2-叔丁基苯酚亚磷酸盐 | 31502-36-0

• 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: 2-叔丁基苯酚亚磷酸盐
• 英文名称: tri(o-t-butylphenyl)phosphite
• 英文别名: Tris(2-tert-butylphenyl) phosphite
• CAS: 31502-36-0
• 化学式: C₃₀H₃₉O₃P
• 分子量: 478.612
• InChiKey: SZPHBONKPMLMCA-UHFFFAOYSA-N

物化性质

• 沸点：
  507.6±49.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  10.5
• 重原子数：
  34
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  [Rh2(μ-S(CH2)3NMe2)2(CO)4] 、 2-叔丁基苯酚亚磷酸盐 以 not given 为溶剂， 生成
  参考文献：
  名称：

  Regioselective hydroformylation of cyclic vinyl and allyl ethers with rhodium catalysts. Crucial influence of the size of the phosphorus cocatalyst

  摘要：

  In the course of studies aimed at developing new catalytic systems, we have explored the possibilities offered by the modification of thiolato bridges in dinuclear rhodium complexes, together with the influence of the cocatalyst, on the selective hydroformylation of cyclic vinyl and allyl ethers. The dinuclear complex [Rh2(mu-S(CH2)3NMe2)2(cod)2] (Cod = 1,5-cyclooctadiene) has been prepared, and its reactivity with CO, phosphines, and phosphites has been investigated. The complex crystallizes m the monoclinic space group C2/c with Z = 8, a = 22.543 (4) angstrom, b = 12.040 (2) angstrom, c = 21.547 (3) angstrom, and beta = 98.77 (1)-degrees. For the determination of the structure 4091 unique reflections were used, and the final refinement gave R = 4.1% and R(w) = 4A%. The molecular structure reveals that the two rhodium atoms are bridged by the two thiolato ligands, and the cyclooctadiene completes the coordination of the metal atoms. The amine groups are not bonded to the rhodium. The dinuclear complex has been used in the hydroformylation of 2,3-dihydrofuran, 2,5-dihydrofuran, 3,4-dihydro-2H-pyran, and 3,6-dihydro-2H-pyran. Hydroformylation reactions of dihydrofurans required conditions milder than those for dihydropyrans. The major product in the hydroformylation of 3,4-dihydro-2H-pyran or 3,6-dihydro-2H-pyran was tetrahydropyran-2-carbaldehyde. A systematic study of the influence of the reaction parameters on the selectivity of the hydroformylation of 2,3-dihydrofuran and 2,5-dihydrofuran was undertaken. The study allowed the rationalization of the observed selectivity and the optimization of the yields and regioselectivities. Thus, by modification of the reaction parameters, tetrahydrofuran-3-carbaldehyde was obtained in quantitative yields from 2,5-dihydrofuran and tetrahydrofuran-2-carbaldehyde can be prepared from either 2,3-dihydrofuran or 2,5-dihydrofuran in approximately 75% yield.

  DOI：

  10.1021/om00059a015
• 作为产物：
  描述：

  2-叔丁基苯酚 在 三乙胺 、 三氯化磷 作用下， 以 四氢呋喃 为溶剂， 反应 24.0h， 以98%的产率得到2-叔丁基苯酚亚磷酸盐
  参考文献：
  名称：

  AuI催化的Nazarov环化的连续四级中心

  摘要：

  阳离子Au I催化的取代烯炔的环化反应通过级联反应生成环戊烯酮。据报道，带有相邻的全碳原子季中心的环戊烯酮具有高度非对映选择性。

  DOI：

  10.1002/ejoc.201800604
• 作为试剂：
  描述：

  芳樟醇 、 一氧化碳 在 methoxy(cyclooctadiene)rhodium(I) dimer 、 2-叔丁基苯酚亚磷酸盐 、 氢气 作用下， 以 甲苯 为溶剂， 50.0 ℃ 、8.11 MPa 条件下， 反应 6.0h， 以86%的产率得到
  参考文献：
  名称：

  Synthesis of fragrance compounds from acyclic monoterpenes: Rhodium catalyzed hydroformylation and tandem hydroformylation/acetalization of linalool and β-citronellene

  摘要：

  Rhodium-catalyzed hydroformylation of acyclic monoterpenic compounds, i.e., linalool and beta-citronellene, was studied in toluene and ethanol solutions in the presence of PPh3 or P(O-o-(BuPh)-Bu-t)(3) ligands. Although both substrates have a monosubstituted terminal double bond, they show different behavior under the hydroformylation conditions. In toluene, linalool gave almost quantitatively a cyclic hemiacetal: whereas the hydroformylation of beta-citronellene resulted in two isomeric aldehydes also in a nearly quantitative combined yield. The reactions occurred approximately two times faster in ethanol than in toluene giving the corresponding acetals even in the absence of additional acid co-catalysts. In the absence of phosphorous ligands, linalool (differently from beta-citronellene) was very resistant to hydroformylation probably due to the binding with rhodium through both the double bond and the hydroxyl group to form stable chelates. The P(O-o-(BuPh)-Bu-t)(3) ligand exerted a remarkable effect on the reactivity of both substrates accelerating the reactions by 5-20 times as compared to the system with PPh3. Several fragrance compounds were obtained in high yields through a simple one-pot procedure starting from the substrates easily available from natural bio-renewable resources. (C) 2013 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.apcata.2013.06.037

文献信息

• Synthese von [(η5-C5H5)2Ti(Cl)(CCSiMe3)]Ni(CO) und dessen Reaktionsverhalten gegenüber Phosphiten: die Festkörperstruktur von (CO)2Ni[P(OC6H4CH3-2)3]2
  作者：E Meichel、Th Stein、J Kralik、G Rheinwald、H Lang

  DOI：10.1016/s0022-328x(02)01117-8

  日期：2002.4

  Treatment of [Ti](Cl)(CCSiMe3) (1) [Ti]=(η5-C5H5)2Ti} with Ni(CO)4 (2) in a 1:1 molar ratio produces the heterobimetallic early–late transition metal complex [Ti](Cl)(CCSiMe3)}Ni(CO) (3), which features a low-valent Ni(CO) entity stabilized by a datively bonded Cl and a η2-coordinated Me3SiCC ligand. As side-products [Ti]Cl2 (8) and [Ti](CCSiMe3)2}Ni(CO) (5) are formed. The latter complex can

  钛[Ti]（CL）（CCSiMe的处理3）（1）[钛] =（η 5 -C 5 H ^ 5）2的Ti}用Ni（CO）4（2在1）：1的摩尔比产生的异早迟过渡金属络合物钛[Ti]（CL）（CCSiMe 3）}的Ni（CO）（3），其设有由datively接合Cl和稳定的低原子价的Ni（CO）实体η 2配位的我3 SiCC配体。作为副产物钛[Ti]氯2（8）和[钛]（CCSiMe 3）2 }的Ni（CO）（5） 形成。后者复杂也可以通过钛[Ti]（CCSiMe反应合成3）2（4）与等摩尔量的2。如果3与化学计算量的P（OR）3（6a，R = C 6 H 5 ; 6b，R = C 6 H 4 CH 3 -2; 6c，R = C 6 H 4 t Bu-2）反应，则双（炔基）钛茂4，（CO）2 Ni [P（OR）3 ] 2（7a，R = C6 H 5；7b，R ＝ C 6 H 4 CH
• Structures, Reactivity, and Catalytic Activity of Dithiolato-Bridged Heterobimetallic MRh (M = Pt, Pd) Complexes
  作者：Jorge Forniés-Cámer、Anna M. Masdeu-Bultó、Carmen Claver、Cristina Tejel、Miguel Angel Ciriano、Christine J. Cardin

  DOI：10.1021/om020042r

  日期：2002.6.1

  Heterobimetallic complexes [(P−P)Pt(μ-S−S)Rh(cod)]ClO4 (P−P = (PPh3)2, Ph2P(CH2)3PPh2 (dppp), and Ph2P(CH2)4PPh2 (dppb); S−S = -S(CH2)2S- (EDT), -S(CH2)3S- (PDT), -S(CH2)4S- (BDT), cod = 1,5-cyclooctadiene) reacted with CO to form the carbonyl complexes [(P−P)Pt(μ-S−S)Rh(CO)2]ClO4 and then with PR3 ligands to give [(P−P)Pt(μ-S−S)Rh(CO)(PR3)]ClO4. The binuclear framework of these cod complexes was maintained

  异双金属配合物[（P-P）Pt（μ-S-S）Rh（cod）] ClO 4（PP =（PPh 3）2，Ph 2 P（CH 2）3 PPh 2（dppp）和Ph 2 P（CH 2）4 PPH 2（DPPB）; S-S = - S（CH 2）2小号-（EDT），- S（CH 2）3小号-（PDT），- S（CH 2）4小号-（BDT），cod = 1,5-环辛二烯）与CO反应形成羰基配合物[（P-P）Pt（μ-S-S）Rh（CO）2 ] ClO 4，然后与PR 3配体形成[（P-P）Pt（μ-S-S）Rh（CO）（PR 3）] ClO 4。这些鳕鱼复合物的双核构架在报道的反应中得以维持。在苯乙烯的加氢甲酰化反应中，将鳕鱼配合物作为催化剂前体进行了测试。HPNMR原位研究表明，单核物质是在催化条件下形成的。
• Metal complexes with atropisomeric sulfur ligands in asymmetric hydroformylation X-ray structure of [Rh2(μ-biphes)(cod)2] (H2biphes = 4,4′-biphenanthrene-3,3′-dithiol)
  作者：Nuria Ruiz、Abdellatif Aaliti、Jorge Forniés-Cámer、Aurora Ruiz、Carmen Claver、Christine J. Cardin、Davide Fabbri、Serafino Gladiali

  DOI：10.1016/s0022-328x(97)00151-4

  日期：1997.1

  The addition of the atropisomeric racemic sulfur compound 4,4′-biphenanthrene-3,3′-dithiol (H2 biphes) to a dichloromethane solution of [M(μ-OMe)(cod)}2] (M = Rh, Ir, cod = cycloocta-1,5-diene) afforded the dithiolate-bridged complexes [Rh2(μ-biphes)(cod)2}n] (n = 2 5 or n = 1 6) and [Ir2(μ-biphes)(cod)2}n]·nCH2Cl27. When 1,1′-binaphthalene-2,2′-dithiol (H2 binas) reacted with [Ir(μ-OMe)(cod)}2]

  将阻转异构的外消旋硫化合物4,4'-联菲-3,3'-二硫醇（H 2 biphes）添加到[M（μ- OMe）（cod）} 2 ]的二氯甲烷溶液中（M = Rh， Ir，cod =环辛-1,5-二烯）得到二硫醇盐桥联的配合物[Rh 2（μ- biphes）（cod）2 } n ]（n = 2 5或n = 1 6）和[Ir 2（μ- biphes）（cod）2 } n ]· n CH 2 Cl 2 7。当1,1'-联萘-2,2'-二硫醇（H2个BINAS）与[的Ir（μ -OMe）（COD）} 2 ]，配合物[Ir 2（μ -binas（COD））2 ] 8获得。配合物5和6与一氧化碳反应，得到二核四羰基配合物[Rh 2（μ- biphes）（CO）4 ] 9。9与PR 3的反应提供了混合配体络合物[Rh 2（μ- biphes）（CO）2（PR 3）2 } 2 ]· xCH 2 Cl
• METHOD FOR PRODUCING ALDEHYDE COMPOUND, AND ACETAL COMPOUND
  申请人：KURARAY CO., LTD.

  公开号：US20170369411A1

  公开（公告）日：2017-12-28

  Provided are a method for producing 3-methylglutaraldehyde in a good yield under a mild condition and a novel acetal compound which is useful for carrying out the foregoing method. The method is a production method of 3-methylglutaraldehyde including a step of hydrolyzing a compound represented by the following general formula (1): wherein R 1 and R 2 each independently represent an alkyl group having 1 to 6 carbon atoms, or are mutually coupled to represent an alkylene group having 2 to 6 carbon atoms.

  提供了一种在温和条件下高产率生产3-甲基戊二醛的方法，以及一种新型缩醛化合物，该化合物对于执行上述方法是有用的。该方法是一种生产3-甲基戊二醛的方法，包括以下一步骤：水解由下述通式（1）表示的化合物：其中R1和R2各自独立地表示具有1至6个碳原子的烷基基团，或者相互偶合以表示具有2至6个碳原子的亚烷基基团。
• Unexpected substitution reactions of bis(phosphine)platinum ethene complexes
  作者：Penny A. Chaloner、Gillian T. L. Broadwood-Strong

  DOI：10.1039/dt9960001039

  日期：——

  Reaction of [Pt(C2H4)(PR3)2](R = Ph or C6H4Me-4) with moderately bulky phosphines at low temperatures did not give the expected tris- or tetrakis-phosphine complexes. Instead, mixed-phosphine complexes of the type [Pt(C2H4)(PR3)(PR′3)](R′= C6H11, C6H4OMe-4, C6H4OMe-2, C6H4Me-4 or CH2Ph) were formed. With less bulky phosphines, chelating diphosphines or phosphites, mixed tetrakis complexes, many of them prone to disproportionation, were formed. The complexes were characterised by 31P and 195Pt NMR spectroscopy in solution.

  在低温下，[Pt(C2H4)(PR3)2](R = Ph或C6H4Me-4)与中等体积的膦反应并未生成预期的三膦或四膦配合物。相反，形成了类型为[Pt(C2H4)(PR3)(PR′3)]的混合膦配合物（R′= C6H11, C6H4OMe-4, C6H4OMe-2, C6H4Me-4或CH2Ph）。与体积较小的膦反应时，形成了配位的二膦或磷酸酯的混合四膦配合物，其中许多配合物易于发生不均匀化。该配合物通过31P和195Pt NMR光谱在溶液中进行了表征。