DE2926021C2 - Process for the preparation of 3-phenoxy-benzaldehydes - Google Patents

Description

The invention relates to a method of manufacture of 3-phenoxy-benzaldehydes.

The conversion of 3-phenoxy-benzal chloride to 3-phenoxy-benzaclehydric acid is already known from DE-OS 28 10 305 known. Then the 3-phenoxy-benzal chloride in aqueous isopropanol with alkali carbonates or in Aqueous dimethylformamide reacted in the presence of hydrobromic acid.

From Dt-OS 27 07 232 the hydrolysis of 3-phenoxy-benzal chloride to 3-phenoxy-benzaldehyde is with Sodium formal in solvents such as formic acid. Alcohols. Ketones and Lthern known.

It is also known from Dt-OS2402457. 3-Phennoxyben / alchlorid with anhydrous sodium acelaf in tiscssig / u to implement 3-phenoxy-benzaldehyde.

From Dt-OS 27 41 764 a process for the preparation of m-phenoxy-benzaldehyde is known in which first the 3-phenoxytoluene used is halogenated in the side chain and then the halogenation mixture is hydrolyzed with dilute mineral acid is disadvantageous with this method. that always in Must work in the presence of organic solvents.

Is a process for the production of 3-phenoxy-phenyl-aldehydes from .i-phenoxy-ben-alchlorides of the I orniel

CHCI;

R W.isserstoll. I luor nder (hlor means.

weaker by hydrolysis in the presence of salts

Acids without / us.il/ ν ground in solvents. the

characterized by 1st. dal '* man the hydrolysis in one of an organic and an aqueous phase existing Kcaktionssystcm in the pll-Hercich of about I. to approximately 7 at a pressure equal to the

Vapor pressure of the Keaklaiitcn int autoclave in the case of the

the setting reaction temperature.

The production of .i-phenoxy-ben / .iilchlorlde is on

known (Dt-OS 27 04 512). You can, for example, by chlorination of the corresponding 3-I'henoxytoluenes in carbon tetrachloride in the presence of a radical initiator such as Azoisobutiersäureniiril, or under Exposure to be made. Such chlorination gives 3-phenoxy-benzal chlorides as well as 3-phenoxy-benzal chlorides also 3-phenoxy-benzyl chloride and 3-phenoxy-benzotrichloride. It is possible for the inventive method.

to use these chlorination mixtures directly without pre-separation.

Such mixtures of side-chlorinated 3-phenoxytoluenes are preferably used in the process according to the invention. soft as high a sound as possible Contain 3-phenoxy-benzal chlorides.

The process according to the invention for the preparation of 3-phenoxy-benzaldehydes is carried out in a reaction system consisting of an organic and an aqueous phase. The organic khase exists essentially from the reaction components, such a two-phase system is obtained. if you have the Implementation in the presence of! .0 to! 0.0 Gev .. parts Carries out water based on I part by weight of the organic phase. Preferred for the method according to the invention ren in the presence of 1.5 to 5.0 parts by weight of water, based on I part by weight of the organic phase

The inventive method is carried out in the pH range from about 1 to 7 performed. Preferred is a pH

Range from 2 to 6.5.

The pH ranges mentioned for the process according to the invention can preferably be stabilized with the aid of a buffer mixture. Buffer mixtures are mixtures of substances whose pH value in aqueous solution changes changes little with the addition of acids or bases, such buffering according to the method according to the invention can be carried out in the presence of salts of weak acids, for example weak inorganic acids or carboxylic acids. As salts of weaker inorganic Examples of acids are phosphates, such as sodium phosphate. Borals, such as sodium borate, and silicates, such as Sodium silicate, called.

As salts of carboxylic acids for the process according to the invention are alkali salts, preferably the sodium and potassium salts, trdalkali saltsc. preferably the magnesium and calcium salts and the aluminum sil/e called by carboxylic acids. In one be the Iu, ' Sodium lormate is cited in the lowering salts. Cold forming. Caklumformiiit. Magnesium chloromate. neutral and basic aluminum formate. Sodium a ^ - ^ does. Potassium.icet.it. K.ilciumacelat Magnesium.icet.it. neutral or has schcs aluminum acetate and aluminum benzene

Preferred salts of carboxylic acids are N.itriunitornii.K. Sodium.icet.it. Calcium lormiate and K.il/iuni.icc· did

The salts of the weaker inorganic acids or carboxylic acids can be dissolved or in suspension

Pullergemlsche which the genius of the invention

are generally based on mixtures, which consist of the SaI / a weaker acid and the weaker acid. For example, mixtures from sodium phosphate-phosphoric acid. Sodium Horate Boric Acid. Sodium acetate-tacetic acid oiler Nairiumformlai-

Formic acid.

