Organic Chemistry

I apply James Woodward’s interventionist theory of causation to organic chemistry, modelling three different ways that chemists are able to manipulate the reaction conditions in order to control the outcome of a reaction. These consist in manipulations to the reaction kinetics, thermodynamics, and whether the kinetics or thermodynamics predominates. It is possible to construct interventionist causal models of all of these kinds of manipulation, and therefore to account for them using Woodward’s theory. However, I show that there is an alternate, (...) more illuminating way of thinking about the third kind of reaction control, according to which chemists are thought of as manipulating which causal system is instantiated. I show that our ability to manipulate which system is instantiated is an important part of our ability to control the world, as is therefore especially relevant to interventionism. Thus, considering examples from organic chemistry leads to the identification of an important extension to Woodward’s theory. Finally, this investigation into reaction control in organic chemistry also has a more general implication: it suggests that interventionism results in a version of pragmatism about causation. (shrink)

ABSTRACT Contrastive and deviant/default accounts of causation are becoming increasingly common. However, discussions of these accounts have neglected important questions, including how the context determines the contrasts, and what shared knowledge is necessary for this to be possible. I address these questions, using organic chemistry as a case study. Focusing on one example—nucleophilic substitution—I show that the kinds of causal claims that can be made about an organic reaction depend on how the reaction is modelled, and argue that paying attention (...) to the various ways that reactions are modelled has important implications for our understanding of causation. _1_ Introduction _2_ General Contrastive Causal Claims in Organic Chemistry _3_ Deviant Causal Claims in Organic Chemistry _4_ Nucleophilic Substitution Reactions _5_ The Causal Modelling Tradition _5.1_ The type/token distinction _6_ Competing Reactions _6.1_ Type- and token-causal claims, variables, and values of variables _7_ Disambiguation of ‘Reaction’ _8_ Reaction Kinds _9_ Specific Reactions _9.1_ Specific reactions and token-causal claims _9.2_ Specific reactions and type-causal claims _10_ Implications _10.1_ Kinds of causal claim _10.2_ Contrastive and deviant causal claims _10.3_ Model relativity. (shrink)

This research examines the structure and development of the organic sesame network from Burkina Faso to explain the declining trend in organic sesame export. The paper addresses particularly the question whether the organic sesame network is structurally (re)shaped as a conventional mainstream market or whether it still presents a real alternative to conventional sesame production and trade. It is found that over the last decade organic sesame is increasingly incorporated into mainstream market channels. But contrary to the well-known case of (...) conventionalization in California, where organic agriculture grew into mainstream agro-food arrangements, this study illustrates a case where organic sesame agriculture shrank into mainstream agro-food arrangements. The weak coherence between the production and marketing nodes in the organic sesame chain resulted in failures to vertically mediate information, balance power relationships in and across sesame chains, build trust, and limit price volatility and speculation, resulting in a shrinking organic sesame market. For developing a viable alternative to conventional sesame trading, relations between production and trading nodes in the organic networks need to be strengthened through public–private partnerships, combined with other public and legal reinforcement. (shrink)

Over the past two decades the growth of the organic sector has been accompanied by a shift away from first party, or peer review, systems of certification and towards third party certification, in which a disinterested party is responsible for the development of organic standards and the verification of producer compliance. This paper explores some of the limitations of the third party certification model and presents the case of Mexico as an example of how an alternative form of participatory certification (...) has emerged. The paper suggests that participatory guarantee systems (PGS) are reflective of the growing “beyond organic” movement, which focuses on reconstructing the local and re-embedding food systems into their socio-ecological contexts. It argues that PGS offers a number of benefits for producers and consumers, particularly in the South, but that it faces a number of challenges as well, such as a lack of formal recognition, social conflicts and dependence on donated resources. (shrink)

Stakeholders in traditional dairy-producing states in the upper Midwest and Northeast hope that the boom in the organic milk market will offer family-scale dairy farms a means to escape the cost-price squeeze of the conventional food system. However, recent trends in organic dairy raise questions about whether organic dairy is conventionalizing, which is to say it is coming to resemble the conventional sector as shown in disparities of power in the value chain that pressure all participants to adopt more industrial (...) practices. This paper reports the results of an exploratory qualitative study of whether and how the organic milk value chain in upstate New York is conventionalizing. Findings lend some support to the conventionalization hypothesis in that organic milk from the beginning has been produced, processed, and marketed as a commodity, and the federal regulations governing organic dairy have facilitated the replication of this commodity-based system. However, there is also evidence that some producers are responding to these pressures not by intensifying, but by going deeper into the alternative organic model, forging more direct and local relationships along the value chain and embracing principles of the organic movement. (shrink)

