General method

The amino acid (0.05 mol) is heated in ethanol (100 ml) saturated with dry HCl. After removal of the solvent under reduced pressure, the residue of the amino acid ester hydrochloride is dissolved in ice-cold water (100 ml), and 2.3% sodium amalgam (200g) is added slowly with stirring, the pH being 

Imidazoles (1) prepared from amidines derived from o -amino acids  

Trituration of the residue with dilute hydrochloric acid, and cooling to 0°C, gives the imidazole hydrochloride salts, which are frequently crystalline. The free bases can be obtained by making the salts alkaline with aqueous sodium hydroxide followed by extraction with ether. The ether is removed to give the products (1). Some free bases precipitate from aqueous alkaline solution and need not be extracted. The aininoaldehydes from aspartic and glutamic acids are best distilled at around 1 mmHg pressure to purify them. 

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This chapter presents a general method for estimating nonidealities in a vapor mixture containing any number of components this method is based on the virial equation of state for ordinary substances and on the chemical theory for strongly associating species such as carboxylic acids. The method is limited to moderate pressures, as commonly encountered in typical chemical engineering equipment, and should only be used for conditions remote from the critical of the mixture. 

In the generalized method of Hayden and O Connell (1975), the pure-component and cross second virial coefficients are given by the sum of two contributions... 

Doebner-von Miller reaction Condensation of an aromatic amine with an aldehyde or ketone in the presence of hydrochloric acid to form a quinoline derivative. A general method, thus aniline and ethanal give 2-methyl-quinoline (quinaldine) and p-phenetidine. 

A very important but rather complex application of surface chemistry is to the separation of various types of solid particles from each other by what is known as flotation. The general method is of enormous importance to the mining industry it permits large-scale and economic processing of crushed ores whereby the desired mineral is separated from the gangue or non-mineral-containing material. Originally applied only to certain sulfide and oxide ores. 

The BET equation filled an annoying gap in the interpretation of adsorption isotherms, and at the time of its appearance in 1938 it was also hailed as a general method for obtaining surface areas from adsorption data. The equation can be put in the form... 

Thus many aspects of statistical mechanics involve techniques appropriate to systems with large N. In this respect, even the non-interacting systems are instructive and lead to non-trivial calculations. The degeneracy fiinction that is considered in this subsection is an essential ingredient of the fonnal and general methods of statistical mechanics. The degeneracy fiinction is often referred to as the density of states. 

Main J, Mandelshtam V A, Wunner G and Taylor H S 1998 Harmonic inversion as a general method for periodic orbit quantization Nonlinearity1015... 

Fischer T H and Almidf J 1992 General methods for geometry and wavefunctlon optimization J. Phys. Chem. 96 9768... 

To use direct dynamics for the study of non-adiabatic systems it is necessary to be able to efficiently and accurately calculate electronic wave functions for excited states. In recent years, density functional theory (DFT) has been gaining ground over traditional Hartree-Fock based SCF calculations for the treatment of the ground state of large molecules. Recent advances mean that so-called time-dependent DFT methods are now also being applied to excited states. Even so, at present, the best general methods for the treatment of the photochemistry of polyatomic organic molecules are MCSCF methods, of which the CASSCF method is particularly powerful. 

Boron forms a whole series of hydrides. The simplest of these is diborane, BjH. It may be prepared by the reduction of boron trichloride in ether by lithium aluminium hydride. This is a general method for the preparation of non-metallic hydrides. 

Originally, general methods of separation were based on small differences in the solubilities of their salts, for examples the nitrates, and a laborious series of fractional crystallisations had to be carried out to obtain the pure salts. In a few cases, individual lanthanides could be separated because they yielded oxidation states other than three. Thus the commonest lanthanide, cerium, exhibits oxidation states of h-3 and -t-4 hence oxidation of a mixture of lanthanide salts in alkaline solution with chlorine yields the soluble chlorates(I) of all the -1-3 lanthanides (which are not oxidised) but gives a precipitate of cerium(IV) hydroxide, Ce(OH)4, since this is too weak a base to form a chlorate(I). In some cases also, preferential reduction to the metal by sodium amalgam could be used to separate out individual lanthanides. 

Figure 7.2 from Alder B J and TE Wainwright 1959. Studies in Molecular Dynamics. 1. General Method. The Journal of Chemical Physics 31 459-466. 

Needleman S B and C D Wunsch 1970. A General Method Applicable to the Search for Similarities in the Amino Acid Sequences of Two Proteins. Journal of Molecular Biology 48 443-453. 

Filtration. Before discussing the practical details of the purification of solid substances by recrystallisation, it is convenient to describe here the general methods of filtration. The two principal occasions in organic chemistry when filtration is necessary are ... 

