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Recherches sur les acides organiques anhydres

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... Treatment of both acid anhydrides with aniline transformed them into benzanilide and acetanilide, respectively. Gerhardt added that he had discovered that phosphorus oxychloride could be used advantageously to prepare the organic chlorides necessary for the preparation of acid anhydrides (Gerhardt, 1852). ...
... Gerhardt wrote that the composition of these acid anhydrides contained twice the acid radical and negated the existence of water in the monobasic acid, in addition, the ratio of the two radicals contained in their constitution was the same as that into an alcohol and its ether. To reinforce this assumption, Gerhardt also prepared the anhydride of mixtures of two acids, i.e., cinnamic and benzoic, cumic (p-isopropylbenzoic acid), and acetic, and cumic and benzoic (Gerhardt, 1852). ...
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Luigi Chiozza (1828-1889) was an Italian chemist who made a detailed study of the preparation, properties, and reactions of organic acids. While studying the reaction of ammonium sulfide with nitrocinnamic acid, he discovered the new compound, carbostyril (2-hydroxyquinoline). He also synthesized monochlorobenzoic acid (o-chlorobenzoic acid) by treating the chlorination product of salicylic acid with phosphorus pentachloride with water. Alone, or with Gerhardt, he developed efficient processes for the preparation of simple and mixed acid anhydrides, as well as numerous new primaries, secondary, and ternary amides. His most important work was the artificial production of the essence of cinnamon (i.e., cinnamic aldehyde).
... The return to the manufacturing facilities of his father was not easy to conciliate with his scientific vocation and the absence of a laboratory. Nevertheless , he succeeded in publishing some original works related to the experiments he had done at Giessen (Gerhardt, 1838a). His father made him a traveling salesman for the industry, a job that discouraged Charles so much that once again he abandoned the parental house. ...
... Liebig's results constitute the basis of the theory of composite radicals. Gerhardt, in his book Precis de Chimie Organique (Gerhardt, 1840), had put in doubt the nature of mellon as a radical and the existence of mellonhydric acid and mellonures. He repeated Liebig's experiments and came to the wrong conclusion that ammelide was actually a previously unknown melanuric acid, C3N3(NH2)(OH)2 (Gerhardt, 1844) . ...
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Resumen Charles Fréderic Gerhardt (1816-1856) fue uno de los químicos más importantes del siglo diecinueve, cu-yas investigaciones y teorías ejercieron una poderosa influencia en el desarrollo de la química. Su teoría de los tipos fue significativa en impulsar hacia ade-lante la clasificación orgánica, poniéndola en una forma más racional, y en destronar el enfoque dua-lista. La teoría de los tipos evolucionó hacia la idea de valencia. Gerhardt generalizó el concepto de homología y equivalentes. Fue asimismo responsa-ble de la síntesis de un gran número de compuestos orgánicos, entre ellos anhidridos y cloruros de ácido, derivados del ácido salicílico, anilidas, y fosfamidas. Abstract Charles Fréderic Gerhardt (1816-1856) was one of the most important chemists of the nineteenth century and whose researches and theories exerted a powerful influence in the development of chemistry. His theory of types was significant in pushing organic classification forward, putting it on a more rational form, and in the dethroning of the dualistic approach.
... Phosphorus pentoxide had been shown to be unable to eliminate water from acids belonging to the fatty and aromatic series. This had led Charles-Frédéric Gerhardt (1816Gerhardt ( -1856 to claim that these acids did not contain water and hence it was necessary to duplicate their formulas (Gerhardt, 1853). Gal and Étard observed that dripping glacial acetic over phosphorus pentoxide resulted in the immediate carbonization of the acid, but performing the inverse operation, that is adding the pentoxide to the acid, did not result in a reaction but only in a small temperature increase if care was taken to submerge immediately the pieces of the pentoxide in the acid. ...
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Henri François Gal (1839-1897), a French chemist who studied in detail the chemical reactions of acid anhydrides, acetyl bromide and chloride, ethers, organic cyanates, organometallic compounds, strychnine and other natural extracts. He also developed analytical methods to distinguish between amines and phosphines, and mono and diamides.
