CH233109A - Process for the preparation of N- (p-aminobenzenesulfonyl) -N'-methylurea. - Google Patents
Process for the preparation of N- (p-aminobenzenesulfonyl) -N'-methylurea.Info
- Publication number
- CH233109A CH233109A CH233109DA CH233109A CH 233109 A CH233109 A CH 233109A CH 233109D A CH233109D A CH 233109DA CH 233109 A CH233109 A CH 233109A
- Authority
- CH
- Switzerland
- Prior art keywords
- sep
- methylurea
- aminobenzenesulfonyl
- acid
- binding substance
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 10
- YDSGJRGCNLXRBD-UHFFFAOYSA-N 1-(4-aminophenyl)sulfonyl-3-methylurea Chemical compound CNC(=O)NS(=O)(=O)C1=CC=C(N)C=C1 YDSGJRGCNLXRBD-UHFFFAOYSA-N 0.000 title claims description 3
- 238000002360 preparation method Methods 0.000 title description 3
- -1 methylcarbamic acid halide Chemical class 0.000 claims description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- QWKKYJLAUWFPDB-UHFFFAOYSA-N 4-nitrobenzenesulfonamide Chemical compound NS(=O)(=O)C1=CC=C([N+]([O-])=O)C=C1 QWKKYJLAUWFPDB-UHFFFAOYSA-N 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 230000001419 dependent effect Effects 0.000 claims 2
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 150000007530 organic bases Chemical class 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 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 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- GNDKYAWHEKZHPJ-UHFFFAOYSA-N 2-nitrobenzenesulfonimidic acid Chemical compound NS(=O)(=O)C1=CC=CC=C1[N+]([O-])=O GNDKYAWHEKZHPJ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- OLSJVTLNNWLLIL-UHFFFAOYSA-N 1,3-disulfonylurea Chemical compound O=S(=O)=NC(=O)N=S(=O)=O OLSJVTLNNWLLIL-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- FQFPRSDCVUYSFJ-UHFFFAOYSA-N 1-methyl-3-(4-nitrophenyl)sulfonylurea Chemical compound CNC(=O)NS(=O)(=O)C1=CC=C([N+]([O-])=O)C=C1 FQFPRSDCVUYSFJ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- OYBOHBVRIWDAII-UHFFFAOYSA-N CC(NC(C=C1)=CC=C1S(NC(NC)=O)(=O)=O)=O Chemical compound CC(NC(C=C1)=CC=C1S(NC(NC)=O)(=O)=O)=O OYBOHBVRIWDAII-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- PKOFBDHYTMYVGJ-UHFFFAOYSA-N n-(4-sulfamoylphenyl)acetamide Chemical compound CC(=O)NC1=CC=C(S(N)(=O)=O)C=C1 PKOFBDHYTMYVGJ-UHFFFAOYSA-N 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010792 warming Methods 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
- C07C311/50—Compounds containing any of the groups, X being a hetero atom, Y being any atom
- C07C311/52—Y being a hetero atom
- C07C311/54—Y being a hetero atom either X or Y, but not both, being nitrogen atoms, e.g. N-sulfonylurea
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von N-(p-Aminobenzolsulfonyl)-N'-methylharnstoff. Im Hauptpatent ist ein Verfahren zur Herstellung des -N-(p-Aminobenzolsulfonyl)- N'-methylharnstoffes beschrieben, gemäss welchem man ein Methylcarbaminsäurehalo- genid mit Acetylsulfanilamid umsetzt und den erhaltenen N-(p-Acetylaminobenzolsulfo- nyl)-N'-methylharnstoff verseift.
Es wurde nun gefunden, dass man die gleiche Verbindung erhält, wenn man gemäss dem vorliegenden Verfahren p-Nitrobenzol- sulfonamid mit einem Methylcarba.minsäure- halogenid umsetzt und den erhaltenen N-(p- Nitrobenzolsulfonyl)-N'-methylharnstoff in der Nitrogruppe reduziert. Man kann zum Beispiel Nitrobenzolsulfonamid in einem Lö sungsmittel, z. B. Aceton oder Dioxan, auf zum Beispiel 50 bis 70 erhitzen.