Observers of agriculture and theenvironment have noted the recent remarkable growth ofthe organic products industry. Is it possible for thisgrowth in the organics market to contribute toprogressive environmental and social goals? From theperspective of green consumerism, the organics marketis a powerful engine for positive change because itpromotes greater environmental awareness andresponsibility among producers and consumers alike.Given its environmental benefits and its ability touse and alter capitalist markets, organic agricultureis currently a positive force for environmentalism.Still, there are contradictions between organic idealsand (...) practice – e.g., the reductionism of organicstandards, the limitations of private organiccertification, and the widespread practice ofinput-substitution – that emerge through thedynamics of the capitalist market. As the marketmatures, these contradictions will increasinglyundermine the very environmental benefits that are thefoundation of organic agriculture. Fundamental change,therefore, is not likely to occur through the marketalone. There are ways, however, that the organicsmarket could contribute to a broader movement leadingto collective action. For instance, the organicsmarket tends to undermine commodity fetishism in theagrifood system, thereby strengthening civil society.In addition, the market provides space and resourcesfor social movement activity, such as in the struggleover the National Organic Standards. (shrink)

We define organic sets and organically stationary sequences, which generalize tight sets and tightly stationary sequences respectively. We show that there are stationary many inorganic sets and stationary many sets that are organic but not tight . Working in the Constructible Universe, we give a characterization of organic and tight sets in terms of fine structure . We answer a related question posed in [J. Cummings, M. Foreman, M. Magidor, Canonical structure in the universe of set theory: Part two, Ann. (...) Pure Appl. Logic 142 55–75] about the combinatorial principle Coherent Squares. (shrink)

The paper studies various functions of Berzelian formulas in European organic chemistry prior to the mid-nineteenth century from a semiotic, historical and epistemological perspective. I argue that chemists applied Berzelian formulas as productive 'paper tools' for creating a chemical order in the 'jungle' of organic chemistry. Beginning in the late 1820s, chemists applied chemical formulas to build models of the binary constitution of organic compounds in analogy to inorganic compounds. Based on these formula models, they constructed new classifications of organic (...) substances. They further applied Berzelian formulas in a twofold way to experimentally investigate organic chemical reactions: as tools which supplemented laboratory tools and as tools for constructing interpretive models of organic reactions. The scrutiny of chemists' performances with chemical formulas on paper also reveals a dialectic which contributed considerably to the formation of the new experimental culture of synthetic carbon chemistry that emerged between the late 1820s and the early 1840s. In an unintended and unforeseen way, the tools reacted back on the goals of their users and contributed to conceptual development and a shift of scientific objects and practices ('substitution') which transcended the originally intended chemical order. (shrink)

Next SectionOne of the indisputable signs of the progress made in organic chemistry over the last two hundred years is the increased ability of chemists to manipulate, control, and design chemical reactions. The technological expertise manifest in contemporary synthetic organic chemistry is, at least in part, due to developments in the theory of organic chemistry. By appealing to a notable chemist's attempts to articulate and codify the heuristics of synthetic design, this paper investigates how understanding theoretical organic chemistry facilitates progress (...) in synthetic organic chemistry. The picture that emerges of how the applications of organic chemistry are grounded in its theory is contrasted with both standard and some more contemporary philosophical accounts of the applications of science. IntroductionTotal Synthesis as Applied ScienceUnderstanding Organic ChemistryThe Heuristics of Synthetic DesignAn Example: LongifoleneConclusion. (shrink)

Organic chemists have been able to develop a robust, theoretical understanding of the phenomena they study; however, the primary theoretical devices employed in this field are not mathematical equations or laws, as is the case in most other physical sciences. Instead it is diagrams, and in particular structural formulas and potential energy diagrams, that carry the explanatory weight in the discipline. To understand how this is so, it is necessary to investigate both the nature of the diagrams employed in organic (...) chemistry and how these diagrams are used in the explanations of the discipline. I will begin this paper by characterizing some of the major ways that structural formulas used in organic chemistry. Next I will present a model of the explanations in organic chemistry and describe how both structural formulas and potential energy diagrams contribute to these explanations. This will be followed by several examples that support my abstract account of the role of diagrams in the explanations of organic chemistry. In particular, I will consider both the appeal to ‘hyperconjugation’ in the explanation of alkene stability and how the idea of ‘ring strain’ was developed to explain the relative stability of cyclic compounds. (shrink)

