Mark Mascal

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Name: Mascal, Mark

Organization: University of California Davis , USA

Department: Department of Chemistry

Title: (PhD)

TOPICS

Organic Chemistry

Chemicals
References

New bio-based monomers: tuneable polyester properties using branched diols from biomass

Co-reporter:Sacha Pérocheau Arnaud;Linglin Wu;Maria-Angelica Wong Chang;James W. Comerford;Thomas J. Farmer;Maximilian Schmid;Fei Chang;Zheng Li

Faraday Discussions 2017 (Volume 202) pp:61-77

Publication Date(Web):2017/09/20

DOI:10.1039/C7FD00057J

A family of monomers, including 2,5-hexandiol, 2,7-octandiol, 2,5-furandicarboxylic acid (FDCA), terephthalic acid (TA), and branched-chain adipic and pimelic acid derivatives, all find a common derivation in the biomass-derived platform molecule 5-(chloromethyl)furfural (CMF). The diol monomers, previously little known to polymer chemistry, have been combined with FDCA and TA derivatives to produce a range of novel polyesters. It is shown that the use of secondary diols leads to polymers with higher glass transition temperatures (Tg) than those prepared from their primary diol equivalents. Two methods of polymerisation were investigated, the first employing activation of the aromatic diacids via the corresponding diacid chlorides and the second using a transesterification procedure. Longer chain diols were found to be more reactive than the shorter chain alternatives, generally giving rise to higher molecular weight polymers, an effect shown to be most pronounced when using the transesterification route. Finally, novel diesters with high degrees of branching in their hydrocarbon chains are introduced as potential monomers for possible low surface energy materials applications.

A Zwitterionic, 10 π Aromatic Hemisphere

Co-reporter:Dr. Nema Hafezi;Wondimagegn T. Shewa;Dr. James C. Fettinger; Mark Mascal

Angewandte Chemie International Edition 2017 Volume 56(Issue 45) pp:14141-14144

Publication Date(Web):2017/11/06

DOI:10.1002/anie.201708521

AbstractA new concept in anionic 10 π aromaticity is described by the embedding of a compensating charge within an aromatic cyclononatetraenide ring by the symmetric superposition of an alkyl ammonium bridge. This is accomplished by the methylation of azatriquinacene to give a quaternary ammonium salt, followed by oxidation to the tetraene and final deprotonation. The resulting zwitterion is a stable [9]annulene with strong aromaticity as shown by its degree of C−C bond equalization and a nucleus-independent chemical shift value lower than that of benzene. The solid-state structure shows an eclipsed stacking motif with the electron-poor ammonium methyl groups occupying the electron-rich cavity of the aromatic bowl.

Introducing Solubility Control for Improved Organic P-Type Dopants

Co-reporter:Jun Li, Guangwu Zhang, Daniella M. Holm, Ian E. Jacobs, Bin Yin, Pieter Stroeve, Mark Mascal, and Adam J. Moulé

Chemistry of Materials 2015 Volume 27(Issue 16) pp:5765

Publication Date(Web):July 24, 2015

DOI:10.1021/acs.chemmater.5b02340

To overcome the poor solubility of the widely used p-type dopant 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ), we have synthesized a series of structure-modified, organic p-type dopants to include alkyl ester groups designed to enable solubility and miscibility control. UV–vis–NIR and cyclic voltammetry measurements show increased solubility of mono- and diester substituted dopants with only modest changes to acceptor strength. Using absorption spectroscopy, photoluminescence, and in-plane conductivity measurements, we demonstrate that the new dopants can successfully p-type dope poly(3-hexylthiophene-2,5-diyl) (P3HT). Monoester substituted dopants are characterized by only slightly reduced electron affinity relative to F4TCNQ, but greater doping effectiveness due to increased miscibility with P3HT. Diester substituted dopants undergo a dimerization reaction before assuming their doped states, which may help anchor dopants into position post deposition, thus decreasing the negative effect of dopant drift and diffusion. We conclude that increased dopant solubility/miscibility increases the overall effectiveness of doping in solution-cast polymer films and that ester modification is a practical approach to achieving solubility/miscibility control in TCNQ-type dopants.

