CH189645A - Process for the preparation of 1- (d-ribityl-amino) -2-amino-4,5-dimethylbenzene. - Google Patents
Process for the preparation of 1- (d-ribityl-amino) -2-amino-4,5-dimethylbenzene.Info
- Publication number
- CH189645A CH189645A CH189645DA CH189645A CH 189645 A CH189645 A CH 189645A CH 189645D A CH189645D A CH 189645DA CH 189645 A CH189645 A CH 189645A
- Authority
- CH
- Switzerland
- Prior art keywords
- amino
- dimethylbenzene
- ribityl
- preparation
- solution
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 4
- 238000002360 preparation method Methods 0.000 title claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-dimethylbenzene Natural products CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000000987 azo dye Substances 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 239000012954 diazonium Substances 0.000 claims description 4
- 150000001989 diazonium salts Chemical class 0.000 claims description 4
- 150000001448 anilines Chemical class 0.000 claims description 2
- 229940079593 drug Drugs 0.000 claims description 2
- 239000003814 drug Substances 0.000 claims description 2
- 239000013067 intermediate product Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- HIMXGTXNXJYFGB-UHFFFAOYSA-N alloxan Chemical compound O=C1NC(=O)C(=O)C(=O)N1 HIMXGTXNXJYFGB-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- HEBKCHPVOIAQTA-NGQZWQHPSA-N d-xylitol Chemical compound OC[C@H](O)C(O)[C@H](O)CO HEBKCHPVOIAQTA-NGQZWQHPSA-N 0.000 description 2
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 150000002211 flavins Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- XSZYBMMYQCYIPC-UHFFFAOYSA-N 4,5-dimethyl-1,2-phenylenediamine Chemical class CC1=CC(N)=C(N)C=C1C XSZYBMMYQCYIPC-UHFFFAOYSA-N 0.000 description 1
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 description 1
- PYMYPHUHKUWMLA-LMVFSUKVSA-N aldehydo-D-ribose Chemical compound OC[C@@H](O)[C@@H](O)[C@@H](O)C=O PYMYPHUHKUWMLA-LMVFSUKVSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 125000003712 glycosamine group Chemical group 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
Verfahren zur Darstellung von 1-[d-Ribityl-amino]-2-amino-4,5-dimethylbenzol. Es wurde gefunden, dass die für den Auf bau von Flavinen wertvollen Abkömmlinge des 1,2-Diamino-4,5-idimethylbenzola, welche in einer Amino.gruppe als Substituenten einen Pentit- oder Hexitrest enthalten und demnach den Formeln
EMI0001.0010
entsprechen, dadurch hergestellt werden kön nen, dass man [3,
4-Dimethyl-phenyll-amino- pentite bezw. -hexite mit Diazoniumsalzen kuppelt und die entstandenen Azofarbstoffe mit Reduktionsmitteln behandelt.
Als Re- duktionsmittel können verwendet werden Wasserstoff und Nickel, Zink und Eisessig, Natriumhydrosulfit und derg#dergleichen. Die Umsetzung verläuft' nach folgender Glei chung, in der R Phenyl-, R, einen Pentit- oder Hegitrest bedeuten:
EMI0001.0030
Die entstandenen Zuckerabkömmlinge des 1,2-Diamino-4,5-dimethylbenzols lassen sich, wie bekannt, durch Einwirkung von Alloxan auf die nach der Reduktion erhaltene Lösung in Flavine überführen.
Dass [3,4-Dimsthyl-phenyl]=aminopentite bezw. -hegite mit Diazoniumsalzen kuppeln würden, war nicht vorauszusehen, da ,sie sich bei chemischen Umsetzungen, zum Beispiel bei der Nitrierung, träge zeigen und ein von einfachen Aminen abweichendes Verhalten aufweisen.
Auoh war es ungewiss, ob bei der eintretenden Kupplung der Azorest die ortho- ,Stellung zur Aminozuokerseitenkette auf suchen würde, da noch zwei andere freie Kupplunbmostellen zur Verfügung stehen.
Gegenstand des vorliegenden Patentes ist ein Verfahren zur Darstellung von 1-[d-Ribi- tyl-amino]-2-amino-4,5-dimethylbenzol, wel ches dadurch gekennzeichnet ist, dass man [3,4-Dimethyl-phenyl]-@d-ribamin mit Diazo- niumsalzen von Anilinen kuppelt und die ent standenen Azofarbstoffe mit Reduktionsmit teln behandelt.
Das 1-[d-Ribityl-amino]-2-amino-4,5-.di- methylbenzol ist neu; es kristallisiert in farblosen, filzigen Nadeln, die bei<B>128'</B> schmelzen.
Es bildet ein Zwischenprodukt für die Herstellung von Arzneimitteln.
<I>Beispiel 1:</I> Man diazotiert 93 Gewichtsteile Anilin in schwefelsaurer Lösung in üblicher Weise und giesst die Diazolösung bei etwa -f- 2 unter Rühren zu 240 Gewichtsteilen [3,4-Di- methyl-phenyl]-d-ribamin (hergestellt durch gleichzeitige Hydrierung von 1-Amino-3,4- dim-ethylbenzo1 und @d-Ribose) in 1900 Ge- wiehtsteilen Wasser. Sobald alles [3,
4-Dime- thyl-phenyl]-d-ribamin gelöst ist, setzt man allmählich so viel etwa 2-n Natronlauge zu, bis die Lösung Kongopapier nur noch schwach violett färbt. Nun rührt man unter Kühlung mit fliessendem Wasser langsam weiter, bis die Diazoreaktion verschwunden ist. Dann wird der ausgeschiedene Farbstoff abfiltriert und mit 50%igem Alkohol ge waschen.