From the beginning to / around the end of the llyerolysis remains thereby the pH value in a weakly acidic range. Ls is also possible to use the l'ulierucmisch in iler way

manufacture that one is the salt of the weaker acid mixed with small amounts of an acid other than that on which the salt used is based. For example, a sodium acetal solution can be used one less. Transfer the amount of hydrochloric acid into the buffer mixture.

However, the method according to the invention is also possible without the addition of an acid, d. H. to be carried out only in the presence of the salt of the weaker acid.

This means that the pH value is before the start of hydrolysis Although in the weakly alkaline range, after the formation of small amounts of hydrochloric acid when the Hydrolysis brought to the weakly acidic buffered area.

The salts of the carboxylic acids or the weaker inorganic acids can be used individually or as a mixture be used. It is also possible to start the implementation with one of these connections and continue on to add another to the reaction.

Of course, it is also possible to use the appropriate Carbonsäj-en or weaker inorganic ones Acids with hydroxides or oxides of the corresponding To use metals.

For the process according to the invention, the amount of the salts can vary within wide limits. In general one can 100 to 150 mol- '»,, preferably 105 to 120 Mol - "... who use the amount of salt equivalent to the content of side-chain chlorine in the feedstock.

The process according to the invention is carried out under pressure. It is therefore advisable to work in a pressure vessel, for example in an autoclave. The erfindungsgenr'Je method is under the The vapor pressure of the reactants is carried out in the autoclave, which occurs at the reaction temperatures.

The reaction temperatures for Jas according to the invention Processes are generally in the range from 130 to 210 C. preferably from 140 to 180 ° C. The reaction is expediently carried out until it has essentially expired; this is generally after 2 to 7 hours happen.

The inventive method can for example can be carried out as follows:

3-Pheno \ y-benzal chloride. Water and optionally the buffer mixture are placed in an autoclave and heated to the reaction temperature. After completion of the reaction, the reaction product can be n.ich aulgearbeitet to known methods For example, separating ^1, one .ib the aqueous layer from the organic phase and isloiert from the organic phase the entsi.indenen 3-pheno \ v-bcn / .ililch > d by distillation "of the corresponding bisullite compound

After the erlinilungsgem.ii.Jen S experienced it is surprisingly possible. 3-Phenoxv-benzaldehyde from 3-phenobenzylurides in a white iron system Perform this way without using an organic solvent of the Re.iktlonsproilukies simplified in a considerable way According to the delightful process, one obtains the 3-Phenov. hcn / .ildehvd in high bulges and large cleanliness

Those which can be produced by the method according to the invention 3-Phenoxy-benzaldehydes of the formula wherein

R is hydrogen, fluorine or chlorine, are intermediates for the synthesis of a variety of pesticides. For example, by reacting 3-phenoxy-benzaIdehyde cyanohydrin effective insecticides and acaricides obtained with cyclopropanecarboxylic acid derivatives (DE-OS 27 30 515).

example 1

539 g of a side-chain chlorinated 3-phenoxytoluene with the following composition:

unknown

3-phenoxy-benzyl chloride

3-phenoxy-benzal chloride

unknown

3-phenoxy-benzotrichloride

unknown

2.0 ",. 11.2" .. 63.8%

2.5 ",, 15.3%

5.1%

with a side chain chlorine content of 28.7%;

! 200 ml of water, 20 ml of acetic acid and 375 g Nalriumacetat (pH of the aqueous solution = 6.0) are stirred in an autoclave for 4 hours at 160 ⁰ C. The aqueous, saline-containing layer is separated off (pH = 3.0) and the organic phase is extracted twice with soda solution to remove the 3-phenoxy-benzoic acid formed.

The organic phase is over a distillation bridge at 1.0 Torr up to an oil bath temperature of Distilled at 190 ° C. Map. receives a distillate of 325 g with a content of 76.1% 3-phenoxybenzene aldehyde.

The yield based on the 3-phenoxybenzal chloride used. is 92 ".. of theory.

Example 2

523 g of a side-chain chlorinated 3-phenoxytoluene with the following composition:

unknown

3-phenoxy-benzyl chloride

3-phenoxy-benzal chloride

unknown

3-phenoxy-benzotrichloride

unknown

2.1% 14.4% 66.0%

2.4% 12.0%

3.0%

with a side chain chlorine content of 28.0%:

346 g of 50% sodium hydroxide solution. 1000 ml of water and 28Og Acetic acid (pH of the aqueous solution = 6.0) are stirred in an autoclave for 4 hours at 160 ° C. and how described in Example 1 worked up. The aqueous boiling / containing phase has a pH of 3.0. Man receives a distillate of 32Og with a content of 76.4 ".. 3-Phenoxy-benzaldehyde. The bulge amounts to based on the 3-phenoxy-benzal chloride used. 90.5% of theory.

