CN113004326B - 一种用于丁二烯氢甲酰化反应的膦配体及其制备方法 - Google Patents
一种用于丁二烯氢甲酰化反应的膦配体及其制备方法 Download PDFInfo
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- CN113004326B CN113004326B CN202110260439.8A CN202110260439A CN113004326B CN 113004326 B CN113004326 B CN 113004326B CN 202110260439 A CN202110260439 A CN 202110260439A CN 113004326 B CN113004326 B CN 113004326B
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- butadiene
- phosphine ligand
- reaction
- bidentate phosphine
- metal precursor
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- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000003446 ligand Substances 0.000 title claims abstract description 56
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 41
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
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- UMHJEEQLYBKSAN-UHFFFAOYSA-N Adipaldehyde Chemical compound O=CCCCCC=O UMHJEEQLYBKSAN-UHFFFAOYSA-N 0.000 claims description 25
- 239000002904 solvent Substances 0.000 claims description 23
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- IETKMTGYQIVLRF-UHFFFAOYSA-N carbon monoxide;rhodium;triphenylphosphane Chemical compound [Rh].[O+]#[C-].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 IETKMTGYQIVLRF-UHFFFAOYSA-N 0.000 claims description 4
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/572—Five-membered rings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
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Abstract
本发明公开了及一种具有通式1的结构的二齿膦配体化合物,及其合成方法,以及该类膦配体在促进金属催化1,3‑丁二烯氢甲酰化反应中的应用。
Description
技术领域
本发明属于催化和精细化工领域,具体而言,涉及一类二齿膦配体化合物及其合成方法,以及该类膦配体在促进金属催化1,3-丁二烯氢甲酰化反应中的应用。
