DE2353532C2 - Process for the preparation of 1-amino-2-chloro-4-hydroxy-anthraquinone - Google Patents
Process for the preparation of 1-amino-2-chloro-4-hydroxy-anthraquinoneInfo
- Publication number
- DE2353532C2 DE2353532C2 DE19732353532 DE2353532A DE2353532C2 DE 2353532 C2 DE2353532 C2 DE 2353532C2 DE 19732353532 DE19732353532 DE 19732353532 DE 2353532 A DE2353532 A DE 2353532A DE 2353532 C2 DE2353532 C2 DE 2353532C2
- Authority
- DE
- Germany
- Prior art keywords
- amino
- anthraquinone
- chloro
- hydroxy
- preparation
- 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 6
- 238000002360 preparation method Methods 0.000 title claims description 3
- MFAVJLWGAQYYNX-UHFFFAOYSA-N 1-amino-2-chloro-4-hydroxyanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(O)=CC(Cl)=C2N MFAVJLWGAQYYNX-UHFFFAOYSA-N 0.000 title claims 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 15
- 239000004327 boric acid Substances 0.000 claims description 7
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 10
- 239000003960 organic solvent Substances 0.000 description 3
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- -1 boric acid ester Chemical class 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- ASGMFNBUXDJWJJ-JLCFBVMHSA-N (1R,3R)-3-[[3-bromo-1-[4-(5-methyl-1,3,4-thiadiazol-2-yl)phenyl]pyrazolo[3,4-d]pyrimidin-6-yl]amino]-N,1-dimethylcyclopentane-1-carboxamide Chemical compound BrC1=NN(C2=NC(=NC=C21)N[C@H]1C[C@@](CC1)(C(=O)NC)C)C1=CC=C(C=C1)C=1SC(=NN=1)C ASGMFNBUXDJWJJ-JLCFBVMHSA-N 0.000 description 1
- BTLXPCBPYBNQNR-UHFFFAOYSA-N 1-Hydroxyanthraquinone Natural products O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2O BTLXPCBPYBNQNR-UHFFFAOYSA-N 0.000 description 1
- 208000031872 Body Remains Diseases 0.000 description 1
- 229940127007 Compound 39 Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000001044 red dye Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000002351 wastewater 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
- C09B1/50—Amino-hydroxy-anthraquinones; Ethers and esters thereof
- C09B1/503—Amino-hydroxy-anthraquinones; Ethers and esters thereof unsubstituted amino-hydroxy anthraquinone
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Gegenstand der Erfindung ist ein Verfahren zur Herstellung von l-Amino^-chlor-^-hydroxy-anthrachinon(l). The invention is a method for Manufacture of l-amino ^ -chlor- ^ - hydroxy-anthraquinone (l).
Das Verfahren ist dadurch gekennzeichnet, daß man l-N-Sulfinyl-amino-Z^-dichlor-anthrachinon (II) bei 60 bis 130° C mit einem Schwefelsäure/Borsäure-Gemisch behandeltThe method is characterized in that one l-N-sulfinyl-amino-Z ^ -dichloro-anthraquinone (II) at 60 up to 130 ° C with a sulfuric acid / boric acid mixture treated
Zweckmäßig setzt man zunächst konzentrierte Schwefelsäure zu und rührt zwischen 60 und 800C, gibt dann Oleum von 5 bis 20% und Borsäure zu und führt die Reaktion zwischen 110 und 1300C zu Ende.Expediently, concentrated sulfuric acid is first added and the mixture is stirred between 60 and 80 ° C., then oleum of 5 to 20% and boric acid are added and the reaction is brought to an end between 110 and 130 ° C.
