CN112275318A - 用于(酯交换)酯化的两性离子催化剂:在氟吲哚衍生物和生物柴油合成中的应用 - Google Patents
用于(酯交换)酯化的两性离子催化剂:在氟吲哚衍生物和生物柴油合成中的应用 Download PDFInfo
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Abstract
酰胺/亚铵两性离子催化剂具有促进酯交换和脱水酯化的催化剂穴尺寸。所述酰胺/亚铵两性离子容易通过使氮丙啶与氨基吡啶反应制备。所述反应可以应用广泛种类的酯化方法,包括生物柴油的大规模合成。所述酰胺/亚铵两性离子允许避免强碱性或酸性条件以及避免产物中的金属污染。反应在环境温度或仅适度升高的温度下进行。所述酰胺/亚铵两性离子催化剂容易再循环并且反应以高产率至定量产率进行。
Description
相关申请的交叉引用
本申请要求于2019年7月24日提交的美国临时申请序列号 62/878,044的权益,该文献的公开内容以其全文(包括全部附图、表和绘图)据此通过引用方式引入。
背景技术
双官能有机催化剂在有机合成中发挥越来越重要的作用。双官能体系中的官能团之间的协同效应使得反应物对紧密靠近以便有效的化学转变。在双官能有机催化剂的设计中通常包括常规组分,例如布朗斯台德碱/ 酸、路易斯(Lewis)碱、二氢键和协同离子配对。新兴类别的双官能有机催化剂是两性离子,其称为内盐,其中阴离子和阳离子在单个分子内部位分离并且这种离子对协同作用以激活反应配伍剂(partners)。使用两性离子的催化保持未开发,这部分地归因于难以识别适合的催化剂体系结构和难以制备两性离子催化剂。
在所报道的两性离子催化体系当中,含氧化物的两性离子是最多研究的。例如,衍生自许多骨架的甜菜碱(含氧化物和铵)已经用于一定范围的催化方法,例如CO2固定、聚合、光氧化还原反应、醛醇/曼尼希(Mannich)型反应和氮丙啶打开。近来,使用手性季铵甜菜碱的不对称催化反应已经报道在 Uraguchi等的Angew.Chem.Int.Ed.2010,49,5567–9、Zhou等的J.Am.Chem. Soc.2016,138,12297–302、Zhang等的Angew.Chem.Int.Ed.2012,51,4085–8和Claraz等的Eur.J.Org.Chem.2013,7693–6当中。甜菜碱Co(III)配合物已经在Chen等的Macromolecules 2018,51,6057–6062中报道用于共聚。原位产生的氧化物/磷翁两性离子催化剂适用于:曼尼希型反应;Strecker型反应;在有机金属骨架影响下的Aldol-Tishchenko反应和二醇的用芳族氧化物的伯羟基选择性酰化。
除铵甜菜碱以外的含离子对的两性离子催化剂是非常稀少的,但是包括用于酰胺水解的硫醇咪唑翁催化剂、用于一些酸催化转化的两性离子含碳酸和促进酯交换(包括烯属酸的中度环内酯化,和芳烃的亲电卤化)的硫离子/亚铵两性离子。所述硫离子/亚铵两性离子:
其中R是N(CH3)2或吡咯烷酮是容易经由异硫氰酸酯通过4-氨基吡啶的亲核加成以形成结构明确的电荷配对体系而制备的有吸引力的催化剂平台,如 Ishihara等的Org.Lett.2008,10,2187–90中报道的那样。所述硫离子/亚铵两性离子作为催化剂允许与互补性反应物的有效相互作用。令人遗憾地,这种硫化两性离子与其前体在溶液中平衡存在,这允许所述异硫氰酸酯在水分存在下水化,这在许多情况下限制其效能。为了克服这种稳定性限制,需要其它亚铵两性离子。为此,提出了新型类别的两性离子有机催化剂,即结构稳定的酰胺阴离子/亚铵阳离子基两性离子。
发明内容
本发明的实施方案涉及稳定的酰胺/亚铵两性离子催化剂。在本发明的一个实施方案中,通过用氨基吡啶加成氮丙啶合成所述酰胺/亚铵两性离子催化剂。在本发明的另一个实施方案中,在所述酰胺/亚铵两性离子催化剂存在下进行酯交换或酯化以形成所需酯。在本发明的一个实施方案中,所述酯是通过酯交换形成的氟吲哚衍生物。在本发明的一个实施方案中,所述酯是在没有金属污染下合成的生物柴油,其如下形成:将甘油三酯和所述两性离子催化剂在室温下溶解在溶剂中,接着将这种溶剂与水和酯结合。接着,在挥发物的萃取和除去后,直接地获得可用的生物柴油产物。在一个实施方案中,所述酯是通过烷基醇与琥珀酸酐,或等效物的反应,通过其它环酸酐的开环形成的二烷基琥珀酸酯。
