SK81794A3 - Method of selective hydrobromation of olefinic non-saturated compounds - Google Patents

Abstract

Selective hydrobromination method of olefinically unsaturated compounds in the presence of activators under the -20 to +50 C is realised by hydrogen bromide or mixture of hydrogen chloride with hydrogen bromide, prepared by at least one technologically available methods, whilst at least one olefinically unsaturated compound is introduced into the contact with the gas containing oxygen as an activator and hydrogen bromide or at least one olefinically unsaturated compound with the gas containing oxygen (particularly molecular oxygen) and the mixture of hydrogen chloride with dry hydrogen bromide and eventually another gas. Whilst the amount of oxygen (O2, O3, super-oxide) or of the mixture of oxygen with organic peroxide as an activator reaches 0.005 to 20 wt. % / olefinically unsaturated compounds. At least one part of the activator can affect the reactants before the hydrobromination step. The hydrobromination does not run without the activator, with the activator just hydrobromination and substantially "in anti-Markovnikov form".

Description

SUMMARY OF THE INVENTION A process for the selective hydrobromination of olefinically unsaturated compounds

Technical field

The invention relates to a process for the highly selective activated "antimarker hydrobromination of olefinically unsaturated compounds, not only with at least" technically pure hydrogen bromide, but also with a mixture thereof with hydrogen chloride and optionally other gases produced by any known or novel process.

BACKGROUND OF THE INVENTION

There is a known method of "antimarker addition of hydrogen bromide to olefinically unsaturated compounds by the action of organic peroxides, hydroperoxides or radiation, in particular ultraviolet light with a wavelength of 335-500 nm" (U.S. Pat. No. 4,643,812); Kazanskij B.A. et al .: Chim. Think. 1960, p. 462; Nachapetjan L.A .: Ž. Ex. chim. 37, 1,808 (1964); Kharash H. S., I.layo P.R .: J. Am. Chem. Soc. 55, 2468 (1933); also .62, 2047 (1940)]. However, the consumption of peroxides and hydroperoxides is high and, moreover, after addition of hydrogen bromide, for safety reasons, the peroxides present must be decomposed before isolation of the main product. In the case of hydrobromination of allyl chloride to 1-bromo-3-chloropropane, the procedure carried out in the presence of oxygen and water, respectively, is protected (U.S. Pat. No. 2,352,782). in the aqueous phase in the presence of oxygen. However, the selectivity is low, while the high selectivity of hydrobromination of allyl chloride to 1-bromo-3-chloropropane is achieved with dry hydrogen bromide with oxygen or a mixture thereof with peroxides (PV 3878-92). However, it is only performed with hydrogen bromide alone and does not apply to other olefinically unsaturated compounds. The dry hydrogen bromide is produced mainly by the addition of bromine with hydrogen at a temperature above 250 ° C (U.S. Pat. No. 3,988,427). Further, displacement of alkali metal or earth broths by treatment with sulfuric acid (US Pat. 3,445,188). A disadvantage is the course of undesirable oxidation of hydrogen bromide with bromine. much

This is more often the production of hydrogen bromide from two-stage bromides. In the first stage, bromine is displaced by chlorine (U.S. Pat. No. 3,442,614), and the latter is burned to hydrogen bromide with hydrogen in the second stage. This principle is also used in the recovery of bromine from various organic and inorganic bromine compounds.

In the event of a mixture of hydrogen bromide and hydrogen chloride, whether by pyrolysis, dehalogenation, dehydrohalogenation of organic bromochloro compounds or resulting from other processes, in order to isolate individual hydrogen halides, the mixture is absorbed in hydroxide, most often alkali or earth, to form a mixture of alkali metal halides or from which bromine is generally displaced selectively by chlorine and is converted to hydrogen bromide by hydrogen combustion in a salt stage (U.S. Pat. No. 3,919,398; Jap. Pat. No. 69-10 091). Chlorides are utilized by conventional procedures such as diaphragm electrolysis and the like. The disadvantage is the multiplicity of hydrogen bromide production. Otherwise, many processes address the dehalogenation of organohalides. These include high-temperature and low-temperature combustion at temperatures of 300 to 2200 ° C, at high temperatures non-catalytic and low catalytic combustion, dehydrohalogenation with alkali metal or earth hydroxides, optionally in the vapor phase on heterogeneous, in particular acidic catalysts, gas-phase hydrogenolysis on precious metals, usually carried out at a temperature of 200 to 350 ° C or hydrotreating catalysts at 250 to 400 ° C / EP 456457,

