CN102993110B - 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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- CN102993110B CN102993110B CN201210223973.2A CN201210223973A CN102993110B CN 102993110 B CN102993110 B CN 102993110B CN 201210223973 A CN201210223973 A CN 201210223973A CN 102993110 B CN102993110 B CN 102993110B
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- disulfonic acid
- diaminobenzil
- diaminostilbene
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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
- 239000002253 acid Substances 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 13
- 238000004043 dyeing Methods 0.000 abstract description 14
- 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
- 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
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000000975 dye Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 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
- 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
- 0 CCNc1ccc(*(C)C2CC2)cc1 Chemical compound CCNc1ccc(*(C)C2CC2)cc1 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- 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
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000005855 radiation Effects 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
- 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
- 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
- 238000007654 immersion Methods 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
- 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
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- CPGFALLZVJRZRO-UHFFFAOYSA-N CC(C)N(CC1)CC[O-]1C1=C=C1 Chemical compound CC(C)N(CC1)CC[O-]1C1=C=C1 CPGFALLZVJRZRO-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
- -1 alkali metal salt Chemical class 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency 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
- 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
- 230000003287 optical effect Effects 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
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 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
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- 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 shown in the description.
Description
Technical field
The present invention relates to one and prepare 4, the midbody compound of 4 '-diaminobenzil-2,2 '-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 product whiteness in the sunlight.
White dyes has been widely used in the industries such as weaving, papermaking, washing powder, pigment.White dyes is applied to cotton fibre, is mainly used in the pre-treatment of cotton, improves cotton whiteness and the inadequate problem of vividness.
But conventional fluorescent whitening agent is mainly combined with fiber, so often can there is the poor problem of the fastness such as washing by the substantivity of whitening agent in the cotton process of dye.
Summary of the invention
Technical problem to be solved by this invention is that to overcome existing white dyes degree of fixation on cotton low, the defect that fastness is bad, and provides class 4,4 '-diaminobenzil-2,2 '-disulfonic acid derivatives and a 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 DEG C, far below the dyeing temperature (being generally about 98 DEG C) of conventional fluorescent whitening agent, therefore, it is possible to minimizing energy consumption, reduce dyeing cost.
Therefore, the present invention relates to a class such as formula 4 shown in A, 4 '-diaminobenzil-2,2 '-disulfonic acid derivatives:
Wherein, R
1for-NH
2; " C is selected from by 1 ~ 2
1~ C
4alkyl, the C that replaced by 1 ~ 2 hydroxyl
1~ C
4alkyl and by the C of 1 ~ 2 carboxyl substituted
1~ C
4alkyl " group replace-NH
2; Anilino; Benzene ring hydrogen is selected from "-SO by 1 ~ 2
3na ,-COCH
3and halogen atom " group replace anilino; Or, the heteroatomic C of O and S is selected from containing 0 ~ 2
3~ C
5saturated rings amido.
Described is selected from " C by 1 ~ 2
1~ C
4alkyl, the C that replaced by 1 ~ 2 hydroxyl
1~ C
4alkyl and by the C of 1 ~ 2 carboxyl substituted
1~ C
4alkyl " group replace-NH
2be preferably-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 " group replace anilino be preferably
The described heteroatomic C being selected from O and S containing 0 ~ 2
3~ C
5saturated rings amido be preferably
R
2for
Of the present invention such as formula 4 shown in A, 4 '-diaminobenzil-2,2 '-disulfonic acid derivatives is preferably following compound:
The invention further relates to the preparation method of formula A compound, it comprises the following steps: such as formula the compound shown in B and R
1h carries out following substitution reaction;
Wherein, radicals R
1and R
2definition ditto described in.
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, described substitution reaction preferably can be carried out in water or under condition of no solvent.Described water and R
1the volume mass of H is 5 ~ 10ml/g than preferably.Described compd B and R
1the mol ratio of H is preferably 1:2 ~ 1:2.2.The pH of described substitution reaction is preferably 2.5 ~ 5.5.The temperature of described substitution reaction is preferably 80 ~ 100 DEG C.Till time of described reaction preferably completes with detection reaction, be generally 2 ~ 4 hours.
After having reacted, described compd A can be passed through saltout, press filtration and drying operation, also directly can carry out spraying dry, obtain the solid of the alkali metal salt such as sodium salt, sylvite or sour form, also can make liquid form.
In the present invention, described compd B can be obtained by following method: by Compound C and R
2h carries out following substitution reaction;
Wherein, radicals R
2definition ditto described in.
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 be water.The solvent of described substitution reaction and the volume mass of Compound C are 5 ~ 10ml/g than preferably.Described Compound C and R
2the mol ratio of H is preferably 1:2 ~ 1:2.2.The pH of described substitution reaction is preferably 2.5 ~ 5.5.The temperature of described substitution reaction is preferably 25 ~ 60 DEG C.Till time of described reaction preferably completes with detection reaction, be generally 5 ~ 8 hours.
In the present invention, described Compound C can be obtained by following method: Compound D and compd E are carried out following substitution reaction;
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, each preferred feature above-mentioned in the present invention can arbitrary combination, obtains the preferred embodiments of the invention.
The invention still further relates to the midbody compound such as formula the preparation formula A compound shown in B:
Wherein, radicals R
2definition ditto described in.
The invention further relates to such as formula 4 shown in A, the application in optical brighteners for which of 4 '-diaminobenzil-2,2 '-disulfonic acid derivatives.Wherein, described white dyes is preferably for the fiber containing hydroxyl and/or amino, or the white dyes of blend fiber containing above-mentioned fiber.The described fiber containing hydroxyl can be cotton and/or fiber crops (as flax) etc.Described can be wool and/or silk etc. containing amino fiber.
Raw material described in the present invention or reagent except special instruction, all commercially.
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 DEG C, far below the dyeing temperature of conventional fluorescent whitening agent, therefore, it is possible to minimizing energy consumption, reduce dyeing cost.
Embodiment
Further illustrate the present invention by embodiment below, but the present invention is not limited.
Raw material used in embodiment or reagent except special instruction, all commercially.
It is R in compd A that embodiment 1 prepares compd A 1(compd A 1
1for-N (CH
2cH
2oH)
2and R
2for
compound)
Step a): preparation Compound C
8ml sodium hydroxide solution (100g/L) is added in the 30ml aqueous solution of 0.01mol 4,4-diaminobenzil-2,2 '-disulfonic acid, make the pH of solution be 7, stand-by.Separately 0.02mol cyanuric chloride (compd E) is pulled an oar in 30ml water, after making beating fully, add above-mentioned 4 wherein, 4-diaminobenzil-2,2 '-sodium disulfonate solution, adds for about 1 hour, react 2 ~ 4 hours between pH1 ~ 7 after adding, obtain the crude product of Compound C.
Step b): preparing compd B 1(compd B 1 is R in compd B
2for
compound)
By 0.02mol para-ester (namely, 4-sulfovinic acid sulfuryl aniline) dissolve with 10.6mL sodium carbonate solution (100g/L), the pH of solution is made to be 6 ~ 7, then, this solution is joined in the crude product of the Compound C of step a) gained, be warming up to 30 ~ 40 DEG C, be incubated 5 ~ 7 hours, keep pH4 ~ 7, the crude product of obtained compd B 1.
Step c): prepare compd A 1
The diethanolamine of 0.03mol is joined in the crude product of the compound B-11 of step b) gained, be warming up to 80 ~ 100 DEG C, condensing reflux reaction 4 ~ 8 hours in this temperature range, reaction terminates, in 130 ~ 135 DEG C of spraying dry, obtain compd A 116.4g, HPLC purity is about 74%.
This compound carries out structural analysis with infrared spectrometer after purifying, and has following characteristic peak: ~ 3350cm
-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, for cotton fabric textiles of printing and dyeing, has excellent washing fastness.
It is R in compd A that embodiment 2 prepares compd A 7(compd A 7
1for
r
2for
compound)
Step a): preparation Compound C
8ml sodium hydroxide solution (100g/L) is joined in the 30ml aqueous solution of 0.01mol 4,4-diaminobenzil-2,2 '-disulfonic acid, 4,4-diaminobenzil-2,2 '-disulfonic acid is dissolved completely.Then above-mentioned solution is joined in the finely dispersed mixture of 0.02mol cyanuric chloride and 40ml water, react 2 ~ 4 hours between pH 1 ~ 7, the crude product of obtained Compound C.
Step b): preparing compd B 1(compd B 1 is R in compd B
2for
compound)
In the crude product of step a) gained Compound C (0.01mol), add 50ml para-ester (0.02mol) solution, be warming up to 30 ~ 40 DEG C, be incubated 5 ~ 7 hours, keep pH4 ~ 7, the crude product of obtained compound B-11.
Step c): prepare compd A 7
In step b) add 0.025mol morpholine in the crude product of gained compound B-11 (0.01mol), and be warming up to 80 ~ 100 DEG C, condensing reflux reaction 4 ~ 8 hours in this temperature range, reaction terminates, in 130 ~ 135 DEG C of spraying dry, obtain compd A 714.3g, HPLC purity is about 78%.
This compound carries out structural analysis with infrared spectrometer after purifying, and has following characteristic peak: ~ 3260cm
-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 prepares compd A 26, A3, A27, A5, A28, A29 and A6
Wherein, compd A 26 is R in compd A
1for-NH
2and R
2for
compound;
Compound A-13 is R in compd A
1for-N (C
2h
5)
2and R
2for
compound;
Compd A 27 is R in compd A
1for
and R
2for
compound;
Compound A-45 is R in compd A
1for
and R
2for
compound;
Compd A 28 is R in compd A
1for
and R
2for
compound;
Compd A 29 is R in compd A
1for
and R
2for
compound;
Compd A 6 is R in 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 in 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, and have following common trait peak: ~ 3260cm
-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, following characteristic peak is also had:
A3：～2960cm
-1，2870cm
-1（CH
3）
A6: ~ 740cm
-1(C-Cl key)
It is R in compd A that embodiment 10 prepares compd A 15(compd A 15
1for
and R
2for
compound)
Step a): preparation Compound C
8ml sodium hydroxide solution (100g/L) is added in the 30ml aqueous solution of 4,4-diaminobenzil-2,2 '-disulfonic acid (0.01mol), 4,4-diaminobenzil-2,2 '-disulfonic acid is dissolved completely.Then above-mentioned solution is joined in water (40ml) in finely dispersed cyanuric chloride (0.02mol), react 2 ~ 4 hours between pH 1 ~ 7, the crude product of obtained Compound C.
Step b): preparing compd B 15(compd B 15 is R in compd B
2for
compound)
In the crude product of step a) gained Compound C (0.01mol), add position ester (0.02mol) solution (pH5.5 ~ 6) between 50mL, be warming up to 25 ~ 35 DEG C, be incubated 3 ~ 5 hours, keep pH4 ~ 6, the crude product of obtained compd B 15.
Step c): prepare compd A 15
In step b) gained compound B-11 5(0.01mol) crude product in add 0.022mol aniline, and be warming up to 90 ~ 100 DEG C, condensing reflux reaction 6 ~ 8 hours in this temperature range, reaction terminates, in 130 ~ 135 DEG C of spraying dry, obtain compd A 1515.1g, HPLC purity is about 68%.
This product, for cotton fabric textiles of printing and dyeing, has excellent washing fastness.
This compound carries out structural analysis with infrared spectrometer after purifying, and has following characteristic peak: ~ 3260cm
-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 prepares compd A 13, A30, A10, A8 and A31
Wherein, compd A 13 is R in compd A
1for-NHCH
2cH
2oH and R
2for
compound;
Compound A-13 0 is R in compd A
1for
and R
2for
compound;
Compd A 10 is R in compd A
1for
and R
2for
compound;
Compound A-28 is R in compd A
1for
and R
2for
compound;
Compound A-13 1 is R in 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 in 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, and have following common trait peak: ~ 3260cm
-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, following characteristic peak is also had:
A13: ~ 3350cm
-1(OH peak), ~ 1025cm
-1(primary alconol C-O)
A8: ~ 1100cm
-1(ehter bond)
It is R in compd A that embodiment 16 prepares compd A 25(compd A 25
1for
and R
2for
compound)
Step a): preparation Compound C
8mL sodium hydroxide solution (100g/L) is added in the 30ml aqueous solution of 4,4-diaminobenzil-2,2 '-disulfonic acid (0.01mol), 4,4-diaminobenzil-2,2 '-disulfonic acid is dissolved completely.Then above-mentioned solution is joined in 40mL water in finely dispersed cyanuric chloride (0.02mol), react 2 ~ 4 hours between pH 1 ~ 7, the crude product of obtained Compound C.
Step b): preparing compd B 25(compd B 25 is R in compd B
2for
compound)
In the crude product of step a) gained Compound C (0.01mol), add 40ml ORTHO AMINO PHENOL SULPHONIC (0.022mol) solution (pH5.5 ~ 6), be warming up to 40 ~ 45 DEG C, be incubated 5 hours, keep pH4 ~ 6, the crude product of obtained compd B 25.）
Step c): prepare compd A 25
In step b) gained compd B 25(0.01mol) crude product in add 0.023mol 2-[(2-amino ethoxy)-2,-chlorine]-bis-ethyl sulfone, and be warming up to 75 ~ 80 DEG C, condensing reflux reaction 6 ~ 8 hours in this temperature range, reaction terminates, in 130 ~ 135 DEG C of spraying dry, obtain compd A 2514.8g, its HPLC purity is about 65%.
This compound carries out structural analysis with infrared spectrometer after purifying, and has following characteristic peak: ~ 3260cm
-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 prepares compd A 23, A32, A33 and A22
Wherein, compd A 23 is R in compd A
1for-N (CH
2cH
2oH)
2and R
2for
compound;
Compound A-13 2 is R in compd A
1for
and R
2for
compound;
Compound A-13 3 is R in compd A
1for
and R
2for
compound;
Compd A 22 is R in 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 in 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, and has following characteristic peak: ~ 3260cm
-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, following characteristic peak is also had:
A23: ~ 3350cm
-1(OH peak), ~ 1025cm
-1(primary alconol C-O).
Embodiment 21: Dyeing Example
The compd A of synthesis and convenience goods 4BK are carried out cotton dyeing, and presses whiteness value and the washing fastness of method test DYED FABRICS described in GB/T8424.2-2001 and GB/T 3921.3-1997, contrast.After dyeing, fastness grading is according to standard GB/T/T 250-2008.
The consumption of synthetic compound A is 0.3% (o.w.f), adds sodium sulfate 20g/L respectively after weighing.After dissolving adds cotton immersion 5min, dye bath was warming up to 60 degree in 20 minutes, maintained after 30 minutes, added sodium carbonate 5g/L.Continue insulation 30 minutes.Taking-up cold water cleans.
Market sell conventional cotton fluorescent agent 4BK(purchased from Zhejiang Anoky Additives Co., Ltd.) dye consumption 0.3%(o.w.f), add sodium sulfate 10g/L after weighing.After dissolving adds cotton immersion 5min, dye bath was warming up to 98 degree in 20 minutes, continued insulation 30 minutes.Taking-up cold water cleans.
The cloth specimen of above-mentioned dye lechery is washed 15 minutes at 95 degree with soaping agent 2g/l.
As can be seen here: the present invention obtains the white dyes that a class can improve prior art deficiency, its whiteness is higher than market product, and washing is faded few, and washing fastness is outstanding.And due in the upper dye of middle temperature (60 degree), obviously more the energy to be saved than the 4BK of 98 degree of high temperature dyeings.
Claims (1)
1. such as formula the midbody compound for the preparation of 4,4 '-diaminobenzil-2,2 '-disulfonic acid derivatives shown in B:
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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| CN201110182826 | 2011-06-30 | ||
| CN201110182826.0 | 2011-06-30 | ||
| CN2011101828260 | 2011-06-30 | ||
| 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 |
| CN201210224020.8A Expired - Fee Related CN102993113B (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 |
| CN201210224020.8A Expired - Fee Related CN102993113B (en) | 2011-06-30 | 2012-06-29 | 4,4'-diaminostilbene-2,2'-disulfonic acid derivative |
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| 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 |
| 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 |
| KR20000048764A (en) * | 1996-10-02 | 2000-07-25 | 다이스타 엘 피 | 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 |
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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 |
|---|
| The role of vinylsulphonyl reactive dyes in prevention of wool damage;D M Lewis,et al.;《JSDC》;19911031;第107卷;357-362 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102993111A (en) | 2013-03-27 |
| CN102993111B (en) | 2015-11-25 |
| CN102993112B (en) | 2015-04-29 |
| CN102993112A (en) | 2013-03-27 |
| CN102993110A (en) | 2013-03-27 |
| CN102993770A (en) | 2013-03-27 |
| CN102993113A (en) | 2013-03-27 |
| CN102993113B (en) | 2015-04-29 |
| CN102993770B (en) | 2014-06-25 |
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