DE2211735A1 - Polyhalobenzyl disulfoxonium compounds and processes for their preparation - Google Patents

Description

Patent attorneys Dipl.-Ing. F. We ic km anon,

Ditl.-Ing. H. ¥ eickmann, Dipl.-Phys. Dr. K. Fincke Dipl.-Ing. RAATeickmann, Dipl.-Chem. B. Huber

8 MUNICH 86, POST BOX 860 820

MÖHLSTR.ASSE 22, NUMBER 48 39 21/22

<9S3921 / 22>

Case 2228

HOOKER CHEMICAL OORPORA'I'IOF, Niagara PaXIs, 2ί.Υ. 14302, box H.

Polyhalobenzyl disulfoxonium compounds and processes for their

Manufacturing

The invention relates to a new class of halogenated organic Compounds, namely polyhalobenzyl disulfoxonium compounds, and processes for their preparation.

Sulfur trioxide is known as a strong oxidizing agent, it has not been widely used as such because of its confusing reactions with hydrocarbons. The reaction product of sulfur trioxide with paraffins and olefins makes a dirty, difficult to handle dark mixture of oxidation, condensation, polymerization, sulfonation and sulfation products are what cause the uncontrollable speed (non-controllability) of the reaction demonstrated. In contrast, sulfur trioxide is used as an aromatic sulfonating agent and widely used as a sulfating agent for alcohols, as this response is well developed and described.

209838/1243

The present invention now explains the new use of sulfur trioxide in oxidation and substitution (introductory) reactions in the absence of uncontrollable competitive reactions, a new class of internal oxonium salts, namely internal disulfoxonium salts, are obtained which are completely stable, but represent highly reactive compounds.

The subject of the invention is therefore a new class of halogenated th organic compounds, as well as processes for their preparation, the new class of compounds for the preparation of the a wide variety of halogenated products can be used, which in turn can be used as monomeric precursor compounds for polymeric systems, z. B. as additives for polymers, in particular to achieve fire resistance, as pesticides and as chemical intermediates, can be used.

In particular, the invention relates to a new class of organic Compounds that can be referred to as polyhalobenzyldisulfoxonium compounds and have the following general formula (A) have:

HaI _1n H _n Ar

SO

CHX-O

SO ₂ Y

where mean:

Ar an aromatic nucleus,

a halogen from the group fluorine, chlorine, bromine and iodine,

a substituent from the group fluorine, chlorine, bromine and hydroxyl,

209 838/1243

m, η and p

a substituent from the group consisting of hydrogen and

he * ^

-0

SO ₂ Y

, wherein Y has the meaning given above;

each integer selected so that their sum is the number of those on the aromatic ring . available substitutable positions corresponds, which is 6 when Ar = benzene, which is 8 when Ar = naphthalene, and which is 10 if Ar = anthra cen or phenanthrene.

The term "aromatic nucleus Ar" as used herein includes the ring structures of benzene, naphthalene, anthracene, phenanthrene and Pyrene. Ar is therefore an aromatic hydrocarbon radical of the benzene series with 1 to 4 six-membered rings, each substitutable hydrogen atom on the ring being substituted with a halogen atom

The new class of compounds can be prepared by reacting the suitable halide aromatic compounds with reagents that contain sulfur trioxide, for example pure sulfur trioxide itself, sulfuric acid solutions of SO ₃ (oleum), sulfur trioxide adducts, for example those with dioxane and amines, and chlorosulfonic acid and fluorosulfonic acid.

The following chemical equations illustrate some of these new ones Realizations:

Cl Cl

Cl Cl

Cl Cl

Cl Cl

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Br

Br

CH ₂ OH + oleum

CH ₂ Cl

+ 2ClSO ₃ H

SO ₂ OH

Br Br

Cl Cl

+ 2HCl

SO ₂ Cl

Cl Cl

A very notable aspect of the present invention is that it has been found that the reaction with sulfur trioxide and sulfur trioxide-containing reagents carried out with simultaneous oxidation of the side chain of the aromatic substrates can be. The significance of this fact lies in the fact that even methyl groups are easily and quantitatively attached to the aromatic nuclei can be oxidized and converted into products of the general formula (A) given above, in which Y in this case is a Means hydroxyl group. In these reactions exactly 1 mole of sulfur trioxide per methyl group is consumed in the oxidation stage with formation of 1 mole of sulfur dioxide, which is illustrated by the following reaction equations:

Cl Cl

Cl Cl

CH ₃ + 3 SO ₃

Cl

+ SO,

SO ₂ OH

Cl

Cl

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-s-

Br Br

O ₃ S

CH ₃ + 6 SO ₃

@
0-CH,

HOSO

Θ / ^5Ο 3 ^Θ CH ₇ -O + 2SO ₀

SO ₉ OH

Br Br

CH ₂ Cl

* 5 SO ₃

Cl Cl

Cl Cl

Another very useful variant of the oxidation reaction is the conversion of the methyl group into a geminal dioxonium derivative with the help of an excess of sulfur trioxide reagent:

Cl Cl

Cl Cl

CH ₃ + 6 SO ₃ -> Cl

CH 0

Cl Cl

Cl Cl

SO-OH

+ SO

Br Br *

Br-K ()> - CH ₃ + 6 SO ₃ > Br

Br Br

Br Br

CH 0

Br Br

SO

SO ₂ OH /

+ 2SO.

8 38/12

It is of considerable synthetic value that the oxidation of methyl or substituted methyl side chains on the aromatic Nuclei, even when using a large excess of sulfur trioxide, do not go beyond the geminal dioxonium level, a fact which leads to the fact that very pure products are obtained in the subsequent conversions (see above).

The wide scope of these new reactions is evident from the wide variety of halogenated aromatic compounds which readily undergo these transformations and yield a variety of useful products. Derivatives of all four of the usual Halogens are equally suitable as starting materials, when they are in the form of mono-, di- or polynuclear aromatic compounds. The latter two classes encompass both the isolated and the condensed aromatic ring systems, some of which are given below and in further the following examples are listed below. All of these halogenated aromatic compounds have one or more side chains, which consist of methyl, halomethyl or hydroxymethyl substituents. As a representative representative of this multitude Suitable substrates for the preparation of the oxonium compounds according to the invention may include, for example, the following compounds to be considered: pentafluorotoluene, tetrafluoro-o-xylene, Trifluoromesitylene, pentachlorotoluene, pentachlorobenzyl chloride, tetrachloro-m-xylene, trichloropseudocumene, β, α'-2,3,5,6-hexachlorop-xylene, Pentachlorobenzyl alcohol, heptachlor-1-methyl-naphthalene, Heptachloro-2-methylnaphthalene, hexachloro-2,7-dimethylnaphthalene, Octachlor-i ^ iO-dimethylanthracene, Octachlor-4,4'-dimethylbiphenyl, Pentabromotoluene, pentabromobenzyl fluoride, tetrabromo-p-xylene, 1,3,5-7-tetrabromo-2,6-dimethylnaphthalene, Tribrommesitylene, Dibromodurol, Pentajodtoluol, Pentajodbenzylfluorid, Tetraiodo-o-xylene, Tetraiodom-xylene, a, o'-dichloro-2,3,5,6-tetraiodo-p-xylene, triiodraesitylene,

, 2-chloro-3,4,5,6-tetraiodotoluene,

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2-chloro-3,5,6-tribromo-4-iodotoluene, Z ^

p-xylene. The reactions of many of these aromatic compounds are explained in more detail in the examples below.

Due to the wide range of reactivities of both the aromatic reactants and the sulfur trioxide containing reagents, there is a fairly wide range of suitable or desirable reaction temperatures. Although the formation of oxonium compounds of benzylic alcohols to take place down to -80 ⁰ C, may be the reactions in which simultaneously an oxidation occurs, most preferably above ⁰ ° C, often at the boiling point of liquid SO-, between 45 and 50 ⁰ C, carried out, and the reactive compounds, the reactions least at temperatures up to and in some cases over 150 ⁰ C. The correct selection of the correct SO ₃ -containing reagent usually eliminates the need to use a foreign solvent and it is often advantageous to use an excess of liquid SOj (which is a good solvent) or sulfuric acid (which is a liquid excipient or carrier). to use. A small amount (5 to 10%) of concentrated sulfuric acid, when added to liquid sulfur trioxide, often has a beneficial effect on increasing the rate of oxidation of the aromatic substrate. However, it has been found that when it is used in large amounts, for example in the form of 20% oleum, as the reaction medium, the sulfuric acid can drastically change the course of the reaction, as can be seen, for example, from reaction (13) below. In a few cases, if necessary or expedient, solvents which are unaffected by the types of sulfur trioxide or which are not easily attacked can be used. Most often, fluorinated aliphatic hydrocarbons such as trichlorofluoroethane, trichlorofluoromethane and 1,1-difluorotetrachloroethane can be used. The reactions are usually at atmospheric pressure

209838/1243. '

carried out, whereupon the application of a vacuum, if desired follows to recover the excess liquid sulfur trioxide. If the reaction is accompanied by oxidation, it should ensure that the gaseous sulfur dioxide by-product Will get removed.

The structure of the oxonium compound is of the general type given above Formula (A) is based on:

1.) the stoichiometry of the implementation; as most of the described Reactions with quantitative conversion take place, the weight of the isolated product is an indication of its composition

from
Settlement; when the reaction / oxidation is accompanied, the amount of sulfur dioxide gas evolved indicates the extent of oxidation and the number of methyl and substituted methyl groups detected thereby;

2.) the elemental analysis of the product, which is also the rough Composition confirmed; Due to their high reactivity and hygroscopic nature, the most appropriate indirect analyzes are for example, after their decomposition with water, carried out and the released sulfuric acid and the

uriü aas lialorrGii

Carbon, the hydrogen, determined by combustion analysis;

3.) Nuclear magnetic resonance spectroscopy, which is the best confirmation of the specific represented by the formula (A) Structure supplies; for example, the single proton nuclear magnetic resonance peak is correct at 6.3 to 6.5 ppm . Downfield from the reference substance tetramethylsilane only match the following structure:

HaIArCH ₂ -O.

so ₃ ^ö

SO ₂ Y

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4.) the numerous reactions of the oxonium compounds, of which many expire in quantitative yield ^ which likewise provides an appropriate verification of the correctness of the by the general Formula (A) allow specified molecular structure.

Representative reactions with the pentachlorobenzyloxonium compound are the following ".

CH ₂ -O · + Η, Ο -} Cl

Cl, Cl

SO ₂ OH

Cl Cl

(2)

Cl Cl

^CH 2 "° v ⁺ NaOH

SO ₂ OH

Cl Cl

(3)

Cl Cl

8 / ^S0 3

+ CCl

SO ₂ OH

Cl Cl

Cl Cl

SO

Cl Cl

CH ₂ OSO ₂ OH

Cl Cl

Cl Cl

+ CHCl.

SO ₂ OH

Cl Cl

Cl Cl

CH ₂ OSO ₂ ONa.O,

Cl Cl

Cl Cl

Cl

CH ₂ Cl

Cl Cl

Cl Cl

Cl ~ \ C3V ^CH 2 ^C1 Cl Cl

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(5)
Cl Cl

- 10 -

CH ₂ -O

SO ₂ OH

+ Cßr

Cl Cl

Cl Cl

CH ₂ -O,

SO ₂ OH

Cl Cl

(7) Cl Cl

Cl Cl

CH ₂ -O

SO ₂ OH

CH ₃ CN _C1

Cl Cl

CH ₂ NHC-CH,

Cl Cl

(8) Cl Cl

Cl Cl

SO

+ H ₉ C = CHCN

Cl

Il

CH ₂ -NHCCH = CH ₂

Cl Cl Cl Cl

Cl H,

κΐ

Cl.

Cl

Cl Cl.

Cl-U) VQI ₂ -O ^ ³ ₊ HCCl = CCl " ² ^ ⁴

ν SO ₉ OH Cl ti Cl Cl

* ^C1 ~ (C _) / ~ ^Cli 2 ^CHC1C00H

Cl ^ l

2098.38 / 12

Cl Cl

- 11 -

+ Cl ₂ C = CCl ₂

Cl-

CH ₉ CCl ₇ COOH

Cl

Cl Cl

cH ₂ -o;

'SO ₂ OH

Cl Cl

Cl Cl

Cl Cl

SO ₀ OH

Cl Cl

Cl Cl

(13)

A variant of these reactions occurs with halogen-aromatic compounds which carry more than one methyl group. if these reactants are oxidized with sulfur trioxide and if the Oxonium compounds obtained are decomposed by water, the corresponding di- or polyhydroxymethyl compounds are analogous to the products of equation (1) t If the oxidation is carried out with a sulfur trioxide / sulfuric acid mixture (for example with 201 Oleum) is carried out, the reaction products are aldehydes in which one of the methyl groups remains intact. This unusual reaction (which is further illustrated in Examples 64 to 67 below) can be carried out using of tetrachloro-p-xylene as a specific reagent by the following Equation (13) can be represented:

Cl

+ 201 oleum

CH.

