CN117402045A - 制备三环癸烷二甲醛的方法 - Google Patents

制备三环癸烷二甲醛的方法 Download PDF

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CN117402045A
CN117402045A CN202310799488.8A CN202310799488A CN117402045A CN 117402045 A CN117402045 A CN 117402045A CN 202310799488 A CN202310799488 A CN 202310799488A CN 117402045 A CN117402045 A CN 117402045A
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dicarboxaldehyde
dicyclopentadiene
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R·弗兰克
C·施奈德
R·杰克斯泰尔
M·贝勒
D·鲁施
H·海格
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Abstract

本发明涉及一种制备三环癸烷二甲醛(Dicidal)的方法，包括以下方法步骤：a)预先置入双环戊二烯；b)添加根据式(I)的化合物：其中R1、R2、R3、R4、R5、R6、R7、R8选自：‑H、‑(C1‑C12)‑烷基、‑Ph；c)添加能够形成配合物的Pt化合物；d)添加碘化合物；e)供应CO和H2；f)加热来自a)‑e)的反应混合物，其中所述双环戊二烯转化为三环癸烷二甲醛。

Description

制备三环癸烷二甲醛的方法
技术领域
本发明涉及一种制备三环癸烷二甲醛(Dicidal)的方法。
背景技术
在US2009/0171125A1中描述了一种用于环烯烃加氢甲酰化的方法。在此使用Rh催化剂。
发明内容
本发明所基于的目的是提供一种新的加氢甲酰化方法。与现有技术已知的方法相比，该方法在此应当提供增加的产率。
该目的通过根据权利要求1的方法实现。
方法，包括以下方法步骤：
a)预先置入双环戊二烯；
b)添加根据式(I)的化合物：
其中R1、R2、R3、R4、R5、R6、R7、R8选自：-H、-(C1-C12)-烷基、-Ph；
c)添加能够形成配合物的Pt化合物；
d)添加碘化合物；
e)供应CO和H2；
f)加热来自a)-e)的反应混合物，其中所述双环戊二烯转化为三环癸烷二甲醛。
在此，方法步骤a)至e)可以以任意顺序进行。然而，CO和H2的加入通常在步骤a)至d)中的反应参与物已经预先置入之后进行。
在此，方法步骤c)和d)也可以在一个步骤中进行，例如通过添加PtI2。
在本方法的一个变体中，在一个步骤中通过添加PtI2来添加Pt化合物和碘化合物。
术语(C1-C12)-烷基包括具有1至12个碳原子的直链和支链烷基。在此这些优选是(C1-C8)-烷基，特别优选(C1-C6)-烷基，最优选(C1-C4)-烷基。
合适的(C1-C12)-烷基特别是甲基、乙基、丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、2-戊基、2-甲基丁基、3-甲基丁基、1,2-二甲基丙基、1,1-二甲基丙基、2,2-二甲基丙基、1-乙基丙基、正己基、2-己基、2-甲基戊基、3-甲基戊基、4-甲基戊基，1,1-二甲基丁基、1,2-二甲基丁基、2,2-二甲基丁基、1,3-二甲基丁基，2,3-二甲基丁基、3,3-二甲基丁基、1,1,2-三甲基丙基、1,2,2-三甲基丙基、1-乙基丁基、1-乙基-2-甲基丙基，正庚基、2-庚基、3-庚基、2-乙基戊基、1-丙基丁基、正辛基、2-乙基己基、2-丙基庚基、壬基、癸基。
在该方法的一个变体中，R1和R4是-H。
在该方法的一个变体中，R5、R6、R7、R8是-Ph。
在该方法的一个变体中，R2和R3是-(C1-C12)-烷基。
在该方法的一个变体中，R2和R3是-CH3。
在该方法的一个变体中，化合物(I)具有结构(1)：
在该方法的一个变体中，Pt化合物选自：Pt(II)I2、Pt(IV)I4、二苯基(1,5-COD)Pt(II)、Pt(II)(acac)2、Pt(0)(PPh3)4、Pt(0)(DVTS)溶液(CAS:68478-92-2)、Pt(0)(乙烯)(PPh3)2、三(亚苄基丙酮)Pt(0)、Pt(II)(OAC)2溶液、Pt(0)(t-Bu)2、Pt(II)(COD)Me2、Pt(II)(COD)I2、Pt(IV)IMe3、Pt(II)(六氟乙酰丙酮合物)2。
在该方法的一个变体中，Pt化合物选自：Pt(II)I2、Pt(II)(acac)2。
在该方法的一个变体中，Pt化合物是Pt(II)I2。
在该方法的一个变体中，碘化合物选自：碱金属卤化物、碱土金属卤化物、NH4X、烷基卤化铵、二烷基卤化物(Dialkylhalogenid)、三烷基卤化物(Trialkylhalogenid)、四烷基卤化物(Tetraalkylhalogenid)和环烷基卤化铵。
在该方法的一个变体中，碘化合物选自：Pt(II)I2、LiI。
在该方法的一个变体中，PtI2以相对于双环戊二烯的以摩尔％测量的如下量添加，使得该值在0.1摩尔％至5摩尔％的范围。
在该方法的一个变体中，PtI2以相对于双环戊二烯的以摩尔％测量的如下量添加，使得该值在0.1摩尔％至3摩尔％的范围。
在该方法的一个变体中，PtI2以相对于双环戊二烯的以摩尔％测量的如下量添加，使得该值在0.1摩尔％至1摩尔％的范围。
在该方法的一个变体中，该方法包括额外的方法步骤e')：
e')添加溶剂。
在该方法的一个变体中，溶剂选自：THF、DCM、ACN、庚烷、DMF、甲苯、Texanol、戊烷、己烷、辛烷、异辛烷、癸烷、十二烷、环己烷、苯、二甲苯、Marlotherm、碳酸亚丙酯、MTBE、二甘醇二甲醚、三甘醇二甲醚、乙醚、二噁烷、异丙醇、叔丁醇、异壬醇、异丁醇、异戊醇、乙酸乙酯。
在该方法的一个变体中，溶剂选自：THF、DCM、ACN、庚烷、DMF、甲苯、Texanol。
在该方法的一个变体中，CO和H2在1MPa(10巴)至6MPa(60巴)的压力下引入。
在该方法的一个变体中，CO和H2在1MPa(20巴)至6MPa(50巴)的压力下引入。
在该方法的一个变体中，加热至25℃至150℃的温度。
在该方法的一个变体中，加热至30℃至130℃的温度。
在该方法的一个变体中，该方法包括额外的方法步骤g)：
g)将三环癸烷二甲醛转化为三环癸烷二甲醇。
在该方法的一个变体中，使用“Shvos催化剂”(CAS 104439-77-2)将三环癸烷二甲醛转化为三环癸烷二甲醇。
具体实施方式
下面将使用示例性实施例更详细地解释本发明。
实验说明
双环戊二烯转化为三环癸烷二甲醛
在氩气下将10mmol双环戊二烯(DCPD)、10ml无水甲苯、0.5mol％PtI2、2.2当量的4,5-双(二苯基膦基)-9,9-二甲基氧杂蒽(Xantphos)(1)(基于Pt)添加到ParrInstruments公司的25ml钢高压釜中。压入40巴的合成气(CO/H2＝1:1)并通过加热至80℃并搅拌开始反应。该反应在40巴/80℃下进行18.5小时。然后冷却高压釜，释放压力并采集GC样品。
在对比实验中添加Rh(acac)(CO)2代替PtI2。
三环癸烷二甲醛收率：
PtI2：89.5％
Rh(acac)(CO)2:<5％
三环癸烷二甲醛转化为三环癸烷二甲醇
在100ml Parr高压釜中在氩气下，将10ml甲苯、5ml乙醇、5.5g三环癸烷二甲醛(28.6mmol)和62.16mg“Shvos催化剂”(CAS 104439-77-2)(基于三环癸烷二甲醛计0.2mol％)和40巴氢气下在搅拌下加热至100℃达20小时并进行反应。然后停止反应，释放压力并在高真空下蒸馏反应混合物。在140℃下获得三环癸烷二甲醇异构体混合物的无色油作为馏分。
三环癸烷二甲醇产率：85％
如实验结果所表明，该目的通过本发明的方法得以实现。

Claims (14)

1.方法，包括以下方法步骤：
a)预先置入双环戊二烯；
b)添加根据式(I)的化合物：
其中R1、R2、R3、R4、R5、R6、R7、R8选自：-H、-(C1-C12)-烷基、-Ph；
c)添加能够形成配合物的Pt化合物；
d)添加碘化合物；
e)供应CO和H2；
f)加热来自a)-e)的反应混合物，其中所述双环戊二烯转化为三环癸烷二甲醛。
2.根据权利要求1所述的方法，
其中R1和R4是-H。
3.根据权利要求1或2中任一项所述的方法，
其中R5、R6、R7、R8是-Ph。
4.根据权利要求1至3中任一项所述的方法，
其中R2和R3是-(C1-C12)-烷基。
5.根据权利要求1至4中任一项所述的方法，
其中R2和R3是-CH3。
6.根据权利要求1至5中任一项所述的方法，
其中化合物(I)具有结构(1)：
7.根据权利要求1至6中任一项所述的方法，
其中Pt化合物选自：Pt(II)I2、Pt(IV)I4、二苯基(1，5-COD)Pt(II)、Pt(II)(acac)2、Pt(0)(PPh3)4、Pt(0)(DVTS)溶液(CAS：68478-92-2)、Pt(0)(乙烯)(PPh3)2、三(亚苄基丙酮)Pt(0)、Pt(II)(OAC)2溶液、Pt(0)(t-Bu)2、Pt(II)(COD)Me2、Pt(II)(COD)I2、Pt(IV)IMe3、Pt(II)(六氟乙酰丙酮合物)2。
8.根据权利要求1至7中任一项所述的方法，
其中所述碘化合物选自：Pt(II)I2、LiI。
9.根据权利要求1至8中任一项所述的方法，
其中PtI2以相对于双环戊二烯的以摩尔％测量的如下量添加，使得该值在0.1摩尔％至5摩尔％的范围。
10.根据权利要求1至9中任一项所述的方法，
包括额外的方法步骤e′)：
e′)添加溶剂。
11.根据权利要求1至10中任一项所述的方法，
其中CO和H2在1MPa(10巴)至6MPa(60巴)的压力下引入。
12.根据权利要求1至11中任一项所述的方法，
其中加热至25℃至150℃的温度。
13.根据权利要求1至12中任一项所述的方法，
其中该方法包括额外的方法步骤g)：
g)将三环癸烷二甲醛转化为三环癸烷二甲醇。
14.根据权利要求13所述的方法，
其中使用“Shvos催化剂”(CAS 104439-77-2)将三环癸烷二甲醛转化为三环癸烷二甲醇。
CN202310799488.8A 2022-07-06 2023-06-30 制备三环癸烷二甲醛的方法 Pending CN117402045A (zh)

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DE60002526T3 (de) * 1999-07-02 2007-08-09 Mitsubishi Gas Chemical Co., Inc. Herstellung von Tricyclodecandicarbaldehyd, Pentacyclopentadecandicarbaldehyd und der entsprechenden Dimethanole
TWI361181B (en) 2007-12-31 2012-04-01 Ind Tech Res Inst A hydroformylation process

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