DE2031290A1 - Process for the production of organic isocyanates - Google Patents

Description

Gases D 21 998/22718

Imperial Chemical Industries Limited London, UK

Process for the division of organic isocyanates Priorities? 24-6, 69 and 24 _£ 4 »1970- Great Britain

The invention relates to the production of isocyanates by reacting compounds that are aliphatic Bound halogen atoms contain »with inorganic cyanates

Ea is well known that this creates organic isocyanates can be obtained that one organic halides, and_ especially those in which the halide is attached to a aliphatic carbon atom is bonded, with alkali, Alkaline earth or ammonium cyanates at elevated temperatures implements

It has now been found that this reaction by the Use of iodine, iodine chlorides, bromine and mixtures thereof can be catalyzed and dees thereby the quantity undesired .by-products is reduced «

009883/2259

BATH ORIGINAL

The invention is therefore based on processes and production. of organic isocyanates »proposed, which is carried out by» that one © ia contains organic halide, daa mindisteas @ia alipfeatiscfe gtböBdtaes' halogen atom, with sin® »alkali -», - Ifislisali «» ods? Araa © raiumcyanat in the presence of JOi ₉ elaee Jodohlorid, Bröa or a mixture daraias as a catalyst

As iodine chlorides, which can be considered to be ₉ , iodine saooshl © ffiä = preferred and mixtures thereof

atoraa can be used © ier mentioned 'iodine trichloride'.

especially

Organic halides »those in the process according to the invention ▼ can be used® are s @ l-eh © «where at least ' a halogen atom which is aliphatically bonded is present, By the term "aliphatically bound" it is meant that the halogen atom is bonded directly to a saturated aliphatic carbon atom and not to a carbon atom in an aromatic or an unsaturated heterocyclic Ring. The expression "aliphatic carbon * atom" also includes carbon atoms in cycloaliphatic]! Either way

Organic halides to which the process according to the invention can be applied are sJc alkyl halides, Cycloalkyl halides, halogenated aliphatic ethers, Haloalkylarenes, haloalenejX-aryl ethers, alkenyl halides, Halogen ester and Haiogenenketone®, *

Examples of the soap organic Halide® that can be used »are s» B »t methyl iodide, £ thylbrd ·» mid, isopropyl chloride »tert-butyl chloride, n ^

009SS3 / 22S9

- ■ 3 -

n-hexyl bromide, cyclohexyl bromide, hexamethylenedi bromide, 3, 4-pi-bromocycXohezen, decyl bromide, decaiiethylenedibroaid, dodecyl chloride. n-octadecyl bromide, allyl chloride; 1,4-Dicnlorobut-2-eni i »3-Chlorobromo-propane, products that are obtained from alcohols and alcohol mixtures by chloro-methyllerenes, such as ε, Β.» Methoxymethyl chloride, ithoxymethyl chloride j 2-chloroethoxymethyl chloride _> 2-ethoxy-tthoxymethyl chloride _f n-butoxymethyl chloride, cyclohexymethyl chloride, ethylene glycol bis-chloromethyl ether, l _f 2-propylene glycol biBom (chloro-methyl) ether blyo) glyco) ether _t ! ether _e l, 4-tetramethylene-bending (chloromethyl) -öther, riiäthylenglycol-to-CchlormethylJäther, dipropylene glycol bis (chlorotnethyl) ether _t 1,1,1-trimethylolpropane (chloromethyl) ether "Allylchloro" · thy1 ether , Beniylchloromethyl-ether, fl-Phenyläthylchloromethyl-Ether, ß-Phenoxyäthyl-Chloromethy1-Ether, p-Xylylenediol-Bie- (chlor6-methyl-ether and 1,4-Bie (2'-chloromethoxy-ethoxy) t> en * olj 2- Chlorotetrahydrofuran ₉ monochlorodioxane, «(r-chloroethylaethyl ether, 1,2-dimethoxy-1 _? 2" -äieh5.oroätnan _t ethyl chloroacetate, ethyl chloroacetate, tris (chloroethyl) phoephate, tria; ß-bromo-propyl) -pho8phit »Bis- (chlorottthyl) phthalatt Compounds which, by chloromethylation, τοη aronatlachen hydrocarbons and eth er are obtained, "ie SB: Beneyl chloride, 2-, 3- and 4-methylbeneyl chloride, 2-, 3 and 4-ethylbenyl chloride, 2 _f 4-dieethylbenzyl chloride, 2,4,6-triloethylbenzyl chloride , m-xylene dichloride, p -Xylylendichlorid, Aje-dimethyl-m-Iylylendichloridj 2,4-bending (chloromethyl) toluene, 2,4-Bia (chloroeethyl) -p _x ylol / Bia (chloromethylj-hemiioellitol, Bia (ohloroaethyl} - durol, bla- (chloromethyl) -iaodurol, tria- (oliloroethyl) -toluene, tria- (chloromethyl) -ethylben «5ol, tria- (chloro» ethyl) - * - xylene and tria (chloroethyl) meetiylen, < -Naphthyl- «ethyl chloride, B-Iaphthylmethylchlorld, 2,6-Bie- (chloroMethyl) naphthalene,

