DE1768347A1 - Process for the production of halogenated phenyl esters of carbonic acid - Google Patents

Description

Troisdorf, April 29, 1968 Dr. Kni / Os (1242)

DYNAMIT NOBEL AKTIENGESELLSCHAFT Troisdorf / Bez. Cologne

Process for the preparation of halogenated phenyl esters

of carbonic acid

The invention is a process for the production of halogenated phenyl esters from halogenated phenols and chloro- » riden the carbon dioxide. The procedure is special because of this characterized in that the reaction is carried out in the presence of catalytic Amounts of tertiary amines, their amino group, if appropriate Can be part of an aromatic ring system., And / or optionally ϊΓ-mono- or -disubstituted acid amides, optionally with the use of solvents Temperatures of 50-250.degree. C., preferably 50-200.degree. C., are carried out.

It is known that chlorocarbonic acid esters react with alcohols or phenols to give carbonic acid esters. However, only poor yields are achieved when highly chlorinated phenols are reacted, and the yield falls to the same extent as the chlorine content of the phenol increases. Barral received (see Comptes Rendus 121.0900), p. 679/681 and Bull.Soc. Chim. Prance 2j_ 23 (1900), pp. 814 to 822) only yields of 0.5 to 4 $> in the reaction of chlorinated sodium phenolate with chlorocarbonic acid esters. If phosgene is introduced into a solution of sodium phenolate and alcohol or into a solution of phenol, alcohol and alkali, yields of the order of magnitude of 25 to 40% - based on the chlorinated phenol - can be achieved.

'. ■ - 2 109847/1877

It has also been described that ethyl pentachlorophenyl carbonate can be prepared by reacting an alkali metal salt of pentachlorophenol with ethyl chlorocarbonate in an organic solvent, for example methyl isobutyl ketone. If, according to the known process, for example sodium pentachlorophenol is reacted with ethyl chlorocarbonate and methyl isobutyl ketone is used as the solvent, a yield of 52 #, based on sodium pentachlorophenol used, is achieved in the most favorable Pail.

It has now been found that halogenated phenyl esters, the carbonic acid can be obtained in considerably better yield if one uses the process for the preparation of halogenated phenyl esters the carbonic acid from halogenated phenols and chlorides of carbonic acid conducts so that the reaction in the presence of catalytic amounts of tertiary amines, the amino group of which may be part of an aromatic ring system

and
kamy or optionally N-mono- or disubstituted acid amides, optionally using inert solvents, at temperatures of 20-250 ° C, preferably 50-200 ° C. The chlorides of carbonic acid react surprisingly quickly with the escape of HCl in the presence of catalytic amounts of the compounds mentioned. Just like the tertiary amines and optionally N-mono- or disubstituted acid amides, the quaternary ammonium compounds which can be derived therefrom also react. The hydrochlorides and the acetates are preferred. Normally, the replacement of the halogen by passing a halogenated phenoxy group by direct methods, ie without the use of neutralizing agents only up to about 20 to 50 i> and only after long reaction times (about 24 hours). With the aid of the catalysts described, it is possible to achieve quantitative conversion after just a few hours.

109847/1877

The reaction according to the above invention is preferably carried out at normal pressure. However, the method can can also be used at an overpressure of up to 25 atmospheres.

To carry out the process according to the invention, single and mixed tert catalysts are used. Amines and acid amides with aliphatic, cycloaliphatic, aromatic and heterocyclic radicals and mixtures thereof are suitable, with imides in the context of the present invention as a species cyclic amides are to be understood.

