DE1593846A1 - Process for the preparation of sulfamic acid aryl esters - Google Patents
Process for the preparation of sulfamic acid aryl estersInfo
- Publication number
- DE1593846A1 DE1593846A1 DE19671593846 DE1593846A DE1593846A1 DE 1593846 A1 DE1593846 A1 DE 1593846A1 DE 19671593846 DE19671593846 DE 19671593846 DE 1593846 A DE1593846 A DE 1593846A DE 1593846 A1 DE1593846 A1 DE 1593846A1
- Authority
- DE
- Germany
- Prior art keywords
- sulfamic acid
- ester
- preparation
- aryl esters
- general formula
- 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.)
- Pending
Links
- -1 sulfamic acid aryl esters Chemical class 0.000 title claims description 19
- 238000000034 method Methods 0.000 title claims description 8
- 238000002360 preparation method Methods 0.000 title claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 150000002148 esters Chemical class 0.000 claims description 8
- 239000012948 isocyanate Substances 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical class NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 2
- 229940124530 sulfonamide Drugs 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- YZGYKEJWCZUPMT-UHFFFAOYSA-N (2,4,6-trichlorophenyl) sulfamate Chemical compound NS(=O)(=O)OC1=C(Cl)C=C(Cl)C=C1Cl YZGYKEJWCZUPMT-UHFFFAOYSA-N 0.000 description 1
- TZQWRNGURLWASA-UHFFFAOYSA-N (3-chlorophenyl) sulfamate Chemical compound NS(=O)(=O)OC1=CC=CC(Cl)=C1 TZQWRNGURLWASA-UHFFFAOYSA-N 0.000 description 1
- CQGQVNKFCSRASR-UHFFFAOYSA-N (4-chlorophenyl) sulfamate Chemical compound NS(=O)(=O)OC1=CC=C(Cl)C=C1 CQGQVNKFCSRASR-UHFFFAOYSA-N 0.000 description 1
- FEKULDKIZHPVIP-UHFFFAOYSA-N (4-cyanophenyl) n-(oxomethylidene)sulfamate Chemical compound O=C=NS(=O)(=O)OC1=CC=C(C#N)C=C1 FEKULDKIZHPVIP-UHFFFAOYSA-N 0.000 description 1
- DRPAPEPUWLQLOU-UHFFFAOYSA-N (4-cyanophenyl)sulfamic acid Chemical compound OS(=O)(=O)NC1=CC=C(C#N)C=C1 DRPAPEPUWLQLOU-UHFFFAOYSA-N 0.000 description 1
- PGLRGMMNMUPZTG-UHFFFAOYSA-N (4-methylphenyl)sulfamic acid Chemical compound CC1=CC=C(NS(O)(=O)=O)C=C1 PGLRGMMNMUPZTG-UHFFFAOYSA-N 0.000 description 1
- SQKXDSADDBSWII-UHFFFAOYSA-N (4-phenylphenyl)sulfamic acid Chemical compound C1=CC(NS(=O)(=O)O)=CC=C1C1=CC=CC=C1 SQKXDSADDBSWII-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- YWHCUBZVNMSWDN-UHFFFAOYSA-N S(=O)(=O)(O)NC1=C(C(=C(C(=C1Cl)Cl)Cl)Cl)Cl Chemical compound S(=O)(=O)(O)NC1=C(C(=C(C(=C1Cl)Cl)Cl)Cl)Cl YWHCUBZVNMSWDN-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000004391 aryl sulfonyl group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000003262 carboxylic acid ester group Chemical class [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- WRJWRGBVPUUDLA-UHFFFAOYSA-N chlorosulfonyl isocyanate Chemical compound ClS(=O)(=O)N=C=O WRJWRGBVPUUDLA-UHFFFAOYSA-N 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- HJBKKJRGKIAUDI-UHFFFAOYSA-N isocyanato n-(oxomethylidene)sulfamate Chemical compound O=C=NOS(=O)(=O)N=C=O HJBKKJRGKIAUDI-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- NVBFHJWHLNUMCV-UHFFFAOYSA-N sulfamide Chemical group NS(N)(=O)=O NVBFHJWHLNUMCV-UHFFFAOYSA-N 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 150000003459 sulfonic acid esters Chemical class 0.000 description 1
