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Two Carbonylations of Methyl Iodide and Trimethylamine to Acetic Acid and N,N-Dimethylacetamide by Rhodium(I) Complex: Stability

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Two Carbonylations of Methyl Iodide and Trimethylamine to Acetic Acid and N,N-Dimethylacetamide by Rhodium(I) Complex: Stability Catalysts 2015, 5, 1969-1982; doi:10.3390/catal5041969 OPEN ACCESS catalysts ISSN 2073-4344 www.mdpi.com/journal/catalysts Article Two Carbonylations of Methyl Iodide and Trimethylamine to Acetic acid and N,N-Dimethylacetamide by Rhodium(I) Complex: Stability of Rhodium(I) Complex under Anhydrous Condition Jang-Hwan Hong Department of Nanopolymer Material Engineering, Pai Chai University, 155-40 Baejae-ro (Doma-Dong), Seo-Gu, Daejon 302-735, Korea; E-Mail: [email protected]; Tel.: +82-42-520-5755; Fax: +82-70-4369-9425 Academic Editor: Georgiy B. Shul'pin Received: 13 October 2015 / Accepted: 2 November 2015 / Published: 19 November 2015 − Abstract: Rhodium(I)-complex [Rh(CO)2I2 ] (1) catalyzed two carbonylations of methyl iodide and trimethylamine in NMP (1-methyl-2-pyrolidone) to acetic acid and DMAC (N,N-dimethylacetamide) in the presence of calcium oxide and water. The carbonylation of trimethylamine continued during the carbonylation and consumption of methyl iodide. In total, 183.8 mmol of carbonylated products was produced while consuming 24.1 mmol methyl iodide via acetic acid formation. These results clearly indicated that there were two carbonylation routes of trimethylamine and methyl iodide and the carbonylation rate of − trimethylamine was faster than that of methyl iodide. Rhodium(I)-complex [Rh(CO)2I2] (1) in the presence of trimethylamine was stable enough to be used 25 times with TON (Turnover Number) of 368 for DMAC and TON of 728 for trimethylamine. Inner-sphere reductive elimination in stepwise procedure was suggested for the formation of DMAC instead of acyl iodide intermediate under anhydrous condition. Keywords: rhodium; carbonylation; trimethylamine; dimethylacetamide; methyl iodide; acetic acid; tetramethylammonium iodide; intramolecular; inner-sphere Catalysts 2015, 5 1970 1. Introduction Rhodium complexes have been intensively studied as well-known catalysts for the carbonylation of methanol to acetic acid [1,2]. In the Monsanto process, the rhodium-complex stability at low water concentrations of less than 10 wt. % have been investigated due to the high cost of product separation and the water gas shift reaction within high water concentrations of 14~15 wt. % [3–6]. Under anhydrous − conditions, deactivation of catalyst occurs, giving rhodium species such as trans-[Rh(CO)2I4 ] and − − [Rh(CO)I4 ] from iodide ligand abstraction by the active rhodium catalyst of [Rh(CO)2I2 ] [7,8]; therefore, substantial amount of water is required to achieve high activity and good stability of the rhodium catalyst in the carbonylations of methanol to acetic acid [9]. On the other hand, Forster reported that it took several hours to produce acyl iodide from the carbonylation of anhydrous methyl iodide at 80 °C with − rhodium(I) complex [Rh(CO)2I2 ] [6]. To synthesize highly active and stable rhodium complexes in very low water concentration, many studies have reported about the design of suitable ligands, mainly in phosphorous containing systems [3,10,11]. Very recently, neutral rhodium(I) complexes of [Rh(CO)2I(L)] (L = monodentate amines) have been synthesized and studied for their reactivity and ligand effects − toward methyl iodide; reaction rates similar to those of well-known rhodium(I) anionic [Rh(CO)2I2 ] species is reported [12]. In this point of view, it is very interesting whether acyl iodide is formed from the carbonylation of methyl iodide by the rhodium(I) complex in trialkylamine, and whether further reaction would give the versatile amide bond [13–15]. Herein, we report two novel carbonylations of methyl iodide and trimethylamine to acetic acid and − DMAC (N,N-dimethylacetamide) with rhodium(I) complex [Rh(CO)2I2 ] (1). The stability of the rhodium(I) complex (1) is demonstrated by recycling it, and a plausible mechanism is suggested (Equation (1)). O O [Rh(CO) I -], CO 2 2 + (1) NMe3 + MeI MeCNMe2 MeCOH 2. Results and Discussion 2.1. Two Carbonylations of Methyl Iodide and Trimethylamine to Acetic Acid and DMAC − The carbonylation of methyl iodide by rhodium(I) complex [Rh(CO)2I2 ] (1) in the presence of trimethylamine in NMP (1-methyl-2-pyrolidone) gave acetic acid with small amount of DMAC with formation of trimethylammonium iodide. The formation of acetic acid was expected since the rhodium (1) is a well-known catalyst of the Monsanto process for the carbonylation of methanol to acetic acid in the presence of water [7,8]. However, DMAC was produced as the major product with small amount of acetic acid when trimethylamine and NMP were added into the reactor through column of 4 Å molecular sieve for carbonylation. Again, acetic acid was observed as the major product from the carbonylation when small amount of water was added into reactants. If there was not enough water to − react in