1126-61-0Relevant academic research and scientific papers
Catechol-Functionalized Polyolefins
Chen, Changle,Na, Yinna
, p. 7953 - 7959 (2020)
The incorporation of comonomers during ethylene polymerization can efficiently modulate important material properties of the polyolefins. Utilizing bioresourced comonomers for the generation of high-performance polyolefin materials is attractive from a sustainability point of view. In this contribution, bioresourced eugenol and related comonomers were incorporated into polyolefins through palladium-catalyzed copolymerization and terpolymerization reactions. Importantly, high-molecular-weight catechol-functionalized polyolefins can be generated. The introduction of different metal ions induces efficient interactions with the incorporated catechol groups, leading to enhanced mechanical properties and self-healing properties. Moreover, the catechol functionality can greatly improve other properties such as surface properties, adhesion properties, and compatibilizing properties. The catechol-functionalized polyolefin was demonstrated as a versatile platform polymer for accessing various materials with dramatically different properties.
Thiol-ene adhesives from clove oil derivatives
Donovan, Brian R.,Cobb, Jared S.,Hoff, Ethan F. T.,Patton, Derek L.
, p. 61927 - 61935 (2014)
This paper reports the synthesis of catechol-functionalized thiol-ene polymer networks as photocurable adhesives, where the adhesive interactions are derived from 4-allylpyrocatechol - a monofunctional alkene readily obtained from natural products of Syzygium aromaticum flower buds (clove). The thiol-ene photopolymerization process enables rapid cure times, low energy input, and solvent-free processing. The resulting polymer networks show improved macroscopic adhesion to a variety of substrates - including glass, marble, aluminum, and steel - by varying the concentration of 4-allylpyrocatechol in the network. Additionally, the effects of the catechol moiety on polymerization kinetics, thermomechanical, and mechanical properties were determined by comparing the synthesized catechol moiety to a series of control monomers such as eugenol (one phenol group) and methyl eugenol (no phenol groups).
Utilization of catecholic functionality in natural safrole and eugenol to synthesize mussel-inspired polymers
Alhaffar, Mouheddin T.,Akhtar, Mohammad N.,Ali, Shaikh A.
, p. 21265 - 21277 (2019)
Naturally occurring safrole I upon epoxidation gave safrole oxide II, which underwent ring opening polymerization using a Lewis acid initiator/catalyst comprising of triphenylmethylphosphonium bromide/triisobutylaluminum to afford new polyether III in excellent yields. Epoxy monomer II and allyl glycidyl ether IV in various proportions have been randomly copolymerized to obtain copolymer V. A mechanism has been proposed for the polymerization reaction involving chain transfer to the monomers. A strategy has been developed for the deprotection of the methylene acetal of V using Pb(OAc)4 whereby one of the methylene protons is replaced with a labile OAc group to give VI. The pendant allyl groups in VI have been elaborated via a thiol-ene reaction using cysteamine hydrochloride and thioglycolic acid to obtain cationic VII and anionic VIII polymers, both containing a mussel-inspired Dopa-based catechol moiety. During aqueous work up, the protecting group containing OAc was deprotected under mild conditions. Cationic VII and anionic VIII were also obtained via an alternate route using epoxide IX derived from 3,4-bis[tert-butyldimethylsilyloxy]allylbenzene. Monomer IX was homo- as well as copolymerized with IV using Lewis acid initiator/catalyst system to obtain homopolymer X and copolymer X1. Copolymer XI was then elaborated using a thiol-ene reaction followed by F- catalysed silyl deprotection to obtain mussel inspired polymers VII and VIII, which by virtue of having charges of opposite algebraic signs were used to form their coacervate.
Pyridine Improves Aluminum Triiodide Induced Selective Cleavage of Alkyl o -Hydroxyphenyl Ethers: A Practical and Efficient Procedure for the Preparation of Hydroxychavicol by Demethylation of Eugenol
Sang, Dayong,Yao, Ming,Tian, Juan,Chen, Xiaoman,Li, Li,Zhan, Hongju,You, Linhong
, p. 138 - 142 (2017)
Demethylation of eugenol with aluminum triiodide is complicated by an unexpected hydrogenation side reaction. The hydrogenation proceeds through a cascade deprotonation, hydroiodination, and hydrogen-halogen exchange process, and can be prevented by suppressing the hydroiodination in advance. A practical demethylation procedure is thus developed that delivers hydryoxychavicol in essentially quantitative yield by using pyridine as an additive. The method is selective towards cleaving alkyl o-hydroxyphenyl ethers and is compatible with a variety of functional groups.
Expeditious synthesis of bioactive allylphenol constituents of the genus Piper through a metal-free photoallylation procedure
Protti, Stefano,Fagnoni, Maurizio,Albini, Angelo
, p. 2868 - 2871 (2005)
Nine bioactive allylphenol (anisole) derivatives (e.g. eugenol, safrole and asaricin) present in several plants of the genus Piper have been synthesized in medium to high yield via aryl cation intermediates. This expeditious metal-free procedure involves the irradiation of the corresponding chlorophenols or chloroanisoles in a polar solvent (MeCN or, better, TFE or aqueous acetonitrile) in the presence of allyltrimethylsilane. Estragole has also been synthesized starting from the corresponding fluoroderivative and diazonium salt, though in a lower yield. The Royal Society of Chemistry 2005.
