Glutaric Anhydride Research Articles

Alternating poly(ester amide)s from glutaric anhydride and α,ω-aminoalcohols: synthesis and thermal properties

Abstract Alternating poly(ester amide)s 6a - e were prepared by polycondensation of α-carboxyl-ω-hydroxyamides 3a - e which were obtained by aminolysis of glutaric anhydride (1) and α,ω-aminoalcohols, H2N-(CH2)x-OH (x = 2 - 6) 2a - e. The polycondensation was performed in dimethylformamide solution using a carbodiimide as activating agent, or in bulk with Bu2Sn(OMe)2, Ti(OBu)4 and Sn(octoate)2 as a catalyst. For the polycondensation in bulk, the influence of catalyst and of temperature on the number-average molecular weight was studied. 1H NMR analyses of the poly(ester amide)s clearly show the alternating microstructure. The poly(ester amide)s from glutaric anhydride and the homologous series of α,ω-aminoalcohols are semicrystalline materials; their melting points show the odd/even effect observed for other poly(ester amide)s.

Synthesis of Discrete Mass Poly(butylene glutarate) Oligomers

A series of discrete mass oligomers of the perfectly alternating copolymer poly(butylene glutarate) containing 2, 4, 8, 16, 32, and 64 structural units have been synthesized from glutaric anhydride and butanediol using an iterative divergent−convergent strategy. These materials were designed to serve as models for more complex polymer distributions. Orthogonal protection of difunctional starting material using 9-fluorenylmethoxycarbonyl chloride and p-methoxybenyl alcohol allowed control of chain growth during coupling with 1-ethyl-3-[3-(dimethylamino)propyl]carbodiimide hydrochloride and (N,N-dimethylamino)pyridine. Condensation products were monofunctionalized by removal of one protecting group using mild acidic or basic conditions that preserved the orthogonal protecting group. The fully unprotected target products were isolated in highly pure form and, with the exception of the 64-mer, in high yield (>70%). The synthetic oligomers were characterized using 1H NMR, HPLC, GPC, EI-MS, CI-MS, LSI-MS, and M...

Lipase-catalyzed synthesis of polyesters from anhydride derivatives involving dehydration

Lipase-catalyzed synthesis of aliphatic polyesters has been achieved by using anhydride derivatives as starting substrate. Candida antarctica lipase efficiently catalyzed the dehydration reaction of polyanhydrides and glycols in toluene, yielding the corresponding polyesters. Effects of the reaction parameters on the polymer yield and molecular weight have been systematically investigated. The dehydration reaction also proceeded in water and supercritical carbon dioxide (scCO 2). The reaction behaviors depended on the monomer structure and reaction media. Cyclic anhydrides, succinic, glutaric, and diglycolic anhydrides, were enzymatically polymerized with α,ω-alkylene glycols in toluene to give the polyesters. Under appropriate reaction conditions, the molecular weight reached 1×10 4.

Synthesis of Enantiomerically Pure all cis‐2,3,6‐Trisubstituted Piperidine: A Silicon Mediated Total Synthesis of (+)‐Carpamic Acid.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Combination of enzymatic procedures with multicomponent condensations

Abstract A new synthetic method based on combination of enzymatic desymmetrization of 3-phenylglutaric anhydrides with multicomponent condensation is outlined. Enzymatic monoesterification of glutaric anhydrides was performed, and the derived monoacids were used as substrates for subsequent Ugi and Passerini multicomponent condensations. Both reactions were combined as two-step, one-pot processes. The choice of solvent and enzyme type has an appreciable effect on the course of reactions.

New polymer syntheses. CXI. Aliphatic polyesters by the ring‐opening polycondensation of glutaric anhydride with ethylene or trimethylene carbonate

AbstractSeveral polycondensations of ethylene carbonate with succinic anhydride or glutaric anhydride (GA) were conducted in bulk. Low molar mass polyesters were obtained with pyridine‐type catalysts and GA. Analogous polycondensations of trimethylene carbonate (TMC) and GA were successful when quinoline, 4‐(N,N‐dimethylamino)pyridine, or BF3 · OEt2 was used as a catalyst. Matrix‐assisted laser desorption/ionization time‐of‐flight mass spectra revealed the formation of cyclic oligoesters and polyesters by backbiting degradation. Monomer mixtures containing an excess of TMC yielded copoly(ester carbonate)s with number‐average molecular weights up to 16,000 Da. Analogous copoly(ester carbonate)s were obtained from TMC and 3,3′‐tetramethylene glutaric anhydride. Furthermore, combined polycondensation/ring‐opening polymerization reactions of TMC and GA with L‐lactide or ϵ‐caprolactone were studied. All copolymers were characterized by viscosity measurements and by IR, 1H, and 13C NMR spectroscopy. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4357–4367, 2002

