Functional Polyamides with gem-Diazido Units: Synthesis ... · Functional Polyamides with gem-Diazido Units: Synthesis and Diversification . Phillip Biallas. a, Janina Heider and

Functional Polyamides with gem-Diazido Units: Synthesis

and Diversification Phillip Biallasa, Janina Heidera and Stefan F. Kirscha,b

a Organic Chemistry, Bergische Universität Wuppertal, Gaußstraße 20, 42119 Wuppertal

b [email protected]

Electronic Supplementary Information 1. General remarks .................................................................................................................. 1

2. General procedures ............................................................................................................. 2

General procedure A for the synthesis of polyamides 5 ......................................................... 2

General procedure B for the synthesis of polyamides 5 ......................................................... 2

General procedure C for the CuAAC to give modified polyamides 8 ................................... 2

3. Experimental details ............................................................................................................ 3

Synthesis of geminal diazide 1 ............................................................................................... 3

Poly[imino(2,2-diazido-1,3-dioxopropane-1,3-diyl)iminopentane-1,5-diyl] (5a).................. 3

Poly[imino(2,2-diazido-1,3-dioxopropane-1,3-diyl)iminohexane-1,6-diyl] (5b) .................. 3

Poly[imino(2,2-diazido-1,3-dioxopropane-1,3-diyl)iminomethylene-1,4-

phenylenmethylene] (5c) ........................................................................................................ 4

Poly[oxyethan-1,2-diyloxyethan-1,2-diylimino(2,2-diazido-1,3-dioxopropane-1,3-

diyl)iminoethan-1,2-diyl] (5d) .............................................................................................. 4

Poly[oxy(dimethyl(silylene)propane-1,3-diylimino(2,2-diazido-1,3-dioxo-propane-1,3-

diyl)iminopropane-1,3-diyl(dimethyl(silylene))] (5e) ............................................................ 4

Poly[imino(2,2-bis(4-phenyl-1H-1,2,3-triazol-1-yl)-1,3-dioxopropane-1,3-

diyl)iminopentane-1,5-diyl] (8a) ............................................................................................ 5

Poly[imino(2,2-bis[4-((4-pyren-1-ylbutanoyl)oxy)methyl-1H-1,2,3-triazol-1-yl]-1,3-

dioxopropane-1,3-diyl)iminopentane-1,5-diyl] (8b) .............................................................. 5

Poly[imino(2,2-bis(4-((2R,3R,4S,5R,6R)-2-(acetoxymethyl)-6-oxymethylenetetrahydro-2H-

pyran-3,4,5-triyl triacetyl)-1H-1,2,3-triazol-1-yl)-1,3-dioxopropane-1,3- diyl)iminopentane-

1,5-diyl] (8c) ........................................................................................................................... 6

Electronic Supplementary Material (ESI) for Polymer Chemistry.This journal is © The Royal Society of Chemistry 2018

Poly[imino(2,2-bis(4-(4,5,6,7,8,9-hexahydro-1H-cycloocta[d])-1H-1,2,3-triazol-1-yl)-1,3-

dioxopropane-1,3-diyl)iminopentane-1,5-diyl] (8d) .............................................................. 7

Diethyl 2,2-bis(4-((((2S,3S,4R,5S,6S)-3,4,5-triacetoxy-6-(acetoxymethyl)tetrahydro-2H-

pyran-2-yl)oxy)methyl)-1H-1,2,3-triazol-1-yl)malonate (11), Diethyl 2-(4-phenyl-1H-1,2,3-

triazol-1-yl)-2-(4-((((2S,3S,4R,5S,6S)-3,4,5-triacetoxy-6-(acetoxymethyl)tetrahydro-2H-

pyran-2-yl)oxy)methyl)-1H-1,2,3-triazol-1-yl)malonate (10) and Diethyl 2,2-bis(4-phenyl-

1H-1,2,3-triazol-1-yl)malonate (9) ......................................................................................... 7

Statistically cofunctionalized polyamide A (8e) .................................................................... 9

Statistically cofunctionalized polyamide B (8f) ................................................................... 10

Atactic Poly[oxyethan-1,2-diyloxyethan-1,2-diylimino(2-amino-1,3-dioxopropane-1,3-

diyl)iminoethan-1,2-diyl] (15) ............................................................................................ 11

4. Extended Discussions ....................................................................................................... 11

a) Competition experiment with a 1:1 mixture of diazide 1 and the dimethyl malonate (6)

(see Scheme 2). ..................................................................................................................... 11

b) NMR-analysis of polyamides 5a-5e. ............................................................................. 12

c) NMR- and IR-analysis for cycloaddition products 8a-8f. ............................................. 13

d) UV/VIS spectroscopy of alkyne 7b and polymers 5a and 8b ....................................... 13

5. Spectra ............................................................................................................................... 15

1

1. General remarks All reactions were operated under air and no measures were taken to exclude water. The

commercially available compounds and solvents were used as received. tert-Butyl (5-

aminopentyl)carbamate was synthesized according to Takao et al.1 The alkynes

(2R,3R,4S,5R,6R)-2-(Acetoxymethyl)-6-(prop-2-yn-1-yloxy)tetrahydro-2H-pyran-3,4,5-triyl

triacetate (7c) and prop-2-yn-1-yl 4-(pyren-1-yl)butanoate (7b) for the copper-catalyzed

azide-alkyne cycloadditions (CuAAC) were prepared analogous to the procedures by

Sureshan et al., Quayle et al. and Tsarevsky et al..2,3,4 TLC was conducted with aluminium

sheets (TLC silica gel 60 F254) and visualized by exposure to UV light (254 nm), stained with

ceric ammonium molybdate (CAM) or basic potassium permanganate (KMnO4) and

subsequent heating. Flash column chromatography was performed on silica gel (40-60 µm),

the eluent used is reported in the particular experiments. IR spectra were measured using

