Maleopimaric Acid Research Articles

Synthesis and reactivity of maleopimaric acid N-aryl(aralkyl)imidoamides

A method of synthesis of maleopimaric acid N-aryl(aralkyl)imidoamides by reaction of the corresponding aromatic amides of maleopimaric acid and amines in p-xylene at reflux was developed. Thermal stability of the synthesized compounds was evaluated by derivatography.

Synthesis and Antifeedant Activities of Rosin-Based Esters Against Armyworm.

A series of rosin based esters have been synthesized from dehydroabietic acid and maleopimaric acid, respectively. Their structures were confirmed by FT-IR, (1)H NMR, (13)C NMR and single crystal X-ray diffraction. Their antifeedant activities against armyworm were examined by leaf plate method. Methyl ester of dehydroabietic acid and maleopimaric acid were crystallized in orthorhombic system with cell dimensions of a = 26.352 [5] Å, b = 6.1020 [12] Å, c = 11.812 [2] Å and a = 7.9216 [11] Å, b = 11.9912 [16] Å, c = 23.425 [3] Å, respectively. They contained classic tricyclic hydrophenanthrene skeleton. The antifeedant results indicated that most rosin-based esters exhibited significant antifeedant activities at a concentration of 0.01 g mL(-1). Their feeding deterrence values were above 70% after 24h. The antifeedant activities for rosin-based esters increased with the growth of chain length of alcohol except (Ia). Some armyworm were found dead during the antifeedant activity test, by which we speculated that these synthetic rosinbased esters had stomach poison activities against armyworm.

Preparation and properties of maleopimaric acid-based polyester polyol dispersion for two-component waterborne polyurethane coating

Abstract An anionic polyol (MPP) dispersion was prepared by introducing maleopimaric acid (MPA) into polyester polyol chain through esterification reaction. The influences of catalyst content, molar ratio of alcohol to acid, 5-sulfoisophtalic acid sodium salt (5-SSIPA) content and MPA content on particle size, stability and rheological property of MPP dispersion were investigated. The optimized conditions for the synthesis of stable MPP dispersion were identified as 1 wt% catalyst content, 1.4:1 molar ratio of alcohol to acid, 2.86 wt% 5-SSIPA content, and 15 wt% MPA content. The MPP dispersion was then applied to the preparation of a novel maleopimaric acid-based two-component waterborne polyurethane (2K-WPU) coating. Incorporating MPA into MPP dispersion leaded to the maleopimaric acid-based 2K-WPU coating with improved tensile strength, gloss, pencil hardness, water resistance and ethanol resistance. The results suggested that MPP dispersion provided a potential application in the field of 2K-WPU coating.

Structure-property correlation study of bio-based multifunctional vinyl ester resin in presence of methacrylated lignin model compounds

Diels-Alder adduct of gum rosin and maleic anhydride (MPA) were treated with trimethylolpropane to obtain trimethylolpropane modified maleopimaric acid adduct (TMPA). This adduct was then epoxidized using epichlorohydrin and KOH as catalyst to synthesize an epoxy resin (TMPAE), which was further esterified using methacrylic acid in the presence of triphenyl phosphine as catalyst and hydroquinone as inhibitor to produce bio-based multifunctional vinyl ester resin (VTMPAE). This article also reports the synthesis of lignin model compounds i.e. methacrylated eugenol (ME) and methacrylated guaiacol (MG) as bio-based reactive monomers for vinyl ester resins. The chemical structures of all synthesized products were analyzed using FTIR, 1HNMR and 13C NMR spectroscopic techniques. The thermal and mechanical properties of the samples were evaluated using Differential Scanning Calorimetry (DSC), Thermogravimetric Analyzer (TGA) and Universal Testing Machine (UTM), respectively. Chemical and corrosion resistance of the above cured VTMPAE samples coated on steel panels were also evaluated as a function of % weight loss by immersing the VTMPAE samples in 1 M HCl, 1 M NaOH, and 1 M NaCl solutions for 90 days. The morphological changes that appear upon such an exposure were also studied with the help of Scanning electron microscopy (SEM).

