DE3036078A1 - METHOD FOR PRODUCING MALACHITE GREEN OXALATE - Google Patents
METHOD FOR PRODUCING MALACHITE GREEN OXALATEInfo
- Publication number
- DE3036078A1 DE3036078A1 DE19803036078 DE3036078A DE3036078A1 DE 3036078 A1 DE3036078 A1 DE 3036078A1 DE 19803036078 DE19803036078 DE 19803036078 DE 3036078 A DE3036078 A DE 3036078A DE 3036078 A1 DE3036078 A1 DE 3036078A1
- Authority
- DE
- Germany
- Prior art keywords
- malachite green
- producing
- green oxalate
- oxalic acid
- water
- 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.)
- Granted
Links
- 229940002712 malachite green oxalate Drugs 0.000 title claims description 6
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 235000006408 oxalic acid Nutrition 0.000 claims description 9
- 229940107698 malachite green Drugs 0.000 claims description 5
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 4
- 239000000975 dye Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
- C09B11/10—Amino derivatives of triarylmethanes
- C09B11/12—Amino derivatives of triarylmethanes without any OH group bound to an aryl nucleus
- C09B11/20—Preparation from other triarylmethane derivatives, e.g. by substitution, by replacement of substituents
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
-Χ--Χ-
BAYER AKTIENGESELLSCHAFT 5090 Leverkusen, BayerwerkBAYER AKTIENGESELLSCHAFT 5090 Leverkusen, Bayerwerk
ZentralbereichCentral area
Patente, Marken und Lizenzen Mi/m-c 2 4. Sep. O-SC Patents, trademarks and licenses Wed / mc 2 Sep 4. O-SC
Verfahren zur Herstellung von Malachitgrün-OxalatProcess for the production of malachite green oxalate
Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung von Malachitgrün-Oxalat durch Umsetzung der Farbbase von Malachitgrün mit Oxalsäure in der Schmelze.The present invention relates to a process for the production of malachite green oxalate by reaction the color base of malachite green with oxalic acid in the melt.
Bevorzugt werden Farbbase und Oxalsäure im Molverhältnis von 1:1,4-2,5, insbesondere von 1:1,4-1,6, in Gegenwart von mindestens 30 - 100 Gew.-% und insbesondere 30 40 Gew.-%, (bezogen auf die Schmelze) Wasser umgesetzt. Die Angabe des Wassergehaltes bezieht sich auf das gesamte in der Reaktionsmischung vorhandene Wasser, d.h., daß sie auch das bei der Neutralisation frei werdende Wasser einschließt.Color base and oxalic acid in a molar ratio are preferred from 1: 1.4-2.5, in particular from 1: 1.4-1.6, in the presence of at least 30-100% by weight and in particular 30-40 % By weight (based on the melt) of water converted. The indication of the water content relates to the total water present in the reaction mixture, i.e. that it also includes the water released during the neutralization.
Die Reaktionstemperatur liegt vorzugsweise bei 40-700C, insbesondere bei 40-600C. Besonders hervorzuheben ist eine Reaktionstemperatur von 4 5-50°c.The reaction temperature is preferably from 40-70 0 C, especially at 40-60 0 C. Particularly noteworthy is a reaction temperature of 5-50 ° c 4.
Die Oxalsäure wird vorzugsweise in kristalliner Form, mit der Zusammensetzung C2H2O,*2H2O verwendet.The oxalic acid is preferably used in crystalline form, with the composition C 2 H 2 O, * 2H 2 O.
Le A 20 605Le A 20 605
Bei dem erfindungsgemäßen Verfahren werden Wassergehalt und Reaktionstemperatur so eingestellt, daß eine bei dieser Temperatur fließ- und rührfähige Schmelze entsteht.In the process according to the invention, the water content and reaction temperature adjusted so that one at at this temperature flowable and stirrable melt is formed.
Die Trocknung des Malachitgrün-Oxalates erfolgt bei maximal 750C, vorzugsweise bei 45-500C, im Vakuum.The drying of the malachite green oxalate is carried out at a maximum of 75 0 C, preferably at 45-50 0 C, in vacuo.
