Organic Chemistry Textbooks Research Articles

Contribution to Pharmacy/pharmacist Education through Writing

The Education Award of the Pharmaceutical Society of Japan (PSJ) was conferred for "Contribution to pharmacy/pharmacist education through writing on organic chemistry." The award-winning activities were described in three parts section 1-3. Section 1 Importance of Research and Education in Organic Chemistry: In this section, it is explained that organic chemistry serves as the fundamental basis for a wide range of natural science disciplines studied in pharmaceutical departments. It emphasizes that having a solid foundation in organic chemistry is essential for pharmacists to understand pharmaceuticals. This knowledge contributes significantly in healthcare settings such as team-based medical care (interprofessional cooperation) with physicians and nurses, as well as in interactions with patients, providing a unique contribution that other professions cannot achieve. Section 2 Two Serial Articles Written on Organic Chemistry: This part mentions two serial articles that are beneficial for pharmacists and pharmaceutical researchers. These articles aimed to broaden specialized knowledge and provide practical information, contributing to pharmaceutical education and professional training for pharmacists. Section 3 Publication of New Organic Chemistry Textbooks: In this section, the introduction of textbooks and reference books in the field of organic chemistry for pharmaceutical education is highlighted. These educational materials were published to offer valuable information to pharmaceutical students and aspiring pharmacists, enhancing their expertise. These three writing activities significantly contributed to pharmaceutical education and the improvement of the professional work of pharmacists.

Quantum chemical explanation and APT atomic charge index of substituent orienting effect proposed by DFT calculation and MO Theory

AbstractIn organic chemistry textbooks, the electron resonance states are used to explain the orienting effect of benzene substituent. However, these resonance states do not exist in the C6H5‐S + E+ electrophilic addition, so the resonance state discussions actually are meaningless. The density functional theory (DFT) calculation shows that the C6H5‐S + E+ addition follows the transition state theory and needs to overcome a barrier. Benzene molecule C6H6 has two degenerate highest occupied molecular orbitals (HOMOs), but after becoming substituted benzenes, the two HOMOs split to HOMO and HOMO‐1 with different orbital energies and electron distributions. It makes the addition barrier on two or three benzene ring carbons is low, and the addition rate is fast, but the barrier of other carbons is high, and the rate is slow. Therefore, substituent splits the two degenerate HOMOs of benzene molecule, which is the origin of substituent orienting effect. For the substituted benzenes with halogen group ‐X and electron‐releasing group, their HOMO images alone can determine that the two types of substituents are the ortho‐ and para‐orienting groups, but for the substituted benzenes with electron‐withdrawing group, their HOMO alone cannot determine whether the substituent is a meta‐orienting group. The study found that atomic polar tensor (APT) charges are a good judgment index of substituent orienting effect because based on its physic‐chemical model, the charges represent the number of active electrons on the benzene ring carbons. The DFT calculation gives the APT charges of 19 mono‐substituted and 12 di‐substituted benzenes and some aromatic molecules. The APT charges can all correctly determine their orienting effects, showing that APT atomic charge from quantum theoretical calculation is a good substituent orienting index.

A PROPAGAÇÃO DO ERRO DO pKa DA ÁGUA NOS LIVROS DE QUÍMICA ORGÂNICA

THE PROPAGATION OF THE ERROR IN THE pKa OF WATER IN ORGANIC CHEMISTRY TEXTBOOKS. In organic chemistry, the pKa is a property used to compare the acidity behavior for many substances, and to locate the position of equilibria in acid-base reactions and to provide information about structure and reactivity. Evidence in the literature shows that the values of pKa for water and hydronium ion, commonly cited in organic chemistry textbooks, are incorrect. The values of 15.74 for H2O and −1.74 for H3O+ are due to a propagated misconception in the equilibrium calculations while the correct values are 14.0 for H2O and 0.0 for H3O+. This subtle difference of 1.74 units on the pKa scale between both values reflects an error greater than 55 times in the level of acidity for these chemical species. An immediate correction of these values is necessary for the adequate teaching of organic chemistry. A literature search was conducted on the most used organic chemistry books in graduate and undergraduate courses in Brazil, revealing that almost all values cited were inadequate. The textbook Chemistry of Organic Compounds, 3rd edition (1965), by Carl Robert Noller is suggested as possible source of this misinformation in organic chemistry textbooks.

