DE164130C - - Google Patents
Info
- Publication number
- DE164130C DE164130C DE1904164130D DE164130DA DE164130C DE 164130 C DE164130 C DE 164130C DE 1904164130 D DE1904164130 D DE 1904164130D DE 164130D A DE164130D A DE 164130DA DE 164130 C DE164130 C DE 164130C
- Authority
- DE
- Germany
- Prior art keywords
- yellow
- needles
- white
- prisms
- nitric 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 - Lifetime
Links
- GRYLNZFGIOXLOG-UHFFFAOYSA-N nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- -1 alkaryl sulfamides Chemical class 0.000 claims description 5
- NVBFHJWHLNUMCV-UHFFFAOYSA-N Sulfamide Chemical compound NS(N)(=O)=O NVBFHJWHLNUMCV-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- JBIJLHTVPXGSAM-UHFFFAOYSA-N 2-Naphthylamine Chemical compound C1=CC=CC2=CC(N)=CC=C21 JBIJLHTVPXGSAM-UHFFFAOYSA-N 0.000 claims description 2
- IMPPGHMHELILKG-UHFFFAOYSA-N 4-ethoxyaniline Chemical compound CCOC1=CC=C(N)C=C1 IMPPGHMHELILKG-UHFFFAOYSA-N 0.000 claims description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 claims description 2
- CSKNSYBAZOQPLR-UHFFFAOYSA-N Benzenesulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC=C1 CSKNSYBAZOQPLR-UHFFFAOYSA-N 0.000 claims 1
- 241000490025 Schefflera digitata Species 0.000 claims 1
- 125000005418 aryl aryl group Chemical group 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 235000015250 liver sausages Nutrition 0.000 claims 1
- 238000000034 method Methods 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-Toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- AASABFUMCBTXRL-UHFFFAOYSA-N N-ethyl-4-methylaniline Chemical compound CCNC1=CC=C(C)C=C1 AASABFUMCBTXRL-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000875 corresponding Effects 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000006396 nitration reaction Methods 0.000 description 2
- 150000002828 nitro derivatives Chemical class 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-Chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 description 1
- 229960000583 Acetic Acid Drugs 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate dianion Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- HXCOCQWMKNUQSA-UHFFFAOYSA-N caesium hydride Inorganic materials [H-].[Cs+] HXCOCQWMKNUQSA-UHFFFAOYSA-N 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- MFPBTSMUPLYGIM-UHFFFAOYSA-N naphthalen-2-yl(phenyl)sulfamic acid Chemical compound C=1C=C2C=CC=CC2=CC=1N(S(=O)(=O)O)C1=CC=CC=C1 MFPBTSMUPLYGIM-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C311/15—Sulfonamides having sulfur atoms of sulfonamide groups bound to carbon atoms of six-membered aromatic rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
Description
KAISERLICHESIMPERIAL
PATENTAMT.PATENT OFFICE.
Die dem Patent 157859 zugrunde liegende Nitrierungsmethode liefert bei Arylsulf amiden mit freier Parastellung einheitlich und in fast theoretischer Ausbeute Paranitroderivate.The nitration method on which patent 157859 is based produces amides in the case of aryl sulfides with free para position uniformly and in almost theoretical yield paranitro derivatives.
Es wurde nun gefunden, daß die gleiche Methode bei Arsylsulfamiden, in welchen die Parastellung nicht frei ist, ebenso einheitlich und quantitativ zu Orthonitroderivaten führt. Das Verfahren führt in gleicher Weise zum Ziel sowohl beim Behandeln der Arylsulfamide in ungelöster Form mit verdünnter Salpetersäure allein als auch bei Anwendung einer Lösung der zu nitrierenden Körper in Alkohol, Benzol, Aceton, Äther und ähnlichen Lösungsmitteln. It has now been found that the same method with Arsylsulfamiden, in which the Para position is not free, just as uniformly and quantitatively leads to orthonitro derivatives. The method leads in the same way to the goal both when treating the aryl sulfamides in undissolved form with dilute nitric acid alone as well as when using a Solution of the bodies to be nitrated in alcohol, benzene, acetone, ether and similar solvents.
Das vorliegende Verfahren unterscheidet sich in gleicher Weise wie das des Patentes 157859 von dem bisher bekannten ähnlichen \7erfahren (vergl. Ber. XXXV, 1441) dadurch, daß hier mit verdünnter Salpetersäure in der Wärme und mit oder ohne Anwendung eines Lösungsmittels gearbeitet wird; das alte Verfahren dagegen verwendet rauchende Salpetersäure in der Kälte unter Zusatz von Eisessig.The present method differs in the same manner as that of patent 157859 experienced by the hitherto known similar \ 7 (see Ber XXXV 1441..) In that is carried out here with dilute nitric acid in the heat and with or without use of a solvent; the old method, on the other hand, uses fuming nitric acid in the cold with the addition of glacial acetic acid.