455,547 and 456,879; WO 91 15444; Kray C .; Castro, C .: J. Am. Chem. Soc. 86, 4603 (1964); Subanna P. et al.: Lnviron. Sci. Technol. 22, 557 (1988); Novak 2.s Chem. sheets 88, 157 (1994); Rollman, R.D .: J. Catal. 46, 243. (1977); Girgis

Gatea 3.C .: Ind. Eng. Chem. Res. 30, 2021 (1991) / · Then oxidation of bromochloro compounds by ozone and peroxides, but also by bacteria of the genus Pseudomonas putida / Vilker V.L., Khan P .: Liotechnol. Prog. 1989, 5 (2): 70; Burkhard J. et al. Che. Avg.

44/60, 49 (1992)].

However, these procedures are only suitable for the removal or disposal of organic halogen compounds.

However, the whole complex of these problems is solved by the method of the invention.

SUMMARY OF THE INVENTION

SUMMARY OF THE INVENTION The present invention provides a process for the selective hydrobromination of olefinically unsaturated compounds by treatment with hydrogen bromide in the presence of an activator at -20 to + 50 ° C, wherein hydrogen bromide or hydrogen bromide / hydrogen chloride is produced synthetically by bromine or bromine / chlorine / hydrogen. - catalytic dehalogenation to dehydrohalogenation of organic bromo-chloro compounds at a temperature of 100 to 1400 ° C and / or displacement from bromide salts or a mixture of salts of bromides with chlorides, carried out by contacting at least one olefinically unsaturated compound other than allyl chloride with gas containing hydrogen or at least one olefinically unsaturated compound with an oxygen-containing gas and a mixture of hydrogen chloride and dry hydrogen bromide and optionally with Salami, under conditions of hydrobromination with an inert gas. The amount of oxygen or mixture of oxygen with organic peroxide and / or hydroperoxide amounts to a total of 0.005 to 20%, calculated on the weight of the olefinically unsaturated compound or mixture of olefinically unsaturated compounds and at least one olefinically unsaturated compound and / or hydrogen bromide can be treated. prior to contacting the hydrogen bromide and / or the hydrogen bromide / hydrogen chloride mixture with at least one olefinically unsaturated compound, and not the converted hydrogen halide or hydrogen chloride mixture, optionally with relatively inert gases, is passed to a saler utilization and the organic bromo compound formed is isolated.

The advantage of the process according to the invention is the selective hydrobromination of olefinically unsaturated compounds even in the presence of hydrogen chloride, which is virtually inactive under the mentioned conditions and also substantial acceleration at high selectivity.

- 4 hydrobromination alone by the presence of an oxygen-containing gas. Then, without separate reaction and process steps, from the mixture of hydrogen bromide and hydrogen chloride first use only hydrogen bromide and then hydrogen chloride. The process makes it possible to use the dechlorination apparatus also for the debromination of organic bromo-chloro compounds by preferably isolating hydrogen bromide by its selective reaction with an olefinically unsaturated compound and converting the hydrogen chloride unchanged into separate uses. Then use also low concentrated hydrogen bromide / hydrogen chloride mixtures, including hydrogen halides. Last but not least, the process makes it possible to utilize mixtures of bromide salts with alkali metal chlorides, resulting from organochemical production.

