer of the hexanoate ester was found to be a glassy thermoplastic and soluble polymer. Copolymerization of the hexanoate ester with EHMA in varying ratios gave polymers that were thermoplastic and more soluble as a result of internal lubrication of the long alkyl pendant groups. Copolymers with styrene were synthesized with relatively high conversion. Reaction of EHMA with adipoyl chloride gave a bis-ester which served as crosslinking agent when copolymerized with different monomers including EHMA itself. In a separate synthesis EHMA was reacted with toluenediisocyanate (TDI). In the absence of catalyst a monourethane was formed. This monomer still contains one isocyanate function and is capable of further reactions subsequent to double bond addition polymerization. This reaction was also carried out on poly-EHMA, with or without catalyst. The products were the mono and the crosslinked bisurethanes as expected. Thus, acyl chlorides and isocyanates were found to be excellent reagents for derivatization of EHMA. © 1993 John Wiley & Sons, Inc.     

Efficient Synthesis of α‐Benzylidene‐γ‐methyl‐γ‐butyrolactones

A concise synthesis of α‐benzylidene‐γ‐methyl‐γ‐butyrolactones 5a – g from substituted benzaldehydes is described. Compounds 1a – g on reaction with phosphorane 2 , provide the pentenoates 3a – g , which can be hydrolyzed to the acids 4a – g . The latter are cyclized to the corresponding butyrolactones 5a – g in excellent yields. The pentenoates 3a – g , on acid catalyzed cyclization, also provide 5a – g in very high yields.     

γ–α Solid–solid transition of isotactic polypropylene

X-ray diffraction patterns have been taken as a function of time and temperature on a sample of polypropylene held under high pressure (4.14 kbar) for 180 hr. at a temperature of 248°C. and subsequently cooled to room temperature. The molded sample initially crystallizes in the triclinic γ–phase but transforms to the γ–phase at elevated temperatures. The rate of conversion from γ to α is a function of time and temperature and tends to approach a constant value with increasing time. The nature of the thermal changes occurring in the sample was also studied by differential scanning calorimetry. It appears that at low scan speeds, there is a solid–solid transformation from the α-phase to the γ–phase, but at high scan speeds, the γ–phase melts without conversion to the α-phase.     

α–γ transition in nylon 6

The α to γ transition that occurs in nylon 6 upon iodine treatment was investigated by infrared spectroscopy, differential thermal analysis, and x-ray diffraction techniques. Thin films of nylon (0.2 mil) were treated in either iodine–potassium iodide aqueous solution or in iodine vapor. Very short treatment times, in the order of 30 sec, were found to effect the transition when a solution 0.5M with respect to iodine was used. The infrared spectra of the iodine nylon complexes formed from either the α- or γ-nylon 6 treated in vapor or dissolved iodine were all similar. This is an indication that molecular iodine is the active species in forming the complex. The temperature of the washing solution used to remove the iodine from the nylon determines whether an α-nylon 6 or γ-nylon 6 is obtained from the complex after washing. Nylon 6 plaque surfaces and thin films are similar in their behavior towards the iodine treatment. The γ-nylon 6 is a stable modification at all temperatures below its melting point. The conversion of the γ form back to the α modification can occur only if the hydrogen bonding is severely affected, e.g., by phenol treatment, iodine treatment, melting, etc. Infrared spectroscopy provided no evidence for an α–γ transition in nylon 6 on heating the sample continuously through its melting point. The shapes of the melting peaks in the above two modifications of nylon 6 were sufficiently different to provide a means of identifying the two crystalline forms.     

γ–α transformation in isotactic polypropylene

A γ-phase to α-phase transformation in a specimen of isotactic polypropylene crystallized under conditions of high pressure was induced by drawing at 100°C. X-ray studies showed that the unoriented component remained in the γ-phase, and that the oriented component was found only in the α-phase. This evidence supports a previous suggestion that the phase transformation is martensitic in character. The consequences of such an assumption are discussed. The role of dislocations in polymeric systems is generally believed to be not too significant, but since martensitic reactions involve cooperative movements of atoms, an exception in this case is suggested. A possible mechanism for the phase transformation is suggested.     

The synthesis of β-heteroarylamino-α,β-dehydro-α-amino acid and β-heteroarylamino-α-amino acid derivatives

From heteroarylaminomethyleneoxazolones 4 , obtained from N-heteroarylformamidines 2 and 2-phenyl-5-oxo-4,5-dihydro-1,3-oxazole ( 3 ), the following β-heteroarylamino-α,β-dehydro-α-amino acid derivatives were prepared: methyl 8 and ethyl esters 9 , amides 10 and 11 , hydrazides 12 , and azides 15 . By catalytic hydrogenation the compounds 4 were converted into β-heteroarylamino substituted amides 18 and β-heteroarylamino-α-amino acids 20 .     

