DE633982C - Process for the preparation of 4-nitroresorcinol - Google Patents
Process for the preparation of 4-nitroresorcinolInfo
- Publication number
- DE633982C DE633982C DEI51835D DEI0051835D DE633982C DE 633982 C DE633982 C DE 633982C DE I51835 D DEI51835 D DE I51835D DE I0051835 D DEI0051835 D DE I0051835D DE 633982 C DE633982 C DE 633982C
- Authority
- DE
- Germany
- Prior art keywords
- nitroresorcinol
- nitration
- resorcinol
- preparation
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000000034 method Methods 0.000 title claims description 8
- CYEZXDVLBGFROE-UHFFFAOYSA-N 2,4-Dihydroxy-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C(O)=C1 CYEZXDVLBGFROE-UHFFFAOYSA-N 0.000 title description 4
- 238000002360 preparation method Methods 0.000 title description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N Resorcinol Natural products OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 3
- 150000003568 thioethers Chemical class 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- 238000006396 nitration reaction Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- ZLCPKMIJYMHZMJ-UHFFFAOYSA-N 2-nitrobenzene-1,3-diol Chemical compound OC1=CC=CC(O)=C1[N+]([O-])=O ZLCPKMIJYMHZMJ-UHFFFAOYSA-N 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- 150000005207 1,3-dihydroxybenzenes Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000000802 nitrating effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WSFCHCRTBQKDOR-UHFFFAOYSA-N 2,4-dihydroxybenzene-1,3,5-trisulfonic acid Chemical compound OC1=C(S(O)(=O)=O)C=C(S(O)(=O)=O)C(O)=C1S(O)(=O)=O WSFCHCRTBQKDOR-UHFFFAOYSA-N 0.000 description 1
- GQTHXQVZAKGYGN-UHFFFAOYSA-N 2,4-dihydroxybenzene-1,3-disulfonic acid Chemical compound OC1=CC=C(S(O)(=O)=O)C(O)=C1S(O)(=O)=O GQTHXQVZAKGYGN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000006277 sulfonation reaction Methods 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Darstellung von 4-Nitroresorcin Aus der Patentschrift 145 190 ist ein Verfahren zur Herstellung von 2-Nitroresorcin durch Nitrieren von Resorcindisulfonsäure ' und Abspaltung der Sulfonsäuregruppen aus dem Nitroprodukt bekannt. Dagegen sind die bisher in der Literatur zur Herstellung von 4-Nitroresorcin beschriebenen Verfahren (vgl. z. B. Beilstein, 4. Auflage, Band 6 [i923), S. 823/24, Ergänzungsband 6 [193i], S. 404, Patentschrift 127 283, Patentschrift 15o 982) umständlich und arbeiten nicht wirtschaftlich.Process for the preparation of 4-nitroresorcinol From the patent 145 190 is a process for the production of 2-nitroresorcinol by nitrating Resorcinol disulfonic acid and splitting off of the sulfonic acid groups from the nitro product known. In contrast, those in the literature for the production of 4-nitroresorcinol have so far been found described method (cf. e.g. Beilstein, 4th edition, Volume 6 [1923), p. 823/24, Supplementary volume 6 [193i], p. 404, patent specification 127 283, patent specification 15o 982) cumbersome and do not work economically.
Es wurde nun gefunden, daß man das 4-N1-' troresorcin in einfacher Weise durch Nitrierung des hochsulfonierten Resorcins, vermutlich der Resorcin-2, 4, 6-trisulfonsäure, und Abspaltung der in dem Nitrierungsprodukt vorhandenen Sulfonsäuregruppen in an sich bekannter Weise in glatt verlaufender Reaktion und guter Ausbeute erhalten kann.It has now been found that 4-N1- 'troresorcinol can be obtained in a simple manner Way by nitration of the highly sulfonated resorcinol, presumably the resorcinol-2, 4,6-trisulfonic acid, and splitting off of the sulfonic acid groups present in the nitration product obtained in a manner known per se in a smooth reaction and good yield can.
