有机化学英文文献翻译

有机化学英文文献翻译
有机化学英文文献翻译

对称八溴代酞菁的合成及其特征

K.R. Venugopala Reddy a,*, J. Keshavayya b

a Department of Studies in Industrial Chemistry, Kuvempu University,

Jnanasahyadri, Shankaraghatta - 577 451Shimoga District,Karnataka, India

b Department of Studies in Chemistry, Kuvempu University,

Jnanasahyadri, Shankaraghatta - 577 451Shimoga District,Karnataka, India

Received 5 November 2001; received in revised form 14 December 2001;

accepted 18 January 2002

* Corresponding author. Tel.: +91-08282-56225; fax: +91-08282-37255.

E-mail address: universitysancharnet.in (K.R. Venugopala Reddy).

摘要

现在已经提出一条既方便又简单合成对称1,3,8,10,15,17,22,24-溴代金属—Cu,Co,Ni,Zn酞菁颜料的路线。金属酞菁是由相应的八氨基取代酞菁合成的。合成的化合物经过元素分析、电子光谱、红外光谱、磁性测试、粉末X射线衍射实验和热重研究来评估其热稳性、结晶度、结构完整性和纯度。经过讨论和分析发现取代基对于电子光谱的影响及轨道对磁矩的贡献远远超过了电子场强的影响。

关键词:酞菁八取代合成热度电子的颜料和染料

1.引言

酞菁在近几年引起广泛的关注不仅是因为酞菁的结构同一些能够维持生命的重要分

子如叶绿素、血红素相似,而且它具有显著的上色功能。这些颜料是被稳定在一些通过在酞菁环外围引入一些合适的取代基的多晶转变体上。卤素取代的金属酞菁颜料在商业上用于颜料及滤色片[1]等的制造。由于酞菁普遍具有共轭芳香基团的发色基,所以在蓝绿色上有着非常高的吸收系数。总之,所有的酞菁都有四苯并四氮杂卟啉结构作为发色基。

由于金属酞菁的着色能力和其华丽的色彩使其在颜料及染料[2]制造业中占有重要的地位。他们对光、热、酸及碱有着显著地稳定性。以上一系列化合物不溶于水和大部分有机溶剂,并被广泛用于制造印刷用油墨、颜料、涂料和塑料。酞菁被用来做彩色打印机和激光打印机[3]的碳粉。酞菁颜料也被用作液晶显示器的滤光镜。一篇文献研究表明合成氯代十六烷、溴代十六烷、碘代十六烷和混合卤代金属酞菁的方法和那些颜料主要用于商业目的[4]。大多数的合成流程都是有文献专利的因为不能通用。关于对称四取代2,9,16,23和1,8,15,22,-溴代金属酞菁的合成和结构的研究报道是可用的[5,6]。但是,关于对称八取代1,3,8,10,15,17,22,24-溴代金属酞菁的合成和结构的研究报道是没有可通用的。基于以上事实,我们开始从事对标题化合物的合成及结构的研究。

在过去的一些文献中我们讨论了关于对称取代1,3,8,10,15,17,22,24-八溴代金属酞菁的合成和结构的研究。文中所提到的工艺经过了适当的改良并应用到合成标题化合物中[5]。1,3,8,10,15,17,22,24位置上的酞菁的主要部分的π电子体系的溴代取代效应和随之引起的电子光谱、热性能、红外光谱和结晶度的数据都在讨论中。

2.实验

在其他地方报道过制备1,3,8,10,15,17,22,24-八氨基取代酞菁的工艺流程[7]。氨基化合物通过改良后的桑德麦尔反应转化为相应的溴代衍生物[8]。合成

1,3,8,10,15,17,22,24-八溴代酞菁的路线如图一所示。所有化学试剂皆为分析纯。

2.1 1,3,8,10,15,17,22,24-八溴代酞菁铜(Ⅱ)颜料的制备

1,3,8,10,15,17,22,24-八氨基酞菁铜(Ⅱ)(5g)与HCl中偶合得到酞菁铜的重氮盐CuPON2+Cl-。并将混合物保存在碎冰中使温度在5℃以下。

将五水硫酸铜(19.6g)和二水溴化钠(11.3g)溶解于50ml的水中,将亚硫酸氢钠(5.12g 溶于30ml水中)缓慢加入上述溶液中并不断搅拌,直至室温。用少量亚硫酸洗涤三次所得沉淀物。将溴化亚铜溶解于20ml48%的HBr中。再将1,3,8,10,15,17,22,24-八溴代酞菁铜(Ⅱ)的冷藏溶液缓慢倒入溴化钠中,并搅拌。由于副产物重氮盐和溴化亚铜的分离,混合物开始变浑浊(CuPON2+Cl_,CuBr)。加成物要不断振荡直至室温。然后水浴加热到60℃使其完成重盐的裂解并且一直加热到没有氮气生成。

