FR2491059A2 - Meta-chloro-aniline(s) prepn. by catalytic dehydrochloridation - with hydrogen, noble metal catalyst and Lewis acid in anhydrous medium, yields plant protection agent intermediates - Google Patents

Meta-chloro-aniline(s) prepn. by catalytic dehydrochloridation - with hydrogen, noble metal catalyst and Lewis acid in anhydrous medium, yields plant protection agent intermediates Download PDF

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FR2491059A2
FR2491059A2 FR8020979A FR8020979A FR2491059A2 FR 2491059 A2 FR2491059 A2 FR 2491059A2 FR 8020979 A FR8020979 A FR 8020979A FR 8020979 A FR8020979 A FR 8020979A FR 2491059 A2 FR2491059 A2 FR 2491059A2
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Prior art keywords
hydrogen
aniline
chloro
aralkyl
catalytic
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FR8020979A
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FR2491059B2 (en
Inventor
Georges Cordier
Pierre Fouilloux
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Bayer CropScience SA
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Rhone Poulenc Agrochimie SA
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Priority to FR8020979A priority Critical patent/FR2491059A2/en
Priority to IL63297A priority patent/IL63297A/en
Priority to US06/283,151 priority patent/US4418213A/en
Priority to IE1738/81A priority patent/IE51457B1/en
Priority to DE8181420115T priority patent/DE3166482D1/en
Priority to CA000382858A priority patent/CA1211470A/en
Priority to AT81420115T priority patent/ATE9686T1/en
Priority to EP81420115A priority patent/EP0045709B1/en
Priority to ES504473A priority patent/ES8306092A1/en
Priority to DK342981A priority patent/DK342981A/en
Priority to HU812244A priority patent/HU187348B/en
Priority to DD81232269A priority patent/DD201673A5/en
Priority to BR8104979A priority patent/BR8104979A/en
Priority to KR1019810002798A priority patent/KR850000148B1/en
Priority to SU813316601A priority patent/SU1176830A3/en
Publication of FR2491059A2 publication Critical patent/FR2491059A2/en
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Publication of FR2491059B2 publication Critical patent/FR2491059B2/fr
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
    • C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
    • C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
    • C07C211/45—Monoamines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
    • C07C211/45—Monoamines
    • C07C211/46—Aniline
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
    • C07C211/52—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring the carbon skeleton being further substituted by halogen atoms or by nitro or nitroso groups

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Process for the prepn. of meta-chloro-aniline derivs. (II), comprises liq.-phase catalytic hydrogenation, at elevated temp.and pressure, in the presence of Group VIII noble metals, of nitrogen and chloro-substd. benzene deriVs. of formula (I). The reaction is conducted in anhydrous medium in the presence of catalytic quantities of at least one Lewis acid catalyst. In (I) Y is H or O, X1, X2 are Cl, H, alkyl, aryl, aralkyl, alkoxy or aralkoxy (all opt. substd.), with the condition that at least one gp. is Cl; R1, R2, R3 are Cl, H, alkyl, aryl, aralkyl, alkoxy or aralkoxy (all gps. opt. substd.), with the condition that at least one is Cl. The poly-chloro-anilines are intermediates, esp. for plant protection agents. Known hydrogenation process for preparing (II) (FR2298531) uses high pressure and large amounts of hydrochloric acid which causes serious corrosion problems, the present invention avoids these corrosion problems.

Description

La présente addition se rapporte à un procédé de préparation d'anilines métachlorées substituées par le chlore en position méta par action de l'hydrogène sur des composés aromatiques azotés plus fortement halogénés. Ces anilines métachlorées sont des intermédiaires notamment pour la fabrication de produits phytosanitaires. The present addition relates to a process for the preparation of metachlorinated anilines substituted by chlorine in the meta position by the action of hydrogen on more highly halogenated nitrogenous aromatic compounds. These metachlorinated anilines are intermediaries in particular for the manufacture of phytosanitary products.