Das Reaktionsgemisch wird in üblicher Weise aufgearbeitet, z.B. wird auf 50 bis 100°C abgekühlte Reaktionsmischung auf Wasser ausgetragen, zur Verseifung des Borsäureesters kurz aufgekocht und dann fest abgeschiedene Reaktionsprodukt durch Filtrieren isoliert. Der Filterrückstand wird mit warmem Wasser neuK-al gewaschen. Zur Reinigung kann man in 5%iger Sodalosung bei 80 bis 100" C I Stunde rühren, absaugen, neu.ral waschen und je nach dem Verwendungszweck gewünschtenfalls trocknen.The reaction mixture is worked up in the usual way, e.g. it is cooled to 50 to 100 ° C The reaction mixture is poured into water, briefly boiled to saponify the boric acid ester and then solid deposited reaction product isolated by filtration. The filter residue is washed with warm water neuK-al washed. For cleaning you can use 5% Stir the soda solution at 80 to 100 "C for 1 hour, suction off, Wash neu.ral and, depending on the intended use, dry if desired.
Der Vorzug dieser Arbeitsweise besteht dann, daß man die Verseifung der N-Sulfinylamino-Gruppe und den Austausch des 4ständigen Chloratoms gegen eine Hydroxygruppe in einer Stufe zusammenfassen kann.The advantage of this mode of operation is that one saponification of the N-sulfinylamino group and can summarize the exchange of the 4-position chlorine atom by a hydroxyl group in one step.
Die Herstellung von (II) ist aus der Literatur bekannt (Russ. Pat. 289 728 (0I.07.I9&8). Erf.: S. S. Tk;ichenko. Ya. B. Shteinberg: Zhurnal Organicheskoi Khimii 9 (1973). Nr. 4. S. 785 bis 78b).The preparation of (II) is known from the literature (Russ. Pat. 289 728 (0I.07.I9 & 8). Re: S. S. Tk; ichenko. Ya. B. Shteinberg: Zhurnal Organicheskoi Khimii 9 (1973). No. 4. pp. 785 to 78b).
Besonders vorteilhaft ist es. das Verfahren in der Weise durchzuführen, daß man l-Amino-anthrachinon mit Thionylchlorid in überschüssigem Thionylchlorid als Lösungsmittel oder einem inerten organischen Lösungsmittel in die N-Siilfinylverbindung überführt, anschließend durch Zugabe von Sulfurylchlorid chloriert, dann das überschüssige Thionylchlorid gegebenenfalls zusammen mit dem inerten organischen Lösungsmittel cntfein· und den Rückstand mit Schwefelsäure und Borsäure unter den genannten Bedingungen behandelt. Die Aufarbeitung erfolgt in der angegebenen Weise.It is particularly beneficial. carry out the process in such a way that one l-amino-anthraquinone with thionyl chloride in excess thionyl chloride as solvent or an inert organic solvent converted into the N-silfinyl compound, then chlorinated by adding sulfuryl chloride, then the excess thionyl chloride, if necessary, together with the inert organic solvent and the residue with sulfuric acid and Boric acid treated under the conditions mentioned. Working up is carried out in the manner indicated.
Als inerte organisches Lösungsmittel kommt bevorzugt C'hlorben/ol in FrageThe inert organic solvent is preferred C'hlorben / ol in question
Die Menge der Schwefelsaure kann in weiten Grenzen schwanken: um jedoch die Belastung des Abwassers mit verdünnter Schwefelsäure gering zu halten, ist es zweckmäßig, möglichst wenig zu verwenden. Dabei zeigt es sich, daß zur Verseifung bereits 12 bis 25 Mol HiSO4 pro Mol Ausgangsverbindung ausreichend sind. Aus der Literatur ist bekannt, daß man zur Oberführung des 1-Amino-Z4-dibrom-anthraehinons in das l-Amino-2-brom-4-hydroxy-anthrachinon pro MoI Ausgangsverbindung 39 Mol Schwefelsäure benötigt (BiOS Final Report Nr. 1484, S. 5).The amount of sulfuric acid can vary within wide limits: however, in order to keep the pollution of the wastewater with dilute sulfuric acid low, it is advisable to use as little as possible. It was found that 12 to 25 moles of HiSO 4 per mole of starting compound are sufficient for saponification. It is known from the literature that to convert the 1-amino-Z4-dibromo-anthraehinone into the l-amino-2-bromo-4-hydroxy-anthraquinone per mol of starting compound 39 moles of sulfuric acid are required (BiOS Final Report No. 1484, P. 5).