Hydrogen bromide or a mixture of hydrogen bromide and hydrogen chloride can be produced by reacting bromine or a mixture of bromine with chlorine and hydrogen, by displacement from bromide salts, respectively. mixtures of salts of chlorides and bromides with sulfuric acid and / or sulfur trioxide, taking into account the minimum contact of hydrogen bromide with sulfuric acid in order to prevent its oxidation to bromine. Other processes are based on the thermal or thermo-catalytic dehalogenation of the organic halogen compounds. It is usually carried out by high-temperature combustion at 800 to 2200 ° C, low-temperature combustion at 300 to 780 ° C, by gas-phase hydrogenolysis on noble metals such as Pd / C, Pt / C, Pd / SiOg and the like at 150 to 450 By hydrogenolysis on hydrotreating catalysts at 200 to 450 ° C, such as e.g. on ITiMoS, ColvíoS, CoMo, chromium oxides, copper oxides, dehydrohalogenation at 150 to 650 ° C, especially on acidic heterogeneous catalysts such as aluminum silicates, silica, alumina and the like. Dehalogenation, however, with the formation of chlorides and bromides, it is also possible to carry out oxides, in particular alkali metal and earth hydroxides, from which, similarly to other bromine salts, hydrogen bromide can be displaced with sulfuric acid and / or sulfur trioxide, respectively. first, displace bromine with chlorine and "burn" it with hydrogen to hydrogen bromide.

At least one olefinically unsaturated compound is at least one of the C8 to C12 alkenes, the cycloalkenes to _C12 , the dienes to C12. In the case of ethylene, although only bromomethane can be produced by hydrobromination, the hydrobromination rate is considerably higher in the presence of oxygen-containing gas or mixtures with peroxides.

Also included are unsaturated halogen compounds, in particular halogenated hydrocarbons, Cg-C ^ g, unsaturated carboxylic acids and θ ^ Ο, unsaturated fatty alcohols, C ₁₂ and C BŽ unsaturated dialkyl ethers and C ^.

The oxygen-containing gas comprises molecular oxygen, air, ozone, mixtures of oxygen with nitrogen and optionally other inert gases. Superoxide is particularly effective, but also toxic.

Suitable organic peroxides are commercially available peroxides, which are usually produced for polymerization and copolymerization purposes. Hydroperoxides, in addition to commercially available, such as tert-butyl hydroperoxide, cumene hydroperoxide and ethylbenzene hydroperoxide, are formed hydroperoxides of olefinically unsaturated compounds prepared for hydrobromination, respectively. generated in situ in the hydrobromation environment ·

An amount of oxygen-containing gas or mixtures thereof with organic peroxides and hydroperoxides below 0.005% by weight per olefin is unsatisfactory in particular for a sufficient hydrobromination rate, above 20% the selectivity of hydrobromination is significantly reduced by oxidizing a portion of hydrogen bromide to bromine by adding bromine to bromine. double bonds also by cleavage of already bound bromine to organic bromo compounds. For this reason, it is best to remove the oxygen-containing gas from the crude hydrobromination product before isolating the bromo compound, for example by stripping with an inert gas, evacuating, adding oxygen scavengers such as antioxidants, sulfur dioxide, and the like.

The process according to the invention is preferably carried out continuously or semi-continuously. However, a discontinuous procedure is also feasible.

Further details of an embodiment of the method of the present invention as well as other advantages are apparent from the examples.

DETAILED DESCRIPTION OF THE INVENTION

Example 1

38 grams of 1-decene are charged to a spiral condenser reactor and dry hydrogen bromide 200 mg / min is fed through a sintered frit at 10-1 ° C. and 16.7 cnr / min. Oxygen for 2 h. The reaction mixture is then stirred for 20 min. orifice with nitrogen at 50 cpm / min. Then, 60 g of the reaction product is differentially distilled at a temperature of up to 115 ° C / 2 kPa. 2.2 g of fraction 1, which is essentially unreacted 1-decene and fraction 2 of b.p. 117-120 ° C / 2 kPa in an amount of 52 g containing 99.4% by weight. 1-bromodecane. Analysis of 1 H and 1 H NMR showed virtually no 2-bromo decane, which may thus be below 0.2 wt%. The distillation residue was 4.4 g. The conversion of 1-decene is 96.4% and the selectivity to 1-bromoidecane is 92

