The Westheimer Report

To justify partly the increased support of chemistry, the Westheimer report emphasized the practical aspects of the products of chemical research. To do so, the report tried to show that undireaed, basic research in chemistry was at the root of much of the success of the multi-billion-dollar chemical industry... 

In terms of computational chemistry, the Westheimer report pointed out evidence of the increasingly important role of computers in chemistry. The... 

In a survey of 125 university chemistry departments, the Westheimer report showed approximately a 50% increase in computing devoted to chemical research from 1963 to 1964. Comparably, the computer use rates for 1961-1964 showed a 40% annual increase, leading the committee to speculate that, if properly financed, computer use for chemistry might be able to grow at a rate of 40-50% per year over the following few years. The phrase if properly financed was, of course, crucial. 

Westheimer, F.H. 1965, Chemistry Opportunities and Needs (The Westheimer Report) , Chemical and Engineering News, Nov. 29, 72-102. 

The Chemical Abstracts Service conducts extensive quantitative investigations of the growth and structure of chemical literature see, for example, IB, Baker, 1976. The Westheimer Report, sponsored by the Committee on Science and Public Policy of the National Academy of Sciences, includes quantitative material on American chemical publications see IB, NAS, 1965, 30-38. 

The growth in federal funding for academic science during the early 1960s helps to explain the tone of the Westheimer Report on Chemistry Opportunities and Needs (IB, NAS, 1965). In his letter of transmittal George B. Kistiakowsky warned that chemistry was not as well supported as is research in other natural sciences, if qualified requests for funds and the training of scientific personnel are proper yardsticks (ibid., iii). 

That values of yj and 7r vary with the reaction and the reaction conditions is readily seen from the results reported in Table XLVIII for the rrans-vinylene group. Values of yj for this group range from 1.01 to 3.28. That the value of yj is dependent upon the reaction is no surprise. Charton has shown (251,252) that the yj values may be calculated from the Kirkwood-Westheimer equation in the form... 

Hendrickson et al. 24 using the Westheimer-Allinger 19 method. Our calculated activation energy (6.0 kcal/mole) is less than those reported by Anet et al25) (10.3, 10.8 kcal/mole). Since, however, the barrier to inversion in per-fluorocyclohexane is 7.5 kcal/mole 26 and since the rates of inversion of cyclohexene and perfluorocyclohexane are very similar, the barrier reported for cyclohexane may be too large. 

Harger " also examined the behaviour of the azide 51a, from which he obtained a mixture of stereoisomeric 2-methoxy-2-oxo-l,2-azaphospholidines (in total yield 60%) together with 16% of an unsaturated phosphonamidic ester. Meanwhile, Wiseman and Westheimer reported on a more detailed examination of the behaviour of this particular... 

Bullseye Powder The following double-base propellant NC(13.25%N) 60.0, NG 39.5 DPhA 0.5%, in the form of circular flakes, diam 0.035 and thickness 0.005 > was subjected during WWII at PicArsn to 65-5°.Surveillance and to 120 134-5 Heat Tests. The results of these tests, reported by Rinkenbach(Ref 1), showed that this propint was of satisfactory stability. According to Westheimer et al(Ref 2), Buiiseye Powder is manufd by Hercules Powder Co, Wilmington, Del, One of their Bullseye propints manufd during WWII was in the form of 7/8" sticks, which consisted of NC(13-25%N) 58.8jNG 40.0, EtCentr 1.0 DPhA 0.2% with some carbon black added(Ref 3)... 

Two sets of data for the mercuration of toluene were already reported in the literature (Klapproth and Westheimer, 1950 Brown and Nelson, 1953). The partial rate factors found in these studies were neither in agreement with the relationship (7) nor with each other. A study of the uncatalyzed and acid-catalyzed mercuration of toluene allowed a test of both the earlier data and the relationship. A re-examination of the results for the substitution of toluene including the data for mercuration and other newly reported observations indicated that the partial rate factors were correlated by an even simpler equation (8) with the theoretical origin (Brown and McGary, 1955a). 

