Benzene with alcohols

Table 5.11. Alkylation of Benzene with Alcohols over Nafion-H Catalyst...

The solubilities of trinitro-m-xylene (m. p. 180.5°C) in mixtures of benzene with alcohol (after Kravchinskii [3]) are given below (Table 89). 

SOLUBILITY OF TRINTTRO-m-XYLENE n MIXTURES OF BENZENE WITH ALCOHOL... 

Paushkin and Topchiev also used H3P()4-BF3 at room temperature to alkylate benzene with olefins (287,402). For alkylation of benzene with alcohols, temperatures of 90-97° and a feed mole ratio of 0.5 alcohol 1.0 benzene 0.5 catalyst were recommended (394). In a recent study (400a) these authors supplemented their previously published views (396) concerning the properties of boron fluoride complexes with phosphoric acid, alcohols, and sulfuric acid as catalysts. Data on the electroconductivity of these catalysts was correlated with their activity in alkylation of isobutane and it was concluded (400a) that the acid ion concentration did not affect the alkylation or polymerization reactions over these catalysts, and therefore the carbonium ion mechanism was not applicable. 

Conversion of the corresponding isocyanates, resulting from the heating of the azides in benzene, with alcohols of general formula R OH, yielded the carbamic acid esters LXXVIb (150), and with amines R"R" NH, the urea derivatives LXXVIc and LXXVIIc (151, 152). 

Mixtures of Benzene with Alcohols.—Benzene is much more easily obtained in quantity than hexane, and behaves in a somewhat similar manner. The lower alcohols are miscible with benzene in all proportions but while methyl, ethyl, isopropyl, w-propyl, tertiary butyl and isobutyl alcohols form mixtures of maximum vapour pressure with that hydrocarbon, isoamyl alcohol does not, and it is practically certain that no alcohol of higher boiling point would form such a mixture. 

Alcohols. Toussaint and Hennion alkylated benzene with alcohols, using boron trifluoride as the acid catalyst and ph( phorus pentoxide, sulfuric acid, and benzenesulfonic acid as assistants. They explained the mechanism on the basis of a dehydration of the alcohol to an olefin ... 

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. 

Crude chlorophyll is prepared commercially from alfalfa meal or nettles by extraction with alcohol and partition into benzene. It is used as a colouring matter, particularly for foods and pharmaceutical products. 

Ethyl bromoacetate (1). Fit a large modified Dean and Stark apparatus provided with a stopcock at the lower end (a convenient size is shown in Fig. Ill, 126, 1) to the 1-htre flask containing the crude bromoacetic acid of the previous preparation and attach a double surface condenser to the upper end. Mix the acid with 155 ml. of absolute ethyl alcohol, 240 ml. of sodium-dried benzene and 1 ml. of concentrated sulphuric acid. Heat the flask on a water bath water, benzene and alcohol will collect in the special apparatus and separate into two layers, the lower layer consisting of approximately 50 per cent, alcohol. Run ofi the lower layer (ca. 75 ml.), which includes all the water formed in the... 

The following give abnormal results when treated with chlorosulphonio acid alone, preferably at 50° for 30-60 minutes —fluobenzene (4 4 -difluorodiplienyl-sulphone, m.p. 98°) j iodobenzene (4 4 -di-iododiphenylsulplione, m.p. 202°) o-diclilorobenzene (3 4 3. -4 -tetrachlorodiphenylsulphone, m.p. 176°) and o-dibromobenzene (3 4 3 4 -tetrabromodiphenylsulphone, m.p. 176-177°). The resulting sulphones may be crystallised from glacial acetic acid, benzene or alcohol, and are satisfactory for identification of the original aryl halide. In some cases sulphones accompany the sulphonyl chloride they are readily separated from the final sulphonamide by their insolubility in cold 6N sodium hydroxide solution the sulphonamides dissolve readily and are reprecipitated by 6iV hydrochloric acid. 

We saw m Section 9 10 that the combination of a Group I metal and liquid ammonia is a powerful reducing system capable of reducing alkynes to trans alkenes In the pres ence of an alcohol this same combination reduces arenes to nonconjugated dienes Thus treatment of benzene with sodium and methanol or ethanol m liquid ammonia converts It to 1 4 cyclohexadiene... 

Reactions with Sahcylaldehydes. Tetraalkyl titanates react in benzene with sahcylaldehyde in a 1 1 or 1 2 molar ratio to give sahcylaldehydotrialkoxy and dialkoxy products, which when heated at reflux seem to undergo a Meewein-Pomidorf reaction to give an aldehyde derived from the alcohol group on the titanate and a reduced titanate complex (37) ... 

The physical and thermodynamic properties of benzene are shown in Table 1 (2). Azeotrope data for benzene with selected compounds are shown in Table 2 (3). Benzene forms minimum-boiling azeotropes with many alcohols and hydrocarbons. Benzene also forms ternary azeotropes. 

Physical properties of some commercially available polyamines appear in Table 1. Generally, they are slightly to moderately viscous, water-soluble Hquids with mild to strong ammoniacal odors. Although completely soluble in water initially, hydrates may form with time, particularly with the heavy ethyleneamines (TETA, TEPA, PEHA, and higher polyamines), to the point that gels may form or the total solution may soHdify under ambient conditions. The amines are also completely miscible with alcohols, acetone, benzene, toluene and ethyl ether, but only slightly soluble in heptane. 

Medium Boiling Esters. Esterificatioa of ethyl and propyl alcohols, ethylene glycol, and glycerol with various acids, eg, chloro- or bromoacetic, or pymvic, by the use of a third component such as bensene, toluene, hexane, cyclohexane, or carbon tetrachloride to remove the water produced is quite common. Bensene has been used as a co-solvent ia the preparatioa of methyl pymvate from pymvic acid (101). The preparatioa of ethyl lactate is described as an example of the general procedure (102). A mixture of 1 mol 80% lactic acid and 2.3 mol 95% ethyl alcohol is added to a volume of benzene equal to half that of the alcohol (ca 43 mL), and the resulting mixture is refluxed for several hours. When distilled, the overhead condensate separates iato layers. The lower layer is extracted to recover the benzene and alcohol, and the water is discarded. The upper layer is returned to the column for reflux. After all the water is removed from the reaction mixture, the excess of alcohol and benzene is removed by distillation, and the ester is fractionated to isolate the pure ester. 

The heptamethylene glycol was separated by continuous ether extraction from the alkaline reduction solution after the latter had been diluted and distilled to remove the alcohol. The nonamethylene glycol was separated from the alkaline liquor by decantation (as above) and distilled. All the others were crystallized from benzene (without alcohol). Equally successful results have also been obtained with larger runs (e.g., 0.5 mole of ester),... 

Diphenylmethane has been prepared with aluminum chloride as a catalyst from methylene chloride and benzene, from chloroform and benzene as a by-product in the preparation of triphenylmethane, and from benzyl chloride and benzene. It has been prepared by the reduction of benzophenone with hydriodic acid and phosphorus, or with sodium and alcohol. It has also been made by heating a solution of benzyl chloride in benzene with zinc dust, or with zinc chloride. The above method is only a slight modification of the original method of Hirst and Cohen. ... 

Water with aniline, benzene, benzyl alcohol, carbon disulfide, carbon tetrachloride, chloroform, cyclohexane, cyclohexanol, cyclohexanone, diethyl ether, ethyl acetate, isoamyl alcohol, methyl ethyl ketone, nitromethane, tributyl phosphate or toluene. 

Benzene with acetone, butyl alcohol, carbon tetrachloride, chloroform, cyclohexane, ethanol, acetonitrile, petroleum ether or pyridine. 

Suitable organic solvents, such as ether, benzene, naphtha and the like, are more soluble than in water. This makes it possible to separate them from other substances which may accompany them in the water solution but which are not soluble in the solvents employed. Hence, one application of solvent extraction is the analytical determination of unsaponifiable oils and waxes in admixture with fatty material by submitting the mixture to vigorous saponification with alcoholic potash or, if necessary, sodium ethylate, and to dilute the product with water and extract with petroleum ether. The soaps remain in the aqueous solution while the unsaponifiable oils and waxes dissolved in the ether. The addition of a salt to an aqueous solution prior to extraction is sometimes practiced in some processes. In older processes, SOj is employed in the separation of aromatic and highly saturated hydrocarbons, taking advantage of the much greater solubility of the solubility of the aromatics and... 

Betulol is a sesquiterpene alcohol of the formula CjjH O, found in oil of birch buds. It can be isolated as a hydrogen phthalate, by warming a solution of betulol in benzene, with phthalic anhydride. It has, according to Soden and Elze, the following characters —... 

Alkylation of benzene using alpha olefins produces linear alkylbenzenes, which are further sulfonated and neutralized to linear alkylbenzene sulfonates (LABS). These compounds constitute, with alcohol ethoxy-sulfates and ethoxylates, the basic active ingredients for household detergents. Production of LABS is discussed in Chapter 10. 

The number of isomeric homologues of benzene with formula Cg n 6-f2n asymptotically proportional to the number of isomeric alcohols with proportionality factor [r(p ) + (p)r(p ) J/2. 

Ethyl benzoylacetate has been prepared by the condensation (by means of sodium ethylate) of ethyl acetate with ethyl benzoate,1 acetophenone with ethyl carbonate,2 and acetophenone with ethyl oxalate, with subsequent heating 3 by treatment of ethyl phenylpropiolate4 or a-bromocinnamic acid 5 with concentrated sulfuric acid, and of ethyl diazoacetate with benzalde-hyde 6 by the condensation of benzene with the monoethyl ester of malonyl monoacid chloride and aluminum chloride,7 of benzoyl chloride with the product of the reaction of magnesium and ethyl chloroacetate in ether,8 of alcohol on benzoylacetimino ethyl... 

Mordenite Alkylation of benzene with benzyl alcohol Higher activity [78]... 

The availability of Nafion on silica has not only lowered the cost of the resin but also has made it versatile (Sun et al., 1997 Harmer et al., 1998). A number of industrially important reactions have been attempted, with considerable success, with these catalysts. Consider the Fries rearrangement of phenyl acetate to p-acetyl phenol (/t-hydroxy acetophenone). This has been accomplished by Hoelderich and co-workers (Heidekum, 1998). In the ca.se of alkylation of benzene with benzyl alcohol, Amberlyst-15 and p-toluene sulphonic acid are ineffective and Nafion on silica works well at 80 °C. 

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