技术领域technical field
本发明涉及一种疏基化合物中间体的制备方法，具体涉及一种制备1-巯基芘及其中间体化合物的合成方法。The invention relates to a method for preparing a mercapto compound intermediate, in particular to a method for preparing 1-mercaptopyrene and its intermediate compound.
背景技术Background technique
疏基化合物的用途广泛，是重要的化工原料和重要的医药中间体，可用做药物、农药及除草剂的中间体，可做解毒剂，橡胶硫化促进剂。巯基是很强的亲核基团，可作为有机反应的重要官能团。此外，巯基可与某些重金属离子有很强的络合作用。同时芘基化合物被广泛用于分子探针、有机发光二极管、有机太阳能电池等光电功能材料和生物科学领域。因此，巯基芘在分子光电功能材料和生物探针材料等新材料领域具有广泛重要的用途。但目前，巯基芘在国内外尚未商业销售，主要是缺乏简便有效的合成方法。Sulfhydryl compounds have a wide range of uses, and are important chemical raw materials and important pharmaceutical intermediates. They can be used as intermediates of drugs, pesticides and herbicides, antidotes, and rubber vulcanization accelerators. Sulfhydryl is a strong nucleophilic group and can be used as an important functional group in organic reactions. In addition, mercapto groups can have strong complexation with certain heavy metal ions. At the same time, pyrene-based compounds are widely used in photoelectric functional materials such as molecular probes, organic light-emitting diodes, organic solar cells, and biological sciences. Therefore, mercaptopyrene has a wide range of important applications in the field of new materials such as molecular optoelectronic functional materials and biological probe materials. But at present, mercaptopyrene has not been commercially sold at home and abroad, mainly due to the lack of simple and effective synthesis methods.
发明内容Contents of the invention
本发明的目的是要提供一种制备1-巯基芘及其中间体化合物的合成方法，解决巯基芘不能简便有效的合成问题。The purpose of the present invention is to provide a kind of synthetic method for preparing 1-mercaptopyrene and its intermediate compound, to solve the simple and effective synthesis problem of mercaptopyrene.
本发明的目的是这样实现的：首先合成1-巯基芘中间体O-1-芘基二甲氨基硫代甲酸酯，然后利用重排反应，生成1-巯基芘中间体S-1-芘基二甲氨基硫代甲酸酯，再水解形成1-巯基芘。The object of the present invention is achieved like this: first synthesize 1-mercaptopyrene intermediate O-1-pyrene dimethylcarbamate, then utilize rearrangement reaction to generate 1-mercaptopyrene intermediate S-1-pyrene Dimethylcarbamate, which is then hydrolyzed to form 1-mercaptopyrene.
所述的1-巯基芘及1-巯基芘中间体化合物的反应式表示如下：The reaction formula of described 1-mercaptopyrene and 1-mercaptopyrene intermediate compound is expressed as follows:
具体方法如下：The specific method is as follows:
1-巯基芘中间体O-1-芘基二甲氨基硫代甲酸酯的合成：Synthesis of 1-mercaptopyrene intermediate O-1-pyrenyl dimethylcarbamate:
在氮气保护下，1-羟基芘溶于N,N-二甲基甲酰胺（DMF），冷却到0～5℃，缓慢加入质量分数为60%的氢化钠，搅拌反应30分钟；加入二甲氨基硫代甲酰氯（DMTCC），升温至80℃；再加入适量碳酸钾，继续反应30小时，冷却，过滤未反应的碳酸钾；加入大量水，产生黄色沉淀，过滤，甲醇重结晶，得黄色的1-巯基芘中间体O-1-芘基二甲氨基硫代甲酸酯，收率为98.0%。Under the protection of nitrogen, dissolve 1-hydroxypyrene in N,N-dimethylformamide (DMF), cool to 0-5°C, slowly add sodium hydride with a mass fraction of 60%, and stir for 30 minutes; add dimethyl Aminothioformyl chloride (DMTCC), heat up to 80°C; add an appropriate amount of potassium carbonate, continue to react for 30 hours, cool, filter unreacted potassium carbonate; add a large amount of water, a yellow precipitate occurs, filter, recrystallize methanol, and get yellow The 1-mercaptopyrene intermediate O-1-pyrenyl dimethylcarbamate, the yield is 98.0%.
1-巯基芘中间体O-1-芘基二甲氨基硫代甲酸酯的分子结构和晶体结构：Molecular structure and crystal structure of 1-mercaptopyrene intermediate O-1-pyrenyl dimethylcarbamate:
该化合物晶体数据，晶系：单斜；空间群：P21；分子式：C19H15ONS；分子量：305.38；晶胞参数：α=90.00°,γ=90.00°；晶胞体积：温度：296(2)K；晶胞密度：1.344g cm–3；结构因子（F(000)）：1280；吸收因子：0.215mm–1；可观测衍射点的S值（GOF on F2）：1.021；结果因子[I>2sigma(I)]：R1=0.0774,wR2=0.1020。熔点137～139℃。Crystal data of the compound, crystal system: monoclinic; space group: P21 ; molecular formula: C19 H15 ONS; molecular weight: 305.38; unit cell parameters: α=90.00°, γ=90.00°; unit cell volume: Temperature: 296(2)K; Unit cell density: 1.344g cm–3 ; Structure factor (F(000)): 1280; Absorption factor: 0.215mm–1 ; S value of observable diffraction point (GOF on F2 ) : 1.021; Outcome factor [I>2sigma(I)]: R1 =0.0774, wR2 =0.1020. The melting point is 137-139°C.