ATR-technique in the range of 400-4000 cm-1. 1H NMR spectra were recorded at 400 MHz or

600 MHz spectrometers, 13C NMR at 101 MHz or 151 MHz. Chemical shifts are reported as

δ-values in ppm, coupling constants J in Hz. Multiplicities were defined by standard

abbreviations. Low-resolution mass spectra (LRMS) were recorded using a LC/MS-

combination (ESI). High-resolution mass spectra (HRMS) were obtained using ESI ionization

methods on a MicroTOF. The GPC analysis based on a conventional polymethyl methacrylate

(PMMA) calibration were carried out with HFIP / 0.05 M potassium trifluoroacetate as the

eluent and with the following column combination PSS PFG, 7 μm, LINEAR M, ID 8.0 mm x

300 mm and PSS PFG, 7 μm, LINEAR M, ID 8.0 mm x 300 mm. The PSS SECcurity 1200

pump was operated at a flow rate of 1.0 mL/min. The injection system PSS SECcurity 1200

autosampler injected 50 μL with a concentration of 3.0 g/L. A PSS SECcurity 1200

Differential Refractometer (RID) was used as detector and the program PSS WinGPC

UniChrom Version 8.2 was used for the evaluation. DSC and TGA analysis was performed on

a TGA / DSC1 STAR system from Mettler Toledo with an argon flow of 50 ml/min and a

heating rate of 10 K/min in a sealed Alox pan or on a STA 449 Jupiter FS system without an

argon flow and a heating rate of 4 K/min in an Al pan. The impact sensitivity tests were

carried out on a BAM (Bundesanstalt für Materialforschung) drophammer by Julius Peter KG,

1 K. Takao, T. Miyashiro, Y. Sugita Chem. Pharm. Bull. 2015, 63, 326. 2 A. M. Vibhute, V. Muvvala, K. M. Sureshan Angew.Chem. Int. Ed. 2016, 55,7782. 3 O. K. Rasheed, A. Lawrence, P. Quayle, P. D. Bailey Synlett 2016, 27, 905. 4 H. Han, N. V. Tsarevsky Chem. Sci., 2014, 5, 4599.

2

Berlin, according to standard norm EN 13631-4. The classification of the tested compounds

results from the “UN Recommendations on the Transport of Dangerous Goods”. Each drop

hammer impact sensitivity test was run with 40 mg of substance and a drop weight of 2.5 kg.

For each drop, the sample is placed in a plunger assembly consisting of two steel rollers, a

hollow steel collar and a centering ring. The minimum impact sensitivity values were

determined by looking at which minimum height 1 out of 6 samples explodes. UV/VIS

spectroscopy was carried out on an Excellence Spectral Photometer from Mettler Toledo in

dimethylformamide (c = 7.5 x 10-3 g/l) at room temperature.

CAUTION! We underline that geminal diazides are still potentially hazardous chemicals that

should be handled with care.

2. General procedures

General procedure A for the synthesis of polyamides 5

Diethyl 2,2-diazidomalonate (1.0 eq.) (1) was initially dissolved in THF (1.00 M), and the

diamine 4 (1.0 eq.) was added. The reaction mixture was stirred for 72 h at room temperature.

The precipitate formed during this time was filtered off, washed with water, ethanol and

diethyl ether and dried under high vacuum. If no precipitate formed in the reaction mixture,

the product was precipitated from cold ethanol, washed and dried as mentioned above. The

resulting solids underwent a Soxhlet-extraction with methanol for 24 h to separate low

molecular weight compounds. Drying under high vacuum then furnished the corresponding

polyamides 5.

General procedure B for the synthesis of polyamides 5

Diethyl 2,2-diazidomalonate (1.0 eq.) (1) was initially dissolved in THF (8.00 M), and the

diamine 4 (1.0 eq.) was added. The reaction mixture was stirred for 72 h at room temperature,

and the solvent was then concentrated under reduced pressure. Drying under high vacuum

furnished the corresponding polyamides 5.

General procedure C for the CuAAC to give modified polyamides 8

A round bottom flask was charged with poly(1,1-diazidomethylene pentamethyleneamide)

(5a) (1.0 eq.) and alkyne 7 (2.1 eq.) in DMF (0.10 M). Sodium ascorbate (0.3 eq.) and copper-

(II) sulfate pentahydrate (0.15 eq.) were added. The reaction mixture was stirred for 24 h at

room temperature and then added to a 5% aq. EDTA-solution Upon stirring for 6 h, a

precipitate occurred. The suspension was centrifuged (4200 rpm, 5 min, 5 °C) and the solvent

3

was decanted. The remaining solid was suspended in water, stirred for 30 min, centrifuged

(4200 rpm, 5 min, 5 °C), and the solvent was decanted. This procedure was repeated with

diethyl ether and the residue was then dried under high vacuum to obtain the modified

polyamides 8.

3. Experimental details

Synthesis of geminal diazide 1

The synthesis of geminal diazides 1 was published recently.5

Poly[imino(2,2-diazido-1,3-dioxopropane-1,3-diyl)iminopentane-1,5-diyl] (5a)

According to general procedure A using (0.50 g, 2.06 mmol) diethyl 2,2-diazidomalonate (1),

poly[imino(2,2-diazido-1,3-dioxopropane-1,3-diyl)iminopentane-1,5-diyl] (5a) was obtained

as a colorless solid. Yield: 208 mg, 40%. Mn = 9080. Mw/Mn = 3.68. IR (ATR): 𝜐𝜐 ̃ [cm-1] =

3302, 2942, 2862, 2125, 1683, 1516, 1458, 1438, 1242, 1058, 709, 615, 542, 469. 1H NMR

(400 MHz, DMSO-d6) δ [ppm] = 8.38 (t, J = 5.7 Hz, 2 H), 3.10 (q, J = 6.7 Hz, 4 H), 1.44

(quin, J = 7.3 Hz, 4 H), 1.21 (m, 2 H). 13C NMR (101 MHz, DMSO-d6) δ [ppm] = 163.0,

81.0, 39.4, 28.2, 23.2.

