CH300941A - Process for preparing 2- (2-methyl-5-chlorophenylthio) -4-chlorobenzoic acid. - Google Patents
Process for preparing 2- (2-methyl-5-chlorophenylthio) -4-chlorobenzoic acid.Info
- Publication number
- CH300941A CH300941A CH300941DA CH300941A CH 300941 A CH300941 A CH 300941A CH 300941D A CH300941D A CH 300941DA CH 300941 A CH300941 A CH 300941A
- Authority
- CH
- Switzerland
- Prior art keywords
- methyl
- acid
- chlorophenylthio
- chlorobenzoic acid
- chlorothiophenol
- Prior art date
Links
- BYPDXGBTQOVTSR-UHFFFAOYSA-N 4-chloro-2-(5-chloro-2-methylphenyl)sulfanylbenzoic acid Chemical compound CC1=C(C=C(C=C1)Cl)SC1=C(C(=O)O)C=CC(=C1)Cl BYPDXGBTQOVTSR-UHFFFAOYSA-N 0.000 title description 3
- 238000004519 manufacturing process Methods 0.000 title description 2
- 239000002253 acid Substances 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- -1 2-methyl-5-chlorophenylthio Chemical group 0.000 claims description 6
- CKUHTPJQIPSKFS-UHFFFAOYSA-N 5-chloro-2-methylbenzenethiol Chemical compound CC1=CC=C(Cl)C=C1S CKUHTPJQIPSKFS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 159000000000 sodium salts Chemical class 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 230000020477 pH reduction Effects 0.000 claims description 2
- IDCFOFYKKXBZRS-UHFFFAOYSA-M potassium;2,4-dichlorobenzoate Chemical compound [K+].[O-]C(=O)C1=CC=C(Cl)C=C1Cl IDCFOFYKKXBZRS-UHFFFAOYSA-M 0.000 claims 1
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical class SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 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 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001559 benzoic acids Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- RZQGSFMCSQMPKT-UHFFFAOYSA-N 2-chloro-5-methylbenzenethiol Chemical compound CC1=CC=C(Cl)C(S)=C1 RZQGSFMCSQMPKT-UHFFFAOYSA-N 0.000 description 1
- CQJDYPZUDYXHLM-UHFFFAOYSA-N 3-chlorobenzenethiol Chemical compound SC1=CC=CC(Cl)=C1 CQJDYPZUDYXHLM-UHFFFAOYSA-N 0.000 description 1
- XRHGYUZYPHTUJZ-UHFFFAOYSA-N 4-chlorobenzoic acid Chemical class OC(=O)C1=CC=C(Cl)C=C1 XRHGYUZYPHTUJZ-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000000973 chemotherapeutic effect Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 150000004704 methoxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
Procédé de préparation de l'acide 2-(2-méthyl-5-chlorophénylthio)-4-chlorobenzoïque. La présente invention se rapporte à la préparation des acides 2-(2-méthyl-5-halophé- nylthio)-benzoïques substituées en 4, répon dant à la formule de structure:
EMI0001.0004
formule dans laquelle R est un halogène, un radical alcoyle inférieur ou un radical alcoxy inférieur. Ces acides benzoïques disubstitués constituent des produits intermédiaires inté ressants pour la préparation de produits chi miothérapeutiques de valeur.
Le substituant en position 4 indiqué dans la formule ci-dessus par la lettre R contient de préférence de 1 à 4 atomes de carbone lors qu'il est constitué par un groupe alcoyle infé rieur ou un groupe alcoxy inférieur et peut être, par e:iemple, le groupe: méthyle, éthyle, n-pro- pyle, isopropyle, n-butyle isobutyle et. 2-bu- tyle, ou le groupe:
méthoxy, éthoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy et 2-butoxy. Lorsque ce substituant est un halogène, ce peut être le chlore, le brome, l'iode ou le fluor.
Le présent breveta pour objet un procédé de préparation de l'un de ces acides benzoï ques disubstitués, savoir l'acide 2-(2-méthyl-5- chl'.orophénylthio)-4-chlorobenzoïque, procédé caractérisé en ce qu'on chauffe un sel métal lique d'un acide 2-halo-4-ehlorobenzoïque avec un sel métallique du 2-m6thyl-5-chloro- thiophénol,
en présence d'un catalyseur com prenant du cuivre et qu'on libère par acidifi- cation l'acide du sel formé.
On. utilise de préférence pour la mise en oeuvre de l'invention les sels de métaux alca lins de l'acide 4-chlorobenzoïque et du thiô- phénol et, comme catalyseur, de la poudre de cuivre. Toutefois, on peut utiliser d'autres sels métalliques tels que les sels alcalino-ter reux, par exemple ceux du calcium, du ma gnésium, etc.; de même, à la place de la pou dre de cuivre, on peut utiliser d'autres cata lyseurs à base de cuivre tels que le chlorure cuivreux, le chlorure cuivrique; etc. La réac tion, lorsqu'on utilise des sels de sodium, peut être représentée par l'équation suivante:
EMI0001.0046
On obtient l'acide libre en acidifiant le mé lange de réaction.
L'exemple donné ci-après se rapporte à la mise en #uvre préférée de la présente inven tion.
<I>Exemple 1:</I> On dissout 3 g de sodium dans 60 cm3 de méthanol et on chauffe à 90 C. On introduit à cette température 54 g de 2-méthyl,5-chloro- thiophénol, 30 g de 2,4-dichlorobenzoate de potassium et 0,5 g de poudre de cuivre. On chauffe avec précaution le mélange à 215 C, mélange dont la température s'élève sponta nément, après liquéfaction, à 225 C. On le maintient à cette température pendant vingt minutes. Pendant ce temps, le contenu du bal lon se solidifie. Après avoir refroidi le mé lange à 100 C, on ajoute du carbonate de soude dilué. On recueille la suspension et on la filtre.
On extrait le filtrat avec de l'éther et on acidifie la phase aqueuse, ce qui produit la séparation d'un produit légèrement gom meux, que l'on filtre, que l'on exprime pour le sécher et qu'on lave avec de la ligroïne; poids 33,4 g. On extrait le filtrat avec de l'éther. On réunit tous les extraits éthérés et on les traite à leur tour avec de la potasse caustique à 10'%. On acidifie la couche aqueuse alcaline, puis on l'extrait avec de l'éther. On chasse le solvant et on soumet le résidu à un entraînement à la vapeur d'eau.
Le produit entraîné donne 13,0 g de thiophé- nol récupéré dont le point d'ébullition est de 115 C sous 10 mm. On filtre le résidu non volatil et on le sèche. Son poids est de 3,6 g, ce qui porte le rendement total en acide re- cherché à 37 g ou 90,5 % de la théorie. Pour l'analyse,
on purifie un échantillon en le re- cristallisant dans le benzène. Le produit, cons titué par l'acide 2-(2-méthyl-5-chlorophényl- thio)-4-chlorobenzo7ique, présente un point de fusion de 199,6 à 201 C (corrigé), après re- cristallisation dans le benzène. Analyse: Calculé pour CIIHioC1202S: C, 53,68; H, 3,21. Trouvé C, 53,60; H, 3,38. Dans l'essai ci-dessus, le rapport du so dium, du sel potassique et du thiophénol est de 1:1:2,5.
Lorsqu'on modifie ce rapport pour le porter à 1: 2:2,6, le rendement en pro duit recherché tombe à 810/a. Cependant, la liquéfaction du mélange de réaction se pro duit à une température inférieure et il suffit de chauffer à 200 C pour obtenir la solidifica tion du mélange. Lorsqu'on n'utilise pas le sodium, aucune réaction ne se produit.
Lorsqu'on effectue la réaction ci-dessus en utilisant un mélange de 2-méthyl-5-chloro- thiophénol et de 2-chloro-5-méthylthiophénol (que l'on obtient suivant lé mode de prépara tion choisi du 2-méthyl-5-chlorothiophénol), il en résulte un mélange "d'acide 2-(2-méthyl-5- chlorophénylthio-4-chlorobenzoïque et d'une faible quantité de l'acide isomère 2-(2-chloro- 5-méthylphénylthio)-4-chlorobenzoïque:
Dans l'exemple ci-dessus, on a utilisé du méthylate de sodium pour former le sel sodi que du 2-méthyl-5-chlorothiophénol; on petit remplacer ce méthylate par d'autres alcoxy- des des métaux alcalins, ces alcoxydes étant de préférence ceux d'un alcool à point d'ébul lition inférieur, comme l'éthanol, l'isopropa- nol, un butanol, un pentanol, etc.
Process for preparing 2- (2-methyl-5-chlorophenylthio) -4-chlorobenzoic acid. The present invention relates to the preparation of 4-substituted 2- (2-methyl-5-halophenylthio) -benzoic acids, corresponding to the structural formula:
EMI0001.0004
formula wherein R is halogen, lower alkyl or lower alkoxy. These disubstituted benzoic acids constitute valuable intermediates for the preparation of valuable chemotherapeutic products.
