DE228868C - - Google Patents
Info
- Publication number
- DE228868C DE228868C DENDAT228868D DE228868DA DE228868C DE 228868 C DE228868 C DE 228868C DE NDAT228868 D DENDAT228868 D DE NDAT228868D DE 228868D A DE228868D A DE 228868DA DE 228868 C DE228868 C DE 228868C
- Authority
- DE
- Germany
- Prior art keywords
- disulfide
- nitrothiophenols
- alkali
- sodium
- alkali metal
- 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
- JKIFPWHZEZQCQA-UHFFFAOYSA-N 2-nitrobenzenethiol Chemical class [O-][N+](=O)C1=CC=CC=C1S JKIFPWHZEZQCQA-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 3
- 150000002019 disulfides Chemical class 0.000 claims description 3
- 230000000875 corresponding Effects 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims 2
- -1 alkali metal disulfide Chemical class 0.000 claims 1
- 229910052977 alkali metal sulfide Inorganic materials 0.000 claims 1
- 150000001340 alkali metals Chemical class 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000011734 sodium Substances 0.000 description 7
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N Thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 2
- 239000003638 reducing agent Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- WYFNYCOJHYLRHJ-UHFFFAOYSA-N 4-nitrobenzenethiol;sodium Chemical compound [Na].[O-][N+](=O)C1=CC=C(S)C=C1 WYFNYCOJHYLRHJ-UHFFFAOYSA-N 0.000 description 1
- 229960000583 Acetic Acid Drugs 0.000 description 1
- GUUVPOWQJOLRAS-UHFFFAOYSA-N Diphenyl disulfide Chemical compound C=1C=CC=CC=1SSC1=CC=CC=C1 GUUVPOWQJOLRAS-UHFFFAOYSA-N 0.000 description 1
- 230000036826 Excretion Effects 0.000 description 1
- FFRBMBIXVSCUFS-UHFFFAOYSA-N Martius yellow Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- SRRKNRDXURUMPP-UHFFFAOYSA-N Sodium disulfide Chemical compound [Na+].[Na+].[S-][S-] SRRKNRDXURUMPP-UHFFFAOYSA-N 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-M Sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N Sodium sulfide Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- QLESGDDAJILMLV-UHFFFAOYSA-N [O-][N+](=O)SS[N+]([O-])=O Chemical class [O-][N+](=O)SS[N+]([O-])=O QLESGDDAJILMLV-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000001476 alcoholic Effects 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000029142 excretion Effects 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
Description
KAISERLICHESIMPERIAL
PATENTAMT.PATENT OFFICE.
PATENTSCHRIFTPATENT LETTERING
- .Μ 228868 KLASSE Uq. GRUPPE- .Μ 228868 CLASS Uq. GROUP
Verfahren zur Darstellung von Nitrothiophenolen. Patentiert im Deutschen Reiche vom 26. November 1908 ab. Process for the preparation of nitrothiophenols. Patented in the German Empire on November 26, 1908.
Wie bekannt, erhält man aus Diphenyldisulfid (»Phenylsulfid«: Beilstein, 3. Aufl., Bd. II, S. 815) und seinen Derivaten durch Einwirkung reduzierender Mittel Phenylsulfhydrate. Durch die Arbeit Leukarts (Journ. f. p. Ch., N. F. 41 [1890], S. 199/200) ist ferner bekannt, daß sich Dinitrodiarylsulfide durch gelind wirkende Reduktionsmittel zu Nitrothiophenolen reduzieren lassen. Doch haften den bis jetzt aus der Literatur bekannt gewordenen diesbezüglichen Reduktionsmethoden Mängel an, die ihre technische Verwertung gänzlich ausschließen. So reduziert Leukart selbst das ρ · ρ' - Dinitrodiphenyldisulfid mit Zinkstaub und Eisessig. Das Verfahren ist zeitraubend, kostspielig und namentlich dann umständlich, wenn die Merkaptane, wie bei den meisten ihrer Umsetzungen, nicht als solche, sondern in Form ihrer AlkalilösungenAs is known, from diphenyl disulfide (»phenyl sulfide«: Beilstein, 3rd ed., Vol. II, p. 815) and its derivatives by the action of reducing agents phenyl sulfhydrates. Through the work of Leukarts (Journ. F. P. Ch., N. F. 41 [1890], p. 199/200) is also known that dinitrodiaryl sulfides are converted to nitrothiophenols by mild reducing agents let reduce. But the ones that have become known from literature up to now are stuck relevant reduction methods to deficiencies that their technical recovery completely exclude. Leukart himself reduces the ρ · ρ '- dinitrodiphenyl disulfide with Zinc dust and glacial acetic acid. The process is time consuming, costly and especially then awkward if the mercaptans, as in most of their conversions, are not considered such, but in the form of their alkali solutions
ao verwendet werden sollen. Diesen Übelstand könnte das Verfahren von Fromm (Ber. 41 [1908], S. 2269) beheben, wonach die Reduktion mit alkoholischem Ätzkali bewirkt werden soll, wenn nicht in diesem Falle die Ausbeutenao should be used. The Fromm method (Ber. 41 [1908], p. 2269), according to which the reduction can be effected with alcoholic caustic potash should, if not in this case the yields
an Nitrothiophenol dadurch litten, daß als Nebenprodukt die alkaliunlösliche Verbindung C24 H20 Ns S2 O1 entstünde.suffered from nitrothiophenol in that the alkali-insoluble compound C 24 H 20 N s S 2 O 1 would arise as a by-product.
