DE123260C - - Google Patents
Info
- Publication number
- DE123260C DE123260C DENDAT123260D DE123260DA DE123260C DE 123260 C DE123260 C DE 123260C DE NDAT123260 D DENDAT123260 D DE NDAT123260D DE 123260D A DE123260D A DE 123260DA DE 123260 C DE123260 C DE 123260C
- Authority
- DE
- Germany
- Prior art keywords
- naphtol
- toluidine
- formaldehyde
- xylidine
- aniline
- 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.)
- Active
Links
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 12
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-Naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 claims description 10
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 claims description 3
- CHMBIJAOCISYEW-UHFFFAOYSA-N N-(4-aminophenyl)acetamide Chemical compound CC(=O)NC1=CC=C(N)C=C1 CHMBIJAOCISYEW-UHFFFAOYSA-N 0.000 claims description 2
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 239000000155 melt Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-Trioxane Chemical group C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000875 corresponding Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- -1 formaldehyde compound Chemical class 0.000 description 2
- 238000004508 fractional distillation Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- JNRLEMMIVRBKJE-UHFFFAOYSA-N 4,4'-Methylenebis(N,N-dimethylaniline) Chemical compound C1=CC(N(C)C)=CC=C1CC1=CC=C(N(C)C)C=C1 JNRLEMMIVRBKJE-UHFFFAOYSA-N 0.000 description 1
- 125000000641 acridinyl group Chemical class C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000005712 crystallization Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 150000003142 primary aromatic amines Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing Effects 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
- C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
- C07D221/04—Ortho- or peri-condensed ring systems
- C07D221/18—Ring systems of four or more rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
Description
KAISERLICHESIMPERIAL
PATENTAMT.PATENT OFFICE.
PATENTSCHRIFTPATENT LETTERING
- M 123260 KLASSE 12j?.- M 123260 CLASS 12y ?.
Zusatz, zum Patente 117472 vom 4. AugustAddendum to patent 117472 dated August 4th
Patentirt im Deutschen Reiche vom 25. Januar 1899 ab. Längste Dauer: 3. August 1913.Patented in the German Empire on January 25, 1899. Longest duration: August 3, 1913.
Bei der weiteren Ausarbeitung des Verfahrens gemäfs Patent 117472 hat sich gezeigt, dafs diese Synthese von Naphtacridinen aus Formaldehyd, ß-Naphtol und p-Toluidin insofern verallgemeinerungsfähig ist, als man an Stelle von p-Toluidin andere primäre aromatische Amine, wie Anilin, o-Toluidin, as-m-Xylidin, Acet-pphenylendiamin, verwenden kann. Diese Amine werden entweder durch Verschmelzen mit ß-Naphtol und Trioxymethylen in das entsprechende Acridinderivat verwandelt, oder man kann durch Behandeln des Amins mit Formaldehyd dieses in die betreffende Formaldehydverbindung überführen und diese dann mit ß-Naphtol umsetzen.In the further elaboration of the method according to patent 117472 it has been shown that this synthesis of naphtacridines from formaldehyde, ß-naphtol and p-toluidine insofar can be generalized when, instead of p-toluidine, other primary aromatic amines, such as aniline, o-toluidine, as-m-xylidine, acet-pphenylenediamine, can use. These amines are either fused with ß-naphthol and trioxymethylene into the corresponding Acridine derivative is transformed, or one can by treating the amine with formaldehyde convert this into the relevant formaldehyde compound and then with Implement ß-naphtol.
1. 10 kg ß-Naphtol, 8 kg Anilin und 1 kg Trioxymethylen werden zusammen auf i6o° erhitzt, wobei sich die Masse unter Abspaltung von Wasser gelbroth färbt. Durch stärkeres Erhitzen wird nun zuerst das unveränderte Anilin und ß-Naphtol entfernt, worauf über 400 ° das Naphtacridin übergeht. Dasselbe wird durch Behandeln mit verdünnter Natronlauge von etwas Naphtol befreit und die erhaltene krystallinische Masse aus einem Gemenge von Benzol und Ligroin umkrystallisirt. Man erhält so das Naphtacridin in gelblichen Krystallen, die bei 1^9,5° schmelzen.1. 10 kg of ß-naphtol, 8 kg of aniline and 1 kg Trioxymethylene are heated together to 160 °, the mass splitting off turns yellow-red with water. By increasing the temperature, the unchanged one becomes the first Aniline and ß-naphtol removed, whereupon the naphtacridine passes over 400 °. The same thing is freed from some naphtol by treatment with dilute sodium hydroxide solution and the obtained crystalline mass recrystallized from a mixture of benzene and ligroin. The naphtacridine is thus obtained in yellowish Crystals melting at 1 ^ 9.5 °.
2. In 10 kg ß-Naphtol, die auf 1500 erhitzt sind, trägt man nach und nach 6 kg Anhydroformaldehyd-o-toluidin ein, die sich leicht unter Gelbfärbung der Masse und Wasserentwickelung auflösen. Durch fractionirte Destillation läfst sich das o-Tolunaphtacridin isoliren, das nach dem Umkrystallisiren aus Benzol-Ligroin bei 143 ° schmilzt.2. In 10 kg of ß-naphtol, which are heated to 150 0 , 6 kg of anhydroformaldehyde-o-toluidine are gradually added, which dissolve easily with yellowing of the mass and evolution of water. Fractional distillation can isolate o-tolunaphtacridine, which, after recrystallization from benzene-ligroin, melts at 143 °.
