DE2717781A1 - METHOD OF PREPARING ALKYLARYL COMPOUNDS - Google Patents

Description

Germany lawyer »file 28 061 April 21, 1977

Process for the preparation of alkylaryl compounds

The invention relates to a new process for the preparation of alkylaryl compounds, as well as those by means of this process obtained alkylaryl compounds.

It is known that alkylaryl ethers can be prepared by reacting alkali metal phenolates with alkyl halides. This However, the method is based on the available phenolates and thiophenolates limited and caused due to the in some cases not completely alkalizing of phenols resp. Thiophenols additional problems. On the other hand, the second reactant, namely the alkyl halides, is not arbitrary available on the market and, in the case of alkoxyalkyl halides, much more expensive than that according to the invention Process required reaction substrates.

The process according to the invention surprisingly gives alkylaryl compounds in very high yields. The products obtained are of high purity, so that in most cases, in contrast to the previous processes, they no longer need to be purified. The reaction conditions are simple and the course of the reaction is easy to keep under control.

7098U / 0Ö4S

The new process for the preparation of alkylaryl compounds of the formula

₍ R - CO, - [(CHR ₁ ), - υ -] _o j _{A. Zn (1)}

R alkyl (C ₁ -C ₆ ), branched or unbranched, optionally

substituted aryl, R ₁ H, alkyl (C ₁ -C ₄ ), A substituted aryl,

' ^R 3 YC, S or N, in which case R is omitted,

^Vr 4

Ro H, optionally substituted alkyl (C ₁ -C ₆ ), branched and unbranched, optionally substituted

Aryl, aroyl,
R, optionally substituted alkyl (C ₁ ^- C ₆₎ branched and unbranched, optionally substituted aryl,

Aroyl, cyclohexyl, where
R ~ and R, with the N atom, can form a heterocyclic ring which contains other heteroatoms in addition to C-

can,

UO or S,
Z is an electron-withdrawing group, especially the NC ^ ^-

Group,

η numbers from 1 to 2,

m numbers from 1 to 6, ρ numbers from 1 to 3 or O, t denotes numbers from 1 to 2 and q denotes 0 or 1, is characterized in that one compounds the formula

Γ 1

R- (Y) - (CHR ₁ ) -UIH (2)

q L i ^y m J _p ι '

in the presence of cations, e.g. alkali metal or ammonium ions,

709844/0948

with compounds of the formula

XAZ _n (3)

in which X denotes halogen and can be present one or more times, and the other symbols under formula (1) have given meaning,

in a two-phase system, namely an aqueous phase and a second phase, consisting of the reactant 3 in liquid form or in the form of a solution in a water-immiscible organic solvent or solvent mixture, wherein the reactant (2) can be present in one or both phases, in the presence of 0.01 to 40 mol percent, preferably 1 to 20 mol percent, based on the amount of the compound (3), quaternary ammonium or phosphonium compounds as Reacts catalysts with thorough mixing in an alkaline pH range.

The radical A of the formula (3) can be substituted by one or more substituents. Examples of possible substituents are: halogen, NO ₂ , alkyl (C ₁ -C ₁₈ ), AlkOXy (CJC-Jg), aryloxy, in particular phenoxy, CN, CF-, SO ₂ A, -N = N-aryl , -NH-CO-NH ₂ , NR ₁ R ₂ , SO ₂ R ₁ , SO ₂ NR ₁ R ₂ , COR ₁ , COOR ₁ , CONR, R ^, where R, and R ~ are the same or different, and in particular H, alkyl (C ₁ -C ₁₂ ) or aryl, such as phenyl. A in the meaning of an aryl radical represents in particular a benzene or naphthalene radical.

Examples of electron-withdrawing groups according to the symbol Z are the NO ₂ "and CN groups, but in particular the NO ₂ group.