Suitable tertiary amines, the amino group of which is not part of an aromatic ring system, with aliphatic radicals bind, for example: trimethylamine, triethylamine, triisopropylamine, triallylamine, triisobutylamine, monoethyldiisopropylamine, monoethyl-di-n-butylamine, tri-n-butylamine, N ₁ N, N *, N'-Tetramethylbutanediamine- (1,4), N, N, N ^f , N ^ tetramethylethylenediamine, optionally substituted, tertiary, aliphatic amines, such as ß-chloropropyldipropyldiamine, tris- (ß-ethoxyethyl) amine, N, N -Dimethylaminoacetonitrile, N-methylaminoacetonitrile, N, N-di-n-butylaminoacetonitrile, Ν, Ν-diisobutylaminopropionitrile, N, N-diisopropylaminoacetonitrile, Nn-butyl-N-methylaminoacetonitrile, N, N-dimethyl-pionopropion-aminopropion-amine -benzonitrile, etc. From the series of amines with cycloaliphatic radicals, the Ν, Ν-Dimethylcyc / ilohexylarain should be mentioned. Also to be mentioned are suitable amines with aromatic radicals, such as N, N-dialkylanilines (Κ, ίΤ-dimethylaniline and K, N-diethylaniline, etc.), p-bromophenyldimethylamine, 2,4-dinitrophenyldimethylamine and benzyldirnethylamine, p-nitrophenyl-di- n-butylamine, 2,4-dichlorophenyl diethylamine, N, N, N ', N'-tetramethylbenzidine. Suitable heterocyclic nitrogen compounds are, for example: K-AIkJfI- or N-arylmorpholines, such as Nn-butylmorpholine, II-phenylnorpholine, N- (4-methylphenyl) morpholine, morpholine acetic acid morpholide, iT, DT dialk; - or !!, I'-diarylpiperazines, e.g.

1038 ^ 7/1877

BAOORtGiNAL

-d

N, N -dimethylpiperazine, Ε, Ν-di-n-butylpiperazine, N, N-diphenylpiperazine, N-substituted piperidine derivatives, N-aryl- or N-alkyl-tetrahydroquinolines or tetrahydroisoquinolines, such as N-n-propyltetrahydroquinoline, N-phenyl-tetrahydroisoquinoline, N-alkyl and N-aryl pyrolidines and their derivatives, e.g. N-methyl pyrrolidine, N-n-buty! .pyrrolidine, N-phenylpyrrolidine and optionally substituted derivatives of the aforementioned compounds.

Suitable tertiary amines whose amino group is part of an aromatic ring system are aromatic, tertiary amines, such as pyridine, quinoline, isoquinoline, pyrazine, oxazine, quinazoline, oxazole, thiazole, oxdiazole, benzthiazole and others

Suitable, likewise N-mono- or -disubstituted acid amides are the carboxamides of monobasic aliphatic, aromatic and araliphatic carboxylic acids with 1 to 18 carbon atoms, such as formic acid, acetic acid, propionic acid, butyric acid, caproic acid, 2-ethylhexanoic acid, caprylic acid, lauric acid, Palmitic acid, stearic acid, benzoic acid, phenylacetic acid and phenylbutyric acid, which can be straight-chain or branched or in the alkyl chain also by a keto group, as in the Pyruvic acid, acetoacetic acid or levulinic acid may be interrupted. As bases that the eligible Acid amides are based, ammonia and mono- or diamines are suitable. Primary or secondary mono- or diamines which differ from the saturated, aliphatic, araliphatic, cycloaliphatic series or from the aromatic series Derive series with only one aromatic ring. Examples of amines are methylamine and dimethylamine Di-η- or -i-propylamine, di-η- or -iso-butylamine, di-2-methylhexylamine, Dilaurylamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, cyclohexylamine, dicyclohexylamine, benzylamine, Dibenzylamine, aniline, N-methyl aniline, toluidine, phenylenediamine

BAO ORIGINAL

10 9 8 4 7/1877 ~

_ C

and called hexahydrophenylenediamine. One or "both of the alkyl groups of the amines can also by the phenyl or toluyl radical or by cycloalkyl groups with 5 to 6 ring carbon atoms, the may optionally also be substituted by alkyl groups, in particular one or two methyl groups, replaced or substituted be. Of those used as an amine component for manufacture of the acid amides particularly suitable diamines are particularly those in which the two amino groups are replaced by one to