背景技术
己二醛(1,6-己二醛),作为重要的有机合成原料,可直接用于应用价值更高、市场需求量更大C6类化合物的合成,如己二酸(1,6-己二酸)、己二胺(1,6-己二胺)、己二醇(1,6-己二醇)等。这些C6化合物都是工业上合成聚酯、聚酰胺(尼龙66或尼龙610)、聚氨酯等材料的关键单体。
目前己二醛的合成主要通过1,6-环己二醇或环己烯的多步氧化反应而制得。这些方法普遍存在反应原料和氧化剂的来源不易获得、价格昂贵、氧化剂不易循环、对环境不友好、以及目标产物己二醛的收率低等问题。理论上,己二醛还可以通过丁二烯氢甲酰化反应制得。丁二烯与合成气在催化剂的作用下,两个C=C双键经过两步羰基化即可生成目标产物己二醛。该研究路线一旦实现突破,将成为新的革新路线,有望替代目前丁二烯氢腈化生产己二腈路线。此外,我国是世界上丁二烯原料的生产大国,开拓丁二烯新的应用和消费领域,延伸产业链,实现其精细化和高端化利用具有重要的经济效益和社会效益。
丁二烯氢甲酰化技术突破的关键在于催化剂的开发,具体来说,在于新型结构膦配体的设计合成。膦配体结构对催化反应的活性和产物的选择性起着决定性的作用。开展丁二烯氢甲酰化反应合成己二醛的研究已有60多年,但目前仍处于实验室研究和探索阶段,尚无工业化报道。早期(1960-1980期间),使用不同烷基或芳基单齿或双齿膦配体-铑基催化体系的丁二烯氢甲酰化制备己二醛反应,存在反应条件苛刻(合成气压力>750bar),己二醛产物选择性低于10%的缺点(如:Tetrahedron Lett.,1969,32,2721-2723;ChemikeZeitung,1975,99,452-458;J.Mol.Catal.,1977,2,211-218;J.Mol.Catal.,1980,8,329-337;J.Mol.Catal.,1985,31,345-353;美国专利4,507,508;3,947,503等)。1994年,美国联合碳化化学品及塑料技术公司(Union Carbide Chemical&Plastics TechnologyCorporation)开发了一类亚磷酸酯类双齿配体-铑催化丁二烯定向转化己二醛反应,反应条件相对温和,己二醛选择性可达到30%。该公司对该催化剂体系申请了美国专利US5312996,世界专利WO 97/40003等对技术进行保护。基于该突破性的结果,一系列新型结构亚磷酸酯类配体被相继开发出来,并应用于丁二烯氢甲酰化反应。德国科学家P.Hofmann及其研究小组在这方面做出了较为***的研究工作,开发了一类新结构磷酸酯类配体(Organometallics 2011,30,3643-3651;ACS Catal.,2014,4,3593-3604;Organometallics 2015,34,841-847;Organometallics 2015,34,4102-4108;ACS Catal.,2016,6,2802-2810等)。
尽管经过60多年的探索研究,目前己二醛的选择性仍低于50%,远达不到工业示范的需要。进一步提高己二醛的选择性是该工艺路线早日实现突破的关键。总而言之,丁二烯经氢甲酰化反应路线定向制备己二醛的挑战在于反应历程复杂、反应速率慢和区域选择性控制难等。显而易见,催化剂的新结构配体的开发将是实现丁二烯氢甲酰化定向制己二醛的关键,直接关系到该反应路线能否迈向工业化。
发明内容
针对上述现有技术中的问题,本发明的一个目的在于提供一种二齿膦配体化合物,其具有通式1的结构,
R2和R3各自独立地选自氢、C1-C6烷基,C1-C6烷氧基,C2-C6烷基胺基、C6-C10芳基、C1-C6烷氧基取代的C6-C10芳基、C1-C6烷基取代的C6-C10芳基、C2-C6烯基取代的C6-C10芳基或C2-C6烷基胺基取代的C6-C10芳基。
R2和R3各自独立地选自如下结构:
更优选地,R2和R3各自独立地选自:
R4和R5是含膦的基团并且各自独立地选自以下结构:
优选地,R4和R5各自独立地选自以下结构:
优选地,所述二齿膦配体选自如下L1至L6中:
根据本发明的另一个方面,本发明的另一个目的在于提供所述二齿膦配体的制备方法,所述方法包括将膦-氯化合物在醚类溶剂中与或者在碱的存在下反应得到,所述膦-氯化合物与或者的摩尔比为5:1-2:1,温度为-78℃-150℃,时间为0.5h-24h;
优选地,所述碱选自三乙胺、二甲氨基吡啶(DMAP)、1,8-二氮杂二环[5.4.0]十一碳-7-烯(DBU)、吡啶、氢化钠(NaH)、双(三甲基硅基)胺基锂(LiHMDS)和正丁基锂(n-BuLi)中的一种或者多种。
优选地,所述醚类溶剂选自四氢呋喃、***、叔丁醚、甲基叔丁基醚,优选为四氢呋喃和***。
优选地,所述膦-氯化合物选自如下结构:
其中将化合物C1与包含R1的对应烯烃或炔烃加入溶剂中,温度控制为100℃-200℃;时间为5h-48h,反应完成后减压蒸馏除去溶剂,得到D1,取代基R1的定义与通式1中的相同。
优选地,所述溶剂为芳香烃类溶剂,优选为甲苯或者二甲苯。
其中,化合物C1的合成可以按照现有技术公开的方法进行,例如Dalton Trans.,2019,48,14777–14782记载的合成方法,该文献的内容通过参考并入本文。
1)A2在DMF或者丙酮溶剂中,以无水碳酸钾为碱,与溴化苄在60℃反应得到化合物B2;
2)是B2在100℃的NaOH溶液中,经锌粉还原得到化合物C2;
3)C2在溶剂中与包含R1的对应烯烃或者炔烃反应得到化合物D2,温度为100℃-200℃,时间为5h-48h;
4)在氢气氛围下,D2在甲醇中由Pd/C催化剂催化还原脱苄基得到E2。
优选地,步骤3)中所述溶剂为芳香烃类溶剂,优选为甲苯或者二甲苯。
根据本发明的另一个目的在于提供所述二齿膦配体在促进金属催化丁二烯氢甲酰化反应中的用途。
根据本发明的另一个目的在于提供一种丁二烯氢甲酰化制备1,6-己二醛的方法,该氢甲酰化反应是丁二烯在合适的溶剂、二齿磷配体、金属前驱体、温度、混合气压力和时间的条件下转化为1,6-己二醛的过程,该方法包括以下步骤:
取适量本发明所述二齿膦配体加入反应釜中,之后加入溶剂、金属前驱体和丁二烯,封闭反应釜,充入一定压力的H2和CO组成的混合气,在设定的温度下反应一定时间。
优选地,溶剂选自脂肪烃类溶剂,芳香烃类溶剂,醇类溶剂或者醚类溶剂。
优选地,所述溶剂选自正己烷、环己烷、辛烷、苯、甲苯、二甲苯、甲醇、乙醇、异丙醇、***、四氢呋喃和二氧六环中的一种或多种,优选为甲苯。
优选地,所述金属前驱体为金属铑和钴的前驱体,选自:Rh(CO)2(acac)、Rh(AcO)2、RhCl3、Rh(NO3)3、RhH(CO)(PPh3)3、[Rh(CO)2Cl]2、RhH(CO)(PPh3)3、[Rh2(m-Cl)2(cod)2]、[Rh(cod)2]BF4、Co(CO)2(acac)、Co(AcO)2、CoCl2、Co(acac)2中的一种或多种,优选为Rh(CO)2(acac)。
优选地,金属前驱体与二齿膦配体的摩尔比为2:1-1:10,优选1:1-1:5,更优选1:1-1:3。
优选地,金属前驱体与丁二烯的摩尔比为1/50-1/5000,优选为1/100-1/1000。
优选地,丁二烯为丁二烯己烷溶液、丁二烯甲苯溶液、丁二烯四氢呋喃溶液、丁二烯甲醇溶液以及纯的丁二烯,优选为丁二烯甲苯溶液。
优选地,所述混合气中H2和CO的体积比为1/2-3/1,优选为1/1-2/1。
优选地,混合气的压力为1MPa-10MPa,优选为2MPa-5MPa。
优选地,反应温度为50℃-200℃,优选为80℃-120℃。
优选地,反应时间为5h-24h,优选为5h-15h。优选地,丁二烯的反应浓度为0.1mol/L-10mol/L,优选为0.5mol/L-3mol/L。
有益效果
本发明中制备的二齿膦配体与活性金属形成的催化剂可以催化1,3-丁二烯氢甲酰化反应制备己二醛,与其他文献报道催化剂相比产物中己二醛的含量明显增高,最优选择性接近60%,副产物相对较少。因此,本发明二齿膦配体与活性金属形成的催化剂有很好的催化效果,为进一步工业化打下了基础。
附图说明
为了更清楚地说明本发明具体实施方式或现有技术中的技术方案,下面将对具体实施方式或现有技术描述中所需要使用的附图作简单的介绍,显而易见地,下面描述中的附图是本发明的一些实施方式,对本领域普通技术人员而言,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。
图1为制备实施例1中的化合物B2的液体核磁氢谱。
图2为制备实施例1中的化合物C2的液体核磁氢谱。
图3为制备实施例1中的化合物D21的液体核磁氢谱。
图4为制备实施例1中的化合物F2的液体核磁氢谱。
图5为制备实施例1中的化合物E21的液体核磁氢谱。
图6为制备实施例1中的二齿膦配体L1的液体核磁氢谱。
图7为制备实施例1中的二齿膦配体L1的液体核磁磷谱。
图8为制备实施例2中的二齿膦配体L2的液体核磁氢谱。
图9为制备实施例2中的二齿膦配体L2的液体核磁磷谱。
图10为制备实施例3中的二齿膦配体L3的液体核磁氢谱。
图11为制备实施例3中的二齿膦配体L3的液体核磁磷谱。
图12为制备实施例4中的二齿膦配体L4的液体核磁氢谱。
图13为制备实施例4中的二齿膦配体L4的液体核磁磷谱。
图14为制备实施例5中的化合物G21的液体核磁氢谱。
图15为制备实施例5中的化合物H21的液体核磁氢谱。
图16为制备实施例5中的二齿膦配体L5的液体核磁氢谱。
图17为制备实施例5中的二齿膦配体L5的液体核磁磷谱。
图18为制备实施例6中的二齿膦配体L6的液体核磁氢谱。
图19为制备实施例6中的二齿膦配体L6的液体核磁磷谱。
具体实施方式
为了更好的理解本发明,下面结合实施例进一步阐明本发明的内容,以下实施例仅是列举本发明实施方案的部分例子,并不对本发明构成任何限制,本领域技术人员可以理解在不偏离本发明的实质和构思的范围内的修改均落入本发明的保护范围。除非特别说明,以下实施例中使用的试剂和仪器均为市售可得产品。
材料表征所用仪器:
(1)气相色谱仪:型号为GC-2010,生产厂家为日本SHIMADZU
(2)气相色谱质谱联用仪:型号为GCMS-QP2010,生产厂家为日本SHIMADZU
(3)液相色谱质谱联用仪:型号为Agilent1290-6430,生产厂家为美国Agilent
(4)核磁共振波谱仪:型号为ASCEND 400MHz和AVANCE-III 600MHz,生产厂家为瑞士布鲁克公司。
具体实施例中,催化体系所选用的金属前驱体为Rh(acac)(CO)2,所用的二齿膦配体结构如下:
制备实施例1:配体L1的合成
步骤1:化合物B2的合成:
取10g 1,8-二羟基蒽醌(化合物A2)加入反应器中,加200ml DMF溶解,之后加17.2g无水K2CO3和21.2g溴化苄,60℃反应过夜。冷却至室温,将反应液加入到600ml水中淬灭,产生大量黄色沉淀,过滤,水洗,60℃真空干燥,得到化合物B2。核磁数据如下:1H NMR(600MHz,CDCl3)δ7.86(d,J=7.6Hz,2H),7.63(d,J=7.4Hz,6H),7.59(t,J=8.0Hz,2H),7.39(t,J=7.5Hz,4H),7.33(d,J=7.7Hz,4H),5.33(s,4H)。
步骤2:化合物C2的合成:
取8.5g化合物B2加入反应器中,加170ml 10%的NaOH溶液,然后加13g锌粉,100℃回流反应过夜。冷却至室温,加200ml水稀释,加300ml乙酸乙酯萃取,有机相用无水硫酸钠干燥,之后柱层析纯化,洗脱剂为石油醚:乙酸乙酯=5:1,分离得到纯的化合物C2。核磁数据如下:1H NMR(400MHz,CDCl3)δ9.46(s,1H),8.33(s,1H),7.63-7.53(m,6H),7.37(m,J=8.3,5.3Hz,8H),6.80(d,J=7.4Hz,2H),5.32(s,4H)。
步骤3:化合物D21的合成:
取2g化合物C2加入反应器中,加20ml二甲苯,然后加1.09g丁炔二酸二甲酯,在氮气保护下回流反应过夜。冷却至室温,加入至50ml石油醚中沉淀,过滤,石油醚洗涤,真空干燥,得到化合物D21。核磁数据如下:1H NMR(400MHz,CDCl3)δ7.44(dd,J=6.5,2.9Hz,4H),7.28(dd,J=5.0,1.8Hz,6H),7.05(d,J=7.2Hz,2H),6.94(d,J=8.1Hz,2H),6.66(d,J=8.1Hz,2H),6.60(s,1H),5.52(s,1H),5.11(s,4H),3.78(d,J=6.1Hz,6H)。
步骤4:化合物F2的合成:
取2.5g化合物D21加入反应器中,加35ml甲醇,取3g NaOH溶于35ml去离子水中,加入到上述反应液中,回流反应4h。冷却至室温,用稀盐酸调pH值至2-3,过滤,水洗,真空干燥。将得到的产物加入到50ml喹啉(quinoline)中,加1.4g铜粉,氮气保护下240℃反应3h。冷却至室温,加100ml乙酸乙酯稀释,用稀盐酸洗掉喹啉,有机相用无水硫酸钠干燥,之后柱层析分离,得到纯的化合物F2。核磁数据如下:1H NMR(400MHz,CDCl3)δ7.49–7.40(m,4H),7.33–7.26(m,6H),7.07–7.01(m,1H),6.99(dd,J=10.4,4.4Hz,3H),6.92–6.85(m,2H),6.64(d,J=7.8Hz,2H),6.27(dd,J=5.9,1.5Hz,1H),5.16(dd,J=5.7,1.5Hz,1H),5.13–5.01(m,4H)。
步骤5:化合物E21的合成:
取2.1g化合物F2加入反应器中,加20ml四氢呋喃溶解,加60ml甲醇稀释,加200mg钯碳,用氢气置换反应器内气体3次,加上氢气球,室温反应过夜。加硅藻土过滤,四氢呋喃洗涤,减压蒸掉溶剂,真空干燥后得到化合物E21。核磁数据如下:1H NMR(600MHz,DMSO)δ9.20(s,2H),6.83(d,J=7.8Hz,2H),6.73(d,J=7.1Hz,2H),6.57(dd,J=8.0,0.6Hz,2H),5.07(s,1H),4.21(d,J=2.5Hz,1H),1.55–1.45(m,5H)。
步骤6:配体L1的合成:
取250mg二吡咯基氯化磷P1加入反应器中,加2ml干燥的四氢呋喃,降温至0℃,另外取100mg化合物E21和128mg三乙胺溶于1ml干燥的四氢呋喃,在0℃将此混合液滴加到上述反应器中,自然升至室温,反应1h。加入10ml水中淬灭,加10ml乙酸乙酯萃取,有机相用无水硫酸钠干燥,柱层析分离,得到配体L1。核磁数据如下:1H NMR(400MHz,CDCl3)δ7.13–6.87(m,12H),6.63–6.55(m,2H),6.34–6.25(m,8H),4.91(s,1H),4.25(s,1H),1.58–1.49(m,2H),1.30–1.23(m,2H)。31P NMR(162MHz,CDCl3)δ108.25。
制备实施例2:配体L2的合成
取100mg制备实施例1中得到的化合物E21加入反应器中,加2ml干燥的DMF溶解,降温至0℃,分批次加36.8mg NaH,升温至室温反应30min,另外取212mg氯化磷P2溶于0.5ml干燥的DMF中,将其慢速滴加到上述反应器中,室温反应过夜。加入10ml水中淬灭,加10ml乙酸乙酯萃取,有机相用无水硫酸钠干燥,柱层析分离,得到配体L2。核磁数据如下:1H NMR(400MHz,C6D6)δ8.53(s,2H),7.75(t,J=14.5Hz,1H),7.41(d,J=7.8Hz,1H),7.34(dd,J=8.0,2.9Hz,1H),7.03(dt,J=25.3,7.6Hz,3H),6.87(dt,J=12.9,7.4Hz,4H),6.64–6.53(m,2H),5.96(s,1H),4.12(s,1H),1.83–1.69(m,2H),1.54(dd,J=13.2,6.0Hz,2H),1.34(d,J=12.5Hz,9H),1.23(d,J=12.5Hz,9H)。31P NMR(162MHz,C6D6)δ118.86,114.85。
制备实施例3:配体L3的合成
取578mg氯化磷P3加入反应器中,加4ml干燥的四氢呋喃,降温至0℃,另外取150mg制备实施例1中得到的化合物E21和334mg三乙胺溶于2ml干燥的四氢呋喃中,在0℃将此混合液滴加到上述反应器中,自然升至室温,反应1h。加入10ml水中淬灭,加10ml乙酸乙酯萃取,有机相用无水硫酸钠干燥,柱层析分离,得到配体L3。核磁数据如下:1H NMR(400MHz,CDCl3)δ7.04(dt,J=8.6,2.0Hz,10H),6.92(d,J=10.3Hz,4H),5.41(s,1H),4.37(s,1H),2.31(d,J=5.3Hz,12H),2.22(d,J=2.7Hz,12H),1.69(s,4H)。31P NMR(162MHz,CDCl3)δ141.03。
制备实施例4:配体L4的合成
取50mg制备实施例1中得到的化合物E21加入反应器中,加2ml干燥的四氢呋喃溶解,加50mg吡啶(pyridine),另取132mg氯化磷P4溶于0.5ml干燥的四氢呋喃中,慢速滴加到反应器中,升温至50℃,氮气保护下3h。降至室温,取63mg二吡咯基氯化磷P1溶于0.5ml干燥的四氢呋喃中,慢速滴加到反应器中,室温反应2h。加10ml水淬灭,加10ml乙酸乙酯萃取,有机相用无水硫酸钠干燥,柱层析分离,得到配体L4。核磁数据如下:1H NMR(400MHz,CDCl3)δ7.17(d,J=9.1Hz,2H),7.07–6.88(m,8H),6.83(d,J=7.9Hz,1H),6.66(d,J=8.1Hz,1H),6.21–6.09(m,4H),5.15(s,1H),4.31(t,J=2.4Hz,1H),2.29(s,3H),2.14(s,3H),1.89(s,3H),1.82(s,3H),1.65–1.60(m,2H),1.53(s,2H),1.42(s,10H),1.32(s,10H)。31P NMR(162MHz,CDCl3)δ132.52,107.42。
制备实施例5:配体L5的合成
步骤1:化合物G21的合成:
取400mg制备实施例1中得到的化合物E21加入反应器中,加8ml DMF溶解,另取613mg NBS溶于1ml DMF中,在-20℃下慢速滴加到反应器中,自然升至室温,搅拌反应过夜。加30ml亚硫酸钠溶液淬灭,加30ml乙酸乙酯萃取,有机相用无水硫酸钠干燥,柱层析分离,得到化合物G21。核磁数据如下:1H NMR(400MHz,DMSO)δ9.68(s,2H),7.12(d,J=8.6Hz,2H),6.60(d,J=8.7Hz,2H),5.14(s,1H),5.01(s,1H),1.63-1.44(m,4H).
步骤2:化合物H21的合成:
取150mg化合物G21、168mg对乙烯基苯硼酸、261mg无水碳酸钾、14mg Pd(dppf)Cl2加入反应器中,加3ml 1,4-二氧六环(dioxane)和1ml去离子水,氩气保护下,升温至100℃,搅拌反应过夜。加30ml水稀释,加30ml乙酸乙酯萃取,有机相用无水硫酸钠干燥,柱层析分离,得到化合物H21。核磁数据如下:1H NMR(400MHz,CDCl3)δ7.17(d,J=9.1Hz,2H),7.07–6.88(m,8H),6.83(d,J=7.9Hz,1H),6.66(d,J=8.1Hz,1H),6.21–6.09(m,4H),5.15(s,1H),4.31(t,J=2.4Hz,1H),2.29(s,3H),2.14(s,3H),1.89(s,3H),1.82(s,3H),1.65–1.60(m,2H),1.53(s,2H),1.42(s,10H),1.32(s,10H)。31P NMR(162MHz,CDCl3)δ132.52,107.42。
步骤3:配体L5的合成:
取67.4mg二吡咯基氯化磷P1加入反应器中,加1ml干燥的四氢呋喃,降温至0℃,另外取50mg化合物H21和34.2mg三乙胺溶于0.5ml干燥的四氢呋喃,在0℃将此混合液滴加到上述反应器中,自然升至室温,搅拌反应1h。加入10ml水中淬灭,加10ml乙酸乙酯萃取,有机相用无水硫酸钠干燥,柱层析分离,得到配体L5。核磁数据如下:1H NMR(400MHz,CDCl3)δ7.23(d,J=8.1Hz,4H),7.15–7.10(m,4H),7.09–6.99(m,10H),6.76–6.65(m,4H),6.39(dd,J=5.2,3.1Hz,4H),6.37–6.33(m,4H),5.76(d,J=17.6Hz,2H),5.28(d,J=11.2Hz,2H),5.14(t,J=2.5Hz,1H),4.91(t,J=2.5Hz,1H),1.54(dd,J=6.7,3.0Hz,2H),1.44–1.41(m,2H)。31P NMR(162MHz,CDCl3)δ108.34。
制备实施例6:配体L6的合成
取104mg氯化磷P3加入反应器中,加1ml干燥的四氢呋喃,降温至0℃,另外取50mg制备实施例5中得到的化合物H21和34.2mg三乙胺溶于0.5ml干燥的四氢呋喃,在0℃将此混合液滴加到上述反应器中,自然升至室温,搅拌反应1h。加入10ml水中淬灭,加10ml乙酸乙酯萃取,有机相用无水硫酸钠干燥,柱层析分离,得到配体L6。核磁数据如下:1H NMR(400MHz,CDCl3)δ7.26(s,2H),7.25(s,2H),7.07(m,12H),6.94(d,J=5.2Hz,4H),6.74(dd,J=17.6,10.9Hz,2H),5.78(d,J=17.6Hz,2H),5.58(t,J=2.5Hz,1H),5.29(d,J=10.5Hz,2H),4.99(t,J=2.4Hz,1H),2.33(d,J=6.9Hz,12H),2.26(d,J=7.7Hz,12H),1.87–1.76(m,2H),1.69–1.60(m,2H)。31P NMR(162MHz,CDCl3)δ140.98。
测试实施例:
分别取5.7umol制备实施例1至6制备得到的二齿膦配体加入到25ml的高压釜内,加3ml甲苯溶解,然后加3.8umol Rh(acac)(CO)2,最后加1ml 1,3-丁二烯甲苯溶液(3mol/L),封闭反应釜,通入一定压力的合成气(H2:CO=1:1),在60~150℃下搅拌反应5-24h小时。降温,加入癸烷做内标,采用GC7820气相色谱检测分析,色谱柱为HP-5,三阶升温程序如下:初始温度45℃,保持2分钟,然后以5℃/min的速率升温至90℃,保持3分钟,然后在以20℃/min的速率升温至250℃,保持10分钟。实验条件及结果见下表1。
表1:
实施例 | 催化剂 | 温度 | 压力 | 时间 | 转化率 | 己二醛百分含量 | 己二醛选择性 |
实施例1 | Rh/L1 | 90℃ | 4MPa | 5h | 82.3% | 9.87% | 12.0% |
实施例2 | Rh/L1 | 80℃ | 4MPa | 12h | 77.6% | 12.4% | 15.9% |
实施例3 | Rh/L2 | 90℃ | 4MPa | 5h | 80.8% | 6.65% | 8.23% |
实施例4 | Rh/L2 | 80℃ | 4MPa | 12h | 75.1% | 10.5% | 14.0% |
实施例5 | Rh/L3 | 90℃ | 2MPa | 12h | 68.5% | 6.56% | 9.58% |
实施例6 | Rh/L3 | 90℃ | 3MPa | 5h | 88.5% | 28.3% | 32.0% |
实施例7 | Rh/L3 | 90℃ | 4MPa | 5h | 97.7% | 39.7% | 40.6% |
实施例8 | Rh/L3 | 80℃ | 4MPa | 12h | 93.5% | 45.6% | 48.8% |
实施例9 | Rh/L4 | 90℃ | 4MPa | 5h | 95.9% | 20.5% | 21.4% |
实施例10 | Rh/L4 | 80℃ | 4MPa | 12h | 81.6% | 23.8% | 29.2% |
实施例11 | Rh/L5 | 90℃ | 4MPa | 5h | 75.3% | 26.4% | 35.1% |
实施例12 | Rh/L5 | 80℃ | 4MPa | 12h | 67.7% | 29.4% | 43.4% |
实施例13 | Rh/L6 | 90℃ | 4MPa | 5h | 98.4% | 44.5% | 45.2% |
实施例14 | Rh/L6 | 80℃ | 4MPa | 12h | 98.2% | 58.1% | 59.8% |
从表1的数据可以看出,根据本发明制备的二齿膦配体可以有效催化1,3-丁二烯转化为己二醛。1,3-丁二烯的转化率可以达到98%以上,己二醛选择性可达进60%。
以上所述,仅为本发明的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,可轻易想到变化或替换,都应涵盖在本发明的保护范围之内。因此,本发明的保护范围应所述以权利要求的保护范围为准。
Claims (8)
4.根据权利要求1所述二齿膦配体在促进金属催化丁二烯氢甲酰化反应中的用途。
5.一种丁二烯氢甲酰化制备1,6-己二醛的方法,包括以下步骤:
取适量权利要求1所述二齿膦配体加入反应釜中,之后加入溶剂、金属前驱体和丁二烯,封闭反应釜,充入一定压力的H2和CO组成的混合气,在设定的温度下反应一定时间。
6.根据权利要求5所述的丁二烯氢甲酰化制备1,6-己二醛的方法,其特征在于,
所述溶剂选自正己烷、环己烷、辛烷、苯、甲苯、二甲苯、甲醇、乙醇、异丙醇、***、四氢呋喃和二氧六环中的一种或多种;
所述金属前驱体为金属铑和钴的前驱体,选自:Rh(CO)2(acac)、Rh(AcO)2、RhCl3、Rh(NO3)3、RhH(CO)(PPh3)3、[Rh(CO)2Cl]2、RhH(CO)(PPh3)3、[Rh2(m-Cl)2(cod)2]、[Rh(cod)2]BF4、Co(CO)2(acac)、Co(AcO)2、CoCl2、Co(acac)2中的一种或多种;
金属前驱体与二齿膦配体的摩尔比为2:1-1:10;
金属前驱体与丁二烯的摩尔比为1/50-1/5000;
丁二烯为丁二烯己烷溶液、丁二烯甲苯溶液、丁二烯四氢呋喃溶液、丁二烯甲醇溶液以及纯的丁二烯;
所述混合气中H2和CO的体积比为1/2-3/1;
混合气的压力为1MPa-10MPa;
反应温度为50℃-200℃;
反应时间为5h-24h;
丁二烯的反应浓度为0.1mol/L-10mol/L。
7.根据权利要求5所述的丁二烯氢甲酰化制备1,6-己二醛的方法,其特征在于,
所述溶剂为甲苯;
所述金属前驱体为Rh(CO)2(acac);
金属前驱体与二齿膦配体的摩尔比为1:1-1:5;
金属前驱体与丁二烯的摩尔比为优选为1/100-1/1000;
丁二烯为丁二烯甲苯溶液;
所述混合气中H2和CO的体积比为1/1-2/1;
混合气的压力为2MPa-5MPa;
反应温度为80℃-120℃;
反应时间为5h-15h;
丁二烯的反应浓度为0.5mol/L-3mol/L。
8.根据权利要求7所述的丁二烯氢甲酰化制备1,6-己二醛的方法,其特征在于,金属前驱体与二齿膦配体的摩尔比为1:1-1:3。
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