Under otherwise similar conditions, but at a temperature of 45-1 ° C, 60 g of 1-octadecene are hydrobromised. The conversion of 1-octadecene was 94% over 2.5 h and the selectivity to 1-chromoctadecane was 86%. At this temperature, however, in addition, in the presence of 60 g of 1-decane and 60 g of ethylene oligomers, representing at least 96% of 1-alkene, the hydrobromination is carried out with dry hydrogen bromide at 150 mg / min. and an oxygen supply of 6 cm @ 2 / min. During

2,5 h. The conversion of 1-alkenes Ο ^ θ reaches 80% and the selectivity to

1-bromoalkane also 88 ‘, S.

Example 2

A mixture of 2.4% by weight, isopropyl bromide and 97.6% is charged to the reactor described in Example 1 as solvent.

- 7 masses, n-propyl bromide. Thereafter, dry hydrogen bromide (150 mg / rain), propylene (41.7 cm @ 3 / min) was fed to the reactor at 10-1 ° C. and 25 cm ^ / min. molecular oxygen. Over 2.5 h, 64 g of the reaction product containing

96.5% by weight. n-propyl bromide and 3.5 µ isoprooyl bromide. In addition to oxygen, the 'off-gas' of the reactor contained only a small amount of propylene; hydrogen bromide is not present. When converting propylene

98.6% and virtually complete hydrogen bromide conversion selectivity to n-propyl bromide reaches 96.5% and to isopropyl bromide 3 »5

However, under otherwise similar conditions, but without oxygen supply, propylene hydrobromation does not occur. The conversion of propylene and hydrogen bromide is below 3% and both gases leave the reactor unconverted.

Example 3

30 g of allyl chloride are weighed into the reactor specified in Example 1, brought to 10-1 ° C, and a mixture of dry hydrogen chloride with hydrogen bromide (96.6% by weight, HBr and 3 * 4% by weight, HCl) and oxygen at 8 is started. 3 cm @ 2 / min. for 1.5 h. 55.3 g of a reaction mixture containing 0.9% by weight, allyl chloride, 0.3% by weight, 1-chloro-2-bromopropane, 98.7% by weight are obtained. % Of 1-bromo-3-chloropropane and below 0.05 wt%. 1,2-dichloropropane and 1,3-dichloropropane conversion · Allyl chloride conversion reaches 98.2%, selectivity to 1-chloro-2-bromopropane 0.3 #. Similar conversion and selectivity is achieved with the same amount of dry and pure hydrogen bromide introduced and otherwise similar conditions. However, without oxygen supply, conversion of allyl chloride containing only dissolved air and traces of allyl chloride hydroperoxide, 60.4 selectivity to 1-bromo-3-chloropropane reaches 93.0% and 4.2% to 1-chloro-2-bromopropane.

Example 4

Three-necked flask of a volume of 1000 cm equipped with a sealed stirrer, weigh 100 g of n-alkanes ^C 10 ^{to C 13, and} 100 g of a mixture of potassium salts, odpadajúcich the production of pharmaceuticals, containing 51.9 wt.% KBr, 27.9% by weight of KCl, 12.9% by weight of KgCOp, the remainder being water and admixtures of organic matter. After drying these salts by elemental analysis, a carbon content of = 1.21%, a hydrogen content of - 0.26%; nitrogen is absent. 96 g of 96 wt.% Sulfuric acid are added over 1 h with stirring and tempering at 50-2 ° C. The hydrogen bromide conversion in hydrobromation reaches 3.8 to 6%, and the hydrogen chloride does not react. However, when air is added to the gas mixture at a rate of 35 cm / min, the hydrogen bromide conversion reaches 98-100, while both hydrogen chloride and carbon dioxide pass through

1-decene unchanged. The selectivity to 1-bromodecane is 98.9%. A mixture of hydrogen chloride and carbon dioxide is absorbed in cold water to form an aqueous solution of hydrochloric acid.

