1,4-dimethyl-6-phenylfulvene | 532987-77-2

• 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: 1,4-dimethyl-6-phenylfulvene
• 英文别名: [(2,5-Dimethylcyclopenta-2,4-dien-1-ylidene)methyl]benzene；(2,5-dimethylcyclopenta-2,4-dien-1-ylidene)methylbenzene
• CAS: 532987-77-2
• 化学式: C₁₄H₁₄
• 分子量: 182.265
• InChiKey: NLPGMHICCBAMSS-UHFFFAOYSA-N

物化性质

• 沸点：
  298.7±7.0 °C(Predicted)
• 密度：
  1.017±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.14
• 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：

  芴 、 1,4-dimethyl-6-phenylfulvene 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 3.0h， 以76%的产率得到2-[α-fluorenylbenzyl]-1,3-dimethylcyclopentadiene
  参考文献：
  名称：

  Fulvene, metallocene catalysts and preparation method thereof, and preparation of polyolefines copolymer using the same

  摘要：

  本发明涉及一种新型富烯化合物及其制备方法，更特别地涉及一种在2-和5-位置具有取代基的富烯化合物，其由在β-位置具有取代基和在α-位置具有卤原子的不饱和酮制备而成，以及其制备方法。本发明还涉及一种金属茂嗪催化剂，其在环戊二烯基桥碳的α-位置具有取代基，仅通过富烯化合物和包括环戊二烯基团的阴离子团的反应而得到，并使用相同的制备方法制备聚烯烃共聚物。

  公开号：

  US20050004385A1
• 作为产物：
  描述：

  9-溴-8-甲基-1,4-二氧杂螺[4.4]壬-8-烯 在 正丁基锂 、 对甲苯磺酸 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 为溶剂， 反应 8.05h， 生成 1,4-dimethyl-6-phenylfulvene
  参考文献：
  名称：

  Fulvene having substituents only on 1-, 4-, and 6-positions: a key intermediate for novel ansa-metallocene complexes

  摘要：

  A synthetic route for 1,4-dimethyl-6-phenylfulvene (4) and 1,4-dimethyl-6,6-diphenylfulvene (5), which are characteristic in that they have substituents only on 1-, 4-, and 6-positions, is developed. The synthetic route is straightforward from 2-bromo-3-methyl-2cyclopenten-1-one ethylene ketal (1), which can be easily synthesized in 100-g scale: Overall yield from 1 is 50 and 47% for 4 and 5, respectively. Synthesis of an ansa-metallocene complex, [Ph(H)C(fluorenyl)(1,3-Me2CP)]ZrCl2 (7), is demonstrated using 4. Much higher comonomer incorporation in ethylene/1-hexene copolymerization and dramatic increase of molecular weight in 1-hexene polymerization are observed with 7 when the reactivity compared with that of the one not having methyl substituents, [Ph(H)C(fluorenyl)(Cp)]ZrCl2. (C) 2003 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0022-328x(03)00388-7

文献信息

• sp ³ ‐C ¹ ‐Bridged 1,3‐Me ₂ Cp/Amido Titanium and Zirconium Complexes and Their Reactivities towards Ethylene Polymerization
  作者：Tae Ho Kim、Young Chul Won、Bun Yeoul Lee、Dong Mok Shin、Young Keun Chung

  DOI：10.1002/ejic.200300703

  日期：2004.4

  abstraction of water from the solvents. The solid structures of (1,3-Me2C5H2−CHPh−NtBu−κN)Zr(NMe2)2, 10, 11, and 12 have been determined by X-ray crystallography. The complexes are active towards the polymerization of ethylene when activated with MAO. The activities are rather low and the molecular weight distributions are broad (Mw/Mn = 10−36). (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany

  sp3-C1-Bridged Cp/amido 钛和锆配合物是通过使用仅在 1-、4-和 6-位具有取代基的新型富烯合成的。因此，叔丁基酰胺锂对 1,4-二甲基-6-苯基富烯、6-(2-呋喃基)-1,4-二甲基富烯和 6-环己基-1,4-二甲基富烯的亲核攻击，以及随后的水处理， tBuN(H)-CHR-C5H3Me2 (R = 苯基, 6; R = 2-呋喃基, 7; R = 环己基, 8) 的产率分别为 80%、88% 和 60%。配体与 M(NMe2)4 (M = Ti 或 Zr) 的反应提供了所需的双（二甲基酰胺）配合物，可以通过用 Me2SiCl2 处理将其转化为二氯化物配合物，（1,3-Me2C5H2-CHR-NtBu -κN)MCl2 (M = Ti, R = 苯基, 10; M = Zr, R = 苯基, 11; M = Ti, R = 2-呋喃基, 13; M = Zr, R
• Preparation of ansa-metallocenes for production of poly(α-olefin) lubricants
  作者：Ji Hae Park、Young Eun Jang、Jong Yeob Jeon、Min Jeong Go、Junseong Lee、Sung Kwan Kim、Sang-Ick Lee、Bun Yeoul Lee

  DOI：10.1039/c4dt00997e

  日期：——

  An ansa-zirconocene bearing methyl substituents at all positions adjacent to the bridgehead [(–C(Ph)HC(Ph)H–)(η5-2,5-Me2C5H2)2ZrCl2] (4) was prepared in high yields (78%) through the reductive dimerization of 1,4-dimethyl-6-phenylfulvene utilizing ZrCl2·DME generated in situ. The structure of 4 was subsequently confirmed using X-ray crystallography. 4 exhibited excellent catalytic performance with regard to 1-decene oligomerization, which was carried out with the intention of preparing lubricant base stocks. High activities (21 × 106 g mol−1 Zr h−1 activity; TON = 150 000; TOF = 42 s−1) were observed at temperatures as high as 120 °C and the oligomer distribution was appropriate for lubricant application. The simulated distillation (SIMDIS) data confirmed that a wide range of oligomers were formed, ranging from the dimer (2-mer) to 20-mer. A minimal amount of the dimer and oligomers larger than the 10-mer was formed (13 and 25 wt%, respectively). Alternatively, a typical unbridged complex such as (η5-nBuC5H4)2ZrCl2 primarily produced dimers (54 wt%), whereas the ansa-zirconocene (EBI)ZrCl2 primarily produced oligomers larger than 10-mer (62 wt%). The methyl substituents at the positions adjacent to the bridgehead in 4 played a significant role in the catalytic performance.

