1,3-二氯-2,4,6-三氟-5-碘苯 | 31612-68-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 1,3-二氯-2,4,6-三氟-5-碘苯
• 英文名称: 1,3-dichloro-2,4,6-trifluoro-5-iodobenzene
• 英文别名: (3,5-C6Cl2F3)I；RfI；1,3-Dichloro-5-iodo-2,4,6-trifluorobenzene
• CAS: 31612-68-7
• 化学式: C₆Cl₂F₃I
• 分子量: 326.872
• InChiKey: UVVGJANJNZSQPO-UHFFFAOYSA-N

物化性质

• 沸点：
  250.4±35.0 °C(Predicted)
• 密度：
  2.208±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1,3-二氯-2,4,6-三氟-5-碘苯 、 bis(pentafluorophenyl)zinc 在 PdCl₂(PhPEWO-F) 作用下， 以 1,4-二氧六环 为溶剂， 反应 9.0h， 以62%的产率得到1,3-二氯-2,4,6-三氟-5-(2,3,4,5,6-五氟苯基)苯
  参考文献：
  名称：

  Selective synthesis of fluorinated biaryls by [MCl₂(PhPEWO-F)] (M = Ni, Pd) catalysed Negishi cross-coupling

  摘要：

  使用偶联促进配体，易于实现含氟芳基与Ni(ii)或Pd(ii)催化剂的选择性Negishi交叉偶联反应。

  DOI：

  10.1039/d1cc04915a
• 作为产物：
  描述：

  3,5-dichloro-2,4,6-trifluoroaniline 在 盐酸 、 sodium nitrite 、 potassium iodide 作用下， 以 水 为溶剂， 反应 6.75h， 以3005 g的产率得到1,3-二氯-2,4,6-三氟-5-碘苯
  参考文献：
  名称：

  一种全卤代衍生物的工业制造方法

  摘要：

  本发明提供了一种全卤代衍生物的工业制造方法，其特征在于：由五氯硝基苯为原料，经氟代、还原、碘代的过程获得目标产物；本发明提供的生产方法简单，区别于现有技术中复杂的生产方式，苛刻的生产条件，严重的污染问题。

  公开号：

  CN105622333A

文献信息

• On the Configuration Resulting from Oxidative Addition of RX to Pd(PPh₃)₄ and the Mechanism of the <i>cis</i>-to-<i>trans</i> Isomerization of [PdRX(PPh₃)₂] Complexes (R = Aryl, X = Halide)
  作者：Arturo L. Casado、Pablo Espinet

  DOI：10.1021/om9709502

  日期：1998.3.1

  isomerization of 2 in THF at 322.6 K reveals a first-order law riso = kiso[2], with kiso = f + g[2]0 + (h + i[2]0)/([PPh3] + j) (f = (1.66 ± 0.03) × 10-4 s-1, g = (2.5 ± 0.2) × 10-3 mol-1 L s-1, h = (1.3 ± 0.7) × 10-8 mol L-1 s-1, i = (4 ± 2) × 10-7 s-1, and j = (1.4 ± 0.7) × 10-5 mol L-1). A four-pathway mechanism accounts for these results:  Two are assigned to the associative replacements of PPh3 coordinated

  氧化加成RI与Pd（0），并进一步顺-到-反式异构化，其涉及在Stille反应等钯催化合成，进行了研究。在室温下，将C 6 Cl 2 F 3 I（1，C 6 Cl 2 F 3 = 3,5-二氯三氟苯基）加到Pd（PPh 3）4的THF中，得到顺式-[Pd（C 6 Cl 2 F 3）I （PPh 3）2 ]（2），可以在异构化之前分离为更稳定的反式-[Pd（C 6 Cl 2 F 3）I（PPh 3）2 ]（3）。甲19的异构化的F NMR动力学研究2在THF中在322.6ķ揭示了一阶法ř异= ķ异丙[ 2 ]，其中ķ异= ˚F +克[ 2 ] 0 +（ħ +我[ 2 ] 0）/（[[PPh 3 ] + j）（f=（1.66±0.03）×10 - 4个小号- 1，克=（2.5±0.2）×10 - 3摩尔- 1大号小号- 1，ħ =（1.3±0.7）×10 - 8摩尔大号- 1个小号- 1，我=（4±2）×10
• Stille Coupling of Alkynyl Stannane and Aryl Iodide, a Many-Pathways Reaction: The Importance of Isomerization
  作者：Mónica H. Pérez-Temprano、Ana M. Gallego、Juan A. Casares、Pablo Espinet

  DOI：10.1021/om100978w

  日期：2011.2.14

  The kinetics of the Stille reaction between C6Cl2F3I and PhCCSnBu3 have been studied for the whole catalytic system and for transmetalations as separate steps. The use of (trifluorodichlorophenyl)palladium derivatives slows down the reactions and allows for the observation of the intermediates cis- and trans-[Pd(C6Cl2F3)I(PPh3)2]. The first is formed in the oxidative addition step and isomerizes to

  C 6 Cl 2 F 3 I和PhCCSnBu 3之间的Stille反应动力学已针对整个催化系统和作为单独步骤的重金属化进行了研究。（三氟二氯苯基）钯衍生物的使用减慢了反应的速度，并允许观察到中间体顺式和反式[Pd（C 6 Cl 2 F 3）I（PPh 3）2]。第一个在氧化加成步骤中形成并异构化为第二个。两者均被研究为整个循环的催化剂。动力学研究比较了每种异构体的重金属化步骤的相关性。竞争的金属转移物同时产生顺式和反式-[Pd（C 6 Cl 2 F 3）（PhCC）（PPh 3）2 ]。前者经历了非常快的C-C耦合，而第二者由于极慢的异构化而积累在溶液中。因此，该系统是对Stille反应中竞争途径的影响及其对催化过程性能的影响的案例研究。
• Mechanism of the Stille Reaction. 1. The Transmetalation Step. Coupling of R¹I and R²SnBu₃ Catalyzed by <i>trans</i>-[PdR¹IL₂] (R¹ = C₆Cl₂F₃; R² = Vinyl, 4-Methoxyphenyl; L = AsPh₃)
  作者：Arturo L. Casado、Pablo Espinet

  DOI：10.1021/ja9742388

  日期：1998.9.1

  The so far accepted mechanism of the Stille reaction (palladium-catalyzed cross-coupling of organotin reagents with organic electrophiles) is criticized. Based on kinetic studies on catalytic reactions, and on reactions with isolated intermediates, a corrected mechanism is proposed. The couplings between (RI)-I-1 (1) (R-1 = C-6- Cl2F3 3,5-dichlorotrifluorophenyl) and (RSnBu3)-Sn-2 (R-2 = CH=CH2, 2a; C6H4-4-OCH3, 2b), catalyzed by trans-[(PdRI)-I-1(AsPh3)(2)] (3a), give R-1-R-2 and obey a first-order law, r(obs) = a[3a][2a]/(b + [AsPh3]), with a (2.31 +/- 0.09) x 10(-5) s(-1) and b = (6.9 +/- 0.3) x 10(-4) mol L-1, for [1] [2a] = 0-0.2 mol L-1, [3a] = 0-0.02 mol L-1, and [AsPh3] = 0-0.07 mol L-1, at 322.6 K in THF, The only organopalladium(II) intermediate detected under catalytic conditions is 3a. The apparent activation parameters found for the coupling of 1 with 2a support an associative transmetalation step (Delta H-obs(double dagger) = 50 +/- 2 kJ mol(-1), Delta S-obs(double dagger) = -155 +/- 7 J K-1 mol(-1) in THF; and Delta H-obs(double dagger) = 70.0 +/- 1.7 kJ mol(-1), Delta S-obs(double dagger) = -104 +/- 6 J K-l mol(-1) in chlorobenzene, with [1](0) = [2](0) = 0.2 mol L-1, [3a] = 0.01 mol L-1). The reactions of 2a with isolated trans-[PdR1 X(AsPh3)(2)] (X = halide) show rates Cl > Br > I. From these observations, the following mechanism is proposed: Oxidative addition of (RX)-X-1 to PdLn, gives cis-[(PdRXL2)-X-1], which isomerizes rapidly to trans-[(PdRXL2)-X-1]. This trans complex reacts with the organotin compound following a S-E(2)(cyclic) mechanism, with release of AsPh3 (which explains the retarding effect of the addition of L), to give a bridged intermediate [(PdRL)-L-1(mu-X)(mu-R-2)SnBu3]. In other words, an L-for-R-2 substitution on the palladium leads R-2 and R-1 to mutually cis positions. From there the elimination of XSnBu3 yields a three-coordinate species cis-[(PdRRL)-R-1-L-2], which readily gives the coupling product R-1-R-2.
• Quantitative Evaluation of the Factors Contributing to the “Copper Effect” in the Stille Reaction
  作者：Arturo L. Casado、Pablo Espinet

  DOI：10.1021/om020896b

  日期：2003.3.1

  The relative importance of the factors contributing to the accelerating effect of CuI on [PdL4]-catalyzed couplings of (RI)-I-1 and (RSnBu3)-Sn-2 (copper effect) has been quantitatively evaluated in THF for R-1 = 3,5-C6Cl2F3; R-2 = vinyl, C6H4-4-OMe; L = AsPh3, PPh3, using spectroscopic and kinetic methods. The F-19 NMR kinetic data show that the rate enhancement produced by addition of CuI is strongly related with the "autoretardation" effect intrinsic to [PdL4] catalysts and is almost independent of the organotin reagent (vinyl, aryl). The "autoretardation" is due to the release of 2 equiv of L during the oxidation of [PdL4] to yield trans-[(PdRIL2)-I-1], which is the species undergoing transmetalation. CuI does not promote the dissociation of L from trans- [(PdRIL2)-I-1], but it captures part of the free neutral ligand L and therefore mitigates the autoretardation produced by the presence of free L on the rate-determining associative transmetalation. In the conditions studied (Pd:Cu = 1:2; T = 322.6 K; THF as solvent), for L = AsPh3 the CuI added captures about 25% of the free AsPh3 and the copper effect compensates only ca. 1% of the autoretardation, whereas for L = PPh3 the CuI captures about 99% of the free PPh3 and the compensation is about 30%. This remarkable variation is caused by the combined effect of two independent factors: W The catalyst [Pd-(PPh3)](4) is more autoretarded than [Pd(AsPh3)(4)]; and (ii) CuI is a more effective scavenger for PPh3 than for AsPh3.
• Problematic Ar^F–Alkynyl Coupling with Fluorinated Aryls. From Partial Success with Alkynyl Stannanes to Efficient Solutions via Mechanistic Understanding of the Hidden Complexity
  作者：Guillermo Marcos-Ayuso、Marconi N. Peñas-Defrutos、Ana M. Gallego、Max García-Melchor、Jesús M. Martínez-Ilarduya、Pablo Espinet

  DOI：10.1021/jacs.2c10842

  日期：2023.1.11