DE82445C - - Google Patents
Info
- Publication number
- DE82445C DE82445C DENDAT82445D DE82445DA DE82445C DE 82445 C DE82445 C DE 82445C DE NDAT82445 D DENDAT82445 D DE NDAT82445D DE 82445D A DE82445D A DE 82445DA DE 82445 C DE82445 C DE 82445C
- Authority
- DE
- Germany
- Prior art keywords
- acid
- pct
- soda
- reduction
- nitro
- 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
- 239000002253 acid Substances 0.000 claims description 11
- 150000002148 esters Chemical class 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- WWXMVRYHLZMQIG-SNAWJCMRSA-N 3-nitrocinnamic acid Chemical compound OC(=O)\C=C\C1=CC=CC([N+]([O-])=O)=C1 WWXMVRYHLZMQIG-SNAWJCMRSA-N 0.000 claims description 4
- BBQDLDVSEDAYAA-AATRIKPKSA-N 2-Nitrocinnamic acid Chemical compound OC(=O)\C=C\C1=CC=CC=C1[N+]([O-])=O BBQDLDVSEDAYAA-AATRIKPKSA-N 0.000 claims description 3
- 150000008064 anhydrides Chemical class 0.000 claims description 3
- -1 nitro hydrocarbons Chemical class 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-N Carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M NaHCO3 Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LJDZFAPLPVPTBD-UHFFFAOYSA-N nitroformic acid Chemical class OC(=O)[N+]([O-])=O LJDZFAPLPVPTBD-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- FFRBMBIXVSCUFS-UHFFFAOYSA-N Martius yellow Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- XMIIGOLPHOKFCH-UHFFFAOYSA-N Phenylpropanoic acid Chemical class OC(=O)CCC1=CC=CC=C1 XMIIGOLPHOKFCH-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- VKKNUVQQEHKTCG-UHFFFAOYSA-N methyl 3-(2-nitrophenyl)prop-2-enoate Chemical compound COC(=O)C=CC1=CC=CC=C1[N+]([O-])=O VKKNUVQQEHKTCG-UHFFFAOYSA-N 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 230000001264 neutralization Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged Effects 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C255/53—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and hydroxy groups bound to the carbon skeleton
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Description
KAISERLICHESIMPERIAL
PATENTAMT.PATENT OFFICE.
PATENTSCHRIFTPATENT LETTERING
KLASSE 12: Chemische Verfahren und Apparate.CLASS 12: Chemical processes and apparatus.
Siebenter Zusatz zum Patente JU 75260 vom 7. Februar 1893.Seventh amendment to patent JU 75260 of February 7, 1893.
Fatentirt im Deutschen Reiche vom 10. Juli 1894 ab. Längste Dauer: Ö.Februar 1908.Fatentirt in the German Empire from July 10, 1894. Longest duration: February 1st, 1908.
In der Patentschrift Nr. 77806 ist gezeigt, dafs bei der elektrolytischen Reduction von Nitrocarbonsäuren Amidophenolcarbonsäuren gebildet werden. In der Patentschrift Nr. 79865 ist diese Reaction auf die Nitrocarbonsäureester übertragen.In the patent specification No. 77806 it is shown that in the electrolytic reduction of Nitrocarboxylic acids Amidophenolcarbonsäuren are formed. In Patent No. 79865 this reaction is transferred to the nitrocarboxylic acid ester.
Beim weiteren Verfolge dieser Arbeiten wurden nun solche Nitrocarbonsäuren und deren Ester geprüft, welche wie die Nitrozimmtsä'uren eine ungesättigte Seitenkette enthalten. Hierbei hätten aus den Nitrozimmtsäuren sowohl Amidooxyzimmtsäuren als auch unter Anlagerung von Wasserstoff und Aufhebung der doppelten Bindung in der Seitenkette Derivate von Hydrozimmtsäuren entstehen können. Der Versuch zeigte nun, dafs die elektrolytische Reduction in normaler Weise zu den Amidooxyzimmtsäuren bezw. zu inneren Anhydriden derselben führt. In analoger Weise verhalten sich die Nitrozimmtsäureester.In the further pursuit of this work, such nitrocarboxylic acids and their esters tested, which like the nitrozimmtsä'uren contain an unsaturated side chain. In this case, both amidooxycyclic acids and with the addition of hydrogen and abolition would have been obtained from the nitrocyclic acids the double bond in the side chain results in derivatives of hydrocinnamic acids can. The experiment now showed that the electrolytic reduction was carried out in a normal manner to the Amidooxyzimmtsäuren respectively. leads to internal anhydrides of the same. In an analogous way behave the Nitrozimmtsäureester.
i. o-Nitrozimmtsäure.
Die elektrolytische Reduction der o-Nitrozimmtsäure selbst wird in der im Haupt-Patente
und dessen Zusätzen beschriebenen Art und Weise ausgeführt.i. o-nitrocinnamic acid.
The electrolytic reduction of the o-nitrocinnamic acid itself is carried out in the manner described in the main patent and its additives.
Das Sulfat der hierbei entstehenden Amidooxyzimmtsäure The sulfate of the amidooxycinnamic acid formed in this process
,CH=CH-COOH, CH = CH-COOH
NH,NH,
fällt auf Zusatz von Eis zu der schwefelsauren Lösung nach längerem Stehen in der Kälte in dunklen Krystallen aus. Kocht man dieselben mit einer concentrirten wässerigen Lösung von neutralem schwefligsauren Natron auf, so erhält man die freie Säure, welche aus viel heifsem Wasser beim Erkalten in Form gelblich gefärbter breiter Nadeln auskrystallisirt. Die Krystalle enthalten 1 Mol. Krystallwasser? welches beim Erwärmen auf 11 o° entweicht, wobei die Substanz eine orangegelbe Farbe annimmt. (Berechnet H2 O = 9,14 pCt. Gefunden 9,25 pCt.)precipitates in dark crystals on addition of ice to the sulfuric acid solution after prolonged standing in the cold. If they are boiled with a concentrated aqueous solution of neutral sulphurous soda, the free acid is obtained, which crystallizes from much hot water on cooling in the form of yellowish broad needles. The crystals contain 1 mol. which escapes when heated to 11 o °, whereby the substance takes on an orange-yellow color. (Calculated H 2 O = 9.14 pCt. Found 9.25 pCt.)
Eine Elementaranalyse der wasserhaltigen Substanz ergab: Berechnet C = 54,82 pCt., H = 5,6 pCt., N = 7,1 pCt. Gefunden C = 54,92 pCt., H = 5,83 pCt. und 2V= 7,3pCt.An elemental analysis of the water-containing substance showed: Calculated C = 54.82 pCt., H = 5.6 pCt., N = 7.1 pCt. Found C = 54.92 pCt., H = 5.83 pCt. and 2V = 7.3 pCt.
In Natron und Soda löst sich die Säure mit gelber Farbe auf. Aus ammoniakalischer Silberlösung scheidet sie Silber ab.In baking soda and soda, the acid dissolves with a yellow color. From ammoniacal silver solution she deposits silver.
Beim Erhitzen tritt Zersetzung ein. Erhitzt man die Substanz mehrere Stunden mit concentrirter Salzsäure im zugeschmolzenen Rohr auf i6o°, so verliert sie aufser dem Krystallwasser intramolecular 1 Mol. Wasser, indem sie in Oxycarbostyril übergeht.Decomposition occurs when heated. If the substance is heated for several hours with more concentrated Hydrochloric acid in the fused tube to 160 °, then it loses on the crystal water intramolecular 1 mole of water while converting to oxycarbostyril.
2. o-Nitrozimmtsäuremethylester.2. o-Nitrocinnamic acid methyl ester.
Verdünnt man die schwefelsaure Reductionslösung mit Wasser, so scheidet sich ein brauner Niederschlag ab, welcher abfiltrirt wird. Das Filtrat wird mit Soda neutralisirt, wobei ein gelber Niederschlag ausfällt, dessen Menge durchIf the sulfuric acid reduction solution is diluted with water, a brown one separates out Precipitate, which is filtered off. The filtrate is neutralized with soda, whereby a yellow precipitate precipitates, the amount of which passes through
(2. Auflage, ausgegeben am /7. August i8g8.) (2nd edition, issued on August 7th, 18/8)
Ausäthern noch vergröfsert werden kann. Derselbe krystallisirt aus Alkohol in Form prächtiger goldgelber Nadeln vom Schmelzpunkt 178 bis 1790 und erwies sich bei der Analyse als Amidooxyzimmtsä'ureester:Ether out can still be increased. The same crystallizes from alcohol in the form of splendid golden yellow needles melting at 178-179 0 and proved in the analysis as Amidooxyzimmtsä'ureester:
HO.HO.
CH=CH-COOCH,CH = CH-COOCH,
NH.NH.
Die Analyse ergab:The analysis showed:
Berechnet:
C = 62,17 pCt.Calculated:
C = 62.17 pCt.
H = 5,7 - H = 5.7 -
N= 7,25 -■ N = 7.25 - ■
Gefunden:
C = 62,16 pCt.
H = 6,26 -Found:
C = 62.16 pCt.
H = 6.26 -
N = 7,45 - · N = 7.45 -
In Natron löst sich der Aether in der Kälte äufserst leicht mit orangegelber Farbe auf; er ist unlöslich in Soda. Ammoniakarische Silberlösung reducirt er in der Kälte.In soda the ether dissolves extremely easily in the cold with an orange-yellow color; he is insoluble in soda. He reduces ammoniacal silver solution in the cold.
3. m-Nitrozimmtsäure.3. m-nitrocinnamic acid.
Bei der elektrolytischen Reduction der m-Nitrozimmtsäure scheidet sich weder direct noch beim Zusatz von Eis ein festes Reductionsproduct ab. Neutralisirt man jedoch die stark mit Wasser verdünnte schwefelsaure Lösung mit fester Soda, so scheiden sich gelbe Krystalle ab, deren Menge durch mehrmaliges Ausäthern der ' alkalischen Flüssigkeit noch vermehrt werden kann.In the electrolytic reduction of m-nitrocinnamic acid a solid reduction product is not separated either directly or when ice is added away. If, however, the sulfuric acid solution, strongly diluted with water, is neutralized with solid soda, yellow crystals separate out, the quantity of which is obtained by repeated etherification the 'alkaline liquid can still be increased.
Die so erhaltene Substanz erwies sich als identisch mit dem bereits bekannten Amidocumarin. Bei der Reduction hat sich sonach in normaler Weise zunächst Amidooxyzimmtsäure von folgender ConstitutionThe substance obtained in this way turned out to be identical to the already known amidocoumarin. In the case of reduction, amidooxycinnamic acid is normally used first of the following constitution
NH.NH.
CH*CH *
OHOH
*CH COOH* CH COOH
gebildet, die dann unter Wasserabspaltung in ihr inneres Anhydrid, das Amidocumarin, übergegangen ist.formed, which then passed into their inner anhydride, the amidocoumarin, with elimination of water is.
4. m-Nitrozimmtsäureäthylester.
Die elektrolytische Reduction des Aethylesters der m-Nitrozimmtsäure liefert in guter
Ausbeute das gleiche Amidocumarin, wie die freie Säure, indem entweder vor der Reduction
der Nitroester verseift wird oder der intermediär entstandene Amidooxyzimmtsäureester Alkohol
abspaltet. Die Ausbeute ist besser als bei Anwendung der freien Säure.4. m-Nitrozimmtsäureäthylester.
The electrolytic reduction of the ethyl ester of m-nitrocinnamic acid gives the same amidocoumarin as the free acid in good yield, either by saponifying the nitroester before the reduction or by splitting off alcohol from the intermediate amidooxycinnamic acid ester. The yield is better than when using the free acid.
Claims (2)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE82445C true DE82445C (en) |
Family
ID=354852
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT82445D Active DE82445C (en) |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE82445C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997031886A1 (en) * | 1996-02-29 | 1997-09-04 | Henkel Kommanditgesellschaft Auf Aktien | Aminophenol derivatives and their use in oxidative hair dyes |
-
0
- DE DENDAT82445D patent/DE82445C/de active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997031886A1 (en) * | 1996-02-29 | 1997-09-04 | Henkel Kommanditgesellschaft Auf Aktien | Aminophenol derivatives and their use in oxidative hair dyes |
| US6635241B1 (en) | 1996-02-29 | 2003-10-21 | Henkel Kommanditgesellschaft Auf Aktien | Aminophenol derivatives and their use in oxidative hair dyes |
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