Example 5

The procedure is similar to that of Example 4, except that the amount of sulfuric acid applied is 48% by weight, higher, i.e. the molar ratio of sulfuric acid: potassium salts = 1.4. In addition, 0.8 g of sulfur and 0, 2 g of red phosphorus. The gas mixture to be released is passed through the frit to the 1-decene together with the added air at 39 cnr / min. Hydrogen bromide is consumed quantitatively for hydrobromination of 1-decene, while hydrogen chloride practically does not react at all under the stated conditions (10 - 1 ° C) with 1-decene and is absorbed in a subsequent scrubber in cold water.

- 9 Example 6

30 g of allyl chloride (0.392 moles) are charged to the reactor described in Example 1 and 57.2 g of hydrogen chloride / hydrogen bromide mixture from dechlorination of bromochloropropane after pre-washing are fed through a frit to the bottom of the reactor for 60 minutes at a temperature of 7-1 ° C. The gases contained 50% by weight of hydrogen bromide (0.35 mol) and 50% by weight of hydrogen chloride (0.784 moles). A separate frit is added simultaneously for 60 min. oxygen in the amount of 3

1000 cm. 'The reactor effluent is sent to the scrubbers; containing aqueous sodium hydroxide solution.

o mass concentration.

The amount of liquid hydrohalogenation product obtained

55.6 g contains 3 → 4% by weight, allyl chloride, S5 → 3% by weight. 1-bromo-3-chloropropane, 0.08 µm, 1-chloro-2-bromopropane, below 0.1 wt%. 1-2- and 1,3-ochichloropropane. The remainder are higher bromochlorinated products.

The conversion of allyl chloride is 93.7% and its selectivity to 1-bromo-3-chloropropane is 91.0%. The selectivity of the conversion of hydrogen bromide to 1-bromo-3-chloropropane is 95.2%. Hydrogen chloride does not convert with allyl chloride at all, so its conversion is 0.0 ^c / t>. It only reacts in sodium hydroxide scrubbing solution to sodium chloride.

Example 7

The distillation residue from the crude allyl chloride hydrobromination product had a molar mass of 213 g / mol and an elemental composition (wt%): C = 21.15, H = 3.28, Cl = 13.28, and Br = 49.74. This residue, in the form of vapors together with hydrogen, is fed to a catalyst containing 0.5 wt.%, Palladium on charcoal, and a vapor stream. J of the distillation residue is 10 g per 50 cm catalyst per hour along with 4 dm / h hydrogen at The gases leaving the reactor are passed through a condenser where they are cooled to 5 to -7 ° C and together with an air admixture of 0.5 dra / h. are fed to a 1-decene reactor, tempered to a temperature

5 to 7 ° C. 1-Decene is merely hydrobromised, while the hydrogen chloride passes unchanged through 1-decene and after separation of the entrained 1-decene vapor with traces of 1-bromodecane is absorbed in cold water (+5 ° C) to form an aqueous hydrochloric acid solution.

Under otherwise similar conditions, the complete dehalogenation of the distillation residue from the distillation of the allyl chloride hydrobromination product in a stream of hydrogen on a nickel-molybdenum oxide catalyst is obtained at 290-10 ° C, on an alumina-nickel oxide-nickel catalyst at 290-320 ° C, worn platinum. radio catalyst (Pt-11h / N-AlgO 4) reforming at 320 to 360 ° C and on Adkins catalyst (CuO, Cr 2 O 4 · BaO) at 540 to 580 ° C.