Radical‐initiated polymerization of β‐methyl‐α‐methylene‐γ‐butyrolactone

β‐Methyl‐α‐methylene‐γ‐butyrolactone (MMBL) was synthesized and then was polymerized in an N,N‐dimethylformamide (DMF) solution with 2,2‐azobisisobutyronitrile (AIBN) initiation. The homopolymer of MMBL was soluble in DMF and acetonitrile. MMBL was homopolymerized without competing depolymerization from 50 to 70 °C. The rate of polymerization (R_p) for MMBL followed the kinetic expression R_p = [AIBN]^0.54[MMBL]^1.04. The overall activation energy was calculated to be 86.9 kJ/mol, k_p/k_t^1/2 was equal to 0.050 (where k_p is the rate constant for propagation and k_t is the rate constant for termination), and the rate of initiation was 2.17 × 10^?8 mol L^?1 s^?1. The free energy of activation, the activation enthalpy, and the activation entropy were 106.0, 84.1, and 0.0658 kJ mol^?1, respectively, for homopolymerization. The initiation efficiency was approximately 1. Styrene and MMBL were copolymerized in DMF solutions at 60 °C with AIBN as the initiator. The reactivity ratios (r₁ = 0.22 and r₂ = 0.73) for this copolymerization were calculated with the Kelen–Tudos method. The general reactivity parameter Q and the polarity parameter e for MMBL were calculated to be 1.54 and 0.55, respectively. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1759–1777, 2003     

Structural effects in the Pd-induced enantioselective deprotection–decarboxylation of β-ketoesters

Structural effects in the chiral base and the influence of some key reaction parameters (catalyst type and solvent) in the Pd-induced enantioselective decarboxylation (cascade reaction) of three different ,-disubstituted benzyl β-ketoesters were explored. The reaction intermediate after debenzylation (β-keto-carboxylic acid) was synthesized and its decarboxylation studied independently. The highest ee (up to 60%) in the cascade reaction was achieved with those substrates that contained an aromatic ring system and with chiral amino alcohols that possessed an extended aromatic ring (quinine and quinidine). Polar solvents with weak H-bond donor and acceptor properties favor enantioselection.     

Emulsion and controlled miniemulsion polymerization of the renewable monomer γ‐methyl‐α‐methylene‐γ‐butyrolactone

The kinetics of free‐radical emulsion polymerization of γ‐methyl‐α‐methylene‐γ‐butyrolactone (MeMBL), a renewable monomer related to methyl methacrylate, are presented in detail for the first time, and stable polymer latices are prepared. The effects of different reaction parameters on free‐radical emulsion polymerization of MeMBL are presented. Homogeneous nucleation is asserted to be the dominant path for particle formation. Miniemulsion copolymerization of MeMBL and styrene is also reported. In this case, the homogeneous nucleation process appears limited when using an oil soluble initiator. Both the RAFT miniemulsion polymerizations and RAFT bulk polymerizations are well controlled and narrow polydispersity copolymers are produced. Rate retardation is observed in the RAFT miniemulsion polymerizations compared with the free‐radical polymerization and RAFT bulk polymerizations and the possible causes of the retardation are discussed. The reactivity ratios of MeMBL and styrene in RAFT bulk copolymerization are also determined. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5929–5944, 2008     

Thermal deesterification and decarboxylation of alternating copolymers of styrene with β-substituted t-butyl α-cyanoacrylates

Alternating copolymers of styrene with β-carboalkoxy-substituted t-butyl α-cyanoacrylates undergo facile deesterification at 150–190°C, about 60°C below the deprotection temperature of poly(t-butyl methacrylate), and decarboxylation at 170–200°C. When the β-substituent is a methyl ester, the two events are clearly separated, with the deesterification occurring at a maximum rate at 165°C and decarboxylation at 193°C. Anhydride formation is negligible in this case. The copolymer with t-butyl cyanofumarate exhibits simultaneous deesterification and decarboxylation events at 180°C with concomitant minor dehydration.     

胆甾-4α-甲基-8-烯-3β，7α-二醇二乙酸酯的结构与性质研究

Lophenol, cholest-4α-methyl-7-en-3β-ol (1), obtained from Dracaena cochinchinensis (Lour.) S. C. Chen, was structurally modified. It was acetylated to protect 3β-hydroxyl group, and then oxidised by selenium dioxide in acetic acid to give cholest-4a-methyl-8-en-3β, Ta-diol diacetate (3). This compound 3 is unstable in chloroform solution or when heated and easily converted to a diene compound, cholest-4a-methyl-7,14-dien-3β-ol acetate (4). The structures of 3 and 4 were elucidated by means of IR, ^1H NMR, ^13C NMR and MS, and the absolute configuration of 3 was established by X-ray crystallography. The property of 3 was also discussed in this paper. Both 3 and 4 are new compounds and were reported for the first time.     