Cl

CHO

Cl

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If, on the other hand, sulfur trioxide is used in the absence of sulfuric acid the implementation follows the course given in equation (1a):

Cl Cl

Cl Cl

CH ₃ + SO ₃

^H 2 °.

CH ₂ OH

Cl Cl

Cl Cl

What is even more surprising is that when the diol itself is exposed to oleum is obtained as the reaction product of methylaldehyde:

(14) Cl Cl

CH ₂ OH + 201 oleum

Cl Cl

CHO

Cl

The products of these new implementations can thus be in the following general formulas are divided into:

The products of the reaction (1) can be represented by the formula (b) will:

Hal _1n Ar (CH ₂ OH) _n

in which Ar, Hai, m and η have the same meanings as in the above have general formula (a);

the products of reaction (2) can be represented by the formula (c)

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will be provided:
Cc)

Hal Ar (CH ₇ OSO ₀ OM) ^

IU LU XL

in which Ar, Hai, m and η have the meanings given above and M is a metal from the group of alkali metals, alkaline earth metals and others! readily available types of cations;

the products of reactions (3), (4) and (5) can be obtained by fol The following formula (d) can be shown:

Hal _m Ar (CH ₂ HaI ^f ) _n

in which Ar, Hal, m and η are as defined above and Hal ¹ denotes a halogen atom, for example chlorine, bromine and iodine;

The products of the reaction (6) can be represented by the formula (e) will:

Hal _1n Ar (CH ₂ Ar) _n

in which Ar, Hal, m and η are as defined above.

Although the reaction has only been illustrated with benzene, a wide variety of aromatic compounds can be used as reactants that at least one for the one explained in equation (6) Substitutjiiansreaktion contain available hydrogen atom. Examples of suitable aromatic substrates are mono-, di- and polyhalogenobenzenes, for example fluorobenzene, chlorobenzene, o-dichlorobenzene, p-dichlorobromobenzene, 1,2,4-trichiorbenzene, bromobenzene, p-chlorobromobenzene, iodobenzene; Mono-, di- and polyalkyl-

209838/124 3

benzenes, ζ. B. toluene, xylenes, mesitylene, pseudocumene, durol, Ethylbenzene, isopropylbenzene, tert-butylbenzene, o-chlorotoluene, Dodecylbenzene; single and condensed di- and polycyclic aromatic compounds, ζ. B. biphenyl, naphthalene, anthracene, Phenanthrene, pyrene, 1-chloronaphthalene, 9,10-dichloranthracene, Triphenylmethane and indene.

The products of reactions (7) and (8) can be obtained by the following Formula (£) are shown:

Hal _1n Ar (CH ₂ NHCR) _n

in which Ar, Hai, m and η are as defined above and R is a hydrocarbon radical, z, B, an aliphatic, cycloaliphatic or aromatic group which can be substituted by Ilalogen atoms, means.

Suitable reactants for the Umsetzuneen (7) and (8) are for example Hydrogen cyanide, acetonitrile, propionitrile, butyronitrile, Trichloroacetonitrile, trifluoroacetonitrile, benzonitrile, p-chlorobenzonitrile, Acrylonitrile, propionic acid nitrile and di- and polynitriles, such as dicyan, glutaronitrile, adiponitrile, phthalonitrile. When di- or polyfunctional oxonium compounds, for example the compounds derived from xylene and mesitylene, with difunctional nitriles, for example malononitrile, succinonitrile, Adiponitrile, are converted, polymeric polyamides are formed.

The products of the reaction (9) can be represented by the following formula (g) are shown:

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■ CII

Hal Ar

CCl

in which Ar, Hal, m and η are as defined above.

The products of the reaction (10) can be represented by the formula (h) will:

Hal _1n Ar (CH ₂ CHClCOOH) _n
in which Ar, Hai, m and η are as defined above.

The products of the reaction (11) can be represented by the formula (i) will:

Hal _1n Ar (CiI ₂ CCl ₂ COOH) _n

in which Hai, Ar, m and η are as defined above.

The products of the reaction (12) can be represented by the formula (j) will:

HaI _1n Ar (CHO) _n

in which Hai, Ar, m and η are as defined above.

The products of reactions (13) and (14) can be represented by the formula (k) are represented:

Hal _m Ar (CH ₃ ) _p (CHG) _q

209838/1243

in which Ar, Hal, m are as defined above and ρ and q are integers mean, where the following relationship applies: ρ + q = n when η is as defined above.

These conversions, which are characterized by a high conversion (conversion) and by the purity of the products and which are associated with various mono-, di- and trioxonium compounds as well as with an-. whose halogenated aromatic compounds proceed in an analogous manner and are therefore very well suited for preparative processes '(Production method). The variety of mono-, si- and polyfunctional End products of these reactions is used as additives for polymers, through which these because of their high Halogen content can be made fire-resistant, as monomers for the production of various polymer systems, as chemical Intermediates and as pesticides.

The following examples are intended to explain the invention in more detail, without however, to limit them to that.

example 1

Preparation of the internal 2,3,4,5,6-pentachlorobenzyldisulfoxonium hydroxide salt from pentachlorotoluene and sulfur trioxide

Cl Cl

Cl

CH ₃ + 3 SO ₃

Cl Cl

+ so.

SO ₂ OH

200 ml (385 g) of liquid sulfur trioxide were added to 26.4 g (0.1 mole) of pure 2,3,4,5,6-Pentachlortuluol (F. 224-225 ⁰ C) in a 500 ml three-necked flask was provided with a stirrer, thermometer and reflux condenser, the end of which was connected to a bubble counter

209838/1243

was, so that the amount of gas evolution occurring during the reaction could be determined visually. The flask was warmed from the outside to bring the sulfur trioxide to reflux. Very soon a light blue color developed, which gradually deepened to a light or lively royal blue. the The change in color was accompanied by the evolution of gas, that of sulfur dioxide was identified. The steady evolution of gas, which began after 10 minutes of reflux, lasted until 3 hours, after which it was it gradually became weaker and the reaction mixture gradually turned a dark green-gray color. The weight of the reaction mixture at this point indicated a loss of 6.9 grams of im Compared to the theoretical loss of 6.4 g, which corresponds to 1 mol of sulfur dioxide evolved. The excess of sulfur trioxide, which also acted as a solvent during the reaction,

was first distilled off at atmospheric pressure, then under a water jet vacuum at a temperature of not more than 70 ^{0 C.} The weight of the product (45.2 g), a greenish gray solid, indicated that it had a composition of C ₇ H ^ Cl ₅ O ₇ S ₂ and this was confirmed by its hydrolysis at 0.2 moles of sulfuric acid , 0.1 mol of pentachlorobenzyl alcohol, identified by elemental analysis, infrared spectroscopy, melting point and nuclear magnetic resonance spectrum (see. Example 23). The development of the reaction was also followed by nuclear magnetic resonance spectroscopy (NMR), which indicated that the characteristic proton resonance of pentachlorotoluene at 2.52 ppm downfield from tetramethylsilane (TMS) disappeared completely in the first stages of the reaction. Instead, a new peak appeared at 4.55 ppm, which can be traced back to the cation radical formed by the loss of an electron from the pentachlorotoluene. During the boiling under reflux and the evolution of sulfur dioxide, two peaks developed with increasing intensities, further peaks approximately in a ratio of 2: 1 at 6.29 and 9.21 to 9.60 ppm (the latter varies somewhat during the reaction). The former corresponds to the two benzyl hydrogen atoms in neighboring

209838/1243

to the oxonium residue and the latter corresponds to the acidic proton of sulfuric acid. The intensity of the peak, which corresponds to the radical cation, to which the intense permanent color is based, corresponds to, decreases after 2 hours of refluxing by a few percent and the intensities of the protons of the oxonium compound remain constant after this period.

Example 2

Manufacture of Pentachlorobenzyl Disulfoxonium Hydroxyd- ' salts of pentachlorobenzyl alcohol and sulfur trioxide

Cl

CH ₂ OH + 2 SO ₃

Cl

SO ₂ OH

The procedure of Example 1 was repeated, but this time the Pentachlortoluol was replaced by an equivalent amount (28.0 g) at Pentachlorbenzylalkohol (F. 195-196 ⁰ C). In contrast to the first-mentioned case, only a temporary blue color appeared, which changed to a greyish green on refluxing, but there was no evolution of gas. The identity of the product with that of the previous example was confirmed by nuclear magnetic resonance which showed the two peaks of the oxonium compound.

209838/1243

Example 3

Preparation of the internal pentachlorobenzyl (chlorosulfonyl) sulfoxonium hydroxide salt from pentachlorobenzyl chloride and sulfur trioxide

Cl. Cl

Cl Cl

+ 2 SUN

Cl

Cl Cl

The procedure of Example 1 was repeated except that the Pentachlortoluol was replaced by an equivalent amount (29.9 g) of Pentachlorbenzylchlorid (F. 100-101 ⁰ Q). Boiling under reflux for 10 minutes was sufficient to convert the halide to the halogenoxonium compound without evolution of gas and without the appearance of a strongly colored solution. With regard to the further implementation of this product, see Examples 49 and 58 below. The chemical shift of this oxonium compound in the SO ^ solution was 6.35 ppm,

Example 4

Production of the monoxonium compound from pentabromotoluene and S wiss FeIT ri oxide

Br Br

C j) - CH, + 3 SO,

Br Br

+ SO-

SO ₂ OH

Br

If the method of Example 1 replacing the pentachlorotoluene with 48.7 g of 2,3,4,5,6-PentabromtciLuoi (F. 284-286 ⁰ C)

209838/124

was repeated, gas evolution and development of a dark green color were observed, which was caused by the formation of the Oxonium compound was accompanied by that in quantitative yield was obtained.

Example 5

Production of the monoxonium compound from pentafluorotoluene and sulfur trioxide

CH ₃ + 3 SO ₃

+ SO,

SO ₂ OH

The procedure of Example 1 was repeated except that the Pentachlortoluol by 18.2 g of 2,3,4,5,6-pentafluorotoluene (bp. 117-118 ⁰ C, n _D ²⁰ = 1.4023) was replaced and the reflux period was extended to 6 hours. The initially colorless solution turned deep red after 3 hours and the methyl protons at 2.44 ppm disappeared, after which the methylene protons appeared at 6.0 ppm and the acid proton at 9.58 ppm. The oxonium compound was hydrolyzed to benzyl alcohol as described in Example 68.

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Example 6

To-

Production of the inner / fcentachlorobenzal bisCdisulfoxonium dihydroxide salt from pentachlorotoluene and sulfur trioxide

Cl

+ 6 SUN

+ 2 SO,

The procedure of Example 1 was repeated, this time the reflux period of the sulfur trioxide being extended to 24 hours became. After this period of time, 398.2 g of reaction product were obtained, which indicates a weight loss of 13.2 g, which corresponds to the evolution of 0.2 moles of sulfur dioxide. After distillation of the excess sulfur trioxide, 313 g of material were obtained, which corresponds to 931 of theory. After stripping the Reaction mixture under the vacuum of a water aspirator resulted in a further weight loss of 22 g and it became 61.1 g isolated of the dioxonium compound, which corresponds to a practically quantitative yield. The identification of the dioxonium compound was made by nuclear magnetic resonance showing two peaks at 8.9 and 10.15 ppm and quantitative analysis of them Hydrolysis products comprising 4 molar equivalents of sulfuric acid and 1 molar equivalent of pentachlorobenzaldehyde (see Example 33). the Formation of sulfur dioxide and the solid product in quantitative yields is only possible with the stoichiometry given above compatible.

209838/1243

Example 7

Preparation of the dioxonium compound from pentabromotoluene and Sulfur trioxide

Br Br

Br Br

Br Br

₃ + 6 SO ₃ 7 Br

Br Br

CH (OI + 2 SO ₂

^x so ₂ oh / ²

The procedure of Example 6 was repeated except that the Pentachlortoluöl was replaced with 48.7 g of 2,3,4,5,6-pentabromotoluene (F. 284-286 ⁰ C). The dioxonium compound was identified by the elemental analysis of its hydrolysis products, which comprised 4 moles of sulfuric acid and 1 mole of pentabromobenzaldehyde (cf. Example 35), and by its formation in quantitative yield according to the stoichiometry given above.

