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Unsymmetrical bis(imino)pyridines iron and cobalt complexes containing halogen, preparation method and use

A technology of pyridine bisimine and cobalt complexes, which is applied in the field of fine chemicals, can solve the problems of high oligomer C4 content and reduced value-added competitiveness, and achieve high oligomerization activity, increased selectivity, and mild reaction conditions Effect

Inactive Publication Date: 2009-03-25
SOUTH CENTRAL UNIVERSITY FOR NATIONALITIES
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the main problem of this type of catalyst is that the C4 content in the oligomer is too high, reaching 30%, which greatly reduces the added value of the product and the competitiveness in the international market

Method used

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  • Unsymmetrical bis(imino)pyridines iron and cobalt complexes containing halogen, preparation method and use
  • Unsymmetrical bis(imino)pyridines iron and cobalt complexes containing halogen, preparation method and use
  • Unsymmetrical bis(imino)pyridines iron and cobalt complexes containing halogen, preparation method and use

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0039] 2-Acetyl-6-{1-[(2-methylphenyl)imine]ethyl}pyridine (D1)

[0040]

[0041] Take 1.64g of DAP and 40ml of methanol in a 100ml flask, add 4-5 drops of glacial acetic acid, take another 1.0g of o-methylaniline in a dropping funnel, add 20ml of methanol, slowly drop the methanol solution of o-methylaniline In the flask containing DAP, react under ultrasonic conditions while adding dropwise, the temperature is 30°C, and the ultrasonic power is 500W. After the reaction was terminated, the solvent was distilled off, and the concentrate was crystallized in methanol to obtain 1.70 g of a yellow solid with a yield of 71.5%. m.p50-52°C. IR (KBr, cm -1 ):3062, 2966, 2926, 1695 (C=O), 1642 (C=N), 1577, 1480, 1359, 1311, 1246, 1224, 1109, 1078, 824,786,747. 1 HNMR (400MHz, CDCl 3 ): δ8.52(d, 1H, Py-Hm), 8.12(d, 1H, Py-Hm), 7.93(t, 1H, Py-Hp), 7.23(m, 2H, ph), 7.05(t, 1H, Ph), 6.68 (d, 1H, Ph), 2.79 (s, 3H, O=C-CH 3 ), 2.35(s, 3H, N=C-CH 3 ), 2.12 (s, 3H, PhCH 3 )

Embodiment 2

[0043] 2-Acetyl-6-{1-[(2-ethylphenyl)imine]ethyl}pyridine (D2)

[0044] The preparation method was the same as that of D1 to obtain a yellow solid with a yield of 56.9%. m.p.43-46℃.IR(KBr, cm -1 ):2970, 2926, 1700 (C=O), 1643 (C=N), 1481, 1444, 1364, 1310, 1226, 1115, 1084, 1047, 819, 787,743. 1 HNMR (400MHz, CDCl 3 ): δ8.52(d, 1H, Py-Hm), 8.12(d, 1H, Py-Hm), 7.95(t, 1H, Py-Hp), 7.23(m, 2H, ph), 7.09(t, 1H, Ph), 6.66 (d, 1H, Ph), 2.79 (S, 3H, O=C-CH 3 ), 2.49 (q, 2H, Ph-CH 2 -), 2.37(s, 3H, N=C-CH 3 ), 1.16(t, 3H, Ph-C-CH 3 )

Embodiment 3

[0046] 2-{1-[(2-methylphenyl)imino]ethyl}-6-{1-[(2-chlorophenyl)imino]ethyl}}pyridine (L1)

[0047]

[0048] In a 50ml Schlenk, add 0.31g (1.25mmol) 2-acetyl-6-{1-[(2-methylphenyl) imino] ethyl} pyridine (D1), 0.185g (1.45mmol ) 2-chloroaniline, 10ml toluene, 1g molecular sieve and 0.2gSi-Al catalyst, N 2 Under protection, stir and react at 35-40°C for 4 days, filter to remove the molecular sieve and Si-Al catalyst, wash the solid with toluene 3-4 times, combine the filtrate and evaporate the solvent toluene with a rotary evaporator, and the remaining concentrate (primary product) Recrystallized from methanol to obtain 0.107 g of a yellow solid with a yield of 23.7%. m.p 80-83℃.IR(KBr, cm -1 ):3062, 3014, 2969, 2921, 1644, 1575, 1465, 1363, 1316, 1220, 1115, 1066, 817, 779, 736. 1 HNMR (400MHz, CDCl 3 ): δ8.42(d, 2H, Py-Hm), 7.90(t, 1H, Py-Hp), 7.20-7.30(m, 4H, ph), 7.05(m, 2H, Ph), 6.85(m, 1H, Ph), 6.68(d, 1H, Ph), 2.38(s, 3H, N=C-CH 3 ), 2.34(s, 3H, N=C-CH 3 ), 2.1...

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Abstract

The invention relates to an anisomerous pyridyl bis-imine iron-cobalt complex containing halogen substituent, and a preparation method and the application thereof; the complex can be used for catalyzing the oligomerization of ethylene and has the shown structural formula ; the anisomerous pyridyl bis-imine iron-cobalt complex provided by the invention not only has simple synthetic method, mild reaction condition, low-cost catalyst and high catalytic activity for the oligomerization of ethylene, but also can regulate the catalytic performance of the complex by the synergy of the steric effect of alkyl and the electronic effect of halogen, particularly the distribution of the oligomerization products, thus realizing the selective controlled oligomerization of ethylene. Under ordinary pressure, the catalytic activity for the oligomerization of ethylene can be higher than 10<5>gmol<-1>h<-1>atm<-1>, under 10 atmospheric pressure, the catalytic activity for the oligomerization of ethylene can achieve more than 10<7>gmol<-1>h<-1>; the oligomerization products do not contain high polymers; the content of linear Alpha-olefin is higher than 98 percent; and compared with the symmetrical pyridyl bis-imine iron complex substituted by alkyl or halogen, the C6-C16 parts with the largest application value in the oligomerization products have significantly-improved selectivity and the content of more than 85 percent, and the content is about 15 to 30 percent higher than that of the C6-C16 parts in the symmetrical pyridyl bis-imine iron complex substituted by alkyl or halogen.

Description

technical field [0001] The invention discloses a halogen-containing unsymmetrical pyridine bis-imine iron and cobalt complex, a preparation method and an application. It belongs to the technical field of metal organic chemistry and also belongs to the technical field of fine chemicals. Background technique [0002] α-Olefin refers to the general formula RCH=CH 2 A terminal olefin, where R is an alkyl group. Among α-olefins, linear α-olefins are the most widely used. Linear α-olefins are an important organic chemical raw material, and are widely used in ethylene comonomers, surfactant synthetic monomers, plasticizers, and synthetic lubricating oils. And oil additives and many other fields. For example, C4~C8 low-carbon linear α-olefins can be used as comonomers of linear low-density polyethylene (LLDPE); C10 and some C8 and C12 α-olefins can be used to prepare polyα-olefins (PAO) for production High-grade lubricating oil used in aviation, combustion resistance and harsh e...

Claims

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Application Information

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IPC IPC(8): C07D213/53C07F15/02C07F15/06C07C2/22
Inventor 谢光勇张东方艾海涛雷禄
Owner SOUTH CENTRAL UNIVERSITY FOR NATIONALITIES