CH186270A - Process for the preparation of 4-oxypyrene. - Google Patents
Process for the preparation of 4-oxypyrene.Info
- Publication number
- CH186270A CH186270A CH186270DA CH186270A CH 186270 A CH186270 A CH 186270A CH 186270D A CH186270D A CH 186270DA CH 186270 A CH186270 A CH 186270A
- Authority
- CH
- Switzerland
- Prior art keywords
- ogypyrene
- oxypyrene
- acid
- sulfonic acid
- weight
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 6
- 238000002360 preparation method Methods 0.000 title claims description 3
- 239000000155 melt Substances 0.000 claims description 6
- DGQLVPJVXFOQEV-JNVSTXMASA-N carminic acid Chemical compound OC1=C2C(=O)C=3C(C)=C(C(O)=O)C(O)=CC=3C(=O)C2=C(O)C(O)=C1[C@@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O DGQLVPJVXFOQEV-JNVSTXMASA-N 0.000 claims description 3
- 150000008049 diazo compounds Chemical class 0.000 claims description 3
- FYQQLQWUQXTBSN-UHFFFAOYSA-N pyrene-4-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC3=CC=CC4=CC=C1C2=C34 FYQQLQWUQXTBSN-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- LGENMBVQXWRZJT-UHFFFAOYSA-N 3-aminopyrene-4-sulfonic acid Chemical compound NC=1C=CC2=CC=C3C=CC=C4C=C(C1C2=C43)S(=O)(=O)O LGENMBVQXWRZJT-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 244000061775 Olea africana Species 0.000 claims description 2
- 235000002852 Olea africana Nutrition 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- NAVBOFQEBMBWLI-UHFFFAOYSA-N 2-aminopyrene-1-sulfonic acid Chemical compound C1=CC=C2C=CC3=C(S(O)(=O)=O)C(N)=CC4=CC=C1C2=C43 NAVBOFQEBMBWLI-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 241001101998 Galium Species 0.000 description 1
- 240000007817 Olea europaea Species 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000002506 high-vacuum sublimation Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- DLOBKMWCBFOUHP-UHFFFAOYSA-N pyrene-1-sulfonic acid Chemical compound C1=C2C(S(=O)(=O)O)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 DLOBKMWCBFOUHP-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- HCOPYCNNZOWMTD-UHFFFAOYSA-M sodium;pyrene-1-sulfonate Chemical compound [Na+].C1=C2C(S(=O)(=O)[O-])=CC=C(C=C3)C2=C2C3=CC=CC2=C1 HCOPYCNNZOWMTD-UHFFFAOYSA-M 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Darstellung von 4-Ogypyren. Es wurde gefunden, dass man 4-Oxypyren leicht erhalten kann, wenn man 3-Amino- pyren-4-sulfosäure, die zum Beispiel nach dem Verfahren gemäss 8ehweizer Patent Nr.
184171 erhältlich ist, diazotiert, die so erhaltene Diazoverbindung nach bekannten Methoden, zum Beispiel durch reduzierendes Verkochen in Pyren-4-sulfosäure überführt, diese mit Alkalihydroxyden verschmilzt und das 4-Oxypyren aus der Schmelze durch Be handlung mit einer Mineralsäure frei macht. Das bisher in der Literatur noch nicht be schriebene 4-Oxypyren schmilzt bei 208 und zeigt in konzentrierter Schwefelsäure eine charakteristische karminrote Lösungs farbe mit brauner, oliver Fluoreszenz.
Im Gegensatz zum 3-Oxypyren vom F.<B>179'</B> (darstellbar durch Alkalischmelze der 3- Pyrensulfonsäure, welche durch Einwirkung von 1 Mol Chlorsulfonsäure auf eine Lösung von Pyren in Tetrachlorkohlenstoff erhältlich ist) kuppelt das 4-Oxypyren glatt mit Diazo- verbindungen. Es soll zur Darstellung von Farbstoffen verschiedener Art Verwendung finden.
.Beispiel: 128 Gewichtsteile des nach dem Beispiel des Patentes Nr. 184171 erhältlichen 3 Aminopyren-4-sulfonsanren Natriums wer den in 254 Gewichtsteilen Wasser und 224 Gewichtsteilen konzentrierter Salzsäure suspendiert.
Hierzu wird unter Kühlung bei' 0 bis 5 eine Lösung von 28 Gewichtsteilen Natriumnitrit in 160 Gewichtsteilen Wasser zugetropft. Allmählich schlägt die Farbe des grauen,.
salzsauren Salzes der Aminopyren- sulfonsäure in die gelbbraune Farbe des Di- azosulfoanhydrids 'um. Nach einstündigem Nachrühren ist die Diazotierung beendet, und das feine kristalline, in Wasser unlös- liehe Diazosulfoanhydrid wird abgesaugt.
Nach gründlichem Auswaschen mit Eiswas ser wird die Paste in 500 Gewichtsteile Al kohol eingerührt und auf dem, Dampfbad un- ter Rühren erwärmt. . Hierbei tritt unter starkem Schäumen und Entwicklung - von Acetaldehyd Lösung ein.
Nach Abdestillie- ren des Alkohols wird mit Wasser aufge nommen und die 4-Pyrensulfonsäure - als Natriumsalz ausgesalzen. Die Ausbeute an 4 pyrensulfonsaurem Natrium beträgt 100 Ge wichtsteile.
62 Gewichtsteile 4-pyrensulfonsaüres Na trium werden in 3-00 Gewichtsteile ge schmolzenes galiumhydrogyd bei 260 bis 270 eingetragen. Unter starkem Schäumen tritt Reaktion ein. Nachdem keine Sulfon- säure mehr nachweisbar ist, .wird die Schmelze auf Bleche gegossen. Die erkal tete Schmelze wird dann gepulvert; in heissem Wasser gelöst und angesäuert.
Nach Absaugen und Trocknen wird ein rohes 4 Ogypyren erhalten, das durch Hochvakuum- sublimation oder durch Umkristallisieren aus Chloibenzol gereinigt werden kann.. Der Schmelzpunkt des reinen 4-Ogypyrens ist <B>208'.</B> Die Lösungsfarbe in konzentrierter Schwefelsäure ist karminrot mit braunoliver Fluoreszenz.
Process for the preparation of 4-ogypyrene. It has been found that 4-oxypyrene can be easily obtained if 3-aminopyrene-4-sulfonic acid is obtained, for example, by the method according to Swiss Patent No.
184171 is available, diazotized, the diazo compound thus obtained is converted by known methods, for example by reducing boiling in pyrene-4-sulfonic acid, this is fused with alkali metal hydroxides and the 4-oxypyrene is free from the melt by treatment with a mineral acid. 4-oxypyrene, which has not yet been described in the literature, melts at 208 and shows a characteristic carmine-red solution color with brown, olive fluorescence in concentrated sulfuric acid.
In contrast to 3-oxypyrene from F. <B> 179 '</B> (can be produced by alkali fusion of 3-pyrene sulfonic acid, which is obtainable by the action of 1 mol of chlorosulfonic acid on a solution of pyrene in carbon tetrachloride), 4-oxypyrene couples smoothly with diazo compounds. It is intended to be used to represent dyes of various types.
.Example: 128 parts by weight of the 3 aminopyrene-4-sulfonsanren sodium obtainable according to the example of patent no. 184171 who suspended in 254 parts by weight of water and 224 parts by weight of concentrated hydrochloric acid.
To this end, a solution of 28 parts by weight of sodium nitrite in 160 parts by weight of water is added dropwise with cooling at '0 to 5. Gradually the color of the gray suggests.
hydrochloric acid salt of aminopyrene sulfonic acid into the yellow-brown color of diazosulfoanhydride. After stirring for one hour, the diazotization is complete and the fine crystalline, water-insoluble diazosulfoanhydride is filtered off with suction.
After washing it thoroughly with ice water, the paste is stirred into 500 parts by weight of alcohol and heated on the steam bath while stirring. . This occurs with strong foaming and development - of acetaldehyde solution.
After the alcohol has been distilled off, it is taken up with water and the 4-pyrenesulfonic acid - salted out as the sodium salt. The yield of 4 sodium pyrensulfonate is 100 parts by weight.
62 parts by weight of 4-pyrensulfonsaüres sodium are registered in 3-00 parts by weight of molten galium hydrogen at 260 to 270. Reaction occurs with strong foaming. When no more sulfonic acid can be detected, the melt is poured onto metal sheets. The cooled melt is then powdered; dissolved in hot water and acidified.
After suctioning off and drying, a crude 4-ogypyrene is obtained, which can be purified by high vacuum sublimation or by recrystallization from chlorobenzene. The melting point of the pure 4-ogypyrene is <B> 208 '. </B> The solution color is in concentrated sulfuric acid carmine red with brown olive fluorescence.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE186270X | 1934-04-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH186270A true CH186270A (en) | 1936-09-15 |
Family
ID=5719821
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH186270D CH186270A (en) | 1934-04-19 | 1935-04-17 | Process for the preparation of 4-oxypyrene. |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH186270A (en) |
-
1935
- 1935-04-17 CH CH186270D patent/CH186270A/en unknown
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