Die technische Durchführung des Verfahrens kann so erfolgen, daß Umsetzung und Trocknung im gleichen Reaktionsapparat (z.B. Vakuumschaufeltrockner) erfolgen. Es kann aber auch die umsetzung in einem Rührwerksbehälter erfol- -|0 gen und die Trocknung des Harzes unter den angegebenen Bedingungen nach einem beliebigen technischen Trockenverfahren. The technical implementation of the process can be carried out in such a way that reaction and drying take place in the same reaction apparatus (e.g. vacuum paddle dryer). It can but the implementation in an agitator tank is also successful. - | 0 gene and the drying of the resin below the specified Conditions according to any technical dry process.
Das bekannte, technisch brauchbare Verfahren zur Herstellung von Malachitgrün (Colour Index 42 000) ist die Kondensation von Benzaldehyd mit Dimethylanilin, Oxidation der Leukobase mit Bleidioxid, Isolierung des Farbstoffes als Pb-SaIz, überführung des Bleisalzes in die Farbstoffbase, Isolieren der Farbbase, Lösen der Base in wäßriger Oxalsäure und Auskristallisieren des Oxalates. Dieses Verfahren ist z.B. beschrieben in Ulimanns Encyclopädie der techn. Chemie Bd. 17 (1966) S. 666-667.The known, technically useful process for the production of malachite green (Color Index 42,000) is Condensation of benzaldehyde with dimethylaniline, oxidation of the leuco base with lead dioxide, isolation of the dye as Pb salt, transfer of the lead salt into the dye base, Isolate the color base, dissolve the base in aqueous oxalic acid and crystallize out the oxalate. This The method is described, for example, in Ulimann's Encyclopedia of techn. Chemie Vol. 17 (1966) pp. 666-667.
Nachteile des auf dieser Grundlage durchgeführten Verfahrens ist die zur Lösung des Farbstoffs erforderliche große Wasermenge. Zur Herstellung einer bei 700C gesättigten wäßrigen Lösung von Malachitgrün-Oxalat ist ca. die vierfache Gewichtsmenge Wasser erforderlich.Disadvantages of the process carried out on this basis is the large amount of water required to dissolve the dye. To produce an aqueous solution of malachite green oxalate which is saturated at 70 ° C., approximately four times the amount by weight of water is required.
Le A 20 605Le A 20 605
Die bei der Isolierung des Farbstoffs nach der Kristallisation anfallende Mutterlauge belastet das Abwasser und bewirkt einen Ausbeuteverlust.The mother liquor obtained during the isolation of the dye after the crystallization pollutes the waste water and causes a loss of yield.
Überraschenderweise wurde nun gefunden, daß nach dem neuen Verfahren, bei dem diese Nachteile vermieden werden, ein Farbstoff erhalten wird, dessen physikalische und coloristische Eigenschaften mit den Eigenschaften des nach dem bekannten Verfahren erhältlichen Farbstoffs identisch sind. Es war insbesondere nicht vorhersehbar, daß die nach den beiden Verfahren hergestellten Farbstoffe eine stochiometrxsch gleiche Zusammensetzung der Kristalle besitzen.Surprisingly, it has now been found that after new process in which these disadvantages are avoided, a dye is obtained, its physical and coloristic properties with the properties of obtainable by the known process dye are identical. In particular, it was unpredictable that the dyes produced by the two processes have a stoichiometrically identical composition of the Own crystals.
