CN1060194C - 制造染料或其中间体的光气化方法 - Google Patents
制造染料或其中间体的光气化方法 Download PDFInfo
- Publication number
- CN1060194C CN1060194C CN95111869A CN95111869A CN1060194C CN 1060194 C CN1060194 C CN 1060194C CN 95111869 A CN95111869 A CN 95111869A CN 95111869 A CN95111869 A CN 95111869A CN 1060194 C CN1060194 C CN 1060194C
- Authority
- CN
- China
- Prior art keywords
- dye
- trichloromethyl
- carbonate
- phosgenation
- phosgene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000000034 method Methods 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 6
- 150000001492 aromatic hydrocarbon derivatives Chemical class 0.000 claims abstract description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 5
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 claims description 18
- 150000007530 organic bases Chemical class 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- -1 azo compound Chemical class 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 239000012736 aqueous medium Substances 0.000 claims description 3
- 239000007853 buffer solution Substances 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims 1
- 150000007529 inorganic bases Chemical class 0.000 claims 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 claims 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 239000007787 solid Substances 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 abstract description 2
- 238000003860 storage Methods 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- DOMVNOGAXIPBGV-UHFFFAOYSA-N dichloromethyl trichloromethyl carbonate Chemical compound ClC(Cl)OC(=O)OC(Cl)(Cl)Cl DOMVNOGAXIPBGV-UHFFFAOYSA-N 0.000 abstract 3
- 239000000463 material Substances 0.000 abstract 1
- 238000012805 post-processing Methods 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000543 intermediate Substances 0.000 description 9
- 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 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 238000005185 salting out Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 description 2
- HBZVNWNSRNTWPS-UHFFFAOYSA-N 6-amino-4-hydroxynaphthalene-2-sulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=C(O)C2=CC(N)=CC=C21 HBZVNWNSRNTWPS-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- ISEIIUARLAEQGU-UHFFFAOYSA-N 2-amino-5-(carbamoylamino)benzenesulfonic acid Chemical compound NC(=O)NC1=CC=C(N)C(S(O)(=O)=O)=C1 ISEIIUARLAEQGU-UHFFFAOYSA-N 0.000 description 1
- LTASFWDWBYFZQQ-UHFFFAOYSA-N 2-amino-5-nitrobenzenesulfonic acid Chemical compound NC1=CC=C([N+]([O-])=O)C=C1S(O)(=O)=O LTASFWDWBYFZQQ-UHFFFAOYSA-N 0.000 description 1