Production of 5-(chloromethyl)furan-2-carbonyl chloride and furan-2,5-dicarbonyl chloride from biomass-derived 5-(chloromethyl)furfural (CMF)

Co-reporter:Saikat Dutta, Linglin Wu and Mark Mascal

Green Chemistry 2015 vol. 17(Issue 7) pp:3737-3739

Publication Date(Web):04 Jun 2015

DOI:10.1039/C5GC00936G

Acid chloride derivatives of 5-(chloromethyl)furan-2-carboxylic acid and furan-2,5-dicarboxylic acid (FDCA) can be produced in high yield by treatment of the precursor aldehydes 5-(chloromethyl) furfural (CMF) and 2,5-diformylfuran (DFF) with tert-butyl hypochlorite, which is inexpensively prepared from commercial bleach and tert-butanol. 5-(Chloromethyl)furan-2-carbonyl chloride (CMFCC) and furan-2,5-dicarbonyl chloride (FDCC) are highly useful intermediates for the production of furoate ester biofuels and polymers of FDCA.

Efficient, metal-free production of succinic acid by oxidation of biomass-derived levulinic acid with hydrogen peroxide

Co-reporter:Saikat Dutta, Linglin Wu and Mark Mascal

Green Chemistry 2015 vol. 17(Issue 4) pp:2335-2338

Publication Date(Web):20 Feb 2015

DOI:10.1039/C5GC00098J

A practical, scalable, metal-free synthesis of succinic acid from the biomass-derived platform chemical levulinic acid is described. Treatment of levulinic acid with the inexpensive, simple oxidant hydrogen peroxide under the catalytic action of trifluoroacetic acid gives succinic acid in high yield and enables facile product isolation by simple distillation of the volatile catalyst and byproducts.

Efficient, Chemical-Catalytic Approach to the Production of 3-Hydroxypropanoic Acid by Oxidation of Biomass-Derived Levulinic Acid With Hydrogen Peroxide

Co-reporter:Dr. Linglin Wu;Dr. Saikat Dutta ; Mark Mascal

ChemSusChem 2015 Volume 8( Issue 7) pp:1167-1169

Publication Date(Web):

DOI:10.1002/cssc.201500025

Abstract

3-Hydroxypropanoic acid (HPA), a precursor to acrylic acid, can be produced in high yield by oxidation of the biomass-derived platform chemical levulinic acid. While treatment of levulinic acid with H₂O₂ under acidic conditions gives predominantly succinic acid, a remarkable reversal of selectivity is observed under basic conditions, leading either directly to HPA or, under modified conditions, initially to 3-(hydroperoxy)propanoic acid, which can be quantitatively hydrogenated to HPA.

5-(Chloromethyl)furfural is the New HMF: Functionally Equivalent But More Practical in Terms of its Production From Biomass

Co-reporter: Mark Mascal

ChemSusChem 2015 Volume 8( Issue 20) pp:3391-3395

Publication Date(Web):

DOI:10.1002/cssc.201500940

Abstract

5-(Chloromethyl)furfural (CMF) is a disruptive innovation in the biorefinery. Chemically, it is at least as versatile as the well-known HMF but, unlike HMF, it is accessible in high yield directly from cellulosic biomass due to its lipophilicity and stability under acidic conditions, which facilitate isolation. It has a rich derivative chemistry that includes biofuels, renewable polymers, specialty chemicals, and value-added agrochemical and pharmaceutical products.

