DE469911C - Process for the preparation of thioethers of the anthraquinone series - Google Patents
Process for the preparation of thioethers of the anthraquinone seriesInfo
- Publication number
- DE469911C DE469911C DEI30204D DEI0030204D DE469911C DE 469911 C DE469911 C DE 469911C DE I30204 D DEI30204 D DE I30204D DE I0030204 D DEI0030204 D DE I0030204D DE 469911 C DE469911 C DE 469911C
- Authority
- DE
- Germany
- Prior art keywords
- thioethers
- anthraquinone series
- preparation
- anthraquinone
- parts
- 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
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 title claims description 11
- 150000004056 anthraquinones Chemical class 0.000 title claims description 10
- 238000000034 method Methods 0.000 title claims description 7
- 150000003568 thioethers Chemical class 0.000 title claims description 6
- 238000002360 preparation method Methods 0.000 title claims description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 3
- 150000008049 diazo compounds Chemical class 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims 1
- 238000012986 modification Methods 0.000 claims 1
- 239000000243 solution Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- QIULLHZMZMGGFH-UHFFFAOYSA-N 2,5-dichlorobenzenethiol Chemical compound SC1=CC(Cl)=CC=C1Cl QIULLHZMZMGGFH-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- -1 aromatic diazo compound Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- KHUFHLFHOQVFGB-UHFFFAOYSA-N 1-aminoanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2N KHUFHLFHOQVFGB-UHFFFAOYSA-N 0.000 description 1
- YWYHGNUFMPSTTR-UHFFFAOYSA-N 1-methyl-4-(4-methylphenoxy)benzene Chemical compound C1=CC(C)=CC=C1OC1=CC=C(C)C=C1 YWYHGNUFMPSTTR-UHFFFAOYSA-N 0.000 description 1
- OECBNLVRTLHUBL-UHFFFAOYSA-N 4-diazonio-10-oxo-3h-anthracen-9-olate Chemical class O=C1C2=CC=CC=C2C(=O)C2=C1C(=[N+]=[N-])CC=C2 OECBNLVRTLHUBL-UHFFFAOYSA-N 0.000 description 1
- WLHCBQAPPJAULW-UHFFFAOYSA-N 4-methylbenzenethiol Chemical compound CC1=CC=C(S)C=C1 WLHCBQAPPJAULW-UHFFFAOYSA-N 0.000 description 1
- RXQNKKRGJJRMKD-UHFFFAOYSA-N 5-bromo-2-methylaniline Chemical compound CC1=CC=C(Br)C=C1N RXQNKKRGJJRMKD-UHFFFAOYSA-N 0.000 description 1
- 238000005684 Liebig rearrangement reaction Methods 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/56—Mercapto-anthraquinones
- C09B1/58—Mercapto-anthraquinones with mercapto groups substituted by aliphatic, cycloaliphatic, araliphatic or aryl radicals
- C09B1/585—Mercapto-anthraquinones with mercapto groups substituted by aliphatic, cycloaliphatic, araliphatic or aryl radicals substituted by aryl radicals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Darstellung von Thioäthern der Antbrachinonreihe Zusatz zum Patent 46o o87 Durch das Hauptpatent 46o o87 ist ein Verfahren zur Darstellung von Thioäthern der Anthrachinonreihe geschützt, nach dem beliebige aromatische Diazoverbindungen auf Anthrachinonmercaptane oder deren Derivate und Substitutionsprodukte zur Einwirkung gebracht werden.Process for the preparation of thioethers of the antbrachinone series addition to the patent 46o o87 by the main patent 46o o87 is a method for the representation protected by thioethers of the anthraquinone series, according to which any aromatic diazo compound on anthraquinone mercaptans or their derivatives and substitution products to act to be brought.
Es wurde nun gefunden ', dal.# man ebenfalls Thioäther der Anthrachinonreihe erhält, wenn man auf Diazoverbindungen der Anthrachinonreihe beliebige, jedoch nicht der Anthrachinonreihe angehörige Mercaptane einwirken läßt. Die Bildung der Thioäthe-r verläuft b meist mit vorzüglichen Ausbeuten. Man kann die Diazoanthrachinone bei dem vorliegenden Verfahren unmittelbar in der stark mineralsauren Lösung anwenden, die man bei ihrer üblichen Darstellung aus Aminoanthrachinon erhält.It has now been found that thioethers of the anthraquinone series are likewise obtained if any mercaptans, but not belonging to the anthraquinone series, are allowed to act on diazo compounds of the anthraquinone series. The formation of the Thioäthe-r b extends mostly with excellent yields. In the present process, the diazoanthraquinones can be used directly in the strongly mineral acidic solution which is obtained from aminoanthraquinone in their usual preparation.
Beispiel i Man bereitet aus 25 Teilen i-Nitro-2-methylanthrachinon nach dem Verfahren der Patentschrift 3604--2 der Klassei2p (Beispieli) eine schwefelsaure Lösung von Antrachinon-i.2-isoxazol und führt diese Lösung nach dem Verfahren des Patents 456 859 (Beispiel Ü in eine solche von r-Diazoanthrachinon-2-#carbonsäure über. In diese ebenfalls no,ci.i stark schwefelsaure Lösung rührt man bei gewöhnlicher Temperatur eine Lösung von 18 Teilen 2,5-Dichlor-i-mercaptobenzol in 4oo Teilen Wasser und 3o Teilen Natronlauge von 3o' B6 ein. Man erhält dabei unter Entweichen von Stickstoff einen gelben Niederschlag der Anthrachinon-i-thio-2', 51-dichlorphenyl-2-carbonsäure. Man kocht auf, saugt ab, wäscht mit Wasser und trocknet. Um die Säure gewünschtenfalls völlig rein zu erhalten, kocht man das Rohprodukt mit Wasser und Magnesia auf, filtriert von unlöslichen Veru#nreinigungen ab und fällt die gelbe Lösung des Magnesiumsalzes mit Salzsäure. Auch das gut kristallisierende Natriumsalz ist zur Reinigung der Säure geeignet.Example i A sulfuric acid solution of anthraquinone-i.2-isoxazole is prepared from 25 parts of i-nitro-2-methylanthraquinone by the method of patent specification 3604-2 of the classei2p (example i) and this solution is carried out according to the method of patent 456 859 (Example U into one of r-diazoanthraquinone-2- # carboxylic acid. A solution of 18 parts of 2,5-dichloro-i-mercaptobenzene in 400 parts is stirred into this likewise no, ci.i strongly sulfuric acid solution Water and 30 parts of sodium hydroxide solution of 30 ' B6 in . A yellow precipitate of anthraquinone-i-thio-2', 51-dichlorophenyl-2-carboxylic acid is obtained with the escape of nitrogen To keep the acid completely pure, if desired, the crude product is boiled with water and magnesia, insoluble impurities are filtered off and the yellow solution of the magnesium salt is precipitated with hydrochloric acid suitable for acid reduction.
Wendet man statt des 2,5-Dichlor-i-mercaptobenzols andere Mercaptane an, z.B. Thioglykolsäure, so erhält man die entsprechenden Thioäther, z. B. die Anthrachinoni-thioglykolsäure-2-carbonsäure. Diese bildet ein gelbbraunes Pulver-, das bei 315 bis 316' unter Zersetzung schmilzt und sich in Schwefelsäure mit violettroter und in Natronlauge mit braungelber Farbe unter gelber Fluoreszenz löst. Beispiel 2 Eine Lösung von 11,9 Teilen i, 5-Diaminoanthrachinon in i2o Teilen Schwefelsäure von 66"B6 wird mit 40 Teilen Nitrosylschw"efelsäure mit einem Gehalt von etwa i3% salpetriger Säure vermischt, worauf man die Mschung auf Eis gießt. Das abgeschiedene Diazosulfat wird abgesaugt und mit etwa 3oo Teilen Wasser angeriffirt. In diese Aufschlämmung rührt man eine Lösung von 13 Teilen 4-Methyl-i-rnercaptobenzol (p-Thiokresol) in 5o Teilen, Natronlauge von 4o'B6 und 5oo Teilen Wasser ein. Nach einiger Zeit kocht man auf, saugt ab, wäscht mit Wasser bis zur neutralen Reaktion und trocknet. Das so erhaltene Produkt ist der in Liebigs Annalen der Chemie, Band 393, Seite 184 beschriebene Di-p-tolyläther des Anthrachinon- i, 5-dimercaptans.If, instead of 2,5-dichloro-i-mercaptobenzene, other mercaptans, for example thioglycolic acid, are used, the corresponding thioethers are obtained, e.g. B. the anthraquinone thioglycolic acid-2-carboxylic acid. This forms a yellow-brown powder, which melts at 315 to 316 'with decomposition and dissolves in sulfuric acid with violet-red color and in sodium hydroxide solution with brown-yellow color under yellow fluorescence. EXAMPLE 2 A solution of 11.9 parts of i, 5-diaminoanthraquinone in 120 parts of sulfuric acid of 66 "B6 is mixed with 40 parts of nitrosylsulfuric acid containing about 13% nitrous acid, whereupon the mixture is poured onto ice. The separated diazosulphate is filtered off with suction and treated with about 300 parts of water. A solution of 13 parts of 4-methyl-i-rnercaptobenzene (p-thiocresol) in 50 parts, sodium hydroxide solution of 40'B6 and 500 parts of water is stirred into this suspension. After a while, it is boiled, filtered off with suction, washed with water until it is neutral and dried. The product thus obtained is the di-p-tolyl ether of anthraquinone 1,5-dimercaptans described in Liebigs Annalen der Chemie, Volume 393, page 184.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEI30204D DE469911C (en) | 1927-02-03 | 1927-02-03 | Process for the preparation of thioethers of the anthraquinone series |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEI30204D DE469911C (en) | 1927-02-03 | 1927-02-03 | Process for the preparation of thioethers of the anthraquinone series |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE469911C true DE469911C (en) | 1928-12-29 |
Family
ID=7187555
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEI30204D Expired DE469911C (en) | 1927-02-03 | 1927-02-03 | Process for the preparation of thioethers of the anthraquinone series |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE469911C (en) |
-
1927
- 1927-02-03 DE DEI30204D patent/DE469911C/en not_active Expired
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