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Innovations in Chemical Biology pp 151–159Cite as

Catalytic Properties of Polyamido Dendrimers

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PAMAM types polyether based dendrimers were synthesized from three branched Jeffamines® . Synthesized compounds bears metylester/tert-butylester, carboxylic acid or amine groups. In the synthesis iterative Micheal type of reaction paths were followed. Catalytic properties of the molecules were studied in homogenous phase.

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References

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  8. General Procedure A (esterification of amine) 1: A 50 wt% methanol solution of methyl acrylate (17 g, 0.2 mol) was added to the methanolic solution of Jeffamine ® T-3000 (100 g, 0.033 mol). This reaction was allowed to stir at room temperature under a nitrogen atmosphere for 48 h. The reaction was then heated to 50 ° C for 1 h. methanol and excess methyl acrylate were removed by rotary evaporator. After the dialysis using membrane filter with a MWCO of 3 D in methanol, the product was obtained as a yellow viscous oil (6 g, 98%). 1 H NMR (CDCl 3, δ), 1.11 (q, OC H2CH2 O), 2.39 (t, NCH2CH2 COO, 6H), 2.76 (m, NC H2CH2 COO, 6H), 3.63 (s, OC H3, 18H). 13C NMR (CDCl3, δ ), 17.2, 17.40 (O CH2CH2 O), 34.50 (NCH2CH2COO), 51.40 (N CH2CH2 COO), 55.20 (OCH3), 173.00 (COCH3). IR (neat) cm −1 : 1736 (ester C=O), 1107 (ester C—O)

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  10. General Procedure B (converting the ester to the acid) 2: A solution of 1 (3.5 g, 0.1 mmol) in formic acid (20 ml) was stirred for 12 h. The formic acid and hydrolyzed esteric groups were removed by rotary evaporator; The aqueous solution of 2 was dialysed (3 D, MWCO membrane). The oily product was obtained quantitatively (3.45 g, 98%). 1H NMR (CDCl3, δ), 1.11 (q, OC H2CH2 O), 2.65 (m, NCH2CH2 COO, 6H and NC H2CH2 COO, 6H), 8.18 (s, CO2H, 6H). 13 C NMR (CDCl3, δ ), 17.11 (O CH2CH2 O), 31.30 (NCH2CH2COO), 50.40 (N CH2CH2COO), 171.00 ( C OOH). IR (neat) cm −1 : 3,480 (br, OH), 1,730 (acid C=O)

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  11. General Procedure C (PAMAM formation) 3: Ethylenediamine (1 g, 18 mmol) was mixed with 20 ml of methanol and a 50% (w/w) methanol solution of 1 (1 g, 0.3 mmol) was added with stirring. The reaction was allowed to proceed under a nitrogen atmosphere at room temperature for 5 days, followed by heating at 50°C for 5 h. Excess ethylenediamine and methanol were removed by rotary evaporation. The remaining ethylenediamine was removed by azeotroping mixture using a 3/1 toluene/methanol. The product 3 as a viscous yellow oil was obtained after removing volatiles by high vacuum and dialyzing with membrane filter, MWCO of 3.0 D in water (13 g, 93% yield). 1 H NMR (CDCl3δ ), 1.09 (q, OC H2CH2O), 2.31 (m, NCH2CH2CO, 12H), 2.63 (m, NHCH2CH2 N, 12H), 2.76 (t, NC H2CH2 CO, 12H), 3.23 (t, NHC H2CH2 N, 12H), 4.79 (bs, NH2,12H), 7.02 (bs, CON HCH2, 6H). 13C NMR (CDCl3, δ), 17.30 (O CH2CH2 O), 35.00 (NCH2CH2CO), 41.00 (NHCH2CH2N), 44.00 (NCH2CH2CO), 46.00 (NCH2CH2CO), 173.00 (CONH). IR (neat) cm−1: 3,347 (br, NH), 1,571 (amide C=O)