Poly[imino(2,2-diazido-1,3-dioxopropane-1,3-diyl)iminohexane-1,6-diyl] (5b)

According to general procedure A (120 h) using (1.30 g, 5.37 mmol) diethyl 2,2-

diazidomalonate (1), poly[imino(2,2-diazido-1,3-dioxopropane-1,3-diyl)iminohexane-1,6-

diyl] (5b) was obtained as a yellow solid. Yield: 822 mg, 58%. Mn = 7910. Mw/Mn = 2.97. IR

(ATR) : 𝜐𝜐 ̃ [cm-1] = 3297, 2932, 2858, 2126, 1684, 1510, 1243, 1061, 909, 728, 607, 543. 1H

NMR (400 MHz, DMSO-d6) δ [ppm] = 8.37 (br. s., 2 H), 3.20 - 3.01 (m, 4 H), 1.42 (br. s., 4

5 H. Erhardt, A.P. Häring, A. Kotthaus, M. Roggel, M.L. Tong, P. Biallas, M. Jübermann, F. Mohr, S.F. Kirsch, J. Org. Chem. 2015, 80, 12460.

O

NH

O

N3 N3

HN

n

O

NH

O

N3 N3

NH n

4

H), 1.22 (br. s., 4 H). 13C NMR (101 MHz, DMSO-d6) δ [ppm] = 162.9, 81.1, 39.4, 28.5,

25.7.

Poly[imino(2,2-diazido-1,3-dioxopropane-1,3-diyl)iminomethylene-1,4-

phenylenmethylene] (5c)

According to general procedure A using (0.80 g, 3.30 mmol) diethyl 2,2-diazidomalonate (1),

poly[imino(2,2-diazido-1,3-dioxopropane-1,3-diyl)iminomethylene-1,4-phenylenmethylene]

(5c) was obtained as a colorless solid. Yield: 498 mg, 52%. Mn = 4800. Mw/Mn = 2.80. IR

(ATR): 𝜐𝜐 ̃ [cm-1] = 3290, 2937, 2108, 1683, 1505, 1420, 1354, 1226, 1070, 528. 1H NMR

(400 MHz, pyridine-d5) δ [ppm] = 9.97 (t, J = 5.8 Hz, 2 H), 7.45 - 7.34 (m, 4 H), 4.66 (d, J =

6.1 Hz, 4 H). 13C NMR (101 MHz, pyridine-d5) δ [ppm] = 165.1, 138.4, 128.5, 83.6, 44.3.

Poly[oxyethan-1,2-diyloxyethan-1,2-diylimino(2,2-diazido-1,3-dioxopropane-1,3-

diyl)iminoethan-1,2-diyl] (5d)

According to general procedure B using (0.60 g, 2.48 mmol) diethyl 2,2-diazidomalonate (1),

poly[oxyethan-1,2-diyloxyethan-1,2-diylimino(2,2-diazido-1,3-dioxopropane-1,3-diyl)

iminoethan-1,2-diyl] (5d) was obtained as an orange oil. Yield: 627 mg, 85%. Mn = 6230.

Mw/Mn = 2.85. IR (ATR): 𝜐𝜐 ̃ [cm-1] = 3324, 2870, 2112, 1684, 1511, 1456, 1350, 1232, 1097,

832, 779, 611, 546. 1H NMR (400 MHz, CDCl3) δ [ppm] = 7.41 (br. s., 2 H), 3.65 - 3.60 (m,

4 H), 3.60 - 3.56 (m, 4 H), 3.50 (m, 4 H). 13C NMR (101 MHz, CDCl3) δ [ppm] = 163.7,

81.4, 70.5, 69.3, 40.3.


diyl)iminopropane-1,3-diyl(dimethyl(silylene))] (5e)

O

NH

O

N3 N3nH

N

O

NH

O

N3 N3n

OO

HN

O

NH

O

N3 N3nSi

OSiN

H

5

According to general procedure B using (0.80 g, 3.30 mmol) diethyl 2,2-diazidomalonate (1),

poly[oxy(dimethyl(silylene)propane-1,3-diylimino(2,2-diazido-1,3-dioxo-propane-1,3-

diyl)iminopropane-1,3-diyl(dimethyl(silylene))] (5e) was obtained as a orange resin. Yield:

1.29 g, 98%. Mn = 3940. Mw/Mn = 2.22. IR (ATR): �̃�𝜐 [cm-1] = 3323, 2954, 2877, 2112, 1687,

1515, 1440, 1250, 1185, 1044, 836, 783, 704, 546. 1H NMR (600 MHz, CDCl3) δ [ppm] =

7.16 (br. s., 2 H), 3.26 (q, J = 6.8 Hz, 4 H), 1.63 - 1.44 (m, 4 H), 0.55 - 0.43 (m, 4 H), 0.05 (s,

12 H). 13C NMR (101 MHz, CDCl3) δ [ppm] = 163.6, 81.7, 43.3, 23.4, 15.5, 0.4.

Poly[imino(2,2-bis(4-phenyl-1H-1,2,3-triazol-1-yl)-1,3-dioxopropane-1,3-

diyl)iminopentane-1,5-diyl] (8a)

According to general procedure C using (100 mg) poly[imino(2,2-diazido-1,3-dioxopropane-

1,3-diyl)iminopentane-1,5-diyl] (5a) and (84 mg, 0.25 mmol) phenylacetylene (7a),

polyamide 8a was obtained as a colorless solid. Yield: 134 mg, 75%. IR (ATR): 𝜐𝜐 ̃ [cm-1] =

3323, 2938, 2862, 1709, 1518, 1483, 1454, 1403, 1243, 1169, 1083, 1020, 907, 812, 761, 692,

514, 467. 1H NMR (400 MHz, CDCl3) δ [ppm] = 8.13 (br. s., 2 H), 8.04 - 7.88 (m, 2 H), 7.58

(br. s., 4 H), 7.26 (s, 6 H), 3.38 (br. s., 4 H), 1.59 (br. s., 4 H), 1.40 (br. s., 2 H). 13C NMR

(101 MHz, CDCl3) δ [ppm] = 161.8, 147.7, 129.2, 129.0, 128.5, 125.9, 122.0, 81.5, 41.0,

28.4, 24.0.

