DE583055C - Process for the preparation of bis (halooxyaryl) sulfides - Google Patents
Process for the preparation of bis (halooxyaryl) sulfidesInfo
- Publication number
- DE583055C DE583055C DEI43463D DEI0043463D DE583055C DE 583055 C DE583055 C DE 583055C DE I43463 D DEI43463 D DE I43463D DE I0043463 D DEI0043463 D DE I0043463D DE 583055 C DE583055 C DE 583055C
- Authority
- DE
- Germany
- Prior art keywords
- bis
- sulfides
- halooxyaryl
- preparation
- 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.)
- Expired
Links
- 238000000034 method Methods 0.000 title claims description 3
- 238000002360 preparation method Methods 0.000 title claims description 3
- 150000003568 thioethers Chemical class 0.000 title claims 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 10
- PXJJSXABGXMUSU-UHFFFAOYSA-N disulfur dichloride Chemical compound ClSSCl PXJJSXABGXMUSU-UHFFFAOYSA-N 0.000 claims description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- -1 Sulfur chlorides Chemical class 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 150000004763 sulfides Chemical class 0.000 description 3
- FAXWFCTVSHEODL-UHFFFAOYSA-N 2,4-dibromophenol Chemical compound OC1=CC=C(Br)C=C1Br FAXWFCTVSHEODL-UHFFFAOYSA-N 0.000 description 2
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- FWMUJAIKEJWSSY-UHFFFAOYSA-N sulfur dichloride Chemical class ClSCl FWMUJAIKEJWSSY-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- HSQFVBWFPBKHEB-UHFFFAOYSA-N 2,3,4-trichlorophenol Chemical compound OC1=CC=C(Cl)C(Cl)=C1Cl HSQFVBWFPBKHEB-UHFFFAOYSA-N 0.000 description 1
- HOLHYSJJBXSLMV-UHFFFAOYSA-N 2,6-dichlorophenol Chemical compound OC1=C(Cl)C=CC=C1Cl HOLHYSJJBXSLMV-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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)
- Catalysts (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Description
Verfahren zur Darstellung von Bis-(halogenoxyaryl)-sulfiden Es ist bekannt, Bis-(halogenoxyaryl)-sulfide durch Kondensation von p-Monohalogenphenolen mit Schwefelchloriden herzustellen. Beim Einwirken von Schwefelchlorid auf Trichlorphenol entstehen jedoch nur harzartige Produkte. Ebenso lassen sich Dihalogenphenole mit .Schwefelchloriden nicht ohne weiteres zu Bis-(halogenoxyaryl)-sulfiden kondensieren.Process for the preparation of bis (halooxyaryl) sulfides It is known bis (halogenoxyaryl) sulfides by condensation of p-monohalophenols with sulfur chlorides. When sulfur chloride acts on trichlorophenol however, only resin-like products are created. Dihalophenols can also be used .Sulfur chlorides do not readily condense to bis (halooxyaryl) sulfides.
Es wurde nun gefunden, daß man die beim Einwirken von Schwefelchloriden auf Di-oder Trihalogenphenole bestehenden Schwierigkeiten überwinden kann, wenn man die. Kondensation in Gegenwart von Aluminiumchlorid durchführt. Beispiel i 82 g 2, 4-Dichlorphenol werden in 250 ccm Schwefelkohlenstoff oder Tetrachlorkohlenstoff gelöst, 5o g fein pulverisiertes Aluminiumchlorid eingetragen und 22 g Schwefelchlorid eingetropft. Es entwickelt sich reichlich Chlorwasserstoff. Nach etwa 12stündigem Stehen zersetzt man mit Eis, gibt noch konzentrierte Salzsäure zu und treibt mit Wasserdampf das Lösungsmittel und etwas unverändertes Chlorphenol ab. Der Rückstand wird abgesaugt und mit Wasser ausgewaschen. Das neue Bis-(dichloroxyphenyl)-sulfid kristallisiert aus Toluol oder verdünntem Alkohol in farblosen Nadeln vom F. z88°.It has now been found that you can overcome the existing difficulties in the action of sulfur chlorides on di- or trihalophenols if you use the. Carries out condensation in the presence of aluminum chloride. Example i 82 g of 2,4-dichlorophenol are dissolved in 250 cc of carbon disulfide or carbon tetrachloride, 50 g of finely powdered aluminum chloride are added and 22 g of sulfur chloride are added dropwise. Plenty of hydrogen chloride develops. After standing for about 12 hours, it is decomposed with ice, concentrated hydrochloric acid is added and the solvent and some unchanged chlorophenol are driven off with steam. The residue is filtered off with suction and washed out with water. The new bis (dichloroxyphenyl) sulfide crystallizes from toluene or dilute alcohol in colorless needles with a temperature of z88 °.
