Iodine with benzene

It is almost insol in water, but sol in ale, eth chlf. Iodobenzene is readily prepd by reaction of iodine with benzene in the presence of an oxidizing agent, or from benzenediazonium sulfate potassium iodide... 

CgH Cl, is produced commercially in the Hquid phase by passing chlorine gas into benzene in the presence of molybdenum chloride at 30—50°C and atmospheric pressure. This continuous process yields a 14 1 ratio of chlorobenzene to j -dicblorobenzene [106-46-7J, The reaction of iodine with... 

A mixture consisting of 0.69 g (10.5 mmoles) of zinc-copper couple, 12 ml of dry ether, and a small crystal of iodine, is stirred with a magnetic stirrer and 2.34 g (0.7 ml, 8.75 mmoles) of methylene iodide is added. The mixture is warmed with an infrared lamp to initiate the reaction which is allowed to proceed for 30 min in a water bath at 35°. A solution of 0.97 g (2.5 mmoles) of cholest-4-en-3/ -ol in 7 ml of dry ether is added over a period of 20 min, and the mixture is stirred for an additional hr at 40°. The reaction mixture is cooled with an ice bath and diluted with a saturated solution of magnesium chloride. The supernatant is decanted from the precipitate, and the precipitate is washed twice with ether. The combined ether extracts are washed with saturated sodium chloride solution and dried over anhydrous sodium sulfate. The solvent is removed under reduced pressure and the residue is chromatographed immediately on 50 g of alumina (activity III). Elution with benzene gives 0.62 g (62%) of crystalline 4/5,5/5-methylene-5 -cholestan-3/5-ol. Recrystallization from acetone gives material of mp 94-95° Hd -10°. 

Chlorination is cariied out in a manner similar- to bromination and provides a ready route to chlorobenzene and related ar-yl chlorides. Fluorination and iodination of benzene and other arenes are rarely perfor-med. Fluorine is so reactive that its reaction with benzene is difficult to control. Iodination is very slow and has an unfavorable equilibrium constant. Syntheses of aryl fluorides and aryl iodides are nor-mally cariied out by way of functional group transformations of arylffluines these reactions will be described in Chapter 22. 

Iodine acetate would seem to be unambiguously present in the iodination of pentamethylbenzene in acetic acid by iodine and mercuric acetate, since the latter components form an equilibrium mixture of iodine acetate and acetoxy-mercuric iodide and mercuric acetate speeds up the iodination332. Second-order rate coefficients of 0.078 (25 °C) and 0.299 (45 °C) were obtained, and these values are intermediate between those obtained for the reaction of bromine acetate with benzene (2.5 xlO-3) and toluene (1.2) at 25 °C, indicating that bromine acetate is the stronger electrophile. 

A fresh sample of this 40% peracetic acid contains about 1.54 equivalents, or 0.77 mole, of peroxide per 100 ml. of solution, corresponding to 1.34 equivalents per 100 g. The concentration can be determined by treating the peroxide solution with potassium iodide and titrating the liberated iodine with standard sodium thiosulfate. The concentration of peroxide in peracetic acid decreases somewhat on long standing and should be checked before the peracetic acid is used. The yield of diacetate is lowered if the concentration of the peroxide is less than 1.0 equivalent per 100 g. of peracetic acid. The total amount of peroxide used should be 2.4 moles, or 4.8 equivalents, for each mole of iodo-benzene. 

