FR2667063A1 - Process for the acylation of aromatic hydrocarbons - Google Patents
Process for the acylation of aromatic hydrocarbons Download PDFInfo
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- FR2667063A1 FR2667063A1 FR9011856A FR9011856A FR2667063A1 FR 2667063 A1 FR2667063 A1 FR 2667063A1 FR 9011856 A FR9011856 A FR 9011856A FR 9011856 A FR9011856 A FR 9011856A FR 2667063 A1 FR2667063 A1 FR 2667063A1
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- reaction
- acylation
- zeolite
- benzene series
- aromatic hydrocarbons
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- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000005917 acylation reaction Methods 0.000 title claims abstract description 16
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 15
- 230000010933 acylation Effects 0.000 title claims abstract description 14
- 239000010457 zeolite Substances 0.000 claims abstract description 24
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- -1 aromatic carboxylic acids Chemical class 0.000 claims abstract description 6
- 150000001555 benzenes Chemical class 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 5
- 150000001735 carboxylic acids Chemical group 0.000 claims description 4
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 125000004001 thioalkyl group Chemical group 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims 1
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 8
- XRHGYUZYPHTUJZ-UHFFFAOYSA-N 4-chlorobenzoic acid Chemical compound OC(=O)C1=CC=C(Cl)C=C1 XRHGYUZYPHTUJZ-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- JJVJYPSXZCEIEQ-UHFFFAOYSA-N (4-chlorophenyl)-(4-methoxyphenyl)methanone Chemical compound C1=CC(OC)=CC=C1C(=O)C1=CC=C(Cl)C=C1 JJVJYPSXZCEIEQ-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 4
- MRIBPIAKCVDXLY-UHFFFAOYSA-N (4-chlorophenyl)-(4-methylphenyl)methanone Chemical compound C1=CC(C)=CC=C1C(=O)C1=CC=C(Cl)C=C1 MRIBPIAKCVDXLY-UHFFFAOYSA-N 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- HNKJADCVZUBCPG-UHFFFAOYSA-N thioanisole Chemical compound CSC1=CC=CC=C1 HNKJADCVZUBCPG-UHFFFAOYSA-N 0.000 description 2
- VFMPCNWWYIQPCN-UHFFFAOYSA-N (4-bromophenyl)-(4-methoxyphenyl)methanone Chemical compound C1=CC(OC)=CC=C1C(=O)C1=CC=C(Br)C=C1 VFMPCNWWYIQPCN-UHFFFAOYSA-N 0.000 description 1
- MXNKVONPGXQVLF-UHFFFAOYSA-N (4-chlorophenyl)-(4-methylsulfanylphenyl)methanone Chemical compound C1=CC(SC)=CC=C1C(=O)C1=CC=C(Cl)C=C1 MXNKVONPGXQVLF-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical class CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- OFQCQIGMURIECL-UHFFFAOYSA-N 2-[2-(diethylamino)ethyl]-2',6'-dimethylspiro[isoquinoline-4,4'-oxane]-1,3-dione;phosphoric acid Chemical compound OP(O)(O)=O.O=C1N(CCN(CC)CC)C(=O)C2=CC=CC=C2C21CC(C)OC(C)C2 OFQCQIGMURIECL-UHFFFAOYSA-N 0.000 description 1
- TUXYZHVUPGXXQG-UHFFFAOYSA-N 4-bromobenzoic acid Chemical compound OC(=O)C1=CC=C(Br)C=C1 TUXYZHVUPGXXQG-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 244000198134 Agave sisalana Species 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- WSFSSNUMVMOOMR-BJUDXGSMSA-N methanone Chemical compound O=[11CH2] WSFSSNUMVMOOMR-BJUDXGSMSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/46—Friedel-Crafts reactions
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
Procédé d'acylation d'hydrocarbures aromatiques
La présente invention concerne un procédé d'acylation d drocarbures aromatiques de la série du benzène par des acides carboxyliques aromatiques de la série du benzène.Process for the acylation of aromatic hydrocarbons
The present invention relates to a process for the acylation of aromatic hydrocarbons of the benzene series with aromatic carboxylic acids of the benzene series.