/ "Bie- (chlorooethyl) Beeltylen, B

009883/2259

BATH ORIGINAL

• t-OhXoroiaethy! -Tetralin * ö-Gnloromethyltetralin, 1,3-Bia- (chloromethyl) tetralin, 9-910 «> Ble« - (chloroi & ethjrl) a! Athracene ₉ 9 f1Q-Bis «(chloromethyl)« ·>! "2 _s 3 ₉ 4" 5 "β _C 7 ₉ 8-octahjteo © nthraoen ₉ 4-Chloromethy! -Diphenyl" 4 "4 ⁵ -3ia- (chloromethyl5dipheayl, 2 _c 4.4'-TrIs-cehioromethyl) diphenyl and related products _e which are obtained by chloromethylation of diphenylalkanes, diphenyl ethers, diphenyl sulfide, diphesyl alfoia and diphtyl alcohols, A ^ methoxybenzyl chloride 4 «ethoxy» benzyl chloride, 2,4-bia «{ehl © roBiethyl5anisole 2,4- "Bis (chloromethyl) -3,5-dimethy! -" anisole, 2 s, 4b 6-Tris (chloromethyl) "3 £ 5-dimethylani8olfi 4-" chlorobenzyl chloride ₅ 39 4 ^OT Diehloro "benzyl chloride, Bis -CchloromethylJ-nionochlorobensol, 2-chloromethyl 1-4-chlorotoluene® 2 ₁ 6 "" bis (chloromethyl) -4-chlorotoluene-2-chloromethyl "4 * -bromoethylbenzol" ad related chloromethylation products * of halogenated alkylated benzenes, l- Chloro-1-phenyl-ethane, 1-chloro ° »2 - '. 4 * -chlorophenyl) ethsns , l «Ghloro ~ 2» (2 ^e _i .4 '"aichlorophenoxy) ethane _i 2 ^""dichlorodiethyl-ethheifjl" (4- ⁵ - "chloromethylphenoxy) -> 2 ~ chloroethaji, 3-nitro-benzyl chloride. j 3 -Nitro- = 4-methyl-benzyl chloride, bis- (chloromethyl) -iB-chloro-aniBOlf 3 ° Chloromethylaoetophenon, 3i3 ⁵ -BiB (efaioro "ethyl)" beösophea © 0 and 1 j 4-BiB- ( 2'-chloroethoxy) beneol ·.

Mixtures of products and ewer inebesondepe j®ae _f obtained by Ghloromethylierung of aromatic Kohlenv / aeeeratoffea ^ ^ can be erweadet "Seiehe Carrion gangs ·" materials are particularly useful for Hersteliuag of liquid laocyanatgemischen-

The process according to the invention is suitable for the production of Xsoeyaratefi aas «gL ^ Halogenalbjlareaea, which one or more <i-Halogeisal.ky! Radical @ ntfe @ lt @ Q _s dl © en an aromatic Eer ^ i ggbuaöen siad ₉ nnä swap lns <= special ferfcindangeßj, di © darcfa Ghloroa-gthylieriaiag ¥ © a 3enzol or an alkyls-filtered bensole- 009883/2289

BATH ORIGMNAL

Alkali metal -,:. Alkaline earth metal or Ammoniumcyanate _e which may be used in the present process are zj, the cyanates of lithium, sodium potassium * * magnesium, strontium GaICiUm ₉ »barium and the Affimohiumion," Further examples are the cyanates of substituted Ammoniuiaionens as ZeB ₃ methylammonium , Dimethylammonium, 9 Triraethyl, ammonium and triethylammonium yanate.

