Tracing Influence in Small Steps: Richard Kirwan's Quantified Affinity Theory

Abstract

This paper presents an attempt to negotiate the familiar historiographical difficulties of tracing influence in science without fear of accusations of whiggishness. Through a close reading of three papers presented to the Royal Society by Richard Kirwan in the early 1780s on specific gravity, proportions and affinity, it seeks to show that the search for the role of influence in the history of science need not be based on a present-centred value judgement of past science. Prevailing historiography tends to link Kirwan's work to notions of definite combining proportions, settling him firmly on the Proust side of the Berthollet–Proust debate and regarding his work as vaguely precursory to Dalton's atomic theory. My reading suggests, however, that these papers may well have had a surprising level of influence on Berthollet's Chemical Statics and should perhaps be viewed through a somewhat different historical lens. I hope to show that the tracing of historical influence can offer valuable insights to historians of science and that when influence is tracked in small steps only, and forwards rather than backwards, we can legitimately follow it without fear of present-centredness clouding our vision.     

Richard Kirwan's phlogiston theory: its success and fate

First proposed in the early 1780s, Richard Kirwan's phlogiston theory was the most successful enunciation of the English pneumatic approach to phlogiston. Phlogiston was identified with a material substance, inflammable air. In this paper, I explore the nature of Kirwan's theory, its success in the mid-1780's, the unprecedented collective attack on Kirwan's Essay on Phlogiston by Lavoisier and his colleagues, and Kirwan's ultimate abandonment of phlogistic explanation.     

Reviews

Abstract

Recent scholarship on Boyle's Sceptical Chymist has emphasised the alchemical context of Boyle's work. In this paper we will draw attention to its specifically sceptical context. Based on Cicero's works on Academic scepticism, the Academica and De Natura Deorum, we give some grounds for Boyle's choice of the literary style of the work and, in particular, for his choice of Carneades as its main character. Based on Sextus Empiricus's Outlines of Pyrrhonism, we show the sceptical nature of the arguments presented by Carneades against the alchemists. Finally, we set Boyle's Sceptical Chymist in the context of Seventeenth-Century skepticism (Gassendi, Mersenne, Descartes, and Glanvill) in order to shed light on the relation exhibited by Boyle's work between scepticism and the new science, in particular the corpuscular theory.     

Novel amides and Schiff's bases derived from 1,3,4-oxadiazole derivatives: synthesis and mesomorphic behaviour

The synthesis and liquid crystalline properties of novel achiral amides (Ia–g, IIa–g and IVa,b), achiral Schiff's bases (IIIa–g and Va–g), chiral amides (VI, VII) and chiral Schiff's bases (VIII–XI) incorporating a 1,3,4-oxadiazole ring are reported. All amides of the series I and II display an enantiotropic smectic A phase. The amide IVa,b did not show mesomorphic properties. Amides of the series Ia–g and IIa–g contain a flexible n-tetradecylthio chain, the other terminal substituent is an n-alkoxy chain and n-alkyl chain, respectively (n?=?4–10) and the 1,3,4-oxadiazole is in the terminal rigid core. Amides Ia–g have broader mesomorphic range and higher thermal stability than the corresponding amides IIa–g. Amides IVa,d contain the 1,3,4-oxadiazole ring in the centre of the rigid core and two flexible alkoxy chains as flexible terminal substituents. Thus, the mesomorphic properties are favoured if 1,3,4-oxadiazole is shifted to a terminal position of the rigid core. Schiff's bases IIIa–g display an enantiotropic dimorphism smectic C–smectic A. Schiff's bases IIIa–g have a broader mesomorphic range than the analogous amides Ia–g. Schiff's bases Va–g exhibit a dimorphism smectic A–nematic, and in contrast to this the analogous amide IVa,b did not show mesomorphism. The chiral amides VI and VII and chiral Schiff's bases X and XI did not show mesomorphic properties and only the chiral Schiff's bases VIII and IX display a chiral smectic C phase in a short mesomorphic range. A density functional theory theoretical study at the B3LYP/6–311++G(d,p) level was performed in order to analyse the structural features that must be related with the mesomorphic behaviour of the reported compounds.     

