JPH0155305B2 - - Google Patents
Info
- Publication number
- JPH0155305B2 JPH0155305B2 JP56148919A JP14891981A JPH0155305B2 JP H0155305 B2 JPH0155305 B2 JP H0155305B2 JP 56148919 A JP56148919 A JP 56148919A JP 14891981 A JP14891981 A JP 14891981A JP H0155305 B2 JPH0155305 B2 JP H0155305B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- malachite green
- oxalic acid
- dye
- reaction
- 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
Links
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 235000006408 oxalic acid Nutrition 0.000 claims description 8
- 229940107698 malachite green Drugs 0.000 claims description 4
- 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 4
- 229940002712 malachite green oxalate Drugs 0.000 claims description 4
- 239000001046 green dye Substances 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 239000000975 dye Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000155 melt Substances 0.000 description 3
- 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
- 238000001035 drying Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000000203 mixture Substances 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
- 238000006887 Ullmann reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000006482 condensation reaction Methods 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 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
- 238000002360 preparation method Methods 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
- 238000000926 separation method Methods 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
【発明の詳細な説明】
本発明は、マラカイト・グリーンの染料塩基を
溶融状態でシユウ酸と反応させることによるマラ
カイト・グリーンシユウ酸塩の製造法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for the preparation of malachite green oxalate by reacting the malachite green dye base in the melt with oxalic acid.
染料塩基及びシユウ酸は、水少くとも30〜100
重量％及び特には30〜40重量％（溶融物に対し
て）の存在下に、１：1.4〜2.5、特には１：1.4〜
1.6のモル比で好適に反応せしめられる。含水量
の値は反応混合物中に存在する全水に関する。即
ちそれは中和中に遊離する水を含む。 The dye base and oxalic acid are mixed with water at least 30-100%
1:1.4-2.5, especially 1:1.4-2.5 in the presence of % by weight and especially 30-40% by weight (based on the melt)
The reaction is preferably carried out at a molar ratio of 1.6. The water content values relate to the total water present in the reaction mixture. That is, it contains the water liberated during neutralization.
反応温度は好ましくは40〜70℃、特には40〜60
℃である。45〜50℃の反応温度は特に言及しう
る。 The reaction temperature is preferably 40-70°C, especially 40-60°C.
It is ℃. Particular mention may be made of reaction temperatures of 45-50°C.
シユウ酸は好ましくは組成C2H2O4・2H2Oの結
晶の形で使用される。 Oxalic acid is preferably used in crystalline form with the composition C 2 H 2 O 4 .2H 2 O.
本発明の方法において、含水量及び反応温度
は、流動せしめうる及び撹拌しうる溶融物がこの
温度で生成するように調節される。 In the process of the invention, the water content and the reaction temperature are adjusted such that a flowable and stirrable melt is produced at this temperature.
マラカイト・グリーンシユウ酸塩を、真空下に
75℃の最高温度で、好ましくは45〜50℃で乾燥す
る。 Malachite green oxalate under vacuum
Dry at a maximum temperature of 75°C, preferably at 45-50°C.
本方法は、反応と乾燥が同一の反応装置（例え
ば真空羽根乾燥機）中で起こるような方法で工業
的に行なうことができる。しかしながら、反応を
撹拌容器中で行ない、樹脂を所望の工業的な乾燥
工程による条件下に乾燥することも可能である。 The process can be carried out industrially in such a way that reaction and drying occur in the same reactor (eg vacuum vane dryer). However, it is also possible to carry out the reaction in a stirred vessel and to dry the resin under the conditions of the desired industrial drying process.
