DE209910C - - Google Patents
Info
- Publication number
- DE209910C DE209910C DENDAT209910D DE209910DA DE209910C DE 209910 C DE209910 C DE 209910C DE NDAT209910 D DENDAT209910 D DE NDAT209910D DE 209910D A DE209910D A DE 209910DA DE 209910 C DE209910 C DE 209910C
- Authority
- DE
- Germany
- Prior art keywords
- indigoid
- group
- coh
- naphtol
- aromatic series
- 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
- 239000000975 dye Substances 0.000 claims description 14
- 150000001299 aldehydes Chemical class 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 125000003172 aldehyde group Chemical group 0.000 claims description 2
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000003776 cleavage reaction Methods 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-Naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- JXDYKVIHCLTXOP-UHFFFAOYSA-N Isatin Chemical class C1=CC=C2C(=O)C(=O)NC2=C1 JXDYKVIHCLTXOP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001311 chemical methods and process Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing Effects 0.000 description 2
- ZTMADXFOCUXMJE-UHFFFAOYSA-N 2-methylbenzene-1,3-diol Chemical compound CC1=C(O)C=CC=C1O ZTMADXFOCUXMJE-UHFFFAOYSA-N 0.000 description 1
- RWZYAGGXGHYGMB-UHFFFAOYSA-N Anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 1
- QFFVPLLCYGOFPU-UHFFFAOYSA-N Barium chromate Chemical compound [Ba+2].[O-][Cr]([O-])(=O)=O QFFVPLLCYGOFPU-UHFFFAOYSA-N 0.000 description 1
- 229910014033 C-OH Inorganic materials 0.000 description 1
- 229910014570 C—OH Inorganic materials 0.000 description 1
- HKOOXMFOFWEVGF-UHFFFAOYSA-N Phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N Resorcinol Natural products OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 150000007857 hydrazones Chemical class 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 229940067157 phenylhydrazine Drugs 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
- C07C45/562—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with nitrogen as the only hetero atom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Indole Compounds (AREA)
Description
KAISERLICHESIMPERIAL
PATENTAMT.PATENT OFFICE.
PATENTSCHRIFTPATENT LETTERING
-M 209910-KLASSE 12 o. GRUPPE -M 209910-CLASS 12 or GROUP
KALLE & CO. AKT-GES. in BIEBRICH -a. Rh.KALLE & CO. ACT-TOTAL in BIEBRICH -a. Rh.
Verfahren zur Darstellung von Aldehyden der aromatischen Reihe mit mindestens einer Oxygruppe in benachbarter Stellung zur Aldehydgruppe. ·Process for the preparation of aldehydes of the aromatic series with at least an oxy group adjacent to the aldehyde group. ·
Patentiert im Deutschen Reiche vom 9. Januar 1908 ab. Patented in the German Empire on January 9, 1908 .
Werden Verbindungen der aliphatischen oder aromatischen Reihe, welche die Atomgruppe Are compounds of the aliphatic or aromatic series, which are the atomic group
-CH9-CO- oder -CH: COH- -CH 9 -CO- or -CH: COH-
C .C.
enthalten, mit reaktionsfähigen α - Isatinderivaten kondensiert, so entstehen indigoide Farbstoffe von folgender allgemeiner Zusammensetzung: contain, condensed with reactive α-isatin derivatives, indigoid dyes are formed of the following general composition:
, — C , - C
c =c =
I C = O I C = O
C Ov C Ov
4545
oder C =. C or C =. C.
C„H4.,C "H 4. ,
Diese Farbstoffe erleiden bei der Behandlung mit Ätzalkalien eine tiefgreifende Veränderung.These dyes undergo a profound change when they are treated with caustic alkalis.
Zuerst lagert sich unter Lösung einer doppelten Bindung Natronlauge an:First, sodium hydroxide solution is deposited under a double bond:
OHOH
I /I /
Il ^ C-ONa Il ^ C-ONa
Ο.Ο.
5555
>CtHt.> C t H t .
