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-RXUQDORI3K\VLFV&RQIHUHQFH6HULHV ,233XEOLVKLQJ GRL 1 New Mannich Base (2R)-4-methyl-2-((S)(phenylamino)(p- tolyl)methyl)cyclohexan-1-one; Synthesis and Spectral

Characterisation

Samraa Ali Hussein and Enaam Ismail Yousif* Department of Chemistry, College of Education for Pure Science (Ibn Al-Haitham), University of Baghdad, Adhamiyah, Baghdad, Iraq.

Email:enaamismail@yahoo.com

Abstrac: The study includes preparation and characterisation of a new Mannich -β-amino carbonyl namely: (2R)-4-methyl-2-((S)(phenylamino)(p-tolyl)methyl)cyclohexan-1-one. was achieved from the reaction of 4-methylcyclohexan-1-one and aniline with 4-methylbenzaldehyde in a 1:1:1 mole ratio, respectively. Calcium chloride was used as catalyst and ethanol as reaction medium. A range of physico-chemical tools were used to charcteris the isolated compound. These include; FT-IR, 1H-

13C-NMR, mass spectra, elemental analysis and melting point.

Keywords: 4-methylbenzaldehyde;

a one-pot reaction; Mannich-base; Three compounds

Structural study;.

Introduction:

Mannich reaction are one of the most important reactions in organic synthesis

C-C bond forming and

medicinal chemistry [1]. In these reactions, three compounds are used as starting materials. The Mannich

reaction is an important synthetic path that played a key role in the development of organic and

biochemistry. The synthesis of various drugs including antibacterial, antiprotozoal [2], and other natural

products [3,4] are derived via Mannich approach. Further, Mannich reaction has used in the synthetic of

intermediates that required in the pharmaceuticals industry. Organic ligands that based on Mannich

approach have used as chelating agents in the field of inorganic and coordination chemistry [5].

Mannichbased ligands with N and carbonyl O atoms and their metal complexes have an important role in

the coordination chemistry and have used as mimics for biomolecules [6].Mannich-based metal

2

complexes have shown anti-anginals, anti-cancer, anti-tuberculosis, anthelmintic action, hypolipidemic

and flavouring activity [7]. More, Mannich compounds have considered as potential scavengers in the

removal of heavy elements from water and waste treatment [8].In this paper, we report the synthesis and

spectral characterization of new Mannich-base compound. Recently, we reported the formation Mannich-

base compounds [9,10 ].

Experimental

Materials and Methods: All reagents used in this work were commercially available and used as

received. The NMR spectra (

1H- and 13C-NMR) was recorded in DMSO-d6 using a Brucker 300 MHZ

instruments (400 MHz for

1H and 100 MHz for 13C) with a tetramethylsilane (TMS) as an internal

reference. The FT-IR spectra were recorded as KBr discs in the range 4000-400cm -1 using FTIR-600 FT-

IR spectrometer. Melting points, were determined on an electro thermal Stuart apparatus, model SMP40.

Elements analysis

(C, H and N) was carried out on a Heraeus instrument (Vario EL).

Synthesis:

Synthesis of (2R)-4-methyl-2-((S)(phenylamino)(p-tolyl)methyl)cyclohexan-1-one.The compound was

prepared according to approach reported in [11-15], which based on Mannich condensing and as follows;

To a solution of anhydrous calcium chloride 0.5g, 5mmol in ethanol (10ml) was added successively; 4- methylbezaldehyde (0.6 ml, 5mmol), aniline (0.46ml, 5mmol) and p-methylcyclohexanone (0.5ml,

5mmol) and three drop of concentration HCl. The reaction mixture allowed stirring about 12h at RT and

a white solid that formed was filtered off, washed with EtOH (30ml) and water (30ml), and then dried in

air, Scheme(1). Yield: 0.35 g (44%), m.p.=166-164 ºC. Mwt =307.44amu. Elemental analysis: (C.H.N Found, (Calc. %); C=82.00 (82.04), H= 8.11 (8.20), N=4.22 (4.56), FT-IR data cm -1 :3410 ν(N-H), 1701

ν(C=O), 1602 δ(N-H), 1519 ν(C=C)

aromatic, 1178 n(C-N), 3028 (C-H)aromatic, 2951, 2922 (C-H)aliphatic. 3 Scheme (1): Synthetic route of (2R)-4-methyl-2-((S)(phenylamino)(p- tolyl)methyl)cyclohexan-1-one.

Results and Discussion:

The formation of the Mannich-base isbased on the reaction of a three component (an aldehyde, ketone and an amine) using a one pot-approach. The reaction was performed in EtOH medium using calcium

chloride as catalyst. The isolated compounds are air stable solids, soluble in DMF and DMSO, bar from

other common organic solvents. The isolated compound was characterised using a range of physico- chemical techniques.

FT-IR spectrum: The FT-IR spectrum of the Mannich-base show characteristic bands that related to the

prominent functional groups ν(N-H), ν(C=O), ν(C=C) aromatic, δ(N-H) and n(C-N). The spectrum indicated band at 3410cm-

1 attributed to ν(N-H) stretching of the secondary amine[16,17], compared with the twin

bands of the NH

2 in the spectrum of the aniline indicating the involvement of the amine group in the

formation of the Mannich compound. The carbonyl group appeared in at 1703 cm -1 [18], Fig.1. 4

NMR spectrum: The

1H-NMR spectrum of the Mannich-base in DMSO-d6 showed peaks at

δH;(400MHz, DMSO-d6):7.23-7.22 (C

13,13`)-H,2H, d, J=4Hz),7.07-7.05(C14,14`)-H ,2H, t, J= 8Hz), 6.94-

6.91, 6.45-6.43 (C

10,10`)-H (2H, d, J = 12Hz),(C9,9`)-H,2H, d, J=8Hz), 6.42-6.40 (C15-H, 1H, t, J=8Hz).

5.96-5.95 (1H, N-H, d, J=4Hz). 4.59;4.56 (C

7-H,1H, dd), (C2)-H (1H, m, J=4Hz), 2.90;2.51 (C6)-H (2H,

t), 2.48 CH

3(C17-H,3H, s,(CH3)),(C5)-H,2H, m), 1.94;1.90 1.56;1.52 C3-H,2H, t), 2.18-2.16 C4-H,1H,

m),0.89-0.86 CH

3,C16-H,3H,d, J=12Hz)), Fig.2. The 13C-NMR spectrum of the Mannich-base in DMSO-

d6 showed peaks at;(100MHz,DMSO-d6): 148.57,139.61,135.95(C

12),(C8), (C11), (C14,14-), (C10,10-), (C9,9-),

(C

15), (C13,13-) 129.09, 128.92, 127.94, 115.81, 113.02, 59.7, 55.3, 40.4, 39.73, 36.16,31.80 (C7) (C2), (C6)

(C

5), (C4),(C3), (C16),(C17) 21.07-21.10, 21.58-21.95 ,C=O, δ=211.4, Fig.3.

Mass spectrum: The positive electrospray mass spectrum of the Mannich-base showed a peak at m/z =307.44amu (M +) for C21H25NO. Peaks detected at m/z =236.34,182.25,104.13,55.03 related to [M- (C

17H18N+)], [M-(C13H12N+)], [M-(C7H6N+)] and [M-(C3H5N)], respectively, Fig.4.

Fig.1:The FT-IR spectrum of (2R)-4-methyl-2-((S)(phenylamino)(p- tolyl)methyl)cyclohexan-1-one. 5 Fig.2: 1H-NMR spectrumspectrum of (2R)-4-methyl-2-((S)(phenylamino)(p- tolyl)methyl)cyclohexan-1-one.

Fig.3:

13C-NMR spectrum of (2R)-4-methyl-2-((S)(phenylamino)(p-

tolyl)methyl)cyclohexan-1-one. 6 Fig.4:The electrospray (+) mass spectrum (2R)-4-methyl-2-((S)(phenylamino)(p- tolyl)methyl)cyclohexan-1-one.

Conclusion: The preparation and characterisation of a new Mannich -β-amino carbonyl ((2R)-4-methyl-

2-((S)(phenylamino)(p-tolyl)methyl)cyclohexan-1-one) are reported. Was achieved from the reaction of

4-methylcyclohexan-1-one and aniline with 4-methylbenzaldehyde in a 1:1:1 mole ratio, respectively.

Mannich-base was characterised using a range of analytical and physical techniques including; FT-IR, 1H-

13C-NMR, mass spectroscopic, elemental analysis and melting point. The physico-chemical data

indicated the formation of the target

Mannich-base.

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