DE2425991A1 - MULTIPLE HALOGENATED PROPENYLBENZENE DERIVATIVES IN THE CORE AND SIDE CHAIN - Google Patents

Description

Iroisdorf, May 28, 1974 055: 74 051 (2349)

ΒΥΙΪΑΜΙΪ JiOTiSL APiIBE & SSEILSOIIAPT ! Droisdorf j District Cologne

In Ee: e: a and side chain - multiply halogenated propenylbenzene

tDiid of the invention is a Tc r guide for manufacturing of Fropenylfa82201- "OeriTatcm which are frequently halogenated in Ke: cn and side chain the Ifcxiiiel I

.CH ₂ -C (X) = C (X) ₂

where X is the halogens chlorine or bromine, and R is alkyl., X or the Crrap-pc '• ■ GJ-L _> ~ GX --- ü (X) r _> ", characterized in that halo-oiotbyl-ρ' ΘΏ-tahalog-eiibeiiaolej, halomethyl-alkyltotrahalognbf.'jjüO'le ₅ or bia ~ (halogennietliyl) ~ tetrahalogenbena oils of Fonael II

H!

v / ox'in X die gonanrite BedcutUii ^, \ χϊΛ 11 'have the meaning H odor • -Ott ,, Χ, mii; Tr: ic! Ilorä: thyle2i or Tribroraäthylcn-in the presence of νου anhydrous ei · AJ.mninj.iiinchloi'id uiagesotzt. v; ol> ei

509851/1041

BATH ORIGINAL

optionally with an excess of Irihalogenäthylen as a solution. medium, or worked in another inert solvent will.

The invention also relates to the new compounds of formula I.

Preferred alkyl groups are those with 1 to 8 carbon atoms, and methyl-j. Kfchyl, n- and i-propyl, and the isomeric butyl groups are highly preferred. ·

The halogen in the nucleus can be chlorine or bromine or both together. In the side chain of bromine can occur _t Verden when used as starting materials Bromine thy 1 compounds. Of particular value are [_2 «3« 3-Trichloropropene - (2) - yl {-pentacblorbenaol, ~ pentabroiabenzene and isomeric methyltetrachloi ¹ -bcmsols of the formula III

Br, or Cl ..

(Br) (Br) or = C (Cl) ₂ , III

₂ or or

vjorin R "denotes methyl, chlorine or bromine; furthermore the isolate Bis- [2.3.3 ~ trihalopropen- (2) ~ yl] -tetrahalogenobenzenes of Formula IV

(Br) (Br) ₂ or or

Br ₇ , or Cl>. /> ^: ^^ - CH _? -C (Cl) = C (Cl) ₀ , IV 4 47 V

or or
(Br) ₂ (Br)

5 0 9 8 51/1041

as well as also Propeny! connections with partial place complete replacement of nuclear chlorine by bromine. The new compounds can be used as water repellants, starting materials for the synthesis of pesticides and intermediate products: used.

Although it is known, 1st i-rDihalogen-3-ary propene by elimination of HCl as well as to used as starting substances .Ί 1 .2 - '^ rihaloge5i- "5 - si'y ^ P ^{r' o} P ^3rj: - 1-Φ Resktionsgei'äft surs * Benisyllialcgeniöeü "form, but there is a dichloroethylene" build-up of the side chain and al, <3 catalyst! a Lev, ^r ia acid _(be-Vorsngt Eiseri-IIL chloride verv cnölc ^r. t '

! fach "Isvectije ^ irademii Kauk SSR, Otdel, Eliiia.Biauk (1955) 993-998, (1959) 652 and 1-028-1035 ωιά (i960) 447-451 are you 3 ~ Aryl ~ 1..1, -diclilorpropene by J? RieöcO- ~ CraftR ~ Eeüktion Benaol, odor substituted Itenaoles lait the cchv / er procurablei ^ «S ^ -i'-richlorpropon, 1.1« 3 ~ 3! Richlorpropon or over halogeniex-th Pro]) enen known. ..

Fach Journal of Ainsricaii Chemical Society 7j5r (1953) 6216 _r is also the reaction of toluene with CrichloräthylöM in the presence of peroxidii-johcr EatalyGatoren εον / iö according to DAS 1 140 565 rait 'fetraclxloräthylen above 500 ⁰ C au not j yes grain halogenated cai 1.1 « Mclilor - ^ - pheny 1-propen, or <1.1.2-5Prichlor ~ 3-phsny! Propen: known.