Example 8

Preparation of the inner bis-pentachlorobenzal (chlorosulfonyl) sulfoxonium hydroxide (disulfoxonium hydroxide) salt from pentachlorobenzyl chloride and sulfur trioxide

Cl

CH ₂ Cl + 5

SO,

Cl

Cl

+ so.

Cl

The procedure of Example 3 was repeated, this time extending the heating period to 24 hours. After stripping of the excess sulfur trioxide and after hydrolysis

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- 23 -

Dioxoniumverbindung the formed 4 moles of sulfuric acid, 1 mole of hydrochloric acid and 1 mol Pentachlorbenzaldehyd (F. 201-203 ⁰ C)

Example 9

. . To-

Preparation of the inner / 2,3,4,5-tetrachloro (p-phenylenedimethylene) bis (disulfoxonium dicydroxide) salt from 2,3,5,6-tetrachloro-pxylene and sulfur trioxide

Cl Cl

- CH ₃ + 6 SO ₃
Cl Cl

The procedure of Example 1 was repeated except that the Pentachlortoluol was replaced by 24.4 g of 2,3,5,6-tetrachloro-p-xylene (F. 218-219 ⁰ C). The oxidation of xylene was evidently faster than that of toluene, which was indicated by the violence of the evolution of sulfur dioxide when the solution, purple from the radical cation, was refluxed. After a reflux period of 0.5 hour only 5% of the radical cation remained in solution containing 95% of the dioxonium compound, which was characterized by the nuclear magnetic resonance proton peaks at 6.36 and 9.73 ppm in the correct ratio of 2: 1. After the excess sulfur trioxide had been distilled off, 93Ί was converted and the recovery and isolation of the dioxonium compound gave a 93% yield. In addition to the nuclear magnetic resonance data given above, the new product was also characterized by quantitative analysis of its hydrolysis products, which comprised 4 molar equivalents of sulfuric acid and 1 molar equivalent of tetrachloro-p-xylene diol, as well as its addition derivatives (cf. Examples 41 and 47).

209838/1243

Example 10

Production of the dioxonium compound from 2,4,5,6-tetrachloro-mxylene and sulfur trioxide

Cl Cl

■ ö- CH ₃ Cl

+ 6 SUN

-> egg

Cl

¹ Γ \

CH ₂ -O ^ ³ ₊ 2 SO ₂ SO-OH

CH ₂ Cl

O ₃ S SO ₂ OH

The procedure of Example 9 was repeated except that p-isomer was replaced by 2,4,5,6-tetrachloro-m-xylene (F. 220-222 ⁰ C). The oxidation of the chlorocarbon occurred easily and was practically complete after a 1 hour reflux period when the nuclear magnetic resonance of the purple colored solution reflected the absence of the starting material and the presence of only 2.51 of the radical cation (chemical shift at 4.68 ppm downfield from the Reference substance tetramethylsilane) and the presence of the dioxonium compound in an amount of 97.5% (indicated by the chemical shifts at 6.40 and 9.8 3 ppm in the correct ratio of 2: 1). The further identification of the new compound was carried out by elemental and spectral analysis of its hydrolysis products, which after stripping off the excess sulfur trioxide comprised 4 moles of sulfuric acid and by the formation of 1 mole equivalent of tetrachloro-m-xylene diol (cf. Examples 42 and 51).

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Example 11

Preparation of the dioxonium compound from 3,4,5,6-tetrachloro-oxylene and sulfur trioxide

+ 6 SUN.

Cl

Cl

Cl Cl

SO

A. ^ * CH ₉ -O-SO ₀ OH

Mk

+ 2 SUN.

CH _? -O®-SO ₉ OH

^L ι ²

The procedure of Example 9 was repeated, this time replacing the p-isomer with 3,4,5,6-tetrachloro-o-xylene (F. 226 ^ · 228 ^ 5 ° Ο) The formation of the radical cation and the dioxonium compound occurred easily, which is reflected in the immediate development of a deep purple solution and the copious evolution of sulfur dioxide on heating. Identifying the The dioxonium compound was carried out as in the previous examples, except that only 3 molar equivalents of sulfuric acid were formed during the hydrolysis were in addition to 1 molar equivalent of the cyclic sulfate of tetrachloro-o-xylene diol (see. Example 31). The presence of the Dioxonium compound of the structure given above was determined directly by nuclear magnetic proton resonance, which the benzyl protons identified by a singlet at 6.32 ppm and the acid protosnene at 9.99 ppm in the correct 2: 1 ratio.

20.9838 / 1243

Example 12

Preparation of the dioxonium compound from 2,3,5,6-tetrabromo-p- »Xylene and sulfur trioxide

Br Br Br Br

SO ₀ OH Br Br

The procedure of Example 9 was repeated except that the tetrachloro compound by 42.2 g of the corresponding 2,3,5,6-tetrabromo-p-xylene (F. 251.5 to 252.8 ⁰ C) was replaced. The oxidation of the chlorinated hydrocarbon occurred easily, which was shown by the formation of a deep blue-green slurry, an indication of radicals, and by the development of sulfur dioxide. The nuclear magnetic proton resonance of the sulfur trioxide solution showed the absence of the starting material (due to the lack of methyl protons at 2.79 ppm) and the presence of the dioxonium compound in an amount of 98% due to the presence of the benzyl protons at 6.66 ppm after only 1 hour of reaction time and the acidic protons at 9.96 ppm in the correct ratio of 2: 1 and the presence of only 2% of the radical species through a peak at 4.74 ppm. After hydrolysis of the highly reactive dioxonium compound, a dark, solid product was obtained, the 4 mol equivalents of sulfuric acid, detected by titration, and 1 mol equivalent of 2,3,5,6-tetrabromo-p-xylene-1,4-diol (cf. Example 29 as well as Examples 44 and 45) provided.

209838/1243

Example 13

Preparation of the dioxonium compound from 2,4,5,6-tetrabromo-m-xylene and sulfur trioxide

Br ■

Br Br

CH ₃ + 6 SO ₃

+ 2 SUN.

@ /

CH ₂ Br

SO ₂ OH

O ₃ SO

SO ₂ OH

When the procedure of Example 12 was applied on 2,4,5,6-tetrabromo-m-xylene (F. 251-252 ⁰ C), to give the corresponding Dioxoniumverbindung, which by its isolation as a reactive solid material in quantitative yield as well as by their hydrolysis, which in turn gave quantitative yields of 4 molar equivalents of sulfuric acid and 1 molar equivalent of 2,4,5,6-tetrabromo-m-xylene-1,3-diol (cf. Example 30).

Example 14

Preparation of the dioxonium compound from 2,3,5,6-tetraiodo-p-xylene

and sulfur trioxide

CH ₃ + 6SO ₃

O-CH.

HO ₃ S

+ 2 SUN.

SO ₂ OH

When repeating the procedure of Example 9 with 61.0 g of 2,3,5,6-tetraiodo-p-xylene (F. 245-247 ⁰ C) in place of the tetrachloro analogue to give a slight oxidation of the Jodkohlenwasserstoffs and the formation of Dioxoniumverbindung in quantitative yield.

2 0 9838/1243

Example IS

Preparation of the dioxonium compound from 1,3,5,7-tetrabromo-2,6-dimethy! Naphthalene and sulfur trioxide

Br

+ 6 SUN

Br

SO ₂ OH + 2 SO ₂

Br

SO ₂ OH

If the method described in Example 12 was repeated, replacing the Tetrabromxylols by 47.2 g of 1,3,5,7-tetrabromo-2,6-dimethylnaphthalene (F. 226-229 ⁰ C), the easy formation of Dioxoniumverbindung occurred in the manner described in the previous examples.

Example 16

Preparation of the inner 2nd, 4,6-tribromo-s-phenenyl-tris (methylene) tris ^ disulfoxonium-trihydroxide salt from 2,4,6-tribromomesitylene and sulfur trioxide

+ 9 SUN,

Br

^S0 2 ^0H

+ 3SO,

SO ₂ OH

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The procedure of Example 12 was repeated except that the tetrabromo-p-xylene was replaced with 35.7 g of 2,4,6-Tribrommesitylen (F.215-217 ⁰ C). Very slight oxidation of the bromohydrocarbon occurred with vigorous evolution of sulfur dioxide, which led to the formation of the trioxonium compound in quantitative yield.

Example 17

Preparation of the dioxonium compound from 2,3,5,6-tetrachloro-pxylene-1,4-diol and sulfur trioxide

Cl

Cl

CH ₂ OH +

HO ₃ S

Cl

° 3 ^S l θ

O-CH

Cl

SO ₂ OH

27.6 g of 2,3,5,6-tetrachloro-p-xylene-1,4-diol dissolved in 100 ml (197 g) of liquid sulfur trioxide without evolution of sulfur dioxide, which only started after 3 hours of refluxing. Obtained after stripping off the excess sulfur dioxide the dioxonium compound which was identical to the compound obtained in Example 9 was obtained.

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Example 18

Preparation of the internal 2,3,5,6-tetrachloro (p-phenylenedimethylene) bis / (chlorosulfonyl) sulfoxonium-7-dihydroxide salt from α, α'-2,3,5,6 · hexachloro-p-xylene and sulfur trioxide

Cl Cl

Cl Cl

O ₃ S.

CICH, - <(I) -CH ₂ Cl + 4SO ₃ > O-CH ^ -i! J> - CH, O '

ClO ₂ S ^

Cl Cl

Cl Cl

The procedure of Example 3 was repeated except that the Pentachlorbenzylchlorid g α by 31.3, α ^f -2,3,5,6-hexachloro-p-xylene (F. 179-181 ⁰ C) was replaced. Although a deep purple solution was formed, no evolution of sulfur dioxide occurred. The deep purple component of the reaction mixture was identified as a benzyl radical by its nuclear magnetic resonance peak at 4.69 ppm, while the dioxonium compound was identified by its chemical shift at 6.41 ppm and by its hydrolysis in quantitative yield with the formation of 4 molar equivalents of sulfuric acid, 2 molar equivalents of hydrochloric acid and 1 Molecular equivalent of 2,3,5,6-tetrachloro-p-xylene-1,4-diol (see Example 69) was identified.

Example 19

Preparation of the dioxonium compound from α, 0'-3,4,5,6-HeXaChIOr-O-

xylene and sulfur trioxide

CH ₂ Cl

CH ₂ Cl

+ 4 SUN

CH ₂ -O.

CH ₂ -O

^S0

SO ₂ Cl. SO ₂ Cl

SO

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When the procedure of Example 3 α g to 31.3, α'-3,4,5,6-hexachloro-o-xylene (F. 92-92.5 ⁰ C) was used to obtain an intensely purple solution however, there was practically no evolution of sulfur dioxide even after refluxing for 3 hours. The intervening biradical was identified by its nuclear magnetic resonance peak at 4.65 ppm (it was present in the reaction mixture in an amount of about 8 to 101), while the dioxonium compound (90 to 921 of the reaction mixture) had a chemical shift of its protons at 6, 31 to 6.33 ppm. After stripping off the excess sulfur trioxide, the dioxonium compound was obtained in the form of a dark yellow viscous oil in'quantitative yield (63.5 g) and further identified by its hydrolysis, the 5 molar equivalents of sulfuric acid, 2 molar equivalents of hydrochloric acid and 1 molar equivalent of the cyclic sulfate of 3 , 4,5,6-tetrachloro-o-xylene-1,2-diol (see Example 32).

Example 20

Preparation of a transition oxonium compound from 2,3,4,5,6-pentachloroethylbenzene and sulfur trioxide

CH ₂ CH ₃ + SO ₃

Cl

Cl

The procedure of Example 1 was repeated, this time the pentachlorotoluene by 27.8 g (0.1 mol) of 2,3,4,5,6-pentachloroethylbenzene was replaced. The oxidation of the chlorinated hydrocarbon showed itself in the formation of the colored (deep purple) radical cation, through the development of sulfur dioxide and in the hydrolysis experiment (cf. Example 62).

209838/1243

Although the transition oxonium product of this experiment was not isolated, its structure can be deduced from the reactants and the product of Example 62 below. The material equilibrium, based on the evolution of SO ₂ , also confirmed the formation of the oxonium salt of the formula given above.

