非诱变性联苯胺系直接染料的研究
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摘要
联苯胺曾是重要的染料中间体，但是它具有强致癌活性，能导致环境性膀胱癌，自20世纪70年代以来，已被各国禁用。近年来，联苯胺的早期替代品联甲苯胺和联大茴香胺也遭到禁用，因此研制新的非诱变性联苯胺替代品具有重要的意义。
论文中采用在诱变性芳胺的氨基邻位以大体积烷氧基取代的方法来获得非诱变染料中间体，合成了三种非诱变性联苯胺衍生物以及三种间苯二胺衍生物，并用于非诱变染料的研究中。染料的应用性能实验结果表明所合成的染料是C．I．直接黑38的优秀代用染料。论文中同时对影响直接染料直接性的结构因素进行了研究。
论文首先进行了联苯胺的代用研究，从邻硝基氯苯出发，合成了3，3’-二丙氧基联苯胺、3，3’-二丁氧基联苯胺和3，3’-二-β-羟乙氧基联苯胺，其中3，3’-二-β-羟乙氧基联苯胺为首次合成。另外，实验中还对中间产物邻硝基苯基-β-羟乙基醚的工艺条件进行了优化，使产率由文献报导的58％升至78％。所合成的中间体经IR、MS、NMR等手段鉴定了结构。
针对染料合成中的另一潜在毒性的中间体间苯二胺进行了代用研究，由2，4-二硝基氯苯出发，合成了2，4-二氨基苯丙醚、2，4-二氨基苯丁醚和2，4-二氨基-β-羟乙基醚三种非诱变中间体。实验中对亲核取代反应中各反应条件进行了研究，合成这三种化合物的总产率分别为91.0％，90.8％和74.1％，并通过质谱法鉴定产物的结构。
将所合成的中间体用于染料的合成中，以三种3，3’-烷氧基取代联苯胺为重氮组分，间苯二胺或三种2，4-二氨基烷氧基苯为偶合组分，共合成出12只新的非诱变性三偶氮黑色直接染料；同时，也利用4，4’-二氨基苯甲酰替苯胺、4，4’-二氨基二苯脲和DSD酸为重氮组分合成出三只非诱变黑色三偶氮染料。所有这15只染料均是C．I．直接黑38的衍生物。利用简单的硅胶柱色谱法，实现了所合成的三偶氮染料的纯化工作，使染料的纯度达到85％以上，并利用质谱法鉴定了
染料的结构，同时确定了反应过程中主要副产物的结构及其形成机理。
测定了所合成15只三偶氮黑色直接染料的染色性能，并与绿光黑色的C．1．
直接黑38相对比。分别测定了这些染料的水洗牢度、耐晒牢度、上染速率曲线
并对所染的个样进行了测色，实验表明，利用烷氧基联苯胺所合成的染料在色
光和牢度上与C．1．直接黑38类似，上染率略低，为绿光黑色染料，尤其是由3，3－
H下一羟乙氧基联苯敬所合成的染料，是C．1．直接黑38优良的代用品。由4，4’一
二氨基苯甲酸替苯脑和4，4’一二氨基二苯源所合成的染料为红光黑色染料，色光
上不如 C，1．直接黑 38及烷氧基取代联苯胺所合成的染料。由 DSD酸合成的染料
上染率为29．l％，不适于代用＊上直接黑38。
利用分子力学计算程序PCMODEL，研究了影响这些直接染料直接性的关键
结构因素。所研究的八种中；司体与H一酸所合成的对称双偶氮染料的直接性大小
次序为：联苯胺＞3．丁一二羟乙氧基联苯胺＞4，个一二氨基二苯晚＞3，T一二丙氧基
联苯胺＞3丁一二丁氧基联苯胺＞个4’一二氨基苯甲飘香苯胺＞＊D酸＞八个一二
氨基苯磺酚替苯胺。计算结果表明，范德华力在染料对纤维素纤维的直接性中
起主要作用，但是，必须同时考虑疏水性基团、来水性基团以及染料的立体结
构对直接性的影响。三种烷氧基取代联苯胺所合成染料的上染率较联苯胺染料
低的原因在于疏水基团的引入导致染色的嫡变增加，从而降低了染色亲和力；
DSD酸染料则是由于亲水性基团磺酸基数目的增加降低了染料的直接性；对于
4，4’一二氨基苯甲酸替苯胺、4，4’一二氨基二本脉和 4，4’一二氨基苯磺酚替苯胺所合
成的染料，它们分子中的芳环不能形成共平面结构，致使染料与纤维间的分子
间作用力降低，而且分子偏离共平面的程度越大，直接性也越低。
Benzidine used to be one of the most important dye intermediates. It was banned from use since 1970s because of its strong mutagenic activities. Recent years, the formerly studied substitute of benzidine, 3,3'-dimethylbenzidine and 3,3'-dimethoxybenzidine were also banned since 1995. So, it is very important to find another substitutes.
