CN109135322A - A kind of azo dispersion dyes compound and its synthetic method and purposes - Google Patents
A kind of azo dispersion dyes compound and its synthetic method and purposes Download PDFInfo
- Publication number
- CN109135322A CN109135322A CN201810947334.8A CN201810947334A CN109135322A CN 109135322 A CN109135322 A CN 109135322A CN 201810947334 A CN201810947334 A CN 201810947334A CN 109135322 A CN109135322 A CN 109135322A
- Authority
- CN
- China
- Prior art keywords
- acid
- dispersion dyes
- reaction
- azo dispersion
- follows
- 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
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
- C09B29/08—Amino benzenes
- C09B29/0833—Amino benzenes characterised by the substituent on the benzene ring excepted the substituents: CH3, C2H5, O-alkyl, NHCO-alkyl, NHCOO-alkyl, NHCO- C6H5, NHCOO-C6H5
- C09B29/0836—Amino benzenes characterised by the substituent on the benzene ring excepted the substituents: CH3, C2H5, O-alkyl, NHCO-alkyl, NHCOO-alkyl, NHCO- C6H5, NHCOO-C6H5 linked through -N=
- C09B29/0838—Amino benzenes characterised by the substituent on the benzene ring excepted the substituents: CH3, C2H5, O-alkyl, NHCO-alkyl, NHCOO-alkyl, NHCO- C6H5, NHCOO-C6H5 linked through -N= specific alkyl-CO-N-, aralkyl CON-, cycloalkyl CON-, alkyl OCON-
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/16—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dispersed, e.g. acetate, dyestuffs
- D06P1/18—Azo dyes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/24—Polyamides; Polyurethanes
- D06P3/28—Preparing azo dyes on the material
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/34—Material containing ester groups
- D06P3/52—Polyesters
- D06P3/56—Preparing azo dyes on the material
Abstract
The present invention provides a kind of azo dispersion dyes compound and its synthetic methods and purposes, specifically: (1) Ugi reacts: in organic solvent, aldehyde, aniline, formic acid and cyclohexyl isonitrile are subjected to tetra- component reaction of Ugi, reaction solution obtains Ugi product through filtering, organic solvent washing；(2) hydrolysis: in alcohols solvent, Ugi product is added and acid carries out selective hydrolysis, reaction solution is neutralized, organic solvent is extracted, is concentrated under reduced pressure, is dried to obtain hydrolysate, that is, synthesizes the coupling component of azo dispersion dyes；(3) coupling reaction: in the presence of organic acid, gained coupling component and 4- nitrophenyl diazonium salt are coupled, adjust reacting liquid pH value by the in the mixed solvent of alcohols and water, solid is filtered, washed, is dried etc. obtains azo dispersion dyes compound.The synthetic method can Effective Regulation dye molecule amount and molecular volume, and introduce amide group, the dyeability on polyester fiber and Fypro is greatly improved.
Description
Technical field:
The present invention relates to a kind of azo dispersion dyes compound and its synthetic methods and purposes.
Background technique:
Disperse dyes are applied to the dyeing of acetate fiber earliest, after with synthetic fibers development, especially polyester fiber
The development of (terylene) and develop rapidly.Disperse dyes are various in style, chromatography is complete, are widely used, and become dyestuff row
Most important major class branch in the industry.China is the first big producer of disperse dyes in the world, is had in the international market relatively strong
The market competitiveness.Disperse dyes structure is simple, and molecular weight is lower, is free of water soluble group, though contain polar group in molecule
(such as hydroxyl, amino, hydroxyl alkylamino, cyanogen alkylamino), still falls within nonionic dye, it be also current hydrophobic fibre (such as
Polyester, polyamide etc.) dyeing a class of dyes the most main.There are two types of mode classifications for disperse dyes, first is that according to application performance,
Disperse dyes can be divided into low form, high temperature modification and middle warm type three categories；Second is that according to chemical structure, it can be by disperse dyes
It is divided into azo, Anthraquinones and heterocyclic and a small amount of quinophthalone class, methine class, ortho-nitrophenyl amine etc..Wherein azo
The disperse dyes of type structure are most important one kind, account about 60%.The disperse dyes of azo-type structure have than more complete
Chromatography can obtain different colours, different dyeabilities by changing the electronic effect of substituent group on diazo component and coupling component
Dyestuff.Dyestuff can be made to generate hyperchromic effect as diazo component introduces electron-withdrawing group or coupling component introducing electron-donating group；
Its vividness and absorption intensity can be improved with heterocycle substitution phenyl ring.In recent years, due to heterocycle type disperse dye bright in color light, color development
Intensity is high, fastness ability is good, has preferable hyperchromic effect and higher molar extinction coefficient, and have good dyeability,
It becomes dyestuff circle and studies a more field.