Example 8

The distillation residue from the hydrobromination of allyl chloride characterized in Example 7 is sprayed onto the molded active clay by extrusion (rollers with a diameter of 1 mm and a length of 10 to 12 mm) in an amount of 50 cn at 15.5 g / h for 2 h. dehydrohalogenisis is carried out at a temperature of 300 to 302 ° C. Contact vapors condense, condensing 13.1 g of allyl chloride containing 1.41% by mass over 2 h,

7.1% by weight, 1-bromo-3-chlorobromopropane and 29.2% by weight. 1,2-dibromo-3-chloropropane, with the remainder being unprotected products. “The flue gas was passed through a frit to 40 g of 1-decene, where moreover, oxygen was supplied at a rate of 300 cm / h. I.The quantity of such hydrohalogenated 1-decene is 46.5 g. This is differentially distilled. Fraction o.t.v. 32 to 62 ° C / / 21 kPa reaches 29.1 g; 2nd fraction of b.p. 62 to

110 ° C / 2.13 kPa, 4.9 g and fraction 3, b.p. 110-115.5 [deg.] C./2 mbar reaches 9.7 g and the distillation residue 0.4 g. The selectivity to 1-bromodecane is £ 99.8, while chlordecane is absent.

Under otherwise similar conditions, however, if oxygen-containing gas is not introduced into the reaction medium, not only the hydrochlorination but also the hydrobromation of 1-decene does not take place.

Example S

An acid heterogeneous catalyst is prepared by extruding hydrochloric acid extracted bentonite, consisting of 75% montmoronite, 22.3% glassy phase and 2.7% silica. This bentonite had a loss on burning of 6% by mass, and its analysis is as follows (% w / w SiOg = 69.55 »AlgO4 ⁼ 1 °, 89j ^ 2θ3 ⁼ ^ -» 55; TiOg = 0.19 Mg = 2.85i CaO Li ₂ O = 0.15i KgO = 0.22 The bentonite slurry in the water free of sand by hydrodynamic separation in three stages is activated by extraction with hydrochloric acid at a total concentration of 2 U at 97 ° C for 8 h. and filtering the slurry and washing with de-mineralized water, the wet slurry filter cake is compacted using an extruder, and the extrudates obtained are dried at 105 ° C to a constant moisture content of 15%.

The dehydrohalogenation is carried out similarly to Example 8, except that the hydrogen bromide / hydrogen chloride mixture is fed to a propylene / oxygen stream (1.2% by weight of oxygen) while propylene is hydrobromised to 1-bromopropane. Conversion of propylene reaches

98.9% and selectivity to 1-bromopropane 99.1 Selectivity to

2-bromopropane is 0.2%. Chloropropanes are absent.

Example 10

The procedure is similar to that in Example 6, except that the mixture of hydrogen bromide and hydrogen chloride, by weight lsl, is prepared by the addition of hydrogen with chlorine and bromine, but cyclohexene is hydrohalogenated instead of allyl chloride. At 9-1 ° C, cyclohexene hydrohalogenation does not take place but, in addition, in the presence of oxygen in an amount of 1.3% by weight, hydrobromination is already carried out on the hydrogen halide mixture until complete cyclohexene conversion is achieved, with selectivity to bromocyclohexane of 9S, 9 $. the result is only achieved with a quarter oxygen feed, but using cyclohexene containing 0.4% by weight, cyclohexene hydroperoxide.

Under otherwise similar conditions in the absence of oxygen, the styrene hydrobromination proceeds with only a slight styrene conversion of only 8% and the selectivity to bromomethylbenzene reaches 63%. However, in the presence of air in an amount of 0.9% by weight, in the hydrogen halide mixture, virtually complete styrene conversion and selectivity to bromomethylbenzene of 89.5% are achieved.

Example 11

The procedure is similar to that of Example 10, except that cyclohezene, previously stored at 25 ° C under 10 psig of air for 10 h, is used for hydrohalogenation of cyclohezene. selectivity 96% to bromocyclohexane. Furthermore, when air is added during hydrohalogenation, complete conversion of cyclohexene and selectivity to bromocyclohexane is achieved.