On en connaît de FR-B-2592039 un procédé d'acylation dthydrocarbures aromatiques par réaction avec des acides carboxyliques ayant au moins deux atomes de
Carbone ou leurs dérivés du type anhydride ou chlorure d'acide, cette réaction étant effectuée en présence d'un catalyseur zéolithique dans lequel l'ion alcalin sodium présent dans sa structure initiale a été remplacé dans une proportion d1au moins 50 % par l'ion
Ce3+ .Plus précisément, il est indiqué que ladite iriention s'applique, de façon avantageuse, aux acides carboxyliques aliphatiques contenant de 2 à 22 atomes de carbone et aux hydrocarbures aromatiques de la série du benzène, et dérivés. Le document FR-B-2592039 enSeL-ne encore que des catalyseurs zéolithiques de type iW de rapport Si/Al = 2,5 ou Al3+NaY de rapport
Si/Al = 2,5 ne conviennent pas pour effectuer cette réaction d'acylation, le pourcentage de conversion en produit acylé étant respectivement égal à 8 et nul.Le catalyseur préconisé selon FR-B-2592039 est une zéolithe de type Ce3+Nat où le pourcentage de cérium en poids est d'au moins 6 %
On Vient à présent de trouver, à l'encontre de l'enseignement précité, que l'acylation sélective en position para d'hydrocarbures aromatiques de la série du benzène par des acides carboxyliques aromatiques de la série du benzène est catalysée dans d'excellentes
Conditions par les zéolithes de type HY ou Hss dont le rapport sisal est supérieur à 10.There is known from FR-B-2592039 a process for the acylation of aromatic hydrocarbons by reaction with carboxylic acids having at least two atoms of
Carbon or their anhydride or acid chloride derivatives, this reaction being carried out in the presence of a zeolitic catalyst in which the sodium alkaline ion present in its initial structure has been replaced in a proportion of at least 50% by the ion
Ce3 +. More specifically, it is indicated that the said guidance applies, advantageously, to aliphatic carboxylic acids containing from 2 to 22 carbon atoms and to aromatic hydrocarbons of the benzene series, and derivatives. The document FR-B-2592039 enSeL-still only zeolitic catalysts of type iW of Si / Al ratio = 2.5 or Al3 + NaY of ratio
If / Al = 2.5 is not suitable for carrying out this acylation reaction, the percentage of conversion to acylated product being equal to 8 and zero respectively. The catalyst recommended according to FR-B-2592039 is a Ce3 + Nat type zeolite where the percentage of cerium by weight is at least 6%
We now come to find, contrary to the above teaching, that the selective acylation in the para position of aromatic hydrocarbons of the benzene series by aromatic carboxylic acids of the benzene series is catalyzed in excellent
Conditions by zeolites of the HY or Hss type whose sisal ratio is greater than 10.
Plus précisément, la présente invention concerne un procédé d'acylation sélective en position para d'hydrocarbures aromatiques de la série du benzène par des acides carboxyliques aromatiques de la série du benzène selon la réaction
dans laquelle
R représente l'atome d'hydrogène, un atome d'halogène ou un groupe cyano et R' représente un groupe alkyle en
C1-C4, un groupe alkoxy en C1-C4 ou un groupe thioalkyle en Cl-C4, cette réaction étant conduite en présence de zéolithe de type HY ou Hss dont le rapport Si/Al est supérieur à 10, de préférence compris entre 10 et 25, à une température de l'ordre de 180 C à 250"C. More specifically, the present invention relates to a process for the selective acylation in the para position of aromatic hydrocarbons of the benzene series with aromatic carboxylic acids of the benzene series according to the reaction.
in which
R represents the hydrogen atom, a halogen atom or a cyano group and R 'represents an alkyl group in
C1-C4, a C1-C4 alkoxy group or a C1-C4 thioalkyl group, this reaction being carried out in the presence of a zeolite of the HY or Hss type whose Si / Al ratio is greater than 10, preferably between 10 and 25, at a temperature of the order of 180 ° C. to 250 ° C.
Par atome d'halogène on entend ici un atome de brome, un atome de fluor, un atome de chlore ou un atome d'iode.By halogen atom is meant here a bromine atom, a fluorine atom, a chlorine atom or an iodine atom.
Par groupe alkyle en Ci -C4, on entend ici un groupe de formule CnH2n+i, linéaire ou ramifié, où n représente un nombre entier de 1 à 4. Le groupe alkyle préféré est le groupe méthyle. By C1-C4alkyl group is meant here a group of formula CnH2n + i, linear or branched, where n represents an integer from 1 to 4. The preferred alkyl group is the methyl group.
Par groupe alkoxy en C1-C4, on entend ici un groupe de formule CnH2n+1 O, linéaire ou ramifié, où n représente un nombre entier de 1 à 4. Le groupe alkoxy préféré est le groupe méthoxy.By C1-C4 alkoxy group is meant here a group of formula CnH2n + 1 O, linear or branched, where n represents an integer from 1 to 4. The preferred alkoxy group is the methoxy group.