en
8 methyl groups are separated. In the diamines, too, the hydrogen atoms still bonded to the nitrogen atom can be substituted up to at least one, for example by alkyl groups having 1 to 4 carbon atoms, the phenyl or toluyl radical or a 5- to 6-membered cycloalkyl radical. Representatives of particularly suitable carboxamides that can be used as catalysts according to the invention include: formamide, methylformamide, dimethylformamide, diethylformamide, acetamide, ίΓ, Ν-dimethylacetamide, N, Ii-di-n- or -i -propylbu'tyramid, N, N-di-n- or -isobutylbutyramide, N-benzylbutyric acid amide, N, F-dipropyl-2-ethylhexanoic acid amide, acetoacetic acid-1T, N-di-n-butylamide, acetoacetic anilide, benzoic acid benzylamide, Ν, Ν, Ν -Dimethylbenzoic acid amide, and N, N · -Diformy! Hexamethylenediamine. Furthermore, cyclic acid amides or imides, such as Ν, Ν-dimethyl succinimide and Ν, Ν-dimethylmaleimide, can also be used. Barbituric acids are also suitable as catalysts, which can be substituted by hydrocarbon radicals, in particular by Cj - C. - alkyl or phenyl groups, such as dimethylbarbituric acid, diethylbarbituric acid, di-i-propylbarbituric acid, diallylbarbituric acid, di-n-butylbarbituric acid and phenylethylbarbituric acid.

But also carbon amides or imides, preferably the N-substituted derivatives, such as F-phenyl urethane, diphenyl cabodiimide, Diphenylguanidine can be used.

109847/1877 BAD ORlGINÄi-e

It is not necessary to use the finished amides directly as catalysts; Components of which they are composed, e.g. a mixture of a primary or secondary mono- or diamine of the above mentioned type and one of the mentioned monocarboxylic acids or the acid chlorides derived from these acids or use anhydrides, which then form the acid amides under the reaction conditions.

Sulf <? Amides are also suitable catalysts, such as 4-sulfamoylaceianiline, N-amidino-sulfanilamide, N-2-pyridylsulfanilamide. Also phosphoric and phosphoric acid amides, such as N, N, N ¹ , N ^f , N ¹ ·, N ¹ · -hexamethylphosphoric acid triamide, Ν, Ν, Ν », H ¹ , N ¹ ·, N '' - hexamethylphosphoric acid triamide, Ν, Ν , Ν ¹ , N ¹ , N ¹ ·, N "- Hexa-η- or iso-butylphosphorigessigsäuretriamid, Phosphorigsäuretrimorpholide can be used as catalysts. The phosphoric acid triamides, however, are somewhat inferior to phosphorous acid in their catalytic effect.

Titanic acid amides and stannic acid amides, such as di-n-propoxy-titan-diamide and di-η- or -iso-butyltin amide, can also can be used as catalysts, but also the amides of the silanols (e.g. diorganosilanols) such as diphenyldi (di-n-butylamino) -silane, Diphenyl-di- ^ TiutylaminoJ-silane, Dimethyl-di- (di-n-propylamino) -silane, diphenyl-di- (diethylamino) -silane.

Pyridine, which in itself has a very good catalytic effect, sublimes at higher reaction temperatures in Form of the resulting pyridine hydrochloride. The catalyst leaves thereby in its catalytic effect during the implementation. Therefore it is appropriate to combine with pyridine

- 7 109847/1877

to use other suitable amines or amides as a catalyst or to apply pressure in the reaction.

The tertiary amines described and the optionally N-mono- or disubstituted acid amides can of course also be used according to the invention in the form of their quaternary ammonium compounds in equal mol percent. The hydrochlorides and acetates have proven to be particularly suitable. Suitable compounds are trimethylbenzylammonium chloride, triethylbenzylammonium hydroxide or acetate and triethalammonium hydrochloride, among others

Particularly preferred types of catalyst are nitrile-containing, Nitro-containing groups, the nitro group of which is aromatic-bound is, and Ν, Ν-dialkyl-substituted acid amides.

The tertiary amines and acid amides used as catalysts are preferably used in amounts of 0.1-2o mol $ 0.2-2 mol #, based on the chloride of carbonic acid, used. They can be added to the batches at once or in several small portions.