It is desirable to use a solvent and awar preferably one in which the cyanate is soluble to some extent. However, it is known that the solubility of metal cyanates in organic solvents is low and ea is therefore desirable ^ that the cyanate introduced in the form of fine particles

Examples of solvents that can be used are: tert-amides ₉ such as _a Bo BirnethyIformamid, sulfoxides such as Z, B-. Dimethyl sulfoxide sulfones such as B Mphenyl sulfones nitriles such as ζ, Β acetonitrile and benzonitrile, ketones such as acetone, methyl ethyl ketone, cyclohexanone and methyl isobutyl ketone, methyl Nsft dimethyl carbamate, ethyl KiH-dimethylcarbamate, N-carbethoxypiperidinij n "Buty lace tat. Pro · * pyl acetate _s ethylene "and propylene carbonate, ethylene glycol dimethyl ether and 2-'methoxyethylaoetat, as well as esters of phosphonic acids, such as s _e B <, the dimethyl ester of methylphosphonic acid, mixtures of such solvents can also be used.' ,,

Polar solvents can be used as solvent mixtures Hydrocarbons or halogenated aromatic hydrocarbons be used. Polar solvents that can be used in such mixtures are ζ, Βο Amides, carbamates, sulfones, ureas, hitriles, nitro compounds and phosphonamides, such as b, B «Dime thy If orisamid.

009883 / 22S9 _Q

P @ MäaaM ₀ ! © gisaaia, KMSethylsestamic!

soprop ^ lf © x? iiamid ₉ Blphesy! formamid-Methyl «äthy 1 ^ fQPtKESU ₉ E! © tfe2fl ^ Itfejl ^ acetamld _s DicycII o» hexylacetaHia
acetamide N ~ X

Ä'tia2fl-I ₉ M ^Q $ iM @ tfoyl ~ @ arTbama b _v H | H-diethylcarbamate ₉ ! "Oarboaetliösj ^ pipsriäiBsi Dimethylsui ·" fön, Tetrametfaylea "" siilf © ag J ^ eataeothyleaaialfonj methyl-äthyl "=

* 8 Ulf OSx,

nitrile * 3-methoxy-pi'opleaitfIIs,

clohexannltril », Bezisyleyasidsi StxccinoEitril ₉ Adipoaitrli?

Nitrobenaols die Hitrotol «© le _s Iitromethaa ₅ Hitroethane and Nitropropaiip

Examples are used for solvent of low polarity "the chen in sol mixtures kSnnen $ siiid Zob ^ i alipha" tables, _e cycloaliphatisehe aromatic and ai? Aliphatic hydrocarbons such as _t ζ <* _Β α Benz ©! ,, toluene xylene ₉ »Diäthylbeaaoi" Isopropylbeazol ₀ lifayinapfctthslins OetaBj -Pe »trolätheff, Gyelohexas and Eä @ ttiy! © yelofa @ 3mn ₉ - fealegierte aromatisofee Eohlemvasserstoff © like g _e B," MoBLOchlorobenzol, diehlorobenzole naö

The response is normally carried out at an atiological pressure and temperature of mageflh? 20 to 25O ⁰ C carried out ₉ although teaperatars aassssrbalb also use this area, the weräeE teönaen «Biae Ibe ^ eyziigt © Reactions tempera tar is 50 to 160 ⁰ C-,

The halide and the Q ^ mmmt werieia in common in the presence of the catalytic converter _? . aSiilieb l © i _s eiaais Joöehlorid _? Bso »or ¹

BAD ORtäM \! AL

Mixture thereof and heated, preferably in the presence of a solvent "The required isrhitzungs since .hängt largely on the used halide, the solvent used, the ^ temperature and OCE way of 2er amount of catalyst used *

There will be at least 1 molar proportion of yanate for each in the out ^ angsmatsrial aliphatically bonded halogen atom used> Paa cyanate is preferably used in excess

v / ends-.

The amount of soda used as a catalyst. Jodchloritfiv bromine or G-emioches thereof, is a catalytic ^ for example .0.01 to 5 percent by weight, based on organic halide _{or the like} . Know it grössare amounts than the _t-called y3 amounts "used" but a surplus is lediglici a wasteful For smaller singeing isv; 3ie Reaktirniie uncommon eu slowly

The isccyanate product can be prepared by any known process are isolated * Ev / corner-wise the inorganic oalae removed by filtration and the product won stillation,

The method for producing characteristic vcn ϊί one isocyanates 'οδ-, ϊ' of isocyanates with a lunktionallität be used by more Awei or ^ Such isocyanates know 2, ur Hei'3-; el <= _$ lung vrcn moüomereG oligomeric or polymeric urethanes or Urinary stoppers can be used by known methods

The invention is illustrated by the following examples. purifies; all parts and percentages in g-ewich * are expressed unless otherwise stated

009883/2259 ORIGINAL BATHROOM.

