Method for purifying crude pnpnh compounds

A compound, R1R2P-N technology, applied in the field of purification of crude PNPNH compounds, can solve problems such as failure

Inactive Publication Date: 2017-06-06
SAUDI BASIC IND CORP SA +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0018] Attempts to purify the crude PNPNH compound by vacuum distillation using a thin-film evaporator appeared to be rather unsuccessful due to the fact that there was hardly any separation between the ligand and the impurity

Method used

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  • Method for purifying crude pnpnh compounds
  • Method for purifying crude pnpnh compounds
  • Method for purifying crude pnpnh compounds

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0053] Example 1: Ligand preparation, laboratory scale

[0054] Preparation of bis(isopropyl-amino-)phenylphosphine (NPN)

[0055] To a stirred solution of isopropylamine (30ml, 352mmol) in diethyl ether (250ml) was added dichlorophenylphosphine (9.63ml, 71mmol, dissolved in 50ml diethyl ether) at 0°C over a period of 30min. After stirring for a total of 72 hours, the solution was filtered. The residue was washed with ether and the solvent was removed under vacuum. The remaining oil was distilled at 0.2 Torr / 76-78°C to produce a colorless liquid with a yield of 33% (5.3 g). 31 P{H}NMR: 49.0ppm.

[0056] After synthesis in crude Ph 2 Some impurities found in the P-N(i-Pr)-P(Ph)-N(i-Pr)-H ligand are shown below.

[0057]

[0058] (Ph) 2 Preparation of PN(i-Pr)P(Ph)NH(i-Pr)(PNPN-H)

[0059] A solution of NPN species (2.4g, 10.7mmol) in tetrahydrofuran (10ml) was added dropwise to triethylamine (6ml) and chlorodiphenylphosphine (2.36g, 10.7mmol) in THF (40ml) at -40°C ) In the stirring ...

Embodiment 2

[0061] [Ph 2 PN(i-Pr)P(Ph)N(i-Pr)-Li] 2 Preparation

[0062] Will Ph 2 PN(i-Pr)P(Ph)N(i-Pr)-H (8.70g, 21.35mmol) was dissolved in 15ml of toluene. After cooling to -78°C, n-butyllithium (12.8ml, 2.5M n-BuLi in n-heptane, 32.0mmol) was added to the solution and the color immediately changed to orange / yellow. The solution was stirred at room temperature for another two hours and a colorless solid precipitated. The precipitate was filtered and washed 3 times with 5 ml of toluene. The remaining solvent was removed under vacuum, resulting in a colorless powder. Yield: 6.73 g (76%). Molecular weight: 414.39g / mol[C 24 H 29 LiN 2 P 2 ]. Elemental analysis: calculated value: C 69.56%, H 7.05&, N 6.76%; found: C 69.25%, H 7.06%, N 6.87%. Melting point: 187-189°C. 1 H NMR(THF-d 8 )δ=7.50-7.57 (m, 6H, aryl-H), 7.20-7.34 (m, 6H, aryl-H), 7.02 (m, 2H, aromatic), 6.93 (m, 1H, aryl- H), 3,70(m, 1H, CHCH 3 ), 3.58(m, 1H, CHCH 3 ), 1.39 (d, J = 6.47 Hz, 3H, CHCH 3 ), 1.25(d, J=6.23Hz, 3H, CH...

Embodiment 3

[0063] Example 3: Ligand purification via metallation of PNPN-H ligand and subsequent reprotonation

[0064] The crude ligand (8.70 g, 21.35 mmol) was dissolved in 15 ml of toluene. Under cooling, n-butyllithium (12.8ml, 2.5M n-BuLi in n-heptane, 32.0mmol) was added to the solution and the color immediately changed to orange / yellow. The solution was stirred at room temperature for another two hours, and a colorless solid precipitated. The precipitate was filtered and washed with 5 ml of toluene. The residue and ammonium chloride (1.70 g, 32 mmol) were suspended in toluene. The suspension was stirred for 10 h. Filtration produces a toluene solution of purified ligand, which can be used in catalytic reactions without further treatment. Alternatively, the solvent was removed in vacuum, yielding 5.41 g (62%). Molecular weight: 408.19g / mol[C 24 H 30 N 2 P 2 ]. Elemental analysis: calculated value: C 70.57%, H 7.40%, N 6.86%; found: C 70.50%, H 7.35%, N 6.87%.

[0065] In addition...

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Abstract

The present invention relates to a process for the purification of crude PNPNH compounds by metalation and reprotonation.

Description

Technical field [0001] The present invention relates to a method for purifying crude PNPNH compounds. Background technique [0002] The compound with the general structure PNPNH is a well-known ligand system, which can be successfully used as a catalyst for ethylene oligomerization. Here, they act as ligands for the reaction with the preferred chromium catalyst. Together with suitable co-catalysts, this system is effective in the di-, tri- and / or tetramerization of ethylene. [0003] For example, EP 2 239 056 B1 describes methods for the di-, tri- and / or tetramerization of catalyst compositions and ethylene. The catalyst composition contains a chromium compound and has the general structure R 1 R 2 P-N(R 3 )-P(R 4 )-N(R 5 )-H ligand and co-catalyst as activator. Ligand Substituent R 1 , R 2 , R 3 , R 4 And R 5 Independently selected from a variety of functional groups, including (among others) C 1 -C 10 -Alkyl, aryl and substituted aryl. Chromium source is selected from CrCl 3 ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J31/14B01J31/18C07F9/00
CPCB01J31/143B01J31/189B01J2231/20B01J2531/62C07F9/4883B01J31/14B01J31/18C07F9/00C07F9/65848C07F9/6587
Inventor 阿尼纳·韦尔安德烈亚斯·迈斯温克尔海因茨·博尔特贝恩德·穆勒沃尔夫冈·穆勒诺门·波尔埃克乌韦·罗森塔尔马尔科·哈夫穆罕默德·H·艾尔-哈兹米阿卜杜拉·阿尔加塔尼沙希德·阿扎姆
Owner SAUDI BASIC IND CORP SA
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