CN1276371A - Process for preparing crystal violet lactone - Google Patents
Process for preparing crystal violet lactone Download PDFInfo
- Publication number
- CN1276371A CN1276371A CN 00113433 CN00113433A CN1276371A CN 1276371 A CN1276371 A CN 1276371A CN 00113433 CN00113433 CN 00113433 CN 00113433 A CN00113433 A CN 00113433A CN 1276371 A CN1276371 A CN 1276371A
- Authority
- CN
- China
- Prior art keywords
- violet lactone
- crystal violet
- colourless crystallization
- preparation
- varsol
- 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
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
- C09B11/14—Preparation from aromatic aldehydes, aromatic carboxylic acids or derivatives thereof and aromatic amines
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A process for preparing crystal voilet lactone with low cost and high quality features that extracting equipment is unnecessary, it is only thing to remove impurities with hydrocarbon solvent, the solvent can be removed by azeotropic distillation for recovering solvent, the catalytic air oxidizing or oxygen oxidizing is used for low cost and high quality, and the mother liquor containing catalyst and alkali solution can be cyclically used for less environmental pollution and lower cost.
Description
The invention belongs to the preparation production method of crystal violet lactone.
The formal name used at school of crystal violet lactone is: 3, and two (4-the dimethylamino phenyl)-6-dimethylamino phthalides of 3-, structural formula is:
Crystal violet lactone (being called for short CVL)
Crystal violet lactone is a kind of pressure sensitive dye, is again a kind of heat sensitive dye, mainly as pressure-sensitive carbon paper and electrothermal sensitive recording paper.
Preparation method about crystal violet lactone once had multiple report abroad.1984 United States Patent (USP) 4455435 reports are earlier with paradimethy laminobenzaldehyde, m-dimethyl amino benzoic acid and N, accelerine is condensation in strongly acidic solution, in basic solution, extract to remove three (to dimethylamino phenyl) methane again, obtain the colourless crystallization violet lactone with toluene:
Colourless crystallization violet lactone (being called for short LCVL)
Then with Potassium Persulphate with the oxidation of colourless crystallization violet lactone, obtain crystal violet lactone, the overall yield of crystal violet lactone is 31.8%.This method has two shortcomings:
1) use toluene when 55 ℃ of extraction three (to dimethylamino phenyl) methane, because the mutual solublization of toluene, colourless crystallization violet lactone and three (to dimethylamino phenyl) methane, part colourless crystallization violet lactone enters organic phase and loses when making extraction, and the toluene solution of methane is emulsified in not only aqueous phase and makes in the colourless crystallization violet lactone sodium salt but also be mixed with impurity three (to dimethylamino phenyl) methane and toluene because the surfactivity of colourless crystallization violet lactone sodium salt is dissolved with impurity three (to dimethylamino phenyl) simultaneously.Such end-result is that the productive rate of colourless crystallization violet lactone is low, and is of poor quality.
2) owing to the employing chemical reagent oxidizes, the poor selectivity of oxidation, reaction is not easy to stop at the crystal violet lactone stage, is easy to generate over oxidation, and productive rate is reduced, and quality product decline, makes the outward appearance of product be brown, fusing point decline.
United States Patent (USP) 4271075 in 1981 has been reported with cobalt complex and has been made catalyzer hydrogen peroxide oxidation colourless crystallization violet lactone, the synthetic crystallization violet lactone, but the ligand 1 of these cobalt complexs-[(2 hydroxy naphthalene base) azo]-2-hydroxyl-5-Phenylsulfonic acid, 1-[(2-hydroxyl naphthyl-5-nitrophenyl) azo]-2-hydroxyl-3,6-naphthalene disulfonic acid, 1-[(1-phenyl-3-methyl-5-pyrazolone-4-yl) azo]-2-hydroxyl-4-naphthene sulfonic acid, 1-[(1-phenyl-3-methyl-5-pyrazolone-4-yl) azo]-complicated molecule that the 2-hydroxyl-4-naphthoic acid etc. is difficult to obtain.
United States Patent (USP) 4233223 had been reported in the presence of the iron cyanogen compound with hydrogen peroxide oxidation colourless crystallization violet lactone synthetic crystallization violet lactone in 1980, but because over oxidation problem, even reach in colourless crystallization violet lactone purity under 99.1% the situation, oxidation products is still impure, and need just can obtain fusing point at the ethylene glycol monobutyl ether recrystallization is 179～180 ℃ product.So both increase running cost, increased raw materials cost again.