... Phosphorus pentoxide had been shown to be unable to eliminate water from acids belonging to the fatty and aromatic series. This had led Charles-Frédéric Gerhardt (1816Gerhardt ( -1856 to claim that these acids did not contain water and hence it was necessary to duplicate their formulas (Gerhardt, 1853). Gal and Étard observed that dripping glacial acetic over phosphorus pentoxide resulted in the immediate carbonization of the acid, but performing the inverse operation, that, is adding the pentoxide to the acid, did not result in a reaction but only in a small temperature increase if care was taken to submerge immediately the pieces of the pentoxide in the acid. ...
Article
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Henri François Gal (1839-1897), a French chemist who studied in detail the chemical reactions of acid anhydrides, acetyl bromide and chloride, ethers, organic cyanates, organometallic compounds, strychnine and other natural extracts. He also developed analytical methods to distinguish between amines and phosphines, and mono and diamides.
... The chemical analysis carried out in 1835 compared salicin to spiric acid, also effective against fever and pain, but extracted from a flowering plant, spirea. In 1853, the Strasbourg resident Charles Frédéric Gerhardt (1816-1856) synthesized an analogue of these molecules, the acetylsalicylic acid [101]. In 1897, Felix Hoffmann (1868-1946), a German chemist under the direction of Arthur Eichengrün (1867-1949) synthesized a pure form of acetylsalicylic acid [102]. ...
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Inflammation has accompanied humans since their first ancestors appeared on Earth. Aulus Cornelius Celsus (25 BC-50 AD), a Roman encyclopedist, offered a still valid statement about inflammation: “Notae vero inflammationis sunt quatuor: rubor et tumor cum calore and dolore”, defining the four cardinal signs of inflammation as redness and swelling with heat and pain. While inflammation has long been considered as a morbid phenomenon, John Hunter (18th century) and Elie Metchnikoff (19th century) understood that it was a natural and beneficial event that aims to address a sterile or an infectious insult. Many other famous scientists and some forgotten ones have identified the different cellular and molecular players, and deciphered the different mechanisms of inflammation. This review pays tribute to some of the giants who made major contributions, from Hippocrates to the late 19th and first half of the 20th century. We particularly address the discoveries related to phagocytes, diapedesis, chemotactism, and fever. We also mention the findings of the various inflammatory mediators and the different approaches designed to treat inflammatory disorders.
... By 1853, primarily due to the work of Charles Adolphe Wurtz, Hoffman, Williamson and Gerhardt, four different types had been identified; the water type, the hydrogen type, the hydrogen chloride type and the ammonia type. The water type included water, alcohols, ethers and carboxylic acids, the hydrogen type, dihydrogen, and alkanes, the hydrogen chloride type included organohalogen compounds such as C 2 H 5 Cl and finally, the ammonia type which included all primary, secondary and tertiary amines [59]. ...
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Today, we universally understand radicals to be chemical species with an unpaired electron. It was not always so, and this article traces the evolution of the term radical and in this journey, monitors the development of some of the great theories of organic chemistry.
... 1853年, Gerhardt [17,18] 及降解等手段, 成功地鉴定青蒿素的结构 [25,26] , 随后 由中国科学院生物物理研究所通过X射线单晶衍射 的 方 法 加 以 确 认 [27] . 1983年 由 Roche制 药 Schmid和 Hofheinz [28] [35~38] . ...
... The active ingredient of willow bark, salicylic acid, was first isolated by Johann Andreas Buchner in 1827 and 2 years later Henri Leroux managed to obtain about 30 g of purified salicin from 1.5 kg of bark [16]. In 1853, the Frenchman Charles Gerhardt who worked as a chemist in Germany and later in Paris at the Jardin des Plantes synthesized a form of acetyl salicylic acid as part of his studies on anhydrides [17]. His career was terminated by an early death at age 39, ascribed to poisoning resulting from his activities in synthetic chemistry. ...
