Supporting Information s20

*Corresponding author. e-mail address: [email protected], [email protected]

Supporting information

Piperidine and Piperazine Immobilized on Iron Oxide Nanoparticles as Magnetically Recyclable

Heterogeneous Catalysts for One-Pot Synthesis of β-Phosphonomalonates

Sara Sobhani,* Maryam Sadat Ghasemzadeh, Moones Honarmand

CN R CHO + + P(OEt)3 CN

O O -Fe O N Si O -Fe2O3 2 3 O Si N HN O O SiO SiO2 2 Piperazine-MNPs Piperidine-MNPs EtO OEt P CN O R CN

Spectral data of unknown β-phosphonomalonates

[1-(3-Bromophenyl)-2,2-dicyanoethyl]phosphonic acid diethylester (1i)

3 3 δH (400 MHz, CDCl3, ppm): 1.14 (t, 3H, JHH = 7.2 Hz), 1.31 (t, 3H, JHH = 7.2 Hz), 3.65 (dd,

2 3 2 3 1H, JHP = 21.6 Hz, JHH = 7.6 Hz), 3.81-4.19 (m, 4H), 4.7 (dd, 1H, JHP = 9.2 Hz, JHH= 8.0

3 3 3 Hz), 7.28 (t, 1H, JHH = 8.0 Hz), 7.44 (d, 1H, JHH = 7.2 Hz), 7.52 (d, 1H, JHH = 8.0 Hz),7.62

3 3 (s, 1H); δC (100 MHz, CDCl3, ppm): 16.1 (d, JCP = 5.0 Hz), 16.2 (d, JCP = 6.0 Hz), 25.3, 43.8

1 2 2 3 (d, JCP= 143.0 Hz), 63.6 (d, JCP = 7.0 Hz), 64.4 (d, JCP = 7.0 Hz), 111.3 (d, JCP = 12.1 Hz),

3 3 2 111.4 (d, JCP = 11.1 Hz), 123.1, 127.9 (d, JCP = 6.0 Hz), 130.8, 132.4 (d, JCP = 6.0 Hz),

3 + + 132.6, 132.8 (d, JCP = 6.0 Hz); MS (70 eV): 370 (M ), 372 (M +2); C14H16BrN2O3P: calcd. C,

45.30; H, 4.34; N, 7.55%; found: C, 44.33; H, 4.12; N, 7.39. [1-(Pyridin-3-yl)-2,2-dicyanoethyl] phosphonic acid diethylester (1k)

3 3 δH (250 MHz, CDCl3, TMS, ppm): 1.18 (t, 3H, JHH = 6.8 Hz), 1.33 (t, 3H, JHH = 7.0 Hz), 3.65

2 3 3 (dd, 1H, JHP = 21.6 Hz, JHH = 6.8 Hz), 3.92-4.21 (m, 4H), 4.63 (t, 1H, JHH = 8.5 Hz), 7.39 (t,

3 3 1H, JHH = 6.5 Hz), 7.95 (d, 1H, JHH = 6.5 Hz), 8.67 (s, 2H); δC (62.9 MHz, CDCl3, TMS,

3 3 1 ppm): 16.1 (d, JCP = 5.0 Hz), 16.2 (d, JCP = 5.0 Hz), 25.3, 42.1 (d, JCP = 144.6 Hz), 63.8 (d,

2 2 3 3 JCP = 7.0 Hz), 64.5 (d, JCP = 7.0 Hz), 110.8 (d, JCP = 10.7 Hz), 111.0 (d, JCP = 11.9 Hz),

+ 124.0, 126.7, 136.5, 150.5, 150.8; δP (101 MHz, CDCl3, ppm): 19.03; MS (70 eV): 293 (M ),

+ 156 [M -P(O)(OEt)2]; C13H16N3O3P: calcd. C 53.24, H 5.50, N 14.33; found C 53.21, H 5.47,

N 14.30.

