CN102086307A - N,N-diacetoxyethyl-m-chloroaniline series azo dyes - Google Patents
N,N-diacetoxyethyl-m-chloroaniline series azo dyes Download PDFInfo
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- CN102086307A CN102086307A CN2010106075183A CN201010607518A CN102086307A CN 102086307 A CN102086307 A CN 102086307A CN 2010106075183 A CN2010106075183 A CN 2010106075183A CN 201010607518 A CN201010607518 A CN 201010607518A CN 102086307 A CN102086307 A CN 102086307A
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Abstract
The invention provides N,N-diacetoxyethyl-m-chloroaniline series azo dyes. The general formula of the dyes is shown below, wherein R1 represents H, NO2, Cl, Br or COMMUNICATION and R2 represents H, NO2, Cl, Br or CN. The preparation method of the dyes comprises the following steps: using paranitroaniline or a derivative of paranitroaniline as diazo component to perform diazotization, and then reacting with N,N-diacetoxyethyl-m-chloroaniline to obtain orange or orange-red disperse dye which can have a single structure and be used to directly prepare dyes with mixed structures. The type of dyes are used to dye polyester fiber in dye liquor which is from weakly acidic to weakly alkaline; and the dyes have bright colors, good levelling property and redyeing property, high lifting force and excellent color fastness properties.
Description
Technical field
The present invention relates in the field of fine chemical class N particularly, N-dicyanoethyl m-chloro aniline series azoic dyestuff.
Background technology
Aromatic amine and vinyl cyanide generation addition reaction can obtain corresponding single adduct and two adduct, when aromatic amine and vinyl cyanide by (mol ratio) addition in 1: 1, its product is referred to as single cyanoethylation product, when aromatic amine and vinyl cyanide by (mol ratio) addition in 1: 2, its product is referred to as the double fluoride ethyl purification product, and they all can be used for the synthetic of dispersed dye.Because single cyanoethyl of aromatic amine is reflected under the catalysis of catalyzer and is easy to carry out, therefore, single cyanoethylation product of aromatic amine is widely used in dispersed dye synthetic.For example, N-cyanoethyl aniline, N-ethyl-N-cyanoethyl aniline, N hydroxyethyl N cyanoethyl aniline, N-cyanoethyl Ortho-Chloro aniline, N-butyl-N-cyanoethyl aniline, N-second propyloic-N-cyanoethyl aniline etc. all have been used to the synthetic of azo dispersion dyes.
In azoic dye, the azoic dye of the two cyanoethyl aromatic amines of introducing often has high molar extinction coefficient, bright colour and high dyefastness and receives much attention.Yet two cyanoethyl reactions of aromatic amine are difficult to carry out, and product yield is generally lower, and the report of the double fluoride ethyl purification product of relevant aromatic amine on azo dispersion dyes is synthetic seldom.At present, only there is N in China, and N-dicyanoethyl aniline, N, N-dicyanoethyl meta-aminotoluene etc. are used for DISPERSE YELLOW 163, disperse the synthetic of three azo dispersion dyes such as tangerine 44 and dispersion tangerine 45.Press (mol ratio) addition in 1: 2 by m-chloro aniline and vinyl cyanide, its product is N, N-dicyanoethyl m-chloro aniline, but do not see that as yet it is used for synthetic azo organism, do not see that it is applied to trevira, urethane, polymeric amide as azo dispersion dyes, the dyeing report of cellulose acetate and BLENDED FABRIC thereof yet.
Summary of the invention
The present invention is that derivative with p-Nitroaniline and p-Nitroaniline is as diazo component, after diazotization with N, the coupling of N-dicyanoethyl m-chloro aniline, obtain containing N, a series of azo organism of N-dicyanoethyl m-chloro aniline, the contriver be used for trevira, urethane, polymeric amide, cellulose acetate, or above four kinds of compositions carries out the dyeing that arbitrary combination forms BLENDED FABRIC by discovering that some of them azo organism can be used as dispersed dye and uses.Their dyeing is bright-coloured orange or orange.