Mon the latter years usually deliver you ;: costly to leomeremgcTaiscliei besides abundant byproducts.

5 0 9 8 5 1/10 41

According to the present process, however, are ü.5.e highly halogenated in the core, "previously unknown Ealogenpropen.ylrryle including bis- (halogenpropenyl / -tetrehalogoiiaryln easily and in good yields in short times aas iCrlhsloß'cvjäthylenen and lcern-halogenated benzyl chlorides or from di d \ '-Xylylenediculoriden under Friedel ~ Gröfts ~ BediiigUBg: ej], whereas surprisingly, the Uir-zetZiVJig with the use of 1,1-dichloroethylene and further with the KatoIysato3? s of FeCl, or SbUl ₁ - does not succeed. The implementation can be illustrated by the following formula for bis- [ö (, ck '-dichloromethyl J.- (2.3.5 «6-tetrschlor-bezoi-pxylol) and! TrJ. eliloräthylen as follows:

Cl Cl.

- CH ₀ Cl + 2 ClCH = CCl

AlCl.

-2IJ01

Cl Cl

Cl Cl

Cl Cl

Me reaction can proceed at temperatures from about 35 bio 160 ⁰ C, preferably be carried out between 40 and 80 ⁰ C. ! The production can preferably be carried out so that taüii anhydrous Alufiiiniucichlorid in dry trichlorethylene

509851 / KH1

BAD ORIGINAL * ^j "

rsü.3peräler!: ■ and intestines add the benzy! halide to be converted. Kap lets the reaction start at about 50 ~ 60 ⁰ G, "causes a temperature of about 67 - 70 ⁰ C by cooling for a time of about 10 to 100 minutes, generally 20 to 60 minutes for the lift reaction. When using, for example 'Carbon tetrachloride as a solvent, it can also be expedient to work at its boiling point ScB.' At 76 to 77 ° 0 and dissipate the heat of reaction by boiling it,

Under all conditions, the propene derivatives / * - are formed predominantly with elimination of one KoI hydrogen halide per side chain. _r .

■ UnterauIb of ETYA 50 ⁰ C, however, are mostly, almost exclusively without elimination of hydrogen halide are known · Propylderivate formed.
The reaction stone temperatures are accordingly critical.

I): The course of the reaction is, however, also of the type of eingüetijtöja. Benzylliologeniäes dependent.

Kacli j: -o; cr; digur.iß the reaction time v / ο. A small amount of R ^ ethanol Ijei etuo 40 ⁰ O is dripped in, and the main amount of aluminum chloride is decomposed.

The 'processing of the AaaStir.e takes place ^ c after the. Löolichkcito e \ &:;Y>'shafts of RuokticDc ^ roduVle im ^ /' icbloräuiylüMabc-rtfchu.fc. oii-o \ / eäor by ctörker: cooling down, Einöcn.pfc.ii _r or überiogüx-d by simple Aufji'ülle »with Mütha

509851/1041
BATH

It has proven to be advantageous not to carry out the reaction solely with aluminum chloride as a catalyst, but also in addition still use small amounts of iodine. Other Friedel-Crafts catalysts such as, - anhydrous iron III chlorift, Boron fluoride or! Eitan-IY-chloride have a significantly worse effect as aluminum chloride, or not at all catalytic "

The reaction takes place in the presence of 1 to 40 mol percent _? preferably 1.5 to 20 mol percent of anhydrous aluminum chloride per mole of starting material, 2 to 5 mol percent being sufficient on an industrial scale and expedient because the temperature control is then easier.

If appropriate, the reaction is carried out in the presence of an additional 0.01 to 0.2 molar percentage of iodine per Ϊ · 1ο1 starting material used, preferably 0.075 to 0 _? 12 mole percent iodine.

If moisture is caused by raw materials, solvents or When handling the apparatus, it is advisable to first j remove a small part of the solvent distill off this water and only then after the suspension has cooled down, add the anhydrous AlCl ^ and carry out the reaction.

Inert solutions can also be used. ·. · ;. Thinners, especially chlorinated aliphotic carbonic substances vn'.e Ethyl chloride, especially in the temperature range uis AO C, 1.2-dichloroitlylerij Carbon tetrachloride or an excess of tri-

509851/1041

chloröthylerj, further chlorinated aromatics such as C hl or benzo 3. or oils dicixlorbei-i / iole ,. as; Olefins, provided that HX are absorbed "should be connected. It is also possible in the absence of. Voraünüvm ^ ii-uiteln ku work.