Poly[imino(2,2-bis[4-((4-pyren-1-ylbutanoyl)oxy)methyl-1H-1,2,3-triazol-1-yl]-1,3-

dioxopropane-1,3-diyl)iminopentane-1,5-diyl] (8b)

nNH

O

NH

O

NNNN

NN

nNH

O

NH

O

NNNN

NN

O O

O

O

6


1,3-diyl)iminopentane-1,5-diyl] (5a) and (59 mg, 0.25 mmol) prop-2-yn-1-yl 4-(pyren-1-

yl)butanoate (7b), polyamide 8b was obtained as a beige solid. Yield: 52 mg, 63%. IR (ATR):

𝜐𝜐 ̃ [cm-1] = 3340, 3040, 2938, 2865, 1713, 1519, 1436, 1416, 1239, 1183, 1142, 1042, 1009,

971, 843, 708, 621. 1H NMR (600 MHz, DMSO-d6) δ [ppm] = 8.45 (br. s., 4 H), 8.16 - 7.87

(m, 18 H), 5.11 (br. s., 4 H), 3.12 (br. s., 8 H), 2.29 (br. s., 4 H), 1.85 (br. s., 4 H), 1.38 (br. s.,

4 H), 1.15 (br. s., 2 H). 13C NMR (151 MHz, DMSO-d6) δ [ppm] = 172.3, 160.5, 141.6,

135.8, 130.7, 130.2, 129.2, 128.0, 127.2, 127.1, 126.3, 125.9, 124.7, 124.6, 124.1, 124.0,

123.1, 81.3, 56.7, 40.1, 32.8, 31.6, 27.7, 26.4, 23.3.

Poly[imino(2,2-bis(4-((2R,3R,4S,5R,6R)-2-(acetoxymethyl)-6-oxymethylenetetrahydro-

2H-pyran-3,4,5-triyl triacetyl)-1H-1,2,3-triazol-1-yl)-1,3-dioxopropane-1,3-

diyl)iminopentane-1,5-diyl] (8c)


1,3-diyl)iminopentane-1,5-diyl] (5a) and (96 mg, 0.25 mmol) (2R,3R,4S,5R,6R)-2-

(acetoxymethyl)-6-(prop-2-yn-1-yloxy)tetrahydro-2H-pyran-3,4,5-triyl triacetate (7c),

polymer 8c was obtained as a colorless solid. Yield: 104 mg, 85%. IR (ATR): 𝜐𝜐 ̃ [cm-1] =

3343, 2942, 2873, 1749, 1713, 1524, 1434, 1368, 1218, 1134, 1037, 906, 600, 489. 1H NMR

(400 MHz, CDCl3) δ [ppm] = 7.73 (br. s., 4 H), 5.20 (t, J = 9.5 Hz, 2 H), 5.07 (t, J = 9.7 Hz, 2

H), 5.01 - 4.83 (m, 4 H), 4.83 - 4.73 (m, 2 H), 4.68 (d, J = 7.8 Hz, 2 H), 4.22 (dd, J = 4.2, 12.3

Hz, 2 H), 4.13 (d, J = 11.6 Hz, 2 H), 3.74 (d, J = 8.1 Hz, 2 H), 3.51 - 3.21 (m, 4 H), 2.06 (s, 6

H), 2.01 (s, 6 H), 2.00 - 1.93 (m, 12 H), 1.71 - 1.53 (m, 4 H), 1.39 (br. s., 2 H). 13C NMR

nNH

O

NH

O

NNNN

NN

OO O

O

O

O O

O

O

O

OO

O

O

O

O

O

O

O

O

7

(101 MHz, CDCl3) δ [ppm] = 170.8, 170.3, 169.7, 169.5, 161.4, 144.5, 125.5, 100.2, 81.3,

72.3, 72.1, 71.5, 68.5, 62.7, 61.9, 41.1, 28.5, 24.1, 20.9, 20.8, 20.7, 20.7.

Poly[imino(2,2-bis(4-(4,5,6,7,8,9-hexahydro-1H-cycloocta[d])-1H-1,2,3-triazol-1-yl)-1,3-

dioxopropane-1,3-diyl)iminopentane-1,5-diyl] (8d)

Poly[imino(2,2-diazido-1,3-dioxopropane-1,3-diyl)iminopentane-1,5-diyl] (5a) (10 mg,

1.0 eq.) and cyclooctine (7d) (17 mg, 0.16 mmol, 4.0 eq.) were dissolved in 0.08 mL

chloroform. The reaction mixture was stirred for 66 h at room temperature and then

concentrated in vacuo. The residue was pecipitated twice out of chloroform/pentane and

centrifuged (4200 rpm, 5 min, 5 °C). The solvent was decanted off and the remaining solid

was dried under high vaccum, thus obtaining polymer 8d as a colorless solid. Yield: 10 mg,

54%. IR (ATR): 𝜐𝜐 ̃ [cm-1] = 3281, 2922, 2853, 1707, 1518, 1439, 1370, 1251, 1143, 1000,

922, 752, 538, 466. 1H NMR (400 MHz, CDCl3) δ [ppm] = 8.51 (br. s., 2 H), 3.51 - 3.31 (m,

4 H), 2.88 (br. s., 4 H), 2.24 (br. s., 4 H), 1.72 (br. s., 4 H), 1.69 - 1.61 (m, 4 H), 1.50 - 1.42

(m, 2 H), 1.37 (br. s., 12 H). 13C NMR (101 MHz, CDCl3) δ [ppm] = 161.8, 146.1, 137.1,

83.2, 41.4, 28.7, 28.1, 26.0, 25.9, 25.0, 24.6, 24.4, 22.2.

