DE45806C - Process for the preparation of mono- and dialkylated amidobenzhydrols - Google Patents
Process for the preparation of mono- and dialkylated amidobenzhydrolsInfo
- Publication number
- DE45806C DE45806C DENDAT45806D DE45806DA DE45806C DE 45806 C DE45806 C DE 45806C DE NDAT45806 D DENDAT45806 D DE NDAT45806D DE 45806D A DE45806D A DE 45806DA DE 45806 C DE45806 C DE 45806C
- Authority
- DE
- Germany
- Prior art keywords
- nitrobenzaldehyde
- bases
- preparation
- amidobenzhydrols
- dimethylaniline
- 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 - Lifetime
Links
- 238000002360 preparation method Methods 0.000 title claims description 4
- 238000000034 method Methods 0.000 title description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N Dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 8
- HUMNYLRZRPPJDN-UHFFFAOYSA-N Benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 7
- BXRFQSNOROATLV-UHFFFAOYSA-N 4-Nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=C(C=O)C=C1 BXRFQSNOROATLV-UHFFFAOYSA-N 0.000 claims description 5
- ZETIVVHRRQLWFW-UHFFFAOYSA-N 3-Nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=CC(C=O)=C1 ZETIVVHRRQLWFW-UHFFFAOYSA-N 0.000 claims description 4
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N Diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 3
- 150000003934 aromatic aldehydes Chemical class 0.000 claims description 3
- 229940095076 benzaldehyde Drugs 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-Methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- OJGMBLNIHDZDGS-UHFFFAOYSA-N N-Ethylaniline Chemical compound CCNC1=CC=CC=C1 OJGMBLNIHDZDGS-UHFFFAOYSA-N 0.000 claims 1
- 150000003513 tertiary aromatic amines Chemical class 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 150000001299 aldehydes Chemical class 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- AAAQKTZKLRYKHR-UHFFFAOYSA-N Triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000875 corresponding Effects 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- HRXZRAXKKNUKRF-UHFFFAOYSA-N 4-ethylaniline Chemical compound CCC1=CC=C(N)C=C1 HRXZRAXKKNUKRF-UHFFFAOYSA-N 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L Zinc chloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000003935 benzaldehydes Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000002349 favourable Effects 0.000 description 1
- 229940083124 ganglion-blocking antiadrenergic Secondary and tertiary amines Drugs 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- UPKAWFACSJWKND-ZXFFUEEESA-J tetrasodium;(6E)-4-amino-6-[[4-[4-[(2Z)-2-(8-amino-1-oxo-5,7-disulfonatonaphthalen-2-ylidene)hydrazinyl]-3-methoxyphenyl]-2-methoxyphenyl]hydrazinylidene]-5-oxonaphthalene-1,3-disulfonate Chemical compound [Na+].[Na+].[Na+].[Na+].C\1=CC2=C(S([O-])(=O)=O)C=C(S([O-])(=O)=O)C(N)=C2C(=O)C/1=N/NC(C(OC)=C1)=CC=C1C1=CC=C(N\N=C\2C(C3=C(N)C(=CC(=C3C=C/2)S([O-])(=O)=O)S([O-])(=O)=O)=O)C(OC)=C1 UPKAWFACSJWKND-ZXFFUEEESA-J 0.000 description 1
- 150000004961 triphenylmethanes Chemical class 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
KAISERLICHESIMPERIAL
PATENTAMT.PATENT OFFICE.
Die einzige bisher bekannt gewordene Methode zur Gewinnung von alkylirten Amidobenzhydrolen ist die der Reduction der entsprechenden Ketonbasen. Auf diesem Wege geschieht die Darstellung der tetraalkylirten Diamidobenzhydrole nach dem PatentNo. 27032.The only method so far known for the preparation of alkylated amidobenzhydrols is that of the reduction of the corresponding ketone bases. On this way the representation of the tetraalkylated diamidobenzhydrols occurs according to Patent No. 27032.
Das vorliegende Verfahren zur Darstellung solcher Hydrolbasen beruht auf der directen Vereinigung gleicher Molecule der aromatischen Aldehyde mit aromatischen Aminen, ζ. Β.:The present process for the preparation of such hydrol bases is based on the direct Association of the same molecules of aromatic aldehydes with aromatic amines, ζ. Β .:
C6 H~C HO + C6 H~N(C H3), ä
= C6H-C H(O H)-C6 H-N(C HJ,. C 6 H ~ C HO + C 6 H ~ N (CH 3 ), the like
= C 6 HC H (OH) -C 6 HN (C HJ ,.