Starting components of the formula (2) are alcohols such as n-octanol, nonanol, cetyl alcohol, hexadecanol, tetracosyl alcohol, Thiols such as octyl mercaptan and tertiary dodecyl mercaptan, cellosolve types such as ethylene

glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, Ethylene glycol mono-isopropyl ether, Ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether,

709844/0946

Ethylene glycol monopentyl ether, ethylene glycol monoisoamyl ether, Ethylene glycol monohexyl ether, ethylene glycol monoallyl ether; Carbitol types, such as diethylene glycol monomethyl ether, Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monopropyl or butyathers, also l-methoxy-2-propanol, l-methoxy-3-propanol, l-methoxy-4-butanol, l-methoxy-5-pentanol, 1-methoxy-6-hexanol, Triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, 1-methoxy-thioethanol, 1-methoxy-thiopropanol, 2-phenoxy-ethanol, 2-phenoxy-propanol, 2-phenoxy-butanol, 1-dimethylamino-1hioä thano1, 1-D imethylamino-thiopropanol, N- (2-hydroxyethyl) aniline, N- (2-hydroxyethyl) -o-toluidine, N- (2-hydroxyethyl) -m-toluidine, N- (2-hydroxyethyl) -p-toluidine, N- (2-hydroxyethyl) -m-chloroaniline, N- (2-hydroxyethyl) -p-chloroaniline, N- (2-hydroxyethyl) -m-nitroaniline, N- (2-hydroxyethyl) -m-bromaniline, N- (2-hydroxyethyl) -m-trifluoromethyl-aniline, N- (2-Hydroxyethyl) -cyclohexylamine, N- (2-HydroxyMthyl) -morpholine, N- (2-hydroxyethyl) piperazine, N- (2-hydroxyethyl) pyrrolidine, N- (2-Hydroxyethyl) -piperidine, N- (2-Hydroxyäthyl) -benzarid, 2-dimethylaminoethanol, 2-diethylaminoethanol, 3-dimethylamino-1-propanol, N- (2-arainoethyl) -aminoethanol.

Examples of compounds of the formula (3) XAZ _n are: 2-C'ilor-nitrobenzene, 4-chloro-nitrobenzene, 4-fluoro-nitrobenzene, 4-bromo-nitrobenzene, 4-iodo-nitrobenzene, 2, 4-difluoro-nitrobenzene, 2,4-dichloro-nitrobenzene, 2,4-dinitrochlorobenzene, 2,4-dinitro-fluorobenzene, 3,4-dinitro-chlorobenzene, 3,4-dichloro-nitrobenzene, 2,6-dichloro nitrobenzene, 2-nitro-5-chloroaniline, 4-nitro-3-chloroaniline, 2-nitro-3,5-dichloroaniline, 2-nitro-4,5-dichloroaniline, 2-nitro-5,6-dichloroaniline, 2- Nitro-4-methyl-5-chloroaniline and 2-nitro-4-ethyl-5-chloroaniline.

Invention wet usable catalysts are quater när e ammonium or phosphonium compounds, such as tetra butylammonium bromide or chloride, dodecyltrimethylammonium

709844/094 «'

chloride, n-hexadecyltributylammonium chloride, tetrapropylammonium chloride, n-hexadecyltributylphosphonium bromide, Benzyltriethylammonium chloride, benzyltributylammonium bromide, Benzyltrihexylammonium bromide, benzyltrioctylammonium bromide, tetrabutylammonium iodide, trioctylmethylammonium chloride, N-octylpyridinium bromide, N-dodecylpyridinium bromide, cyclohexyl triethylammonium bromide, n-dodecyltriethylammonium bromide, n-Octyltributylammonium bromide, n-Hexadecyltrimethylammonium bromide, n-Hexadecyltriethylammonium bromide, n-Hexadecyltripropylammonium bromide, Tetrabutylphosphonium chloride, tetraphenylphosphonium bromide, Trioctylmethylphosphonium bromide, Trioctylethylphosphonium bromide, n-dodecyl-bis (0-hydroxyethyl) -benzylammonium chloride and n-hexadecyl-tri- (ß-hydroxyethyl) ammonium chloride.

It is useful if the catalysts are both in Water and are soluble in the organic solvents used. As organic, immiscible with water Solvents come mainly e.g. aliphatic and aromatic chlorinated hydrocarbons, such as carbon tetrachloride, Trichlorethylene, especially methylene chloride and chloroform, or mono- and dichlorobenzene are suitable.

The reaction is carried out in simple reaction vessels with a reflux condenser and stirrer or in a stirred autoclave, which means that you can work under pressure as well as without pressure.

The reaction temperature varies in a wide range from room temperature to 120 ^° C. and is dependent on the reactivity of the components used. For example, if in the compound of the formula (2) U = S, may be from room temperature to 50 ⁰ C worked, U represents oxygen, however, a reaction temperature of 80 to 11O ° C is zweckroässig.