- MTJGVAJYTOXFJH-UHFFFAOYSA-N 3-aminonaphthalene-1,5-disulfonic acid Chemical compound C1=CC=C(S(O)(=O)=O)C2=CC(N)=CC(S(O)(=O)=O)=C21 MTJGVAJYTOXFJH-UHFFFAOYSA-N 0.000 description 1
- PCGISRHGYLRXSR-UHFFFAOYSA-N 4-hydroxy-7-[(5-hydroxy-7-sulfonaphthalen-2-yl)carbamoylamino]naphthalene-2-sulfonic acid Chemical compound OC1=CC(S(O)(=O)=O)=CC2=CC(NC(=O)NC=3C=C4C=C(C=C(C4=CC=3)O)S(O)(=O)=O)=CC=C21 PCGISRHGYLRXSR-UHFFFAOYSA-N 0.000 description 1
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 description 1
- STOOUUMSJPLRNI-UHFFFAOYSA-N 5-amino-4-hydroxy-3-[[4-[4-[(4-hydroxyphenyl)diazenyl]phenyl]phenyl]diazenyl]-6-[(4-nitrophenyl)diazenyl]naphthalene-2,7-disulfonic acid Chemical compound OS(=O)(=O)C1=CC2=CC(S(O)(=O)=O)=C(N=NC=3C=CC(=CC=3)C=3C=CC(=CC=3)N=NC=3C=CC(O)=CC=3)C(O)=C2C(N)=C1N=NC1=CC=C([N+]([O-])=O)C=C1 STOOUUMSJPLRNI-UHFFFAOYSA-N 0.000 description 1
- KYARBIJYVGJZLB-UHFFFAOYSA-N 7-amino-4-hydroxy-2-naphthalenesulfonic acid Chemical compound OC1=CC(S(O)(=O)=O)=CC2=CC(N)=CC=C21 KYARBIJYVGJZLB-UHFFFAOYSA-N 0.000 description 1
- 229910018828 PO3H2 Inorganic materials 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- PGWPNHMAKPHTMA-UHFFFAOYSA-N chembl1091601 Chemical compound OS(=O)(=O)C1=CC(O)=C2C(N=NC3=CC=C(C=C3S(O)(=O)=O)NC(=O)NC3=CC=C(C(=C3)S(O)(=O)=O)N=NC3=C4C(O)=CC(=CC4=CC=C3N)S(O)(=O)=O)=C(N)C=CC2=C1 PGWPNHMAKPHTMA-UHFFFAOYSA-N 0.000 description 1
- ONTQJDKFANPPKK-UHFFFAOYSA-L chembl3185981 Chemical compound [Na+].[Na+].CC1=CC(C)=C(S([O-])(=O)=O)C=C1N=NC1=CC(S([O-])(=O)=O)=C(C=CC=C2)C2=C1O ONTQJDKFANPPKK-UHFFFAOYSA-L 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- HZBTZQVWJPRVDN-UHFFFAOYSA-J copper;disodium;5-[[4-[4-[[2,6-dioxido-3-[(2-oxido-5-sulfonatophenyl)diazenyl]phenyl]diazenyl]phenyl]phenyl]diazenyl]-2-oxidobenzoate;hydron Chemical compound [H+].[H+].[Na+].[Na+].[Cu+2].C1=C([O-])C(C(=O)[O-])=CC(N=NC=2C=CC(=CC=2)C=2C=CC(=CC=2)N=NC=2C(=C(N=NC=3C(=CC=C(C=3)S([O-])(=O)=O)[O-])C=CC=2[O-])[O-])=C1 HZBTZQVWJPRVDN-UHFFFAOYSA-J 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 239000000982 direct dye Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000001624 naphthyl group Chemical class 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- OCDYNJNATDIUQK-UHFFFAOYSA-N sodium 5-[[4-[[4-[(3-carboxy-4-hydroxyphenyl)diazenyl]phenyl]carbamoylamino]phenyl]diazenyl]-2-hydroxybenzoic acid Chemical compound C1=CC(=CC=C1NC(=O)NC2=CC=C(C=C2)N=NC3=CC(=C(C=C3)O)C(=O)O)N=NC4=CC(=C(C=C4)O)C(=O)O.[Na+] OCDYNJNATDIUQK-UHFFFAOYSA-N 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XRFRTDKENRGSSX-UHFFFAOYSA-J tetrasodium;3-[[4-[[4-[(4,8-disulfonatonaphthalen-2-yl)diazenyl]-3-methylphenyl]carbamoylamino]-2-methylphenyl]diazenyl]naphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].[Na+].[Na+].C1=CC=C(S([O-])(=O)=O)C2=CC(N=NC3=CC=C(NC(=O)NC=4C=C(C)C(N=NC=5C=C6C(=CC=CC6=C(C=5)S([O-])(=O)=O)S([O-])(=O)=O)=CC=4)C=C3C)=CC(S([O-])(=O)=O)=C21 XRFRTDKENRGSSX-UHFFFAOYSA-J 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- VRVDFJOCCWSFLI-UHFFFAOYSA-K trisodium 3-[[4-[(6-anilino-1-hydroxy-3-sulfonatonaphthalen-2-yl)diazenyl]-5-methoxy-2-methylphenyl]diazenyl]naphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].[Na+].COc1cc(N=Nc2cc(c3cccc(c3c2)S([O-])(=O)=O)S([O-])(=O)=O)c(C)cc1N=Nc1c(O)c2ccc(Nc3ccccc3)cc2cc1S([O-])(=O)=O VRVDFJOCCWSFLI-UHFFFAOYSA-K 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B43/00—Preparation of azo dyes from other azo compounds
- C09B43/12—Preparation of azo dyes from other azo compounds by acylation of amino groups
- C09B43/136—Preparation of azo dyes from other azo compounds by acylation of amino groups with polyfunctional acylating agents
- C09B43/14—Preparation of azo dyes from other azo compounds by acylation of amino groups with polyfunctional acylating agents with phosgene or thiophosgene
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明描述了一种制造染料及其中间体的新光气化方法，即利用二(三氯甲基)碳酸酯作为光气的替代物，在水相介质中，与含氨基的水溶性芳烃衍生物或其它偶氮化合物进行光气化反应，形成脲类结构的染料或染料中间体。由于二(三氯甲基)碳酸酯为稳定的固体结晶，运输、贮存、使用极为方便，可准确投料，避免了光气对生态环境毒害的危险性，同时也消除了光气在反应中不断逸出而造成的浪费，节省了资源，免去了复杂的尾气后处理工序和设备。
Description
本发明属于染料及其中间体的制造方法。
许多染料及其中间体的生产要使用光气，如脲类的直接染料：
再如：N，N’－二(2－甲氧基－4氨基－5－磺酸基苯基)－脲：N，N’－二(3－磺酸基－4－氨基苯基)－脲：
它们的合成方法，都是将含有氨基的中间体或单偶氮染料，在中性水溶液中通入光气进行反应而制得：在反应中，滴加氢氧化钠水溶液，保持PH值在中性状态。
上述制备脲类化合物的工艺过程存在以下严重缺点：
1．反应中使用剧毒的光气，给劳动保护和生态环境带来严重的威胁。
2．光气作为气体参加反应时，气液两相反应物接触不好，因而反应速度慢，反应所需时间长；
3．光气在向溶液内不断通入的同时，也不断向外逸出，造成光气的用量常为理论量的4～10倍，不仅造成资源浪费，生产成本增加，而且不得不使用许多设备去处理剧毒尾气；
4．通入光气的量难于控制，因而不能进行定量的光气化反应。
本发明的目的是利用固态的二－(三氯甲基)碳酸酯(简称BTC)替代光气用于上述染料及在中间体的制造过程，以消除使用光气造成的种种缺点。
本发明制造染料或其中间体的光气化方法，其特征在于该方法所用的光气化试剂是二－(三氯甲基)碳酸酯(BTC)，在水介质中，用或不用有机碱作催化剂，于0～100℃的反应温度，调节pH值，将含有氨基的芳烃衍生物或偶氮化合物与二－(三氯甲基)碳酸酯按1∶0．17～0．85的摩尔比进行反应，即生成脲类结构的染料或染料中间体。
所适用的染料包括C．I．直接黄26，33，41，42，44，49，50，51，67，69，70等；C．I．直接橙49，69，83，85，96，102，108等；C．I．直接红4，14，23，26，31，36，49，54，62，72，73，75，79，80，83，98，101，120，122，173等；C．I直接紫6，47，62，80，83等；C．I．直接棕112，126，146，148等；C．I．直接绿55等及其中间体的合成。这些化合物都具有如下通式结构：反应式为：其中：Ar、Ar’可以相同或不同。Ar，Ar’可为苯环、萘环或杂环的芳烃，或含这些芳环的单偶氮或多偶氮化合物；芳环上带有－SO3H，－SO3M，－NO2，－OH，－NH2，－CHO，－COOH，－COOM，－F，－Cl，－Br，－I，－NHCOR，－OR，－COOR，－PO3H2，－PO3M2，－PO2H，－PO(OR)2等基团，其中R为含1～12个碳的烷烃或芳烃，或－R’－O－R”(其中R’、R”为含1～12个碳的烷烃或芳烃)，M可以是K＋，
生成脲的反应是在水相中进行，水介质最好使用PH缓冲溶液，如：磷酸盐体系、硼酸盐体系等。将上述带有氨基的胺类化合物Ar－NH2或Ar’－NH2溶于水中或悬浮于水中，在很好的搅拌下加入BTC，Ar－NH2Ar’－NH2与BTC的摩尔比为1∶0．17～0．85，反应温度0～100℃，反应过程中加入浓度为1～20％碱(如：NaOH，KOH，Na2CO3等)的水溶液，调节PH值的范围为5．0～8．5，反应中可加入有机碱，如吡啶，甲基吡啶，三乙胺，二甲基甲酰胺，二甲基亚砜等进行催化，有机碱的加入量与Ar－NH2或Ar’－NH2的摩尔比为0～0．1∶1，反应中用薄层或液相色谱控制，原料消失或接近消失为终点。然后，按通常方法进行盐析，得到ArNHCONHAr’(Ar，Ar’可相同或不同)的产品。
本发明利用BTC替代光气用于水相合成染料及其中间体，可避免光气对生态环境毒害的危险性，反应物投料可以准确计量，BTC为稳定的固体结晶，运输、贮存、使用方便。由于没有光气的逸出问题，因此，BTC的用量一般为理论量或稍过量。节省了资源，达到安全生产，消除了污染，减去了原来有毒尾气复杂的后处理工序及其设备。
实施例1
2克 2－氨基－5－萘酚－7－磺酸 溶于50毫升水中，搅拌，滴加10％氢氧化钠，调节pH值为7，升温至40℃，然后加入0．6克BTC，pH控制7左右，反应8小时，升温至60℃，加食盐15克，继续搅拌半小时，冷却，过滤，得猩红酸2．1克，收率为94％。
实施例2
取 2－萘胺－4，8－二磺酸 与间甲苯胺制得单偶氮染料1．9克，溶于40毫升水中，加入0．3克BTC，pH值控制在7．5左右，室温下反应12小时，然后盐析得(C．I．直接黄50)染料1．6克，收率为85％。
实施例3
取水杨酸与对硝基苯胺重氮化、偶合。还原制得的单偶氮染料1．6克溶于60毫升水中，加入0．7克BTC，PH值控制在7．5左右，室温下反应15小时，然后盐析得染料(C．I．直接黄26)1．2克，收率为80％。
实施例4
取对硝基苯胺邻磺酸重氮化与2－氨基－8－萘酚－6－磺酸偶合后还原制得的单偶氮染料2克，溶于PH值为7的磷酸钠盐体系的缓冲溶液中，加入0．2克BTC，搅拌，控制PH值为7左右，于30℃左右下反应8小时，酸析得染料(C．I．直接红75)1．9克，收率为95％左右。
Claims (2)
1．一种制造染料或其中间体的光气化方法，其特征在于该方法所用的光气化试剂是二－(三氯甲基)碳酸酯(BTC)，在水介质中，用或不用有机碱作催化剂，于0～100℃的反应温度，调节pH值，将含有氨基的芳烃衍生物或偶氮化合物与二－(三氯甲基)碳酸酯按1∶0．17～0．85的摩尔比进行反应，即生成脲类结构的染料或染料中间体。
2．按照权利要求1所述的光气化方法，其特征在于光气化反应时，含氨基的芳烃衍生物或偶氮化合物与二－(三氯甲基)碳酸酯的摩尔比在1∶0．17～0．85，反应温度为0～100℃时，pH值用无机碱调控在5．0～8．5，水介质为磷酸盐或硼酸盐缓冲溶液体系；用有机碱作催化剂，有机碱是吡啶、甲基吡啶、三乙胺、二甲基甲酰胺或二甲基亚砜，含氨基的芳烃衍生物或偶氮化合物与有机碱的摩尔比为1∶0～0．1。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95111869A CN1060194C (zh) | 1995-07-11 | 1995-07-11 | 制造染料或其中间体的光气化方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95111869A CN1060194C (zh) | 1995-07-11 | 1995-07-11 | 制造染料或其中间体的光气化方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1125239A CN1125239A (zh) | 1996-06-26 |
| CN1060194C true CN1060194C (zh) | 2001-01-03 |
Family
ID=5079104
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95111869A Expired - Fee Related CN1060194C (zh) | 1995-07-11 | 1995-07-11 | 制造染料或其中间体的光气化方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1060194C (zh) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100402491C (zh) * | 2006-07-28 | 2008-07-16 | 浙江工业大学 | N-取代氨基苯甲醛类化合物的合成方法 |
| CN106590017A (zh) * | 2016-12-07 | 2017-04-26 | 天津市亚东化工有限公司 | 直接耐晒黄rs染料制备工艺 |
| CN114539804B (zh) * | 2022-03-10 | 2023-12-15 | 浙江闰土染料有限公司 | 红色直接混纺染料的制备方法 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4699628A (en) * | 1985-08-16 | 1987-10-13 | The Atul Products Limited | Process for the preparation of a water soluble direct green polyazo dyestuffs mixture in situ and water soluble direct green polyazo dyestuffs mixture obtained thereby |
-
1995
- 1995-07-11 CN CN95111869A patent/CN1060194C/zh not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4699628A (en) * | 1985-08-16 | 1987-10-13 | The Atul Products Limited | Process for the preparation of a water soluble direct green polyazo dyestuffs mixture in situ and water soluble direct green polyazo dyestuffs mixture obtained thereby |
| EP0253933A1 (en) * | 1985-08-16 | 1988-01-27 | Atul Products Limited | A process for the preparation of a water soluble direct green polyazo dyestuffs mixture in situ and water soluble direct green polyazo dyestuffs mixture obtained thereby |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1125239A (zh) | 1996-06-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4257770A (en) | Disazo dye composition | |
| JPS58160362A (ja) | 反応染料組成物、その製法およびそれを用いる繊維の染色方法 | |
| CN1060194C (zh) | 制造染料或其中间体的光气化方法 | |
| EP0772653B1 (de) | Reaktive azofarbstoffe mit einer kupplungskomponente aus der aminonaphthalinreihe | |
| KR880002292B1 (ko) | 디스아조 화합물의 제조방법 | |
| US4563520A (en) | Metal complexes of dis- or trisazo compounds containing a middle component twice substituted by hydroxy and/or amino | |
| GB1455284A (en) | Process for the preparation of disazo pigments | |
| KR960008248B1 (ko) | 아조 안료의 제조방법 | |
| US5026830A (en) | Process for the preparation of azo dyes by carrying out coupling in the presence of an alkali metal chloride and ammonium chloride | |
| US4996303A (en) | Preparation of 1:2 metal complex dyes by coupling in the presence of a metal donor in an inert gas atmosphere | |
| EP0068245A1 (de) | Sulfonsäuregruppenhaltige Farbstoffe | |
| EP0011873B1 (de) | Polyazofarbstoffe, deren Herstellung und Verwendung zum Färben von Cellulosematerialien | |
| US5962740A (en) | Processes for producing 4,6-bis (substituted)phenylazoresorcinols | |
| US2816884A (en) | Process for the production of aromatic o-hydroxydiazo compounds | |
| US4994561A (en) | Process for the preparation of metallizable azo dyes carrying out coupling in an inert gas atmosphere in the presence of an ammonium salt | |
| CN108299253B (zh) | 具有非线性光学特性的偶氮化合物及其合成方法 | |
| KR100411189B1 (ko) | 비닐설폰 반응기를 갖는 분산 반응성 염료 | |
| US5003051A (en) | Process for the preparation of metallizable monoazo dyes in the presence of ketones | |
| JPH0693197A (ja) | 繊維反応性ホルマザン染料の製法並びにアミノフェノール | |
| CN112110837B (zh) | 一种新型砜苄基化试剂用于合成有机砜分子的方法 | |
| US3684425A (en) | Process for dyeing paper with disazo dyestuffs and compositions therefor | |
| JP5130681B2 (ja) | 反応性アゾ化合物の製造方法と反応性アゾ化合物及びその反応物 | |
| EP0212412A2 (de) | Polyazofarbstoffe | |
| KR840005835A (ko) | 1:2-코발트 착물 아조 염료 및 1:2-크롬 착 아조 염료 혼합물의 제조방법 | |
| KR900008468B1 (ko) | 반응성 흑색염료의 제조방법 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |