Isohexide hydroxy esters: synthesis and application of a new class of biobased AB-type building blocks

RSC Advances ◽  
2014 ◽  
Vol 4 (89) ◽  
pp. 47937-47950 ◽  
Author(s):  
Shanmugam Thiyagarajan ◽  
Jing Wu ◽  
Rutger J. I. Knoop ◽  
Jacco van Haveren ◽  
Martin Lutz ◽  
...  
Keyword(s):  
Methyl Ester ◽  
Building Blocks ◽  
Ester Group ◽  
Hydroxyl Group ◽  
Secondary Hydroxyl ◽  
New Class ◽  
New Family ◽  
Hydroxy Esters

Here we present the synthesis of a new family of sugar derived 1,4:3,6-dianhydrohexitol based AB-type monomers, containing one methyl ester group and a secondary hydroxyl group in all four possible stereo isomers (RR, RS, SR, SS).

scholarly journals Characteristics and Kinetics Study of Glycerolabietate from Glycerol and Abietic Acid from Rosin

2021 ◽  
Vol 15 (2) ◽  
pp. 170
Author(s):  
Danang Tri Hartanto
Keyword(s):  
Abietic Acid ◽  
Ester Group ◽  
Acid Number ◽  
Hydroxyl Group ◽  
Esterification Reaction ◽  
Hydroxyl Groups ◽  
Carboxylic Group ◽  
Secondary Hydroxyl ◽  
Reaction Rate Constants ◽  
Natural Resin

Rosin is a natural resin from the coniferous tree sap, which separated from its oil content (terpenes). Rosin is brittle. Therefore modifications are needed to improve its mechanical properties. The main content of rosin is abietic acid which has a carboxylic group, so it can form an ester group when reacted with polyhydric alcohol (polyalcohol) such as glycerol. The research aimed to study the kinetics of the esterification reaction between the hydroxyl group in glycerol and the carboxylic group in abietic acid from rosin at various reaction temperatures and reactant compositions. This reaction is carried out in a three-neck flask at atmospheric pressure without a catalyst. The reaction temperatures used were 180˚C, 200˚C, and 220˚C, and the ratio of rosin and glycerol was 1:1, 1:3, and 1:5. The reaction kinetics calculations were analyzed with acid number data over the reaction time using three different models. The calculations showed that this reaction involves positioning a hydroxyl group on glycerol, which the primary and secondary hydroxyl groups contribute to forming a rosin ester (glycerolabietate). The rate of reaction constants of primary hydroxyl of glycerol and abietic acid were in the range 6.25x10-4 - 3.90x10-3 g/(mgeq.min), while reaction rate constants of secondary hydroxyl and abietic acid were in the range 1.06x10-5 - 1.15x10-4 g/(mgeq.min). FTIR analysis showed a change in the hydroxyl, carboxylate, and ester groups which were assigned by a shift of wavenumber and a difference of intensity at 3200-3570 cm-1, 1697.36 cm-1, and 1273.02 cm-1.

A Bottom-Up Approach to Solution-Processed, Atomically Precise Graphitic Cylinders on Surfaces

2018 ◽  
Author(s):  
Erik Leonhardt ◽  
Jeff M. Van Raden ◽  
David Miller ◽  
Lev N. Zakharov ◽  
Benjamin Aleman ◽  
...  
Keyword(s):  
Self Assembly ◽  
Carbon Nanostructures ◽  
Carbon Nanomaterials ◽  
Circle Packing ◽  
Pyrolytic Graphite ◽  
Building Blocks ◽  
Bottom Up ◽  
Casting Technique ◽  
New Class ◽  
Solution Casting Technique

Extended carbon nanostructures, such as carbon nanotubes (CNTs), exhibit remarkable properties but are difficult to synthesize uniformly. Herein, we present a new class of carbon nanomaterials constructed via the bottom-up self-assembly of cylindrical, atomically-precise small molecules. Guided by supramolecular design principles and circle packing theory, we have designed and synthesized a fluorinated nanohoop that, in the solid-state, self-assembles into nanotube-like arrays with channel diameters of precisely 1.63 nm. A mild solution-casting technique is then used to construct vertical “forests” of these arrays on a highly-ordered pyrolytic graphite (HOPG) surface through epitaxial growth. Furthermore, we show that a basic property of nanohoops, fluorescence, is readily transferred to the bulk phase, implying that the properties of these materials can be directly altered via precise functionalization of their nanohoop building blocks. The strategy presented is expected to have broader applications in the development of new graphitic nanomaterials with π-rich cavities reminiscent of CNTs.

scholarly journals Survival and Reliability Analysis with an Epsilon-Positive Family of Distributions with Applications

Symmetry ◽  
2021 ◽  
Vol 13 (5) ◽  
pp. 908
Author(s):  
Perla Celis ◽  
Rolando de la Cruz ◽  
Claudio Fuentes ◽  
Héctor W. Gómez
Keyword(s):  
Survival Data ◽  
Maximum Likelihood Estimates ◽  
New Class ◽  
New Family ◽  
Gamma Distributions ◽  
Special Cases ◽  
Log Normal ◽  
Positive Support ◽  
Positive Distributions ◽  
Family Of Distributions