Bei der Ausführung des Verfahrens ist es nicht notwendig, von dem abgetrennten' hochsulfonierten Resorcin auszugehen; man kann vielmehr in der Weise arbeiten, daß man die Nitrierung in der 4-Stellung unmittelbar in dem Sulfonierungsgemisch vornimmt und anschließend die Sulfonsäuregruppen abspaltet, z. B. durch Verdünnen des Nitrierungsgemisches mit Wasser und Erwärmen.. Beispiel i i o kg gemahlenes Resorcin werden in 590 1 20%iges 0leum (D. 1,89) unter Rühren so eingetragen, daß die Temperatur etwa auf ioo bis 120' steigt. Unter Rühren läßt man allmählich die Temperatur. aufs etwa io ° fallen und trägt bei gleichzeitiger Kühlung ein Gemisch von i061 Zo%igem Oleum und 46,8 1 rauchender Salpetersäure (D. 1,52) so langsam ein, daß während des Nitrierungsvorganges die Temperatur' 15' nicht übersteigt. Die ursprünglich dickbreiige Nitrierungsmasse geht dabei allmählich fast vollkommen in Lösung. Man rührt noch einige Stunden bei langsam steigender Temperatur auf etwa 25 bis 30 ° nach und läßt die Lösung in etwa i 60o kg Eiswasser einlaufen. -Zur Befreiung von etwa gebildetem 2-Nitroresorcin wird die stark schwefelsaure Lösung mit Wasserdampf destilliert, bis das 2-Nitroresorcin nicht mehr übergeht. Den Destillationsrückstand kühlt man allmählich auf etwa 5o°, befreit von den geringen Mengen brauner Zersetzungsprodukte, und überläßt ihn der Kristallisation, welche nach völligem Erkalten in reichlichem Maße stattfindet.When carrying out the process, it is not necessary to start from the separated highly sulfonated resorcinol; Rather, one can work in such a way that the nitration in the 4-position is carried out directly in the sulfonation mixture and then the sulfonic acid groups are split off, e.g. B. by diluting the nitration mixture with water and heating .. Example iio kg of ground resorcinol are added to 590 1 20% iges iges iges (D. 1.89) with stirring so that the temperature rises to about 100 to 120 '. The temperature is gradually left with stirring. fall to about 10 ° and with simultaneous cooling introduces a mixture of 1061 10% oleum and 46.8 liters of fuming nitric acid (D. 1.52) so slowly that the temperature does not exceed '15' during the nitration process. The originally thick, pulpy nitration compound gradually dissolves almost completely. The mixture is stirred for a few more hours at a slowly increasing temperature to about 25 to 30 ° and the solution is allowed to run into about 160o kg of ice water. - To free any 2-nitroresorcinol that has formed, the strong sulfuric acid solution is distilled with steam until the 2-nitroresorcinol no longer passes over. The distillation residue is gradually cooled to about 50 °, freed from the small amounts of brown decomposition products, and left to crystallize, which takes place in abundance after complete cooling.
Das 4-Nitroresorcin kristallisiert mit Kristallwasser, von welchem befreit es den Schmelzpunkt 115° zeigt. Selbstverständlich läßt sieh bei diesem Verfahren 'die Salpetersäure durch ihre Salze ersetzen. Auch niedrigere Sulfonierungs- und höhere Nitrierungstemperaturen führen zu dem gewünschten Produkt, wie auch die Schwefelsäure- und Salpetersä urel:onzentrationen geändert werden können.The 4-nitroresorcinol crystallizes with water of crystallization, of which freed it shows the melting point 115 °. Of course leaves See in this process' replace nitric acid with its salts. Lower ones too Sulphonation and higher nitration temperatures lead to the desired product, as well as the sulfuric acid and nitric acid concentrations can be changed.
Ersetzt man z. B. das oben angegebene Salpeter-Schwefclsäure-Gemisch durch eine Nitriersäure, welche aus 67 °i, reiner Schwefelsäure tind 33°/o reiner Salpetersäure besteht, so gelangt'mati,in ebenso glatter Weise zu dem gewünschten d.-.'Titroresorcin.If you replace z. If, for example, the above-mentioned nitric-sulfuric acid mixture is mixed with a nitrating acid, which consists of 67 % pure sulfuric acid and 33% pure nitric acid, the desired d.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEI51835D DE633982C (en) | 1935-03-09 | 1935-03-09 | Process for the preparation of 4-nitroresorcinol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEI51835D DE633982C (en) | 1935-03-09 | 1935-03-09 | Process for the preparation of 4-nitroresorcinol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE633982C true DE633982C (en) | 1936-08-18 |
Family
ID=7193178
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEI51835D Expired DE633982C (en) | 1935-03-09 | 1935-03-09 | Process for the preparation of 4-nitroresorcinol |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE633982C (en) |
-
1935
- 1935-03-09 DE DEI51835D patent/DE633982C/en not_active Expired
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