Das vorliegende Verfahren zeichnet sich ferner vor dem bekannten durch eine fast theoretische Ausbeute sowie dadurch aus, daß nur eine Nitrogruppe und diese stets in der Orthostellung zur Sulfamidogruppe eintritt.The present method is further distinguished from the known by an almost theoretical one Yield and from the fact that only one nitro group and this always occurs in the ortho position to the sulfamido group.
Die entstandenen o-Nitroderivate können durch Abspaltung des Arylsulforestes mittels konzentrierter Schwefelsäure in der Kälte leicht in die entsprechenden ο-Nitroamine übergeführt werden. Durch Reduktion der o-Nitroarylsulfamide werden Aminoderivate erhalten, die ebenso durch Abspaltung des Arylsulforestes in ο-Diamine übergeführt werden können.The resulting o-nitro derivatives can by splitting off the Arylsulforestes by means of concentrated sulfuric acid in the cold easily into the corresponding ο-nitroamines be transferred. Amino derivatives are formed by reducing the o-nitroarylsulfamides obtained, which are also converted into ο-diamines by splitting off the Arylsulforestes can be.
Alle diese Produkte sollen als Ausgangsmaterialien für die Farbstoffabrikation Ver-Wendung finden.All of these products are intended to be used as raw materials for dye manufacture Find.
I. 281,5 kg p-Tolylsulfo-p-chloranilid werden mit einer Mischung von 1000 1 Wasser und 422 kg Salpetersäure von 22,5° Be. auf dem Dampfbade langsam angewärmt und drei Stunden lang unter gutem Rühren auf etwa 950 erhitzt. Das Sulfamid schmilzt anfänglich, wird zusehends gelber, um allmählich zu Bröckchen zu erstarren. Nach dem Erkalten wird abgesaugt und ausgewaschen. Aus Alkohol umkristallisiert zeigt das o-Nitro-p-chlor-p-tolylsulfoanilid den Schmelzpunkt iio°.I. 281.5 kg of p-tolylsulfo-p-chloroanilide are treated with a mixture of 1000 1 of water and 422 kg of nitric acid at 22.5 ° Be. warmed slowly on the steam bath and heated to about 95 0 for three hours with thorough stirring. The sulfamide initially melts, becomes noticeably more yellow, and gradually solidifies into lumps. After cooling, it is suctioned off and washed out. Recrystallized from alcohol, the o-nitro-p-chloro-p-tolylsulfoanilide has a melting point of 10 °.
II. 291 kg p-Tolylsulfo-p-phenetidid werden mit 800 kg Alkohol und 660 kg Salpetersäure von 22,5° Be. am Rückflußkühler auf dem Dampfbade zum Sieden erhitzt. Schon während der Nitrierung scheiden sich gelbe Kristalle des o-Nitroderivates ab. Nach zehnII. 291 kg of p-tolylsulfo-p-phenetidide become with 800 kg of alcohol and 660 kg of nitric acid of 22.5 ° Be. heated to boiling on the reflux condenser on the steam bath. Nice yellow crystals of the o-nitro derivative separate out during the nitration. After ten
Stunden ist die Reaktion beendet, und beim Erkalten scheidet sich der Nitrokörper in gelben Nadeln vom Schmelzpunkt 980 aus.Hours the reaction is stopped, and on cooling the nitro body excretes into yellow needles of melting point 98 0 out.
III. 24,7 kg Phenylsulfo-p-toluidid werden mit 60 kg Wasser und 42 kg verdünnter Salpetersäure (1,18 spez. Gewicht) übergössen und unter Rühren auf dem Dampfbade erwärmt. Das Sulfamid schmilzt und färbt sich tiefgelb. Nach etwa drei Stunden erstarrt das gelbe öl beim Erkalten zu einer festen Kristallkruste, die abgesaugt, gepulvert und ausgewaschen wird. Aus Alkohol kristallisiert das entstandene 3-Nitro-4-phenylsulfo-p-toluidid in gelben Prismen vom Schmelzpunkt 89°.III. 24.7 kg of phenylsulfo-p-toluidide are used with 60 kg of water and 42 kg of dilute nitric acid (1.18 specific weight) poured over it and heated while stirring on the steam bath. The sulfamide melts and turns deep yellow. After about three hours, the yellow oil solidifies to a solid crystal crust when it cools, which is sucked off, powdered and washed out. The 3-nitro-4-phenylsulfo-p-toluidide formed crystallizes from alcohol yellow prisms with a melting point of 89 °.
IV. 27,3 kg Phenylsulfo-2-naphtylamin werden am Rückflußkühler mit 140 kg Äthylalkohol und 47 kg verdünnter Salpetersäure (1,18 spez. Gewicht) gekocht. Schon nach etwa Y2 Stunde beginnt das entstandene Nitroderivat sich in gelben Kristallen abzuscheiden. Nach fünfstündigem Sieden erstarrt beim Erkalten alles zu einem Kristallbrei, der abgesaugt und getrocknet wird. Das i-Nitro-2-phenylsulfonaphtylamin schmilzt bei 1560.IV. 27.3 kg of phenylsulfo-2-naphthylamine are boiled in a reflux condenser with 140 kg of ethyl alcohol and 47 kg of dilute nitric acid (1.18 specific weight). After about 2 hours, the resulting nitro derivative begins to separate out in yellow crystals. After boiling for five hours, everything solidifies to a crystal paste when it cools, which is suctioned off and dried. The i-nitro-2-phenylsulfonaphtylamine melts at 156 ° .