The objective of the invention is to prepare a class azoic dyestuff, have the orange or the orange dispersed dye of bright-coloured color.Azoic dyestuff provided by the present invention can comprise it being that slightly acidic dyes in weakly alkaline (as PH=3～9) dye liquor, level-dyeing property and redying property are good, the lifting force height, and have outstanding every colour fastness.
Technical scheme of the present invention is with N, and N-dicyanoethyl m-chloro aniline is the coupling component, and the derivative of p-Nitroaniline and p-Nitroaniline is a diazo component.Diazo component through diazotization reaction, is carried out coupling with the coupling component again, obtain corresponding azo organism.
Its general structure of azo organism of the present invention is:
Formula I
Among the formula I: R
1=H, NO
2, Cl, Br or CN;
R
2=H, NO
2, Cl, Br or CN.
Azo organism shown in contriver's formula I can be used as dispersed dye and uses.Be used for trevira, urethane, polymeric amide, cellulose acetate, or above four kinds of compositions carry out the dyeing that arbitrary combination forms BLENDED FABRIC.Their dyeing is bright-coloured orange or orange.
The preparation method of dyestuff is: with the derivative of p-Nitroaniline or p-Nitroaniline, under 0 ℃～15 ℃, get diazonium liquid with Sodium Nitrite+sulfuric acid or nitrosyl sulfuric acid diazotization 1h～4h, then in acidic medium with N, N-dicyanoethyl m-chloro aniline carries out coupling under 0 ℃～15 ℃, after coupling is finished, 40 ℃～90 ℃ insulation 1h～6h heat up, carry out crystallization, after filtration, wash, blot, drying, solid dye.
Dyestuff is selected from the mixture of one or more in the structure shown in the formula I.
The structure of dyestuff determines that method is: synthetic drying solid dyestuff is determined its chemical structure with analysis detection meanss such as ultraviolet, infrared, nuclear-magnetism, mass spectrum and ultimate analyses.
The dyeing process of dyestuff is: with diffusant, dispersion agent, water sand milling, drying obtains corresponding commercial dye with synthetic drying solid dyestuff.Adopt high-temperature and high pressure dyeing process that fabrics such as trevira are dyeed then, dye sample after soaping, washing, fabric is orange or orange.
Employed coupling component N among the present invention, N-dicyanoethyl m-chloro aniline is compared by N, N-dicyanoethyl aniline, N, N-dicyanoethyl meta-aminotoluene is made the corresponding azo organism of coupling component institute synthetic, and its maximum absorption visible wavelength will be lacked (generation blue shift), and fusing point is higher.Therefore, should be used for saying as dispersed dye, they to the dyeing of polyester, urethane, polymeric amide, cellulose acetate or their BLENDED FABRIC, embody bright-coloured orange or orange in slightly acidic or weakly alkaline (being PH=3～9) dye liquor, level-dyeing property and redying property are good.And compare other orange or orange azo type disperse dyes, embody the higher characteristic of colour fastness and lifting force.
In sum, the azo dispersion dyes of orange of the present invention or orange has the tinting power height, and coloured light is bright-coloured, and the feature of environmental protection is good.Dyestuff is used to dye trevira, to the dyeing of weakly alkaline dye liquor outstanding colour fastness and dyeing behavior is arranged at weak acid, and dyestuff also is suitable for to urethane the dyeing of polymeric amide, cellulose acetate or their BLENDED FABRIC simultaneously.
Embodiment
Following examples are intended to illustrate the present invention rather than limitation of the invention further.