Studies on hydrolytic degradation of epoxy‐polyester resins cured with glutaric anhydride

AbstractBiodegradable epoxy‐polyester resins were synthesized in two steps: (1) synthesis of the polyesters with allyl pendent groups; (2) epoxidation of allyl groups in the polyesters. Polyesters with allyl pendent groups were synthesized by melt copolymerization of succinic anhydride (SA) and allyl glycidyl ether (AGE) in the presence of benzyltrimethylammonium chloride (BTMAC) as a catalyst. Functionality of some polyesters was reduced by replacing a part of AGE with butyl glycidyl ether (BGE). The epoxidation of the polyesters obtained was carried out using m‐chloroperbenzoic acid (MCPBA). The multifunctional epoxy‐polyester resins were cured using different amounts of glutaric anhydride (GA) and without use of it. The cured resins were degraded in aqueous buffer of pH = 7.4 at 70 and 37 °C. The hydrolytic degradation was monitored by determination of mass loss. Fracture surfaces of the samples were examined by scanning electron microscopy. Influence of the composition of initial resins and amount of GA used on the hydrolytic degradation was studied. The products of degradation were identified by HPLC and 1H‐NMR. Copyright © 2003 John Wiley & Sons, Ltd.

Synthesis of enantiomerically pure all cis-2,3,6-trisubstituted piperidine: a silicon mediated total synthesis of (+)-carpamic acid

A stereoselective total synthesis of (+)-carpamic acid 1 has been achieved from the σ-symmetric 3-[dimethyl(phenyl)silyl]glutaric anhydride 11 featuring its asymmetric desymmetrisation using oxazolidinone 12 . The dimethyl(phenyl)silyl group is not only acting as a masked hydroxy group but also stereodirects ester enolate methylation and facilitates the Curtius reaction of the β-silyl-amide 23 . A highly stereoselective hydrogenation of the imine 10 is the key step in the construction of the all cis-2,3,6-trisubstituted piperidine.

Sol-Gel Materials, 1. Synthesis and Hydrolytic Condensation of New Cross-Linking Alkoxysilane Methacrylates and Light-Curing Composites Based upon the Condensates

New methacryloyxyalkylaminoalkylalkoxysilanes have been synthesised by Michael addition of the corresponding acryloyloxyalkyl methacrylates with (3-aminopropyl)triethoxysilane (APTES). Low-viscosity polycondensates have been formed by hydrolysis and condensation of these silanes in the presence of ammonium fluoride (NH 4 F). The reaciton of APTES with the addition product of succinic or glutaric anhydride with glycerol dimethacrylate results in the formation of new dimeth-acrylate-functionalised 3-amidopropyltrithoxysilanes. The hydrolic condensation of these silanes was carried out in the presence of 0.5 M HCI. The hydrolysis and condensation of the silanes have been studied by 29 Si NMR spectroscopy. Cross-linked inorganic-organic materials have been obtained by free-radical photopolymerisation of the polycondensates and their mixtures in the presence of camphorquinone and ethyl 4-(dimethylamino)benzoate with visible light (VL). The synthesised polycondensates enable the preparation of diluent-free composites. The mechanical properties of VL-cured polycondensates and composites have been investigated.

Crystalline-state photochromism and thermochromism of new spiroxazine

New spiroxazine 7 carrying a long alkyl chain was prepared by condensation of spiroxazine 5 with glutaric anhydride. The first example of solid-state photochromism and thermochromism in spiroxazine 7 is reported.

DNA microarrays with PAMAM dendritic linker systems.

The DNA microarray-based analysis of single nucleotide polymorphisms (SNPs) is important for the correlation of genetic variations and individual phenotypes, and for locating disease-causing genes. To facilitate the development of surfaces suitable for immobilization of oligonucleotides, we report here a novel method for the surface immobilization of DNA using pre-fabricated polyamidoamine (PAMAM) starburst dendrimers as mediator moieties. Dendrimers containing 64 primary amino groups in their outer sphere are covalently attached to silylated glass supports and, subsequently, the dendritic macromolecules are modified with glutaric anhydride and activated with N-hydroxysuccinimide. As a result of the dendritic PAMAM linker system the surfaces reveal both a very high immobilization efficiency for amino-modified DNA-oligomers, and also a remarkable high stability during repeated regeneration and re-using cycles. The performance of dendrimer-based DNA microarrays in the discrimination of SNPs is demonstrated.

Synthesis and Characteristics of Biodegradable Epoxy-Polyester Resins Cured with Glutaric Anhydride

Biodegradable epoxy–polyester resins were synthesized in two steps: (1) the synthesis of the polyesters with allyl pendant groups, and (2) the epoxidation of the allyl groups in the polyesters. Polyesters with allyl pendant groups were synthesized by the melt copolymerization of succinic anhydride (SA) and allyl glycidyl ether (AGE) in the presence of benzyltrimethylammonium chloride (BTMAC) as the catalyst. The functionality of some polyesters was reduced by replacing a part of AGE with butyl glycidyl ether (BGE). The epoxidation of the polyesters obtained was carried out using m-chloroperbenzoic acid (MCPBA). The multifunctional epoxy–polyester resins were cured with different amounts of glutaric anhydride (GA). The course of the curing process was monitored using DSC method. The following parameters of the process were determined: heat of curing, onset, maximal and end temperatures. Glass transition temperatures (Tg s) of the cured resins were determined by dynamic mechanical thermal analysis (DMTA). The influence of the composition of the initial resins and amount of GA on the properties of the cured products, such as density, hardness, Tg values, swelling and water sorption, were examined. Epoxy–polyester resins were subjected to the test of accelerated hydrolytic degradation in an aqueous phosphate buffer of pH = 7.4 at 70°C.

A mild and efficient catalytic alkylative monofunctionalization of cyclic anhydrides.

Substituted succinic and glutaric anhydrides undergo a nickel-catalyzed monofunctionalization with organozinc reagents as nucleophiles. The reaction proceeds readily with a variety of substrates, employs commercially available or readily attainable reagents, tolerates sensitive functionality on both partners, and affords the product ketoacids in moderate to high yields. The use of a chiral phosphinooxazoline results in a desymmetrization of a meso anhydride to provide the ketoacid in 85% yield and 79% ee.

Syntheses of imido-substituted glycosans and their photocyclisation towards highly functionalised heterotricycles

Reaction of O-protected amino-1,6-anhydro-β- d-hexopyranoses with succinic or glutaric anhydride and subsequent intramolecular acylation afforded the succinimido- and glutarimido-substituted glycosans. Irradiation with UV light of 254 nm wavelength led to γ-hydrogen abstraction at the pyranose ring by the excited carbonyl function. The stereoselective recombination of the resulting 1,4-diradicals gave annelated azetidinols, which fragmented by a retrotransannular ring opening reaction to give the glycosan-annelated azepanedione and azocanedione systems, respectively.

New Polymer Syntheses. 110. Ring-Opening Polycondensation of Two Cyclic Monomers−Polyesters from Ethylene Sulfite and Cyclic Anhydrides

Ethylene sulfite and succinic anhydride undergo a polycondensation reaction evolving SO2 when heated above 160 °C in the presence of suitable catalysts. Both quinoline and Lewis acids (BF3 or SnCl4) proved to be useful catalysts yielding polyesters which were characterized by IR and 1H and 13C NMR spectroscopy. Analogous polycondensations were conducted with mixtures of ethylene sulfite and glutaric anhydride, 3,3-tetramethylene glutaric anhydride, adipic anhydride, and sebacic anhydride. The resulting polyesters had number average molecular weights (Mns) in the range of 5000−10 000 Da (based on PS-calibrated SEC), and the MALDI−TOF mass spectra indicated the formation of cyclic oligoesters and polyesters along with linear chains. Polycondensations of ethylene sulfite and succinyl sulfide yielded S-free polyesters, a result important for the mechanistic discussion. No polycondensations were observed for mixtures of ethylene sulfite and dicarboxylic acids, whereas oligoesters containing diethylene glycol units were obtained from acid-catalyzed polycondensations of ethylene glycol and cyclic anhydrides. The unusual thermodynamic aspects of this ring-opening polycondensation concept are also discussed.

Monoclonal Antibody-based Immunoassays for the Phytotoxin Coronatine

Coronatine (COR) is composed of two structural components, coronafacic acid (CFA) and the amino acid coronamic acid (CMA), which are joined by an amide bond. Monoclonal antibodies (MAbs) were prepared against COR and used in competitive ELISAs. MAbs were secreted by hybridoma cell lines that were prepared from mice immunized with two different COR analogues conjugated to ovalbumin (OVA). The first hapten was prepared by reduction of the keto-oxygen on the cyclopentane ring of the CFA moiety of COR and subsequent reaction of the hydroxyl group with succinic or glutaric anhydride, which liberated a terminal carboxyl. This carboxyl group was coupled to carrier proteins using active ester chemistry. For preparation of the second hapten, a CMA analogue was synthesized containing a protected methylsulphydryl function at the 2-position of the cyclopropane ring in place of the 2-ethyl group of CMA, and the carboxylic acid was protected as a methyl ester. The hapten was then prepared by reaction of coronafacoyl chloride with the amine function of the CMA analogue. Following deprotection, the hapten was conjugated to OVA and used to immunize mice. Hybridoma cell lines secreting high affinity MAbs 11B8 (hapten 1) and 11G8 (hapten 2) were isolated. MAb 11B8 predominantly recognized the coronamyl amide features of coronatine whereas 11G8 recognized the coronafacoyl amide of COR. Immunoassays were developed using each of the antibodies. COR could be quantitated in the range 0.5-40 ng ml−1 (limit of detection 100 pg ml−1) and 3-100 ng ml−1 (limit of detection 800 pg ml−1) for 11B8 and 11G8 respectively.