- BUXTXUBQAKIQKS-UHFFFAOYSA-N sulfuryl diisocyanate Chemical class O=C=NS(=O)(=O)N=C=O BUXTXUBQAKIQKS-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/91—Dibenzofurans; Hydrogenated dibenzofurans
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B43/00—Preparation of azo dyes from other azo compounds
- C09B43/18—Preparation of azo dyes from other azo compounds by acylation of hydroxyl group or of mercapto group
- C09B43/20—Preparation of azo dyes from other azo compounds by acylation of hydroxyl group or of mercapto group with monocarboxylic acids, carbamic acid esters or halides, mono- isocyanates or haloformic acid esters
- C09B43/206—Preparation of azo dyes from other azo compounds by acylation of hydroxyl group or of mercapto group with monocarboxylic acids, carbamic acid esters or halides, mono- isocyanates or haloformic acid esters with formation of OCXN or OSO2N group
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
1593.8481593.848
25, Januar 19β7 Dr.Kl/WkJanuary 25, 19β7 Dr.Kl / Wk
-5287-5287
Verfahren zur Herstellung von Sulfamidsäure-arylesternProcess for the preparation of sulfamic acid aryl esters
Ester der Sulfamidsäure mit Phenolen sind bisher nicht bekannt geworden. Die vorliegende Erfindung betrifft ein sehr einfaches und mit guter Ausbeute verlaufendes Verfahren zur Herstellung von Verbindungen dieser neuen Körperklasse.Esters of sulfamic acid with phenols are not yet known become. The present invention relates to a very simple process which proceeds with good yield to make connections of this new body class.
Es wurde gefunden, daß man Sulfamidsäure-arylester der allge-.meinen Formel IIt has been found that sulfamic acid aryl esters of the general Formula I.
Ar(OlSO2-NH2)n , (i)Ar (OlSO 2 -NH 2 ) n , (i)
worin Ar für einen gegebenenfalls substituierten aromatischen Rest steht und η 1 oder 2 bedeutet, erhält, wenn man Aryloxysulfonylisocyanate der allgemeinen Formel IIwherein Ar is an optionally substituted aromatic The remainder is and η is 1 or 2 is obtained when aryloxysulfonyl isocyanate is used of the general formula II
Ar(O-SO2-NCO)n , (il)Ar (O-SO 2 -NCO) n , (il)
worin Ar und η die oben angegebenen Bedeutungen haben, mit Wasser umsetzt.wherein Ar and η have the meanings given above, with Converts water.
/2/ 2
109809/2052109809/2052
|U BAD ORIGINAL | U BAD ORIGINAL
Bei der Umsetzung entstehen primär die Sulfamidsäurearylester-N-carbonsäuren, die jedoch im allgemeinen spontan Kohlendioxid verlieren und in die SuIfamidsäure-arylester übergehen. In manchen Fällen ist mäßiges Nacherhitzen auf Temperaturen bis etwa 80° C zur Beschleunigung der Kohlendioxidabspaltung vorteilhaft. Die Umsetzung ist also durch die ReaktionsfolgeThe aryl sulfamic acid N-carboxylic acids are primarily formed during the reaction, which, however, generally lose carbon dioxide spontaneously and convert into the sulfamic acid aryl esters. In In some cases, moderate post-heating to temperatures of up to about 80 ° C. is necessary to accelerate the elimination of carbon dioxide advantageous. The implementation is therefore through the reaction sequence
Ar(O-SO2-NCO)n + η H3O --Ar(O-SO2-NH-COOH)n Ar (O-SO 2 -NCO) n + η H 3 O --Ar (O-SO 2 -NH-COOH) n
"Ar(O-SO2-NHg)n + η CO2 "Ar (O-SO 2 -NHg) n + η CO 2
zu beschreiben.to describe.
