Supplementary report

Novel and efficient method for Esterification catalyzed by 1-Glycyl-3-Methyl Imidazolium Chloride-Iron (III) Complex

Parasuraman Karthikeyan. Pundlik Rambhau Bhagat. R.V. Jagadeesh

a Organic Chemistry Division, School of Advanced Sciences, VIT University, Vellore,-632 014, India.

Experimental

  1. General

All solvents and chemicals were commercially available and used without further purification unless otherwise stated. [Gmim]Cl-Fe(III) complex was characterized by powder X-ray diffraction (P-XRD) diffractometer, a Bruker D8 (advance model); Germany and lynx eye detector operating with nickel filtered Cu-K radiation. The 1H-NMR spectra was recorded on a Bruker 500 MHz using CDCl3/ DMSO-d6 as the solvent and mass spectra were recorded on JEOL GC MATE II HRMS (EI) spectrometer. FT-IR was recorded on AVATRA 330 spectrometer with DTGS detector. Column chromatography was performed on silica gel (200-300 mesh). Analytical thin-layer chromatography (TLC) was carried out on precoated silica gel GF-254 plates.AFM and SEM was analyzed by (Nano Surf Easy Scan-2 Switzerland), (Carl Zeiss EVO MA 15(model))respectively.

2. Preparation of [Gmim]Cl-Fe (III)complex

2. 2. 1. Protection of amino group using Di. Tert Butyl pyrocarbonate (Boc)

A solution of the glycine (10 mmol) in a mixture of dioxane (10 mL), water (5 mL) and 0.5 N NaOH (5 mL) was stirred and cooled in an ice-water bath. Boc (8 mmol) was added and agitation continued at ambient temperature for 30 to 45 minutes. The resulting solution was concentrated in vacuo, cooled in an ice-water bath, covered with a layer of ethyl acetate (15 mL). Then, the reaction mixture was acidified to pH 2-3 using KHSO4. The aqueous phase was extracted with ethyl acetate (3 x 10 mL). The ethyl acetate layer washed with water, dried over anhydrous Na2SO4 and evaporated in vacuo. The residue was recrystallized using ethanol [1-2].

2. 2. 2. Protection of acid group using methyl ester

Boc-glycine (10 mmol) was suspended in 2, 2-di methoxypropane (DMP) (50 mL) and concentrated HCl (5 mL) was added. The mixture was allowed to stand at ambient temperature over night. The volatile reactant was removed in vacuo at 60 OC, the residue dissolved in a minimum amount of dry methanol and the solution diluted with dry ether (50 mL). The crystalline methyl ester hydrochloride was collected on a filter, washed with ether and dried in vacuo over NaOH. Recrystallization from methanol-ether (9:1mL) affords the analytically pure ester [3].

2. 2. 3. Chlorination of Protected glycine

In 100 mL RB, Thionyl chloride (6 mmol) was added and cooled in an ice-water bath. The protected glycine (4 mmol) was dissolved in ethanol and added to RB drop wise at (0OC) and stirred at ambient temperature for 48 hours. The resulting solution was concentrated under vacuo, cooled in an ice-water bath to get the desired precipitate. Recrystallization of the product using ethanol-ether affords the analytically pure chloroglycine.

2. 2. 4. Removal of protecting group using hydrobromic acid in acetic acid

An about 33 % (10 mL) solution of HBr in acetic acid is placed in a 100 mL RB flask and protected chloroglycine (4 mmol) was added with stirring. The flask was closed with a cotton filled drying tube and swirled to effect complete dissolution of the protected chloroglycine. The deprotection occurred with evolution of CO2 and heat. When the gas evolution ceases, dry ether (50 mL) was added with swirling and the reaction mixture was stored in an ice-bath. The precipitated chloroglycine ester was collected on a filter, washed with ether and dried over NaOH in vacuo.

Furthermore, a solution chloroglycine ester (4 mmol) in methanol (10 mL) was surrounded by water bath at ambient temperature and NaOH (20 mL) was added with stirring. The mixture was stored at ambient temperature for overnight. Dilute HCl (10 mL) was added and methanol removed in vacuo. The aqueous solution was cooled in ice-water for two hours. Chloroglycine was collected on a filter, washed with ether and dried in air [4-5].

2. 2. 5.Synthesis of 1-glycyl-3-methyl imidazolium chloride [Gmim]Cl:

Initially, chloroglycine (0.01 mol) reacted with N-Methylimidazole (0.011 mol) in 50 mL acetonitrile at 70OC for 24 hours to generate chloroglycine ligand modified by imidazole salt (3-(amino(carboxy)methyl)-1-methyl-1H-imidazol-3-ium chloride) [Gmim]Cl. The solvent (acetonitrile) was removed under reduced pressure at 80 OC (water bath temperature). Then the residue was mixed with 50 mL water and extracted with ethyl acetate (3 x 5 mL). Further, the water phase was evaporated under reduced pressure at 80 OC until the mass of the residue did not change. 1H-NMR (500 MHz, DMSO-d6): δ 2.2 (s, 1H), 3.3 (s, 3H), 5.0 (s, 2H), 6.92 (d, 1H), 7.0 (d, 1H), 7.6 (s, 1H), 9.1 (s, 1H). HR-MS (EI): C6H10ClN3O2 (found: 191.10), cal (191.05). FT-IR (KBr, cm-1): 3429, 3372, 2933, 2855, 1628, 1526 and 1382.

2. 2. 6. Synthesis of 1-glycyl-3-methyl imidazolium chloride-Iron (III) complex [Gmim]Cl-Fe (III)

In RB, [Gmim]Cl (0.03mmol) was treated with FeCl3 (0.01 mmol) in 100 mL methanol at 50 OC for 12 hours to deliver the [Gmim]Cl modified by iron complex [Gmim]Cl–Fe (III). The solvent (methanol) was removed under reduced pressure at 80 OC (water bath temperature). Finally,brownish yellow solid [Gmim]Cl-Fe (III) complex was obtained in 95% [6].

3. Conformation for iron complex

3.1. Characterization iron complex

[Gmim]Cl-Fe (III) catalyst has been characterized by FT-IR, XRD, SEM and AFM

3. 1. 1. FT-IR analysis

Compounds / C-N / C=O / Fe-O / Fe-N / O-H / N-H
[Gmim]Cl-Fe (III) / 1394s / 1723s / 480m / 407m / -- / 3342m
[Gmim]Cl / 1382s / 1626s / -- / -- / 3429s / 3372m
Chloroglycine / 1392s / 1625s / -- / -- / 3378s / 3335m

FT-IR spectra of [Gmim]Cl-Fe (III) at different dissociation degrees are shown in Fig. 2. For carboxylate ion, the absorption band at 1723 cm-1 corresponds to carbonyl symmetric stretching. The asymmetric stretching of carboxylate was shifted to 1626 cm-1[Gmim]Cl in contrast with the shift to 1625 cm-1 in chloroglycine, which appeared when [Gmim]Cl was treated with FeCl3 and thus the carbonyl stretching was decreased.

However, the plane of C–OH at 3378, 3429 cm-1 was present in chloroglycine, [Gmim]Cl respectively, but when the network were treated with FeCl3 no signal was observed for the –OH group, indicates the formation of Fe-O (480 cm-1) bond. Although, the NH2 signal in chloroglycine, [Gmim]Cl was detected at 3335, 3372 cm-1 with doublet, but in the case of [Gmim]Cl-Fe (III), we also found the doublet at 3342 cm-1, this also shows the formation of Fe-NH (407 cm-1) bond in the catalyst[7]. In all spectra, stretching of C-N was observed at 1394, 1382 and 1392 cm-1, respectively. Notably, the FT-IR spectra revealed that a series of new Iron complex with ionisable groups had been synthesized.

3. 1. 2. Powder XRD analysis

The formation of the Fe(III) catalyst was also supported by the XRD patterns with those ofglycine, chloroglycine, Fe(III) complex. In comparison with glycine, chloroglycine, Fe(III) complex which showed major peaks respectively at 20.55, 28.98, 25.12, 31.80 and 45.82 (confirming Iron peak with JCPDS data care no: 99-101-1980for Fe (III)), the [Gmim]Cl-Fe (III)pattern was in good aggrement with peak at 31.80 & 45.82 (fig 3).

  1. 1. 3 SEM analysis

The SEM image of the catalyst is shown inFig 4. From this image it is clear that [Gmim] Cl-Fe (III)has nanospherelike morphology with particles of dimensions ca. 250-300 nm andthese are distributed uniformly throughout the material.

3. 1. 4. AFM analysis

The 3D AFM images of the 1-glycyl-3-methyl imidazolium chloride and [Gmim]Cl-Fe (III)complex is shown in Fig 5. The 3D image for 1-glycyl-3-methyl imidazolium chloride was present 10.2 μm2 size of theparticles. It can be seen that the surface was very smooth crystalline ligand are notably different, the grain size and the shape vary significantly (fig 5 (a)). After doping the FeCl3 to the [Gmim]Cl, fig 5 (b) 3D AFM image was obtained. From this image, the larger scan size also emphasizes the differences between the [Gmim]Cl and [Gmim]Cl-Fe (III). The surface of iron doped ionic liquid, showed in the rough topography that confirmed the formation of film with iron complex in the size of 2.1 μm2.

Fig2 FT-IR of (a) chloroglycine (b) 1-glycyl-3-methyl imidazolium chloride [Gmim]Cl (c) 1-glycyl-3-methyl imidazolium chloride-iron (III) complex [Gmim]Cl-Fe (III).

Fig 3 Powder X-ray diffraction patterns of (a) glycine (b) chloroglycine c)1-glycyl-3-methyl imidazolium chloride-iron (III) complex [Gmim] Cl-Fe (III)

Fig 4 SEM image of [Gmim]Cl-Fe (III)

Fig 5 (a) AFM image of 1-glycyl-3-methyl imidazolium chloride

Fig 5 (b) AFM image of 3-(amino (carboxy) methyl)-1-methyl-1H-imidazol-3-ium chloride supported iron complex

References

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