FR2462411A1 - PROCESS FOR THE PREPARATION OF P-TERTIOBUTYLBENZALDEHYDE - Google Patents

Abstract

THE INVENTION RELATES TO A PROCESS FOR THE PREPARATION OF P-TERTIOBUTYLBENZALDEHYDE CHARACTERIZED BY THE FACT THAT THE FOLLOWING STEPS ARE CARRIED OUT AT LEAST ONCE: IN ELECTROLYZING CERIUM III NITRATE OR AMMONIUM-CERIUM III NITRATE USING A CHAMBER III NITRATE CATHODE CONTAINING WATER CONTAINING IONS NITRATE OR A MIXTURE OF WATER AND LOWER FATTY ACID CONTAINING IONS NITRATE AND AN ANODE CHAMBER CONTAINING A MIXTURE OF WATER AND LOWER FATTY ACID CONTAINING SALT OF CERIUM, TO OBTAIN A MIXTURE OF WATER AND LOWER FATTY ACID CONTAINING CERIUMIV NITRATE OR AMONIUM-CERIUMIV NITRATE AND B OXIDIZING P-TERTIOBUTYLTOLUENE BY MEANS OF THE MIXTURE OBTAINED TO OBTAIN P-TERTIOBUTYLBENDE.

Description

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The invention relates to a process for the preparation of ptertiobutylbenzaldehyde.

P-tertiobutylbenzaldehyde is an important compound

  so much, for example for the manufacture of perfumes. There is already known, for the preparation of p-tertiobutylbenzaldehyde by oxidation of ptertiobutyltoluene, a process

in which manganese dioxide is used as the oxidant

  born and an automatic oxidation process using a cobaltbrome system. However, these methods give a large amount of a more oxidized by-product which is p-tert-butylbenzoic acid if an attempt is made to achieve an increased conversion, they involve difficulties in treating the oxidant and the catalyst with a view to rejection.

  and require a complicated process for regeneration

tion of these bodies.

  It is also generally known to oxidize a group

methyl attached to a benzene ring by means of an oxy-

air or air. However, the use of chemical oxidants

ques like potassium permanganate and potassium dichromate poses many problems of pollution, toxicity, economy etc. In addition, the use of air

requires a special catalyst, gives a low yield

  ment, involves difficulties in processing the

  product and catalyst and requires special treatment, for example a reaction at high temperature and high

  pressure, which also creates fitting difficulties.

  In Tetrahedron Letter, 1966, 4493, it is said that

  p-methylanisole is oxidized using ammonium nitrate

nium-cerium (IV) in an aqueous solution of nitric acid

that, acetic acid, perchloric acid etc. for

get anisaldehyde. In this case, we isolate the pro-

duit as 2,4-dinitrophenylhydrazone

  corresponding. By applying this very careful process-

  exactly as described for the oxidation of the

p-methylanisole, after separation and ana-

  detailed lysis of the reaction mixture, that the process provides 43% of anisaldehyde, 16% of a quinone which seems to result from the chain by oxidation between

  the raw material and the anisaldehyde formed as pro-

  duit, is various other by-products of unidentified structure. In the process described, no attempt is made to recycle the oxidant. The literature says nothing about the electrolytic oxidation of the oxidant after the

  oxidation reaction, using the same solvent, or

  an effective separation process for the desired product.

  DE-OS 1 804 727 describes the oxidation of naphthalene, anthracene etc. with cerium (IV) sulfate or ammonium cerium (IV) sulfate in an aqueous solution

sulfuric or nitric acid for the preparation

tion of a quinone and the regeneration by electrolysis of the cerium salt obtained.- In addition, Bull. Chem. Soc. Japan, 35, 1751-1755 (1962) describes the oxidation of p-xylene

with cerium (IV) sulfate for the preparation of p-

tolualdehyde and electrolytic oxidation of cerium (III) sulphate for repeated use. However, nothing is said about p-tertiobutyltoluene. The disadvantages of the methods described are that they have a low current yield and a low conversion into the desired product and

  that they involve a further decrease in the conversion

  or yield as the salt is reused

of cerium.

  We have found that the optimal conditions for the re-

oxidation action of compounds by means of a cerium salt are markedly different depending on the nature of the

raw material to be oxidized.

The object of the invention is to provide an oxy-

  donation of p-tertiobutyltoluene in a very short time, giving ptertiobutylbenzaldehyde with a yield

high and high conversion.

  Another object of the invention is to provide a pro-

  yielded from the preparation of p-tertiobutylbenzaldehyde by means of an oxidizer which can be regenerated easily, so

  semi-permanent and quantitative for repeated use.