709844/094 "

- «he -

The reaction component of the formula (2)

is advantageous in a small stoichiometric excess, if appropriate, however, up to a 50% excess of component X-A-Z is used.

The reaction is carried out in an alkaline medium. The alkali component can, for example, as an aqueous concentrated solution (approx. 10 to 50% strength) before the start of the reaction Component of the formula (2) can be added. This water content is usually sufficient for the formation of the two-phase system (Water-solvent mixture). When using highly concentrated alkali, it may be necessary to add Water required. The procedure is as follows:

The starting component of the formula (2) should be in the form of an aqueous alkali solution and / or the solution or suspension should show a clearly alkaline reaction. This solution is placed in a reaction vessel, whereupon a solution of the reaction component XAZ in a water-immiscible solvent is added, the catalyst as defined is then added and the mixture is stirred ^{at temperatures between room temperature and 120 ° C. for a period of up to 10 hours.} The solvent and any excess reactants are then removed from the reaction system by steam distillation, and these can be reused for a new batch, whereupon it is cooled, the precipitated product is filtered off and washed neutral with water.

Another embodiment of the reaction according to the invention is that the reaction component XAZ _{n is} added to the reaction mixture in solid form and melted by heating, which means that the organic solvent is superfluous, since this melt simultaneously represents part of the reaction medium and thus the organic phase.

709844/09 * 8

to

The product of the formula (1) obtained has the purity required for further processing. The yields are usually over 70% of theory.

The compounds of formula (1) prepared by the new process are valuable intermediates for Dye synthesis, e.g. after prior reduction of the Nitro group and possibly sulfonation as diazo components for the production of azo dyes.

Compared to the above-mentioned production method using the alkyl halides and phenolates, it has above all surprised that with the hydroxy compounds of formula (2), respectively. their alkali or ammonium compounds in the low reaction temperatures of the process according to the invention, a very high degree of conversion of the reaction components is achieved, the product obtained also being very pure.

According to the inventive method a water-immiscible solvent is used in a mixture of water and worked with the process control is easy and the solvent used after workup of the reaction mixture, for example, can be used again by steam distillation for the next reaction, whereby a minimal environmental impact is caused .

The advantages of the new method are inally also see further "in the fairly simple process engineering operation.

The following examples illustrate the operation of the method according to the invention without referring to it to limit these examples. The temperatures are given in degrees Celsius. Parts (T) mean units of weight. ,

709844/094 *

example 1

A mixture of 40 ml of a 50% sodium hydroxide solution and 60 ml Ethylene glycol monomethyl ether heated for 15 minutes and then the suspension of 78.8 g of p-chloro-nitrobenzene and 9.6 g of the catalyst tetrabutylammonium bromide in 150 ml of chlorobenzene were added. This reaction mixture is under good stirring for 4 hours at an internal temperature of 100 ° held. After cooling, the reaction product has partially crystallized out. The used chlorobenzene is separated off by steam distillation and reused for the next reaction batch. The remaining The solution is cooled with stirring, whereupon the reaction product of the formula at 55 to 60 °

H ₃ CO-C ₂ H ₄ -O- ^ f_V-NO ₂

is obtained as a pale yellow colored, coarsely crystalline precipitate. The reaction product becomes neutral with V7asser washed and dried in vacuo. 82 g of product are obtained - = 83% of theory. with a melting point of 79 to 82 °.

Proceed as described in Example 1, used however, instead of ethylene glycol monomethyl ether, corresponding amounts of those mentioned in column I of table 1 are used Alcohols and the halobenzenes mentioned in column II, the alkylaryl ethers of column III are obtained.

7098U / 09A8

-Jf -

r-l iH

U ■ CM co I. CM CM CM CM 33 SO CM Lathe O CM
5 O O O O O O ι — ι
fr JS I. "T I. α I. I. I. I. in the 5 T r-l ! O O • \
CJ CJ
CO CM O iH O CJ T I.
O I Il I. T 33 33 I. CO CJ O
I. O O I.
O 33 *
CM
CJ 33 <t X I. A. CO CM CM 33
CM
CJ
a CJ CJ O M.
M. CJ I.
O co CM CM M. Q I. O 33 33 O I. O 33 33 I. m CM CO U CM CJ
O O X CM CO CJ co S. 33 I. 33 I. I. 33 i-l
O
Kl 8th O CM C. co CJ CJ CM (U 33 co I. CO Z X) CM 33 O C. CJ EJ v ^^ x * ^^ o> co I ^ Π to 33 I IJ O Q t 33 I-I
CJ M. M. 33 33 O r-l
O O 33 koh I. I. 33 * f-H <f CM 33 CM
CJ
I. CM / "^ I. O S. O co CM
CJ I. 33 m •
α
CO 8th CM
CJ O 33 ta co I. 33 * M. 8th CM
CJ ^ co co I. X 8th CO 33 «N

709844/0948

Continuation table

E.g.