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  12. The product 4 was synthesized according to General Procedure A except reactiontime: A 50 wt% methanol solution of methyl acrylate (34 g, 0.4 mol) was added to the methanolic solution of 3 (92.5 g, 0.025 mol). This reaction was allowed to stir at room temperature under a nitrogen atmosphere for 5 days. The reaction was then heated to 50°C for 1 more day. Rotary evaporator was used to remove methanol and excess methyl acrylate. The product was obtained as a yellow viscous oil after removing volatiles by high vacuum and dialyzing with molecular weight cutoff, 3,500 (MWCO=3.5 D) in methanol, the purity of product was correlated via TLC (6 g, 88% yield). 1H NMR (CDCl3, δ ): 1.09 (q, OC H2CH2O), 2.40 (t, NCH2CH2CO. 30H), 2.50 (t, NHCH2CH2N 12H), 2.72 (µ, NCH2CH2 CO, 30H), 3.23 (t, NHCH2CH2N, 12H), 3.63 (s, OCH3, 36H), 7.15 (bs, CONHCH2, 6H). 13 C NMR (CDCl3, δ): 17.4 (OCH2CH2O), 32.6 (NCH2CH2CO), 49 (NHCH2CH2N), 51.5 (NCH2CH2CO), 52.2 (OCH3), 172.9 (COCH3). IR (neat) cm −1 : 3,440 (NH), 1,728 (ester C=O), 1,663 (amide C=O), 1,102 (ester C–O)

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  13. The product 5 was synthesized according to General Procedure B. A solution of 4 (4.7 g, 0.1 mmol) in formic acid (30 ml) was stirred for 12 h. After removing formic acid and methanol by rotary evaporator oily product was dialyzed with MWCO of 3.5 D in water and obtained quantitatively (4.4 g, 100%). 1 H NMR (CDCl3, δ ): 1.05 (q, OCH2CH2 O), 2.6 (m, NCH2CH2CO, 30H and NHCH2CH2N, 12H), 2.75 (µ, NCH2CH2CO, 30H). 3.10 (t, NHCH2CH2N, 12H), 8.16 (bs, CONHCH2, 6H), 9.97 (s, CO2H, 12H). 13C NMR (CDCl3, δ ): 16.95 (OCH2CH2O), 29.55 (NCH2CH2 CO), 49.00 (NHCH2CH2 N), 52.00 (NCH2CH2 CO), 172.00 ( C OOH). IR (neat) cm —1: 3,438 (br, NH and OH), 1,731 (acid C=O), 1,664 (amide C=O)

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  14. The product 6 was synthesized according to General Procedure C: Ethylenediamine (1 g, 18 mmol) was mixed with 20 ml of methanol and a 50% (w/w) methanol solution of 4 (2 g, 0.04 mmol). The reaction was allowed to proceed under a nitrogen atmosphere at room temperature for 10 days, followed by heating at 50°C for 2 days. Excess ethylenediamine and methanol were removed by rotary evaporator. The remaining ethylenediamine was removed by azeotrping using a 3/1 toluene/methanol mixture. The oily product was dialyzed with membrane filter of MWCO of 5 D in water (1.8 g, 84%). 1H NMR (CDCl3, δ ): 1.11 (q, OCH2CH2O), 2.34 (m, NCH2CH2CO, 36H), 2.64 (m, NHCH2CH2N. 36H), 2.78 (t, NCH2CH2CO, 36H), 3.26 (t, NHCH2CH2N, 36H), 4.87 (bs, NH2, 24H), 7.02 (bs, CONHCH2, 18H). 13 C NMR (CDCl3, δ ): 17.30 (OCH2CH2O), 34.30 (NCH2CH2CO), 44.00 (NHCH2CH2 N), 45.00 (NCH2CH2 CO), 46.30 (NCH2CH2CO), 173.00 (CONH). IR (neat) cm –1: 3,360 (NH), 1,644, 1,559 (amide C=O)

