CN114957327A - 基于苯的四膦配体的合成方法 - Google Patents

基于苯的四膦配体的合成方法 Download PDF

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CN114957327A
CN114957327A CN202110194142.6A CN202110194142A CN114957327A CN 114957327 A CN114957327 A CN 114957327A CN 202110194142 A CN202110194142 A CN 202110194142A CN 114957327 A CN114957327 A CN 114957327A
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张润通
王建新
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Huizhou Kailisi Technology Co ltd
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Abstract

本发明涉及一种用于烷氧羰基化的基于苯的四膦配体，即：1,2,4,5‑四(二叔丁基膦甲基)苯及其衍生物的制备方法。该类新型四齿膦配体具有如通式Ⅰ所示的结构，其中通式I中取代基R1，R2可以分别选自烷基、环烷基或芳基。同时，本发明公开了该新型四齿膦配体的合成方法，以及其与金属钯前体的络合物作为催化剂在烯烃烷氧羰基化或氢羧基化反应中的应用。

Description

基于苯的四膦配体的合成方法
技术领域
本发明涉及化学合成技术领域，一种新型基于苯的四膦配体的合成方法与其在烯烃烷氧羰基化(或氢羧基化)反应中的应用。
背景技术
烯烃的氢酯基化反应是在金属化合物/膦配体作用下，烯烃与一氧化碳和醇反应得到比烯烃多一个碳原子的酯。在众多合成有机羧酸酯的方法中，这是一种最原子经济、简便的方法。以下方案显示了烯烃氢酯基化反应的通用反应方程式：烯烃化合物的烷氧基羰基化是具有越来越重要的意义的工艺过程。烷氧基羰基化是指烯烃与一氧化碳和醇在金属体配合物的存在下反应生成相应的酯。通常地，使用钯作为金属。下面的示意式显示了氧基羰基化的一般反应方程式:
Figure BDA0002945953250000011
氢羧基化反应是指烯烃与一氧化碳和羧酸在金属体配合物的存在下反应生成相应的羧酸。通常地，使用钯作为金属。下面的示意式显示了氢羧基化反应的一般反应方程式:
Figure BDA0002945953250000012
有机羧酸酯是一类重要的含氧化合物，广泛应用于精细化工产品、医药、农药、食品添加剂、香料、涂料、油漆等领域。例如，丙酸甲酯作为溶剂、添加剂、防腐剂或香料，广泛应用于食品、饲料、化妆品行业。此外，它还是重要的化工中间体，它是生产聚甲基丙烯酸甲酯(PMMA)关键的原料。PMMA拥有良好的耐候性，适中的密度，刚性，稳定性，透明性等优点而广泛应用于汽车、led 核心原件材料、建筑、航空等领域。因此，开发有机羧酸酯高效合成方法具有重要的意义。
目前，已报道的催化剂体系主要是由中心金属、相关膦配体、酸添加剂组成。中心金属是viii、x副族过渡金属如Rh、Pd、Ni、Co、Cu等，其中研究最多的就是金属Pd。相关膦配体如烷基膦、环烷基膦、二齿膦等的研究已经在许多专利中进行了描述，例如EPA04489472、EPA0499329、EPA0495547、 US2005085671A1、US6284919B1、US2001051745A1、US6476255B1等。尤其是璐彩特(Lucite)公司公开了一组具有取代芳基桥的二齿膦化物，1,2-双(二叔丁基膦基甲基)苯(dtbpx)可以提供显著得高于先前公开的那些催化剂的反应速率和产生少许或不产生杂质，且具有高转化率(Chem.Commun.,1999,1877-1878； WO96/19434；WO2004/014552A1)。此外，赢创德固赛(Evonik-Degusa)公司也公开了1,1’-双(叔丁基苯基膦基)-二茂铁配体，对于烯烃的烷氧羰基化反应具有高的催化性能(Angew.Chem.Int.Ed.,2017,56(19),5267-5271； US2017/0022234Al)。
