CH162146A - A method of manufacturing 1-amino-5-benzoylamino-anthraquinone. - Google Patents
A method of manufacturing 1-amino-5-benzoylamino-anthraquinone.Info
- Publication number
- CH162146A CH162146A CH162146DA CH162146A CH 162146 A CH162146 A CH 162146A CH 162146D A CH162146D A CH 162146DA CH 162146 A CH162146 A CH 162146A
- Authority
- CH
- Switzerland
- Prior art keywords
- anthraquinone
- amino
- product
- benzoylamino
- remove
- Prior art date
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- FWEQPMZEKHHFTB-UHFFFAOYSA-N n-(5-amino-9,10-dioxoanthracen-1-yl)benzamide Chemical compound C1=CC=C2C(=O)C=3C(N)=CC=CC=3C(=O)C2=C1NC(=O)C1=CC=CC=C1 FWEQPMZEKHHFTB-UHFFFAOYSA-N 0.000 title claims 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 230000003301 hydrolyzing effect Effects 0.000 claims description 3
- 229940124530 sulfonamide Drugs 0.000 claims description 3
- LMYRWZFENFIFIT-UHFFFAOYSA-N toluene-4-sulfonamide Chemical group CC1=CC=C(S(N)(=O)=O)C=C1 LMYRWZFENFIFIT-UHFFFAOYSA-N 0.000 claims description 3
- 125000004391 aryl sulfonyl group Chemical group 0.000 claims description 2
- 239000007859 condensation product Substances 0.000 claims description 2
- VDCUNNJIPITONP-UHFFFAOYSA-N n-(5-chloro-9,10-dioxoanthracen-1-yl)benzamide Chemical compound C1=CC=C2C(=O)C=3C(Cl)=CC=CC=3C(=O)C2=C1NC(=O)C1=CC=CC=C1 VDCUNNJIPITONP-UHFFFAOYSA-N 0.000 claims description 2
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims 1
- 238000009833 condensation Methods 0.000 claims 1
- -1 o-toluenesulfonyl group Chemical group 0.000 claims 1
- 150000003456 sulfonamides Chemical class 0.000 claims 1
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229940117389 dichlorobenzene Drugs 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- YCMLQMDWSXFTIF-UHFFFAOYSA-N 2-methylbenzenesulfonimidic acid Chemical compound CC1=CC=CC=C1S(N)(=O)=O YCMLQMDWSXFTIF-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 240000007817 Olea europaea Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000984 vat dye Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Procédé de fabAeation de 1-amino-5-benzoylaanino-anthraquinone. On a trouvé qu'on peut obtenir facile ment des amino-acydamino-anthraquinones en soumettant des arydsulfonamid-o-a,cylamino- anthraquinones à l'action d'un agent hydro lysant, de façon que seuls les groupes aryl- su;lfonyl soient éliminés.
La présente invention a pour but la pré paTation de 1-amino-5-benzoyla.mino-anthra- quinone, qui est déjà décrit dans la littérature et qui est un produit intermédiaire précieux ,dans la synthèse de colorants de cuve, ce pro duit étant, par exemple, employé dans la fa- brication de Ja 5.5'-dibenzoyl-;diamino- 1 . l'-dianthrimide.
Suivant le procédé de l'invention, on fait réagir ensemble dans des proportions mono- moléculaires une 1-halogène-5-benzoylami.no- anthraquinone et une sulfonamide de la for mule R .
SOZ-NH,, par exemple l'ortho ou para-toluènesulfonamide, et traite le produit de condensation par un agent hydrolysant, de façon à n'éliminer que le groupe arylsuffo- nyl, de préférence au moyen de l'acide sulfu rique d'environ 100% à une température qui n'excède pas 30 C.
Exemple: On prépare la 5-benzoyllamino-1-p-toluèn-3- sulfonamidoanthraquinone comme suit: On dissout 20 parties de 1-chloro-5- benzoylamino-anthraquinone dans 100 partis de o-@dichlorobenzène à l'ébullition. On ajoute à la solution 20 parties de carbonate de po tassium pur, 0,2 partie d'acétate de cuivre et 0,3 partie de chlorure cupreux, pendant qu'on remue convenablement.
On élève la tempéra ture au point d'ébullition et, sans cesser de remuer, on ajoute- 20 parties de p-toluène- sulfonamide au cours d'une période de 3 heu res. A la fin de cette période, on continue à faire bouillir pendant 6 heures, on refroi dit alors: le produit fondu, on le distille à. la vapeur pour éliminer le a-dichlorobenzène, on sépare la matière solide par filtration, on la lave parfaitement à l'aide d'eau et on la sè che.