Le A 20 605Le A 20 605
In einen auf 4 5 bis 500C erwärmten Rührwerksbehälter werden unter Rühren 100 kg feuchte Malachitgrünfarbbase (Wassergehalt 28,2 %) und innerhalb von 5 Minuten 25 kg kristalline Oxalsäure (C3H4O4"2H2O) eingetragen. Nach100 kg of moist malachite green color base (water content 28.2%) and, within 5 minutes, 25 kg of crystalline oxalic acid (C 3 H 4 O 4 "2H 2 O) are introduced into a stirred tank heated to 45 to 50 ° C. With stirring
maximal 10 Minuten ist der Ansatz dünnflüssig und homogen. Nun werden insgesamt 1 .600 kg der Farbbase und 40 0 kg der kristallinen Oxalsäure in Portionen zugegeben. In die dünnflüssige homogene Mischung werden dann noch 223 kg kristalline Oxalsäure gegeben. Dabei wird eine Temperatur von 45 - 500C aufrechterhalten. Es wird eine Stunde bei 45°C gerührt. Die Schmelze wird dann im Vakuum bei 4 5-500C getrocknet.The mixture is thin and homogeneous for a maximum of 10 minutes. Now a total of 1,600 kg of the color base and 40 0 kg of the crystalline oxalic acid are added in portions. 223 kg of crystalline oxalic acid are then added to the thin, homogeneous mixture. A temperature of 45-50 ° C. is maintained during this. The mixture is stirred at 45 ° C. for one hour. The melt is then dried in vacuo at 4 5-50 0 C.
Le A 20 605Le A 20 605
Claims (3)
Molverhältnis 1:1,4-1,6 in Gegenwart von mindestens 30 Gew.-% Wasser bei 40-700C umsetzt.2. The method according to claim 1, characterized in that malachite green color base and oxalic acid in
Molar ratio 1: 1.4-1.6 in the presence of at least 30% by weight of water at 40-70 0 C.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19803036078 DE3036078A1 (en) | 1980-09-25 | 1980-09-25 | METHOD FOR PRODUCING MALACHITE GREEN OXALATE |
| JP56148919A JPS5785856A (en) | 1980-09-25 | 1981-09-22 | Manufacture of malachite green oxalate |
| GB8128953A GB2084604B (en) | 1980-09-25 | 1981-09-24 | Process for the preparation of malachite green oxalate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19803036078 DE3036078A1 (en) | 1980-09-25 | 1980-09-25 | METHOD FOR PRODUCING MALACHITE GREEN OXALATE |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| DE3036078A1 true DE3036078A1 (en) | 1982-05-06 |
| DE3036078C2 DE3036078C2 (en) | 1988-07-07 |
Family
ID=6112778
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19803036078 Granted DE3036078A1 (en) | 1980-09-25 | 1980-09-25 | METHOD FOR PRODUCING MALACHITE GREEN OXALATE |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPS5785856A (en) |
| DE (1) | DE3036078A1 (en) |
| GB (1) | GB2084604B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2322973C1 (en) * | 2006-11-29 | 2008-04-27 | Михаил Владимирович Кутушов | Use of malachite green as drug in treatment of malignant neoplasm |
| US8436195B2 (en) | 2006-11-29 | 2013-05-07 | Evgeny Pavlovich Germanov | Use of malachite green oxalate for treating malignant neoplasms |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2928466A1 (en) * | 1979-07-13 | 1981-01-29 | Bayer Ag | METHOD FOR PRODUCING CATIONIC DYES |
-
1980
- 1980-09-25 DE DE19803036078 patent/DE3036078A1/en active Granted
-
1981
- 1981-09-22 JP JP56148919A patent/JPS5785856A/en active Granted
- 1981-09-24 GB GB8128953A patent/GB2084604B/en not_active Expired
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2928466A1 (en) * | 1979-07-13 | 1981-01-29 | Bayer Ag | METHOD FOR PRODUCING CATIONIC DYES |
Non-Patent Citations (1)
| Title |
|---|
| ULLMANN: Encyklopädie der technischen Chemie, Bd.17, (1966), S.666-667 * |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2084604A (en) | 1982-04-15 |
| JPS5785856A (en) | 1982-05-28 |
| GB2084604B (en) | 1984-06-06 |
| JPH0155305B2 (en) | 1989-11-24 |
| DE3036078C2 (en) | 1988-07-07 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 8110 | Request for examination paragraph 44 | ||
| D2 | Grant after examination | ||
| 8364 | No opposition during term of opposition | ||
| 8339 | Ceased/non-payment of the annual fee |