DE202632C - - Google Patents
Info
- Publication number
- DE202632C DE202632C DENDAT202632D DE202632DA DE202632C DE 202632 C DE202632 C DE 202632C DE NDAT202632 D DENDAT202632 D DE NDAT202632D DE 202632D A DE202632D A DE 202632DA DE 202632 C DE202632 C DE 202632C
- Authority
- DE
- Germany
- Prior art keywords
- acetyl
- alkyloxy
- thiophenols
- thiophenol
- chloride
- 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.)
- Active
Links
- VSCWAEJMTAWNJL-UHFFFAOYSA-K Aluminium chloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- WETWJCDKMRHUPV-UHFFFAOYSA-N Acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 claims description 4
- 239000012346 acetyl chloride Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N carbon bisulphide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- -1 5-methoxy-2-acetyl-i-thiophenol forms Chemical group 0.000 description 2
- YSZCMTXSXVWPNV-UHFFFAOYSA-N COC1=CS(O)C=C1 Chemical compound COC1=CS(O)C=C1 YSZCMTXSXVWPNV-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-Aminophenol Chemical class NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000002152 alkylating Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000875 corresponding Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- TUCNEACPLKLKNU-UHFFFAOYSA-N ethanone Chemical compound C[C]=O TUCNEACPLKLKNU-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Substances SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
KAISERLICHESIMPERIAL
PATENTAMT.PATENT OFFICE.
Es wurde gefunden, daß man 5-Alkyloxy-2-acetyl-i-thiophenole von der allgemeinen Formel:It has been found that 5-alkyloxy-2-acetyl-i-thiophenols from the general formula:
O · Alkyl O · alkyl
erhält, wenn man auf 3-Alkyloxy-i-thiophenole bei Gegenwart von Aluminiumchlorid Acetylchlorid einwirken läßt.obtained when one on 3-alkyloxy-i-thiophenols in the presence of aluminum chloride, acetyl chloride is allowed to act.
Die zur Ausführung dieses Verfahrens erforderlichen 3-Alkyloxy-i-thiophenole erhält man aus den alkylierten m-Phenolsulfosäuren oder deren Chloriden durch Reduktion mit Zinkstaub und verdünnter Schwefelsäure (Ber. 23 [1890] S. 3394) oder aus m-Aminophenolen durch Alkylieren der Hydroxylgruppe, und Ersatz der Aminogruppe durch den Rest SH nach bekannten Verfahren. Kondensiert man nun diese 3-Alkyloxy-i-thiophenole mit Acetylchlorid bei Gegenwart von Kondensationsmitteln, wie Aluminiumchlorid, so tritt der Acetylrest in p-Stellung zur Alkyloxygruppe.The 3-alkyloxy-i-thiophenols required to carry out this process are obtained from the alkylated m-phenol sulfonic acids or their chlorides by reduction with zinc dust and dilute sulfuric acid (Ber. 23 [1890] p. 3394) or from m-aminophenols by alkylating the Hydroxyl group, and replacement of the amino group by the radical SH according to known processes. If these 3-alkyloxy-i-thiophenols are now condensed with acetyl chloride in the presence of condensing agents such as aluminum chloride, the acetyl radical occurs in the p-position to the alkyloxy group.
Es bilden sich zunächst 5-Alkyloxy-z-acetyli-acetylthiophenole der allgemeinen Formel:Initially, 5-alkyloxy-z-acetyli-acetylthiophenols are formed the general formula:
CO-CH^CO-CH ^
-S-CO.-S-CO.
Ο- Alkyl, Ο- alkyl,
3535
4040
welche beim Erwärmen mit verdünnten Mineralsäuren mit Leichtigkeit die an Schwefel gebundene Acetylgruppe unter Bildung von S-Alkyloxy-a-acetyl-i-thiophenolen abspalten. Diese sind schön kristallisierende, in Ätzalkalien sowie Schwefelalkalien lösliche Verbindungen, welche bei geeignet geleiteter Oxydation (Patent 198509, Kl. 22 e). irt schwefel- haltige Farbstoffe übergehen.which when heated with dilute mineral acids easily those of sulfur split off bonded acetyl group to form S-alkyloxy-a-acetyl-i-thiophenols. These are nicely crystallizing compounds that are soluble in caustic alkalis and sulfur alkalis, which in the case of suitably conducted oxidation (patent 198509, class 22 e). irt sulfur containing dyes pass over.
