CN105523959A - Method for preparing azoaniline compound - Google Patents
Method for preparing azoaniline compound Download PDFInfo
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- CN105523959A CN105523959A CN201410509979.5A CN201410509979A CN105523959A CN 105523959 A CN105523959 A CN 105523959A CN 201410509979 A CN201410509979 A CN 201410509979A CN 105523959 A CN105523959 A CN 105523959A
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- 238000000034 method Methods 0.000 title claims abstract description 26
- -1 azoaniline compound Chemical class 0.000 title description 6
- 229940125904 compound 1 Drugs 0.000 claims abstract description 14
- IDWXQRMUCRXFAK-UHFFFAOYSA-N (2-phenyldiazenylhydrazinyl)benzene Chemical compound C=1C=CC=CC=1N=NNNC1=CC=CC=C1 IDWXQRMUCRXFAK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims description 54
- 238000006243 chemical reaction Methods 0.000 claims description 30
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 27
- 238000005859 coupling reaction Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 238000006193 diazotization reaction Methods 0.000 claims description 24
- 238000006482 condensation reaction Methods 0.000 claims description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- 229940125782 compound 2 Drugs 0.000 claims description 10
- 238000005886 esterification reaction Methods 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 8
- RXQNKKRGJJRMKD-UHFFFAOYSA-N 5-bromo-2-methylaniline Chemical compound CC1=CC=C(Br)C=C1N RXQNKKRGJJRMKD-UHFFFAOYSA-N 0.000 claims description 7
- 229940126214 compound 3 Drugs 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 6
- 229940125898 compound 5 Drugs 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 6
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 6
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical group [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 239000011260 aqueous acid Substances 0.000 claims description 5
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims description 5
- 229940106681 chloroacetic acid Drugs 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 229910001508 alkali metal halide Inorganic materials 0.000 claims description 4
- 150000008045 alkali metal halides Chemical group 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 235000010288 sodium nitrite Nutrition 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000011161 development Methods 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 235000009518 sodium iodide Nutrition 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 239000000835 fiber Substances 0.000 abstract description 19
- 238000004043 dyeing Methods 0.000 abstract description 9
- 238000000859 sublimation Methods 0.000 abstract description 8
- 230000008022 sublimation Effects 0.000 abstract description 8
- 238000005406 washing Methods 0.000 abstract description 8
- 239000004753 textile Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 4
- 238000009987 spinning Methods 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 12
- 229920000728 polyester Polymers 0.000 description 10
- 239000000986 disperse dye Substances 0.000 description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- 0 CN(CI1*C1)*1c(*)cc(*)cc1 Chemical compound CN(CI1*C1)*1c(*)cc(*)cc1 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000035515 penetration Effects 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- PEMGGJDINLGTON-UHFFFAOYSA-N n-(3-aminophenyl)acetamide Chemical compound CC(=O)NC1=CC=CC(N)=C1 PEMGGJDINLGTON-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- LXQOQPGNCGEELI-UHFFFAOYSA-N 2,4-dinitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O LXQOQPGNCGEELI-UHFFFAOYSA-N 0.000 description 1
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 229920006221 acetate fiber Polymers 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- AEDZKIACDBYJLQ-UHFFFAOYSA-N ethane-1,2-diol;hydrate Chemical compound O.OCCO AEDZKIACDBYJLQ-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing an azoaniline compound 1 represented by a formula shown in the description. The azoaniline compound 1 prepared by the method has satisfactory washing fastness and outstanding fastness to sublimation, is novel in structure and is applicable to the dyeing and printing of polyester-fiber textile materials and blended spinning fiber products thereof.
Description
Technical Field
The invention relates to a preparation method of azoaniline compounds.
Background
The disperse dye is a nonionic dye which has simple structure and low water solubility and mainly exists in a dispersion state as micro particles in a dye bath, is mainly used for dyeing and printing polyester fibers and blended fabrics thereof, and can also be used for dyeing and printing hydrophobic textile materials such as acetate fibers, polyamide fibers and the like. In recent years, with the increasing production and consumption of polyester fibers, disperse dyes have been an important place in the world and domestic dye markets.
At present, the green environment and healthy life become increasingly concerned topics, and the safety of textile wear also becomes important concern, which puts forward higher and higher application requirements on dyes used for textiles. The color fastness is one of important indexes for characterizing the application performance of the dye, and the color fastness relates to a plurality of contents, wherein the color fastness is the color fastness to washing and the color fastness to sublimation.
The conventional dye varieties widely applied in the market at present still have room for improvement in sublimation fastness and washing fastness.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of azoaniline compounds for overcoming the defects of poor sublimation fastness and washing fastness of the existing dye. The azoaniline compound has satisfactory fastness to washing and excellent fastness to sublimation, has a novel structure, and is suitable for dyeing and printing polyester fiber textile materials and blended fiber products thereof.
The invention provides an azoaniline compound 1:
wherein R is1Is composed ofOr a hydrogen atom; r2Is C1-C4Alkyl (e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, or tert-butyl); r3Is composed ofOrR4Is C1-C3Alkyl (e.g., methyl, ethyl, propyl, or isopropyl) or a hydrogen atom.
R1Preferably a hydrogen atom; r2Preferably methyl or ethyl; r4Methyl is preferred.
The present invention also provides a process for the preparation of compound 1, comprising the steps of: in water and in the presence of acid, carrying out coupling reaction on the compound 2 and the compound 3 to obtain a compound 1;
wherein R is1、R2And R3The definitions of (a) and (b) are all as described above,is Cl-、CH2COO-、H2PO4 -、HSO4 -Or NO3 -。
The coupling reaction can be carried out according to methods customary in the art for such reactions, with particular preference given to the following reaction methods and conditions:
in the coupling reaction, the volume molar ratio of the water to the compound 2 is preferably 1.6L/mol to 4.7L/mol, more preferably 2.3L/mol to 3.5L/mol, and still more preferably 2.7L/mol to 3.0L/mol.
In the coupling reaction, the acid is preferably one or more of hydrochloric acid, acetic acid, phosphoric acid, nitric acid and sulfuric acid, more preferably one or more of hydrochloric acid, acetic acid and sulfuric acid, and still more preferably sulfuric acid and/or hydrochloric acid; the acid may participate in the reaction in the form of an aqueous acid solution, and the mass fraction of the aqueous acid solution is preferably 3% to 98%, and more preferably 5% to 80%.
In the coupling reaction, the volume ratio of the acid to the water is preferably 0.01 to 0.06, more preferably 0.015 to 0.04, and still more preferably 0.033.
In the coupling reaction, the molar ratio of the compound 2 to the compound 3 is preferably 1.5:1 to 1:1, more preferably 1.2:1 to 1:1, and still more preferably 1.1: 1.
In the coupling reaction, the temperature of the coupling reaction is preferably-10 ℃ to 30 ℃, more preferably-10 ℃ to 10 ℃, and still more preferably-5 ℃ to 5 ℃.
In the coupling reaction, the progress of the coupling reaction can be monitored by a conventional test method in the field (such as a filter paper ring penetration method), the non-color development of the compound 2 ring penetration is taken as a reaction endpoint, the reaction time is preferably 1 h-3 h, and further preferably 2 h.
The preparation method of the compound 1 can further comprise the following steps: when R is3Is composed ofOrIn the absence of solventCarrying out diazotization reaction on nitrosyl sulfuric acid and a compound 8 in the presence of concentrated sulfuric acid to obtain a compound 3; when R is3Is composed ofIn the presence of acid, carrying out diazotization reaction on nitrite or nitrosyl sulfuric acid and a compound 8 to obtain a compound 3;
wherein,the definitions of (A) and (B) are as described above.
The diazotisation reaction may be carried out according to methods conventional in the art for such reactions, with particular preference given to the following reaction methods and conditions:
in the diazotization reaction, the condition without solvent is the condition without water and/or the condition without organic solvent.
In the diazotization reaction, the concentrated sulfuric acid preferably has a mass fraction of 98%.
In the diazotization reaction, when R is3Is composed ofWhen this is the case, it is preferably carried out in the presence of water; the volume molar ratio of the water to the compound 8 is preferably 0.13L/mol to 1.33L/mol, and more preferably 0.27L/mol to 0.67L/mol.
In the diazotization reaction, when R is3Is composed ofWhen the reaction is carried out in the absence of a solvent.
In the diazotization reaction, when R is3Is composed ofWhen the acid is used, the acid is preferably one or more of hydrochloric acid, acetic acid and sulfuric acid, and further preferably sulfuric acid and/or hydrochloric acid; the acid may participate in the reaction in the form of an aqueous acid solution, and the mass fraction of the aqueous acid solution is preferably 5% to 99%, and more preferably 10% to 80%.
In the diazotization reaction, the molar ratio of the compound 8 to the acid is preferably 1:2 to 1:5, more preferably 1:2.5 to 1:4, and still more preferably 1: 2.8.