Diethyl 2,2-bis(4-((((2S,3S,4R,5S,6S)-3,4,5-triacetoxy-6-(acetoxymethyl)tetrahydro-2H-

pyran-2-yl)oxy)methyl)-1H-1,2,3-triazol-1-yl)malonate (11), Diethyl 2-(4-phenyl-1H-

1,2,3-triazol-1-yl)-2-(4-((((2S,3S,4R,5S,6S)-3,4,5-triacetoxy-6-(acetoxymethyl)tetrahydro-

2H-pyran-2-yl)oxy)methyl)-1H-1,2,3-triazol-1-yl)malonate (10) and Diethyl 2,2-bis(4-

phenyl-1H-1,2,3-triazol-1-yl)malonate (9)

O

O

C23H22N6O4446,4670

O

O

N NN

NNN

PhPh

O O

N NNN N

N

O O

O

O

O

OO O

O

O

O

OO

O

O OO

OO O

OO

O O

N NNN N

NPh

O O

O

O

O OO

OO O

OO

C41H54N6O24

1014,9010

+ +

C32H38N6O14730,6840

n

HN

O

O

HNN

NNNNN

8

Diethyl 2,2-diazidomalonate (1) (50 mg, 0.21 mmol, 1.0 eq.) was dissolved in 1.4 mL DMF.

(2R,3R,4S,5R,6R)-2-(Acetoxymethyl)-6-(prop-2-yn-1-yloxy)tetrahydro-2H-pyran-3,4,5-triyl

triacetate (7c) (88 mg, 0.23 mmol, 1.1 eq.), phenylacetylene (7a) (23 mg, 0.23 mmol, 1.1 eq.),

sodium ascorbate (82 mg, 0.41 mmol, 2.0 eq.) and copper (II) sulfate pentahydrate (77 mg,

0.41 mmol, 2.0 eq.) were added and stirred for 24 h at room temperature. A 5% aq. EDTA-

solution was added and the resulting mixture was extracted with DCM (3x). The organic

phase was dried over sodium sulfate and evaporated in vacuo. The residue was

chromatographed over silica (EA:PE 2:8 → 8:2) to give diethyl 2,2-bis(4-((((2S,3S,4R,5S,6S)-

3,4,5-triacetoxy-6-(acetoxymethyl)tetrahydro-2H-pyran-2-yl)oxy)methyl)-1H-1,2,3-triazol-1-

yl)malonate (11) (42 mg, 0.04 mmol, 20%), diethyl 2-(4-phenyl-1H-1,2,3-triazol-1-yl)-2-(4-

((((2S,3S,4R,5S,6S)-3,4,5-triacetoxy-6-(acetoxymethyl)tetrahydro-2H-pyran-2-

yl)oxy)methyl)-1H-1,2,3-triazol-1-yl)malonate (10) (41 mg, 0.06 mmol, 27%) and diethyl

2,2-bis(4-phenyl-1H-1,2,3-triazol-1-yl)malonate (9) (17 mg, 0.04 mmol, 19%) as colorless

solids. (11) TLC: Rf = 0.18 (EA:PE 1:1) [CAM]. IR (ATR): �̃�𝜐 [cm-1] = 3167, 2983, 2958,

2943, 1743, 1430, 1368, 1210, 1166, 1145, 1032, 905, 840, 734, 700, 599, 487. 1H NMR

(400 MHz, CDCl3) δ [ppm] = 8.20 (s, 2 H), 5.15 (t, J = 9.6 Hz, 2 H), 5.05 (t, J = 9.9 Hz, 2 H),

4.97 (dd, J = 7.8, 9.6 Hz, 2 H), 4.87 (d, J = 13.1 Hz, 2 H), 4.79 (d, J = 13.1 Hz, 2 H), 4.60 (d,

J = 8.1 Hz, 2 H), 4.48 (q, J = 7.1 Hz, 4 H), 4.22 (dd, J = 4.8, 12.4 Hz, 2 H), 4.10 (dd, J = 2.5,

12.4 Hz, 2 H), 3.72 - 3.65 (m, 2 H), 2.07 (s, 6 H), 1.99 (s, 6 H), 1.96 (s, 6 H), 1.96 (s, 6 H),

1.33 (t, J = 7.1 Hz, 6 H). 13C NMR (101 MHz, CDCl3) δ [ppm] = 170.7, 170.3, 169.4, 160.4,

144.6, 124.3, 99.9, 79.3, 72.8, 72.0, 71.2, 68.4, 65.2, 62.4, 61.9, 20.8, 20.6, 20.6, 13.8. LRMS

(ESI): [m/z] 1015.3 (100) [M+H+]. HRMS (ESI): [m/z] 1037.3084 (calcd. for

C41H54N6O24Na1+: 1037.3082).

(10) TLC: Rf = 0.48 (EA:PE 1:1) [UV,CAM]. IR (ATR): �̃�𝜐 [cm-1] = 3151, 2983, 2962, 1753,

1368, 1214, 1037, 922, 766, 696. 1H NMR (400 MHz, CDCl3) δ [ppm] = 8.45 (s, 1 H), 8.25

(s, 1 H), 7.84 - 7.79 (m, 2 H), 7.45 - 7.38 (m, 2 H), 7.37 - 7.31 (m, 1 H), 5.21 - 5.12 (m, 1 H),

5.11 - 4.96 (m, 2 H), 4.93 - 4.78 (m, 2 H), 4.63 (d, J = 7.8 Hz, 1 H), 4.58 - 4.49 (m, 4 H), 4.28

- 4.09 (m, 2 H), 3.74 - 3.64 (m, 1 H), 2.09 (s, 3 H), 2.01 (s, 3 H), 1.98 (s, 3 H), 1.94 (s, 3 H),

1.42 - 1.36 (m, 6 H). 13C NMR (101 MHz, CDCl3) δ [ppm] = 170.8, 170.3, 169.5, 169.5,

160.5, 148.3, 144.7, 129.6, 129.0, 128.9, 126.0, 124.4, 120.6, 99.8, 79.6, 72.9, 72.1, 71.2,

9

68.5, 65.2, 62.3, 62.0, 20.8, 20.7, 20.6, 13.9. LRMS (ESI): [m/z] 731.2 (100) [M+H+].

