DE1643290A1 - Process for the preparation of phenyl esters - Google Patents

Description

Xrpisdorf, the

DYUiMII NOBEL AK2IMGESELLSCHA] ?! D Troisdorf, Beζ, Cologne

Process for the production of (addition to patent application D51 806 IYb / 12 qu and its additional applications D 51 921 IVb / 12 qu and D 51 923 IVb / 12 qu)

The subject of the invention of patent application D 51 806 ITb / 12 qu is a process for the preparation of phenyl esters from halogenated, monohydric phenols and acid chlorides of monohydric carboxylic acids. The process is particularly characterized in that the carboxylic acid chlorides are mixed with the halogenated, monohydric phenols in the presence of catalytic amounts of tertiary amines, the amino group of which is not part of an aromatic ring system, optionally using inert solvents, at a temperature of 50-25O ⁰ C, preferably 80-180 ⁰ C converts.

In the additional application with the file number D 51 921 IVb / 12 qu the use of these catalysts will also affect the Conversion of acid chlorides from polycarboxylic acids and halogenated, monohydric phenols claimed, while in the Zusatzenmelduag with the file number D 51 923 IVb / 12 qu for the application of these catalysts to the implementation of

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monovalent acid chlorides with halogenated, polyvalent _: phenol protection "is claimed. _; : l..,

In a modification of this procedure it has now been found that ^ one the Implementation also in an advantageous manner in the presence of catalytic pools Amounts of tertiary amines, the amino group of which is part of an aromatic ring system, and / or optionally Carry out Η-mono- or -disubstituted acid amides can.

The process can be carried out with single or mixed tert. Amines, the amino group of which can also be part of an aromatic ring system, and / or optionally N-mono- or -disubstituted acid amides or -imides are carried out, substituted imides for the purposes of the present invention should be understood as a type of cyclic amide. Suitable aromatic, tert. Amines are quinoline, isoquinoline, Pyrazine, oxazine, oxazole, thiazole, oxdiazole, benzthiazole, etc. Suitable, optionally N-mono- or -disubstituted acid amides are the carboxamides of monobasic aliphatic, aromatic and araliphatic carboxylic acids with 1 to 18 Ö atoms,

The monobasic acids mentioned, such as formic acid, acetic acid, propionic acid, butyric acid, caproic acid, 2-ethylhexanoic acid, oaprylic acid, liauric acid, palmitic acid, stearic acid, benzoic acid, phenylacetic acid and phenylbutyric acid can be straight-chain or branched in the alkyl chain. as in pyruvic acid, aoeteaslg "or myulinic acid" _f . AIa bases that

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the amides in question are based on ammonia or mono- or diamines. Primary or secondary mono- or diamines which are derived from the saturated, aliphatic, araliphatic, cycloaliphatic series or from the aromatic series with only one aromatic ring are preferred. -1-propylamine, di-η- "or -iso-butylamine, di-2-methylhesylamine, dilaurylamine, ethylenediamine, tetramethylenediamine. Hexamethylenediamine, cyclohe ^ -amine, dicyelohexylamine, benzylamine, dibenzylamine, aniline, N-methylaniline, loluidine, Ühenylenediamine and hexahydrophenylenediamine. One or both of the alkyl groups of the amines can also be replaced or substituted by the phenyl or toluyl radical or by cycloalkyl groups with 5 M 6 ring carbon atoms, which can optionally also be substituted by alkyl groups, in particular one or two methyl groups Amine component diamines particularly suitable for the preparation of the acid amides are particularly those in which the two amino groups are separated by one to 8 methylene groups C atoms, the phenyl or toluyl radical or a 5- to 6-membered cycloalkyl radical. Representatives of particularly suitable carboxamides which are used as catalysts according to the invention can be listed by name:

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Formamide, methylformamide, acetamide, Η, Η-dimethylacetamide, H ₉ H-di-n- or -i-propylbutyramide, Π, Π-di-n- or -isobutylbutyramide, H-benzylbutyric acid amide, H, H-dipropyl-2 -äthylhexansäureamid, acetoacetic acid-IfyH-di-n-butylamide, acetoacetic anilide, benzoic acid benzylamide, H, H-dimethylbenzoic acid amide, and ΪΓ, Η "--— Biformylhexamethylenediamine.

Furthermore, cyclic acid amides or imides can also be used be, there are also barbituric acids as catalysts

W motors in embossing, by hydrocarbon radicals, in particular by Ο .. - may be substituted (K-alkyl or phenyl groups such dimethylbarbituric, Diäthylbarbitursäure ₉ Di-i-propylbarbituric, Mallylbarbitursäure, di-n-butylbarbituric acid and Phenyläthylbarbitursäure But Eohlensäureamide. or -imides, preferably the F-substituted derivatives, such as ΪΓ-phenyl urethane, diphenylcarbodiimide, diphenylguanidine, can be used.Sulfonamides are also suitable catalysts »such as

m 4-sulfamoylacetaniline, N ^ -amidino-sulfanilamide, K ^% -2-fyridylsulfanilamide.