Es ist bekannt, daß Sulfonylisocyanate der allgemeinen Formel R-SOp-NCO bei der Umsetzung mit Wasser in die Sulfonamide übergehen. Bei diesen Verbindungen, die eine nicht hydrolysiert bare Kohlenstoff-Schwefel-Bindung enthalten, ist auch keine andere Reaktion möglich. Anders liegen die Verhältnisse dagegen bei den Verbindungen der vorliegenden Erfindung. Sie enthalten die hydrolytisch leicht spaltbare Arylester-Bindung, und «s war daher nicht vorauszusehen, daß eine selektive Hydrolyse der Isocyanatgruppe ohne Spaltung der Esterbindung möglich sein würde. Auch die Tatsache, daß die strukturell so einfach erscheinenden erfindungsgemäß herstellbaren Verbindungen bisher nicht bekannt waren, ist als Hinweis auf ihre Empfindlichkeit anzusehen.It is known that sulfonyl isocyanates of the general formula R-SOp-NCO are converted into the sulfonamides when reacted with water pass over. In the case of these compounds, which contain a non-hydrolysed carbon-sulfur bond, there is also none other reaction possible. On the other hand, the situation is different for the compounds of the present invention. They contain the hydrolytically easily cleavable aryl ester bond, and it was therefore it cannot be foreseen that selective hydrolysis of the isocyanate group will be possible without cleavage of the ester bond would. Also the fact that the compounds which appear to be structurally simple according to the invention have hitherto been produced were not known, is to be regarded as an indication of their sensitivity.
Die verfahrensgemäß als Ausgangsverbindungen eingesetzten Aryloxysulfonylisocyanate der allgemeinen Formel II sind nach dem Verfahren der deutschen Auslegeschrift 1 230 017 durch Umsetzung von aromatischen Verbindungen, die eine oder zwei phenolische Hydroxygruppen enthalten, mit Chlorsulfonylieocyanat leicht zugänglich. Dabei ist es gar nicht erforderlich, die Isocyanate rein zu isolieren, sondern man kann direkt die Lösungen, die bei ihrer Herstellung anfallen, mit Wasser umsetzen und die ausgefallenen Sulfamidsaureeatdr abfiltrieren.The process used as starting compounds Aryloxysulfonyl isocyanates of the general formula II are prepared according to the method of German Auslegeschrift 1 230 017 Reaction of aromatic compounds containing one or two phenolic hydroxyl groups with chlorosulfonylieocyanate easily accessible. It is not at all necessary to isolate the isocyanates purely, but you can directly the solutions, which arise in their production, with water convert and filter off the precipitated Sulfamidsaureeatdr.
109809/2052 bad original109809/2052 bad original
Als Substituenten am Arylkern kommen insbesondere Halogenatome, Alkyl-, Aryl-, Alkoxy-, Cyan , Alkylsulfonyl-, Arylsulfonyl-, Carbonsäureester-, Sulfonsäureester- und Phenylazogruppen in Betracht. .The substituents on the aryl nucleus are, in particular, halogen atoms, Alkyl, aryl, alkoxy, cyano, alkylsulfonyl, arylsulfonyl, Carboxylic acid ester, sulfonic acid ester and phenylazo groups in Consideration. .
Die Reaktion wird in einem Temperaturbereich von etwa 0 bis etwa .12.00C, vorzugsweise etwa 20Q bis etwa 80° C durchgeführt.The reaction is conducted in a temperature range of about 0 to about .12.0 0 C, preferably about 20 Q to about 80 ° C.
Die erfindungsgemäße Umsetzung wird vorteilhaft in einem Lösungsmittel durchgeführt. Wählt man mit Wasser nicht mischbare wenig polare Verdünnungsmittel, wie Kohlenwasserstoffe oder Halogen-Kohlenwasserstoffe, so fallen die Ester im allgemeinen direkt kristallin aus und können durch Abfiltrieren in hohem Reinheitsgrad und nahezu" quantitativer Ausbeute direkt isoliex't werden. Bei Verwendung eines mit Wasser mischbaren Lösungsmittels, beispielsweise Aceton, Dioxan, Tetrahydrofuran, gibt nan zweckmäßig die für die Umsetzung erforderliche Menge . Wasser langsam zu, um eine zu starke Erwärmung und zu plötzliche Kohlendioxid-Entwicklung zu vermeiden und fällt anschließend das Reaktionsprodukt mit Eis oder kaltem Wasser aus. Eine andere Möglichkeit, die Reaktion durchzuführen, besteht darin, daß man mit Wasserdampf beladene Inertgase mit dem Isocyanat in Berührung bringt.The inventive implementation is advantageous in one Solvent carried out. If you choose water-immiscible, slightly polar diluents, such as hydrocarbons or halohydrocarbons, the esters generally fall directly crystalline and can be filtered off in a high degree of purity and almost "quantitative yield directly isoliex't be. When using a water-miscible solvent, for example acetone, dioxane, tetrahydrofuran, appropriately gives the amount required for the implementation. Water slowly to too much heating and too sudden Avoid carbon dioxide development and then fall the reaction product with ice or cold water. One Another way of carrying out the reaction is to mix inert gases laden with water vapor with the isocyanate brings in touch.