附图说明
图1示出了根据本发明实施方案的酰胺/亚铵两性离子催化剂的示例性制备的反应流程。
图2示出了基于根据本发明一个实施方案的两性离子5a的单晶的X 射线结晶结构。
图3示出了计算机模拟结构5a,指示根据本发明一个实施方案的酰胺 /亚铵两性离子催化剂内的静电势。
图4示出了根据本发明一个实施方案甘油三酯与甲醇酯交换成脂肪酸甲酯(FAME)的反应流程并示出了采用根据本发明实施方案的酰胺/亚铵两性离子催化剂及其它现有技术催化剂在等同条件下的对比产率的表。
图5示出了根据本发明一个实施方案甘油三酯与甲醇酯交换成FAME 的反应流程,并示出了采用根据本发明实施方案的酰胺/亚铵两性离子催化剂5d对于酯上的各种单元的对比产率的表。
图6示出了根据本发明一个实施方案甘油三酯与甲醇酯交换成FAME 伴有副产物甘油转化成甘油三乙酸酯的再循环反应流程。
图7示出了根据本发明实施方案使用各种酰胺/亚铵两性离子催化剂使苄醇与乙酸乙酯酯交换形成乙酸苄酯的反应流程。
图8示出了根据本发明一个实施方案使用酰胺/亚铵两性离子催化剂 5d使乙酸乙酯与各种醇酯交换形成所述醇的乙酸酯的反应流程。
图9示出了根据本发明一个实施方案使用酰胺/亚铵两性离子催化剂 5d使乙酸乙酯与各种氟吲哚酯交换的反应流程和各种所得的酯的产率。
图10示出了根据本发明一个实施方案使各种羧酸酯与各种醇酯交换的反应流程,和根据本发明实施方案采用酰胺/亚铵两性离子催化剂5d的产率的表。
图11示出了根据本发明一个实施方案用苄醇将琥珀酸酐酯化的反应流程。
图12示出了根据本发明一个实施方案采用酰胺/亚铵两性离子催化剂 5d用各种醇将琥珀酸酐酯化的反应流程。
图13示出了根据本发明一个实施方案用苄醇将戊二酸酐酯化的反应流程。
图14示出了根据本发明一个实施方案采用酰胺/亚铵两性离子催化剂 5d用苄醇将各种单-和二-羧酸酯化的反应流程。
图15示出了所计算的自由能曲线的示意图,该自由能曲线符合根据本发明一个实施方案使用酰胺/亚铵两性离子催化剂脱水酯化的合理机理。
图16示出了图15的反应图的中间体和过渡状态的经计算几何结构,连同相互作用原子之间的距离(埃)和催化剂和酸的原子上的氮和氧NBO 原子电荷。
图17示出了符合酯交换机理的合理机理的经计算自由能线图的示意图,该经计算自由能线图与所述反应图的中间体和过渡状态的经计算几何结构叠加。
具体实施方式
根据本发明一个实施方案,新型类别的两性离子催化剂包含酰胺/亚铵两性离子,其将磺酰胺上的电荷中心和衍生自4-氨基吡啶的亚铵分隔3-7个键。根据本发明一个实施方案的酰胺/亚铵两性离子催化剂具有以下结构:
其中:n是1、2、3或4;R独立地是H、芳基、C1-C6烷基取代的芳基、 C1-C6烷基、芳基取代的C1-C6烷基,其中所述烷基或芳基的碳中的任一个是未取代的或取代有C1-C6烷基醚、芳基醚、C1-C6烷基硫醚、芳基硫醚,其中所述烷基是直链、支化或环状烷基,其中所述烷基中的任一个可以用O或S 插入一次或多次;R1是芳基、硝基取代的芳基、C1-C6烷基取代的芳基、C1-C6烷基或C1-C6全氟烷基;和R2和R3独立地是C1-C6烷基或组合地与亚铵氮形成5-或6-元环杂环,其中所述环任选地用一个或多个O或NR’单元插入,其中R’是芳基、C1-C6烷基取代的芳基或C1-C6烷基。在本发明的一个示例性实施方案中,SO2R1是甲苯磺酰基或甲磺酰基,R2和R3是甲基或NR2R3结合为吡咯烷酮(PPY),如下面指示那样:
在本发明的一个实施方案中,酰胺/亚铵两性离子催化剂的制备通过4-氨基吡啶对二环氮丙啶的亲核攻击产生,如图1所示。环应变的释放导致在能量方面更加有利的两性离子,这抑制逆反应。该N-磺化氮丙啶容易由该环烷基亚胺制备,后者容易地如Watson等的Org.Synth.2010,87,161-9中所公开那样形成。在回流乙腈中通过4-(N,N-二甲基氨基)吡啶(DMAP,2a)使甲苯磺酰基氮丙啶4a打开而以72%产率获得两性离子5a,如图1所示。同样地,通过在氮丙啶处改变N-磺酰胺和/或形成氨基吡啶类似物5b-5f。基于两性离子5a 的单晶的X射线结晶结构示于图2中。来自X射线数据的1.34的N(3)-C (9)亚铵键长度显著地短于典型的C-N单键,这符合具有相当多C=N性质的成键,其中N(3)氮是带正电的。亚铵阳离子的正电性看来似乎得到显著提高,因为反阴离子磺酰胺以很大程度有效离解,这归因于其在碳骨架中的部位孤立。对5a的静电势的计算还指示亚铵结构部分具有相当大的正电荷,如图3所示。两性离子5a-5f是结构上稳定的,在加热时观察不到分解,这符合以均分位置存在的吡啶翁结构部分和磺酰胺抑制由于取代或霍夫曼消除引起的分解。有利地,两性离子5a-5f是不吸湿的并容易地加以处理而进行催化反应。
在本发明的一个实施方案中,酰胺/亚铵两性离子催化剂促进甘油三酯酯交换成脂肪酸甲酯(FAME),后者常用作生物柴油。如图4所示,当在23℃下将脂肪酸酯6a悬浮在含5mol%的各种酰胺/亚铵两性离子催化剂的MeOH 中时,形成FAME。当使用两性离子5a-c时,酯交换平稳地进行并以70-79%离析产率获得FAME 7a。当使用同时带有甲磺酰基和PPY的两性离子5d时,效率非常高。反应可以在低的催化剂装载量下运转,例如,2mol%的5d,在70℃下运转2h,以99%产率获得FAME 7a。当以更大的规模进行时,反应定量地产生7a。呈鲜明对照,当使用现有技术硫化物/亚铵两性离子3b作为催化剂时,没有观察到反应,这推测上归因于该催化剂经由与该两性离子平衡的异硫氰酸酯的甲醇分解而分解。使用与5a-d中相似的方法制备带有更加贫电子性磺酰胺的备选两性离子5e-f、显示不同骨架刚性的备选两性离子5g-h和显示阳离子和阴离子间不同距离的备选两性离子5i-k,显示相比5d的劣等性能。这些结果表明,由对于磺酰胺和吡啶基取代基具有赤道位置的环烷基环施加的结构刚性和5d中存在的阳离子/阴离子距离是催化性能的一个重要因素。同样地,包括布朗斯台德碱(NaOMe,tBuOK)、路易斯碱(Et3N,DMAP,PPY, PPh3)和铵盐(碘化四-正丁基铵(TBAI)、氯化三-正十二烷基甲基铵和甲基碳酸四甲基铵)的其它催化剂在等同条件下对于促进酯交换反应有效性低得多。
甘油三酯的酯交换适用于其它脂肪酸酯,例如,如图5,6b-f所示。对于6f的情况,以定量的产率获得相应的FAME 7f,同时保持不饱和体系完整。根据本发明一个实施方案,用于形成FAME的糖苷可以具有以下结构:
其中R独立地是具有1-6的不饱和度的直链或支化C1-C26烷基链、直链或支化 C3-C26烯基链。可以是所述甘油三酯一部分的脂肪酸的非唯一性清单包括,但不限于丁酸、戊酸、己酸、庚酸、辛酸、壬酸、癸酸、十一烷酸、月桂酸、十三烷酸、肉豆蔻酸、十五烷酸、棕榈酸、珠光脂酸、硬脂酸、十九烷酸;花生酸、二十一烷酸、山俞酸、二十三烷酸、二十四烷酸、二十五烷酸、蜡酸、二十七烷酸、褐煤酸、二十九烷酸、三十烷酸、三十一烷酸、紫胶蜡酸、三十三烷酸、格地酸、卅六烷酸、三十六烷酸、三十七烷酸、三十八烷酸、三十九烷酸、四十烷酸、α-亚麻酸、十八碳四烯酸、二十碳五烯酸、二十二碳六烯酸、亚油酸、反亚油酸、γ-亚麻酸、二高-γ-亚麻酸、花生四烯酸、二十二碳四烯酸、棕榈油酸、十八碳烯酸、二十烯碳酸、油酸、反油酸、二十碳-11-烯酸、芥酸、神经酸和二十碳三烯酸。根据本发明一个实施方案,用于形成FAME 的醇可以包括任何C1-C10醇,包括但不限于甲醇、乙醇、1-丙醇、正丁醇、异丁醇、1-戊醇、异戊醇、2-甲基-1-丁醇、1-己醇、1-庚醇、1-辛醇、1-壬醇、 1-癸醇、苄醇或苯乙醇。