In some of the following examples an internal standard for gas chromatographic determinations (Y-P, C < ) of the reaction mixture added to the reactants, Examples are Durol and n * = Ootadecan They are among the conditions used are non-reactive and they only serve as calibration standards,

Beis piel Ί

A mixture of 20 _f 2 parts' llethoxymethylohloridj 20.1 parts Natriumcyanatj 99 parts of xylene ₉ 1 part Ν, Ν-Bimethyri »formamide and O ₅ 55 parts of iodine was stirred at Riickflußtemperatur 6 hours under a nitrogen atmosphere The reaction mixture was allowed to cool and filtered, and the piltrate was distilled to give 16 _f l parts of methoxymethyl isocyanate-

when the above reaction was carried out with the leave of iodine was, then only 6 parts of liethoxymethyliso «cyanate were obtained

Example 2

A mix of 11 _; 6 parts 1,4-bisf cfaloromethyljdtwo ;. 7/3 parts of sodium eyanate, 44 parts of JCyIoI ₅ 47 parts of I _; ff ~ dimethylformamide and 0 ₉ 3 parts of iodine was added at Rückflußten · - stirred "temperature nin Within 30 showed the Gaschromatcgranmji that the Umv / andlung / bis (" isocyana-tomethyl) äurol finished v / ar

If the above reaction was carried out with the omission of the iodine ₉ then it required until complete conversion into bis (isocyanatomethyl) d «rol 4 st-

009883/2259

Example 3

A mixture of 11 ^ -6 parts of bis {ehloromethyl) aurol, 7 _} 3 parts of netrium cyanate and 50% of mono-chlorobenzene; 50 parts by volume of Ν, Ν-dimethylacetamide and 0 _; 3 parts of iodine were stirred at the low flow temperature under a nitrogen atmosphere. After 20 minutes the gas chromatogram (V ₀ P ₅ C.)? that the conversion to BiaCisocyanatomethylJdurol had reached an estimated yield of 95 #.

If the iodine was omitted from a similar manufacturing 9 then it took 150 minutes until the reaction finished warj the estimated Aasbeute of diisocyanate amounted to only 45 ■ $ * ■

Example 4

A mixture of 1O ₉ 9 parts Bis (ahloromethyl) mesitylene _s 7 _ä 4 parts Natriumcyan ^ t, VOLn 50 parts of monochlorobenzene "VoI 50, parts by U / ii-dimethylacetamide» 0.5 parts of durene (inner V ^ P ^ Co -Standerd) and Q ₉ 3 parts; Iodine was stirred at racfc flow temperature under a nitrogen atmosphere. After 25 minutes, gas chromatography gave a single peak that could be assigned to bis (isocyanatomethyl) mesitylene, filtration and subsequent evaporation of the filtrate gave 6qO parts of crude isocyanate, distillation gave 6.0 parts of bis (isocyanatomethyl) mesitylene as a viscous Ö1 _P aas crystallized on standing, Pp: 49 ° C .->

If the iodine was left out in a similar procedure, then just a mixture of starting material was made Monochloro-monoiaocyanatomethyl-mesitylene and from bis (iso ~ cyanatoaethyl) aesitylene obtained

009883/2259 bad or _{! Ö (} na.

ίο

A MisöhuQg from 20 _δ 7 T @ ilea bis (iodouethyl) daröl "9 0 parts Kali" jBejsaat ₉ 75 parts by volume W

75 ¥ 'Vj., =. Seilea Moaoelil © 3? © lb®a5iol aad 3 (inner IF, Po G ■> StasäaxN!) Wbk! ® Tö © i under a stick

showed di @ SaseliroiaatogJiaptel® (l-, f, Q <-) _p flaas

ssuenäe was mnä daei fii © durol 78 pounds

Reaction okethyl) - -

Minutes showed
that the

A similar preparation is carried out for 0.3 parts of iodine "According to ViP-C * t that the Heaktiom EmtaäB wa, in diisocyanate was $ 87"

