Benzene isolation

In contrast to benzene, isolation of dihydrodiol metabolites has been achieved for a number of phenyl-containing drugs, and, particularly, for neu-... 

At 350 - 400°C, thermal degradation rate is considerably increased, and the reaction proceeds with benzene isolation. In 380 - 440°C temperature range, degradation products display cyclosiloxane components of Dn composition, D4<1.5%. Note also that pyrolysis temperature increase induces sharp increase of CFfi, D3 and D4 compounds extracted. Liberation of benzene and methane is due to =Si-C and C-H bond break, which induces cross-linking at the expense of methyl and phenyl groups [47],... 

Addition has also been shown to occur when the pyridinlum iodide (139) is irradiated. The product Is assigned the structure (140) and the relevance of this reaction to the photoreactivity of Kosower solvent polarity probes has been discussed. The use of osmium tetroxide to hydroxylate alkenes is a well known procedure which is often carried out in aromatic solvents. These arene solvents form charge transfer complexes with the osmium tetroxide and the photochemistry of these has now been examined. It is shown that with benzene and alkyl benzenes isolable adducts are formed that from benzene Is assigned structure (141). 

For an account of the discovery of benzene and of the many names applied to it, see Badger, G. M. Aromatic Character and Aromaticity Cambridge University Press Cambridge, 1969 p. 1 ff. Visitors to London may visit the Faraday Museum in the Royal Institution, which has displayed what was reported to be the very sample of benzene isolated by Faraday in 1825. Also see Berson, J. A. Chemical Discovery and the Logicians Program A Problematic Pairing, Wiley-Interscience Wemheim, 2003. 

Insoluble in benzene isolated by JICl etching of collageneous material. 

Soon after thiophene was discovered by Victor Meyer, reports from his group gave the first examples of halogenated thiophenes - dibromothiophene (now known to be 2,5-dibromothiophene) and monoiodothiophene [77]. Monoiodothiophene (now known to be 2-iodothiophene) was synthesised from a mixture with benzene isolated from coal tar containing 50-60% of thiophene ( raw thiophene ). Here the higher reactivity of thiophene in comparison to benzene in halogenations was observed and used. Thus for benzene, iodination requires elevated temperatures, but thiophene was iodinated at room temperature. It was found that 2-iodothiophene can be synthesised either by the treatment with a mixture of iodine and iodic acid or... 

C2H4N2O3, NH2CONHCOOH. Unknown in the free state as it breaks down immediately to urea and COi- The NH4, Ba, Ca, K and Na salts are known and are prepared by treating ethyl allophanate with the appropriate hydroxide. The esters with alcohols and phenols are crystalline solids, sparingly soluble in water and alcohol. They are formed by passing cyanic acid into alcohols or a solution of an alcohol or phenol in benzene. The amide of allophanic acid is biuret. Alcohols are sometimes isolated and identified by means of their allophanates. 

Benzene was first isolated by Faraday in 1825 from the liquid condensed by compressing oil gas. It is the lightest fraction obtained from the distillation of the coal-tar hydrocarbons, but most benzene is now manufactured from suitable petroleum fractions by dehydrogenation (54%) and dealkylation processes. Its principal industrial use is as a starting point for other chemicals, particularly ethylbenzene, cumene, cyclohexane, styrene (45%), phenol (20%), and Nylon (17%) precursors. U.S. production 1979 2-6 B gals. 

Picrates. The picrates of benzene and toluene are isolated only with extreme difficulty and are not used for purposes of identification. 

Alternatively, the following procedure for isolating the glycol may be used. Dilute the partly cooled mixture with 250 ml. of water, transfer to a distilling flask, and distil from an oil bath until the temperature reaches 95°. Transfer the hot residue to an apparatus for continuous extraction with ether (e.g.. Fig. II, 44, 2). The extraction is a slow process (36-48 hours) as the glycol is not very soluble in ether. (Benzene may also be employed as the extraction solvent.) Distil off the ether and, after removal of the water and alcohol, distil the glycol under reduced pressure from a Claisen flask. 

Hexamethylene glycol, HO(CH2)gOH. Use 60 g. of sodium, 81 g. of diethyl adipate (Sections 111,99 and III,100) and 600 ml. of super-d ethyl alcohol. All other experimental detaUs, including amounts of water, hydrochloric acid and potassium carbonate, are identical with those for Telramelhylene Glycol. The yield of hexamethylene glycol, b.p. 146-149°/ 7 mm., is 30 g. The glycol may also be isolated by continuous extraction with ether or benzene. 

Prepare a Grignard reagent from 24 -5 g. of magnesium turnings, 179 g. (157 ml.) of n-heptyl bromide (Section 111,37), and 300 ml. of di-n-butyl ether (1). Cool the solution to 0° and, with vigorous stirring, add an excess of ethylene oxide. Maintain the temperature at 0° for 1 hour after the ethylene oxide has been introduced, then allow the temperature to rise to 40° and maintain the mixture at this temperature for 1 hour. Finally heat the mixture on a water bath for 2 hours. Decompose the addition product and isolate the alcohol according to the procedure for n-hexyl alcohol (Section 111,18) the addition of benzene is unnecessary. Collect the n-nonyl alcohol at 95-100°/12 mm. The yield is 95 g. 

Ethyl maleate of almost equal purity may be obtained by refluxing a mixture of 20 g. of pure maleic a.oid, 37 g. (47 ml.) of absolute ethyl alcohol, 05 ml. of sodium-dried benzene and 4 ml. of concentrated sulphuric acid for 12 hours. The ester is isolated as described for Diethyl Adipate (Section 111,100). The yield of diethyl maleate, b.p. 219-220°, is 26 g. 

Method 2. Into a 500 ml. round-bottomed flask place 120 ml. of dry A.R. benzene, and 35 g. (29 ml.) of redistilled benzoyl chloride. Weigh out 30 g. of finely-powdered, anhydrous aluminium chloride into a dry corked test-tube, and add the solid, with frequent shaking, during 10 minutes to the contents of the flask. Fit a reflux condenser to the flask, and heat on a water bath for 3 hours or until hydrogen chloride is no longer evolved. Pour the contents of the flask wliile still warm into a mixture of 200 g. of crushed ice and 100 ml. of concentrated hydrochloric acid. Separate the upper benzene layer (filter first, if necessary), wash it with 50 ml. of 5 per cent, sodium hydroxide solution, then with water, and dry with anhydrous magnesium sulphate. Isolate the benzophenone as in Method 1. The yield is 30 g. 

In an alternative method of preparation, benzophenone is used. Prepare the Grignard reagent from 13 -5 g. of magnesium turnings as above, cool in cold water, and add a solution of 91 g. of benzophenone (Section IV,139) in 200 ml. of dry benzene at such a rate that the mixture refluxes gently. Reflux the mixture for 60 minutes, and isolate the triphenylcarbinol in the manner described above. The yield is of the same order. 

The catalyst is inactive for the hydrogenation of the (isolated) benzene nucleus and so may bo used for the hydrogenation of aromatic compounds containing aldehyde, keto, carbalkoxy or amide groups to the corresponding alcohols, amines, etc., e.g., ethyl benzoate to benzyl alcohol methyl p-toluate to p-methylbenzyl alcohol ethyl cinnamate to 3 phenyl 1-propanol. 

C bol the solution of re-butyl-hthium to — 35° in a Dry Ice - acetone bath and add, whilst stirring vigorously, a solution of 48 g. of ni-chlorobromo-benzene (Section IV,62) in 75 ml. of anhydrous ether. Stir for 8-10 minutes and pour the mixture with stirring on to a large excess of sohd carbon dioxide in the form of a Dry Ice - ether slush contained in a -htre beaker. Isolate the acid as detailed above for p-Toluic acid and recrystal-lise it from hot water. The yield of ni-chlorobenzoic acid, m.p. 150-151°, is 27 g. 

The electronic theory provides by these means a description of the influence of substituents upon the distribution of electrons in the ground state of an aromatic molecule as it changes the situation in benzene. It then assumes that an electrophile will react preferentially at positions which are relatively enriched with electrons, providing in this way an isolated molecule theory of reactivity. 

A 20% excess of ethylmagnesium bromide was prepared from magnesium (6.5 g) in ether (80 ml) by adding ethyl bromide (30 g) in ether (30 ml). Indole (25.8 g) in benzene (50 ml) was then added slowly with stirring and stirring was continued for 20 min after addition was complete. A solution of allyl bromide (29.2 g) in benzene (20 ml) was then added slowly. The mixture was stirred overnight and then diluted with ether and the product isolated and purified by distillation (22.7 g, 70% yield). 

The reactions are carried out by warming the ester in an inert solvent such as chloroform or benzene with PjSj on the steam bath for 8 to 10 hr (Scheme 106). Products are isolated by ether extraction of the aqueous alkali-treated reaction mixture. 

DiaminO 4,4-dimethyl-l,3,5-thiadiazine hydrobromide was isolated as by-product (418). Benzene sulfonates of cyanohydrin prepared from sodium cyanide and an halobenzoaldehyde, when treated with thiourea or its derivatives, afford 2,4-diamino-5-(p-halogenophenyl)-thiazole benzene sulfonates (447). Similarly, cyanoamido thiocarbamates obtained from cyanamide and isothiocyanates yield substituted 2,4-diaminothiazoles (598). 

The same thought occurred to early chemists However the complete absence of natu rally occurring compounds based on cyclobutadiene and cyclooctatetraene contrasted starkly with the abundance of compounds containing a benzene unit Attempts to syn thesize cyclobutadiene and cyclooctatetraene met with failure and reinforced the grow mg conviction that these compounds would prove to be quite unlike benzene if m fact they could be isolated at all... 

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