Norman

Chemical and Biological Defence Sector PLSDy Porton Down, Salisbury SP4 OJQ, U,K. 

It is likely that the material referred to as tarry mustard will be of an almost indefinable composition as varied as the wide number of formulations of mustard that have been used in the past to fill munitions and the complex chemistry displayed by mustard gas in its pure form. 

This paper will highlight these complex aspects of mustard formulation and chemistry and will describe initial attempts to identify the chemical species present in one sample of tarry mustard . The rich chemistry of mustard gas is too extensive to describe fully in this short article, and the examples cited within are merely examples of the different types of reactivity displayed by mustard gas . 

The presentation will conclude with a brief description of a process being developed in the UK that offers the potential of rendering the contents of old mustard munitions safe, irrespective of the nature of the organic species that might be present in the munition. 

The major disadvantage with this process was the production of molecular sulphur which had to be removed at the end of the process. Carried out at low temperature, this reaction was the basis for the Levinstein Process which was extensively used for mustard production during and after the First World War. 

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Principles of Organic Synthesis", R. 0. C. Norman, Methuen, 1968 A taxtbook of organic chemistry from the point of view of synthesis. An excellent source book for all the reactions used in this programme. 

TM 29, made by this route, did indeed turn out to be identical with the compound Robinson had made, and you might like to work out how it was formed. The reaction is discussed in Norman, p.501. The synthesis is described in J. Amer. Chem. Soc., 1926, 1080 ... 

If you are unfamihar with the Wittig reaction see Norman p.297-299 or Tedder, Paid 3, p.233-6. 

If you re not sure about why this is so, or don t understand the mechanism of the Friedel-Crafis reaction, you will find help in Tedder, part 2, pages 212-215 or Norman, pages 363-370. 

The nitrile is described in a patent tChem. Abs.. 1955, 15963) the last stages were carried out by A. R. Battersby s research group at Cambridge. Chloromethylation is described in Tedder, Vol 2, p.213 and Norman P.372-3. 

There is no danger that the tertiary alcohol group will form an ester under these conditions. Ester exchange is described in Norman p. 134-5. 

If you want to know more about this reaction, see Norman p.l 16 or Tedder, vol 1, p.108. 

Tliis hydroxylation gives cis addition to the double bond (see Norman p.502-3 or Tedder vol. 1, p.61-2 if you re not sure about this). How then could you make TM 152 ... 

Another way to make cyclohexenes is by the partial reduction of benzene rings ( Birch reduction, described in Norman, p.553-557) such as ... 

Note that the stereochemistry comes out right. H s a and b are cis because they were cis in the starting quinone and the Diels-Alder reaction is stereospecific in this respect. H is also cis to and H " because the Diels-Alder reaction is stereoselectively endo. These points are described in more detail in Norman p.284-6 and explained in Ian Fleming Frontier Orbitals and Organic Chemical Reactions, Wiley 1976, p. 106-109. How would you make diene A ... 

Synthesis The most economical route will therefore be to make both the acid chloride and TM 244 from the nitrile (see Norman, p.614-5) ... 

There are many special methods to making heterocycles if you want to read about them, see Tedder, part 3, pp.115-131 and 205-220, or Norman, Chapter 18, p.5SS. We are more interested in applying these general methods to molecules in which a heterocyclic ring is only part of the problem. How would you make TM 263 from simple starting materials ... 

This is the Darzens reaction (frames 172-3) (see Norman, p.231 if you want more details). How would you make... 

This is the allowed process by the Woodward-Hoffmaim rules (see Tedder, Part 3, pp. 383-387 or Norman p. 292 ff if you want to know more). There are obviously two disconnections for any given cyclobutane but it is often easy to see the better at once. How would you make ... 

We have meet NO2 and CN before, but a primary amine can also be made from an amide by the Hofmann degradation (see Norman p.446-7 or Tedder, vol.2, p.281-2). 

In a later paper Knowles and Norman compared more fully nitrations of benzylic compounds in acetyl nitrate and in mixed acid (table 5.9), and interpreted the results in terms of three factors nitronium ion nitration in both media some degree of protonation of the oxygen... 

The argtiments of Norman and his co-workers seem to give affirmative answers to the first and second of these questions, but it is doubtful if the available data further require such an answer for the third question. It can be argued that the crucial comparison made between the behaviour of benzyltrimethylammonium ion and protonated benzyl methyl ether is invalid, and that it is possible to interpret the results in terms of nitration by the nitronium ion, modified by protonation of the oxygen atom of the ether a case for the possible involvement of the nitro-nium ion in specific interaction leading to o-substitution has been made. ... 

Norman, R. O. C. Taylor, R. (1963). Electrophilic Substitution in Ben-zenoid Compounds. London Elsevier. 

Structural drawings of carbohydrates of this type are called Haworth formulas, after the British chemist Sir Walter Norman Haworth (St Andrew s University and the University of Birmingham) Early m his career Haworth contributed to the discovery that carbohydrates exist as cyclic hemiacetals rather than m open chain forms Later he col laborated on an efficient synthesis of vitamin C from carbohydrate precursors This was the first chemical synthesis of a vitamin and provided an inexpensive route to its prepa ration on a commercial scale Haworth was a corecipient of the Nobel Prize for chem istry m 1937... 

Note MMh- is derived from the public domain code developed by Dr. Norman Allinger, referred to as MM2(1977), and distributed by the Quantum Chemistry Program Exchange (QCPE). The code for MMh- is not derived from Dr. Allinger s present version of code, which is trademarked MM2 . Specifically, QCMPOlO was used as a starting point for HyperChem MMh- code. The code was extensively modified and extended over several years to include molecular dynamics, switching functions for cubic stretch terms, periodic boundary conditions, superimposed restraints, a default (additional) parameter scheme, and so on. 

The focus of this section is the emission of ultraviolet and visible radiation following thermal or electrical excitation of atoms. Atomic emission spectroscopy has a long history. Qualitative applications based on the color of flames were used in the smelting of ores as early as 1550 and were more fully developed around 1830 with the observation of atomic spectra generated by flame emission and spark emission.Quantitative applications based on the atomic emission from electrical sparks were developed by Norman Lockyer (1836-1920) in the early 1870s, and quantitative applications based on flame emission were pioneered by IT. G. Lunde-gardh in 1930. Atomic emission based on emission from a plasma was introduced in 1964. 

W. S. Norman, Mbsorption, Disti/htion and Cooling Towers Longmans, Green Co., Ltd. (Wiley) New York, 1962. 

P. Sabatier, Catalysis In Organic Chemisty, Van Nostrand Reinhold, New York, 1922 Brit. Pat. 1,515 (1903), W. Norman. 

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