HRMS (ESI): [m/z] 753.2337 (calcd. for C32H38N6O14Na1+: 753.2338).

(9) TLC: Rf = 0.83 (EA:PE 1:1) [UV]. 1H NMR (400 MHz, CDCl3) δ [ppm] = 8.48 (s, 2 H),

7.88 - 7.77 (m, 4 H), 7.46 - 7.37 (m, 4 H), 7.36 - 7.28 (m, 2 H), 4.57 (q, J = 7.2 Hz, 4 H), 1.41

(t, J = 7.1 Hz, 6 H). 13C NMR (101 MHz, CDCl3) δ [ppm] = 160.7, 148.3, 129.6, 129.0,

128.8, 126.0, 120.6, 79.7, 65.2, 13.9. The analytical data are in agreement with previously

reported ones.6

Statistically cofunctionalized polyamide A (8e)


1.0 eq.), phenylacetylene (7a) (30 mg, 0.29 mmol, 1.05 eq.) and (2R,3R,4S,5R,6R)-2-

(acetoxymethyl)-6-(prop-2-yn-1-yloxy)tetrahydro-2H-pyran-3,4,5-triyl triacetate (7c)

(112 mg, 0.29 mmol, 1.05 eq.) were dissolved in DMF (0.10 M). Sodium ascorbate (16 mg,

0.08 mmol, 0.3 eq.) and copper-(II) sulfate pentahydrate (10 mg, 0.04 mmol, 0.15 eq.) were

added. The reaction mixture was stirred for 24 h at room temperature and then precipitated via

stirring for 6 h in a 5% aq. EDTA-solution. The suspension was centrifuged (4200 rpm, 5

min, 5 °C) and the solvent was decanted off. The remaining solid was suspended in water,

stirred for 30 min, centrifuged (4200 rpm, 5 min, 5 °C) and the solvent was again decanted

off. This procedure was repeated with diethyl ether and afterwards the residue was dried

under high vacuum thus obtaining polyamide 8e in 81% yield (165 mg) as a colorless solid.

IR (ATR): �̃�𝜐 [cm-1] = 3349, 2943, 2863, 1751, 1713, 1522, 1436, 1367, 1217, 1165, 1036,

905, 765, 599, 482. 1H NMR (400 MHz, CDCl3) δ [ppm] =8.15 - 7.57 (m, 5 H), 7.55 - 7.27

(m, 3 H), 5.17 (br. s., 1 H), 5.05 (br. s., 1 H), 4.95 - 4.55 (m, 4 H), 4.30 - 4.03 (m, 2 H), 3.69

(br. s., 1 H), 3.39 (br. s., 4 H), 2.12 - 1.84 (m, 12 H), 1.61 (br. s., 4 H), 1.40 (br. s., 2 H). 13C

NMR (101 MHz, CDCl3) δ [ppm] = 170.8, 170.3, 169.7, 169.5, 161.7, 161.5, 161.4, 147.7,

R =

O OO

O

O

O

O

O

OO

R' =

O

n

NN

NN

NN

ONH

R

R

NH

O

n

NN

NN

NN

ONH

R'

R'

NH

O

n

NN

NN

NN

ONH

R'

R

NH

10

144.3, 144.3, 129.2, 129.0, 125.9, 125.6, 122.0, 100.1, 100.0, 81.5, 81.3, 81.2, 72.7, 72.0,

71.4, 68.4, 62.5, 62.4, 61.9, 40.9, 28.4, 24.0, 20.8, 20.7, 20.6.

Statistically cofunctionalized polyamide B (8f)


1.0 eq.) and (2R,3R,4S,5R,6R)-2-(acetoxymethyl)-6-(prop-2-yn-1-yloxy)tetrahydro-2H-pyran-

3,4,5-triyl triacetate (7c) (106 mg, 0.28 mmol, 1.0 eq.) were dissolved in DMF (0.10 M).

Sodium ascorbate (9 mg, 0.04 mmol, 0.16 eq.) and copper-(II) sulfate pentahydrate (5 mg,

0.02 mmol, 0.08 eq.) were added. The reaction mixture was stirred for 24 h at room

temperature and then precipitated via stirring for 6 h in a 5% aq. EDTA-solution. The

suspension was centrifuged (4200 rpm, 5 min, 5 °C) and the solvent was decanted off. The

remaining solid was suspended in water, stirred for 30 min, centrifuged (4200 rpm, 5 min,

5 °C) and the solvent was again decanted off. This procedure was repeated with diethyl ether

and afterwards the residue was dried under high vacuum thus obtaining 147 mg of half

functionalized polymer. The crude product and phenylacetylene (7a) (30 mg, 0.29 mmol, 1.05

eq.) were again dissolved in DMF (0.10 M). The reaction mixture was stirred for 24 h at room

temperature and then precipitated via stirring for 6 h in a 5% aq. EDTA-solution. The

suspension was centrifuged (4200 rpm, 5 min, 5 °C) and the solvent was decanted off. The

remaining solid was suspended in water, stirred for 30 min, centrifuged (4200 rpm, 5 min,

5 °C) and the solvent was again decanted off. This procedure was repeated with diethyl ether

and afterwards the residue was dried under high vacuum obtaining polyamide 8f in 67% yield