Allyl/propenyl phenol synthases from the creosote bush and engineering production of specialty/commodity chemicals, eugenol/isoeugenol, in Escherichia coli
Kim, Sung-Jin,Vassao, Daniel G.,Moinuddin, Syed G.A.,Bedgar, Diana L.,Davin, Laurence B.,Lewis, Norman G.
, p. 37 - 46 (2014)
The creosote bush (Larrea tridentata) harbors members of the monolignol acyltransferase, allylphenol synthase, and propenylphenol synthase gene families, whose products together are able to catalyze distinct regiospecific conversions of various monolignols into their corresponding allyl- and propenyl-phenols, respectively. In this study, co-expression of a monolignol acyltransferase with either substrate versatile allylphenol or propenylphenol synthases in Escherichia coli established that various monolignol substrates were efficiently converted into their corresponding allyl/propenyl phenols, as well as providing proof of concept for efficacious conversion in a bacterial platform. This capability thus potentially provides an alternate source to these important plant phytochemicals, whether for flavor/fragrance and fine chemicals, or ultimately as commodities, e.g.; for renewable energy or other intermediate chemical purposes. Previous reports had indicated that specific and highly conserved amino acid residues 84 (Phe or Val) and 87 (Ile or Tyr) of two highly homologous allyl/propenyl phenol synthases (circa 96% identity) from a Clarkia species mainly dictate their distinct regiospecific catalyzed conversions to afford either allyl- or propenyl-phenols, respectively. However, several other allyl/propenyl phenol synthase homologs isolated by us have established that the two corresponding amino acid 84 and 87 residues are not, in fact, conserved.
Chemical analysis and in vitro bioactivity of essential oil of laurelia sempervirens and safrole derivatives against oomycete fish pathogens
Caro, Nelson,Cuellar, Mauricio A.,Godoy, Patricio,Madrid, Alejandro,Melo, Mirna,Montenegro, Iván,Morales, Ana Lizeth,Saffirio, Valentina,Said, Bastián,Werner, Enrique
, (2021/11/08)
In this study, the essential oil (EO) from Laurelia sempervirens was analyzed by GC/MS and safrole (1) was identified as the major metabolite 1, was subjected to direct reactions on the oxygenated groups in the aromatic ring and in the side chain, and eight compounds (4 to 12) were obtained by the process. EO and compounds 4–12 were subjected to biological assays on 24 strains of the genus Saprolegnia, specifically of the species 12 S. parasitica and 12 S. australis. EO showed a significant effect against Saprolegnia strains. Compound 6 presents the highest activity against two resistant strains, with minimum inhibitory concentration (MIC) and minimum oomyceticidal concentration (MOC) values of 25 to 100 and 75 to 125 μg/mL, respectively. The results show that compound 6 exhibited superior activities compared to the commercial controls bronopol and azoxystrobin used to combat these pathogens.
Structure–Activity Relationship of Anti-malarial Allylpyrocatechol Isolated from Piper betle
Horii, Toshihiro,Itagaki, Sawako,Kawano, Tomikazu,Miyoshi, Akihito,Murakami, Nobutoshi,Tamura, Satoru
, p. 784 - 790 (2020/09/18)
Malaria disease remains a serious worldwide health problem. In South-East Asia, one of the malaria infection “hot-spots,” medicinal plants such as Piper betle have traditionally been used for the treatment of malaria, and allylpyrocatechol (1), a constituent of P. betle, has been shown to exhibit anti-malarial activities. In this study, we verified that 1 showed in vivo anti-malarial activity through not only intraperitoneal (i.p.) but also peroral (p.o.) administration. Additionally, some analogs of 1 were synthesized and the structure–activity relationship was analyzed to disclose the crucial sub-structures for the potent activity.
PROCESS FOR THE PREPARATION AND IDENTIFICATION OF DEUTERATED EUGENOL
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Page/Page column 14-15, (2021/01/22)
The present invention provides a novel, simple, unique and viable processes for the synthesis of deuterium incorporated eugenols, such as deuterated eugenol (II), regioisomeric deuterated eugenol (III), and deuterated variant of methyl eugenol (V).
Anchimerically Assisted Selective Cleavage of Acid-Labile Aryl Alkyl Ethers by Aluminum Triiodide and N, N-Dimethylformamide Dimethyl Acetal
Sang, Dayong,Yue, Huaxin,Zhao, Zhengdong,Yang, Pengtao,Tian, Juan
, p. 6429 - 6440 (2020/07/14)
Aluminum triiodide is harnessed by N,N-dimethylformamide dimethyl acetal (DMF-DMA) for the selective cleavage of ethers via neighboring group participation. Various acid-labile functional groups, including carboxylate, allyl, tert-butyldimethylsilyl (TBS), and tert-butoxycarbonyl (Boc), suffer the conditions intact. The method offers an efficient approach to cleaving catechol monoalkyl ethers and to uncovering phenols from acetal-type protecting groups such as methoxymethyl (MOM), methoxyethoxymethyl (MEM), and tetrahydropyranyl (THP) chemoselectively.