FAME 6a容易通过水洗涤分离以除去甘油和两性离子催化剂5d。含甘油的副产物混合物(通常生物柴油生产中的大型副产物)在催化剂5d存在下经历与乙酸乙酯的酯交换而以高产率产生甘油三乙酸酯,如图6中指示那样,其可以用作生物柴油添加剂、抗爆剂或加以离析以便用作食品添加剂或增塑剂。两性离子催化剂5d容易地再循环并以相似的催化剂性能再用于后续FAME 7合成,如图6所示。与其它FAME制备方法,例如要求脱水条件以避免酯水解形成羧酸的碱催化酯交换,和要求高温/高压力和特殊设备的在超临界MeOH 中的无催化剂酯交换形成对比,这种几乎中性的酰胺/亚铵两性离子催化剂促进的生产可以在无需排除水分或使用脱水醇属溶剂的情况下运转。当在1atm 的环境条件和23℃下使用常规设备达到清洁转化时,生物柴油的合成可容易地在温和条件下升级。
根据本发明一个实施方案,酰胺/亚铵两性离子催化剂,例如5d催化单酯与醇的酯交换。如图7所示,苄醇8a在采用分子筛的回流乙酸乙酯中经历反应以除去作为副产物形成的乙醇。如在FAME合成的情况下,5d的催化性能优于其它类似物。使用3mol%的两性离子5d在更高的反应物浓度下采用苄醇及其它醇,酯交换反应平稳地进行,如图8所示。采用具有供电子或吸电子取代基的各种脂族醇8a-i,反应平稳地进行。当所述醇含有对常规酸介导的酯交换条件敏感的官能度时,包括使用烯烃8j-l、炔烃8m和呋喃8n,与两性离子催化的体系的相容性允许以好至优异的离析产率形成相应的乙酸酯产物9j-n。二醇8o和8p的乙酰化产生双乙酸酯9o(91%)和9p(97%)。三乙酰化糖衍生物9q以好的离析产率形成。与醇的要求使用乙酰氯或乙酸酐的常规乙酰化(在复杂合成期间最常用的保护方法)形成对比,根据本发明实施方案的酯交换在没有施加酸性条件的情况下容易地将保护基乙酸酯导入醇中。根据本发明一个实施方案,该酰胺/亚铵两性离子催化的酯交换可以扩展至氟吲哚衍生物,如图9所示。根据本发明一个实施方案,甲酯与不同醇配伍剂的酯交换允许相等摩尔量的醇8和甲酯10反应,同时除去作为共沸物的甲醇,例如采用回流正庚烷,如图10中的表所示。该酯交换与各种官能度相容。例如,水杨酸甲酯(10b)容易地经历与苄醇(8a)的酯交换而以98%产率获得11b。甲酯10d和二醇8q的2:1混合物以91%产率获得酯交换的二酯产物11f。该催化规程与α,β-不饱和酯10e、大体积酯10f和乙酯10g相容。在3小时后,在所采用的浓度下(0.25M),经由羟基酯10h的分子内酯交换定量地获得内酯 11j。
根据本发明一个实施方案,可以用于与羧酸酯进行酯交换的醇包括,但不限于结构HOC(H)xR3-x的伯或仲C1-C30醇,其中x是1-3,R独立地是直链、支化或环状烷基;直链、支化或环状烯基;直链、支化或环状炔基;芳基;直链、支化或环状烷芳基;直链、支化或环状烯芳基;直链、支化或环状炔芳基;含1-4个杂原子的含N、O和/或S杂环物,其中R的碳可以用O、S、C (O)、NR”或C(O)NR”插入一次或多次,其中R的碳原子中的任一个可以取代有C1-C10直链、支化或环状烷基,直链、支化或环状烯基,直链、支化或环状炔基,芳基,直链、支化或环状烷芳基,直链、支化或环状烯芳基,直链、支化或环状炔芳基,含一个或多个杂原子的含N、O和/或S杂环物,卤素,烷氧基,R”2N,其中R”独立地是芳基、C1-C10烷基或C1-C10烯基。醇包括伯和仲醇、二醇、三醇和多元醇,其中形成单-、二-、三-或多元-酯。多元醇可以是碳水化合物,包括单糖、二糖和多元醇例如,但不限于葡萄糖、半乳糖、果糖、木糖、蔗糖、乳糖、麦芽糖、海藻糖、山梨糖醇和甘露糖醇。所述酯可以具有结构:RC(O)OR’,其中:R选自,但不限于H,直链、支化或环状烷基;直链、支化或环状烯基;直链、支化或环状炔基;芳基;直链、支化或环状烷芳基;直链、支化或环状烯芳基;直链、支化或环状炔芳基;含 1-4个杂原子的含N、O和/或S杂环物,其中R的碳可以用O、S、C(O)或 C(O)NR”插入一次或多次,其中R”独立地是芳基、C1-C10烷基或C1-C10烯基,其中R的碳原子中的任一个可以取代有C1-C10直链、支化或环状烷基,直链、支化或环状烯基,直链、支化或环状炔基,芳基,直链、支化或环状烷芳基,直链、支化或环状烯芳基,直链、支化或环状炔芳基,含1-4个杂原子的含N、O和/或S杂环物,卤素和烷氧基;和R’选自甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基或新戊基。