Synthesis of the Insecticide Prothrin and Its Analogues from Biomass-Derived 5-(Chloromethyl)furfural

Co-reporter:Fei Chang, Saikat Dutta, James J. Becnel, Alden S. Estep, and Mark Mascal

Journal of Agricultural and Food Chemistry 2014 Volume 62(Issue 2) pp:476-480

Publication Date(Web):December 19, 2013

DOI:10.1021/jf4045843

Prothrin, a synthetic pyrethroid insecticide, was synthesized from the biomass-derived platform chemical 5-(chloromethyl)furfural in six steps and overall 65% yield. Two structural analogues of prothrin were also prepared following the same synthetic approach. Preliminary testing of these furan-based pyrethroids against the yellow fever mosquito Aedes aegypti indicates promising insecticidal activities.

Hydrodeoxygenation of the Angelica Lactone Dimer, a Cellulose-Based Feedstock: Simple, High-Yield Synthesis of Branched C7C10 Gasoline-like Hydrocarbons

Co-reporter: Mark Mascal;Dr. Saikat Dutta ;Dr. Inaki Garias

Angewandte Chemie 2014 Volume 126( Issue 7) pp:1885-1888

Publication Date(Web):

DOI:10.1002/ange.201308143

Abstract

Dehydration of biomass-derived levulinic acid under solid acid catalysis and treatment of the resulting angelica lactone with catalytic K₂CO₃ produces the angelica lactone dimer in excellent yield. This dimer serves as a novel feedstock for hydrodeoxygenation, which proceeds under relatively mild conditions with a combination of oxophilic metal and noble metal catalysts to yield branched C₇–C₁₀ hydrocarbons in the gasoline volatility range. Considering that levulinic acid is available in >80 % conversion from raw biomass, a field-to-tank yield of drop-in, cellulosic gasoline of >60 % is possible.

Hydrodeoxygenation of the Angelica Lactone Dimer, a Cellulose-Based Feedstock: Simple, High-Yield Synthesis of Branched C7C10 Gasoline-like Hydrocarbons

Co-reporter: Mark Mascal;Dr. Saikat Dutta ;Dr. Inaki Garias

Angewandte Chemie International Edition 2014 Volume 53( Issue 7) pp:1854-1857

Publication Date(Web):

DOI:10.1002/anie.201308143

Abstract

Novel Pathways to 2,5-Dimethylfuran via Biomass-Derived 5-(Chloromethyl)furfural

Co-reporter:Dr. Saikat Dutta ; Mark Mascal

ChemSusChem 2014 Volume 7( Issue 11) pp:3028-3030

Publication Date(Web):

DOI:10.1002/cssc.201402702

Abstract

2,5-Dimethylfuran (DMF) is one of the most actively pursued biomass-derived chemicals due to the fact that it can serve both as a biofuel and an intermediate for drop-in terephthalate polymers. DMF can be accessed via catalytic hydrogenation of 5-(hydroxymethyl)furfural (HMF), but the difficult accessibility of HMF from cellulosic biomass is a major impediment to the commercial development of such a process. Alternatively, 5-(chloromethyl)furfural (CMF) is freely accessible in high yield directly from raw biomass and is shown here to be efficiently reduced to DMF under mild conditions via simple derivatives (aldimine, acetal).

Extreme Oxatriquinanes: Structural Characterization of α-Oxyoxonium Species with Extraordinarily Long Carbon–Oxygen Bonds

Co-reporter:Gorkem Gunbas ; William L. Sheppard ; James C. Fettinger ; Marilyn M. Olmstead

Journal of the American Chemical Society 2013 Volume 135(Issue 22) pp:8173-8176

Publication Date(Web):May 17, 2013

DOI:10.1021/ja4032715

The first stable α-oxyoxonium species have been synthesized and characterized. Strong donation of nonbonding electrons on oxygen into the adjacent σ*(C–O+) orbital was predicted by modeling to result in unheard of carbon–oxygen bond lengths. The kinetic stability of the triquinane ring system provides a platform upon which to study these otherwise elusive species, which are evocative of intermediates on the acetalization reaction pathway. Crystallographic analysis of the α-hydroxy and α-methoxy oxatriquinane triflates reveals 1.658 and 1.619 Å C–O+ bond lengths, respectively, the former of which is a new record for the C–O bond.