The following examples are intended to demonstrate the usefulness of the invention Oxonium compounds for the preparation of various new and known halogen-containing compounds in simple Explain reactions and in high conversions (conversions).

Example 21

SO ₂ OH

Production of the sodium salt of pentachlorobenzyl hydrogen sulfate

Cl Cl

3NaOH + H ₂ 0-> Ct ^ jVcH ₂ OSO ₂ ONa. 1 / 2H _? 0

Cl Cl

Na ₂ SO ₄ .7H ₂ O

The oxonium salt prepared in Example 1 was added slowly and with cooling to 1 liter of a mixture of 75 parts by volume of water and 25 parts by volume of ethyl alcohol. After filtering, 200 ml of a 1.0 η aqueous sodium hydroxide solution was added to the resulting solution, whereby a white crystalline salt was precipitated from the solution, which was identified as the above-mentioned title compound by elemental analysis and nuclear magnetic resonance. The nuclear magnetic resonance in dimethyl sulfoxide (DMSO) showed a methylene singlet at 5.05 ppm (region 2) and a water peak at 3.30 ppm (region 1).
Analysis for C ₇ II ₂ Cl ₅ NaO ₄ S. 1 / 2H ₂ O

Calculated: C 21.5; H 0.77; Cl 45.3; S 8.2 Measured values: 21.6; 0.8; 43.2; 8.51

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Example 22

Production of the ammonium salt of pentachlorobenzyl hydrogen sulfate

Cl Cl

Cl Cl

Cl Cl

^4NH

sa ₂ ci

₂ so ₄

Cl Cl

^NH 4 ^C1

The procedure of Example 21 was repeated, this time the reaction product obtained in Example 3 being concentrated aqueous ammonium hydroxide solution was added. The title compound which crystallized out was purified by filtration in 42% conversion isolated and by elemental analysis and by their nuclear magnetic proton resonance spectrum identified. Nuclear magnetic resonance (in DMSO) showed a methylene singlet at 5.09 ppm and a broad band at 7.1 to 7.4 ppm, respectively the protons of the ammonium cation,

Analysis for C ₇ H ₆ Cl ₅ NO ₄ S.! / 2H ₂ O:

Calculated: C 21.3; H 1.8; Cl 44.2; N 3.7; S 8.9 Measured values: 21.7; 1.8; 45.8 3.6; 8.8i

Example 23

Production of 2,3,4,5,6-pentachlorobenzyl alcohol

^S0

CH ₂ O + 2H ₂ O

Cl Cl

cH ₂ OH +

The light green solid residue obtained by repeating the process according to Example 1 was added to 500 ml of water and

2Q9838 / 12A3

then the resulting white aqueous slurry was refluxed for 15 minutes. After filtering, a white, powdery material was obtained which, after filtering off, washing and drying, had a weight of 26.6 g. It was purified by refluxing 150 ml of glacial acetic acid containing a trace of sulfuric acid for 20 minutes and filtering off a small amount (2.7 g) of insoluble material identified as follows. The excess acetic acid was distilled off from the filtrate and the solid residue obtained was refluxed for 30 minutes with 200 ml of a 10% methanolic potassium hydroxide solution. The reaction mixture obtained was poured into water and the solid precipitate was filtered off. After washing with water and subsequent drying gave 24.5 g of pure 2,3,4,5,6-Pentachlorbenzylalkohol, F. 195.0 to 196.5 ⁰ C, which corresponds to a yield of 9U. This structure was confirmed by the infrared spectrum and the nuclear magnetic resonance spectrum in comparison with an authentic sample and by the mixed melting point. A dilute DMSO solution of the test sample showed a doublet at 4.74 ppm, which corresponds to the benzyl protons, and a triplet at 5.5 ppm (at 54 ° C.) and at 5.39 ppm (at 60 ^° C.), which corresponds to the hydroxyl protons is equivalent to. The cause of the multiplicity is the mutual coupling with a J value of around 5.5 Hz. The two multiplets were present in the correct ratio of 2: 1 of the corresponding areas (areas).

The 2.7 g of acetic acid found in the insoluble material was purified by trituration with hot toluene into a soluble and insoluble ^1. Faction separated. The hot toluene solution yielded on cooling 1.75 g of a white crystalline material by the infrared spectrum, nuclear magnetic resonance and mixed melting point with an authentic sample as Decachlordibenzyläther, F. 223-225 ⁰ C, was identified. Its infrared spectrum, determined in tetrachlorethylene and carbon disulfide solutions, showed

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strong maxima at 1365, 1232, 1125, 1078 and 682 cm. Its nuclear magnetic Proton resonance spectrum, determined in a deuterochloroform solution, had a singlet at 4.92 ppm.

The 0.5 g of the hot toluene insoluble material was identified by infrared spectrum, nuclear magnetic resonance spectrum and mass spectrum as a mixture of 0.25 g 2,3,4,5,6,2 ', 5', 4'-5 ', o'-Decachiordiphenylmethan, 0.12 g of 2,4,5,6,2 ^1, 3', ^f 4, ^f 5, 6'-Nonachlor-3-methyidiphenylmethan and 0.13 g of 2,3,5, 6,2 ', 3', 4 ', 5', 6'-nonachloro-4-methyldiphenylmethane. ,

Almost identical results were obtained when the residues of Examples 2 and 3 were worked up according to the procedure given in Example 23.

Example 24

Preparation of the disodium salt of 2,3,5,6-tetrachloro-p-xylene ^ a, ct'-diol dihydrogen sulfate

Cl Cl Cl

+ 6NaCl + 2H ₂ O-> NaO ₃ SOCH ₂ - / (^) Y-CH ₂ OSO ₃ Na. 2H ₂

₂ H) {

^{C1 ei} Cl Cl + 2Na ₂ SO ₄ + 6HCl

If that after stripping off the unreacted sulfur trioxide When the dark residue obtained in Example 9 was added to a mixture of ice and a saturated sodium chloride solution, a white solid formed, which appeared after filtering off and drying the weight of the air was 24.1 g. After recrystallization from water, an analytically pure sample of the above

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benen title compound with a characteristic singlet of the benzyl protons at 5.13 ppm and the water protons at 3.40 ppm in the nuclear magnetic proton resonance spectrum produced in DMSO solution.

Analysis for

Calcd .: C 18.64; H 1.56; Cl 27.41; H ₂ O 7.01 Measured values: 19.0; 1.4; 28.7; 7.31

Example 25

Production of 2,3,5,6-tetrachloro-p-xylene-ct, a'-diol

HO ₃ S '

Cl

-CH

Cl

Cl

HIGH

CII ₂ OH +

Cl

When the dioxonium compound obtained in Example 9 was added to ice and the resulting white slurry was refluxed with an equal amount of a 20% hydrochloric acid aqueous solution, an easily filterable precipitate was obtained, which was washed with water and dried. After recrystallization from dioxane gave white crystals, mp 226-23O ⁰ C, with authentic 2,3,5,6-tetrachloro-p-xylene-a, ^I-diol ct were identical, as evidenced by mixed melting point, infrared spectrum and nuclear magnetic resonance spectrum was confirmed. The infrared spectrum of the pure diol carried out in "Fluorolube" and mineral oil gauze had maxima at 3200, 1350, 1240, 1185, 1130, 1035, 1018, 950, 828, 690, 650 and 525 cm ~. The nuclear magnetic resonance spectrum of a DMSO solution showed the methylene protons in the form of a doublet at 4.67 ppm and the hydroxyl proton at 5.32 ppm in the form of a triplet.

209838/12 A3

In another work-up, the residue from Example 9 was obtained one directly the diol. This consisted of adding the dark residue to ice and adding the resulting slurry on top of one Steam bath heated until hydrolysis of the glyodrogensulfate ester essentially terminated xvar. After filtering off the somewhat gray-white Precipitation and after washing the same with water were obtained in almost quantitative yield without recrystallization the pure diol.

Example 26

Preparation of the disodium salt of 2,4,5,6-tetrachloro-m-xylene-a, a ¹ -diol dihydrogen sulfate

+ 6NaOH

■ »ei

SO ₂ OH

° 3 ^S - °

© y ^CH 2 ^C1
θ? /

SO ₂ OH

CH ₂ OSO ₃ Na + 2Na ₂ SO ₄

SO ₃ Na

When the dark, almost black residue of Example 10 is added to ice and with 400 ml of an ice-cold,! above sodium hydroxide solution had been neutralized, a clear solution of the sodium salt of the sulfuric acid ester was obtained. After evaporation of the whole Free water was obtained 104.8 g of a pale pink colored solid, whose nuclear magnetic proton resonance spectrum in a DMSO solution showed that it was mainly the title compound acted as evidenced by the presence of the benzyl protons at 5.07 ppm (the reaction mixture which, after stripping of the water, contained, as by the stoichiometry indicated, also 2 molar equivalents of hydrated sodium sulfate). To

209838/1243

the elution with hot methanol (1000 ml) left a large part of the inorganic salt, but because of the high solubility of this compound iv Kasser no analytically pure organic sample could be isolated.

Example 27

Preparation of 2,4,5,6-tetrachloro-m-xylene-a, a'-diol

Cl Cl

4H ₂ O HCl

Cl-

θ /

CH ₂ Cl

CII ₂ OH +

HIGH

C) ₃ SO

SO ₂ OH

The procedure of Example 26 was repeated and the solid product (104.8 g) was dissolved in 325 ml of water and acidified with 110 ml of concentrated hydrochloric acid after evaporation of the volatile inorganic substances left 132 g of residue, the after washing with water, filtering and drying 22.3 g or SI% of pure 2,4,5,6-tetrachloro-m-xylal-ct, a'-diol, mp 228-230 ° C, yielded, its identity is confirmed by its infrared spectrum and its nuclear magnetic resonance spectrum as well as by the mixed melting point His infrared spectrum (carried out in Nujol-Mull) showed Maxima / 3250, 1430, 1350, 1310, 1265, 1250, 1110, 1015, 965, 895, 652,

_1

542 and 475 cm, the nuclear magnetic resonance spectrum carried out in DMSO contained the benzyl hydrogen atoms in the form of a Doublets at 4.72 ppm and the hydroxyl protons in the form of a triplet at 5.37 ppm.

209838/1243

Example 28

Production of the disodium salt of 2,3,5,6-tetrabromo-p-xylene-a, a ^l diol-bis (hydrogen sulfate)

Br · Br

Br Br

Br Br + 6NaOH -> NaO ₃ SOCH ₂ -ZTjV

Br Br

cH ₂ OSO ₃ Na +

The dark solid residue obtained in Example 12 became simultaneously with the addition of an ice-cold 1 oily aqueous sodium hydroxide solution in added small portions to ice water, which kept the pH slightly on the alkaline side. All in all 360 ml of base were required. After filtering and then Washing with ice water gave a filter cake which, after drying, had a weight of 60.6 g, which corresponds to about 92% of the theoretical amount) the nuclear magnetic resonance spectrum confirmed this structure by the correct chemical shift of the benzyl protons at 5.23 ppm (DMSO solution).

Example 29

Production of 2,3,5,6-tetrabromo-p-xylene-a, a ^f -diol

Br Br

Br Br

Br Br

HIGH

: CII ₂ OH +

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The solid residue obtained in Example 12 after stripping off the sulfur trioxide was added to an excess (500 ml) of ice water and the temperature was allowed to rise gradually. The resulting slurry was mechanically stirred and refluxed for 1/2 hour. After filtering and thoroughly washing the filter cake, 41.2 g of a pale gray-white product were obtained after drying, which corresponds to a yield of 91%. After recrystallization from dioxane to give gray-white crystals, mp 248-252 ⁰ C, the infrared spectrum (maxima in nujol mull at 3280, 1330, 1257, 1237, 1162, 1096, 1020, 983, 945, 812, 648, 575, 545 and 490 cm ") and nuclear magnetic resonance spectrum (benzyl protons at 4.93 ppm, hydroxyl protons at 5.23 ppm in DMSO solution) confirmed the structure given above.

Analysis for C ₈ H ₆ Br ₄ O ₂ : Calculated C 21.17; H 1.33; Br 70.44

found 20.8; 0.9; 70.0%

Example 30

Preparation of 2,4,5,6-tetrabromo-m-xylene-a, a'-diol

Br

SO.

Br

Br

HIGH

CH ₂ OH

When repeating the procedure of Example 29 with the residue of Example 13 to give the title compound in 93liger yield, mp 248-252 ⁰ C. IR maxima in nujol mull were at 3280, 1525, 1340, 1310, 1260, 1225, 1212, 1196, 1068, 1032, 1028,

996, 965, 952, 838, 625, 603 and 487 cm and the nuclear magnetic

2Q9838 / 1 243

The resonance spectrum showed the benzyl protons at 4.95 ppm in DMSO solution.