In this paper, the mutagencity of the diamines is removed by incorporating huge alkoxyl substituents ortho to the amine groups, and these nonmutagenic diamines are used in the synthesis of nonmutagenic dyes. The influences of the dyes structure to substantivity are also studied.
Firstly, the nonmutagenic 3,3'-dialkoxybenzidine are synthesized in 3 steps from o-nitrochlorobenzene. namely alkaline hydrolysis, nucleophilic substitute reaction and benzidine arrangement. Totally three diamines are synthesized, and the yield of 3,3'-dipropoxybenzidine, 3,3'-dibutoxybenzidine and 3,3'-di~p-hydroxy-ethoxybenzidine are 53%, 58% and 51% based on the corresponding nitro compounds, respectively. The process for the synthesis of o-nitrobenzenyl-|3-hydroxyethyl ether is optimized by orthogonal experiment, and the yield was raised from 58% to 78%. The structure of all these compounds is determined by IR, MS and NMR method.
Then three nonmutagenic derivatives of meta-phenylenediamine, a potential mutagenic diamine, is synthesized in 2 steps from 2,4-dinitrochlorobenzene, namely nucleophilic substitute reaction and catalytic hydrogenation. The yield of 2, 4-diamino-l-n-propoxybenzene, 2, 4-diamino-l-n-butoxybenzene and 2, 4-diamino-P-hydroxyethoxybenzene based on l-chloro-2,4-dinitrobenzene are 91.0%, 90.8% and 74.1% respectively. The structures of them are determined by MS spectrum.
Using above mentioned three 3,3'-dialkoxybenzidine as diazo components, and three 2.4-diamino-l-alkoxylbenzene as coupling component, totally 12 new greenish black trisazo direct dyes are synthesized which are the analogues of C.I.direct black
38. At the same time, three other black trisazo direct dyes sunthesized from three bridged diamines, 4,4'-diaminobenzanilide, N,N'-di-(4-aminophenyl)-urea and 4,4'-diamino- 2,2'-stilbenzene disulfonic acid (DSD acid), are synthesized. All of these dyes are nonmutagenic dyes and hopeful substitutes for C.I. direct black 38.
After the synthesis of dyes, the purification process are performed on a silicagel chromatography column and obtained the dye with 85% purity. The structure of the dyes are determined by MS spectrum, so does one major by-product. The formation mechanism of this by-product is also discussed.
The applied performances of all these fifteen trisazo black dyes are measured and compared with C.I. direct black 38. The experiment shows that the light fastness and washing fastness of the dyes using 3,3'-alkoxybenzidine as diazo components is similar with C.I. direct black 38, while the exhaustion degree is a little lower than it. Such dyes' color is greenish black and very similar with C.I. direct black 38, among which the dyes derived from 3,3'-di-(3-hydroxy-ethoxybenzidine are especially well in that its exhaustion degree is only 7.1% lower than C.I. direct black 38. The dyes derived from 4,4'-diaminobenzanilide and N,N'-di-(4-aminophenyl)-urea are reddish black and not as good as C.I. direct black 38 and the' dyes derived from 3,3'-dialkoxybenzene. The exhaustion degree of the dye synthesized from DSD acid is only 29.1% and not suitable as substitute of C.I. direct black 38.