Extraordinary Modes of Bonding Enabled by the Triquinane Framework

Co-reporter:Gorkem Gunbas and Mark Mascal

The Journal of Organic Chemistry 2013 Volume 78(Issue 19) pp:9579-9583

Publication Date(Web):September 6, 2013

DOI:10.1021/jo401715s

Incorporation of triquinane ring systems into a macrobicyclic framework enables the stabilization of unusual bonding arrangements, including 3-center-2-electron cation, 3-center-3-electron radical, and 3-center-4-electron anion systems, linear divalent fluorine, triplet carbenes, record short C–C bonds, a powerful proton sponge effect, and oxadionium (R4O2+) ions. The means to stabilize and conceivably isolate such species derives from the rigid, convex nature of the triquinane ring system, as well as the substitution of positions adjacent to the bridgeheads atoms which would otherwise be vulnerable to elimination. The potential realization of hitherto undescribed bonding outcomes makes these macrocycles provocative synthetic targets.

Synthesis of N-substituted Pyrido[4,3-d]pyrimidines for the Large-Scale Production of Self-Assembled Rosettes and Nanotubes

Co-reporter:Asuman Durmus, Gorkem Gunbas, Steven C. Farmer, Marilyn M. Olmstead, Mark Mascal, Belete Legese, Jae-Young Cho, Rachel L. Beingessner, Takeshi Yamazaki, and Hicham Fenniri

The Journal of Organic Chemistry 2013 Volume 78(Issue 22) pp:11421-11426

Publication Date(Web):October 16, 2013

DOI:10.1021/jo4019792

N-substituted pyrido[4,3-d]pyrimidines are heterocycles which exhibit the asymmetric hydrogen bonding codes of both guanine and cytosine at 60° angles to each other, such that the molecules self-organize unambiguously into a cyclic hexamer, assembled via 18 intermolecular hydrogen bonds. The synthesis is straightforward and can be concluded in six steps from the commercially available malononitrile dimer. X-ray crystallographic analysis of the supermacrocyclic structure shows an undulating disk with a ca. 10.5 Å cavity, the centers of which do not overlap sufficiently to describe a channel in the solid state. However, AFM, SEM, and TEM imaging in solution reveals the formation of 1D nanostructures in agreement with their self-assembly into rosette supermacrocycles, which then stack linearly to form rosette nanotubes.

Synthesis of anti-inflammatory furan fatty acids from biomass-derived 5-(chloromethyl)furfural

Co-reporter:Fei Chang, Wan-Hsuan Hsu, Mark Mascal

Sustainable Chemistry and Pharmacy (June 2015) Volume 1() pp:14-18

Publication Date(Web):1 June 2015

DOI:10.1016/j.scp.2015.09.002

•Furan fatty acids (FFAs) are natural antioxidants with anti-atherosclerotic properties.•An efficient synthetic approach has been developed which gives FFAs in 60% overall yield.•The starting material for the synthesis is the biomass-derived platform chemical 5-(chloromethyl)furfural.•The free radical scavenging potential of synthetic FFAs were demonstrated by 2,2-diphenyl-1-picrylhydrazyl (DPPH) assay.An efficient synthetic approach to furan fatty acids starting from the biomass-derived platform chemical 5-(chloromethyl)furfural (CMF) is described. The route involves seven steps and has a 60% overall yield. Furan fatty acids are dietary antioxidants that occur naturally in fish and are proposed to have anti-atherosclerotic properties. The free radical scavenging abilities of synthetic furan fatty acids were evaluated against butylated hydroxytoluene (BHT) by 2,2-diphenyl-1-picrylhydrazyl (DPPH) assay.Download full-size image