Analysis for CgH ₆ Br ₄ O ₂ : Calculated C 21.17; II 1.33; Br 70.44

found 21.0; 1.1; 69.91.

Example 31

Preparation of the cyclic sulfate of 3,4,5,6-tetrachloro-o-xylene-α, α'-diol

SO ₃ H

CH ₂ -O-SO ₃ H

so.

+ 2H ₇ O

Cl

Cl

S. + 3H ₂ SO ₄ CH ₂ - (T 0

The dark, pasty residue from Example 11 was added to ice in portions. The reaction was strongly exothermic and gave a rusty colored product which was filtered off and washed with water (or with a dilute aqueous sodium hydroxide solution)> until it was acid-free. The product had a weight of 32.0 g, which corresponds to 951 of theory. After recrystallization from trichlorethylene zxveimaligen yellow crystals, mp 186 to 188.5 ⁰ C obtained whose structure was confirmed as a typical sulfate by elemental analysis, molecular weight determination and the infrared and nuclear magnetic ResonaiEspektren. The infrared maxima in C ₂ Cl ₄ and CS ₂ solutions occurred at 1420, 1380, 1330, 1308, 1278, 1212, 1198, 1176, 1031, 1004, 975, 950, 840, 658, 650, 645, 574, 566 , 525, 514, 484 and 450 cir. ™; the nuclear magnetic resonance spectrum (in deuterochloroform solution) showed a singlet at 5.65 ppm field down from tetramethylsilane.

209838/1243

Analysis for C ₃ II ₄ Cl ₄ O ₄ S (MW 338.01) calcd. C 28.43; H 1.19; Cl 41.96; S 9.49 (MW 338 by vapor phase osmometry in tetrahydrofuran as solvent) found C 28.8; H 1.2; Cl 43.0; S 9.81.

In the work-up by neutralization with a sodium hydroxide solution of p, Asten-like solid supplies of Example 11 occasionally also lower amounts of Tetrachlorphthalat, F. 214-216 ⁰ C, a known compound, which by mixing with the cyclic sulfate, by the presence of a singlet at 5 , 12 ppm in their nuclear magnetic resonance spectrum, which is due to the benzyl protons ", could be easily identified.

Example 32

Preparation of the cyclic sulfate of 3,4,5,6-tetrachloro-oxylene-α, α'-diel

+ 2HCl + 3H ₉ SO

After adding the distillation residue from Example 19 to ice or to an ice-cold dilute aqueous sodium hydroxide solution the cyclic sulfate described and identified in Example 31 was obtained.

2Q9838 / 1243

Example 33

Manufacture of pentachlorobenzaldehyde

Cl

Cl

Cl

Cl

3H ₂ O

σιο +

By adding the dark dioxonium compound of Example 6 to 500 g of ice and then briefly heating to 85 ° C. and filtering the warm slurry, followed by washing with water and drying, 26.6 g of a yellowish, powdery material were obtained, which was like the Gas chromatography, nuclear magnetic resonance and infrared spectroscopy showed pure pentachlorobenzaldehyde. After recrystallization from chlorobenzene, a pale yellow crystalline material was obtained, mp 201-2O3 ° C., which was not reduced by the addition of authentic pentachlorobenzaldehyde. Its infrared spectrum, performed in tetrachlorethylene and carbon disulfide solution, had characteristic maxima at 2850, 1715, 1525, 1345, 1310, 1232, 1220, 1190, 1128, 946, 692, 659 and 522 cm; its nuclear magnetic resonance spectrum showed the aldehyde proton in the form of a singlet at 10.32 ppm (in deuterochloroform solution) or at 10.26 ppm (in hexadeuterodimethyl sulfoxide solution).

Example 54

Manufacture of pentachlorobenzaldehyde

απ SO t ό

/ \ Q — oO—.

"~ ^ 2) ~ ^c 4-so ₂

Cl Cl. so, ⁹

CHO + HCl +

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In a similar work-up to that of the previous example unta: Use of the residue from Example 8 was obtained
one again pentacnlorobenzaldehyde, m.p. 201-203 C, in practical
quantitative conversion '. The product was not even contaminated by traces of pentachlorobenzoic acid,

Example 35. '.

Manufacture of pentabromenzaldehyde

0-SO ₃ H

0-SO ₃ H

+ 3H ₂ O

Br

CHO + 4H ₂ SO ₄

Br

By adding the dark residue from Example 7 to 500 g of ice
and then briefly heating to 75 ^° C., filtering, washing

and drying gave 49.0 g of a light brown powder in which

' ^open

as gas chromatography showed, it was 97 % Hig / pure

bromobenzaldehyde acted. The yield was accordingly 94.5%. After recrystallization from chlorobenzene, the color was improved
to give the pure aldehyde as a bright kremartig colored, fine-crystalline material, F., which was identified by infrared spectrum and nuclear magnetic resonance spectrum 281-283 ⁰ C. Even the crude product was very pure and free from pentabromobenzoic acid. The infrared analysis of the pure aldehyde in C ₂ Cl and CS ₂ solutions showed maxima at 2840, 1720, 1300, 1250, 1170, 1068,
896 and 558 cm "; its nuclear magnetic resonance spectrum shows the single proton at 9.81 ppm in DMSO solution and at 9.13 ppm in
Hexadeuterobenzene solution.

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Example 56

Preparation of α, 2,3,4,5,6-hexachlorotoluene

Cl Cl. > Cl Cl

Cl Cl

+ 21I ₂ SO ₄

The slow addition, with cooling, of an excess (400 ml) of carbon tetrachloride to the oxonium compound prepared in Example 1 led to an exothermic reaction, which is accompanied by strong evolution of gas (phosgene and gaseous hydrochloric acid, good ventilation or, preferably, absorption of the emerging gases in a strong aqueous alkali solution recommended) was accompanied. After completion of the addition, the purple solution was heated to reflux temperature (76-8O ⁰ C) and 20 minutes held at this temperature. During this time, another amount of gas evolved. Solid, anhydrous sodium carbonate was added in small portions to the reaction mixture until the evolution of carbon dioxide ceased. The resulting dark yellow smear was filtered, washed with carbon tetrachloride and the solution was removed from the solvent on a rotary evaporator to give an amber colored liquid. This became pale yellow on addition to ice, filtered with suction and dried. Its structure was determined by the melting point (100-101 ⁰ C), of the infrared and nuclear magnetic resonance spectrum and the weight of 29.0 g _t corresponding to 98% yield, as α Pentachlorbenzylchlorid (2,3,4,5, 6-IIexachlortoluol ) identified. The infrared spectrum of the product prepared in tetrachlorethylene and carbon disulfide solution had maxima at 1355, 1302, 1272, 1240, 1128, 958, 926, 766, 698, 682, 608 and 495 cm ". The nuclear magnetic resonance spectrum showed the

f .. ■
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Benzyl hydrogen in the form of a singlet at 4.86 ppm in a deuterochloroform solution.

Example 57

Preparation of _α , 2,3,4,5,6-hexachlorotoluene

Cl Cl

• .so

+ HCCl ₃ + 2H ₂ O

SO ₃ H

Cl Cl

Cl Cl

CII ₂ Cl + CO + 2HCl + 2H ₂ SO ₄

After the slow addition of chloroform with external cooling The solid residue from Example 11 was obtained after refluxing for 15 minutes and after working up as in Example 36 in high yield (approx. 70 l) the title compound.

Example 38

Preparation of α, α, 2, 3,4,5,6-IIeptachlorotoluene

Cl

Cl Cl

CtICl

COC1 ₂ + 4H ₂ SO ₄

Cl

When repeating the procedure of Example 36 with the Received distillation residue from Example 6 instead of that of Example 1; nan the α, α, 2,3,4,5,6-IIeptachlorotoluene (Pentachlorbenzalciilorid), 'l ·', l! ü-119 ° C. Its in tetrachlorethylene and

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An infrared spectrum made from carbon disulfide solution Maxima on at 3045, 1540, 1352, 1278, 1232, 1227, 1127, 962, 776, 76 2, 712, 680, 614 and 506 cm "and its nuclear magnetic resonance spectrum showed a single peak in deutochloroform solution 7.55 ppm.

Example 59

Preparation of α-bromo-2,3,4,5,6-pentachlorotoluene

© / ^ ^bü 3 CII ₀ -O + 2CBr,

SO ₃ H

Cl

ClIBr + 3C ₂ Br ₂ Cl ₄

+ 2C0 ₂ + 3S0 ₂ + H ₉ S0 ₄

The procedure of Example 36 was repeated, this time one Solution of 35.0 g (0.11 mol) of carbon tetrabromide in 100 ml of tetrachlorethylene was used in place of carbon tetrachloride. When working up by the same procedure and after evaporation of the solvent gave 64.6 g of a yellow crystalline material which, as was later shown, was a mixture of α-bromo-2,3,4,5,6-pentachlorotoluene (pentachlorobenzyl bromide) and 1,2-dibromotetrachloroethane depicted. The yield of these materials was 94.55. After repeated recrystallization Ethanol, the benzyl bromide was obtained as the less soluble component, m.p. 109.5-112.5 ° C, which was obtained by mixing with an authentic Sample was not lowered. That in tetrachlorethylene and carbon disulfide solution produced infrared spectrum showed maxima at 1535, 1430, 1326, 1291, 1236, 1225, 1122, 955, 887, 871, 758, 732, 695, 678, 650, 558 and 485 cm "; its nuclear magnetic resonance spectrum in deuterochloroform solution had a singlet at 4.74 ppm.

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Analysis for C ₇ H ₂ BrCl ₅ : Calculated C 24.49; H 0.58; Br 23.28; Cl 51.64

found 22.4; 0.6; 23.2; 51.61.

The recrystallization nut liquor was evaporated to dryness and the residue was dissolved in pentane, treated with activated charcoal, filtered and recrystallized from methanol and white crystals, F; 138 ⁰ C (decomposition). Its infrared spectrum showed maxima at 810, 760, 720, 636 and 615 cm " ¹ .

Analysis for C ₂ Br ₂ Cl ₄ (MW 325.67): C 7.38; Br 49.07;

(MG 330 by vapor pressure osmometry in chloroform solution)

found C 7.38; Br 45.81.

Example 40

Production of α-iodine-2,3,4,5,6-pentachlorotoluene

Cl Cl Cl Cl

J ₂ + CO + SO ₂ + H ₂ SO ₄

+ HCJ ₇ + -) Cl

The procedure of Example 36 was repeated, this time using a saturated solution of a slight excess of iodoform in methylene chloride instead of carbon tetrachloride; after a similar work-up, a pure sample of the title compound, namely pentachlorobenzyl iodide, was obtained in the form of pale yellow, shiny flakes which, after recrystallization from cyclohexane, had a melting point of 138.5-14.5.degree. The infrared spectrum had maxima at 1540, 1424, 1360, 1318, 1232, 1160, 1119, 1104, 953, 836, 756, 729, 678, 512 and 478 cm " ¹ , while the resonance of the benzyl protons in the nuclear magnetic resonance

209838/1243

Spectrum occurred at 4.65 ppm in deuterochloroform solution.

Analysis for C ₇ H ₂ Cl ₅ J: Calculated C 21.54; II 0.52; Cl 45.42; J 32.51

found 21, 6; 0.5; 45.4; 32.5%,

Example 41

Preparation of α, α ', 2,3,5,6-hexachloro-p-xylene

O-CH

»Ο,

CH ₂ -O + 2CCl ₄ + 4H ₂ O - ) SO ₃ H

Cl ei

CH ₂ Cl + COCH ₂ 2HCl + 4H ₂ SO ₄

The procedure of Example 36 was repeated using the paste-like residue of Example 9; there was obtained 30.3 g of yellow solids, the white after recrystallisation from carbon tetrachloride crystals, mp 179-182 ⁰ C, in a yield of 28.1 g delivered. The infrared and nuclear magnetic resonance spectrum, the elemental analysis and the mixed melting point showed that this reaction product was the title compound, which was obtained in 90% yield. The infrared spectrum showed maxima at 1436, 1372, 1362, 1269, 1251, 1147, 914, 837, 745, 685, 660, 632, 609, 490 and 460 cm and the nuclear magnetic resonance spectrum showed the benzyl protons in the form of a singlet at 4.89 ppm in deuterochloroform solution.