Der Wert der neuen Verbindungen liegt in ihrer*großen Reaktivität, So lassen sich beispielsweise phenolische Hydroxygruppen durch '"'berführung in die wieder hydrolysierbaren Sulfamidsäureester vorübergehend gegenüber anderen Reaktionen schützen.- Weiterhin lassen sich die verfahrensgemäß hert-teilbaren Εε. " sehr gut zur Übertragung von Sulfamidgruppen auf andere Verbindungen verwenden. Durch Veränderung der Phenolkomponente, also vor allem durch Zahl, Art und Stellung von Substituenten im Rest Ar der obigen Formel hat man es in der Hand, die Reaktivität der Ester innerhalb weiter Grenzen zu variieren und damit den jeweils gegebenen Bedingungen anzupassen. x The value of the new compounds is their * large reactivity Thus, for example, phenolic hydroxy groups by '''berführung in the back hydrolyzable Sulfamidsäureester temporarily over other reactions schützen.- possible, furthermore, the process according to hert-divisible Εε. "Very good for the transmission of sulfamide groups to use on other compounds. By changing the phenol component, that is, above all by the number, type and position of substituents in the radical Ar of the above formula, it is possible to vary the reactivity of the ester within wide limits and thus to adapt it to the respective conditions. x
109809/2052. bad ORIGINAL.109809/2052. bad ORIGINAL.
Zu einer Lösung von 64 g 4-Cyan-phenoxysulfonylisocyanat in 500 ml Tetrachlorkohlenstoff tropft man bei 30 - 40° C 15 ml Wasser und isoliert den ausgefallenen Sulfamidsäure 4-cyanphenylester durch Filtration. Die Ausbeute der bei 155 C schmelzenden Verbindung beträgt 55 g (97 % d. Th.). Ber.: C 42,4 H 3,1 .N l4,l % 15 ml of water are added dropwise at 30.degree.-40.degree. C. to a solution of 64 g of 4-cyano-phenoxysulfonyl isocyanate in 500 ml of carbon tetrachloride, and the precipitated 4-cyanophenyl sulfamic acid is isolated by filtration. The yield of the compound melting at 155 ° C. is 55 g (97 % of theory ). Calc .: C 42.4 H 3.1 .N 14.1 %
Gef.: C 42,4 H 3,2 N 14,0 % Found: C 42.4 H 3.2 N 14.0 %
Zu einer Lösung von 128,5 g 4-Chlorphenol in 300 ml Toluol tropft man eine Lösung von 144 g Chlorsulfonylisocyanat in 100 ml Toluol und erhitzt 15 Stunden auf 110 C. Anschließend kühlt man auf -200C, filtriert von 8,6 g einer kristallin abgeschiedenen Verbindung ab und tropft zu der auf Raumtemperatur erwärmten Lösung langsam 25 g Wasser. Die Lösung erwärmt sich und bei kräftiger Kohlendioxid-Entwicklung scheidet sich der Sulfamidsäure-4-chlorphenyl-ester kristallin ab. Die Ausbeute beträgt 155 g (75 ^ d. Th. ), der Schmelzpunkt 105° C.To a solution of 128.5 g of 4-chlorophenol in 300 ml of toluene is added dropwise a solution of 144 g of chlorosulfonyl isocyanate in 100 ml of toluene and heated 15 hours at 110 C. It is then cooled to -20 0 C, filtered, 8.6 g of a crystalline separated compound and 25 g of water are slowly added dropwise to the solution, which has been warmed to room temperature. The solution heats up and, with strong evolution of carbon dioxide, the sulfamic acid 4-chlorophenyl ester separates out in crystalline form. The yield is 155 g (75 ^ d. Th.), The melting point 105 ° C.