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, such as 4-fluorophenol, pentafluorophenol, the chlorinated, such as 2-, 5-, 4-chlorophenol, 2,3-, 2,4-, 2,5-, 2,6-, 3 , 4-, 3,5-dichlorophenol, 2,4-dichloro-6-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, which are brominated like 2-, 3-, 4-eromphenol. 2.4-, 2.6-dibromo

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- 8th

phenol, 2,4,6-tribromophenol and pentabromophenol and the iodinated, such as 2,4-, 2,6-diiodophenol and 2,4,6-triiodophenol. But also halogenated naphtha oils and heterocycles with phenolic Characters can be used such as l-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 can be derived, such as 2-chloro- or 2-bromohydroquinone, tri- and Tetrachlorohydroquinone, 2,4,6-tribromoresorcinol and others

Polynuclear, polyvalent, halogenated phenols, the cores of which are not condensed, correspond to the general one, for example formula

< ^X > a <*> b

HO II OH

ο or

in which X identical or different halogen atoms, a or b is an integer from 1 to 4 and Y is oxygen, a carbonyl, Sulphide, disulphide or sulphone bridge or an optionally may be phenyl-substituted alkylene or cycloalkylene. Basic types of these phenols are the dihydroxydiephenyls, e.g. 2,2'-, 2,4'-, 3,3'-, A, 4'-dihydroxydiphenyl, 4,4'-dihydroxy-2-methyldiphenyl, 4,4'-dihydroxy-2,2-dimethyldiphenyl, 4,4'-dihydroxy-3,3'-dimethyldiphenyl, 6,6'-dihydroxy-3 »3'-dimethyldiphenyl i.a.

Dihydroxybenzolephenones such as: 2,2'-, 3,3'-, 2,4'-, 3,3'-, 3,4'-, 4,4'-, 4,6'- 6,6'-dihydroxybenzopherone and the like;

BAD ORiGiNAL. 1098 ^ 7/1877 "~~~

Dihydroxydiphenylsulfide: phenol sulfide;

like: 2,2-, 4,4'-dihydroxydi-

Dihydroxydiphenyl disulfide;

Dihydroxydiphenyl sulfones such as: 2,2'-, 4,4 ^f -dihydroxydiphenyl sulfones j

Dihydroxydiphenylalkanes or -cycloalkanes, such as: '2,2'-, 4,4'-dihydroxydibenzyl, 2,2'-, 5,3'-, 2,4'-, 2,3'-, 2,6 · -, 3.3'-, 3.4'-, 3.5'-, 3.6-, 4.4'-, 4.5'-, 4.6-, 5.5'-, · 5.6 - 6.6 x - * dihydroxydiphenyl-2,2-propane, 2,2, 4,4 Dihydroxydiphenylinethan, 4,4'-dihydroxy-3,3 ^t -dimethyldiphenylraethan, 4.4 '-Dihydroxydiphenylmethylmethane, 4 »4'-dihydroxydiphenylphenylmethane, 4,4'-dihydroxydiphenyldiphenylmethane, bis- (4-hydroxyphenyl) -4'-methylphenylmethane, 1,1-bis- (4-hydroxyphenyl) -cyclohexane, bis- ( 4-hydroxyphenyl) -cyclohexylmethane, 1,1-bis- (4-hydroxyphenyl) -athane and others

The halogenated, polyhydric phenols used according to the invention are derived from these types, such as: bis- (4-hydroxy-3,5-dichlorophenyl) methane, Bis - ^ - hydroxy-3,5-dibrompheny]) - methane, Bis (4-h3'-hydroxy-3,5-difluorophenyl) methane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, 2,2-bis- (3,5-dichloro-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 ', 5,5'-tetrachlorodiphenyl. The corresponding tetrabromo or tetrachloro derivatives of 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxybenzophenone and 4,4'-dihydroxydiphenyl sulfone. The polynuclear, condensed, polyhydric phenols are derived, among other things, from the dihydroxynaphihalins or anthracene etc., such as from 1: 3-, 1: 4-, 1: 5-, 1: 6-, 1: 7-, 1: 8-, 2: 6- and 2: 7-dihydroxynaphthalene .

109847/1877

- 1o

- ίο -

Suitable halogenated phenols are, for example, the diehlor and dibromine compounds as well as the tetrabromine and (Tetrachloride dihydroxynaph thaline.