1-巯基芘中间体S-1-芘基二甲氨基硫代甲酸酯的合成：Synthesis of 1-mercaptopyrene intermediate S-1-pyrenyl dimethylcarbamate:
将干燥结晶态的O-1-芘基二甲氨基硫代甲酸酯加入到不锈钢反应釜内，存在或缺失溶剂，氮气保护条件下，温度快速升至260～290℃，反应45～100分钟，经柱层析分离得1-巯基芘中间体S-1-芘基二甲氨基硫代甲酸酯，收率为40.0～87.2%。Add dry crystalline O-1-pyrenyldimethylcarbamate into a stainless steel reaction kettle with or without solvent, and under nitrogen protection, the temperature rises rapidly to 260-290°C and reacts for 45-100 minutes , and separated by column chromatography to obtain 1-mercaptopyrene intermediate S-1-pyrenyl dimethylcarbamate with a yield of 40.0-87.2%.
1-巯基芘中间体S-1-芘基二甲氨基硫代甲酸酯的分子结构和晶体结构：Molecular structure and crystal structure of 1-mercaptopyrene intermediate S-1-pyrenyl dimethylcarbamate:
该化合物晶体数据，晶系：正交；空间群：Pbca；分子式：C19H15ONS；分子量：305.38；晶胞参数：晶胞参数：α=90.00°,β=90.00°,γ=90.00°；晶胞体积：温度：123(2)K；晶胞密度：1.363g cm–3；结构因子（F(000)）：2560；吸收因子：0.218mm–1；可观测衍射点的S值（GOF on F2）：0.957；结果因子[I>2sigma(I)]：R1=0.0690,wR2=0.1077。熔点131～134℃。Crystal data of the compound, crystal system: Orthogonal; space group: Pbca; molecular formula: C19 H15 ONS; molecular weight: 305.38; unit cell parameters: unit cell parameters: α=90.00°, β=90.00°, γ=90.00°; unit cell volume: Temperature: 123(2)K; Unit cell density: 1.363g cm–3 ; Structure factor (F(000)): 2560; Absorption factor: 0.218mm–1 ; S value of observable diffraction point (GOF on F2 ) : 0.957; Outcome factor [I>2sigma(I)]: R1 =0.0690, wR2 =0.1077. The melting point is 131-134°C.
1-巯基芘的合成：Synthesis of 1-mercaptopyrene:
在氮气保护下，在水和乙二醇的混合溶液（1:7体积比）中加入氢氧化钾，再加入S-芘-1-基二甲基氨基甲硫酸酯，回流1.5小时；完全冷却后，将反应溶液倾入冰水中，加氯仿振荡，弃去氯仿层，水层用质量分数5%的稀盐酸小心酸化，再用氯仿提取，蒸干后得到黄色的1-巯基芘，收率为86.5%。Under nitrogen protection, add potassium hydroxide to a mixed solution of water and ethylene glycol (1:7 volume ratio), then add S-pyrene-1-yldimethylcarbamate, and reflux for 1.5 hours; completely cool Finally, the reaction solution was poured into ice water, chloroform was added to shake, and the chloroform layer was discarded. The aqueous layer was acidified carefully with 5% dilute hydrochloric acid, extracted with chloroform, and evaporated to dryness to obtain yellow 1-mercaptopyrene. The yield was was 86.5%.
1-巯基芘含有芘基发光基团和巯基官能团，分子结构如下：1-Mercaptopyrene contains a pyrenyl luminescent group and a mercapto functional group, and its molecular structure is as follows:
熔点86～89℃。The melting point is 86-89°C.
有益效果，由于采用了上述方案，1-巯基芘合成比较简便，操作简单，收率高（全收率可达到73.9%），可用于实验室制备和较大规模的生产。首先利用简单的亲核取代反应高收率的合成O-1-芘基二甲氨基硫代甲酸酯；其次利用著名的Newman-Kwart重排反应合成了S-1-芘基二甲氨基硫代甲酸酯；最后基于传统的水解反应合成了1-巯基芘。Beneficial effect, due to the adoption of the above scheme, the synthesis of 1-mercaptopyrene is relatively simple, easy to operate, and the yield is high (the total yield can reach 73.9%), which can be used for laboratory preparation and large-scale production. First, a simple nucleophilic substitution reaction was used to synthesize O-1-pyrenyl dimethylaminothiocarbamate in high yield; secondly, S-1-pyrenyl dimethylaminothiocarbamate was synthesized by using the famous Newman-Kwart rearrangement reaction Substituted formate; Finally, 1-mercaptopyrene was synthesized based on the traditional hydrolysis reaction.
优点：采用本方案合成1-巯基芘及其中间体具有副反应少，收率高，容易分离纯化，反应时间短，反应操作简单，可放大规模化生产等优点。此外，完全可用于合成2-巯基芘和4-巯基芘。Advantages: The method for synthesizing 1-mercaptopyrene and its intermediates has the advantages of few side reactions, high yield, easy separation and purification, short reaction time, simple reaction operation, and large-scale production. In addition, it can be used in the synthesis of 2-mercaptopyrene and 4-mercaptopyrene.