Currently, as hyperfine polyester fiber, environment-friendly type acid fiber by polylactic, differential terylene easily contaminate fiber and tencel
Occur, the dyeing ability of most of existing disperse dyes has shown deficiency.Disperse dyes show as Yi Jinyi on fiber and go out
The phenomenon that, lead to that its washing fastness is poor, application performance is bad.To find out its cause, mainly disperse dyes and these fibers is affine
Power is poor, and when the temperature is excessively high, dye molecule warm-up movement aggravation is migrated from fibrous inside to fiber sheath.Disperse dyes heat is moved
Fastness decline problem caused by moving is by the common concern of insider institute, research day of the domestic and international people in the industry to this respect
Become to increasing.
The main method for improving affinity between disperse dyes and fiber is the molecular weight for effectively improving disperse dyes, with
The increase of molecular weight, the Van der Waals force enhancing between dye molecule and fiber, resistance to thermal migration, the dyeabilities such as fastness to sublimation
It can be improved.Therefore, increase disperse dyes to the affinity of fiber, be expected to fundamentally solve and improve the above problem.It opens
Disperse dyes that send out structure novel, that dyeability is excellent have significant application value.
Summary of the invention:
The first aspect of the present invention purpose is to provide a kind of azo dispersion dyes compound, and the disperse dye compound is to poly-
The dyeing of ester fiber, Fypro has significant effect.
The technical solution adopted by the present invention is as follows:
A kind of azo dispersion dyes compound, structural formula are as shown in Equation 1:
In formula: R1For H, CH3, R2For H, Br.
A kind of azo dispersion dyes compound of the present invention, be structurally characterized in that: molecular weight and molecular volume are moderate,
Contain an amide groups structural unit (- CONH-).Those design features have weight to the raising of the dyeability of the new dye
It influences:
(1) dye molecule volume and molecular weight effectively increase, and improve the contact surface between dyestuff and fiber, enhance
The Van der Waals force of dyestuff and fiber improves its dyeability and color fastness to improve the affinity of dyestuff and fiber.
(2) by introduce amide groups (- CONH-) this characteristic group, can in fiber by hydrogen group, for hydrogen group shape
It at hydrogen bond, and is mutually suitable for enhancing mutual active force with the structure of polyester fiber, to improve dyeability.
(3) in azo dyes synthesis, the group on diazo component has weight to the maximum absorption wavelength and color of dyestuff
It influences.In the identical situation of coupling component, select different substituent groups that can obtain the idol of different colours in diazo component
Nitrogen dyestuff provides great convenience for the diversity synthesis of azo dispersion dyes.
A kind of azo dispersion dyes compound of the invention can be selected from one kind of following compound:
The second aspect of the present invention purpose is to provide a kind of preparation method of aforementioned azo dispersion dyes compound, feature
It is, comprising the following steps:
(1) Ugi reacts: in organic solvent, by a certain amount of aldehyde, aniline, formic acid and cyclohexyl isonitrile in certain temperature
Lower progress tetra- component reaction of Ugi, reaction solution obtain Ugi product through filtering, organic solvent washing；
(2) hydrolysis: in alcohols solvent, Ugi product is added and certain density acid is selected at a certain temperature
Property hydrolysis, reaction solution is neutralized, organic solvent extract, is concentrated under reduced pressure, is dried to obtain hydrolysate, that is, synthesize azo dispersion dyes
Coupling component；
(3) coupling reaction: in the presence of organic acid, the in the mixed solvent of alcohols and water, by gained coupling component and 4- nitro
Arenediazonium salts are coupled at a certain temperature, adjust reacting liquid pH value, solid is filtered, washed, is dried etc. obtain it is novel
Disperse dye compound.
Reaction equation of the present invention is as follows:
In reaction equation, R is 4-Me and 2-Br
Further it is provided in:
In step (1):
The organic solvent is any one in toluene, methanol, ethyl alcohol or acetonitrile.
The molar ratio of the aldehyde, aniline, cyclohexyl isonitrile, formic acid are as follows: 1:1~1.2:1~1.2:1~1.2.
The reaction temperature is 40-100 DEG C, and reaction condition is more mild, the reaction time are as follows: 36-48h.
In step (2):
Shown in alcohols solvent are as follows: methanol, ethyl alcohol, any one in isopropanol.
The acid are as follows: hydrochloric acid, sulfuric acid, any one in phosphoric acid.
The mass concentration of the acid are as follows: 36.5% (hydrochloric acid), 40%-60% (sulfuric acid).
The molar ratio of the Ugi product and acid are as follows: 1:10-20.
The reaction temperature is 60-120 DEG C, the reaction time are as follows: 2-6h.
The alkali are as follows: sodium hydroxide, potassium hydroxide, any one in sodium bicarbonate, molar concentration 2-8mol/L.
The organic solvent that the extraction uses is ethyl acetate or methylene chloride, after organic phase saturated common salt water washing
It is dried with anhydrous sodium sulfate.
In step (3):
The organic acid are as follows: formic acid, acetic acid, sulfonic acid, any one in benzoic acid.
The molar ratio of the coupling component and 4- nitrophenyl diazonium salt are as follows: 1:1-2.
The reaction temperature is 0-5 DEG C, reaction time 24-36h.