Es wurde nun ein Verfahren gefunden, welches ermöglicht, die Dinitrodisulfide zu Nitrothiophenolen zu reduzieren, wobei sehr gute Ausbeuten an Nitrothiophenolen, und zwar in Form ihrer Alkalisalze erhalten werden, welche bei vielen technisch verwertbaren Umsetzungen in gelöstem Zustande unmittelbar ohne Abscheidung weiter verarbeitet werden können. Dieses Verfahren besteht darin, daß man Dinitrodiaryldisulfide in Gegenwart von freiem Alkali mit etwa V2 Äquivalent Natriumsulfhydrat bzw. mit den folgenden Gleichungen entsprechenden Mengen Natriumsulfid oder Natriumdisulfid behandelt:A process has now been found which enables the dinitrodisulfides to be reduced to nitrothiophenols, with very good yields of nitrothiophenols being obtained in the form of their alkali salts which, in many industrially usable reactions, can be processed further in the dissolved state without separation. This process consists in treating dinitrodiaryl disulfide in the presence of free alkali with about V 2 equivalent of sodium sulfhydrate or with the amounts of sodium sulfide or sodium disulfide corresponding to the following equations:
NaSH + NaOH - >- Na2S + H2O NaSH + NaOH - > - Na 2 S + H 2 O
,'. 2 NaSH -H2 = Na2S2. , '. 2 NaSH -H 2 = Na 2 S 2 .
Die Umsetzung des Dinitrpphenyldisulfids erfolgt, von der Salzbildung des Thiophenols abgesehen, entsprechend den Gleichungen:The conversion of the Dinitrpphenyldisulfids takes place, from the salt formation of the thiophenol apart from, according to the equations:
NO,NO,
NO,NO,
,NO9 , NO 9
C6H4, NO0 C 6 H 4 , NO 0
-f 3H2O + 2NaSH = 8C6#4< + Na2S2O3, -f 3H 2 O + 2NaSH = 8C 6 # 4 <+ Na 2 S 2 O 3 ,
,NO9 , NO 9
+ 5 H2O + 2 Na2 S = 8 Ce#4<+ 5 H 2 O + 2 Na 2 S = 8 C e # 4 <
"-SH + Na2S2O3 + 2 NaOH, "-SH + Na 2 S 2 O 3 + 2 NaOH,
,NO,, NO,
NO9 NO 9
ς r ν ς r ν
+ 5 H2O + .ZVa2S3 = 6C6F4< + 5 H 2 O + .ZVa 2 S 3 = 6C 6 F 4 <
/JVO,/ JVO,
+ Na2S2O9. + Na 2 S 2 O 9 .
Wenn an Stelle des Disulfide Polysulfide verwendet werden, so scheidet sich Schwefel ab; es ist also zwecklos, mehr Schwefel hinzuzufügen, als dem Disulfid entspricht.If polysulphides are used in place of the disulphide, sulfur separates away; it is therefore pointless to add more sulfur than corresponds to the disulfide.
30 Teile fein gepulvertes ρ · p'-Dinitrophenyldisulfid (1 Äquivalent) erwärmt man unter kräftigem Umrühren auf dem Wasserbade mit etwa 80 Teilen Alkohol und einer Mischung von 8 bis 10 Teilen Ätznatron (etwas mehr wie 2 Äquivalente) und einer Menge Natriumsulfhydrat (1Z2 Äquivalent), welche man technisch herstellen kann durch Sättigen von 2,6 bis 3 Teilen Ätznatron mit Schwefelwasserstoff. 30 parts of finely powdered ρ p'-dinitrophenyl disulphide (1 equivalent) are heated with vigorous stirring on the water bath with about 80 parts of alcohol and a mixture of 8 to 10 parts of caustic soda (a little more than 2 equivalents) and a quantity of sodium sulphydrate ( 1 point 2 equivalent), which can be produced industrially by saturating 2.6 to 3 parts of caustic soda with hydrogen sulfide.
Nach einiger Zeit ist alles gelöst, und die Reaktionsmasse wird fest durch Ausscheidung von p-Nitrothiophenolnatrium, das goldgelbe, glänzende Blättchen bildet. Durch Säuren wird aus ihm das ρ - Nitrothiophenol abgeschieden. After a while everything is dissolved and the reaction mass becomes solid by excretion of p-nitrothiophenol sodium, which forms golden yellow, shiny flakes. Acids the ρ-nitrothiophenol is deposited from it.
In analoger Weise wird aus ο · o-Dinitrodiphenyldisulüd das o-Nitrothiophenol gebildet.In an analogous manner, the o-nitrothiophenol is formed from o-dinitrodiphenyl disulfide.
Claims (1)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE228868C true DE228868C (en) |
Family
ID=489229
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT228868D Active DE228868C (en) |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE228868C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2466963A (en) * | 1945-06-16 | 1949-04-12 | Thiokol Corp | Polysulfide polymer |
| US2479542A (en) * | 1944-08-26 | 1949-08-16 | Thiokol Corp | Preparation of mercaptans |
-
0
- DE DENDAT228868D patent/DE228868C/de active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2479542A (en) * | 1944-08-26 | 1949-08-16 | Thiokol Corp | Preparation of mercaptans |
| US2466963A (en) * | 1945-06-16 | 1949-04-12 | Thiokol Corp | Polysulfide polymer |
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