CH357384A - Process for preparing 5,5'-dinitro-2,2'-dichlorobenzil - Google Patents
Process for preparing 5,5'-dinitro-2,2'-dichlorobenzilInfo
- Publication number
- CH357384A CH357384A CH357384DA CH357384A CH 357384 A CH357384 A CH 357384A CH 357384D A CH357384D A CH 357384DA CH 357384 A CH357384 A CH 357384A
- Authority
- CH
- Switzerland
- Prior art keywords
- parts
- dinitro
- dichlorobenzil
- mixture
- preparing
- Prior art date
Links
- WXKBWMUUZHRBHK-UHFFFAOYSA-N [N+](=O)([O-])C=1C=CC(=C(C=1)C(=O)C(=O)C1=C(C=CC(=C1)[N+](=O)[O-])Cl)Cl Chemical compound [N+](=O)([O-])C=1C=CC(=C(C=1)C(=O)C(=O)C1=C(C=CC(=C1)[N+](=O)[O-])Cl)Cl WXKBWMUUZHRBHK-UHFFFAOYSA-N 0.000 title 1
- 238000004519 manufacturing process Methods 0.000 title 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VOSNNSVWVJFJCR-UHFFFAOYSA-N 1,2-bis(2-chlorophenyl)ethane-1,2-dione Chemical compound ClC1=CC=CC=C1C(=O)C(=O)C1=CC=CC=C1Cl VOSNNSVWVJFJCR-UHFFFAOYSA-N 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- FPYUJUBAXZAQNL-UHFFFAOYSA-N 2-chlorobenzaldehyde Chemical compound ClC1=CC=CC=C1C=O FPYUJUBAXZAQNL-UHFFFAOYSA-N 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 206010006500 Brucellosis Diseases 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- 208000003495 Coccidiosis Diseases 0.000 description 1
- 206010023076 Isosporiasis Diseases 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 206010040047 Sepsis Diseases 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 206010046793 Uterine inflammation Diseases 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000002365 anti-tubercular Effects 0.000 description 1
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 1
- 230000001684 chronic effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 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
- 125000006286 dichlorobenzyl group Chemical group 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- -1 o-chlorobenzole aldehyde Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000003285 pharmacodynamic effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 208000013223 septicemia Diseases 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Procédé de préparation du dinitro-5, 5' dichloro-2, 2' benzile
La présente invention a pour objet un procédé de préparation du dinitro-5, 5' dichloro-2, 2' benzile de formule :
EMI1.1
Selon le procédé de l'invention, ce nouveau compose est préparé par nitration du dichloro-2,2' benzile qui peut tre obtenu selon H. H. Hodgson & W. Rosenberg (J. Chem. Soc., 1930,14). Ces auteurs l'ont obtenu par oxydation de la benzine correspondante résultant elle-mme de l'action du cyanure de potassium sur l'aldéhyde o-chlorobenzoi- que en solution hydroalcoolique.
Le dinitro-5,5 dichloro-2, 2'benzile possède des propriétés pharmacodynamiques qui en permettent l'emploi en médecine humaine et vétérinaire. Il possède en particulier une activité antituberculeuse importante. Il peut en outre tre employé en médecine vétérinaire contre les coccidioses, les septicémies des jeunes animaux, les métrites purulentes chronique, rebelles, la colibacillose mammaire et la brucellose.
Dans l'exemple qui suit, dans lequel les parties s'entendent en poids, on a décrit la préparation de la matière première, selon une méthode améliorée par rapport à celle des auteurs précités. Les points de fusion cités ont été déterminés au banc Kofler.
Exemple a) Dichloro-2, 2' benzile
110 parties d'o-chlorobenzaldéhyde sont dissoutes dans 175 parties d'alcool éthylique à 95 O/o en volume et on ajoute une solution de 22 parties de cyanure de potassium dans 120 parties d'eau.
La teinte de la solution primitivement jaune clair vire au rouge orangé. On porte au reflux pendant une heure, on refroidit, on ajoute 170 parties d'une solution saturée de bicarbonate de sodium et on extrait à l'éther avec deux fois 200 parties d'éther.
La solution éthérée est lavée avec 300 parties d'une solution de bisulfite de sodium à 10 O/o, puis à l'eau et est séchée sur sulfate de sodium anhydre.
L'éther est chassé complètement. Le résidu gom- meux est soumis directement à l'oxydation.
Pour ce faire, il est repris par 200 parties d'acide acétique. La solution limpide obtenue est transvasée dans un récipient ayant un volume triple. On ajoute un mélange oxydant constitué par 46 parties de nitrate d'ammonium et 0,5 partie d'acétate de cuivre cristallisé. On chauffe d'abord avec précaution jusqu'à ce que le dégagement d'azote soit calmé, puis on porte au reflux pendant une heure.
Par simple refroidissement, on a une abondante cristallisation de dichloro-2, 2'benzile, qu'on filtre, lave à l'acide acétique et sèche. On obtient 60 parties de dichloro-2,2'benzile fondant à 130-1320. b) Dinitro-5, 5' dichlora-2, 2' benzile
100 parties du dichloro-2, 2'benzile brut précé- dent sont mises en suspension sans précautions spé- ciales dans 730 parties d'acide sulfurique concentré (d= 1, 83).
On ajoute goutte à goutte en une demiheure, et sous agitation mécanique, un mélange composé de 440 parties d'acide sulfurique concentré (d= 1,83) et de 120 parties d'acide nitrique fumant (d = 1,52) tout en refroidissant, de manière que la température soit maintenue entre 40 et 450. On laisse ensuite revenir à la température ambiante en maintenant l'agitation pendant 6 heures, et on laisse au repos pendant une nuit. La suspension est versée sur 1500 parties de glace broyée. Le solide jaune qui se sépare est filtré, essoré, et lavé à l'eau distillée jusqu'à disparition totale des ions sulfuriques.
Après séchage, on obtient 130 parties d'un produit fondant à 1600.
On peut le purifier par cristallisation dans l'acide acétique cristallisable à raison de 130 parties de benzile pour 800 parties de solvant. Il fond alors à 179 .
Le dinitro-5, 5' dichloro-2, 2' benzile est une poudre cristalline jaune pâle, insoluble dans l'eau et les solutions aqueuses alcalines, moyennement soluble dans l'alcool éthylique et l'acide acétique.
Process for the preparation of 5, 5 'dichloro-2,2' benzyl
The present invention relates to a process for the preparation of dinitro-5, 5 'dichloro-2, 2' benzyl of formula:
EMI1.1
According to the process of the invention, this new compound is prepared by nitration of 2,2'-dichlorobenzil which can be obtained according to H. H. Hodgson & W. Rosenberg (J. Chem. Soc., 1930,14). These authors obtained it by oxidation of the corresponding benzine resulting itself from the action of potassium cyanide on o-chlorobenzole aldehyde in hydroalcoholic solution.
Dinitro-5,5 dichloro-2, 2'benzile has pharmacodynamic properties which allow its use in human and veterinary medicine. In particular, it has significant anti-tuberculosis activity. It can also be used in veterinary medicine against coccidiosis, septicemia in young animals, chronic purulent metritis, rebellious, mammary colibacillosis and brucellosis.
In the example which follows, in which the parts are understood by weight, the preparation of the raw material has been described, according to a method improved with respect to that of the aforementioned authors. The melting points cited were determined on the Kofler bench.
Example a) 2,2 'dichloro benzyl
110 parts of o-chlorobenzaldehyde are dissolved in 175 parts of ethyl alcohol at 95 O / o by volume and a solution of 22 parts of potassium cyanide in 120 parts of water is added.
The color of the initially light yellow solution turns to orange red. The mixture is refluxed for one hour, cooled, 170 parts of a saturated solution of sodium bicarbonate are added and the mixture is extracted with ether with twice 200 parts of ether.
The ethereal solution is washed with 300 parts of a 10 O / o sodium bisulfite solution, then with water and is dried over anhydrous sodium sulfate.
The ether is driven out completely. The gummy residue is subjected directly to the oxidation.
To do this, it is taken up in 200 parts of acetic acid. The clear solution obtained is transferred to a container having a triple volume. An oxidizing mixture consisting of 46 parts of ammonium nitrate and 0.5 part of crystallized copper acetate is added. The mixture is first carefully heated until the evolution of nitrogen has subsided, then the mixture is refluxed for one hour.
By simple cooling, there is an abundant crystallization of 2-dichloro, 2'benzile, which is filtered, washed with acetic acid and dried. 60 parts of 2,2'-dichlorobenzil are obtained, melting at 130-1320. b) Dinitro-5, 5 'dichlora-2, 2' benzyl
100 parts of the above crude 2,2-dichloro-benzil are suspended without special precautions in 730 parts of concentrated sulfuric acid (d = 1.83).
A mixture composed of 440 parts of concentrated sulfuric acid (d = 1.83) and 120 parts of fuming nitric acid (d = 1.52) is added dropwise over half an hour, and with mechanical stirring, while cooling, so that the temperature is maintained between 40 and 450. The mixture is then allowed to return to ambient temperature while maintaining stirring for 6 hours, and the mixture is left to stand overnight. The suspension is poured onto 1500 parts of crushed ice. The yellow solid which separates is filtered, drained, and washed with distilled water until the sulfuric ions have completely disappeared.
After drying, 130 parts of a product melting at 1600 are obtained.
It can be purified by crystallization from crystallizable acetic acid in an amount of 130 parts of benzil per 800 parts of solvent. It then melts to 179.
Dinitro-5, 5 'dichloro-2, 2' benzyl is a pale yellow crystalline powder, insoluble in water and aqueous alkaline solutions, moderately soluble in ethyl alcohol and acetic acid.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH357384T | 1957-06-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH357384A true CH357384A (en) | 1961-10-15 |
Family
ID=4511547
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH357384D CH357384A (en) | 1957-06-12 | 1957-06-12 | Process for preparing 5,5'-dinitro-2,2'-dichlorobenzil |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH357384A (en) |
-
1957
- 1957-06-12 CH CH357384D patent/CH357384A/en unknown
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