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The application of aspirin-like drugs in modern medicine is very broad, encompassing the treatment of inflammation, pain and a variety of cardiovascular conditions. Although anecdotal accounts of willow bark extract as an anti-inflammatory drug have occurred since written records began (for example by Hippocrates), the first convincing demonstration of a potent anti-pyretic effect of willow bark containing salicylates was made by the English cleric Edward Stone in the late eighteenth century. Here, we discuss the route to optimizing and understanding the mechanism of action of anti-inflammatory drugs that have their origins in Stone's seminal study, 'An account of the success of the bark of the willow in the cure of agues'. This commentary was written to celebrate the 350th anniversary of the journal Philosophical Transactions of the Royal Society.
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This study intends to assess the analgesic effects, physical facilitation, and safety of willow bark use in patients with arthritis. Our study was conducted based on the Preferred Reporting Items for Systematic Reviews and Meta-Analyses statement. PubMed, Scopus, EMBASE, Web of Science, Cochrane, and ClinicalTrials.gov were searched for relative randomized controlled trials (RCTs) describing the efficacy or adverse events of willow bark in patients with arthritis until 12 April 2023. We used Cochrane ROB 2.0 and the Grading of Recommendations, Assessment, Development, and Evaluations system to evaluate the quality of studies and evidence. The meta-analysis was carried out by the fix-effects model. This study included five studies with six RCTs consisting of 329 patients with arthritis. The results showed significant differences in pain relief and improvement in physical status for patients with arthritis between willow bark treatment and placebo groups, and no significant differences in the risk of all adverse events in patients with arthritis between willow bark treatment and placebo. Owing to the potential bias, the certainty and evidence of our findings are still inadequate. Therefore, further RCTs are needed to confirm our results.
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Promover la reflexión sobre las preguntas, evidencias, personajes y controversias que potenciaron el desarrollo del conoci-miento científico a lo largo de la historia, es una cuestión ampliamente reconocida en la educación científica. En este trabajo se presenta una reconstrucción histórica de la vida, obra y legado de Charles Gerhardt (1816-1856). Un brillante y polémico químico francés que realizó valiosas aportaciones en el marco de la teoría unitaria, las cuales sentaron las bases del inci-piente campo de la química orgánica en la década de 1850. El impacto de su obra fue tan relevante que, algunos especia-listas, lo consideran un precursor del periodo de desarrollo epistemológico denominado como segunda revolución química.
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Inhibiting HIV reverse transcriptase is one of the different treatments available to fight the disease caused by this virus, whose role is to block its development in the body and maintain the balance between its presence in the body and its defense system. Indeed, the literature review identified a number of 107 derivatives of 1 - [(2-hydroxyethoxy) methyl] -6 (phenylthio) thymine (HEPT) with potent and selective HIV reverse transcriptase inhibition activities. The analysis of the experimental data thus collected shows a strong dependence of biological activity on the variation in the nature, number and position of the groups carried by the thiophényl cycle and by the thymine. To understand and interpret these dependencies on the one hand and to develop QSAR models on the other hand, quantum chemistry calculations at the DFT / B3LYP / 6-311 + G (d, p) level were performed on 83 HEPT derivatives. Structural characteristics and electronic properties were evaluated and analyzed, namely, chemical potential, ionization potential, electronic affinity, softness, hardness, electronegativity, electrophilicity index. In addition, reliable, stable and predictive QSAR models for predicting the HIV activity of HEPTs using multiple linear regression and a combination of molecular descriptors of a quantum nature among which of the Fukui indices. The best QSAR model obtained was developed on a series of 60 molecules. It is able to describe about 81% of the variance of experimental activity and could be used effectively to estimate the activity of derivatives for which experimental data are unavailable.