Example 6

A mixture of 11.6 parts of bis (chloromethyl) durol, 7.3 parts of sodium yanate, 50 parts of honeycomb sol, 50 parts of NjN-dimethyacetamide and 2 parts of n-Oetad-jcan (inner VoP, G. » Standard) was stirred at Rttekflußtemperator under a nitrogen atmosphere _β The time until the end of the reaction * determined therefore ν, Ρ, Ο », was 150 min, the estimated yield of bis (.i80cyanatmethyl) duroL was 45 $ o 'The following table shows the effect of adding different amounts loä sa the above manufacturing process-

TABLE I.

fod (wt ^)
based on
the halide reaction time
(miss) estimated off
loot ($) O
0.26
2.6
5.2 150
70
35
25th .45. -
70
87
84

00 * 883/2259

BATH ORIGINAL

I, Λ

Bine vision from 11 _; 6 parts of bis (chloromethylduroi) -7 3 parts of sodium cyanate 50 parts by volume of monochlorobenzene> 50 parts by volume of N, N-dimeth, / acetamide? 2 parts of n-Qctadecen (inner VP, 0 - standard) and O _r 3 parts of iodine was stirred at the HUckflrBtemperetur under a nitrogen atmosphere After 2'z min seen was the Gasohromatographie that the reaction-doing Aar and durene bis (iBOeyanatoraethyl) in a Yield of 95: ° had been obtained

If, in a similar production, the iodine is reduced by 0.38 parts ^! .! 3tiiumjoäid was replaced, then VP C- showed that the intermediate product, monocloromethi'l-monoisocyarmtoineth'-aurole, was still present after 45 minutes.

Example 8

A M5rcl'uag aas' -. 11.6 Divide bis (chlorciauthyl) durol _? . ^T ! Parts of sodium cyanate, 50 parts by volume of uranium cyanate, 50 parts by volume of N-D5.methyJ acetamide were stirred at the low temperature under a nitrogen atmosphere. 150 min Keigte V.PrC · - that; i: one more heakti-cn took place and d-333 56 ^ the theoretical yield of bis (iso'oya>ietc3i; ih.vl} duror-- '■ liMD.r had been formed

Tabel. 2 gives details ^ 011 other manufacturing processes. diii as outlined above, v / obei ^ eccch Joe and Iodine trichloride as a catalyst and also a number of well-known ones Catalysts were used - the table shows the superiority of the invented catalysts

009883 / 22S9.

BATH ORIGINAL

TAx3EI.EE 2

Production ^ = · »'

Reaction time ^ formation aa I BIH (through

0
X

2
3

Iodine 0.3

Iodine <M

Iodine 0 _? 3

0.12

0 _s 12

!nearly

Copper bronze

0: 3

ι H-Br omoe! ic c in " j inücl 0.22

Beiaglel g

Sine KisGhung of Ii _f 6 ropes Bis (oh? .Sromet ^ i} darol _? 9 _S 0 Tel «lea laliqmoyanatc 50 Volraateeile
share H _f K «Iiiaethylacetainid ₉ 2 part

VP-; C ₅ -standard); 0 _r 5 divisors

009883/2259

BATH

Iodine was stirred at the reverse flow temperature under a nitrogen atmosphere. After 15 minutes there is V <, P, C <, a single peak ₉ which can be assigned to bis (iaocyanatomethyl) durol? the estimated yield was 89% «'

A similar preparation, in which the iodine was replaced by O ₉ 2 parts iodine monochloride ₉ showed that the conversion to diisocyanate was acidic in 45 minutes. The yield of bis (isoeyanatomethyl) durol was 79% *

Example 10

A mixture of 11 "6 parts of bis (chloromethyl © methyl) durene ₉ 9 $ O ropes potassium cyanate, 50 parts by volume of monochlorobenzene" 50 YoIiotteilen N, N-Dimethy! Acetamide and O "5 parts of bromine was stirred at the Hlickflußtemperatur under nitrogen _a After 60 Minutes VP0 _e s showed that the reaction leading to the diisocyanate was sinful _o

An identical production, but in which the bromine is omitted took 105 minutes to convert to the diisocyanate

Example 11

A mixture of 4 ₉ 0 parts Ä'thylenglykol-bis (cliloroiB.ethyl) ether, 5.0 parts of potassium cyanate, 47 ₈ 5 Yolumteileia Monoehloro »benzene and 2.5 Voluiiteilen Ν, Ν-Dimethylacetamia was in HiiclEflußtemperatur under a nitrogen atmosphere stirred *

At the same time, a similar preparation was carried out using 0.15 parts of iodine