La demande de brevet français principal 80/17324 décrit un procédé de préparation d'anilines substituées en position méta par du chlore, par hydrogénation catalytique en phase liquide, à chaud et sous pression, en présence de métaux nobles du groupe VIII de la classification périodi que, de dérivés benzéniques azotés et chlorés, de formule dans laquelle

Figure img00010001
The main French patent application 80/17324 describes a process for the preparation of anilines substituted in the meta position with chlorine, by catalytic hydrogenation in the liquid phase, hot and under pressure, in the presence of noble metals from group VIII of the periodic classification. that of nitrogenous and chlorinated benzene derivatives, of formula in which
Figure img00010001

- Y représente l'atome d'hydrogène cu l'atome d'oxygène,
- X et X", identiques ou différents entre eux, représentent chacun un atome de chlore ou un radical alcoyle ou aryle ou aralcoyle ou alcoxyle ou aralcoxyle éventuellement substitué, au moins l'un des X' et X" pouvant, de plus être 11 hydrogène,
- R', R" et R"', identiques ou différents entre eux, représentent chacun un atome de chlore ou un radical alcoyle ou aralcoyle ou alcoxyle ou aryloxyle éventuellement substitué, l'un au moins de ces trois symboles représentant l'atome de chlore, au plus deux des R', R" ou R"' pouvant, de plus, être l'hydrogène, caractérisé en ce que la réaction est effectuée en milieu essentiellement anhydre, en présence d'une quantité catalytique d'au moins un acide de Lewis comme catalyseur.- Y represents the hydrogen atom or the oxygen atom,
- X and X ", which are identical or different from each other, each represent a chlorine atom or an alkyl or aryl or aralkyl or aralkyl or alkoxyl or aralkoxyl radical optionally substituted, at least one of X 'and X" which can moreover be 11 hydrogen,
- R ', R "and R"', identical or different from each other, each represent a chlorine atom or an optionally substituted alkyl or aralkyl or alkoxyl or aryloxyl radical, at least one of these three symbols representing the atom of chlorine, at most two of the R ′, R ″ or R ″ ′ which, moreover, can be hydrogen, characterized in that the reaction is carried out in an essentially anhydrous medium, in the presence of a catalytic amount of at least one Lewis acid as a catalyst.

La pression, à laquelle s'effectue la réaction, est généralement supérieure à 3 bars. I1 n'y a pas de limite supérieure critique pour la pression mais pour des raisons d'ordre économique, il est avantageux d'opérer à des pressions inférieures à 100 bars, les pressions inférieures à 20 bars étant préférées. The pressure at which the reaction takes place is generally greater than 3 bars. There is no critical upper limit for the pressure, but for economic reasons, it is advantageous to operate at pressures below 100 bar, pressures below 20 bar being preferred.

La demanderesse a maintenant découvert, et c'est ce qui fait l'objet de la présente addition, que la réaction peut être effectuée à des pressions relatives à 3 bars, sans que le rendement de la réaction ni la sé- lectivité de l'hydrodéchloration n'en soient affectés. En particulier, de bons résultats ont été obtenus en opérant à la pression atmosphérique. Par ailleurs, bien que cela ne soit pas avantageux, on peut opérer sous pression réduite par exemple en milieu solvant et à l'ébullition. The Applicant has now discovered, and this is the subject of the present addition, that the reaction can be carried out at pressures relative to 3 bars, without the yield of the reaction nor the selectivity of the are affected. In particular, good results have been obtained by operating at atmospheric pressure. Furthermore, although this is not advantageous, it is possible to operate under reduced pressure, for example in a solvent medium and at boiling point.

Le travail à pression atmosphérique permet d'apporter l'hydrogène sous forme de courant à un débit réglable. Working at atmospheric pressure makes it possible to supply hydrogen in the form of a current at an adjustable flow rate.

Par ailleurs, outre le cyclohexanne illustré dans la demande principale, on peut utiliser comme solvant organique inerte anhydre, de préférence à point d'ébullition élevé, un solvant aliphatique comme le dodécane ou un solvant aromatique tels que le chlorobenzène et les polychlorobenzènes. Ces derniers, en particulier, ne sont pas hydrochlorés dans les conditions de la réaction. Furthermore, in addition to the cyclohexane illustrated in the main application, an anhydrous inert organic solvent, preferably with a high boiling point, can be used an aliphatic solvent such as dodecane or an aromatic solvent such as chlorobenzene and polychlorobenzenes. The latter, in particular, are not hydrochlorinated under the conditions of the reaction.

Les exemples suivants sont donnés à titre non limitatif pour illustrer l'invention. The following examples are given without implied limitation to illustrate the invention.