[1,1-Dicyanopentan-2-yl] phosphonic acid diethyl ester (1l)

3 3 δH (250 MHz, CDCl3, TMS, ppm): 1.00 (t, 3H, JHH = 7.0 Hz), 1.37 (t, 6H, JHH =7.0 Hz),

3 1.61 (q, 2H, JHH = 7.0 Hz), 1.73-2.10 (m, 2H), 2.29-2.34 (m, 1H), 4.16-4.25 (m, 4H), 4.29-

3 2 4.35 (m, 1H); δC (62.9 MHz, CDCl3, TMS, ppm): 13.7, 16.3 (d, JCP = 5.6 Hz), 20.7 (d, JCP =

1 2 3 7.6 Hz), 23.7, 29.2, 37.8 (d, JCP = 144.9 Hz), 63.2 (d, JCP = 11.0 Hz), 110.7 (d, JCP = 5.0 Hz),

3 + + 112.2 (d, JCP = 17.0 Hz); MS (70 eV): 259 (M +1), 121 [M -P(O)(OEt)2]; C11H19N2O3P: calcd. C 51.16, H 7.42, N 10.85; found C 50.99, H 7.57, N 10.71.

[1, 1-Dicyanooctan-2-yl] phosphonic acid diethyl ester (1m)

3 δH (250 MHz, CDCl3, TMS, ppm): 0.81 (t, 3H, JHH = 6.8 Hz), 1.23-1.25 (m, 6H), 1.29 (t, 6 H,

3 JHH = 7.2 Hz), 1.45-1.50 (m, 2H), 1.66-1.79 (m, 1H), 1.86-1.98 (m, 1H), 2.25-2.34 (m, 1 H),

3 3 4.08-4.16 (m, 4H), 4.36 (dd, 1H, JHP = 13.2 Hz, JHH = 3.6 Hz); δC (62.9 MHz, CDCl3, TMS,

3 3 ppm): 13.9, 16.21 (d, JCP = 5.0 Hz), 22.3, 23.7, 27.1, 27.2 (d, JCP = 6.0 Hz), 28.8, 31.2, 37.7

1 2 3 3 (d, JCP = 143.0 Hz), 63.1 (d, JCP = 7.0 Hz), 111.1 (d, JCP = 3.0 Hz), 112.3 (d, JCP = 17.0 Hz);

+ + MS (70 eV): 301 (M +1), 163 [M -P(O)(OEt)2]; C14H25N2O3P: calcd. C 55.99, H 8.39, N

9.33; found C 55.36, H 8.03, N 9.20. Spectral data of known β-phosphonomalonates

[1-(4-Chlorophenyl)-2,2-dicyanoethyl] phosphonic acid diethyl ester (1a) [1,2]

1 3 3 δH H NMR (250 MHz, CDCl3, TMS, ppm): 1.16 (t, 3H, JHH = 7.0 Hz), 1.33 (t, 3H, JHH = 7.0

2 3 3 Hz), 3.62 (dd, 1H, JHP = 21.5, JHH = 7.5 Hz), 3.82-4.19 (m, 4H), 4.55 (t, 1H, JHH = 7.7 Hz),

7.42 (s, 4H).

[1-(4-Chlorophenyl)-2,2-dicyanoethyl] phosphonic acid dimethyl ester (1b) [2]

1 3 δH H NMR (400 MHz, CDCl3, TMS, ppm): 3.61-3.68 (m, 3H), 3.86 (d, 4H, JHH = 11.2 Hz),

3 4.51 (t, 1H, JHH = 8.0 Hz), 7.47 (m, 4H).