Efficient synthesis of maleopimaric acid N-arylimides

An efficient approach toward synthesis of maleopimaric acid N-arylimides starting from rosin maleic anhydride adduct without isolation of maleopimaric acid has been elaborated. Terpenoid diimide diacids and their esters have been synthesized based on the obtained N-arylimides. Thermal stability of the products has been estimated by derivatography.

Synthesis and characterization of novel fluorosilicone rubber using imide modified vinyl‐containing fluorosilicone resin as cross‐linker

ABSTRACTA novel imide modified vinyl‐containing fluorosilicone resin (MP‐VFS) was firstly prepared from maleopimaric acid (MPA), and characterized by1H NMR and13C NMR. Containing MPA based imide heterocycle (MPABI), MP‐VFS was further used as a novel cross‐linker to prepare MPA modified fluorosilicone rubber (MP‐FSR). Morphology, mechanical and oil‐resistance properties, thermal properties, and low temperature resistance of MP‐FSR had been studied. Microphase separation was observed in MP‐FSR. Although the tensile strength of fluorosilicone rubber was not significantly enhanced, the tearing strength, breaking elongation, rebound resilience and hardness were effectively improved. When the MP‐VFS content was 2.0 wt %, the tearing strength of MP‐FSR was increased by 23.5%, breaking elongation by 18.6% and rebound resilience by 9.7%. The thermal stability was enhanced due to the incorporation of MPABI. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem.2015,53, 1769–1776

Retraction Note to: Fully biobased epoxy from isosorbide diglycidyl ether cured by biobased curing agents with enhanced properties

In this study, isosorbide diglycidyl ether (isosorbide epoxy) was cured by a variety of biobased curing agent of terpene maleic anhydride (TMA) and maleopimaric acid (MPA) to prepare fully biobased epoxy resins. The structures of isosorbide epoxy and biobased curing agents were synthesized and characterized by NMR. The non-isothermal curing kinetics of fully biobased epoxies were studied using differential scanning calorimetry (DSC). The bis-phenol A type epoxy and petroleum based curing agent methyl Nadic anhydride (MNA) bearing similar caged structure was also studied for comparison. The mechanical properties of the biobased epoxy resins were evaluated using dynamic mechanical analysis (DMA) and the thermal stability was characterized by thermogravimetric analysis (TGA), respectively. The fully biobased epoxies have comparable or even better mechanical properties and thermal stability than the biophenol A type epoxies cured by petroleum based curing agents, showing that the biobased isosorbide epoxies have great potential application as substitute for those petroleum based epoxies.

Synthesis of a 2,3-Dienoate Based on Methyl Maleopimarate

In continuation of research on the synthesis of stable allenoates of N-substituted amino acids [1–3], we proposed a synthetic pathway to 2,3-dienoate 1 as a convenient synthon for further transformations that contained a maleopimaric acid moiety in its structure. Maleopimaric acid and its derivatives are known to exhibit high biological activity [4, 5]. Allene 1 was synthesized from methyl maleopimarate (2) and -aminobutyric acid (3, GABA). The N-substituted GABA of methyl maleopimarate (4) was obtained via direct fusion or condensation in DMF in yields of 52 and 72%, respectively. Then, 4 was refluxed in anhydrous C6H6 with an excess of thionylchloride for 3 h. The resulting acid chloride and Et3N gave ketene 5, which reacted with methyl(triphenylphosphoranylidene)acetate afforded the corresponding allenoate 1 in 66% yield (Scheme 1).