Zu 60 Teilen fein gepulvertem Aluminiumchlorid, die mit trockenem Schwefelkohlenstoff überschichtet sind, setzt man unter Rühren .35 Teile Acetylchlorid und läßt inTo 60 parts of finely powdered aluminum chloride with dry carbon disulfide are covered, is set with stirring .35 parts of acetyl chloride and leaves in
dieses Gemenge unter weiterem Rühren und zweckmäßig unter Kühlung 30 Teile 3-Methoxy-i-thiophenol (Siedepunkt 96 bis ioo° bei 9 bis 10 mm) einfließen. Die Reaktion beginnt sofort unter lebhafter Salzsäureentwicklung. Ist diese beendet, so trennt sich das Reaktionsgemisch nach kurzem Stehen in zwei Schichten : Man gießt die untere nach Entfernung der Schwefelkohlenstofflösung auf Eiswasser, isoliert das sich ausscheidende öl und erhitzt dieses einige Zeit mit verdünnter Salzsäure . unter Rückflußkühlung. Durch Aufnehmen des Öls in verdünnter Natronlauge entfernt man alkaliunlösliche Reaktionsprodukte und reinigt nach dem Ansäuern das 5-Methoxy-2 - acetyl-i -thiophenol:this mixture with further stirring and advantageously with cooling 30 parts of 3-methoxy-i-thiophenol (Boiling point 96 to 100 ° at 9 to 10 mm). The reaction begins immediately with vigorous development of hydrochloric acid. When this has ended, the reaction mixture separates into two layers after standing for a short time : Pour the lower one onto ice water after removing the carbon disulfide solution, isolates the oil that separates out and heats it for some time with dilute hydrochloric acid . under reflux. Removed by absorbing the oil in dilute sodium hydroxide solution alkali-insoluble reaction products and, after acidification, the 5-methoxy-2 is purified - acetyl-i -thiophenol:
C0CH.t C0CH. t
-SH-SH
X6/X 6 /
OCH-OCH-
durch Destillation im Vakuum oder Umkristallisieren zweckmäßig aus Alkohol.by distillation in vacuo or recrystallization expediently from alcohol.
Das 5-Methoxy-2-acetyl-i-thiophenol bildet farblose, bei 94 bis 960 schmelzende tafelförmige Kristalle, die schwer löslich in Äther, Ligroin und. kaltem Alkohol, leicht löslich in warmem Alkohol, Natronlauge oder Schwefelalkalien sind.The 5-methoxy-2-acetyl-i-thiophenol forms colorless tabular crystals which melt at 94 to 96 0 and are sparingly soluble in ether, ligroin and. cold alcohol, easily soluble in warm alcohol, caustic soda or alkaline sulfur.
Ersetzt man in obigem Beispiel in sinngemäßer Weise das 3-Methoxy-i-thiophenol durch 3-Äthoxy-i-thiophenol (Siedepunkt 104 bis 1050 bei 9 bis ro mm), so erhält man das entsprechende S-Äthoxy^-acetyl-i-thiophenol. Es bildet farblose, ebenfalls in Äther, Ligroin und kaltem Alkohol schwer lösliche, bei 64 bis 650 schmelzende Kristalle.By replacing in the above example in analogous manner, the 3-methoxy-i-thiophenol for 3-ethoxy-i-thiophenol (boiling point 104-105 0 at 9 to ro mm), one obtains the corresponding S-ethoxy ^ -acetyl-i -thiophenol. It forms colorless, also in ether, ligroin and cold alcohol sparingly soluble, at 64-65 0 crystals melting.
Claims (1)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE202632C true DE202632C (en) |
Family
ID=465109
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT202632D Active DE202632C (en) |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE202632C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2472471A (en) * | 1945-08-04 | 1949-06-07 | Standard Oil Dev Co | Process for the preparation of thioethers |
-
0
- DE DENDAT202632D patent/DE202632C/de active Active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2472471A (en) * | 1945-08-04 | 1949-06-07 | Standard Oil Dev Co | Process for the preparation of thioethers |
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