In the diazotization reaction, the nitrite is preferably sodium nitrite.
In the diazotization reaction, the molar ratio of the compound 8 to the nitrite or the nitrosyl sulfuric acid is preferably 1:1 to 1:1.2, more preferably 1:1 to 1:1.1, and still more preferably 1: 1.05.
In the diazotization reaction, the reaction temperature is preferably-10-30 ℃, and further preferably-10-20 ℃.
In the diazotization reaction, the progress of the diazotization reaction can be monitored by a conventional test method in the field (such as TLC), and the reaction time is preferably 1h to 5h, and more preferably 2h to 3h, with the end point being the end point when the compound 8 is not reacted any more.
The preparation method of the compound 1 can further comprise the following steps: in the presence of a catalyst and alkali, carrying out condensation reaction on a compound 4 and a compound 5 to obtain a compound 2; the catalyst is alkali metal halide;
wherein R is1And R2The definitions of (A) and (B) are as described above.
The condensation reaction can be carried out according to the conventional methods for such reactions in the art, and the following reaction methods and conditions are particularly preferred:
in the condensation reaction, the reaction is preferably carried out in the absence of a solvent.
In the condensation reaction, the alkali metal halide is preferably one or more of potassium iodide, sodium iodide, potassium bromide and sodium bromide, and further preferably sodium bromide.
In the condensation reaction, the molar ratio of the catalyst to the compound 4 is preferably 0.01:1 to 1:1, more preferably 0.2:1 to 0.4:1, and still more preferably 0.24: 1.
In the condensation reaction, the base is preferably an inorganic base, the inorganic base is preferably one or more of sodium hydroxide, potassium carbonate, sodium bicarbonate, potassium bicarbonate and anhydrous sodium carbonate, and anhydrous sodium carbonate is further preferred.
In the condensation reaction, the molar ratio of the base to the compound 4 is preferably 1.0:1 to 5:1, more preferably 1.0:1 to 1.5:1, and still more preferably 1.2: 1.
In the condensation reaction, the molar ratio of the compound 4 to the compound 5 is preferably 1:2 to 1:2.5, and more preferably 1:2 to 1: 2.2.
In the condensation reaction, the temperature of the condensation reaction is preferably 50 to 150 ℃, more preferably 70 to 120 ℃, and still more preferably 100 ℃.
In the condensation reaction, the progress of the condensation reaction can be monitored by a test method (such as HPLC) which is conventional in the art, and the reaction time is preferably 2 to 10 hours, more preferably 4 to 8 hours, with the compound 4 no longer reacting as a reaction end point.
The preparation method of the compound 1 can further comprise the following steps: carrying out esterification reaction on the compound 6 and chloroacetic acid to obtain a compound 5;
wherein R is2The definition of (A) is as described above.
The esterification reaction may be carried out according to a conventional method of such a reaction in the art, and the following reaction methods and conditions are particularly preferred:
in the esterification reaction, the reaction is preferably carried out in the absence of a solvent.
In the esterification reaction, the reaction is preferably carried out under the catalysis of a catalyst; the catalyst may be a strong acid, preferably sulfuric acid and/or p-toluenesulfonic acid, further preferably p-toluenesulfonic acid; the molar ratio of the catalyst to the compound 6 is preferably 0.01:1 to 1:1, more preferably 0.03:1 to 0.1:1, and still more preferably 0.05: 1.
In the esterification reaction, the molar ratio of the chloroacetic acid to the compound 6 is preferably 1:1 to 1:1.2, and more preferably 1:1 to 1: 1.1.
In the esterification reaction, the temperature of the esterification reaction is preferably 70 to 150 ℃, more preferably 100 to 130 ℃, and still more preferably 120 ℃.
In the esterification reaction, the progress of the esterification reaction can be monitored by a test method (such as TLC) which is conventional in the art, and the reaction time is preferably 2h to 6h, more preferably 3h to 5h, with chloroacetic acid not reacting any more as a reaction end point.
The invention also provides an intermediate compound which can be used for preparing the compound 1 and isWherein R is1And R2Is as defined in any one of claims 1 to 3.
The invention also provides application of the compound 1 as a disperse dye. Compound 1 of the present invention can be processed according to conventional processing methods in the art (e.g., sand milling) to give commercially available disperse dyes.