Synthesis and characterization of imide modified poly(dimethylsiloxane) with maleopimaric acid as raw material

With the natural rosin derivative (maleopimaric acid, MPA) as the raw material, imide modified vinyl poly(dimethylsiloxane) (MP-VMS) was synthesized and characterized by 1H NMR and 13C NMR. The curing kinetic parameters of MP-VMS were determined by differential scanning calorimetry (DSC) at various heating rates (5, 8, 10, 15 °C/min) from the Kissingner, Ozawa and Crane methods. The activation energy (Ea), pre-exponential factor (A) and reaction order (n) were respectively 18.6 kJ/mol, 71,108 and 0.902. The low-temperature and high-temperature resistance of its curing product were respectively investigated by DSC and thermogravimetric analysis. The results showed that incorporation of MPA could significantly improve the thermal stability of silicone while had no effect on the low-temperature resistance, and the Tmax (the temperature corresponding to the maximum weight loss rate) increased by 70.7 °C.

Synthesis and anticancer activity of quinopimaric and maleopimaric acids’ derivatives

A series of quinopimaric and maleopimaric acids’ derivatives modified in the E-ring, at the carbonyl- and carboxyl-groups were synthesized and their in vitro cytotoxic activity was evaluated at the National Cancer Institute, USA. Methyl esters of dihydroquinopimaric, 1a,4a-dehydroquinopimaric, 2,3-epoxyquinopimaric, 1-ethylenketal-dihydroquinopimaric, 1-ethylenketal-4-hydroxyiminodihydroquinopimaric acids displayed an activity on renal cancer, leukemia, colon cancer and breast cancer cell lines in concentration 10−5M. Methyl 1,4-dihydroxyiminodihydroquinopimarate showed both a potent and broad spectrum of cytotoxic activity against NSC lung cancer, colon cancer, breast cancer, renal cancer and leukemia and revealed in vivo antineoplastic activity towards mouse solid transplantable mammary carcinoma Ca755 and colon adenocarcinoma AKATOL. The information about antineoplastic activity of the studied quinopimaric and maleopimaric acids’ derivatives will be used for hit to lead optimization in these chemical series.

Synthesis, characterization and application of a dispersant based on rosin for coal-water slurry

A rosin derivative and maleopimaric acid diethanolamide (MAD), was synthesized, characterized by FTIR and 1H NMR, and applied as dispersant for the coal-water slurry (CWS) prepared from Chinese Shenfu coal. The CWS application performance investigation shows that the MAD dispersant has better abilities in reducing CWS viscosity and stabilizing the slurry than a commercial dispersant—sulfonated naphthalene-formaldehyde condensate (SNF). The physicochemical property investigation of the two tested dispersants shows that the adsorption amount of the MAD at coal-water interface is much larger than that of SNF, and the MAD has better wetting property than the SNF on the coal surface. It indicated that the excellent capabilities of MAD are related to the adsorption mode of standing upright on the coal surface. Based on the above, the mechanism of dispersion and stabilization of the CWS prepared from MAD dispersant is presented.

Synthesis and antitumor activity evaluation of maleopimaric acid N-aryl imide atropisomers

Maleopimaric acid N-aryl imides (2) and methyl maleopimaric acid N-aryl imides (3) were designed and synthesized. Their atropisomers (A and B) were separated into their enantiomeric pure forms and the anti-proliferative activity was tested against NCI, A549, Hep G-2, MGC-803 and Hct-116 cell lines, respectively. A significant difference in the level of cytotoxicity was observed between R and S conformers. Atropisomers A with an R configuration exhibited significant toxicity (the IC50 values ranging from 7.51 to 32.1μM). Further experiments proved that antitumor activity of 2A was achieved through the induction of cell apoptosis by G1 cell-cycle arrest.