Alkyl groups in organic molecules are NOT inductively electron-releasing.

It is commonly stated that alkyl groups exert an inductive electron-releasing effect when compared to hydrogen. This information has been given in numerous organic chemistry textbooks over the last 75 years. The evidence for this position is weak, and does not withstand scrutiny, and there is some evidence for the contrary position. We provide a significant body of computational data that clearly show that alkyl groups exert an inductive electron-withdrawing (-I) effect when compared to hydrogen. This revised position is not in conflict with experimental data, since alkyl group inductive effects are small and are likely to be masked by hyperconjugation/polarizability effects (particularly in charged species), and also by solvent effects.

Unusual Single Electron Transfer Reactions between Alkenes and Iodine Electrophiles†

Comprehensive SummaryThe electrophilic addition to an alkene with an electrophile has been widely studied and applied in organic synthesis. The organic chemistry textbook describes the classical reaction between an alkene and an iodine electrophile (such as elemental iodine and N‐iodosuccinimide (NIS)) as a typical ionic reaction, in which an iodonium ion is formed and then attacked by a nucleophile. However, in this article, we report a new and unusual reaction mode between an alkene and NIS; that is, a single electron transfer (SET) process occurs between these two reactants by forming an electron‐donor acceptor complex. Not only does this unusual single electron transfer reaction between an alkene and NIS add fundamentally important knowledge to organic chemistry, it also provides a valuable synthetic method as the new SET reaction mode with opposite regioselectivity as compared with the traditional ionic mode.

Computational prediction of complex cationic rearrangement outcomes.

Recent years have seen revived interest in computer-assisted organic synthesis1,2. The use of reaction- and neural-network algorithms that can plan multistep synthetic pathways have revolutionized this field1,3-7, including examples leading to advanced natural products6,7. Such methods typically operate on full, literature-derived 'substrate(s)-to-product' reaction rules and cannot be easily extended to the analysis of reaction mechanisms. Here we show that computers equipped with a comprehensive knowledge-base of mechanistic steps augmented by physical-organic chemistry rules, as well as quantum mechanical and kinetic calculations, can use a reaction-network approach to analyse the mechanisms of some of the most complex organic transformations: namely, cationic rearrangements. Such rearrangements are a cornerstone of organic chemistry textbooks and entail notable changes in the molecule's carbon skeleton8-12. The algorithm we describe and deploy at https://HopCat.allchemy.net/ generates, within minutes, networks of possible mechanistic steps, traces plausible step sequences and calculates expected product distributions. We validate this algorithm by three sets of experiments whose analysis would probably prove challenging even to highly trained chemists: (1) predicting the outcomes of tail-to-head terpene (THT) cyclizations in which substantially different outcomes are encoded in modular precursors differing in minute structural details; (2) comparing the outcome of THT cyclizations in solution or in a supramolecular capsule; and (3) analysing complex reaction mixtures. Our results support a vision in which computers no longer just manipulate known reaction types1-7 but will help rationalize and discover new, mechanistically complex transformations.

Ring-closing C–O/C–O metathesis of ethers with primary aliphatic alcohols

In canonical organic chemistry textbooks, the widely adopted mechanism for the classic transetherifications between ethers and alcohols starts with the activation of the ether in order to weaken the C–O bond, followed by the nucleophilic attack by the alcohol hydroxy group, resulting in a net C–O/O–H σ-bond metathesis. In this manuscript, our experimental and computational investigation of a Re2O7 mediated ring-closing transetherification challenges the fundamental tenets of the traditional transetherification mechanism. Instead of ether activation, the alternative activation of the hydroxy group followed by nucleophilic attack of ether is realized by commercially available Re2O7 through the formation of perrhenate ester intermediate in hexafluoroisopropanol (HFIP), which results in an unusual C–O/C–O σ-bond metathesis. Due to the preference for the activation of alcohol rather than ether, this intramolecular transetherification reaction is therefore suitable for substrates bearing multiple ether moieties, unparalleled by any previous methods.

Clarifying the structures of imidines: using crystallographic characterization to identify tautomers and localized systems of π-bonding.

Nitrogen heterocycles are a class of organic compounds with extremely versatile functionality. Imidines, HN[C(NH)R]2, are a rare class of heterocycles related to imides, HN[C(O)R]2, in which the O atoms of the carbonyl groups are replaced by N-H groups. The useful synthesis of the imidine compounds succinimidine and glutarimidine, as well as their partially hydrolyzed imino-imide congeners, was first described in the mid-1950s, though structural characterization is presented for the first time in this article. In the solid state, these structures are different from the proposed imidine form: succinimidine crystallizes as an imino-amine, 2-imino-3,4-dihydro-2H-pyrrol-5-amine, C4H7N2 (1), glutarimidine as 6-imino-3,4,5,6-tetrahydropyridin-2-amine methanol monosolvate, C5H9N3·CH3OH (2), and the corresponding hydrolyzed imino-imide compounds as amino-amides 5-amino-3,4-dihydro-2H-pyrrol-2-one, C4H6N2O (3), and 6-amino-4,5-dihydropyridin-2(3H)-one, C5H8N2O (4). Imidine 1 was also determined as the hydrochloride salt solvate 5-amino-3,4-dihydro-2H-pyrrol-2-iminium chloride-2-imino-3,4-dihydro-2H-pyrrol-5-amine-water (1/1/1), C4H8N3+·Cl-·C4H7N3·H2O (1·HCl). As such, 1 and 2 show alternating short and long C-N bonds across the molecule, revealing distinct imino (C=NH) and amine (C-NH2) groups throughout the C-N backbone. These structures provide definitive evidence for the predominant imino-amine tautomer in the solid state, which serves to enrich the previously proposed imidine-focused structures that have appeared in organic chemistry textbooks since the discovery of this class of compounds in 1883.

A Controversy in the Textbooks of Organic Chemistry: The Origin of the Stability of Ethane Conformations

A Controversy in the Textbooks of Organic Chemistry: The Origin of the Stability of Ethane Conformations

Historical Development and Experience of Construction for Organic Chemistry Textbooks by Peking University

Historical Development and Experience of Construction for Organic Chemistry Textbooks by Peking University

Comparison of the Knowledge Frameworks and Teaching Contents of Typical Organic Chemistry Textbooks at Home and Abroad

Comparison of the Knowledge Frameworks and Teaching Contents of Typical Organic Chemistry Textbooks at Home and Abroad

Bianka Tchoubar: A Revolutionary in French Organic Chemistry

Virtually unknown in her homeland, Bianka Tchoubar, born in 1910 in Kharkiv, brought about a true paradigm shift in French organic chemistry of the 20th century. Originality of research ideas, scientific rigor and legendary perseverance earned her respect and recognition in the world scientific community. This eccentric Parisian of Ukrainian origin became the first woman to enter the French National Center for Scientific Research (Centre National de la Recherche Scientifique, CNRS) upon its creation in 1939. Bianka Tchoubar’s contribution to the study of reaction mechanisms and salt effects in organic chemistry were of paramount importance, and so were her efforts to present these novel scientific concepts to the audience of French organic chemists through the clear and concise expression of her books. The name of this great Ukrainian researcher may be found in the pages of French organic chemistry textbooks, where the Demjanov ring expansion reaction is called the Demjanov–Tiffeneau–Tchoubar rearrangement. This article aims at presenting the outstanding scientific legacy and turbulent life path of this researcher to the world scientific community.

A Practical Oxidation Experiment for Undergraduate Students: Bobbitt’s Salt as a “Green” Alternative