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 aforementioned halogenated phenols can also be used according to the invention for the reaction

In addition to phosgene, the ester chlorides (chloroformic acid esters or chlorocarbonic acid esters), aliphatic cycloaliphatic !; araliphatis rather and more heterocyclic Alcohols and the phenols implemented according to the invention will. Suitable chloroformic acid esters are, for example, methyl chloroformate, ethyl chloroformate, n-butyl chloroformate, Isobutyl chloroformate, allyl chloroformate, n-octyl chloroformate, N-decyl chloroformate, n-dodecyl chloroformate etc. as well as trichloromethyl chloroformate, 2-bromoethyl chloroformate, 2-chloroethyl chloroformate, 2-trichloroethyl chloroformate, 2-methoxyethyl chloroformate, Cyclohexyl chloroformate, benzyl chloroformate, 2- (2,4-dichlorophenoxy) ethyl chloroformate, Phenyl chloroformate, 4-chlorophenyl chloroformate, 4-methylphenyl chloroformate, 3,4,5-trichlorophenyl chloroformate i.a.

Of course, those ester chlorides can also be used as starting materials the carbonic acid are used, which are obtained by reacting polyhydric alcohols or polyhydric phenols with phosgene can be formed, with at least 1 mole of phosgene being required per mole of alcoholic or phenolic OH group.

109847/1877

The reaction can be carried out either in the melt or in inert solvents, the inert solvent can have both the puncture of a real solvent and that of a dispersant. Suitable inert Solvents in the context of the present invention are both aliphatic and aromatic hydrocarbons as well simple and cyclic ethers. Aliphatic hydrocarbons are both uniform compounds and mixtures to name the same, such as isooctane and gasoline fractions, for example those with a boiling range of 120 - 200 C. Also Cycloaliphatic compounds such as decahydronaphthalene can be used. Benzene, toluene, xylene and mixtures of isomers of hexylcumene, cyclohexyltoluene, cyclohexylethylbenzene, Isopropylethylbenzene, dihexylbenzenes, di-p-tolylmethane as well as diphenyl, among others, are examples of suitable aromatic hydrocarbons. As the ether necessary to carry out the reaction are suitable, would be to mention: diisopropyl ether, diisoamyl ether, dimethyl ether of ethylene and diethylene glycol, Diphenyl ether, 1,4-dioxane, etc. This list shows that both aliphatic and aromatic, cyclic and open-chain ethers can be used. It can continue polar solvents such as nitrobenzene, dimethyl sulfoxide and dimethylformamide can be used. Solvents such as chlorinated aliphatic and aromatic hydrocarbons are also suitable, whose halogen atoms have a low mobility, e.g. carbon tetrachloride, tetrachloroethane, tetrachlorethylene, Pentachloroethane, o-dichlorobenzene, trichlorobenzene, ß, ß-dichloroethylbenzene and others

Under the conditions according to the invention, the condensation takes place quickly after the release of gaseous HGl. This advantage the accompanying figures clearly show.

109847/1877 _12

FIG. 1 illustrates the course over time of the elimination of HCl from batches from boiling xylene solution (150 ml) of 36.6 g of di- (3t5-dichloro-4-hydroxyphenyl) propane and 31.2 g of phenyl chloroformate.

In Figure 1:

1. without a catalyst,

2. in the presence of 1% by weight,

based on the amount of acid chloride, N, N-dimethylbenzoic acid

amide

3. "" "" ". Ν, Ν-di-r.-butyl-

aminoacetonitrile t N-methylpyrrolidine »formamide« Hr-N-dimethylcyclo-

hexylamine

“Tri-n-butylamine t quinoline

FIG. 2 shows the same determination for batches made from 26.65 g of pentachlorophenol and 13.65 g of n-butyl chloroformate in 120 ml of boiling xylene.

In Figure 2:

9. without a catalyst,

10. in the presence of 1 wt.

based on the amount of acid chloride, N-methylpyrrolidine

11. "« »" ", Ν, Ν-dimethylcyclo-

hexylamine

12. "" "» ", quinoline

4th η ti It dd M. 5. dd N η It It 6th It Il It dd ti 7th Il It dd dd dd 8th. η It η Il

- 13

1098 ^ 7/1877

FIG. 3 shows the same determination for batches made from 15.6 g of chloroformic phenyl ester and 26.6 g of pentachlorophenol in 120 ml boiling xylene.

In Figure 3:

13. without a catalyst,

14. in the presence of 1% by weight,

based on the amount of acid chloride, N, N-di-n-butyl

benzoic acid amide

15. "" "" ", NiN-dimethylcyclo-.

hexylamine

16. "" "", quinoline

17. ^M "" · "", N-methyl pyrrolidine

The halogenated phenyl esters of carbonic acid prepared according to the invention are bactericidal and fungicidal because of their properties Properties as a pesticide, seed protection agent, etc. usable.