Während die aromatischen Aldehyde mit den aromatischen Basen bei Gegenwart von Chlorzink oder anderen wasserentziehenden Mitteln Leukobasen des Triphenylmethans liefern, indem ι Molecül des Aldehyds mit 2 Molecülen der Base in Reaction tritt, findet eine Vereinigung des Aldehyds und der Base zu gleichen Molecülen statt, wenn die Basen mit den Aldehyden bei Gegenwart überschüssiger Mineralsäuren erwärmt werden. Die Verwendung von Salzsäure oder verdünnter Schwefelsäure als Condensationsmittel ergab das günstigste Resultat. Die Hydrolbildung findet nur statt, wenn ein Ueberschufs von Säure angewendet wird; derselbe darf ebenso wie die Verdünnung innerhalb weiter Grenzen schwanken. So genügen 5 Theile Salzsäure auf 1 Theil Aldehyd, um bei Gegenwart eines Amins die Bildung der Hydrolbase herbeizuführen; doch ist es zur Erzielung reiner Producte 'zweckmäfsig, einen gröfseren Ueberschufs zu wählen, nämlich auf ι Theil Aldehyd 20 Theile Salzsäure (210B.) oder 20 Theile Schwefelsäure (66° B.), welche mit ungefähr dem gleichen Gewicht Wasser verdünnt ist.While the aromatic aldehydes with the aromatic bases in the presence of zinc chloride or other dehydrating agents supply leuco bases of triphenylmethane by ι Molecül of the aldehyde with 2 Moleculen of the base in reaction, a union of the aldehyde and the base takes place to form the same molecules when the Bases with the aldehydes are heated in the presence of excess mineral acids. The use of hydrochloric acid or dilute sulfuric acid as a condensing agent gave the most favorable result. Hydrol formation takes place only when an excess of acid is used; Like the dilution, it may vary within wide limits. Thus 5 parts hydrochloric acid to 1 part aldehyde suffice to induce the formation of the hydrol base in the presence of an amine; but it is' zweckmäfsig to obtain pure products of to choose a gröfseren About Schufs, namely ι part aldehyde 20 parts of hydrochloric acid (21 0 B.) or 20 parts of sulfuric acid (66 ° B), which is diluted with about an equal weight of water .
Die Hydrolbasen sind die directen Einwirkungsproducte der Aldehyde auf die Amine und verdanken ihre Entstehung nicht etwa einer Spaltung zuerst gebildeter Leukobasen.The hydrolic bases are the direct products of the action of the aldehydes on the amines and do not owe their emergence to a cleavage of the leuco bases that were first formed.
Darstellung des p-Nitrodimethylamidobenzhydrols. Representation of p-nitrodimethylamidobenzhydrol.
15,1 kg ρ - Nitrobenzaldehyd, 12,1 kg Dimethylanilin, 300 kg Salzsäure (210B.) werden ca. 40 Stunden lang auf ioo° erhitzt. Alsdann wird mit dem gleichen Volumen Wasser verdünnt und die Flüssigkeit nach dem Erkalten filtrirt. Die Lösung wird neutralisirt und das in gelben Flocken ausgeschiedene ρ - Nitrodimethylamidobenzhydrol abfiltrirt. Die reine Verbindung krystallisirt aus verdünntem Alkohol in gelben Nadeln vom Schmelzpunkt 950. Das p-Nitrodimethylamidobenzhydrol liefert bei der Reduction unsymmetrisches Dimethyldiamidobenzhydrol, welches eine dem von M i ch 1 er und Dupertuis (Ber. IX, 1900) beschriebenen Tetramethyldiamidobenzhydrol sehr ähnliche Verbindung ist und mit diesem Körper die Eigenschaft gemein hat, sich in Eisessig mit intensiv blauer Farbe zu lösen.15.1 kg ρ - nitrobenzaldehyde, 12.1 kg dimethylaniline, 300 kg hydrochloric acid (21 0 B.) are heated to 100 ° for about 40 hours. Then it is diluted with the same volume of water, and the liquid is filtered after cooling. The solution is neutralized, and the ρ-nitrodimethylamidobenzhydrol which has separated out in yellow flakes is filtered off. The pure compound crystallizes from dilute alcohol in yellow needles with a melting point of 95 ° . The reduction of p-Nitrodimethylamidobenzhydrol gives unsymmetrical dimethyldiamidobenzhydrol, which is a compound very similar to the tetramethyldiamidobenzhydrol described by Micher and Dupertuis (Ber Color to solve.