  Another object of the invention is to provide a

24624 1 1

  process for the preparation of p-tertiobutylbenzaldehyde used

  reading clean electrical energy without giving

by-products which may cause pollution.

These and other objects of the invention

  will appear in the following description.

The invention provides a process for the preparation of ptertiobutylbenzaldehyde, characterized in that the following steps are carried out at least once: (a) electrolyzing cerium (III) nitrate or nitrate

  ammonium-cerium (III) using a cathode chamber

  of which contains water containing nitrate ions or a mixture of water and lower fatty acid containing nitrate ions and an anode chamber which contains a mixture of water and lower fatty acid containing salt of cerium, to obtain a mixture of water and fatty acid

  lower containing cerium (IV) nitrate or ni-

  ammonium-cerium trate (IV) and (b) oxidize p-pertio-

  butyltoluene using the mixture obtained to obtain ppertiobutylbenzaldehyde. By the process of the invention, the

  desired product with high yields and conver-

  high ions, in a very short time, starting from an easily accessible material at low cost, using

  an oxidant which can be regenerated semi-perma-

  nent and quantitative for repeated use. The pro-

sold uses clean electrical energy and does not

carries no formation of by-products that could cause

pollution.

  The electrolytic oxidation of the invention takes place

  tick as follows. We place in a room

anode a mixture of water and lower fatty acid

containing cerium (III) nitrate or ammonium nitrate

  nium-cerium (III) which has been taken from a reaction mixture

  oxidation by separating therefrom the p-tertio-

  butylbenzaldehyde. It is helpful to add a small amount of nitric acid or ammonium nitrate to the mixture. Water is placed in a cathode chamber

containing nitrate ions -or a mixture of water and a-

lower fatty acid containing nitrate ions. Various compounds can be used as the source of nitrate ions

  such as nitric acid, ammonium nitrate, ni-

  sodium trate, potassium nitrate, alkylammonium nitrates, etc., nitric acid and ammonium nitrate being preferred. Examples of preferred lower fatty acids are those which contain

  1 to 3 carbon atoms like formic acids, acé

  tick, propionic etc. These acids can be used

separately or as a mixture.

  The electrolytic oxidation of the invention is carried out in the two above chambers which can be used without any diaphragm. However, the chambers are preferably separated by a porcelain diaphragm, a

  ion exchange diaphragm etc. Electrolytic oxidation

tick quantitatively provides a mixture of water and acid

  lower fat that contains cerium (IV) nitrate

  or ammonium cerium (IV) nitrate. The density of

  The electrolysis rate is not particularly limited and it is determined as desired according to the size of the electrolytic cell, the reaction time, etc. The electrodes can be formed in any known manner such as platinum, iron, stainless steel, carbon, titanium oxide, lead oxide, lead dioxide etc. The electrolytic reaction, which can be carried out at a temperature of about 0 to 1000C, is carried out

  preferably between 10 and 600C approximately.

  When mixed with p-tertiobutyltoluene with agi-

  tation the mixture of water and fatty acid containing cerium nitrate (IV) or ammonium cerium nitrate (IV), an oxidation reaction takes place quickly giving

p-tertiobutylbenzaldehyde with a high yield.

  The reaction temperature, which is not particularly

  limited, is preferably about 50 to 1200C, pre-

ference still about 60 to 100IC, when it is desired to complete the reaction in a short time. The mixture of water and lower fatty acid containing cerium (IV) nitrate or ammonium cerium (IV) nitrate and serving

  oxidant for the oxidation reaction must contain

  about 20 to 90% by weight of lower fatty acid, pre-

ference about 30 to 80%, on the total weight of water and

  lower fatty acid, so that the mixture is

  ble to oxidize p-tert-butyltoluene, that the desired product is obtained, that the product can be separated, that the cerium salts initial and obtained as product are soluble, that the cerium (III) salt is stable

  during electrolytic oxidation, that this salt converges

  weaves in cerium (IV) salt etc. When there are approximately

  90% by weight of lower fatty acid, the salt of

  rium (IV) acts effectively to oxidize p-

  tertiobutyltoluene and the desired product which is p-tertiobutylbenzaldehyde can be effectively separated. In

  in addition, the cerium (IV) salt is then very soluble tan-

say that the cerium (III) salt resulting from the oxidation reaction also has good solubility. The product, namely p-tertiobutylbenzaldehyde, can be separated from

mixing by known means. For example, we can easily-

  ment extract the product with a solvent such as an ether, an ester, an aromatic hydrocarbon, an aliphatic hydrocarbon, a halohydrocarbon, etc. The mixture of water and lower fatty acid separated from p-tert-butylbenzaldehyde and containing cerium (III) nitrate or ammonium cerium nitrate is subjected to the electrolytic oxidation reaction already described.

