CN1486303A - 三嗪基氨基均二苯代乙烯-二磺酸化合物的制备方法 - Google Patents
三嗪基氨基均二苯代乙烯-二磺酸化合物的制备方法 Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000002253 acid Substances 0.000 title description 5
- 239000000203 mixture Substances 0.000 claims abstract description 17
- -1 4,4'-bistriazinylamino-stilbene-2,2'-disulphonic acid compound Chemical class 0.000 claims abstract description 11
- 150000001412 amines Chemical class 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 5
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 4
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 4
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 3
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 3
- 125000002112 pyrrolidino group Chemical group [*]N1C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 claims abstract description 3
- 125000005843 halogen group Chemical group 0.000 claims abstract 2
- 238000009472 formulation Methods 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 150000002431 hydrogen Chemical group 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 150000003973 alkyl amines Chemical class 0.000 claims 1
- 150000007514 bases Chemical class 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 4
- 239000000370 acceptor Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
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- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229940068886 polyethylene glycol 300 Drugs 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
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- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001448 anilines Chemical class 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 125000006705 (C5-C7) cycloalkyl group Chemical group 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- UAGYXNZCZVTVJG-UHFFFAOYSA-N 3-amino-6-(2-phenylethenyl)benzene-1,2-disulfonic acid Chemical compound OS(=O)(=O)C1=C(S(O)(=O)=O)C(N)=CC=C1C=CC1=CC=CC=C1 UAGYXNZCZVTVJG-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 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 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000012669 liquid formulation Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004998 naphthylethyl group Chemical group C1(=CC=CC2=CC=CC=C12)CC* 0.000 description 1
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/04—Sodium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/54—Three nitrogen atoms
- C07D251/68—Triazinylamino stilbenes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Cosmetics (AREA)
Abstract
通式(I)的4，4’－双三嗪基氨基－均二苯代乙烯－2，2’－二磺酸化合物或其混合物的制备方法，其中，各个R1独立地代表－NH2、－NH(C1－10烷基)、－N(C1－10烷基)2、－NH(C2－4羟基烷基)、－N(C2－4羟基烷基)2、－N(C1－10烷基)(C2－4羟基烷基)、－NH(C1－4烷氧基－C2－4羟基烷基)、－N(C1－4烷氧基－C2－4羟基烷基)2、－N(C1－4烷氧基－C2－4羟基烷基)(C1－10烷基)、－N(C1－4烷氧基－C2－4羟基烷基)(C2－4羟基烷基)、－NH(C1－4烷氧基－C1－4烷氧基－C1－4烷基)、－N(C1－4烷氧基－C1－4烷氧基－C1－4烷基)2、－N(C1－4烷氧基－C1－4烷氧基－C1－4烷基)(C1－4烷基)、－N(C1－4烷氧基－C1－4烷氧基－C2－4烷基)(C2－4羟基烷基)、－NH(C5－7环烷基)、－N(C5－7环烷基)2、－NH(C6－13芳基)、－NH(C7－10芳烷基)或吗啉子基、哌啶子基或吡咯烷残基；M代表H、Na、Li、K、Ca、Mg、铵或被C1－4烷基、C2－4羟基烷基单－、二－、三－或四取代的铵，该方法的特征是通式(II)的化合物(其中R2代表取代或未取代的C1－10烷基，和X代表卤素)与至少4摩尔的通式R1H(3)的胺或其混合物反应。
Description
本发明涉及4，4’-双三嗪基氨基均二苯代乙烯-2，2’-二磺酸化合物的制备方法。
在美国专利5939379中描述了如下式的新化合物
其中Y可以是其中R3和R4是氢或C1-4烷基的-C(＝O)NR3R4，X可以是NH和R2是C1-4烷基或苯基，此化合物可用作紫外线吸收剂(UVA‘s)和荧光增白剂(FWA’s)。通式(I)的化合物以任意所需的顺序，通过将氰尿酰氯与氨基均二苯代乙烯-二磺酸反应，可以导入下式基团的苯胺衍生物
和与可以导入-XR2基团的化合物反应来制备。但是，此制备方法的缺点是由于上述苯胺衍生物即难于制备又价格昂贵，故不易获得。
但是现在令人惊奇地发现通式(1)的化合物或其混合物通过将通式(2)的化合物与至少4摩尔的通式(3)的R1H或其混合物反应，可以很容易地以高纯度和高产率获得
其中，各个R1独立地代表-NH2、-NH(C1-10烷基)、-N(C1-10烷基)2、-NH(C2-4羟基烷基)、-N(C2-4羟基烷基)2、-N(C1-10烷基)(C2-4羟基烷基)、-NH(C1-4烷氧基-C2-4羟基烷基)、-N(C1-4烷氧基-C2-4羟基烷基)2、-N(C1-4烷氧基-C2-4羟基烷基)(C1-10烷基)、-N(C1-4烷氧基-C2-4羟基烷基)(C2-4羟基烷基)、-NH(C1-4烷氧基-C1-4烷氧基-C1-4烷基)、-N(C1-4烷氧基-C1-4烷氧基-C1-4烷基)2、-N(C1-4烷氧基-C1-4烷氧基-C1-4烷基)(C1-4烷基)、-N(C1-4烷氧基-C1-4烷氧基-C2-4烷基)(C2-4羟基烷基)、-NH(C5-7环烷基)、-N(C5-7环烷基)2、-NH(C6-10芳基)、-NH(C7-13芳烷基)或吗啉子基、哌啶子基或吡咯烷基；M代表H、Na、Li、K、Ca、Mg、铵或被C1-4烷基、C2-4羟基烷基单-、二-、三-或四取代的铵
其中R2代表取代或未取代的C1-10烷基，和X代表卤素。
本发明的方法特别适用于制备其中R1基团是相同的基团的通式(1)化合物，更适合于制备式(4)化合物
并也适合于式(5)化合物的制备
优选其中R2是C1-4烷基，特别是甲基或乙基，和X是氟或特别是氯的式(2)化合物作为原料。
本发明的方法特别适用于通式(1)化合物的制备，并更特别适用于那些其中R1是-NH(C1-4烷基)、-N(C1-4烷基)2、-NH(C2-4羟基烷基)或-N(C2-4羟基烷基)2和M是氢、K或Na的通式(4)和通式(5)的化合物的制备，最特别适用于其中R1是单-或二甲基氨基、单-或二乙基氨基、或单-或二羟基乙基氨基的通式(4)化合物。
在通式(1)到(5)的化合物的范围内，C1-10烷基的定义是甲基、乙基、正丙基、异丙基、正丁基、仲丁基或叔丁基、戊基、己基、庚基、壬基或癸基，C2-4羟基烷基是羟乙基、羟丙基或羟丁基，和C1-4烷氧基是指甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、仲丁氧基或叔丁氧基。作为C5-7环烷基的定义是环戊基、环己基或环庚基，C6-10芳基可以是未取代或被C1-4烷基或C1-4烷氧基取代的苯基或，另外萘和C7-13芳烷基是例如取代或未取代的苄基、苯乙基、萘基甲基或萘基乙基。
在通式(2)化合物中的卤素是溴、氟或，特别是氯。
与通式(2)化合物反应的通式(3)的胺的量应该相应于至少化学计算量，即相对于每摩尔通式(2)的化合物摩尔量为4摩尔。但是，由于胺还可具有酸受体的功能，所以优选过量使用，其可以具有作为反应溶剂的另外功能。另外，也可以使用有利于反应进行的溶剂，在反应过程中可以使用不同于通式(3)的胺的二级碱作为酸受体。很清楚地，当使用通式(3)的胺的混合物时，所得到的反应产物将由相应的通式(1)的混合物组成。
通式(2)化合物与通式(3)的胺反应可以使用的适合的溶剂是例如偶极非质子溶剂如二甲基甲酰胺、二甲亚砜、N-甲基吡咯烷酮或四甲基脲，醇如甲醇、乙醇、正丙醇或异丙醇或丁醇，酮如丙酮或丁酮或特别是水或它们的混合物。
反应中作为酸受体可以使用的适合的二级碱是例如有机叔胺如三乙胺、三丙胺或三丁胺，或无机碱碳酸钾或碳酸钠、碳酸氢钾、碳酸氢钠或氢氧化钾或氢氧化钠并可以使用其他无机酸受体如氧化钙或氧化镁。
通式(2)化合物与通式(3)的胺反应的温度可以在非常广泛的范围中进行，例如在约20℃至约200℃的范围中进行，这取决于所使用的胺组分。但是，温度范围一般为约50℃至约150℃，特别是约80℃至约130℃。
根据反应温度和使用的通式(3)的胺化合物，可以在常压、减压或加压下进行反应，其中可以使用适合的压力容器如高压釜。
在本发明的另一方面，可以向反应混合物中加入作为反应溶剂的适合的配制剂，可以从反应混合物中直接获得稳定的液体制剂。通过控制反应混合物的浓度或以例如水稀释制剂可以容易地获得所需的制剂浓度。
本发明可以使用的适合的配制剂是例如多羟基化合物如甘油或乙二醇或丙二醇或，特别是聚乙二醇如聚乙二醇150、200、600、1500和特别是聚乙二醇300。
通式(2)和(3)的原料是容易获得或可以通过已知方法获得的已知化合物。
以下实施例进一步说明本发明但不限制本发明；除非另有说明，份和百分比是以重量计。
实施例1
按美国专利5744599的方法，将85％活性组分的2.0g上式(100)化合物加到1.5g乙醇胺和1.0g聚乙二醇300的混合物中。将此混合物加热至120℃，在100℃得到澄清溶液。在120℃搅拌4小时后，将此混合物冷却至80℃并加入3.7g水。得到稳定的制剂，其含22％通式(101)化合物，
14％乙醇胺
12.5％聚乙二醇300，
2.5％氯化钠和
49％水。
实施例2
将含85％活性组分的2.5g通式(100)化合物加到16.0g 40％的甲胺水溶液中并置于玻璃高压釜中。密闭高压釜后，将此反应混合物在90℃搅拌3小时，冷却并用2.2ml 2N氢氧化钠溶液处理。抽滤沉淀的固体并干燥，得到通式(102)化合物，以所使用的化合物(100)的量计算为80％产率，按美国专利5939379所描述的方法制备并根据HPLC和UV色谱进行样品鉴别。
Claims (10)
1.式(1)的4，4’-双三嗪基氨基均二苯代乙烯-2，2’-二磺酸化合物的制备方法
其中，
R1各自独立地代表-NH2、-NH(C1-10烷基)、-N(C1-10烷基)2、-NH(C2-4羟基烷基)、-N(C2-4羟基烷基)2、-N(C1-10烷基)(C2-4羟基烷基)、-NH(C1-4烷氧基-C2-4羟基烷基)、-N(C1-4烷氧基-C2-4羟基烷基)2、-N(C1-4烷氧基-C2-4羟基烷基)(C1-10烷基)、-N(C1-4烷氧基-C2-4羟基烷基)(C2-4羟基烷基)、-NH(C1-4烷氧基-C1-4烷氧基-C1-4烷基)、-N(C1-4烷氧基-C1-4烷氧基-C1-4烷基)2、-N(C1-4烷氧基-C1-4烷氧基-C1-4烷基)(C1-4烷基)、-N(C1-4烷氧基-C1-4烷氧基-C2-4烷基)(C2-4羟基烷基)、-NH(C5-7环烷基)、-N(C5-7环烷基)2、-NH(C6-10芳基)、-NH(C7-13芳烷基)或吗啉子基、哌啶子基或吡咯烷基；
M代表H、Na、Li、K、Ca、Mg、铵或被C1-4烷基、C2-4羟基烷基单-、二-、三-或四取代的铵，
该方法的特征是通式(2)的化合物与至少4摩尔的通式R1H(3)的胺或其混合物反应
其中R2代表取代或未取代的C1-10烷基，和X代表卤素。
2.权利要求1的方法，其中各个R1基团是相同的。
3.制备下式化合物的权利要求1或2的方法。
4.制备下式化合物的权利要求1或2的方法。
5.上述任一权利要求的方法，其中
R2是C1-4烷基和X是氯。
6.上述任一权利要求的方法，其中
R1是-NH(C1-4烷基)、-N(C1-4烷基)2、-NH(C2-4羟基烷基)或-N(C2-4羟基烷基)2和M是氢、K或Na。
7.制备通式(4)化合物的权利要求6的方法。
8.制备通式(5)化合物的权利要求6的方法。
9.上述任一权利要求的方法，其中反应是在除R1H胺外的碱性化合物存在下进行。
10.上述任一权利要求的方法，其中反应是在配制剂特别是聚乙二醇的存在下进行。
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| EP01810028.9 | 2001-01-12 | ||
| EP01810028 | 2001-01-12 |
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| US (1) | US20040063706A1 (zh) |
| EP (1) | EP1358166A1 (zh) |
| JP (1) | JP2004517139A (zh) |
| KR (1) | KR20040002852A (zh) |
| CN (1) | CN1486303A (zh) |
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| WO2005019189A1 (en) * | 2003-08-21 | 2005-03-03 | Ciba Specialty Chemicals Holding Inc. | Optical brighteners |
| EP1802592A1 (en) * | 2004-10-20 | 2007-07-04 | CIBA SPECIALTY CHEMICALS HOLDING INC. Patent Departement | Amphoteric 4,4'-bis(triazinylamino)stilbene-2,2'-disulfonic acid derivatives as optical brighteners for paper |
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| DE19500791C1 (de) * | 1995-01-13 | 1996-08-01 | Bayer Ag | Verfahren zur Herstellung von substituierten 4,4'-Diaminostilben-2,2'-disulfonsäuresalzen |
| GB9503474D0 (en) * | 1995-02-22 | 1995-04-12 | Ciba Geigy Ag | Compounds and their use |
| GB9617322D0 (en) * | 1996-08-17 | 1996-09-25 | Ciba Geigy Ag | Triazine derivatives and their use |
| JP2001518919A (ja) * | 1997-03-25 | 2001-10-16 | チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド | 蛍光増白剤 |
| ES2228013T3 (es) * | 1998-02-20 | 2005-04-01 | Ciba Specialty Chemicals Holding Inc. | Unprocedimdiento para la preparacion de compuestos de estilbeno. |
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- 2002-01-07 KR KR10-2003-7009281A patent/KR20040002852A/ko not_active Application Discontinuation
- 2002-01-07 EP EP02715396A patent/EP1358166A1/en not_active Withdrawn
- 2002-01-07 US US10/250,843 patent/US20040063706A1/en not_active Abandoned
- 2002-01-07 JP JP2002556179A patent/JP2004517139A/ja active Pending
- 2002-01-07 WO PCT/EP2002/000070 patent/WO2002055509A1/en not_active Application Discontinuation
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| BR0206398A (pt) | 2004-02-10 |
| EP1358166A1 (en) | 2003-11-05 |
| WO2002055509A1 (en) | 2002-07-18 |
| US20040063706A1 (en) | 2004-04-01 |
| KR20040002852A (ko) | 2004-01-07 |
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