CH210338A - Process for the preparation of 2,4-dichloro-6-nitrophenyl-1-trifluoromethylsulfone. - Google Patents
Process for the preparation of 2,4-dichloro-6-nitrophenyl-1-trifluoromethylsulfone.Info
- Publication number
- CH210338A CH210338A CH210338DA CH210338A CH 210338 A CH210338 A CH 210338A CH 210338D A CH210338D A CH 210338DA CH 210338 A CH210338 A CH 210338A
- Authority
- CH
- Switzerland
- Prior art keywords
- nitrophenyl
- dichloro
- preparation
- trifluoromethylsulfone
- nitric acid
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 4
- 238000002360 preparation method Methods 0.000 title description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 3
- 229960001760 dimethyl sulfoxide Drugs 0.000 claims 1
- 239000000155 melt Substances 0.000 claims 1
- 238000006396 nitration reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 150000003462 sulfoxides Chemical class 0.000 description 3
- WZAJOJWOOXXUCT-UHFFFAOYSA-N trifluoromethylsulfinylbenzene Chemical class FC(F)(F)S(=O)C1=CC=CC=C1 WZAJOJWOOXXUCT-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ODNBVEIAQAZNNM-UHFFFAOYSA-N 1-(6-chloroimidazo[1,2-b]pyridazin-3-yl)ethanone Chemical compound C1=CC(Cl)=NN2C(C(=O)C)=CN=C21 ODNBVEIAQAZNNM-UHFFFAOYSA-N 0.000 description 1
- YEUYZNNBXLMFCW-UHFFFAOYSA-N 1-bromo-4-methylsulfanylbenzene Chemical compound CSC1=CC=C(Br)C=C1 YEUYZNNBXLMFCW-UHFFFAOYSA-N 0.000 description 1
- WCZWCGYJADVMJH-UHFFFAOYSA-N 1-nitro-2-(2-nitrophenyl)sulfinylbenzene Chemical class [O-][N+](=O)C1=CC=CC=C1S(=O)C1=CC=CC=C1[N+]([O-])=O WCZWCGYJADVMJH-UHFFFAOYSA-N 0.000 description 1
- -1 2,4-dichloro-6-nitrophenyl Chemical group 0.000 description 1
- GUNJVIDCYZYFGV-UHFFFAOYSA-K Antimony trifluoride Inorganic materials F[Sb](F)F GUNJVIDCYZYFGV-UHFFFAOYSA-K 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229940117975 chromium trioxide Drugs 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- VBQUDDWATQWCPP-UHFFFAOYSA-N ethylsulfonylbenzene Chemical compound CCS(=O)(=O)C1=CC=CC=C1 VBQUDDWATQWCPP-UHFFFAOYSA-N 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- JCDWETOKTFWTHA-UHFFFAOYSA-N methylsulfonylbenzene Chemical compound CS(=O)(=O)C1=CC=CC=C1 JCDWETOKTFWTHA-UHFFFAOYSA-N 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- ZODDGFAZWTZOSI-UHFFFAOYSA-N nitric acid;sulfuric acid Chemical compound O[N+]([O-])=O.OS(O)(=O)=O ZODDGFAZWTZOSI-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- PXIIUHJVQVAEEM-UHFFFAOYSA-N trichloromethylsulfanylbenzene Chemical class ClC(Cl)(Cl)SC1=CC=CC=C1 PXIIUHJVQVAEEM-UHFFFAOYSA-N 0.000 description 1
- YQQKTCBMKQQOSM-UHFFFAOYSA-N trifluoromethylsulfanylbenzene Chemical class FC(F)(F)SC1=CC=CC=C1 YQQKTCBMKQQOSM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/14—Sulfones; Sulfoxides having sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von 2.4-Diehlor-6-nitropbenyl-l-trii < uormethylsulfon. Nach den Angaben im Chemischen Zen tralblatt 1925, Seite 1671, führt die Nitrie- rung des Methylphenylsulfons nur zu m-Deri- vaten. Ein nach p-Stellung lenkender Ein fluss der Methansulfonylgruppe konnte nicht festgestellt werden.
Eine ähnliche Konstitu tion wie das 1M' ethylphenylsulfon besitzt auch das Trifluoi#niethylphenylsulfon der Formel
EMI0001.0012
Daher erfolgt auch bei dieser Verbindung, wie zu erwarten war, die Nitrierung eben falls ausschliesslich in m-Stellung. o- und p- Nitrophenyltrifluorinethylsulfone können also auf diesem Wege nicht erhalten werden.
Es wurde nun gefunden, dass man zu den o- und p-Nitroderivaten der Trifluorme- thylpheriylsulfone gelangt, wenn man auf die durch Einwirkung von technisch wasser freiem Fluorwasserstoff unter Druck oder Antimontrifluorid auf Trichlormethylphenyl- sulfide bei erhöhter Temperatur erhältlichen Trifltiormetbylphenylsulfide Salpetersäure in Gegenwart von Schwefelsäure einwirken lässt und die entstehenden Nitrophenyltrifluorme- thylsulfoxyde oxydiert.
Da nun die Trifluor- methylphenylsulfide unter den angegebenen Bedingungen zunächst zu den Trifluormethyl- phenylsulfoxyden oxydiert und diese dann in der zweiten Phase zu den Nitrophenyltri- fluormethylsulfoxyden nitriert werden, können auch die in Anlehnung an die Angaben im Chemischen Zentralblatt 1927, Seite 1821,
durch Einwirkung von Salpetersäure auf Ti-ifluormethylphenylsulfide darstellbaren Tri- fluormethylphenylsulfoxyde als Ausgangsma terial für die Herstellung der o- und p-Nitro- phenyltrifluormethylsulfone verwendet werden.
Der Eintritt der Nitrogruppe erfolgt stets in o- oder p-Stellung zu der SO . CFs-Gruppe. Der einheitliche und glatte Reaktions verlauf bei der Einwirkung von Salpeter säure in Gegenwart von Schwefelsäure auf die Trifluoi-inethylplieriylsulfide bezw. die Trifluormethylphenylsulfoxyde ist durchaus überraschend, da bei der Einwirkung von Salpetersäure auf p - Bromthioanisol und Thionanisol nur die entsprechenden Sulf- oxyde,
aber keine nitrierten Sulfoxyde erhalten werden (vergl. Chemisches Zentralblatt 1927, Seite 1822).
Die gleichzeitige Oxydation und Nitrie- rung der Trifluorinethylplieriylsulfide bezw. die Nitrierung der Trifluorinetliy lplienyisulf- oxyde mittels Salpetersäure in Gegenwart von Schwefelsäure verläuft sehr glatt, und man erhält die Niti@ophenylti-ifluornietliylsulf- oxyde in besten Ausbeuten.
Diese lassen sich nun mit den üblichen Oxydationsmitteln leicht zu den entsprechenden Nitrophenyl- ti-ifluornietliylsulfonen oxydieren, die wichtige Ausgangsmaterialien, zum Beispiel für die Herstellung von Farbstoffen oder Arznei mitteln, darstellen.
Gegenstand des vorliegenden Patentes ist ein Verfahren zur Herstellung von 2.4- Dichlor-6-nitrophenyl-1-trifluoi-methylsulfon, welches dadurch gekennzeichnet ist, dass man auf 2.4-Dichlorphenyl-l-trifliiormetliyls(ilfid Salpetersäure in Gegenwart von Schwefel säure einwirken lässt und das so erhaltene 2 . 4-Diclilor- 6 -nitroplienyl -1- trifluoi,inetliyl- sulfoxyd oxydiert.
Die erhaltene Verbindung stellt einen wertvollen Ausgangsstoff für die Herstellung von Farbstoffen und Arzneimitteln dar.
<I>Beispiel:</I> In 75 Volumteile eines Salpetersäure- Schwefelsäuregemisches, das etwa 30 /o reine Salpetersäure und etwa 70 % Monohydrat enthält, lässt man unter Rühren auf dein Dampfbade bei etwa 60 bis<B>70'C</B> 25 Gewichts- teile 2.4-Dichlorphenyl-l-trifluormethylsulfid einlaufen. Man rührt noch kurze Zeit bei 70 bis 80 C nach und gibt dann auf Eis.
Das ausgeschiedene 2.4-Dichlor-6-nitrophenyl-(- trifluormetliylsulfoxyd wird abgesaugt und ausgewaschen. Man erhält es in nahezu quantitativer Ausbeute als schwach gelblich gefärbtes Pulver. Durch Umkristallisieren, beispielsweise aus Trichloräthylen, erhält man schöne Kristalle, die bei 100 C schmelzen.
31 Gewichtsteile 2.4-Dichlor-6-riitrophe- ny 1-1-trifluorinethylsulfoxyd werden in 100 bis 150 Volumteilen Eisessig gelöst. In die Lösung trägt inan bei etwa 401' C unter Rühren portionsweise etwa 10 Gewichtsteile Chromtrioxyd ein. Nach dem Eintragen er hitzt man die Flüssigkeit noch i/2 bis 1 Stunde auf 70 bis<B>800</B> C. Man verdünnt dann finit Wasser und saugt das abgeschie dene 2.4-Diclilor-6-riitropheriyl-l-trifluorme- thyIsulfon ab. Die Ausbeute ist fast quan titativ.
1)ie so erhaltene neue Verbindung kri stallisiert beispielsweise aus Benzin in schwach gelblichen Kristallen, die bei<B>760C</B> schmelzen.
Process for the preparation of 2,4-Diehlor-6-nitropbenyl-1-trii <uormethylsulfon. According to the information in the Chemisches Zen tralblatt 1925, page 1671, the nitration of methylphenylsulfone only leads to m-derivatives. An influence of the methanesulfonyl group directing towards the p-position could not be determined.
The trifluoro # niethylphenylsulfone of the formula also has a similar constitution to the 1M 'ethylphenylsulfone
EMI0001.0012
Therefore, as was to be expected, the nitration also takes place exclusively in the m-position with this compound. So o- and p-nitrophenyltrifluorinethylsulfones cannot be obtained in this way.
It has now been found that the o- and p-nitro derivatives of trifluoromethylphenylsulfones are obtained if sulfuric acid in the presence of sulfuric acid in the presence of technically anhydrous hydrogen fluoride under pressure or antimony trifluoride on trichloromethylphenyl sulfides at elevated temperature is used Let it take effect and oxidize the resulting nitrophenyltrifluoromethylsulfoxides.
Since the trifluoromethylphenylsulphides are first oxidized to the trifluoromethylphenylsulphoxides under the specified conditions and these are then nitrated in the second phase to the nitrophenyltrifluoromethylsulphoxides, the following can also be used based on the information in the Chemisches Zentralblatt 1927, page 1821,
trifluoromethylphenylsulfoxides, which can be prepared by the action of nitric acid on Ti-ifluormethylphenylsulfide be used as starting material for the production of the o- and p-nitrophenyltrifluoromethylsulfones.
The entry of the nitro group always takes place in the o or p position to the SO. CFs group. The uniform and smooth reaction proceeds when nitric acid acts in the presence of sulfuric acid on the Trifluoi-inethylplieriylsulfide respectively. the trifluoromethylphenylsulfoxides is quite surprising, since when nitric acid acts on p-bromothioanisole and thionanisole only the corresponding sulfoxides,
but no nitrated sulfoxides are obtained (see Chemisches Zentralblatt 1927, page 1822).
The simultaneous oxidation and nitration of Trifluorinethylplieriylsulfide respectively. the nitration of the trifluorinethyl sulfoxide by means of nitric acid in the presence of sulfuric acid proceeds very smoothly, and the nitrophenyl sulfoxides are obtained in the best yields.
These can now easily be oxidized with the usual oxidizing agents to the corresponding nitrophenyl-ti-ifluoronietliyl sulfones, which are important starting materials, for example for the production of dyes or drugs.
The subject of the present patent is a process for the preparation of 2.4-dichloro-6-nitrophenyl-1-trifluoro-methylsulfone, which is characterized in that 2.4-dichlorophenyl-1-trifliiormetliyls (ilfid nitric acid is allowed to act in the presence of sulfuric acid and the resulting 2,4-dicloro-6-nitroplienyl -1-trifluoro, inetliyl-sulfoxide is oxidized.
The compound obtained is a valuable starting material for the production of dyes and medicines.
<I> Example: </I> In 75 parts by volume of a nitric acid-sulfuric acid mixture containing about 30 / o pure nitric acid and about 70% monohydrate, the mixture is left with stirring on the steam bath at about 60 to <B> 70'C </ B> 25 parts by weight of 2,4-dichlorophenyl-1-trifluoromethyl sulfide run in. The mixture is stirred for a short time at 70 to 80 ° C. and then poured onto ice.
The precipitated 2,4-dichloro-6-nitrophenyl - (- trifluoromethylsulfoxide is filtered off with suction and washed out. It is obtained in almost quantitative yield as a pale yellowish colored powder. By recrystallization, for example from trichlorethylene, beautiful crystals which melt at 100 ° C. are obtained.
31 parts by weight of 2,4-dichloro-6-riitropheny 1-1-trifluorinethylsulfoxide are dissolved in 100 to 150 parts by volume of glacial acetic acid. At about 401 ° C., about 10 parts by weight of chromium trioxide are added in portions to the solution while stirring. After entering, the liquid is heated for a further 1/2 to 1 hour to 70 to 800 C. It is then finely diluted with water and the precipitated 2.4-dicloro-6-riitropheriyl-l-trifluorme- thyIsulfon off. The yield is almost quantitative.
1) The new compound obtained in this way crystallizes from gasoline, for example, in pale yellowish crystals that melt at <B> 760C </B>.
Claims (1)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE210338X | 1937-10-05 | ||
| DE211773X | 1937-10-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH210338A true CH210338A (en) | 1940-07-15 |
Family
ID=32991730
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH210338D CH210338A (en) | 1937-10-05 | 1938-09-29 | Process for the preparation of 2,4-dichloro-6-nitrophenyl-1-trifluoromethylsulfone. |
| CH211773D CH211773A (en) | 1937-10-05 | 1938-09-29 | Process for the preparation of 2,5-dichloro-4-nitrophenyl-1-trifluoromethylsulfone. |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH211773D CH211773A (en) | 1937-10-05 | 1938-09-29 | Process for the preparation of 2,5-dichloro-4-nitrophenyl-1-trifluoromethylsulfone. |
Country Status (1)
| Country | Link |
|---|---|
| CH (2) | CH210338A (en) |
-
1938
- 1938-09-29 CH CH210338D patent/CH210338A/en unknown
- 1938-09-29 CH CH211773D patent/CH211773A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CH211773A (en) | 1940-10-15 |
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