CN1111158C - Process for preparing crystal violet lactone - Google Patents
Process for preparing crystal violet lactone Download PDFInfo
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- CN1111158C CN1111158C CN 00113433 CN00113433A CN1111158C CN 1111158 C CN1111158 C CN 1111158C CN 00113433 CN00113433 CN 00113433 CN 00113433 A CN00113433 A CN 00113433A CN 1111158 C CN1111158 C CN 1111158C
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- violet lactone
- crystal violet
- colourless crystallization
- varsol
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- 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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses a process for preparing crystal violet lactone, which overcomes the defects of high cost and low quality in the existing producing process of the crystal violet lactone. The adoption of the present invention does not need an extraction device; impurities in leuco crystal violet lactone can be removed only by the treatment of hydrocarbon solvents; 2) solvents which remain in the leuco crystal violet lactone are removed by azeotropic distillation; the solvents are recycled, and the drying process is omitted; 3) catalytic air oxidation or oxygen oxidation is adopted; cost is reduced, and quality is increased; 4) an oxidation catalyst and a catalyst ligand of the present invention are usual compounds; the price is cheap, and the oxidation catalyst and the catalyst ligand are easily obtained; 5) mother liquid which comprises catalysts and alkaline liquid is recovered and is circularly used, and accordingly, the crystal violet lactone can not only sufficiently save cost, but also reduce environmental pollution.
Description
Affiliated technical field
The invention belongs to the preparation production method of crystal violet lactone.
Background technology
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.
Summary of the invention
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 objective of the invention is to realize in the following way: a kind of preparation method of crystal violet lactone, 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 under 50～100 ℃ temperature in the presence of the strong acid of the urea of 0.4～1.5 molar part and 1～6 molar part; With condensated liquid cooling, with in the alkaline aqueous solution and slightly acidic, precipitated crystal, filter colourless crystallization violet lactone crude product; Colourless crystallization violet lactone crude product 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.
The present invention is with 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.
Varsol used in 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 colourless crystallization violet lactone crude product that the present invention puts 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.
The varsol colourless crystallization violet lactone filter cake that contains that the present invention will make with extra care is out directly put into the oxidizing reactor that water trap is housed, and adds alkali aqueous solution, with the method for component distillation remove and reclaim remain in the colourless crystallization violet lactone hydro carbons flux.
The pH of medium was 8～14 when component distillation of the present invention was removed varsol and catalytic air oxidation or dioxygen oxidation.
Transistion metal compound mainly is cobalt compound, copper-containing compound or iron containing compounds in the used catalyzer of atmospheric oxidation of the present invention or dioxygen oxidation.
Cobalt compound of the present invention is halogenation cobalt, Xiao Suangu, Cobaltous diacetate, cobaltous hydroxide.
Copper-containing compound of the present invention is cuprous halide, copper halide, neutralized verdigris, cuprous acetate, cupric nitrate, copper hydroxide.
Iron containing compounds of the present invention 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 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.
Catalytic air oxidation of the present invention or dioxygen oxidation temperature are 40～100 ℃, are preferably 60～80 ℃.
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 reclaimed solvent, economize except drying process again.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) 427 1075 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.
Embodiment
The present invention will be further described below in conjunction with embodiment:
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, added 900 ml waters, be 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 that alcohol acid negatively charged ion, amino acid negatively charged ion, complexone negatively charged ion, cyanogen root the moon are from giving (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 |
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| CN1276371A CN1276371A (en) | 2000-12-13 |
| CN1111158C true CN1111158C (en) | 2003-06-11 |
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| CN 00113433 Expired - Fee Related CN1111158C (en) | 2000-05-16 | 2000-05-16 | Process for preparing crystal violet lactone |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| 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 |
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