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  15. The product 7 was synthesized according to General Procedure A except reaction time: A 50% (wt/w) methanol solution of methyl acrylate (17 g, 0.2 mol) was added to the methanolic solution of 6 (21 g, 42 mmol). This reaction was allowed to stir at room temperature under a nitrogen atmosphere for 2 weeks. The reaction was then heated to 50°C for 2 days. Rotary evaporation under vacuum was used to remove methanol and excess methyl acrylate. The oily product was dialyzed with membrane filter of MWCO of 5 D in water (8 g, 88%). 1H NMR (CDCl3, δ): 1.11 (q,OCH2CH2O), 2.42 (t, NCH2CH2CO, 84H), 2.52 (t, NHCH2CH2N. 36H), 2.74 (m, NCH2CH2 CO, 84H), 3.26 (m, NHCH2CH2 N, 36H). 3.65 (s, OC H3. 72H), 7.15 (bs, CONHCH2, 18H). 13C NMR (CDCl3, δ): 17.20 (OCH2CH2O), 32.50 (NCH2CH2CO), 49.00 (NHCH2CH2N), 51.00 (NCH2CH2CO), 52.00 (OCH3), 172.00 (COCH3), 174.00 (CONH). IR (neat) cm –1: 3,308 (NH), 1,735 (ester C=O), 1,653 and 1,543 (for two amides C=O), 1,045 (ester C-O)

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  16. The product 8 was synthesized according to general procedure B: A solution of 6 (7.1 g, 0.1 mmol) in formic acid (20 ml) was stirred for 12 h. After removing formic acid and methanol by rotary evaporator The oily product was dialyzed with membrane filter of MWCO of 5 D in water (6.8 g, 95%). 1 H NMR (CDCl3, δ ): 1.11 (q, OCH2CH2O), 2.50 (t, NCH2CH2CO, 84H), 2.66 (t, NHCH2CH2N, 36H), 2.85 (m, NCH2CH2CO, 84H), 3.33 (m, NHCH2CH2N, 36H), 8.23 (bs, CONHCH2, 18H), 8.31 (s, CO2H, 24H). 13C NMR (CDCl3, δ ): 17.00 (OCH2CH2O), 31.50 (NCH2CH2 CO), 49.00 (NHCH2CH2N), 51.00 (NCH2CH2CO), 172.00 ( COOH), 173.00 (CONH). IR (neat) cm –1: 3,426 (br, NH and OH), 1,726 (acid C=O), 1,660 and 1,588 (for two amide C=O)

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  17. The product 9 was synthesized according to General Procedure C: Ethylenediamine (1 g, 18 mmol) was mixed with 20 ml of methanol and a 50% (w/w) methanol solution of 7 (2 g, 0.03 mmol). The reaction was allowed to proceed under a nitrogen atmosphere at room temperature for 14 days, followed by heating at 50°C for 2 days. Excess ethylenediamine and methanol were removed by rotary evaporation under vacuum. The remaining ethylenediamine was removed by dialysis (Spectra/Por MWCO of 5D) and The product was a viscous yellow oil (1.5 g, 70% yield). 1H NMR (CDCl3, δ ): 1.11 (q, OCH2CH2O), 2.33 (m, NCH2CH2CO, 84H), 2.63 (m, NHCH2CH2N, 84H), 2.78 (t, NCH2CH2CO, 84H). 3.25 (t, NHCH2CH2N, 84H), 7.02 (bs, CONHCH2, 18H), 13 C NMR (CDCl3, δ ): 17.30 (OCH2CH2O), 34.00 (NCH2CH2CO), 41.00 (NHCH2CH2N), 44.00 (NCH2CH2CO), 49.00 (NCH2CH2CO), 173.00 (CONH). IR (neat) cm–1: 3,347 (NH2), 1,643 and 1,566 (for two amides C=O)

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Authors and Affiliations

  1. Department of Chemistry, Fatih University, 34500 B. æekmece, Istanbul, Turkey

    Metin Tülü & Mehmet Şenel

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  1. Metin Tülü
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  1. Gazi University, Ankara, Turkey

    Bilge Şener

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Tülü, M., Şenel, M. (2009). Catalytic Properties of Polyamido Dendrimers. In: Şener, B. (eds) Innovations in Chemical Biology. Springer, Dordrecht. https://doi.org/10.1007/978-1-4020-6955-0_14

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