Figure BDA0002945953250000021
这两个配体是目前烯烃氢酯基化反应中最高效的配体。这些案例指出高活性的重要因素来源于叔碳烷基膦配体结构。虽然这两个配体在氢酯基化反应中表现出良好的性能，在烷氧基羰基化反应中，特别是乙烯与甲醇反应生成3-甲基丙酸酯(乙烯-甲氧基羰基化)作为甲基丙烯酸甲酯(MMA)的制备的中间步骤具有重要意义(Cata.Comun.,2014,44,73-75)。乙烯甲氧基羰基化反应是在温和的条件下以甲醇作为溶剂使用被配体改性的钯催化剂而进行。
本发明的目的在于提供了用于烷氧基羰基化的新型体，使用其可以实现更好的l/b选择性，更高的酯收率，更温和的反应条件。特别地，本发明的配体应当还适用于烯烃化合物的氢甲酰化反应、氢胺甲基化反应。烯烃存在其他官能团的情况也适用。
发明内容
本发明的目的是为了开发一种新型四齿膦配体及其衍生物的高效合成方法。其特备是易于合成、收率较高和可以放大合成。该化合物及其衍生物的结构表示如下：
Figure BDA0002945953250000031
通式I的结构中，R1、R2表示各自独立地任选取代的有机基团，如上式所示。该类四膦配体的合成路线(以L1为例)如下：
路线1
Figure BDA0002945953250000041
路线2
Figure BDA0002945953250000042
路线3
Figure BDA0002945953250000043
路线4
Figure BDA0002945953250000051
附图说明
图1，本发明配体化合物L1的1H NMR(400MHz,CDCl3)示意图；
图2，本发明配体化合物L1的31P NMR(400MHz,CDCl3)示意图；
图3，本发明配体化合物L1的13C NMR(400MHz,CDCl3)示意图。
具体实施方式
下面通过实施例对本发明的以上路线进行具体的描述，有必要指出的是，本实施例只用于对本发明作进一步说明，但并不对本发明构成任何限制。该领域的技术人员可以根据本发明的内容作出一些非本质的改进和调整。
实施例1
1,2,4,5-苯四羧酸的制备(路线1)
Figure BDA0002945953250000052
500ml的反应瓶中先后加入蒽2.7g(0.015mol)、60ml四氯化碳、60ml 乙腈、100ml水、30g(0.14mol)高碘酸钠、0.12g(0.0006mol)无水三氯化铑，搅拌30分钟后升温到60℃反应过夜。旋蒸溶剂后先用水洗、再用二氯甲烷洗得固体。用丙酮溶解固体、过滤，滤液旋蒸再用甲醇溶解、加二氯甲烷打浆获得白色固体2.5g。1H NMR((CD3)2SO,400MHz)δ:13.52(s,4H),7.92(s,2H)；13C NMR ((CD3)2SO,100MHz)δ:167.3,134.6,128.5.
实施例2
1,2,4,5-苯四甲酸四甲酯的制备(路线1)
Figure BDA0002945953250000061
1L的反应瓶中加入15g的1,2,4,5-苯四羧酸后置换为N2，再加入150ml 甲醇降温到0℃搅拌。稳定后慢速滴加94.7ml的二氯亚砜，滴加完成后升温回流反应过夜，尾气用碱液吸收。反应结束后冰水浴加入碳酸氢钠溶液淬灭反应，加入乙酸乙酯/水，萃取两次合并有机相，无水硫酸钠干燥、过滤、旋蒸后柱层析得到7.3g白色固体。1H NMR(CDCl3,400MHz)δ:8.04(s,2H),3.91(s,12H)；13C NMR(CDCl3,100MHz)δ:166.2,135.1,134.1,129.5,53.0.
实施例3
1,2,4,5-四苯甲醇的制备(路线1)
Figure BDA0002945953250000062
250ml的反应瓶中加入3.04g(80mmol)氢化锂铝和30ml四氢呋喃，搅拌并降温到0℃，再滴加6.2g(20mmol)1,2,4,5-苯四甲酸四甲酯和60ml四氢呋喃的溶液，回流反应过夜。降温到室温后滴加3ml水淬灭反应，然后加入 50ml(15％W/M)硫酸溶液搅拌30分钟，用二氯甲烷萃取两次合并有机相无水硫酸钠干燥，旋蒸后用正己烷/乙酸乙酯重结晶得到固体1.2g。1H NMR((CD3)2SO, 400MHz)δ:7.37(s,2H),5.87(s,4H),4.61(s,8H)；13C NMR((CD3)2SO,100MHz) δ:136.0,127.5,62.8.
