Supporting Information
Platinum Nanowires Catalyzed Direct Amidation with Aldehydes and Amines
Dawei Xu, Linyan Shi, Danhua Ge, Xueqin Cao, Hongwei Gu
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science & Collaborative Innovation Center of Suzhou Nano Science and Technology, Soochow University, Suzhou 215123, China
General information:
All experiments were carried out under an atmosohere of air. Flash column chromatography was performed over silica-gel powder 200-300 mesh (75-48 μm). 1H NMR and 13C NMR spectra were recorded on a Agilent (400 MHz) instrument internally referenced to SiMe4 signal. The structures of known compounds were further corroborated by comparing their 1H NMR data and 13C NMR data with those of literature. All reagents were used as received from commercial sources without further purification. All aldehydes and amines employed were reagent grade materials and used as received.
Figure S1. TEM of Pt NWs
Preparation of Pt NPs (3-5 nm):
Pt(acac)2 (100 mg), octadecene (10 mL), oleic acid (1 mL), and oleylamine (1 mL) were mixed under stirring and bubbled by N2 for 5 minutes. The mixture was then heated to 65 oC to dissolve Pt(acac)2. The temperature was raised to about 180 oC in 20 minutes. A solution of Fe(CO)5 in hexane (0.1 mL, prepared by adding 0.1 mL Fe(CO)5 in 1 mL hexane under argon) was quickly injected into the hot solution. The solution was further heated to 200 oC and kept at this temperature for 1 hour before it was cooled down to room temperature. 40 mL of isopropanol was added and then the suspension was centrifuged to separate the NPs. The NPs were dispersed in 10 mL hexane and precipitated with ethanol. The process was repeated one more time to purify the nanoparticles. The final product was dispersed in 10 mL of ethanol for further use.
Figure S2. TEM of Pt NPs
Preparation of Pt NRs (diameter:3-5 nm):
Pt(acac)2 (200 mg), sodium oleate (150 mg) were added to oleylamine (20 mL) under Ar and stirring for about 5 minute. The mixture was then heated to 120 oC for 15 min. As the solution turned clear yellow, a drop of Fe(CO)5 (~0.005mL) was quickly injected into the hot solution. The solution turned dark in color quickly. The temperature was further heated to 250 oC and kept at this temperature for 30 min before it was cooled down to room temperature. The sample was centrifuged in excess isopropanol to separate the NRs. The NRs were dispersed in 10 mL toluene and precipitated with ethanol. The process was repeated one more time to purify the nanorods. The final product was dispersed in 10 mL of ethanol for further use.
Figure S3. TEM of Pt NRs
Amide synthesis using Pt NWs as the catalyst:
Pt NWs catalyst in methanol were added in a explosion-proof tube and the methanol was evacuated by pressure reducing. Aluminum chloride, pyridine, amine, aldehyde, tert-butylhydroperoxide and solvent were added into the reaction tube and then sealed. The reaction tube was placed in an oil-bathing at a certain temperature. After reaction, the resultant product mixtures were analyzed by GC (VARIAN CP-3800 GC, HP-5 capillary column, FID detector) and GC-MS (VARIAN 450-GC & VARIAN 240-GC) equipped with a CP8944 capillary column (30 m×0.25 mm) and an FID detector. The amides were characterized by 1H NMR and 13C NMR.
Table S1. N-Phenylbenzamide Formation with different catalysta
Entry / Catalyst / T(oC) / Yield (%)b1 / Pt NWs / 100 / 92
2 / Pt NPs / 100 / 70
3 / Pt NRs / 100 / 79
4 / FePt NWs / 100 / 58
a All reactions were carried out with 0.5% mmol cat., 1 mmol of aniline, 1.1 mmol of benzaldehyde, AlCl3 (0.25 mmol), pyridine (1 mmol), TBHP (3.6 mmol) and solvent (2 mL) for 18h. b GC yield.
Table S2. N-Phenylbenzamide Formation with different catalysta
Entry / Catalyst / T(oC) / Yield (%)bPyridine/μL / AlCl3/mg
1 / 80 / 33 / 100 / 92
2 / 100 / 33 / 100 / 70
3 / 80 / - / 100 / 15
4 / - / 80 / 19
a All reactions were carried out with Pt NWs (0.5% mmol), 1 mmol of aniline, 1.1 mmol of benzaldehyde, TBHP (3.6 mmol) and solvent (2 mL) for 18h. b GC yield.