Oxidation reactions are critical components of the synthetic toolbox taught to undergraduate students during introductory organic chemistry courses. However, the oxidation reactions discussed in the undergraduate curriculum are often outdated as many organic chemistry textbooks emphasize chromium-based oxidants that are no longer in regular use by practitioners, which may limit an instructor’s time to allocate to discussion of other oxidants. Further, laboratory courses have since either removed oxidation experiments or replaced them with oxidative processes not discussed in lectures, thus leading to a disconnect between the two learning settings. As part of an effort to bridge this divide and modernize the oxidation reactions discussed in our curricula, we have developed a new laboratory experiment that uses a commercially available oxoammonium salt (Bobbitt’s salt) to cleanly oxidize cinnamyl alcohol to cinnamaldehyde. In addition to being a safe, convenient, colorimetric, and “green oxidant” suitable for use in the undergraduate teaching laboratory, the hydride-transfer mechanism allows for overlap with key course concepts presented in both introductory and advanced lecture courses. The procedure is well-suited for small and large organic I, II, or advanced laboratory sections alike and can be completed within a standard 3–4 h laboratory period. Aside from exposing students to a modern green oxidation protocol, the experiment contains expanded opportunities for interpretation of 1H NMR, 13C NMR, and IR spectra. An optional addendum for advanced students involving Hammett correlations was also developed.

Evaluating the Effectiveness of Organic Chemistry Textbooks for Promoting Representational Competence

Evaluating the Effectiveness of Organic Chemistry Textbooks for Promoting Representational Competence

Limonene in Citrus: A String of Unchecked Literature Citings?

In organic chemistry textbooks (S)-(−)-limonene, (−)-limonene or l-limonene, is often given credit for the smell of lemons, while the R-analogue, (+)-limonene or d-limonene, is credited with that of oranges. Results from two odor tests revealed that few persons in the test associated (R)-(+)-limonene with oranges and (S)-(−)-limonene with lemons, when these compounds were of analytical grade. Quality and composition of standard compounds and mixtures used in these olfactory tests were corroborated by gas chromatographic analyses. The statement of (R)-(+)-limonene being responsible for orange odor and (S)-(−)-limonene for the lemon odor apparently stems from an often quoted article from 1971. This investigation was a lesson for both our students and us. Textbooks in organic chemistry that still promote (R)-(+)- and (S)-(−)-limonene as, respectively, the “orange” and “lemon” smell ingredient should be corrected.

Improving Learning Outcomes and Metacognitive Monitoring: Replacing Traditional Textbook Readings with Question-Embedded Videos

When students effectively engage with textbooks or videos prior to class, more active and collaborative learning activities can be incorporated into subsequent face-to-face learning. Such pre-lecture assignments are particularly important in flipped classrooms, where a portion of the content is delivered primarily before face-to-face instruction. While a large amount of research has addressed the need to improve active learning during lectures, little work has examined the need to improve out-of-class preparation. Most often, out-of-class preparation consists of videos or assigned textbook readings, but question-embedded videos have also been shown to be effective. When using question-embedded videos, students must pause the video and solve problems as they watch the video, transforming their passive video watching into an active learning experience. Here, we present the results of a randomized control trial study that compares learning behaviors and outcomes between students using content-equivalent resources: organic chemistry textbook readings or question-embedded videos. We found that students who used question-embedded videos for their preparation had significantly higher learning gains and metacognitive monitoring proficiencies than students who used textbook readings. These results indicate that question-embedded videos enforce more productive feedback-driven problem-solving behaviors than textbook readings, which leads to substantial gains in performance and metacognitive monitoring, better preparing students for in-class instruction.

Representations in Organic Chemistry Textbooks: Nucleophilic Substitution and Elimination Reactions of Alkyl Halides

Alkil halojenürlerin nükleofilik yer değiştirme ve ayrılma tepkimeleri, organik kimya dersi içerisinde pek çok kez karşılaşılan temel tepkimelerin başında gelmektedir. Bu açıdan ders kitaplarında organik kimya dersi açısından son derece önemli yere sahip olan bu tepkimelerde farklı gösterimlere yer verilmesi ve bunların birbiriyle bütünleştirilmesi önem taşımaktadır. Bu nedenle, bu araştırmada Türkiye’deki Kimya Eğitimi Anabilim Dallarında organik kimya derslerinde sıklıkla yararlanılan ders kitaplarında alkil halojenürlerin nükleofilik yer değiştirme ve ayrılma tepkimelerine ilişkin ne tür gösterimlerin kullanıldığının ortaya konulması amaçlanmıştır. Bu amaçla, dört ders kitabında bu tepkimelerin sözel, sembolik ve görsel gösterim türlerine göre nasıl temsil edildiği betimsel olarak incelenmiştir. Analiz sonuçları, hem yer değiştirme hem de ayrılma tepkimelerinde en çok sözel gösterimlere yer verildiğini, bunun ardından sembolik gösterimin geldiğini ortaya koymuştur. Ayrıca araştırmada stereokimya gibi oldukça soyut olan konu içeriğinde dahi görsel gösterimlere tüm ders kitaplarında son derece az yer verildiği belirlenmiştir. Son olarak araştırma, ayırma reaksiyonlarında nükleofilik yer değiştirme reaksiyonlarından daha az görsel temsil olduğunu ortaya koymuştur.

COVERAGE OF INTERMOLECULAR FORCES IN ORGANIC CHEMISTRY TEXTBOOKS

The paper analyzes fifteen organic chemistry textbooks commonly used in Brazilian universities to examine intermolecular forces’ coverage in them. The findings revealed that the intermolecular forces are spread over a few pages (less than 1%) in a fragmented way, and over several chapters that do not provide enough information to help create a clear image in the student’s mind. Thirteen textbooks contained end-of-chapter problems related to intermolecular forces. However, less than 1.3% of the total (212) are associated with intermolecular forces. This deficient approach to intermolecular forces in Organic textbooks can lead to teachers’ lack of interest in teaching the subject, leading to students failing to learn this important organic chemistry topic

Harold Hart

ACS NEWS Harold Hart ShareShare onFacebookTwitterWechatLinked InRedditEmail C&EN, 2020, 98 (42), p 36November 2, 2020Cite this:C&EN 98, 42, 36AbstractHarold Hart, 97, died Nov. 17, 2019, in Kalamazoo, Michigan. “Harold joined Michigan State University in 1946. He helped transform the Chemistry Department into one that emphasized both teaching and research. His research contributed to synthetic and physical organic chemistry, and he wrote the first organic chemistry textbook designed for nonchemistry majors (with R. D. Schuetz ). He served as editor of Chemical Reviews from 1967 to 1976. In later years, he assembled a portrait collection of renowned chemists. He was an ACS member for 77 years, a mentor to students and young faculty, and husband to Geraldine, the love of his life.”—David J. Hart, son Most recent title: Emeritus professor of chemistry, Michigan State University Education: BS, chemistry, University of Illinois at Urbana-Champaign, 1941; PhD, chemistry, Penn State University, 1947 Survivors: Daughters, Ariel Anderson, Diana, and Leslie Craine; son, David; eight grandchildren; eight great-grandchildren To recognize your late lovedView: PDF | Full Text HTML

“Greenness” in Chemistry Education – Look into Textbook Reaction Examples

Chemistry has played a dual role in the unfolding picture of global development.1 The chemical sciences have significantly improved overall quality of life but have also caused several severe environmental problems. To alter the public perception of chemistry from a “troublemaker” to a positive field necessary for global advancement, the United Nations sustainable development goals (SDGs) must be used to reposition chemistry in a broader context.2 The SDGs are just beginning to be incorporated into post-secondary chemistry education, creating the essential foundation for teaching students about the role of chemistry as the central sustainability science.3
 
 We are investigating how sustainability has been incorporated into chemistry education. The work was carried out by analyzing the organic reactions used as examples in a widely adopted organic chemistry textbook (Organic Chemistry, 2nd edition, Oxford Press). These reactions were examined using a sustainability framework consisting of several existing mass- and energy- based “green chemistry” metrics. The idea of “green chemistry” was formulated in the 1990s to address the environmental crises caused by expanding urbanization, and provides a direction chemistry must take to ensure its development is sustainable. The results of our textbook analysis create a quantitative indicator of the overall “greenness” of the content used as the basis for chemistry courses in Canada.
 
 
 Anastas, P.; Zimmerman, J. B., Chem 2016, 1 (1), 10-12.
 Matlin, S.; Mehta, G.; Hopf, H.; Krief, A., Nature Chemistry 2015, 7, 941.
 Armstrong, L. B.; Rivas, M. C.; Douskey, M. C.; Baranger, A. M., Current Opinion in Green and Sustainable Chemistry 2018, 13, 61-67.