Das Haupt produkt ist in diesem Falle aber häufig der N,N'-Di-p-nitrobenzolsulfonylharnstoff, der offenbar durch Zersetzung des primär entstan denen Nitrobenzolsulfonylmethylharnstoffes gebildet wurde. Zweckmässiger ist es, säure bindende Stoffe zuzusetzen, wie z. B.
Ka- liumkarbonat, Soda, Pyridin und andere, oder von den Salzen des Nitrobenzolsulfonamids auszugehen. Hierbei erhält man den Nitro- benzolsulfonyl-methylharnstoff ohne Bei mengung des symmetrischen Disulfonylharn- stoffes. Durch Reduktion der Nitrogruppe nach üblichen Methoden, z.
B. mit Zink und Salzsäure, erhält man den N-(p-Aminoben- zolsulfonyl)-N.'-methylharnstoff, dessen Ka- liumsalz aus Alkohol kristallisiert, den F. 208 bis 210 hat und ziemlich leicht lös lich in Wasser ist. <I>Beispiel 1:</I> 20,2 g p-Nitrobenzolsulfonamid, 10,5 g Monumethylcarbamidchlorid, 14,0 g was.#r- freies Kaliumcarbonat, 100 cm' trockenes Aceton werden 24 Stunden bei 60 gerührt.
Nach dem Abdampfen des Acetons wird der Rückstand in Wasser aufgenommen, mit kon zentrierter Salzsäure kongosauer gemacht, abgesaugt, in Wasser suspendiert und mit überschüssigem Natriumcarbonat verrührt.
EMI0002.0001
Aus <SEP> der <SEP> abfiltrierten <SEP> Bicarbonatlösunö <SEP> wird
<tb> der <SEP> in <SEP> Lösung <SEP> gegangene <SEP> Niti-olienzolsulfo nyl-methylharnstoff <SEP> durch <SEP> Ansäuern <SEP> niit
<tb> Salzsäure <SEP> in. <SEP> Freiheit <SEP> besetzt. <SEP> Durch <SEP> Kristal lisation. <SEP> aus <SEP> 80%igem <SEP> Alkohol <SEP> erhält <SEP> man
<tb> ihn <SEP> in <SEP> schönen <SEP> Nadeln <SEP> vom <SEP> F. <SEP> 201 <SEP> unter
<tb> Zersetzun-.
<SEP> Titra.tion <SEP> mit <SEP> n <SEP> -- <SEP> Na011 <SEP> gegen
<tb> ._ <SEP> 10
<tb> Phenolphtalein <SEP> ergibt <SEP> ein <SEP> 31olel@ularge -iclit
<tb> von <SEP> 26:3, <SEP> berechnet <SEP> 259.
<tb> Reduktion <SEP> mit <SEP> Zink <SEP> und <SEP> Salzsä.tire, <SEP> Ab stumpfen <SEP> der <SEP> überschüssigen <SEP> Salzsäure <SEP> durch
<tb> Zugabe <SEP> von <SEP> Natriumacetat <SEP> liefert <SEP> den <SEP> freien
<tb> N- <SEP> (p-Amiilol)enzolsulfon <SEP> vl)-N'-inethylbarn stoff <SEP> in <SEP> Form <SEP> von <SEP> feinen <SEP> Nädelchen, <SEP> dessen
<tb> durch <SEP> Kristallisation <SEP> aus <SEP> Alkohol <SEP> erhält liches <SEP> Kaliumsalz <SEP> den <SEP> F. <SEP> 208 <SEP> bis <SEP> 210 <SEP> hat
<tb> und <SEP> in <SEP> M'asser <SEP> ziemlich <SEP> leicht <SEP> löslich. <SEP> ist.