3. 12 kg as-m-Xylidin werden mit einer Lösung von 2 kg Kalihydrat in 4 1 Alkohol gemischt und unter Rühren mit 5 kg Formaldehyd (39 pCt.) versetzt. Die sich ölig ausscheidende Methylenbase wird nach und nach fest und bildet nach dem Filtriren und Auswaschen mit Wasser weifse Krystalle, die bei 68° schmelzen. 5 kg vorstehenden Condensationsproductes werden mit 3,5 kg ß-Naphtol verschmolzen, die gelbgefärbte Schmelze auf ca. 200° erhitzt, nach dem Abkühlen in verdünnte Natronlauge eingetragen und das gebildete as-m-Xylidin mit Wasserdampf abgetrieben. Der Rückstand wird nach dem Filtriren und Waschen durch !Crystallisation aus Alkohol oder Benzol gereinigt. Man erhält so das Dimethylnaphtacridin in Gestalt schwachgelber Nadeln, die bei 1520 schmelzen.3. 12 kg of as-m-xylidine are mixed with a solution of 2 kg of potassium hydrate in 4 l of alcohol and 5 kg of formaldehyde (39 pct.) Are added while stirring. The oily methylene base which separates out gradually solidifies and, after filtering and washing out with water, forms white crystals which melt at 68 °. 5 kg of the above condensation products are fused with 3.5 kg of ß-naphtol, the yellow-colored melt is heated to approx. 200 °, after cooling it is added to dilute sodium hydroxide solution and the as-m-xylidine formed is driven off with steam. After filtering and washing, the residue is purified by crystallization from alcohol or benzene. This gives the Dimethylnaphtacridin in the form of pale yellow needles, melting at 152 0th
4. Acetyl-p-phenylendiamin wird in heifsem Wasser gelöst und mit der berechneten Menge •Formaldehyd versetzt. Beim Erkalten krystallisirt die entsprechende Formaldehydverbindung aus, welche weifse Krystalle bildet, die unscharf zwischen 195 bis 2000 schmelzen.4. Acetyl-p-phenylenediamine is dissolved in hot water and the calculated amount of formaldehyde is added. On cooling, the corresponding formaldehyde compound crystallizes from which forms whiteness crystals, melting blurred between 195-200 0th
5 kg Anhydroformaldehyd-acet-p-phenylendiamin werden mit 12 kg ß-Naphtol bei einer Temperatur von 150 bis i8o° verschmolzen. Das durch Behandeln mit verdünnter Natronlauge erhaltene Rohproduct bildet nach dem Umkrystallisiren aus Alkohol gelbliche verfilzte Nädelchen, die bei 25 5 ° schmelzen.5 kg of anhydroformaldehyde-acet-p-phenylenediamine are fused with 12 kg of ß-naphthol at a temperature of 150 to 180 °. The crude product obtained by treating with dilute sodium hydroxide solution forms after the Recrystallize from alcohol yellowish matted needles which melt at 25 5 °.
Durch Verseifen dieses Acetylamidonaphtoacridins erhält man Amidonaphtacridin, das aus Alkohol in gelben Nadeln krystallisirt, bei 238° schmilzt und folgende Constitution besitzt:By saponifying this acetylamidonaphtoacridine amidonaphtacridine is obtained, which crystallizes from alcohol in yellow needles, melts at 238 °, and the following Constitution possesses:
5. 5 kg Methylendiphenyldiimid werden in 4 kg geschmolzenes ß-Naphtol eingetragen, worin es sich unter Wasserdampfentwickelung mit gelber Farbe löst.' Nachdem die Temperatur der Schmelze kurze Zeit auf 180 bis 2000 gehalten wird, unterwirft man dieselbe der fractionirten Destillation und isolirt das Naphtoacridin aus dem über 400 ° übergehenden Antheil auf die unter Beispiel 1 angegebene Weise. Schmelzpunkt und Eigenschaften sind völlig identisch mit denen der bereits erwähnten Producte.5. 5 kg of methylenediphenyldiimide are introduced into 4 kg of molten β-naphthol, in which it dissolves with the development of water vapor with a yellow color. After the temperature of the melt a short time is maintained at 180 to 200 0, is subjected to the same fractional distillation and the insulated Naphtoacridin from about 400 ° merges share are listed under Example 1. Melting point and properties are completely identical to those of the products already mentioned.
Claims (1)
Weitere Ausbildung des durch Patent 117472 geschützten Verfahrens zur Darstellung von Derivaten des Naphtacridins, darin bestehend, dafs man an Stelle des p-Toluidins, hier Anilin, o-Toluidin, as-m-Xylidin und Acetyl-p-phenylendiamin nach dem Verfahren genannten Patentes mit ß-Naphtol und Formaldehyd in Reaction bringt.Patent claim:
Further development of the process for the preparation of derivatives of naphtacridine, protected by patent 117472, consists in using the patent mentioned in place of p-toluidine, here aniline, o-toluidine, as-m-xylidine and acetyl-p-phenylenediamine brings into reaction with ß-naphtol and formaldehyde.
Publications (1)
Publication Number | Publication Date |
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DE123260C true DE123260C (en) |
Family
ID=392124
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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DENDAT123260D Active DE123260C (en) |
Country Status (1)
Country | Link |
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DE (1) | DE123260C (en) |
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- DE DENDAT123260D patent/DE123260C/de active Active
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