マラカイト・グリーン（Colour Indcx 42000）
の製造に工業的に使用できる公知の方法は、ベン
ズアルデヒドをジメチルアニリンとの縮合反応に
供し、リユーコ塩基を二酸化鉛で酸化し、染料を
鉛塩として分離し、鉛塩を染料塩基に転化し、染
料塩基を分離し、塩基を水性シユウ酸に溶解し及
びシユウ酸塩を晶出させることを含んでなる。こ
の方法は例えばUllmanns Encyclopadie der
techn.Chemie、第17巻、666〜667頁（1966年）
に記述されている。 Malachite Green (Colour Indcx 42000)
A known method that can be used industrially for the production of is subjecting benzaldehyde to a condensation reaction with dimethylaniline, oxidizing the lyuco base with lead dioxide, separating the dye as a lead salt, converting the lead salt to the dye base, The method comprises separating the dye base, dissolving the base in aqueous oxalic acid, and crystallizing the oxalate salt. This method is described, for example, in Ullmanns Encyclopadie der
techn.Chemie, Vol. 17, pp. 666-667 (1966)
It is described in
この基準で行なわれる方法の欠点は、染料を溶
解させるために多量の水が必要なことである。70
℃で飽和のマラカイト・グリーンシユウ酸塩の水
溶液を製造るためには、重量で約４倍量の水が必
要である。染料の分離中、結晶後に得られる母液
は排水を汚染し、収率を低下させる。 A disadvantage of the process carried out on this basis is that a large amount of water is required to dissolve the dye. 70
To prepare a saturated aqueous solution of malachite green oxalate at .degree. C., approximately 4 times the amount of water by weight is required. During the separation of the dye, the mother liquor obtained after crystallization pollutes the waste water and reduces the yield.
驚くことに、物理的な及び色彩の性質が公知の
方法で製造される染料の性質に同等である染料
が、上述の欠点を回避する新規な方法で製造でき
ることが今回発見された。特に２つの方法で製造
される染料の結晶の組成は化学量論的に同一であ
るということは予見できるものではなかつた。 Surprisingly, it has now been found that dyes whose physical and color properties are comparable to those of dyes produced by known methods can be produced by a new method that avoids the above-mentioned drawbacks. In particular, it was not foreseeable that the composition of the dye crystals produced by the two methods would be stoichiometrically identical.
実施例
撹拌しながら45〜50℃までに暖めた容器中に湿
つたマラカイト・グリーン染料塩基（含水量：
28.2％）100Kgを導入し、結晶シユウ酸
（C2H2O4・2H2O）25Kgを５分間に亘つて添加し
た。高々10分後、バツチは流動性となり、均一と
なつた。染料塩基1600Kg及び結晶シユウ酸400Kg
の全量を一部ずつ添加した。次いで更なる結晶シ
ユウ酸223Kgを流動性の均一な混合物中に導入し
た。この工程中、温度45〜50℃に保つた。撹拌を
45℃で１時間継続した。次いで溶融物を真空下に
45〜50℃で乾燥した。EXAMPLE Malachite green dye base (water content:
28.2%) and 25 kg of crystalline oxalic acid (C 2 H 2 O 4 .2H 2 O) were added over 5 minutes. After at most 10 minutes, the batch became fluid and homogeneous. Dye base 1600Kg and crystalline oxalic acid 400Kg
The entire amount was added in portions. A further 223 kg of crystalline oxalic acid was then introduced into the fluid homogeneous mixture. During this step, the temperature was kept at 45-50°C. stir
It lasted for 1 hour at 45°C. The melt is then placed under vacuum
Dry at 45-50°C.
Claims (1)
を溶融状態で、モル比１：1.4〜2.5で、40〜70℃
において、30〜100重量％の水の存在下に、ここ
に水の量は反応混合物中に存在するすべての水の
量である、反応させることを特徴とするマラカイ
ト・グリーンシユウ酸塩の製造方法。1 Malachite green dye base and oxalic acid in a molten state at a molar ratio of 1:1.4 to 2.5 at 40 to 70°C
A process for producing malachite green oxalate, characterized in that it is reacted in the presence of 30 to 100% by weight of water, where the amount of water is the amount of all water present in the reaction mixture. .
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 |
|---|---|
| JPS5785856A JPS5785856A (en) | 1982-05-28 |
| JPH0155305B2 true JPH0155305B2 (en) | 1989-11-24 |
Family
ID=6112778
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56148919A Granted JPS5785856A (en) | 1980-09-25 | 1981-09-22 | Manufacture of 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 |
|---|---|---|---|---|
| EP2100603A4 (en) | 2006-11-29 | 2011-06-22 | Germanov Evgeny Pavlovich | Use of malachite green in the form of drug for treating malignant neoplasms |
| RU2322973C1 (en) * | 2006-11-29 | 2008-04-27 | Михаил Владимирович Кутушов | Use of malachite green as drug in treatment of malignant neoplasm |
Family Cites Families (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
Also Published As
| Publication number | Publication date |
|---|---|
| DE3036078C2 (en) | 1988-07-07 |
| DE3036078A1 (en) | 1982-05-06 |
| GB2084604B (en) | 1984-06-06 |
| GB2084604A (en) | 1982-04-15 |
| JPS5785856A (en) | 1982-05-28 |
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