附图说明Description of drawings
图1为本发明的反应方程式图。Fig. 1 is the reaction equation figure of the present invention.
具体实施方式Detailed ways
下面通过实例详述本发明，然而，本发明不限于下述的实施例。The present invention is described in detail below by examples, however, the present invention is not limited to the following examples.
实施例1首先合成1-巯基芘中间体O-1-芘基二甲氨基硫代甲酸酯，然后利用重排反应，生成1-巯基芘中间体S-1-芘基二甲氨基硫代甲酸酯，再水解形成1-巯基芘。Example 1 First synthesize 1-mercaptopyrene intermediate O-1-pyrenyl dimethylaminothiocarbamate, and then use rearrangement reaction to generate 1-mercaptopyrene intermediate S-1-pyrenyl dimethylaminothiocarbamate Formate, and then hydrolyzed to form 1-mercaptopyrene.
所述的1-巯基芘及1-巯基芘中间体化合物的反应式表示如下：The reaction formula of described 1-mercaptopyrene and 1-mercaptopyrene intermediate compound is expressed as follows:
具体方法如下：The specific method is as follows:
1-巯基芘中间体O-1-芘基二甲氨基硫代甲酸酯的合成：Synthesis of 1-mercaptopyrene intermediate O-1-pyrenyl dimethylcarbamate:
在氮气保护下，1-羟基芘溶于N,N-二甲基甲酰胺（DMF），冷却到0～5℃，缓慢加入质量分数为60%的氢化钠，搅拌反应30分钟；加入二甲氨基硫代甲酰氯（DMTCC），升温至80℃；再加入适量碳酸钾，继续反应30小时，冷却，过滤未反应的碳酸钾；加入大量水，产生黄色沉淀，过滤，甲醇重结晶，得黄色的1-巯基芘中间体O-1-芘基二甲氨基硫代甲酸酯，收率为98.0%。Under the protection of nitrogen, dissolve 1-hydroxypyrene in N,N-dimethylformamide (DMF), cool to 0-5°C, slowly add sodium hydride with a mass fraction of 60%, and stir for 30 minutes; add dimethyl Aminothioformyl chloride (DMTCC), heat up to 80°C; add an appropriate amount of potassium carbonate, continue to react for 30 hours, cool, filter unreacted potassium carbonate; add a large amount of water, a yellow precipitate occurs, filter, recrystallize methanol, and get yellow The 1-mercaptopyrene intermediate O-1-pyrenyl dimethylcarbamate, the yield is 98.0%.
1-巯基芘中间体O-1-芘基二甲氨基硫代甲酸酯的分子结构和晶体结构：Molecular structure and crystal structure of 1-mercaptopyrene intermediate O-1-pyrenyl dimethylcarbamate:
该化合物晶体数据，晶系：单斜；空间群：P21；分子式：C19H15ONS；分子量：305.38；晶胞参数：α=90.00°,β=90.702(4)°,γ=90.00°；晶胞体积：温度：296(2)K；晶胞密度：1.344g cm–3；结构因子（F(000)）：1280；吸收因子：0.215mm–1；可观测衍射点的S值（GOF on F2）：1.021；结果因子[I>2sigma(I)]：R1=0.0774,wR2=0.1020。熔点137～139℃。Crystal data of the compound, crystal system: monoclinic; space group: P21 ; molecular formula: C19 H15 ONS; molecular weight: 305.38; unit cell parameters: α=90.00°, β=90.702(4)°, γ=90.00°; unit cell volume: Temperature: 296(2)K; Unit cell density: 1.344g cm–3 ; Structure factor (F(000)): 1280; Absorption factor: 0.215mm–1 ; S value of observable diffraction point (GOF on F2 ) : 1.021; Outcome factor [I>2sigma(I)]: R1 =0.0774, wR2 =0.1020. The melting point is 137-139°C.
1-巯基芘中间体S-1-芘基二甲氨基硫代甲酸酯的合成：Synthesis of 1-mercaptopyrene intermediate S-1-pyrenyl dimethylcarbamate:
将干燥结晶态的O-1-芘基二甲氨基硫代甲酸酯加入到不锈钢反应釜内，存在或缺失溶剂，氮气保护条件下，温度快速升至260～290℃，反应45～100分钟，经柱层析分离得1-巯基芘中间体S-1-芘基二甲氨基硫代甲酸酯，收率为40.0～87.2%。Add dry crystalline O-1-pyrenyldimethylcarbamate into a stainless steel reaction kettle with or without solvent, and under nitrogen protection, the temperature rises rapidly to 260-290°C and reacts for 45-100 minutes , and separated by column chromatography to obtain 1-mercaptopyrene intermediate S-1-pyrenyl dimethylcarbamate with a yield of 40.0-87.2%.
1-巯基芘中间体S-1-芘基二甲氨基硫代甲酸酯的分子结构和晶体结构：Molecular structure and crystal structure of 1-mercaptopyrene intermediate S-1-pyrenyl dimethylcarbamate:
该化合物晶体数据，晶系：正交；空间群：Pbca；分子式：C19H15ONS；分子量：305.38；晶胞参数：晶胞参数：α=90.00°,β=90.00°,γ=90.00°；晶胞体积：温度：123(2)K；晶胞密度：1.363g cm–3；结构因子（F(000)）：2560；吸收因子：0.218mm–1；可观测衍射点的S值（GOF on F2）：0.957；结果因子[I>2sigma(I)]：R1=0.0690,wR2=0.1077。熔点131～134℃。Crystal data of the compound, crystal system: Orthogonal; space group: Pbca; molecular formula: C19 H15 ONS; molecular weight: 305.38; unit cell parameters: unit cell parameters: α=90.00°, β=90.00°, γ=90.00°; unit cell volume: Temperature: 123(2)K; Unit cell density: 1.363g cm–3 ; Structure factor (F(000)): 2560; Absorption factor: 0.218mm–1 ; S value of observable diffraction point (GOF on F2 ) : 0.957; Outcome factor [I>2sigma(I)]: R1 =0.0690, wR2 =0.1077. The melting point is 131-134°C.
1-巯基芘的合成：Synthesis of 1-mercaptopyrene:
在氮气保护下，在水和乙二醇的混合溶液（1:7体积比）中加入氢氧化钾，再加入S-1-芘基二甲氨基硫代甲酸酯，回流1.5小时；完全冷却后，将反应溶液倾入冰水中，加氯仿振荡，弃去氯仿层，水层用质量分数5%的稀盐酸小心酸化，再用氯仿提取，蒸干后得到黄色的1-巯基芘，收率为86.5%。Under the protection of nitrogen, add potassium hydroxide to the mixed solution of water and ethylene glycol (1:7 volume ratio), then add S-1-pyrenyl dimethylcarbamate, reflux for 1.5 hours; completely cool Finally, the reaction solution was poured into ice water, chloroform was added to shake, and the chloroform layer was discarded. The aqueous layer was acidified carefully with 5% dilute hydrochloric acid, extracted with chloroform, and evaporated to dryness to obtain yellow 1-mercaptopyrene. The yield was was 86.5%.
1-巯基芘含有芘基发光基团和巯基官能团，分子结构如下：1-Mercaptopyrene contains a pyrenyl luminescent group and a mercapto functional group, and its molecular structure is as follows:
熔点86～89℃。The melting point is 86-89°C.
实施例2：Example 2:
1、1-巯基芘中间体O-1-芘基二甲氨基硫代甲酸酯的合成：1. Synthesis of 1-mercaptopyrene intermediate O-1-pyrenyl dimethylcarbamate:
在氮气保护下，6.54克1-羟基芘溶于50毫升N,N-二甲基甲酰胺（DMF），冷却到0～5℃，缓慢加入2.40克质量分数为60%的氢化钠，搅拌反应30分钟，加入6.00克二甲氨基硫代甲酰氯（DMTCC），缓慢升温至80℃；再加入3.25克碳酸钾，继续反应30小时；冷却，过滤未反应的碳酸钾；加入100毫升蒸馏水，产生黄色沉淀，过滤，甲醇重结晶，得到黄色的1-巯基芘中间体O-1-芘基二甲氨基硫代甲酸酯，收率为98.0%。Under nitrogen protection, 6.54 grams of 1-hydroxypyrene was dissolved in 50 milliliters of N,N-dimethylformamide (DMF), cooled to 0-5°C, and 2.40 grams of sodium hydride with a mass fraction of 60% was slowly added, and the reaction was stirred After 30 minutes, add 6.00 g of dimethylaminothioformyl chloride (DMTCC), and slowly raise the temperature to 80°C; then add 3.25 g of potassium carbonate, and continue the reaction for 30 hours; cool, filter unreacted potassium carbonate; add 100 ml of distilled water to produce The yellow precipitate was filtered and recrystallized from methanol to obtain the yellow 1-mercaptopyrene intermediate O-1-pyrenyldimethylcarbamate with a yield of 98.0%.
其结构表征数据如下：Its structural characterization data are as follows:
红外光谱：KBr，ν（cm-1）：3038.89(Ar-H)，2933.05(C–H),1530.38(s,C=C),1231.24(C–O),1130.43(s,C=S)。Infrared spectrum: KBr, ν (cm-1 ): 3038.89(Ar-H), 2933.05(C–H), 1530.38(s, C=C), 1231.24(C–O), 1130.43(s, C=S) .
质谱分析：m/z(%)：305(30,M+),189(30),88(10),72(100)。Mass spectrometry: m/z (%): 305 (30, M+ ), 189 (30), 88 (10), 72 (100).
核磁数据：1H-NMR(CDC13)(400MHz),δ3.482-3.689(6H,t,N-CH3),7.753-8.181(9H,m,Ar)。NMR data:1 H-NMR (CDC13 ) (400MHz), δ3.482-3.689 (6H, t, N-CH3 ), 7.753-8.181 (9H, m, Ar).
该化合物主要晶体数据。晶系：单斜；空间群：P21；分子式：C19H15ONS；分子量：305.38；晶胞参数：α=90.00°,β=90.702(4)°,γ=90.00°；晶胞体积：温度：296(2)K；晶胞密度：1.344g cm–3；结构因子（F(000)）：1280；吸收因子：0.215mm–1；可观测衍射点的S值（GOF on F2）：1.021；结果因子[I>2sigma(I)]：R1=0.0774,wR2=0.1020；熔点137～139℃。The main crystal data of this compound. Crystal system: monoclinic; space group: P21 ; molecular formula: C19 H15 ONS; molecular weight: 305.38; unit cell parameters: α=90.00°, β=90.702(4)°, γ=90.00°; unit cell volume: Temperature: 296(2)K; Unit cell density: 1.344g cm–3 ; Structure factor (F(000)): 1280; Absorption factor: 0.215mm–1 ; S value of observable diffraction point (GOF on F2 ) : 1.021; result factor [I>2sigma(I)]: R1 =0.0774, wR2 =0.1020; melting point 137-139°C.