Von der Borsäure werden vorzugsweise 1 bis 3 MoL bezogen auf 1 Mol der Verbindung IL eingetelzt.The boric acid is preferably 1 to 3 mol, based on 1 mol of the compound IL.
1 -Amino^-chlor-'t-hydroxyanthrnchinon ist ein wertvolles Zwischenprodukt, vor allem zur Herstellung roter Farbstoffe, die sich zum Färben von synthetischen Fasern eignen (vgL beispielsweise Deutsche Offenlegungsschrift 16 44 509 = Britische Patentschrift 10 85 685).1-Amino ^ -chlor-'t-hydroxyanthrnquinone is a valuable one Intermediate product, mainly used in the manufacture of red dyes, which can be used to dye synthetic Fibers are suitable (see e.g. German Offenlegungsschrift 16 44 509 = British patent specification 10 85 685).
B e i s ρ i e I 1B e i s ρ i e I 1
a) 1-N-SuIfinyl-amino-anthrachinona) 1-N-sulfinyl-amino-anthraquinone
23 g l-Amino-anthrachinon werden in 100 ml Thionylchlorid 2 Stunden bei 80° C gerührt. Man erhält eine klare gelbe Lösung.23 g of l-amino-anthraquinone are dissolved in 100 ml of thionyl chloride Stirred at 80 ° C. for 2 hours. A clear yellow solution is obtained.
b) 1 -N-SuifinyI-amino-Z4-dichloΓ-anthΓachinonb) 1 -N-SuifinyI-amino-Z4-dichloΓ-anthΓachinon
Bei 54 bis 55° C werden 21 ml Sulfurylchlorid eingetropft. Es tritt eine heftige Entwicklung von HCIAt 54 to 55 ° C, 21 ml of sulfuryl chloride dripped in. A violent development of HCI occurs
jo und SO2 auf. Die Temperatur steigt auf 58°. Man rührt 3 Stunden bei 55 C nach und 1 Stunde bei 700C. Wenr die Chlorierung nicht vollständig ist, so setzt man noch 1 bis 2 ml Sulfurylchlorid nach. Es muß warm eine klare Lösung vorliegen. Das überschüssige Thionylchloridjo and SO2 on. The temperature rises to 58 °. The mixture is stirred for 3 hours at 55 C. and 1 hour at 70 0 C. Wenr the chlorination is not complete, so it is still 1 according to 2 ml of sulfuryl chloride. A clear solution must be present when warm. The excess thionyl chloride
J5 wird unter Normaldruck abdestilliert, der Rest im Vakuum entfernt. Es bleibt ein fester, braungelber Körper zurück.J5 is distilled off under normal pressure, the rest in Vacuum removed. A firm, brownish-yellow body remains.
Nach dem Umkristallisieren aus Toluol-I.igroin 2 : 1 schmilzt die hygroskopische Substanz bei 171" C.After recrystallization from toluene-I.igroin 2: 1 the hygroscopic substance melts at 171 "C.
. .. .
Analyse:Analysis:
Ber.:
Gef.:Ber .:
Found:
CI2I.0
Cl 21.2CI2I.0
Cl 21.2
N 4.1
N 4.2N 4.1
N 4.2
S 9,5
S 8.7S 9.5
S 8.7
c) I -Amino^-chlor^-hydroxyanthriichinonc) I-amino ^ -chloro ^ -hydroxyanthriquinone
Der nach b) erhaltene Rückstand wird mit 55 ml konz Schwefelsäure überschichtet. Es tritt Schäumen unter Entwicklung von SO; auf. Man erwärmt dann auf 80 C . Nach 2 Stunden hat die SO.-FntwicWjng aufgehört. Man setzt dann 55 ml 20%igcs Oleum und I 5 g Borsäure nach und erwärmt 5 Stunden unler Rühren auf 125 C. Ab II5X bcginrt die HCI-Abspuliung. Anschließend trägt man auf 300 ml Wasser aus. kocht kurz auf. saugt ab. wäscht neutral und trocKiiet. Ausbeute 25.9 g. Schmp. 224 C/Cl-Gehalt I 3.6%. berechnet I 3.0%.The residue obtained according to b) is concentrated with 55 ml Sulfuric acid overlaid. Foaming occurs Development of SO; on. It is then heated to 80.degree. After 2 hours the SO.-FntwicWjng stopped. 55 ml of 20% oleum and 15 g of boric acid are then added and the mixture is heated to 125 ° C. for 5 hours without stirring. From II5X, HCI rinsing stops. Afterward is carried out on 300 ml of water. boils briefly. sucks. washes neutral and dry. Yield 25.9 g. Mp. 224 C / Cl content I 3.6%. calculated I 3.0%.
Zur Reinigung kann das Produkt vor dem Trocknen in 300 ml 5%iger Sodalösung eine Stunde bei 90 bis 100 C gerührt werden. Man wascht dünn wieder neutral und trocknet.Before drying, the product can be cleaned in 300 ml 5% soda solution for one hour at 90 to 100 ° C be stirred. Wash thinly neutral again and dry.
Claims (1)
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19732353532 DE2353532C2 (en) | 1973-10-25 | 1973-10-25 | Process for the preparation of 1-amino-2-chloro-4-hydroxy-anthraquinone |
| CH1421174A CH605652A5 (en) | 1973-10-25 | 1974-10-23 | |
| GB4603874A GB1447194A (en) | 1973-10-25 | 1974-10-24 | Process for the preparation of 1-amino-2-chloro-4-hydroxy- anthraquinone |
| FR7435854A FR2249073B1 (en) | 1973-10-25 | 1974-10-25 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19732353532 DE2353532C2 (en) | 1973-10-25 | 1973-10-25 | Process for the preparation of 1-amino-2-chloro-4-hydroxy-anthraquinone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| DE2353532A1 DE2353532A1 (en) | 1975-05-07 |
| DE2353532C2 true DE2353532C2 (en) | 1982-02-25 |
Family
ID=5896416
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19732353532 Expired DE2353532C2 (en) | 1973-10-25 | 1973-10-25 | Process for the preparation of 1-amino-2-chloro-4-hydroxy-anthraquinone |
Country Status (4)
| Country | Link |
|---|---|
| CH (1) | CH605652A5 (en) |
| DE (1) | DE2353532C2 (en) |
| FR (1) | FR2249073B1 (en) |
| GB (1) | GB1447194A (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1798156A (en) * | 1928-02-06 | 1931-03-31 | Newport Chemical Corp | 1-amino-2-chloro-4-hydroxy anthraquinone and process of preparing the same |
-
1973
- 1973-10-25 DE DE19732353532 patent/DE2353532C2/en not_active Expired
-
1974
- 1974-10-23 CH CH1421174A patent/CH605652A5/xx not_active IP Right Cessation
- 1974-10-24 GB GB4603874A patent/GB1447194A/en not_active Expired
- 1974-10-25 FR FR7435854A patent/FR2249073B1/fr not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| FR2249073A1 (en) | 1975-05-23 |
| FR2249073B1 (en) | 1978-04-28 |
| GB1447194A (en) | 1976-08-25 |
| CH605652A5 (en) | 1978-10-13 |
| DE2353532A1 (en) | 1975-05-07 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| OD | Request for examination | ||
| D2 | Grant after examination | ||
| 8339 | Ceased/non-payment of the annual fee |