The purpose of this invention is to provide a kind of overall yield height, cost is low, and the equipment closing operation is all simple, the method for preparing crystal violet lactone of good product quality.
The present invention handles m-dimethyl amino benzoic acid with varsol, paradimethy laminobenzaldehyde and N, accelerine in the acidic solution condensation and the crude product of colourless crystallization violet lactone, to remove impurity three (to dimethylamino phenyl) methane, after leaching varsol, component distillation is removed residual hydro carbons flux under alkaline condition, add transistion metal compound and part, or make catalyzer by the salt that part negatively charged ion and transition metal ion are formed, bubbling air or oxygen a few hours under heating condition, suction filtration or centrifugal, washing, be drying to obtain the product crystal violet lactone, the product fusing point is 180～181 ℃.The mother liquor of oxidation after-filtration contains catalyzer and alkali lye, and this mother liquor is reclaimed, and recycles during as oxidation next time, with abundant saving cost.
The used varsol of the present invention is gasoline, kerosene, diesel oil, Skellysolve A, normal hexane, hexanaphthene, suberane, heptane, sherwood oil, petroleum naphtha, benzene, toluene, p-Xylol, o-Xylol, m-xylene, biphenyl, biphenyl derivatives, chlorobenzene, or by two or three mixed solvent of being formed of above-mentioned solvent, the mixed solvent formed of benzene and sherwood oil preferably.
The present invention is 8-14 in the pH of the used alkaline condition of component distillation value.
Transistion metal compound mainly is cobalt compound, copper-containing compound and iron containing compounds in the used oxide catalyst of the present invention.Cobalt compound is halogenation cobalt, Xiao Suangu, Cobaltous diacetate, cobaltous hydroxide etc. preferably, copper-containing compound is cuprous halide, copper halide, neutralized verdigris, cuprous acetate preferably, cupric nitrate, copper hydroxide etc., iron containing compounds preferably is ferrous halide, iron halide, iron acetate, Iron diacetate, iron nitrate, the Trisodium hexacyanoferrate, the Tripotassium iron hexacyanide, yellow prussiate of potash, yellow prussiate of soda, ironic hydroxide, ferrous hydroxide.
The part of the composition catalyzer that the present invention is used has alcohol acid negatively charged ion, amino acid negatively charged ion, complexone negatively charged ion, cyanogen root (CN
-) negatively charged ion, nitrogen-containing heterocycle compound etc., best ligand reagent is tartrate and other sodium salt, sylvite and ammonium salt, ethylenediamine tetraacetic acid (EDTA) and other sodium salt, sylvite, Whitfield's ointment and other sodium salt, sylvite and ammonium salt, potassium cyanide, sodium cyanide, dimethyl formyl ammonium, oxine.
Atmospheric oxidation of the present invention or dioxygen oxidation temperature are 40～100 ℃.
The present invention obviously is better than prior art.This technology has following advantage: 1) do not need extraction plant, only need to handle the impurity that just can remove in the colourless crystallization violet lactone with varsol.2) remove by component distillation and remain in solvent in the colourless crystallization violet lactone, both, economized except drying process again with having received solvent.3) adopt catalytic air oxidation or dioxygen oxidation,, prevented over oxidation, thereby improved productive rate and quality product compared with adopting the chemical reagent oxidizes method both to reduce cost.The productive rate in one step of oxidation reaches 95%, and overall yield can reach 45%～50%, and the product fusing point reaches 181～183 ℃.4) oxide catalyst of the present invention and catalyst ligand compound of usually seeing of right and wrong all is cheap and easy to get.Especially catalyst ligand, the part that the present invention uses compared with United States Patent (USP) 4271075 such as 1-[(2-hydroxyl naphthyl) azo]-2-hydroxyl-5-Phenylsulfonic acid, 1-[(2-hydroxyl naphthyl-5-nitrophenyl) azo]-2-hydroxyl-3,6-naphthalene disulfonic acid, 1-[(1-phenyl-3-methyl-5-pyrazolone-4-yl) azo]-2-hydroxyl-4-naphthene sulfonic acid, 1-[(1-phenyl-3-methyl 5-pyrazolone-4-yl) azo]-2-hydroxyl-cobalt complex parts such as 4-naphthoic acid want much cheap and easy to get.5) will contain catalyzer and the recycling use of alkali lye oxygen mother liquor, both fully provide cost savings, reduce environmental pollution again.
The embodiment of the invention 1
Toward agitator is housed; adding 135 kilograms of concentration in 500 liters of reactors of thermometer is 22～25% hydrochloric acid (814～925 moles); 12 kilograms of ureas (200 moles); 33 kilograms of m-dimethyl amino benzoic acids (200 moles); 31 kilograms of paradimethy laminobenzaldehydes (200 moles); 26 kilograms of N, accelerine (215 moles), under nitrogen protection in 94 ℃ of stirring reactions 6.5～7.5 hours.Cooling, the aqueous sodium hydroxide solution with 20% are neutralized to pH5.0 to be settled out the colourless crystallization violet lactone, filter, the dry thick product of colourless crystallization violet lactone that gets.
The thick product of colourless crystallization violet lactone is put into 500 liters of reactors, add 300 kilograms of benzene and sherwood oil (2: 1) mixture, refluxed 0.5 hour, filter.Filter cake is put in 1000 liters of still kettles that the moisture content separator is housed, add 500 kg of water (28 kilomol), be adjusted to pH8.5～9 with sodium hydroxide, remove residual organic solvent by moisture content separator component distillation, add 2.4 kilograms of iron trichlorides, 5.7 kilograms of potassium cyanide, 70～80 ℃ of air that are blown into 0.12MPa pressure 7 hours, cooling is filtered, and reclaims filtrate in order to reusing.Filter cake is washed with 0.5% aqueous sodium hydroxide washes, washes with water again, is drying to obtain 37.6 kilograms of crystal violet lactones, 181～183 ℃ of fusing points.
The embodiment of the invention 2
With 180 ml waters; the 53 gram vitriol oils; 30 gram m-dimethyl amino benzoic acids; 34 gram N; N xylidine and 35 gram paradimethy laminobenzaldehydes mix in reaction flask, stir cooling 8 hours in 95 ℃ under nitrogen protection; the sodium hydroxide solution pH5.0 that neutralizes, the thick product of solid collected by filtration colourless crystallization violet lactone.
The thick product of colourless crystallization violet lactone is put into the reaction flask that has water trap, add 500 milliliters of toluene and sherwood oil (2: 1) mixed solvent, component distillation, refluxed 15 minutes except that after anhydrating by water trap, filtered.Filter cake is put in the matrass, and adding 900, ml water are adjusted to pH8.5～9 with sodium hydroxide, component distillation is removed residual organic solvent, add 0.02 mole of cobalt dichloride, 0.02 mole of Seignette salt was 70～80 ℃ of oxygen that are blown into 0.1MPa pressure 10 hours, cooling, filter, wash filter cake, wash filter cake again with water with 0.5% aqueous sodium hydroxide washes, be drying to obtain 43 gram crystal violet lactones, 181～183 ℃ of fusing points.
The embodiment of the invention 3
By the embodiment 1 thick product of method synthesizing colourless crystal violet lactone of saying with benzene and the thick product of sherwood oil mixture process colourless crystallization violet lactone.Filter.Filter cake is put in 1000 liters of still kettles, added the oxidation mother liquor that embodiment 1 reclaims, be adjusted to pH8.5～9 with sodium hydroxide, component distillation is removed residual solvent, 70～80 ℃ of air that are blown into 0.12MPa pressure 7 hours, and cooling, filter, reclaim filtrate in order to reusing.Filter cake is washed with 0.5% aqueous sodium hydroxide washes, washes with water again, is drying to obtain 37 kilograms of part crystal violet lactones, 181～183 ℃ of fusing points.
The embodiment of the invention 4
The thick product of colourless crystallization violet lactone that will obtain wetting according to embodiment 1 described method is drying not, directly put in 500 liters of reactors that the moisture content separator is housed, add 300 kilograms of benzene and sherwood oil (2: 1) mixture, remove moisture content by moisture content separator component distillation, refluxed 0.5 hour, and filtered.Filter cake is put in 1000 liters of still kettles that the moisture content separator is housed, add 500 kg of water, be adjusted to pH8.5～9 with sodium hydroxide, remove residual organic solvent by moisture content separator component distillation, add 6.5 kilograms of Tripotassium iron hexacyanides, 70～80 ℃ of air that are blown into 0.12MPa pressure 6 hours, cooling, filter, reclaim filtrate in order to reusing.Filter cake is washed with 0.5% aqueous sodium hydroxide washes, washes with water again, is drying to obtain 31 kilograms of crystal violet lactones, 181～183 ℃ of fusing points.
