CN113087684A - 二（三苯基膦）羰基一水合二氯化钌的应用 - Google Patents

二（三苯基膦）羰基一水合二氯化钌的应用 Download PDF

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CN113087684A
CN113087684A CN202110308135.4A CN202110308135A CN113087684A CN 113087684 A CN113087684 A CN 113087684A CN 202110308135 A CN202110308135 A CN 202110308135A CN 113087684 A CN113087684 A CN 113087684A
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thiomorpholine
triphenylphosphine
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bis
ruthenium dichloride
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许丹倩
李晨
夏爱宝
求元锐
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Zhejiang University of Technology ZJUT
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Abstract

本发明提供了一种二(三苯基膦)羰基一水合二氯化钌，所述方法为：将三苯基膦加入有机溶剂A中，升温至50～100℃使其溶解，得到溶液A；将三氯化钌加入有机溶剂B中，溶解，得到溶液B；然后将溶液B与质量分数为37％的甲醛水溶液依次快速加入到所述溶液A中，80～130℃反应0.5h～2h；所得反应液A经后处理A，得二(三苯基膦)羰基一水合二氯化钌。与Colt等人合成方法相比，本发明能很好的避免强酸的使用，减少实验过程中对操作人员的伤害，同时反应时间大幅度缩短，以及实验后处理简洁，提高了实验效率。

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二(三苯基膦)羰基一水合二氯化钌的应用
(一)技术领域
本发明涉及一种含三苯基膦配体的钌催化剂，二(三苯基膦)羰基一水合二氯化钌的应用。
(二)背景技术
贵金属催化剂在催化反应中扮演着越来越重要的角色。其中由于钌金属外层电子结构特点，在周期表中所有元素中具有最多氧化价，每个电子结构又具有多种几何结构，这为合成多种钌配合物提供了基础。又由于钌催化剂优异的催化性能，相对于其他贵金属价格便宜的特点，使其发展更加迅速、应用更广。目前，钌催化剂主要应用的领域有(不对称)催化加氢、烯烃复分解、碳烷基化、氮烷基化等。而在醇作为反应物的碳烷基化或氮烷基化反应过程中，只有无污染的水做为副产物产生，符合绿色发展的要求，所以吸引了越来越多研究者的兴趣。这对于催化剂的合成和研究提出的更高的要求。自从1981年Grigg等人第一次报道了通过借氢机理，醇在钌催化剂下直接氮烷基化合成胺以后。越来越多的贵金属催化剂被用于此研究方向。然而由于硫原子对贵金属明显的毒化作用，几乎很少有报道贵金属催化含硫化合物。但是含硫胺化合物在药物和天然产物中占有重要地位，因此寻找一种能催化含硫化合物的催化剂显得尤为重要。
(三)发明内容
本发明所要解决的问题是在提供一种钌催化剂的合成方法，及其该催化剂在含硫胺化物氮烷基化的应用。
为了实现上述目的，本发明采用如下技术方案：
本发明二(三苯基膦)羰基一水合二氯化钌是用一种新方法制备的，所述方法为：
将三苯基膦加入有机溶剂A中，升温至50～100℃(优选为100℃)使其溶解，得到溶液A；将三氯化钌加入有机溶剂B中，溶解，得到溶液B；然后将溶液B与质量分数为37％的甲醛水溶液依次快速加入到所述溶液A中，80～130℃(优选为120℃)反应0.5h～2h(最优选为0.8h)；所得反应液A经后处理A，得二(三苯基膦)羰基一水合二氯化钌；所述三氯化钌与三苯基膦的物质的量之比为1:1～6(优选1:3)，所述质量分数为37％的甲醛水溶液的体积以三氯化钌的物质的量计为5～15mL/mmol(优选10mL/mmol)；所述有机溶剂A与有机溶剂B都是有机溶剂，这里用A、B只是为了区分不同阶段加入的有机溶剂。优选有机溶剂A与有机溶剂B为相同溶剂。
进一步，所述的有机溶剂A和有机溶剂B分别独立为乙醇、乙腈、乙二醇甲醚或甲苯，优选为乙二醇甲醚。
优选地，所述的有机溶剂A的体积以三苯基膦的物质的量计为5～15mL/mmol，最优选为6.7mL/mmol。
优选地，所述的有机溶剂B的体积以三氯化钌的物质的量计为5～15mL/mmol，最优选为10mL/mmol。
进一步，所述后处理A为：将所述反应液A冷却，抽滤，空气干燥，即得所述二(三苯基膦)羰基一水合二氯化钌。
优选地，所述冷却的温度为20℃～50℃，最优选为25℃；所述空气干燥温度为40℃～100℃，干燥时间2h～10h，最优选为50℃，8h。
本发明的主要目的是提出了一种二(三苯基膦)羰基一水合二氯化钌作为均相催化剂在含硫胺化物的氮烷基化反应中的应用。
进一步，所述的应用为：将化合物1和化合物2溶于有机溶剂D中，加入二(三苯基膦)羰基一水合二氯化钌，80℃～160℃(优选为140℃)反应2h～10h(优选为6h)，所得反应液B经后处理B，得到式3所示化合物；化合物1与化合物2的物质的量之比为0.5～10:1，最优选为3:1；所述二(三苯基膦)羰基一水合二氯化钌的用量为0.2～5mol/100mol化合物2；
Figure BDA0002988421960000021
式1和3中，R1选自下列之一：苯基、2-甲基苯基、3-甲基苯基、4-甲基苯基、2-甲氧基苯基、3-甲氧基苯基、4-甲氧基苯基、4-联二苯基、2-氟苯基、3-氟苯基、4-氟苯基、2-溴苯基、3-溴苯基、4-溴苯基、2-碘苯基、3-碘苯基、4-碘苯基、2-三氟甲基苯基、3-三氟甲基苯基、4-三氟甲基苯基、3,5-二甲氧基苯基、3,5-二氟苯基、2-吡啶基、2-噻吩基、1-萘基、甲基、乙基、丙基、丁基、戊基、己基、环丙甲基、环丁甲基、环戊甲基、环己甲基、氧杂环丁基、2-四氢呋喃甲基、金刚烷甲基、环丙基、环丁基、环戊基、环己基、苯甲基、苯乙基、苯丙基、3-羟基丙基、4-羟基丁基、3-甲基丁基、3,3-二甲基丁基、甲氧基甲基、甲氧基丙基、甲硫基甲基、1-乙酮基；
式2中R2与R3连接成环，式2所示结构式选自下列之一：
Figure BDA0002988421960000031
