CN107337623B - 1-硝基-2,4-间二苄硫醇及其制备方法和在光敏感巯基试剂的应用 - Google Patents
1-硝基-2,4-间二苄硫醇及其制备方法和在光敏感巯基试剂的应用 Download PDFInfo
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- UENWRTRMUIOCKN-UHFFFAOYSA-N benzyl thiol Chemical class SCC1=CC=CC=C1 UENWRTRMUIOCKN-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000003153 chemical reaction reagent Substances 0.000 title abstract description 10
- 125000003396 thiol group Chemical class [H]S* 0.000 title abstract description 8
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 claims abstract description 14
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 7
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims abstract description 6
- 235000010262 sodium metabisulphite Nutrition 0.000 claims abstract description 6
- 239000007858 starting material Substances 0.000 claims abstract description 3
- 238000010511 deprotection reaction Methods 0.000 claims abstract 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 21
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- 230000006837 decompression Effects 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 230000001546 nitrifying effect Effects 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
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- 239000003937 drug carrier Substances 0.000 abstract description 2
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- 238000006467 substitution reaction Methods 0.000 abstract 1
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- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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Abstract
本发明公开了一种1‑硝基‑2,4‑间二苄硫醇及其制备方法和在光敏感巯基试剂的应用,以间二溴苄、硫酸、硝酸、硫脲、焦亚硫酸钠为主要起始原料,经过一系列硝化、取代,还原脱保护反应,得到目标产物1‑硝基‑2,4‑间二苄硫醇。本发明的优点是制备方法简单,操作方便,原料易得,产率较高,在敏感型药物载体领域中具有广泛的应用前景。
Description
技术领域
本发明属于有机化学领域,具体是指1-硝基-2,4-间二苄硫醇及其制备方法和在光敏感巯基试剂的应用。
背景技术
巯基试剂是一种反应活性和反应效率都特别高的亲核试剂,硫醇盐和硫醇是一种高度反应活性的物质,在相对良性的反应条件下就可以获得较高的产率,因此被广泛地应用到各种反应过程中。其中巯基-双键点击化学是最被化学工作者所熟知的迈克尔加成反应,是被Sharpless及其他工作者高度推崇的一种高效且可模型化的反应。另外巯基因其反应活性高,在相对较为温和的条件下还可以与环氧,卤素,异氰酸酯进行高效的点击化学反应。
光敏感是一种比较温和的降解方式,邻硝基苯衍生物是目前应用比较广泛的光敏感物质,很多离去的基团可以直接附加在苄基的位置上。
发明内容
本发明的目的是为了克服现有技术存在的缺点和不足,而提供一种全新分子结构的1-硝基-2,4-间二苄硫醇,该化学物可作为光敏感巯基试剂。
本发明的第二个目的是提供一种1-硝基-2,4-间二苄硫醇制备方法。
本发明的第三个目的是提供一种1-硝基-2,4-间二苄硫醇在光敏感巯基试剂的用途。
为实现本发明的第一个发明目的,其技术方案是其分子结构式为
为实现本发明的第二个目的,其技术方案是一种1-硝基-2,4-间二苄硫醇的制备方法,其特征在于:
以间二溴苄,硫酸、硝酸、硫脲、焦亚硫酸钠为起始原料,经过硝化、取代,还原脱保护反应,得到目标产物1-硝基-2,4-间二苄硫醇,其制备路线如以下化学式所示
进一步设置是包括以下步骤:
(1)在冰浴下,控制所述间二溴苄、氯仿、98%浓硫酸按质量比为1:2-3:5-6混合,2.-3质量份的69%浓硝酸用恒压滴液漏斗缓慢滴加进去,在冰浴下以800-1200r/min的转速搅拌下反应1-2h后转至室温反应4-6h;
(2)用100-200质量份冰水及30-50质量份氯仿分三次萃取洗涤反应所得1-硝基-2,4-间二溴苄,收集氯仿相浓缩,用2-4质量份无水硫酸钠干燥,减压抽除溶剂,得淡黄色液体1-硝基-2,4-间二溴苄;
(3)在室温下,将步骤(2)所得1-硝基-2,4-间二溴苄、硫脲与干燥的四氢呋喃按照质量比为:1:8-10:8-15混合,在800-1400r/min的转速下搅拌反应16-20h,反应生成淡黄色不溶物;
(4)用50-80质量份的乙酸乙酯分三次洗涤步骤(3)中所得淡黄色不溶物,过滤收集不溶物,在真空干燥箱中0.01MPa,45℃下干燥12-16h;
(5)将步骤(4)所得产物溶于二氯甲烷,其质量比为1:17—28,另取3-4质量份的焦亚硫酸钠溶于5-8质量份的纯水中,再将其加入到二氯甲烷溶液中,在氮气的氛围中,45-52℃下,以800-1400r/min的搅拌速度,回流反应6-10h;
(6)将步骤(5)所得混合溶液分液,水层用45-75质量份的二氯甲烷分三次洗涤,收集有机层,用2-4质量份的无水硫酸钠干燥,减压抽除二氯甲烷,得淡黄色液体1-硝基-2,4-间二苄硫醇。
进一步设置是具体组分及质量比为:间二溴苄:氯仿:98%浓硫酸:69%浓硝酸:水:硫脲:四氢呋喃:乙酸乙酯:焦亚硫酸钠:二氯甲烷=1:32-64:5-6:2-3:110-175:9.5-10.5:9.5-18:60-83:5.4-7.2:100-200。
本发明还提供一种基于1-硝基-2,4-间二苄硫醇的用途,将该1-硝基-2,4-间二苄硫醇作为光敏感巯基试剂使用。
本发明的优点是,本发明所用到的原料和试剂都简单易得,反应条件比较温和,操作方法难度不高,产物在有机化学和高分子药物载体的领域内具有广泛的应用前景。
本发明还具有光敏感的特性。其光敏感是指在当在接近中性的环境下,用大于300nm的紫外光照射一定时间后后,可以使一个硝基旁边的硫醇离去,生成醛类。其降解机理如下化学式所示:
下面结合说明书附图和具体实施方式对本发明做进一步介绍。
附图说明
图1本发明实施例1的反应方程式;
图2本发明实施例1产物的核磁共振谱图;
图3本发明实施例1产物的红外光谱图。
具体实施方式
下面通过实施例对本发明进行具体的描述,只用于对本发明进行进一步说明,不能理解为对本发明保护范围的限定,该领域的技术工程师可根据上述发明的内容对本发明作出一些非本质的改进和调整。
实施例1
如图1至图3所示,为本发明实施例1中,包括以下步骤:
(1)在冰浴下,取1g(3.8mmol)间二溴苄溶于1.5mL氯仿,加入4mL98%浓硫酸,混合,另取2.5mL69%浓硝酸于恒压滴液漏斗中,用以1滴/10s缓慢滴加进去,在冰浴下以800-1200r/min的转速搅拌下反应1-2h后转至室温反应4-6h;
(2)向步骤1中混合物加入30mL冰水,用30mL*3的氯仿分三次萃取洗涤至中性,收集氯仿相浓缩,用3g无水硫酸钠干燥,减压抽除溶剂,得淡黄色液体1-硝基-2,4-间二溴苄1.05g(产率90%)。
(3)在室温下,将步骤(2)所得1.05g(3.4mmol)1-硝基-2,4-间二溴苄与0.62g(8.2mmol)硫脲与12mL干燥的四氢呋喃混合,在800-1400r/min的转速下搅拌反应16-20h,反应生成淡黄色不溶物。
(4)用20mL*3的乙酸乙酯分三次洗涤步骤(3)中所得淡黄色不溶物,过滤收集不溶物,在真空干燥箱中0.01MPa,45℃下干燥12-16h得白色固体1.09g(产率70%)。
(5)将步骤(4)所得1.09g(2.4mmol)产物溶于30mL二氯甲烷,另取3.6g(18.9mmol)的焦亚硫酸钠溶于10mL纯水中,再将其加入到二氯甲烷溶液中,在氮气的氛围中,45-52℃下,以800-1400r/min的搅拌速度,回流反应6-10h。
(6)将步骤(5)所得混合溶液分液,水层用45-75质量份的二氯甲烷分三次洗涤,收集有机层,用3g的无水硫酸钠干燥,减压抽除二氯甲烷,得淡黄色液体1-硝基-2,4-间二苄硫醇0.47g(产率97%)。
参照图1所示:实施例1的反应方程式。
参照图2所示:实施例1所得产物1-硝基-2,4-间二苄硫醇的核磁共振氢谱图。1HNMR(500MHz,CDCl3)δ8.03(t,J=24.7Hz,1H),7.42(td,J=17.1,8.6Hz,2H),4.02(d,J=8.5Hz,2H),3.80(dd,J=19.0,8.0Hz,2H),1.85(q,J=7.7Hz,2H)。
参照图3所示:实施例1所得产物1-硝基-2,4-间二苄硫醇的红外光谱图。从红外谱图中可以看出,在3461cm-1处有一较宽吸收峰,判定为-SH,在1532cm-1有一强吸收峰,判定为-NO2。
图2和图3同时证明了实例1所得产物1-硝基-2,4-间二苄硫醇的成功合成,其结构式为
以上仅为本发明的一个实施例,但是在本领域的技术人员应当理解,在不脱离本发明精神的情况下,可以对本文的实施例进行改变。当然不能以此来限定本发明之权利范围,因此依本发明权利要求所作的等同变化,仍属本发明所涵盖的范围。
Claims (1)
1.一种1-硝基-2,4-间二苄硫醇的制备方法,其特征在于:
以间二溴苄,硫酸、硝酸、硫脲、焦亚硫酸钠为起始原料,经过硝化、取代,还原脱保护反应,得到目标产物1-硝基-2,4-间二苄硫醇,其制备路线如以下化学式所示
,包括以下步骤:
(1)在冰浴下,取1g间二溴苄溶于1.5mL氯仿,加入4mL98%浓硫酸,混合,另取2.5mL69%浓硝酸于恒压滴液漏斗中,用以1滴/10s缓慢滴加进去,在冰浴下以800-1200r/min的转速搅拌下反应1-2h后转至室温反应4-6h;
(2)向步骤1中混合物加入30mL冰水,用30mL*3的氯仿分三次萃取洗涤至中性,收集氯仿相浓缩,用3g无水硫酸钠干燥,减压抽除溶剂,得淡黄色液体1-硝基-2,4-间二溴苄1.05g;
(3)在室温下,将步骤(2)所得1.05g1-硝基-2,4-间二溴苄与0.62g硫脲与12mL干燥的四氢呋喃混合,在800-1400r/min的转速下搅拌反应16-20h,反应生成淡黄色不溶物;
(4)用20mL*3的乙酸乙酯分三次洗涤步骤(3)中所得淡黄色不溶物,过滤收集不溶物,在真空干燥箱中0.01MPa,45℃下干燥12-16h得白色固体1.09g;
(5)将步骤(4)所得1.09g产物溶于30mL二氯甲烷,另取3.6g的焦亚硫酸钠溶于10mL纯水中,再将其加入到二氯甲烷溶液中,在氮气的氛围中,45-52℃下,以800-1400r/min的搅拌速度,回流反应6-10h;
(6)将步骤(5)所得混合溶液分液,水层用45-75质量份的二氯甲烷分三次洗涤,收集有机层,用3g的无水硫酸钠干燥,减压抽除二氯甲烷,得淡黄色液体1-硝基-2,4-间二苄硫醇0.47g。
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