Claims (12)
1. the preparation method of a crystal violet lactone, it is characterized in that with the m-dimethyl amino benzoic acid of 1～1.5 molar part, the paradimethy laminobenzaldehyde of 1～2 molar part and the N of 1～2.5 molar part accelerine carries out condensation 4～20 hours in the presence of the strong acid of the urea of 0.4～1.5 molar part and 1～6 molar part under 50～100 ℃ temperature; With condensated liquid cooling, with in the alkaline aqueous solution and slightly acidic, precipitated crystal, filter colourless crystallization violet lactone coarse-grain; Colourless crystallization violet lactone coarse-grain is put in the varsol, refluxed, leach varsol,, reclaim purified colourless crystallization violet lactone to remove impurity three (to dimethylamino phenyl) methane; Purified colourless crystallization violet lactone is put into water, and regulating the pH value is alkalescence, and component distillation is removed residual hydro carbons flux; Add transistion metal compound and part, or make catalyzer by the salt that part negatively charged ion and transition metal ion are formed, bubbling air or oxygen a few hours filter under heating condition, collect filter cake and get the product crystal violet lactone, reclaim the filtrate directly catalyzer and the oxidizing medium of conduct oxidation next time.
2. crystal violet lactone preparation method according to claim 1, it is characterized in that will be from dimethylaminobenzoic acid, paradimethy laminobenzaldehyde and N, the accelerine condensation and colourless crystallization violet lactone crude product reflux by colourless crystallization violet lactone crude product being put into varsol, remove by filter the method that is dissolved with impurity filtrate and make with extra care; Return time is more than 0.5 hour; The consumption of varsol is 3～9 times of suitable colourless crystallization violet lactone weight.
3. crystal violet lactone preparation method according to claim 1 and 2, it is characterized in that employed varsol is gasoline, kerosene, diesel oil, Skellysolve A, normal hexane, hexanaphthene, suberane, heptane, sherwood oil, petroleum naphtha, benzene, toluene, p-Xylol, o-Xylol, m-xylene, biphenyl, biphenyl derivatives, chlorobenzene, or by two or three mixed solvent of being formed of above-mentioned solvent.
4. crystal violet lactone preparation method according to claim 2, the colourless crystallization violet lactone crude product that it is characterized in that putting into varsol can be through exsiccant; Also can be that wet colourless crystallization violet lactone crude product is directly put into varsol, distillation by water trap is housed or reflux carry out component distillation and dewater.
5. crystal violet lactone preparation method according to claim 1, it is characterized in that the varsol colourless crystallization violet lactone filter cake that contains that will make with extra care out directly puts into the oxidizing reactor that water trap is housed, add alkali aqueous solution, with the method for component distillation remove and reclaim remain in the colourless crystallization violet lactone hydro carbons flux.
6. crystal violet lactone preparation method according to claim 1 is characterized in that the pH of medium was 8～14 when component distillation was removed varsol and catalytic air oxidation or dioxygen oxidation.
7. crystal violet lactone preparation method according to claim 1 is characterized in that transistion metal compound mainly is cobalt compound, copper-containing compound or iron containing compounds in the used catalyzer of atmospheric oxidation or dioxygen oxidation.
8. crystal violet lactone preparation method according to claim 7 is characterized in that cobalt compound is halogenation cobalt, Xiao Suangu, Cobaltous diacetate, cobaltous hydroxide.
9. crystal violet lactone preparation method according to claim 7 is characterized in that copper-containing compound is cuprous halide, copper halide, neutralized verdigris, cuprous acetate, cupric nitrate, copper hydroxide.
10. the preparation method of crystal violet lactone according to claim 7, it is characterized in that iron containing compounds is ferrous halide, iron halide, iron acetate, Iron diacetate, iron nitrate, the Trisodium hexacyanoferrate, the Tripotassium iron hexacyanide, yellow prussiate of potash, yellow prussiate of soda, ironic hydroxide, ferrous hydroxide.
11. crystal violet lactone preparation method according to claim 1, the part that it is characterized in that used composition catalyzer is alcohol acid negatively charged ion, amino acid negatively charged ion, complexone negatively charged ion, cyanogen root negatively charged ion (CN
-), nitrogen-containing heterocycle compound etc., ligand reagent is tartrate and sodium salt, sylvite and ammonium salt, edta and its sodium salt and sylvite; Whitfield's ointment and sodium salt thereof, sylvite and ammonium salt, potassium cyanide, sodium cyanide, dimethyl formyl ammonium, oxine.
12. crystal violet lactone preparation method according to claim 1 is characterized in that catalytic air oxidation or dioxygen oxidation temperature are 40～100 ℃, is preferably 60～80 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00113433 CN1111158C (en) | 2000-05-16 | 2000-05-16 | Process for preparing crystal violet lactone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00113433 CN1111158C (en) | 2000-05-16 | 2000-05-16 | Process for preparing crystal violet lactone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1276371A true CN1276371A (en) | 2000-12-13 |
| CN1111158C CN1111158C (en) | 2003-06-11 |
Family
ID=4583217
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00113433 Expired - Fee Related CN1111158C (en) | 2000-05-16 | 2000-05-16 | Process for preparing crystal violet lactone |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1111158C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102241652A (en) * | 2011-05-18 | 2011-11-16 | 湖南亚帝科技有限公司 | Preparation method of crystal violet lactone |
| CN102796009A (en) * | 2012-08-29 | 2012-11-28 | 上海化工研究院 | Synthesis method for stable isotope labeled leucomalachite green |
| CN104910019A (en) * | 2015-04-14 | 2015-09-16 | 上海应用技术学院 | Preparation method of bis-4'-N,N-dimethylaniline-1-naphthyl methane compound |
-
2000
- 2000-05-16 CN CN 00113433 patent/CN1111158C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102241652A (en) * | 2011-05-18 | 2011-11-16 | 湖南亚帝科技有限公司 | Preparation method of crystal violet lactone |
| CN102796009A (en) * | 2012-08-29 | 2012-11-28 | 上海化工研究院 | Synthesis method for stable isotope labeled leucomalachite green |
| CN104910019A (en) * | 2015-04-14 | 2015-09-16 | 上海应用技术学院 | Preparation method of bis-4'-N,N-dimethylaniline-1-naphthyl methane compound |
| CN104910019B (en) * | 2015-04-14 | 2017-01-11 | 上海应用技术学院 | Preparation method of bis-4'-N,N-dimethylaniline-1-naphthyl methane compound |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1111158C (en) | 2003-06-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1089449A (en) | Methods and catalysts for removing mercaptans and mercaptide compounds from aqueous alkaline solutions | |
| CN102584650B (en) | Preparation method of 2-nitro-4-methylsulphonylbenzoic acid | |
| CN108191674A (en) | A kind of synthetic method of benzidine compound | |
| CN102516139A (en) | Synthesis method of phenyl sulfide compound | |
| CN113387851B (en) | Preparation method of 4, 4' -dichlorodiphenyl sulfone | |
| CN101440040A (en) | Process for synthesizing p-aminophenol by catalytic hydrogenation of nitrobenzene | |
| CN1111158C (en) | Process for preparing crystal violet lactone | |
| CN103274928A (en) | Production method of p-tert-butyl benzoic acid | |
| CN116640047A (en) | Preparation method of 4-hydroxy biphenyl | |
| CN102603547B (en) | New synthesis process of 1-amino-2-acetylanthraquinone and derivatives thereof | |
| CN113045440B (en) | Preparation method of 1-aminoanthraquinone | |
| CN1107489A (en) | Purification of indigo | |
| CN1319581A (en) | Process for preparation of p-hydroxy-benzaldehyde | |
| CN1066446A (en) | The synthetic method of ORTHO AMINO PHENOL SULPHONIC | |
| CN101306386A (en) | Palladium catalyst for synthesizing oxalate using liquid phase coupling method and use thereof | |
| CN107935837A (en) | A kind of method of metacresol catalysis oxidation synthesis m-hydroxybenzoic acid | |
| CN101659620B (en) | Green synthetic method of 2,5-diaminotoluene | |
| CN110330428B (en) | Method for preparing diisobutyl phthalate | |
| CN114478243A (en) | Method for synthesizing dihydroxy dimethyl terephthalate by oxygen catalytic oxidation method | |
| CN111253272B (en) | Method for preparing benzamide compound | |
| US4243551A (en) | Catalyst for oxidizing mercaptans and mercaptide compounds and method for preparing | |
| CN105001096B (en) | A kind of method for preparing 4 amino N alkylbenzylamines | |
| WO1997025144A1 (en) | An esterification catalyst and a process for its preparation | |
| US3140292A (en) | Preparation of metal phthalocyanines | |
| CN113698355B (en) | Synthesis method of 4, 5-dihydroxypyridazine |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |