3,3'-di-isopropylbiphenyl | 69375-12-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 3,3'-di-isopropylbiphenyl
• 英文别名: 3,3'-diisopropylbiphenyl；3,3'-DIPB；3,3' diisopropylbiphenyl；1-propan-2-yl-3-(3-propan-2-ylphenyl)benzene
• CAS: 69375-12-8
• 化学式: C₁₈H₂₂
• 分子量: 238.373
• InChiKey: PYXYYRWLLNHRLM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.8
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  3,3'-di-isopropylbiphenyl 在 三氯化铝 、 异丙苯 、 苯 作用下， 反应 7.0h， 生成 3,4-二异丙基联苯
  参考文献：
  名称：

  烷基联苯异构转化的平衡

  摘要：

  摘要 研究了液相中单、二和三烷基联苯 ( abp ) 相互转化的平衡，温度为 308 至 423 K。根据实验平衡常数，ΔrHmo/(kJ·mol−1) 值和ΔrSmo/(J·K-1·mol-1)被计算。下面分别给出：Et-bp (I)、i-Pr-bp (II) 和 t-Bu-bp (III) 的反应、化合物和值： 4- abp = 3- abp , I, 0.23, 5.76 ; 二、(0.45±0.41)、(5.72±1.13)；三、(0.48±0.53)、(4.83±0.53)；2- abp = 4- abp , I, -3.3, -5.76; II、-12.6、-5.76；III、-15.4、-5.76；3,5-di-abp = 3,3'-di-abp, I, -0.1, 5.76; 二、(0±0.60)、(5.98±1.65)；三、(-1.34±0.67)、(4.48±1.87)；3

  DOI：

  10.1016/0021-9614(87)90137-6
• 作为产物：
  描述：

  3,5-di-isopropylbiphenyl 在 三氯化铝 、 1,3-二异丙基苯 、 苯 作用下， 反应 7.0h， 生成 3,3'-di-isopropylbiphenyl
  参考文献：
  名称：

  烷基联苯异构转化的平衡

  摘要：

  摘要 研究了液相中单、二和三烷基联苯 ( abp ) 相互转化的平衡，温度为 308 至 423 K。根据实验平衡常数，ΔrHmo/(kJ·mol−1) 值和ΔrSmo/(J·K-1·mol-1)被计算。下面分别给出：Et-bp (I)、i-Pr-bp (II) 和 t-Bu-bp (III) 的反应、化合物和值： 4- abp = 3- abp , I, 0.23, 5.76 ; 二、(0.45±0.41)、(5.72±1.13)；三、(0.48±0.53)、(4.83±0.53)；2- abp = 4- abp , I, -3.3, -5.76; II、-12.6、-5.76；III、-15.4、-5.76；3,5-di-abp = 3,3'-di-abp, I, -0.1, 5.76; 二、(0±0.60)、(5.98±1.65)；三、(-1.34±0.67)、(4.48±1.87)；3

  DOI：

  10.1016/0021-9614(87)90137-6

文献信息

• The Alkylation of Biphenyl over Fourteen-Membered Ring Zeolites. The Influence of Zeolite Structure and Alkylating Agent on the Selectivity for 4,4′-Dialkylbiphenyl
  作者：Yoshihiro Sugi、Hiroyoshi Maekawa、Shafeek Abdul Rashid Mulla、Akira Ito、Chikayo Naitoh、Kazunori Nakagawa、Kenichi Komura、Yoshihiro Kubota、Jong-Ho Kim、Gon Seo

  DOI：10.1246/bcsj.80.1418

  日期：——

  Alkylation, i.e. isopropylation, s-butylation, and t-butylation, of biphenyl (BP) was examined over fourteen-membered ring (14-MR) zeolites, CIT-5, UTD-1, and SSZ-53, in order to elucidate the relationships between structure of zeolites and bulkiness of alkylating agents on the shape-selective catalysis. CIT-5 zeolite (CFI) yielded 4,4′-diisopropylbiphenyl (4,4′-DIPB) in the level of 50–60% in the isopropylation in the range of 150–300 °C. 2,2′-, 2,3′-, and 2,4′-DIPB (2,x′-DIPB) isomers were obtained as the predominant DIPB isomers at lower temperatures, and the formation of 3,4′- and 3,3′-DIPB isomers increased with an increase in the temperature. However, the selectivities were in the level of 10–15% for UTD-1 (DON) and SSZ-53 (SFH) zeolites in the range of 150–350 °C. The s-butylation with 1-butene gave results similar to the isopropylation, although the selectivities for 4,4′-di-s-butylbiphenyl (4,4′-DSBB) were higher than those for 4,4′-DIPB at 250 °C: 80–85% for CFI, 40–50% for DON, and 30–40% for SFH. High selectivity for 4,4′-di-t-butylbiphenyl (4,4′-DTBB) was observed in the t-butylation at 250 °C: 95% for CFI, 90% for DON, and 80% for SFH. These differences are due to the spatial difference in their channels, and also due to bulkiness of alkylating agents, propene, 1-butene, and 2-methylpropene. The selectivity for 4,4′-dialkylbiphenyl (4,4′-DABP) was governed by the exclusion of the bulky DABP isomers at the transition state by steric restriction in the zeolite channels.

  研究了联苯（BP）在十四元环（14-MR）沸石（CIT-5、UTD-1 和 SSZ-53）上的烷基化反应，即异丙基化、正丁基化和叔丁基化，以阐明沸石结构和烷化剂体积对形状选择性催化的关系。CIT-5 沸石（CFI）在 150-300 ℃范围内进行异丙基化时，4,4′-二异丙基联苯（4,4′-DIPB）的产率为 50-60%。在较低温度下，2,2′-、2,3′- 和 2,4′-DIPB （2,x′-DIPB）异构体是主要的 DIPB 异构体，而随着温度的升高，3,4′- 和 3,3′-DIPB 异构体的生成量增加。不过，在 150-350 °C 的范围内，UTD-1（DON）和 SSZ-53（SFH）沸石的选择性在 10-15% 之间。用 1-丁烯进行 s-丁基化反应的结果与异丙基化反应相似，但在 250 ℃ 时，4,4′-二-s-丁基联苯（4,4′-DSBB）的选择性高于 4,4′-DIPB：CFI为80-85%，DON为40-50%，SFH为30-40%。在 250 ℃ 的 t 丁基化反应中，4,4′-二叔丁基联苯（4,4′-DTBB）具有较高的选择性：CFI为 95%，DON 为 90%，SFH 为 80%。这些差异是由于它们通道的空间差异以及烷基化剂丙烯、1-丁烯和 2-甲基丙烯的体积差异造成的。对 4,4′-二烷基联苯（4,4′-DABP）的选择性取决于沸石通道中的立体限制对过渡态笨重的 DABP 异构体的排斥。
• Continuous Process for preparing 4,4'-diisopropylbiphenyl
  申请人：GENERAL ELECTRIC COMPANY

  公开号：EP1533288A3

  公开（公告）日：2005-06-01

  A continuous flow process has been discovered for the highly selective isopropylation of biphenyl to 4,4'-diisopropylbiphenyl. Thus biphenyl and propene in decalin are passed through a solid catalyst bed contained in a flow reactor at moderate temperature (220°C) and pressure (10-30 atm) together with a continuous stream of nitrogen. The catalyst is an acidic zeolite catalyst having a molar ratio of SiO2 to Al2O3 in a range between about 20 to 1 and about 500 to 1. Optimal catalytic performance is achieved when 35% or more of the active sites in the catalyst have an activation energy of ammonia desorption in a range between about 145 kJ/mol and about 170 kJ/mol. Additional enhancements of catalyst performance can be achieved by pretreating the acidic zeolite catalyst with a volatile basic agent prior to the alkylation reaction.

  已发现一种连续流程，用于高选择性异丙基化二苯生成4,4'-二异丙基二苯。因此，将二苯和丙烯在癸烷中通过固体催化剂床在适中温度（220°C）和压力（10-30大气压）下，连同一股氮气连续流过流动反应器。催化剂是一种酸性沸石催化剂，其硅氧比在约20:1至约500:1之间。当催化剂中35%或更多的活性位点的活化能在约145千焦耳/摩尔至约170千焦耳/摩尔之间时，可以实现最佳催化性能。通过在烷基化反应之前使用挥发性碱性试剂对酸性沸石催化剂进行预处理，可以进一步提高催化剂性能。
• Shape-Selective Alkylation of Biphenyl over H-[Al]-SSZ-24 Zeolites with AFI Topology
  作者：Akira Ito、Hiroyoshi Maekawa、Hiroaki Kawagoe、Kenichi Komura、Yoshihiro Kubota、Yoshihiro Sugi

  DOI：10.1246/bcsj.80.215

  日期：2007.1

  H-[Al]-SSZ-24 zeolites with AFI topology were synthesized through the alumination of [B]-SSZ-24 zeolites, and applied for the alkylation of biphenyl (BP). H-[Al]-SSZ-24 zeolites have high activity for the isopropylation. The shape-selective formation of 4,4′-diisopropylbiphenyl (4,4′-DIPB) occurred at moderate temperature; however, the selectivity for 4,4′-DIPB decreased with an increase in the reaction temperature. Isomerization of 4,4′-DIPB occurred at higher temperatures over internal and external acid sites when there are enough acid sites inside the channels. The channels can discriminate 4,4′-DIPB from the other DIPB isomers in their transition states; however, they can not prevent the isomerization of 4,4′-DIPB at higher temperatures. The selectivity for the least bulky 4,4′-dialkylbiphenyl increased with the bulkiness of alkylating agents in the order: isopropylation < s-butylation < t-butylation. These results strongly support the shape-selective formation of the least bulky products inside the channels of H-[Al]-SSZ-24 zeolites.

  通过矾化[B]-SSZ-24沸石合成了具有 AFI 拓扑结构的 H-[Al]-SSZ-24 沸石，并将其应用于联苯（BP）的烷基化反应。H-[Al]-SSZ-24沸石具有较高的异丙基化活性。在中等温度下，4,4′-二异丙基联苯（4,4′-DIPB）的形成具有形状选择性；然而，4,4′-DIPB 的选择性随着反应温度的升高而降低。当通道内有足够的酸性位点时，4,4′-DIPB 在较高温度下通过内部和外部酸性位点发生异构化。通道可以区分处于过渡态的 4,4′-DIPB 和其他 DIPB 异构体，但不能阻止 4,4′-DIPB 在较高温度下发生异构化。对体积最小的 4,4′-二烷基联苯的选择性随着烷基化剂体积的增加而增加，其顺序为：异丙基化 < s-丁基化 < t-丁基化。这些结果有力地支持了在 H-[Al]-SSZ-24 沸石通道内形成最不笨重产物的形状选择性。
• The Alkylation of Biphenyl over One-Dimensional Twelve-Membered Ring Zeolites. The Influence of Zeolite Structure and Alkylating Agent on the Selectivity for 4,4′-Dialkylbiphenyl
  作者：Yoshihiro Sugi、Hiroyoshi Maekawa、Akira Ito、Chikako Ozawa、Tomoko Shibata、Akihiro Niimi、Chihara Asaoka、Kenichi Komura、Yoshihiro Kubota、Jae-Youl Lee、Jong-Ho Kim、Gon Seo

  DOI：10.1246/bcsj.80.2232

  日期：2007.11.15

  Alkylation, i.e., isopropylation, s-butylation, and t-butylation, of biphenyl (BP) was examined over one-dimensional twelve-membered (12-MR) zeolites: Mordenite (MOR) and SSZ-24 (AFI) with straight channels, and SSZ-55 (ATS) and SSZ-42 (IFR) with corrugated channels. Types of zeolites and alkylating agents highly influenced the selectivities for dialkylbiphenyl (DABP) isomers. Shape-selective formation of 4,4′-diisopropylbiphenyl (4,4′-DIPB) was observed over MOR and AFI; however, ATS and IFR gave 4,4′-DIPB only in low selectivities at 250 °C: 87% over MOR, 60% over AFI, 20% over ATS, and 30% over IFR. The selectivities for 4,4′-di-s-butylbiphenyl (4,4′-DSBB) in the s-butylation were higher than those for 4,4′-DIPB: 95% over MOR, 85% over AFI, 75% over ATS, and 50% over IFR. The t-butylation afforded selectively 4,4′-di-t-butylbiphenyl (4,4′-DTBB) over the zeolites: 96–97% over MOR and AFI, 90% over ATS, and 80% over IFR. These results in the alkylation indicate the exclusion of 4,4′-DABP from other bulky DABP isomers by steric restriction in zeolite channels is an important key for the high shape-selectivity. Even zeolites with large channels, such as ATS and IFR, can have shape-selective nature if the bulky moieties, such as s-butyl and t-butyl groups, are large enough to differentiate the transition state of the least bulky 4,4′-DABP from those of the other isomers inside their channels. The selectivity for 4,4′-DABP decreased at high temperatures in some alkylations: isopropylation over MOR, and s-butylation and t-butylation over MOR, AFI, and ATS. The decreases are due to the isomerization of 4,4′-DABP at external acid sites, because the channels are not large enough for the isomerization of 4,4′-DABP to bulkier 3,4′-DABP. However, the isopropylation over AFI was accompanied by the isomerization of 4,4′-DIPB at external and internal acid sites, because the channels are large enough for the isomerization of 4,4′-DIPB.

  研究了联苯（BP）在一维十二元（12-MR）沸石上的烷基化，即异丙基化、叔丁基化和叔丁基化：这些沸石包括具有直槽的 Mordenite (MOR) 和 SSZ-24 (AFI)，以及具有波纹槽的 SSZ-55 (ATS) 和 SSZ-42 (IFR)。沸石和烷化剂的类型对二烷基联苯（DABP）异构体的选择性有很大影响。在 MOR 和 AFI 上观察到了 4,4′-二异丙基联苯（4,4′-DIPB）的形状选择性形成；然而，ATS 和 IFR 在 250 °C 时只能以较低的选择性生成 4,4′-DIPB：对 MOR 的选择率为 87%，对 AFI 的选择率为 60%，对 ATS 的选择率为 20%，对 IFR 的选择率为 30%。4,4′-di-s-butylbiphenyl (4,4′-DSBB) 在 s-butylation 中的选择性高于 4,4′-DIPB 的选择性：对 MOR 的选择性为 95%，对 AFI 的选择性为 85%，对 ATS 的选择性为 75%，对 IFR 的选择性为 50%。在 t-丁基化反应中，沸石可选择性地生成 4,4′-二对丁基联苯（4,4′-DTBB）：比 MOR 和 AFI 高 96-97%，比 ATS 高 90%，比 IFR 高 80%。这些烷基化结果表明，沸石通道中的立体限制将 4,4′-DABP 与其他笨重的 DABP 异构体排除在外，是实现高形状选择性的重要关键。即使是具有大通道的沸石，如 ATS 和 IFR，如果其通道内的笨重分子（如 s-丁基和 t-丁基）足够大，足以将最不笨重的 4,4′-DABP 的过渡态与其他异构体的过渡态区分开来，也会具有形状选择性。在某些烷基化反应中，4,4′-DABP 的选择性在高温下会降低：异丙基化反应优于 MOR，s-丁基化反应和 t-丁基化反应优于 MOR、AFI 和 ATS。温度降低的原因是 4,4′-DABP 在外部酸位点发生了异构化，因为通道不够大，无法将 4,4′-DABP 异构化为体积更大的 3,4′-DABP 。然而，AFI 上的异丙基化伴随着 4,4′-DIPB 在外部和内部酸位点的异构化，因为通道足够大，可以使 4,4′-DIPB 异构化。
• The isopropylation of biphenyl over transition metal substituted aluminophosphates: MAPO-5 (M: Co and Ni)
  作者：Hui Xing Zhang、Anand Chokkalingam、Priya V. Subramaniam、Stalin Joseph、Seiji Takeuchi、Ming Deng Wei、Abdullah M. Al-Enizi、Hoi-Gu Jang、Jong-Ho Kim、Gon Seo、Kenichi Komura、Yoshihiro Sugi、Ajayan Vinu

  DOI：10.1016/j.molcata.2015.11.006

  日期：2016.2

  the restricted transition state selectivity mechanism. MAPO-5 (M: Co and Ni) has the same level of the selectivities for 4,4′-DIPB to SSZ-24 and other MAPO-5 (M: Si, Mg, and Zn), and these selectivities were originated by the AFI channels. The selectivities for 4,4′-DIPB were kept 65–75% at low and moderate temperatures over MAPO-5 (M: Co and Ni); however, they were decreased by the isomerization to

  在具有AFI拓扑结构的12元（12-MR）氧环孔入口的过渡金属取代的磷酸铝盐（MAPO-5; M：Co和Ni）上检查了联苯（BP）的异丙基化。以三甲胺为结构导向剂，通过干凝胶转化法合成了MAPO-5样品，并通过XRD，XPS，SEM，N 2吸附，NH 3 -TPD，吡啶吸附和邻位表征了其性质。-二甲苯吸收。它们是透明的晶体，没有杂质相和附聚物，并且发现了少量的布朗斯台德酸位点，这些位点有望对酸催化起作用。在250°C时BP在Co（5）APO-5和Ni（5）APO-5上的异丙基化使4,4'-DIPB的选择性高：65-75％。4-IPBP几乎是4,4'-和3,4'-DIPB的专有前体。尽管3-IPBP在后期的IPBP异构体中占主导地位，但3-IPBP并未受到太大关注：MAPO-5通道允许4-IPBP优先进入，并由于反应物选择性机制而阻止3-IPBP进入。通过受限的过渡态选择性机制，通过过渡态与