CN102993110A - Intermediate of 4,4'-diaminostilbene-2,2'-disulfonic acid derivative - Google Patents
Intermediate of 4,4'-diaminostilbene-2,2'-disulfonic acid derivative Download PDFInfo
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- CN102993110A CN102993110A CN2012102239732A CN201210223973A CN102993110A CN 102993110 A CN102993110 A CN 102993110A CN 2012102239732 A CN2012102239732 A CN 2012102239732A CN 201210223973 A CN201210223973 A CN 201210223973A CN 102993110 A CN102993110 A CN 102993110A
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- disulfonic acid
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- diaminobenzil
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- REJHVSOVQBJEBF-OWOJBTEDSA-N 5-azaniumyl-2-[(e)-2-(4-azaniumyl-2-sulfonatophenyl)ethenyl]benzenesulfonate Chemical class OS(=O)(=O)C1=CC(N)=CC=C1\C=C\C1=CC=C(N)C=C1S(O)(=O)=O REJHVSOVQBJEBF-OWOJBTEDSA-N 0.000 title abstract 3
- 150000001875 compounds Chemical class 0.000 claims description 47
- 238000002360 preparation method Methods 0.000 claims description 28
- 239000002253 acid Substances 0.000 claims description 16
- 238000004043 dyeing Methods 0.000 abstract description 15
- 239000006081 fluorescent whitening agent Substances 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 3
- OMFXVFTZEKFJBZ-HJTSIMOOSA-N corticosterone Chemical compound O=C1CC[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@H](CC4)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 OMFXVFTZEKFJBZ-HJTSIMOOSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000012043 crude product Substances 0.000 description 16
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- 239000000975 dye Substances 0.000 description 14
- 238000006467 substitution reaction Methods 0.000 description 13
- 229920000742 Cotton Polymers 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 0 *c1c(C=C[C@@]2C=CC(Nc3nc(Cl)nc(Cl)n3)=CC2*2=CC2)ccc(Nc2nc(Cl)nc(Cl)n2)c1 Chemical compound *c1c(C=C[C@@]2C=CC(Nc3nc(Cl)nc(Cl)n3)=CC2*2=CC2)ccc(Nc2nc(Cl)nc(Cl)n2)c1 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 238000010792 warming Methods 0.000 description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000000835 fiber Substances 0.000 description 8
- 238000004128 high performance liquid chromatography Methods 0.000 description 7
- 238000012916 structural analysis Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- 206010013786 Dry skin Diseases 0.000 description 4
- LWLSVNFEVKJDBZ-UHFFFAOYSA-N N-[4-(trifluoromethoxy)phenyl]-4-[[3-[5-(trifluoromethyl)pyridin-2-yl]oxyphenyl]methyl]piperidine-1-carboxamide Chemical compound FC(OC1=CC=C(C=C1)NC(=O)N1CCC(CC1)CC1=CC(=CC=C1)OC1=NC=C(C=C1)C(F)(F)F)(F)F LWLSVNFEVKJDBZ-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 125000006414 CCl Chemical group ClC* 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- -1 Anilino Chemical group 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-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
- 125000003368 amide group Chemical group 0.000 description 2
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- QLRBNEZOQPLERN-UHFFFAOYSA-N (sulfonylamino)benzene Chemical compound O=S(=O)=NC1=CC=CC=C1 QLRBNEZOQPLERN-UHFFFAOYSA-N 0.000 description 1
- MBDUIEKYVPVZJH-UHFFFAOYSA-N 1-ethylsulfonylethane Chemical class CCS(=O)(=O)CC MBDUIEKYVPVZJH-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- SJRJJKPEHAURKC-UHFFFAOYSA-N CN1CCOCC1 Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 1
- 241000208202 Linaceae Species 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Landscapes
- Coloring (AREA)
Abstract
The invention discloses an intermediate B for preparing a 4,4'-diaminostilbene-2,2'-disulfonic acid derivative. The 4,4'-diaminostilbene-2,2'-disulfonic acid derivative disclosed by the invention can improve the fastness and the degree of fixation of a fluorescent whitening agent, and the dyeing temperature is about 60 DEG C and is far lower than that of the traditional fluorescent whitening agent, so that the energy consumption can be reduced and the dyeing cost can be reduced, wherein, R2 is as follows.
Description
Technical field
The present invention relates to a kind ofly prepare 4,4 '-diaminobenzil-2, the midbody compound of 2 '-disulfonic acid derivatives.
Background technology
White dyes is transformed into indigo fluorescent radiation by the sightless ultraviolet radiation that goods are absorbed, with original gold-tinted radiation each other complementary color become white light, improve the whiteness of product under daylight.
White dyes has been widely used in the industries such as weaving, papermaking, washing powder, pigment.White dyes is applied to cotton fibre, mainly is used in the pre-treatment of cotton, improves the inadequate problem of cotton whiteness and vividness.
But the conventional fluorescent whitening agent mainly is to be combined with fiber by the substantivity of whitening agent in dying cotton process, so often can there be the relatively poor problems of fastness such as washing.
Summary of the invention
Technical problem to be solved by this invention is that to have overcome existing white dyes degree of fixation on cotton low, the defective that fastness is bad, and provide a class 4,4 '-diaminobenzil-2,2 '-disulfonic acid derivatives and midbody compound thereof.Of the present invention 4,4 '-diaminobenzil-2,2 '-disulfonic acid derivatives can improve fastness and the degree of fixation of white dyes, and dyeing temperature is about 60 ℃, dyeing temperature (being generally about 98 ℃) far below the conventional fluorescent whitening agent, therefore can reduce energy consumption, reduce the dyeing cost.
Therefore, the present invention relates to a class suc as formula 4 shown in the A, 4 '-diaminobenzil-2,2 '-disulfonic acid derivatives:
Wherein, R
1For-NH
2Be selected from " C by 1 ~ 2
1~ C
4Alkyl, the C that is replaced by 1 ~ 2 hydroxyl
1~ C
4Alkyl and by the C of 1 ~ 2 carboxyl substituted
1~ C
4Alkyl " group replace-NH
2Anilino; The benzene ring hydrogen is selected from " SO by 1 ~ 2
3Na ,-COCH
3And halogen atom " the anilino that replaces of group; Or, contain 0 ~ 2 heteroatomic C that is selected from O and S
3~ C
5The saturated rings amido.
Describedly be selected from " C by 1 ~ 2
1~ C
4Alkyl, the C that is replaced by 1 ~ 2 hydroxyl
1~ C
4Alkyl and by the C of 1 ~ 2 carboxyl substituted
1~ C
4Alkyl " group replace-NH
2Better is-N (CH
2CH
2OH)
2,-NHCH
2CH
2OH ,-N (C
2H
5)
2Or-NHCH
2COOH.
Described benzene ring hydrogen is selected from " SO by 1 ~ 2
3Na ,-COCH
3And halogen atom " the anilino that replaces of group better be
Describedly contain 0 ~ 2 heteroatomic C that is selected from O and S
3~ C
5The saturated rings amido better be
R
2For
Of the present invention suc as formula 4 shown in the A, 4 '-diaminobenzil-2, what 2 '-disulfonic acid derivatives was better is following compound:
The invention further relates to the preparation method of formula A compound, it comprises the following steps: suc as formula the compound shown in the B and R
1H carries out following substitution reaction, gets final product;
Wherein, radicals R
1And R
2Definition ditto described.
Wherein, the method for described substitution reaction and condition all can be ordinary method and the condition of this type of reaction of this area.What wherein, described substitution reaction was better can carry out in water or under condition of no solvent.Described water and R
1That the volume mass of H is better is 5 ~ 10ml/g.Described compd B and R
1That the mol ratio of H is better is 1:2 ~ 1:2.2.What the pH of described substitution reaction was better is 2.5 ~ 5.5.What the temperature of described substitution reaction was better is 80 ~ 100 ℃.The time of described reaction is better finish with detection reaction till, be generally 2 ~ 4 hours.
After reaction was finished, described compd A can also can directly carry out spraying drying through oversalting, press filtration and drying operation, obtained the solid of the alkali metal salt such as sodium salt, sylvite or sour form, also can make liquid form.
Among the present invention, described compd B can be made by following method: with Compound C and R
2H carries out following substitution reaction, gets final product;
Wherein, radicals R
2Definition ditto described.
Wherein, the method for described substitution reaction and condition all can be ordinary method and the condition of this type of reaction of this area.Wherein, the preferred solvents of described substitution reaction is water.That the solvent of described substitution reaction and the volume mass of Compound C are better is 5 ~ 10ml/g.Described Compound C and R
2That the mol ratio of H is better is 1:2 ~ 1:2.2.What the pH of described substitution reaction was better is 2.5 ~ 5.5.What the temperature of described substitution reaction was better is 25 ~ 60 ℃.The time of described reaction is better finish with detection reaction till, be generally 5 ~ 8 hours.
Among the present invention, described Compound C can be made by following method: Compound D and compd E are carried out following substitution reaction, get final product;
Wherein, the method for described substitution reaction and condition all can be ordinary method and the condition of this type of reaction of this area.
Without prejudice to the field on the basis of common sense, but above-mentioned each preferred feature arbitrary combination among the present invention namely gets the preferred embodiments of the invention.
The invention still further relates to the midbody compound suc as formula the preparation formula A compound shown in the B:
Wherein, radicals R
2Definition ditto described.
The invention further relates to suc as formula 4 shown in the A application in white dyes of 4 '-diaminobenzil-2,2 '-disulfonic acid derivatives.Wherein, what described white dyes was better contains hydroxyl and/or amino fiber for being used for, or contains the white dyes of the blend fiber of above-mentioned fiber.The described fiber that contains hydroxyl can be cotton and/or fiber crops (such as flax) etc.The described fiber that contains amino can be wool and/or silk etc.
Raw material described in the present invention or reagent except specifying, equal commercially available getting.
Positive progressive effect of the present invention is: of the present invention 4,4 '-diaminobenzil-2,2 '-disulfonic acid derivatives can improve fastness and the degree of fixation of white dyes, and dyeing temperature is about 60 ℃, dyeing temperature far below the conventional fluorescent whitening agent, therefore can reduce energy consumption, reduce the dyeing cost.
Embodiment
The below further specifies the present invention with embodiment, but the present invention is not limited.
Used raw material or reagent is except specifying among the embodiment, all commercially available getting.
Embodiment 1 preparation compd A 1(compd A 1 is R in the compd A
1For-N (CH
2CH
2OH)
2And R
2For
Compound)
Step a): preparation Compound C
8ml sodium hydroxide solution (100g/L) is added 0.01mol 4, and 4-diaminobenzil-2 in the 30ml aqueous solution of 2 '-disulfonic acid, makes the pH of solution be 7, and is stand-by.In addition 0.02mol cyanuric chloride (compd E) is pulled an oar in 30ml water, after making beating fully, to wherein adding above-mentioned 4,4-diaminobenzil-2,2 '-sodium disulfonate solution added in about 1 hour, between pH1 ~ 7, reacted 2 ~ 4 hours after adding, obtain the crude product of Compound C.
Step b): preparation compd B 1(compd B 1 is R in the compd B
2For
Compound)
With the 0.02mol para-ester (namely, 4-sulfovinic acid sulfuryl aniline) with 10.6mL sodium carbonate solution (100g/L) dissolving, the pH that makes solution is 6 ~ 7, then, this solution is joined in the crude product of Compound C of step a) gained, be warming up to 30 ~ 40 ℃, be incubated 5 ~ 7 hours, keep pH4 ~ 7, make the crude product of compd B 1.
Step c): preparation compd A 1
The diethanolamine of 0.03mol is joined in the crude product of compound B-11 of step b) gained, be warming up to 80 ~ 100 ℃, the condensing reflux reaction is 4 ~ 8 hours in this temperature range, reaction finishes, in 130 ~ 135 ℃ of spraying dryings, obtain compd A 116.4g, HPLC purity is about 74%.
This compound carries out structural analysis with infrared spectrometer after purifying, following characteristic peak :～3350cm is arranged
-1(OH peak);～2930cm
-1, 2860cm
-1(CH
2); ~ 1600cm
-1, 1580cm
-1, 1510cm
-1, 1460cm
-1(phenyl ring);～1240cm
-1(sulfuric ester);～1025cm
-1(primary alconol C-O).
This product is used for printing and dyeing cotton fabric textiles, and good washing fastness is arranged.
Embodiment 2 preparation compd A 7(compd As 7 are R in the compd A
1For
R
2For
Compound)
Step a): preparation Compound C
8ml sodium hydroxide solution (100g/L) is joined 0.01mol 4, and 4-diaminobenzil-2 in the 30ml aqueous solution of 2 '-disulfonic acid, makes 4,4-diaminobenzil-2, and 2 '-disulfonic acid dissolves fully.Then mentioned solution is joined in the finely dispersed mixture of 0.02mol cyanuric chloride and 40ml water, between pH 1 ~ 7, reacted 2 ~ 4 hours, make the crude product of Compound C.
Step b): preparation compd B 1(compd B 1 is R in the compd B
2For
Compound)
A) add 50ml para-ester (0.02mol) solution in the crude product of gained Compound C (0.01mol) in step, be warming up to 30 ~ 40 ℃, be incubated 5 ~ 7 hours, maintenance pH4 ~ 7 make the crude product of compound B-11.
Step c): preparation compd A 7
At step b) add the 0.025mol morpholine in the crude product of gained compound B-11 (0.01mol), and be warming up to 80 ~ 100 ℃, the condensing reflux reaction is 4 ~ 8 hours in this temperature range, reaction finishes, in 130 ~ 135 ℃ of spraying dryings, obtain compd A 714.3g, HPLC purity is about 78%.
This compound carries out structural analysis with infrared spectrometer after purifying, following characteristic peak :～3260cm is arranged
-1, 3180cm
-1(NH peak);～2930cm
-1, 2860cm
-1(CH
2);～1240cm
-1(sulfuric ester); 1600cm
-1, 1580cm
-1, 1510cm
-1, 1460cm
-1(phenyl ring); ~ 1100cm
-1(ehter bond).
Embodiment 3 ~ 9 preparation compd As 26, A3, A27, A5, A28, A29 and A6
Wherein, compd A 26 is R in the compd A
1For-NH
2And R
2For
Compound;
Compound A-13 is R in the compd A
1For-N (C
2H
5)
2And R
2For
Compound;
Compd A 27 is R in the compd A
1For
And R
2For
Compound;
Compound A-45 is R in the compd A
1For
And R
2For
Compound;
Compd A 28 is R in the compd A
1For
And R
2For
Compound;
Compd A 29 is R in the compd A
1For
And R
2For
Compound;
Compd A 6 is R in the compd A
1For
And R
2For
Compound.
The preparation method of compd A 26, A3, A27, A5, A28, A29 and A6 is with the preparation method of compd A 1 among the embodiment 1, and the HPLC purity of above-claimed cpd is between 60 ~ 80%.
These 7 compounds carry out structural analysis with infrared spectrometer after purifying, following common trait peak :～3260cm is arranged
-1, 3180cm
-1(NH peak);～2930cm
-1, 2860cm
-1(CH
2); ~ 1600cm
-1, 1580cm
-1, 1510cm
-1, 1460cm
-1(phenyl ring);～1240cm
-1(sulfuric ester).
In addition, also have following characteristic peak:
A3：～2960cm
-1，2870cm
-1（CH
3）
A6 :～740cm
-1(C-Cl key)
Embodiment 10 preparation compd A 15(compd As 15 are R in the compd A
1For
And R
2For
Compound)
Step a): preparation Compound C
8ml sodium hydroxide solution (100g/L) is added 4,4-diaminobenzil-2, in the 30ml aqueous solution of 2 '-disulfonic acid (0.01mol), make 4,4-diaminobenzil-2,2 '-disulfonic acid dissolves fully.Then mentioned solution is joined in water (40ml) and in the finely dispersed cyanuric chloride (0.02mol), between pH 1 ~ 7, reacted 2 ~ 4 hours, make the crude product of Compound C.
Step b): preparation compd B 15(compd B 15 is R in the compd B
2For
Compound)
A) add position ester (0.02mol) solution (pH5.5 ~ 6) between 50mL in the crude product of gained Compound C (0.01mol) in step, be warming up to 25 ~ 35 ℃, be incubated 3 ~ 5 hours, maintenance pH4 ~ 6 make the crude product of compd B 15.
Step c): preparation compd A 15
At step b) gained compound B-11 5(0.01mol) crude product in add 0.022mol aniline, and be warming up to 90 ~ 100 ℃, the condensing reflux reaction is 6 ~ 8 hours in this temperature range, reaction finishes, in 130 ~ 135 ℃ of spraying dryings, obtain compd A 1515.1g, HPLC purity is about 68%.
This product is used for printing and dyeing cotton fabric textiles, and good washing fastness is arranged.
This compound carries out structural analysis with infrared spectrometer after purifying, following characteristic peak :～3260cm is arranged
-1, 3180cm
-1(NH peak);～2930cm
-1, 2860cm
-1(CH
2);～1600cm
-1, 1580cm
-1, 1510cm
-1, 1460cm
-1(phenyl ring);～1240cm
-1(sulfuric ester).
Embodiment 11 ~ 15 preparation compd As 13, A30, A10, A8 and A31
Wherein, compd A 13 is R in the compd A
1For-NHCH
2CH
2OH and R
2For
Compound;
Compound A-13 0 is R in the compd A
1For
And R
2For
Compound;
Compd A 10 is R in the compd A
1For
And R
2For
Compound;
Compound A-28 is R in the compd A
1For
And R
2For
Compound;
Compound A-13 1 is R in the compd A
1For
And R
2For
Compound;
The preparation method of compd A 13, A30, A10, A8 and A31 is with the preparation method of compd A 15 among the embodiment 10, and the HPLC purity of above-claimed cpd is between 60 ~ 70%.
These 7 compounds carry out structural analysis with infrared spectrometer after purifying, following common trait peak :～3260cm is arranged
-1, 3180cm
-1(NH peak);～2930cm
-1, 2860cm
-1(CH
2);～1240cm
-1(sulfuric ester); ~ 1600cm
-1, 1580cm
-1, 1510cm
-1, 1460cm
-1(phenyl ring).
In addition, also have following characteristic peak:
A13 :～3350cm
-1(OH peak) ,～1025cm
-1(primary alconol C-O)
A8 :～1100cm
-1(ehter bond)
Embodiment 16 preparation compd A 25(compd As 25 are R in the compd A
1For
And R
2For
Compound)
Step a): preparation Compound C
8mL sodium hydroxide solution (100g/L) is added 4,4-diaminobenzil-2, in the 30ml aqueous solution of 2 '-disulfonic acid (0.01mol), make 4,4-diaminobenzil-2,2 '-disulfonic acid dissolves fully.Then mentioned solution is joined in 40mL water and in the finely dispersed cyanuric chloride (0.02mol), between pH 1 ~ 7, reacted 2 ~ 4 hours, make the crude product of Compound C.
Step b): preparation compd B 25(compd B 25 is R in the compd B
2For
Compound)
A) add 40ml ORTHO AMINO PHENOL SULPHONIC (0.022mol) solution (pH5.5 ~ 6) in the crude product of gained Compound C (0.01mol) in step, be warming up to 40 ~ 45 ℃, be incubated 5 hours, maintenance pH4 ~ 6 make the crude product of compd B 25.）
Step c): preparation compd A 25
At step b) gained compd B 25(0.01mol) crude product in add 0.023mol 2-[(2-amino ethoxy)-2,-chlorine]-two ethyl sulfones, and be warming up to 75 ~ 80 ℃, the condensing reflux reaction is 6 ~ 8 hours in this temperature range, reaction finishes, in 130 ~ 135 ℃ of spraying dryings, obtain compd A 2514.8g, its HPLC purity is about 65%.
This compound carries out structural analysis with infrared spectrometer after purifying, following characteristic peak :～3260cm is arranged
-1, 3180cm
-1(NH peak);～2930cm
-1, 2860cm
-1(CH
2); ~ 1600cm
-1, 1580cm
-1, 1510cm
-1, 1460cm
-1(phenyl ring);～1309cm
-1(R-SO
2-R); ~ 1100cm
-1(ehter bond);～680cm
-1(C-Cl key).
Embodiment 17 ~ 20 preparation compd A 23, A32, A33 and A22
Wherein, compd A 23 is R in the compd A
1For-N (CH
2CH
2OH)
2And R
2For
Compound;
Compound A-13 2 is R in the compd A
1For
And R
2For
Compound;
Compound A-13 3 is R in the compd A
1For
And R
2For
Compound;
Compd A 22 is R in the compd A
1For
And R
2For
Compound;
The preparation method of compd A 23, A32, A33 and A22 is with the preparation method of compd A 25 among the embodiment 16, and the HPLC purity of above-claimed cpd is between 65 ~ 80%.
This compound carries out structural analysis with infrared spectrometer after purifying, following characteristic peak :～3260cm is arranged
-1, 3180cm
-1(NH peak);～2930cm
-1, 2860cm
-1(CH
2); ~ 1600cm
-1, 1580cm
-1, 1510cm
-1, 1460cm
-1(phenyl ring);～1309cm
-1(R-SO
2-R); ~ 1100cm
-1(ehter bond);～680cm
-1(C-Cl key).
In addition, also have following characteristic peak:
A23 :～3350cm
-1(OH peak) ,～1025cm
-1(primary alconol C-O).
Embodiment 21: dyeing embodiment
Synthetic compd A and convenience goods 4BK are carried out cotton dyeing, and press whiteness value and the washing fastness of GB/T8424.2-2001 and the described method test of GB/T 3921.3-1997 DYED FABRICS, compare.The fastness grading is according to standard GB/T/T 250-2008 after the dyeing.
The consumption of synthetic compound A is 0.3% (o.w.f), adds respectively sodium sulfate 20g/L after the weighing.Dissolving adds after cotton soaks 5min, and dye bath was warming up to 60 degree in 20 minutes, keep 30 minutes after, add yellow soda ash 5g/L.Continue insulation 30 minutes.Taking-up cold water cleans.
Market is sold cotton commonly used and is used fluorescent agent 4BK(available from Zhejiang Anoky Additives Co., Ltd.) dyeing consumption 0.3%(o.w.f), add sodium sulfate 10g/L after the weighing.After dissolving added cotton immersion 5min, dye bath was warming up to 98 degree in 20 minutes, continue insulation 30 minutes.Taking-up cold water cleans.
The above-mentioned cloth specimen that dyes lechery was washed 15 minutes with soaping agent 2g/l at 95 degree.
This shows: the present invention obtains the white dyes that a class can be improved the prior art deficiency, and its whiteness is higher than market product, and washing is faded few, and washing fastness is outstanding.And owing to dye in middle temperature (60 degree), obviously the 4BK than 98 degree high temperature dyeings will more save the energy.
Claims (1)
- Suc as formula shown in the B for the preparation of 4,4 '-diaminobenzil-2, the midbody compound of 2 '-disulfonic acid derivatives:
Wherein, R 2For
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| CN201210223973.2A CN102993110B (en) | 2011-06-30 | 2012-06-29 | Intermediate of 4,4'-diaminostilbene-2,2'-disulfonic acid derivative |
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| CN201210224487.2A Expired - Fee Related CN102993111B (en) | 2011-06-30 | 2012-06-29 | 4, the preparation method of 4 '-diaminobenzil-2,2 '-disulfonic acid derivatives |
| CN201210224003.4A Expired - Fee Related CN102993112B (en) | 2011-06-30 | 2012-06-29 | 4,4'-diaminostilbene-2,2'-disulfonic acid derivative |
| CN201210223973.2A Expired - Fee Related CN102993110B (en) | 2011-06-30 | 2012-06-29 | Intermediate of 4,4'-diaminostilbene-2,2'-disulfonic acid derivative |
| CN201210223744.0A Expired - Fee Related CN102993770B (en) | 2011-06-30 | 2012-06-29 | Application of 4,4'-diaminostilbene-2,2'-disulfonic acid derivative |
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| CN201210224487.2A Expired - Fee Related CN102993111B (en) | 2011-06-30 | 2012-06-29 | 4, the preparation method of 4 '-diaminobenzil-2,2 '-disulfonic acid derivatives |
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| CN103468017A (en) * | 2013-09-02 | 2013-12-25 | 山西青山化工有限公司 | Preparation method of ultrawhite high-efficiency low-impurity fluorescent whitening agent |
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| CN107245058A (en) * | 2017-07-03 | 2017-10-13 | 上海安诺其集团股份有限公司 | Stilbene-based compound, its intermediate, preparation method and application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5741905A (en) * | 1994-07-23 | 1998-04-21 | Ciba Specialty Chemicals Corporation | Triazine ultraviolet absorbers useful for improving the sun protection factor of textiles |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1469218B1 (en) * | 1964-06-30 | 1971-09-08 | Hoechst Ag | 4,4'-bis-triazinylamino-stilbene compounds and their use as reactive optical brightening agents |
| CH640899A5 (en) * | 1979-05-14 | 1984-01-31 | Ciba Geigy Ag | Stable stilbene brightener solutions |
| GB9503474D0 (en) * | 1995-02-22 | 1995-04-12 | Ciba Geigy Ag | Compounds and their use |
| AU3409597A (en) * | 1996-10-02 | 1998-04-24 | Dystar, L.P. | Fiber-reactive brighteners of bis-s-triazinylaminostilbene |
| JP2001330935A (en) * | 2000-05-18 | 2001-11-30 | Fuji Photo Film Co Ltd | Silver halide photographic element and recording material each provided with authenticity, and authenticating and identifying method |
| CN101298437A (en) * | 2008-06-27 | 2008-11-05 | 山东大学 | Fluorescent whitening agent containing p-aminobenzoic acid group quaternary ammonium salt, synthesis and use thereof |
-
2012
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5741905A (en) * | 1994-07-23 | 1998-04-21 | Ciba Specialty Chemicals Corporation | Triazine ultraviolet absorbers useful for improving the sun protection factor of textiles |
Non-Patent Citations (1)
| Title |
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| D M LEWIS,ET AL.: "The role of vinylsulphonyl reactive dyes in prevention of wool damage", 《JSDC》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103468017A (en) * | 2013-09-02 | 2013-12-25 | 山西青山化工有限公司 | Preparation method of ultrawhite high-efficiency low-impurity fluorescent whitening agent |
| CN103468017B (en) * | 2013-09-02 | 2015-04-01 | 山西青山化工有限公司 | Preparation method of ultrawhite high-efficiency low-impurity fluorescent whitening agent |
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| CN102993113B (en) | 2015-04-29 |
| CN102993111A (en) | 2013-03-27 |
| CN102993770A (en) | 2013-03-27 |
| CN102993112A (en) | 2013-03-27 |
| CN102993111B (en) | 2015-11-25 |
| CN102993112B (en) | 2015-04-29 |
| CN102993113A (en) | 2013-03-27 |
| CN102993770B (en) | 2014-06-25 |
| CN102993110B (en) | 2015-06-24 |
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