作为优选，式1和3中，R1为苯基、2-甲基苯基、3-甲基苯基、4-甲基苯基、2-甲氧基苯基、3-甲氧基苯基、2-氟苯基、3-氟苯基、2-溴苯基、3-溴苯基、2-碘苯基、3-碘苯基、3-三氟甲基苯基、3,5-二甲氧基苯基、3,5-二氟苯基、2-吡啶基、2-噻吩基、1-萘基、乙基、丙基、丁基、戊基、环戊基、环己基、苯甲基、苯乙基、甲氧基甲基、甲氧基丙基、甲硫基甲基或1-乙酮基。
进一步优选，所述化合物3为下列之一：
(1)4-苄基硫代吗啉
(2)4-(2-甲基苄基)硫代吗啉
(3)4-(3-甲基苄基)硫代吗啉
(4)4-(4-甲基苄基)硫代吗啉
(5)4-(3-甲氧基苄基)硫代吗啉
(6)4-(3-氟苄基)硫代吗啉
(7)4-(3-溴苄基)硫代吗啉
(8)4-(3-碘苄基)硫代吗啉
(9)4-(3-三氟甲基苄基)硫代吗啉
(10)4-(3,5-二甲氧基苄基)硫代吗啉
(11)4-(3,5-二氟苄基)硫代吗啉
(12)4-(吡啶-2-基甲基)硫代吗啉
(13)4-(噻吩-2-基甲基)硫代吗啉
(14)4-(萘-1-基甲基)硫代吗啉
(15)4-丙基硫代吗啉
(16)4-丁基硫代吗啉
(17)4-(环己基甲基)硫代吗啉
(18)4-苯乙基硫代吗啉
(19)4-(3-苯丙基)硫代吗啉
(20)4-(2-甲氧基乙基)硫代吗啉
(21)4-(2-羰基丙基)硫代吗啉
(22)4-苄基-2-乙基硫代吗啉
(23)4-苄基-2,2-二甲基硫代吗啉
(24)4-丙基-3,4-二氢-2H-苯并[b][1,4]噻嗪
(25)4-苄硫基吗啉1,1-二氧化物
(26)6-(2-(甲硫基)乙基)-4,5,6,7-四氢噻吩并[2,3-c]吡啶
(27)3-(4-丙基哌嗪-1-基)苯并[d]异噻唑
(28)N，N-二丙基-4-((三氟甲基)硫代)苯胺
(29)3-(甲硫基)-N，N-二丙基苯胺
(30)4-((4-硝基苯基)硫基)-N，N-二丙基苯胺。
反应体系温度大于溶剂沸点时，优选所述反应在耐压管中进行。
进一步，所述有机溶剂D为四氢呋喃、二氧六环、甲苯、二甲苯、N,N-二甲基甲酰胺、二甲基亚砜或叔戊醇，最优选为甲苯。
优选地，所述有机溶剂D的体积以所述胺类化合物2的物质的量计为0.1～5mL/mmol，最优选为1mL/mmol。
进一步，所述后处理B为：将所述反应液B冷却至室温，脱溶，利用快速制备液相色谱仪纯化，以体积比为2～20:100(优选为5:100)的乙酸乙酯与石油醚的混合溶液为洗脱液进行洗脱，收集含目标化合物的洗脱液，减压旋蒸得到式3所示化合物。
与现有技术相比，本发明的有益效果在于：
相比于其他钌催化剂而言，二(三苯基膦)羰基一水合二氯化钌在催化醇类化合物和胺类化合物的反应中催化活性更高。
(四)附图说明
图1.二(三苯基膦)羰基一水合二氯化钌单晶结构。
(五)具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例，对本发明进一步详细说明。在一些专业术语的使用上，为了使普通读者更好地理解，本发明提出了很多技术细节。但是，即使没有这些技术细节和对以下各实施方式的一些改变和修改，也可以实现本申请所要求保护的技术方案。
下述实施例中收率的计算公式(不考虑纯度)为：
Y＝(m产量/M产物)/N原料
m产量为包括杂质的产物的质量，M产物为目标产物的相对分子质量，N原料为物质的量较小的反应物的物质的量。
以下实施例中所用快速制备液相色谱仪为Biotage公司的纯化仪，型号是BiotageIsolera One。
实施例1：二(三苯基膦)羰基一水合二氯化钌的合成
将3.16g(12mmol)三苯基膦加入到80mL乙二醇甲醚中，升温至100℃使其溶解形成三苯基膦溶液；将1.04g(4mmol)水合三氯化钌加入到40mL乙二醇甲醚中，搅拌均匀使其溶解形成三氯化钌溶液；然后与40mL质量分数为37％的甲醛水溶液依次快速加入到三苯基膦溶液中；将反应升温至120℃，反应0.8h；最后将上述反应液冷却，抽滤，空气干燥，即获得2.82g二(三苯基膦)羰基一水合二氯化钌固体，收率为95％，液相纯度98％。通过单晶X-射线衍射分析，确定催化剂结构如图1所示。
实施例2：二(三苯基膦)羰基一水合二氯化钌的合成
将3.16g(12mmol)三苯基膦加入到60mL乙醇中，升温至50℃使其溶解形成三苯基膦溶液；将0.5g(2mmol)水合三氯化钌加入到30mL乙醇中，搅拌均匀使其溶解形成三氯化钌溶液；然后与10mL质量分数为37％的甲醛水溶液依次快速加入到三苯基膦溶液中；将反应升温至80℃，反应2h；最后将上述反应液冷却，抽滤，空气干燥，即获得1.19g二(三苯基膦)羰基一水合二氯化钌固体，收率为40％，液相纯度96％。
实施例3：二(三苯基膦)羰基一水合二氯化钌的合成
将3.16g(12mmol)三苯基膦加入到180mL乙腈中，升温至80℃使其溶解形成三苯基膦溶液；将3g(12mmol)水合三氯化钌加入到60mL乙腈中，搅拌均匀使其溶解形成三氯化钌溶液；然后与180mL质量分数为37％的甲醛水溶液依次快速加入到三苯基膦溶液中；将反应升温至90℃，反应0.5h；最后将上述反应液冷却，抽滤，空气干燥，即获得3.12g二(三苯基膦)羰基一水合二氯化钌固体，收率为30％，液相纯度96％。
实施例4：二(三苯基膦)羰基一水合二氯化钌的合成
将3.16g(12mmol)三苯基膦加入到80mL甲苯中，升温至100℃使其溶解形成三苯基膦溶液；、将1.04g(4mmol)水合三氯化钌加入到40mL甲苯中，搅拌均匀使其溶解形成三氯化钌溶液；然后与40mL质量分数为37％的甲醛水溶液依次快速加入到三苯基膦溶液中；将反应升温至130℃，反应1.2h；最后将上述反应液冷却，抽滤，空气干燥，即获得2.73g二(三苯基膦)羰基一水合二氯化钌固体，收率为92％，液相纯度97％。
实施例5：4-苄基硫代吗啉的合成
Figure BDA0002988421960000061
将苄醇(0.324g,3mmol)和硫代吗啉(0.103g,1mmol)溶于1mL甲苯中，并与0.01mmol(7.4mg)的二(三苯基膦)羰基一水合二氯化钌一同加入耐压管中，140℃反应6h。所得反应液冷却至室温，脱溶，快速制备液相色谱仪纯化(乙酸乙酯：石油醚的体积比为5:100)，收集含目标化合物的洗脱液，减压旋蒸得到0.183g式3所示化合物，收率95％，液相纯度99％。1H NMR(500MHz,CDCl3)δ7.38–7.31(m,4H),7.30–7.25(m,1H),3.54(s,2H),2.77–2.65(m,8H).13C NMR(126MHz,CDCl3)δ138.01,129.00(2C),128.20(2C),127.05,63.64,54.87(2C),27.97(2C).HRMS(ES+)m/z calcd for C11H15NS([M+H]+)194.0098,found194.0999.
