1

Electronic Supplementary Data

H-beta zeolite catalysed synthesis of N-benzylbenzamide from benzonitrile and benzyl alcohol

Kalpeshgiri A Gosai, Adarsh S Bhatt, Mihir R Belani, R S Somani* & H C Bajaj*

Inorganic Materials & Catalysis Division, CSIR-Central Salt and Marine Chemicals Research Institute (CSIR-CSMCRI), GB Marg, Bhavnagar 364 002, India

Email: rssomani@csmcri.org (RSS)/ hcbajaj@csmcri.org (HCB)

No. Contents Pg No.

1 Table S1 – Ritter reaction GC conversion and impurity profile 2

2 GC-MS data of Ritter reaction 2

3 1H and 13C NMR analysis 8

4 References 27

2

Table S1 – Ritter reaction GC conversion and impurity profile

Entries Conversion

( % )

Product

(%)

Impurity (%)

(ether +aromatic)

Isolated yield

(%)

Solvent free 90.9 95.30 4.7 87%

Toluene 95.4 95.43 4.6 91%

GC-MS data of Ritter reaction in solvent free condition

3

GC-MS data of Ritter reaction with solvent (Toluene)

4

5

NMR data of products

N-benzyl benzamide (3a)

Yellow solid, 91% yield, mp 96-98 °C;

1H NMR (200 MHz, CDCl3) ; δ 7.80 (d, J = 6.6 Hz, 2H, ArH), 7.52 (t, J =6 Hz, 2H, ArH), 7.46 (t, 1H, ArH),

7.41-7.31 (m, 4H, ArH), 7.28-7.19 (m, 1H, ArH), 6.53 (br s, 1H, NH), 4.65 (d, J = 5.6 Hz, 2H, CH2); 13C NMR

(125 MHz, CDCl3) δ 167.3,138.2, 134.3, 131.5, 128.7, 128.5, 127.9, 127.6, 126.9, 44.1.

N-benzyl-4-chlorobenzamide (3b)

Maize yellow solid, 79% yield. mp 162-165 °C;

1H NMR (200 MHz, CDCl3) δ 7.45 (d, J = 8.6 Hz, 2H, ArH), 7.40 (s, 1H, ArH), 7.36 (s, 1H, ArH), 7.36-7.34

(m, 4H, ArH), 6.48 (br s, 1H, NH), 4.63 (d, J = 5.6 Hz, 2H, CH2);13C NMR (125 MHz, CDCl3) δ 166.4, 137.9,

137.7, 132.7, 128.8, 128.4,127.8, 127.6, 44

N-benzyl-4-methylbenzamide (3c)

Light yellow solid, 91% yield, mp 132-135 °C.

1H NMR (500 MHz, CDCl3) δ 7.63 (d, J = 8.1 Hz, 2H, ArH), 7.28-7.16 (m, 5H, ArH), 7.43 (d, J = 8.2 Hz, 2H,

ArH),6.37 (br s, 1H, NH), 4.55 (d, J = 5.6 Hz, 2H, CH2), 2.31 (s, 3H, CH3); 13C NMR (125 MHz, CDCl3) δ

166.4, 137.9, 137.7, 132.7, 128.8, 128.4,127.8, 127.6, 44.

N-benzyl 4-acetylbenzamide (3d)

Light yellow solid, 76% yield.mp 112-113°C;

1H NMR (CHCl3, 200 MHz): δ 7.90 (d, J = 8.4 Hz, 2H, ArH), 7.78 (d, J = 7.8Hz, 2H, ArH), 7.27-7.00 (m, 5H,

ArH), 6.61(br s, 1H, N,) , 4.56(d, J=5.8, 2H, CH2 ), 2.54 (s, 3H, OCH3)13C NMR (125 MHz, CDCl3) δ 166.3,

139.1, 138.2, 137.7, 128.8, 128.5, 127.9, 127.2, 44.0, 26.