10 11 12 13 14

H ₅ C ₂ O- (CH ₂ ) ₃ -OH

H ₇ C ₃ OC ₂ H ₄ -OH

H ₇ C ₃ O- (CH ₂ ) ₃ -OH

H ₇ C ₃ O- (CH ₂ ) ₄ -OH

H ₉ C ₄ OC ₂ H ₄ -OH

H ₉ C ₄ O- (CH ₂ ) ₃ -OH

II

CH

^C1 ~ O ~ ^N0 2

Il

• I

III

CH,

H ₅ C ₂ O-

H ₅ C ₂ O- (CH ₂ ) ₄ -0 - \ J / - NO ₂

H ₇ C ₃ OC ₂ H ₄ -OA-NO ₂

7 V-NO.

H ₇ C ₃ O- (ch ₂ ) ₄ -o

H ₉ C ₄ OC ₂ H ₄ -O- ^ J) -NO ₂ H ₉ C ₄ O- (CH ₂ ) ₃ -O ·

NO,

Continuation table

E.g.

15 16 17

18th

19th

20th

21

H ₉ C ₄ O- (CH ₂ ) ₄ -OH

H ₃ CO-C ₂ H ₄ -SH

H ₃ CO-C ₂ H ₄ -OH

H ₃ CO-C ₂ H ₄ -OH

H ₃ CO-C ₂ H ₄ -OH

H ₃ CO-C ₂ H ₄ -OH

Il

II

Cl - (/ V-CH.

NO

NH

Cl-

III

H ₉ C ₄ O- (CH ₂ ) ₄ -

H ₃ CO-C ₂ Il ₄ -S - (^) - NO,

H ₃ CO-C ₂ H ₄ -O

NO

NO,

H ₃ CO-C ₂ H ₄ -O

NO

Table 1 continued

E.g. H ₃ I. II ν NH ₂ H ₃ CO-C ₂ H ₄ -O III ) - NO ₂ Cl Cl NH ₂ 22nd CO-C ₂ H ₄ -OH OCH ₃ Cl-Q-NO ₂ H-CO-C ₉ H, -0
■ 5 cm ^ T -O " ^N0 2
\
OCH ₃ 2 Cl H ₃ CO-C ₂ H ₄ -O - χ ^ 709f 23 Il 24 H ₃ CO-C ₂ H ₄ -OH «Ό ) - NO ₂ Φ ^ -C ₂ H ₄ -OCH ₃

Example 25

2.2 g of sodium hydroxide are dissolved in a 100 ml round bottom flask equipped with a stirrer, thermometer and reflux condenser in 20 ml of water, uses 7.6 g of 2-phenoxyethanol, 7.88 g of p-chloro-nitrobenzene and 1.33 g of the catalyst Tributylbenzylammonium bromide and the entire mixture is refluxed for 8 hours. After cooling down, this will be Reaction product of the formula

obtained as a pale yellow colored precipitate which is filtered off, washed neutral and dried in vacuo. Yield: 11.3 g = 87% of theory Mp: 83-85 °.

This procedure allows the reaction to be carried out in an aqueous medium without the addition of an organic solvent.

Similar high yields are obtained if one
2-Phenoxyethanol replaced by 2-phenoxypropanol or 2-phenoxybutanol and works as described under otherwise identical conditions.

709844/0946

Examples 26 to 37

The procedure is as described in Example 25, but using appropriate amounts instead of 2-phenoxyethanol of the hydroxy or thio compounds mentioned in column I of table 2, the alkylaryl ethers of column II are obtained.

709844/0946

- Vf-1%

U • ds CM CM CM CM CM CM CM CO CM Q) CQ Q O O O O O O O Q j I I. I. CM I. XO I. [ I. 1 J δ I. l-l ill O CM
X ^ b ^ n *> ^ CM [C IJ L IJ U U Γ ι] CJ |> ^ J S. O l-l I. CM I. I. I. I. I. CTN co κ-Ν X
f} O
i-l O SL O
CM X κ ~ Ν 1-4
< CM r-l δ O CM δ CO CM CM CM CM δ Μ
M. N ^ X
O δ δ δ X
O co N-κ ν- ' Ν-κ O CO CJ X cn co CO CO δ U
CM U δ X
CJ δ t> 0 X
CJ C. CJ 3 CO Ό co C. (CH
j 1-i X CO Q) κ-ν X O T- *
O
t O CM CM X H X O CJ CM
δ H CM O (U X S. χ X χ CTN χ • σ ο co O O O O X CO M. O CM X r-4 m CM egg* κ-Ν
CM I. X
CJ ^ CJ ^ l-l
CM ι-)
κ-Ν
CM ι-Ι
κ-ν
CM δ
CM CM δ > t
O δ δ δ δ CO Ν-κ co δ Ν-κ Ν-κ N ^ ο CO •O δ CM CO CO CO CO δ P *.
X νθ CCH δ X
CJ δ δ CO CM co CO CTN O ι-Ι CO co CM CM CO CO δ CM

709844/0946

Continuation table

O (D HO

E.g.

· «Nnnr

N-CH ₉ CH ₉ CH ₅ OH

^{Z Δ L}

Cl

- OCH ₂ CH ₂ OH

Cl

- SCH ₂ CH ₂ OH

CH, CH,

Cl

Cl-

II

'2

assa-Λ-

- VT -

Example 38

In a 100 ml stal autoclave become a solution from 5 g of NaOH in 20 ml of water 14.4 g of N- (2-hydroxyethyl) morpholine, 3.2 g of the catalyst tetrabutylammonium bromide and a solution of 15.75 g of p-chloronitrobenzene in 30 ml Chlorobenzene added.

The autoclave is closed and the mixture is stirred ^{at 100 ° C. for 8 hours.} When the reaction has ended, the chlorobenzene is removed by steam distillation. After cooling, the product of the formula falls out of the aqueous phase

in the form of a yellow precipitate. This is filtered off, washed neutral and dried in vacuo.

If the reaction is carried out as described in Example 38, but using N- (2-hydroxyethyl) morpholine instead corresponding amounts of hydroxy or thiol compounds as in column I of Table 3 and halobenzenes as in Column II of Table 3, then the alkyl aryl ethers are obtained of column III.

709844/0948

Table 3

E.g.

⁴⁰

43

Hydroxy or thiol compounds

CIL

H> -NH-C ₂ H ₄ -OH

-C ₂ H ₄ OH

Ih NC ₂ H ₄ -OH

II

Halobenzenes

NO,

ti

dd

III

Alkylaryl ethers

(/ \\ _ M-CH. -O CH ₀

H V-NH-

-NO,

Continuation table

• Ρ » ■ P-

E.g.

45 46

47

50

-OH

1-NH-C ₀ H, -OH

II C <+

H ₃ C

H ₃ C, H ₃ C

^ N- (CH ₂ ) ₃ -OH

H ₂ NC ₂ H ₄ -NH-C ₂ H ₄ -OH

NH ₇ C ₀ -SH ⁴

II

• I

Il

Il

III

NO,

H ₃ C

H ₂ NC ₂ H ₄ -NH-C ₂ H

₂ H ₄

H ₃ C _n H ₃ C

^N " ^C 2 ^H 4" ^S

Example 51

In a 500 ml round bottom flask equipped with a stirrer 27.2 g of 3-phenyl-1-propanol, 160 ml of an aqueous 30% Submitted NaOH solution and 34.6 g of 1-chloro-4-nitrobenzene. To 7.2 g of benzyltributylammonium bromide as a catalyst are added under reflux cooling and vigorous stirring at 112.degree heated for 8 hours.

The mixture is then subjected to steam distillation. After 1 liter of distillate is available, the Cooled residue and extracted with toluene.

The toluene extract is dried and concentrated in vacuo.

The product is 38.6 g of 4- (3-phenylpropoxy) nitrobenzene = 75% of theory with a melting point of 76 to 78 ° C.