Solid‐state conformations of linear depsipeptide amides with an alternating sequence of α,α‐disubstituted α‐amino acid and α‐hydroxy acid

Depsipeptides and cyclodepsipeptides are analogues of the corresponding peptides in which one or more amide groups are replaced by ester functions. Reports of crystal structures of linear depsipeptides are rare. The crystal structures and conformational analyses of four depsipeptides with an alternating sequence of an α,α‐disubstituted α‐amino acid and an α‐hydroxy acid are reported. The molecules in the linear hexadepsipeptide amide in (S)‐Pms‐Acp‐(S)‐Pms‐Acp‐(S)‐Pms‐Acp‐NMe₂ acetonitrile solvate, C₄₇H₅₈N₄O₉·C₂H₃N, ( 3b ), as well as in the related linear tetradepsipeptide amide (S)‐Pms‐Aib‐(S)‐Pms‐Aib‐NMe₂, C₂₈H₃₇N₃O₆, ( 5a ), the diastereoisomeric mixture (S,R)‐Pms‐Acp‐(R,S)‐Pms‐Acp‐NMe₂/(R,S)‐Pms‐Acp‐(R,S)‐Pms‐Acp‐NMe₂ (1:1), C₃₂H₄₁N₃O₆, ( 5b ), and (R,S)‐Mns‐Acp‐(S,R)‐Mns‐Acp‐NMe₂, C₃₀H₃₇N₃O₆, ( 5c ) (Pms is phenyllactic acid, Acp is 1‐aminocyclopentanecarboxylic acid and Mns is mandelic acid), generally adopt a β‐turn conformation in the solid state, which is stabilized by intramolecular N—H…O hydrogen bonds. Whereas β‐turns of type I (or I′) are formed in the cases of ( 3b ), ( 5a ) and ( 5b ), which contain phenyllactic acid, the torsion angles for ( 5c ), which incorporates mandelic acid, indicate a β‐turn in between type I and type III. Intermolecular N—H…O and O—H…O hydrogen bonds link the molecules of ( 3a ) and ( 5b ) into extended chains, and those of ( 5a ) and ( 5c ) into two‐dimensional networks.     

The α and α parameters for spin polarized Hartree–Fock–Slater calculations

α and α are derived for use in spin polarized Hartree–Fock–Slater programs. They are assumed to depend only on the number of up and down spin electrons in the atom. The calculated eigenvalues show a slight improvement only for carbon, nitrogen, and oxygen.     

A novel synthesis of α-hydroxy- and α,α′-dihydroxyketone from α-iodo and α,α′-diiodo ketone using photoirradiation

A novel reaction of α-iodo ketone (α-iodocycloalkanone, α-iodo-β-alkoxy ester, and α-iodoacyclicketone) with irradiation under a high-pressure mercury lamp gave the corresponding α-hydroxyketone in good yields. In the case of α,α′-diiodo ketone, α,α′-dihydroxyketone which little has been reported until now was obtained. This reaction affords a new, clean and convenient synthetic method for α-hydroxy- and α,α′-dihydroxyketone.     

Stereocomplex formation between enantiomeric poly(α‐methyl‐α‐ethyl‐β‐propiolactones): Effect of molecular weight

Optically pure S(?) and R(+)‐poly(α‐methyl‐α‐ethyl‐β‐propiolactones) (PMEPLs) of controlled low molecular weights were synthesized by anionic polymerization of the corresponding optically active monomers, and characterized using gel permeation chromatography, Maldi‐TOF mass spectrometry, and NMR spectroscopy. Blends of PMEPLs of opposite configurations and different molecular weights were investigated. All blends lead to the formation of a stereocomplex and its crystallization prevails over a wide range of mixing ratios. The stereocomplex melts 30–40 °C above that of the corresponding pure polymers, depending on the molecular weight; pairs of polymers having similar molecular weights exhibit the highest melting temperatures and enthalpies of fusion. Finally, when the stereocomplex is dispersed in a PMEPL matrix, it acts as a very effective nucleation agent for the crystallization of the polymer in excess. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2380–2389, 2007     

Preparation and structure-property studies on copolypeptides of γ-methyl glutamate-glutamic acid and γ-methyl glutamate–γ-benzyl glutamate

A series of copolypeptides of poly(methyl glutamate-glutamic acid) (PBC) and poly(methyl benzyl glutamate) (PMB) were prepared from homopolymeric poly(methyl D-glutamate) (PMDG) via a variety of synthetic routes. Following their characterization, these copolymers were then investigated via dynamic mechanical spectroscopy, stress-strain analysis (wet and dry), and wide-angle x-ray scattering (WAXS). It was found that the copolymers could be prepared from homopolymeric PMDG with minimal chain degradation or side reactions. The mechanical properties of either series did not follow a simple trend, in that specific properties such as Young's modulus went through either a maximum or minimum with composition ratio of the two comonomers. based on the WAXS studies, some rationalization for this behavior was established. Specifically, the nature of the side-chain interaction, and therefore chain packing, was strongly affected by comonomer ratio.