倾析得到澄清溶液,并用水冲洗残留物。将绿色产物离心分离并分别用1M NaOH和1M

HCl洗涤四次,最后用蒸馏水清洗。固体1,3,8,10,15,17,22,24-八溴代酞菁铜(Ⅱ)在50℃下干燥一1h。颜料粉末是通过酸附着过程得到的,即一份粉末溶于6-10份的浓硫酸中。将混合物静止1-2h,然后放进冰块中并搅拌彻底。得到颜料并用热水冲洗。最后重复用纯酒精洗涤并放在真空干燥器中干燥2天[9]。这种方法是用于Cu(Ⅱ),Co(Ⅱ)和Ni(Ⅱ),但是Zn(Ⅱ)要经历金属移除反应。

Ni(Ⅱ)、Co(Ⅱ)和Zn(Ⅱ)的八溴代酞菁衍生物是分别通过各自的金属氨基酞菁衍生物用上述方法制备的。

在印度昌迪加尔的旁遮普大学的精细仪器中心对C、H、N做了元素分析。对磁性的研究是在室温下通过Gouy磁天平法即包括NP-53型电磁体和半微量天平进行研究的。Pacal 常数是用来计算抗磁修正的。Hg [Co (SCN)4] 化合物作为岛津紫外可见分光光度计的校准物[10],UV-160A使用来研究电子吸收光谱。红外光谱是通过Nicolet MX-FT红外分光仪测量的。PW1710X-ray 衍射仪是用来研究化合物衍射部分的。光谱是在40Kv,20mA,7mm宽的孔道且图表速度为10mm/min进行记录的。TGA/SDTA热分析仪是用来研究热分解的。3.结果与讨论

由于金属原子半径非常接近于1.35A所以形成的金属酞菁化合物具有热稳定性和抗酸腐蚀性。八溴代酞菁Cu(Ⅱ)、Zn(Ⅱ)和Co(Ⅱ)衍生物制备完毕,且都为深绿色,但是只有Zn带有些许棕色。它们浓硫酸中为澄清溶液也完全溶于DMSO、DMF和吡啶中,但是不溶于水及大部分有机溶液如乙醇、乙醚、四氯化碳和苯中。对C、H、N及金属的分析结果如表一所示。

4.红外光谱

红外光谱红外数据记录总结在表2中,光谱为图2。所有化合物在3394-3410cm-1上有宽峰吸收,即显示出酞菁高分子中的氮氢键[11]。在1533-1613cm-1处有尖锐的峰行,即表示出有碳碳双键存在。在1341-1352cm-1处有吸收峰是因为碳氮键的存在。在752-757cm-1处

有吸收峰是因为碳溴键的伸缩频率。剩下的吸收峰是由于酞菁骨架振动引起的[12]。

5.磁性

磁性和磁矩都是在化合物为固态情况下测量的,数据显示CuPOBr和CoPOBr为顺磁性的,ZnPOBr为逆磁性的。CuPOBr和CoPOBr的磁矩比未成对电子的要高。高出来的大概是由于简并轨道的贡献。这种轨道作用会随电子磁场的增强而增加。只有在高电子磁场下化合物的磁矩与自旋对应。CuPOBr和CoPOBr在u eff上的较高的数据可能是因为在π电子云下分子间的磁性各向异性[12.13]。

人们可能注意从Xm和u eff的变化趋势注意到CoPOBr中相邻金属原子的自旋偶合和在CuPOBr的酞菁分子中氮原子的超交换[13.14]。

由于酞菁环上[15.16]的金属轨道和π轨道的相互作用,在高电子场中发现了预期中的CuPOBr和CoPOBr的数值比未取代的酞菁要高。但是得到的数据并不与原来的未取代的金属酞菁相符合[17]。这个可能是占主导地位的阻碍叠加超过预期中的功能团的霍尔迁移。

6.电子光谱

溴代酞菁是在18M的硫酸中进行电子光谱测量,且浓度围为5.1-5.2×10-4M。数据记录总结在表2中。所有化合物的峰值都在611-647nm的围,此围为酞菁特征峰值。在224-231nm 上的波峰显示有碳键。所有的化合物在471-482nm上的波峰为a2u-e g的贡献。

7.X射线衍射分析

Cu(Ⅱ)、Co(Ⅱ)、Ni(Ⅱ)、Zn(Ⅱ)的酞菁粉末衍射是在2θ,6-70°下显示出与弱结晶性相符的显著的特点。人们能在图3明显的观察到在未取代的金属酞菁的峰值面积会扩大。这显示出标题化合物比未取代的金属酞菁的结晶度要小。这可能是因为体积较为庞大的溴原子在堆积金属酞菁的衍生物中占了主导地位。粉末X射线衍射结果只能定性的解释结晶度。溴取代的效果可能在第一个d数据中显示出来。

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