The Ausößsr ^ si-v'SjüfTe are mostly large-scale products. by. Nuclear Halogenation and Soitün ^ ettenhslogenic- vim ?; from Soluol »xylenes and ent apre cbeuö from Alkyl-Raetbyi-ben» olen bav; _t tliylen in the trap dec iOrlcliloratliylemi durcli chlorination ν όχι Ά, erl) whether olt be.

As an example for. the device according to the invention HöloGousul) -

alüßonide are ßeismmtt in Öiiiisolnen

p (j / cC ^ iOyl and po (»<* '-Di-.chlor (2.5.5.6-tc- !; rö ¹ brc.r.0-xylene _r Bowie the estcspreclier.den iaetaodor ortlio-Te-rMiK' Umgon, the ο-, in-, or p-Mstayl-oiilorineifcyl "· (2-. 3« 5 «G-tetraeb-lorben ^ ole), PontochlorbexiKylcblorid, Porrfcabxoriit.enEyleblorJd sovvie rA _t cA '-Dibron- (2« .3c S.fi-tetrabrora-p-cylol) nrA deBöen meta- and ortho ~ lso)? Iorsn.

Be2TÜß3..I dor quantitative behavior bc-? I the implementation of the according to the invention Method v / are the following areas as advantageous, err-rboitet:

However, particularly men employed per mole of starting the Bensslvlialogeniä ~ 2 to 12 times its Gewiohtsmenge to Trihalogeuäthylen, the 4- to 6 ~ <Fähe amount mono- _t of aluminum chloride are used per MQI Benay halide 5 - 50 g, particularly advantageously however 10 - 35 g. Even small ones are enough for the co-catalyst JOd

509851/1041
BATH ORIGINAL

Amount - ::;, n & üXieh 10 mg to 250 mg per mol of benzyl halide used, but especially 80 to 120 mg.

The ancestor vircl geηa preferably at atmospheric pressure, optionally under the autogenous pressure of the reaction mixture Mixing vessel carried out, which against the humidity e.g. through a kit; An example of this is an acidic desiccant filled rs absent: ion sr ear is secured.

The data obtained after the process of the invention _s new materials provide colorless ₅ generally well crystallizing compounds cicjr vary their .Schmelzpunkte over a wider range.

The neci-ifclgcndon examples illustrate the scope of the invention however, they do not.

509851/1041
BATH ORIGINAL

Be i hv ί ο 1 1

Preparation of 1 - [2.3.ji-trichloropropene - (2) -yl] -2-raetbyl- (5 «4 ° 5.6 ~ tetra-chlorobenzole) :

15 g sublimed; _} powdered AlurainivKiclilorid in 915 g (- 625 ml) technical, rciuom, trocl> .ene: a itrichloräthj ^ lcn suspended with stirring. In the suspension are men 15'iog iodine and warmed to 50 ⁰ O. At this time, vre'ixlen then in portions "\ '59, 2 β (0 ^ 5 mol) 96» 3 Gev ;. - ^ igen l ~ CiiXo -rmethyl-2-iäethyl · »( ? _t 4.5. ö-totrachlorbensol) from the Scirtöp, -96-99 ⁰ C-registered in such a way that the '0 upstairs door of the Real'-bionfsgßriiincliCfi is not VJbor 6O ⁰ C alisteigt _v Eb 1 h} x:. i GO ⁰ G nochgerährt-y it £ tm about 4Q ~ 45 ⁰ 0 left & W :: i \ !. ILCN and Wc-it-err-ühren- 50 ml methanol teclm reinos ej "dropwise. _5. With a slight increase in comparison, resgistricht vrira. During the course of the drop, the dark brown hoolr.t.iojis ~ also clearly brightens and! Te: ilriiOKgan of the raw action product. Precipitate in crystalline form ) ⁰ C is completed, then the auDgeffllerra crystals are abeagt off, washed with a little methanol, whereupon it rises again to-- ·

509851/1041
BATH ORIGINAL

UcIIt ₅ and dried. 169 g _{} are obtained,} corresponding to a yield of 90.5 Gev /..--/ £ of the theoretically possible amount. By working up the mother liquor, the yield can still be increased. ·

The melting point of the pale brownish crude product is found to be 152 15 ^ ⁰ G. By umkristallisatioii from benzene one obtains colorless * large? hard, coarse crystals from Schisp * 155 - 15G ⁰ C. Kochn: oily uracrystallization from chloroethylene yields small crystals with an unchanged melting point. . i

C ₁₀ H ₅ Ol ₇ (MW 375.32) ϊ CH Cl j

Calculated: 32.15 # 1.34 ^ 66.51 £ i

Found:. '. 31.97 % $ 1.29 66.72 ^ ^;

The structure was safeguarded by means of IR / BMR spectra, as well as by manse spectroscopy. j

lj

Ilorstellimg of · 1- [2.3.3 ~ "triclilor-propc; W- (2) -ylj (?. 3.5 = 6- iotrachlorbtin? Io'j):

Cl Cl

Cl Cl

509351/1041

A.) The procedure is as in Example 1, but "without the addition of iodine * 30 g of aluminum chloride, suspended in 1500 g of trichloroethyl ^{nylon, are added at 60 0} with 278.4 g (1 mol) of 1-methyl-4-ehlor2urfcbyl- (2.3 .5.6-tetrachlorberiCol) of mp. 98 104 ⁰ C - (. 96.5 Gcw ..- $ ig) added in portions so that the temperature is kept at "70 ~ 72 ⁰ C." This was followed by 2 hours at 70 ⁰ C. in particular, stirred au .Anfang the llealctiori is observed strong Entv.'icklung of Chlonvöonor "sweetener. ;

The dark- to black-brown reaction mixture is obtained by distilling about 1 liter of the trichlorethylene-oil. in narrowly, whereby in the end some substance from- 'k'rist-alliBiort ", the slightly cooled concentrate vrixd öoaDiuj with constant stirring with 2 liters of methanol * The color of the mixture is lightened strongly and the formed -iPrichlorpropeoyl-iKethyl -tstrsGhlorbenzoX above ΪΌχώ) ©! precipitates in flaky, crystalline form. After exhaustion »washing with a little methanol and drying will be Yj ?. g, corresponding to 94 % yield. The crude product scl'i & ilst at 94-98 ⁰ C Umkriotalli & ütion of 350 g from 1.8 liters

supply j-ether (methyl cellosolve)

302 Q colorless pure crystal from the Schvai). 104 ~ 106 ⁰ O nkt with -the output a ~ -Benzy! Halide 7 * 5 -

5098 51/1 0 A 1

C ₁₀ II ₅ Cl ₇ (MW 373.32): C II Cl

Calculated: - £ 32.18 1.34 1> 66.47 #

Found ί 32.40 g 1.26 5 $ 66.19 #

B) In methylene chloride els solvent:

20 g Alumlniumchlorid were dissolved in 465 g - suspended methylene "chloride then _t at room temperature, 139 _f 2 g (0> 5 Hol 5 Bens (350 al); y entered halide, the mixture to about 40 - heated 42 ⁰ C with stirring and! at this temperature: ·: in about 15 minutes. 69 g (0.5 mol + 5% animal shot) 'J? r: 1 · · * chloroethylcn dripped. That reaction takes 2 hours, "at etv; a 42 ⁰ nachgerü.lirt G. Thereafter, 50 lal methanol ί rage dropwise and -. portrayed 20 ⁰ C.

The precipitated product is filtered off with suction, washed with a little: methanol and dried. Aufshcute 14> g (77 _s 0 * a-Schrap. 101 - 106 ⁰ C. Outline allieation of 120 g from θtv? N 1600 ml ifjopropanol yields a forbioes Kr: If.le'Jliaat from Scliiap * 104- - 106 ⁰ Cs , I-iiscliGschmelzpunkt with Ausg -.- m ^ siiaterirjl 81 - 85 ⁰ C and indentiechen analysis values as in experiment Α .. Structure, in particular that toxliandrjoin of the rioprjolbin.'Ti'-iC} their position, as well as the position of the Cl-Substitutiort f > ind sprk-. troscopically ßiehergostellt ^

Production of 1 - [2.3 * 3-- £ richlor ~ propsn ~ (2) ~ yl] -3 t ο 4.5 ♦ 6 ~ t6traclilorl? 3HEol):

509851/1041
BATH ORIGINAL

- - ■ - - —- ~ 2-42-599l ·

Cl - <'\> - CH ₂ -C = CCl ₂

Cl

H ₃ C Cl

In 915 g (- '625 -ml) trichlorethylene and 15 g Aluminiumehloriä under stirring at 60 ⁰ C 139.2 g (0.5 mol) of l-öhlorinethyl-3- "Heth5 ^r l- (2.4.5.ö- . 88 ⁰ C and 98 percent purity -foigev so entered stir under that temperature of the dio Keaktionsgeroiecliefs to "holds at 70 ⁰ C - tetrachlorbensol) from S.cbmp 85th!. 'To it . then "is 2 hours" nach.gertih.rt at 6O ⁰ C, whereupon: about 40 - "45 ⁰ C 50 ml of methanol are added dropwise with stirring, Me mixture was then a few hours" stored at -2O ⁰ C and then the crystallized product separated and processed by Häehwaöohen with methanol and drying. Yield 148j5. β (79.5 &) blaßbrnimec Krlstellisat voia Sctirap "111-116 ⁰ C, of 1- (2 ':. 5.3 Irichlorproperiyl) -5-methyl- (2,4,5,6-tetrahydro ·· - chlörbenaol) dürfjtelltt A very pure ₅ ferbloscß product _$ . that the dchmp. 117 - 1-1 "besltst 9 ⁰ C, maxi obtained by Üiakri.otöl- ■ isation of Hothylcellosolve (1: 7 _5?) Emoute Umkrißtalli-!." Organization from cyclohexane (1; 4) changes the SeViEip. not.

C ₁₀ B ₃ Ol ₇ (MW 373.32): CH Cl-

Calculated 32.18 ^ 1.34 55 66.4-7 56;

hleni "^ 2.14 ^ 1 _f 22> fe 66.68 ^

509851/1041

-H-

The position of the chlorine atoms is clear by NMR spectroscopy ig secured.

Preparation of 1,4-bis- [2.3.3-tricb.lorpropen- (2) -yl] -2.3.5.0 * tetrahalorbensol:

Cl Cl

II
Cl Cl

According to the working groups of Example 1, the following sub ri ssur reaction failed:

1.83 kg (- 1.25 mTOR) Iricbloräthyleo, 30 β v / asDerfreics, powdered Aliisiiniumch and 313 g · (1 mole) _1% A * bis-Cchlomethyl) -2.3.5.G-tetracltlorbenssol (Sohrap 172-. 177 ⁰ C \ 96 Gcv /.- ^ ig

The suspension of the A liuüiniumeliloriels iw Irichloxäthylen submitted to 6O ⁰ C vorgov / äratj Urid in this Ceraperotur the Benjsylha'Jogeaid so under is {. Watches entered "that! Temperature does not exceed 7O ⁰ C addition. At 6O ⁰ C intestine is so long (about 20 min.) Nachgtmihri ;, until solidification of the KciBgeüiiüche: · occurs. The Uiücot ^ une; is of strong Clilor

509851/1041

accompanied by hydrogen evolution. Kach cooling to about 40 ⁰ C is eingatrögen the Resktionogeinisch kräftigein under stirring in 2.5 liters of methanol and then the yellowish white crystal & l- "lisat sharp aspirated and after JTacbv / ash dried with methanol.

Yield 472 g ( $ 93) of the Sclimp. 167-172 ⁰ C. A Umkrietallisation ous methoxy-ethyl chloride in the ratio i ί 17 supplies, .a completely colorless and analyeoyireino "substance; Yoia Sehnp. 176.-. 178 ⁰ C. Mieichschraelapunkt with the starting material · 147 ~ 15O ⁰ C..

Mo EleTiöntarosaiyse the pure crystals gives the following Worth

C ₁₂ M ₄ Cl ₁₀ (KG! 5.02.7): 0 H Cl

Calculated i 28.63 i- 0 _s 00 # 70.60 ^c />

Göfuriden: - "· ■ 28.57 ί> 0 _} 91 ^ 70.46 ^ -

The position of the double bonds and the position of the carbon atoms In the Söitewiketten .IR ™ and BKR ~ spectror> Kopiceh's research confirms

Example 5

> ^ nm ι μ Ii ■ in 1 * 1 n. im _ ^ iii-i m

The production of 1,4-bis- [2.3.3 ~ trichloropropen- (2) - yl ~] 2.3.5.6-tetrachlorobenzene with various amounts of aluminum chloride shows its influence, among other things on the yield. In a three-necked flask equipped with a stirrer, condenser, thermometer, 62 _f 6 g of 1,4-ε ie- (chlorometh3 "l) -tetrichlorobenzene

5098 5 1/1041

(0.2 mol), 1.25 g of AlCL ₅ , 65.7 g of trichloroethylon (0.5 mol) and 217 g of CCl, added and slowly heated. The exothermic reaction started at approx. 55 ^{° C.} The temperature was up to the boiling point of the CCl. (76.7 ⁰ C) increased and left at this temperature for about 3 hours. The mixture was then cooled to about 5O ⁰ C, diluted with 250 ml of methanol, and after complete cooling to room temperature the precipitate was filtered ₉ washed with methanol and dried. The product is slightly gray in color, but very pure according to GG and MI-IR investigations.

Ausb.i 95 g (92.5 $ d.Tb.) Pp.ί 177-178 ⁰ C

The following is the procedure of Examples 5 * 1 to 5 * 7 given using example 5 »7:

In the apparatus already described, 62.6 g (0.2 JKoI) 1 _e 4-bis- (chloromethyl) -tetrachlorobenzene, 1.25 g anhydrous aluminum chloride - corresponding to 1.99% by weight of the Aucgangsbenzy! Halide- and 283 g (2 _15? mol) Trichloratlrylen presented.

The mixture is slowly heated while stirring.

The exothermic reaction starts at 55 ^° C. and is intercepted at 68-69 ° C. by weak cooling. After the exothermic reaction has subsided, approx.

1 hour at 68-70 ⁰ C stirred further. Sodsim is cooled to about 4O ⁰ C $ 250 ml of methanol, further cooled with stirring, and the filtriort dsncch Kristcllbrei,

509851/1041

The crystals v / ith nachcewaschen with methanol and dried, 94.2 g (93.7 '& theory) of pure white substance of mp. 177 17S ⁰ O, G-mit.einer .C. purity over 99.5 jS v / ird received. The table below gives the result that was obtained with the same procedure with different amounts of AlGl ^ -M ^ (Examples 5-1 to 5.6)

Bej Gp, Ir,

Benzyl halide 0.2 mole

62.6 g

62.6 g 62.6 g 62.6 g

"62-.6 g 62.6 g

.62.6 g

! Trichlor-I: ethylene

Aluminum chloride ¹ yield.

of
materials

366 g = 2.79 moles

366 g 366 g 366 g 366 g 283 g 283 g

1.5

0.75

0.375

1.0

1.25

9.6 22.5

4.79
2.39
1.198

0.599
1,596
2, OO

86.9

11.25

90.5 88.5

5.63
2 j 81

1.41
3.75
4.68 i 93.7

M.p. » ⁰ ° C

177-79 178-79

176-79

Hardly! Response 93.7 1177-78

M77-78

The gas chromatographic purity (G-.C.) Of the reaction product is above 99 _f 5 5 ^ _{c in all batches}

Example 6

Preparation of 1.5 ~ £ ii> ~ (2.3 «I-triohlorpropcn- (2) ~ yl) -2.4 * 5.6-

509851/1041

Cl Cl
Cl -

Il Cl

Cl

Cl ₉ C = CH ₀ C Cl

As in "Example 4, 1.83 kg of trichlorethylene, 30 g of aluiaijiimiLcb.lor.id and 315 β (1 mol) 1,3-bis (chloroTBethyl) -2.4.5."& ev /. ~ $ ig; Schm.p. 137 «137.5 ⁰ O) at 60 - 65 ^ 0 üjmges-stst".
1 Stmidü v / ith at 60 ⁰ C iiochgeriibrt.

After cooling to normal temperature, the reaction mixture is stirred with 2.5 liters of cold I-lethonol, the yellowish-vjeirjsc Pällungr.product is suctioned off, refilled with methanol and dried. This gives 480 g (95.5 £) of crude product from Schwp. 99 - 102 ⁰ O. Umkristollisation of Gcöaistproöiüctes from 10 liters Ißopropeaol yields colorless, matted needles Scbrop. 102 - 103 ⁰ C ^:

C ₁₂ H ₄ Cl ₁₀ (MW 502.69): CH Cl;

Calculated:. $ 28.63 0, SO & 7O ₄ GO #

a found: $ 29.03 $ 0.82 i 70 _} $ 41 \

509851/1041

- 19 Production of '. [2.3.-3-Trich, lQrpropen- (2) -yl] pentachlorobene-

Cl 01-

'__ [Cl Cl

■ ■ Vi ^{fc ci}

Cl Ol

60 β PeniQoblorlienwyloiiloicici virden in 250 ml dry Wr i ~ cliloräthylc},! nit 6 g waowerfx-oiem aluminum chlorides from Example 4 -.- "bcBCliriebG'n-j boi 7O ⁰ C implemented" anise de-2t 6rliölteten _s scliwarnbraiiisen Rsoktionsgniucli were da "

1 - [2.3 · ^ - ^ riclilor- _: propon- (2) -yl] -2 «3.4.5.6-pentacTilorbenEol by addition, precipitated from 350 ml of Kethsnol} sucked off, mil; some Hetlicriol Kactigeviasclieii mid gctroclrfiet. 66 _t 3 gj corresponds to 84 ^c ß> yield »from botop. 136 - 139 ⁰ C v / urdcn obtained. li / iikr-istalliüatiGn from 400 131 GycXohe-xcm with the addition of AktiVkolile supplies the i'üine substance from Schiup. ■ 144/145 ⁰ C. The structure -was by KMPv- and Maßsenspektroskopischo UntcrsiclicrgGstsllt.

C ₉ H ₂ Cl ₈ (MW 593.77) GH Cl

Calculated: $ 27.46> $ 0.51 5 72.05 ^c / '

^: ·. 27-, 51S ^ O _s 55 ^e /> 72.19? '

509851/1041

Example 8

Preparation of a [2.5.3-irichloropropene- (2) ~ y1J containing some chlorine in the nucleus -pentabrombsnzols:

The starting benzyl halide is made from pentabrointoluene as follows manufactured:

(Mp. 284-287 ⁰ C) 486.7 g (1 mole) pentabromotoluene are suspended in 700 ml of hexachlorobutadiene, iag the approach to the masking of iron traces 490, - $ 0.1 to Pentebronitoluol = -. added to ethylene diamine tetraacetic acid, and the mixture to 185 - 190 ⁰ C accommodated. At this temperature, the. On the surface of the slowly stirred mixture, chlorine was introduced to such an extent that only a little chlorine appears in the offgas in addition to the hydrogen chloride formed. An oversupply of chlorine is to be avoided if one wants to obtain a pentabromobenzyl chloride with only a weak chlorine content. If the excess of chlorine is too high, the Br-Gl exchange visibly occurs when bromine vapors occur in the reaction vessel. The required amount of chlorine can comfortably be introduced in about 120-150 minutes, with the uptake going slowly at the end of the reaction. The starting material goes completely into solution during the reaction and the end of the chlorination-up to Bsnzylchlorid-

509851/1041

level is clearly evident from the fact that also with bromine vapors occur when there is a small supply of chlorine.

The supply of chlorine is stopped and the reaction mixture is allowed to cool. The chlorination product largely crystallizes out. It is filtered off, washed with petroleum ether and dried. 453 g ( $ 87) of a yellow-brownish criotallizate with a melting point of 1-6-2-166 ⁰ C v / earth obtained. Recrystallized from cyclohexane 1 ί 20 pale yellow! Blame Schmp.i from 170-172 ⁰ C, which have summarily true for Pentabrombenzlychlorid analysis values.
C ₇ H ₀ Br ₁ -Cl (MW 521.10)

Calculated: C £ 16.13; H 0.39 ^ j Br £ 76.68; Cl 6.80 #. Found; C 16.44 1 ° \ H 0.40 $>% Br 76.80 #j Cl 6.30 #. The spectrographic examination showed that per Pormelunit an average of 4.5 bromine and 0.5 chlorine are bound in the core. The remaining amount of bromine is bound in the benzyl side chain ο

Production of the propeny derivative:

20 g of anhydrous aluminum chloride are suspended in 3.75 liters of dry trichlorethylene, 1.563 kg (3 mol) of benzyl halide prepared as above are stirred in and the reaction is carried out according to the method of Example 5, the exothermic reaction starting at 65-70 ° C. The brown reaction mixture is cooled, kept for 2 hours at -20 ⁰ C, and the precipitated crystals are filtered off, the brown crystals are washed with methanol and dried.

5 0 9 8 51/10 41

There were 1.56 kg (84.5 ^σ / °) blaßgelbbraunc substance of mp .: 159 - received 163 ⁰ G. Recrystallization from benzene 1: pale yellow crystals m.p .: 161- 164 ⁰ C. Mischsehmp. with the starting material 130-149 ° C.

According to IR / HMB analysis, the product consists of one at its core weakly mixed Br / Cl-halogenated irichloro-3 ~ (pentabroiaphenyl) -propene. ! Accordingly, the molar ratio Br / Cl = 4.5 / 0.5 was retained in the core when the side chain was built up, however there is little or no bromine in the side chain.

The elemental analysis provides the following values:

C 18.38 > \ H 0.38 %; Br $ 63.42, CL $ 17.86 and is in agreement with what has been said, as can be seen from the sum comparison calculated values for pure ^ 2.3.3 ~ irichloropropene- (2) -yl] -pentabromobenzene, namely

C 17.55 ¥> \ H 0.33 %; Br 64.86 #; Cl 17 _? 26 ° / o _f can be seen.

Setst men correspond to the procedure described in Example 3, m ™ or p-BiS "(broK! Kethyl) ~ tetrachlorobenzene with trichlorethylene, removes the 'Jlrichloräthylenabsruß in a vacuum and stirs the remaining dark oil with about 200 ml of methanol, so laajj obtained in about 90 / ager iusboute ri- or p-bending (trihiilogen-propenyl) compounds scnaolsen in the case of IA-90 Isoraeron ^c G, un when p-Inomeren 19O ⁰ C. Mc · substances are not uniform, but represent, on the basis of mass spectroscopic examination, mixtures in which the bromine sits in different positions of the side chain,

5 0 9 8 51/10 4 1

yes even within the m- or p-isomers on a side chain is bound in the 2 position, on the second side chain in the! position.

During this reaction, mainly splitting off of hydrogen chloride occurs and only a little hydrogen bromide, as can be seen from the chlorine-bromine analysis of the reaction products. Was found: Br $ 21; Cl 54 #.

The bromine-containing propenylbenzene derivatives have the advantage of better solubility in organic solvents.

Example 10.

A bundle of viscose fibers is dipped into a 10 G-strength solution of the product according to Example 1 in OrichlO: ethylene and then dried by pressing and evaporating the solvent. The Viasseraufnshme the so hydrophobized Fasom VBT compared to that of the original fibers by? _5 ^ reduced. '· ·. *

509851/1 0A1

Claims (1)

- 24 patent claims 1. Process for the production of core and side chain multiply halogenated propenylbenzene derivatives of the formula CH ₂ -G (X) = C (X) ₂ , where X is the halogens chlorine or bromine, and R is alkyl, X or the group -CHp-CX = C (X) _? mean, characterized in that halides thy 1-pentahalogenbenzenes, halomethyl-alkyltetrahalogenobenzenes or bis (halomethyl) -tetrahalogenobenzenes of the formula II wherein X has the stated meaning and R 'has the meaning -R or -CHpX, with trichlorethylene or tribromoethylene in The presence of anhydrous aluminum chloride can be reacted, optionally with an excess of trihaloethylene is carried out as a solvent, or in another inert solvent. . 2. "The method according to claim 1, characterized in that the reaction ^{temperature between 35 0} C and 160 ⁰ C, is preferred 509851/1041 is between 4O ⁰ G and 80 ⁰ G .. 3. The method according to any one of claims 1 or 2, characterized in that that the reaction is carried out in the presence of 1-40 mole percent anhydrous aluminum chloride per mole of starting material, carried out particularly advantageously with 1.5 "to 20 mol percent aluminum chloride. 4. The method according to any one of claims 1 "to 3 _}, characterized in that the reaction is optionally carried out in the presence of an additional 0.01 to 0.2 mole percent iodine per mole of starting material used _s, preferably 0.075-0.12 percent by weight iodine. 5. The method according to any one of claims 1 to 4 »characterized in that that the reaction in trichlorethylene, or an inert diluent, especially chlorinated Hydrocarbons, such as methylene chloride or carbon tetrachloride, are used, 2 to 12 times the amount by weight of the starting materials, in particular 4 to 6 times Amount used. 6. Compounds of the general formula I. Dr La/Be S09851 / 1CK1