In entsprechender Weise werden bei anderen aromatischen Arylsulfamiden ebenfalls die Orthonitroderivate erhalten, z. B. beim Äthylp-toluidin. In a corresponding manner, with other aromatic aryl sulfamides, the Orthonitro derivatives obtained, e.g. B. with ethyl p-toluidine.
Die als Ausgangsmaterial dienenden Aryl-■surf amide werden durch Behandlung der ρ - substituierten primären oder sekundären aromatischen Basen mit Benzolsulf ο - oder p-Toluolsulfochlorid unter Zusatz von Alkalicarbonat oder Ätzalkali dargestellt. Die Eigenschaften einer Anzahl dieser Arylsulfamide sowie der daraus entstehenden o-Nitroderivate sind in der nachfolgenden Tabelle zusammengestellt. ·.'.■.■'Serving as starting material aryl ■ surf amides are substituted by treating the ρ - primary or secondary aromatic bases with benzenesulf ο - or p-toluenesulfochloride with the addition of alkali carbonate or caustic alkali. The properties of a number of these aryl sulfamides and the resulting o-nitro derivatives are compiled in the table below. ·. '. ■. ■'
austhe end
p-Toluolsulfochlorid p-toluenesulfonyl chloride
mitwith
Sulfamid KonstitutionSulfamide constitution
Aussehen Appearance
NitroderivatNitro derivative
Austhe end
Konstitutionconstitution
sehensee
Smp.M.p.
NH-SO2-C6H1-CH3 NH-SO 2 -C 6 H 1 -CH 3 NH-SO2-C6Hi-CH3 NH-SO 2 -C 6 Hi-CH 3
p-Phenetidinp-phenetidine
weiße Nadelnwhite needles
gelbe Nadelnyellow needles
94°94 °
p-Toluidinp-toluidine
NH-SO2-CsH1-CH3 NH-SO 2 -CsH 1 -CH 3
CH3 CH 3
weiße Prismen JVH-SO2-C6H4-CH3
-WO2 white prisms JVH-SO 2 -C 6 H 4 -CH 3
-WO 2
CH3 CH 3
gelbeyellow
Nädel-Needle
chenchen
98"98 "
NH-SO2-C6Hi-CH3 NH-SO 2 -C 6 Hi-CH 3 NH-SO2-C6Hi-CH3 NH-SO 2 -C 6 Hi-CH 3
p-Chloranilin p-chloroaniline
weiße Prismen gelbewhite prisms yellow
Nädel-Needle
chenchen
2-Naphtylamin 2-naphthylamine
N H-SO2-C6H1-CH3 N H-SO 2 -C 6 H 1 -CH 3
weiße Prismenwhite prisms
WO2
\/Vw H-SO2-C6H1-CH3 WHERE 2
\ / Vw H-SO 2 -C 6 H 1 -CH 3
gelbe Nadelnyellow needles
■59■ 59
OO
Äthylp-toluidin Ethyl p-toluidine
-CH3 -CH 3
weiße Nadelnwhite needles
CH3 CH 3
|\S O2- C6Hi- CH3
-JVO2 | \ SO 2 -C 6 Hi-CH 3
-JVO 2
CH3 CH 3
gelblichweiße Nädelchen yellowish white needles
127°127 °
Claims (1)
Benzol-
sulfochlorid
mitthe end
Benzene-
sulfochloride
with
KonstitutionSulfamide
constitution
sehenthe end
see
KonstitutionNitroderii
constitution
Aus
sehen y at
the end
see
Nadeln1 white
Needles 1
Ai-IVO2
CH3 NH-SO 2 - C 6 H 5
Ai-IVO 2
CH 3
Prismenyellow
Prisms
filzige
Kristall
nadelnwhite,
felty
crystal
needles
A-NO2
OC2H5 NH-SO 2 -CcH 5
A-NO 2
OC 2 H 5
filzige
Nadelnyellow,
felty
Needles
amin2-naphthyl
amine
weiße
Prismenthickness,
white
Prisms
Prismenyellow
Prisms
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT24280D AT24280B (en) | 1904-08-26 | 1905-03-24 | Process for the preparation of o-nitro derivatives of p-substituted aromatic aryl and alkaryl sulfamides. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE164130C true DE164130C (en) |
Family
ID=429751
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE1904164130D Expired - Lifetime DE164130C (en) | 1904-08-26 | 1904-08-26 |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE164130C (en) |
-
1904
- 1904-08-26 DE DE1904164130D patent/DE164130C/de not_active Expired - Lifetime
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