(136 mg) as a colorless solid. IR (ATR): 𝜐𝜐 ̃ [cm-1] = 3352, 2940, 2865, 1750, 1712, 1522,

1437, 1367, 1217, 1164, 1036, 905, 765, 695, 599, 488. 1H NMR (400 MHz, CDCl3) δ [ppm]

= 8.37 - 7.52 (m, 5 H), 7.26 (s, 3 H), 5.28 - 5.13 (m, 1 H), 5.13 - 5.01 (m, 1 H), 5.00 - 4.59

R =

O OO

O

O

O

O

O

OO

R' =

O

n

NN

NN

NN

ONH

R

R

NH

O

n

NN

NN

NN

ONH

R'

R'

NH

11

(m, 4 H), 4.33 - 4.01 (m, 2 H), 3.72 (br. s., 1 H), 3.37 (br. s., 4 H), 2.16 - 1.87 (m, 12 H), 1.59

(br. s., 4 H), 1.47 - 1.29 (m, 2 H). 13C NMR (101 MHz, CDCl3) δ [ppm] = 170.8, 170.3,

169.6, 169.5, 161.8, 161.4, 147.7, 144.4, 130.0, 128.5, 125.9, 125.5, 122.0, 100.1, 81.4, 81.3,

72.7, 72.1, 71.4, 68.4, 62.6, 61.9, 50.0, 28.4, 24.0, 20.9, 20.8, 20.7.

Atactic Poly[oxyethan-1,2-diyloxyethan-1,2-diylimino(2-amino-1,3-dioxopropane-1,3-

diyl)iminoethan-1,2-diyl] (15)


diyl)iminopropane-1,3-diyl(dimethyl(silylene))] (5e) (107 mg, 1.0 eq.) was dissolved in

methanol (0.20 M) and Palladium on activated charcoal (43 mg, 0.04 mmol, 15 mol%) was

added. The reaction mixture was stirred for 48 h at room temperature in an autoclave with a

hydrogen pressure of 500 psi. Filtration over celite, concentration under reduced pressure and

drying under high vacuum afforded the corresponding polyamide 15 as a pale yellow solid.

Yield: 89 mg, quant. IR (ATR): 𝜐𝜐 ̃ [cm-1] = 3240, 3062, 2953, 2932, 2876, 1672, 1544, 1443,

1251, 1187, 1030, 837, 789, 704, 601. 1H NMR (400 MHz, DMSO-d6) δ [ppm] = 8.78 (br. s.,

1 H), 6.36 (br. s., 1.5 H), 4.32 (br. s., 0.5 H), 3.22 - 2.94 (m, 4 H), 1.57 - 1.28 (m, 4 H), 0.55 -

0.37 (m, 4 H), 0.02 (s, 12 H). 13C NMR (151 MHz, Methanol-d4) δ [ppm] = 169.5, 58.4, 44.1,

24.5, 16.6, 0.7.

4. Extended Discussions

a) Competition experiment with a 1:1 mixture of diazide 1 and the dimethyl

malonate (6) (see Scheme 2).

The competition experiment was carried out as follows:

Diethyl 2,2-diazidomalonate (70 mg, 0.29 mmol, 1.0 eq.) (1) and dimethylmalonate (39.4 mg,

0.29 mmol, 1.0 eq.) (6) were initially dissolved in THF (1.00 M), and benzylamine (65 mg,

0.29 mmol, 1.0 eq.) (2a) was added. The reaction mixture was stirred for 16 h at room

temperature. Concentration under reduced pressure afforded the crude mixture, which was

NMR-spectroscopically analyzed in CDCl3 as the solvent.

O

NH

O

nSiO

SiNH NH2

12

b) NMR-analysis of polyamides 5a-5e.

The proposed microstructure of the five polyamides 5a-e was confirmed by NMR

spectroscopy, as exemplified for 5e (Figure 1). In the 1H NMR spectrum, all the proton

signals expected for the polyamide 5e are clearly observed, and the peak integrations relative

to the amide protons c (δ = 7.16 ppm, in CDCl3) are in accordance with the theoretical ratios,

further confirming the polymeric structure of 5e. In addition, the 13C NMR spectrum also

supported the proposed structure with the appearance of the carbonyl peak b (δ = 163.6 ppm),

and the carbon of the geminal diazido group was found to have a signal at δ = 81.7 ppm (a).

In the case of 5e (and of 5c and 5b), it was possible to calculate the number of repeating

monomer units from the integral values of the end groups in the 1H NMR spectrum: n(5e) ≈

11, n(5c) ≈ 22, n(5b) ≈ 24. End group analysis was not possible for 5a and 5d since end group

signals were not unequivocally detected in the 1H NMR spectrum.

Figure 1. 1H NMR (A) and 13C NMR (B) spectra of 5e.

13

c) NMR- and IR-analysis for cycloaddition products 8a-8f.

The cycloaddition reactions were typically run until complete conversion of the azide groups

was achieved. As exemplified in Figure 2 for the formation of 8a, IR spectroscopy confirmed

the total consumption of the azide moieties: While the polyamide 5a showed a prevailing IR

signal at 2125 cm-1, the IR spectrum of 8a revealed no such signal and thus verified the

absence of any azide group. The 1H NMR spectrum of 8a showed the additional proton

signals expected for the newly formed 1,2,3-triazole core at 7.95 ppm (in CDCl3); the peak

integrations relative to the methylene units neighboring the amide nitrogen atoms (δ = 3.38

ppm, in CDCl3) are in accordance with the theoretical ratios (see spectral data). The

microstructures of the polyamides 8b-d were confirmed in an analogous manner (see spectral

data).

Figure 2. IR spectrum from 5a (above) and 8a (below).

d) UV/VIS spectroscopy of alkyne 7b and polymers 5a and 8b

Polymer 5a, bearing only azide groups, shows no absorption in the range of 250 – 400 nm

(Figure 3, green). The chromophore 7b, however, shows a significant absorption in the range

of 260 – 285 nm and 305 – 355 nm, with a absorbtion maximum at 280 nm (Figure 3, blue).

