CH172068A - Process for the preparation of the lactam of 1-aminoanthraquinone-2,5-bisthioglycolic acid. - Google Patents
Process for the preparation of the lactam of 1-aminoanthraquinone-2,5-bisthioglycolic acid.Info
- Publication number
- CH172068A CH172068A CH172068DA CH172068A CH 172068 A CH172068 A CH 172068A CH 172068D A CH172068D A CH 172068DA CH 172068 A CH172068 A CH 172068A
- Authority
- CH
- Switzerland
- Prior art keywords
- acid
- lactam
- aminoanthraquinone
- preparation
- bisthioglycolic
- Prior art date
Links
- 150000003951 lactams Chemical class 0.000 title claims description 6
- 238000000034 method Methods 0.000 title claims description 4
- -1 1-aminoanthraquinone-2,5-bisthioglycolic acid Chemical compound 0.000 title claims description 3
- 238000002360 preparation method Methods 0.000 title claims description 3
- 239000002253 acid Substances 0.000 claims description 5
- BEQOZTJJZZOVBR-UHFFFAOYSA-N 5-amino-9,10-dioxoanthracene-1-sulfonic acid Chemical compound O=C1C=2C(N)=CC=CC=2C(=O)C2=C1C=CC=C2S(O)(=O)=O BEQOZTJJZZOVBR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052977 alkali metal sulfide Inorganic materials 0.000 claims description 2
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims description 2
- 229940106681 chloroacetic acid Drugs 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 235000005811 Viola adunca Nutrition 0.000 description 2
- 240000009038 Viola odorata Species 0.000 description 2
- 235000013487 Viola odorata Nutrition 0.000 description 2
- 235000002254 Viola papilionacea Nutrition 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 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
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 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
- C09B5/00—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings
- C09B5/24—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings the heterocyclic rings being only condensed with an anthraquinone nucleus in 1-2 or 2-3 position
- C09B5/44—Azines of the anthracene series
- C09B5/60—Thiazines; Oxazines
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung des Laetams von 1-Aminoanthrachinon-2. 5-bisthloglycolsäure. Es wurde gefunden, dass wenn 1-Amino- anthrachinon-5-sulfosäure mit Alkalimetall- sulfid erhitzt wird, die Sulfogruppe durch -SH ersetzt wird und eine zweite -SH Gruppe in ortho Stellung zur Aminogruppe eintritt.
Das so erhaltene 1-Amino-2.5-di- rnercaptoarithrachinon, welches als Alkali metall ausgesalzen werden kann, wird gemäss dem Verfahren der Erfindung mit wenigstens zwei Mol Chloressigsäure zur 1-Aminoanthra- chinorr-2. 5-bisthioglycolsäure kondensiert und diese dann durch Behandlung mit Säure in das Lactam der Formel
EMI0001.0021
überführt.
Beispiel: 100 Teile Natrium-l-arninoanthrachinon- 5-sulfonat werden unter Umrühren 2000 Teilen Natriumsulfidkristallen bei<B>90-1000</B> C zu gesetzt und das Gemisch wird drei Stunden auf 140 C erhitzt, wobei Wasserdampf ent weichen gelassen wird. Ein Rückflusskonden- sator wird bei 140 C angeschlossen und die Erhitzung bei 140 C wird 5 Stunden fort gesetzt.
Die Schmelze wird etwas abkühlen ge lassen und wird dann in 4000 Teilen Wasser aufgelöst. Der so erhaltenen blauvioletten Lösung werden 400 Teile Salz zugesetzt, um die Mercaptane als Natriumsalz zu fällen. Das Natriumsalz wird abfiltriert, mit 15 pro zentigem Salzwasser reingewaschen und zweckmässig als Paste aufbewahrt.
1 Mol des so erhaltenen Natriumsalzes des Mercaptans, welches sich in warmem Wasser zu einer blauvioletten Lösung auflöst, wird mit wenigstens 2 Mol chloressigsaurem Natrium auf 90 C erwärmt. Hierbei wird eine hellrote Lösung des Natriumsalzes aus 1-Aminoanthrachinon - 2 . 5 - bisthioglycolsäur e erhalten.
Durch Zusatz eines Überschusses von Chlorwasserstoffsäure zu dieser Lösung und Kochen während 15 Minuten wird eine Orangesuspension des Lactam von 1-Amino- anthrachinon-2.5-bisthioglycolsäure erhalten.
Diese Verbindung kristallisiert in orange farbigen Tönen aus Nitrobenzol. Sie löst sich in Alkalien, um orangefarbige oder rote Lö sungen und in konzentrierter Schwefelsäure eine blaurote Lösung zu ergeben, deren Fär bung durch Zusatz von Formaldehyd oliv braun wird.
Das Produkt ist neu und wird als ein Farbstoffzwischenprodukt verwendet.
Process for the preparation of the laetam of 1-aminoanthraquinone-2. 5-bisthloglycolic acid. It has been found that when 1-amino-anthraquinone-5-sulfonic acid is heated with alkali metal sulfide, the sulfo group is replaced by —SH and a second —SH group occurs in the ortho position to the amino group.
The 1-amino-2,5-di- rnercaptoarithraquinone thus obtained, which can be salted out as an alkali metal, is converted into 1-aminoanthraquinorr-2 according to the process of the invention with at least two moles of chloroacetic acid. 5-bisthioglycolic acid is condensed and this is then converted into the lactam of the formula by treatment with acid
EMI0001.0021
convicted.
Example: 100 parts of sodium 1-arninoanthraquinone-5-sulfonate are added with stirring to 2000 parts of sodium sulfide crystals at 90-1000 C and the mixture is heated to 140 C for three hours, with steam being allowed to escape . A reflux condenser is connected at 140 ° C. and the heating at 140 ° C. is continued for 5 hours.
The melt is allowed to cool slightly and is then dissolved in 4000 parts of water. 400 parts of salt are added to the blue-violet solution thus obtained in order to precipitate the mercaptans as the sodium salt. The sodium salt is filtered off, washed clean with 15 percent salt water and conveniently stored as a paste.
1 mol of the sodium salt of mercaptan thus obtained, which dissolves in warm water to form a blue-violet solution, is heated to 90 ° C. with at least 2 mol of sodium chloroacetate. A light red solution of the sodium salt of 1-aminoanthraquinone - 2. 5 - bisthioglycolic acid obtained.
By adding an excess of hydrochloric acid to this solution and boiling for 15 minutes, an orange suspension of the lactam of 1-aminoanthraquinone-2,5-bisthioglycolic acid is obtained.
This compound crystallizes from nitrobenzene in orange tones. It dissolves in alkalis to give orange or red solutions and in concentrated sulfuric acid a blue-red solution, the color of which turns olive-brown when formaldehyde is added.
The product is new and is used as a dye intermediate.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH172068T | 1933-07-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH172068A true CH172068A (en) | 1934-09-30 |
Family
ID=4423586
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH172068D CH172068A (en) | 1933-07-12 | 1933-07-05 | Process for the preparation of the lactam of 1-aminoanthraquinone-2,5-bisthioglycolic acid. |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH172068A (en) |
-
1933
- 1933-07-05 CH CH172068D patent/CH172068A/en unknown
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