Analysis for C ₈ H ₄ Cl ₅ : Calculated C 30.71; II 1.29; Cl 68.0

found 30.6; 1.3; 68.2%.

209838/1 2 4 3

Example 42

Production of α, α ', 2,4,5,6-hexachloro-ni-xylene

Cl

CII ₂ -O

+ 2CCl ₄ + 41I ₂ O -) Cl

Cl

Cl

CII ₂ Cl + 2COCl ₂

ClCH ₂ Cl ^{+ 2HC1 + 4Ii} 2 ^SO 4

Repeating the procedure of Example 41 with the residue obtained in Example 10 gave the title compound, mp 136-138 ° C., in 92% yield. The infrared spectrum showed maxima at 1555, 1448, 1398, 1376, 1278, 1268, 1160, 1129, 1010, 932, 910, 906, 770, 752, 730, 682, 618, 608, 6O4, ₅ 540, 530, 446 and

-1

436 cm. Kernuic.gnetic resonance absorption at 4.86 ppm in CDC1 "-

Solution.

Analysis for CgH ₄ Cl ₆ : Calculated C 30.71; II 1.29; Cl 68.0

found 30.5; 1.3; 68.31.

Example 4 3

Preparation of α, α ', 3,4,5,6-hexachloro-o-xylene

Cl _v

^S0 3 ⁿ + 2CCl ₁ + 4H ₉ O -> SO ₃ H * ^l

Cl

Cl

CH ₂ Cl

_i
Iu

+ 2COCl ₂ + 2HCl

, + 4H-S0. l 2 4

209838/124 3

When the process according to Example 41 was repeated, in which the reaction was carried out with the product of Example 11 instead of with carbon tetrachloride, the title compound was obtained in 94% yield. After recrystallization from methanol gave the pure compound, F. 8 ⁰ 4 to 84.7 C. The infrared spectrum showed maxima at 2998, 2898, 1550, 1480, 1450, 1400, 1375, 1278, 1270, 1240, 1196, 1153, 951, 940, 890, 723, 716, 692, 612, 609, 532 and 462 cm "(carried out in C ₂ Cl. And CS ^ solutions); the nuclear magnetic resonance spectrum showed a peak in the form of a singlet at 4 , 85 ppm in deuterochloroform solution.

Analysis for

: Calculated C, 30.71; H 1.29; Cl 68.0 found. 30.7; 1.3; 67.8%.

Example 44

Preparation of 2,3,5,6-tetrabromo-a, a'-dichloro-p-xylene

Br

SO

CH ₂ -O + 2CC1 ₄ + 4H ₂ O ->

ClCH.

SO ₃ H

Br

2COCl

CH ₂ Cl

2HC1 + 4H £ ₉

The procedure of Example 41 was repeated using instead of Carbon tetrachloride the product of Example 12 was used. The title compound was obtained in almost quantitative yield,

F. 232-235 C. The infrared spectrum had maxima at 1435, 1350, 1330, 1265, 1257, 1134, 1104, 904, 740, 625, 597 and 544 cm "¹; the nuclear magnetic resonance spectrum showed" the benzyl protons in the form of a Singlets at 5.11 ppm ia deuterochloroform solution.

209838/1243

Example 45

Preparation of α, α ¹ , 2,3,5,6-hexabromo-p-xylene

SO.

, 0-CH ₂

OK. S.

Br

+ 2CBr ₄ -> BrCH ^

Br

Br

+ 3SO ₉ + H ₉ SUN. _Br 2 2 4

When repeating the previous example, but instead of of carbon tetrachloride an excess of carbon tetrabromide was added to the dioxonium compound was obtained in FIG 90% yield of the title compound, mp 267.5-270, 8 ° C. The characteristic Maxima of its infrared spectrum were at 1104, 868 and 638 cm ", the weakness of the bands was due to the low solubility attributed to the compound in infrared solvents. The nuclear magnetic resonance spectrum showed a singlet of the benzyl protons at 4.79 ppm in a CDCl, solution.

Analysis for CgII ₄ Br ₆ : Calculated C 16.52; H 0.70; Br 82.78

found 16.4; 0.6; 82.11.

Example 46

Production of 2,3,4,5,6-pentachlorodiphenylmethane

CH-O

Cl

Cl Cl

SO ₃ H

Cl

Cl

+ 2H ₂ SO ₄

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After adding the oxonium compound prepared in Example 1 to 200 ml of benzene with cooling and stirring and subsequent addition of water, separating the two layers and stripping off the excess benzene, 28.8 g of a light brown solid were obtained which were white after recrystallization from ethanol and hexane needles found 112.5 to 113.5 F. ⁰ C. show elemental analysis, infrared and nuclear magnetic resonance spectra indicated that it was the reaction product of the title compound · Pentachlordiphenylmethan. The yield was 83%, the infrared spectrum had maxima at 3075, 3052, 3022, 2928, 2840, 1601, 1542, 1495, 1450, 1438, 1360, 1352, 1337, 1310, 1282, 1230, 1180, 1118, 1112, 1072, 1038, 946, 884, 776, 726, 692, 678, 638, 618, 602, 540, 522 and 448 cm " ¹ in C ^ Cl. And CS ₂ solution; the nuclear magnetic resonance spectrum showed in CDCl" - Solve the methylene protons at 4.37 ppm in the form of a singlet and the aromatic protons at 7.18 ppm in the form of multiplets in the correct area ratio of 2: 5.

Analysis for C ₁₃ H ₇ Cl ₅ : Calculated C 45.85; H 2.07; Cl 52.07

found 45.9; 2.1; 52.11.

- Example 47

Production of 2,3,5,6-tetrachloro-a, a'-diphenyl-p-xylene

Cl Cl

Cl Cl

Cl Cl

Cl Cl

When the dioxonium compound prepared in Example 9 in portions and with cooling to an excess (200 ml) of benzene was added and the reaction mixture was taken up as in the previous example.

20983 8 / 1,243

was worked, 21.6 g of a yellow solid were obtained which, after crystallization from carbon tetrachloride, had a melting point
from 179.5 to 181, O had ^0C. The infrared and nuclear magnetic resonance spectra and the elemental analysis confirmed that this product had the structure of the title compound given above. The infrared spectrum (carried out in C ₉ Cl ₄ and CS ₉ solutions) showed maxima at 3075, 3052, 3022, 2922, 2835, 1600, 1498, 1452, 1430, 1390, 1370, 1282, 1250, 1158, 1133, 1100, 1072, 1029, 932, 883, 729, 693, 654, 618, 580, 524, 500 and 447 cm. In the nuclear magnetic resonance spectrum, the benzylic hydrogens in CDCl solution were found at 4.41 ppm and the aromatic protons at 7.20 ppm (in the form of multiples) in the correct area ratio of 2: 5.

Analysis for

: Calculated C, 60.60; H 3.53; Cl 35.87
found 60.7; 3.6; 35.7%.

Example 48

Production of 2-chloro-3-pentachlorophenylpropanoic acid

Cl

Cl -

CH ₂ -O + Cl ₂ C = CHCl + 3H ₂ O - * Cl - / (

SO ₃ H

Cl

Cl

Cl

CH-COOH + 2HCl

+ 2H ₂ SO ₄

The procedure of Example 1 was repeated and an excess of 100% was added to the obtained oxonium compound with cooling and stirring
ml) of trichlorethylene was added. After about 20 minutes of implementation
the mixture was measured in water and the excess solvent was separated from the organic phase in vacuo. 34.2 g of a white solid were obtained which, after Uw crystallization, had a melting point of 170-172.5 ° C. The infrared spectrum in mineral oil gauze had maxima at 1722, 1424, 1350, 1318, 1292,

209838/1243

1268, 1230, 1195, 1168, 1118, 1058, 956, 943, 928, 890, 775, 765, 724, 690, 680, 632, 628, 598, 514 and 497 cm " ¹ and the nuclear magnetic resonance spectrum in DMSO solution showed the benzyl protons in the form of a doublet at 3.66 ppm and the single Procon adjacent to the carboxyl group in perm of a triplet at 4.77 ppm, where J = 7 Hz.

Analysis for C ₉ H ₄ Cl ₆ O ₂ : Calculated C 30.29; II 1.13; Cl 59.63

found, 30.1; 1.1; 59.2%.

Example 49

Production of 2-chloro-3-pentachlorophenylpropanoic acid

Cl Cl

Cl ₂ C = CHCl + 4H ₂ O

Cl Cl

CH ₂ CH-COOH

^ + 3HCl + 2H-SO. Cl Cl ^{2 4}

To the oxonium compound obtained in Example 5, before the addition of 150 ml of trichlorethylene 10 ml of sulfuric acid added what was carried out under ice cooling. After working up as in the previous example, 35.6 g (in quantitative Yield) of the acid identical to that of the previous example.

Example 50

Production of 2,3,5,6-tetrachloro-p-benzene-bis (2-chloropropionic acid)

Cl

Cl

so ^{θ C1}

© / ^U 3 I.

CIi.0 + 2Cl, C = CClIi + 6H, O-CHCH -4 HOOC ₀

SO ₃ H

209838/1243

Cl

'-CH ₂ CHCOOH

When the dioxonium compound prepared in Example 9 was mixed with 20 ml of concentrated sulfuric acid and the mixture obtained was added to 100 ml of trichlorethylene and then stirred at room temperature for 1 hour and refluxed for a further hour, treated with ice, separated off, dried and excess solvent was removed by stripping under reduced pressure, 42.3 g of the title compound in einer.Ausbeute of 99%, which had a melting point between 240 and 25O ⁰ C with decomposition after recrystallization from o-chlorotoluene. The nuclear magnetic resonance spectrum carried out in hexadeuteroacetone showed the benzyl protons in the form of a doublet at 3.85 ppm and the neighboring proton in the form of a triplet at 4.88 ppm with a coupling constant of 8 Hz.

Analysis for

: Calculated C, 33.57; H 1.87; Cl 49.58 found. 33.5; 2.0; 47, H.

The implementation of the dioxonium compound with trichlorethylene is called Addition (or substitution) reaction, which in turn is a Oxonium compound (50A) according to the following equation gives:

Cl

_H0 / II

^H0 3 ^b ClCl

Cl Cl
(5OA)

Cl

CH, CH-C-O Cl Cl

The structure of the formula 5OA was determined by its nuclear magnetic resonance spectrum, that before their hydrolysis to the above in the title compound

i> named

dung / dipropionic acid was carried out. The nuclear magnetic Resonance spectrum of the compound of the formula 50A in a trichlara ethylene solution showed the benzyl protons in the form of a doublet

209838/1243

at 4.39 ppm, the neighboring single proton in the form of a triplet at 5.58 ppm with a coupling constant of 7 Hz and the acidic
Protons in the form of a singlet at 5.03 ppm. During hydrolysis
of the compound of the formula 50A to the title compound, the geminal chlorine atoms were converted into a carbonyl function with the formation of the final organic acid product.

Example 51

Production of 2,4,5,6-tetrachloro-m-benzene-bis (2-chloropropionic acid)

2Cl ₂ C = CHCl + 6H ₂ O -> Cl-

Cl

-CH ₂ -CH-COOII + 4HCl

CH.

Cl

Cl-CH-COOH

When the procedure of the above example with that obtained in Example 10 Dioxoniumverbindung was obtained in quantitative yield 42.9 g of the title compound, mp 196-199 ⁰ C. Its infrared spectrum (in Nujol mull) showed maxima at 1730, 1692, 1330, 1288,
1279, 1252, 1212, 1172, 1110, 965, 955, 929, 780, 750, 72O ₈ 700 »
603, 554 and 470 cm "and its performed in hexadeuteroacetone
Nuclear magnetic resonance spectrum showed benzyl protons in the form of a doublet at 3.78 ppm, the neighboring single proton in the form of a triplet at 4.83 ppm with a coupling constant of 8 Hz.

Analysis for

: Calculated C, 33.57; H 1.87; Cl 49.58 gcf. 33.9; 2.10; 49.61.

209838/1243

Example 52

Production of 3,4,5,6-tetrachloro-o-benzene-bis (2-chloropropionic acid)

Cl

Cl

SC-

: h ₂ -o-so ₃ h

Θ +2 Cl ₂ C = CHCl + 6H ₂ O - ^

CH ₂ -O-SO ₃ II

so.