Use of eugenol and rosin as feedstocks for biobased epoxy resins and study of curing and performance properties

In this study, an epoxy based on eugenol and an anhydride curing agent based on rosin were prepared. Curing of the eugenol epoxy with a commercial anhydride curing agent and with the rosin-derived anhydride curing agent was studied. For comparison, a commercial bisphenol A type epoxy, DER353, was also selected in the curing study. The syntheses of the eugenol epoxy and rosin anhydride were investigated and the chemical structures of the products and intermediates were characterized using 1H NMR and Fourier transform infrared spectroscopies. Non-isothermal curing of the eugenol epoxy with hexahydrophthalic anhydride and the rosin-derived maleopimaric acid was studied using differential scanning calorimetry. Thermomechanical properties and thermal stability of the cured epoxy resins were evaluated using dynamic mechanical analysis and thermogravimetric analysis, respectively. Addition of 2-ethyl-4-methylimidazole as catalyst greatly decreased the curing temperature and promoted the completion of cure reactions. The results suggest that the eugenol epoxy and the bisphenol A type epoxy have similar reactivity, dynamic mechanical properties and thermal stability. © 2013 Society of Chemical Industry

Preparation and Antimicrobial Activity of Rosin-based Carbamate Group-containing Quaternary Ammonium Salt Derivatives

A novel rosin-based carbamate was prepared by the reaction of N,N-dimethylaminopropylamine with rosin-based cyclic carbonate. Using LiBr in conjunction with ethylene glycol as a catalyst, carbon dioxide was treated with triglycidyl ester of maleopimaric acid to prepare the rosin-based cyclic carbonate. The carbamate was then quaternized to form three rosin-based carbamate group-containing quaternary ammonium salt derivatives. The chemical structures of all new compounds were characterized by IR, 1H NMR, and 13C NMR. The antimicrobial activities of the carbamate and quaternary ammonium salt derivatives were investigated. The bioassay test results showed that all derivatives exhibited strong inhibition against Staphylococcus aureus, Escherichia coli, Bacillus subtilis, Bacillus thuringiensis, and Streptomyces microflavus. However, no visible antifungal activity was found against Saccharomyces cerevisiae or Aspergillus niger, except for the activity of the carbamate derivative against S. cerevisiae.

Synthesis and characterization of a novel rosin-based monomer: free-radical polymerization and epoxy curing

Rosin, an abundant raw material from pine trees, has attracted much attention due to its use as a feedstock for the preparation of polymers in the age of the depletion of crude oil. Maleopimaric acid (MPA) is one of most impor-tant rosin derivatives obtained via Diels-Alder reaction between gum rosin and maleic anhydride. In this article, the authors reported a synthetic strategy to prepare a novel vinyl ester of MPA (AMPA) by sequential reaction of MPA with oxalyl chloride and allyl alcohol. The structure and properties of AMPA were characterized by fourier transform infrared spectroscopy (FT-IR), gas chromatography–mass spectrometry, 1H NMR, 13C NMR and differential scanning calorimetry (DSC). The results showed that AMPA has high purity and could undergo free-radical polymerization. In particular, AMPA was used as a curing agent to carry out noniso-thermal curing reaction with epoxy resin by DSC, and cured polymers were characterized by FT-IR and thermogra-vimetric analysis. The results suggested that AMPA has a great potential to prepare rosin-based unsaturated resin and epoxy resin.

Regioselective oxidation of the methyl ester of maleopimaric acid by dimethyldioxirane

Reaction of the methyl ester of maleopimaric acid and dimethyldioxirane resulted in regioselective oxidation of the bridging double bond to form the 13(15)-en-14S-hydroxy derivative.

Study on the Regioselectivie of Grignard Reagent Addition Reaction of Maleopimaric Acid Trimethyl Ester

Two regioselectivite adducts (compounds 3 and 4) were firstly synthesized from the Grignard reagent and maleopimaric acid trimethyl ester (2). The structures of all compounds were characterized by elemental analyses, NMR and MS, and stero-structures of 3 were further determined by COSY, HMQC and HMBC. The spatial structure of 3 was further confirmed by X-ray single crystal diffraction analysis method. Owing to the addition reaction selectivity of 2 was dependent on the steric hindrance of three methyl groups, the TADDOL (tetraaryl-1,3-dioxolane-4,5-dimethanols) product was prevented because of the formation of lactone 3, but the stereo-structure of the rosin-ring did not changed. Products of 3 and 4 are expected to apply as chiral derivatization reagents. Keywords maleopimaric acid trimethyl ester; grignard reagent; 2D NMR; regioselectivity

