CN109053349B - 一种钯/感官组分催化的联芳化合物的合成方法 - Google Patents
一种钯/感官组分催化的联芳化合物的合成方法 Download PDFInfo
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Abstract
一种钯/感官组分催化的联芳化合物的合成方法，其特征在于：以卤代化合物为原料、钯化合物和感官组分为催化剂，用N,N‑二甲基甲酰胺作为溶剂，加入一定量的碱，加热反应24‑48小时，反应完全后，经乙酸乙酯萃取、干燥、硅胶柱层析分离，制得联芳化合物；本发明首次实现了感官组分在有机合成上的应用，实现了钯/感官组分催化的各种联芳化合物的合成。其优点如下：应用感官组分、无需还原剂和配体，适用范围广。
Description
技术领域
本发明属于有机合成化学技术领域，具体是一种钯/感官组分催化的联芳化合物的合成方法，即钯/感官组分催化的卤代芳香化合物的还原偶联方法。
背景技术
烟草行业从业人数众多，是某些地方政府的经济支柱，每年为国家提供超过一万亿元的利税，对国计民生具有重要的意义，然而，当前社会对控烟的呼声越来越高涨，这就对烟草行业的发展起到较大的限制。将烟叶中的感官组分用于化学反应，得到具有更高价值的化合物，无疑将对打破这种限制起到很大的作用。
用凝胶柱色谱分离并结合感官组学可得到烟叶中的感官组分。目前，应用感官组学的方法研究最多的是天然产物中引发或调节香气的嗅觉成分以及甜味、鲜味、苦味、酸味的味觉成分，在食品分析中有较多的应用，然而，该方法在烟叶分析中的应用直到近几年才有报道，如鲍峰玉等申请的中国专利《一种适用于配制电子烟烟液的辣味组分的富集方法》（ ZL201510741819.8）；张启东等发表的《初烤烟叶提取物中关键甜味成分的感官导向分析》，烟草科技49（6）, 58（2016）；迟广俊等发表的《初烤烟叶提取物中酸味关键成分的感官导向分析》，烟草科技48（12）, 27（2015），将烟叶中的感官组分应用于化学反应中还未见报道。
在无数天然产物、生物活性化合物、农药、染料和配体中都有联芳类化合物的结构（J. Buter, D. Heijnen, C. Vila, V. Hornillos, E, Otten, M. Giannerini, A. J.Minnaard, B. L, Feringa, Angew, Chem. Int. Ed., 55, 3620(2016)），因此发展合成联芳类化合物的方法具有非常重要意义。在合成联芳类化合物的方法中，获得诺贝尔奖的铃木偶联反应(Suzuki cross-coupling reaction)和根岸偶联反应（Negishi cross-coupling reaction）都是亲核试剂和亲电试剂的反应，提供了合成联芳类化合物另外一条途径的卤代烃与卤代烃之间的还原偶联反应则是亲电试剂和亲电试剂之间的反应，一般来说，该类反应需要另外加入化工产品作为还原剂或配体。到目前为止，把来自天然的感官组分用于钯催化的卤代烃的偶联反应合成联芳类化合物还没有实现。其意义在于首次把天然的感官组分应用有机化学反应，应用于联芳化合物的合成，而且由于感官组分的加入，不用再另外加入还原剂和配体。
发明内容
本发明的目的正是基于上述现有技术状况而提供的一种把天然的感官组分用于钯催化的卤代烃的偶联反应合成联芳类化合物的新方法，合成了多种联芳类化合物。该方法无需再额外添加还原剂和配体。本发明首次实现了感官组分在有机化学反应中的应用。
本发明的目的是通过以下技术方案来实现的：