Finally, the influences of the dyes structure to substantivity are studied by molecular mechanics program PCMODEL. The dyes used in the experiment are symmetric diazo dyes using benzidine, three 3,3'-dialkoxybenzidine, 4,4'-diamino-benzanilide, N,N'-di-(4-aminophenyl)-urea, DSD acid and 4,4'-diamino-benzenesulfonamide as dizao components and H-acid as coupling component. The subtantivity sequence of these eight dyes derived from the eight diamines is as follows: benzidine> 3,3'-di-p-hydroxyethoxybenzidine> N,N'-di-
(4-aminophenyl)-urea> 3,3'-diprop
论文中采用在诱变性芳胺的氨基邻位以大体积烷氧基取代的方法来获得非诱变染料中间体，合成了三种非诱变性联苯胺衍生物以及三种间苯二胺衍生物，并用于非诱变染料的研究中。染料的应用性能实验结果表明所合成的染料是C．I．直接黑38的优秀代用染料。论文中同时对影响直接染料直接性的结构因素进行了研究。
论文首先进行了联苯胺的代用研究，从邻硝基氯苯出发，合成了3，3’-二丙氧基联苯胺、3，3’-二丁氧基联苯胺和3，3’-二-β-羟乙氧基联苯胺，其中3，3’-二-β-羟乙氧基联苯胺为首次合成。另外，实验中还对中间产物邻硝基苯基-β-羟乙基醚的工艺条件进行了优化，使产率由文献报导的58％升至78％。所合成的中间体经IR、MS、NMR等手段鉴定了结构。
针对染料合成中的另一潜在毒性的中间体间苯二胺进行了代用研究，由2，4-二硝基氯苯出发，合成了2，4-二氨基苯丙醚、2，4-二氨基苯丁醚和2，4-二氨基-β-羟乙基醚三种非诱变中间体。实验中对亲核取代反应中各反应条件进行了研究，合成这三种化合物的总产率分别为91.0％，90.8％和74.1％，并通过质谱法鉴定产物的结构。
将所合成的中间体用于染料的合成中，以三种3，3’-烷氧基取代联苯胺为重氮组分，间苯二胺或三种2，4-二氨基烷氧基苯为偶合组分，共合成出12只新的非诱变性三偶氮黑色直接染料；同时，也利用4，4’-二氨基苯甲酰替苯胺、4，4’-二氨基二苯脲和DSD酸为重氮组分合成出三只非诱变黑色三偶氮染料。所有这15只染料均是C．I．直接黑38的衍生物。利用简单的硅胶柱色谱法，实现了所合成的三偶氮染料的纯化工作，使染料的纯度达到85％以上，并利用质谱法鉴定了
染料的结构，同时确定了反应过程中主要副产物的结构及其形成机理。
测定了所合成15只三偶氮黑色直接染料的染色性能，并与绿光黑色的C．1．
直接黑38相对比。分别测定了这些染料的水洗牢度、耐晒牢度、上染速率曲线
并对所染的个样进行了测色，实验表明，利用烷氧基联苯胺所合成的染料在色
光和牢度上与C．1．直接黑38类似，上染率略低，为绿光黑色染料，尤其是由3，3－
H下一羟乙氧基联苯敬所合成的染料，是C．1．直接黑38优良的代用品。由4，4’一
二氨基苯甲酸替苯脑和4，4’一二氨基二苯源所合成的染料为红光黑色染料，色光
上不如 C，1．直接黑 38及烷氧基取代联苯胺所合成的染料。由 DSD酸合成的染料
上染率为29．l％，不适于代用＊上直接黑38。
利用分子力学计算程序PCMODEL，研究了影响这些直接染料直接性的关键
结构因素。所研究的八种中；司体与H一酸所合成的对称双偶氮染料的直接性大小
次序为：联苯胺＞3．丁一二羟乙氧基联苯胺＞4，个一二氨基二苯晚＞3，T一二丙氧基
联苯胺＞3丁一二丁氧基联苯胺＞个4’一二氨基苯甲飘香苯胺＞＊D酸＞八个一二
氨基苯磺酚替苯胺。计算结果表明，范德华力在染料对纤维素纤维的直接性中
起主要作用，但是，必须同时考虑疏水性基团、来水性基团以及染料的立体结
构对直接性的影响。三种烷氧基取代联苯胺所合成染料的上染率较联苯胺染料
低的原因在于疏水基团的引入导致染色的嫡变增加，从而降低了染色亲和力；
DSD酸染料则是由于亲水性基团磺酸基数目的增加降低了染料的直接性；对于
4，4’一二氨基苯甲酸替苯胺、4，4’一二氨基二本脉和 4，4’一二氨基苯磺酚替苯胺所合
成的染料，它们分子中的芳环不能形成共平面结构，致使染料与纤维间的分子
间作用力降低，而且分子偏离共平面的程度越大，直接性也越低。
Benzidine used to be one of the most important dye intermediates. It was banned from use since 1970s because of its strong mutagenic activities. Recent years, the formerly studied substitute of benzidine, 3,3'-dimethylbenzidine and 3,3'-dimethoxybenzidine were also banned since 1995. So, it is very important to find another substitutes.
In this paper, the mutagencity of the diamines is removed by incorporating huge alkoxyl substituents ortho to the amine groups, and these nonmutagenic diamines are used in the synthesis of nonmutagenic dyes. The influences of the dyes structure to substantivity are also studied.
Firstly, the nonmutagenic 3,3'-dialkoxybenzidine are synthesized in 3 steps from o-nitrochlorobenzene. namely alkaline hydrolysis, nucleophilic substitute reaction and benzidine arrangement. Totally three diamines are synthesized, and the yield of 3,3'-dipropoxybenzidine, 3,3'-dibutoxybenzidine and 3,3'-di~p-hydroxy-ethoxybenzidine are 53%, 58% and 51% based on the corresponding nitro compounds, respectively. The process for the synthesis of o-nitrobenzenyl-|3-hydroxyethyl ether is optimized by orthogonal experiment, and the yield was raised from 58% to 78%. The structure of all these compounds is determined by IR, MS and NMR method.
Then three nonmutagenic derivatives of meta-phenylenediamine, a potential mutagenic diamine, is synthesized in 2 steps from 2,4-dinitrochlorobenzene, namely nucleophilic substitute reaction and catalytic hydrogenation. The yield of 2, 4-diamino-l-n-propoxybenzene, 2, 4-diamino-l-n-butoxybenzene and 2, 4-diamino-P-hydroxyethoxybenzene based on l-chloro-2,4-dinitrobenzene are 91.0%, 90.8% and 74.1% respectively. The structures of them are determined by MS spectrum.
Using above mentioned three 3,3'-dialkoxybenzidine as diazo components, and three 2.4-diamino-l-alkoxylbenzene as coupling component, totally 12 new greenish black trisazo direct dyes are synthesized which are the analogues of C.I.direct black
38. At the same time, three other black trisazo direct dyes sunthesized from three bridged diamines, 4,4'-diaminobenzanilide, N,N'-di-(4-aminophenyl)-urea and 4,4'-diamino- 2,2'-stilbenzene disulfonic acid (DSD acid), are synthesized. All of these dyes are nonmutagenic dyes and hopeful substitutes for C.I. direct black 38.
After the synthesis of dyes, the purification process are performed on a silicagel chromatography column and obtained the dye with 85% purity. The structure of the dyes are determined by MS spectrum, so does one major by-product. The formation mechanism of this by-product is also discussed.
The applied performances of all these fifteen trisazo black dyes are measured and compared with C.I. direct black 38. The experiment shows that the light fastness and washing fastness of the dyes using 3,3'-alkoxybenzidine as diazo components is similar with C.I. direct black 38, while the exhaustion degree is a little lower than it. Such dyes' color is greenish black and very similar with C.I. direct black 38, among which the dyes derived from 3,3'-di-(3-hydroxy-ethoxybenzidine are especially well in that its exhaustion degree is only 7.1% lower than C.I. direct black 38. The dyes derived from 4,4'-diaminobenzanilide and N,N'-di-(4-aminophenyl)-urea are reddish black and not as good as C.I. direct black 38 and the' dyes derived from 3,3'-dialkoxybenzene. The exhaustion degree of the dye synthesized from DSD acid is only 29.1% and not suitable as substitute of C.I. direct black 38.
Finally, the influences of the dyes structure to substantivity are studied by molecular mechanics program PCMODEL. The dyes used in the experiment are symmetric diazo dyes using benzidine, three 3,3'-dialkoxybenzidine, 4,4'-diamino-benzanilide, N,N'-di-(4-aminophenyl)-urea, DSD acid and 4,4'-diamino-benzenesulfonamide as dizao components and H-acid as coupling component. The subtantivity sequence of these eight dyes derived from the eight diamines is as follows: benzidine> 3,3'-di-p-hydroxyethoxybenzidine> N,N'-di-
(4-aminophenyl)-urea> 3,3'-diprop
引文
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