Synthesis of maleopimaric and citraconopimaric acids N-[3-(pyrimidin-2-yl)aryl]amides

Acylation of 6-methyl-N-[4-(pyridin-3-yl)pyrimidin-2-yl]benzene-1,3-diamine, 4-methyl-N-[4-(pyridin-3-yl)pyrimidin-2-yl]benzene-1,3-diamine, and N-[4-(pyridin-3-yl)pyrimidin-2-yl]benzene-1,3-diamine with maleopimaric and citraconopimaric acid chlorides, with benzotriazolyl maleopimarate afforded N-[3-(pyrimidin-2-yl)aryl]amides of maleopimaric and citraconopimaric acids. By the reaction of substituted N-arylamides of maleopimaric acid with methanesulfonic acid biologically active methanesulfonates were obtained.

Novel One-Component Positive-Tone Chemically Amplified I-Line Molecular Glass Photoresists

Maleopimaric acid, cycloaddition reaction product of rosin with maleic anhydride, was reacted with hydroxylamine to afford N-hydroxy maleopimarimide, which was then further esterified with 2-diazo-1-naphthoquinone-4-sulfonyl chloride (2,1,4-DNQ-Cl) to give N-hydroxy maleopimarimide sulfonate. The carboxylic acid group of the compound was then protected by the reaction of this compound with vinyl ether compounds to give the corresponding molecular glass compounds. Upon irradiation to 365 nm light, the 2,1,4-DNQ group undergo photolysis not only to be converted into indene carboxylic acid but also generate a few amount of sulfonic acid which can catalyze the deprotection of the acid labile group. So, novel one-component positive-tone chemically amplified i-line photoresists can be formed by the molecular glass compounds. The lithographic performance of the resists was evaluated using i-line exposure system with high photosensitivity and resolution.

Synthesis of diterpenoid steviol derivative containing a posphorus-carbon bond on the basis of Pudovik reaction

Organophosphorus compounds involving P–C bond (phosphonolipids, phosphonopyruvic acid, phosphinothricin and its analog, etc.) are regarded usually as formal analogs of phosphates, with the difference that their biological properties (for example, anti-microbial, antiviral, anticancer activity, enzyme inhibition, etc.) are much higher and more varied due to certain difficulties of enzymatic degradation of the phosphorus–carbon bond compared with the phosphorus–oxygen bond [1, 2]. Despite this circumstance, there is a significant number of natural metabolites of high biological activity with the phosphorus–carbon bond [3]. Various methods for their preparation including the Arbuzov, Michaelis–Becker, Pudovik, and Abramov reactions have been reported [1, 2]. Isoprenoid phosphorus-containing derivatives with a P–C bond have not been found in natural sources, but the synthesis of these compounds was performed on the basis of secondary metabolites of monoterpenoid (citral, menthane, carane, pinane, bornane derivatives [4–13]), diterpenoid (abietane derivatives [14, 15]) and steroid (cholestane derivatives [16]) series. They were obtained by the Pudovik reaction of unsaturated isoprenoids (limonene, carvomenthone, camphene, αand β-pinenes) with diethyl phosphite [5, 6]; the reaction of alkali metals arylphosphides with menthyl chloride [7, 8], hydroxy derivatives of maleopimaric and fumaropimaric acids [14, 15] and cholestan-3-one [16]; the reaction of some α,β-unsaturated isoprenoid oxocompounds (citral, carvone, pinocarvone, 3-caren4-one) and nitriles of monoterpenoid series with threeand dialkylphosphites [4], dibenzylphosphine oxide [9–11] and sodium diethylphosphide [12]; the Diels– Alder reaction of α-phellandrene with trans-vinylenebis(diphenylphosphine sulfide) [13].