CHCI ₂

65

Example 3

536 g of a rope-ketic-lacquered 3-phenoxy-toluene with a composition as described in Example I.

1200 ml of water. 20 ml of formic acid and 310 g Natriumformial (pH Weri = 4.4) are worked up as described in Example I in an autoclave for 4 hours at 17O ⁰ C and gerühri. The aqueous, saline-containing layer has a pH of 1.5. You get a

Distillate of 301 g with a content of 75.8 "., 3-phenoxy-benzaldehyde.

The yield is, based on! ' 3-phenoxy-benzal chloride used 85.2% of theory.

the pH of the aqueous phase 4.2. A distillate of 77.9 g with a content of 68 "" 3-phenoxy-benzaldehyde is obtained. The yield is based on the amount used 3-phenoxy-benzal chloride, 8 (J "" der Iheori :.

Example 4

536 g of a side-chain chlorinated 3-phenoxytoluene with one like in example! I described composition.

1200 ml of water, 20 ml of formic acid and 422 g of calcium formate (pH = 3.4) are stirred in an autoclave for 4 hours at 160 ° C. and worked up as described in Example 1. The pH of the aqueous phase is 1.6. A distillate of 266 g with a content of 85.1 % 3-phenoxybenzaldehyde is obtained. The yield, based on the 3-phenoxy-benzal chloride used, is 85 "of theory.

Example 5

262 g of a chain-chlorinated 3-phenoxytoluene with one as described in Example 2. Composition,

600 ml of water, 100 g of calcium oxide and 222 g of acetic acid (pH = 6.0) are stirred in an autoclave for 4 hours at 160 ° C. and worked up as described in Example 1. After the hydrolysis, the pH of the aqueous phase is 2.0. A distillate of 152 g with a content of 75% 3-phenoxy-benzaldehyde is obtained. The yield, based on the 3-phenoxybenzal chloride used, is 84 "of theory.

Example 6

133 g of a side-chain chlorinated 3-phenoxytoluene with a composition as described in Example 1,

400 ml of water, 30 g of boric acid and 235 g of Na ₂ B ₄ O- · 10H ₂ O (pH = 7.0) are stirred in an Autolav 4 hours at 180 ° C. and worked up as described in Example 1. After hydrolysis is

Example 7

136 g of a side-chain chlorinated 6-chloro-3-pheiv.ixytoluene with a content of 68 "., 6-chloro-3-phenox> benzal chloride. 300 ml of water. 2 ml conc. Hydrochloric acid and 98 g sodium acetate (pH value of the aqueous phase = 6.0) are stirred in an autoclave for 6 hours at 180 Γ and worked up as in Example 1 (pH of the aqueous Phase after hydrolysis = 2.9). A distillate of 91 g containing 6-chloro-3-phenoxy-benzaldehyde is obtained of 75 ", .. The yield, based on the 6-C chloro-3-phenoxy-benzene chloride used, is 91 ",, d. Th.

20th

Example 8

95g of a side-chain chlorinated 4-Huor-3-phenox> toluene with a content of 4-Flujr-2-phenoxy-benzal chloride of 67.6 ",,. 300 ml of water and 72.4 g of sodium acetal are in an autoclave for 4 hours at 170'C stirred and worked out as in Example I. You get egg;. Distillate of 48.8 g with a content of 4-Huor-3-phenoxy-benzaldehyde of 87.2 ".,. The yield, based on the 4-Huor-3-phenoxy-benzal chloride used, is 83 ",. D. Th.

Example 9

133 g of a side-chain chlorinated 3-phenoxytoluene with a composition as described in Example 1. 900 ml of water. 200 g of sodium benzoate and 25 g of benzoic acid are stored in an autoclave at 160 ° C. for 4 hours stirred and as described in Example I, worked up. A distillate of 52 g with a content of 90.5 ",, 3-phenoxy-benzaldehyde. The yield is based on the 3-phenoxy-benzal chloride used, 71 ",, d. Th.

Claims (1)

Claim: Process for the preparation of 3-phenoxy-benzal-dehydes from 3-phenoxy-benzal chlorides of the formula • α orin R means hydrogen, fluorine or chlorine, weaker by hydrolysis in the presence of salts Acids without the addition of solvents, characterized in that the hydrolysis is carried out in one A reaction system consisting of an organic and an aqueous phase in the pH range of about 1 to approximately 7 at a pressure equal to the vapor pressure of the reactants in the autoclave at the the reaction temperature that is established corresponds to.