Laboratory syntheses

Dehydrogenation of alkanes is not a practical laboratory synthesis for the vast majority of alkenes The principal methods by which alkenes are prepared m the labo ratory are two other (3 eliminations the dehydration of alcohols and the dehydrohalo genation of alkyl halides A discussion of these two methods makes up the remainder of this chapter... 

Although a variety of oxidizing agents are available for this transformation it occurs so readily that thiols are slowly converted to disulfides by the oxygen m the air Dithiols give cyclic disulfides by intramolecular sulfur-sulfur bond formation An example of a cyclic disulfide is the coenzyme a lipoic acid The last step m the laboratory synthesis of a lipoic acid IS an iron(III) catalyzed oxidation of the dithiol shown... 

Lactones whose rings are three or four membered (a lactones and p lactones) are very reactive making their isolation difficult Special methods are normally required for the laboratory synthesis of small ring lactones as well as those that contain rings larger than SIX membered... 

The customary method for the laboratory synthesis of acid anhydrides is the reac tion of acyl chlorides with carboxylic acids (Table 20 1)... 

Isoprene has sometimes been used as a starting matenal in the laboratory synthesis of ter penes In one such synthesis the first step is the electrophilic addition of 2 moles of hydrogen bromide to isoprene to give 1 3 dibromo 3 methylbutane... 

The most widely used method for the laboratory synthesis of a ammo acids is a modification of the malonic ester synthesis (Section 21 7) The key reagent is diethyl acetamidomalonate a derivative of malonic ester that already has the critical nitrogen substituent m place at the a carbon atom The side chain is introduced by alkylating diethyl acetamidomalonate m the same way as diethyl malonate itself is alkylated... 

Synthesis. In contrast to pituitary hormones, which usually can be obtained in pure form only after extraction from animal tissues, brain oligopeptides are readily available because of their small size. The synthetic repHca represents the most economical and readily accessible source for the oligopeptides. Two techniques are available for laboratory synthesis of oligopeptides, ie, solution chemistry and soHd-phase peptide synthesis (SPPS). 

Synthesis. The classic laboratory synthesis of /V-nitrosamines is the reaction of a secondary amine with acidic nitrite [14797-65-0] at ca pH 3. The primary nitrosating intermediate is N2O2 arising from nitrous acid [7782-77-6] (48). 

Other examples of oxidation of amyl alcohols using hydrogen peroxide (54), Ru02/NaCl0 (55), BaMnO (56), and chromic acid (57,58) have been described for laboratory synthesis, but have not been utili2ed commercially. 

From Boron Halides. Using boron haUdes is not economically desirable because boron haUdes are made from boric acid. However, this method does provide a convenient laboratory synthesis of boric acid esters. The esterification of boron haUdes with alcohol is analogous to the classical conversion of carboxyUc acid haUdes to carboxyUc esters. Simple mixing of the reactants at room temperature or below ia a solvent such as methylene chloride, chloroform, pentane, etc, yields hydrogen haUde and the borate ia high yield. 

Cobalt is one of twenty-seven known elements essential to humans (28) (see Mineral NUTRIENTS). It is an integral part of the cyanocobalamin [68-19-9] molecule, ie, vitamin B 2> only documented biochemically active cobalt component in humans (29,30) (see Vitamins, VITAMIN Vitamin B 2 is not synthesized by animals or higher plants, rather the primary source is bacterial flora in the digestive system of sheep and cattle (8). Except for humans, nonmminants do not appear to requite cobalt. Humans have between 2 and 5 mg of vitamin B22, and deficiency results in the development of pernicious anemia. The wasting disease in sheep and cattle is known as bush sickness in New Zealand, salt sickness in Florida, pine sickness in Scotland, and coast disease in AustraUa. These are essentially the same symptomatically, and are caused by cobalt deficiency. Symptoms include initial lack of appetite followed by scaliness of skin, lack of coordination, loss of flesh, pale mucous membranes, and retarded growth. The total laboratory synthesis of vitamin B 2 was completed in 65—70 steps over a period of eleven years (31). The complex stmcture was reported by Dorothy Crowfoot-Hodgkin in 1961 (32) for which she was awarded a Nobel prize in 1964. 

A convenient laboratory synthesis of high purity CA is hydrolysis of cyanuric chloride (7). On a commercial scale, CA is produced by pyrolysis of urea [57-13-6]. When urea is heated at - 250 ° C for about an hour, it is converted to crude CA with evolution of ammonia. 

The best laboratory synthesis of thymine (947) is probably from 3-methylmalic acid (945) which gives 2-formylpropionic acid (946 R = H) in situ by decarboxylation and oxidation in fuming sulfuric acid prior to condensation with urea (46JA912) a similar method from ethyl 2-formylpropionate (946 R = Et) is also described (68IZV918). 