Le catalyseur utilisé est une zéolithe de type Y ou de type 13 sous forme protonique. Pour accéder à la forme protonique, la zéolithe échangée dans une solution aqueuse de chlorure d'ammonium doit être calcinée. La température de calcination est comprise entre 300 et 600-C, de préférence de l'ordre de 400 à 5506C. The catalyst used is a type Y or type 13 zeolite in proton form. To access the proton form, the zeolite exchanged in an aqueous ammonium chloride solution must be calcined. The calcination temperature is between 300 and 600-C, preferably of the order of 400 to 5506C.
Les zéolithes HY et Hss sont telles que le rapport Si/AI est supérieur à 10, de préférence compris entre 10 et 25. On utilisera avantageusement les zéolithes HY(15) et Hss(15) dont le rapport Si/Al est de l'ordre de 15 et tes zéolithes HY(20) et Hss(20) dont le rapport Si/Al est de l'ordre de 20.The HY and Hss zeolites are such that the Si / Al ratio is greater than 10, preferably between 10 and 25. The HY (15) and Hss (15) zeolites with an Si / Al ratio of order of 15 and your HY (20) and Hss (20) zeolites whose Si / Al ratio is of the order of 20.
Le procédé selon l'invention consiste en une acylation selective en position para d'hydrocarbures aromatiques de lss série du benzène par des acides carboxyliques aroaotiques de la série du benzène. Au cours de cette réaction il se forme néanmoins les isomères acylés en position méta et ortho de 1 l'hydrocarbure aromatique mais en quantité non prépondérante par rapport à l'isomère para.The process according to the invention consists of a selective acylation in the para position of aromatic hydrocarbons of the benzene series by aroaotic carboxylic acids of the benzene series. During this reaction, however, the acylated isomers are formed in the meta and ortho position of 1 the aromatic hydrocarbon but in a non-preponderant amount relative to the para isomer.
Un avantage du procédé selon l'invention consiste donc en la sélectivité de l'acylation de l'hydrocarbure aromatique en position para. An advantage of the process according to the invention therefore consists in the selectivity of the acylation of the aromatic hydrocarbon in the para position.
De facon avantageuse le procédé selon l'invention concerne la réaction d'acylation (I) où ie substituant
R de l'acide carboxylique aromatique est en position para par rapport à la fonction acide carboxylique, la réaction (I) étant effectuée en présence de zéolithe de type 1113 ou HY dont le rapport Si/Al est de l'ordre de 15 à 20.Advantageously, the process according to the invention relates to the acylation reaction (I) where the substituent
R of the aromatic carboxylic acid is in the para position relative to the carboxylic acid function, the reaction (I) being carried out in the presence of a zeolite of type 1113 or HY whose Si / Al ratio is of the order of 15 to 20 .
Le procédé selon l'invention sera avantageusement conduit à une température de l'ordre de 200"C, l'hydrocarbure aromatique étant en excès, de préférence en quantité 1 à 3 fois molaire par rapport à l'acide carboxylique aromatique, dans un solvant organique anhydre, de préférence les hydrocarbures aromatiques halogénés ou non, comme par exemple le toluène ou le chlorobenzène, le solvant pouvant également être constitué par un exces de l'hydrocarbure aromatique intrant dans la réaction, la réaction étant conduite en autoclave, sous pression d'un gaz inerte, ou dans un réacteur de type continu sur un lit fixe de zéolithe.The process according to the invention will advantageously be carried out at a temperature of the order of 200 ° C., the aromatic hydrocarbon being in excess, preferably in an amount 1 to 3 times molar with respect to the aromatic carboxylic acid, in a solvent anhydrous organic, preferably aromatic hydrocarbons, halogenated or not, such as for example toluene or chlorobenzene, the solvent can also consist of an excess of the aromatic hydrocarbon entering the reaction, the reaction being carried out in an autoclave, under pressure d '' an inert gas, or in a continuous type reactor on a fixed bed of zeolite.
L'invention sera mieux comprise à la lecture des eXemples qui suivent. Ces exemples sont donnés pour illustrer l'invention sans toutefois la limiter dans ses équivalents à la portée de l'homme de l'art. The invention will be better understood on reading the examples which follow. These examples are given to illustrate the invention without, however, limiting it to its equivalents within the reach of ordinary skill in the art.