Ber. : N 6,8 % S 15,4 % Ber. : N 6.8 % S 15.4 %
Gef. : N ^,1 % S 15,3 % Found: N ^, 1 % S 15.3 %
Man löst 3,2 g l,-4-Phenylen-di-(oxy-sulfonylisocyanat) in 6 ml Aceton, gibt tropfenweise 0,5 ml Wasser zu bis zur Beendigung der Kohlendioxid-Entwicklung und fällt dann den Hydrochinon bis-sulfarnidsäureester mit Eis aus. Ausbeute 2,3 g (85 c% d. Th.), Schmelzpunkt 200° C.3.2 g of -4-phenylene-di- (oxy-sulfonyl isocyanate) are dissolved in 6 ml of acetone, 0.5 ml of water is added dropwise until the evolution of carbon dioxide has ceased, and the hydroquinone bis-sulfamic acid ester is then precipitated with ice . Yield 2.3 g (85 c % of theory ), melting point 200 ° C.
Ber. : N 10,4 S 23,9 *'Ber. : N 10.4 S 23.9 * '
Gef.: N 10,6 S 24,1 % ■Found: N 10.6 S 24.1 % ■
-5 109809/2052 SAD -5 109809/2052 SAD
3 g 3-Chlorphenoxysuifonylisoeyanat bringt man wasserdampfbeladener Luft in Berührung. Dabei wandelt sich das flüssige Isocyanat in den kristallinen Sulfamidsäure-3-chlorphenylester vom Schmelzpunkt 80° C um. Die Ausbeute beträgt 2,7 g- .3 g of 3-chlorophenoxysulfonyl isoeyanate are brought into the water vapor-laden Air in contact. The liquid isocyanate is converted into the crystalline sulfamic acid 3-chlorophenyl ester from melting point 80 ° C to. The yield is 2.7 g.
Ber. : N 6,8 .S 15,4 %
Gef. : N 6,6 S 15,2 % Ber. : N 6.8 .S 15.4 %
Found: N 6.6 S 15.2 %
Nach der Verfahrensweise der Beispiele 1-4 lassen sich z.B. die folgenden Sulfamidsäureester herstellen.Following the procedure of Examples 1-4 can e.g. produce the following sulfamic acid esters.
. Schmp. 0C. M.p. 0 ° C
1 Sulfamidsäure-phenylester · 861 Phenyl sulfamic acid ester · 86
2 Sulfamidsäure-4-kresylester 802 4-cresyl sulfamic acid 80
5 SuIfamidsäure-J-kresylester 885 SuIfamic acid J-cresyl ester 88
4 Sulfafnidsäure-2>6-dimethylphenylester 1104 sulfafnidic acid 2 > 6-dimethylphenyl ester 110
5 Sulfamidsäure-2,3-dlmethylphenylester 785 2,3-dlmethylphenyl sulfamic acid 78
6 Sulfamidsäure-2,5-dimethylphenylester 1046 sulfamic acid 2,5-dimethylphenyl ester 104
7 _Sulfamidsäure-2,4,5-trichlorphenylester 1587 _Sulfamic acid-2,4,5-trichlorophenyl ester 158
8 Sulfamidsäure-2,4,6-trichlorphenylester 1448 sulfamic acid 2,4,6-trichlorophenyl ester 144
9 Sulfamidsäure-2,4,6-tribromphenylester 1649 2,4,6-tribromophenyl sulfamic acid 164
Sulfamidsäure-pentachlorphenylester 215Pentachlorophenyl sulfamic acid 215
Sulfamidsäure-A-methoxyphenylester 65Sulphamic acid A-methoxyphenyl ester 65
3uifamidsäure-4-niethylsulfonyl-phenylester I573-sulfamic acid 4-diethylsulfonyl-phenyl ester 157
Sulfamidsäure-3-inethoxycarbonyl-phenylester 1513-ynethoxycarbonyl-phenyl sulfamic acid 151
Sulfamidsäure-4-phenyl-phenylester 1654-phenyl-phenyl sulfamic acid 165
Sulfamidsäure-4-(phenylazo)-phenylester I60Sulphamic acid 4- (phenylazo) -phenyl ester 160
Sulfamidsäureester des 3-Hydroxydlphenylenoxids 156Sulfamic acid ester of 3-hydroxydlphenylene oxide 156
Dieses Beispiel zeigt die Verwendbarkelt der Sulfamidsäurearylester zur übertragung der Sulfanjldgruppe. This example shows the usability of the aryl sulfamic acid esters for transferring the sulfanyl group.