一种钯/感官组分催化的联芳化合物的合成方法，是以卤代化合物为原料、钯化合物和感官组分为催化剂，用N, N-二甲基甲酰胺作为溶剂，加入一定量的碱，加热反应24-48小时，反应完全后，经乙酸乙酯萃取、干燥、硅胶柱层析分离，制得联芳化合物；
卤代化合物与钯化合物的摩尔比为1∶0.05-0.1，优选1∶0.1；
卤代化合物与碱的摩尔比为1∶1-2，优选1∶2；
每0.5毫摩尔卤代化合物对应加入8-16mg感官组分，优选8mg。
其反应方程式如下：
R为氢原子、烷基、烷氧基、氰基、酯基、羟基、醛基、酮基、三氟甲基；
所述卤代化合物可以是卤代芳香化合物、卤代杂环芳香化合物，优选为碘代芳香化合物，包括：1-碘萘、碘苯、4-碘苯甲酸甲酯、4-碘苯酚。
所述感官组分为酸味组分：苹果酸、乳酸、乙酰丙酸、柠檬酸、富马酸；或为甜味组分：果糖、葡萄糖、肌糖、蔗糖；或为苦味组分：麦斯明；或为辣味组分：烟碱。
所述钯化合物为醋酸钯、双三苯基膦二氯化钯。
所述碱为碳酸钾、磷酸钾、醋酸钾、氢氧化钾、叔丁醇钾、三乙胺、四甲基胍、1，8-二氮杂二环十一碳-7-烯。
所述加热反应或为油浴加热，100℃，24小时；或为电加热套加热回流，48小时。
所述感官组分来源于烟叶、食品。
具体加料反应过程如下：向有机溶剂N,N-二甲基甲酰胺（5.0-10.0毫升）中加入上述提到的卤代化合物（0.5毫摩尔），加入上述提到的某一类催化剂（0.05毫摩尔）和某一种感官组分（8毫克），加入上述提到的某一类碱（1毫摩尔）。加毕，油浴100 oC搅拌24-48小时，或电加热套加热回流搅拌24-48小时，经后处理（萃取、干燥、硅胶柱层析分离）得到联芳类化合物，收率在40-91%。
本发明相比现有技术的突出优点在于：首次实现了感官组分在有机合成上的应用，实现了钯/感官组分催化的各种联芳化合物的合成。其优点如下：应用感官组分、无需还原剂和配体，适用范围广。
附图说明
图1为联萘1H-NMR核磁共振谱（实施例1制得产物）；
图2为联苯1H-NMR核磁共振谱（实施例2制得产物）；
图3为4，4'-联苯甲酸甲酯1H-NMR核磁共振谱（实施例3制得产物）；
图4为4，4'-联苯酚1H-NMR核磁共振谱（实施例4制得产物）。
具体实施方式
本发明以下结合实施例（附图）做进一步描述：
实施例1
在50mL圆底烧瓶中加入0.011g醋酸钯（0.05毫摩尔）、10mL有机溶剂N, N-二甲基甲酰胺、0.008g酸味组分（主要包括苹果酸等酸味组分）、0.138g碳酸钾（1毫摩尔）、0.073mL1-碘萘（0.5毫摩尔)，加热100 oC24小时，至反应完全（薄层色谱TLC检测）。将反应混合物倒入20mL蒸馏水中，以乙酸乙酯萃取（10mL×3）。合并有机相，用无水硫酸镁干燥。蒸除溶剂后，剩余物用硅胶柱层析分离（洗脱剂为石油醚）得到浅黄色固体0.0554g，产率为87%，核磁共振谱图如图1。
实施例2
在50mL圆底烧瓶中加入0.011g醋酸钯（也可为双三苯基膦二氯化钯）（0.05毫摩尔）、10mL有机溶剂N, N-二甲基甲酰胺、0.008g辣味组分（主要为烟碱）、0.138g碳酸钾（也可更换为磷酸钾）（1毫摩尔）、0.056mL碘苯（0.5毫摩尔)，加热100 oC24小时，至反应完全（薄层色谱TLC检测）。将反应混合物倒入20mL蒸馏水中，以乙酸乙酯萃取（10mL×3）。合并有机相，用无水硫酸镁干燥。蒸除溶剂后，剩余物用硅胶柱层析分离（洗脱剂为石油醚）得到白色固体0.0312g，产率为81%，核磁共振谱图如图2。
实施例3
在50mL圆底烧瓶中加入0.011g醋酸钯（0.05毫摩尔）、10mL有机溶剂N, N-二甲基甲酰胺、0.008g辣味组分如烟碱、0.138g碳酸钾（1毫摩尔）、0.131g4-碘苯甲酸甲酯（0.5毫摩尔)，加热100 oC24小时，至反应完全（薄层色谱TLC检测）。将反应混合物倒入20mL蒸馏水中，以乙酸乙酯萃取（10mL×3）。合并有机相，用无水硫酸镁干燥。蒸除溶剂后，剩余物用硅胶柱层析分离（洗脱剂为乙酸乙酯：石油醚=1：3）得到白色固体0.0513g，产率为76%，核磁共振谱图如图3。
实施例4
在50mL圆底烧瓶中加入0.011g醋酸钯（0.05毫摩尔）、10mL有机溶剂N, N-二甲基甲酰胺、0.008g辣味组分（也可更换为甜味组分或苦味组分）、0.138g碳酸钾（也可更换为醋酸钾）（1毫摩尔）、0.110g4-碘苯酚（0.5毫摩尔)，电加热套加热回流48小时，至反应完全（薄层色谱TLC检测）。将反应混合物倒入20mL蒸馏水中，以乙酸乙酯萃取（10mL×3）。合并有机相，用无水硫酸镁干燥。蒸除溶剂后，剩余物用硅胶柱层析分离（洗脱剂为乙酸乙酯：石油醚=1：5）得到黄色固体0.0246g，产率为53%，核磁共振谱图如图4。
Claims (4)
1.一种钯/感官组分催化的联芳化合物的合成方法，其特征在于：以卤代化合物为原料、钯化合物和感官组分为催化剂，用N, N-二甲基甲酰胺作为溶剂，加入一定量的碱，加热反应,加热反应或为油浴加热，100℃，24小时；或为电加热套加热回流，48小时；反应完全后，经乙酸乙酯萃取、干燥、硅胶柱层析分离，制得联芳化合物；
卤代化合物与钯化合物的摩尔比为1∶0.05-0.1，所述钯化合物为醋酸钯、双三苯基膦二氯化钯；
卤代化合物与碱的摩尔比为1∶1-2，所述碱为碳酸钾、磷酸钾、醋酸钾；
每0.5毫摩尔卤代化合物对应加入8-16mg感官组分，所述卤代化合物为卤代芳香化合物、卤代杂环芳香化合物；
所述感官组分来源于烟叶、食品，所述感官组分为酸味组分：苹果酸、乳酸、乙酰丙酸、柠檬酸、富马酸；或为甜味组分：果糖、葡萄糖、肌糖、蔗糖；或为苦味组分：麦斯明；或为辣味组分：烟碱。
2.根据权利要求1所述的合成方法，其特征在于：
卤代化合物与钯化合物的摩尔比为1∶0.1，
卤代化合物与碱的摩尔比为1∶2,
每0.5毫摩尔卤代化合物对应加入8mg感官组分。
3.根据权利要求1所述的合成方法，其特征在于：所述卤代化合物为碘代芳香化合物。
4.根据权利要求3所述的合成方法，其特征在于：所述碘代芳香化合物为1-碘萘、碘苯、4-碘苯甲酸甲酯、4-碘苯酚。
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| IL98209A (en) * | 1991-05-22 | 1995-11-27 | Bromine Compounds Ltd | Production of biaryl derivatives |
| CN101054330A (zh) * | 2007-05-23 | 2007-10-17 | 浙江工业大学 | 一种联苯型化合物的合成方法 |
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| IL98209A (en) * | 1991-05-22 | 1995-11-27 | Bromine Compounds Ltd | Production of biaryl derivatives |
| CN101054330A (zh) * | 2007-05-23 | 2007-10-17 | 浙江工业大学 | 一种联苯型化合物的合成方法 |
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