  (III) to obtain by regeneration the cerium salt (IV).

According to the invention, driving at least once

  the electrolytic oxidation step and the oxidative step

  tion of p-tertiobutyltoluene to obtain p-tertio-

butylbenzaldehyde with high yield. A remarkable advantage of the invention is that even when these steps are repeated a large number of times, the desired product can be obtained with a high yield, of at least 95%

about each time.

The invention will now be described with reference to

examples and the comparative example below.

Example 1

  200 mg of ptertiobutyltoluene and 3.70 g of ammonium cerium (IV) nitrate are placed in a reactor equipped with a condenser, then 10 ml of aqueous solution

  acetic acid at 50% by weight. We then stir vigorously

  the mixture for 30 minutes, the reactor being placed in an oil bath between 70 and 100 C. The mixture is subjected to extraction with hexane (n), the extract is washed with an aqueous bicarbonate solution of sodium and with an aqueous solution of sodium chloride and dried over anhydrous sodium sulfate. By removing the solvent from the dry extract, 211 mg of p-tert-butylbenzaldehyde (99% purity) are obtained. Yield

96.5%.

Place the mixture of water and acetic acid containing

  ammonium cerium (III) nitrate, separated from the former

  line, in an anode chamber separated from a cathode chamber by a porcelain diaphragm. 200 mg nitrate solution is placed in the cathode chamber

  of ammonium in 20 ml of aqueous solution of acetic acid

  than 50% by weight. With platinum electrodes installed in the anode and cathode chambers, the cerium salt is electrolyzed with a constant current of

  mA to pass a quantity between the electrodes

  1.2 F / mol electricity tee. The solution is removed from the anode chamber after completion of the electrolysis

then it is reacted on 200 mg of p-tertiobutyltoluene.

Then repeat the above process to get

  210.0 mg of p-tertiobutylbenzaldehyde. Yield 96.0%.

Examples 2 to 10

The oxidation of p-tertio-

  butyltoluene and the electrolytic oxidation of ammonium cerium (III) nitrate, practically in the same way as in Example 1, under the conditions indicated in Table 1 which also indicates the results. (See table

1 page 9).

Examples 11 to 18 The process of Example 1 is repeated under the conditions indicated in Table 2 below, using a carbon or lead oxide anode and a stainless steel cathode (SUS). Results are shown

  in Table 2. (See Table 2 page-0).

Example 19

  The same process is repeated as in Example 1 using an aqueous solution of nitric acid at 3% by weight in the cathode chamber for electrolysis; p-tertiobutylbenzaldehyde is obtained with a yield

96.2%.

Example 20

  We put in a anode chamber a solution of

  2.46 g of cerium (III) nitrate in an aqueous solution

  se of acetic acid ç 65% by weight. 20 ml of a 65% by weight aqueous solution of acetic acid containing 200 mg of dissolved ammonium nitrate are placed in a cathode chamber. The cerium salt is electrolyzed with a constant current of 50 mA so as to pass an amount of electricity of 1.2 F / mol between the electrodes. The solution withdrawn from the anode chamber is reacted after the completion of the electrolysis on mg of p-tert-butyltoluene, in the same way as

  in Example 1 and p-tertiobutylbenzal- is obtained

dehyde with a yield of 95.9 3.

Example 21

In a reactor equipped with a refrigerant, we put

  mg of p-tertiobutyltoluene, 3.70 g of amitrate

  monium-cerium (IV) and 10 ml of aqueous acetic acid solution at 30% by weight. The mixture is vigorously stirred for 30 minutes, the reactor being placed in an oil bath between 70 and 1000C. The mixture is subjected to benzene extraction, the extract is washed with an aqueous solution of sodium bicarbonate and with an aqueous solution of sodium chloride and dried over anhydrous sodium sulfate. By removing the solvent

  from the dry extract, p-tertiobutylbenzaldé is obtained

hyde with a yield of 94.7%.

  The mixture of water and acetic acid is placed,

holding ammonium cerium (III) nitrate and separated from the extract, in an anode chamber separated from a cathode chamber by an ion exchange diaphragm. An aqueous solution is placed in the cathode chamber.

  % acetic acid containing 200 mg of amino nitrate

  monium. Using platinum electrodes, the cerium salt is electrolyzed at 15 C with a constant current of 50 mA

  so as to pass between the electrodes a quan-

electricity rate of 1.1 F / mol. After completion of the electrolysis, p-tertiobutyltoluene is treated with the solution contained in the anode chamber, in the same way

  way as above, to get the p-tertiobutylben-

  zaldehyde with a yield of 95.1%.