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Die elektrochemisch dualistische Sichtweise von J. J. Berzelius (1779-1848) hatte in den 20er Jahren des 19. Jahrhunderts die Grundlagen für das Verständnis der Anorganischen Chemie gelegt. Der Zugang zur Systematik der organischen Verbindungen erwies sich als bedeutend schwieriger: Berzelius’ duales Konzept ging von einer Elektrizitätstheorie aus, die zwei Arten der Elektrizität, positive und negative, unterschied. Die Atome der Elemente sollten zumindest zwei Pole mit unterschiedlichen Elektrizitätsmengen aufweisen, Verbindungen vermittels elektrischer Kräfte durch Zusammenlagerung entstehen. Berzelius nahm an, dass sauerstoffhaltige organische Verbindungen analog zu den anorganischen Oxiden aufgebaut sind. Die Rolle des Elements, welches den elektronegativen Sauerstoff ausgleicht, sollte in den organischen Verbindungen jedoch ein aus mehreren Elementen zusammengesetztes Radikal, wahrnehmen, Das Konzept der Radikal-theorie schien 1832 durch die Arbeiten von Liebig und Wöhler zum Benzoylradikal bestätigt zu werden. Erste Berichte (1834) über die Substitution von Wasserstoff durch Chlor und schließlich 1838 die Photochlorierung der Essigsäure zur Trichloressigsäure durch J. B. Dumas (1800-1884) führten zur Entwicklung der älteren Typentheorie. Nicht der duale Aufbau wie bei Berzelius und J. Liebig (1803-1873) / F. Wöhler (1800-1882), sondern Anzahl und Anordnung der Atome sollten danach der Schlüssel zu Struktur und Reaktionsverhalten der organischen Verbindungen sein. Die Substitutionstheorie basierte auf Empirie, Berzelius Theorie dagegen auf physikalischen Grundlagen. Berzelius lehnte die Substitutionstheorie vehement ab, ebenso wie elektronegative Elemente in den zusammengesetzten Radikalen. Er sah komplexere Verbindungen - insbesondere vielatomige - nun aus einzelnen, seiner Sichtweise entsprechenden Teil-Komponenten zusammengesetzt. Darüber hinaus sollten seiner Überzeugung nach auch duale Verbindungen mit mehr als sieben Sauerstoffatomen weder in Organik noch in Anorganik existieren. C. Gerhardt (1816-1856) hatte 1839 neben Salzbildung und Substitution einen neuen Verbindungstyp (substance copulative) postuliert, der z.B. bei der Reaktion von Schwefelsäure mit inerten Körpern entsteht. Berzelius übernahm den Namen und bezeichnete ab 1841 seine Gruppierungen als „gepaarte Verbindungen“. Diese wurden bei Berzelius ubiquitär: Je mehr er sich dabei als innovativ erwies, desto weniger folgte ihm die wissenschaftliche Welt, die sich ohnehin im Zustand der Verunsicherung befand: Man benutzte unterschiedliche Atomgewichte, Begriffe wie Atom- und Äquivalentgewicht waren diffus und mancherorts wandte man sich sogar vom Atombegriff ab. Die neue, langsam populär werdende neue Typentheorie von Gerhardt 1852 entsprach der allgemeinen empirisch-phänomenologischen Sichtweise. Die Radikaltheorie erfuhr Anfang der 50er Jahre noch eine kurze Wiederbelebung und H. Kolbe (1818-1884) entwickelte ein modifiziertes Paarlingskonzept, das allerdings bereits ca. 1857 von ihm wieder aufgegeben wurde. [Veröffentlicht in: Mitteilungen, Gesellschaft Deutscher Chemiker / Fachgruppe Geschichte der Chemie (Frankfurt/ Main) Bd. 25 (2017), S.74-124 --- ISSN 0934-8506 --- https://www.gdch.de/netzwerk-strukturen/fachstrukturen/geschichte-der-chemie/mitteilungen-der-fachgruppe-online.html]
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C'est en francais et non en allemand que Charles Frederic Gerhardt (1816-1856) a publie en 1853 une synthese de ce qu'il croyait etre un anhydride mixte et qui etait en realite l'acide acetylsalicylique. La meme annee, une publication allemande tres souvent citee du meme auteur reprit les memes resultats. L'acide acetylsalicylique fut prepare et decrit par Von Gilm en 1859 puis identifie au produit de Gerhardt en 1869.