Comparison of experimental order parameters of nematogens with Faber's theory

Abstract

Orientational order parameters ?P₄ ?, ?P₆ ? and ?P₈ ?, as calculated from our X-ray diffraction studies with aligned nematic samples, have been compared with the predictions of Faber's continuum and Maier-Saupe mean-field theories. In contradiction to our previous finding regarding ?P₂ ? and ?P₄ ?, the agreement with Faber's theory is not good. However, experimental inaccuracies and truncation errors during calculations preclude any definite conclusion on this matter.     

Textual Alchemy: The Transformation of Pseudo-Albertus Magnus's Semita Recta into the Mirror of Lights

Abstract

This article explores the strategies of and the reasons behind the reworking of pseudo-Albertus Magnus's Semita recta into the Mirror of Lights. I argue that the redactor sought to provide a more comprehensive defence of the legitimacy of alchemy than found in the Semita recta. In the process of doing so, he reshaped the original text so as to present three units that addressed different parts of the alchemical opus: first, theory and justification of alchemy; second, basic information on substances and procedures; and, third, practice. The redactor employed sophisticated textual tools identical to those seen in scholastic texts. These strategies, I argue, constitute part of the redactor's attempt to bring authority and credibility to his project and to alchemy in general. Certainly, much more attention needs to be paid to these experiments of textual alchemy in order to understand the practice of alchemy in the late medieval period.     

Establishing the Canon: George Ripley and his Alchemical Sources

Abstract

George Ripley, Canon of Bridlington (ca. 1415 to ca. 1490) was one of England's most famous alchemists, whose alchemical opera attracted study and commentary throughout the sixteenth and seventeenth centuries, and were printed and translated both in England and abroad. Yet Ripley's frequently baffling texts have proved resistant to scholarly interpretation. This paper attempts to unravel some of Ripley's alchemical theories and practice, firstly by identifying his major sources, and secondly by gauging his response to these texts. For instance, although Ripley's interest in the corpus of alchemical texts pseudonymously attributed to Ramon Lull is well documented, it transpires that his best known work, the Compound of Alchemy, or Twelve Gates, is actually based not on a Lullian work, but on a Latin treatise that Ripley attributed to the little-known alchemist, Guido de Montanor. Further clues to Ripley's alchemical thought can be obtained by considering his handling of a potential conflict between his two authorities, Lull and Guido. The resulting insights into Ripley's alchemy provide an instrument for assessing which of Ripley's pseudoepigraphic works can be truly called "canonical".     

Phosphorus Version of the Fritsch-Buttenberg-Wiechell Reaction

Abstract

Utilizing phosphorus version of the Fritsch-Buttenberg-Wiechell (FBW) reaction, arylphosphaalkynes are prepared from 2,2-dihalo-1-aryl-1-phosphaalkenes, and theoretical calculations were carried out to obtain some basic insight into intramolecular rearrangement in the phosphorus system of interest.

[Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements for the following free supplemental resource: Density functional theory (DFT) and ab initio MP2 calculations.]

[Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfer, and Silicon for the following free supplemental files: Additional tables, figures, and references.]     

The Synthesis of D,L-15-Acetoxypallescensin-A: An Intramolecular Oxidative Free-Radical Approach

The synthesis of d,l-15-acetoxypallescensin-A 3 is reported. An intramolecular oxidative radical cyclization was used as a stereoselective entry to trans-decalin 12 which was converted in two steps to the pallescensin-A skeleton 14 by modification of Hagiwara's furan procedure.     

Synthesis and Structural Analysis of Higher Analogs of Sucrose

ABSTRACT

Three sucrose monoalcohols with free hydroxyl groups at C-1', C-6, and C-6' (1, 4, and 6) were prepared selectively and in good yield from 2,3,3',4,4'-penta-O-benzylsucrose. These compounds were oxidized to aldehydes and reacted with stabilized ylide, Ph₃P=CHCO₂Me to afford appropriate α,β-unsaturated esters 10, 11, and 12. Each olefin was cis-hydroxylated with OsO₄/NMO to stereoisomeric diols 13/14, 15/16, and 17/18, configurations of which were assigned by chemical correlation and CD evaluation. Stereoselectivity of the osmylation reaction was surprisingly low (ca 3:2), especially as compared to a similar process performed on simple derivatives of 6,7-unsaturated methyl glycosides for which the ratio of isomeric diols was assigned as 10:1. The osmylation of 11 (derivative homologated by a C₂-unit at the glucose part) did not obey Kishi's rule. Horner-Emmons reaction of sucrose aldehyde 7 with a sugar-derived phosphonate 22 afforded α,β-unsaturated derivative 24, homologated by a C₇-unit at the glucose end.     

From phlogiston to caloric: chemical ontologies

The ‘triumph of the anti-phlogistians’ is a familiar story to the historians and philosophers of science who characterize the Chemical Revolution as a broad conceptual shift. The apparent “incommensurability” of the paradigms across the revolutionary divide has caused much anxiety. Chemists could identify phlogiston and oxygen, however, only with different sets of instrumental practices, theoretical schemes, and philosophical commitments. In addition, the substantive counterpart to phlogiston in the new chemistry was not oxygen, but caloric. By focusing on the changing visions of chemical body across the revolutionary divide with a more sensitive probe into the historical actors’ material manipulations and linguistic usage, we can historicize their laboratory realities and philosophical agenda. An archeology of chemical bodies that configures the fragile stability of the material worlds chemists created in succession promises a philosophical horizon that would recognize our hybrid (natural–artificial) environment as an evolving investigative object of science.     

Interpretation and the Hieroglyphic Monad: John Dee's Reading of Pantheus's Voarchadumia

Abstract

John Dee's marginalia in his copy of Johannes Pantheus's Voarchadumia (now in the British Library) are an interesting source of information about the development of Dee's scientific ideas in the period between the Propaedeumata Aphoristica (1558) and the Monas Hieroglyphica (1564). In reading the book, Dee has systematically compared the text with Pantheus's earlier work, the Ars Metallicae, and noted any differences between the two largely identical works. Therefore, most of Dee's comments are not indications of his own interests, as has previously been assumed. Only the marginalia that are not concerned with comparing the two texts can be taken to express Dee's own views. These marginalia, probably written in 1559, provide evidence that Dee had already at this time a strong interest in cabbalistic methods as a means of gaining knowledge about natural substances. Cabbalistic speculation was to be central to Dee's thought in the Monas Hieroglyphica, and has previously been taken to indicate a dramatic change in Dee's scientific outlook, towards a spiritual quest. In his marginalia in the Voarchadumia, however, Dee appears to be using cabbalistic methods to gain information on wholly material, non-spiritual matters. The abundant use of the symbol of the hieroglyphic monad in the marginalia provides a further source of insight into the alchemical import of the symbol, five years before the publication of the Monas Hieroglyphica.     

Emil Wohlwill's “Entdeckung des Isomorphismus”: A Nineteenth-Century “Material Biography” of Crystallography

Abstract

Eilhard Mitscherlich's experimental work on isomorphism in the crystallisation of many inorganic compounds was regarded by Emil Wohlwill (1835–1912) as a milestone in the history of the atomic–molecular theory. Despite his positivist account, Wohlwill's 1866 survey was primarily concerned with the material conditions that shaped Mitscherlich's theoretical assumptions on iso- and polymorphic crystallisation, narrowing the range of possible alternative models. Following an account of Wohlwill's exposition, and a discussion of his historiographic views, the paper shows how, from a historico-epistemological perspective, technical improvements in crystallography (an emerging branch of early-nineteenth-century mineralogy) were deeply entangled with a new interest in crystal formation as a cutting-edge research field of inorganic chemistry. This had fundamental implications for the development of atomic and molecular theory.     

2-Keto-3-mercaptocinchoninic Acids as Precursors for Novel Thiazino[6,5-c]quinoline-1,5-dione Derivatives

2-Keto-3-mercaptocinchoninic acid derivatives 1a and b react with Schiff's bases 2a–d in toluene at refluxing temperature to give thiazino[6,5-c]quinoline derivatives 4a–h. Also, refluxing of 1a and b with arylazomalononitriles 5a–d in acetic acid afforded the thiazolo[6,5-c]quinoline derivatives 7a–d. The structure of all the newly synthesized products was confirmed based on elemental and spectral data.     

Synthesis and antimicrobial activity of new derivatives of pyrano[4',3':4',5']pyrido[3',2':4,5]thieno[3,2-d]pyrimidine and new heterocyclic systems

Taking into account previously obtained biological results on some polyheterocyclic compounds (containing different heteroatoms) and in particular on several 8-amino-5-isopropyl-2,2-dimethyl-10-(methylthio)-1,4-dihydro-2H-pyrano[4’’,3’’:4’,5’]pyrido[3’,2’:4,5]thieno[3,2-d]pyrimidines Ia-v we have carried out the synthesis of twentyone 8-amino-5-isobutyl-2,2-dimethyl-10-(methylthio)-1,4-dihydro-2H-pyrano[4’’,3’’:4’,5’]pyrido[3’,2’:4,5]thieno[3,2-d]pyrimidines 6. Therefore we have slightly modified the structure of the previously studied I introducing at C-5 an isobutyl group instead of the previously examined isopropyl ones in order to see if this variation (changing a little the lipophilicity) will affect the biological activity. Furthermore thieno[3,2-d]pyrimidine-8-thione 7 and their S-alkylated 8 were synthesized. Finally by alkylation of 5-isobutyl-2,2-dimethyl-10-thioxo-1,4,10,11-tetrahydro-2H-pyrano[4'',3'':4',5']pyrido[3',2':4,5]thieno[3,2-d]pyrimidin-8(9H)-one 3 with alkyl dichlorides (bifunctional reagents) we realized the cyclization of a thiazole or thiazine ring on the [b] side of the pyrimidine ring with formation of the new condensed pentaheterocyclic systems: pyrano[4'',3'':4',5']pyrido[3',2':4,5]thieno[3,2-d][1,3]thiazolo[3,2-a]pyrimidin-8-one 11 and pyrano[4''',3''':4'',5'']pyrido[3'',2'':4',5']thieno[3',2':4,5]pyrimido[2,1-b][1,3]thiazin-8-one 12. It was found that some of the synthesized compounds showed interesting antimicrobial activity (by agar diffusion method) against some gram-positive and gram-negative bacilli strains.     

Effect of Temperature on Henry's Constant in Simple Mixtures

Abstract

The molecular theory of dense fluids is progressing rapidly and its extension to mixtures is well underway. The purpose of this note is to call attention to a possibly serious difficulty in comparing experimental Henry's constants with those calculated from theory. The difficulty arises because whereas theorists choose temperature and density as independent variables, experimental equilibrium measurements on mixtures are often made along the saturation line where (at fixed composition) temperature and density are not both independent variables. Unless Henry's constants are defined with care, the effect of temperature on Henry's constants calculated from molecular theory may be qualitatively different from that observed.     

Synthesis of (R)-4,5-Dihydro-3H-Dinaphtho-[2,1-c:1',2'-e]Selenepin Oxide and Preliminary Studies on Its Use in the Oxidation of Sulfides

The first synthesis (R)-4,5-dihydro-3H-dinaphtho-[2,1-c:1',2'-e]-selenepin oxide 1 has been achieved from (R)-(+)-1,1'-bi-2-naphthol, which in turn was obtained by resolution of rac-1,1'-bi-2-naphthol. Palladium catalyzed alkoxy-carbonylation of ditriflate 4 gave dimethyl ester 5 which was then reduced and the resultant diol converted to key intermediate chloride 8. Cyclization with sodium selenolate gave novel enantiomerically pure selenide 9, which upon oxidation yielded the desired selenoxide (R)-1. Preliminary studies on the oxidation of sulfides to sulfoxides using 1 and 2,2,2-trifluoroethane sulfonic acid are also described.     

Studies on Pyrazine Derivatives,XLII: Synthesis and Tuberculostatic Activity of 6-(1,4-Dioxa-8-azaspiro- [4, 5]-decano)- and 6-(1-Ethoxycarbonylpiperazino)- pyrazinocarboxylic Acid Derivatives

The 2-cyano-6-chloropyrazine's chlorine atom reactivity was substituted with amines 1,4-dioxo-8-azaspiro-[4, 5]-decane and 1-ethoxycarbonylpiperazine. The substrates thus obtained were used in the syntheses of the new derivatives, which were tested for their tuberculostatic activity. Minimum inhibitory concentration (MIC) value of the most active ones ( 5b , 12a , 14b , 16b , 21b ) was 25 μ g/mL.