Electron-impact studies XCII–Negative ion-molecule reactions in anhydride systems. Perfluoroacetic anhydride with succinic,maleic and phthalic anhydrides. An ion cyclotron resonance study

The trifluoroacetate anion undergoes reaction with succinic, maleic and phthalic anhydrides to yield 1 : 1 adducts. The molecular anions of maleic and phthalic anhydride also undergo reaction with perfluoroacetic anhydride to produce [CF₃CO₂]^?· Maleic anhydride parent ions produce [M + CF₃CO·]^? ions when allowed to react with perfluoroacetic anhydride.     

Synthesis oftertiaryamidomethyl derivatives of 2-isobornyl-4-methylphenol

Derivatives containing tertiary amidomethyl groups were prepared by reaction of a secondary aminomethyl derivative of 2-isobornyl-4-methylphenol with succinic and phthalic anhydrides and (1S)-camphanic acid chloride.     

Synthesis of periodic copolymers via ring‐opening copolymerizations of cyclic anhydrides with tetrahydrofuran using nonafluorobutanesulfonimide as an organic catalyst and subsequent transformation to aliphatic polyesters

To synthesize polyesters and periodic copolymers catalyzed by nonafluorobutanesulfonimide (Nf₂NH), we performed ring‐opening copolymerizations of cyclic anhydrides with tetrahydrofuran (THF) at 50–120 °C. At high temperature (100–120 °C), the cyclic anhydrides, such as succinic anhydride (SAn), glutaric anhydride (GAn), phthalic anhydride (PAn), maleic anhydride (MAn), and citraconic anhydride (CAn), copolymerized with THF via ring‐opening to produce polyesters (M_n = 0.8–6.8 × 10³, M_n/M_w = 2.03–3.51). Ether units were temporarily formed during this copolymerization and subsequently, the ether units were transformed into esters by chain transfer reaction, thus giving the corresponding polyester. On the other hand, at low temperature (25–50 °C), ring‐opening copolymerizations of the cyclic anhydrides with THF produced poly(ester‐ether) (M_n = 3.4–12.1 × 10³, M_w/M_n = 1.44–2.10). NMR and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectra revealed that when toluene (4 M) was used as a solvent, GAn reacted with THF (unit ratio: 1:2) to produce periodic copolymers (M_n = 5.9 × 10³, M_w/M_n = 2.10). We have also performed model reactions to delineate the mechanism by which periodic copolymers containing both ester and ether units were transformed into polyesters by raising the reaction temperature to 120 °C. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Polycondensations of hydroxycarboxylic acids derived from optically active aminoalcohols and acid anhydrides—syntheses of functional poly(ester-amide)s

Syntheses and polycondensations of optically active hydroxycarboxylic acids prepared from acid anhydrides and aminoalcohols were carried out. Novel polymers with M̄_n 9900–27,200 were obtained by the polycondensations of hydroxycaboxylic acids derived from maleic or succinic acid using 1.2 eq. of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC · HCl) in DMF (2M) at room temperature for 8 h in satisfactory yields. Meanwhile, a hydroxycarboxylic acid obtained from phthalic acid afforded no polymer but a phthalimide derivative. The radical additions of ethanethiol or mercaptoethanol with the polymers derived from maleic anhydride proceeded smoothly in satisfactory incorporation ratios (65–98%), respectively. The polymer obtained from succinic anhydride and 2-aminoethanol showed hydrolytic degradability. © 1997 John Wiley & Sons, Inc.     

Integration of Succinic Acid and Ethanol Production With Potential Application in a Corn or Barley Biorefinery

Production of succinic acid from glucose by Escherichia coli strain AFP184 was studied in a batch fermentor. The bases used for pH control included NaOH, KOH, NH₄OH, and Na₂CO₃. The yield of succinic acid without and with carbon dioxide supplied by an adjacent ethanol fermentor using either corn or barley as feedstock was examined. The carbon dioxide gas from the ethanol fermentor was sparged directly into the liquid media in the succinic acid fermentor without any pretreatment. Without the CO₂ supplement, the highest succinic acid yield was observed with Na₂CO₃, followed by NH₄OH, and lowest with the other two bases. When the CO₂ produced in the ethanol fermentation was sparged into the media in the succinic acid fermentor, no improvement of succinic acid yield was observed with Na₂CO₃. However, several-fold increases in succinic acid yield were observed with the other bases, with NH₄OH giving the highest yield increase. The yield of succinic acid with CO₂ supplement from the ethanol fermentor when NH₄OH was used for pH control was equal to that obtained when Na₂CO₃ was used, with or without CO₂ supplementation. The benefit of sparging CO₂ from ethanol fermentation on the yield of succinic acid demonstrated the feasibility of integration of succinic acid fermentation with ethanol fermentation in a biorefinery for production of fuels and industrial chemicals.     