Note that this is only a particular case of Williamson s general method for the preparation of ethers. 

One of the general methods for the preparation of acid chlorides is the action of phosphorus pentachloride on the corresponding carboxylic acid ... 

In this way the student s knowledge of the organic reactions is consolidated as he proceeds through the sections, his experience of the general method of identification steadily increases, and the investigation of the unknown compounds forms a welcome break from the systematic pursuit of the sectional work. 

Since the silver salts of the carboxylic acids are usually soluble in dilute nitric acid, they must be prepared by treating an aqueous solution of a neutral salt of the acid (and not the free acid itself) with silver nitrate solution. It is not practicable to attempt to neutralise the acid with sodium or potassium hydroxide solution, because the least excess of alkali would subsequently cause the white silver salt to be contaminated with brown silver oxide. The general method used therefore to obtain a neutral solution j to dissolve the acid in a small excess of ammonia solution, and then to boil the solution until all free... 

The most general method i.s a form of parametric mapping in which the transformation functions, and in Equation (2.26), are polynomials... 

Most problems in chemistry [all, according to Dirac (1929)] could be solved if we had a general method of obtaining exact solutions of the Schroedinger equation... 

A general method for the synthesis of l -alkenes is provided by the action of a Grignard reagent upon allyl bromide, for example ... 

Three general methods are available for the preparation of iodides from alcohols —... 

Nitration products. Although no general method of nitration can be given, the following procedure is wddely applicable. 

An important general method of preparing indoles, known as the Fischer Indole synthesis, consists in heating the phenylhydrazone of an aldehyde, ketone or keto-acld in the presence of a catalyst such as zinc chloride, hydrochloric acid or glacial acetic acid. Thus acrtophenone phenylhydrazone (I) gives 2-phenyllndole (I V). The synthesis involves an intramolecular condensation with the elimination of ammonia. The following is a plausible mechanism of the reaction ... 

Sulphur. The general method is to heat the compound at 200-260° with the theoretical amount of sulphur required to bring it to the aromatic state ... 

The general method to be adopted for the analysis of mixtures of organic compounds is to separate them into their components and to... 

In 1824 Berzelius, generally credited with the discovery, prepared amorphous silicon by the same general method and purified the product by removing the fluosilicates by repeated washings. Deville in 1854 first prepared crystalline silicon, the second allotropic form of the element. 

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 ... 

A mixture of 0.30 mol of the acetylenic tosylate (prepared according to the general method described in VlII-3, Exp. 3 from the corresponding acetylenic alcohol, which was prepared from HC=CHgBr and CgHi3CH=0 in THF, as described in Ref. l)and 100 ml of dry acetone was added to a solution of 0.40 mol of anhydrous... 

The most general methods for the syntheses of 1,2-difunctional molecules are based on the oxidation of carbon-carbon multiple bonds (p. 117) and the opening of oxiranes by hetero atoms (p. 123fl.). There exist, however, also a few useful reactions in which an a - and a d -synthon or two r -synthons are combined. The classical polar reaction is the addition of cyanide anion to carbonyl groups, which leads to a-hydroxynitriles (cyanohydrins). It is used, for example, in Strecker s synthesis of amino acids and in the homologization of monosaccharides. The ff-hydroxy group of a nitrile can be easily substituted by various nucleophiles, the nitrile can be solvolyzed or reduced. Therefore a large variety of terminal difunctional molecules with one additional carbon atom can be made. Equally versatile are a-methylsulfinyl ketones (H.G. Hauthal, 1971 T. Durst, 1979 O. DeLucchi, 1991), which are available from acid chlorides or esters and the dimsyl anion. Carbanions of these compounds can also be used for the synthesis of 1,4-dicarbonyl compounds (p. 65f.). 

E. Vedejs (1978) developed a general method for the sterically controlled electrophilic or-hydroxylation of enolates. This uses a bulky molybdenum(VI) peroxide complex, MoO(02)2(HMPTA)(Py), which is rather stable and can be stored below 0 °C. If this peroxide is added to the enolate in THF solution (base e.g. LDA) at low temperatures, oneO—O bond is broken, and a molybdyl ester is formed. Excess peroxide is quenched with sodium sulfite after the reaction has occurred, and the molybdyl ester is cleaved to give the a-hydroxy car-... 

Primary and secondary amines are susceptible to oxidation and replacement reactions involving the N—H bonds. Within the development of peptide synthesis numerous protective groups for N—H bonds have been found (M, Bodanszky, 1976 L.A. Carpino, 1973), and we shall discuss five of the more general methods used involving the reversible formation of... 

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