Also thosphorous acid amides, such as H ₁ IT ₉ V *, H ¹ , N ⁿ , n ⁿ -hexamethylphoephorous acid triamide, ir, N, V ^f jN » ₉ K ^w , V-hexamethylphosphoric _{acid triamide, H 9} H ₉ H ¹ _? H « ₉ H ^M , H ⁿ -Hexa-n- or -iBO-butylph © ephorigsäuretriamid, Phosphorigsäuretrimorpholide can be used as catalysts. The phosphorus @ äuretriaiaide _s DL® also be used as catalysts _can: but are somewhat inferior in their catalytic effect of Biosphorigsäure.

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Titanium acid amides and stannic acid amides, such as di-n-propoxytitanium diamide and di-η- or -iso-butyltin diamide can also be used as catalysts. It is not necessary as catalysts ^ already the to use finished amides directly, but you can too the components from which they are built, e.g. a Mixture of a primary or secondary mono- or Diamine of the type mentioned above and one of those mentioned Monocarboxylic acids or those derived from these acids Use acid chlorides or anhydrides, as f | then form the acid amides under the reaction conditions. Of course, mixtures of the aforementioned amines and Acid amides can be used as catalysts. Mixtures too with tert. Amines of the main application D 51 806 XVb / 12qu or their quaternary ammonium salts, such as iri-methylbenzylammonium chloride, Triethylbenzylammonium hydroside or acetate or «triethylammonium hydrochloride» can be used.

Pyridine, which has in itself a very good catalytic effect, sublimated at higher reaction temperatures in (|!. The resulting pyridine hydrochloride form, the catalyst can be characterized in its catalytic effect during the implemen tation of why it 1st expedient pyridine in combination with other suitable To use amines or amides as a catalyst or to apply pressure in the reaction.

The tertiary amines and acid amides used as catalysts are used in amounts of 0.1-20 mol $, preferably 0.2-2 mol,

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based on the acid halide. You can do the approaches at once as well as in several small ones Portions are added.

You can implement both in the melt and in inert Solvents are carried out, wherein the inert solvent can have both the puncture of a real solvent and that of a dispersant. Suitable Solvents for the purposes of the present invention are already mentioned in the main application. Also suitable are solvents such as chlorinated aliphatic and aromatic hydrocarbons, e.g. tetrachloroethane, tetrachlorethylene, pentachloroethane, trichlorobenzene, dichloroethylbenzene and others, alkylbenzenes, such as isomer mixtures of hexylcumene, cyelohexyltoluene, cyclohexylethylbenzene, cyclohexylethylbenzene, di-methylbenzylethylbenzol, cyclohexylethylbenzyl, and di-methylbenzylethylbenzene, cyclohexylethylbenzol, and di-methylbenzylethylbenzyl, cyclohexylethylbenzyl, cyclohexylethylbenzol, and di-methylbenzylethylbenzene, tetrachlorethylene, pentachlorethane, trichlorobenzene and isopropylbenzene, as well as di-benzylethylbenzene, cyclohexylethylbenzene, cyclohexylethylbenzene, cyclohexylethylbenzene, cyclohexylethylbenzene, cyclohexylethylbenzene, cyclohexylethylbenzene, cyclohexylethylbenzene, cyclohexylethylbenzene, cyclohexylethylbenzene, cyclohexyl ethyl Diphenyl.

The condensation takes place under the conditions according to the invention rapidly with the release of practically stoichiometric amounts of gaseous HCl. The enclosed Figures 1 and 2 clearly. FIG. 1 illustrates the course over time of the HCl elimination of batches 53.3 g pentachlorophenol and 15.5 g succinic acid dichloride in 200 ml boiling xylene * It means:

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1. without a catalyst

2. in the presence of 1 wt.

based on the amount of acid chloride, dimethylaniline,

3. It It It It N , Di-n-p-tolylcarbo- diimid, 4th η η it η It , ß- (di-n-butylamino) - propionitrile, 5. It It N It Il , Formamide, 6th it it tt It It , Di-n-butyibenzoic acid amide,

7. ^H "" ■ ", Ν, ϊϊ, Ν» ₉ N «,,

Hexamethylphosphorous acid triamide,

8. "n η it it _f fri-n-butylamine,

9. ⁿ " ⁿ ■ ^w , quinoline.