根据本发明一个实施方案,酰胺/亚铵两性离子催化剂促进酸酐,例如,琥珀酸酐12和醇,例如,苄醇(BnOH 8a)之间的反应,而获得二酯,例如 13a,如图11所示。反应经由以下一锅两步次序进行:(1)12通过8a开环产生单酯12’,接着(2)12’脱水酯化而获得二酯13a。根据本发明一个实施方案,这种反应体系的概述在图12中显示。可以用Dean-Stark设备在回流正庚烷中进行反应以除去脱水酯化步骤中的水副产物。带有富电子或贫电子取代基的宽范围的醇8是相容的并且在温和条件下以好的离析产率获得相应的二酯产物13b-13l。当用戊二酸酐(14)替换琥珀酸酐(12)时,以相似的78%产率获得相应的二酯15,如图13中显示那样。二酯(用于嵌段共聚物生产的有用的起始材料)一般使用苛刻条件合成。可以用于由酰胺/亚铵两性离子催化剂催化的酯化的酸酐包括,但不限于结构RC(O)OC(O)R的直链酸酐,其中R独立地是H、直链、支化或环状烷基;直链、支化或环状烯基;直链、支化或环状炔基;芳基;直链、支化或环状烷芳基;直链、支化或环状烯芳基;直链、支化或环状炔芳基;含1-4个杂原子的含N、O和/或S杂环物,其中 R的碳可以用O、S、C(O)或C(O)NR”插入一次或多次,其中R”独立地是芳基、C1-C10烷基或C1-C10烯基,其中R的碳原子中的任一个可以取代有 C1-C10直链、支化或环状烷基,直链、支化或环状烯基,直链、支化或环状炔基,芳基,直链、支化或环状烷芳基,直链、支化或环状烯芳基,直链、支化或环状炔芳基,含1-4个杂原子的含N、O和/或S杂环物,卤素和烷氧基。酸酐可以是环酸酐例如,但不限于琥珀酸酐、戊二酸酐、己二酸酐或庚二酸酐。用于与所述酸酐酯化的醇可以是,但不限于结构HOC(H)xR3-x的伯或仲C1-C30醇,其中x是1-3,R独立地是直链、支化或环状烷基;直链、支化或环状烯基;直链、支化或环状炔基;芳基;直链、支化或环状烷芳基;直链、支化或环状烯芳基;直链、支化或环状炔芳基;含1-4个杂原子的含N、O和/或S 杂环物,其中R的碳可以用O、S、C(O)、NR”或C(O)NR”插入一次或多次,其中R的碳原子中的任一个可以取代有C1-C10直链、支化或环状烷基,直链、支化或环状烯基,直链、支化或环状炔基,芳基,直链、支化或环状烷芳基,直链、支化或环状烯芳基,直链、支化或环状炔芳基,含一个或多个杂原子的含N、O和/或S杂环物,卤素,烷氧基,R”2N,其中R”独立地是芳基、C1-C10烷基或C1-C10烯基。
酸酐酯化的脱水酯化步骤促进催化羧酸和醇之间的脱水酯化,这种脱水酯化已知是挑战性的,这归因于要求强酸性催化剂激活羧酸底物的高反应阻隔。硫化物/亚铵两性离子3b发现在催化脱水酯化方面是无效的,这归因于其构成组分3,5-(双三氟甲基)苯基异硫氰酸酯由苄醇引起的醇解。根据本发明一个实施方案,从羧酸(例如,图14的16a-i)和醇(例如苄醇8a)开始的脱水酯化产生所需的酯产物,例如,可读取地,17a-i。同样地,从二酸16j-m开始,以75%-83%产率获得相应的二酯17j-m。所述羧酸可以具有,但不限于结构RC(O)OH,其中R独立地是:H;直链、支化或环状烷基;直链、支化或环状烯基;直链、支化或环状炔基;芳基;直链、支化或环状烷芳基;直链、支化或环状烯芳基;直链、支化或环状炔芳基;或含1-4个杂原子的含N、O 和/或S杂环物,其中R的碳任选地用O、S、C(O)或C(O)NR”插入一次或多次,其中R”独立地是芳基、C1-C10烷基或C1-C10烯基,其中R的碳原子中的任一个可以取代有卤素,C1-C10直链、支化或环状烷氧基,C1-C10直链、支化或环状烷基,直链、支化或环状烯基,直链、支化或环状炔基,芳基,直链、支化或环状烷芳基,直链、支化或环状烯芳基,直链、支化或环状炔芳基,含1-4个杂原子的含N、O和/或S杂环物。用于与所述酸酯化的醇可以是,但不限于结构HOC(H)xR3-x的伯或仲C1-C30醇,其中x是1-3,R独立地是直链、支化或环状烷基;直链、支化或环状烯基;直链、支化或环状炔基;芳基;直链、支化或环状烷芳基;直链、支化或环状烯芳基;直链、支化或环状炔芳基;含1-4个杂原子的含N、O和/或S杂环物,其中R的碳可以用O、S、 C(O)、NR”或C(O)NR”插入一次或多次,其中R的碳原子中的任一个可以取代有C1-C10直链、支化或环状烷基,直链、支化或环状烯基,直链、支化或环状炔基,芳基,直链、支化或环状烷芳基,直链、支化或环状烯芳基,直链、支化或环状炔芳基,含一个或多个杂原子的含N、O和/或S杂环物,卤素,烷氧基,R”2N,其中R”独立地是芳基、C1-C10烷基或C1-C10烯基。
脱水酯化的机理是尤其值得注意的,因为该反应采用非酸性催化剂。与 5d混合的苄醇8a和与5d混合的乙酸的1H NMR实验显示所述醇和羧酸可以与所述两性离子5d相互作用。对于丁酸(16i)和苄醇(8a)之间的反应在 M06-2X(具有Grimme D3)/6-311G(d,p)的水平下的密度功能理论(DFT) 计算允许更好理解该反应,如图15所示,其中考虑两个反应路径:(1)磺酰胺将羧酸去质子化;或(2)磺酰胺将醇去质子化。如图15所示,该计算显示两性离子5d与羧酸16i相互作用形成中间体Acid-R,其比加合物5d-R(通过两性离子5d将8a去质子化而形成)稳定3.2千卡/摩尔。然而,羰基碳被醇亲核攻击的后续步骤(Acid-TS1)被高度阻碍,原因在于高的自由能垒(energy barrier)几何结构优化与两性离子/醇加合物5d-R 在羰基碳处经历亲核取代而经由5d-TS1获得原酸酯中间体5d-IM一致,这具有小得多的自由能垒如由艾林方程预计的那样,与这种小能垒相联系的速率常数比Acid-TS1中42.2千卡/摩尔的能垒的速率常数大大约108倍。Acid-R和5d-R之间的互换能垒很可能显著地小于42.2千卡 /摩尔和28.7千卡/摩尔的能垒。因此,Acid-R看来似乎是催化循环中的陷阱,并且反应可能经由控速步骤5d-R→5d-TS1继续进行至最终产物。原酯5d-IM 经由5d-TS2的后续瓦解产生酯产物17i和水连同两性离子催化剂5d的再生。从反应体系连续除去水副产物促进产物形成。
在5d-TS1的优化几何结构中,两性离子5d中与亚铵阳离子相邻的吡咯烷质子以和的距离紧密靠近16i的羰基氧,如图 16所示。这些值在典型的氢键作用力的范围内。因此,非典型氢键看来似乎使所述中间体稳定并降低能垒。这种结果与NMR研究一致,其中吡咯烷的质子信号在醇添加后向前场移动,这可能地归因于烷氧根阴离子与吡咯烷的质子经由所述非典型氢键的相互作用。还通过DFT分析含DMAP衍生的催化剂5b 的体系。与5d-TS1相比,在控速步骤5b-TS1反应遭遇高得多的能垒 这种差异可能归因于5d中的吡咯烷质子由于刚性PPY结构部分而可获得的受限构象,这导致比两性离子5b的DMAP结构部分中构象自由旋转甲基可能达到的更大的羧酸稳定化,从而使所述甲基在经由非典型氢键使过渡状态TS1稳定化时不那么有效。5b-TS1中羰基氧和甲基质子之间的最近距离计算为和这平均起来比5d-TS1中长得多。这些计算研究揭示两性离子5d中的电荷对在脱水酯化方面的协同性质。
苄醇(8a)和乙酸乙酯之间用两性离子催化剂5d的酯交换反应的DFT 计算在图17中以图形表示。稳定的复合物Ester-R源自5d和8a之间的氢键作用力,这与NMR结果一致。基于优化的能线图,8a经由Ester-TS1攻击该酯而获得四面体中间体Ester-IM1,其通过7.2千卡/摩尔稳定化。与脱水酯化的情况相似,通过源自吡咯烷质子的非典型氢键(Ester-TS1, )激活乙酸乙酯的羰基。步骤Ester-R→Ester-TS1是控速步骤 复合物的再组织(Ester-IM1→Ester-IM2)接着四面体中间体经由Ester-TS2的瓦解获得酯交换产物,乙酸苄酯(9a)。
虽然两性离子不是布朗斯台德酸性的,但是5d中的非典型氢键看来似乎分别在脱水酯化和酯交换中在激活羧酸和酯的羰基方面发挥重要作用。由两性离子体系中的阴离子和阳离子之间的距离界定的适合的催化剂穴(pocket)尺寸看来似乎对于高催化性能在容纳反应配伍剂方面是关键性的。
