Poly(acryloyl hydrazide), a versatile scaffold for the preparation of functional polymers: synthesis and post-polymerisation modification

Here we present the synthesis of poly(acryloyl hydrazide), a versatile scaffold for the preparation of functional polymers, and its post-polymerisation modification using a wide range of conditions.


Fig. S3
1 H-NMR spectra of a representative polymerisation of acryloyl hydrazide (M2) with CTA1 in 1M acetate buffer pH 5 at 70 o C. The NMR samples were spiked with syringic acid as an internal standard. The integration of the monomer's alkene peaks (6.18 and 5.68 ppm) was compared to the integration of the aromatic peak of syringic acid (7.17 ppm) to obtain the % conversion.

Fig. S4
1 H-NMR spectra of a representative polymerisation of tert-butyl 2-acryloylhydrazinecarboxylate (M1) with CTA1 in DMSO at 70 o C. The NMR samples were spiked with syringic acid as an internal standard. The integration of the monomer's alkene peaks (6.18 and 5.68 ppm) was compared against the integration of the aromatic peak of syringic acid (7.20 ppm) to obtain the % conversion.

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Fig. S9
Representative 1 H-NMR spectra of the reaction of P 40 with 0.9 eq. of 4-imidazolecarboxaldehyde (1) at different reaction times. 1 H NMR spectra of the reaction of P 40 with 1 eq. of 4-imidazolecarboxaldehyde (1) analysed at different intervals. Right: Change of integral value for the signal corresponding to the aldehyde (9.65 ppm) as a function of time. Sample were incubated for 2 h at r.t. prior to NMR analysis. 1 H NMR spectra of the reaction of P 40 with 1 eq. of 4-imidazolecarboxaldehyde (1) analysed at different intervals. In both cases, samples were incubated for 2 h at r.t. and diluted two fold prior to NMR analysis.

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Fig. S13
Representative 1 H-NMR spectra of the functionalisation of P 40 with 1 eq. of 4-imidazolecarboxaldehyde (1) in 95% DMSO-d6 / 5% AcOH in D 2 O. The sample was spiked with equimolar amounts of syringic acid. The integration values of the aromatic syringic acid signals (7.20 ppm) and imidazole signals for the free and conjugated aldehyde were compared to the free aldehyde CHO signal.

Fig. S14
Representative 1 H-NMR spectra of glyceraldehyde (left) and the reaction of P 40 with 1.0 eq. of glyceraldehyde (3) in 95% DMSO-d6 / 5% AcOH in D 2 O (right). The samples were spiked with equimolar amounts of syringic acid. The integration values of the methoxy syringic acid signals (3.79 ppm) and glyceraldehyde signals for free and conjugated were compared to the free aldehyde signal and the hydrazone signal (7.38 ppm). The broad signal observed at 3.52 ppm for glyceraldehyde (3) corresponds to the self-condensation of this aldehyde under these conditions, which is reduced as the functionalisation progresses.

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Fig. S15
Representative 1 H NMR spectra for the coupling of P 40 with 1 eq. of different aldehydes. The sample were spiked with equimolar amounts of syringic acid. The integration values of the aromatic syringic acid signals (7.20 ppm) and the aromatic signals for the free and conjugated aldehydes were compared to the free aldehyde signal. *denotes the N-NHR impurity.

Table S2
Percentage loading in coupling reactions of P 40 with selected aldehydes.

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Fig. S16
Representative 1 H-NMR spectra of the reaction of P 40 with 1 eq. of aldehyde (A), the reaction of the aldehyde with hydrazine monohydrate to afford mostly disubstituted hydrazine (B), the reaction of the aldehyde with hydrazine monohydrate to afford mostly monosubstituted hydrazine (C), and the aldehyde used (D). Left: benzaldehyde (7), Right: 4hydroxybenzaldehyde (9). All samples were incubated in 95% DMSO-d6 / 5% AcOH in D 2 O.

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Fig. S17
1 H-NMR spectra of the reaction of P 40 reacted with 0.25 eq. of benzaldehyde (7) monitored at different intervals (B-F).
1 H-NMR spectra of the reaction of benzaldehyde (7) with 4 eq. (A) and 1 eq. (G) are shown for comparison. (H-I) Relative changes in the intensity of the signal corresponding to aldehyde 7, monohydrazone, dihydrazone and conjugated to the polymer as a function of time. The area for each peak was calculated using Mnova 8.1 line fitting tool. All samples were incubated in 95% DMSO-d6 / 5% AcOH in D 2 O. Scheme S1 Proposed mechanism for the formation of the impurities observed in the presence of aromatic aldehydes.