The present invention has significant technical effect due to using above technical scheme.By changing taking for starting material
Can be obtained the coupling component of different molecular weight and different molecular volume for base or structure, realize Novel disperse dyestuff molecular volume and
Effective control of molecular weight, thus controllable disperse dyeing performance and color fastness.
The third aspect of the present invention purpose is to provide a kind of aforementioned azo dispersion dyes compound in polyester fiber and polyamides
Purposes in amine stock-dye, is verified by experiments, fine to polyester fiber, polyamide using above-mentioned azo dispersion dyes compound
Dimension is dyed, and carries out color fastness test to 1:1 standard dyeing sample, and test result shows polyester and Fypro dyeing
The washing fastness of sample is more significantly improved, and especially fastness to dryheat is significantly improved.
The present invention is elaborated further below in conjunction with the drawings and specific embodiments:
Detailed description of the invention:
Fig. 1 is the hydrogen nuclear magnetic resonance figure of dyestuff 1a of the present invention；
Fig. 2 is the hydrogen nuclear magnetic resonance figure of dyestuff 1b of the present invention；
Fig. 3 is the absorption spectrum curve comparison diagram of dyestuff 1a of the present invention and disperse orange 3.
Fig. 4 is the absorption spectrum curve comparison diagram of dyestuff 1b of the present invention and disperse orange 3.
Specific embodiment:
Embodiment 1: dyestuff 1a
Embodiment 1-1: the preparation of dyestuff 1a
(1) tetra- component reaction of Ugi:
In 250mL round-bottomed flask, sequentially add anhydrous methanol (150mL), aniline (4.39mL, 48.16mmol,
1.05eq), p-tolyl aldehyde (4.9mL, 48.16mmol, 1.05eq), formic acid (2.07mL, 55.04mmol, 1.2eq), and
Cyclohexyl acetonitrile (5.69mL, 45.87mmol, 1.0eq).Reaction mixture heating stirring 48h in 80 DEG C of oil baths, through TLC points
Analysis, fully reacting.After reaction solution is cooled to room temperature, at a refrigerator lower layer cooling night, white solid is generated.It filters (when suction filtration
Rinsed with the solution of EA:PE=1:5) obtained solid 7.0925g, filtrate is spin-dried for, weigh to obtain 4.6563g.That is gained Ugi product
Total 11.7488g, yield add up to 73%.Reaction equation is as follows:
Product confirmation:
IR(film)3273,3085,2926,1668,165,1559,700cm-1.
1H NMR(400MHz,CDCl3)δ8.39(s,1H),7.26-7.25,7.26-7.25(m,3H),7.19-7.16(m,
2H), 7.12 (d, J=8.0Hz, 2H), 7.06 (d, J=8.0Hz, 2H), 5.96 (s, 1H), 5.77 (br d, J=8.0Hz,
1H),3.88-3.81(m,1H),2.30(s,1H),1.95-1.89(m,2H),1.70-1.57(m,3H),1.39-1.30(m,
2H),1.17-1.05(m,3H).
13C NMR(100MHz,CDCl3)δ168.0,163.1,139.4,138.4,131.1,129.6(×2),129.3
(×2),128.9(×2),128.2(×2),127.7,63.6,48.8,32.8,25.5,24.8,24.7,21.1.MS(+
ESI): m/z (%)=351 (52) [M+H+].
(2) hydrolysis:
In 250mL round-bottomed flask, Ugi reaction product (7.0925g, 20.26mmol), anhydrous methanol are sequentially added
(70mL), by 17.5mL H2The dense H of O and 17.5mL2SO4(98%) it is added dropwise in flask after mixing.It is stirred in 90 DEG C of oil baths
2h is reacted, contact plate is analyzed through TLC, fully reacting.Reaction solution in flask is adjusted to the laggard of pH=7 with 5mol/L NaOH
Row extraction, is added water and ethyl acetate washs 2 times, and stratification, organic phase is dried, filtered with anhydrous sodium sulfate, is rotated, dry
Weigh to obtain m=6.0156g, yield 92%.Reaction equation is as follows:
Product confirmation:
IR(film)3300,2930,2854,1647,1504,749cm-1.
1H NMR(400MHz,CDCl3) δ 7.33 (d, J=8.4Hz, 2H), 7.23-7.19 (m, 4H), 6.82 (dd, J=
7.6,7.2Hz, 1H), 6.68 (br d, J=8.0Hz, 1H), 6.65 (dd, J=8.8,1.2Hz, 2H), 4.69 (s, 1H),
3.85-3.80 (m, 1H), 2.37 (s, 3H), 1.93-1.81 (m, 2H), 1.72-1.58 (m, 3H), 1.40-1.29 (m, 2H),
1.22-1.03(m,3H).
13C NMR(100MHz,CDCl3)δ170.2,146.8,138.3,136.0,129.9(×2),129.3(×2),
127.3(×2),119.1,113.9(×2),64.1,48.1,33.0,32.8,25.4,24.8,24.7,21.2.MS(+ESI):
M/z (%)=323 (100) [M+H+].