Embodiment 1:4-nitro-2 '-chloro-4 '-(N, N-dicyanoethyl) aminoazobenzene
In having the 100mL there-necked flask of agitator, add the dense H of 30mL
2SO
4And 1.40g (0.02mol) NaNO
2, stirring and dissolving.Change in the cryogenic liquid recycle pump, be cooled to 0～5 ℃, add 2.76g (0.02mol) p-Nitroaniline, be incubated 0～5 ℃ and stir 4h down, get diazonium salt.Meanwhile, in having the 100mL there-necked flask of agitator, add the rare H of 30mL
2SO
4And 4.67g (0.02mol) N, N-dicyanoethyl m-chloro aniline changes in the cryogenic liquid recycle pump, be cooled to 0～5 ℃, under agitation slowly splash into diazonium salt, drip off, continue to react to diazo component and disappear, after coupling is finished, 60 ℃～70 ℃ insulation 4h that heat up, suction filtration, be washed to neutrality, drain, drying gets brown solid dyestuff 5.3g.222～225 ℃ of fusing points.Through ultraviolet, infrared, nuclear-magnetism, mass spectrum and ultimate analysis, its result is as follows: λ
Max=478nm (acetone), ε=1.28 * 10
4 1H NMR (CDCl
3, 400MHz), δ: 2.76 (t, 4H, CH
2), 3.96 (t, 4H, CH
2), 6.79～8.02 (m, 3H, C
6H
3), 8.32～8.38 (m, 2H, C
6H
2); IR (KBr), v:2959,2248,1594,1561,1518,1496,1416,1369,1353,992,834,773,688cm
-1MS (m/z): 382,342,295,288,241,122; Anal.calcdfor C
18H
15N
6O
2Cl:C 56.53, and H 3.96, and N 21.99; Found C 56.35, H 4.03, and N 21.85.The result shows that the chemical structure of institute's synthetic solid dye is a target product.
The above-mentioned dry product dyestuff that obtains is mixed with diffusant, and its ratio is dyestuff (dry product): dispersing agent MF: sodium lignosulfonate: water=1: 1: 1: 6.0, sand milling to particle diameter less than 1U, drying obtains commercial dye.In the dye vat that fills 200g water, add the above-mentioned commercial dye of 0.10g, dyestuff dissolves the back fully and adds the 5.0g polyester textile, transfer pH value after 4.5～5.5 with Glacial acetic acid, airtight dye vat is put into high temperature-pressure dyeing machine, heat up with 2 ℃/min, be incubated 45min after rising to 130 ℃, the cooling back is taken out and is dyed sample, after soaping, wash, drying, this fabric presents even, bright-coloured orange.Through the fastness test, its fastness to soaping is 4～5 grades, and light fastness is 7 grades, and fastness to wet rubbing is 4～5 grades.The continuous dyeing experiment of carrying out for three times under the identical conditions all has identical coloration result.
Embodiment 2:2-chloro-4-nitro-2 '-chloro-4 '-(N, N-dicyanoethyl) aminoazobenzene
Press embodiment 1, replace p-Nitroaniline, get red solid dyestuff 6.4g, 211～214 ℃ of fusing points with 2-chloro-4-N-methyl-p-nitroaniline (0.02mol).Through ultraviolet, infrared, nuclear-magnetism, mass spectrum and ultimate analysis, its result is as follows: λ
Max=484nm (acetone), ε=1.15 * 10
4 1H?NMR(CDCl
3，400MHz)，δ：2.76(t，4H，CH
2)，3.94(t，4H，CH
2)，6.66～8.02(m，3H，C
6H
3)，8.16～8.48(m，3H，C
6H
3)；IR(KBr)，v：3080，3070，2969，2926，2247，1599，1514，1391，1366，1340，858，843，814，756，685cm
-1；MS(m/z)：416.5，375.5，330，323，340，277，156；Anal.calcd?for?C
18H
14N
6O
2?Br：C?51.92，H?3.39，N20.19；found?C?51.74，H?3.43，N?20.11。The result shows that the chemical structure of institute's synthetic solid dye is a target product.