N-benzyl-4-methoxybenzamide (3e)

Light yellow solid, 89% yield.mp 121-122 °C;

1H NMR (200MHz, CDCl3) δ 7.68 (d, J = 8.6 Hz, 2H, ArH),7.62-7.08 (m, 5H, ArH),6.63(d, J = 8.6 Hz, 2H,

ArH), 6.33 (br s, 1H,NH), 4.54 (d, J = 5.8 Hz, 2H, CH2), 3.76 (s, 3H, OCH3); 13C NMR (125 MHz, CDCl3) δ

166.8, 162.1, 138.2, 129.2, 128.7, 127.8, 127.5, 126.9, 113.7, 55.0, 44.0

4-chloro-N-(1-phenylethyl)benzamide (3f)

Dirty yellow solid 70% yield, mp. 137-138 0C

1H NMR (200 MHz, CDCl3) δ7.31-7.09 (m, 9H, ArH), 6.39 (s, J=2.8 1H, N-H,), 4.21-4.06 (m, 1H,) and 2.31

(s, 3H,); δ 13C NMR (75 MHz; CDCl3) δ 167.5. 143.5, 132.2, 128.8, 128.5, 127.9, 127.2, 126.1, 51.0, 21.5

N-(cyclo hexyl) benzamide (3g)

Of white solid, 81% yield.mp 137-140 oC

1H NMR (200 MHz, CDCl3)δ 7.67 (d, J = 6.4 Hz, 2H, ArH),7.42 (m, 3H, ArH), 6.0 (s, 1H, NH), 3.82-3.98

(m, 1H, NCH2), 1.94(d, J = 1.2 Hz, 2H, CH2), 1.85-1.63 (m, 2H, CH2), 1.56-1.08(m, 6H, CH).13 C NMR

(125 MHz, CDCl3) δ 166.7, 135.9, 131.2, 1285, 126.8, 48.7, 33.2, 25.6, 24.9

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N-(cyclo hexyl)-4-bromobenzamide (3h)

White powder 82% Yield, mp: 180-181 °C

1H NMR (200 MHz, CDCl3)δ 7.62(d, J = 8.6 Hz, 2H, ArH), 7.52(d, J = 8.8 Hz, 2H, ArH),5.95 (d, j=5.4Hz,

1H, NH),4.00-3.905 (m, 1H, NCH2), 2.048-1.987(m, 2H, CH2), 1.79-1.65 (m, 2H, CH2), 1.45-1.19

(m, 6H, CH), 13 C NMR (125 MHz, CDCl3) δ 165.7, 135.7, 131.7, 125.9, 48.8,33.25,25.5,24.9

N-(cyclo hexyl)-4-Methylbenzamide (3i)

White powder 84% Yield, mp: 155°C

1H NMR (200 MHz, CDCl3) δ 7.6 (d, J = 8 Hz, 2H, ArH), 7.19-7.11 (m, 1H,ArH), 5.94 (br d, J = 5.4 Hz, 1H,

NH),3.96-3.82 (m, 1H, NCH2), 2.30 (s, 3H, CH3),2.14 (d, 2H, CH2),1.92-1.62 (m, 2H, CH2), 1.56-1.12

(m, 6H, CH), 13C NMR (CHCl3, 100 MHz): δ 166.6, 141.6, 132.2, 129.2, 126.8, 48.6,48.6, 33.1, 25.6, 24.9

N-benzyl-2-methylbenzamide; (3j)

White powder 60% Yield, mp 104-105°C

1H NMR (200 MHz, CDCl3) δ 8.17 (dd, J = 7.8 Hz, 2H, ArH),7.36-7.17(m, 5H, ArH),7.00 (t, J = 7.8 1H,

ArH),6.87 (d, J = 8.2, 1H, ArH), 6.46 (br s,1H, NH),4.6 (d, J = 5.8 Hz, 1H, NCH2),3.82 (s, 3H, CH3),13C NMR

(125 MHz, C DCl3) δ 165.4,157.5, 138.8, 132.9, 138.7, 127.7, 121.4,111.4, 55.9, 44.8

N-(cyclo hexyl)-4-chorobenzamide (3k)

hite powder, 79% Yield. mp: 180-181 °C;

1H NMR (200 MHz, CDCl3)δ 7.62 (d, J = 8.4 Hz, 2H, ArH),7.32(m, J = 8.4 2H, ArH),5.86 (br d, J = 4.2 1H,

NH),3.92-3.85(m, 1H, NCH2) 1.95 (d, J = 11, 2H, CH2), 1.72-1.46 (m 2H, CH2), 1.39-1.09 (m, 6H, CH2),13C

NMR (125 MHz, C DCl3) δ 165.6, 137.5, 133.7, 128.8, 128.8, 48.9, 33.2, 29.7, 24.9

N-benzyl 3-Bromobenzamide (3l)

Yellow solid, 78% yield.mp 87-88 °C

1H NMR (500 MHz, CDCl3) δ 7.84 (s, 1H, ArH) 7.61(s, J = 7.8 Hz, 1H, ArH), 7.53(s, J = 8.0Hz, 1H,

ArH),7.25-7.109(m, 6H, ArH), 6.59 (br s, 1H, NH)4.52(d, J = 5.6 Hz, 2H, CH2);13CNMR (125 MHz, CDCl3) δ

166.1, 137.8, 136.4, 134.6, 130.3, 130.2, 128. 9, 125.7, 122.8, 44.3.

N-benzyl-3-Clorobenzamide (3m)

Maize yellow solid, 78% yield.mp 98-99 °C

1H NMR (500 MHz, CDCl3)

δ 7.69 (s, 1H, ArH) 7.56(s, J = 7.6 Hz, 1H, ArH),7.37(s, J = 8.2 Hz, 1H, ArH),7.25-7.109(m, 6H, ArH), 6.57

(br s, 1H, NH),4.51(d, J = 5.6 Hz, 2H, NCH2);13C NMR (125 MHz, C DCl3) δ 166.2, 137.7, 136.0, 134.6,

131.5,129.8, 128.7,127.8, 127.3, 125.0,44.

N-benzyl 3-florobenzamide (3n)

White solid, 80% yield.mp 350 °C

1H NMR (500 MHz, CDCl3) δ 7.54-7.48 (m, 2H, ArH),7.43(s, 1H, ArH),7.40-7.14(m, 6H, ArH),7.25-7.109

(m, 6H, ArH), 6.46 (br s, 1H, NH),4.53(d, J = 9.0 Hz, 2H, NCH2);13C NMR (125 MHz, C DCl3) δ 166.1, 137.9,

136.65, 130.3, 128.9, 128.0,122.4, 118.7, 118.5, 114.6, 44.32.

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N-benzyl 4-iodobenzamide (3o)

Dirty white solid, 81% yield, mp 167-168 °C

1H NMR (200 MHz, CDCl3)δ 7.77 (d, J = 8.2 Hz, 2H, ArH), 7.50(m, J = 8.2Hz, 2H, ArH), 7.34-7.09 (m, 6H,

ArH), 6.68 (d, J = 8.0Hz, 2H, NH), 3.95 (d, J = 7.2, 2H, NCH2),13C NMR (125 MHz, C DCl3) 166.7, 133.8,

129.4, 129.4, 128.9, 128.6, 128.0, 127.8, 98.5, 44.3

N-benzyl 4-(tri fluoro methyl) benzamide (3p)

Brick-red solid, 75% yield.mp 169-170 °C

1H NMR (200 MHz, CDCl3)δ 7.76 (d, J = 8.4 Hz, 2H, ArH), 7.50(d, J = 8.4 Hz, 2H, ArH),7.33-7.09 (m, 5H,

ArH),6.68 (d, J = 1.0 Hz, 1H, NH), 4.61 (d, J = 5.6, 2H, NCH2),13C NMR (125 MHz, CDCl3) δ 166.1, 137.7,

133.2, 128.9 , 128.4,128.0, 127.9, 127.5, 125.7, 124.7, 122.6, 44.3

N-benzylthiophene-2-carboxamide (3q)

Grey solid, 71% yield. mp 114-115°C

1H NMR (200 MHz, CDCl3)δ 7.48 (dd, J = 3.6 Hz, 2H, ArH), 7.31-7.24 (m, 5H, ArH),7.03 (t, 2H, ArH),6.57