(3) disperse dyes synthesize:
1, diazonium salt synthesizes: (0.64g, 4.65mmol, 1.5eq) paranitroanilinum is added in 50mL round-bottomed flask, it will
4mL H2It is added drop-wise in flask after the dense HCl of O and 4mL (36.5%) mixing, is dissolved (about 2h) under the conditions of 40 DEG C~60 DEG C.
After solution is cooled to room temperature, it is placed in ice-water bath.Sodium nitrite (0.32g, 4.65mmol, 1.5eq) is used into 4mL H2O dissolution
In test tube, it is placed in ice-water bath and places 2min or so.By above-mentioned NaNO2Aqueous solution is slowly added to dropwise, after being added dropwise to complete
Ice-water bath reacts 2h.
2, coupling reaction: in 100mL round-bottomed flask, being added 10mL methanol, 2mL acetic acid and 5mL water, in embodiment 1-1
(2) gained coupling component (1g, 3.10mmol, 1.0eq), stirring to coupling component are completely dissolved.It, will be upper under the conditions of ice-water bath
It states 4- nitrophenyl diazonium salt slowly to instill dropwise, be stirred at 0~5 DEG C for 24 hours, thin-layer sample application tracks reaction process.It has reacted
PH is adjusted to alkalescent, filtering, organic solvent (EA:PE=1:5) washing, using acetic acid second with the sodium hydroxide of 5mol/L after finishing
Ester recrystallization method obtains sterling dyestuff 1a, the dry 1.3934g that weighs to obtain, yield 95%.Reaction equation is as follows:
The IR of disperse dyes 1a,1H-NMR、13C-NMR and MS data are as follows:
IR(film)3401,2932,1667,1515,1339,1141,860cm-1.
1H NMR(400MHz,CDCl3) δ ppm 8.34 (d, J=9.2Hz, 2H), 7.93 (d, J=9.2Hz, 2H), 7.84
(d, J=9.2Hz, 2H), 7.35 (d, J=8.0Hz, 2H), 7.23 (d, J=8.0Hz, 2H), 6.68 (d, J=8.8Hz, 2H),
5.89 (br d, J=8.4Hz, 1H), 5.66 (d, J=3.6Hz, 1H), 4.85 (d, J=3.6Hz, 1H), 3.84-3.76 (m,
1H), 2.38 (s, 3H), 1.93 (d, J=12.0Hz, 1H), 1.78-1.58 (m, 4H), 1.39-1.28 (m, 2H), 1.17-1.10
(m,2H),1.03-0.98(m,1H).
13C NMR(100MHz,CDCl3)δ169.1,156.5,150.4,147.7,145.4,138.7,135.3,130.2
(×2),127.0(×2),126.0(×2),124.7(×2),122.8(×2),113.5(×2),62.1,48.6,32.9,
32.6,25.3,24.7,24.5,21.2.
(%)=588 (100) MS (+ESI): m/z, 472 (35) [M+H+].
Embodiment 1-2:
Spectral absorption performance: weighing 0.05 gram of dyestuff 1a, dissolves constant volume in 50mL n,N-Dimethylformamide, dilution
Certain multiple makes concentration 0.006g/L, is measured and is inhaled using UV-2450 ultraviolet-uisible spectrophotometer (Japanese Shimadzu Corporation)
The curve of spectrum is received, and compared with 3 solution absorption spectra curve of same concentrations 0.006g/L disperse orange, sees Fig. 3.
From the absorption spectrum curve in figure it can be found that compared with disperse orange 3, the maximum absorption wavelength of dyestuff 1a is to short
Wave direction offsets by 3nm, becomes 464nm from original 467nm.After measured, specific performance index is as shown in following table 1-1:
Table 1-1, dyestuff absorption spectrum performance parameter
| Dyestuff title | Maximum absorption wavelength/nm | Molar extinction coefficient ε |
| Disperse orange 3 | 467 | 30777 |
| Dyestuff 1a | 464 | 29393 |
Embodiment 1-3:
Product fastness properties detection: the dyeing by dyestuff 1a manufactured in the present embodiment and disperse orange 3, applied to terylene.
Its test method is as follows, and dyeability result is as shown in table 1-2.
Test method: 0.5000g dyestuff 1a (or disperse orange 3) and 0.5000g Dispersant MF accurately are weighed, is put into mortar
In, little water is added, is ground, transfer is settled to the volumetric flask of 500mL after 20min, and being configured to dye content is 1g/L's
Mother liquor draws this mother liquor into the dye liquor of various concentration, 180min is dyed under the conditions of 130 DEG C, obtains 1:1 standard color sample
The dye sample of color depth value, using its Washing of ISO 105-C06:1994 (E) standard test, using ISO 105-P01:1993
(E) standard test color fastness to dry heat, using GB/T3920-2008 standard test crock fastness.
Table 1-2, dyestuff compare the fastness properties of dyeing terylene
In terms of upper table experimental data: every fastness properties of dyestuff 1a and disperse orange 3 only have improvement slightly, still,
Fastness to dryheat has achieved the effect that expected imagination, and staining fastness increase rate is larger, illustrates that dyestuff 1a really has fiber
Biggish affinity, dyestuff are not easy to come out from internal migration.