■ /

7098 * 4/0946

Claims (12)

Claims
lJ Process for the preparation of alkylaryl compounds
ler formula Γ r- -.1 A - Z _n (1) j R- (T), - [(CHRp _1n -U -] 1 I Jt wherein R alkyl (C ₁ -C ₆ ), branched or unbranched, optionally substituted aryl,
R ₁ H, alkyl (C ₁ -C ₄ ),
A substituted aryl, ^ Y 0, S or -ν ', in which case R is omitted, R-, H, optionally substituted alkyl (C ₁ -C ₆ ), branched and unbranched, optionally substituted aryl, aroyl, R, optionally substituted alkyl (C ₁ -C, -), branched and unbranched, optionally substituted aryl, aroyl, Cyclohexyl, where
R «and R, with the N atom, can form a heterocyclic ring which, in addition to C-, also contains other heteroatoms can, U 0 or S,
Z is an electron-withdrawing group, especially the N0 ~ - Group, η numbers from 1 to 2,
m numbers from 1 to 6,
ρ numbers from 1 to 3 or t numbers from 1 to 2 and q 0 or 1, mean, characterized in that one compounds of the formula R- (Y) _q - [(CH _Rl ) _m -UJH (2) in the presence of cations, e.g. alkali metal or ammonium ions, with compounds of the formula XAZ _n (3) 709844/0946 ORIGINAL INSPECTED in which X denotes halogen and can be present one or more times, and the other symbols are those given under formula (1) Have meaning in a two-phase system, namely an aqueous phase and a second phase, consisting of the reactants (3) in In liquid form or in the form of a solution in a water-immiscible organic solvent or solvent mixture, wherein the reactant (2) can be present in one or both phases, in the presence of 0.01 to 40 mol percent, preferably 1 to 20 mol percent, based on the amount of the compound (3), quaternary ammonium or phosphonium compounds as Catalyst converts with thorough mixing in an alkaline pH range. 2. The method according to claim 1, characterized in that compounds of the formula (1) are prepared, where ρ and t = 1 and q = 0 and the remaining indices are those given above Have meaning. 3. Process according to Claims 1 and 2, characterized in that the reaction is carried out in a two-phase mixture is, one being the aqueous phase by means of which the reactant (2) is made to react, and the other phase is off a water-immiscible solvent or solvent mixture, by means of which the reactant (3) for reaction is brought. 4. Process according to Claims 1 and 2, characterized in that the reaction is carried out in a two-phase mixture, one being the aqueous phase by means of which the reactant (2) is reacted and the other is from the melt of the reactant (3). 5. Process according to Claims 1 and 2, characterized in that the reaction component X-A-Z is added to the reaction mixture in solid form and melted by heating. 709844/0946 6. The method according to claims 1 and 2, characterized in that A carries one or more of the following substituents: halogen, N0 ₂ »alkyl- (C, -C, g), alkoxy- (Cj-C,«), aryloxy, in particular Phenoxy, CN, CF ₃ , SO ₂ A, -N = N-aryl, -NH-CO-NH ₂ , -NR ₁ R, SO ₂ R ₁ , -SO ₂ NR ₁ R ₂ , COR ₁ , COOR ₁ , CONR ₁ R ₂ , where R ₁ and R _{2 are} identical or different, and in particular H, alkyl- (C-. -C ₁₂ ) or aryl, such as phenyl. 7. Process according to Claims 1 and 2, characterized in that A is a benzene or naphthalene radical. 8. The method according to claim 1, characterized in that that Z as an electron-withdrawing group means the NO ₂ group. 9. The method according to claims 1 to 6, characterized in that the reaction in the temperature interval between Room temperature and 120 ° C. 10. The method according to claims 1 to 9, characterized in that the water-immiscible organic Solvents aliphatic and aromatic chlorinated hydrocarbons, such as, in particular, monochlorobenzene, dichlorobenzene, Methylene chloride or chloroform can be used. 11. The method according to claims 1 to 10, characterized in that the catalysts are tetrabutylammonium bromide or chloride, dodecyltrimethylammonium chloride, n-hexadecyl, tributylammonium chloride, tetrapropylammonium chloride, n-hexadecyltributylphosphonium bromide, benzyltriMthylammoniumchlorId and Benzyltributylamaonumbromld used. 12. The alkylary compounds produced by the process according to claims 1 to 11. fOIIM / 0 »* · · ORIGINAL INSPECTED