200 Gewichtsteile Farbstoff wer-den mit 3200 Gewichtsteilen Methanol übergossen, 50 Gewichtsteile Nickel in Form eines akti ven Katalysators zugesetzt und bei 60-75 und 15 atü hydriert.
Aus,der vom Katalysa tor abfiltrierten Lösung wird darauf das Ani lin mit Waeserda"mpf abgeblasen und die Lösung im Vakuum fast eingedampft. Hier auf fällt man @da-s 1-[d-Ribityl-amino]-2- amino-4,5-,dimethylbenzol mit Äther und kri stallisiert den Niederschlag mehrmals aus ab solutem Äthylalkohol um.
<I>Beispiel 2:</I> [3,4-Dimethyl-phenyl]-d-ribamin (herge- stellt durch Kondensation und .gletohzeitige Hydrierung von 1-Amino-$,4--dimethylbenzol und d-Ribose) werden in wässeriger Lösung mit diazotiertem p-Nitranilin vereinigt. Den ausgefallenen Azofarbstoff reduziert man nach dem Umkristallisieren aus verdünntem Alkohol mit Wasserstoff und Nickel oder Zink und Essigsäure.
Die entstehende Lö sung enthält das 1-[@d-R.ibityl-amino]-2- amino-4,5--dimethylbenzol. Wird die Lösung mit Alioaan versetzt, so entsteht das 6,7-Di- methyl-9- [d-ribityl] -isoallogazin.
Process for the preparation of 1- [d-ribityl-amino] -2-amino-4,5-dimethylbenzene. It has been found that the derivatives of 1,2-diamino-4,5-idimethylbenzola which are valuable for the construction of flavins and which contain a pentitol or hexitol radical in an amino group as a substituent and therefore the formulas
EMI0001.0010
correspond to, can be produced by [3,
4-dimethyl-phenyl-aminopentite respectively. -hexite couples with diazonium salts and treats the resulting azo dyes with reducing agents.
Hydrogen and nickel, zinc and glacial acetic acid, sodium hydrosulfite and the like can be used as reducing agents. The reaction proceeds according to the following equation, in which R is phenyl, R is a pentitol or hegite radical:
EMI0001.0030
The resulting sugar derivatives of 1,2-diamino-4,5-dimethylbenzene can, as is known, be converted into flavins by the action of alloxan on the solution obtained after the reduction.
That [3,4-dimethylphenyl] = aminopentite respectively. -hegites would couple with diazonium salts, as they would be sluggish in chemical reactions, for example in nitration, and behave differently from simple amines.
It was also uncertain whether the azo group would seek the ortho position to the amino-sugar side chain when the coupling occurred, since two other free coupling positions are still available.
The present patent is a process for the preparation of 1- [d-ribityl-amino] -2-amino-4,5-dimethylbenzene, wel Ches is characterized in that [3,4-dimethyl-phenyl] - @ d-ribamin is coupled with diazonium salts of anilines and the azo dyes formed are treated with reducing agents.
1- [d-Ribityl-amino] -2-amino-4,5-dimethylbenzene is new; it crystallizes in colorless, felt-like needles that melt at <B> 128 '</B>.
It is an intermediate product for the manufacture of medicines.
<I> Example 1: </I> 93 parts by weight of aniline are diazotized in a sulfuric acid solution in the customary manner and the diazo solution is poured at about -f- 2 with stirring to give 240 parts by weight of [3,4-dimethylphenyl] -d- ribamin (produced by simultaneous hydrogenation of 1-amino-3,4-dim-ethylbenzo1 and @ d-ribose) in 1900 parts by weight of water. As soon as everything [3,
4-Dimethyl-phenyl] -d-ribamine is dissolved, gradually adding about 2N sodium hydroxide solution until the solution turns Congo paper only slightly violet. The mixture is then slowly stirred further, while cooling with running water, until the diazo reaction has disappeared. Then the precipitated dye is filtered off and washed with 50% alcohol.
3200 parts by weight of methanol are poured over 200 parts by weight of dye, 50 parts by weight of nickel are added in the form of an active catalyst and the mixture is hydrogenated at 60-75 and 15 atmospheres.
From the solution filtered off from the catalyst, the aniline is then blown off with Waeserda "mpf and the solution is almost evaporated in vacuo. 5-, dimethylbenzene with ether and crystallizes the precipitate several times from absolute ethyl alcohol.
<I> Example 2: </I> [3,4-dimethyl-phenyl] -d-ribamine (produced by condensation and hydrogenation of 1-amino- $, 4-dimethylbenzene and d-ribose) combined in aqueous solution with diazotized p-nitroaniline. The precipitated azo dye is reduced after recrystallization from dilute alcohol with hydrogen and nickel or zinc and acetic acid.
The resulting solution contains the 1 - [@ d-R.ibityl-amino] -2-amino-4,5 - dimethylbenzene. If the solution is mixed with alioan, the 6,7-dimethyl-9- [d-ribityl] -isoallogazine is formed.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE189645X | 1935-08-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH189645A true CH189645A (en) | 1937-03-15 |
Family
ID=5721417
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH189645D CH189645A (en) | 1935-08-23 | 1936-07-08 | Process for the preparation of 1- (d-ribityl-amino) -2-amino-4,5-dimethylbenzene. |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH189645A (en) |
-
1936
- 1936-07-08 CH CH189645D patent/CH189645A/en unknown
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