Comparative example 1

  2.0 g of p-tert-butylto- are placed in a reactor

  luene and 3.70 g of ammonium cerium (IV) nitrate, then 100 ml of water. The mixture is vigorously stirred between and 1000C for 30 minutes. The mixture is extracted with hexane (n), the extract is washed with an aqueous solution of sodium bicarbonate and with a solution

aqueous sodium chloride and dried over sul-

  anhydrous sodium fate. When the dry extract is distilled after removal of the solvent, only the

raw material and we don't get p-tertiobutyl-

benzaldehyde.

TABLE 1

  Electrolytic reaction Electrodes (+) (-) (mA) Current, Quantity Sulphate of electricity, ammonium, (F / mole) (mg)

Oxidation of p-

tertiobutyl-

  toluene Temp- Time, erosion, (Oc) (h) 2 Pt 3 Pt 4 Pt Pt 6 Pt 7 Pt 8 Pt 9 Pt Pt

Example

Render-

ment, (%) Pt Pt Pt Pt Pt Pt Pt Pt Pt 1.2 1.2 1.1 1.1 1.1 1.0 1.0 1.0 1.0 to 95 to 95 to 85 to 95 to 75 to 60 to 95 to 95 to 95 0.5 0.5 0.5 o0.5 0.5 0.5 0.5 o0.5 o0.5 96.0 96.7, 8 97.0 96.6 , 4, 6 96.1 96.4 6 '6 9' 6 L'S6

P 54 '96

ú'96 T'L6 2.'g6 o'A g'66 L'96 O'L6 (-p) Il ueu -epueet '0 ç'0 60' o g'0 g'0 & o 'IlO' O

 6 '58

6 '58

g9 * q gg 6 l 58 56 5g 6 q g8 L q 59 6, g8 6 q gs (tt) (Oo) gdwej, PdW9ej, 00z 00z 00z 00z 00z Qo z oo? 00z (2w) UInTuowWe, p ou4nTo4 -I. & nqoT4ae4 -d np uoT $ pxxd 0'I 0'T1 1'1 1'1 (erowu /, I) 9q.TOTOOI9 a enbT. z lnvaiav oL oL OL OL OL OL OL oL sns sns sns sns sns sns sas sas z oc Zo o o o o o1 Lt 9t CZT t '(ViiU) (-) ÀkrOajoei: UO-j0,09- Oedmexa -w -t' Co%

246 241 1

Claims (10)

  1 - Process for the preparation of p-tertiobutylbenzal-   dehyde characterized in that the following steps are carried out at least once: (a) electrolyzing cerium (III) nitrate or ammonium cerium (III) nitrate using a cathode chamber which contains l water containing nitrate ions or a mixture of water and lower fatty acid containing nitrate ions and an anode chamber which contains a mixture of water and lower fatty acid containing the cerium salt, for   obtain a mixture of water and lower fatty acid   of cerium (IV) nitrate or ammonium nitrate-   cerium (IV) and (b) oxidize p-tertiobutyltoluene to   means of the mixture obtained to obtain p-tertiobutyl- benzaldehyde. 2 - Method according to claim 1, characterized   by the fact that the source of nitrate ion is the acid ni-   stick, ammonium nitrate, sodium nitrate,   potassium nitrate or an alkylammonium nitrate.   3 - Method according to claim 2, characterized by the fact that the source of nitrate ion is the acid ni- stick or ammonium nitrate. 4 - Method according to claim 1, characterized   by the fact that the lower fatty acid is formic acid that, acetic or propionic.   - Method according to claim 1, characterized   by the fact that the mixture of water and fatty acid contains   the cerium salt and intended to be electrolyzed additionally contains nitric acid or nitrate ammonium.   6 - Method according to claim 1, characterized in that the mixture resulting from step (a) contains about 20 to 90% by weight of fatty acid, on total water and fatty acid.   7 - Process according to claim 6, characterized in that the proportion of fatty acid in the mixture is about 30 to 80 56 by weight. 8-- Method according to claim 1, characterized in that the cathode chamber is separated from   the anode chamber by a diaphragm. 9 - Process according to claim 1, characterized in that lion oxidizes p-tertiobutyltoluene between and about 1200C.   - Method according to claim 9, characterized in that the oxidation reaction is carried out between 60 and 1000C approximately.   11 - Process according to claim 1, characterized in that the cerium salt is electrolyzed between 0 and 1000C approximately. 12 - Process according to claim 11, characterized in that the electrolysis is carried out between 10 and 600C approximately.