In entsprechender Weise entsteht aus 2, 5-Dichlorphenol ein Bis-(dichloroxyphenyl)-sulfid vom F. t77°, aus 2, 6-Dichlorphenol vom F. i4o° und aus 2, 4, 6-Trichlorphenot,vom F. 285°. Beispiel e 126 g 2, 4-Dibromphenol werden in 6oo ccm Schwefelkohlenstoff gelöst und 5o g fein gepulvertes Aluminiumchlorid eingetragen. In die entstandene klare Lösung werden unter Eiskühlung und Rühren langsam 22 g Schwefelchlorid eingetropft, und es wird, wie in Beispiel i angegeben, aufgearbeitet.In a corresponding manner, 5-dichlorophenol formed from 2, a bis (dichloroxyphenyl) sulfide, melting at t77 °, from 2, 6-dichlorophenol, melting i4o ° and 2, 4, 6-Trichlorphenot, mp 285 ° . Example e 1 26 g of 2,4-dibromophenol are dissolved in 600 cc of carbon disulfide and 50 g of finely powdered aluminum chloride are added. 22 g of sulfur chloride are slowly added dropwise to the resulting clear solution, while cooling with ice and stirring, and it is worked up as indicated in Example i.
Das neue Bis-(dibromoxyphenyl)-sulfid kristallisiert aus Toluol in farblosen glänzenden Nadeln vom F. 2i2°. Beispici3 82 g 2, 4-Dichlorphenol werden in 25o ccm Schwefelkohlenstoff gelöst, dann bei 2o bis 22° ioo g fein gepulvertes Aluminiumchlorid eingetragen und 35 g Schwefelchlorür eingetropft. Nach 8stündigem Rühren gibt man auf Eis und bläst das Lösungsmittel ab. Der Rückstand wird durch Lösen in verdünnter Natronlauge und Fällen mit Salzsäure gereinigt.The new bis (dibromoxyphenyl) sulfide crystallizes from toluene in colorless shiny needles of F. 2i2 °. Beispici3 82 g of 2,4-dichlorophenol Dissolved in 25o ccm carbon disulfide, then at 20 to 22 ° 100 g finely powdered Entered aluminum chloride and added dropwise 35 g of sulfuric chloride. After 8 hours Stirring is added to ice and the solvent is blown off. Of the Residue is cleaned by dissolving in dilute sodium hydroxide solution and precipitating with hydrochloric acid.
Aus Toluol oder Eisessig umkristallisiert schmilzt das Kondensationsprodukt bei z85°. Der Mischschmelzpunkt mit dem nach Beispiel i erhaltenen zeigt keine Depression.Recrystallized from toluene or glacial acetic acid, the condensation product melts at z85 °. The mixed melting point with that obtained according to Example i shows no depression.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEI43463D DE583055C (en) | 1932-01-13 | 1932-01-13 | Process for the preparation of bis (halooxyaryl) sulfides |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEI43463D DE583055C (en) | 1932-01-13 | 1932-01-13 | Process for the preparation of bis (halooxyaryl) sulfides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE583055C true DE583055C (en) | 1933-08-28 |
Family
ID=7191039
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEI43463D Expired DE583055C (en) | 1932-01-13 | 1932-01-13 | Process for the preparation of bis (halooxyaryl) sulfides |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE583055C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1024089B (en) * | 1955-05-18 | 1958-02-13 | Bayer Ag | Process for the production of sulfides of multiply halogenated phenols |
| US2849494A (en) * | 1956-05-17 | 1958-08-26 | Monsanto Chemicals | 2, 2'-thiobis |
| US2868841A (en) * | 1956-05-31 | 1959-01-13 | Monsanto Chemicals | Purifying 2, 2'-thiobis(polyhalophenols) |
| US2937208A (en) * | 1955-05-18 | 1960-05-17 | Bayer Ag | Metasulfides of polyhalogenated phenols |
-
1932
- 1932-01-13 DE DEI43463D patent/DE583055C/en not_active Expired
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1024089B (en) * | 1955-05-18 | 1958-02-13 | Bayer Ag | Process for the production of sulfides of multiply halogenated phenols |
| US2937208A (en) * | 1955-05-18 | 1960-05-17 | Bayer Ag | Metasulfides of polyhalogenated phenols |
| US2849494A (en) * | 1956-05-17 | 1958-08-26 | Monsanto Chemicals | 2, 2'-thiobis |
| US2868841A (en) * | 1956-05-31 | 1959-01-13 | Monsanto Chemicals | Purifying 2, 2'-thiobis(polyhalophenols) |
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