DE2308262C3 - Process for the preparation of aromatic sulfonic acid halides - Google Patents
Process for the preparation of aromatic sulfonic acid halidesInfo
- Publication number
- DE2308262C3 DE2308262C3 DE19732308262 DE2308262A DE2308262C3 DE 2308262 C3 DE2308262 C3 DE 2308262C3 DE 19732308262 DE19732308262 DE 19732308262 DE 2308262 A DE2308262 A DE 2308262A DE 2308262 C3 DE2308262 C3 DE 2308262C3
- Authority
- DE
- Germany
- Prior art keywords
- sulfonic acid
- preparation
- weight
- parts
- theory
- 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
- -1 aromatic sulfonic acid halides Chemical class 0.000 title claims description 9
- 238000000034 method Methods 0.000 title claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 8
- 239000012954 diazonium Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 239000005749 Copper compound Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 150000001880 copper compounds Chemical class 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims 1
- 239000000243 solution Substances 0.000 description 5
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 4
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- WREICNIHNBOUJV-UHFFFAOYSA-N 2-methyl-4-nitrobenzenesulfonyl chloride Chemical compound CC1=CC([N+]([O-])=O)=CC=C1S(Cl)(=O)=O WREICNIHNBOUJV-UHFFFAOYSA-N 0.000 description 1
- SAJYSJVBNGUWJK-UHFFFAOYSA-N 4-amino-2-nitrobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C([N+]([O-])=O)=C1 SAJYSJVBNGUWJK-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 150000001502 aryl halides Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000385 dialysis solution Substances 0.000 description 1
- 150000008049 diazo compounds Chemical class 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229940079826 hydrogen sulfite Drugs 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Description
1515th
Es ist bekannt, daß man aromatische Sulfonsäurehalogenide herstellen kann, indem man auf Aryl- φαζοηι um halogenide, insbesondere Aryldiazonium-(thloride oder -bromide, entweder bei Abwesenheit ίο Von Wasser in einem organischen Lösungsmittel oder t>ei Anwesenheit von Wasser in stark salzsaurcr Lösung (enter Zusatz wasserlöslicher organischer Sauren in Gegenwart von Kupfer oder Kupferverbindungen Schwefeldioxid einwirken laßt (vgl. DT-PS 8 59 461).It is known that one can produce aromatic sulfonyl halides by φαζοηι on aryl halides, in particular aryl diazonium (thloride or bromides, either in the absence ίο of water in an organic solvent or t> ei presence of water in strong solution salzsaurcr (Enter addition of water-soluble organic acids in the presence of copper or copper compounds allow sulfur dioxide to act (cf. DT-PS 8 59 461).
Das Verfahren hat den Nachteil, daß es technisch ichwierig durchführbar ist, da flüssiges bzw. gasförmiges Schwefeldioxid verwendet wird und durch die mit-♦erwendeten organischen Lösungsmittel eine Verteuerung des Verfahrens sowie eine starke Abwasserbelastung eintritt. Außerdem sind die Ausbeuten für tin technisches Verfahren in vielen Fallen nicht befriedigend. The process has the disadvantage that it is technically difficult to carry out because it is liquid or gaseous Sulfur dioxide is used and by the with- ♦ used organic solvents make the process more expensive as well as heavy wastewater pollution entry. In addition, the yields for a technical process are in many cases unsatisfactory.
Es wurde nun gefunden, daß man aromatische Sulfonsäurehalogenide aus aromatischen Diazonium-Verbindungen wesentlich einfacher und wirtschaftlicher und teilweise auch in besserer Ausbeute auf die im Anspruch angegebene Weise herstellen kann.It has now been found that aromatic sulfonic acid halides can be obtained from aromatic diazonium compounds much easier and more economical and sometimes also in better yield on the can produce specified manner in the claim.
Das Verfahren wird zweckmäßig in der Weise durchgeführt, daß man eine in üblicher Weise herge-•teilte Diazoniumchlorid- oder -bromid-Lösung in Gegenwart von Kupfer oder Kupferverbindungen, in Abwesenheit von organischen Lösungsmitteln, mit tiner Mischung aus Alkalihydrogensulfit und HaIogenwassersloffsäure behandelt. Vorteilhaft verwendet man die technisch leicht zugängliche Natriumbisulfitlauge und Salzsäure.The process is expediently carried out in such a way that one prepared in a customary manner Diazonium chloride or bromide solution in the presence of copper or copper compounds, in Absence of organic solvents, with a tine mixture of alkali hydrogen sulfite and halohydrohydric acid treated. The technically easily accessible sodium bisulfite liquor is advantageously used and hydrochloric acid.
