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Hydroaminomethylation of olefins

A technology for aminomethylation and olefins, applied in the field of hydrogen aminomethylation of olefins, can solve the problems of increased processing costs, prolonged reaction time and the use of process equipment

Inactive Publication Date: 2007-02-21
UNION CARBIDE CHEM & PLASTICS TECH CORP
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Also, long reaction times require extended use of process equipment, which leads to increased processing costs

Method used

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  • Hydroaminomethylation of olefins
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  • Hydroaminomethylation of olefins

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] Example 1 - Preparation of dimethylaminomethylalkane mixture

[0026]

[0027] A Neodene(R) olefin blend (10 / 1112 / 13 / 12, 319 g, obtained from Shell Chemical) olefin substrate was charged to a 1-gal (4-L) reactor in THF (680 g). Dimethylamine (222 g) was added to this solution, and from [Rh(CO) 2 A solution of a complex prepared from (acac)] (3.7 g) and tris(2,4-di-tert-butylphenyl)phosphite (46.2 g, obtained from Aldrich Chemical) in THF (374 g). The final rhodium concentration was about 900 ppm by weight. This mixture was heated to 80°C and pressurized to 600 psi (4140 kPa) with syngas and stirred under these conditions for 7 hours. The reactor was cooled to 21°C overnight and the gas phase was vented. After stirring under nitrogen flow for about 1 hour to remove most of the excess dimethylamine, the reactor contents were decanted, THF stripped and distilled using a Kugelrohr apparatus to give a colorless mobile liquid (427 g, 99% yield).

Embodiment 2

[0028] The hydroaminomethylation of embodiment 2-oleic acid diethanolamide and diethanolamine

[0029]

[0030] Oleamide (13.49 g), diethanolamine (4.51 g) and THF solvent (20 mL) were added via syringe to the nitrogen purged reactor. The reactor was stirred under approximately 200 psi (1380 kPa) syngas to saturate the solution. After venting, the [Rh(CO) 2 (acac)] (5351 ppm by weight of Rh) and tris(2,4-di-tert-butylphenyl)phosphite ligand (5.00 moles of ligand / mole of Rh) in THF Aliquots of pre-prepared catalyst solutions A sample (10.4 g) was charged to the reactor. The reactor was sealed and pressurized with synthesis gas and heated to 80°C. The pressure was increased to 600 psi (4140 kPa) with additional syngas, and then fed at this pressure throughout the reaction as needed. After 4.5 hours, the reactor was cooled, vented and the reactor contents drained. The amber solution was extracted with cyclohexane, then toluene, and the supernatant was discarded. Acetonit...

Embodiment 3

[0031] Embodiment 3-hydroaminomethylation of terminally unsaturated isopolypropylene and dibenzylamine

[0032]

[0033] Vinylidene terminated polypropylene (5.43 g, obtained from Baker-Hughes Corporation) having a weight average molecular weight Mw of about 1800 g / mol was dissolved in toluene (70 mL). A portion of this solution (65 mL) was transferred to a 100 mL Parr reactor, whereupon dibenzylamine (2 mL, 9.8 mmols) was added and a solution containing the complex (20 mL of a stock solution prepared by dissolving [Rh( CO) 2 (acac)] (2.56 g), 2,4-di-tert-butylphenyl phosphite (32.09 g) to give a total solution mass of 200.73 g). The reactor was sealed and pressurized to 600 psi (4140 kPa) syngas and heated to 80°C for 130 minutes. After the reaction, the pressure was released and the reactor was opened while the temperature was still at 60°C, and the contents were drained into a glass beaker. The polymer product was precipitated by adding methanol (approximately 2 x vol...

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Abstract

The present invention relates to a method comprising the step of contacting under hydroaminomethylation conditions, an olefin, an amine, a rhodium-phosphorous ligand, and synthesis gas (syngas). In particular, it has been discovered that, under some circumstances, a neutral rhodium-monodentate phosphite ligand is prescribed. The invention provides a simple way of making, in high yields and regiospecificity, a variety of products, including pharmacologically active products such as ibutilide, terfenadine, and fexofenadine, and derivatives thereof.

Description

Background of the invention [0001] The present invention relates to the hydroaminomethylation of olefins. Aliphatic amines are used in a variety of applications including agrochemical and pharmaceutical products and intermediates, and polymer precursors such as polyurethanes. Homogeneous hydroaminomethylation reactions were reported by Reppe at BASF using homogeneous cobalt carbonyl catalysts (Liebigs Ann. Chem. 1953, 582, 133-161). This reaction consists of a tandem, one-step olefin hydroformylation / reductive amination sequence in which an intermediate aldehyde is reacted with a primary or secondary amine to form an imine or enamine intermediate, which undergoes hydrogenation to form a secondary or tertiary amine amine. US 3,513,200 reports the use of a homogeneous rhodium triphenylphosphine catalyst for the synthesis of tertiary amines by hydroaminomethylation. The use of hydroaminomethylation of ethylene to form n-propylamine is reported by Jones in J. Organomet. Chem. 1...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C209/26C07C209/60C07C211/03
Inventor J·R·布里格斯G·T·怀特克J·克洛西
Owner UNION CARBIDE CHEM & PLASTICS TECH CORP
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