The substituent in position 4 indicated in the above formula by the letter R preferably contains from 1 to 4 carbon atoms when it is constituted by a lower alkyl group or a lower alkoxy group and can be, by e: For example, the group: methyl, ethyl, n-propyl, isopropyl, n-butyl isobutyl and. 2-butyle, or the group:
methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy and 2-butoxy. When this substituent is a halogen, it can be chlorine, bromine, iodine or fluorine.
The present patent relates to a process for the preparation of one of these disubstituted benzoic acids, namely 2- (2-methyl-5- chl'.orophenylthio) -4-chlorobenzoic acid, a process characterized in that heats a metal salt of a 2-halo-4-ehlorobenzoic acid with a metal salt of 2-methyl-5-chlorothiophenol,
in the presence of a catalyst comprising copper and the acid being freed from the salt formed by acidification.
We. Preferably uses for the implementation of the invention the alkaline metal salts of 4-chlorobenzoic acid and thiophenol and, as catalyst, copper powder. However, other metal salts can be used such as alkaline earth salts, for example those of calcium, magnesium, etc .; similarly, instead of copper powder, other copper-based catalysts can be used, such as cuprous chloride or cupric chloride; etc. The reaction, when using sodium salts, can be represented by the following equation:
EMI0001.0046
The free acid is obtained by acidifying the reaction mixture.
The example given below relates to the preferred embodiment of the present invention.
<I> Example 1: </I> 3 g of sodium are dissolved in 60 cm3 of methanol and the mixture is heated to 90 C. 54 g of 2-methyl, 5-chlorothiophenol, 30 g of 2 are introduced at this temperature. , Potassium 4-dichlorobenzoate and 0.5 g of copper powder. The mixture is carefully heated to 215 ° C., the temperature of which rises spontaneously, after liquefaction, to 225 ° C. It is maintained at this temperature for twenty minutes. During this time, the contents of the ball solidify. After cooling the mixture to 100 ° C., dilute sodium carbonate is added. The suspension is collected and filtered.
The filtrate is extracted with ether and the aqueous phase is acidified, resulting in the separation of a slightly gummy product, which is filtered, squeezed to dry and washed with water. ligroin; weight 33.4 g. The filtrate is extracted with ether. All of the ethereal extracts are combined and treated in turn with 10% caustic potash. The alkaline aqueous layer is acidified and then extracted with ether. The solvent is removed and the residue is subjected to steam stripping.
The entrained product gives 13.0 g of recovered thiophenol, the boiling point of which is 115 ° C. at 10 mm. The non-volatile residue is filtered off and dried. Its weight is 3.6 g, which brings the total yield of acid sought to 37 g or 90.5% of theory. For analysis,
a sample is purified by recrystallizing it from benzene. The product, consisting of 2- (2-methyl-5-chlorophenyl-thio) -4-chlorobenzo7ic acid, has a melting point of 199.6 at 201 C (corrected), after recrystallization from benzene. . Analysis: Calculated for CIIH10C1202S: C, 53.68; H, 3.21. Found C, 53.60; H, 3.38. In the above test, the ratio of sodium, potassium salt and thiophenol is 1: 1: 2.5.
When this ratio is changed to 1: 2: 2.6, the desired product yield drops to 810 / a. However, the liquefaction of the reaction mixture takes place at a lower temperature and it is sufficient to heat to 200 ° C to achieve solidification of the mixture. When sodium is not used, no reaction occurs.
When the above reaction is carried out using a mixture of 2-methyl-5-chlorothiophenol and 2-chloro-5-methylthiophenol (obtained according to the selected method of preparation of 2-methyl- 5-chlorothiophenol), this results in a mixture of "2- (2-methyl-5-chlorophenylthio-4-chlorobenzoic acid) and a small amount of the isomer 2- (2-chloro-5-methylphenylthio) acid -4-chlorobenzoic acid:
In the example above, sodium methoxide was used to form the sodium salt of 2-methyl-5-chlorothiophenol; this methoxide can be replaced by other alkoxides of the alkali metals, these alkoxides preferably being those of an alcohol with a lower boiling point, such as ethanol, isopropanol, a butanol, a pentanol , etc.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US300941XA | 1950-11-22 | 1950-11-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH300941A true CH300941A (en) | 1954-08-31 |
Family
ID=21852458
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH300941D CH300941A (en) | 1950-11-22 | 1951-11-22 | Process for preparing 2- (2-methyl-5-chlorophenylthio) -4-chlorobenzoic acid. |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH300941A (en) |
-
1951
- 1951-11-22 CH CH300941D patent/CH300941A/en unknown
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