EMI0002.0002
<I>Beispiel <SEP> 2:</I>
<tb> 2(l, <SEP> 2 <SEP> g <SEP> Nitrobenzolsulfonainid, <SEP> <B>11),5</B> <SEP> g <SEP> Mono methyleitrbamitlcliloi,id <SEP> und <SEP> 40 <SEP> ein" <SEP> trockenes
<tb> Diozan <SEP> -erden <SEP> vermischt <SEP> und <SEP> vorsichtig <SEP> mit
<tb> 16 <SEP> g <SEP> Py <SEP> ridin <SEP> verrührt. <SEP> Dabei <SEP> erwärmt <SEP> sieh
<tb> die <SEP> Masse <SEP> und <SEP> löst <SEP> sich <SEP> auf. <SEP> Nach <SEP> :18stündi _.;*f,nl <SEP> Erwärmen <SEP> auf <SEP> <B>70'</B> <SEP> wird <SEP> tlie <SEP> 'lasse <SEP> in
<tb> Wasser <SEP> gegossen, <SEP> anbes:
itiert <SEP> 11n(1 <SEP> der <SEP> ausge fallene <SEP> Niederschlag <SEP> wie <SEP> nach <SEP> Beispiel <SEP> 1 <SEP> auf gearbeitet. <SEP> Man <SEP> erhält <SEP> die <SEP> gleiche <SEP> Ve <SEP> rbin dun-, <SEP> in <SEP> ähnlicher <SEP> Ausheule.
<tb> <I>Beispiel <SEP> 3:</I>
<tb> 20,2 <SEP> g <SEP> Niti-obenzolsufonaniid, <SEP> 70,5 <SEP> g <SEP> Mono nieth"-learl,aniidchloric1 <SEP> und <SEP> :10 <SEP> ein:' <SEP> Diotan
<tb> werden <SEP> 40 <SEP> Stunden <SEP> auf <SEP> 70" <SEP> erhitzt. <SEP> Aufariici- tun- wie nach Beispiel 2.
Neben viel sym metrischem N,N'-Di-p-nitrobenzolsulfonyl- harnstoff wird der N-Nitrobenzolsulfonyl-N'- methylharnstoff mit den oben angegebenen Eigenschaften isoliert, der dann auf die glei che Weise in die Aminoverbindtmg überge führt wird.
Process for the preparation of N- (p-aminobenzenesulfonyl) -N'-methylurea. The main patent describes a process for the preparation of -N- (p-aminobenzenesulfonyl) - N'-methylurea, according to which a methylcarbamic acid halide is reacted with acetylsulfanilamide and the resulting N- (p-acetylaminobenzenesulfonyl) -N'-methylurea saponified.
It has now been found that the same compound is obtained if, according to the present process, p-nitrobenzenesulfonamide is reacted with a Methylcarba.minsäure- halide and the resulting N- (p-nitrobenzenesulfonyl) -N'-methylurea is reduced in the nitro group . You can, for example, nitrobenzenesulfonamide in a solvent such. B. acetone or dioxane, for example 50 to 70 heat.
In this case, however, the main product is often the N, N'-di-p-nitrobenzenesulfonylurea, which was apparently formed by decomposition of the primarily formed nitrobenzenesulfonylmethylurea. It is more useful to add acid-binding substances, such as. B.
Potassium carbonate, soda, pyridine and others, or starting from the salts of nitrobenzenesulfonamide. The nitrobenzenesulfonylmethylurea is obtained here without adding the symmetrical disulfonylurea. By reducing the nitro group by customary methods, e.g.
With zinc and hydrochloric acid, for example, one obtains N- (p-aminobenzenesulfonyl) -N .'-methylurea, the potassium salt of which crystallizes from alcohol, has a melting point of 208 to 210 and is fairly easily soluble in water. <I> Example 1: </I> 20.2 g of p-nitrobenzenesulfonamide, 10.5 g of mono-methyl carbamide chloride, 14.0 g of potassium carbonate free from water, 100 cm of dry acetone are stirred at 60 for 24 hours.
After the acetone has evaporated, the residue is taken up in water, made Congo acidic with concentrated hydrochloric acid, filtered off with suction, suspended in water and stirred with excess sodium carbonate.
EMI0002.0001
<SEP> the <SEP> filtered off <SEP> bicarbonate solution becomes <SEP>
<tb> the <SEP> in the <SEP> solution <SEP> <SEP> niti-olienzo-sulfonyl-methylurea <SEP> by <SEP> acidification <SEP> niit
<tb> hydrochloric acid <SEP> in. <SEP> freedom <SEP> occupied. <SEP> By <SEP> crystallization. <SEP> from <SEP> 80% <SEP> alcohol <SEP> is obtained <SEP> man
<tb> him <SEP> in <SEP> beautiful <SEP> needles <SEP> from <SEP> F. <SEP> 201 <SEP> under
<tb> decomposition.