应当理解,这里所述的实施例和实施方案仅仅是用于说明性目的并且对它们的各种修改或改变对本领域技术人员是显而易见的并应包括在本申请的精神和权限内。另外,这里所公开的任何发明或其实施方案的任何元素或限制可以与这里所公开的任何其它发明或其实施方案的任何和/或全部其它元素或限制(单独地或以任何组合)结合,并且所有这样的组合预期在本发明范围内,但不限于此。这里涉及或引用的所有出版物按与本说明书的明确教导不矛盾的程度通过参考以全文(包括所有附图和表)引入。
Claims (24)
1.酰胺/亚铵两性离子催化剂,包含磺酰胺负电部位和亚铵正电部位,其中三至七个键存在于所述磺酰胺负电部位和亚铵正电部位之间。
2.根据权利要求1所述的酰胺/亚铵两性离子催化剂,其中所述亚铵衍生自4-氨基吡啶、N-烷基吡咯烷酮或N-烷基咪唑。
3.根据权利要求1所述的酰胺/亚铵两性离子催化剂,其中所述结构是:
其中:n是1、2、3或4;R独立地是H、芳基、C1-C6烷基取代的芳基、C1-C6烷基、芳基取代的C1-C6烷基,其中所述烷基或芳基的碳中的任一个是未取代的或取代有C1-C6烷基醚、芳基醚、C1-C6烷基硫醚、芳基硫醚,其中所述烷基是直链、支化或环状烷基,其中所述烷基任选地用O或S插入一次或多次;R1是芳基、硝基取代的芳基、C1-C6烷基取代的芳基、C1-C6烷基或C1-C6全氟烷基;R2和R3独立地是C1-C6烷基或组合地形成5-或6-元环杂环,其中所述环任选地用一个或多个O、N或NR'单元插入,其中R'是芳基、C1-C6烷基取代的芳基或C1-C6烷基。
6.用于形成根据权利要求1所述的酰胺/亚铵两性离子催化剂的方法,包括:
提供N-磺化氮丙啶;
提供含氮杂环物;
将所述N-磺化氮丙啶和杂环物结合;和
离析所述酰胺/亚铵两性离子催化剂。
7.根据权利要求6所述的方法,其中所述N-磺化氮丙啶是N-磺化环烷基氮丙啶。
9.根据权利要求6所述的方法,其中所述N-磺化氮丙啶是甲磺酰基亚环己基亚胺或甲苯磺酰基亚环己基亚胺。
10.根据权利要求6所述的方法,其中所述含氮杂环物是N-烷基吡咯烷酮、N-烷基咪唑、4-(N,N-二烷基氨基)吡啶或4-吡咯烷基吡啶。
12.酯化方法,包括:
提供根据权利要求1所述的酰胺/亚铵两性离子催化剂;
提供含羧酸或羧酸衍生物的分子;
提供含醇的分子;
将所述含羧酸的分子或含羧酸衍生物的分子、含醇的分子和所述酰胺/亚铵两性离子催化剂结合;和
离析含酯的分子。
13.根据权利要求12所述的酯化方法,其中所述酰胺/亚铵两性离子催化剂当中所述亚铵衍生自4-氨基吡啶、N-烷基吡咯烷酮或N-烷基咪唑。
14.根据权利要求12所述的酯化方法,其中所述酰胺/亚铵两性离子催化剂是:
其中:n是1、2、3或4;R独立地是H、芳基、C1-C6烷基取代的芳基、C1-C6烷基、芳基取代的C1-C6烷基,其中所述烷基或芳基的碳中的任一个是未取代的或取代有C1-C6烷基醚、芳基醚、C1-C6烷基硫醚、芳基硫醚,其中所述烷基是直链、支化或环状烷基,其中所述烷基任选地用O或S插入一次或多次;R1是芳基、硝基取代的芳基、C1-C6烷基取代的芳基、C1-C6烷基或C1-C6全氟烷基;和R2和R3独立地是C1-C6烷基或组合地形成5-或6-元环杂环,其中所述环任选地用一个或多个O、N或NR'单元插入,其中R'是芳基、C1-C6烷基取代的芳基或C1-C6烷基。
16.根据权利要求12所述的酯化方法,其中所述含醇的分子是结构HOC(H)xR3-x的C1-C30醇,其中x是1-3,R独立地是直链、支化或环状烷基;直链、支化或环状烯基;直链、支化或环状炔基;芳基;直链、支化或环状烷芳基;直链、支化或环状烯芳基;直链、支化或环状炔芳基;含1-4个杂原子的含N、O和/或S杂环物,其中R的碳可以用O、S、C(O)、NR”或C(O)NR”插入一次或多次,其中R的碳原子中的任一个可以取代有C1-C10直链、支化或环状烷基,直链、支化或环状烯基,直链、支化或环状炔基,芳基,直链、支化或环状烷芳基,直链、支化或环状烯芳基,直链、支化或环状炔芳基,含一个或多个杂原子的含N、O和/或S杂环物,卤素,烷氧基,R”2N,其中R”独立地是芳基、C1-C10烷基或C1-C10烯基。