The commercial disperse dye prepared from the compound can be applied to dyeing and printing of polyester fibers and blended fiber products thereof according to the conventional dyeing method of the disperse dye in the field. The polyester fiber, namely the polyethylene terephthalate fiber and the blended fiber products thereof, such as polyester/cotton and polyester/wool are the conventional polyester fiber and the blended fiber products thereof in the field. The blended fiber product may be in the form conventionally found in the art, such as fibers, yarns, wovens, knits or nonwovens.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The room temperature in the invention is 10-30 ℃.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows: the azoaniline compound has satisfactory fastness to washing, excellent fastness to sublimation, novel structure and suitability for dyeing and printing polyester fiber textile materials and blended fiber products thereof.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
The LC-MS data in the invention is obtained by a Waters UPLC-SQD liquid chromatograph-mass spectrometer (the mobile phase is an acetonitrile/water system, 60-90% acetonitrile V/V, the column temperature is 40 ℃) test.
EXAMPLE 1 preparation of Compound 5-1
ClCH2COOCH2CH2OCH35-1
In a dry 100ml three-neck flask, 17.08g of ethylene glycol monomethyl ether was added at room temperature, and then about 18.9g of chloroacetic acid and 2g of p-toluenesulfonic acid were added with stirring and stirred uniformly. After being stirred evenly, the mixture is slowly heated to 120 ℃ for heat preservation and reflux, and the raw materials are reacted completely after about 3 hours of reaction. Cooling to room temperature, distilling under reduced pressure to 80 ℃ to remove excessive ethylene glycol monomethyl ether and water, continuing heating, and collecting fractions at 100-140 ℃. Then, the distillate was distilled under reduced pressure to remove water, to obtain 5-125.1g of the compound, with a yield of 82.25% and a purity of 96.3%.
EXAMPLE 2 preparation of Compounds 2-3
About 23.5g of compound 5-1 was placed in a dry 100ml three-necked flask at room temperature, followed by stirring with 10.51g of m-aminoacetanilide, 8.92g of anhydrous sodium carbonate and 1.75g of sodium bromide and stirring to homogenize. Then slowly raising the temperature to 100 ℃ and preserving the temperature for reaction. The reaction was monitored by HPLC until the m-aminoacetanilide reaction was complete. About 20ml of water was added to dissolve the solid, the pH was adjusted to neutral, and the mixture was poured into a separatory funnel and allowed to stand for separation. Removing water layer, adding about 20ml water, shaking thoroughly, standing for layering, collecting organic phase, distilling under reduced pressure to remove water to obtain 2-325.4g compound with yield of 94.89% and purity of 96.5%, and determining compound 2-3 by LC-MS to obtain [ M + H ]]+383.52，[M+Na]+405.5。
Compounds 2-1 to 2-4 were prepared according to the methods of examples 1 to 2, and the relevant experimental data and structural identification data are shown in Table 1.
TABLE 1 Experimental data and Structure identification data for Compounds 2-1-2-4
EXAMPLE 3 preparation of Compounds 1-3
Adding 11.2g of 98% sulfuric acid and 13.34g of 40% sulfuric acid solution of nitrosyl sulfuric acid into a dry 100ml three-neck flask at room temperature, uniformly stirring, cooling to 10-15 ℃ in an ice bath, slowly adding about 7.32g of 2, 4-dinitroaniline for about 1h, and preserving heat for 3h at 10-15 ℃ after the addition is finished to obtain a transparent diazo liquid. Then adding 120ml of water and 4ml of concentrated sulfuric acid into a 2000ml beaker to prepare a coupling base solution, adding ice to reduce the temperature to 0-5 ℃, then simultaneously dropwise adding 16.64g of compound 2-3 and the diazo solution within 1 hour to carry out coupling reaction, and determining by a ring penetration experiment during the dropwise adding process to ensure that the compound 2-3 is in slight excess. After the dripping is finished, ice is added to control the temperature to be 0-5 ℃, the heat preservation is carried out for 2h to finish the coupling, then the mixture is naturally stirred to the room temperature, filtered, washed and dried, and 21.3g of dye filter cakes of the compounds 1-3 are obtained. The yield thereof was found to be 92.37%. HPLC purity 94.5%. LC-MS determination of Compounds 1 to 3 gave [ M + H]+577.6，[M+Na]+599.5。
EXAMPLE 4 preparation of Compounds 1-5
