DE1806758A1 - Process for the preparation of halogenated phenoxysilanes - Google Patents

Description

68 154 / (1353) Troisdorf, October 30, 1968

DYNAMIT PLANE AOIEIiGESELLSCHAFiD Iroisdorf, District Cologne

Process for the preparation of halogenated phenoxysilanes

The invention relates to a process for the production of halogenated phenoxysilanes from halogenated phenols and chlorosilanes. The process is particularly characterized by that the reaction in the presence of catalytic amounts of compounds of the general formula

«2

R ¹ - X - R ⁵ ,

in which X phosphorus, arsenic or antimony, R ' ^{1J can be} an identical or different radical from the group Y / hydrogen, fluorine-free alkyl, cycloalkyl or aryl radical, or their quaternary compounds, optionally with the use of solvents, at temperatures of 20 -250 C, preferably 50-20O ⁰ C, carries out.

According to J. Org. Chemistry 2 ^, (1965), p. 1645 .τ 1648, attempts have already been made to produce halogenated phenoxysilanes by reacting the corresponding sodium phenates with halosilanes in xylene. In this way, for the first time,

009828/1945

180R758

St.

to produce the phenoxysilanes of pentachlorophenol and 2,4,6-trichlorophenol in yields of about $ 60. The disadvantages of this process are, in addition to the low yield, the unavoidable use of metallic sodium to obtain the sodium phenates in the required high degree of purity and the formation of large amounts of by-products, including inorganic salts, which means that the pure halogenated phenoxysilanes can be separated off, mainly because of de-) ren poor solubility and is made considerably more difficult by the suitability for hydrolysis. This process is therefore not used for industrial production.

Other general methods are known for preparing phenoxysilanes. For example, it is customary to prepare special phenoxysilanes from readily available esters, for example from ithoxysilanes, by transesterification, optionally in the presence of acidic or alkaline catalysts, such as p-toluene- tk sulfonic acid. It has been shown, however , that this process cannot be applied to the preparation of organo-halo genphenoxysilanes of halogenated phenols. If one tries, for example, to implement such phenols with organoorganoxysilanes in melt or in solution with or without Ka catalyst , it is observed that the condensation begins very slowly at first and finally comes to a standstill without the desired phenoxysilanes having been formed quantitatively.

Another method for the synthesis of Phenoxysiianen is the direct Kondensation.Yjon _Q Halö_gen.silan with phenols with

_% 180R758

or without a solvent with the escape of gaseous HCl. However, if you try to implement halogenated phenols by this process, it turns out that here too the Condensation runs very slowly and incompletely and comes to a standstill. This reaction can be in the presence of excess or stoichiometric amounts of amines are carried out, these amines acting as HCl-Tänger. In addition, a certain catalytic effect is ascribed to the amines, which consists in the fact that the amines with the Forming halosilane Lewis acid complexes. It is further known that halogenated phenols also in the presence of excess or stoichiometric amounts of amine, e.g. pyridine, do not react with the formation of phenoxysilanes, but As a result of their usually higher acidity, they form ammonium salts, which are then no longer capable of phenoxysilane formation.

It has now been found that halogenated phenoxysilanes can also be obtained in significantly better yield if the process for preparing halogenated phenoxysilanes from halogenated phenols and chlorosilanes is conducted in such a way that the reaction is carried out in the presence of catalytic amounts of compounds of the general formula

R ²

R ¹ - XI

in which X phosphorus, arsenic or antimony, R '*> * can be an identical or different radical from the group consisting of hydrogen, fluorine-free alkyl, cycloalkyl or aryl radicals, or their quaternary compounds, optionally using inert solvents, at temperatures from

009828/1945 - 4 -

20-25O ⁰ O, preferably from 50-2OQ ⁰ O carried out.

The catalysts can be used in amounts of 0.1-20 mol $, preferably 0.2-2 mol $, based on the amount of chlorosilane, can be used. You can use the approaches both at once and in several small portions can be added.

The implementation according to the above invention will preferably carried out at normal pressure. The method however, it can also be used at an overpressure of up to 25 atu applied v / earth.

The catalysts according to the present invention are phosphines, arsines and stibines or those derivable therefrom quaternary compounds such as phosphonium, arsonium and stibonium compounds.

Phosphines which can be used according to the invention as catalysts are for example: trimethyl-phosphine, triethyl-phosphine, Tri-n-butyl-phosphine, triphenyl-phosphine, diphenylethyl-phosphine, Diethyl phosphine, phenylphosphine and others

Suitable arsines are, for example: trimethyl arsine, Triethyl arsine, triphenyl arsine, diethyi arsine, diphenyl arsine i.a.

Suitable stibines are, for example: trimethylstibine,

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Triethyl-stibine, tri-n-butyl-stibine, triphenyl-stibine, Tri- (2-tolyl) ~ stibine, tri- (3-tolyl) ~ stibine, tri (4-tolyl) -stibine Etc.

Suitable quaternary compounds of the phosphines, arsines, and stibines can be: the hydroxides, hydrochlorides, chlorides and acylates. As an organic acid component of the Acylates are particularly suitable for the lower carboxylic acids with up to 4 carbon atoms.

Suitable phosphonium compounds are: triphenylmethylphosphonium iodide, iriphenylbenzyl phosphonium chloride, p-xylylene bis (triphenyl phosphonium) dichloride, p-xylylenbis (triethyl-phoöphonium) -dibromidloc (Dräthyl-bräthyl-phosphomidloc, te- ethyl bromide-phosphonium -phosphonium iodide, I, 4-butane bis (triethyl phosphonium) diacetate, etc.

Suitable arsonium compounds are: Triphenylmefchyl-arsonium-iodide, Triplienylmethyl arsonium hydroxide, triphenylethyl arsonium iodide, Triphenylhydroxyethyl arsonium chloride Etc.

The catalysts of the present invention can also be used in conjunction with known catalysts as well as tertiary Amines, the amino group of which can optionally be part of an aromatic ring system, and optionally N-mono- or dl-substituted acid amides and acid

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BATH ORIGINAL

imides or their quaternary ammonium compounds are used.

Suitable starting materials for carrying out the process are, if appropriate, alkyl-substituted, mononuclear or polynuclear, halogenated, monohydric or polyhydric phenols, which can be both condensed and non-condensed.

Suitable monohydric phenols are, for example, the fluorinated ones, such as 4-fluorophenol, pentafluorophenol, the chlorinated, such as 2-, 3-, 4-chlorophenol, 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5-dichlorophenol, S ^ -Dichlor-ö-methylphenol, 2,6-dichloro-4-tert-butylphenol, 2,3,5-, 2,4,5- and 2,4,6-trichlorophenol, 2,3,4,6-tetrachlorophenol and pentachlorophenol, the brorinated, such as 2-, 3- »4-broraphenol, 2,4-, 2,6-dibromophenol, 2,4,6-! Dribromophenol and pentabromophenol and those iodinated such as 2,4-, 2,6-diiodophenol and 2,4,6-triiodophenol. However, halogenated naphthols and heterocycles with a phenolic character can also be used such as 1-hydroxy-2,4-dibromonaphthalene and 8-hydroxy-5,7-dibromoquinoline.

Suitable halogenated, polyhydric phenols are, for example, the mononuclear ones derived from hydroquinone, resorcinol, pyrocatechol, pyrogallol, phloroglucinol and 1,2,4- trihydroxybenzene, such as 2-chloro- or 2-bromohydroquinone, tri- and tetrachlorohydroquinone, 2,4,6-tribromoresorcinol et al

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Polynuclear, halogenated phenols whose cores are not are condensed, for example, correspond to the general formula

(x) _a (D

HO

in which X identical or different halogen atoms, a or b an integer from 1 to 4 and T is oxygen or sulfur, a carbonyl, disulphide or sulphon bridge, or an optionally phenyl substituted alkylene or cycloalkyl enrest can be.

Basic types of these phenols are the dihydroxydiphenyls, for example 2,2 "-, 2,4 ^l -, 3,3'-, 4,4'-dihydroxydiphenyl, 4,4 ^f -dihydroxy-2-methyldiphenyl, 4,4 ^! -Dihydroxy-2,2'-dimethyldiphenyl, 4,4'-dihydroxy-3,3'-dimethyldiphenyl, 6,6 "-dihydroxy-3"3'-dimethyl-diphenyl and others

Dihydroxybenzophenones such as: 2,2'-, 2,3'- »2,4'-, 3» 3 ^! - _f 3,4 ", 4,4'-, 4,6'-, 6,6'-Dihydroxybenzoph.enon et al

Dihydroxydiphenyl sulfides such as: 2,2S 4,4 ^f -dihydroxydiphenyl sulfide;

Dihydroxydiphenyldisulfidej

Dihydroxydiphenyl sulfones such as: 2,2 · -, 4,4 ^I -Dlhydroxydiphenylsulfone;

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Dihydroxydiphenylalkanes or -cycloalkanes, such as: 2,2'-, 4,4'-dihydroxydibenzyl, 2.2 "-, 2.3'-, 2.4 ^f -, 2.5" -, 2.6 "- , 3.3'-, 3.4 ^l -, 3.5'-, 3.6 · -, 4.4'-, 4.5 ^r -, 4.6 '», 5.5'-j 5 , 6'-, 6,6'-, dihydroxydiphenyl ~ 2,2 ~ propane, 2,2'-, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxy-3,3'-dimethyl diphenylmethane, 4,4 '-Dihydroxydiphenylmethylmethane, 4,4'-dihydroxydiphenylphenylmethane, 4,4'-dihydroxy-diphenyldiphenylraethane, bis- (4-hydroxyphenyl) -4 ^f -methylphenylmethane, 1,1-bis (4-hydroxyphenyl) -cyclohexane, bis- (4 hydroxyphenyl) cyclohexyl methane, 1,1-bis (4-hydroxyphenyl) ethane and others

The halogenated, polyhydric phenols used according to the invention are derived from these types, such as, for example: bis- (4-hydroxy-3,5-dichlorophenyl) -methane, bis- (4-hydroxy-3,5-dibromophenyl) -methane, bis - (4-hydroxy-3,5 ~ difluorophenyl) -methane, 2,2-bis- (4-hydroxy-3-chlorophenyl) -propane, 2,2-bis- (3,5-diohlor-4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dibromo-4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -butane, 4,4'-dihydroxy- 5.5 ^! -difluorodiphenyl-methane, 1,1-bis (3,5-dichloro-4-hydroxyphenyl) -1-phenylethane, 2,2-bis- (3,5-dibromo-4-hydroxyphenyl) -hexane, 4.4 '-Dihydroxy-3,3', 5 £ '-tetrachlorodiphenyl. The corresponding tetrabromo or. Tetrachloride derivatives of 4,4 ^f -dihydroxyo - ".

* phenyl ethers, 4,4'-dihydroxybenzophenones and 4,4 * -diy- ^ roxydiphenylsulfone. The multinuclear, condensed, multinuclear

. -valent phenols are derived from the Dihydroxynaphthaco .

flrine or anthracene etc. from, as from 1: 3- »1: 4-, 1s5-, 1: 6-, cn · '

1: 7, 1: 8, 2: 6 and 2: 7 dihydroxynaphthalene.

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Suitable halogenated phenols are, for example, also the dichloro and dibromo compounds and the tetrabromo and tetrachlorodihydroxynaphthalenes.

In addition to alkyl groups, the phenyl groups can be of the aforementioned monohydric and polyhydric phenols also carry alkoxy, carboxy and phenoxy groups as substituents. Of course Mixtures of the abovementioned halogenated phenols can also be used according to the invention for the reaction will.

To carry out the method according to the invention can as chlorosilanes in addition to tetrachlorosilane, trichlorosilane and Dichlorosilane also organo-, organooxy- and organo-organooxychlorosilanes be used. The organo-, organooxy- or organo-organooxychlorosilanes can, for example, from be derived from the following general formulas:

(R ⁴ ) _m Si (Cl) ₄ _ _B and

T -Aj-

_ _n (Cl) - _

(R ⁵ ) _n ^ Si -Aj-Si-

In these formulas, R can mean a branched or unzipped / own, optionally aryl-substituted alkyl (e.g. methyl, ethyl, i-propyl, n-propyl, i-butyl, η-Butyl-, n-Dodecyl-, n-Octadecyl-, Benzylreat etc.) » Alkenyl (e.g. vinyl, allyl, etc.), cycloalkyl (such as cyclopentyl, cyclohexyl, etc.), aryl, such as phenyl,

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Napthtyl radical, etc., optionally substituted with aryl Alkoxy (e.g. methoxy, ethoxy, n-propoxy, n-butoxy, i-butoxy-, tert-butoxy-, benzyloxy- and the like) as well as an optionally alkyl-substituted aryloxy radical (e.g. phenoxy , α- and β-maphthoxy,;? - tert-butylphenoxy radical, etc.), R can be hydrogen or Rm 1, 2 or 3, n and ο 0.1 and 2, while A is oxygen or an alkylene group optionally containing ether or thioether groups, Glycoalkylene, aralkylene or arylene radical can be.

Typical representatives of the aforementioned classes of substances are, for example: vinyl trichlorosilane, allyl trichlorosilane, Methylvinyldichlorosilane, n-decyltrichlorosilane, phenyltrichlorosilane, Mphenyldichlorosilane, hexachlorodisiloxane, Dimethyltetrachlorodisiloxane, Diphenyltetrahlorodisiloxane, Divinyltetrachlorodisiloxane, 1,2-bis-trichlorsiljlpropane, 1,2-bis-trichlorosilylethane, 1,2-bis-dichlorosilylethane, ß- (methyldichlorosilyl) ethyltrichlorosilane, 1,2-bis-methyldichlorosisylethane, Poly (dichloro) silylethylene, 1,2-4-bis (trichlorosilylethyl) -cyclohexane, Bis (trlchloroslylethyl) benzene or compounds in which one or more chlorine atoms of the compounds listed are replaced by alkoxy or Aryloxy radicals are substituted.

To prepare the halogenated phenoxyslane, the chlorosilanes and halogenated phenols are used, preferably in an atoichiometric ratio, i.e. one mole of halogenated phenol is used per mole of chlorine in the silane. The yields of halogenated phenoxysilanes can be

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use of an excess of phenolic compounds "Be improved.

The special goal part of the method according to the invention is to be seen in the fact that the implementation is complete Replacement of the chlorine by the halogenated phenols continues and not at a certain stage of conversion stops, as was the case with previously known methods of the Pail.

The reaction can be carried out either in the melt or in inert solvents, it being possible for the inert solvent to function both as a real solvent and as a dispersant. Suitable inert solvents for the purposes of the present invention are both aliphatic and aromatic hydrocarbons and simple and cyclic ethers. As aliphatic hydrocarbons, both single compounds as well as mixtures thereof can be mentioned, such as isooctane and petroleum fractions, for example those with a boiling range of 120 - 200 ⁰ C. Also, cycloaliphatic compounds such as decahydronaphthalene may be used. Benzene, toluene, xylene and isomer mixtures of hexylcumene, cyclohexyltoluene, cyclohexylethylbenzene, isopropylethylbenzene, dihexylbenzenes, di-p-tolylmethane and diphenyl, among others, are examples of suitable aromatic hydrocarbons. As ethers, which are suitable for carrying out the reaction, would be to

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name: disopropyl ether, diisoamyl ether, pearyl ether of ethylene and dietylene glycol, diphenyl ether, 1,4 ~ Dioxane et al. This list shows that aliphatic as well as aromatic, cyclic and open-chain Ether can be used. Polar solvents such as nitrobenzene, dimethyl sulfoxide and dimethylformamide can also be used. Solvents are also suitable, such as chlorinated aliphatic and aromatic hydrocarbons, the halogen atoms of which have a low mobility own, e.g. tetrachloride than, tetrachloroethane, tetrachlorethylene, pentachloroethane, o-dichlorobenzene, Trichlorobenzene, β, β-dichloroethylbenzene, etc.

The end products can be worked up by methods known per se. When using solvents Isolation of the halogenated phenoxysilanes by stripping off the solvent can be used as a condensation medium or by precipitation, ideally with polar solvents such as methanol, ethanol, acetone, tetrahydrofuran etc. can be achieved.

The reaction takes place under the conditions according to the invention of the halogenated phenols with the chlorosilanes rapidly with the release of practically stoichiometric amounts of gaseous HGl. The enclosed FIGS. 1 and 2 clearly show this advantage. Figure 1 illustrates the Time course of the.HCl elimination of approaches 79.95 g of pentachlorophenol and 16.15 "g of vinyltrichlorosilane in

0 0 9 8 2 8/19 A 5.

BATH ORIGINAL

80R758

150 ml of boiling toluene.

Bs mean:

1. without a catalyst,

2. in the presence of 1 wt .- ^, based on the amount Chlorosilane, methyltriphenylarsonium chloride and

3. in the presence of 1 wt. ~ $, Based on the quantity Chlorosilane, tri-n-butylphosphine.

The temporal course of the HOl separation of approaches from 26.65 g of pentachlorophenol and 7.05 g of phenyltrichlorosilane in 50 ml of boiling toluene is shown in FIG. 2, in which:

4. without a catalyst,

5. in the presence of 1% by weight, based on the amount of phenyltrichlorosilane, tri-n-butylphosphine,

6. In the opposite of I wt .- $, based on the amount Phenyltrichlorailane, methyltriphenylarsonium chloride and

7. in the opposite of I wt .- $, based on the quantity Phenyltrichlorosilane, triphenylphosphine.

The halogenated ones made according to the present invention Phenoxyoilanes are suitable as plastic additives and textile auxiliaries, in particular because of their fire-retardant, fungicidal, phytotoxic, bacterial and partly also insectic properties.

0 09828/194 5 BAD ORIGINAL · \, r J ii ■ - ■?

The various embodiments of the method according to FIG present invention are illustrated by the following examples:

Example 1: (Diphenyl-di- (2,4,6-tribromophenoxy) -silane)

In a three-necked flask equipped with a stirrer, condenser and inlet tube for Np, 66.24 g of 2,4,6-tribromophenol (0.2 mol) were dissolved in 150 ml of o-dichlorobenzene at 20O ⁰ C and then .25.32 g (0.1 mol) of diphenyldichlorosilane and 0.5 g of triphenylmethylarsonium hydroxide were added. A strong HGl development set in immediately. The resulting HÖl gas was flushed from the reaction medium with a stream of dry nitrogen. When awake for 25 hours, $ 92 of the theoretical amount of HOl had been split off. The o-dichlorobenzene was drawn off under a water jet vacuum (12 mm Hg). The residue had a melting point 152-162 ⁰ C, it was recrystallised from cyclohexane, mp 173 ⁰ C;. Yield: 83 #.

Example 2: (Diphenyl-di- (pentachlorophenoxy) -silane)

According to Example 1, 26.65 g (0.1 mol) of pentachlorophenol in 120 ml of xylene at 14O ⁰ C and then dissolved 12.66 g (0.06 mol) of diphenyldichlorosilane, and 0.5 g of tri-n-butylphosphine was added. After about 20 hours, the theoretical amount of hydrogen chloride had been split off. The product precipitated when the solution cooled. 192 ^° C .; Yield: 92 96.

Example 3: (vinyl-tri- (pentachlorophenoxy) -silane)

According to Example I were dissolved in 150 ml toluene at 80 ⁰ G and then 16.15 g (0.1 mol) of vinyltrichlorosilane, and 0.5 ml of tri-n-butylphosphine was added 79.95 g (0.3 mol) of pentachlorophenol. A strong evolution of HCl began immediately. The HCl gas formed was flushed out of the reaction medium with a stream of dry nitrogen. As soon as an approx. 50% conversion was achieved, the temperature rose to

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12O ⁰ C increased. The reaction was over after 23 hours. The toluene was distilled off under a water jet vacuum (12 mm Hg). The residue had a melting point yon 160-162 ⁰ O, it was recrystallized from toluene, m.p., 187-188 0, Off

prey: 80 f>. 0: 28 Theor. 27 found Analysis': Cl: 62 , 2 Jt; 62 Si: 3 , 5 #; 3 , 6 Jt; , 29 7 &; .21 $> \

Dr.Kni / Wed

00 9828/1945

Claims (2)

180R758 a t e n t claims; 1. Process for the production of halogenated phenoxysilanes, characterized in that the reaction of the halogenated phenols and chlorosilanes in the presence of catalytic amounts of compounds of the general formula H ² R ¹ - X - R ^ 12 3 in which X phosphorus, arsenic or antimony, R '^{J> can be} an identical or different radical from the group consisting of hydrogen, fluorine-free alkyl, cycoalkyl or aryl radicals, or their quaternary compounds, optionally using inert solvents, at temperatures of 20 - 25O ⁰ O, preferably 50-200 ⁰ C, is carried out. 2. The method according to claim 1, characterized in that the catalysts in amounts of 0.1-20 mol #, preferably 0.2-2 mol $, based on the amount of chlorine, silane, begins. Dr.Kni / Wed 0.98 23/1 9 A 5
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