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1. Photohalogenation. Scope of the Reaction

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1. Photohalogenation. Scope of the Reaction Chapter 37 Photohalogenation 1. Photohalogenation. Scope of the reaction The effect of light on the reactions of chlorine and bromine with or­ ganic compounds is a phenomenon ranking as one of the oldest and most frequently investigated in organic photochemistry. It is noteworthy that one of these well-known reactions, the photochlorination of benzene, has achieved great industrial importance since it was found that one of the stereoisomers from the group of hexachlorocyclohexanes formed is an excellent insecticide (Gammexane). The photochemical action of chlorine takes place in principle in the same manner as for bromine, and the following discussion of the mechanism of photochlorination is also valid for that of photobromination. A more com­ plete account on free-radical halogenations will be found elsewhere (cf. [1]). The mechanism of photochlorination proceeds according to the fol­ lowing pathways: hv C12 ~ 2Cl • • C1 + R.CH --->- HCl + RaC, RaC, + C12 --------+ R.CCI + Cl Termination of the chain reaction can be brought about either by the combination of two chlorine radicals or by the combination of two free alkyl groups. The length of the chain reaction is adversely affected by the reaction of chlorine radicals with any impurity, e.g. oxygen, phenols and amines. The addition of chlorine to olefines also takes place via the formation of free chlorine radicals: hv C12 --->- 2 Cl. R2C=CR2 + Cl. --------+ R2C-CR2 I • Cl R2C-CR2 + C12 --------+ R2C-CR2 + CI. I • I I Cl Cl Cl Referenm, pp. 360-361 A. Schönberg, Preparative Organic Photochemistry © Springer-Verlag Berlin · Heidelberg 1968 342 Halogenation It is therefore not surprising that in the chlorination of unsaturated compounds, e. g. aromatic hydrocarbons, chlorination under irradiation leads to the formation of products involving both addition and substi­ tution reactions. The photochlorination (photobromination) of alkyl aromatic compounds takes place primarily in the side-chain. The hydrogen atoms attAched to the IX-carbon atom are replaced with particular ease by halogens. Of particular interest from the preparative standpoint are those photo­ halogenations which produce better results than the corresponding dark reactions. This is the case, for example, in the preparation of chlorocyclo­ propane from cyclopropane. Both thermal chlorination and photochlorina­ tion lead to the formation of chlorocyclopropane, but the photochlorination is to be preferred since the product of the thermal reaction contains con­ siderable quantities of allyl chloride [2]. For preparative purposes it is also significant that photohalogenation frequently follows a very selective course. HASS et al. [3] observed that in the photochlorination of propane at _60° 2-chloropropane is obtained in a yield of 73 %. RUSSELL and BROWN [4] obtained 2-bromo-2,3,3-trimethyl­ butane in almost quantitative yield from the photochemical action of bro­ mine on 2,2,3-trimethylbutane at 80°. Examples of the photohalogenation of acetylene compounds have also become known. According to HASZELDINE [5] the photochlorination of hexafluoro-2-butyne with UV-light produces 2,3-dichloro-l,1,1,4,4,4- hexafluoro-2-butene. hy --+ Derivatives of butadiene react with chlorine photochemically in such a fashion that first one double bond and then the other is saturated with chlorine. FASEEH [6] was able to show that 5-phenyl-2,4-pentadienoic acid (1) does not react with chlorine in the dark, but that in the light the reaction is such that at first 2,3-dichloro-5-phenyl-4-pentenoic acid (2) and then 2,3,4,S-tetrachloro-5-phenylvaleric acid (3) is formed. hy C6H5CH=CH-CH=CH-COOH --+ C6H5CH= CH-CHCl-CHCI-COOH Cl2 1 2 hy --+ C6H5CHCI-CHCl-CHCl-CHCl-COOH Cl2 3 The photo chlorination of benzene is, as was mentioned previously, a process of great technical significance since, as was found in 1943, one of the hexachlorocyclohexanes, known as the y-isomer, is a powerful insecticide [8]. The y-isomer was first obtained by VAN DER LINDEN [9]. References, pp. 360-361 Photohalogenation. Scope of the reaction 343 In order to obtain the best possible yield of the y-isomer, extensive experiments regarding the operative wavelengths, the choice of solvent, the reaction temperature and the concentration of the reactants were under­ taken. Although there are many descriptions of the formation of 1,2,3,4,5,6- hexachlorocyclohexane in the patent literature (cf. [10]), examples suited to serve as a laboratory experiment do not appear to be readily available. Hence, the authors are indebted to Mr. J. H. BROWN (lCI, General Chemi­ ca.ls Division) [11] for details of the irradiation procedure. 1,2-Dichloro-l,1,3,3,3-pentaHuoro-2-methylpropane [7]. A sealed Pyrex tube (30 ml) containing 1,1,3,3,3-pentafluoro-2-methylpropene (2.7 g) and a slight excess of chlorine was exposed to sunlight (20 min). The tube was filled to the exclusion of air and moisture by using a vacuum system. 1,2-Dichloro-l,1,3,3,3-pentafluoro-2-methyl­ propane was obtained in a yield of 100%, b.p.; 75-76°. 2,3-Dichloro-5-phenyl-4-pentenoic acid (2) [6]. Chlorine was led into a solution of 1 (43.5 g; 0.25 Mol) in carbon tetrachloride (435 g) and the solution was irradiated with sunlight at 37°. The absorption of the CI2 (0.25 Mol) took 1 hr., during which time the reaction mixture became clearer and the temperature rose to 57°. Chlorine (0.125 Mol) was then passed into the solution for a further hour and afterwards the vessel was placed in sunlight for a third hour. The yellow color disappeared and a small quantity of colorless crystals separated out. After filtration, the solvent was evaporated and the viscous residue was stirred with light petroleum/xylene. The colorless precipitate which formed was recrystallized from light petroleum/xylene and yielded 2,3-dichloro-5-phenyl-4-pentenoic acid (2) (yield 57.7 g; m.p. 126-127°). 1,2,3,4,5,6-Hexachlorocyclohexanes [11]. "500 g benzene (which should be of high purity - free of thiophene and cycloparaffins) are placed in a round bottomed glass flask supported in a cold water bath. The flask should be fitted with a stirrer, chlorine inlet pipe dipping below the benzene level, a thermometer, and reflux condenser. The system is illuminated by a source of light containing light of wavelength less than 500 m[L. Medium to high pressure mercury arc lamps rich in the Hg blue (454 m[L) line are particularly suitable and are exemplified by the 400 W 'Mercra' lamp manufac­ tured by British Thomson Houston Ltd. This is placed about 20 cm from the reactor. Air is removed from the system by a nitrogen purge and chlorine is then admitted to the flask at about 251/hour, the temperature of the system being maintained at about 25°. At this temperature crystals of the less soluble (t<, ~) isomers will begin to separate after some 90 g chlorine has been absorbed into the system (corresponding to some 5% conversion of the benzene). At this point it is convenient to stop the chlorine feed and after allowing a short further period of illumination to consume chlorine dissolved in the system, the excess benzene along with traces of monochlorobenzene formed in the re­ action, is removed by steam distillation. The solid product is ground and dried in an oven at 80°. The product obtained contains approximately 63 % t<, 7 % ~, 14 % y, and 8 % a-benzene hexachloride isomers with smaller quantities of the E-isomer and higher polychlorocyclohexanes. Efficiency of chlorine conversion to benzene hexachloride ex­ ceeds 95%." 3-Chlorocoumarin [12]. Coumarin (219 g; 1.5 Mol) in carbon tetrachloride (450 g) is heated, whilst stirring, to 75° in a glass flask fitted with a reflux condenser. Cl2 is passed into the solution, which is stirred and irradiated _(Hg-lamp; the emitted light should include the wavelengths 280 mfL to 540 mfL). The temperature is kept at 75° and the influx of the chlorine is so regulated that 106 g (1.5 Mol) is passed in within one hour. 344 Halogenation Following this, the solvent is rapidly evaporated and the residue heated (ca. 200°, 60 to 90 min.). After the recommended period of heating, no further generation of hydrogen chloride occurs. The pale raw product so obtained (m.p. ca. 118°) is recrystallized from isopropanol (800 ml) to give a 95.2 % yield of 3-chlorocoumarin, m.p.122°. 9-Bromofluorene [13]. Over the course of 4 hours, 8 g bromine in carbon tetra­ chloride (20 ml) is added dropwise to a gently boiling solution of pure fluorene (8.3 g; 0.05 Mol) in 45 ml carbon tetrachloride. (Bath temperature not above 85°). The red­ brown solution is further heated until it becomes yellow in color. After distilling off the solvent under reduced pressure, the residue (12 g) is twice recrystallized from cyclohexane. Colorless needles are obtained (m.p. 103-104°; yield 70% of theoretical). In direct sunlight, the same bromination is complete within 15 min. In boiling chloro­ form the 2-bromofluorene forms in the dark, and only in sunlight is the 9-bromofluorene formed. p-Bromobenzyl bromide [14]. The reaction is carried out in a three-necked Pyrex flask, fitted with dropping funnel, stirrer and reflux condenser. p-Bromotoluene (102 g) (0.60 Mol) is heated to 120° and then exposed to the radiation from a 100 Watt lamp. Bromine (102 g; 0.64 Mol) is added dropwise over three hours, and the mixture is stirred throughout. When the generation of hydrobromic acid ceases, the mixture is cooled and after some time the solid reaction product is filtered off. The product is washed three times with 30 ml alcohol (m.
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