实施例6：4-苄基硫代吗啉的合成
Figure BDA0002988421960000071
将苄醇(0.324g,3mmol)和硫代吗啉(0.103g,1mmol)溶于1mL甲苯中，并与0.01mmol(9.4mg)的三(三苯基膦)二氯化钌一同加入耐压管中，140℃反应6h。所得反应液冷却至室温，脱溶，快速制备液相色谱仪纯化(乙酸乙酯：石油醚的体积比为5:100)，收集含目标化合物的洗脱液，减压旋蒸得到0.023g式3所示化合物，收率12％，液相纯度99％。
实施例7：4-苄基硫代吗啉的合成
Figure BDA0002988421960000072
将苄醇(0.108g,1mmol)和硫代吗啉(0.103g,1mmol)溶于0.1mL四氢呋喃中，并与0.01mmol(7.4mg)的二(三苯基膦)羰基一水合二氯化钌一同加入耐压管中，80℃反应6h。所得反应液冷却至室温，脱溶，快速制备液相色谱仪纯化(乙酸乙酯：石油醚的体积比为5:100)，收集含目标化合物的洗脱液，减压旋蒸得到0.088g式3所示化合物，收率46％，液相纯度99％。
实施例8：4-苄基硫代吗啉的合成
Figure BDA0002988421960000073
将苄醇(1.08g,10mmol)和硫代吗啉(0.103g,1mmol)溶于1mL二甲苯中，并与0.01mmol(7.4mg)的二(三苯基膦)羰基一水合二氯化钌一同加入耐压管中，140℃反应6h。所得反应液冷却至室温，脱溶，快速制备液相色谱仪纯化(乙酸乙酯：石油醚的体积比为5:100)，收集含目标化合物的洗脱液，减压旋蒸得到0.164g式3所示化合物，收率85％，液相纯度99％。
实施例9：4-苄基硫代吗啉的合成
Figure BDA0002988421960000074
将苄醇(0.324g,3mmol)和硫代吗啉(0.103g,1mmol)溶于5mL二氧六环中，并与0.01mmol(7.4mg)的二(三苯基膦)羰基一水合二氯化钌一同加入耐压管中，80℃反应6h。所得反应液冷却至室温，脱溶，快速制备液相色谱仪纯化(乙酸乙酯：石油醚的体积比为5:100)，收集含目标化合物的洗脱液，减压旋蒸得到0.106g式3所示化合物，收率55％，液相纯度99％。
实施例10：4-苄基硫代吗啉的合成
Figure BDA0002988421960000081
将苄醇(0.324g,3mmol)和硫代吗啉(0.103g,1mmol)溶于1mL N,N-二甲基甲酰胺中，并与0.002mmol(1.4mg)的二(三苯基膦)羰基一水合二氯化钌一同加入耐压管中，160℃反应2h。所得反应液冷却至室温，脱溶，快速制备液相色谱仪纯化(乙酸乙酯：石油醚的体积比为5:100)，收集含目标化合物的洗脱液，减压旋蒸得到0.073g式3所示化合物，收率38％，液相纯度99％。
实施例11：4-苄基硫代吗啉的合成
Figure BDA0002988421960000082
将苄醇(0.324g,3mmol)和硫代吗啉(0.103g,1mmol)溶于1mL二甲基亚砜中，并与0.05mmol(37.2mg)的二(三苯基膦)羰基一水合二氯化钌一同加入耐压管中，140℃反应10h。所得反应液冷却至室温，脱溶，快速制备液相色谱仪纯化(乙酸乙酯：石油醚的体积比为5:100)，收集含目标化合物的洗脱液，减压旋蒸得到0.121g式3所示化合物，收率63％，液相纯度99％。
实施例12：4-苄基硫代吗啉的合成
Figure BDA0002988421960000083
将苄醇(0.324g,3mmol)和硫代吗啉(0.103g,1mmol)溶于1mL叔戊醇中，并与0.05mmol(37.2mg)的二(三苯基膦)羰基一水合二氯化钌一同加入耐压管中，140℃反应10h。所得反应液冷却至室温，脱溶，快速制备液相色谱仪纯化(乙酸乙酯：石油醚的体积比为5:100)，收集含目标化合物的洗脱液，减压旋蒸得到0.150g式3所示化合物，收率78％，液相纯度99％。
实施例13：4-(2-甲基苄基)硫代吗啉的合成
Figure BDA0002988421960000091
将2-甲基苄醇(0.360g,3mmol)和硫代吗啉(0.103g,1mmol)溶于1mL甲苯中，并与0.01mmol(7.4mg)的二(三苯基膦)羰基一水合二氯化钌一同加入耐压管中，140℃反应6h。所得反应液冷却至室温，脱溶，快速制备液相色谱仪纯化(乙酸乙酯：石油醚的体积比为5:100)，收集含目标化合物的洗脱液，减压旋蒸得到0.168g式3所示化合物，收率81％，液相纯度99％。1H NMR(500MHz,CDCl3)δ7.30–7.24(m,1H),7.22–7.13(m,3H),3.48(s,2H),2.73(dd,J＝6.3,2.8Hz,4H),2.67(dd,J＝5.4,4.0Hz,4H),2.37(s,3H).13C NMR(126MHz,CDCl3)δ137.58,136.19,130.31,129.83,127.10,125.46,61.56,54.99(2C),28.15(2C),19.22.HRMS(ES+)m/z calcd for C12H17NS([M+H]+)208.1154,found 208.1155.
实施例14：4-(3-甲基苄基)硫代吗啉的合成
Figure BDA0002988421960000092
将3-甲基苄醇(0.360g,3mmol)和硫代吗啉(0.103g,1mmol)溶于1mL甲苯中，并与0.01mmol(7.4mg)的二(三苯基膦)羰基一水合二氯化钌一同加入耐压管中，140℃反应6h。所得反应液冷却至室温，脱溶，快速制备液相色谱仪纯化(乙酸乙酯：石油醚的体积比为5:100)，收集含目标化合物的洗脱液，减压旋蒸得到0.193g式3所示化合物，收率93％，液相纯度99％。1H NMR(500MHz,CDCl3)δ7.22(t,J＝7.5Hz,1H),7.15–7.07(m,3H),3.50(s,2H),2.76–2.66(m,8H),2.37(s,3H).13C NMR(126MHz,CDCl3)δ137.88,137.83,129.79,128.10,127.84,126.16,63.69,54.92(2C),27.97(2C),21.37.HRMS(ES+)m/z calcd for C12H17NS([M+H]+)208.1154,found 208.1158.
实施例15：4-(4-甲基苄基)硫代吗啉的合成
Figure BDA0002988421960000093
将4-甲基苄醇(0.360g,3mmol)和硫代吗啉(0.103g,1mmol)溶于1mL甲苯中，并与0.01mmol(7.4mg)的二(三苯基膦)羰基一水合二氯化钌一同加入耐压管中，140℃反应6h。所得反应液冷却至室温，脱溶，快速制备液相色谱仪纯化(乙酸乙酯：石油醚的体积比为5:100)，收集含目标化合物的洗脱液，减压旋蒸得到0.194g式3所示化合物，收率94％，液相纯度99％。1H NMR(500MHz,CDCl3)δ7.21(d,J＝7.9Hz,2H),7.14(d,J＝7.9Hz,2H),3.50(s,2H),2.75–2.65(m,8H),2.38–2.32(m,3H).13C NMR(126MHz,CDCl3)δ136.69,134.88,129.04(2C),128.92(2C),63.41,54.86(2C),28.01(2C),21.07.HRMS(ES+)m/z calcd forC12H17NS([M+H]+)208.1154,found 208.1155.
实施例16：4-(3-甲氧基苄基)硫代吗啉的合成
Figure BDA0002988421960000101
将3-甲氧基苄醇(0.408g,3mmol)和硫代吗啉(0.103g,1mmol)溶于1mL甲苯中，并与0.01mmol(7.4mg)的二(三苯基膦)羰基一水合二氯化钌一同加入耐压管中，140℃反应6h。所得反应液冷却至室温，脱溶，快速制备液相色谱仪纯化(乙酸乙酯：石油醚的体积比为5:100)，收集含目标化合物的洗脱液，减压旋蒸得到0.178g式3所示化合物，收率80％，液相纯度99％。1H NMR(500MHz,CDCl3)δ7.26–7.21(m,1H),6.93–6.88(M,2H),6.84–6.78(m,1H),3.82(s,3H),3.51(s,2H),2.76–2.66(m,8H).13C NMR(126MHz,CDCl3)δ159.68,139.81,129.17,121.30,114.48,112.46,63.57,55.18,54.92(2C),28.01(2C).HRMS(ES+)m/zcalcd for C12H17NOS([M+H]+)224.1104,found 224.1110.
实施例17：4-(3-氟苄基)硫代吗啉的合成
Figure BDA0002988421960000102
将3-氟苄醇(0.378g,3mmol)和硫代吗啉(0.103g,1mmol)溶于1mL甲苯中，并与0.01mmol(7.4mg)的二(三苯基膦)羰基一水合二氯化钌一同加入耐压管中，140℃反应6h。所得反应液冷却至室温，脱溶，快速制备液相色谱仪纯化(乙酸乙酯：石油醚的体积比为5:100)，收集含目标化合物的洗脱液，减压旋蒸得到0.148g式3所示化合物，收率70％，液相纯度99％。1H NMR(500MHz,CDCl3)δ7.37(td,J＝7.5,1.7Hz,1H),7.28–7.21(m,1H),7.12(td,J＝7.5,1.0Hz,1H),7.06–7.01(m,1H),3.61(s,2H),2.79–2.73(m,4H),2.73–2.67(m,4H).13CNMR(126MHz,CDCl3)δ161.43(d,1JC-F＝246.6Hz,1C),131.41(d,3JC-F＝4.54Hz,1C),128.82(d,3JC-F＝8.3Hz,1C),124.45(d,2JC-F＝14.6Hz,1C),123.85(d,4JC-F＝3.5Hz,1C),115.27(d,2JC-F＝22.2Hz,1C),55.96(d,JC-F＝1.76Hz,1C),54.62(2C),27.98(2C).HRMS(ES+)m/zcalcd for C11H14FNS([M+H]+)212.0904,found 212.0909.
实施例18：4-(3-溴苄基)硫代吗啉的合成
Figure BDA0002988421960000111
将3-溴苄醇(0.561g,3mmol)和硫代吗啉(0.103g,1mmol)溶于1mL甲苯中，并与0.01mmol(7.4mg)的二(三苯基膦)羰基一水合二氯化钌一同加入耐压管中，140℃反应6h。所得反应液冷却至室温，脱溶，快速制备液相色谱仪纯化(乙酸乙酯：石油醚的体积比为5:100)，收集含目标化合物的洗脱液，减压旋蒸得到0.261g式3所示化合物，收率96％，液相纯度99％。1H NMR(500MHz,CDCl3)δ7.48(s,1H),7.40–7.36(m,1H),7.23(d,J＝7.7Hz,1H),7.18(t,J＝7.7Hz,1H),3.47(s,2H),2.73–2.63(m,8H).13C NMR(126MHz,CDCl3)δ140.62,131.72,130.12,129.74,127.41,122.41,62.87,54.81(2C),27.91(2C).HRMS(ES+)m/zcalcd for C11H14BrNS([M+H]+)274.0082,found 274.0092.
实施例19：4-(3-碘苄基)硫代吗啉的合成
Figure BDA0002988421960000112
将3-碘苄醇(0.702g,3mmol)和硫代吗啉(0.103g,1mmol)溶于1mL甲苯中，并与0.01mmol(7.4mg)的二(三苯基膦)羰基一水合二氯化钌一同加入耐压管中，140℃反应6h。所得反应液冷却至室温，脱溶，快速制备液相色谱仪纯化(乙酸乙酯：石油醚的体积比为5:100)，收集含目标化合物的洗脱液，减压旋蒸得到0.313g式3所示化合物，收率98％，液相纯度99％。1H NMR(500MHz,CDCl3)δ7.69(s,1H),7.60(d,J＝7.9Hz,1H),7.28(d,J＝6.4Hz,1H),7.06(t,J＝7.7Hz,1H),3.46(s,2H),2.75–2.65(m,8H).13C NMR(126MHz,CDCl3)δ140.64,137.81,136.21,130.02,128.20,94.41,62.86,54.88(2C),27.95(2C).HRMS(ES+)m/z calcd for C11H14INS([M+H]+)319.9964,found 319.9970.
实施例20：4-(3-三氟甲基苄基)硫代吗啉的合成
Figure BDA0002988421960000121
将3-三氟甲基苄醇(0.558g,3mmol)和硫代吗啉(0.103g,1mmol)溶于1mL甲苯中，并与0.01mmol(7.4mg)的二(三苯基膦)羰基一水合二氯化钌一同加入耐压管中，140℃反应6h。所得反应液冷却至室温，脱溶，快速制备液相色谱仪纯化(乙酸乙酯：石油醚的体积比为5:100)，收集含目标化合物的洗脱液，减压旋蒸得到0.149g式3所示化合物，收率57％，液相纯度99％。1H NMR(500MHz,CDCl3)δ7.79(d,J＝7.7Hz,1H),7.64(d,J＝7.8Hz,1H),7.53(t,J＝7.5Hz,1H),7.34(t,J＝7.6Hz,1H),3.68(s,2H),2.73(td,J＝9.4,3.4Hz,8H).13C NMR(126MHz,CDCl3)δ137.79,131.73,130.15,128.68(q,2JC-F＝30.2Hz,1C),126.81,125.78(q,3JC-F＝5.9Hz,1C),124.5(q,1JC-F＝274.6Hz,1C),58.90,55.08(2C),28.11(2C).HRMS(ES+)m/z calcd for C12H14F3NS([M+H]+)262.0872,found 262.0879.
实施例21：4-(3,5-二甲氧基苄基)硫代吗啉的合成
Figure BDA0002988421960000122
将3,5-二甲氧基苄醇(0.504g,3mmol)和硫代吗啉(0.103g,1mmol)溶于1mL甲苯中，并与0.01mmol(7.4mg)的二(三苯基膦)羰基一水合二氯化钌一同加入耐压管中，140℃反应6h。所得反应液冷却至室温，脱溶，快速制备液相色谱仪纯化(乙酸乙酯：石油醚的体积比为5:100)，收集含目标化合物的洗脱液，减压旋蒸得到0.202g式3所示化合物，收率80％，液相纯度99％。1H NMR(500MHz,CDCl3)δ6.50(d,J＝2.3Hz,2H),6.37(t,J＝2.3Hz,1H),3.80(s,6H),3.47(s,2H),2.70(q,J＝6.7Hz,8H).13C NMR(126MHz,CDCl3)δ160.75(2C),140.66,106.78(2C),98.99,63.69,55.30(2C),54.92(2C),28.00(2C).HRMS(ES+)m/z calcd forC13H19NO2S([M+H]+)254.1209,found 254.1217.
实施例22：4-(3,5-二氟苄基)硫代吗啉的合成
Figure BDA0002988421960000131
将3,5-二氟苄醇(0.432g,3mmol)和硫代吗啉(0.103g,1mmol)溶于1mL甲苯中，并与0.01mmol(7.4mg)的二(三苯基膦)羰基一水合二氯化钌一同加入耐压管中，140℃反应6h。所得反应液冷却至室温，脱溶，快速制备液相色谱仪纯化(乙酸乙酯：石油醚的体积比为5:100)，收集含目标化合物的洗脱液，减压旋蒸得到0.133g式3所示化合物，收率58％，液相纯度99％。1H NMR(500MHz,CDCl3)δ6.92–6.85(m,2H),6.69(tt,J＝8.9,2.4Hz,1H),3.49(s,2H),2.76–2.65(m,8H).13C NMR(126MHz,CDCl3)δ163.03(dd,1JC-F＝248.2,12.7Hz,2C),142.72(t,3JC-F＝8.7Hz,1C),111.19(dd,2JC-F＝19.3,5.7Hz,2C),102.40(t,2JC-F＝25.4Hz,1C),62.70(t,4JC-F＝2.0Hz,1C),54.90(2C),27.98(2C).HRMS(ES+)m/z calcd forC11H13F2NS([M+H]+)230.0810,found 230.0820.
实施例23：4-(吡啶-2-基甲基)硫代吗啉的合成
Figure BDA0002988421960000132
将2-吡啶甲醇(0.327g,3mmol)和硫代吗啉(0.103g,1mmol)溶于1mL甲苯中，并与0.01mmol(7.4mg)的二(三苯基膦)羰基一水合二氯化钌一同加入耐压管中，140℃反应6h。所得反应液冷却至室温，脱溶，快速制备液相色谱仪纯化(乙酸乙酯：石油醚的体积比为5:100)，收集含目标化合物的洗脱液，减压旋蒸得到0.155g式3所示化合物，收率80％，液相纯度99％。1H NMR(500MHz,CDCl3)δ8.41(m,1H),7.50(m,1H),7.25(d,J＝7.7Hz,1H),7.25(d,J＝7.7Hz,1H),7.02(m,2H),2.61(m,4H),2.58–2.49(m,4H).13C NMR(126MHz,CDCl3)δ158.00,148.82,135.99,122.70,121.66,64.79,54.67(2C),27.50(2C).HRMS(ES+)m/zcalcd for C10H14N2S([M+H]+)195.0950,found 195.0958.
实施例24：4-(噻吩-2-基甲基)硫代吗啉的合成
Figure BDA0002988421960000133
将2-噻吩甲醇(0.342g,3mmol)和硫代吗啉(0.103g,1mmol)溶于1mL甲苯中，并与0.01mmol(7.4mg)的二(三苯基膦)羰基一水合二氯化钌一同加入耐压管中，140℃反应6h。所得反应液冷却至室温，脱溶，快速制备液相色谱仪纯化(乙酸乙酯：石油醚的体积比为5:100)，收集含目标化合物的洗脱液，减压旋蒸得到0.173g式3所示化合物，收率87％，液相纯度99％。1H NMR(500MHz,CDCl3)δ7.27-7.23(m,1H),6.98–6.94(m,1H),6.93–6.89(m,1H),3.75(s,2H),2.81-2.73(m,4H),2.73–2.65(m,4H).13C NMR(126MHz,CDCl3)δ141.46,126.48,126.08,125.12,57.89,54.61(2C),28.02(2C).HRMS(ES+)m/z calcd for C9H13NS2([M+H]+)200.0562,found 200.0561.
实施例25：4-(萘-1-基甲基)硫代吗啉的合成
Figure BDA0002988421960000141
将1-萘甲醇(0.474g,3mmol)和硫代吗啉(0.103g,1mmol)溶于1mL甲苯中，并与0.01mmol(7.4mg)的二(三苯基膦)羰基一水合二氯化钌一同加入耐压管中，140℃反应6h。所得反应液冷却至室温，脱溶，快速制备液相色谱仪纯化(乙酸乙酯：石油醚的体积比为5:100)，收集含目标化合物的洗脱液，减压旋蒸得到0.156g式3所示化合物，收率64％，液相纯度99％。1H NMR(500MHz,CDCl3)δ8.31(d,J＝8.3Hz,1H),7.91–7.86(m,1H),7.81(dd,J＝7.0,2.1Hz,1H),7.57–7.50(m,2H),7.47–7.40(m,2H),3.94(s,2H),2.85–2.78(m,4H),2.71–2.64(m,4H).13C NMR(126MHz,CDCl3)δ133.87,133.79,132.52,128.39,128.01,127.44,125.71,125.62,125.05,124.73,61.84,55.10(2C),28.09(2C).HRMS(ES+)m/zcalcd for C15H17NS([M+H]+)244.1154,found 244.1158.
实施例26：4-丙基硫代吗啉的合成
Figure BDA0002988421960000142
将正丙醇(0.180g,3mmol)和硫代吗啉(0.103g,1mmol)溶于1mL甲苯中，并与0.01mmol(7.4mg)的二(三苯基膦)羰基一水合二氯化钌一同加入耐压管中，140℃反应6h。所得反应液冷却至室温，脱溶，快速制备液相色谱仪纯化(乙酸乙酯：石油醚的体积比为5:100)，收集含目标化合物的洗脱液，减压旋蒸得到0.126g式3所示化合物，收率87％，液相纯度99％。1H NMR(500MHz,CDCl3)δ2.76–2.62(m,8H),2.35–2.27(m,2H),1.54–1.43(m,2H),0.88(t,J＝7.4Hz,3H).13C NMR(126MHz,CDCl3)δ61.35,54.99(2C),27.97(2C),19.58,11.87.HRMS(ES+)m/z calcd for C7H15NS([M+H]+)146.0998,found 146.1000.
实施例27：4-丁基硫代吗啉的合成
Figure BDA0002988421960000151
将正丁醇(0.222g,3mmol)和硫代吗啉(0.103g,1mmol)溶于1mL甲苯中，并与0.01mmol(7.4mg)的二(三苯基膦)羰基一水合二氯化钌一同加入耐压管中，140℃反应6h。所得反应液冷却至室温，脱溶，快速制备液相色谱仪纯化(乙酸乙酯：石油醚的体积比为5:100)，收集含目标化合物的洗脱液，减压旋蒸得到0.121g式3所示化合物，收率76％，液相纯度99％。1H NMR(500MHz,CDCl3)δ2.76–2.63(m,8H),2.39–2.30(m,2H),1.51–1.40(m,2H),1.35–1.22(m,2H),0.91(t,J＝7.3Hz,3H).13C NMR(126MHz,CDCl3)δ59.17,55.03(2C),28.63,27.98(2C),20.71,13.99.HRMS(ES+)m/z calcd for C8H17NS([M+H]+)160.1154,found 160.1158.
实施例28：4-(环己基甲基)硫代吗啉的合成
Figure BDA0002988421960000152
将环己基甲醇(0.342g,3mmol)和硫代吗啉(0.103g,1mmol)溶于1mL甲苯中，并与0.01mmol(7.4mg)的二(三苯基膦)羰基一水合二氯化钌一同加入耐压管中，140℃反应6h。所得反应液冷却至室温，脱溶，快速制备液相色谱仪纯化(乙酸乙酯：石油醚的体积比为5:100)，收集含目标化合物的洗脱液，减压旋蒸得到0.173g式3所示化合物，收率87％，液相纯度99％。1H NMR(500MHz,CDCl3)δ2.70–2.59(m,8H),2.12(d,J＝7.1Hz,2H),1.78–1.61(m,5H),1.52–1.41(m,1H),1.27–1.09(m,3H),0.91–0.77(m,2H).13C NMR(126MHz,CDCl3)δ66.28,55.61(2C),35.03,31.85(2C),27.99(2C),26.79,26.13(2C).HRMS(ES+)m/z calcdfor C11H21NS([M+H]+)200.1467,found 200.1474.
实施例29：4-苯乙基硫代吗啉的合成
Figure BDA0002988421960000153
将2-苯乙醇(0.360g,3mmol)和硫代吗啉(0.103g,1mmol)溶于1mL甲苯中，并与0.01mmol(7.4mg)的二(三苯基膦)羰基一水合二氯化钌一同加入耐压管中，140℃反应6h。所得反应液冷却至室温，脱溶，快速制备液相色谱仪纯化(乙酸乙酯：石油醚的体积比为5:100)，收集含目标化合物的洗脱液，减压旋蒸得到0.124g式3所示化合物，收率60％，液相纯度99％。1H NMR(500MHz,CDCl3)δ7.33–7.27(m,2H),7.25–7.18(m,3H),2.87–2.76(m,6H),2.76–2.70(m,4H),2.69–2.62(m,2H).13C NMR(126MHz,CDCl3)δ140.21,128.69(2C),128.40(2C),126.07,61.19,54.92(2C),33.10,27.97(2C).HRMS(ES+)m/z calcd for C12H17NS([M+H]+)208.1154,found 208.1156.
实施例30：4-(3-苯丙基)硫代吗啉的合成
Figure BDA0002988421960000161
将3-苯丙醇(0.402g,3mmol)和硫代吗啉(0.103g,1mmol)溶于1mL甲苯中，并与0.01mmol(7.4mg)的二(三苯基膦)羰基一水合二氯化钌一同加入耐压管中，140℃反应6h。所得反应液冷却至室温，脱溶，快速制备液相色谱仪纯化(乙酸乙酯：石油醚的体积比为5:100)，收集含目标化合物的洗脱液，减压旋蒸得到0.133g式3所示化合物，收率60％，液相纯度99％。1H NMR(500MHz,CDCl3)δ7.32–7.26(m,2H),7.24–7.16(m,3H),2.76–2.67(m,8H),2.67–2.61(m,2H),2.46–2.38(m,2H),1.87–1.78(m,2H).13C NMR(126MHz,CDCl3)δ142.00,128.35(2C),128.29(2C),125.76,58.55,54.95(2C),33.56,28.12,27.93(2C).HRMS(ES+)m/z calcd for C13H19NS([M+H]+)222.1311,found 222.1317.
实施例31：4-(2-甲氧基乙基)硫代吗啉的合成
Figure BDA0002988421960000162
将乙二醇甲醚(0.228g,3mmol)和硫代吗啉(0.103g,1mmol)溶于1mL甲苯中，并与0.01mmol(7.4mg)的二(三苯基膦)羰基一水合二氯化钌一同加入耐压管中，140℃反应6h。所得反应液冷却至室温，脱溶，快速制备液相色谱仪纯化(乙酸乙酯：石油醚的体积比为5:100)，收集含目标化合物的洗脱液，减压旋蒸得到0.090g式3所示化合物，收率56％，液相纯度99％。1H NMR(500MHz,CDCl3)δ3.50(t,J＝5.6Hz,2H),3.34(s,3H),2.80–2.74(m,4H),2.72–2.67(m,4H),2.61(t,J＝5.6Hz,2H).13C NMR(126MHz,CDCl3)δ69.93,58.88,58.56,55.27(2C),27.71(2C).HRMS(ES+)m/z calcd for C7H15NOS([M+H]+)162.0947,found162.0948.
实施例32：4-(2-羰基丙基)硫代吗啉的合成
Figure BDA0002988421960000171
将2-羟基丙酮(0.222g,3mmol)和硫代吗啉(0.103g,1mmol)溶于1mL甲苯中，并与0.01mmol(7.4mg)的二(三苯基膦)羰基一水合二氯化钌一同加入耐压管中，140℃反应6h。所得反应液冷却至室温，脱溶，快速制备液相色谱仪纯化(乙酸乙酯：石油醚的体积比为5:100)，收集含目标化合物的洗脱液，减压旋蒸得到0.116g式3所示化合物，收率73％，液相纯度99％。1H NMR(500MHz,CDCl3)δ3.18(s,2H),2.76–2.67(m,8H),2.13(s,3H).13C NMR(126MHz,CDCl3)δ206.66,68.78,55.07(2C),27.73(2C),27.62.HRMS(ES+)m/z calcd forC7H13NOS([M+H]+)160.0791,found 160.0790.
实施例33：4-苄基-2-乙基硫代吗啉的合成
Figure BDA0002988421960000172
将苄醇(0.324g,3mmol)和2-乙基硫代吗啉(0.131g,1mmol)溶于1mL甲苯中，并与0.01mmol(7.4mg)的二(三苯基膦)羰基一水合二氯化钌一同加入耐压管中，140℃反应6h。所得反应液冷却至室温，脱溶，快速制备液相色谱仪纯化(乙酸乙酯：石油醚的体积比为5:100)，收集含目标化合物的洗脱液，减压旋蒸得到0.137g式3所示化合物，收率62％，液相纯度99％。1H NMR(500MHz,CDCl3)δ7.44–7.20(m,5H),3.55(q,J＝13.3Hz,2H),3.08–2.94(m,2H),2.89–2.80(m,2H),2.64–2.53(m,1H),2.42–2.33(m,1H),2.18(dd,J＝11.6,9.4Hz,1H),1.64–1.41(m,2H),0.99(t,J＝7.5Hz,3H).13C NMR(126MHz,CDCl3)δ138.19,128.89(2C),128.18(2C),126.99,63.44,60.98,54.61,42.75,27.68,26.54,11.53.HRMS(ES+)m/zcalcd for C13H19NS([M+H]+)222.1311,found 222.1319.
实施例34：4-苄基-2,2-二甲基硫代吗啉的合成
Figure BDA0002988421960000181
将苄醇(0.324g,3mmol)和2-乙基硫代吗啉(0.131g,1mmol)溶于1mL甲苯中，并与0.01mmol(7.4mg)的二(三苯基膦)羰基一水合二氯化钌一同加入耐压管中，140℃反应6h。所得反应液冷却至室温，脱溶，快速制备液相色谱仪纯化(乙酸乙酯：石油醚的体积比为5:100)，收集含目标化合物的洗脱液，减压旋蒸得到0.150g式3所示化合物，收率68％，液相纯度99％。1H NMR(500MHz,CDCl3)δ7.44–7.32(m,5H),3.55(s,2H),2.84–2.65(m,4H),2.44(s,2H),1.37(s,6H).13C NMR(126MHz,CDCl3)δ138.75,128.61(2C),128.16(2C),126.91,67.42,63.35,54.83,39.91,27.89(2C),26.20.HRMS(ES+)m/z calcd for C13H19NS([M+H]+)222.1311,found 222.1319.
实施例35：4-丙基-3,4-二氢-2H-苯并[b][1,4]噻嗪的合成
Figure BDA0002988421960000182
将正丙醇(0.180g,3mmol)和3,4-二氢-2H-苯并[b][1,4]噻嗪(0.151g,1mmol)溶于1mL甲苯中，并与0.01mmol(7.4mg)的二(三苯基膦)羰基一水合二氯化钌一同加入耐压管中，140℃反应6h。所得反应液冷却至室温，脱溶，快速制备液相色谱仪纯化(乙酸乙酯：石油醚的体积比为5:100)，收集含目标化合物的洗脱液，减压旋蒸得到0.112g式3所示化合物，收率58％，液相纯度99％。1HNMR(500MHz,CDCl3)δ7.09(d,J＝7.6Hz,1H),7.07–7.00(m,1H),6.72(d,J＝8.3Hz,1H),6.65(t,J＝7.4Hz,1H),3.70–3.61(m,2H),3.33–3.25(m,2H),3.11–3.03(m,2H),1.71(dd,J＝15.0,7.5Hz,2H),1.02(td,J＝7.3,1.0Hz,3H).13C NMR(126MHz,CDCl3)δ143.21,127.71,125.73,117.26,116.70,112.48,54.25,49.85,25.55,19.47,11.38.HRMS(ES+)m/z calcd for C11H15NS([M+H]+)194.0998,found 194.0996.
实施例36：4-苄硫基吗啉1,1-二氧化物的合成
Figure BDA0002988421960000191
将苄醇(0.324g,3mmol)和硫代吗啉氧化物(0.135g,1mmol)溶于1mL甲苯中，并与0.01mmol(7.4mg)的二(三苯基膦)羰基一水合二氯化钌一同加入耐压管中，140℃反应6h。所得反应液冷却至室温，脱溶，快速制备液相色谱仪纯化(乙酸乙酯：石油醚的体积比为5:100)，收集含目标化合物的洗脱液，减压旋蒸得到0.221g式3所示化合物，收率98％，液相纯度99％。1H NMR(500MHz,CDCl3)δ7.40–7.20(m,5H),3.65(s,2H),3.13–3.03(m,4H),3.00–2.93(m,4H).13C NMR(126MHz,CDCl3)δ137.18,128.69(2C),128.46(2C),127.56,61.32,51.35(2C),50.44(2C).HRMS(ES+)m/z calcd for C11H15NO2S([M+H]+)226.0896,found226.0903.
实施例37：6-(2-(甲硫基)乙基)-4,5,6,7-四氢噻吩并[2,3-c]吡啶的合成
Figure BDA0002988421960000192
将甲硫基乙醇(0.276g,3mmol)和4,5,6,7-四氢噻吩并[2,3-c]吡啶(0.139g,1mmol)溶于1mL甲苯中，并与0.01mmol(7.4mg)的二(三苯基膦)羰基一水合二氯化钌一同加入耐压管中，140℃反应6h全。所得反应液冷却至室温，脱溶，快速制备液相色谱仪纯化(乙酸乙酯：石油醚的体积比为5:100)，收集含目标化合物的洗脱液，减压旋蒸得到0.153g式3所示化合物，收率72％，液相纯度99％。1H NMR(500MHz,CDCl3)δ7.08(d,J＝5.1Hz,1H),6.73(d,J＝5.1Hz,1H),3.62(t,J＝1.5Hz,2H),2.91(t,J＝5.4Hz,2H),2.87–2.78(m,4H),2.75–2.70(m,2H),2.16(s,3H).13C NMR(126MHz,CDCl3)δ133.47,133.25,125.12,122.66,57.11,52.90,50.77,31.80,25.30,15.83.HRMS(ES+)m/z calcd for C10H15NS2([M+H]+)214.0719,found 214.0725.
实施例38：3-(4-丙基哌嗪-1-基)苯并[d]异噻唑的合成
Figure BDA0002988421960000201
将正丙醇(0.180g,3mmol)和3-(哌嗪-1-基)苯并[d]异噻唑(0.219g,1mmol)溶于1mL甲苯中，并与0.01mmol(7.4mg)的二(三苯基膦)羰基一水合二氯化钌一同加入耐压管中，140℃反应6h。所得反应液冷却至室温，脱溶，快速制备液相色谱仪纯化(乙酸乙酯：石油醚的体积比为5:100)，收集含目标化合物的洗脱液，减压旋蒸得到0.201g式3所示化合物，收率77％，液相纯度99％。1H NMR(500MHz,CDCl3)δ7.83(dd,J＝59.3,8.2Hz,2H),7.37(dt,J＝15.2,7.3Hz,2H),3.60–3.49(m,4H),2.70–2.61(m,4H),2.42–2.33(m,2H),1.61–1.48(m,2H),0.93(t,J＝7.4Hz,3H).13C NMR(126MHz,CDCl3)δ163.83,152.64,127.94,127.35,123.81,123.71,120.41,60.63,52.94(2C),49.96(2C),19.89,11.87.HRMS(ES+)m/z calcdfor C14H19N3S([M+H]+)262.1372,found 262.1384.
实施例39：N，N-二丙基-4-((三氟甲基)硫代)苯胺的合成
Figure BDA0002988421960000202
将正丙醇(0.180g,3mmol)和4-((三氟甲基)硫代)苯胺(0.193g,1mmol)溶于1mL甲苯中，并与0.01mmol(7.4mg)的二(三苯基膦)羰基一水合二氯化钌一同加入耐压管中，140℃反应6h。所得反应液冷却至室温，脱溶，快速制备液相色谱仪纯化(乙酸乙酯：石油醚的体积比为5:100)，收集含目标化合物的洗脱液，减压旋蒸得到0.258g式3所示化合物，收率93％，液相纯度99％。1H NMR(500MHz,CDCl3)δ7.48–7.42(m,2H),6.66–6.59(m,2H),3.34–3.22(m,4H),1.72–1.60(m,4H),0.97(t,J＝7.4Hz,6H).13C NMR(126MHz,CDCl3)δ149.98,138.13(2C),129.88(q,1JC-F＝309.2Hz,1C),111.90(2C),106.98,52.79(2C),20.28(2C),11.34(2C).HRMS(ES+)m/z calcd for C13H18F3NS([M+H]+)278.1185,found 278.1197.
实施例40：3-(甲硫基)-N，N-二丙基苯胺的合成
Figure BDA0002988421960000211
将正丙醇(0.180g,3mmol)和3-(甲硫基)苯胺(0.139g,1mmol)溶于1mL甲苯中，并与0.01mmol(7.4mg)的二(三苯基膦)羰基一水合二氯化钌一同加入耐压管中，140℃反应6h。所得反应液冷却至室温，脱溶，快速制备液相色谱仪纯化(乙酸乙酯：石油醚的体积比为5:100)，收集含目标化合物的洗脱液，减压旋蒸得到0.199g式3所示化合物，收率89％，液相纯度99％。1H NMR(500MHz,CDCl3)δ7.16(t,J＝8.0Hz,1H),6.59(d,J＝7.0Hz,2H),6.49(dd,J＝9.0,2.0Hz,1H),3.34–3.22(m,4H),2.52(s,3H),1.66(dd,J＝15.1,7.5Hz,4H),0.98(t,J＝7.4Hz,6H).13C NMR(126MHz,CDCl3)δ148.45,138.88,129.44,113.49,110.10,109.08,52.80(2C),20.38(2C),16.01,11.39(2C).HRMS(ES+)m/z calcd for C13H21NS([M+H]+)224.1467,found 224.1476.
实施例41：4-((4-硝基苯基)硫基)-N，N-二丙基苯胺的合成
Figure BDA0002988421960000212
将正丙醇(0.180g,3mmol)和4-((4-硝基苯基)硫代)苯胺(0.246g,1mmol)溶于1mL甲苯中，并与0.01mmol(7.4mg)的二(三苯基膦)羰基一水合二氯化钌一同加入耐压管中，140℃反应6h。所得反应液冷却至室温，脱溶，快速制备液相色谱仪纯化(乙酸乙酯：石油醚的体积比为5:100)，收集含目标化合物的洗脱液，减压旋蒸得到0.182g式3所示化合物，收率55％，液相纯度99％。1H NMR(500MHz,CDCl3)δ8.06–8.00(m,2H),7.39–7.31(m,2H),7.15–7.08(m,2H),6.72–6.66(m,2H),3.34–3.27(m,4H),1.73–1.61(m,4H),0.98(t,J＝7.4Hz,6H).13C NMR(126MHz,CDCl3)δ151.86,149.39,144.66,137.09(2C),125.03(2C),123.79(2C),112.61(2C),111.96,52.79(2C),20.35(2C),11.40(2C).HRMS(ES+)m/z calcd forC18H22N2O2S([M+H]+)331.1475,found 331.1483。

Claims (10)

1.一种二(三苯基膦)羰基一水合二氯化钌作为均相催化剂在含硫胺化物的氮烷基化反应中的应用。
2.如权利要求1所述的应用，其特征在于所述的应用为：将化合物1和化合物2溶于有机溶剂D中，加入二(三苯基膦)羰基一水合二氯化钌，80℃～160℃反应2h～10h，所得反应液B经后处理B，得到式3所示化合物；化合物1与化合物2的物质的量之比为0.5～10:1；所述二(三苯基膦)羰基一水合二氯化钌的用量为0.2～5mol/100mol化合物2％；
Figure FDA0002988421950000011
式1和3中，R1选自下列之一：苯基、2-甲基苯基、3-甲基苯基、4-甲基苯基、2-甲氧基苯基、3-甲氧基苯基、4-甲氧基苯基、4-联二苯基、2-氟苯基、3-氟苯基、4-氟苯基、2-溴苯基、3-溴苯基、4-溴苯基、2-碘苯基、3-碘苯基、4-碘苯基、2-三氟甲基苯基、3-三氟甲基苯基、4-三氟甲基苯基、3,5-二甲氧基苯基、3,5-二氟苯基、2-吡啶基、2-噻吩基、1-萘基、甲基、乙基、丙基、丁基、戊基、己基、环丙甲基、环丁甲基、环戊甲基、环己甲基、氧杂环丁基、2-四氢呋喃甲基、金刚烷甲基、环丙基、环丁基、环戊基、环己基、苯甲基、苯乙基、苯丙基、3-羟基丙基、4-羟基丁基、3-甲基丁基、3,3-二甲基丁基、甲氧基甲基、甲氧基丙基、甲硫基甲基、1-乙酮基；
式2中R2与R3连接成环，式2所示结构式选自下列之一：
Figure FDA0002988421950000021
3.如权利要求2所述的应用，其特征在于：式1和3中，R1为苯基、2-甲基苯基、3-甲基苯基、4-甲基苯基、2-甲氧基苯基、3-甲氧基苯基、2-氟苯基、3-氟苯基、2-溴苯基、3-溴苯基、2-碘苯基、3-碘苯基、3-三氟甲基苯基、3,5-二甲氧基苯基、3,5-二氟苯基、2-吡啶基、2-噻吩基、1-萘基、乙基、丙基、丁基、戊基、环戊基、环己基、苯甲基、苯乙基、甲氧基甲基、甲氧基丙基、甲硫基甲基或1-乙酮基。
4.如权利要求2所述的应用，其特征在于所述化合物3为下列之一：
4-苄基硫代吗啉、4-(2-甲基苄基)硫代吗啉、4-(3-甲基苄基)硫代吗啉、4-(4-甲基苄基)硫代吗啉、4-(3-甲氧基苄基)硫代吗啉、4-(3-氟苄基)硫代吗啉、4-(3-溴苄基)硫代吗啉、4-(3-碘苄基)硫代吗啉、4-(3-三氟甲基苄基)硫代吗啉、4-(3,5-二甲氧基苄基)硫代吗啉、4-(3,5-二氟苄基)硫代吗啉、4-(吡啶-2-基甲基)硫代吗啉、4-(噻吩-2-基甲基)硫代吗啉、4-(萘-1-基甲基)硫代吗啉、4-丙基硫代吗啉、4-丁基硫代吗啉、4-(环己基甲基)硫代吗啉、4-苯乙基硫代吗啉、4-(3-苯丙基)硫代吗啉、4-(2-甲氧基乙基)硫代吗啉、4-(2-羰基丙基)硫代吗啉、4-苄基-2-乙基硫代吗啉、4-苄基-2,2-二甲基硫代吗啉、4-丙基-3,4-二氢-2H-苯并[b][1,4]噻嗪、4-苄硫基吗啉1,1-二氧化物、6-(2-(甲硫基)乙基)-4,5,6,7-四氢噻吩并[2,3-c]吡啶、3-(4-丙基哌嗪-1-基)苯并[d]异噻唑、N，N-二丙基-4-((三氟甲基)硫代)苯胺、3-(甲硫基)-N，N-二丙基苯胺、4-((4-硝基苯基)硫基)-N，N-二丙基苯胺。
5.如权利要求2所述的应用，其特征在于：所述有机溶剂D为四氢呋喃、二氧六环、甲苯、二甲苯、N,N-二甲基甲酰胺、二甲基亚砜或叔戊醇。
6.如权利要求4所述的应用，其特征在于：所述有机溶剂D为甲苯。
7.如权利要求4所述的应用，其特征在于：所述有机溶剂D的体积以所述胺类化合物2的物质的量计为0.1～5mL/mmol。
8.如权利要求2所述的应用，其特征在于：反应条件为140℃反应6h。
9.如权利要求2所述的应用，其特征在于：所述化合物1与化合物2的物质的量之比为3:1。
10.如权利要求2所述的应用，其特征在于所述后处理B为：将所述反应液B冷却至室温，脱溶，利用快速制备液相色谱仪纯化，以体积比为2～20:100的乙酸乙酯与石油醚的混合溶液为洗脱液进行洗脱，收集含目标化合物的洗脱液，减压旋蒸得到式3所示化合物。
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0034480A2 (en) * 1980-02-14 1981-08-26 Grigg, Ronald Ernest Alkylation of amines
CN102874914A (zh) * 2012-10-10 2013-01-16 同济大学 一种利用负载型钌催化剂去除饮用水中污染物的方法
CN110790794A (zh) * 2019-10-25 2020-02-14 西安凯立新材料股份有限公司 三（三苯基膦)羰基氢氯钌固体的制备方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0034480A2 (en) * 1980-02-14 1981-08-26 Grigg, Ronald Ernest Alkylation of amines
CN102874914A (zh) * 2012-10-10 2013-01-16 同济大学 一种利用负载型钌催化剂去除饮用水中污染物的方法
CN110790794A (zh) * 2019-10-25 2020-02-14 西安凯立新材料股份有限公司 三（三苯基膦)羰基氢氯钌固体的制备方法

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
DONGHUI GUO，ET AL.: ""Ruthenium-Catalyzed Atropoenantioselective Synthesis of Axial Biaryls via Reductive Amination and Dynamic Kinetic Resolution"", 《ORG. LETT.》 *
SEOKSUN KIM，ET AL.: ""Ruthenium-Catalyzed Aminomethylation and Methylation of Phenol Derivatives Utilizing Methanol as the C1 Source"", 《ADV. SYNTH. CATAL.》 *
TUAN THANH DANG，ET AL.: ""Efficient Ruthenium-Catalyzed N‑Methylation of Amines Using Methanol"", 《ACS CATAL.》 *
YUPENG PAN，ET AL.: ""Asymmetric Synthesis of γ‑Secondary Amino Alcohols via a Borrowing-Hydrogen Cascade"", 《ORG. LETT.》 *

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