"Organic" has become a central term in twentieth century cultural discourse. It connotes change, evolution, multi-faceted and multi-layered interrelatedness, and flexible responsiveness. It has become a new paradigm through which contemporary society interprets the world. Notions of the organic have increasingly appeared in theology providing focal concepts, models and metaphors for interpreting God and God-world relations. Process and feminist theologians such as Charles Hartshorne, John Cobb, Delwin Brown, Marjorie Suchocki, Sallie McFague, Catherine Keller, and Rosemary Ruether all construct theologies in (...) which the organic plays a central, defining role. The exploration, clarification and extension of the way these theologians, among others, apply the organic to God provide substantive resources for thinking theologically today about God and the world. ;This dissertation presents an organic view of how God functions in the world through interrelatedness, creativity, and balance of value. As theologians have often done, I analyze appropriate philosophical, scientific, and theological texts, contrast them and then expand their meanings. An analysis and elaboration of mechanistic, as defined by George E. Moore, biological, as defined by Ann Plamondon, and Whiteheadian understandings of organic provide a preliminary working definition of organic. This preliminary definition frames how process and feminist applications of the organic to God are explored, assessed, compared and elaborated. These applications are dealt with as proposals that need clarification and whose meanings can be expanded. Critiques of feminist and process concepts of organic made by Robert Neville, Jurgen Moltmann and Nancy Frankenberry are also presented as part of the task of clarification. ;This combined analysis results in a more consistent definition of organic and its application to God than process or feminist theology has offered thus far. Furthermore, it results in an expanded view of how the organic can be applied to God. In these two respects, my task is both critical and constructive. The analysis and construction done here set the stage for rigorous discourse about God that can resonate widely in the context of the contemporary organic paradigm. (shrink)

The outstanding scientific work of Christopher Kelk Ingold was the focus of considerable discussion, celebration and evaluation during the year of the centenary of his birth. In addition to understanding his prolific and highly original scientific output as a pioneer in the application of physical methods to organic chemistry and, indeed, as a founder of physical organic chemistry, it is also important to examine other aspects of Ingold's career, in particular his role in shaping the institutional context in which he (...) developed his work. From 1930 until his death, Ingold was attached to a major international centre, the Chemistry Department of University College London. From 1937 to 1961, as its Head and Director of Laboratories, continuing the policies of his predecessor on chemical education and the organization of research, he developed a very distinctive chemistry department. (shrink)

In 1915, after acquiring first-hand knowledge of the new free radical chemistry at the Swiss Federal Institute of Technology in Zurich, Antonio García Banús became professor of organic chemistry at the University of Barcelona and created his own research group, which was to last from 1915 until 1936. He was a gifted teacher and a prolific writer who attempted to introduce international scientific standards into his local environment. This paper analyses the bridges that Banús built between the experimental culture of (...) organic chemistry at the ETH and the University of Barcelona. It presents a case study which aims to provide new historical data for the general analysis of groups who conducted their work in the European periphery. (shrink)

Proclaiming Louis Pasteur as the “Founder of Stereochemistry”, the distinguished Scottish chemist, Crum Brown, addressing a late nineteenth-century audience of Edinburgh savants, drew attention—as Pasteur had incessantly done—to the intimate relationship between living organisms and the optical activity of compounds sustaining them. It seemed to Crum Brown “that we must go very much further down in the scale of animate existence than Buridan's ass, before we come to a being incapable of giving practical expression to a distinct preference for one (...) of two objects differing only in being one to the right and the other to the left”. Crum Brown's lecture must have been entertaining, but it was also motivated by a serious desire to do justice to a particular assertion of Pasteur—an assertion which had, moreover, been misunderstood and dismissed by no less a chemical genius than Wilhelm Ostwald. Writing at a time when the majority of his colleagues were stressing the resemblances between inorganic and organic compounds, Pasteur had insisted that he “could not point out the existence of any more profound distinction between the products formed under the influence of life and all others” than that “artificial products have … no molecular asymmetry”. Pasteur was obliged to concede that the chemist might produce enantiomorphic pairs of isomers, but without resorting to a manual separation of crystals he was powerless to imitate Nature's performance, powerless to fabricate by chemical means a separate optical isomer, divorced from its partner. Now it was not only Crum Brown who felt that chemists had brushed aside this proposition of Pasteur. In his 1898 Presidential Address to the chemical section of the British Association, Professor F. R. Japp also complained that the possible vitalistic implications of Pasteur's distinction between natural and artificial products had been misapprehended or tacitly ignored. (shrink)

Organic cotton productionboomed in the early 1990s only to fall steeplymid-decade. Production is currently rising, butslowly, and has yet to reach previous levels.This is in marked contrast to the steady growthin organic food production during the 1990s.Why, when other areas of organic productionexperienced steady growth, did organic cottonexperience a boom and bust? A study of thecotton production and processing industryreveals a long and heavily industrializedproduction chain that has presented numerouschallenges to growers and processors trying tointroduce an organic product. In addition, (...) muchof the surge in demand for organic cotton clothoriginated with clothing manufacturersresponding to increased consumer environmentalconcern and interest in improving theirenvironmental reputations. This demandevaporated when clothing companies encountereda lack of consumer awareness of theenvironmental costs of conventional cottonproduction and the benefits of organic cotton.Organic clothing lines were abandoned and manycotton farmers, left with no market for theirorganic bales, were forced to either store thebales or sell them on the conventional marketfor a loss. An examination of the social andtechnical aspects of organic cotton productionidentifies some of the critical variables, suchas the risks farmers face in agriculturalproduction, the organic standards, sources ofinnovation in technological change, and the roleof consumer demand in supporting moresustainable technology, all of which shape thecontinuing development of organic products. (shrink)

This paper examines a facet of the rise of the Hughes-Ingold Theory of Nucleophilic Substitution in Organic Chemistry 1933-1942, arguing that the SN1/SN2 model of reaction mechanism used by Hughes and Ingold is an example of a fuzzy model. Many real world 'Fuzzy Logic' Controlling Devices gave better results compared to classical logic controlling devices in the period 1975-1985. I propose that the adoption of fuzzy principles in the Hughes-Ingold program 1933-1940 led to scientific advance at a time when the (...) rival programs, based on classical principles, had stalled owing to problems associated with the fuzziness of the data. I suggest also that there is an analogy between the success of second generation fuzzy logic controllers 1985-95 and the success of the successor Winstein model from 1956 onwards. (shrink)

This paper evaluates a general argument for the conclusion that visual representations in science must play the role of truth bearers if they are to figure as legitimate contributors to scientific arguments and explanations. The argument is found to be unsound. An alternative approach to assessing the role of visual representations in science is exemplified by an examination of the role of structural formulas in organic chemistry. Structural formulas are found not to play the role of truth bearers; nonetheless, they (...) contribute to the arguments and explanations of organic chemistry. An early success of conformational analysis is presented in order to illustrate the role of structural formulas in the discourse of organic chemistry. *Received January 2007; revised July 2009. †To contact the author, please write to: Department of Philosophy and Religious Studies, Rowan University, 201 Mullica Hill Road, Glassboro, NJ 08028; e‐mail: goodwin@rowan.edu. (shrink)

This article examines a scientific controversy that raged for twenty years in physical organic chemistry during the second half of the twentieth century. After explaining what was at stake in the non-classical ion debate, I attempt—by examining the methodological reflections of some of the participants—a partial explanation of what sustained this controversy, particularly during its early stages. Instead of suggesting a breakdown of scientific method or the unavoidable historical contingency of scientific development, the endurance of this controversy instead reveals the (...) heuristic and pragmatic character of many of the explanations and predictions generated by theoretical organic chemistry. The results in this case are used to suggest a new role for the study of scientific controversies in revealing the economics of scientific inquiry. 1 Introduction2 The Non-classical Ion Debate3 Models for the 2-Norbornyl System4 Soft Theories and Reasoning by Analogy5 Scientific Controversy and the Non-classical Ion Debate6 Conclusion. (shrink)

The foundations of modern organic chemistry were laid by the seminal work of Hughes and Ingold. The rise from being an interesting alternative hypothesis in 1933 to being the leading theory (outside the USA) in 1942 was achieved by a multiplicity of methods. This include:the construction of a new scientific notation, the rationalisation of some seemingly contradictory reported data, the refutation of the experimental work of one of their persistent critics, the use of conceptual arguments and also the achievement of (...) a score of successful predictions which exceeded the score of unsuccessful predictions. Within the USA it was felt that the Hughes/Ingold system, whilst representing a considerable advance, had achieved spectacular success in spite ofits attractively simple basic assumptions, and represented merely an interim stage on the way towards a more comprehensive theory. However,the flexible, simple notation was adopted without modification, leading to a change in the way practitioners of synthetic organic chemistry were, and still are, trained to think. In a conclusion the author claims that this historical episode does not lend any support to the philosophical position of Thomas Kuhn. (shrink)

This paper studies the semiotic,epistemological and historical aspects of Berzelianformulas in early nineteenth-century organicchemistry. I argue that Berzelian formulas wereenormously productive `paper tools' for representingchemical reactions of organic substances, and forcreating different pathways of reactions. Moreover, myanalysis of Jean Dumas's application of Berzelianformulas to model the creation of chloral from alcoholand chlorine exemplifies the role played by chemicalformulas in conceptual development (the concept ofsubstitution). Studying the dialectic of chemists'collectively shared goals and tools, I argue thatpaper tools, like laboratory instruments, areresources (...) whose possibilities are not exhausted byscientists' attempts to achieve existing goals, butrather whose applications generate new goals. The term`paper tools' is introduced to emphasize that thepragmatic and syntactic aspects of symbol systems arefully comparable to physical laboratory tools. (shrink)

In 1870–75 Markovnikov enunciatedan empirical Rule which generalized theregiochemical outcome of addition reactions tounsymmetrical alkenes. This Rule remaineduseful for about 75 years, until suchreactions came to be better understood inmechanistic terms. Thereafter the Rule couldbe deduced from principles of relativecarbocation stabilization and ceased to servean independent purpose. Nevertheless, mostorganic textbooks continue to cite it (oftenin a historically inaccurate, anachronisticway), thereby distracting student attentionfrom the underlying principles. This paperadvocates doing away with the Rule in organicchemistry textbooks and classrooms.

This article investigates how understanding the theory of organic chemistry facilitates the total synthesis of organic compounds. After locating the philosophical significance of this question within the methodology or epistemology of applied science, I summarize the results of previous work on this issue—roughly that theoretical organic chemistry underwrites a sequence of heuristic policies that help to isolate plausible synthetic routes from the array of possibilities provided by structural or descriptive organic chemistry. While this prior account makes a solid start, it (...) does not capture all of the ways that the theory of organic chemistry contributes to total synthesis. This article aspires to enrich this account by exploring some additional ways that theory contributes. More specifically, I investigate how understanding the theory of organic chemistry can facilitate both the development of novel synthetic reactions and the implementation of a synthetic plan. The role of theory in these aspects of total synthesis will be explored by considering a particular, novel synthesis of longifolene. (shrink)

The acidity function is a thermodynamic quantitative measure of acid strength for non-aqueous and concentrated aqueous Brønsted acids, with acid strength being defined as the extent to which the acid protonates a base of known basicity. The acidity function, which was developed, both theoretically and experimentally, by Louis P. Hammett of Columbia University during the 1930s, has proven useful in the area of physical organic chemistry where it has been used to correlate rates of acid-catalyzed reactions and to quantitate the (...) acidity of superacids, acids with protonating abilities greater than pure sulfuric acid. All Brønsted acids can now be compared using a common measure. Karl Popper’s seminal idea of theory falsification does not apply here because of the many successful applications of the acidity function. Likewise, Thomas Kuhn’s idea of a paradigm shift does not apply here, even though the acidity function concept was revolutionary, because the acidity function is commensurate with classical concepts of acidity. (shrink)

The paper illustrates how organic chemists dramatically altered their practices in the middle part of the twentieth century through the adoption of analytical instrumentation — such as ultraviolet and infrared absorption spectroscopy and nuclear magnetic resonance spectroscopy — through which the difficult process of structure determination for small molecules became routine. Changes in practice were manifested in two ways: in the use of these instruments in the development of ‘rule-based’ theories; and in an increased focus on synthesis, at the expense (...) of chemical analysis. These rule-based theories took the form of generalizations relating structure to chemical and physical properties, as measured by instrumentation. This ‘Instrumental Revolution’ in organic chemistry was two-fold: encompassing an embrace of new tools that provided unprecedented access to structures, and a new way of thinking about molecules and their reactivity in terms of shape and structure. These practices suggest the possibility of a change in the ontological status of chemical structures, brought about by the regular use of instruments. The career of Robert Burns Woodward provides the central historical examples for the paper. Woodward was an organic chemist at Harvard from 1937 until the time of his death. In 1965, he won the Nobel Prize in Chemistry. (shrink)