reactants, DMAC was formed. These results indicated that Rhodium(I)-complex [Rh(CO)2I2] had catalyzed two carbonylations of methyl iodide and trimethylamine to acetic acid and DMAC in the presence of limited water (Equation (2)) [16]. Catalysts 2015, 5 1971 [Rh(CO) I -]/NMP O O MeI + NMe 2 2 + Me NHI 3 MeCOH + MeCNMe2 3 (2) 1,000 psi of CO, 275 °C 2.2. Carbonylation of Trimethylamine in the Presence of Calcium Oxide and Repetive Using Catalyst From the above results, the amount of water in reactants seemed to be critical for the formation of DMAC; therefore, calcium oxide was added into reactants with other reagents for carbonylation. − Surprisingly, the carbonylation reaction by rhodium(I) complex [Rh(CO)2I2 ] (1) with methyl iodide, trimethylamine, and calcium oxide gave only DMAC with no formation of acetic acid and trimethylammonium iodide, the yield of DMAC was observed as 97% based on trimethylamine (the mole ratio of trimethylamine to catalyst (1); 27.7 mmol to 3.78 mmol, Equation (3)). - O [Rh(CO)2I2 ]/NMP NMe3 + MeI + CaO MeCNMe2 (3) 1,000 psi of CO, 275 °C Whether the catalyst can be used repeatedly is an interesting question; therefore, repetive using catalyst was performed. On using catalyst repetively, DMAC was obtained as the major product with no acetic acid up to the third time or fourth time using, but further using of the catalyst resulted in delay for the pressure decreasing of carbon monoxide in reactor due to its lost of catalytic activity. In this case, if additional methyl iodide was added into the reaction medium, then again DMAC was produced as the major from the carbonylation. However, upon repetive using catalyst, byproducts of MAA (N-methylacetamide) and DMF (Dimethylformamide) were produced and a large amount of solid was formed in the reactor. After volatiles were removed by short-path distillation from the reaction mixture, the resulted residual solid was confirmed as mixture of CaI2(NMP)6, CaI2(DMAC)6, and Ca(OAc)2. For their identification, separately solvated calcium iodides were prepared from the reaction of calcium iodide hydrate with NMP and DMAC. The mole ratio of CaI2 to Ca(OAc)2 was confirmed as 1:1 by 1H-NMR spectroscopy. When the amount of calcium oxide was reduced to one third, the activity of catalyst was lost quickly with rapid increasing of MAA and DMF byproducts. Trimethylamine of 12.5 g (211.8 mmol) and methyl iodide 3.4 g (24.1 mmol) were used totally for the carbonylation during five times recycling of catalyst. The yields of DMAC, MAA, and DMF were 11.87 g (136.2 mmol, 64.3%), 1.18 g (29.8 mmol, 14.1%), and 1.30 g (17.8 mmol, 8.4%), respectively. The conversion rate of trimethylamine was 86.8% and the selectivity of DMAC was 74.1% (Equation (4)). O - O O [Rh(CO)2I2 ]/NMP NMe3 + MeI + CaO MeCNMe2 ++MeCNHMe HCNMe2 1,000 psi of CO, 275°C (4) (64.3%) (14.1%) (8.4%) -CaI2, - Ca(OAc)2 − These results showed that in the presence of calcium hydroxide rhodium(I) complex [Rh(CO)2I2 ] (1) had catalyzed two carbonylations of trimethylamine and methyl iodide to DMAC and acetate moiety of calcium acetate with formation of calcium iodide via acylation procedure until no methyl iodide remained in reactants during the carbonylation reaction. From the above results, it was concluded that during two carbonylations of trimethylamine and methyl iodide, calcium hydroxide and/or calcium oxide had retarded completely the consumption of methyl iodide by removing water and/or lowering its reactivity as hydroxide while they were transformed into Catalysts 2015, 5 1972 calcium iodide and calcium acetate via acylation procedure of methyl iodide and in the end the carbonylation of trimethylamine was halted due to complete consumption of methyl iodide in reaction mixture. Surprisingly, the carbonylation of trimethylamine had been continued with sustaining stability of − rhodium(I) complex [Rh(CO)2I2 ] (1) during the carbonylation and consuming of methyl iodide. In total 183.8 mmol of DMAC, MAA, and DMF was produced during the consuming of 24.1 mmol methyl iodide via acetic acid formation. These results clearly indicated that there were two carbonylation routes of trimethylamine and methyl iodide and the carbonylation rate of trimethylamine was faster than that of methyl iodide in the presence of calcium oxide and/or calcium hydroxide. 2.3. Carbonylation of Trimethylamine in the Presence of Calcium Oxide under Anhydrous Condition and Repetive Using Catalyst − Whether rhodium(I) complex [Rh(CO)2I2 ] (1) can be used repeatedly for the carbonylation of trimethylamine with no formation of calcium salt under anhydrous condition is an interesting question; therefore, to prepare anhydrous trimethylamine, it was passed through a KOH column, 4 Հ molecular sieve column, and dry ice-cold trap sequentially, since commercial trimethylamine is produced with water from condensation of methanol and ammonia on alumino-silicate catalyst. − The carbonylation of anhydrous trimethylamine in NMP by rhodium(I) complex [Rh(CO)2I2 ] (1) with methyl iodide and calcium oxide gave DMAC as the major product with no acetic acid.
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