CN112321572A - Compound used as blue pressure-sensitive dye and preparation method and application thereof - Google Patents
Compound used as blue pressure-sensitive dye and preparation method and application thereof Download PDFInfo
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- CN112321572A CN112321572A CN202011392869.7A CN202011392869A CN112321572A CN 112321572 A CN112321572 A CN 112321572A CN 202011392869 A CN202011392869 A CN 202011392869A CN 112321572 A CN112321572 A CN 112321572A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- 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
- C09B57/00—Other synthetic dyes of known constitution
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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
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0097—Dye preparations of special physical nature; Tablets, films, extrusion, microcapsules, sheets, pads, bags with dyes
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Abstract
The invention relates to a compound used as a blue pressure-sensitive dye, which has the following structural general formula:
wherein R is1Is CH3、CH2CH3、CH2CH2CH3Or CH2CH2CH2CH3；R2Is CH3Or CH2CH3. The invention adopts three key intermediates of substituted indole, active hydrogen substituted m-aminophenol and chlorophthalic anhydride to obtain a target compound used as blue pressure-sensitive dye through two-step condensation. The raw materials required by the synthesis are easy to obtain, the conversion rate of each step in the synthesis process is high, and the intermediate process is not neededA complicated purification process is required. The target compound has high color development, the molar absorption coefficient of the target compound is 1.8 times of that of CVL, and the same color development effect of the CVL can be achieved under the lower use concentration of the pressure-sensitive dye.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a blue pressure-sensitive dye and a preparation method and application thereof.
Background
The pressure sensitive dye is mainly used as a color former of the carbonless copy paper, and the Crystal Violet Lactone (CVL) pressure sensitive dye is a main variety of the color former of the carbonless copy paper. In the using process, under the catalytic action of an acid color developing agent, the crystal violet lactone ring of the pressure-sensitive dye microcapsule core material presents an intramolecular C-O bond heterolytic cleavage ring to become anode ions, and the anode ions are rearranged to develop color.
As the main variety of pressure sensitive dyes, CVL has high market share, people pay attention to the CVL and research is continuous, wherein more research focuses on the synthesis of the CVL, and the CVL route mainly comprises the reaction of 4-dimethylaminobenzaldehyde and N, N-dimethylaniline to obtain Michler's base, or Michler's base (Michler's base, N, N, N', N '-tetra-phenyl methane), Michler's ketone (N, N, N ', N' -tetra-phenyl benzophenone) or other technological routes to obtain Michler's alcohol, and then the Michler's alcohol reacts with m-dimethylaminobenzoic acid to obtain substituted triphenylmethane LCVL, and then the CVL is obtained through oxidation and cyclization.
The european union "registration, evaluation, authorization and restriction of chemicals" regulation REACH, in the seventh list of substances of high interest SVHC, contains the michelson and the michelson for CVL synthesis, with serial numbers 79 and 80 in order, which means that the staff engaged in the production of CVL has the possibility of being exposed to the substances of high interest. Also, the natural degradation products of the pressure sensitive dyes after use will be related to these highly interesting substances.
The invention avoids substances with high concern of REACH, designs and prepares a novel blue pressure-sensitive dye, the molar absorption coefficient of the novel blue pressure-sensitive dye reaches 1.8 times of CVL, and the same color development effect of the CVL can be achieved under the lower use concentration of the pressure-sensitive dye.
Disclosure of Invention
The invention aims to provide a compound used as a blue pressure-sensitive dye, which does not have the molecular framework of tris- (4-dimethylaminophenyl) methane, reduces the corresponding environmental risk and can be synthesized by a green process.
The invention also provides a preparation method and application of the compound used as the blue pressure-sensitive dye.
In order to achieve the purpose, the invention adopts the following technical scheme:
a compound used as a blue pressure sensitive dye has a structural general formula as follows:
wherein R is1Is CH3、CH2CH3、CH2CH2CH3Or CH2CH2CH2CH3；R2Is CH3Or CH2CH3。
The invention provides a preparation method of the compound used as the blue pressure-sensitive dye, and the synthetic route is as follows:
the method specifically comprises the following steps:
1) heating and refluxing 2-methylindole a, carbonate I, N dimethylformamide and potassium carbonate under the action of a phase transfer catalyst for 10-15h, and carrying out post-treatment to obtain a compound c (N-alkyl-2-methylindole); wherein, 2-methylindole a is taken as a raw material, carbonate I is an alkylating reagent and a solvent, N, N Dimethylformamide (DMF) is taken as a cosolvent, and potassium carbonate is taken as a catalyst;
2) in a stainless steel pressure reaction kettle, m-aminophenol b, carbonic ester II and sodium hydroxide react for 18-24h under the action of a phase transfer catalyst at the temperature of 120-180 ℃, and a compound d (3-N, N-dialkyl aminophenol ether) is obtained through post treatment; wherein, m-aminophenol b is used as a raw material, carbonate II is used as an alkylating reagent and a reaction solvent, and sodium hydroxide is used as a catalyst;
3) heating and refluxing the compound c and 4-chlorophthalic anhydride e in toluene for 12-24h, and carrying out post-treatment to obtain a compound f;
4) reacting the compound d with the compound f in acetic anhydride for 18-20h at room temperature, and carrying out post-treatment to obtain a compound g.