Die Umsetzung der Diazoniumhalogenide erfolgt im allgemein schon bei Zimmertemperatur.The conversion of the diazonium halides generally takes place at room temperature.
Die gebildeten Arylsulfonsäurehalogenide scheiden sich im allgemeinen schon im Verlauf der Reaktion in flüssiger oder fester Form ab und werden durch Abtrennung oder Abfiltrieren isoliert.The arylsulfonic acid halides formed generally separate in the course of the reaction in liquid or solid form and are isolated by separation or filtration.
Die nachstehenden Beispiele dienen zur Erläuterung des erimdungsgemäßen Verfahrens.The following examples serve to illustrate the process according to the invention.
100 Gewichtsteile 2-Nitro-4-aminobenzoesäure ν erden mit 97,5 üewichtsteiien 4ÖVoiger Nairiumniinilösung und 400 Gewichtsteilen technischer Salzsäure bei 0 bis f'C diazotiert und nach einer Klärfiltration innerhalb von etwa 2 Stunden in eine auf 3 bis 5 C uekühlte Mischung aus 1000 Gewichtsteilen lechn. Salzsäure, 10 Gewichtsteilen krist. Kupfersulfat und 175 Gewichtsteilen 40%iger Natriumsulfitlauge unter die Oberfläche getropft. Gleichzeitig mit der Dia/olösung werden weitere 175 Gewichtsteile 40"Oige Natriumbisulfitlauge unter die Oberfläche /ugeiropit Unter lebhafter Stickstoffentwicklung setzt sich die Diazoverbindung zum Sulfochlorid um. Nach kurzem Nachrühren ist praktisch keine Dia/overbindung mehr nachzuweisen. Das Sulfochlorid wird abgesaugt. mit 2000 Volumteilen Wasser gewaschen und getrocknet. 100 parts by weight of 2-nitro-4-aminobenzoic acid ν are diazotized with 97.5 parts by weight of 4ÖVoiger sodium nitrate solution and 400 parts by weight of technical hydrochloric acid at 0 to f'C and, after a clarifying filtration, within about 2 hours in a mixture of 1000 that is cooled to 3 to 5 ° C Parts by weight lechn. Hydrochloric acid, 10 parts by weight of crystall. Copper sulfate and 175 parts by weight of 40% sodium sulfite liquor were dropped under the surface. Simultaneously with the slide solution, another 175 parts by weight of 40% sodium bisulphite liquor are added below the surface. With vigorous evolution of nitrogen, the diazo compound converts to sulfochloride. After a short period of stirring, practically no more slide bond can be detected Water washed and dried.
Man erhält 121 Gewichtsteile 2-Nitro-l-henzoesäure-4-sulfonsäurechlorid = K3% der 'I heorie mm Schmelzpunkt 190 bis 191 C.121 parts by weight of 2-nitro-1-benzoic acid-4-sulfonic acid chloride are obtained = K3% of 'I theory mm Melting point 190 to 191 C.
200 Gewichtsteile l-Amino-2-methyl-4-nitrobcii/.>! werden bei 0 bis 5rC mittels 400Gewichisiei!-,-n 30%iger Salzsäure und 235 Gewichtsteilen 40",.ig-ji Natriumnitritlusung diazotierl. Die geklärte Dia/olösung läßt man unter schwacher Außenkühlung unterdie Oberfläche einer Mischung aus 13(X)(.iewichtsteilen 30%iger Salzsäure. 33 Gewichtsteilen krist. Kupfersulfat und 330 Gcwichlstcilen 40'^iger Natriumbisulfitlauge laufen und gibt gleichzeitig weitere 330 Gewichtsteile 40%igc Natriumbisulfhlauge zu. Nach etwa 45 Minuten wird das abgeschiedene Sulfonsäurcchlorid abgesaugt, mit 2000 Volumteileii kaltem Wasser gewaschen und getrocknet. Man erhält das 2-Methyl-4-nitrobenzolsulfonsäureehlorid in einer Ausbeute von 85% der Theorie vom Schmelzpunkt 105 bis 106 C.200 parts by weight of l-amino-2-methyl-4-nitrobcii /.>! are diazotized at 0 to 5 r C by means of 400 weights of 30% hydrochloric acid and 235 parts by weight of 40 ", .ig-ji sodium nitrite solution. The clarified dialysis solution is left under the surface of a mixture of 13 (X) with slight external cooling. (30% by weight hydrochloric acid. 33 parts by weight of crystalline copper sulfate and 330 parts by weight of 40% sodium bisulfite liquor run and at the same time a further 330 parts by weight of 40% sodium bisulfite liquor are added. After about 45 minutes, the sulfonic acid chloride which has separated out is filtered off with suction and washed with 2000 parts by volume of cold water The 2-methyl-4-nitrobenzenesulphonic acid chloride is obtained in a yield of 85% of theory with a melting point of 105 to 106.degree.
In analoger Weise lassen sich die nachstehenden Sulfonsäurechloride herstellen:The following sulfonic acid chlorides can be prepared in an analogous manner:
Verbindungconnection
Schmelzpunkt b/.w. Siedepunkt AusbeuteMelting point b / .w. Boiling point yield
NO,NO,
96 bis 97 C S3% der Theorie96 to 97 C S3% of theory
'/ — SO:CI'/ - SO : CI
NO2
f 'V-SO1ClNO 2
f 'V-SO 1 Cl
"o der Theorie"o the theory
bis 145 12 Torr 90% der Theorieto 145 12 Torr 90% of theory
Verbindungconnection
Cl-^ / SO2CI Cl- ^ / SO 2 CI
α—<^ ^-so,ciα - <^ ^ -so, ci
NO,NO,
Cl-χ Xf>- SO-.Cl Cl- χ X f> - SO-.Cl
Svhnv:i/pu!iMSvhnv: i / pu! IM
5.Ί C5.Ί C
5S bis 59 C5S to 59 C
91% der Theorie91% of theory
90"Ό der Theone90 "Ό the Theone
75°u der Theorie75 ° u of theory
CH2=CH-SO,— χ >- SO2Cl CH 2 = CH-SO, - χ > - SO 2 Cl
F—\" SO-ClF- \ "SO-Cl
OH
/-''V-COOHOH
/ - '' V-COOH
SO-CI
NO2 C!SO-CI
NO 2 C!
χ *>- SO2CI χ *> - SO 2 CI
Cl
χ" V-SO2CI
99 hi.s ΙΟ) CCl
χ "V-SO 2 CI 99 hi.s ΙΟ) C
35 bis 36 C35 to 36 C
bis "7N Cto " 7 NC
9Uuo der Theorie9U u o the theory
71 % der Theorie71% of theory
I"; C iZerselzune) 75°ο der TheorieI "; C iZerselzune) 75 ° ο of theory
79" η der Theone79 "η the Theone
120 bis 125 C !4 Torr 78°,. der Theorie120 to 125 C! 4 Torr 78 ° ,. the theory
HOOC—f ^-SO,C1HOOC-f ^ -SO, C1
NO,—ί v— SO1ClNO, - v - SO 1 Cl
NO,—C "— SO-CINO, - C "- SO-CI
(Ί(Ί
SO-, ClSO-, Cl
232 C232 C
76 C76 C
75"o der Theone75 "o the Theone
179 bis ISO i 7 Torr S8"<- der Theorie179 to ISO i 7 Torr S8 "<- the theory
S5"ii der TheorieS5 "ii of theory
der Theonethe Theone
Claims (1)
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19732308262 DE2308262C3 (en) | 1973-02-20 | Process for the preparation of aromatic sulfonic acid halides | |
| CH217974A CH590830A5 (en) | 1973-02-20 | 1974-02-15 | |
| JP1867074A JPS5724782B2 (en) | 1973-02-20 | 1974-02-18 | |
| GB744274A GB1426405A (en) | 1973-02-20 | 1974-02-19 | Process for the manufacture of aromatic sulphonic acid chlorides and bromides |
| FR7405710A FR2218329B1 (en) | 1973-02-20 | 1974-02-20 | |
| US05/444,260 US3947512A (en) | 1973-02-20 | 1974-02-20 | Process for the manufacture of aromatic sulfonic acid halides |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19732308262 DE2308262C3 (en) | 1973-02-20 | Process for the preparation of aromatic sulfonic acid halides |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DE2308262A1 DE2308262A1 (en) | 1974-08-29 |
| DE2308262B2 DE2308262B2 (en) | 1975-07-24 |
| DE2308262C3 true DE2308262C3 (en) | 1976-03-04 |
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