NMR data of the Amides:
1. N-Phenylbenzamide
1H NMR (400 MHz, CDCl3): δ = 8.12-8.10(d, 1H, H9), 7.89-7.87 (d, 2H, H4, H6) , 7.66-7.64 (d, 2H, H11, H15) , 7.56-7.54 (d, 1H, H2) , 7.51-7.48 (m, 2H, H1, H3) , 7.4-7.36 (m, 2H, H12, H14) , 7.18-7.14 (m, 1H, H13).
13C NMR (100 MHz, CDCl3): δ = 166.11, 138.15, 135.16, 132.04, 129.29, 128.97, 127.28, 124.78, 120.50.
2. 4-Methyl-N-phenylbenzamide
1H NMR (400 MHz, CDCl3): δ = 8.00-7.98(d, 1H, H9), 7.76-7.74(d, 2H, H4, H6) , 7.67-7.62(m, 2H, H11, H15) , 7.35-7.31 (m, 2H, H12, H14) , 7.26-7.22 (m, 2H, H1, H3) , 7.14-7.10 (m, 1H, H13) , 2.41-2.39 (d, 3H, H16).
13C NMR (100 MHz, CDCl3): δ = 167.07, 142.54, 130.42, 129.59, 129.39, 129.24, 127.33, 124.63, 120.52, 21.71.
3. 4-Chloro-N-phenylbenzanilide
1H NMR (400 MHz, (CD3)2SO): δ = 10.32(s, 1H, H9), 7.99-7.93 (m, 2H, H4, H6) , 7.77-7.75(d, 2H, H11, H15) , 7.62-7.56(m, 2H, H1, H3) , 7.37-7.34 (m, 2H, H12, H14) , 7.13-7.09 (m, 1H, H13).
13C NMR (100 MHz, (CD3)2SO): δ = 169.83, 141.79, 139.05, 136.55, 135.03, 134.03, 133.86, 129.23, 125.82.
4. 4-Bromo-N-phenylbenzanilide
1H NMR (400 MHz, CDCl3): δ = 7.88-7.87(d, 1H, H9), 7.80-7.74(m, 2H, H4,H6) , 7.66-7.54(m, 2H, H11, H15) , 7.52-7.48(m, 2H, H1, H3) , 7.40-7.36(m, 2H, H12, H14), 7.19-7.14 (m, 1H, H13).
13C NMR (100 MHz, CDCl3): δ = 167.18, 137.67, 133.83, 132.05, 129.16, 128.66, 126.60, 124.82, 120.26.
5. 4-Methoxy-N-phenylbenzanilide
1H NMR (400 MHz, CDCl3): δ = 9.36(s, 1H, H9), 7.86-7.84(m, 2H, H4, H6), 7.69-7.62(m, 2H, H11, H15), 7.43-7.35(m, 2H, H12,H14), 7.16-7.12(m, 1H, H13), 6.99-6.94(m, 2H, H1,H3), 3.88(s, 3H, H17).
13C NMR (100 MHz, CDCl3): δ = 166.75, 165.89, 132.52, 129.27, 124.58, 120.42, 114.16, 113.92, 55.69.
6. 4-Butoxy-N-phenylbenzanilid
1H NMR (400 MHz, CDCl3): δ = 7.89-7.82 (m, 2H, H4, H6 ), 7.66-7.62 (m, 2H, H11, H15) , 7.40-7.34(m, 2H, H12,H14) , 7.16-7.12(m, 1H, H13) , 6.97-6.95 (m, 2H, H1, H3) , 4.04-4.01 (m, 2H, H17) , 1.83-1.76 (s, 2H, H18), 1.26(s, 2H, H19), 1.01-0.96(m, 3H, H20).
13C NMR (100 MHz, CDCl3): δ = 165.28, 162.13, 138.17, 129.06, 128.87, 127.03, 124.30, 120.14, 114.46, 67.96, 30.93, 19.20, 13.83.