At room temperature, 20ml of water and 12.17g of 36% hydrochloric acid were placed in a 100ml three-neck flask, followed by 4.14g of p-nitrobenzene with stirringAnd (3) uniformly stirring amine, heating to 70 ℃, preserving heat for 2 hours to fully dissolve p-nitroaniline, naturally cooling to 50 ℃, and cooling to 0-5 ℃ by using an ice bath. Then controlling the temperature at 0-5 ℃, slowly dripping 9.12g of 25% sodium nitrite aqueous solution for about 20min, and preserving the temperature for 1h at 0-5 ℃ after finishing the dripping to obtain the diazo liquid. Then 90ml of water and 3ml of concentrated sulfuric acid are added into a 1000ml beaker to prepare a coupling base solution, ice is added to reduce the temperature to 0-5 ℃, then 10.55g of compound 2-1 and the diazo solution are simultaneously dripped within 1 hour to carry out coupling reaction, and the slight excess of the compound 2-1 is ensured by measuring in a ring penetration experiment during the dripping process. After the dripping is finished, ice is added to control the temperature to be 0-5 ℃, the heat preservation is carried out for 2h to finish the coupling, then the mixture is naturally stirred to the room temperature, filtered, washed and dried, and 13.4g of dye filter cakes of the compounds 1-5 are obtained. The yield thereof was found to be 94.2%. HPLC purity 95.3%. LC-MS determination of Compounds 1 to 5 gave [ M + H]+475.4，[M+Na]+497.5。
Compounds 1-1 to 1-12 were prepared according to the methods of examples 1 to 4. The relevant experimental data and structural identification data are shown in table 2.
TABLE 2 Experimental data and Structure identification data for Compounds 1-12
Effect example 1
5g of the compound 1-3 prepared in example 3 is dispersed in 500 ml of water, 20ml of the water is absorbed and mixed with 80 ml of the water, the pH value of a dye bath is adjusted to 4-5 by acetic acid, the dye bath is heated to 70 ℃, 5g of polyester fiber cloth is placed for dyeing, the temperature is raised from 70 ℃ to 130 ℃ within 30 minutes, the temperature is kept for 50 minutes, and the water is drained and cleaned after the temperature is cooled to below 90 ℃. The cloth sample was then washed in 100ml of reducing wash solution containing 1 g/l of caustic soda and 3 g/l of sodium hydrosulfite at 80 ℃ for 20 minutes.
Disperse dyes prepared from the compounds 1-1 to 1-12 and the comparative compounds I to III are dyed by the method of the effect example 1, and the washing fastness and the sublimation fastness are tested by using national standards GB/T3921-2008 and GB/T5718-1997, and the test results are shown in Table 3.
TABLE 3 dyeing effect data of disperse dyes prepared from compounds 1-1 to 1-12
The data in table 3 show: compared with conventional dye compounds I-III with similar structures in the market, the disperse dye disclosed by the invention not only has higher washing fastness, but also has excellent sublimation fastness.
Claims (10)
1. The preparation method of the azoaniline compound 1 is characterized by comprising the following steps: in water and in the presence of acid, carrying out coupling reaction on the compound 2 and the compound 3 to obtain a compound 1;
wherein R is1Is composed ofOr a hydrogen atom, R2Is C1-C4Alkyl of R3Is composed of R4Is C1-C3Alkyl or hydrogen atom of (a); a. theIs Cl-、CH2COO-、H2PO4 -、HSO4 -Or NO3 -。
2. The method according to claim 1, wherein C is1-C4Alkyl of (a) is methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl;
and/or, said C1-C3The alkyl group of (a) is methyl, ethyl, propyl or isopropyl.
3. The method of claim 2, wherein R is1Is a hydrogen atom; and/or, said R2Is methyl or ethyl; and/or, said R4Is methyl.
4. The method of claim 1, wherein compound 1 is any one of the following compounds:
5. the process according to any one of claims 1 to 4, wherein the volume molar ratio of the water to the compound 2 in the coupling reaction is 1.6L/mol to 4.7L/mol;
and/or, in the coupling reaction, the acid is one or more of hydrochloric acid, acetic acid, phosphoric acid, nitric acid and sulfuric acid;
and/or, in the coupling reaction, the acid participates in the reaction in the form of an acid aqueous solution, and the mass fraction of the acid aqueous solution is 3-98%;
and/or, in the coupling reaction, the volume ratio of the acid to the solvent is 0.01-0.06;
and/or in the coupling reaction, the molar ratio of the compound 2 to the compound 3 is 1.5: 1-1: 1;
and/or, in the coupling reaction, the temperature of the coupling reaction is-10 ℃ to 30 ℃;
and/or, in the coupling reaction, the progress of the coupling reaction takes the non-color development of the compound 2 ring as a reaction endpoint.
6. The method according to any one of claims 1 to 5, further comprising the steps of: when R is3Is composed ofIn the absence of a solvent, carrying out diazotization reaction on nitrosyl sulfuric acid and a compound 8 in the presence of concentrated sulfuric acid to obtain a compound 3; when R is3Is composed ofIn the presence of acid, carrying out diazotization reaction on nitrite or nitrosyl sulfuric acid and a compound 8 to obtainCompound 3 is obtained;
7. the method according to claim 6, wherein R is the same as R in the diazotization reaction3Is composed ofWhen the diazotization reaction is carried out in the presence of water; the volume mol ratio of the water to the compound 8 is 0.13L/mol to 1.33L/mol;
and/or, in the diazotization reaction, when R is3Is composed ofWhen the acid is hydrochloric acid, acetic acid or sulfuric acid, the acid is one or more of hydrochloric acid, acetic acid and sulfuric acid; the acid takes part in the reaction in the form of an aqueous acid solution;
and/or in the diazotization reaction, the molar ratio of the compound 8 to the acid is 1: 2-1: 5;
and/or, in the diazotization reaction, the nitrite is sodium nitrite;
and/or, in the diazotization reaction, the molar ratio of the compound 8 to the nitrite or the nitrosyl sulfuric acid is 1: 1-1: 1.2;
and/or, in the diazotization reaction, the temperature of the reaction is-10 ℃ to 30 ℃;
and/or, in the diazotization reaction, the diazotization reaction takes the compound 8 as a reaction end point when the reaction is not carried out any more.
8. The method of any one of claims 1 to 7, further comprising the steps of: in the presence of a catalyst and alkali, carrying out condensation reaction on a compound 4 and a compound 5 to obtain a compound 2; the catalyst is alkali metal halide;
9. the method of claim 8, wherein in the condensation reaction, the alkali metal halide is one or more of potassium iodide, sodium iodide, potassium bromide, and sodium bromide;
and/or, in the condensation reaction, the molar ratio of the catalyst to the compound 4 is 0.01: 1-1: 1;
and/or, in the condensation reaction, the alkali is inorganic alkali;
and/or, in the condensation reaction, the molar ratio of the alkali to the compound 4 is 1.0: 1-5: 1;
and/or in the condensation reaction, the molar ratio of the compound 4 to the compound 5 is 1: 2-1: 2.5;
and/or, in the condensation reaction, the temperature of the condensation reaction is 50-150 ℃;
and/or, in the condensation reaction, the condensation reaction takes the compound 4 as a reaction end point when no longer reacting.
10. The method of claim 8 or claim 9, further comprising the steps of: carrying out esterification reaction on the compound 6 and chloroacetic acid to obtain a compound 5;
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|---|---|---|---|---|
| CN111041858A (en) * | 2019-12-18 | 2020-04-21 | 山东理工大学 | Azo structure carboxylic acid type dye for dyeing alginate fiber, preparation method and dyeing process thereof |
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| JPS55116754A (en) * | 1979-03-05 | 1980-09-08 | Mitsui Toatsu Chem Inc | Monoazo compound, its preparation, and dyeing of synthetic fiber |
| JPS6141382A (en) * | 1984-07-27 | 1986-02-27 | 三菱化学株式会社 | Alkali resist style composition for polyester fiber |
| EP0684287A1 (en) * | 1994-05-20 | 1995-11-29 | Hoechst Mitsubishi Kasei Co., Ltd. | Water insoluble red monoazo dyes, their preparation and the use thereof |
| CN1059456C (en) * | 1993-05-06 | 2000-12-13 | 希巴特殊化学控股公司 | Azo dyes |
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| US4119624A (en) * | 1972-06-08 | 1978-10-10 | Imperial Chemical Industries Limited | Disperse monoazo dyestuffs |
| JPS5070673A (en) * | 1973-10-30 | 1975-06-12 | ||
| JPS55116754A (en) * | 1979-03-05 | 1980-09-08 | Mitsui Toatsu Chem Inc | Monoazo compound, its preparation, and dyeing of synthetic fiber |
| JPS6141382A (en) * | 1984-07-27 | 1986-02-27 | 三菱化学株式会社 | Alkali resist style composition for polyester fiber |
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| CN111041858A (en) * | 2019-12-18 | 2020-04-21 | 山东理工大学 | Azo structure carboxylic acid type dye for dyeing alginate fiber, preparation method and dyeing process thereof |
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