[1-(3-Chlorophenyl)-2,2-dicyanoethyl] phosphonic acid diethyl ester (1c) [1]

2 3 3 Hz), 3.60 (dd, 1H, JHP = 21.2 Hz, JHH = 8.0 Hz), 3.83-4.26 (m, 4H), 4.56 (dd, 1H, JHP = 9.2

3 Hz, JHH = 8.0 Hz), 7.41-7.45 (m, 3H), 7.50 (s, 1H).

[1-(2-Chlorophenyl)-2,2-dicyanoethyl] phosphonic acid diethyl ester (1d) [3]

2 3 3 Hz,), 3.75-4.30 (m, 4H), 4.46 (dd, 1H, JHP = 21.2 Hz, JHH = 8.2), 4.61 (t, 1H, JHH = 8.5 Hz),

3 3 7.35 (d, 2H, JHH = 4 Hz), 7.47 (s, 1H), 7.75 (d, 1H, JHH = 5.3 Hz).

[1-Phenyl-2,2-dicyanoethyl] phosphonic acid diethyl ester (1e) [1]

1 3 3 δH H NMR (400 MHz, CDCl3, TMS, ppm): 1.11 (t, 3H, JHH = 6.8 Hz), 1.33 (t, 3H, JHH =

2 3 3 7.0 Hz), 3.65 (dd, 1H, JHP = 21.0 Hz, JHH = 8.0), 3.91-4.21 (m, 4H), 4.55 (t, 1H, JHH = 8.3

Hz), 7.43 (s, 5H).

[1-(4-Methoxy)-2,2-dicyanoethyl] phosphonic acid diethyl ester (1f) [3] 1 3 3 δH H NMR (400 MHz, CDCl3, TMS, ppm): 1.17 (t, 3H, JHH = 7.2 Hz), 1.37 (t, 3H, JHH = 7.2

2 3 Hz), 3.57 (dd, 1H, JHP = 21.2, JHH = 8.0 Hz), 3.84 (s, 3H), 4.00-4.24 (m, 4 H), 4.51 (dd, 1H,

3 3 3 JHP = 8.8 Hz, JHH = 8.0 Hz), 6.97 (d, 2H, JHH = 8.8 Hz), 7.41-7.44 (m, 2H).

[1-(4-Methyl)-2,2-dicyanoethyl] phosphonic acid diethyl ester (1g) [3]

1 3 3 δH H NMR (400 MHz, CDCl3, TMS, ppm): 1.16 (t, 3H, JHH = 7.2 Hz), 1.38 (t, 3H, JHH = 7.2 Hz), 2.40 (s,

2 3 3 3H), 3.57 (dd, 1H, JHP = 21.2, JHH = 8.0 Hz), 3.74-4.06 (m, 2H), 4.14-4.25 (m, 2H), 4.50 (dd, 1H, JHH =

9.0, 8.4 Hz), 7.25-7.29 (m, 2H), 7.37-7.39 (m, 2H).

[1-(4-Bromophenyl)-2,2-dicyanoethyl] phosphonic acid diethyl ester (1h) [3]

2 3 3 Hz), 3.58 (dd, 1H, JHP = 21.5 Hz, JHH = 7.50 Hz), 3.79–4.18 (m, 4H), 4.56 (t, 1H, JHH = 7.75

3 3 Hz), 7.36 (d, 2H, JHH = 8.25 Hz), 7.56 (d, 2H, JHH = 8.0 Hz).

[1-(Furan-2-yl)-2,2-dicyanoethyl] phosphonic acid diethyl ester (1j) [4]

1 2 δH H NMR (250 MHz, CDCl3, TMS, ppm): 1.24-1.37 (m, 6H), 3.87 (dd, 1H, JHP = 22.7 Hz,

3 3 JHH = 6.5 Hz), 3.98- 4.23 (m, 4H), 4.51 (t, 1H, JHH = 8.7 Hz), 6.44 (s, 1H), 6.62 (s, 1H), 7.49

(s, 1H).

References

1. Hosseini-Sarvari M, Etemad S (2008) Tetrahedron 64:5519.

2. Fahmy AA, Ismail NA., Hafez TS (1992) Phosphorus Sulfur Silicon Relat Elem 66:201.

3. Kolla SR, Lee YR (2012) Tetrahedron 68:226.

4. Abdou WM, Khidre MD, Mahran MR (1990) J Prakt Chem 332:1029.