Example 12

The procedure is analogous to Example 11, except that ethyl acrylate is hydrobromised instead of cyclohexene. While the conversion of ethyl acrylate takes place without oxygen, but the selectivity to ethyl bromoacrylate is 8%, with oxygen at complete conversion the selectivity to ethyl bromoacrylate is 88% ·

Example 13

The procedure is analogous to Example 11, except that instead of cyclohexene, a mixture of C C-hydrocarbons consisting of (? Wt) of 22% 1-butene, 31% n-butones, 21% isobutylene,

0.7% of 1,3-butan-2-diene, the remainder being n-butane and isobutane.

Without oxygen supply, hyarobromation is practically non-existent (version 13 is below 5 5 »), with oxygen supply, alkene conversion reaches 86% and selectivity to bromobutanes 90.2

Industrial usability

The process of the present invention is applicable to all hydrobromations of olefinically unsaturated compounds, especially for _(I antimarker hydrobromination, e.g., allyl chloride to 1-bromo-3-chloropropane, 1-dodecene to 1-bromododecane and the like), to utilize waste organic bromochlorine waste. mixtures of hydrogen bromide with hydrogen chloride; and mixtures of salts of bromides and chlorides of alkali metals and soils.

Claims (6)

A process for the selective hydrobromination of olefinically unsaturated compounds by treatment with hydrogen bromide in the presence of activators at a temperature of -20 to + 50 ° C, wherein hydrogen bromide or a mixture of hydrogen bromide and hydrogen chloride is produced by at least one of bromine addition or bromine / chlorine hydrogen. by thermo-catalytic dehalogenation to dehydrohalogenation of organic bromochloro compounds at a temperature of from 1 ° C to 1200 ° C, displacement with sulfuric acid or sulfur trioxide (Z) salts of bromides or mixtures of salts of bromides with chlorides, produced by dehydrohalogenation of alkali metals or soils; at least one olefinically unsaturated compound other than allyl chloride is contacted with an oxygen-containing gas and hydrogen sulphide or at least one olefinically unsaturated compound with an oxygen-containing gas and a mixture of hydrogen chloride and dry hydrogen bromide and optionally further, in inert gas hydrobromination conditions, wherein the amount of oxygen or oxygen blend with organic peroxide and / or hydroperoxide is in total 0.005 to 20% calculated on the weight of the olefinically unsaturated compound or mixture of olefinically unsaturated compounds and at least one olefinically unsaturated the compound and / or hydrogen bromide prior to contacting the hydrogen bromide and / or the hydrogen bromide / hydrogen chloride mixture with at least one olefinically unsaturated compound, and the unconverted hydrogen halide or hydrogen chloride mixture, optionally with relatively inert gases, is led for further use and the organic bromo compound formed is isolated. The method of claim 1 wherein the at least one olefinically unsaturated compound is selected from alkenes Cg-C ^ Q, ^ C and dienes, unsaturated halo carbon Cg-C ^ g, the unsaturated carboxylic acid and _c Ck, unsaturated aliphatic alcohols and unsaturated C ^ g to C ^ dialkyl ethers. The method according to claims 1 and 2, characterized in that the oxygen-containing gas is selected from the molecules of oxygen, ozone, air and other oxygen-containing inert gases. Process according to claims 1 to 3, characterized in that at least one olefinically unsaturated compound is treated with an oxygen-containing gas prior to hydrohalogenation to increase the amount of dissolved oxygen up to the formation of hydroperoxides. f * Process according to Claims 1 to 4, characterized in that the mixture remaining from 1 to 10% by weight, of hydrogen chloride and hydrogen bromide, is produced by thermal and / or tertiary-catalytic dehalogenation and / or dehydrohalogenation and / or combustion of organic bromine compounds. or bromochloro compounds, preferably low-valued minor-bromo-chloro compounds to waste. Method according to claims 1 to 5, characterized in that an organic peroxide, preferably a hydroperoxide, is introduced into the at least one olefinically unsaturated compound. Process according to claims 1 to 6, characterized in that the oxygen-containing gas is removed from the crude hydrobromination product. V side like stripping dry inert gas, suctioning and / or adding antioxidants ·