17.根据权利要求12所述的酯化方法,其中所述含羧酸或羧酸衍生物的分子是羧酸RC(O)OH,其中R独立地是:H;直链、支化或环状烷基;直链、支化或环状烯基;直链、支化或环状炔基;芳基;直链、支化或环状烷芳基;直链、支化或环状烯芳基;直链、支化或环状炔芳基;或含1-4个杂原子的含N、O和/或S杂环物,其中R的碳任选地用O、S、C(O)或C(O)NR”插入一次或多次,其中R”独立地是芳基、C1-C10烷基或C1-C10烯基,其中R的碳原子中的任一个可以取代有卤素,C1-C10直链、支化或环状烷氧基,C1-C10直链、支化或环状烷基,直链、支化或环状烯基,直链、支化或环状炔基,芳基,直链、支化或环状烷芳基,直链、支化或环状烯芳基,直链、支化或环状炔芳基,含1-4个杂原子的含N、O和/或S杂环物。
18.根据权利要求12所述的酯化方法,其中所述含羧酸或羧酸衍生物的分子是结构RC(O)OR'的羧酸酯,其中:R选自,但不限于H,直链、支化或环状烷基;直链、支化或环状烯基;直链、支化或环状炔基;芳基;直链、支化或环状烷芳基;直链、支化或环状烯芳基;直链、支化或环状炔芳基;含1-4个杂原子的含N、O和/或S杂环物,其中R的碳任选地用O、S、C(O)或C(O)NR”插入一次或多次,其中R”独立地是芳基、C1-C10烷基或C1-C10烯基,其中R的碳原子中的任一个可以取代有C1-C10直链、支化或环状烷基,直链、支化或环状烯基,直链、支化或环状炔基,芳基,直链、支化或环状烷芳基,直链、支化或环状烯芳基,直链、支化或环状炔芳基,含1-4个杂原子的含N、O和/或S杂环物,卤素和烷氧基;R'选自甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基或新戊基。
20.根据权利要求12所述的酯化方法,其中所述含羧酸或羧酸衍生物的分子是结构RC(O)OC(O)R的羧酸酐,其中R独立地是H、直链、支化或环状烷基;直链、支化或环状烯基;直链、支化或环状炔基;芳基;直链、支化或环状烷芳基;直链、支化或环状烯芳基;直链、支化或环状炔芳基;含1-4个杂原子的含N、O和/或S杂环物,其中R的碳任选地用O、S、C(O)或C(O)NR”插入一次或多次,其中R”独立地是芳基、C1-C10烷基或C1-C10烯基,其中R的碳原子中的任一个可以取代有C1-C10直链、支化或环状烷基,直链、支化或环状烯基,直链、支化或环状炔基,芳基,直链、支化或环状烷芳基,直链、支化或环状烯芳基,直链、支化或环状炔芳基,含1-4个杂原子的含N、O和/或S杂环物,卤素或烷氧基。
21.根据权利要求12所述的酯化方法,其中所述含羧酸或羧酸衍生物的分子是甘油三酯并且所述含酯的分子是脂肪酸甲酯FAME。
22.根据权利要求21所述的酯化方法,其中所述FAME是丁酸、戊酸、己酸、庚酸、辛酸、壬酸、癸酸、十一烷酸、月桂酸、十三烷酸、肉豆蔻酸、十五烷酸、棕榈酸、珠光脂酸、硬脂酸、十九烷酸;花生酸、二十一烷酸、山俞酸、二十三烷酸、二十四烷酸、二十五烷酸、蜡酸、二十七烷酸、褐煤酸、二十九烷酸、三十烷酸、三十一烷酸、紫胶蜡酸、三十三烷酸、格地酸、卅六烷酸、三十六烷酸、三十七烷酸、三十八烷酸、三十九烷酸、四十烷酸、α-亚麻酸、十八碳四烯酸、二十碳五烯酸、二十二碳六烯酸、亚油酸、反亚油酸、γ-亚麻酸、二高-γ-亚麻酸、花生四烯酸、二十二碳四烯酸、棕榈油酸、十八碳烯酸、二十烯碳酸、油酸、反油酸、二十碳-11-烯酸、芥酸、神经酸、二十碳三烯酸或它们的任何组合。
23.根据权利要求12所述的酯化方法,其中将所述含羧酸或羧酸衍生物的分子和含醇的分子结合为结构HO(CH2)xC(O)OR的醇取代羧酸酯,其中x是3-5,R'选自甲基、乙基或丙基,其中含酯的分子是内酯。
24.根据权利要求12所述的酯化方法,其中所述含酯的分子是氟吲哚衍生物。
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