Embodiment 1-4:
Dyeing by dyestuff 1a manufactured in the present embodiment and disperse orange 3, applied to Fypro.Its test method is such as
Under, dyeability result is as shown in table 1-3.
Test method: 0.5000g dyestuff 1a (or disperse orange 3) and 0.5000g Dispersant MF accurately are weighed, is put into mortar
In, little water is added, is ground, transfer is settled to the volumetric flask of 500mL after 20min, and being configured to dye content is 1g/L's
Mother liquor draws this mother liquor into the dye liquor of various concentration, 60min is dyed under the conditions of 100 DEG C, obtains 1:1 standard color sample
The dye sample of color depth value, using its Washing of ISO 105-C06:1994 (E) standard test, using ISO 105-P01:1993
(E) standard test color fastness to dry heat, using GB/T3920-2008 standard test crock fastness.
The fastness properties that table 1-3, dyestuff dye Fypro compare
In terms of upper table experimental data: dyestuff 1a has greatly improved than every fastness properties of disperse orange 3, to various fibres
The staining fastness increase rate of dimension is larger, and especially fastness to dryheat has achieved the effect that expected imagination, illustrates that dyestuff 1a is certain
There is biggish affinity to fiber, dyestuff is not easy to come out from internal migration.
Embodiment 2: dyestuff 1b
Embodiment 2-1: the preparation of dyestuff 1b
(1) tetra- component reaction of Ugi:
In 250mL round-bottomed flask, sequentially add anhydrous methanol (150mL), aniline (4.39mL, 48.16mmol,
1.05eq), o-bromobenzaldehye (5.63mL, 48.16mmol, 1.05eq), formic acid (2.07mL, 55.04mmol, 1.2eq), hexamethylene
Base acetonitrile (5.69mL, 45.87mmol, 1.0eq).Reaction mixture heats 48h in 80 DEG C of oil baths, analyzes, has reacted through TLC
Entirely.After reaction solution is cooled to room temperature, at a refrigerator lower layer cooling night, white solid is generated.Suction filtration (uses EA:PE=when suction filtration
The solution of 1:5 rinses) obtained solid 7.8915g, filtrate is spin-dried for, weigh to obtain 6.7571g.Gained Ugi product is total
14.6486 yield adds up to 77%.Reaction equation is as follows:
Product confirmation:
IR(film)3347,2929,1692,1663,766,700cm-1.
1H NMR(400MHz,CDCl3) δ 8.42 (s, 1H), 7.50 (d, J=6.8Hz, 1H), 7.31-7.29 (m, 3H),
7.19-7.18 (m, 3H), 7.12-7.06 (m, 2H), 6.32 (s, 1H), 5.78 (d, J=6.8Hz, 1H), 3.89-3.87 (m,
1H),2.06-1.92(m,2H),1.75-1.60(m,3H),1.37-1.35(m,2H),1.24-1.09(m,3H).
13C NMR(100MHz,CDCl3)δ.167.6,163.0,138.3,133.5,133.0,131.8,130.2,128.7
(×2),128.4(×2),127.9,127.3,125.8,62.5,49.1,32.7(×2),25.5,24.8,24.7.
MS (+ESI): m/z (%)=415 (100) [M+H+].
(2) hydrolysis:
In 250mL round-bottomed flask, Ugi reaction product (7.8915g, 19.02mmol), anhydrous methanol are sequentially added
(70mL), by 17.5mL H2The dense H of O and 17.5mL2SO4(98%) it is added dropwise in flask after mixing.It is heated in 90 DEG C of oil baths
2h is reacted, analyzes fully reacting through TLC.Extract after reaction solution in flask is adjusted to pH=7 with 5mol/L NaOH
It takes, water is added and ethyl acetate washs 2 times, stratification, organic phase is dried, filtered with anhydrous sodium sulfate, rotates to obtain hydrolysis production
Object, the dry 7.0243g that weighs to obtain, yield 96%.Reaction equation is as follows:
Product confirmation:
IR(film)3396,3349,2932,1674,1603,1508,747cm-1.
1H NMR(400MHz,CDCl3) δ 7.62 (d, J=8.8Hz, 1H), 7.49 (d, J=9.2Hz, 1H), 7.31 (d, J
=8.4,7.6Hz, 1H), 7.21-7.14 (m, 3H), 6.75 (dd, J=7.2,7.2Hz, 1H), 6.57 (d, J=8.4Hz, 1H),
6.41 (br d, J=7.2Hz, 1H), 5.27 (s, 1H), 5.06 (br s, 1H), 5.09 (br s, 1H), 3.86-3.78 (m,
1H), 1.97 (d, J=15.2Hz, 1H), 1.77-1.70 (m, 2H), 1.60-1.58 (m, 2H), 1.45-1.12 (m, 5H),
1.08-1.02(m,1H).
13C NMR(100MHz,CDCl3)δ169.0,146.1,138.5,133.1,129.8,129.3,128.7(×2),
128.5,123.8,118.4,113.5(×2),61.2,48.4,32.8,32.5,25.4,24.5,24.4.
