DE32914C - Process for the preparation of m-methoxy-p-nitrobenzaldehyde and ferulic acid for the production of vanillin - Google Patents
Process for the preparation of m-methoxy-p-nitrobenzaldehyde and ferulic acid for the production of vanillinInfo
- Publication number
- DE32914C DE32914C DENDAT32914D DE32914DA DE32914C DE 32914 C DE32914 C DE 32914C DE NDAT32914 D DENDAT32914 D DE NDAT32914D DE 32914D A DE32914D A DE 32914DA DE 32914 C DE32914 C DE 32914C
- Authority
- DE
- Germany
- Prior art keywords
- methoxy
- acid
- preparation
- nitrobenzaldehyde
- vanillin
- 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
- KSEBMYQBYZTDHS-HWKANZROSA-M (E)-Ferulic acid Natural products COC1=CC(\C=C\C([O-])=O)=CC=C1O KSEBMYQBYZTDHS-HWKANZROSA-M 0.000 title claims description 6
- KSEBMYQBYZTDHS-HWKANZROSA-N Ferulic acid Chemical compound COC1=CC(\C=C\C(O)=O)=CC=C1O KSEBMYQBYZTDHS-HWKANZROSA-N 0.000 title claims description 6
- 229940114124 ferulic acid Drugs 0.000 title claims description 6
- 235000001785 ferulic acid Nutrition 0.000 title claims description 6
- WUTIWOZYHHSBBU-UHFFFAOYSA-N 3-methoxy-4-nitrobenzaldehyde Chemical compound COC1=CC(C=O)=CC=C1[N+]([O-])=O WUTIWOZYHHSBBU-UHFFFAOYSA-N 0.000 title claims description 4
- 238000002360 preparation method Methods 0.000 title claims description 4
- MWOOGOJBHIARFG-UHFFFAOYSA-N Vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 title description 8
- 229940117960 vanillin Drugs 0.000 title description 4
- 235000012141 vanillin Nutrition 0.000 title description 4
- 238000004519 manufacturing process Methods 0.000 title 1
- 238000000034 method Methods 0.000 title 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 150000002170 ethers Chemical class 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- LZPNXAULYJPXEH-UHFFFAOYSA-N 3-(3-methoxyphenyl)prop-2-enoic acid Chemical compound COC1=CC=CC(C=CC(O)=O)=C1 LZPNXAULYJPXEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 238000006396 nitration reaction Methods 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 150000008049 diazo compounds Chemical group 0.000 claims 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- REJOBCUTAMAPIS-UHFFFAOYSA-N 3-(3-methoxy-4-nitrophenyl)prop-2-enoic acid Chemical compound COC1=CC(C=CC(O)=O)=CC=C1[N+]([O-])=O REJOBCUTAMAPIS-UHFFFAOYSA-N 0.000 description 2
- VZJVWSHVAAUDKD-UHFFFAOYSA-N Potassium permanganate Chemical compound [K+].[O-][Mn](=O)(=O)=O VZJVWSHVAAUDKD-UHFFFAOYSA-N 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M Sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N Carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical class N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000875 corresponding Effects 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 229910000460 iron oxide Inorganic materials 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000003638 reducing agent Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
KAISERLICHESIMPERIAL
PATENTAMT.PATENT OFFICE.
MORITZ ULRICH in GENF.MORITZ ULRICH in GENEVA.
i. Darstellung von m-Methoxyp-nitro benzaldehyd.i. Presentation of m-methoxyp-nitro benzaldehyde.
Die zu diesem Zweck erforderliche Methoxynitrozimmtsäure wird aus der m-Methoxyzimmtsäure oder aus deren Aethern durch Nitrirung dargestellt.The methoxynitrocytic acid required for this purpose is obtained from m-methoxycytic acid or from their ethers by nitration.
Der m-Methoxyzimmtsäuremethyläther giebt, in die fünffache Menge Salpetersäure vom spec. Gew. 1,46 bei 00C. eingetragen, ein Nitroproduct, welches sich beim Verdünnen der salpetersauren Lösung mit Eiswasser weifs und hart ausscheidet. Dasselbe wird in der zehnfachen Menge heifsen Alkohols gelöst und es krystallisirt beim Erkalten der m-Methoxyp-nitrozimmtsäuremethyläther in weifsen, flachen Nadeln, die bei 1630 C schmelzen.The m-Methoxyzimmtsäuremethyläther gives, in five times the amount of nitric acid of the spec. Wt. Added 1.46 at 0 0 C., a nitro product which separates out upon dilution of the nitric acid solution with ice water and knows hard. The same is torrid in ten times the amount of alcohol released and crystallizes on cooling of the m-Methoxyp-nitrozimmtsäuremethyläther in whites, flat needles, melting at 163 0 C.
Die Verseifung des Aethers gelingt leicht durch Erwärmung desselben mit 0,5 proc. Kalilauge.The saponification of the ether can easily be achieved by heating it to 0.5 per cent. Potassium hydroxide.
Die m-Methoxy-p-nitrozimmtsäure ist in Alkohol schwer löslich und krystallisirt daraus in feinen weifsen Nadeln. Sie fängt bei 2180C. an unter Zersetzung zu schmelzen.The m-methoxy-p-nitro-cinnamic acid is sparingly soluble in alcohol and crystallizes from it in fine white needles. It begins to melt at 218 ° C. with decomposition.
Aus dieser Säure wird in folgender Weise der m-Methoxy-p-nitrobenzaldehyd dargestellt.The m-methoxy-p-nitrobenzaldehyde is prepared from this acid in the following manner.
Die bei der Verseifung des m ~ Methoxyp-nitrozimmtsäuremethyläthers entstehende Lösung des Kaliumsalzes der m-Methoxy-p-nitrozimmtsäure wird soweit mit Wasser verdünnt, dafs auf 1 Theil Säure 100 Theile Wasser vorhanden sind. Dann wird eine kalte 1 proc. Lösung von Kaliumpermanganat nach und nach zugesetzt, bis im Filtrat keine Zimmtsäure mehr nachzuweisen ist. Der entstandene Aldehyd ist theils mit dem Manganniederschlag in weifsen Nadeln ausgefallen, theils ist er in der Lösung vorhanden. Die Mischung wird auf dem Wasserbade auf 750 C, erwärmt und dem Filtrat der Aldehyd durch Aether entzogen. Der vor dem Erwärmen ausgeschiedene Aldehyd krystallisirt beim Erkalten des Filtrats wieder aus in haarfeinen Nädelchen. Er schmilzt bei 62° C, ist löslich in Wasser, Alkohol, Benzol u. s. w., mit Aceton und Natronlauge giebt er zunächst eine farblose Lösung, aus welcher nach einiger Zeit ein Haufwerk feiner Nadeln krystallisirt. Der Schmelzpunkt dieses Condensätionsproduct es ist 84 ° C.The solution of the potassium salt of m-methoxy-p-nitrocinnamic acid which results from the saponification of m-methoxy-p-nitrozimmtsic acid is diluted with water to such an extent that 100 parts of water are present for 1 part of the acid. Then a cold 1 proc. Potassium permanganate solution gradually added until no more room acid can be detected in the filtrate. The aldehyde formed is partly precipitated in white needles with the manganese precipitate, and partly is present in the solution. The mixture is heated to 75 ° C. in the water bath and the aldehyde is removed from the filtrate by means of ether. The aldehyde separated out before heating crystallizes out again in hair-thin needles when the filtrate cools. It melts at 62 ° C, is soluble in water, alcohol, benzene, etc., with acetone and sodium hydroxide solution it first gives a colorless solution, from which after a time a pile of fine needles crystallizes. The melting point of this condensation product is 84 ° C.
2. Darstellung von Ferulasäure.2. Preparation of ferulic acid.
Als Ausgangsproduct dient auch hier m - Methoxyzimmtsäure. Letztere selbst oder einer ihrer Aether werden nitrirt, durch reducirende Mittel in die entsprechenden Amidoverbindungen und diese mit Hülfe von salpetrigsaurem Natron in Ferulasäure oder deren Aether übergeführt.Here, too, m-methoxycinnamic acid is used as the starting product. The latter itself or one of their ethers is nitrated by reducing agents into the corresponding amido compounds and these converted into ferulic acid or its ether with the aid of nitric acid soda.
m-Methoxyzimmtsäuremethyläther wird, wie unter 1. beschrieben, nitrirt und der m-Methoxyp - nitrozimmtsäuremethyläther verseift. Das Ammoniaksalz der m-Methoxy-p-nitrozimmtsäure wird in viel Wasser gelöst, die zur Reduction nöthige Menge Eisenvitriol eingetragen und darauf Ammoniakwasser bis zur alkalischen Reaction hinzugegossen. Nachdem ca. 20 Minuten auf dem Wasserbade digerirt worden ist, fällt aus der vom Eisenoxydniederschlag abfiltrirten Lösung durch Essigsäure nach einigerm-Methoxyzimmtsäuremethyläther is, as described under 1., nitrated and the m-methoxyp - saponified nitrozimmtsäuremethyläther. The ammonia salt of m-methoxy-p-nitrozimmtsäure is dissolved in a great deal of water, and the amount of iron vitriol necessary for the reduction is introduced and then ammonia water was poured in until it had an alkaline reaction. After about 20 minutes has been digested on the water bath, falls from the iron oxide precipitate filtered off Solution by acetic acid after some
Zeit die m - Methoxy - ρ - amidozimmtsäure in gelben Nädelchen, deren Schmelzpunkt bei ι 58° C. liegt.Time the m - methoxy - ρ - amidozimmtsäure in yellow needles, whose melting point at ι 58 ° C.
Durch Diazotirung mittelst Natriumnitrits und Erwärmen des Diazokörpers mit Wasser wird das salzsaure Salz der m-Methoxy-p-amidozimmtsäure in Ferulasäure umgewandelt.By diazotization by means of sodium nitrite and heating of the diazo body with water the hydrochloric acid salt of m-methoxy-p-amidozimmtsäure converted into ferulic acid.
m - Methoxy - ρ - nitrobenzaldehyd ist in bekannter Weise in Vanillin überzuführen.m - Methoxy - ρ - nitrobenzaldehyde can be converted into vanillin in a known manner.
Ferulasäure liefert nach Tiemann, Berl. Ber. XI, 650, bei der Oxydation Vanillin.Ferulic acid is supplied to Tiemann, Berl. Ber. XI, 650, vanillin on oxidation.
Claims (1)
Darstellung von m-Methoxy-p-nitrobenzaldehyd durch Oxydation der m-Methoxyp-nitrozimmtsäure. ■ : ■ ■
Darstellung von Ferulasäure oder deren Aethern aus m - Methoxyzimmtsäure oder deren Aethern durch auf einander folgende Nitrirung, Reduction, Behandlung der gebildeten p-Amidoverbindungen mitsalpetriger Säure und Zersetzen der entstandenen Diazo- - verbindung durch Erwärmen mit Wasser.P ATENT claims:
Preparation of m-methoxy-p-nitrobenzaldehyde by oxidation of m-methoxyp-nitrozimmtsäure. ■ : ■ ■
Preparation of ferulic acid or its ethers from m-methoxycinnamic acid or its ethers by successive nitration, reduction, treatment of the p-amido compounds formed with nitrous acid and decomposition of the diazo compound formed by heating with water.
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE32914C true DE32914C (en) |
Family
ID=308900
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT32914D Expired - Lifetime DE32914C (en) | Process for the preparation of m-methoxy-p-nitrobenzaldehyde and ferulic acid for the production of vanillin |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE32914C (en) |
-
0
- DE DENDAT32914D patent/DE32914C/en not_active Expired - Lifetime
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