Exemple 1 :
Dans un ballon de capacité 100 ml, muni d'un agitateur central tournant à 1000 tours/mn, d'un réfrigérant, d'un thermomètre et d'une arrivée de gaz, on charge
- 2 g (environ 0,01 mole) de trichloro-3,4,5-aniline,
- 0,6 g (2,25 x 10-3 mole) de bromure d'aluminium (AlBr3),
- 0,8 g d'un catalyseur au palladium à 5 % sur charbon actif,
- 20 ml de dodécane.Example 1:
In a 100 ml capacity flask fitted with a central agitator rotating at 1000 rpm, a coolant, a thermometer and a gas supply, the charge is made
- 2 g (approximately 0.01 mole) of 3,4,4,5-aniline trichloro,
- 0.6 g (2.25 x 10-3 mole) of aluminum bromide (AlBr3),
- 0.8 g of a 5% palladium catalyst on activated carbon,
- 20 ml of dodecane.

On maintient une température de 1600 et un courant d'hydrogène de 6 litres/h pendant 30 mn. Maintaining a temperature of 1600 and a hydrogen stream of 6 liters / h for 30 min.

La masse réactionnelle est ensuite traitée par de l'eau puis de l'éther. On sépare le catalyseur puis l'eau. The reaction mass is then treated with water and then with ether. The catalyst is separated then the water.

On élimine les solvants par distillation.The solvents are removed by distillation.

Dans ces cònditions, on obtient la dichloro-3,5-aniline avec un rendement de 99,5 %. Le taux de transformation de la trichloro-3,4,5 aniline est de 100 %. In these conditions, 3,5-dichloro-aniline is obtained with a yield of 99.5%. The transformation rate of 3,4,5,5-aniline trichloro is 100%.

Exemple 2
On opère comme à l'exemple précédent dans un réacteur de 250 mi, équipé de la même manière, avec les charges suivantes
- 19,7 g (0,1 mole) de trichloro-3,4,5-aniline,
- 3,0 g (1,12 x 10 2~mole) de bromure d'aluminium (AlBr3),
- 0,5 g du catalyseur au palladium à 5 % sur charbon actif,
- 60 ml de trichloro-1,2,4-benzène. Example 2
The procedure is as in the previous example in a 250 mi reactor, equipped in the same way, with the following charges
- 19.7 g (0.1 mole) of 3,4,5-trichloro-aniline,
- 3.0 g (1.12 x 10 2 ~ mole) of aluminum bromide (AlBr3),
- 0.5 g of the 5% palladium catalyst on activated carbon,
- 60 ml of 1,2,4-trichlorobenzene.

Le milieu réactionnel étant mis sous agitation, on maintient une température de 1600C et un courant d'hydrogène de 27 l/h pendant 4 heures. The reaction medium being stirred, a temperature of 1600 ° C. and a hydrogen stream of 27 l / h are maintained for 4 hours.

En opérant comme à l'exemple précédent, on obtient la dichloro-3,5 aniline avec un rendement de 100 %.  By operating as in the previous example, 3,5-dichloro aniline is obtained with a yield of 100%.

Claims (3)

REVENDICATIONS 1 - Procédé selon la revendication 1 de la demande de brevet principal 80/17324 de préparation d'anilines substituées en position méta par du chlore, par hydrogénation catalytique en milieu liquide, essentiellement anhydre, à chaud et sous pression, en présence de métaux nobles du groupe VIII de la classification périodique et une quantité catalytique d'au moins un acide de Lewis, de dérivés benzéniques azotés et chlorés, de formule dans laquelle 1 - Process according to claim 1 of main patent application 80/17324 for the preparation of anilines substituted in the meta position with chlorine, by catalytic hydrogenation in a liquid medium, essentially anhydrous, hot and under pressure, in the presence of noble metals of group VIII of the periodic table and a catalytic amount of at least one Lewis acid, of nitrogenous and chlorinated benzene derivatives, of formula in which
Figure img00040001
Figure img00040001
 ou gale/ pression inférieure/ bars. or scab / lower pressure / bars. - R', R" et R"', identiques ou différents entre eux, représentent chacun un atome de chlore ou un radical alcoyle ou aralcoyle ou alcoxyle ou aryloxyle éventuellement sub situés l'un au moins de ces trois symboles représentant l'atome de chlore, au plus deux des R', R" ou R"' pouvant, de plus, être l'hydrogène, caractérisé en ce guella la réaction est effectuée à une  - R ', R "and R"', identical or different from each other, each represent a chlorine atom or an alkyl or aralkyl or alkoxyl or aryloxyl radical optionally located at least one of these three symbols representing the atom of chlorine, at most two of R ', R "or R"' which can, moreover, be hydrogen, characterized in that the reaction is carried out at a - X' et X", identiques ou différents entre eux, représentent chacun un atome de chlore ou un radical alcoyle ou aryle ou aralcoyle ou alcoxyle ou aralcoxyle éventuellement substitué, au moins l'un des X' et X" pouvant, de plus, être l'hydrogène, - X ′ and X ″, identical or different from each other, each represent a chlorine atom or an alkyl or aryl or aralkyl or aralkyl or alkoxyl or aralkoxyl radical optionally substituted, at least one of X ′ and X ″ which can, moreover, to be hydrogen, - Y représente l'atome d'hydrogène ou l'atome d'oxygène, - Y represents the hydrogen atom or the oxygen atom, 2 - Procédé selon la revendication 1, caractérisé en ce que la réaction est effectuée à la pression atmosphérique. 2 - Process according to claim 1, characterized in that the reaction is carried out at atmospheric pressure. 3 - Procédé selon l'une des revendications 1 ou 2, caractérisé en ce qu'on prépare la dichloro-3,5-aniline à partir de la trichloro-3,4,5-aniline, dans un solvant organique, en présence de Palladium et de bromure d'aluminium.  3 - Method according to one of claims 1 or 2, characterized in that the dichloro-3,5-aniline is prepared from trichloro-3,4,5-aniline, in an organic solvent, in the presence of Palladium and aluminum bromide.
FR8020979A 1980-08-01 1980-09-26 Meta-chloro-aniline(s) prepn. by catalytic dehydrochloridation - with hydrogen, noble metal catalyst and Lewis acid in anhydrous medium, yields plant protection agent intermediates Granted FR2491059A2 (en)

Priority Applications (15)

Application Number Priority Date Filing Date Title
FR8020979A FR2491059A2 (en) 1980-09-26 1980-09-26 Meta-chloro-aniline(s) prepn. by catalytic dehydrochloridation - with hydrogen, noble metal catalyst and Lewis acid in anhydrous medium, yields plant protection agent intermediates
IL63297A IL63297A (en) 1980-08-01 1981-07-13 Selective preparation of meta-chloroanilines
US06/283,151 US4418213A (en) 1980-08-01 1981-07-14 Process for the selective preparation of meta-chloroanilines
DE8181420115T DE3166482D1 (en) 1980-08-01 1981-07-30 Process for the preparation of meta-chlorinated anilines
CA000382858A CA1211470A (en) 1980-08-01 1981-07-30 Process for the preparation of anilines substituted in the meta-position(s) by chlorine
AT81420115T ATE9686T1 (en) 1980-08-01 1981-07-30 PROCESS FOR THE PRODUCTION OF META-CHLORINATED ANILINES.
EP81420115A EP0045709B1 (en) 1980-08-01 1981-07-30 Process for the preparation of meta-chlorinated anilines
IE1738/81A IE51457B1 (en) 1980-08-01 1981-07-30 Process for the preparation of anilines substituted in the meta-position(s)by chlorine
ES504473A ES8306092A1 (en) 1980-08-01 1981-07-31 Process for the preparation of meta-chlorinated anilines.
DK342981A DK342981A (en) 1980-08-01 1981-07-31 PROCEDURE FOR SELECTIVE PREPARATION OF M-CHLORANILINES
HU812244A HU187348B (en) 1980-08-01 1981-07-31 Process for the selective production of meta-chloro-anilines
DD81232269A DD201673A5 (en) 1980-08-01 1981-07-31 METHOD FOR THE SELECTIVE PREPARATION OF M-CHLORINE ANILINE
BR8104979A BR8104979A (en) 1980-08-01 1981-07-31 PROCESS OF PREPARING ANILINES REPLACED IN TARGET POSITION BY CHLORINE
KR1019810002798A KR850000148B1 (en) 1980-08-01 1981-08-01 Process for the preparation of meta-choroanilines
SU813316601A SU1176830A3 (en) 1980-08-01 1981-08-01 Method of producing 3,5-dichloroaniline

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR8020979A FR2491059A2 (en) 1980-09-26 1980-09-26 Meta-chloro-aniline(s) prepn. by catalytic dehydrochloridation - with hydrogen, noble metal catalyst and Lewis acid in anhydrous medium, yields plant protection agent intermediates

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FR2491059A2 true FR2491059A2 (en) 1982-04-02
FR2491059B2 FR2491059B2 (en) 1984-03-09

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FR8020979A Granted FR2491059A2 (en) 1980-08-01 1980-09-26 Meta-chloro-aniline(s) prepn. by catalytic dehydrochloridation - with hydrogen, noble metal catalyst and Lewis acid in anhydrous medium, yields plant protection agent intermediates

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