Sowohl aus dem p-Nitrodimetylamidobenzhydrol als auch aus dem Dimetyldiamidobenzhydrol werden bei der Condensation mit primären, secundären und tertiären Aminen Derivate des Triphenylmethans erhalten. So entsteht aus ρ - Nitrodimethylamidobenzhydfol und Dimethylanilin das von O. Fischer (Ber. XIV, 2526) beschriebene, bei 176 bis 1770 Derivatives of triphenylmethane are obtained both from p-nitrodimetylamidobenzhydrol and from dimethyldiamidobenzhydrol in the condensation with primary, secondary and tertiary amines. Thus, from ρ - nitrodimethylamidobenzhydfol and dimethylaniline, that described by O. Fischer (Ber. XIV, 2526), at 176 to 177 0
schmelzende p-Nitroleukomalachitgrün. Die aus ρ - Nitrodimethylamidobenzhydrol gewonnenen Nitroleukobasen gehen bei der Reduction in die entsprechenden Amidoverbindungen über, welche mit den durch Condensation des Dimethyldiamidobenzhydrols mit den gleichen Aminen entstehenden Basen identisch sind. Die Leukobasen liefern bei der Oxydation Farbstoffe; die aus den Nitroleukobasen entstehenden färbenmelting p-nitroleukomalachite green. From Nitroleucobases obtained from nitrodimethylamidobenzhydrol go into the reduction the corresponding amido compounds, which with the condensation of Dimethyldiamidobenzhydrols with the same amines formed bases are identical. The leuco bases produce dyes on oxidation; the color resulting from the nitroleuco bases
grün,green,
die aus den Amidoleukobasenthose from the amidoleuco bases
rothviolett bis reinblau.red-violet to pure blue.
Dargestellt wurden folgende Hydrolbasen:The following hydrolic bases were shown:
Aus 15,1 kg p-Nitrobenzaldehyd und 12,1 kg Dimethylanilin ein Hydrolderivat vom Schmelzp.From 15.1 kg of p-nitrobenzaldehyde and 12.1 kg of dimethylaniline a hydrolic derivative of melting point.
laut vorhergehendem Beispiel und in entsprechender Behandlung; aus 15,1 kg p-Nitrobenzaldehyd und 14,9 kg Diäthylanilin ein Hydrolderivat vom Schmelzp.according to the previous example and with appropriate treatment; from 15.1 kg of p-nitrobenzaldehyde and 14.9 kg of diethylaniline a hydrolic derivative of melting point.
- 15,1 kg p-Nitrobenzaldehyd und 10,7 kg Monomethylanilin - - -- 15.1 kg p-nitrobenzaldehyde and 10.7 kg monomethylaniline - - -
- 15,1 kg p-Nitrobenzaldehyd und 12,1 kg Monoäthylanilin - -- 15.1 kg p-nitrobenzaldehyde and 12.1 kg monoethylaniline - -
- 15,1 kg m-Nitrobenzaldehyd und 12,1 kg Dimethylanilin - - -- 15.1 kg of m-nitrobenzaldehyde and 12.1 kg of dimethylaniline - - -
- 15,1 kg m-Nitrobenzaldehyd und 14,9 kg Diäthylanilin - -- 15.1 kg of m-nitrobenzaldehyde and 14.9 kg of diethylaniline - -
- 10,6 kg Benzaldehyd und 12,1 kg Dimethylanilin - - -- 10.6 kg benzaldehyde and 12.1 kg dimethylaniline - - -
Diese Hydrolbasen sind sämmtlich in Wasser unlösliche, in Alkohol sehr leicht lösliche krystallisirte Körper. Die Hydrolbasen aus Benzaldehyd sind farblos, die aus den nitrirten Benzaldehyden gelb gefärbt. Mit Säuren liefern sie 92-io8° 99° 74° 65° 7o°.These hydrolic bases are all crystallized bodies which are insoluble in water and very easily soluble in alcohol. The hydrolic bases from benzaldehyde are colorless, those from the nitrated benzaldehydes are colored yellow. With acids they give 92-io8 ° 99 ° 74 ° 65 ° 7 °.
sämmtlich in der Kälte farblose Lösungen, welche beim Erwärmen gelb werden. Mit Aminen lassen sie sich leicht zu Leukobasen des Triphenylmethans vereinigen.all solutions colorless in the cold, which turn yellow on warming. With Amines can easily be combined to form triphenylmethane leuco bases.
Claims (1)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE45806C true DE45806C (en) |
Family
ID=320951
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT45806D Expired - Lifetime DE45806C (en) | Process for the preparation of mono- and dialkylated amidobenzhydrols |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE45806C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2513063A (en) * | 1949-01-04 | 1950-06-27 | Gulf Oil Corp | Antioxidants for mineral oil lubricants and compositions containing the same |
-
0
- DE DENDAT45806D patent/DE45806C/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2513063A (en) * | 1949-01-04 | 1950-06-27 | Gulf Oil Corp | Antioxidants for mineral oil lubricants and compositions containing the same |
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