6060
Die entstandenen Additionsverbindungen sind noch gefärbt, werden aber bei der weiteren Behandlung entfärbt und vollständig gespalten, wobei Oxyaldehyde und Anthranilsäure entstehen:The resulting addition compounds are still colored, but will become in the further treatment discolored and completely split, producing oxyaldehydes and anthranilic acid:
s ,0 C00Hs s, 0 C00H s
C-c/ :+ Il \ff ■ . ■ NH/ C-OH 65 Cc / : + Il \ ff ■. ■ NH / C-OH 65
Bei den indigoiden Farbstoffen, die einen Komponenten der aliphatischen Reihe enthalten, geht die Reaktion noch weiter, indem Zersetzung der aliphatischen OxyaldehydeIn the case of the indigoid dyes, the one Containing components of the aliphatic series, the reaction continues by adding Decomposition of the aliphatic oxyaldehydes
7070
erfolgt, so daß sie nicht gefaßt werden können.takes place so that they cannot be caught.
Der chemische Vorgang sei an folgenden typischen Beispielen erläutert:The chemical process is explained using the following typical examples:
Indigoide Farbstoffe aus a - Isatinderivaten + β - Naphtol:Indigoid dyes from a - isatin derivatives + β - naphtol:
C ° C °
IiIi
C-HC-H
K/OHK / OH
COOKCOOK
NH,NH,
CHCH
Indigoide Farbstoffe aus α - Isatinderivaten -f α-Naphtol: O Indigoid dyes from α - isatin derivatives -f α-naphtol: O
COOH, NH,COOH, NH,
Indigoide Farbstoffe aus α - Isatinderivaten -f- Resorcin:Indigoid dyes from α - isatin derivatives -f- resorcinol:
C Os C O s
•Ν η/ Oi? • Ν η / Oi?
COHCOH
Es ist selbstverständlich, daß bei Verwendung entsprechender Substitutionsprodukte der indigoiden Farbstoffe auch substituierte Oxyaldehyde erhalten werden. Die aufgefundene Synthese von Oxyaldehyden verläuft in allen bisher geprüften Fällen gut und stellt einen einfachen Weg zur Darstellung dieser Körper vor.It goes without saying that if appropriate substitution products are used, the indigoid dyes also substituted oxyaldehydes can be obtained. The found synthesis of oxyaldehydes proceeds well in all cases examined so far and represents one easy way to represent this body.
Aus dem chemischen Vorgang der gekennzeichneten Reaktion ergibt sich, daß die aufgefundene Synthese nicht an die Verwendung von Isatinderivaten gebunden ist; sie stellen lediglich ein Mittel zur Einführung des mit zwei Valenzen gebundenen Kohlenstoffs vor.From the chemical process of the marked reaction it follows that the one found Synthesis is not tied to the use of isatin derivatives; they merely provide a means of introducing the with two valences of bonded carbon.
„ Beispiel." Example.
ι kg des aus α-Naphtol und α - Isatinanilid dargestellten Farbstoffes werden mit 10 kg Natronlauge von 10 Prozent erwärmt, bis die zunächst grüngefärbte Lösung hellgelb wird und beim Ansäuern keinen Farbstoff mehr abscheidet. Ist dieser Punkt erreicht, so läßt man erkalten; es kristallisiert dann beim Stehen das Natronsalz des i-Oxy-2-naphtaldehyds in gelblichen Kristallen aus. Da dieseι kg of the from α-naphtol and α - isatin anilide The dye shown are heated with 10 kg of 10 percent sodium hydroxide solution until the initially green-colored solution turns pale yellow and no more dye when acidified separates. Once this point has been reached, one lets it cool down; it then crystallizes at the Are the sodium salt of i-oxy-2-naphthaldehyde in yellowish crystals. This one
ziemlich leicht löslich sind, so erfolgt nur beim Arbeiten in großer Konzentration Abscheidung. Um den Aldehyd aus der Reaktionsmasse zu isolieren,. säuert man an, destilliert mit Wasserdampf, mit dem die Verbindung nur schwer flüchtig ist, oder versetzt die alkalische Lösung mit Kochsalz, wodurch sich das in Kochsalzlösung fast unlösliche Natronsalz des Aldehyds in grünlich gelblichen Blättchen abscheidet. Aus Alkohol umkristallisiert, erhält man den Oxyaldehyd in langen kompakten Nadeln vom F. P.,600; in Wasser sind sie unlöslich, in den gebräuchlichen Lösungsmitteln leicht löslich. Mit Phenylhydrazin erhält man (beim Erwärmen in essigsaurer Lösung) ein schwer lösliches Hydrazon. Mit Methylsulfat wird der Methyläther des Aldehyds erhalten, der sich noch in Bisulfit löst. Der i-Oxy-2-naphtaldehyd besitzt einen angenehmen Geruch.are fairly easily soluble, separation only takes place when working in high concentrations. To isolate the aldehyde from the reaction mass. it is acidified, distilled with steam, with which the compound is only slightly volatile, or the alkaline solution is mixed with common salt, whereby the sodium salt of the aldehyde, which is almost insoluble in common salt solution, is deposited in greenish yellowish flakes. Recrystallized from alcohol, the oxyaldehyde is obtained in long, compact needles from FP, 60 0 ; they are insoluble in water and easily soluble in common solvents. With phenylhydrazine, a sparingly soluble hydrazone is obtained (when heated in acetic acid solution). With methyl sulfate, the methyl ether of the aldehyde is obtained, which still dissolves in bisulfite. The i-oxy-2-naphthaldehyde has a pleasant odor.
Bei Verwendung des aus ß-Naphtol erhältlichen indigoiden Farbstoffes wird der bekannte 2-Oxy-i-naphtaldehyd vom F. P. 820 erhalten.When using the indigoid dye obtainable from ß-naphtol, the known 2-oxy-i-naphthaldehyde is obtained from FP 82 0 .
Im folgenden seien noch die Eigenschaften einiger nach Vorliegendem Verfahren erhältlicher Aldehyde angegeben:In the following, the properties of some of the properties that can be obtained using the present process are also available Aldehydes stated:
a)a)
OHOH
ίο aus dem indigoiden Farbstoff aus a-Methoxyft - naphtol:ίο from the indigoid dye from a-methoxyft - naphtol:
Zitronengelbe Nadeln, schwer flüchtig mit Wasserdampf, fast geruchlos; F. P. ioo°.Lemon-yellow needles, hardly volatile with steam, almost odorless; F. P. ioo °.
■ ' b)■ 'b)
OHOH
ιι
/Cl/ Cl
COHCOH
aus dem indigoiden Farbstoff aus 2-Chloret
- naphtol:
F. P. 2io° unter Zersetzung.from the indigoid dye from 2-chloroet - naphtol:
FP 2io ° with decomposition.
OHOH
COHCOH
aus dem indigoiden Farbstoff aus Monomethylresorcinäther: from the indigoid dye from monomethylresorcinol ether:
F. P. 410 (nicht 620, wie in der Literatur angegeben), besitzt einen starken angenehmen Geruch.FP 41 0 (not 62 0 , as stated in the literature) has a strong, pleasant odor.
Claims (1)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE209910C true DE209910C (en) |
Family
ID=471844
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT209910D Active DE209910C (en) |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE209910C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5155277A (en) * | 1990-06-11 | 1992-10-13 | Rhone-Poulenc Nutrition Animale | Process for converting tertiary amine n-oxides to aldehydes |
| WO2008154484A1 (en) * | 2007-06-08 | 2008-12-18 | Mannkind Corporation | Ire-1a inhibitors |
-
0
- DE DENDAT209910D patent/DE209910C/de active Active
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5155277A (en) * | 1990-06-11 | 1992-10-13 | Rhone-Poulenc Nutrition Animale | Process for converting tertiary amine n-oxides to aldehydes |
| WO2008154484A1 (en) * | 2007-06-08 | 2008-12-18 | Mannkind Corporation | Ire-1a inhibitors |
| US7858666B2 (en) | 2007-06-08 | 2010-12-28 | Mannkind Corporation | IRE-1α inhibitors |
| JP2011121964A (en) * | 2007-06-08 | 2011-06-23 | Mannkind Corp | IRE-1alpha INHIBITOR |
| US8614253B2 (en) | 2007-06-08 | 2013-12-24 | Mannkind Corporation | IRE-1α inhibitors |
| US9241942B2 (en) | 2007-06-08 | 2016-01-26 | Mannkind Corporation | IRE-1α inhibitors |
| US9546149B2 (en) | 2007-06-08 | 2017-01-17 | Mannkind Corporation | IRE-1α inhibitors |
| US9981901B2 (en) | 2007-06-08 | 2018-05-29 | Fosun Orinove Pharmatech, Inc. | IRE-1α inhibitors |
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