Cyanide and thiocyanate anions in aqueous solution can be determined as cyanogen bromide after reaction with bromine [686]. The thiocyanate anion can be quantitatively determined in the presence of cyanide by adding an excess of formaldehyde solution to the sample, which converts the cyanide ion to the unreactive cyanohydrin. The detection limits for the cyanide and thiocyanate anions were less than 0.01 ppm with an electron-capture detector. Iodine in acid solution reacts with acetone to form monoiodoacetone, which can be detected at high sensitivity with an electron-capture detector [687]. The reaction is specific for iodine, iodide being determined after oxidation with iodate. The nitrate anion can be determined in aqueous solution after conversion to nitrobenzene by reaction with benzene in the presence of sulfuric acid [688,689]. The detection limit for the nitrate anion was less than 0.1 ppm. The nitrite anion can be determined after oxidation to nitrate with potassium permanganate. Nitrite can be determined directly by alkylation with an alkaline solution of pentafluorobenzyl bromide [690]. The yield of derivative was about 80t.with a detection limit of 0.46 ng in 0.1 ml of aqueous sample. Pentafluorobenzyl p-toluenesulfonate has been used to derivatize carboxylate and phenolate anions and to simultaneously derivatize bromide, iodide, cyanide, thiocyanate, nitrite, nitrate and sulfide in a two-phase system using tetrapentylammonium cWoride as a phase transfer catalyst [691]. Detection limits wer Hi the ppm range. 

It is unlikely that the compound (27) is derived directly from the reaction of an excited benzene with tetrafluorobenzyne even though the compound (27) is formally analogous to the photo-adducts formed by the irradiation of olefins in benzene 74,75) A number of other products derived from the o-iodotetrafluorophenyl radical were also obtained 73>. These results suggest either that the tetrafluoro-o-phenylene di-radical (32) is identical with tetrafluorobenzyne or that if it is produced at a higher energy level it returns rapidly to the groundstate before it reacts with benzene. An alternative and perhaps more likely explanation is that the tetrafluorobenzyne formed arises by the concerted loss of both iodine atoms. 

Synthesis of Radical Cation Perchlorates and Subsequent Coupling with NucleophilesT Syntheses of the radical cation perchlorates of BP and 6-methylBP (12) were accomplished by the method reported earlier for the preparation of the perylene radical cation (13,14). More recently we have also synthesized the radical cation perchlorate of 6-fluoroBP (15). Oxidation of the PAH with iodine in benzene in the presence of AgClO. instantaneously produces a black precipitate containing the radical cation perchlorate adsorbed on Agl with... 

This effect was interpreted as complex formation of iodine with the aromatic substance. In n-heptane and carbon tetrachloride, Benesi and Hildebrand (1949) determined the constants for the formation of this complex in benzene and mesitylene. The formation of a 1 1 complex as assumed and the concentration of the complex formed was determined spectrophotometrically. The A-values determined by... 

Kinetic smdies of the iodination of benzene and acetanilide by iodine, diiodine pentoxide, and sulfuric acid in acetic acid indicate that benzene is involved in an equilibrium reaction prior to the rate-limiting <7-complex formation." It is proposed that this equilibrium involves the formation of a itt-complex between iodine adsorbed on diiodine pentoxide and the benzene as it is adsorbed. In the case of acetanilide the a-complex is formed directly with activated iodine adsorbed on the diiodine pentoxide. 

Let us now consider the formation of aryl iodides from aryl diazonium salts and potassium iodide in methanol (Singh and Kumar 1972a, 1972b). Electron-donor substituents decelerate the process as compared with benzene diazonium (the substituent is hydrogen), whereas electron acceptor substituents accelerate it. Oxygen inhibits the reaction, and photoirradiation speeds it up. As the authors pointed out, in the case of 4-nitrobenzene diazonium, the reaction leads not only to 4-iodonitrobenzene but also to nitrobenzene, elemental iodine, and formaldehyde. All of these facts support the following sequence of events ... 

Isomerically pure chlorofullerene C oClg has been reported to be the predominant product of the reaction of with an excess of iodine monochloride in benzene or toluene at room temperature (Scheme 9.11) [79], The product is very soluble in benzene, carbon disulfide and tetrachloromethane. Deep orange crystals can be obtained by recrystallization from pentane. The synthesis of CjoClg using toluene as a solvent proceeds more slowly than with benzene, indicating that radicals are involved and are scavenged by the toluene [79],... 

Although in part this order may be affected by subsequent reaction of the iodine with the organic solvent under the influence of catalytic material in the charcoal (Schmidt, Z it KoUoid. Ghem. XIV. 242, 1914) yet similar alterations have been noted by Freundlich (ibid. p. 260) with other solutes, e.g. benzoic and picric acids, who found the following order for decreasing adsorption for benzoic acid water, benzene, ethyl ether, acetone for picric acid, water, ethyl, alcohol, benzene. 

In the presence of anhydrous Lewis acid (e.g. FeCls or FeBrs), benzene reacts readily with halogens (bromine or chlorine) to produce halobenzenes (bromobenzene or chlorobenzene). Fluorine (Fy reacts so rapidly with benzene that it requires special conditions and apparatus to carry out fluorination. On the other hand, iodine (I2) is so unreactive that an oxidizing agent (e.g. HNO ) has to be used to carry out iodination. 

A bicyclo[5.2.0]nonen-l-ol derivative was transformed to a mixture of cis- and trans-4-iodocy-clononenone derivatives 7 on treatment with mercury(II) oxide and iodine in benzene.40... 

Similarly with the raising of the b.p. in violet or reddish-violet soln. of iodine in benzophenone, carbon disulphide, ethyl chloride, chloroform, carbon tetrachloride, ethylene chloride or benzene or in brown soln. of ethyl alcohol, methyl alcohol, thymol, ethyl ether, methylal, or acetone. The values for the last three solvents were rather low, presumably because of the chemical action of solute on solvent. High values with benzene are attributed to the formation of a solid soln. of solvent and solid. Confirmatory results were found by J. Hertz with naphthalene, and by E. Beckmann and P. Wantig with pyridine. The results by I. von Ostromisslensky (o-nitrotoluene), by G. Kriiss and E. Thiele (glacial acetic acid), and by H. Gautier and G. Charpy indicate polymerization, but they are not considered to be reliable. 

The induction period of the reaction may be curtailed 2 by (1) the presence of an excess of iodic acid, (2) an increase in the concentrations of the reactants, (3) the addition of a trace of arsenic acid, (4) the addition of a mineral acid and (5) exposure to sunlight. On the other hand, the period may be prolonged by the addition of mercuric chloride or by violent shaking. The proportion of the iodine liberated increases with the arsenious acid concentration and passes through a maximum. The iodine appears on the surface of the solution even though the latter may be covered with benzene (or occasionally it appears at a nucleus on the glass). The reduction of periodate to iodate by means of arsenite is a bimolecular reaction and is of the first order with respect to both components.3 At 25° C. it proceeds according to the velocity equation... 

Cyclohexene reacts with tetrafluoroethylene and sulfur to give 4,5 -tetramethylene- 2,2,3,3-tetrafluorothiolane (2,2,3,3-tetrafluoro-octahydrobenzo[6]thiophene) (32).249 Tetrafluoroethylene and sulfur also react with benzene to give mainly perfluorothiolane, together with some 2,2,3,3-tetrafluoro-2,3,3a,7a-tetrahydrobenzo[i>]thiophene (33) and the dihydro derivative (34)250 in the presence of iodine more complex products are obtained.251... 

Iodobenzene [591-50-4], C6HBI, mol wt 204.02, 62.23% I, mp —30°C, bp 188—189°C, is a colodess liquid that rapidly becomes yellow and has a characteristic odor. It is insoluble in water, but completely miscible with alcohol, chloroform, and ether. It has a density of 1.832 g/mL at 20°C and a refractive index of 1.621 at 4°C. Iodobenzene is prepared by the reaction of iodine and benzene in the presence of an oxidizing agent and from benzeneiazonium sulfate and potassium iodide (122). Iodobenzene is used as a heavy liquid for refractive index determinations, but probably its principal use is in the synthesis of iodoso compounds, RIO iodoxy compounds, RI02 and iodonium salts, R IX. 

---