MS (+ESI): m/z (%)=386 (100) [M+].
(3) disperse dyes synthesize:
1, prepared by diazonium salt: (0.64g, 4.65mmol, 1.5eq) 4- nitroaniline is added in 50mL round-bottomed flask, it will
4mLH2It is added drop-wise in flask after the dense HCl of O and 4mL (36.5%) mixing, is dissolved (about 2h) under the conditions of 40~60 DEG C.It will
After solution is cooled to room temperature, it is placed in ice-water bath.By (0.32g, 4.65mmol, 1.5eq) sodium nitrite 4mL H2O is dissolved in
In test tube, it is placed in ice-water bath and places 2min or so, by above-mentioned NaNO2Aqueous solution is slowly added to dropwise, in ice after being added dropwise to complete
Water-bath 2h.
2, coupling reaction: in 100mL round-bottomed flask, being added 10mL methanol, 2mL acetic acid and 5mL water, in embodiment 2-1
(2) gained coupling component (1g, 2.59mmol, 1.0eq), stirring are completely dissolved to coupling component, under the conditions of ice-water bath, will make
The 4- nitrophenyl diazonium salt got ready slowly instills dropwise, and thin-layer sample application tracks reaction process.After completion of the reaction with 5mol/L's
NaOH adjusts pH to alkalescent, filters, organic solvent (EA:PE=1:5) washing obtains dyestuff using re-crystallizing in ethyl acetate
1b, dry crude product 1.017g, yield 74%, reaction equation is as follows:
The IR of disperse dyes 1b,1H-NMR,13C-NMR and MS data are as follows:
IR(KBr)3308,2930,1676,1601,1333,1136cm-1.
1H NMR(400MHz,CDCl3) δ ppm 8.33 (d, J=8.8Hz, 2H), 7.91 (d, J=8.8Hz, 2H), 7.83
(d, J=8.8Hz, 2H), 7.66 (dd, J=8.0,0.8Hz, 1H), 7.49 (dd, J=7.6,1.6Hz, 1H), 7.33 (dd, J=
7.6,7.6Hz, 1H), 7.22 (ddd, J=7.6,7.6,1.2Hz, 1H), 6.60 (d, J=8.8Hz, 1H), 6.12 (d, J=
4.8Hz, 1H), 6.10 (d, J=7.6Hz, 1H), 5.45 (d, J=4.8Hz, 1H), 3.84-3.75 (m, 1H), 1.99-1.95
(m,1H),1.73-1.69(m,2H),1.62-1.57(m,2H),1.46-1.19(m,4H),1.11-1.01(m,1H).
13C NMR(100MHz,CDCl3)δ167.8,156.3,149.7,147.6,145.0,137.6,133.2,130.2,
128.9,128.3,126.4,124.7,123.2,122.7,113.3,59.4,48.7,32.7,32.3,25.3,24.4,24.3.
MS (+ESI): m/z (%)=536 (45) [M+H+],538(53)[M+2+H+].
Embodiment 2-2:
Spectral absorption performance: weighing 0.05 gram of dyestuff 1b, dissolves constant volume in 50mL n,N-Dimethylformamide, dilution
Certain multiple makes concentration 0.006g/L, is measured and is inhaled using UV-2450 ultraviolet-uisible spectrophotometer (Japanese Shimadzu Corporation)
The curve of spectrum is received, and compared with 3 solution absorption spectra curve of same concentrations 0.006g/L disperse orange.See Fig. 4.
From the absorption spectrum curve in figure it can be found that compared with disperse orange 3, the maximum absorption wavelength of dyestuff 1b is to short
Wave direction offsets by 6nm, becomes 461nm from original 467nm.After measured, specific performance index is as shown in following table 2-1:
Table 2-1, dyestuff absorption spectrum performance parameter
| Dyestuff title | Maximum absorption wavelength/nm | Molar extinction coefficient ε |
| Disperse orange 3 | 467 | 30777 |
| Dyestuff 1b | 461 | 34323 |
Embodiment 2-3:
Product fastness properties detection: the dyeing by dyestuff 1b manufactured in the present embodiment and disperse orange 3, applied to terylene.
Its test method is as follows, and dyeability result is as shown in table 2-2.
Test method: 0.5000g dyestuff 1b (or disperse orange 3) and 0.5000g Dispersant MF accurately are weighed, is put into mortar
In, little water is added, is ground, transfer is settled to the volumetric flask of 500mL after 20min, and being configured to dye content is 1g/L's
Mother liquor draws this mother liquor into the dye liquor of various concentration, 180min is dyed under the conditions of 130 DEG C, obtains 1:1 standard color sample
The dye sample of color depth value, using its Washing of ISO 105-C06:1994 (E) standard test, using ISO 105-P01:1993
(E) standard test color fastness to dry heat, using GB/T3920-2008 standard test crock fastness.
Table 2-2, dyestuff compare the fastness properties of dyeing terylene
In terms of upper table experimental data: every fastness properties of dyestuff 1b and disperse orange 3 only have improvement slightly, still,
Fastness to dryheat has achieved the effect that expected imagination, and staining fastness increase rate is larger, illustrates that dyestuff 1b really has fiber
Biggish affinity, dyestuff are not easy to come out from internal migration.
Embodiment 2-4:
Dyeing by dyestuff 1b manufactured in the present embodiment and disperse orange 3, applied to Fypro.Its test method is such as
Under, dyeability result is as shown in table 2-3.
Test method: 0.5000g dyestuff 1b (or disperse orange 3) and 0.5000g Dispersant MF accurately are weighed, is put into mortar
In, little water is added, is ground, transfer is settled to the volumetric flask of 500mL after 20min, and being configured to dye content is 1g/L's
Mother liquor draws this mother liquor into the dye liquor of various concentration, 60min is dyed under the conditions of 100 DEG C, obtains 1:1 standard color sample
The dye sample of color depth value, using its Washing of ISO 105-C06:1994 (E) standard test, using ISO 105-P01:1993
(E) standard test color fastness to dry heat, using GB/T3920-2008 standard test crock fastness.
The fastness properties that table 2-3, dyestuff dye Fypro compare
In terms of upper table experimental data: dyestuff 1b has greatly improved than every fastness properties of disperse orange 3, to various fibres
The staining fastness increase rate of dimension is larger, and especially fastness to dryheat has obtained large increase, illustrates dyestuff 1b really to fiber
With biggish affinity, dyestuff is not easy to come out from internal migration.
Claims (10)
1. a kind of azo dispersion dyes compound, structural formula are as shown in Equation 1:
In formula: R1For H, CH3, R2For H, Br.
2. a kind of azo dispersion dyes compound according to claim 1, which is characterized in that one selected from following compound
Kind:
3. the preparation method of azo dispersion dyes compound described in a kind of claim 1, which comprises the following steps:
(1) Ugi reacts: in organic solvent, aldehyde, aniline, formic acid and cyclohexyl isonitrile being carried out tetra- component reaction of Ugi, reaction
Liquid obtains Ugi product through filtering, organic solvent washing；
(2) hydrolysis: in alcohols solvent, Ugi product is added and acid carries out selective hydrolysis, reaction solution is neutralized, You Jirong
Agent extracts, is concentrated under reduced pressure, being dried to obtain the coupling component of synthesis azo dispersion dyes；
(3) coupling reaction: in the presence of organic acid, the in the mixed solvent of alcohols and water, by gained coupling component and 4- nitrobenzophenone
Diazonium salt, which is coupled, adjusts reacting liquid pH value, solid is filtered, washed, is dried etc. obtains disperse dyes chemical combination shown in formula 1
Object.
4. a kind of preparation method of azo dispersion dyes compound according to claim 3, which is characterized in that in step (1):
The organic solvent is any one in toluene, methanol, ethyl alcohol or acetonitrile；The benzaldehyde, aniline, cyclohexyl are different
The molar ratio of nitrile, formic acid are as follows: 1:1~1.2:1~1.2:1~1.2.
5. a kind of preparation method of azo dispersion dyes compound according to claim 3, which is characterized in that in step (1):
The reaction temperature is 40-100 DEG C, and reaction condition is more mild, the reaction time are as follows: 36-48h.
6. a kind of preparation method of azo dispersion dyes compound according to claim 3, which is characterized in that in step (2):
Shown in alcohols solvent are as follows: methanol, ethyl alcohol, any one in isopropanol；The acid are as follows: hydrochloric acid, sulfuric acid, appointing in phosphoric acid
It anticipates one kind；The molar ratio of the Ugi product and acid are as follows: 1:10-20；The alkali are as follows: sodium hydroxide, potassium hydroxide, carbonic acid
Any one in hydrogen sodium；The organic solvent that the extraction uses is ethyl acetate or methylene chloride, organic phase saturation food
It is dried after salt water washing with anhydrous sodium sulfate.
7. a kind of preparation method of azo dispersion dyes compound according to claim 3, which is characterized in that in step (2):
The reaction temperature is 60-120 DEG C, the reaction time are as follows: 2-6h.
8. a kind of preparation method of azo dispersion dyes compound according to claim 3, which is characterized in that in step (3):
The organic acid are as follows: formic acid, acetic acid, sulfonic acid, any one in benzoic acid；The coupling component and 4- nitrobenzene
The molar ratio of aryldiazonium salt are as follows: 1:1-2.
9. a kind of preparation method of azo dispersion dyes compound according to claim 3, which is characterized in that in step (3):
The reaction temperature is 0-5 DEG C, reaction time 24-36h.