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Alexander William Williamson (1824-1904) discovered accidentally the synthesis of ethers by reacting an alcohol with alkyl iodide in the presence of sulfuric acid (Williamson's synthesis), a decisive fact in overthrowing Berzelius' dual theory. He promoted the use of water type as the single type for deducing the constitution of inorganic compounds and most of the organic ones. In spite of serious physical disabilities, he became one of the few students who were awarded a doctoral degree by Liebig.
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Even at the beginning of the next millennium, aspirin will still offer surprises. Its relatively young pharmacological history compares with the early use of salicylate-containing plants since antiquity. The Assyrians and the Egyptians were aware of the analgesic effects of a decoction of myrtle or willow leaves for joint pains. Hippocrates recommended chewing willow leaves for analgesia in childbirth and the Reverend Edward Stones is acknowledged as the first person to scientifically define the beneficial antipyretic effects of willow bark. At the beginning of the 19th century salicin was extracted from willow bark and purified. Although a French chemist, Charles Gerhardt, was the first to synthesize aspirin in a crude form, the compound was ignored, and later studied by Felix Hoffmann. He reportedly tested the rediscovered agent on himself and on his father, who suffered from chronic arthritis--a legend was born and Bayer Laboratories rose to the heights of the pharmacological world. First used for its potent analgesic, antipyretic and anti-inflammatory properties, aspirin was successfully used as an antithrombotic agent. Sir John Vane elucidated aspirin's active mechanism as an inhibitor of prostaglandin synthetase and received the Nobel Price in Medicine for this work in 1982. Two isoform of cyclooxygenase (COX-1 and COX-2) have now been identified, each possessing similar activities, but differing in characteristic tissue expression. The cox enzyme is now a target of drug interventions against the inflammatory process. After two centuries of evaluation, aspirin remains topical, and new therapeutic indications are increasingly being studied.
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For a long time, the synthesis of quinine constituted an elusive target. In 2004, which marked the 60th anniversary of the publication of the approach used by Woodward and Doering to synthesize quinine, two new stereocontrolled total syntheses of the natural product were accomplished. Together with the well-publicized first stereocontrolled total synthesis of quinine by Stork in 2001, these publications evidence the revival of interest of organic chemists in the synthesis of this compound, once considered a miracle drug. The recently disclosed syntheses of quinine also testify in a remarkable manner the huge progress made by organic synthesis during the last three decades since the first series of partially controlled syntheses of quinine by the group of Uskokovic. Following an account of the historical importance of quinine as an antimalarial drug and a brief description of the experiments which contributed to its isolation and structural elucidation, the first reconstructions of quinine and the total syntheses of the natural product are discussed.
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Medicines procured from herbs, animals or the soil have been with humanity since the dawn of civilization. Mostly, we assume, as cures for our ailments, but also to our detriment, as Socrates’ hemlock and Shakespeare’s ‘juice of cursed hebona’ attest (although we might argue that the murder of Hamlet’s father was not to the detriment but the benefit of our literary world). Were there any ‘ototoxic’ drugs among these remedies, adversely affecting hearing or balance? Undoubtedly, as we can deduce with near certainty from modern experience. Some of the most valuable drugs of our times have originated from plants, molds or bacteria, and notable among the ototoxic compounds of natural origin are quinine and salicylates (from tree bark) and the aminoglycoside antibiotics (from soil-dwelling bacteria). Even though we have reaped innumerable benefits, we are still suffering the consequences of the ototoxic potential of both natural and synthetic drugs (table 1). As diverse as the pharmacological properties of these drugs are their effects on the auditory system. These effects may vary in the location (organ of Corti or stria vascularis) and the nature of the hearing impairment (temporary or permanent threshold shift, tinnitus). However, admittedly, we knew little about toxic side effects of medications until modern times.
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