7. 4-Dodecyloxy-N-phenylbenzanilide
1H NMR (400 MHz, CDCl3): δ = 7.98-7.76 (m, 2H, H4, H6), 7.63-7.59 (m, 2H, H11, H15) , 7.55-7.48(m, 2H, H12,H14) , 7.11-7.09 (d, 1H, H13), 7.05-7.03(m, 2H, H1, H3) , 4.17-4.11(m, 2H, H17) , 2.31 (s, 2H,H18), 1.40 (s, 14H,H19-25), 1.02 (s, 3H,H26).
13C NMR (100 MHz, CDCl3): δ = 165.25, 162.13, 138.16, 129.07, 128.86, 126.85, 124.30, 120.11, 114.46, 68.26, 31.92, 29.64, 29.13, 26.00, 22.70, 14.13.
8. 4-Benzyloxy-N-phenylbenzanilide
1H NMR (400 MHz, (CD3)2SO): δ = 12.05(s, 1H, H9), 7.97-7.88 (m, 2H, H4, H6) , 7.78-7.76 (m, 2H, H11, H15), 7.47-7.34(m, 7H, H12,H14, H19-23) , 7.16-7.09(m, 3H, H1, H3, H13) , 5.21-5.18 (d, 2H, H17) .
13C NMR (100 MHz, (CD3)2SO): δ = 172.37, 141.91, 136.75, 133.89, 133.40, 133.21, 131.66, 128.55, 125.79, 120.00, 74.84.
9. 4-Cyano-N-phenylbenzanilide
1H NMR (400 MHz, (CD3)2SO): δ = 10.50 (s, 1H, H9), 8.11-8.02 (m, 4H, H1, H3, H4, H6) , 7.78-7.76(d, 2H, H11, H15) , 7.39-7.35 (m, 2H, H12,H14), 7.15-7.11 (m, 1H, H13).
13C NMR (100 MHz, (CD3)2SO): δ = 169.56, 144.37, 144.13, 137.86, 134.09, 133.10, 129.50, 125.85, 123.74, 119.22.
10. 4-[(phenylamino)carbonyl]-terephthalanilic acid
1H NMR (400 MHz, (CD3)2SO2): δ =10.42(s, 1H, H16), 8.10 (s, 2H, H1, H3), 8.06(s, 2H, H4, H6), 7.81-7.78 (m, 2H, H11, H15), 7.37(s, 2H, H12,H14), 7.12(s, 1H, H13).
13C NMR (100 MHz, (CD3)2SO): δ = 172.18, 170.26, 144.34, 144.12, 138.64, 134.59, 133.33, 129.31, 125.82.
11. 4-Nitro-N-phenylbenzanilide
1H NMR (400 MHz, (CD3)2SO): δ =10.62(s, 1H, H9), 8.38-8.33 (m, 2H, H1, H3) , 8.21-8.19(d, 2H, H4, H6) , 7.80-7.78(d, 2H, H11, H15) , 7.40-7.36 (m, 2H, H12,H14) , 7.16-7.13 (m, 1H, H13).
13C NMR (100 MHz, (CD3)2SO): δ = 154.52, 146.02, 144.11, 138.26, 134.62, 134.12, 129.58, 128.95, 125.87.
12. N-(2-Methylphenyl)benzamide
1H NMR (400 MHz, CDCl3): δ =8.14-8.12 (d, 1H, H9), 7.88-7.87 (d, 3H, H4, H6, H15) , 7.55-7.42(m, 5H, H1-3, H12, H14) , 6.99-6.96 (d, 1H, H13) , 2.38 (s, 3H, H16).
13C NMR (100 MHz, CDCl3): δ = 166.35, 135.18, 133.80, 131.93, 130.35, 128.86, 127.36, 125.59, 121.35, 117.80, 21.70.
13. N-(3-Methylphenyl)benzamide
1H NMR (400 MHz, CDCl3): δ = 7.90-7.89 (d, 2H, H4, H6), 7.57-7.44 (m, 5H, H1-3, H11, H15) , 7.30-7.26 (m, 1H, H14) , 7.01-7.99 (d, 1H, H13) , 2.40 (s, 3H, H16).
13C NMR (100 MHz, CDCl3): δ = 166.08, 138.90, 137.98, 135.04, 131.70, 128.82, 128.65, 127.15, 125.36, 121.15, 117.60, 21.48.
14. N-(4-Methylphenyl)benzamide
1H NMR (400 MHz, CDCl3): δ =7.87-7.85(d, 2H, H4, H6), 7.54-7.45 (m, 5H, H1-3, H11, H15), 7.18-7.16 (d, 2H, H12, H14), 2.34 (s, 3H, H16).
13C NMR (100 MHz, CDCl3): δ = 166.13, 135.61, 135.21, 134.40, 131.88, 129.72, 128.87, 127.36, 120.69, 21.11.
15. N-(4-Chlorophenyl)benzamide
1H NMR (400 MHz, (CD3)2SO): δ =10.37 (s, 1H, H9), 7.95-7.94 (d, 2H, H4, H6), 7.62-7.48(m, 5H, H1-3, H11, H15), 7.42-7.40(d, 2H, H12, H14).
13C NMR (100 MHz, (CD3)2SO): δ = 171.07, 140.10, 138.28, 137.12, 134.67, 133.93, 133.83, 133.09, 127.22, 127.40, 126.38, 125.95.
16. N-(4-Bromophenyl)benzamide
1H NMR (400 MHz, (CD3)2SO): δ =10.37 (s, 1H, H9), 7.95-7.94 (d, 2H, H4, H6), 7.78-7.76 (d, 2H, H11, H15), 7.64-7.48(m, 5H, H1-3, H12, H14).
13C NMR (100 MHz, (CD3)2SO): δ =172.73, 138.38, 137.13, 136.84, 134.67, 133.97, 133.83, 133.09, 127.59.
17. N-(4-Acetylphenyl)benzanilide
1H NMR (400 MHz, CDCl3): δ =10.57(s, 1H, H9), 7.98-7.94 (m, 6H, H4, H6, H11, H12, H14, H15 ), 7.62-7.60(d,1H, H2), 7.57-7.53(m, 2H, H1, H3),2.55(s, 3H, H18).
13C NMR (100 MHz, CDCl3): δ = 198.19, 167.02, 144.01, 134.82, 132.68, 129.96, 129.20, 128.33,27.02.
18. 4-(Benzoylamino)benzoic acid ethyl ester
1H NMR (400 MHz, CDCl3): δ =10.58(s, 1H, H9), 7.99-7.94 (m, 6H, H4, H6, H11, H12, H14, H15), 7.65-7.61(m, 1H, H2), 7.58-7.54(m, 2H, H1, H3), 4.33-4.28(m, 2H, H19), 1.35-1.31(m, 3H, H20).
13C NMR (100 MHz, CDCl3): δ = 159.37, 142.13, 138.71, 133.71, 132.19, 129.68, 128.98, 128.72, 127.96, 127.40, 126.38, 125.95.
19. N-(n-Dodecyl)benzamide
1H NMR (400 MHz, CDCl3): δ =7.76-7.74 (d, 2H, H4, H6), 7.51-7.47 (m, 1H, H2), 7.44-7.40(m, 2H, H1, H3), 3.47-3.42(m, 2H, H10), 1.64-1.57(m, 2H, H11),1.37-1.25(m, 18H, H12-20), 0.89-0.86(m, 3H, H21).
13C NMR (100 MHz, CDCl3): δ = 167.62, 134.85, 131.22, 128.44, 126.92, 40.15, 31.92, 29.66, 29.64, 29.60, 29.57, 29.35, 20.07, 22.68, 14.12.
20. N-Benylbenzamide
1H NMR (400 MHz, CDCl3): δ =8.13-8.11 (d, 1H, H9), 7.81-7.79 (d, 2H, H4, H6), 7.64-7.60 (m, 1H, H2), 7.51-7.48 (m, 2H, H1, H3), 7.46-7.42 (m, 2H, H13, H15), 7.37-7.36 (m, 3H, H12, H14, H16), 4.67-4.66(d, 2H, H10).
13C NMR (400 MHz, CDCl3): δ = 167.84, 138.50, 134.72, 134.08, 132.02, 130.58, 129.79, 129.23, 129.03, 128.88, 128.37, 128.08, 127.37, 44.60.
21. N-tert-butylbenzamide
1H NMR (400 MHz, CDCl3): δ =7.80-7.75(m, 2H, H4, H6), 7.50-7.40 (m, 3H, H1, H2, H3), 1.38(s, 9H, H11-13).
13C NMR (100 MHz, CDCl3): δ = 166.33, 135.90, 130.72, 128.00, 127.35, 50.77, 28.61.