Samples of the two preparations were made after cooling and checked after centrifugation by Znfrarotepefctoskopie, whereby

009883 / 22S9 ' _BA D

031290

HatriiaiießlG2? Iäi8sßQgsa8ll (i3Qi with a siasr üegläsge of 0.1 mm used ϊϊογοθβ-, The © ptisehea Biohtesnsss ^ agaa the Isoeyanet = - epitze at 2260 ei ° seigt © öi @ Ifirfeaag of iodine, The Angabea do you see οθ? following table 5--

2t SJLt ttÄ Bit, <Jüi @Ha s iodine 26th St. 0
1 O ₉ 55 sgas ^ a. '"Ti ·. ¹ , - ^ sl ^ -J ^ e
"0 ", 27 58 ή . 2 0.45 - 0 , 23 105 W. 3 Op 42 0 , 23

An examination of sample reactions showed that the tbyl- xmä Ble (isocyaa koi was

4 «refa f» Ρ * 0 »wäteenä dea progress of the

ei äas

ith © i? * => ä @ rivaten ττοη Ithylengly «

an end product

el

Bias Usehong aas

H © Beetiioj? © b © ag @ l sa

Ropes

Bise cifeslioae Herstelinag jeäoefe practice doei wdggelaessa

l @ i @ lis @ itig aiasg®fütet

BATH ORIGINAL

Samples were taken from both preparations and examined by infrared spectroscopy, using sodium chloride solution _{bells with a range of O 4} 1 mm. Optical Dichtenmeeaungen on the isocyanate peak cm at 2275 "brought the results shown in Table 4 below, which show that _r iodine conversion Isooyanat increases.

Table 4

Optical density measurement RGO peak at 2275 cm

■ ** JL

t
Time I min sample with iodine without iodine I! 23 ■ 11 O ; ο- 0 t 96 U • i ί O e 134 H 2 I .ο, 31 C. , 02 169 3 I o _f 40 • C _: 05 4th j ο. 35 0 -07

Example. 3 3

? A mixture 'of 3 _S 5 parts of n-amyl bromide, 2.5 .Teilen Ka "liumcyanat * liitrotenzol 50 parts by volume, 2 parts of n-decane (internal VP, C standard) and _G: 075 parts iodine 7 / urde ■ under a nitrogen atmosphere stirred at 64-165 ° C - a comparison test bef. When the iodine was omitted, an optical density measurement was carried out at the same time. The desired "Ieooyenatspi'tse at 2275 oa * -" in the infrared spectrum after 125 minutes gave values of 0.69 or 0.57 after a prolonged period Heating, the individual values were 0.06 hew- 0.02-

009883/2259

BATH ORIGINAL

In both experiments, samples were also examined by chromatography. The time to a maximum Isocyanate yield in the catalyzed and in the uncat & ~ The ionized response was 200 minutes and 280 minutes, respectively.

009883 / 22E9 BAO ORIGINAL

Claims (1)

Claims A process for the preparation of organic isocyanates by reacting an organic halide ,, containing at least one aliphatically bonded halogen atom, with an alkali _s "alkaline earth metal or Ammonimneyanat in Gegegenwart a catalyst _F characterized in that iodine as a _catalyst? an iodine chloride, bromine or a mixture thereof is used « . 2-, method according to claim 1, characterized in that iodine, iodine monochloride _? Bromine or a mixture thereof is used c The method according to claim 1, characterized in that as Catalyst iodine, iodine monohydrate or a mixture thereof is used. Method according to claim i or 2, characterized in that that the organic halide is one-halogen alkyl-oxarene is used, the one or more «sa-haloalkyl radicals containsi which are bound to an aromatic nucleus " 5 " Method according to claim 4, characterized ₅ - that a compound is used as * b * haloalkylarene which is obtained by chloromethylation of benzene or an alkyl-substituted benzene» 6 ,. Method according to claim $ _? characterized in that bis (chloromethyl) durol is used as the oil »haloalkylarene. BATH ORIGINAL ^{009883/2259 ö} , Procedure according to one of the preceding ». Claims, thereby marked-: that it is aitsg & fUxrt in a solvent will - The method according to any one of the preceding claims, characterized in that the reactants together to a temperature yoo. 50 to 160 ⁰ C are heated «, 9- The method according to one of the preceding claims ₅ characterized by the fact that the amount of catalyst used is O ₉ oil to 5 _y O percent by weight based on the organic halide - BATH 00 9 883/22 5 9