There are three general methods of interest for the preparation of vinyl chloride, one for laboratory synthesis and the other two for commercial production. Vinyl chloride (a gas boiling at -14°C) is most conveniently prepared in the laboratory by the addition of ethylene dichloride (1,2-dichloroethane) in drops on to a warm 10% solution of sodium hydroxide or potassium hydroxide in a 1 1 ethyl alcohol-water mixture Figure 12.1). At one time this method was of commercial interest. It does, however, suffer from the disadvantage that half the chlorine of the ethylene dichloride is consumed in the manufacture of common salt. 

The reader is referred to the simple undergraduate laboratory synthesis of 2,5-dimethyl-1-phenylpyrrole in the Journal of Chemical Education. ... 

Like peganine a laboratory synthesis of rutaecarpine (51a) under physiological conditions has been realized by condensation of o-aminobenzaldehyde with a -carboline (Scheme 16). 

There are many reasons for carrying out the laboratory synthesis of an organic compound. In the pharmaceutical industry, new organic molecules are designed and synthesized in the hope that some might be useful new drugs. In the chemical industry, syntheses are done to devise more economical routes to known compounds. In academic laboratories, the synthesis of complex molecules is... 

Why put such extraordinary effort into the laboratory synthesis of a molecule so easily obtained from natural sources There are many reasons. On a basic human level, a chemist might be motivated primarily by the challenge, much as a climber might be challenged by the ascent of a difficult peak. Beyond the pure challenge, the completion of a difficult synthesis is also valuable for the way in which it establishes new standards and raises the field to a new level. If vitamin Bj2 can t>e made, then why can t any molecule found in nature be made Indeed, the three and a half decades that have... 

Ethers with a tertiary, benzylic, or allylic group cleave by an S l or FI mechanism because these substrates can produce stable intermediate carbocations. These reactions are often fast and take place at moderate temperatures. fcrf-Butyl ethers, for example, react by an El mechanism on treatment with trifluoroacetic acid at 0 °C. We ll see in Section 26.7 that the reaction is often used in the laboratory synthesis of peptides. 

We ll see in Section 26.7 that this DCC-induced method of amide formation is the key step in the laboratory synthesis of small proteins, or peptides. For instance, when one amino acid with its NH2 rendered unreactive and a second... 

The key step in a reported laboratory synthesis of sativene, a hydrocarbon isolated from the mold Helminthosporiuni sativum, involves the following base treatment of a keto tosylate. What kind of reaction is occurring How would you complete the synthesis ... 

Gilbert Stork (1921-1 was born on Mew Year s eve in Brussels, Belgium. He received his secondary education in France, his undergraduate degree atthe University of Florida, and his Ph.D. with Samuel McElvain atthe University of Wisconsin in 1945. Following s period on the faculty at Harvard University, he has been professor of chemistry at Columbia University since 1953. A world leader in the development of organic synthesis. Stork has devised many useful new synthetic procedures and has accomplished the laboratory synthesis of many complex molecules. 

With numerous —OH groups of similar reactivity, polysaccharides are so. structurally complex that their laboratory synthesis has been a particularly difficult problem. Several methods have recently been devised, however, that have... 

The synthesis of an a-amino acid from an achiral precursor by any of the methods described in the previous section yields a racemic mixture, with equal amounts of S and R enantiomers. To use an amino acid in the laboratory synthesis of a naturally occurring protein, however, the pure S enantiomer must be obtained. 

Show the steps involved in a laboratory synthesis of the DNA fragment with the sequence CTAG. 

The wide variety of natural minerals with [2 x 2] tunnels already indicates that a huge number of different compounds of the a-Mn02 type can be obtained by a laboratory synthesis. Most chemical syn-... 

The partially aromatic PAs are exclusively made of die diamine-diacid type and not die amine-acid type. The aromatic diamines, similar to phenylene diamines, color easily and dieir polymers are conjugated, having a golden brown color. The aromatic diacids used in the formation of partially aromatic PAs are mainly terephthalic and isophthalic acids. Starting with the diacids, the PA salt is made first and with this the salt prepolymers are prepared. The prepolymerization is usually carried out in an autoclave to prevent die sublimation of the reactants. In a laboratory synthesis it would be preferable to avoid this autoclave step as one is not always available. It is possible to start with the more reactive esters, such as diphenyl isophtiialate, or with the acid chlorides starting with the reactive isocyanates is, in principle, also possible. The terephthalic and isophthalic acids are also used to modify PA-6,6 and PA-4,6 to more dimensionally stable copolymers.6,18... 

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