Cl

Cl I

CIl ₂ -CH-COOiI

+ 4HCl + 41I ₉ SO. ClI, -CH-CCOII

Cl

When repeating the procedure of Example _1, however, the Dioxoniumverbindung 5O obtained in Example 11 was used in which, to obtain 27.0 g or 631 of the title compound, mp 250-25 2 ⁰ C to ·· crystallized from diethyl ether. Their infrared spectrum, made in mineral oil gauze, had maxima at 1750, 1724, 1370, 1308, 1268, 1225, 1172, 1150, 1055, 942, 305, 745, 693, 663, 620 and

-1

538 cm and its nuclear magnetic resonance spectrum, the complex showed 4 benzyl protons at 3.8 ppm, the neighboring protons at 4.7 ppm.

Analysis for C. ^ Ii C1.0 .: her, C 33.5 7; H 1.8 7

ge f .. 33.7; 1.9%.

Example 53

Production of 2,4,5,6-Te t r from rom-m-be η :: ο 1-1 > is (2-chloropropionic acid)

+ 2 Cl ₇ C = CHCl + 6

209838/1 243

Br

Br

ClClI I

Br

Cl

Using the procedure described in Example 50 on the dioxonium compound obtained in Example 13 was obtained 36.4 g of the title compound, m.p. 205-212 C, which corresponds to a yield of λοη 60%.

Example 54

Production of 2,3,5,6-tetrachloro-p-benzene-bis (2-chloropropionic acid)

^C1

^0Cii 2 \ O / ^CH 2 "°

Cl

Li

^{2 C1} 2 ^{C = CHC1}

_{cl C1}

+ 6IiCl +

In repeating the procedure of Example 50 with that in Example 18 obtained dioxoniura compound was obtained in practically quantitative yield 42.0 g of the title compound, which with the in Example 50 was identical to the product described,

Example 55

Production of 2,2-dichloro * -3-phenylpropä.nsäure

Cl Cl

Cl

Cl

Cl-

so

CH ₀ -O + Cl ₀ C = CCl ₉

L \ LL

^X S0 ₃ H

Cl Cl

Cl- Cl

CH ₂ CCl ₂ COOH + 2HC1 + 2H ₂ SO ₄

When repeating the procedure of Example 48, but when instead of trichlorethylene tetrachlorethylene to the oxonium compound added x / urde, one obtained after work-up, as there

0 983 8/1243

stated, 40.0 g of a gray-white solid. Its nuclear magnetic resonance spectrum showed the presence of 5% pentachlorobenzyl chloride, 5% 2 · chloro-S-pentachlorophenylpropenoic acid and 92% of the title compound. After trituration with hexane and recrystallization from benzene gave white crystals, mp 173-176 ⁰ C showed whose infrared and ke.rnmagnetische resonance spectra and the analysis, it dais thereby acting to give the pure title compound. Their infrared spectrum, made in mineral oil gauze, had maxima at 1722, 1425, 1360, 1325, 1262, 1250, 1230, 1112, 1042, 979, 958, 932, 864, 774, 725, 700, 672, 653, 640 , 600, 542, 520 and 460 cm " ¹ , their nuclear magnetic resonance spectrum in DMSO showed the benzyl protons in the form of a singlet at 4.31 ppm.

Analysis for C ₉ H ₃ Cl ₇ O ₂ : Calculated C 27.64; H 0.77; Cl 63.43

found 27.8; 0.8; 63.5%.

Example 56

Production of α, 2,3,4,5,6-IIexachlorocinnamic acid

+ Cl ₂ C = CCl ₂ + 3H ₂ O Cl

-CII = CC1-COOII + 3HCl

When repeating the procedure of the previous example, However, in which the tetrachlorethylene solution was refluxed for 1/2 hour, the work-up was as above described 28, Og of a crude product whose nuclear magnetic Resonance spectrum (carried out in ilexadeuteroacetone) the presence both propenoic acid (main component) and propanoic acid, indicated. After recrystallization from tetrachlorethylene, 23.1 g (68% yield) of the pure title compound were obtained,

209838/1243

F. 242-243 ⁰ C. Your infrared spectrum in Nujol-Mull had maxima at 1715, 1698, 1525, 1426, 1348, 1328, 1300, 1260, 1241, 1220, 1125, 1032, 955, 908, S68, 790, 754, 740, 722, 696, 672, 628, 588, 540 and 484 cm "and their nuclear magnetic resonance spectrum showed the olefin proton at 7.89 ppm in acidic deuteroacetone.

Analysis for C ₉ H ₂ Cl ₆ O ₂ : Calculated C 30.05; H 0.57 Cl 59.95

found 30.4; 0.6; 60, U.

Example 57

Preparation of α, 2,2,3,3,4,5,6,7-nonachloro-1-indanoacetic acid

Cl Cl I

II CII-COOH

+ 2 Cl ₂ C = CHCl + 4H ₂ O- * I f) ~ J> -C1 ₂ + 2HCl + 4H ₂ SO

When an excess has been added (125 ml) in trichlorethylene to the δ prepared in Example Dioxoniumverbindung and the resulting mixture was heated to 60 ⁰ C for 30 minutes and if this ater then added to V /, the organic phase separated and dried with anhydrous calcium sulfate , filtered and vacuum stripped on a rotary evaporator gave 42.6 g of an orange oil. On trituration with hexane 22.1 g (45.5%) of the title compound, which isation after Umkristal-!, From benzene a melting point of 214 to 216 ⁰ C had "Its infrared spectrum showed the expected peaks and their nuclear magnetic resonance spectrum in hexadeuteroacetone showed an AB quartet at 5.46 and 6.45 ppm at J = 11 Hz.

Analysis for C ₁₁ Ii ₃ Cl ₉ O ₉ : Calculated C 27.16; H 0.62; Cl 65 ₈ 62

found 27.7; 0.7; 62.1%.

209838/1243

Example 58

Production of 1,1,2,2,4,5,6,7-0ctachlorindane

~ cf ~~ "

β / ^S0 3

+ Cl ₂ C = CHCl ^

HCl

+ 2H ₂ SO

The oxonium compound of Example 3 was prepared. The SchwefeItrioxydüberschuß was vacuum stripped to a pot temperature of 4O ⁰ C at 5 mm Hg and the residue was cooled to 10 ° C. Then 100 ml of trichlorethylene were added in one portion and, after the exothermic reaction had ended, the mixture obtained was stirred for 15 minutes, poured onto ice and most of the solvent was stripped from the organic phase under reduced pressure. After nitrating the thick slurry, 39.4 g (quantitative yield) of the title compound were obtained which, after recrystallization from benzene, had a melting point of 145.5-147 ° C. Their infrared spectrum fcies in Nujol-Mull maxima on at 1380, 1304, 1242, 1230, 1188, 1120, 96S, 932, 918, 793, 745, 725, 680, 658, 555, 518 and 480 cm; their nuclear magnetic resonance spectrum showed the benzy] protons in the form of a single peak at 4.38 ppm in DMSO solution and at 3.71 ppm in hexadeuterobenzene solution.

Analysis for

here. C 27.50; iof. 28.1;

H 0.51;
0.7;

Cl

72.0

71.4 ^? ό

209838 / i 243

Example 5 9

Production of 1,1,2,2,4,5,5,6,6, S-becachlor-1,2,3,5,6,7-hexahydro-s-indacene

2 C1 ₂ C = CIIC1 + 4H ₂ O - »CK <If } \ > C1 _O + 2HC1

When the procedure of vo out previous example was performed using the compound prepared in Example 18 Dioxoniumverbindung to yield 50.3 g (a quantitative yield) of the title compound, mp 175.5 to 177 ⁰ C, after recrystallization from benzene. Their infrared spectrum in tetrachlorethylene and carbon disulfide solution showed maxima at 1600, 1430, 1374, 1308, 1257, 1180, 1140, 1108, 994, 947, 916, 852, 754, 698, 657, 617, 538, 507 and 468 cm " ¹ and its nuclear magnetic resonance spectrum contained a single peak at 4.48 ppm in hexadeuteroacetone solution and at 3.77 ppm in hexadeutero · benzene solution.

Analysis for .C ₁ 2H ₄ Cl ₁ O: Calculated C 28.66; H 0.80; Cl 70.52

found 29.5; 1.0; 69.3%.

Example 60

Production of N-pentachlorobenzyl acetainide

Cl Cl

so ₃ ^e

₉ -O + CH ₃ CN + 2H ₂ O ^C1 ~ \ ()) "" CH ₂ NHCCH ₃ +

SO, H

Cl

209838/1243

When an excess (125 ml) of acetonitrile was added all at once to the oxonium compound prepared in Example 1, a violent reaction occurred, but was kept under control with strong cooling. After the completion of the reaction, the mixture was refluxed and the light yellow slurry was poured into water. The precipitated white powder was filtered off and air-dried, after which it had a weight of 36.0 g. After recrystallization from methanol, the title compound, M, 223.5 to 224 ⁰ C, whose structure was confirmed by spectroscopy and by elemental analysis was obtained 21.3 g (yield 661). Its infrared spectrum in Nujol-Mull had maxima at 3270, 1630, 1540, 1360, 1320, 1278, 1248 1232, 1210, 1124, 1040, 1010, 770, 725, 682, 632, 592, 510 and 464 cm and its nuclear magnetic The resonance spectrum in DMSO showed the benzyl protons at 4.57 ppm, the methyl protons at 2.5-3 ppm and the NH proton at 3.32 ppm.

Analysis for C ₉ H ₆ Cl ₅ NO: Calculated C 33.62; H 1.89; Cl 55.16

found 33.7; 2.0; 55.34.

Example 61

Production of N-pentachlorobenzyl acrylamide

Cl Cl Cl Cl

+ CH ₂ = CHCN + 2H ₂ O - »Cl- <f J) -CH ₂ NHCCH = CH ₂ + 2H ₂ SO ₄

SO TjH
Cl Cl Cl

The procedure of Example 1 was exactly repeated, and 125 ml of methylene chloride was added to the oxonium compound obtained, and then 125 ml of acrylonitrile was added. After the exothermic reaction, the pale yellow slurry obtained was heated 1/2 hour at 6O ⁰ C. After filtration, 12.5 g of a solid were obtained, which, as by infra-

209838/1243

red and nuclear magnetic resonance spectra and shown by elecretic analysis to be the title compound. The yield was 37.5%. Nach.der Rev ~ istallisation from methanol there were obtained crystals with a melting point of 213-214 ⁰ C. The nuclear magnetic resonance spectrum in .DMSO showed the vinyl proton multiplets at 6.0 to 6.4 and 5.5 to 5.7 ppm, the benzyl protons at 4.64 ppm and the amide proton at 3.34 ppm.

Analysis for C ₁₀ H ₆ Cl ₅ NO: Calculated C 36.01; H 1.82; Cl 53.19

found 36.0; 1.8; 53.1%.

Example 62

Production of the sodium salt of trans-2- (pentachlorophenyl) ethanesulfonic acid

Cl

CII ₂ CH ₃

NaOH H ₂ O

CH = CIISO ₃ Na-H ₂ O +

When the procedure of Example 1 2,3,4,5,6-Pentachloräthylbenzol (F. ⁰ 56-57 C) instead of Pentachlortoluol and after 5 hours boiling under reflux the reaction mixture, stripping of the Schwefeltrioxydüberschusses a dark residue there was obtained that has been poured into ice water. After neutralization with a dilute aqueous sodium hydroxide solution and after filtering, 17.5 g (431 of theory) of the title compound were obtained in the form of the monohydrate. After recrystallization from ethanol, an analytically pure sample which could not be melted ^{below 300 ° C. was obtained.} Its nuclear magnetic resonance spectrum (carried out in DMSO) showed the olefinic protons in the form of an AB quartet at 6.73 and 6.97 ppm with a coupling constant of 16 Hz, the infrared spectrum (carried out in Fluorolube and mineral oil gauze) showed maxima 3580, 3506, 1610, 1375, 1340, 1304, 1190, 1062, 946, 856, 77O ₈ 718,

20 9 838/1243

688, 6-52, 630, 600, 552, 540 and 510 cm " ¹ .

Analysis for CgH ₂ Cl ₅ NaO ₃ SJI ₂ O: Calculated C 24.23; II 0.51; Cl 44.72; S 8.09

found 24.6; 0.9; 44.5; 8.2%.

Example 63

Preparation of the sodium salt of pentachlorobenzenesulfonic acid

Cl

NaOH
4 »

egg -

H ₉ O

Cl Cl

SO-Na. 11.0 + SO ₉

Cl

The procedure of Example 1 was repeated except that the toluene by 29.2 g of 2,3,4,5,6-Pentachlorcumol (F. 78,5-8O ⁰ C, bp / 0.05 mm Hg = 106-108 C) was replaced. After refluxing for 5 hours, the excess sulfur trioxide was distilled off and the dark residue was poured onto ice and neutralized with a dilute aqueous sodium hydroxide solution. After filtering off the solids, a moist sludge was obtained which, after trituration with dioxane, gave a white powder which represented 63% of the title compound which contained 1 mole of water of crystallization.

Analysis for C ₆ Cl ₅ NaO ₃ SJI ₂ O: Calculated C 19.45; II 0.55; Cl 47.86; S 8.65

found 19.3; 0.7; 46.6; 8.5%.

Example 64

Production of 2,3,5,6-tetrachloro-p-tolualdehyde

Cl

Cl

+ SO ₃ + H ₂ SO ₄

Cl

-CHO + SO ₂ +

209838/1243

The procedure of Example 9 was repeated, this time using an excess of 2O ^? Often fuming sulfuric acid (700 g) was used and heated to a temperature between 90 and 100 ° C for 4 hours. During this time, a deep purple-red colored solution developed and the heating of the reaction mixture was accompanied by a strong evolution of gas (acid smoke). After cooling to room temperature, the solution was slowly added to ice with thorough stirring. An orange-yellow precipitate was formed which was filtered off, washed repeatedly with water and air-dried to give 24.3 g of product. After recrystallization from ethyl acetate and carbon tetrachloride, pale gray-white colored crystals, mp 200-206.5 ° C., were obtained, the spectra and elemental analyzes of which showed that it was the title compound. Its infrared spectrum in tetrachlorethylene and carbon disulfide solution showed maxima at 2855, 1720, 1350, 1244, 1230, 1140, 1027, 988, 832, 730, 696, 648, 529 and 46S cm ~; their nuclear magnetic resonance spectrum in deuterochloroform showed two singlets, the aldehyde proton at 10.4 ppm and the methyl protons at 2.70 ppm in the correct ratio of 1: 3.

Analysis for CgH ₄ Cl ₄ O: Calculated C 37.25; H 1.56; Cl 54.98

found 37.3; 1.6; 54.81.

I-

Example 65

Production of 2,3,5,6-tetrachloro-p-tolualdehyde

"egg egg egg

+ SO ₃ + H ₂ SO ₄

CHO + SO ₂ + 2HCl +

Cl Cl

Cl Cl

When repeating the procedure of Example 64 with α, α ¹ , 2,3 5,6-IIexachloro-p-xylene instead of 2.3.5 _t 6-tetrachloro-p-xylene as

2098.38 / 124 3

As a reactant, the title compound was obtained in an amount of 19.6 g, this corresponds to a yield of 76%.

Example 66

Production of 2,3,5,6-tetrachloro-p-tolualdehyde

Cl Cl

HIGH ₂ -Ci j VCII ₂ OH + SO- +

Cl Cl

Cl

Cl

CHO + SO ₂ + H ₂ SO ₄

Cl

When the procedure of Example 64 was followed by replacing tetrachloro-p-xylene with an equimolar amount (27.6 g) of 2,3,5,6-tetrachloro-p-xylene-a, a'-diol became a strong one Development of sulfur dioxide (identified qualitatively by iodine paper) was observed, but the solution obtained did not turn purple, instead it assumed a brownish-yellow color. After 4 hours of heating to a temperature between 90 and 94 ^° C., the clear solution, after cooling to room temperature, was poured onto ice and a yellow slurry was obtained. Since the filtration took too long, the slurry was extracted with diethyl ether and obtained after evaporation of the solvent 19.0 g of a light yellow solid, the identity of which was determined by infrared and nuclear magnetic resonance spectra which were consistent with the spectra described in Example 64.

Example 67

Production of 3,4,5,6-tetrachloro-o-tolualdehyde

egg

\ ■

Cl

♦ so ₂ ♦ H ₂ SO ₄

209838/1243

. egg

When following the procedure of Example 64 using the p-isomer instead of Tetrachloro-o-xyloi was repeated, was obtained in 60% yield the title compound, m.p. 187-194 ° C. Their infrared spectrum showed maxima at 2860, 1705, 1435, 1376, 1348, 1304, 1228, 1170, 1038, 956, 894, 660 and 520 cm "and their nuclear magnetic resonance spectrum in CDC1 ~ showed the aldehyde proton at 10.50 ppm and the methyl protons at 2.62 ppm in an area ratio of 1: 3.

Analysis for CgH ₄ Cl ₄ O: Calculated C 37.25; H 1.56; Cl 54.98

found 37.3; '1.6; 53.6%.

Example 68

Production of 2,3,4,5,67 pentafluorobenzyl alcohol

2H ₂ O

CH ₂ OII + 2

When the procedure of Example 23 was repeated with the oxonium compound prepared in Example 5, a crude product was obtained in a yield of 14.9 g. Gas chromatography of the oil resulted in the isolation of the title compound which consisted of 85% product and man. received 12.6 g of it, which corresponds to a yield of 63.51. In the isolated pure form, the alcohol in CDCI solution had nuclear magnetic resonance peaks at 4.72 and 3.85 ppm with an area ratio of 2: 1, these correspond the benzyl and hydroxyl protons. The infrared spectrum (in Nujol-Mull) had maxima at 3602, 3320, 1498, 1302, 1278, 1216, 1118, 1022, 948, 922, 750, .668, 598, 560 and 478 cm " ¹ .

209838/124 3

Example 69

Preparation of 2, 3,5, δ-tetrachloro-p-xylene-c ^ a'-diol

Cl Cl

ClO ₂ S

O-CK

Cl

Cl Cl

HIGH

Cl

+ 4H ₂ SO ₄ + 2IIC1

If following the procedure of Example 25 without adding hydrochloric acid with the dioxonium compound prepared in Example 18 repeated the title compound was obtained in practically quantitative yield. The quantitative analysis of the aqueous phase showed the Presence of 4 molar equivalents of sulfuric acid and 2 molar equivalents of hydrochloric acid, corresponding to the stoichiometry given above.

Example 70

Production of 2,3,4,5-tetrabromo-6-chlorobenzaldehyde

CIi- + 6SO 3

Br

CHO + 411

Br Br

When replacing Pentabrcmtoluol by 2,3,4,5-tetrabromo-6-chlorotoluene, F. 268-269 ⁰ C, in the example 7 was obtained after hydrolysis of the Dioxoniumvürbindung thus obtained according to the method of Example 35 in virtually quantitative yield the title compound. The structure of the new high-melting point compound was confirmed by infrared and nuclear magnetics, the romance spectra and by elemental analysis.

^tiss - 209838/1243

Example 71

Manufacture of pentachlorobenzaldehyde

Cl Cl.

CH ₂ Cl + SO ₃ + H ₂ SO ₄

Cl Cl

Cl Cl

■) Cl

CIIO + HCl + SO

This example illustrates the production of pentachlorobenzaldehyde in an oxy dation stage, which was carried out using 20ligem oleum (fuming sulfuric acid). When 50.0 g (0.1 mol) Pentachlorbenzylchlorid and 200 g of 20% fuming sulfuric acid was slowly heated with good stirring to give a dark green slurry "After the temperature reached 82 ⁰ C, gas evolution began (acidic smoke), which at 85 ⁰ C was very violent. In the course of 2 hours the color of the slurry changed to brown and after heating between 82 and 85 ° C. for 3 hours, the evolution of gas ceased. The heating was stopped. After cooling to room temperature, the reaction mixture was added to ice, filtered, washed and dried, giving 24.7 g of a dark yellow colored product which was identified by nuclear magnetic resonance and infrared spectra and elemental analysis as pentachlorobenzaldehyde, which was identified with the in the examples 33 and 34 were identical. The yield was 88.5% of theory.

209838/12 43

Claims (1)

Pat ent ans ρ rüche 1, polyhalobenzyldisulfoxonium compound, characterized by the general formula: Hal H Ar / "CHX-C) 7 mn - \. - ρ SO ₂ Y where mean: Ar an aromatic nucleus, Hai is a halogen from the group consisting of fluorine, chlorine, bromine and iodine; X is a substituent from the group —H, —CH, and ^S0e -0, where Y is a substituent from the ^ SO ~ Y group fluorine, chlorine, bromine and hydroxyl means; m, η and ρ are each integers selected so that their sum corresponds to the number of substitutable positions available on the aromatic ring, this sum being 6 when Ar is benzene, 8 when Ar is naphthalene and 10 when Ar means anthracene, phenanthrene and pyrene. 2, compound according to claim 1, characterized by the formula: ^Br so ^θ 209838/1243 3. A compound according to claim 1, characterized by the formula Cl Cl Cl- ' SO θ CH-O ' CH ^S0 3 ^H Cl Cl ^U1 3 ^ύ 4. A compound according to claim 1, characterized in that in the general formula Ar is benzene, Y is hydroxyl or chlorine and X is hydrogen mean. 5. Compound according to claim 1, characterized by the formula: θ. O ^ CHo Br ⁶ O S- ⁰
° 3 ^b I CH Br CH. Br @ 0-SO ₂ OH -SO ₂ OH 6. A compound according to claim 4, characterized by the formula: Hal CH ₂ -O or SO ₃ H 209838/12 A3 wherein Hal at least one halogen from the group fluorine, chlorine, Means bromine and iodine. 7. Compound according to claim 6, characterized by the formula: Cl Cl SO ₂ OH 8. A compound according to claim 6, characterized by the formula: Br Br SO ₂ OII Br Br 9. A compound according to claim 6, characterized by the formula: F F SO ₂ OH 209838/1243 10. Compound according to claim 6, characterized by the formula: Cl Cl O ₃ S HO ₃ S ' O-CH. Cl Cl 11. Compound according to claim 6, characterized by the formula: SO ₂ OH SO ₂ OH 12, compound according to claim 6, characterized by the formula: Cl SO. Cl Cl Cl CH ₂ -O-SO ₂ OH CH ₉ -O-SO-OH I so ₃ ^e 209838/1243 13. A compound according to claim 6, characterized by the formula Br HO, S Br Br SO ₂ OH 14. A compound according to claim 6, characterized by the formula Br Bi O ₃ S SO ₂ OH SO ₂ OH 15. A compound according to claim 6, characterized by the formula Θ, HO ₅ S- JJ
\, O-CH SO CH ₂ -O J J SO ₂ OH 16. Compound nacii claim 4, characterized in that in the general formula Y is chlorine and η 0 is. 209838/1 17. A compound according to claim 16, characterized by the general Form1: Shark, θ 1 CH, -0 ' SUN, ⁹ SO ₂ Cl Shark or where Hai at least one halogen from the group fluorine * chlorine, Means bromine and iodine. 18. A compound according to claim 16, characterized by the formula: Cl Cl Cl Cl SO ₂ Cl 19. A compound according to claim 16, characterized by the formula Cl Cl SO ₂ Cl Cl Cl 209838/1243 20. Compound according to claim 16, characterized by the formula: Cl 21. A compound according to claim 1, characterized in that in the general formula Ar is benzene, Y is independently hydroxyl or chlorine and X is the substituent _Ω , SO » -0 SO ₂ Y mean. 22. Compound according to claim 21, characterized by the formula: Cl Cl- Cl 23. A compound according to claim 21, characterized by the formula: Shark Shark or SO CH - SO ₃ II so -SO, H 209838/1243 wherein Hal at least one halogen from the group fluorine, chlorine, Means bromine and iodine. 24. Compound according to claim 23, characterized by the formula: • Cl Cl Cl- Cl Cl SO ₂ OII 25. A compound according to claim 23, characterized by the formula: Dr Br CH 0 26. A method for producing a compound according to claim 23,
characterized in that sulfur trioxide is reacted with a compound of the general formula: _n II _n Ar / ~ CHXY_7p where mean: Ar is an aromatic nucleus; Hal at least one halogen from the group fluorine, chlorine, Bromine and iodine; Y is a substitute from the group consisting of fluorine, chlorine, Bromine, hydrogen and hydroxyl; X is a substituent from the group consisting of fluorine, chlorine, Bromine and hydrogen; 209838/1243 m, η and ρ are each integers selected so that their sum is equal to the number of substitutable positions available in the aromatic ring, this sum being 6 when Ar ss benzene, 8 when Ar = naphthalene ₉ and 10 is when Ar = anthracene, phenanthrene and pyrene. 27. The method according to claim 23, characterized in that as Reactant an excess of pure liquid sulfur trioxide is used. 28. The method according to claim 23, characterized in that the sulfur trioxide reactant. in the form of a $ 1 to $ 50 smoker Sulfuric acid solution is used. 209838/1243