Press embodiment 1, adopt this dyestuff that polyester textile is dyeed, soaps, washes, dries after, this fabric presents uniform, bright-coloured orange.Measure through fastness, its fastness to soaping is 4～5 grades, and light fastness is 7 grades, and fastness to wet rubbing is 4～5 grades.The continuous dyeing experiment of carrying out for three times under the identical conditions all has identical coloration result.
Embodiment 3:2,4-dinitrobenzene-6-chloro-2 '-chloro-4 '-(N, N-dicyanoethyl) aminoazobenzene presses embodiment 1, with 2,4-dinitrobenzene-6-chloroaniline (0.02mol) replaces p-Nitroaniline, purple solid dye 8.2g, 178～181 ℃ of fusing points.Through ultraviolet, infrared, nuclear-magnetism, mass spectrum and ultimate analysis, its result is as follows: λ
Max=488nm (acetone), ε=1.33 * 10
4 1H NMR (CDCl
3, 400MHz), δ: 2.76 (t, 4H, CH
2), 3.96 (t, 4H, CH
2), 6.66～7.94 (m, 3H, C
6H
3), 8.46～8.75 (m, 2H, C
6H
2); IR (KBr), v:3087,3073,2959,2924,2248,1597,1538,1511,1405,1385,1371,1341,986,812,762,740cm
-1MS (m/z): 461.5,420.5,368,319; Anal.calcd for C
18H
13N
7O
4Cl
2: C 46.85, and H 2.84, and N 21.26; Found C 46.69, H 2.91, and N 21.15.The result shows that the chemical structure of institute's synthetic solid dye is a target product.
The above-mentioned dry product dyestuff that obtains is mixed with diffusant, and its ratio is dyestuff (dry product): dispersing agent MF: sodium lignosulfonate: water=1: 1: 1: 8.0, sand milling to particle diameter less than 1U, drying obtains commercial dye.In the dye vat that fills 200g water, add the above-mentioned commercial dye of 0.20g, dyestuff dissolves the back fully and adds the 5.0g polyester textile, transfer pH value after 8～9, airtight dye vat is put into high temperature-pressure dyeing machine, heat up with 2 ℃/min, rise to 120 ℃ of insulation 60min, the cooling back is taken out and is dyed sample, after soaping, wash, dry after, this fabric presents uniform, bright-coloured orange.Measure through fastness, its fastness to soaping is 4 grades, and light fastness is 6 grades, and fastness to wet rubbing is 4 grades.The continuous dyeing experiment of carrying out for three times under the identical conditions all has close coloration result.
Embodiment 4:2,4-dinitrobenzene-6-bromo-2 '-chloro-4 '-(N, N-dicyanoethyl) aminoazobenzene
Press embodiment 1, replace p-Nitroaniline, get brown solid dyestuff 8.1g, 188～191 ℃ of fusing points with 2,4 dinitro 6 bromo aniline (0.02mol).Through ultraviolet, infrared, nuclear-magnetism, mass spectrum and ultimate analysis, its result is as follows: λ
Max=487.5nm (acetone), ε=1.19 * 10
4 1H NMR (CDCl
3, 400MHz), δ: 2.75 (t, 4H, CH
2), 3.96 (t, 4H, CH
2), 6.69～7.96 (m, 3H, C
6H
3), 8.60～9.13 (m, 2H, C
6H
2); IR (KBr), v:3083,3070,2961,2928,2248,1596,1538,1526,1510,1402,1371,1340,986,848,812,739,727,576cm
-1MS (m/z): 505,464,411.5,364,292; Anal.calcd for C
18H
13N
7O
4ClBr:C 42.77, H2.59, and N 19.41; Found C 42.53, H 2.67, and N 19.16.The result shows that the chemical structure of institute's synthetic solid dye is a target product.
Press embodiment 3, adopt this dyestuff to dye polyester and polymeric amide BLENDED FABRIC, after soaping, wash, drying, this fabric presents uniform, bright-coloured orange.Measure through fastness, its fastness to soaping is 4 grades, and light fastness is 6 grades, and fastness to wet rubbing is 3～4 grades.The continuous dyeing experiment of carrying out for three times under the identical conditions all has close coloration result.
Among each embodiment, coupling component N, the consumption of N-dicyanoethyl m-chloro aniline is 0.02mol, with the proportioning (mol) of other each component and operation with embodiment 1, obtain the azo dispersion dyes of a series of orange or orange.The structure of diazo component sees the following form
| Embodiment | R 1 | R 2 | Embodiment | R 1 | R 2 |
| 1 | H | H | 9 | H | CN |
| 2 | H | Cl | 10 | H | Br |
| 3 | NO 2 | Cl | 11 | CN | Br |
| 4 | NO 2 | Br | 12 | CN | Cl |
| 5 | NO 2 | H | 13 | CN | CN |
| 6 | NO 2 | CN | 14 | Cl | Cl |
| 7 | NO 2 | NO 2 | 15 | Cl | Br |
| 8 | H | NO 2 | 16 | Br | Br |
Claims (5)
1. a class azoic dyestuff has the general formula shown in the formula I, and the coupling component of described dyestuff is N, and N-dicyanoethyl m-chloro aniline is the derivative of p-Nitroaniline and p-Nitroaniline on diazo component,
Formula I
Among the formula I: R
1=H, NO
2, Cl, Br or CN;
R
2=H, NO
2, Cl, Br or CN.
2. the described azoic dyestuff of claim 1 is used for the dyeing that trevira, urethane, polymeric amide, cellulose acetate or above four kinds of compositions carry out the BLENDED FABRIC that arbitrary combination forms.
3. according to the application of claim 2, dyestuff is selected from the mixture of one or more in the structure shown in the formula I.
4. the described azoic dyestuff of claim 1 is used for the application as the dispersed dye of orange or orange.
5. according to the application of claim 4, dyestuff is selected from the mixture of one or more in the structure shown in the formula I.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102604413A (en) * | 2011-12-26 | 2012-07-25 | 浙江吉华集团有限公司 | Middle-temperature type disperse dye compound and preparation method and application thereof |
| CN103073910A (en) * | 2013-01-31 | 2013-05-01 | 江苏远征化工有限公司 | Preparation method for producing disperse orange by salt-free diazotization method and high-temperature coupling method |
| CN113201233A (en) * | 2021-04-29 | 2021-08-03 | 宁波中苑颜料有限公司 | Photochromic organic pigment and preparation method thereof |
| CN115521636A (en) * | 2022-10-24 | 2022-12-27 | 浙江博澳新材料股份有限公司 | Dicyan-containing sun-proof anthraquinone disperse dye and preparation method thereof |
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2010
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102604413A (en) * | 2011-12-26 | 2012-07-25 | 浙江吉华集团有限公司 | Middle-temperature type disperse dye compound and preparation method and application thereof |
| CN102604413B (en) * | 2011-12-26 | 2013-08-21 | 浙江吉华集团股份有限公司 | Middle-temperature type disperse dye compound and preparation method and application thereof |
| CN103073910A (en) * | 2013-01-31 | 2013-05-01 | 江苏远征化工有限公司 | Preparation method for producing disperse orange by salt-free diazotization method and high-temperature coupling method |
| CN113201233A (en) * | 2021-04-29 | 2021-08-03 | 宁波中苑颜料有限公司 | Photochromic organic pigment and preparation method thereof |
| CN113201233B (en) * | 2021-04-29 | 2022-07-01 | 宁波中苑颜料有限公司 | Photochromic organic pigment and preparation method thereof |
| CN115521636A (en) * | 2022-10-24 | 2022-12-27 | 浙江博澳新材料股份有限公司 | Dicyan-containing sun-proof anthraquinone disperse dye and preparation method thereof |
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Application publication date: 20110608 |