The following examples illustrate the invention Procedure.

Example 1:

In a three-necked flask equipped with a stirrer, condenser and inlet tube, 26.6 g (0.1 mol) of pentachlorophenol and 17.25 g (0.1 mol) of phenyl chloroformate in the presence of 0.5 mol of N-methylpyrrolidine in 120 ml of xylene brought to reaction. The reaction mixture was stirred at the boiling point of the xylene. The HCl gas formed was flushed out of the reaction mixture using Ng and taken up in NaOH and titrated after the reaction had ended. The evolution of hydrochloric acid ended after about 11 hours of reaction. After evaporation of the solvent left a solid product Phenj'l-pentachlorphenylcarbonat, mp. 98 ° C, in 95 ^c / ^ yield back.

109847/1877

The crude product was washed with ether; Pp. 108 C, yield

after cleaning 92 #.
Example 2:

Analogously to Example 1, 32.4 g of 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) propane were obtained and 29 g of allyl chloroformate in the presence of 0.5 ml of di-n-butylacetaminonitrile in 15ο ml Xylene made to react, - '•' • after completion of the elimination of hydrochloric acid and evaporation of the solvent remained a solid product, diallyl- (2,2- is- (3 »5-dichloro-4-hydroxyphenyl) propane) Diecarbonat, P.p. 94 ° C, back in 61% yield.

Example 3 s

Analogously to Example 1, 36.6 g of 2,2-bis (3 »5-dichloro-4-hydroxyphenyl) propane and 31> 2 g of phenyl chloroformate in the presence of 0.5 g of Ν, Ν-dimethylcyclohexylamine in 150 ml of xylene were used Brought reaction. After the elimination of hydrochloric acid had ended and the solvent had evaporated, a gray, solid residue remained, diphenyl (2,2-bts- (3 »5-dichloro-4-hydroxyt> henyr) propane) dicarbonate, pp. 156-159 ° C, Yield: 95 ¹ P * The crude product was washed with ether; Mp. 164 C, yield: 92 fo.

Example 4:

Analogously to Example 1, 15-25 g of n-butyl chloroformate and 26.6 g of pentachlorophenol were reacted in the presence of 0.5 ml of N-methylpyrrolidine in 120 ml of xylene. After 11 hours the reaction was virtually complete, ^ remained alas evaporation of the solvent a solid residue, Pp. 48 - 5o ° C, yield 92 "/> to n ^ utyl-pentachlorphenylcarbonat back The crude product was washed with A-feher.? Mp. 57 ° C, yield: 89 #

109847/1877

- 15 Example 5 :

Analogously to Example 1, 17.25 g (0.1 mol) of p-chlorophenyl chloroformate were reacted with 26.6 g (0.1 mol) of pentachlorophenol in 120 ml of xylene in the presence of 0.5 ml of quinoline as a catalyst. The elimination of HCl was complete after about 12 hours. Pentachlorophenyl (4-chlorophenyl) carbonate was obtained in 93 #iger yield, Pp. 123 ⁰ C (with ether washed).

Example 6:

Analogously to Example 1, 19.75 g (0.1 mol) of 2,4,5-trichlorophenol were obtained with 15 »25 g (0.1 mol) of n-butyl chloroformate in 100 ml of xylene in the presence of 0.5 ml of N, N-dimethylaniline as Catalyst brought to reaction. The end product boils at 13o - 134 ° C at a pressure of 3 - 3 * 5 mm Hg; Yield 95 #.

Example 7t

In a three-necked flask equipped with a stirrer, condenser and inlet pipe, 12.05 g (0.1 mol) of allyl chloroformate and 19.8 g (0.1 mol) of ^2,46-l: richlorophenol were added in the presence of 0.3 ml of N, N-di-n-butylaniline in 12o ml of xylene reacted. The reaction mixture was kept at the boiling point of the xylene with stirring. The HCl gas formed was flushed out of the reaction mixture by means of Np and taken up in NaOH solution and titrated.

The evolution of hydrochloric acid was practically complete after about 5 hours. Sales approx. 75 #.

The solvent was evaporated. The product distilled at a temperature of 152 C and 0.6 mm Hg: n ^,: 1.5448.

109847/1877

- 16 - '
Example 8;

In a three-necked flask equipped with a stirrer, condenser and Inlet tube, 13 »66 g (0.1 mol) of chloroformic acid n-butyl ester and 18.3 g (0.05 moles) of 2,2-Bi- (3,5-dichloro-4-hydroxyphenyl) propane brought to reaction in the presence of 0.3 ml of quinole in 12o ml of xylene. The reaction mixture was stirred up Maintained the boiling temperature of the xylenes. The HCl gas formed was flushed out of the reaction mixture by means of Np and poured into NaOH solution taken up and titrated.

The evolution of hydrochloric acid ended after 5 1/2 hours. The solvent was distilled off. The residue has a melting point of 75 - 76 ° C. Yield 82 %.

Analysis; Ber. ^ Found «J»

C: 53, oo fo 53.22 +

H: 4.95 i » 4.65 %

Cl: 25.1o% 26.40 %

Example 9:

In a three-necked flask equipped with a stirrer, condenser and inlet pipe, 27.2 g (0.05 moles) of 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane were added and 15.6 g (0.1 mol) phenyl chloroformate reacted in the presence of 0.3 ml of formamide in 12o ml of xylene. The reaction mixture was stirred up the boiling temperature of the xylenes is kept. The resulting HCl-Gae was flushed out of the reaction mixture by means of N «and in a NaOH solution? recorded and titrated.

The evolution of hydrochloric acid; was practically over after about 6 hours. The product which precipitated out on cooling was filtered off, washed in ether and dried. Pp 176-178 ° C. Yield: 9o ^c '>.

109847/1877

BAD ORIQtNAC ¹⁷

Analysis: Ber. j » Found j>

C: 44.8 <fo 45, o5 $> H: 2.55 # 2.59 # Br: 4o, o9 $> 38.8 #

Example 1o;

8.8 g of 2,2-bis- (4-phenyl chloroformate) propane were placed in a three-necked flask equipped with a stirrer, condenser and inlet tube and 13.3 g of pentachlorophenol in the presence of 0.3 ml of di-n-butyl-benzoic acid amide as a catalyst in 12o ml Xylene reacted. The reaction mixture was kept at the boiling point of xylene with stirring. The resulting HCl gas was flushed out of the reaction mixture by means of Ng and taken up in NaOH solution and titrated.

The evolution of hydrochloric acid ended after about 7 hours. Sales approx. $ 98. The solvent was distilled off. The residue washed in ether and dried. Mp. 124-126 C. The same approach was carried out with the catalyst. After 24 hours, only about 10 fi of the calculated amount of HCl had been split off.

109847/1877

Claims (8)

Claims 1. Process for the production of halogenated phenyl esters of carbonic acid from halogenated phenols and chlorides of carbonic acid, characterized in » that the reaction is carried out in the presence of τοη catalytic amounts of tertiary amines, the amino group of which can optionally be part of an aromatic ring system, and / or optionally N-mono- or disubstituted acid amides, optionally using inert solvents, at temperature
performs. at temperatures of 50-250 ° C, preferably 50-200 ° C, 2. The method according to claim 1, characterized in that the tertiary amines or acid amides in amounts of o _f o1 to 2o mol #, preferably o, 2 to 2 mol #, based on the chloride of carbonic acid, are used. 3. The method according to claim 1 and 2, characterized in that the tertiary amines or acid amides are used in the form of their quaternary ammonium compound. 4. The method according to claim 3, characterized in that the hydrochloride is used as the quaternary ammonium compound. 5. The method according to claim 1 and 2, characterized in that there is used as the acid amide carbodiimides. 6. The method according to claim 1 and 2, characterized in that the tertiary amine used is aliphatic-aromatic amines. 109847/1877 7. The method according to claim 1-6, characterized in that there is used as ter & ares amine and / or acid amide containing nitrile groups. 8. The method according to claims 1-7, characterized in that ale tertiary amine and / or acid amide containing nitro groups are used, the nitro group of which is aromatic. Patent department
Dr. Kni / Oa 109847/1877 Λ « Blank page