实施例4
1,2,4,5-四氯苄的制备(路线1)
Figure BDA0002945953250000063
250ml的反应瓶中加入1,2,4,5-四苯甲醇5.0g(25mmol)、100ml二氯甲烷并搅拌，4.34ml二氯亚砜慢慢滴加到反应体系中，反应5小时。旋蒸除去溶剂和过量的二氯亚砜，再用乙醚溶解，水洗，无水硫酸钠干燥，旋蒸，用甲醇重结晶得固体5.7g。1H NMR(CDCl3,400MHz)δ:4.75(s,8H),7.46(s,2H)；13C NMR(CDCl3,100MHz)δ:137.4,130.5,45.1.
实施例5
1,2,4,5-四氯苄的制备(路线3)
Figure BDA0002945953250000071
250ml的反应瓶中加入1,2,4,5-四溴苄6.75g(15mmol)、100ml的N,N- 二甲基甲酰胺、5.01g(120mol)无水氯化锂，室温下搅拌过夜。加入70ml (5％W/M)盐酸溶液，再用乙酸乙酯萃取2次合并有机相，加饱和氯化钠溶液洗一次，无水硫酸钠干燥、过滤、旋蒸，用正己烷重结晶得白色固体3.7g。
实施例6
1,2,4,5-四氯苄的氯化镁(或溴化镁)格氏试剂的制备(路线2和3)
Figure BDA0002945953250000072
250ml的反应瓶中加入镁屑3.84g(160mmol)、少许碘，氮气置换后加入 50ml超干四氢呋喃，搅拌回流并滴加5.44g(20mmol)的1,2,4,5-四氯苄和 30ml的四氢呋喃溶液。1小时滴加完，体系由无色变成灰黑色。继续回流2小时停止加热。滴定格式试剂浓度为0.18M，低温储存备用。
实施例7
二叔丁基膦氯的氯化镁格氏试剂的制备(路线2)
Figure BDA0002945953250000073
250ml的反应瓶中加入镁屑3.84g(160mmol)、少许碘，氮气置换后加入 80ml超干四氢呋喃，搅拌回流并滴加14.46g(80mmol)二叔丁基膦氯和30ml 的四氢呋喃溶液。1小时滴加完，体系由无色变成灰黑色。继续回流2小时停止加热。滴定格式试剂浓度为0.58M，低温储存备用。
实施例8
1,2,4,5-四(二叔丁基膦甲基)苯的制备(路线1)
Figure BDA0002945953250000081
500ml的反应瓶中置换为氮气，加入11.8g(81mmol)二叔丁基膦和100ml 四氢呋喃，搅拌并降温到-78℃，滴加32.5ml(2.5M)正丁基锂/四氢呋喃溶液后升温到室温反应2小时。再降温到-78℃，滴加5.44g(20mmol)的1,2,4,5- 四氯苄和100ml四氢呋喃溶液，慢慢升温到室温，反应2小时后旋蒸除去溶剂，加入脱气水到体系中搅拌，再用脱气二氯甲烷萃取2次，用无水硫酸钠干燥，旋蒸得到的固体用脱气甲醇重结晶得白色固体10.81g。1H NMR(CDCl3,400MHz) δ:7.48(s,2H),3.03(s,8H),1.09-1.11(d,72H)；31P NMR(CDCl3,162MHz)δ: 28.65.
实施例9
1,2,4,5-四(二叔丁基膦甲基)苯的制备(路线2和3)
Figure BDA0002945953250000082
500ml的反应瓶中置换为氮气，加入100ml四氢呋喃和14.46g(80mmol) 二叔丁基膦氯，搅拌并降温到0℃。慢速滴加100ml(0.18M)化合物2'，滴加完后升温到40℃反应2小时。旋蒸除去溶剂，加入脱气水到体系中搅拌，再用脱气二氯甲烷萃取2次，用无水硫酸钠干燥，旋蒸得到的固体用脱气甲醇重结晶得白色固体7.2g。1H NMR(CDCl3,400MHz)δ:7.48(s,2H),3.03(s,8H), 1.09-1.11(d,72H)；31P NMR(CDCl3,162MHz)δ:28.65.
实施例10
1,2,4,5-四(二叔丁基膦甲基)苯的制备(路线4)
Figure BDA0002945953250000091
500ml的反应瓶中置换为氮气，加入100ml(0.58M)二叔丁基膦氯化镁/ 四氢呋喃溶液，搅拌并降温到0℃。缓慢滴加5.85g(13mmol)1,2,4,5-四溴苄和50ml四氢呋喃溶液，滴加完后升温到40℃反应2小时。旋蒸除去溶剂，加入脱气水到体系中搅拌，再用脱气二氯甲烷萃取2次，用无水硫酸钠干燥，旋蒸得到的固体用脱气甲醇重结晶得白色固体7.82g。1HNMR(CDCl3,400MHz)δ:7.48 (s,2H),3.03(s,8H),1.09-1.11(d,72H)；31P NMR(CDCl3,162MHz)δ:28.65.
作为本发明的一种优选技术方案，烯烃氢酯基化(或氢羧基化)反应制备有机羧酸酯(或羧酸)的方法，是在钯化合物/四齿膦配体/酸性添加剂组合催化剂作用下，在有机溶剂中，末端烯烃、一氧化碳和醇(或羧酸)进行氢酯基化(或氢羧基化)反应生成较烯烃多一个碳的有机羧酸酯(或羧酸)。
为了测试新型联苯四膦在混合/醚后碳四中的反应活性，我们在接近相同的反应条件下对比测试其它商业化和文献报道过的配体，在以下实施例中所使用的配体Ligand1-12具有如下的结构：
Figure BDA0002945953250000101
对比实施例1：烷氧羰基化反应对比试验
在氩气氛围下，向200ml装有压力传感器、温度探针、在线取样口和安全泄压阀等装置的不锈钢高压反应釜中加入一定量的Pd(OAc)2(0.26μmol,0.06 mg)、一定量的配体Ligand 1-12(0.52-2.08μmol)和过量的甲基磺酸(2.6-5.2 μmol)，加入一定体积的甲醇(5ml)和内标物甲苯，用磁子搅拌络合30分钟，生成钯与配体的催化络合物。随后，连接气体管线并充分置换后，在两位四通阀的切换下，用带计量功能的柱塞泵向反应釜内加入一定比例液态化的乙烯(26 mmol)。向反应装置内充入一氧化碳与至4.5MPa。将反应釜升至所需温度80℃，反应中持续补充一氧化碳保持总压力恒定在4.5MPa左右。反应8个小时后，将反应釜接入-40℃冷套降温，待釜温降至常温后，在不开釜的情况下，打开在线取样口取样，用色谱级的乙酸乙酯稀释后，气相色谱仪(GC)测定正异比和转化率。开釜后，在通风橱内将高压反应釜内的气体释放完全，取样称重。结果如表1所示。
表1
Figure BDA0002945953250000112
Figure BDA0002945953250000111
＊Reaction conditions：45bar，80℃，8h.
[b]Conversion and I/b ratio is determined by GC.
[c]TON is calculated by conversion×100000.
对比实施例2：氢羧基化反应对比试验
在氩气氛围下，向200ml装有压力传感器、温度探针、在线取样口和安全泄压阀等装置的不锈钢高压反应釜中加入一定量的Pd(acac)2(10μmol，3.0mg)、一定量的配体Ligand 1-12(20-80μmol)和过量的对甲苯磺酸(0.15-0.4mmol)，加入一定体积的醋酸(2.0ml)和内标物甲苯，用磁子搅拌络合30分钟，生成钯与配体的催化络合物。随后，连接气体管线并充分置换后，在两位四通阀的切换下，用带计量功能的柱塞泵向反应釜内加入一定比例液态化的乙烯(4mmol)。向反应装置内充入一氧化碳与至5.0MPa。将反应釜升至所需温度100℃，反应中持续补充一氧化碳保持总压力恒定在5.0MPa左右。反应10个小时后，将反应釜接入-40℃冷套降温，待釜温降至常温后，在不开釜的情况下，打开在线取样口取样，用色谱级的乙酸乙酯稀释后，气相色谱仪(GC)测定正异比。开釜后，在通风橱内将高压反应釜内的气体释放完全，取样称重。结果如表2所示。
表2
Figure BDA0002945953250000122
Figure BDA0002945953250000121
＊Reaction conditions：50bar，100℃，10h.
[b]Conversion and I/b ratio is determined by GC.
[c]TON is calculated by conversion×400.
以上内容是结合具体的优选实施方式对本发明所作的进一步详细说明，不能认定本发明的具体实施只局限于这些说明。对于本发明所属技术领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干简单推演或替换，都应当视为属于本发明的保护范围。

Claims (10)

1.一种基于苯的四膦配体，即：1,2,4,5-四(二叔丁基膦甲基)苯及其衍生物的制备方法，其特征在于，具有以下通式I的结构：
Figure FDA0002945953240000011
从蒽或卤代四甲基苯出发，通过氧化反应、酯化反应、还原反应或者格氏试剂的方法，得到四膦配体；其中，用通式I表示的一类新型四磷配体结构如下：
Figure FDA0002945953240000012
Figure FDA0002945953240000021
2.根据权利要求1的所述的一种基于苯的四膦配体的制备方法，其特征在于，四膦配体(通式I)的骨架前体(1,2,4,5-苯四羧酸，2)需通过氧化反应实现：
Figure FDA0002945953240000022
3.根据权利要求1的所述的一种基于苯的四膦配体的制备方法，其特征在于，四膦配体(通式I)的骨架前体(1,2,4,5-苯四甲酸四甲酯，3)需通过酯化反应实现：
Figure FDA0002945953240000023
4.根据权利要求1的所述的一种基于苯的四膦配体的制备方法，其特征在于，四膦配体(通式I)的骨架前体(1,2,4,5-四苯甲醇，4)需通过还原反应实现：
Figure FDA0002945953240000024
5.根据权利要求1的所述的一种基于苯的四膦配体的制备方法，其特征在于，四膦配体(通式I)的骨架前体(1,2,4,5-四氯苄，5)需通过以下反应实现：
Figure FDA0002945953240000031
6.根据权利要求1的所述的一种基于苯的四膦配体的制备方法，其特征在于，四膦配体(通式I)需通过以下反应实现：
Figure FDA0002945953240000032
或者可以通过硼烷保护的磷氢化合物，先上膦做成硼烷保护的四膦配体，再脱去保护基得到四膦配体，其具体反应路线如下：
Figure FDA0002945953240000033
其中以上反应的特征在于，反应所使用的醚类溶剂可以为苯甲醚、乙二醇二甲醚、二乙二醇二甲醚、四氢呋喃、甲基叔丁基醚、乙基叔丁基醚、乙醚、异丙醚、丁醚、2-甲基四氢呋喃或二氧六环中的任意一种。
7.根据权利要求1的所述的一种基于苯的四膦配体的制备方法，其特征在于，四膦配体(通式I)可以通过格氏试剂的方法实现，其具体反应路线如下：
Figure FDA0002945953240000041
同时，上述反应所使用的醚类溶剂可以为苯甲醚、乙二醇二甲醚、二乙二醇二甲醚、四氢呋喃、甲基叔丁基醚、乙基叔丁基醚、乙醚、异丙醚、丁醚、2-甲基四氢呋喃或二氧六环中的任意一种。
8.根据权利要求7的所述的一种基于苯的四膦配体的制备方法，以上反应也可以先做成膦氯的格氏试剂，再与1,2,4,5-四氯(或溴)苄反应得到最终产品，其具体反应路线如下：
Figure FDA0002945953240000042
9.一种以新型四膦化合物作为配体应用于烯烃甲氧基羰基化(或氢羧基化)反应，该方法的特征在于，使用权利要求1所述化合物与金属钯前体的络合物作为催化剂，在有机溶剂中，烯烃、一氧化碳和醇(或羧酸)进行氢酯基化(或氢羧基化)反应生成较烯烃多一个碳的有机羧酸酯(或羧酸)；
上述烷氧羰基化或氢羧基化反应所使用的烯烃为碳原子数为2～19的烯烃，如乙烯、丙烯、1-丁烯、顺式-和/或反式-2-丁烯、异丁烯、1，3-丁二烯、1-戊烯、顺式-和/或反式-2-戊烯、2,4,4-三甲基-1-戊烯、2,4,4-三甲基-2-戊烯、2-甲基-1-丁烯、3-甲基-1-丁烯、2-甲基-2-丁烯、3,3-二甲基-1-丁烯、2,3,3-三甲基-1-丁烯、2,3-二甲基-1-丁烯、2,3-二甲基-2-丁烯、己烯、四甲基乙烯、庚烯、1-辛烯、2-辛烯、二正丁烯、二异丁烯、正癸烯、环己烯、环庚烯、环辛烯、3-戊烯酸甲酯、4-戊烯酸甲酯、2-己烯酸甲酯、3-己烯酸甲酯、5-己烯酸甲酯、2-庚烯酸甲酯、(E)-2-辛烯酸甲酯、(E)-2-壬烯酸甲酯、10-烯酸甲酯、11-烯酸甲酯、(Z)-油酸甲酯、(E)-油酸甲酯中的一种或其混合物；
上述烷氧羰基化反应所使用的醇为含1-20个碳原子的脂肪族醇化合物或环脂族醇化合物，如甲醇、乙醇、1-丙醇、异丙醇、异丁醇、叔丁醇、1-丁醇、2-丁醇、1-戊醇、2-戊醇、3-戊醇、1-己醇、环己醇、2-乙基己醇、异壬醇、2-丙基庚醇、环己烷-1,2-二醇、1,2-乙二醇、1,3-丙二醇、丙三醇、1,2,4-丁三醇、2-羟基甲基-1,3-丙二醇、季戊四醇、1,2,6-三羟基己烷、1,1,1-三(羟基甲基)乙烷一种或其混合物；
上述氢羧基化反应所使用的羧酸为含1-20个碳原子的脂肪族或芳香族多元或一元羧酸化合物，如草酸，丙二酸，琥珀酸，己二酸，壬二酸，马来酸，富马酸，柠康酸等；芳香族多元羧酸如苯二甲酸，间苯二甲酸，对苯二甲酸，萘二甲酸，苯三甲酸等；脂环族多元羧酸如环戊烷二甲酸，环己烷二甲酸，环庚烷二甲酸，等；除多元酸之外可用于氢羧基化反应的有机羧酸及其衍生物的实例包括脂族一元羧酸，如甲酸，乙酸，丙酸，丁酸，戊酸，月桂酸，硬脂酸，苯乙酸，溴乙酸，丙烯酸，甲基丙烯酸等；芳香族一元羧酸如苯甲酸，甲基苯甲酸，萘甲酸，联苯甲酸等；脂环族一元羧酸如环戊烷甲酸，环己烷甲酸，环庚烷甲酸等；在这些化合物中，乙酸，丙酸，甲基丙烯酸和苯甲酸等是优选的。
10.如权利要求9中所述的一种以新型四膦化合物作为配体应用于烯烃甲氧基羰基化(或氢羧基化)反应。该方法的特征在于，按照以下工艺步骤及参数实现：
(1).在反应装置内，于惰性气体保护下，依次往带有聚四氟内衬的反应釜里加入一定比例的钯化合物、四齿膦配体和酸性添加剂，四膦配体与钯化合物的摩尔比为0.2:1～120:1(优选1:1～20:1)；酸性添加剂与钯化合物的摩尔比为0.2:1～200:1(优选1:1～50:1)；组合催化剂的用量以钯化合物相对烯烃的用量计：钯化合物的摩尔量为烯烃摩尔量的0.000001～1％(优选0.00005～0.001％)；
(2).随后，于惰性气体保护下，用带计量功能的柱塞泵往反应釜内加入一定比例液态的混合烯烃，一定比例的甲醇(或乙酸)，使铑催化剂的总溶液浓度控制在10～200ppm左右，再室温均匀搅拌5～10分钟；
(3).搅拌均匀后，向反应装置内充入一定压力的CO，反应总压控制在1.0MPa至15.0MPa之间；反应温度控制在在40～200℃，反应时间控制在4～20个小时；
上述反应中，所述钯化合物选自醋酸钯、氯化钯、双(三苯基膦)二氯化钯、双(乙腈)二氯化钯、(1,5-环辛二烯)二氯化钯、烯丙基氯化钯、四三苯基膦钯、乙酰丙酮钯、双(二亚苄基丙酮)钯以及三(二亚苄基丙酮)二钯中的一种。优选PdCl2、Pd(acac)2，双(乙腈)二氯化钯、(1,5-环辛二烯)二氯化钯、烯丙基氯化钯、碘化钯、溴化钯；
上述反应中，所述酸性添加剂选自高氯酸、硫酸、磷酸、盐酸、甲酸、乙酸、草酸、甲磺酸(MsOH)、三氟甲磺酸(TfOH)、叔丁烷磺酸、对甲苯磺酸(PTSA)、2-羟-基丙烷-2-磺酸、2,4,6-三甲基苯磺酸和十二烷基磺酸、三氟甲磺酸铝的一种。优选对甲苯磺酸、甲磺酸、三氟甲磺酸、叔丁烷磺酸、2,4,6-三甲基苯磺酸、十二烷基磺酸。
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