Chemical Modification of A Vinyl Ester Resin by Acid Anhydrides and Characterization of the Products by l3C NMR

A vinyl ester resin was modified into half ester-acids by reaction with phthalic, maleic, and succinic anhydrides, using pyridine as catalyst. GPC analysis indicated that the reaction proceeds without crosslinking or polymerization. ¹³C-NMR analysis showed that the β-isomer of the vinyl ester resin containing a primary hydroxyl group reacts much more rapidly than the α-isomer with a secondary hydroxyl group.     

Sequence Control in Asymmetric Terpolymerizations of meso-Epoxides,CO2, and Phthalic Anhydride: Unprecedented Statistical Ester–Carbonate Distributions

The statistical terpolymerization of epoxides, CO₂ and cyclic anhydrides remains challenging, mainly because epoxide/CO₂ and epoxide/anhydride copolymerizations typically proceed at considerably different rates. Herein, we report the syntheses of novel chiral terpolymers with unprecedented statistical distributions of carbonate and ester units (up to 50 % junction units) via the one-pot reaction of cyclohexene oxide, phthalic anhydride, and CO₂ under mild conditions using enantiopure bimetallic aluminum-complex-based catalyst systems. Notably, all resulting terpolymers exhibited excellent enantioselectivities (≥96 % ee) that were independent of the carbonate–ester distribution. The statistical compositions of the carbonate and ester units in the resulting terpolymers were determined via ¹H and ¹³C NMR spectroscopies. Furthermore, thermal properties were tuned by altering the ester content of the chiral terpolymer without influencing the enantioselective ring-opening step involving the meso-epoxide. This asymmetric terpolymerization methodology is also compatible with a variety of meso-epoxides to afford the corresponding terpolymers with 17 %–25 % junction units and excellent enantioselectivities (94 %–99 % ee). The present study is expected to provide new guidelines for preparing a broad range of biodegradable polymers with excellent enantioselectivities and adjustable properties.     

Regioselective phthalation and succinylation of D-glucose and D-galactose using protecting groups: Conversion of the products to organotin derivatives

1,2: 5,6-Di-O-isopropylidene-α-D -glucofuranose was acylated at the free 0-3 position with phthalic and succinic anhydrides. Removal of the protecting groups gave the 3-O-acylglucopyranose compounds which were converted to their acetyl and organostannyl derivatives. A similar sequence of reactions was carried out with 1,2:3,4-di-O-isopropylidene-α-D -galactopyranose.     

Synthesis and properties of 3-substituted 3-azabicyclo-[3.3.1]nonan-9-amines

Catalytic hydrogenation of 3-benzyl- and 3-tert-butoxycarbonyl-3-azabicyclo[3.3.1]nonan-9-one oximes over Raney nickel gave the corresponding 3-substituted 3-azabicyclo[3.3.1]nonan-9-amines which were converted into amides via reactions with acetyl and chloroacetyl chlorides and maleic and succinic anhydrides, into Schiff bases by condensation with benzaldehyde and 4-chlorobenzaldehyde, and into isothiocyanates by treatment with thiophosgene in the presence of K₂CO₃. 3-Benzyl- and 3-tert-butoxycarbonyl-3-azabicyclo-[3.3.1]nonan-9-yl isothiocyanates readily reacted with methanol, aniline, and sodium azide to produce methyl thiocarbamate, thiourea, and dihydrotetrazole-5-thione derivatives having a 3-azabicyclo[3.3.1]nonane fragment.     

Bimetallic Al(III) Compounds as Catalysts for the Synthesis of Biodegradable Polyesters and Polycarbonates

Ethylenediamine bridged benzoxazine proligands were synthesized by a modified Mannich condensation reaction. The reaction of the proligands with two equivalents of AlMe₃ resulted in the formation of dinuclear Al(III) compounds in high yield and purity. When the ligand binds to the Al(III) center, it forms two separate six-membered N,O-chelates with the two Al atoms that resembles the N-alkylated salan moiety. Each aluminum atom adopts a distorted tetrahedral geometry as revealed from the single-crystal X-ray diffraction studies of 1 . The catalytic activity of these aluminum compounds was investigated towards the ROP of rac-LA and ROCOP of epoxides (PO, CHO, tBuGE) and phthalic anhydride and ROCOP of CHO with CO₂. These aluminum compounds showed notable catalytic activity towards the ROP and ROCOP reactions in the absence of cocatalyst.     

Enantioselective Preparation of β2‐Amino Acids with Aspartate,Glutamate, Asparagine,and Glutamine Side Chains

(S)‐β²‐Homoamino acids with the side chains of Asp, Glu, Asn, and Gln have been prepared and suitably protected (N‐Fmoc, CO₂^tBu, CONHTrt) for solid‐phase peptide syntheses. The key steps of the syntheses are: N‐acylation of 5,5‐diphenyl‐4‐isopropyl‐1,3‐oxazolidin‐2‐one (DIOZ) with succinic and glutaric anhydrides (Scheme 2), alkylation of the corresponding Li‐enolates with benzyl iodoacetate and Curtius degradation (Scheme 4), and removal of the chiral auxiliary (Scheme 5). In addition, numerous functional‐group manipulations (CO₂H?CO₂^tBu, CO₂Bn?CO₂H, CbzNH→FmocNH, CO₂H→CO₂NH₂→CONHTrt; Schemes 2, 4, 5, and 6) were necessary, in order to arrive at the four target structures. The configurational assignments were confirmed by X‐ray crystal‐structure determinations (Scheme 2 and Fig. 3). The enantiomeric purities of a β²hAsn and of a β²hGln derivative were determined by HPLC on a Chiralcel column to be 99.7 : 0.3 and >99 : 1, respectively (Fig. 4). Notably, it took up to twelve steps to prepare a suitably protected trifunctional product with a single stereogenic center (overall yield of 10% from DIOZ and succinic anhydride)!     

Enzymatic Ring‐Opening Polymerization of Oxiranes and Dicarboxylic Anhydrides

Oxiranes, such as glycidyl phenyl ether, benzyl glycidate, glycidyl methyl ether, and styrene oxide, were copolymerized with dicarboxylic anhydrides, such as succinic anhydride, phthalic anhydride, and maleic anhydride, by the action of an enzyme in a stepwise reaction to produce the corresponding polyesters containing some ether linkages having a maximum M _w of 13 500. Oxiranes, such as glycidol and glycidyl phenyl ether, were also homopolymerized and copolymerized with other oxiranes by the enzyme to produce the corresponding polyethers.

Enzymatic polymerization of oxiranes and dicarboxylic anhydrides.     

Acyl Iodides in Organic Synthesis: V. Reactions with Carboxylic Acid Esters

Acyl iodides react with alkyl, alkenyl, and aralkyl esters derived from saturated, unsaturated, and aromatic mono- and dicarboxylic acids in the absence of a catalyst. The reaction involves cleavage of the OR bond and formation of organic iodide RI (including CH₂=CHI) and one or two symmetric carboxylic acid anhydrides. Phenyl acetate reacts with benzoyl iodide to give acetyl iodide and phenyl benzoate as a result of cleavage of the (O=)C–O bond. The reaction of diethyl fumarate with acetyl iodide is accompanied by cis– trans isomerization to afford maleic anhydride. In the reactions of acetyl iodide with diethyl oxalate and diethyl malonate, CO and CO₂ and CO₂ and polyketene are formed, respectively, in addition to ethyl iodide and acetic anhydride. Ethyl esters of strong organic acids, e.g., ethyl trihaloacetates, failed to react with acyl iodides under analogous conditions.     

Kinetic Investigations of Reactions with Maleic Anhydride Copolymers and Model Compounds

Alternating copolymers that contain maleic anhydride (MAn) as a component occur in two different stereochemical configurations which are differentiated by their reactivity. Model compounds, 2, 3-dialkylsuccinic acids and their anhydrides, were investigated and it was demonstrated that there is a distinct difference between threo and erythro configurations in their chemical and physical behavior. Both configurations also occur in the alternating copolymers. Beside the model compounds, the alternating copolymers ethylene-MAn, propylene-MAn, and styrene-MAn were investigated in their reactions with amines, alcohols, and water (hydrolysis). The cis configurations showed the higher reaction rates. Reactions of the anhydride moieties with equimolar amounts of aniline, ethanol, and water demonstrated that reactions follow second-order rate laws. With excess reactant, the reaction follows a pseudo-first-order rate law. The rate constants depend on the degree of polymerization and on the comonomer. Increasing steric hindrance and molecular weight lead to a decrease of the reaction rate. Catalysis of the hydrolysis reaction by tertiary amines results in similar rate constants for the configurations of the substituted succinic acid anhydrides. The reasons are discussed.     

Thermally stable polymers based on bismaleimides containing amide,imide, and ester linkages

Seven new structurally different bismaleimides were synthesized and characterized by infrared and proton nuclear magnetic resonance spectroscopy. The chain of these polymer precursors was extended by incorporating amidized, imidized, and esterified 4-chloroformyl phthalic anhydride. The bismaleimides containing amide and imide linkages were prepared by a simple synthetic route based on the reaction of the monomaleamic acid derived from various aromatic diamines (1 mol) with 4-chloroformyl phthalic anhydride (0.5 mol) and subsequent cyclodehydration of the intermediate triamic acid. In addition, chain extended bismaleimides were prepared by reacting the monomaleamic acid derived from p-phenylenediamine with several dianhydrides such as p-phenylene bis(trimellitamide anhydride), p-phenylene bis(trimellitate anhydride), and bis-phenol A bis(trimellitate anhydride). The differential thermal analysis scans of bismaleimides showed exotherms at 221–304°C associated with their polymerization reactions. The thermogravimetric analysis traces of polymers did not show a weight loss up to 351–393 and 344–372°C in N₂ and air atmospheres, respectively. The anaerobic char yield of polymers at 800°C was 44–61%. These polymers can be used for fabrication of composites having improved properties.     

An efficient one-pot synthesis of anthraquinone derivatives catalyzed by alum in aqueous media

Abstract

Alum (KAl(SO₄)₂·12H₂O) performs as a novel catalyst for the synthesis of anthraquinone derivatives from phthalic anhydride and substituted benzenes in good to excellent yields (70–96%) using water as a solvent at ambient temperature. Several solvents were examined for this reaction; however, in terms of reaction yield and time, water was found to be the optimum solvent. The remarkable advantages offered by this method are an inexpensive and easily available catalyst, a simple procedure, mild conditions, and much faster (60–120 min) reactions.     

Production of succinic acid by anaerobiospirillum succiniciproducens

The effect of an external supply of carbon dioxide and pH on the production of succinic acid byAnaerobiospirillum succiniciproducens was studied. In a rich medium containing yeast extract and peptone, when the external carbon dioxide supply was provided by a 1.5M Na₂CO₃ solution that also was used to maintain the pH at 6.0, no additional carbon dioxide supply was needed. In fact, sparging CO₂ gas into the fermenter at 0.025 L/L-min or higher rates resulted in significant decreases in both production rate and yield of succinate. Under the same conditions, the production of the main by-product acetate was not affected by sparging CO₂ gas into the fermenter. The optimum pH (pH 6.0) for the production of succinic acid was found to be in agreement with results previously reported in the literature. Succinic acid production also was studied in an industrial-type inexpensive medium in which light steep water was the only source of organic nutrients. At pH 6.0 and with a CO₂ gas sparge rate of 0.08 L/L-min, succinate concentration reached a maximum of 32 g/L in 27 h with a yield of 0.99 g succinate/g glucose consumed.     

d-Glucosamine as an efficient and green additive for palladium-catalyzed Heck reaction

The Heck coupling of haloarenes with various alkenes was successfully performed in the presence of 0.5 mole % Pd(OAc)₂ and 1.0 mole % d-glucosamine as an additive with K₂CO₃ as the optimal base in a mixture of H₂O/iPrOH (φ _r = 2: 1) as the reaction solvent at 80°C after 6 h. d-Glucosamine was found to be an inexpensive, air-stable, easy to available, and efficient additive in palladium-catalyzed Heck reactions of aryl iodides (67–95 % conversion) and bromides (38–72 % conversion).     

The Inhibition of Calcite Dissolution/Precipitation: 1,2-Dicarboxylic Acids

The dissolution of calcite under conditions of high pH (8.0-9.0) is shown to be strongly inhibited by ca. 10 mM levels of the fully deprotonated forms of succinic acid, phthalic acid, and maleic acid. Channel flow cell measurements are used in each case to deduce the appropriate rate law for dissolution. For the maleate dianion it is demonstrated that the inhibition is likely due to the blocking of dissolution/growth sites at which CaCO₃ units are incorporated into or removed from the crystal lattice, whereas for the other two ions it arises from competitive Langmuirian adsorption of the dicarboxylate ions and CO^2-₃ on the calcite surface.