Kokesh, F.C. and Westheimer, F.H. (1971) Reporter group at the active site of acetoacetate decarboxylase. II. Ionization constant of the amino group./. Am. Chem. Soc., 93, 7270. 

The absence so far of unequivocal proof of carbene formation by a-elimination of hydrogen halide from organic halides and related reactions using hydroxide and alkoxide ions or weaker bases suggests that more detailed investigations of some reported carbenoid reactions may be justified. Thus carbenoid behaviour in the reaction between benzal chloride and potassium t-butoxide in the presence of olefins seems to be critically dependent upon the nature of the solvent (McElvain and Weyna, 1959 Cawley and Westheimer, 1960) and the reaction temperature (Hodgkins et al., 1964). 

The use of PAL in enzyme modifications was first described in 1962, when Westheimer and coworkers reported on the use of a diazoacetyl group to inactivate chymotrypsin [29]. Considerable research on the development of new PAL reagents has taken place ever since [27, 28, 30-36], but only a few photophores, which largely meet the above-mentioned requirements, are being used nowadays in A/BPs. These are aryl azides (first reported use in 1969) [37], diazirines (1973) [38] and benzophenones (1973) [39]. The chemistry of these three photoreactive groups after photolysis as well as their use in recently reported A/BPs will be discussed in Sects. 3.1-3.5. 

Equation 21 depicts the reaction of the simplest NAD+/NADH-dependent enzyme, alcohol dehydrogenase153. This enzyme performs the last reaction in ethanol fermentation. Indicated in the equation is the fundamental finding on such reactions first reported by Westheimer, Vennesland and coworkers154-157. The hydrogen transfer is not only direct in both directions (as opposed to solvent-mediated), but is totally stereospecific in both directions for both the coenzyme and the substrate. The pro-R hydrogen is transferred from both the coenzyme and the substrate ethanol. This was an observation of enormous implications for NAD+-dependent reactions, in particular, and enzyme catalyzed reactions, in general, that has been borne out by literally hundreds of examples. 

This was part of a programme of investigations into enzyme mechanisms by F. H. Westheimer and group, J, Am. Chem. Soc., 1971, 93, 7266, 7270. They caiied the p-nitrophenoi a reporter group . 

Equation 21 depicts the reaction of the simplest NAD /NADH-dependent enzyme, alcohol dehydrogenase . This enzyme performs the last reaction in ethanol fermentation. Indicated in the equation is the fundamental finding on such reactions first reported by Westheimer, Vennesland and coworkers The hydrogen transfer is not only... 

To address the funding problem, in February 1964 Frank Westheimer, an organic chemist at Harvard University, was elected to head a committee, under the auspices of the Committee on Science and Public Policy of the National Academy of Sciences, to make a comprehensive study of American basic research in chemistry. The report of the committee, titled Chemistry Opportunities and Needs, came to the basic conclusion that scientific opportunities were being lost for lack of support- ... 

Westheimer has reported on the results of a more deta d study of the formation of monomeric metaphosphate anion from (1,2-dibromo-l-phenyl-propyl)phosphonic acid, and its reaction with acetophenone. The yields of phenylethenyl phosphate can be raised to 40—80 % by careful choice of the nature and concentration of base. The effect of the pJ Ta of the added base appears to be complex some hindered bases, e.g., 2,2,4,4-tetramethylpiperidine and diisopropylamine, raise yields (to the maximum observed), but others, e.g. diisopropyl-methylamine, have the opposite effect. ... 

No objectively sound conclusions can be made. The scarcity of activation parameters detailed in the literature is unfortunate, since relief of ring strain in five-membered systems is such a fundamental postulate for nucleophilic substitution reactions at phosphorus and for Westheimer s guidelines. The inconsistency in the reported data is not surprising the hydrophobicity of many phosphoryl species, such as triesters, dictates mixed solvent systems, which, combined with complex pH/rate profiles, makes prediction of proton and hydroxide activity at different temperatures fraught with uncertainty. 

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