Specifically, in the step 1), the carbonate ester one includes dimethyl carbonate, diethyl carbonate, dipropyl carbonate or dibutyl carbonate. In the step 1) and the step 2), the phase transfer catalyst comprises tetrabutylammonium chloride or triethylbenzylammonium chloride and the like.
Specifically, in the step 1), the carbonate I is both a reaction reagent and a solvent, the molar ratio of the carbonate I to the 2-methylindole is more than or equal to 1, and the weight ratio of the N, N-dimethylformamide to the carbonate I is 0.1-10:1, preferably 0.25: 1; the molar ratio of the potassium carbonate to the 2-methylindole is 0.5-10: 1, preferably 1: 1; the molar ratio of the phase transfer catalyst to the 2-methylindole is as follows: 0.01-0.1:1, preferably 0.05: 1.
Specifically, in the step 2), the carbonate II is a reaction reagent and a solvent, the carbonate II comprises dimethyl carbonate or diethyl carbonate, the molar ratio of the carbonate II to m-aminophenol is not less than 3, and the molar ratio of sodium hydroxide to m-aminophenol is not less than 3; the molar ratio of the phase transfer catalyst to the m-aminophenol is 0.01 to 0.1:1, preferably: 0.05:1.
Further, in the step 3), the molar ratio of the compound c to the 4-chlorophthalic anhydride e is 1: 1; in the step 4), the molar ratio of the compound d to the compound f is 1: 1.
The invention also provides the application of the compound as a pressure sensitive dye.
The compound is used as a pressure sensitive dye, and particularly, the compound can be used as a microcapsule core material of the pressure sensitive dye.
The whole synthesis process of the invention adopts three key intermediates of substituted indole, active hydrogen substituted m-aminophenol and chlorophthalic anhydride, and obtains the target product through two-step condensation. Since the pressure sensitive dye needs better light resistance, the phthalic acid structural unit in the dye structure has poorer light resistance, proper chlorination can improve the light resistance, but excessive chlorination can influence the solubility of the pressure sensitive dye of the final product. Therefore, 4-chlorophthalic anhydride is selected as the third group rather than the conventional phthalic anhydride in order to adjust the solubility and light resistance of the final product.
The invention takes 2-methylindole as a raw material and carbonic ester as an alkylating reagent to synthesize an N-alkyl-2-methylindole intermediate. Methyl or ethylate 3-aminophenol with dimethyl carbonate or diethyl carbonate to obtain 3-N, N-dimethylaminobenzene ether or 3-N, N-diethylaminophenetole intermediate. Heating and refluxing the N-alkyl-2-alkyl indole intermediate and 4-chlorophthalic anhydride in toluene to obtain compound indolone acid, and reacting with intermediate 3-N, N-dimethylaminobenzene ether or 3-N, N-diethylaminophenetole in acetic anhydride at room temperature to obtain target compound chloroindole violet lactone. The method adopts green carbonate as an alkylating reagent, and avoids the conventional use of alkylating reagents with serious toxicity, such as alkyl halide or dimethyl sulfate. Compared with the prior art, the invention has the following beneficial effects:
1) three key intermediates of substituted indole, active hydrogen substituted m-aminophenol and chlorophthalic anhydride are adopted to obtain a target product through two-step condensation. The target compound has high color rendering property, raw materials required by synthesis are easy to obtain, the conversion rate of each step in the synthesis process is high, and a complex purification process is not required in the intermediate process;
2) the invention avoids substances with high concern of REACH, designs and prepares a novel blue pressure-sensitive dye, the molar absorption coefficient of the novel blue pressure-sensitive dye reaches 1.8 times of CVL, and the same color development effect of the CVL can be achieved under the lower use concentration of the pressure-sensitive dye.
Drawings
FIG. 1 shows the UV absorption spectrum of the pressure sensitive dye chloroindole violet lactone (product CIL) synthesized in example 1.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following examples, but the scope of the present invention is not limited thereto.
Example 1
1. Synthesis of N-methylated methylindole (Compound c)
In a 100mL three-necked flask, 2-methylindole a (3g,22.9mmol), potassium carbonate (2g, 14) were added.5mmol), tetrabutylammonium chloride (0.36g,1.3mmol), dimethyl carbonate (40g,444.4mmol) and N, N-dimethylformamide (10g,137.0mmol), heating to 95 deg.C, refluxing for 12h, cooling, filtering the reaction solution, and evaporating the solvent under reduced pressure. Then, 25mL of water was added, extraction was performed 2 times with ethyl acetate, and the organic layer was dried over anhydrous sodium sulfate and concentrated to give 3.25g of N-methylated methylindole (compound c) as a product with a yield of 98.2%;1H NMR(400MHz,CDCl3),δ:7.52(d,J＝7.6Hz,1H),7.25(d,J＝8.0Hz，1H),7.14(t,J＝7.2Hz,1H),7.05(t,J＝8.0Hz,1H),6.24(s,1H),3.65(s,3H),2.42(s,3H)。
2. synthesis of 3- (N, N-dimethylamino) -anisole (Compound d)
In a stainless steel autoclave, 3-aminophenol b (m-aminophenol, 3g,27.5mmol), sodium hydroxide (3.5g, 87.5mmol), tetrabutylammonium chloride (0.5g, 1.8mmol) and dimethyl carbonate (40g,444.4mmol) were added, followed by reaction at 160 ℃ for 20-24 h. After cooling, the reaction solution is filtered, the solvent is evaporated under reduced pressure, then 20mL of water is added, extraction is carried out for 2 times by using dichloromethane, an organic layer is dried by anhydrous sodium sulfate, and concentration is carried out, so that 4.0g of a product 3- (N, N-dimethylamino) -anisole (a compound d) is obtained, and the yield is 96.3%;1H NMR(400MHz,CDCl3),δ:7.14(t，J＝8.0Hz,1H),6.35(dd，J1＝8.4Hz,J2＝2.4Hz,1H),6.30-6.27(m，2H),3.82(s,3H),2.93(s,6H)。
3. synthesis of (N-methyl) -2-methylindolonoic acid (Compound f)
Adding 1.2g (8.28mmol) of N-methylated methylindole (compound c), 1.47g (8.28mmol) of 4-chlorophthalic anhydride e and 35mL of toluene into a reaction bottle, heating to 110 ℃, refluxing for reaction for 15-16h, cooling, precipitating, filtering, washing a filter cake with toluene, and drying to obtain 2.46g of light red solid powder product (N-methyl) -2-methylindolone acid (compound f) in a yield of 90.6%;1H NMR(400MHz,DMSO),δ:7.99(dd,J＝8.0Hz,J＝2.4Hz,1H),7.74-7.67(dd，J1＝18.4Hz,J2＝8.0Hz,1H),7.53(d,J＝8.0Hz,1H),δ7.38-7.35(dd,J＝9.6Hz,J＝2.4Hz,1H),δ7.19-7.16(m,1H),7.13-7.11(m,1H),7.09-7.02(m,1H),3.74(s,3H),2.42(s,3H)。
4. synthesis of pressure sensitive dye chloroindole violet lactone (product CIL)
Adding 1.17g (3.6mmol) of (N-methyl) -2-methylindolone acid (compound f), 0.54g (3.6mmol) of 3- (N, N-dimethylamino) -anisole (compound d) and 15mL of acetic anhydride into a 50mL reaction bottle, stirring at room temperature for reacting for 18-20h, adding 25mL of ethanol after the reaction is finished, stirring for 1h, distilling the ethanol out, washing with petroleum ether, and drying to obtain 1.5g of solid powder pressure sensitive dye chloroindole violet lactone (product CIL), wherein the yield is 90.3%;1H NMR(400MHz,DMSO),δ:7.90(d,J＝8.4Hz,1H,11-H),7.66(d,J＝7.6Hz,2H,14-H,15-H,δ7.39(dd,J＝8.4Hz,1H,5-H),7.12(d,J＝8.4Hz,1H,21-H),δ7.02(t,J＝7.2Hz,1H,6-H),6.80(t,J＝7.2Hz,1H,7-H),6.49(d,J＝8.0Hz,1H,8-H),6.31-6.27(m,2H，18-H,19-H),3.64(s,3H,N-CH3),3.47(s,3H,-O-CH3),2.91(s,6H,24-H,25-H),2.0(s,3H，2-CH3)；ESI–MS m/Z:461.9[M]+。
and (3) testing: ultraviolet spectrum of product CIL:
the product CIL was subjected to UV spectroscopy (see FIG. 1), and FIG. 1 shows that: the CIL in the ethanol solution has no absorption in the range of the wavelength of 350-700 nm. At a concentration of 3X 10-3In mol/L ethanol HCl solution, the maximum absorption wavelength of the compound CIL is 578nm, and the molar absorption coefficient is epsilon 4.98 multiplied by 104mol-1.cm-1。
The molar absorptivity ε of Crystal Violet Lactone (CVL) was also measured to be 2.65X 104mol-1.cm-1。
The molar absorptivity epsilon indicates the degree of absorption of light energy, and for dyes, the epsilon value characterizes the concentration of the color developed. The molar absorption coefficient of the compound CIL synthesized by the method is 1.8 times of that of CVL, which shows that the compound CIL can achieve the same color development effect of CVL under lower use concentration.
Application test:
the preparation of the carbonless copy paper microcapsules can be carried out by the conventional techniques in the field, as follows.
1) Preparing a CIL capsule core material: adding 1.0g of compound CIL into 40g of isomeric decaethanol solvent, heating to 60-70 ℃ to dissolve to obtain capsule core material for later use.
2) Preparing CIL microcapsules: taking 8.0g of hexamethylol melamine, adding 80g of pure water, 0.2g of non-ionic emulsifier Tween 80 and 1.5g of aqueous solution (resin content is 30 percent, pH is 7.0) of solid acrylic resin (model Basf 678 resin) as a dispersing agent, and uniformly mixing. Slowly adding the capsule core material (oil phase) into the water phase with the dispersing agent and the emulsifying agent under high-speed stirring (1000-1500rpm), continuously stirring at high speed for 20min after the dripping is finished, heating to 55-60 ℃ under stirring, adjusting the pH to 4.0-4.5 by using 10% lactic acid aqueous solution, preserving the temperature for 120min, cooling to room temperature, and adjusting the pH to 7.5-8.0 by using 5% sodium hydroxide aqueous solution to obtain the microcapsule emulsion.
3) And (3) color development test: 0.1g of hydroxyethyl cellulose, 10g of carboxylic styrene-butadiene latex and 30g of water are taken, dissolved and dispersed uniformly, 50g of the microcapsule emulsion is added, and the mixture is stirred until the emulsion is uniform, so that the back (CB) coating of the carbonless copy paper is obtained. The coating was uniformly applied to a base paper by a coating bar, dried, and then stacked on a front side (CF) paper with a developer, and printed in a needle printer to develop a blue color.
The above test results show that: the compound CIL can be used for pressure sensitive dyes, namely can be used as microcapsule core materials of the pressure sensitive dyes.
Claims (8)
1. A compound for use as a blue pressure sensitive dye, characterized by the general structural formula:
wherein R is1Is CH3、CH2CH3、CH2CH2CH3Or CH2CH2CH2CH3；R2Is CH3Or CH2CH3。
2. A process for preparing a compound of claim 1 for use as a blue pressure sensitive dye, wherein the synthetic route is as follows:
the method specifically comprises the following steps:
1) heating and refluxing 2-methylindole a, carbonate I, N dimethylformamide and potassium carbonate under the action of a phase transfer catalyst for 10-15h, and carrying out post-treatment to obtain a compound c;
2) reacting m-aminophenol b, carbonic ester II and sodium hydroxide for 18-24h at the temperature of 120-180 ℃ under the action of a phase transfer catalyst, and performing post-treatment to obtain a compound d;
3) heating and refluxing the compound c and 4-chlorophthalic anhydride e in toluene for 12-24h, and carrying out post-treatment to obtain a compound f;
4) reacting the compound d with the compound f in acetic anhydride for 18-20h at room temperature, and carrying out post-treatment to obtain a compound g.
3. The method of claim 2, wherein in step 1), the carbonate one is dimethyl carbonate, diethyl carbonate, dipropyl carbonate or dibutyl carbonate; in the step 1) and the step 2), the phase transfer catalyst comprises tetrabutylammonium chloride or triethylbenzylammonium chloride.
4. The method for preparing a compound used as a blue pressure sensitive dye according to claim 3, wherein in the step 1), the molar ratio of the carbonate I to the 2-methylindole is not less than 1, the weight ratio of the N, N-dimethylformamide to the carbonate I is 0.1-10:1, and the molar ratio of the potassium carbonate to the 2-methylindole is 0.5-10: 1.
5. the method for preparing a compound for use as a blue pressure sensitive dye according to claim 3, wherein the carbonate bis is dimethyl carbonate or diethyl carbonate in the step 2), the molar ratio of the carbonate bis to m-aminophenol is 3 or more, and the molar ratio of sodium hydroxide to m-aminophenol is 3 or more.
6. The process for preparing a compound useful as blue pressure sensitive dye according to claim 3, wherein in step 3), the molar ratio of compound c to 4-chlorophthalic anhydride e is 1: 1; in the step 4), the molar ratio of the compound d to the compound f is 1: 1.
7. Use of a compound according to claim 1 as a pressure sensitive dye.
8. Use of a compound according to claim 7 as a pressure sensitive dye, wherein the compound is used as a microcapsule core material for a pressure sensitive dye.
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| US3829322A (en) * | 1970-12-28 | 1974-08-13 | Hodogaya Chemical Co Ltd | Pressure-sensitive phthalide compound copying sheet |
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Application publication date: 20210205 |