PREPARATION I
Acylation du toluène Par l'acide para-chlorobenzoïque
Dans un autoclave de 100 ml, on introduit 50 ml de toluène, 0,25 g d'acide para-chlorobenzoïque et 0,5 g de zéolithe Hss(20) préalablement calcinée à 400 C.PREPARATION I
Acylation of toluene By para-chlorobenzoic acid
50 ml of toluene, 0.25 g of para-chlorobenzoic acid and 0.5 g of Hss zeolite (20) previously calcined at 400 C. are introduced into a 100 ml autoclave.
Avant de chauffer le mélange, on effectue un balayage à l'azote pendant 15 minutes. On introduit ensuite de l'azote jusqu a obtenir une pression égale à 2.105 Pa et on chauffe le mélange réactionnel. L'agitation est mise en route lorsque la température atteint 200 C. Before heating the mixture, a nitrogen sweep is carried out for 15 minutes. Nitrogen is then introduced until a pressure equal to 2.105 Pa is obtained and the reaction mixture is heated. Agitation is started when the temperature reaches 200 C.
Après 4 heures de réaction à cette température un prélèvement est analysé par chromatographie en phase gazeuse. On obtient 84,4 % de (4-méthylphényl) 4-chlorophényl) méthanone.After 4 hours of reaction at this temperature, a sample is analyzed by gas chromatography. 84.4% of (4-methylphenyl) 4-chlorophenyl) methanone is obtained.
Dans les mêmes conditions, en utilisant une zéolithe Hss(5) préalablement calcinée à 500 C, on obtient 74BS % de (4-méthylphényl) (4-chlorophényl) méthanone.Under the same conditions, using an Hss (5) zeolite previously calcined at 500 ° C., 74BS% of (4-methylphenyl) (4-chlorophenyl) methanone is obtained.
flans les mêmes conditions, en utilisant une zéolithe bY(1S) préalablement calcinée à 550 C, on obtient 73 % de (4-méthylphényl) (4-chlorophényl) méthanone. under the same conditions, using a bY (1S) zeolite previously calcined at 550 ° C., 73% of (4-methylphenyl) (4-chlorophenyl) methanone is obtained.
Exemple comparatif
Dans les mêmes conditions, en utilisant une zéolithe CeNaY (70 % de Ce ; Si/Al = 2,3) préalablement calcinée à 500-C, on obtient 41 % de (4-méthylphényl) (4-chlorophényl) méthanone. Comparative example
Under the same conditions, using a CeNaY zeolite (70% Ce; Si / Al = 2.3) previously calcined at 500-C, 41% of (4-methylphenyl) (4-chlorophenyl) methanone is obtained.
PREPARATION II
Acylation de l'anisole par l'acide para-chlorobenzoïque
Selon le mode opératoire décrit dans la préparation I, au départ de 1 g d'acide para-chlorobenzoïque, 2 ml d'anisole dans 50 ml de chlorobenzène, les réactifs étant séchés sur tamis moléculaires, et en présence de 0,5 g de zéolithe H13(20) préalablement calcinée à as0 C, on obtient 49 % de (4-méthoxyphényl) (4-chlorophényl) méthanone.PREPARATION II
Acylation of anisole with para-chlorobenzoic acid
According to the procedure described in preparation I, starting from 1 g of para-chlorobenzoic acid, 2 ml of anisole in 50 ml of chlorobenzene, the reagents being dried over molecular sieves, and in the presence of 0.5 g of zeolite H13 (20) previously calcined at as0 C, 49% of (4-methoxyphenyl) (4-chlorophenyl) methanone is obtained.
Dans les mêmes conditions, en utilisant une zéolithe
HY(15) préalablement calcinée à 550=C, on obtient 83 % de (4-méthoxyphényl) (4-chlorophényl) méthanone.Under the same conditions, using a zeolite
HY (15) previously calcined at 550 = C, 83% of (4-methoxyphenyl) (4-chlorophenyl) methanone is obtained.
Dans les mêmes conditions, en utilisant une zéolithe HYt20) préalablement calcinée à 6502G, on obtient 77 % de (4-méthoxyphényl) (4-chlorophényl) méthanone.Under the same conditions, using a zeolite HYt20) previously calcined at 6502G, 77% of (4-methoxyphenyl) (4-chlorophenyl) methanone is obtained.
Exemple comparatif
Dans les memes conditions, en utilisant une zéolithe
CeNaY (70 % de Ce ; Si/Al = 2,3) préalablement calcinée à aD0-C, on obtient 9 % de (4-méthoxyphényl) (4-chlorophényl) méthanone.Comparative example
In the same conditions, using a zeolite
CeNaY (70% Ce; Si / Al = 2.3) previously calcined at aD0-C, 9% of (4-methoxyphenyl) (4-chlorophenyl) methanone is obtained.
PREPARATION III
Acylation de l'anisole par l'acide narabromobenzoïque. PREPARATION III
Acylation of anisole with narabromobenzoic acid.
Selon le mode opératoire décrit dans la préparation I au départ de 1 g d'acide parabromobenzoïque, 2 ml d > anisole dans 50 ml de chlorobenzène, les réactifs étant séchés sur tamis moléculaires, et en présence de 0,5 g de zéolithe HY(20) préalablement calcinée à D50 C, on obtient 70 % de (4-méthoxyphényl) (4-bromophényl) méthanone.According to the procedure described in preparation I, starting from 1 g of parabromobenzoic acid, 2 ml of anisole in 50 ml of chlorobenzene, the reagents being dried over molecular sieves, and in the presence of 0.5 g of HY zeolite ( 20) previously calcined at D50 C, 70% of (4-methoxyphenyl) (4-bromophenyl) methanone is obtained.
PREPARATION IV
Acylation du thioanisole par l'acide parachlorobenzoïque.PREPARATION IV
Acylation of thioanisole with parachlorobenzoic acid.
Selon le mode opératoire décrit dans la préparation I au départ de 1 g d'acide parachlorobenzoïque, 1 ml de thioanisole dans 50 ml de chlorobenzène, les réactifs étant séchés sur tamis moléculaires, et en présence de 1 o de zéolithe HY(20) préalablement calcinée à 500 C, on obtient 75 % de (4-chlorophényl) (4-methylthiophényl) méthanone. According to the procedure described in preparation I, starting from 1 g of parachlorobenzoic acid, 1 ml of thioanisole in 50 ml of chlorobenzene, the reagents being dried over molecular sieves, and in the presence of 1 o of HY zeolite (20) calcined at 500 ° C., 75% of (4-chlorophenyl) (4-methylthiophenyl) methanone is obtained.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9011856A FR2667063B1 (en) | 1990-09-26 | 1990-09-26 | PROCESS FOR ACYLATION OF AROMATIC HYDROCARBONS. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9011856A FR2667063B1 (en) | 1990-09-26 | 1990-09-26 | PROCESS FOR ACYLATION OF AROMATIC HYDROCARBONS. |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| FR2667063A1 true FR2667063A1 (en) | 1992-03-27 |
| FR2667063B1 FR2667063B1 (en) | 1994-05-13 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| FR9011856A Expired - Fee Related FR2667063B1 (en) | 1990-09-26 | 1990-09-26 | PROCESS FOR ACYLATION OF AROMATIC HYDROCARBONS. |
Country Status (1)
| Country | Link |
|---|---|
| FR (1) | FR2667063B1 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993022268A1 (en) * | 1992-05-06 | 1993-11-11 | Technische Universiteit Delft | Process for the preparation of polyhydroxybenzophenones |
| WO1996035655A1 (en) * | 1995-05-12 | 1996-11-14 | Rhone-Poulenc Chimie | Aromatic ether acylation process |
| WO1996035656A1 (en) * | 1995-05-12 | 1996-11-14 | Rhone-Poulenc Chimie | Aromatic ether acylation process |
| WO1997017324A1 (en) * | 1995-11-10 | 1997-05-15 | Rhodia Chimie | Aromatic thioether acylation method |
| US5679865A (en) * | 1992-05-06 | 1997-10-21 | Technische Universiteit Delft | Process for the preparation of polyhydroxybenzophenones |
| WO1997048665A1 (en) * | 1996-06-20 | 1997-12-24 | Rhodia Chimie | Acylation method for an aromatic compound |
| WO2001090037A1 (en) * | 2000-05-24 | 2001-11-29 | Bayer Aktiengesellschaft | Method for producing acylated phenol ethers |
| WO2001089689A1 (en) * | 2000-05-22 | 2001-11-29 | Consejo Superior De Investigaciones Cientificas | Itq-7 acylation catalyst |
| US6525226B2 (en) | 2000-10-10 | 2003-02-25 | Council Of Scientific And Industrial Research | Process for preparation of substituted aromatic compound employing friedel-crafts reaction using a reusable basic anionic clay catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2307786A1 (en) * | 1975-04-18 | 1976-11-12 | Koppers Co Inc | PROCESS FOR THE ACYLATION OF NON-HYDROXYL AROMATIC COMPOUNDS |
| EP0334096A2 (en) * | 1988-03-19 | 1989-09-27 | Bayer Ag | Process for the preparation of phenyl ketones etherified in position 4 |
-
1990
- 1990-09-26 FR FR9011856A patent/FR2667063B1/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2307786A1 (en) * | 1975-04-18 | 1976-11-12 | Koppers Co Inc | PROCESS FOR THE ACYLATION OF NON-HYDROXYL AROMATIC COMPOUNDS |
| EP0334096A2 (en) * | 1988-03-19 | 1989-09-27 | Bayer Ag | Process for the preparation of phenyl ketones etherified in position 4 |
Non-Patent Citations (1)
| Title |
|---|
| APPLIED CATALYSIS, vol. 49, 1989, pages 109-123, Elsevier Science Publishers B.V., Amsterdam, NL; A. CORMA et al.: "Design of synthetic zeolites as catalysts in organic reactions. Acylation of anisole by acyl chlorides or carboxylic acids over acid zeolites" * |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5679865A (en) * | 1992-05-06 | 1997-10-21 | Technische Universiteit Delft | Process for the preparation of polyhydroxybenzophenones |
| WO1993022268A1 (en) * | 1992-05-06 | 1993-11-11 | Technische Universiteit Delft | Process for the preparation of polyhydroxybenzophenones |
| US6013840A (en) * | 1995-05-12 | 2000-01-11 | Rhodia Chimie | Process for the acylation of aromatic ethers |
| WO1996035655A1 (en) * | 1995-05-12 | 1996-11-14 | Rhone-Poulenc Chimie | Aromatic ether acylation process |
| WO1996035656A1 (en) * | 1995-05-12 | 1996-11-14 | Rhone-Poulenc Chimie | Aromatic ether acylation process |
| FR2733979A1 (en) * | 1995-05-12 | 1996-11-15 | Rhone Poulenc Chimie | PROCESS FOR ACYLATION OF SUBSTITUTE AROMATIC ETHERS |
| FR2733980A1 (en) * | 1995-05-12 | 1996-11-15 | Rhone Poulenc Chimie | PROCESS FOR ACYLATION OF NON-SUBSTITUTED AROMATIC ETHERS |
| US5817878A (en) * | 1995-05-12 | 1998-10-06 | Rhone-Poulenc Chimie | Process for the acylation of aromatic ethers |
| WO1997017324A1 (en) * | 1995-11-10 | 1997-05-15 | Rhodia Chimie | Aromatic thioether acylation method |
| FR2741067A1 (en) * | 1995-11-10 | 1997-05-16 | Rhone Poulenc Chimie | PROCESS FOR ACYLATION OF AN AROMATIC THIOETHER |
| JP3439220B2 (en) | 1995-11-10 | 2003-08-25 | ロデイア・シミ | Acylation method of aromatic thioether |
| WO1997048665A1 (en) * | 1996-06-20 | 1997-12-24 | Rhodia Chimie | Acylation method for an aromatic compound |
| US6194616B1 (en) | 1996-06-20 | 2001-02-27 | Rhodia Chimie | Acylation method for an aromatic compound |
| FR2750132A1 (en) * | 1996-06-20 | 1997-12-26 | Rhone Poulenc Chimie | PROCESS FOR ACYLATION OF AN AROMATIC ETHER OR THIOETHER |
| WO2001089689A1 (en) * | 2000-05-22 | 2001-11-29 | Consejo Superior De Investigaciones Cientificas | Itq-7 acylation catalyst |
| ES2168963A1 (en) * | 2000-05-22 | 2002-06-16 | Univ Valencia Politecnica | ITQ-7 ACILATION CATALYST |
| WO2001090037A1 (en) * | 2000-05-24 | 2001-11-29 | Bayer Aktiengesellschaft | Method for producing acylated phenol ethers |
| US6525226B2 (en) | 2000-10-10 | 2003-02-25 | Council Of Scientific And Industrial Research | Process for preparation of substituted aromatic compound employing friedel-crafts reaction using a reusable basic anionic clay catalyst |
| US6548722B1 (en) | 2000-10-10 | 2003-04-15 | Council Of Scientific And Industrial Research | Process for the preparation of substituted aromatic compound employing friedel-crafts reaction using a reusable basic anionic clay catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2667063B1 (en) | 1994-05-13 |
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