<SEP> Titra.tion <SEP> with <SEP> n <SEP> - <SEP> Na011 <SEP> against
<tb> ._ <SEP> 10
<tb> Phenolphthalein <SEP> results in <SEP> a <SEP> 31olel @ ularge -iclit
<tb> from <SEP> 26: 3, <SEP> calculates <SEP> 259.
<tb> Reduction <SEP> with <SEP> zinc <SEP> and <SEP> hydrochloric acid, <SEP> blunt <SEP> the <SEP> excess <SEP> hydrochloric acid <SEP> through
<tb> Adding <SEP> of <SEP> sodium acetate <SEP> delivers <SEP> the <SEP> free
<tb> N- <SEP> (p-Amiilol) enzolsulfon <SEP> vl) -N'-inethylbarn substance <SEP> in <SEP> form <SEP> of <SEP> fine <SEP> needles, <SEP> its
<tb> by <SEP> crystallization <SEP> from <SEP> alcohol <SEP> <SEP> potassium salt <SEP> obtainable <SEP> F. <SEP> 208 <SEP> to <SEP> 210 <SEP> has
<tb> and <SEP> in <SEP> M'asser <SEP> fairly <SEP> slightly <SEP> soluble. <SEP> is.
EMI0002.0002
<I> Example <SEP> 2: </I>
<tb> 2 (l, <SEP> 2 <SEP> g <SEP> nitrobenzenesulfonainide, <SEP> <B> 11), 5 </B> <SEP> g <SEP> Mono methyleitrbamitlcliloi, id <SEP> and < SEP> 40 <SEP> a "<SEP> dry
<tb> Diozan <SEP> -erden <SEP> mixes <SEP> and <SEP> carefully with <SEP>
<tb> 16 <SEP> g <SEP> Py <SEP> ridin <SEP> stirred. <SEP> Thereby <SEP> heated <SEP> see
<tb> the <SEP> mass <SEP> and <SEP> dissolves <SEP> <SEP>. <SEP> After <SEP>: 18hours _.; * F, nl <SEP> Warming <SEP> to <SEP> <B> 70 '</B> <SEP> becomes <SEP> tlie <SEP>' let < SEP> in
<tb> water <SEP> poured, <SEP> besides:
ited <SEP> 11n (1 <SEP> the <SEP> failed <SEP> precipitation <SEP> like <SEP> after <SEP> example <SEP> 1 <SEP> worked. <SEP> One receives <SEP> <SEP> the <SEP> same <SEP> Ve <SEP> rbin dun-, <SEP> in <SEP> similar <SEP> howling.
<tb> <I> Example <SEP> 3: </I>
<tb> 20.2 <SEP> g <SEP> niti-above-zolsufonaniid, <SEP> 70.5 <SEP> g <SEP> Mono nieth "-learl, aniidchloric1 <SEP> and <SEP>: 10 <SEP> : '<SEP> Diotan
<tb> <SEP> 40 <SEP> hours <SEP> are heated to <SEP> 70 "<SEP>. <SEP> Aufariici- do - as in example 2.
In addition to a lot of symmetrical N, N'-di-p-nitrobenzenesulfonylurea, the N-nitrobenzenesulfonyl-N'-methylurea with the properties given above is isolated, which is then converted into the amino compound in the same way.
Claims (1)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH227035T | 1941-12-23 | ||
| CH233109T | 1941-12-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH233109A true CH233109A (en) | 1944-06-30 |
Family
ID=25727058
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH233109D CH233109A (en) | 1941-12-23 | 1941-12-23 | Process for the preparation of N- (p-aminobenzenesulfonyl) -N'-methylurea. |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH233109A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2977375A (en) * | 1953-02-11 | 1961-03-28 | Boehringer & Soehne Gmbh | Process of manufacturing n-sulphanilyl ureas |
| US3015673A (en) * | 1956-09-28 | 1962-01-02 | Swiss Serum And Vaccine Inst | New urea derivatives and preparation thereof |
-
1941
- 1941-12-23 CH CH233109D patent/CH233109A/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2977375A (en) * | 1953-02-11 | 1961-03-28 | Boehringer & Soehne Gmbh | Process of manufacturing n-sulphanilyl ureas |
| US3015673A (en) * | 1956-09-28 | 1962-01-02 | Swiss Serum And Vaccine Inst | New urea derivatives and preparation thereof |
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