10. a kind of use of azo dispersion dyes compound described in claim 1 in polyester fiber and Fypro dyeing
On the way.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810947334.8A CN109135322B (en) | 2018-08-20 | 2018-08-20 | Azo disperse dye compound and synthesis method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810947334.8A CN109135322B (en) | 2018-08-20 | 2018-08-20 | Azo disperse dye compound and synthesis method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109135322A true CN109135322A (en) | 2019-01-04 |
| CN109135322B CN109135322B (en) | 2020-04-21 |
Family
ID=64790312
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810947334.8A Active CN109135322B (en) | 2018-08-20 | 2018-08-20 | Azo disperse dye compound and synthesis method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109135322B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115637057A (en) * | 2022-10-28 | 2023-01-24 | 绍兴文理学院 | Synthesis method of double-crosslinking azo disperse dye |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1328258A (en) * | 1969-10-16 | 1973-08-30 | Ciba Geigy Ag | Valuable disperse azo dyestuffs containing n-substituted carbamyl-methyl-amino groupls their manufacture and use |
| US4026663A (en) * | 1975-02-05 | 1977-05-31 | American Color & Chemical Corporation | Polyester fabric dyed with monoazo dyestuffs |
| WO2011084803A3 (en) * | 2009-12-21 | 2011-11-24 | Living Proof, Inc. | Coloring agents and methods of use thereof |
| CN103079598A (en) * | 2010-04-02 | 2013-05-01 | 药物影像股份有限公司 | Single isomeric conjugates of rhodamine dyes |
-
2018
- 2018-08-20 CN CN201810947334.8A patent/CN109135322B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1328258A (en) * | 1969-10-16 | 1973-08-30 | Ciba Geigy Ag | Valuable disperse azo dyestuffs containing n-substituted carbamyl-methyl-amino groupls their manufacture and use |
| US4026663A (en) * | 1975-02-05 | 1977-05-31 | American Color & Chemical Corporation | Polyester fabric dyed with monoazo dyestuffs |
| WO2011084803A3 (en) * | 2009-12-21 | 2011-11-24 | Living Proof, Inc. | Coloring agents and methods of use thereof |
| CN103079598A (en) * | 2010-04-02 | 2013-05-01 | 药物影像股份有限公司 | Single isomeric conjugates of rhodamine dyes |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115637057A (en) * | 2022-10-28 | 2023-01-24 | 绍兴文理学院 | Synthesis method of double-crosslinking azo disperse dye |
| CN115637057B (en) * | 2022-10-28 | 2023-10-20 | 绍兴文理学院 | Synthesis method of double-crosslinking azo disperse dye |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109135322B (en) | 2020-04-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104672103B (en) | A kind of disperse dye compound and preparation method thereof and purposes | |
| CN104804464A (en) | Disperse dye compound as well as preparation method and application thereof | |
| CN109135322A (en) | A kind of azo dispersion dyes compound and its synthetic method and purposes | |
| Patel et al. | Synthesis and characterization of reactive dyes based on 2-phenyl-3-[4′-(4 ″-aminophenylsulphonamido)] phenyl-4 (3H)-quinazolinone-6-sulphonic acid | |
| CN104761923A (en) | A disperse dye compound, and a preparing method and uses thereof | |
| KR20100031607A (en) | Azo dyes | |
| CN109233338A (en) | A kind of disperse dye compound and its synthetic method and purposes | |
| US4283196A (en) | Process for coloring fiber materials with azo dyestuff containing --SO2 CH2 CH2 OSO3 H and --N(CH2 CH2 OSO.sub. H)2 groups | |
| CN113683903B (en) | Thiazole heterocycle azo type reactive dye and preparation method thereof | |
| CN111635644A (en) | Azo disperse dye compound and preparation and application method thereof | |
| US4271072A (en) | Azo dyestuffs containing -SO2 CH2 CH2 OSO3 H and -N(CH2 CH2 OSO3 H)2 groups | |
| CN111718594A (en) | Disperse dye and preparation and application methods thereof | |
| Wang et al. | Theoretical design, prediction and synthesis of a magenta dye SCFX-AYRL for sustainable coloration of natural fibers in SCF-CO2 | |
| CN105038296B (en) | A kind of preparation method of heterocycle azo dyestuff | |
| Li et al. | Diversity-oriented synthesis of azo disperse dyes with improved fastness properties via employing Ugi four-component reaction | |
| CN104693141A (en) | Disperse dye compound as well as preparation method and use of disperse dye compound | |
| CN102898868A (en) | Reactive orange dye and preparation method thereof | |
| US20150232668A1 (en) | Yellow Reactive Dye Compound | |
| CN109517407A (en) | A kind of novel amido-containing acid ester azo dispersion dyes and its preparation and purposes | |
| CN111704807A (en) | Azo dye and preparation method and application thereof | |
| Qian et al. | An alternative strategy for the synthesis of disazo disperse dyes and their application on polyester fabric | |
| Patel et al. | Novel 2-phenyl-3-{4'-[n-(4''-aminophenyl) carbamoyl]-phenyl}-quinazoline-4 (3H) one-6-sulphonic acid based mono azo reactive dyes | |
| JPS5940171B2 (en) | azo dye | |
| CN104531137B (en) | Imidazoles fluorescent emission luminous organic material and preparation method thereof | |
| Patel et al. | Synthesis, characterization and dyeing performance of new bisazo–bisazomethine disperse dyes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |