CH152251A - Process for the preparation of an aromatic monoaroyldiamino compound. - Google Patents
Process for the preparation of an aromatic monoaroyldiamino compound.Info
- Publication number
- CH152251A CH152251A CH152251DA CH152251A CH 152251 A CH152251 A CH 152251A CH 152251D A CH152251D A CH 152251DA CH 152251 A CH152251 A CH 152251A
- Authority
- CH
- Switzerland
- Prior art keywords
- aromatic
- compound
- monoaroyldiamino
- preparation
- acid
- Prior art date
Links
- 150000001875 compounds Chemical class 0.000 title claims description 10
- 238000000034 method Methods 0.000 title claims description 8
- 125000003118 aryl group Chemical group 0.000 title claims description 7
- 238000002360 preparation method Methods 0.000 title description 3
- -1 benzoyl halide Chemical class 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 3
- ZRRGOUHITGRLBA-UHFFFAOYSA-N stattic Chemical compound [O-][N+](=O)C1=CC=C2C=CS(=O)(=O)C2=C1 ZRRGOUHITGRLBA-UHFFFAOYSA-N 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-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 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-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
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- SFDJOSRHYKHMOK-UHFFFAOYSA-N nitramide Chemical class N[N+]([O-])=O SFDJOSRHYKHMOK-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 238000006480 benzoylation reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- LEVJVKGPFAQPOI-UHFFFAOYSA-N phenylmethanone Chemical compound O=[C]C1=CC=CC=C1 LEVJVKGPFAQPOI-UHFFFAOYSA-N 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical group NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Darstellung einer -aromatischen Nonoaroyldiaminoverbindung. Die technische Herstellung aromatischer Monoaroylamidverbindungen durch Reduk- 1ion der entsprechenden Aroylnitroaniinover- bindungen bereitet in vielen Fällen, infolge der Schwerlöslichkeit der Nitro, und Amino- verbindungen in Wasser und den gebräuch lichen organischen Lösungsmitteln, Schwie rigkeiten.
Es wurde gefunden, dess man in -glatt ver- laufender Reaktion zu Monoaroylaminover- bindungen derBenzol- und Na,phthalinreihe ge langt, wenn man die nach bekannten Verfah ren erhältlichen Nitroa.rylsulfaminsäuren mit Aroylierungsmitteln, wie aromatischen oder aromatisch-.aliphatischen Karbonsäurehaloge- niden behandelt und durch Erwärmung mit verdünnter Mineralsäure die Sulfogruppe ab spaltet.
EMI0001.0027
Der Vorteil dieses Verfahrens liegt darin, dass erstens die Anwendung von Lösungs- mitteln wegfällt, da durch die wasserlöslich machende Sulfamingruppe sämtliche Reak- tionsstufen in wässeriger Lösung - durchge führt werden können, zweitens die Anwen dung von Eisen, als dem billigsten Reduk- tionsmittel, gestattet ist,
drittens die Her stellung mancher Monöaroyldiaminoverbin- dungen ermöglicht wird, die auf anderem Wege nur sehr schwer zu erhalten sind, wie aus folgenden Beispielen ersichtlich:
EMI0002.0011
Nach dem neuen Verfahren sind diese Körper zugänglich von den entsprechenden Nitroaminen folgender Formel:
EMI0002.0013
Im andern Falle müsste man von folgen den erheblich schwerer zugänglichen Nitro aminen ausgehen:
EMI0002.0015
Das beanspruchte Verfahren bedeutet für die Herstellung von Monöarc>yldiaminoverbiu- dungen der Benzol- und Naphthalinreihe, die als Diazokomponenten für Azofarbstoffe, besonders solchen, die auf der Faser erzeugt werden, Bedeutung gewonnen haben, einen wichtigen technischen Fortschritt.
Es ist bekannt, aromatische Diamine, zum Beispiel mit Oxalsäure, in aromatische Monooxalyldiaminoverbindungen und darauf hin mit Benzoylchlo@rid in die entsprechen den aromatischen Ogalylbenzoyldiaminover- bindungen überzuführen. Bei der Behaud- lung mit verseifenden Mitteln wird jedoch je nach den Bedingungen der Benzoylrest mehr oder weniger verseift.
Gegenstand vorliegender Erfindung ist nun ein Verfahren zur Darstellung des be kannten 4 - Amido - 6 - benzoylamino - 1. 3- dimethylbenzols, das zur- Herstellung von Farbstoffen Verwendung finden soll, da durch gekennzeichnet, dass man: 6-Nitro-1. 3- dimethylphenyl-4-sulfaminsäure reduziert, das Reduktionsprodukt mit Benzoylhalogenid behandelt und durch Erwärmen mit ver dünnter Mineralsäure die Sulfogruppe ab spaltet.
<I>Beispiel:</I> 2!68 kg 6-nitro-l.3-dimethylphenyl-4- sulfaminsaures Natrium (hergestellt durch Sulfamidierung von 6-Nitro-4-amido-1.3- dimethylbenzol mit Chlorsulfonsäure in Ge- genwart einer tertiären Baste) werden bei 60 bis<B>70'</B> mit Eisen und Ameisensäure in üblicher Weise reduziert.
Nach beendeter Reduktion macht man alkalisch, presst die sich in Lösung befindende Aminoverbindung vom Eisenoxydschlamm ab, gibt zum Filtrat bei 25 bis<B>30'</B> allmählich unter gutem Rüh ren 145 kg Benzoylchlorid hinzu und hält mit Soda dauernd schwach alkalisch.
Nach beendeter Benzoylierung erwärmt man auf 70 bis<B>80',</B> macht 'mit Salzsäure schwach kongosauer und steigert gleichzeitig die Tem- peratur auf 80 bis<B>9,0'.</B> Die Verseifung ist in kurzer Zeit beendet, das Salzsäure Salz des 4-Amino-6-benzoylamido-l.3-dimethyl- benzols fällt bereits in der Wärme in wei ssen. :
glänzenden Nadeln aus und wird durch Zusatz von Kochsalz fast quantitativ ab.ge-- schieden. Man saugt ab, löst es wieder in heissem Wasser, filtriert und fällt die Base mit Soda. Weisse Nadeln; Schmelzpunkt 176 , Ausbeute 88 %, berechnet auf die ver wendete Nitroarylsulfaminsäure.
Process for the preparation of an aromatic nonoaroyldiamino compound. The industrial production of aromatic monoaroylamide compounds by reducing the corresponding aroylnitroaniino compounds is difficult in many cases because of the poor solubility of the nitro and amino compounds in water and the common organic solvents.
It has been found that monoaroylamino compounds of the benzene and sodium phthalene series are obtained in a smooth reaction if the nitro aryl sulfamic acids obtainable by known processes are mixed with aroylating agents such as aromatic or aromatic aliphatic carboxylic acid halides treated and the sulfo group splits off by heating with dilute mineral acid.
EMI0001.0027
The advantage of this process is that, firstly, there is no need to use solvents, since all the reaction stages can be carried out in aqueous solution thanks to the water-solubilizing sulfamine group, and secondly, the use of iron as the cheapest reducing agent. is permitted
thirdly, the production of some monoaroyldiamino compounds is made possible, which are very difficult to obtain in other ways, as can be seen from the following examples:
EMI0002.0011
According to the new procedure, these bodies are accessible from the corresponding nitroamines of the following formula:
EMI0002.0013
Otherwise one would have to assume the following nitroamines, which are much more difficult to access:
EMI0002.0015
The claimed process means an important technical advance for the production of monoarc> yldiamino compounds of the benzene and naphthalene series, which have gained importance as diazo components for azo dyes, especially those which are produced on the fiber.
It is known to convert aromatic diamines, for example with oxalic acid, into aromatic monooxalyldiamino compounds and then with benzoylchloride into the corresponding aromatic ogalylbenzoyldiamino compounds. When treated with saponifying agents, however, the benzoyl radical is more or less saponified depending on the conditions.
The present invention now relates to a process for the preparation of the known 4 - amido - 6 - benzoylamino - 1,3-dimethylbenzene, which is to be used for the production of dyes, characterized in that: 6-nitro-1. Reduced 3- dimethylphenyl-4-sulfamic acid, treated the reduction product with benzoyl halide and cleaved the sulfo group by heating with ver dilute mineral acid.
<I> Example: </I> 2! 68 kg of 6-nitro-1,3-dimethylphenyl-4-sulfamic acid sodium (produced by sulfamidation of 6-nitro-4-amido-1,3-dimethylbenzene with chlorosulfonic acid in the presence of a tertiary bastes) are reduced in the usual way at 60 to <B> 70 '</B> with iron and formic acid.
After the reduction is complete, the solution is made alkaline, the amino compound in solution is pressed from the iron oxide sludge, 145 kg of benzoyl chloride are gradually added to the filtrate at 25 to 30 'with good stirring and kept permanently weakly alkaline with soda.
When the benzoylation is complete, the mixture is heated to 70 to 80 ', <B> makes the Congo acidic with hydrochloric acid and at the same time increases the temperature to 80 to <B> 9.0'. </B> The saponification is in finished shortly, the hydrochloric acid salt of 4-amino-6-benzoylamido-1,3-dimethylbenzene already falls in the warmth in white. :
shiny needles and is separated out almost quantitatively by the addition of table salt. It is filtered off with suction, dissolved again in hot water, filtered and the base is precipitated with soda. White needles; Melting point 176, yield 88%, calculated on the nitroarylsulfamic acid used.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE152251X | 1930-01-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH152251A true CH152251A (en) | 1932-01-31 |
Family
ID=5674953
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH152251D CH152251A (en) | 1930-01-15 | 1931-01-06 | Process for the preparation of an aromatic monoaroyldiamino compound. |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH152251A (en) |
-
1931
- 1931-01-06 CH CH152251D patent/CH152251A/en unknown
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