  通过1,4-二甲基-6-苯基富烯的还原二聚化，利用原位生成的ZrCl2·DME，制备了在所有相邻位置都带有甲基取代基的ansa-锆茂[(–C(Ph)HC(Ph)H–)(Μ5-2,5-Me2C5H2)2ZrCl2] (4)，且收率很高（78%）。随后利用X射线晶体学确认了4的结构。4在1-癸烯低聚反应中表现出优异的催化性能，该反应的目的是制备润滑油基础油。在高达120°C的温度下观察到高活性（21×106 g mol–1 Zr h–1活性；TON = 150000；TOF = 42 s–1），且低聚物的分布适合润滑油应用。模拟蒸馏（SIMDIS）数据证实，形成了从二聚体（2-mer）到20-mer的各种低聚物。形成了极少量的二聚体和大于10-mer的低聚物（分别占13%和25%）。另外，典型的非桥联络合物（Μ5-nBuC5H4）2ZrCl2主要产生二聚体（54%），而ansa-锆茂（EBI）Zr
• 알파-올레핀 올리고머 조성물 및 이를 포함하는 윤활 기유
  申请人：SK Innovation Co., Ltd. 에스케이이노베이션 주식회사(120070287265) Corp. No ▼ 110111-3710385BRN ▼101-86-32319

  公开号：KR20150135631A

  公开（公告）日：2015-12-03

  본 발명은 하기 화학식 1로 표시되는 안사-메탈로센 화합물을 포함하는 촉매 조성물 및 탄소수 6 내지 20의 알파-올레핀 단량체를 사용하여 합성되는 알파-올레핀 올리고머 조성물에 관한 것으로서, 보다 상세하게는 알파-위치에만 치환체가 있는 안사-메탈로센 화합물(화학식 1)을 촉매로 사용함으로써, 윤활 기유로 사용하기 적합한 중합도 분포 및 유동점을 갖고, 각 올리고머의 위치 규칙성이 뛰어난 알파-올레핀계 올리고머 조성물에 관한 것이다.

  本发明涉及一种催化剂组合物，其中包含用α-烯烃单体，其碳数为6至20，并合成α-烯烃共聚物组合物的安萨-金属洛芬化合物，其用化学式1表示。更具体地，本发明涉及使用仅在α位上具有取代基的安萨-金属洛芬化合物(化学式1)作为催化剂，从而具有适用于润滑油的高聚物分布和流动点，并具有高度规则的α-烯烃共聚物组合物的位置。
• Fulvene, metallocene catalysts and preparation method thereof, and preparation of polyolefines copolymer using the same
  申请人：Park Young-Whan

  公开号：US20050004385A1

  公开（公告）日：2005-01-06

  The present invention relates to a novel fulvene compound and a preparation method thereof, and more particularly to a fulvene compound having substituted groups in the 2- and 5-positions, prepared from an unsaturated ketone having a substituted group in the β-position and a halogen atom in the α-position, and a preparation method thereof. The present invention also relates to a metallocene catalyst having a substituted group in the α-position carbon of the bridge of the cyclopentadienyl group only by reaction of a fulvene compound and an anion group including the cyclopentadienyl group, and a preparation method of a polyolefin copolymer using the same.

  本发明涉及一种新型富烯化合物及其制备方法，更特别地涉及一种在2-和5-位置具有取代基的富烯化合物，其由在β-位置具有取代基和在α-位置具有卤原子的不饱和酮制备而成，以及其制备方法。本发明还涉及一种金属茂嗪催化剂，其在环戊二烯基桥碳的α-位置具有取代基，仅通过富烯化合物和包括环戊二烯基团的阴离子团的反应而得到，并使用相同的制备方法制备聚烯烃共聚物。
• Fulvene having substituents only on 1-, 4-, and 6-positions: a key intermediate for novel ansa-metallocene complexes
  作者：Young Chul Won、Heon Yong Kwon、Bun Yeoul Lee、Young-Whan Park

  DOI：10.1016/s0022-328x(03)00388-7

  日期：2003.7

  A synthetic route for 1,4-dimethyl-6-phenylfulvene (4) and 1,4-dimethyl-6,6-diphenylfulvene (5), which are characteristic in that they have substituents only on 1-, 4-, and 6-positions, is developed. The synthetic route is straightforward from 2-bromo-3-methyl-2cyclopenten-1-one ethylene ketal (1), which can be easily synthesized in 100-g scale: Overall yield from 1 is 50 and 47% for 4 and 5, respectively. Synthesis of an ansa-metallocene complex, [Ph(H)C(fluorenyl)(1,3-Me2CP)]ZrCl2 (7), is demonstrated using 4. Much higher comonomer incorporation in ethylene/1-hexene copolymerization and dramatic increase of molecular weight in 1-hexene polymerization are observed with 7 when the reactivity compared with that of the one not having methyl substituents, [Ph(H)C(fluorenyl)(Cp)]ZrCl2. (C) 2003 Elsevier Science B.V. All rights reserved.