FIG. 2 shows the same determination for batches from 24 »6 g 2,4,6-tribromophenol and 14 »5 g of benzoyl chloride in 150 ml of boiling Xylene.

In Figure 2:

10. without a catalyst

11. in the presence of 1 wt. $> _T

based on the amount of acid chloride »biphenylguanidine,

12. ⁿ «η« η _t cyanguanidine j

13. "« i »w ·« _t ! »N-biisobutylamino-

acetonitrile u »tri-

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15. in the presence of 1 wt. $ 6,

based on the amount of acid chloride, DÜsobutylamino-

acetonitrile,

16. ^w ■ "« η _f diisopropyl carbon

diimid,

17. " ^{WM M} ", Ιϊ, ϊϊ-dimethylcyclo-

, hexylamine,

18. "» ^w »» ■, di-p-tolylcarbodiimide

u. Ν, ΙΓ-diisopropylcarbodiimide (1: 1)

Otherwise, the convertible starting materials for carrying out the process according to the invention and the conversion conditions correspond those of the main registration and those of the additional registrations.

The following examples illustrate various embodiments of the method according to the invention:

Example 1;
Terephthalic acid di (pentachlorophenoxy) ester

In a three-necked flask equipped with stirrer, condenser and inlet tube for N _2, were 53.3 g (0.2 mol) of pentachlorophenol and 17.9 g (0.1 mol) with 0.5 ml lerephthalsäuredichlorid Ν, Ν-di- N-butylbenzoic acid amide reacted as a catalyst in 200 ml of xylene.

The splitting off of HCl was complete after about 18 hours. The resulting white precipitate was filtered off, with a little

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Benzene washed and dried, pp. 341-343 ⁰ O, yield approx.

The same approach was carried out without a catalyst; after 24 hours only about 10 Ί »of the theoretical amount of hydrogen chloride had been split off.

Example 2;

In accordance with Example 1, 91.5 g (0.5 mol) of adipic acid chloride were obtained and 266.5 g (1 mol) of pentachlorophenol in 500 ml of xylene with 2 g of acetoacetic anilide to react.

After the elimination of HCl had ended, the solvent was evaporated.

The residue has a melting point of 190 ^° C., yield: $ 95. Example 3; '

As in Example 1, 53.3 g of pentachlorophenol and 15.5 g of succinic acid dichloride in 200 ml of xylene were reacted with 0.5 ml of formamide. The reaction had ended after about 12 hours. The product had a melting point of 252 ^° C., yield: 94 #.

The same approach was carried out without a catalyst. To about 24 hours only about 20,96 HCl had been split off.

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Example 4:

As in Example 1, 10.4 g (0 * 1 mol) of acrylic acid chloride and 26.15 (0.1 mol) of pentachlorophenol were reacted in 120 ml of toluene and in the presence of 0.5 g of di-n-butylbutyramide. After the elimination of HCl had ended, the solvent was distilled off.
The residue has a melting point of 78 -. 80 ^0C, yield about

Example 5:

In a three-necked flask equipped with a stirrer, condenser and inlet tube for Hg was 36.6 g (0.1 mol) of 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane and 32.4 g (0.2 mol) of caprylic acid chloride in 220 ml of xylene with 0.5 ml of di-n-butylbenzoic acid amide brought to reaction.

After the elimination of HCl had ended, the xylene was completely distilled off, the residue is a pale yellow liquid; n £ ₀ : 1.534.

Example 6:

As in Example 3, 0.5 ml of phosphorous acid amide was used as a catalyst instead of formamide. The reaction was over for about 10 hours. The product had a boiling point of 251 ⁰ O _1, yield: 95 J *.

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Example 7:

In a three-necked basket equipped with a stirrer, condenser and inlet _{pipe for IT 2} *, 24.6 g of tri-2,4 »6-bromophenol and 14.5 g of benzoyl chloride in 150 ml of xylene were reacted with 0.5 g of diisopropylcarbodiimide as a catalyst .

The reaction had ended after about 22 hours. The xylene was completely distilled off, the residue has a melting point of 79 ^° C. (from alcohol), yield: 87 #.

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Claims (3)

Claims 1. Modification of the process for the production of phenyl esters from halogenated phenols and acid chlorides according to patent application D 51 806 ITb / 12 qu and their Additional registrations D 51 921 IVb / 12 qu and D 51 923 IVb / 12 qu, characterized in that instead of the tertiary " Amines whose amino group is not part of an aromatic Ring system, tertiary amines whose amino group is part of an aromatic ring system, and / or optionally K mono- or disubstituted Acid amides used. 2. The method according to claim 1, characterized in that the tertiary amines or acid amides in the form of their qua ternary ammonium compounds are used. 3. The method according to claim 1, characterized in that the acid amides used are carbodiimides « Pat.Abt.
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