(br s, 1H, NH), 4.57(d, J = 5.8, 2H, NCH2),13 C NMR (125 MHz, CDCl3) δ 166.8, 138.8, 138.0, 130.0,

128.7,128.1, 127.9, 127.6, 127.64, 44.0

N-benzyl-4-bromobenzamide (3s)

Yellow solid, 81% yield.mp 162-165 °C

1H NMR (200MHz, CDCl3) δ 7.57 (d, J = 8.6 Hz, 2H, ArH) 7.46 (d, J = 8.6 Hz, 2H, ArH), 7.25-7.11 (m, 5H,

ArH), 6.47 (br s, 1H, NH), 4.53 (d, J = 5.6 Hz, 2H, CH2);13C NMR (125 MHz, CDCl3) δ 166.4, 137.9, 133.9,

131.8, 128.8,128.6,127.9, 127.7, 44.2.

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1H and 13C NMR spectra

N-benzyl benzamide (3a), proton CDCl3

N-benzyl benzamide (3a), 13C CDCl3

9

N-benzyl-4-chlorobenzamide (3b), proton CDCl3

N-benzyl-4-chlorobenzamide (3b), 13C CDCl3

10

N-benzyl-4-methylbenzamide (3c), proton CDCl3

N-benzyl-4-methylbenzamide (3c), proton CDCl3

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N-benzyl 4-acetylbenzamide (3d), proton CDCl3

N-benzyl 4-acetylbenzamide (3d), 13C CDCl3

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N-benzyl-4-methoxybenzamide (3e) proton CDCl3

N-benzyl-4-methoxybenzamide (3e) 13C CDCl3

13

4-chloro-N-(1-phenylethyl)benzamide (3f), proton CDCl3

4-chloro-N-(1-phenylethyl)benzamide (3f), 13C CDCl3

14

N-(cyclo hexyl)benzamide (3g), proton CDCl3

N-(cyclo hexyl)benzamide (3g), proton CDCl3

15

N-(cyclo hexyl)-4-bromobenzamide (3h), proton CDCl3

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N-(cyclo hexyl)-4-bromobenzamide (3h), 13C CDCl3

N-(cyclo hexyl)-4-Methylbenzamide (3i), proton CDCl3

17

N-(cyclo hexyl)-4-Methylbenzamide (3i), 13C CDCl3

N-benzyl 2-methylbenzamide (3j), proton CDCl3

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N-benzyl 2-methylbenzamide (3j), proton CDCl3

N-(cyclo hexyl)-4-cholobenzamide (3k), proton CDCl3

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N-(cyclo hexyl)-4-cholobenzamide (3k), 13C CDCl3

N-benzyl-3-Bromobenzamide (3l), proton CDCl3

20

N-benzyl-3-Bromobenzamide (3l), 13C CDCl3

N-benzyl 3-Clorobenzamide (3m), proton CDCl3

21

N-benzyl-3-Clorobenzamide (3m), 13CCDCl3

N-benzyl- 3-flolobenzamide (3n), proton CDCl3

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N-benzyl-3-Clorobenzamide (3n), 13C CDCl3

N-benzyl-4-iodobenzamide (3o), proton CDCl3

23

N-benzyl-3-Clorobenzamide (3o), 13C CDCl3

N-benzyl-(4-trifloromethyl)benzamide (3p), proton CDCl3

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N-benzyl-(4-trifloromethyl) benzamide(3p), 13C CDCl3

N-benzylthiophene-2-carboxamide (3q), proton CDCl3

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N-benzylthiophene-2-carboxamide (3q), 13C CDCl3

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N-benzyl-4-bromobenzamide (3p), proton CDCl3

N-benzyl-bromo benzamide (3p), 13C CDCl3

27

References

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3. Wang N, Zou X, Ma J & Li F, Chem comm, 50 (2014) 8303.

4. Khalafi-N, Foroughi H o, Doroodmand M M & Panahi F, J. Mater Chem A, 21 (2011)12842.