Rendement: 2,7 parties, soit 99 % du ren dement théorique.
On peut purifier la matière en la cristal lisant ,dans -du nitrobenzène. Le produit est composé -d'aiguilles jaunes. N = 5,48 (N théorique, 5,6 %). Point de fusion, 266 à 268 C.
Ce produit est soluble dans l'acide sul furique froid et donne une solution vert olive. qui vire au brun rougeâtre lorsqu'on chauffe légèrement et fonce si l'on continue à, chauf fer.
L'hydrolyse peut être réalisée comme suit: On dissout lentement 1.0 parties de ce pro -duit dans 100 parties d'acide sulfurique à 95 % pendant qu'on remue et maintient la température au-dessous de 20' C. Lorsque l'addition est terminée, on élève et maintient la température à 2,8 C pendant une heure de plus, puis on noie le produit dans de l'eau. On isole la matière solide par filtra tion, on la lave pour éliminer l'acide et on la sèche. Le rendement est presque théorique et le produit a une teneur en azote de 8,15 en comparaison de la valeur théorique de 8,18%. Il fond à 251-25'3 C.
On peut cristalliser la matière à l'aide de nitrobenzène et l'on obtient des plaques rou geâtres fondant à 261 C.
Method for manufacturing 1-amino-5-benzoylaanino-anthraquinone. It has been found that amino-acydamino-anthraquinones can be easily obtained by subjecting arydsulfonamid-oa, cylamino-anthraquinones to the action of a hydrolysing agent, so that only aryl-sulfonyl groups are removed. .
The object of the present invention is the preparation of 1-amino-5-benzoyla.mino-anthraquinone, which is already described in the literature and which is a valuable intermediate product, in the synthesis of vat dyes, this product. being, for example, employed in the manufacture of Ja 5.5'-dibenzoyl-; diamino-1. 1'-dianthrimide.
According to the process of the invention, a 1-halogen-5-benzoylami.no- anthraquinone and a sulphonamide of the formula R are reacted together in monolecular proportions.
SOZ-NH ,, for example ortho or para-toluenesulfonamide, and treats the condensation product with a hydrolysing agent, so as to remove only the arylsuffonyl group, preferably by means of sulfuric acid d '' approximately 100% at a temperature not exceeding 30 C.
Example: 5-Benzoyllamino-1-p-toluen-3-sulfonamidoanthraquinone is prepared as follows: 20 parts of 1-chloro-5-benzoylamino-anthraquinone are dissolved in 100 parts of o- @ dichlorobenzene at the boiling point. 20 parts of pure potassium carbonate, 0.2 part of copper acetate and 0.3 part of cuprous chloride are added to the solution, while stirring well.
The temperature is raised to the boiling point and, with continued stirring, 20 parts of p-toluenesulfonamide are added over a 3 hour period. At the end of this period, we continue to boil for 6 hours, we cool it then says: the melted product, we distilled it. steam to remove α-dichlorobenzene, the solid is separated by filtration, washed thoroughly with water and dried.
Yield: 2.7 parts, ie 99% of the theoretical yield.
The material can be purified by reading it in nitrobenzene. The product is made up of yellow needles. N = 5.48 (theoretical N, 5.6%). Melting point, 266-268 C.
This product is soluble in cold sulfuric acid and gives an olive green solution. which turns reddish brown when heated slightly and darkens when heated.
The hydrolysis can be carried out as follows: 1.0 parts of this product are slowly dissolved in 100 parts of 95% sulfuric acid while stirring and the temperature is maintained below 20 ° C. When the addition is completed, the temperature is raised and maintained at 2.8 ° C. for an additional hour, then the product is flooded in water. The solid material is isolated by filtration, washed to remove the acid and dried. The yield is almost theoretical and the product has a nitrogen content of 8.15 compared to the theoretical value of 8.18%. It melts at 251-25'3 C.
The material can be crystallized using nitrobenzene and reddish plaques are obtained, melting at 261 C.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB162146X | 1931-03-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH162146A true CH162146A (en) | 1933-06-15 |
Family
ID=10073240
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH162146D CH162146A (en) | 1931-03-30 | 1932-03-30 | A method of manufacturing 1-amino-5-benzoylamino-anthraquinone. |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH162146A (en) |
-
1932
- 1932-03-30 CH CH162146D patent/CH162146A/en unknown
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