CN100491474C - Antibiotic azo dye comprising quaternary ammonium salt group and its preparation and uses - Google Patents
Antibiotic azo dye comprising quaternary ammonium salt group and its preparation and uses Download PDFInfo
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- CN100491474C CN100491474C CNB2006102003743A CN200610200374A CN100491474C CN 100491474 C CN100491474 C CN 100491474C CN B2006102003743 A CNB2006102003743 A CN B2006102003743A CN 200610200374 A CN200610200374 A CN 200610200374A CN 100491474 C CN100491474 C CN 100491474C
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- quaternary ammonium
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- 239000000987 azo dye Substances 0.000 title claims abstract description 17
- 230000003115 biocidal effect Effects 0.000 title claims description 16
- 150000003242 quaternary ammonium salts Chemical group 0.000 title claims description 16
- 238000002360 preparation method Methods 0.000 title claims description 14
- 239000000975 dye Substances 0.000 claims abstract description 59
- 230000008878 coupling Effects 0.000 claims abstract description 27
- 238000010168 coupling process Methods 0.000 claims abstract description 27
- 238000005859 coupling reaction Methods 0.000 claims abstract description 27
- 229920002972 Acrylic fiber Polymers 0.000 claims abstract description 19
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical compound O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims description 32
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 230000006837 decompression Effects 0.000 claims description 14
- 239000012954 diazonium Substances 0.000 claims description 14
- 125000003368 amide group Chemical group 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000012043 crude product Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 235000010288 sodium nitrite Nutrition 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 230000002829 reductive effect Effects 0.000 claims description 4
- 235000011150 stannous chloride Nutrition 0.000 claims description 4
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 4
- 150000001989 diazonium salts Chemical class 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical group 0.000 claims description 3
- 235000012976 tarts Nutrition 0.000 claims description 3
- 150000003512 tertiary amines Chemical class 0.000 claims description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 2
- 241000894006 Bacteria Species 0.000 abstract description 12
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 241000191967 Staphylococcus aureus Species 0.000 abstract description 4
- 241000588724 Escherichia coli Species 0.000 abstract description 3
- 125000003118 aryl group Chemical group 0.000 abstract description 3
- 150000001768 cations Chemical class 0.000 abstract description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract 1
- 241000192125 Firmicutes Species 0.000 abstract 1
- UBQKCCHYAOITMY-UHFFFAOYSA-N pyridin-2-ol Chemical compound OC1=CC=CC=N1 UBQKCCHYAOITMY-UHFFFAOYSA-N 0.000 abstract 1
- 238000010186 staining Methods 0.000 abstract 1
- 238000004043 dyeing Methods 0.000 description 19
- 230000000845 anti-microbial effect Effects 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 230000002194 synthesizing effect Effects 0.000 description 7
- 125000002091 cationic group Chemical group 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 230000002147 killing effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- -1 1-phenyl-3-methyl-5-pyrazolones ketone Chemical class 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 230000000968 intestinal effect Effects 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- LVWZTYCIRDMTEY-UHFFFAOYSA-N metamizole Chemical compound O=C1C(N(CS(O)(=O)=O)C)=C(C)N(C)N1C1=CC=CC=C1 LVWZTYCIRDMTEY-UHFFFAOYSA-N 0.000 description 2
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical class OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- CMEWLCATCRTSGF-UHFFFAOYSA-N N,N-dimethyl-4-nitrosoaniline Chemical compound CN(C)C1=CC=C(N=O)C=C1 CMEWLCATCRTSGF-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 239000001000 anthraquinone dye Substances 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000003287 bathing Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000007730 finishing process Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000006916 nutrient agar Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- Coloring (AREA)
Abstract
This invention relates to a quaternary antibacterial azo dye, characterizing: structural formula is indicated as formula(1), wherein: A is a quaternary group, B is a coupling group comprising aromatic ammonia group, pyridinone or pyrazolone. This invented dye can dye acrylic fibre according to the conventional cation staining, with the color fastness meeting the using requirement. The dye water solution and dyed acrylic fibre can kill or suppress Gram-positive bacteria and Gram-negative bacteria like Staphylococcus aureus and Escherichia coli.
Description
Technical field
The present invention relates to azoic dyestuff, specifically a kind of antibacterial cation azoic dyestuff and preparation and application that contains quaternary ammonium salt group.
Background technology
Numerous hole that distributing on the textile surface, surface-area is very big, should grow a large amount of bacteriums under suitable temperature and humidity condition.The existence of various unwanted bacterias has caused transmission of disease, and human beings'health is produced adverse influence.Antibacterial finish is the essential step of after-finishing of textile products, especially to children, medical personnel, the textiles of soldier etc. contact is particularly important.When dyeing was identical with antibacterial finishing process, the two can be handled with bathing; But the two technology is not simultaneously, just can only bathe in addition after dyeing and carry out antibacterial finish.At this moment will consume a large amount of energy, the waste water of its generation has caused pollution to environment.At present, develop the research focus that the functional dye with specific finishing effect is becoming the dyestuff scholar.Maminghua etc. have synthesized a class antimicrobial form anthraquinone dye and (have seen " DyesandPigments " 2003; 58:27-35 and 2004; 63:39-49 and 2005; 66:33-41).They have connected quaternary ammonium salt group on the anthraquinone parent, given dyestuff with bactericidal properties.This dyestuff can on dye acrylic fibers, dyeing back cloth specimen has killing action to bacterium.
Azoic dyestuff surpasses half in existing dye species, and coloured light is complete, and technology is simple, and is with low cost.
Summary of the invention
The object of the present invention is to provide a kind of antibiotic azo dye and preparation and application that contains quaternary ammonium salt group; The present invention is structured in quaternary ammonium salt group in the azoic dyestuff, has obtained the antibacterial cation azoic dyestuff; The gained dyestuff has also possessed antibacterial when having kept dyeing behavior.
For achieving the above object, the technical solution used in the present invention is:
A kind of antibiotic azo dye that contains quaternary ammonium salt group, its general structure be as the formula (1):
(1)
Wherein: A represents quaternary ammonium salt group, and structure can be:
Perhaps
N1=0-17 wherein, n2=1-4; The X=halogen
B is amino for containing virtue, the coupling group of pyridone or pyrazolone.
Wherein the structure of coupling group B can be:
Wherein: R1 is H, C
1-C
4Alkyl, aryl, hydroxyethyl ,-CH
2NR
4COR
5Or cyclohexyl, R4 is H, C
1-C
4Alkyl, aryl, hydroxyethyl or cyclohexyl, R5 are H or C
1-C
4Alkyl; R2 be H ,-CN or halogen etc.; R3 is C
1-C
4Alkyl, C
1-C
4Alkoxyl group, C
1-C
4Alkylamino, hydroxyl or-CH
2COOH etc.;
Perhaps be,
Wherein: R1 and R2 are respectively: H, C
1-C
4Alkyl ,-CH
2CH
2OH or NHCOR
3, R wherein
3Be H or C1-4 alkyl;
Perhaps be,
Wherein R4 is H or C
1-C
4Alkyl, R5 are CH
3Or-COOR
6, R wherein
6Represent C
1-C
4Alkyl.
Described dyestuff can prepare according to the following procedure:
1) the nitro thing is synthetic: in one-tenth: add the tertiary amine 3g of feedstock fat family of group A part or 3g more than (the double solvent of doing reaction of tertiary amine), 20～80 ℃ were reacted 2～18 hours in 1-(an end position halogen-alkoxyl group)-4-oil of mirbane or 1-(an end position halogen-alkyl)-4-oil of mirbane 5g; Adopt hexanaphthene or normal hexane washing crude product, obtain the nitro thing;
2) the amido thing is synthetic: nitro thing 7g, be dissolved in 30～150ml ethanol, and dropping 8.5～30g tin protochloride and 9～35g weight concentration are the mixture of 36% concentrated hydrochloric acid under stirring, and drip to finish in 20～70 ℃ of reactions 4～20 hours; Reaction is reduced to room temperature after finishing, and adds concentrated base, and transferring PH is 8～10, filters, and filtrate decompression obtains crude product, adds anhydrous alcohol solution again, the undissolved salt of filtering, and ethanol is removed in decompression, obtains the amido thing;
3) dyestuff is synthetic:
1. the preparation of diazonium salt solution: 0.5g amido thing, adding weight concentration are concentrated hydrochloric acid 0.5～3ml of 36%, 0～2 ℃ of sodium nitrite in aqueous solution that descends dropping and amido thing equimolar amount, and stirring reaction obtained diazonium liquid in 0.5～5 hour;
2. the preparation of coupling solution C: the raw material of getting with amido thing equimolar amount that contains the amino coupling group B part of virtue is dissolved among the tart aqueous solution 10～50ml, obtains coupling solution C;
The preparation of coupling solution D; The raw material of getting with the coupling group B part that contains pyridone or pyrazolone of amido thing equimolar amount is dissolved in 15～25ml alkaline aqueous solution, obtains coupling solution D;
3. coupling solution C or D are once joined in the diazonium liquid, hierarchy of control pH value is 5～8,5～15 ℃ of reactions 2～8 hours; Saltout with sodium-chlor, leach precipitation, drying, with anhydrous alcohol solution precipitation, the undissolved salt of filtering, ethanol is removed in decompression, obtains the target dyestuff.
Described antibiotic azo dye is mainly used to the BLENDED FABRIC of dying acrylic fiber or containing acrylic fiber.
The present invention has following advantage:
1. synthetic method is simple.The present invention is an antibiotic azo dye, adopts the diazonium coupling prepared in reaction, and synthesis technique is simple and easy to do; The arylamine of anamorphic zone quaternary ammonium salt group at first, arylamine obtains diazonium salt through diazotization reaction, generates monoazo-dyes with different coupling component reaction again.
2. Color is good.The molecular structure of azoic dyestuff involved in the present invention comprises two portions: monoazo color bodies and quaternary ammonium salt group.The monoazo color bodies has determined the color of whole dyestuff, and positively charged quaternary ammonium salt group (can be used as cats product), for dyestuff provides anti-microbial property.Therefore antibiotic azo dye belongs in the cationic dyestuff, can be used to dye acrylic fibers.When dying acrylic fibers on traditional cationic dyestuff, when dyeing temperature reached certain value, dyeing speed was very fast, easily caused dyeing uneven.When dying acrylic fibers on the antibiotic azo dye of the present invention, can slow down dyeing kinetics, play certain slow dying and the level dyeing effect.After dying acrylic fibers on the antibiotic azo dye, the light fastness of fiber and fastness to washing have reached 4～5 grades, can satisfy service requirements.
3. the anti-microbial property that has wide spectrum.Dyestuff of the present invention has the anti-microbial property of wide spectrum.The aqueous solution of dyestuff is to being that the gram-positive microorganism and the Gram-negative bacteria of representative has killing action with streptococcus aureus and intestinal bacteria.Acrylic fiber after the dyeing has anti-microbial effect equally, and through still having anti-microbial effect after 10 washings.
Embodiment
Embodiment 1
Synthetic route (one):
Synthesizing of intermediate 1: 10g 4-nitrophenols, 6g sodium hydroxide, 150ml water add in the four-hole bottle, after the heating for dissolving, add the 60g ethylene dibromide, Tetrabutyl amonium bromide 0.25g, 90 ℃ were reacted 12 hours down.Decompression removes and anhydrates and ethylene dibromide, uses the hot ethanol dissolved residue, removes undissolved salt, cooling, and product is separated out in ethanol, obtains the 15g product; Yield: 79%.The product fusing point is 64 ℃, and it is a target product;
Synthesizing of intermediate 2: 8g intermediate 1, add 20g NN-dimethyl amino dodecane, 60 ℃ were reacted 7 hours down; Wash crude product with hexanaphthene, obtain the 14.25g product, yield: 95%;
Synthesizing of intermediate 3: 7g intermediate 2, be dissolved in the 50ml ethanol, stirring drips the mixture of the concentrated hydrochloric acid of 14g tin protochloride and 19g weight concentration 36% down, drips to finish under 50 ℃ to react 8 hours; Reaction is reduced to room temperature after finishing, and adds concentrated base, and transferring PH is that alkaline ph value is 8～10, filters, and filtrate decompression obtains crude product, adds anhydrous alcohol solution again, the undissolved salt of filtering, and ethanol is removed in decompression, obtains the 4.91g product, yield: 75%;
Synthesizing of dyestuff 4: 0.5g intermediate 3, add concentrated hydrochloric acid 1ml, 0～2 ℃ drips the aqueous solution that contains the 0.09g Sodium Nitrite down, and stirring reaction obtained diazonium liquid in 2 hours; 0.15gN, accelerine is dissolved among the tart aqueous solution 20ml, obtains coupling solution; Coupling solution is once joined in the diazonium liquid, and the adjustment system is neutral, and 5～15 ℃ were reacted 5 hours; Saltout with sodium-chlor, leach precipitation, drying, with anhydrous alcohol solution precipitation, the undissolved salt of filtering, ethanol is removed in decompression, obtains the 0.466g dyestuff; Yield: 78%.
The total recovery 44% of dyestuff 4;
IR(KBr，cm
-1)：2920，2840(CH
3(CH
2)
10CH
2-)；1400(N＝N)；1360(-N(CH
3)
2)；1240，1060(Ar-O-CH
3)；
1H-NMR(300MHz，CDCl
3，δ)：0.855-0.900(t，3H)，1.252(bs，16H)，1.360(bs，2H)，1.816(bs，2H)，3.093(s，6H)，3.494(s，6H)，3.592(bs.2H)，4.266(bs，2H)，4.489(bs，2H)，6.723-6.745(d，2H)，6.951-6.980(d，2H)，7.727-7.812(m，4H)；
ESI-MS(m/z，M
+-Br+H)：482.4。
Embodiment 2
Preparation, shown in synthetic route (), intermediate 1,2 and 3 syntheticly see embodiment 1;
Synthesizing of dyestuff 5: 0.8g intermediate 3, add concentrated hydrochloric acid 1.6ml, ice bath (0～2 ℃) drips the aqueous solution that contains the 0.131g Sodium Nitrite down, and stirring reaction obtained diazonium liquid in 2 hours.0.35g 1-phenyl-3-methyl-5-pyrazolones ketone is dissolved in the 20ml aqueous sodium carbonate, obtains coupling solution.Coupling solution is once joined in the diazonium liquid, and the system pH value is controlled at subacidity to neutral, and 5～15 ℃ were reacted 5 hours.Saltout with sodium-chlor, leach precipitation, drying, with anhydrous alcohol solution precipitation, the undissolved salt of filtering, ethanol is removed in decompression, obtains the 0.977g dyestuff; Yield: 85%.
The total recovery 47.8% of dyestuff 5;
IR(KBr，cm
-1)：3440(-NH-)；2920，2850(CH
3(CH
2)
10CH
2-)；1610(-C＝O)；1240，1000(Ar-O-CH
3)；
1H-NMR(300MHz，CDCl
3+(CF
3CO)
2O，δ)：0.853-0.898(t，3H)，1.262(bs，16H)，1.340(d，2H)，1.773(bs.2H)，2.303(s，3H)，3.203(s，6H)，3.384(bs，2H)，3.875(bs.2H)，4.477(bs，2H)，6.988-7.014(d，2H)，7.130-7.179(d，2H)，7.297(s，1H)，7.324-7.348(d，2H)，7.607-7.631(d，2H)；
ESI-MS(m/z，M
+-Br+H)：535.6。
Embodiment 3
The synthetic route of dyestuff is as follows:
Synthesizing of intermediate 6: 5g adds 15g N to the nitro bromobenzyl, N-dimethyl amino dodecane, and 60 ℃ were reacted 5 hours down; Wash crude product with hexanaphthene, obtain the 9g product, yield: 92.1%;
Intermediate 7 synthetic: 4g intermediate 6, be dissolved in the 30ml ethanol, stir and drip the mixture that 8g tin protochloride and 10g weight concentration are 36% concentrated hydrochloric acid down, drip and finish in 50 ℃ of reactions 8 hours down.Reaction is reduced to room temperature after finishing, and adds concentrated base, and transferring pH value is alkalescence, filters, and filtrate decompression obtains crude product, adds anhydrous alcohol solution again, the undissolved salt of filtering, and ethanol is removed in decompression, obtains the 2.98g product, yield: 80%;
Synthesizing of dyestuff 8: 1g intermediate 7, add concentrated hydrochloric acid 2.1ml, 0～2 ℃ drips the aqueous solution that contains the 0.174g Sodium Nitrite down, and stirring reaction obtained diazonium liquid in 2 hours.0.44g 1-phenyl-3-methyl-5-pyrazolones ketone is dissolved in the 20ml aqueous sodium carbonate, obtains coupling solution.Coupling solution is once joined in the diazonium liquid, and the system pH value is controlled at subacidity to neutral, and 5～15 ℃ were reacted 5 hours.Saltout with sodium-chlor, leach precipitation, drying, with anhydrous alcohol solution precipitation, the undissolved salt of filtering, ethanol is removed in decompression, obtains the 1.17g dyestuff; Yield: 80%.
The total recovery 58.94% of dyestuff 8;
IR(KBr，cm
-1)：3360(-NH-)；2920，2830(CH
3(CH
2)
10CH
2-)；1660(-C＝O)；
1H-NMR(300MHz，CDCl
3，δ)：0.851-0.895(t，3H)，1.241(bs，18H)，1.754(bs.2H)，2.362(s，3H)，3.238(s，6H)，3.415(bs，2H)，5.228(bs，2H)，7.109-7.132(d，2H)，7.208-7.233(d，2H)，7.338(s，1H)，7.424-7.450(d，2H)，7.918-7.943(d，2H)，13.581(s，1H)；
ESI-MS(m/z，M
+-Br+H)：505.7。
The dyeing of embodiment 4 antibiotic azo dyes:
Antibiotic azo dye is a cationic dyestuff, can on dye acrylic fiber, its dyeing is with the dyeing of traditional cationic dyestuff.
Dyeing recipe is: dye level 1%, and bath raio 1:50, glacial acetic acid 1%, crystallization sodium acetate 1%, anhydrous sodium sulphate 10%, OP-10 1%, dye bath PH4～6;
In dye bath, add the various auxiliary agents of dye well, be warming up to 70 ℃, add acrylic fiber, after 10 minutes, be warming up to 100 ℃, in 20 minutes, be cooled to 60 ℃ after 60 minutes in continuation dyeing under this temperature with 2 ℃/minute speed, take out fiber, the flowing water flushing, 60 ℃ are dry down.
According to the acrylic fiber that dyes on this dyeing, light fastness and fastness to washing reach 4～5 grades.
Embodiment 5
The anti-microbial property test of aqueous dye solutions: adopt minimal inhibitory concentration method (MIC).
Test bacterial classification: streptococcus aureus (S.aureus) and intestinal bacteria (E.coli)
Method: with 1ml 10
6～10
7The bacteria suspension of CFU/ml joins mixing in the dye solution of 9ml different concns successively.After 24 hours, take out the 100ul bacteria suspension successively, and rare with aseptic distilled water to 100ml.Therefrom take out 100ul and drop on the nutrient agar, cultivated 24 hours down for 37 ℃.Replace dye solution to repeat top-operation with distilled water.
Evaluation criteria: with no bacterial growth is benchmark.
The minimal inhibitory concentration of three aqueous dye solutions of table 1
| MIC(ppm) | Dyestuff 4 | Dyestuff 5 | Dyestuff 8 |
| S.aureus | 20 | 80 | 150 |
| E.coli | 20 | 100 | 200 |
Embodiment 6
The anti-microbial property test of dyeing back acrylic fiber: detection method is with the testing method of conventional fibre after antimicrobial treatment.
Table 2 does not wash and washs the anti-microbial property of back acrylic fiber.
The numeral dyestuff is to the killing rate of bacterium in the table.
Dyestuff of the present invention dyes acrylic fibers on the cationic dyeing method routinely, and dyefastness can satisfy service requirements.Acrylic fiber after the aqueous solution of dyestuff and the dyeing is to being that the gram-positive microorganism and the Gram-negative bacteria of representative has killing action with streptococcus aureus and intestinal bacteria.
Claims (4)
1. antibiotic azo dye that contains quaternary ammonium salt group is characterized in that: its general structure as the formula (1):
Wherein: A represents quaternary ammonium salt group, and structure is:
Perhaps
N1=0-17 wherein, n2=1-4; The X=halogen
B is the coupling group that contains fragrant amino or pyrazolone.
2. according to the described antibiotic azo dye that contains quaternary ammonium salt group of claim 1, it is characterized in that: the structure of wherein said coupling group B is:
Wherein: R1 and R2 are respectively: H, C
1-C
4Alkyl ,-CH
2CH
2OH or NHCOR
3, R wherein
3Be H or C1-4 alkyl; Perhaps be,
Wherein R4 is H or C
1-C
4Alkyl, R5 are CH
3Or-COOR
6, R wherein
6Represent C
1-C
4Alkyl.
3. described preparation method who contains the antibiotic azo dye of quaternary ammonium salt group of claim 1 is characterized in that:
Described dyestuff prepares according to the following procedure:
1) the nitro thing is synthetic: add more than the tertiary amine 3g of feedstock fat family of group A part in 1-(end halogen-alkoxyl group)-4-oil of mirbane or 1-(an end position halogen-alkyl)-4-oil of mirbane 5g, 20～80 ℃ were reacted 2～18 hours; Adopt hexanaphthene or normal hexane washing crude product, obtain the nitro thing;
2) the amido thing is synthetic: nitro thing 7g, be dissolved in 30～150ml ethanol, and stir and drip the mixture that 8.5～30g tin protochloride and 9～35g weight concentration are 36% concentrated hydrochloric acid down, drip and finish in 20～70 ℃ of reactions 4～20 hours; Reaction is reduced to room temperature after finishing, and adds concentrated base, and transferring pH value is 8～10, filters, and filtrate decompression obtains crude product, adds anhydrous alcohol solution again, the undissolved salt of filtering, and ethanol is removed in decompression, obtains the amido thing;
3) dyestuff is synthetic:
1. the preparation of diazonium salt solution: 0.5g amido thing, adding weight concentration are concentrated hydrochloric acid 0.5～3ml of 36%, 0～5 ℃ of aqueous solution that descends the Sodium Nitrite of dropping and amido thing equimolar amount, and stirring reaction obtained diazonium liquid in 0.5～5 hour;
2. the preparation of coupling solution C: the raw material of getting with amido thing equimolar amount that contains the amino coupling group B part of virtue is dissolved among the tart aqueous solution 10～50ml, obtains coupling solution C;
The preparation of coupling solution D: the raw material of getting with the coupling group B part that contains pyrazolone of amido thing equimolar amount is dissolved in 15～25ml alkaline aqueous solution, obtains coupling solution D;
3. coupling solution C or D are once joined in the diazonium liquid, hierarchy of control PH is 5～8,5～15 ℃ of reactions 2～8 hours; Saltout with sodium-chlor, leach precipitation, drying, with anhydrous alcohol solution precipitation, the undissolved salt of filtering, ethanol is removed in decompression, obtains the target dyestuff.
4. described application that contains the antibiotic azo dye of quaternary ammonium salt group of claim 1, it is characterized in that: described antibiotic azo dye is used for dying acrylic fiber or contains the BLENDED FABRIC of acrylic fiber.
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| WO2013148269A1 (en) * | 2012-03-28 | 2013-10-03 | Massachusetts Eye & Ear Infirmary | Methods and compositions for reducing the proliferation of gram positive bacteria |
| CN105012322B (en) * | 2014-04-17 | 2017-11-28 | 中国人民解放军军事医学科学院生物工程研究所 | Application of the sunset yellow in anti-bacillus anthracis |
| CN104357940B (en) * | 2014-10-28 | 2016-04-13 | 江苏工程职业技术学院 | A kind of antibiotic azo dye prepares the method for composite polyamide fiber |
| CN104448896B (en) * | 2014-10-28 | 2016-06-08 | 江苏工程职业技术学院 | A kind of preparation of dyestuff method for the dyeing of antimicrobial form azo tynex |
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Non-Patent Citations (3)
| Title |
|---|
| Antimicrobial cationic dyes: part 1: synthesis andcharacterization.. Minghua Ma, et al..Dyes and Pigments,Vol.58 . 2003 * |
| Antimicrobialcationicdyes:part1:synthesisandcharacterization..MinghuaMa et al..Dyes and Pigments * |
| 季铵型阳离子活性染料. 肖刚.染料与染色，第42卷第1期. 2005 * |
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