特征键长键角：键长C芳–O,1.401(5);C–O,1.362(4);C=S：1.657(4)；键角(°)：C芳–O–C，118.6(3);O–C–N,110.3(3);O–C=S,123.7(3);N–C=S,126.0(3)。Characteristic bond length bond angle: bond length C-aromatic –O,1.401(5); C–O,1.362(4); C=S: 1.657(4); bond angle (°): C-aromatic –O–C, 118.6(3);O–C– N,110.3(3); O–C=S,123.7(3); N–C=S,126.0(3).
2、1-巯基芘中间体S-1-芘基二甲氨基硫代甲酸酯的合成：2. Synthesis of 1-mercaptopyrene intermediate S-1-pyrenyl dimethylcarbamate:
将干燥的、结晶态的4.0克O-1-芘基二甲氨基硫代甲酸酯加入到不锈钢反应釜内，在氮气保护条件下，温度快速升至290℃，反应1小时，经柱层析（二氯甲烷：石油醚=2.5:1（体积比））得1-巯基芘中间体S-1-芘基二甲氨基硫代甲酸酯，收率为76.5%。Add 4.0 grams of dry, crystalline O-1-pyrenyl dimethylcarbamate into a stainless steel reactor, and under nitrogen protection, the temperature rises rapidly to 290°C, reacts for 1 hour, passes through the column layer Analysis (dichloromethane:petroleum ether=2.5:1 (volume ratio)) yielded 1-mercaptopyrene intermediate S-1-pyrenyldimethylcarbamate with a yield of 76.5%.
红外光谱：KBr,ν(cm-1)3038.89(Ar-H),2933.05(C–H),1165.95(s,C=O),688.67(C–S)。Infrared spectrum: KBr, ν (cm-1 ) 3038.89 (Ar-H), 2933.05 (C-H), 1165.95 (s, C=O), 688.67 (C-S).
质谱分析：m/z(%)：305(30,M+,189(25),88(10),72(100)。Mass spectrometry: m/z (%): 305 (30, M+ , 189 (25), 88 (10), 72 (100).
核磁数据：1H-NMR(CDCl3)(400MHz),δ3.050-3.306(6H,t,N-CH3),8.013-8.583(9H,m,Ar)。NMR data:1 H-NMR (CDCl3 ) (400MHz), δ3.050-3.306 (6H, t, N-CH3 ), 8.013-8.583 (9H, m, Ar).
该化合物主要晶体数据。晶系：正交；空间群：Pbca；分子式：C19H15ONS；分子量：305.38；晶胞参数：晶胞参数：α=90.00°,β=90.00°,γ=90.00°；晶胞体积：温度：123(2)K；晶胞密度：1.363g cm–3；结构因子（F(000)）：2560；吸收因子：0.218mm–1；可观测衍射点的S值(GOF on F2)：0.957；结果因子[I>2sigma(I)]：R1=0.0690,wR2=0.1077；熔点131～134℃。The main crystal data of this compound. Crystal system: Orthogonal; Space group: Pbca; Molecular formula: C19 H15 ONS; Molecular weight: 305.38; Unit cell parameters: Unit cell parameters: α=90.00°, β=90.00°, γ=90.00°; unit cell volume: Temperature: 123(2)K; Unit cell density: 1.363g cm–3 ; Structure factor (F(000)): 2560; Absorption factor: 0.218mm–1 ; S value of observable diffraction point (GOF on F2 ) : 0.957; result factor [I>2sigma(I)]: R1 =0.0690, wR2 =0.1077; melting point 131-134°C.
特征键长键角：键长C芳–S,1.781(3);C–S,1.816(3);C=O:1.231(3);键角(°):C芳–S–C,102.79(15);O=C–N,124.6(2);O=C–S,122.19(18);N–C–S,113.1(2)。Characteristic bond length bond angle: bond length Cfang –S,1.781(3); C–S,1.816(3); C=O:1.231(3); Bond angle (°): Cfang –S–C,102.79(15);O=C– N, 124.6(2); O=C–S, 122.19(18); N–C–S, 113.1(2).
3、1-巯基芘的合成：在氮气保护下，在水和乙二醇的混合溶液（1:7体积比）中加入氢氧化钾，再加入S-1-芘基二甲氨基硫代甲酸酯，回流1.5小时；完全冷却后，将反应溶液倾入冰水中，加氯仿振荡，弃去氯仿层，水层用质量分数5%的稀盐酸小心酸化，再用氯仿提取，蒸干后得到黄色的1-巯基芘,收率为86%。熔点86～89℃。3. Synthesis of 1-mercaptopyrene: under nitrogen protection, add potassium hydroxide to a mixed solution of water and ethylene glycol (1:7 volume ratio), and then add S-1-pyrenyldimethylaminothioform acid ester, reflux for 1.5 hours; after complete cooling, pour the reaction solution into ice water, add chloroform to shake, discard the chloroform layer, carefully acidify the water layer with 5% dilute hydrochloric acid, extract with chloroform, and evaporate to dryness to obtain The yield of yellow 1-mercaptopyrene was 86%. The melting point is 86-89°C.
红外光谱：KBr,ν(cm-1):3038.89(AR-H),2920.10(C–H),2528.91(S–H)。Infrared spectrum: KBr, ν (cm-1 ): 3038.89 (AR-H), 2920.10 (C-H), 2528.91 (S-H).
质谱分析：m/z(%):243(100,M+),202(95),117(20)。Mass spectrometry: m/z (%): 243 (100, M+ ), 202 (95), 117 (20).
核磁数据：1H-NMR(CDCl3)(400MHz),δ3.857(1H,s,S-H),8.002-8.188(9H,m,Ar)。NMR data:1 H-NMR (CDCl3 ) (400MHz), δ3.857 (1H, s, SH), 8.002-8.188 (9H, m, Ar).
实施例3：Example 3:
1、1-巯基芘中间体O-1-芘基二甲氨基硫代甲酸酯的合成：1. Synthesis of 1-mercaptopyrene intermediate O-1-pyrenyl dimethylcarbamate:
在氮气保护下，6.54克1-羟基芘溶于50毫升N,N-二甲基甲酰胺，冷却到0～5℃，缓慢加入2.40克质量分数为60%的氢化钠，搅拌反应30分钟，加入6.00克二甲氨基硫代甲酰氯，缓慢升温至80℃；再加入3.25克碳酸钾，继续反应30小时；冷却，过滤未反应的碳酸钾；加入100毫升蒸馏水，产生黄色沉淀，过滤，甲醇重结晶，得到黄色的1-巯基芘中间体O-1-芘基二甲氨基硫代甲酸酯，收率为98.0%。Under nitrogen protection, 6.54 grams of 1-hydroxypyrene was dissolved in 50 milliliters of N,N-dimethylformamide, cooled to 0-5°C, 2.40 grams of sodium hydride with a mass fraction of 60% was slowly added, and the reaction was stirred for 30 minutes. Add 6.00 g of dimethylaminothioformyl chloride and slowly heat up to 80°C; then add 3.25 g of potassium carbonate and continue the reaction for 30 hours; cool and filter the unreacted potassium carbonate; add 100 ml of distilled water to produce a yellow precipitate, filter and methanol Recrystallization gave the yellow 1-mercaptopyrene intermediate O-1-pyrenyldimethylcarbamate with a yield of 98.0%.
2、1-巯基芘中间体S-1-芘基二甲氨基硫代甲酸酯的合成：2. Synthesis of 1-mercaptopyrene intermediate S-1-pyrenyl dimethylcarbamate:
将干燥的、结晶态的4.0克O-1-芘基二甲氨基硫代甲酸酯加入到不锈钢反应釜内，在氮气保护条件下，温度快速升至260℃反应45分钟，经柱层析（二氯甲烷：石油醚=2.5:1（体积比））得1-巯基芘中间体S-1-芘基二甲氨基硫代甲酸酯，收率为40.0%。Add 4.0 grams of dry, crystalline O-1-pyrenyl dimethylcarbamoate into a stainless steel reactor, and under nitrogen protection, the temperature is rapidly raised to 260°C for 45 minutes, and the reaction is performed by column chromatography. (dichloromethane:petroleum ether=2.5:1 (volume ratio)) to obtain 1-mercaptopyrene intermediate S-1-pyrenyldimethylcarbamoate with a yield of 40.0%.
3、1-巯基芘的合成：在氮气保护下，在5毫升水和35毫升乙二醇的混合溶液（1:7体积比）中加入1.08克氢氧化钾，再加入2.52克S-1-芘基二甲氨基硫代甲酸酯，回流1.5小时；完全冷却后，将反应溶液倾入冰水中，加氯仿振荡，弃去氯仿层，水层用质量分数5%的稀盐酸小心酸化，再用氯仿提取，蒸干后得到黄色的1-巯基芘，收率为86.5%。3. Synthesis of 1-mercaptopyrene: under nitrogen protection, add 1.08 grams of potassium hydroxide to a mixed solution of 5 milliliters of water and 35 milliliters of ethylene glycol (1:7 volume ratio), and then add 2.52 grams of S-1- Pyrenyl dimethylcarbamate, reflux for 1.5 hours; after complete cooling, pour the reaction solution into ice water, add chloroform to shake, discard the chloroform layer, carefully acidify the water layer with 5% dilute hydrochloric acid, and then It was extracted with chloroform and evaporated to dryness to obtain yellow 1-mercaptopyrene with a yield of 86.5%.
实施例4：Example 4:
1、1-巯基芘中间体O-1-芘基二甲氨基硫代甲酸酯的合成：1. Synthesis of 1-mercaptopyrene intermediate O-1-pyrenyl dimethylcarbamate:
在氮气保护下，6.54克1-羟基芘溶于50毫升N,N-二甲基甲酰胺，冷却到0～5℃，缓慢加入2.40克质量分数为60%的氢化钠，搅拌反应30分钟，加入6.00克二甲氨基硫代甲酰氯，缓慢升温至80℃；再加入3.25克碳酸钾，继续反应30小时；冷却，过滤未反应的碳酸钾；加入100毫升蒸馏水，产生黄色沉淀，过滤，甲醇重结晶，得到黄色的1-巯基芘中间体O-1-芘基二甲氨基硫代甲酸酯，收率为98%。Under nitrogen protection, 6.54 grams of 1-hydroxypyrene was dissolved in 50 milliliters of N,N-dimethylformamide, cooled to 0-5°C, 2.40 grams of sodium hydride with a mass fraction of 60% was slowly added, and the reaction was stirred for 30 minutes. Add 6.00 g of dimethylaminothioformyl chloride and slowly heat up to 80°C; then add 3.25 g of potassium carbonate and continue the reaction for 30 hours; cool and filter the unreacted potassium carbonate; add 100 ml of distilled water to produce a yellow precipitate, filter and methanol After recrystallization, the yellow 1-mercaptopyrene intermediate O-1-pyrenyl dimethylcarbamate was obtained with a yield of 98%.
2、1-巯基芘中间体S-1-芘基二甲氨基硫代甲酸酯的合成：2. Synthesis of 1-mercaptopyrene intermediate S-1-pyrenyl dimethylcarbamate:
将干燥的、结晶态的4.0克O-1-芘基二甲氨基硫代甲酸酯加入到不锈钢反应釜内，在氮气保护条件下，温度快速升至290℃，反应45分钟，经柱层析（二氯甲烷：石油醚=2.5:1（体积比））得1-巯基芘中间体S-1-芘基二甲氨基硫代甲酸酯，收率为60.5%。Add 4.0 grams of dry, crystalline O-1-pyrenyl dimethylcarbamate into a stainless steel reactor, and under nitrogen protection, the temperature rises rapidly to 290°C, reacts for 45 minutes, passes through the column layer Analysis (dichloromethane:petroleum ether=2.5:1 (volume ratio)) gave 1-mercaptopyrene intermediate S-1-pyrenyldimethylcarbamoate with a yield of 60.5%.
3、1-巯基芘的合成：在氮气保护下，在5毫升水和35毫升乙二醇的混合溶液（1:7体积比）中加入1.08克氢氧化钾，再加入2.52克S-1-芘基二甲氨基硫代甲酸酯，回流1.5小时；完全冷却后，将反应溶液倾入冰水中，加氯仿振荡，弃去氯仿层，水层用质量分数5%的稀盐酸小心酸化，再用氯仿提取，蒸干后得到黄色的1-巯基芘，收率为86.5%。3. Synthesis of 1-mercaptopyrene: under nitrogen protection, add 1.08 grams of potassium hydroxide to a mixed solution of 5 milliliters of water and 35 milliliters of ethylene glycol (1:7 volume ratio), and then add 2.52 grams of S-1- Pyrenyl dimethylcarbamate, reflux for 1.5 hours; after complete cooling, pour the reaction solution into ice water, add chloroform to shake, discard the chloroform layer, carefully acidify the water layer with 5% dilute hydrochloric acid, and then It was extracted with chloroform and evaporated to dryness to obtain yellow 1-mercaptopyrene with a yield of 86.5%.
实施例5：Example 5:
1、1-巯基芘中间体O-1-芘基二甲氨基硫代甲酸酯的合成：1. Synthesis of 1-mercaptopyrene intermediate O-1-pyrenyl dimethylcarbamate:
在氮气保护下，6.54克1-羟基芘溶于50毫升N,N-二甲基甲酰胺，冷却到0～5℃，缓慢加入2.40克质量分数为60%的氢化钠，搅拌反应30分钟，加入6.00克二甲氨基硫代甲酰氯，缓慢升温至80℃；再加入3.25克碳酸钾，继续反应30小时；冷却，过滤未反应的碳酸钾；加入100毫升蒸馏水，产生黄色沉淀，过滤，甲醇重结晶，得到黄色的1-巯基芘中间体O-1-芘基二甲氨基硫代甲酸酯，收率为98.0%。Under nitrogen protection, 6.54 grams of 1-hydroxypyrene was dissolved in 50 milliliters of N,N-dimethylformamide, cooled to 0-5°C, 2.40 grams of sodium hydride with a mass fraction of 60% was slowly added, and the reaction was stirred for 30 minutes. Add 6.00 g of dimethylaminothioformyl chloride and slowly heat up to 80°C; then add 3.25 g of potassium carbonate and continue the reaction for 30 hours; cool and filter the unreacted potassium carbonate; add 100 ml of distilled water to produce a yellow precipitate, filter and methanol Recrystallization gave the yellow 1-mercaptopyrene intermediate O-1-pyrenyldimethylcarbamate with a yield of 98.0%.
2、1-巯基芘中间体S-1-芘基二甲氨基硫代甲酸酯的合成：2. Synthesis of 1-mercaptopyrene intermediate S-1-pyrenyl dimethylcarbamate:
将干燥的、结晶态的4.0克O-1-芘基二甲氨基硫代甲酸酯加入到不锈钢反应釜内，在氮气保护条件下，温度快速升至285℃，反应100分钟，经柱层析（二氯甲烷：石油醚=2.5:1（体积比））得1-巯基芘中间体S-1-芘基二甲氨基硫代甲酸酯，熔点131～134℃,收率为75.0%。Add 4.0 grams of dry, crystalline O-1-pyrenyl dimethylcarbamate into a stainless steel reactor, and under nitrogen protection, the temperature rises rapidly to 285°C, reacts for 100 minutes, passes through the column layer Analysis (dichloromethane: petroleum ether = 2.5:1 (volume ratio)) to obtain 1-mercaptopyrene intermediate S-1-pyrenyl dimethylcarbamate, melting point 131 ~ 134 ° C, yield 75.0% .
3、1-巯基芘的合成：在氮气保护下，在5毫升水和35毫升乙二醇的混合溶液（1:7体积比）中加入1.08克氢氧化钾，再加入2.52克S-1-芘基二甲氨基硫代甲酸酯，回流1.5小时；完全冷却后，将反应溶液倾入冰水中，加氯仿振荡，弃去氯仿层，水层用质量分数5%的稀盐酸小心酸化，再用氯仿提取，蒸干后得到黄色的1-巯基芘，收率为86.5%。3. Synthesis of 1-mercaptopyrene: under nitrogen protection, add 1.08 grams of potassium hydroxide to a mixed solution of 5 milliliters of water and 35 milliliters of ethylene glycol (1:7 volume ratio), and then add 2.52 grams of S-1- Pyrenyl dimethylcarbamate, reflux for 1.5 hours; after complete cooling, pour the reaction solution into ice water, add chloroform to shake, discard the chloroform layer, carefully acidify the water layer with 5% dilute hydrochloric acid, and then It was extracted with chloroform and evaporated to dryness to obtain yellow 1-mercaptopyrene with a yield of 86.5%.
实施例6：Embodiment 6:
1、1-巯基芘中间体O-1-芘基二甲氨基硫代甲酸酯的合成：1. Synthesis of 1-mercaptopyrene intermediate O-1-pyrenyl dimethylcarbamate:
在氮气保护下，6.54克1-羟基芘溶于50毫升N,N-二甲基甲酰胺，冷却到0～5℃，缓慢加入2.40克质量分数为60%的氢化钠，搅拌反应30分钟，加入6.00克二甲氨基硫代甲酰氯，缓慢升温至80℃；再加入3.25克碳酸钾，继续反应30小时；冷却，过滤未反应的碳酸钾；加入100毫升蒸馏水，产生黄色沉淀，过滤，甲醇重结晶，得到黄色的1-巯基芘中间体O-1-芘基二甲氨基硫代甲酸酯，收率为98.0%。Under nitrogen protection, 6.54 grams of 1-hydroxypyrene was dissolved in 50 milliliters of N,N-dimethylformamide, cooled to 0-5°C, 2.40 grams of sodium hydride with a mass fraction of 60% was slowly added, and the reaction was stirred for 30 minutes. Add 6.00 g of dimethylaminothioformyl chloride and slowly heat up to 80°C; then add 3.25 g of potassium carbonate and continue the reaction for 30 hours; cool and filter the unreacted potassium carbonate; add 100 ml of distilled water to produce a yellow precipitate, filter and methanol Recrystallization gave the yellow 1-mercaptopyrene intermediate O-1-pyrenyldimethylcarbamate with a yield of 98.0%.
2、1-巯基芘中间体S-1-芘基二甲氨基硫代甲酸酯的合成：2. Synthesis of 1-mercaptopyrene intermediate S-1-pyrenyl dimethylcarbamate:
将干燥的、结晶态的4.0克O-1-芘基二甲氨基硫代甲酸酯和4.0克二苯醚混合物加入到不锈钢反应釜内，在氮气保护条件下，温度快速升至290℃，反应70分钟后，冷却后经柱层析（二氯甲烷：石油醚=2.5:1（体积比））得1-巯基芘中间体S-1-芘基二甲氨基硫代甲酸酯，收率为87.2%。Add dry, crystalline 4.0 grams of O-1-pyrenyl dimethylcarbamate and 4.0 grams of diphenyl ether mixture into a stainless steel reactor, and under nitrogen protection, the temperature rises rapidly to 290°C. After reacting for 70 minutes, after cooling, the 1-mercaptopyrene intermediate S-1-pyrenyldimethylcarbamate was obtained by column chromatography (dichloromethane:petroleum ether=2.5:1 (volume ratio)). The rate is 87.2%.
3、1-巯基芘的合成：在氮气保护下，在5毫升水和35毫升乙二醇的混合溶液（1:7体积比）中加入1.08克氢氧化钾，再加入2.52克S-1-芘基二甲氨基硫代甲酸酯，回流1.5小时；完全冷却后，将反应溶液倾入冰水中，加氯仿振荡，弃去氯仿层，水层用质量分数5%的稀盐酸小心酸化，再用氯仿提取，蒸干后得到黄色的1-巯基芘，收率为86.5%。3. Synthesis of 1-mercaptopyrene: under nitrogen protection, add 1.08 grams of potassium hydroxide to a mixed solution of 5 milliliters of water and 35 milliliters of ethylene glycol (1:7 volume ratio), and then add 2.52 grams of S-1- Pyrenyl dimethylcarbamate, reflux for 1.5 hours; after complete cooling, pour the reaction solution into ice water, add chloroform to shake, discard the chloroform layer, carefully acidify the water layer with 5% dilute hydrochloric acid, and then It was extracted with chloroform and evaporated to dryness to obtain yellow 1-mercaptopyrene with a yield of 86.5%.
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