Basicity of benzene

The reduction of basicity of benzene by halogen substitution similarly applies to the case of toluene, as deduced by Tamres (1952) from I.R. measurements and by Ogimachi et al. (1955) from complex formation with ICl. The basicity decreases even more for multiple halogen substitution (Tamres, 1952). 

In order to study the effect of methyl groups on the basicity of benzene more exactly, Ehrenson (1961, 1962) carried out calculations for the... 

Another kinetic method of determining relative adsorption constants does show that toluene is adsorbed more strongly than benzene on the platinum metals. The method determines the effect of the partial pressure of toluene on the rate of hydrogenation of benzene. With the assumption that adsorption is reversible, the ratio of adsorption coefficients, br/bB, is evaluated by the use of equation (37) where U°B and Ub(T) represent the rate of hydrogenation of benzene in the absence of toluene and in its presence at stated partial pressures of toluene (Ft) and benzene (Pb). This method avoids the determination of the relative individual rate constants that is required by the method of Wauquier and Jungers. Xylene inhibits the hydrogenation of alkenes on Pd more effectively than does benzene, which is consistent with the effect of alkyl groups on the basicity of benzene. ... 

The low basicity of benzene prevents to obtain AljBr, under usual conditions (cf. 

Returning to the problem at hand, both 2 and 3 react quickly and easily with HBr, so the ti-bonds in each molecule are considered to be good Br0nsted-Lowry bases in their reactions with mineral acids. Benzene does not react with HBr, even with heating. Benzene has six 7i-electrons 2 has only two, so benzene is more electron rich relative to 2. The fact that benzene does not react suggests that it is too weak a base, which is a good indication that the six p-electrons are held tightly by the molecule and are not available for donation. The poor basicity of benzene in a reaction with HBr is presented as evidence of the special stability of benzene, and the explanation for that stability is the resonance delocalization shown for 1C. 

Some of the common aromatics found in crude oil are the simple derivatives of benzene in which one or more alkyl groups (CHg) are attached to the basic benzene molecule as a side chain which takes the place of a hydrogen atom. These arenes are either liquids or solids under standard conditions. 

An OH group affects the UV VIS spectrum of benzene m a way similar to that of an NH2 group but to a smaller extent In basic solution m which OH is converted to 0 however the shift to longer wavelengths exceeds that of an NH2 group... 

Pyrrole has a planar, pentagonal (C2 ) stmcture and is aromatic in that it has a sextet of electrons. It is isoelectronic with the cyclopentadienyl anion. The TT-electrons are delocalized throughout the ring system, thus pyrrole is best characterized as a resonance hybrid, with contributing stmctures (1 5). These stmctures explain its lack of basicity (which is less than that of pyridine), its unexpectedly high acidity, and its pronounced aromatic character. The resonance energy which has been estimated at about 100 kj/mol (23.9 kcal/mol) is intermediate between that of furan and thiophene, or about two-thirds that of benzene (5). 

AH commercial processes for the manufacture of caprolactam ate based on either toluene or benzene, each of which occurs in refinery BTX-extract streams (see BTX processing). Alkylation of benzene with propylene yields cumene (qv), which is a source of phenol and acetone ca 10% of U.S. phenol is converted to caprolactam. Purified benzene can be hydrogenated over platinum catalyst to cyclohexane nearly aH of the latter is used in the manufacture of nylon-6 and nylon-6,6 chemical intermediates. A block diagram of the five main process routes to caprolactam from basic taw materials, eg, hydrogen (which is usuaHy prepared from natural gas) and sulfur, is given in Eigute 2. 

These authors have prepared quite a variety of crown-related esters and have incorporated numerous heterocyclic subunits in the macrorings. The structural variety can be gleaned from a perusal of the tables at the end of this chapter. Despite this variety, one basic approach has been utilized in most of the syntheses thus far presented. This method involves simultaneous addition of separate benzene solutions of the diacyl halide and diol to an additional several volumes of benzene heated at 45—60°. After the ad-... 

A total of 3 g (0.13 moles) of sodium hydride is added to a solution consisting of 10 g of 17 -hydroxy-5a-androstan-3-one (36 mmoles) in 200 ml of benzene and 10 ml of ethyl formate. The reaction mixture is allowed to stand under nitrogen for 3 days followed by dropwise addition of 10 ml of methanol to decompose the excess of sodium hydride. The solution is then diluted with 300 ml water and the layers are separated. The basic aqueous solution is extracted with ether to remove neutral material. The aqueous layer is acidified with 80 ml of 3 A hydrochloric acid and the hydroxymethylene steroid is extracted with benzene and ether. The combined organic extracts are washed with water and saturated sodium chloride solution and then dried over magnesium sulfate and concentrated. The residue, a reddish-yellow oil, crystallized from 10 ml of ether to yield 9.12 g (83%) of 17 -hydroxy-2-hydroxymethylene-5a-androstan-3-one mp 162-162.5°. Recrystallization from chloroform-ether gives an analytical sample mp 165-165.5° [a]o 53° (ethanol) 2 ° 252 mjj. (g 11,500), 307 m u (e 5,800). 

W-OCH3 group should lower the basicity of naphthoic acids (both a and j8) and the nucleophilic reactivity of aza-benzene derivatives. In terms of a, the substituent effect for alkoxy groups wiU be negative at all positions. The w-SCHg group behaves similarly. 

Reaction of 2-(A -allylamino)-3-formyl-4//-pyrido[l, 2-u]pyrimidin-4-ones 219 in EtOH with HONH2 HCI yielded ( )-oximes 220 at 0°C and 221 (R = PhCH2) under reflux. Heating 220 (R = H) in a boiling solvent afforded cw-fused tetracyclic cycloadducts 221 (R = H). In an aprotic solvent (e.g., benzene or MeCN) the main a>fused cycloadducts 221 (R = H) were accompanied by a mixture of trauA-fused cycloadducts 222, A -oxides 223 and tetracyclic isoxazoline 224 (96T887). The basicity of the 2-allylamino moiety of compounds 219 affected the rate of the conversion. Cycloadditions were also investigated in dioxane and BuOH. 

The reaction mixture was poured into 25 ml of water and the mixture made strongly basic with ION sodium hydroxide solution. The mixture was extracted 3 times with 50 ml portions of benzene, the combined extracts washed with water and concentrated to a volume of approximately 50 ml. The solution was saturated with dry hydrogen chloride and the white crystalline product collected and dried. The yield of product, MP 251.6° to 252.6°C (dec.) was 2.5 g. Recrystallization from a mixture of absolute alcohol and absolute ether gave a product, MP 252.6° to 253.6°C. A sample was analyzed after drying for 7 hours at 110°C over phosphorus pentoxide in vacuo. 

The benzene layer is removed by decantation and the remaining mixture is rendered basic with 10% sodium hydroxide solution and is extracted with three 1,500 ml portions of benzene. The benzene extracts are washed, then dried with anhydrous sodium sulfate and concentrated in a vacuum leaving a residue of 1,530 grams, gas and thin layer chromatography analysis show this to be a cis/trans mixture (approx. 4 1) of 11-dimethylamino-propylidene-6,11-dihydrodibenz-(b,e)oxepin (90% yield). This mixture has substantially more activity pharmacologically than the cis/trans mixture obtained by the Grignard route disclosed in the Belgian Patent 641,498. This base is then converted to the hydrochloride with HCI. 

That benzene hexachloride isomer mixture is then the raw material for lindane production. The production of lindane per se is not a chemical synthesis operation but a physical separation process. It is possible to influence the gamma isomer content of benzene hexachloride to an extent during the synthesis process. Basically, however, one is faced with the problem of separating a 99%-plus purity gamma isomer from a crude product containing perhaps 12 to 15% of the gamma isomer. The separation and concentration process is done by a carefully controlled solvent extraction and crystallization process. One such process is described by R.D. Donaldson et al. Another description of hexachlorocyclohexane isomer separation is given by R.H. Kimball. 

A mixture of 1B g of 1 -acetamido-3,5-dimethvladamantane, 3B g of sodium hydroxide, and 300 ml of diethylene glycol was refluxed for a period of 6 hours. The reaction product mixture was cooled and poured onto about IfiQQ ml of crushed Ice. The basic solution thus obtained was extracted five times with 250-ml portions of benzene and the aqueous layer was discarded. The combined benzene extracts were dried over sodium hydroxide and the dried benzene solution concentrated in vacuo to give a crude oil weighing 14 g and having np =... 

The methanol in the reaction mixture (pale yellow solution) is then removed by evaporation under reduced pressure to leave a residue which is subsequently dissolved in 30 ml of benzene. The benzene solution is shaken four times with 20 ml of 4 N hydrochloric acid each time to extract the basic substance. Each of the hydrochloric acid layers is washed once with 20 ml of benzene and combined together to be neutralized with potassium carbonate while being ice-cooled until it becomes basic (pH = 10). 

Wilkes and co-workers have investigated the chlorination of benzene in both acidic and basic chloroaluminate(III) ionic liquids [66]. In the acidic ionic liquid [EMIM]C1/A1C13 (X(A1C13) > 0.5), the chlorination reaction initially gave chlorobenzene, which in turn reacted with a second molecule of chlorine to give dichlorobenzenes. In the basic ionic liquid, the reaction was more complex. In addition to the... 

Scheme 5.1-38 The chlorination of benzene in acidic and basic chloroaluminate ionic liquids.

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. 

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