BAD ORIGINAL "7-109809/2052 BAD ORIGINAL " 7-109809/2052
Man schüttelt 1,35 g Sulfamidsäure-2,4,5-trichlorphenylester mit einer Lösung von 0,9 g Morpholin in 5 ml Methylenchlorid. Der Ester geht innerhalb weniger Sekunden in Lösung und nach Ga. 1 Minute kristallisiert das Morpholin-N-sulfonamid vom Schmp. l6o°Caus. Die Ausbeute beträgt 0,71 g (85 % d.Th.).1.35 g of 2,4,5-trichlorophenyl sulfamic acid are shaken with a solution of 0.9 g of morpholine in 5 ml of methylene chloride. The ester goes into solution within a few seconds and after 1 minute the morpholine-N-sulfonamide crystallizes with a melting point of 160 ° C. The yield is 0.71 g (85 % of theory).
Ber.: N 16,9 S 19,3 %
Gef.: N 17,0 S 19,6 % Calc .: N 16.9 S 19.3 %
Found: N 17.0 S 19.6 %
10 9809/20 6210 9809/20 62
- y ' : -8-ÖAD ÖRlQiNAL - y ' : -8- ÖAD ÖRlQi NAL
Claims (2)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF0051375 | 1967-01-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1593846A1 true DE1593846A1 (en) | 1971-02-25 |
Family
ID=7104556
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19671593846 Pending DE1593846A1 (en) | 1967-01-28 | 1967-01-28 | Process for the preparation of sulfamic acid aryl esters |
Country Status (2)
| Country | Link |
|---|---|
| DE (1) | DE1593846A1 (en) |
| FR (1) | FR1554976A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0403185A3 (en) * | 1989-06-12 | 1992-12-16 | A.H. Robins Company, Incorporated | Compounds having one or more aminosulfonyloxy radicals useful as pharmaceuticals |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5273993A (en) * | 1989-06-12 | 1993-12-28 | A. H. Robins Company, Incorporated | Compounds having one or more aminosulfonyloxy radicals useful as pharmaceuticals |
| US5194446A (en) * | 1989-06-12 | 1993-03-16 | A. H. Robins Company, Incorporated | Compounds having one or more aminosulfaonyloxy radicals useful as pharmaceuticals |
| US5025031A (en) * | 1989-11-30 | 1991-06-18 | A. H. Robins Co., Inc. | Aryl and aryloxyalkyl sulfamate esters useful as anticonvulsants |
| US6476011B1 (en) | 1991-08-28 | 2002-11-05 | Sterix Limited | Methods for introducing an estrogenic compound |
| GB9118478D0 (en) * | 1991-08-29 | 1991-10-16 | Imperial College | Steroid sulphatase inhibitors |
| US6903084B2 (en) | 1991-08-28 | 2005-06-07 | Sterix Limited | Steroid sulphatase inhibitors |
| US6011024A (en) | 1991-08-28 | 2000-01-04 | Imperial College Of Science Technology & Medicine | Steroid sulphatase inhibitors |
| FR2791977B1 (en) * | 1999-04-08 | 2003-04-11 | Rhodia Chimie Sa | HALOGENATION IN THE META POSITION OF AN AROMATIC PRESENTING A PHENOL FUNCTION PROTECTED BY CONDENSATION WITH AN ACID |
| US7335650B2 (en) | 2000-01-14 | 2008-02-26 | Sterix Limited | Composition |
-
1967
- 1967-01-28 DE DE19671593846 patent/DE1593846A1/en active Pending
-
1968
- 1968-01-26 FR FR1554976D patent/FR1554976A/fr not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0403185A3 (en) * | 1989-06-12 | 1992-12-16 | A.H. Robins Company, Incorporated | Compounds having one or more aminosulfonyloxy radicals useful as pharmaceuticals |
Also Published As
| Publication number | Publication date |
|---|---|
| FR1554976A (en) | 1969-01-24 |
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