We introduce a new class of distributions called the epsilon–positive family, which can be viewed as generalization of the distributions with positive support. The construction of the epsilon–positive family is motivated by the ideas behind the generation of skew distributions using symmetric kernels. This new class of distributions has as special cases the exponential, Weibull, log–normal, log–logistic and gamma distributions, and it provides an alternative for analyzing reliability and survival data. An interesting feature of the epsilon–positive family is that it can viewed as a finite scale mixture of positive distributions, facilitating the derivation and implementation of EM–type algorithms to obtain maximum likelihood estimates (MLE) with (un)censored data. We illustrate the flexibility of this family to analyze censored and uncensored data using two real examples. One of them was previously discussed in the literature; the second one consists of a new application to model recidivism data of a group of inmates released from the Chilean prisons during 2007. The results show that this new family of distributions has a better performance fitting the data than some common alternatives such as the exponential distribution.

Cocaine: Pharmacokinetics and biotransformation in man

1989 ◽  
Vol 67 (9) ◽  
pp. 1154-1157 ◽  
Author(s):  
T. Inaba
Keyword(s):  
Methyl Ester ◽  
Ester Group ◽  
Oral Route ◽  
Plasma Cholinesterase ◽  
Pharmacokinetic Studies ◽  
Hydrolytic Cleavage ◽  
Bicyclic Structure ◽  
Anesthetic Action ◽  
Pharmacologically Active ◽  
Cytochrome P 450

Pharmacokinetic studies of cocaine have been carried out only in the last decade, although its local anesthetic action and addictive properties have been known for almost 100 years. Elimination half-lives of cocaine in man estimated from serial plasma concentration are relatively short and range from 0.5 to 1.1 h after i.v. and 0.9–1.5 h after administration by the nasal or oral route. The bioavailability after nasal inhalation is about 60%. The bicyclic structure of cocaine is characterized by functional groups including N-methyl, carboxyl methyl ester, and benzoyl ester, which are susceptible to biotransformation. Hydrolysis of the benzoyl group to ecgonine methyl ester is catalyzed by plasma cholinesterase and is thus under monogenic control. The hydrolytic cleavage of the other ester group, methyl ester, to benzoyl ecgonine occurs spontaneously at body temperature. In contrast, N-demethylation of cocaine mediated by microsomal cytochrome P-450 produces norcocaine and this metabolite was shown to be pharmacologically active, the action being similar to cocaine.Key words: cocaine, hydrolysis, plasma cholinesterase, cytochrome P-450.

scholarly journals Stereoselective total syntheses of (±)-sinularene and (±)-5-epi-sinularene: a general intramolecular Diels–Alder approach to tricyclic sesquiterpenes

1985 ◽  
Vol 63 (4) ◽  
pp. 993-995 ◽  
Author(s):  
Kazimierz Antczak ◽  
John F. Kingston ◽  
Alex G. Fallis
Keyword(s):  
Double Bond ◽  
Methyl Ester ◽  
Total Synthesis ◽  
Ring System ◽  
Diels Alder ◽  
Exocyclic Double Bond ◽  
Total Syntheses ◽  
Methyl Group ◽  
Secondary Hydroxyl ◽  
Selective Hydrogenolysis

Stereoselective total synthesis of (±)-sinularene and (±)-5-epi-sinularene are described. The sequence employs a "blocked" cyclopentadiene in which the cyclopropane unit also serves as a latent methyl group. Thus intramolecular [4 + 2] cycloaddition of the substituted methyl spiro[2.4]hepta-4,6-dien-1-yl)-2-pentenoate 11 affords 5-benzyloxy-6-isopropyl-8-carbomethoxytetracyclo[5.4.01,7.02,4.02,9]undec-10-ene (12) which after selective hydrogenolysis generates the tricyclo[4.4.01,6.02,8]decane (sinularene) ring system. Removal of the secondary hydroxyl function (Ph3P/CCl4/CH3CN; H2/Pd/C), reduction of the methyl ester (LiAlH4), and introduction of the exocyclic double bond (acetate pyrolysis, 550 °C) completes the synthesis of (±)-sinularene in 14 steps from cyclopentadiene. A parallel series of reactions employing the isopropyl epimer of 12 affords (±)-5-epi-sinularene.

scholarly journals Synthesis of new Cα-tetrasubstituted α-amino acids

2009 ◽  
Vol 5 ◽  
Author(s):  
Andreas A Grauer ◽  
Burkhard König
Keyword(s):  
Amino Acids ◽  
Secondary Structure ◽  
Aromatic Aldehydes ◽  
Building Blocks ◽  
Reaction Conditions ◽  
Peptide Backbone ◽  
Aliphatic Aldehydes ◽  
New Class ◽  
Cyclic Amino Acids

Cα-Tetrasubstituted α-amino acids are important building blocks for the synthesis of peptidemimetics with stabilized secondary structure, because of their ability to rigidify the peptide backbone. Recently our group reported a new class of cyclic Cα-tetrasubstituted tetrahydrofuran α-amino acids prepared from methionine and aromatic aldehydes. We now report the extension of this methodology to aliphatic aldehydes. Although such aldehydes are prone to give aldol products under the reaction conditions used, we were able to obtain the target cyclic amino acids in low to moderate yields and in some cases with good diastereoselectivity.

scholarly journals Cu/Pd-catalyzed borocarbonylative trifunctionalization of alkynes and allenes: synthesis of β-geminal-diboryl ketones

2021 ◽  
Author(s):  
Yang Yuan ◽  
Fu-Peng Wu ◽  
Anke Spannenberg ◽  
Xiao-Feng Wu
Keyword(s):  
Organic Synthesis ◽  
Functional Group ◽  
Building Blocks ◽  
Mechanistic Studies ◽  
Efficient Strategy ◽  
New Class ◽  
Reaction Proceeds

AbstractFunctionalized bisboryl compounds have recently emerged as a new class of synthetically useful building blocks in organic synthesis. Herein, we report an efficient strategy to synthesize β-geminal-diboryl ketones enabled by a Cu/Pd-catalyzed borocarbonylative trifunctionalization of readily available alkynes and allenes. This reaction promises to be a useful method for the synthesis of functionalized β-geminal-diboryl ketones with broad functional group tolerance. Mechanistic studies suggest that the reaction proceeds through borocarbonylation/hydroboration cascade of both alkynes and allenes.

scholarly journals Electronically Excited States of Potential Interstellar, Anionic Building Blocks for Astrobiological Nucleic Acids

2021 ◽  
Vol 8 ◽  
Author(s):  
Taylor J. Santaloci ◽  
Marie E. Strauss ◽  
Ryan C. Fortenberry
Keyword(s):  
Nucleic Acids ◽  
Excited States ◽  
Lone Pair ◽  
Building Blocks ◽  
Hydroxyl Group ◽  
Quantum Chemical Analysis ◽  
Electronically Excited States ◽  
Neutral Radical ◽  
Electronically Excited ◽  
Electron Withdrawing Group

Functionalizing deprotonated polycyclic aromatic hydrocarbon (PAH) anion derivatives gives rise to electronically excited states in the resulting anions. While functionalization with −OH and −C2H, done presently, does not result in the richness of electronically excited states as it does with −CN done previously, the presence of dipole-bound excited states and even some valence excited states are predicted in this quantum chemical analysis. Most notably, the more electron withdrawing −C2H group leads to valence excited states once the number of rings in the molecule reaches three. Dipole-bound excited states arise when the dipole moment of the corresponding neutral radical is large enough (likely around 2.0 D), and this is most pronounced when the hydrogen atom is removed from the functional group itself regardless of whether functionalized by a hydroxyl or enthynyl group. Deprotonatation of the hydroxyl group in the PAH creates a ketone with a delocalized highest occupied molecular orbital (HOMO) unlike deprotonation of a hydrogen on the ring where a localized lone pair on one of the carbon atoms serves as the HOMO. As a result, hydroxyl functionlization and subsequent deprotonation of PAHs creates molecules that begin to exhibit structures akin to nucleic acids. However, the electron withdrawing −C2H has more excited states than the electron donating −OH functionalized PAH. This implies that the −C2H electron withdrawing group can absorb a larger energy range of photons, which signifies an increasing likelihood of being stabilized in the harsh conditions of the interstellar medium.

‘One-pot’ synthesis and redox evaluations of chiral chalcogenocysteinol and β-bis-chalcogenoamine derivatives from l-serine methyl ester

2017 ◽  
Vol 41 (15) ◽  
pp. 7424-7431 ◽  
Author(s):  
Patrícia Foletto ◽  
Luciano Dornelles ◽  
Bernardo A. Iglesias ◽  
Andressa C. Bevilacqua ◽  
Paulo Piquini ◽  
...  
Keyword(s):  
Methyl Ester ◽  
One Pot ◽  
New Class ◽  
One Pot Synthesis

The synthesis of a new class of potential antioxidant chiral chalcogenocysteinols and bis-chalcogenoamines is described in this study.

A new class of quaternary generalized cyclotomic sequences of order 2d and length 2pm with high linear complexity

2018 ◽  
Vol 16 (01) ◽  
pp. 1850006 ◽  
Author(s):  
Longfei Liu ◽  
Xiaoyuan Yang ◽  
Bin Wei ◽  
Liqiang Wu
Keyword(s):  
Finite Fields ◽  
Linear Complexity ◽  
Periodic Sequences ◽  
New Class ◽  
New Family ◽  
Generalized Cyclotomic Classes ◽  
Cyclotomic Sequences

Periodic sequences over finite fields, constructed by classical cyclotomic classes and generalized cyclotomic classes, have good pseudo-random properties. The linear complexity of a period sequence plays a fundamental role in the randomness of sequences. In this paper, we construct a new family of quaternary generalized cyclotomic sequences with order [Formula: see text] and length [Formula: see text], which generalize the sequences constructed by Ke et al. in 2012. In addition, we determine its linear complexity using cyclotomic theory. The conclusions reveal that these sequences have high linear complexity, which means they can resist linear attacks.

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