A detailed study of thermal degradation of poly(2-hydroxyethyl methacrylate)

The thermal degradation behaviour of poly-2-hydroxyethyl methachrylate and of its deuterium derivative have been studied using thermogravimetry under nitrogen atmosphere, with programmed heating at 10°C/min. At first, the partially degraded polymer has been examined by IR. The cold ring fraction (CRF) was trapped at two ranges from ambient temperature to 340°C and 340–400°C. These CRFs were characterized by IR, 1H, 13C NMR, and GC–MS. When the polymer decomposes thermally at two temperature ranges which are from ambient temperature to 340°C and 340–400°C, at both CRFs, the major product is monomer due to depolymerisation reaction. The side products arising from ester decomposition are a six-membered glutaric anhydride type of ring, an oxolane type of ring, 2-isopropenyl ethyl methacrylate, methacrylic acid and CO 2. A mechanism which accounts for all these products has been formulated. The activation energy for the thermal degradation of poly(HEMA) is predicted as 129.8 kJ/mol

MALDI-TOF MS analysis of a library of polymerizable cyclodextrin derivatives.

Polymerizable cyclodextrin derivatives (PCDs) have been proposed as candidates for use in dental therapeutics (Bowen, 1996; Bowen and Reed, 1997). Here, PCD "libraries" were synthesized by quasi-random reactions of 6 moles of methacrylic anhydride plus 6 moles of cyclic glutaric anhydride per mole of beta-cyclodextrin (BCD) in solution. BCD has 21 reactive sites on each of its molecules. These proportions were based on probability calculations, which predicted that the products should have a minimum of 2 polymerizable substituents and acidic ligand groups on practically every one of the diverse product molecules. Matrix-assisted laser desorption/ionization (MALDI) time of flight (TOF) mass spectrometry (MS) gave valuable information regarding the masses of molecular ions representing the molecules that made up the PCD libraries. For the MALDI-TOF MS analyses, small samples were analyzed by the successive application of 3 solutions to the sample holder: the matrix in acetone, the products in water, and sodium trifluoroacetate in water. The resulting spectra had > 40 envelopes of mass peaks above background. The ionic-abundance peak heights had quasi-Gaussian configurations, with central peaks having masses in the neighborhood of 2000 g/mol (Daltons). Regardless of structural permutations within each peak, the range of these peaks was between about 1500 g/mol and 2900 g/mol. This range of masses was in accord with, but perhaps somewhat more narrow than, that predicted by the statistical method, which was based on equal reactivity of all hydroxyl groups. Analysis by MALDI-TOF MS gave valuable data regarding the masses, structures, and characteristics of the products formed and provided unanticipated information to facilitate improvements in future PCD syntheses.

The first example of the copolymerization of cyclic acid anhydrides with oxetane by bulky titanium bisphenolates

The copolymerization of oxetane with glutaric anhydride was found to proceed with bulky titanium bisphenolate (1) as the initiator. The 1H NMR spectrum of the produced copolymer shows that the copolymer contains both alternating units and oxytrimethylene units in the polymer main chain. 1 was also effective for the copolymerization of oxetane with other cyclic acid anhydrides, affording the corresponding copolymers. With the titanium bisalkolate complex (4), a copolymer rich in alternating sequences was obtained.

2,3,4,5,6,7-Hexahydro-9,10-dimethoxy-1,2-benzothiazonin-3-one 1,1-dioxide

The amide group in the nine-membered ring of the title compound, C13H17NO5S, has the trans conformation. The molecules are linked into infinite one-dimensional chains by bifurcated intermolecular N-H...O hydrogen bonds involving the amide O atom and one of the sulfonyl O atoms of the same neigh- bouring molecule. The compound was prepared by the Friedel-Crafts acylation of 1,2-dimethoxybenzene and glutaric acid anhydride, followed by reduction of the aryl ketone, esterification, chlorosulfonation, treatment with ammonia, saponification and cyclization of the corresponding 5-(2-sulfamoylphenyl)butanoic acid.