The cycloaddition of polymer 5a with chromophore 7b to the functionalized polymer 8b leads

14

to complete adaption of the absorption properties of the chromophore, thus resulting to very

similar absorption spectra of polymer 8b compared to alkyne 7b.

Figure 3. UV/VIS spectrum from 5a (green), 8b (red) and 7b (blue).

0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

255 275 295 315 335 355 375 395

Abso

rban

ce [a

.u.]

Wavelenght [nm]

15

5. Spectra

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)

0

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

Nor

mal

ized

Inte

nsity

2.234.064.001.90

DMSO

Water

8.39

8.38

8.36

3.13

3.11

3.09

3.08

1.47

1.45

1.44

1.42

1.40

1.22

1.21

1.19

O

NH

O

N3 N3

NH n

5a

16

168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16Chemical Shift (ppm)

0

0.05

0.10

0.15

0.20

0.25

Nor

mal

ized

Inte

nsity

162.

95

81.0

4

39.4

1

28.1

6

23.2

4

17

18

19


0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

0.60

0.65

0.70

0.75

0.80

0.85

0.90

0.95

Nor

mal

ized

Inte

nsity

4.214.124.001.99

DMSOWater

8.37

3.12

3.11

3.10

3.09

2.52

1.42

1.22

O

NH

O

N3 N3

HN

n

5b

20

176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0Chemical Shift (ppm)

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

Nor

mal

ized

Inte

nsity

162.

91

81.1

0

39.4

3

28.5

125

.71

21

22

23

10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

0.60

0.65

0.70

0.75

0.80

0.85

0.90

0.95

Nor

mal

ized

Inte

nsity

4.004.162.13

PYRIDINE-d5

PYRIDINE-d5

PYRIDINE-d5

9.97

7.41

7.38

4.67

4.65

O

NH

O

N3 N3nH

N

5c

24


0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

0.60

0.65

0.70

0.75

0.80

0.85

0.90

0.95

Nor

mal

ized

Inte

nsity

PYRIDINE-d5

PYRIDINE-d5PYRIDINE-d5

165.

11

138.

38

128.

47

83.6

1

44.2

9

25

26

27


0

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

0.60

0.65

0.70

0.75

0.80

0.85

0.90

0.95

Nor

mal

ized

Inte

nsity

4.024.543.971.71

7.41

3.62

3.60

3.59

3.58

3.57

3.51

3.49

O

NH

O

N3 N3n

OO

HN

5d

28


0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

0.60

0.65

0.70

Nor

mal

ized

Inte

nsity

163.

65

81.3

6

77.3

6

70.5

069

.29

40.2

5

29

30

31

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 -0.5Chemical Shift (ppm)

0

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

0.60

0.65

0.70

0.75

0.80

0.85

0.90

0.95

Nor

mal

ized

Inte

nsity

12.304.324.524.001.73

7.16

3.28

3.27

3.26

3.24

1.55

1.54

1.54

1.53

1.52

0.51

0.50

0.49

0.49

0.48

0.05

O

NH

O

N3 N3nSi

OSiN

H

5e

32

176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 -8Chemical Shift (ppm)

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

0.60

0.65

0.70

0.75

0.80

0.85

0.90

0.95

Nor

mal

ized

Inte

nsity

163.

56

81.6

8

43.3

4

23.3

8

15.4

6

0.39

33

34

35


0

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

0.60

0.65

0.70

0.75

0.80

0.85

0.90

0.95

Nor

mal

ized

Inte

nsity

2.374.153.997.024.062.101.80

8.13

7.96

7.94

7.58

7.26

3.38

1.59

1.40

nNH

O

NH

O

NNNN

NN

8a

36


0.01

0.02

0.03

0.04

0.05

0.06

0.07

0.08

0.09

0.10

0.11

0.12

0.13

Nor

mal

ized

Inte

nsity

161.

81

147.

65

129.

1712

8.96

128.

5112

5.86

121.

99

81.4

8

40.9

8

28.3

8

23.9

4

37

nNH

O

NH

O

NNNN

NN

O O

O

O

8b

38


0

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

0.60

0.65

0.70

0.75

0.80

0.85

0.90

0.95

Nor

mal

ized

Inte

nsity

2.664.234.004.487.553.6118.203.76

DMSO-d6water

8.45

8.12

8.08

8.05

7.95

7.94

5.11

3.12

2.29

1.85

1.38

1.15


0.005

0.010

0.015

0.020

0.025

0.030

0.035

0.040

0.045

0.050

0.055

0.060

0.065

0.070

0.075

0.080

0.085

0.090

0.095

0.100

0.105

0.110

0.115

Nor

mal

ized

Inte

nsity

172.

31

160.

51

141.

56

135.

7713

0.70

129.

1812

7.20

127.

0712

4.72

124.

5812

4.07

124.

00

81.2

9

56.6

7

40.0

5

32.7

631

.59

27.7

026

.42

23.3

4

39

40


0

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

0.60

0.65

0.70

0.75

0.80

0.85

0.90

0.95

Nor

mal

ized

Inte

nsity

2.204.3712.235.856.304.002.212.162.291.982.114.082.512.163.62

1.39

1.60

1.62

1.90

1.93

1.97

1.98

2.01

2.04

2.06

3.38

3.39

3.73

3.75

4.12

4.15

4.20

4.21

4.68

4.69

4.85

4.89

4.92

4.94

5.04

5.07

5.09

5.17

5.20

5.22

7.26

7.73

nNH

O

NH

O

NNNN

NN

OO O

O

O

O O

O

O

O

OO

O

O

O

O

O

O

O

O

8c

41


0.01

0.02

0.03

0.04

0.05

0.06

0.07

0.08

0.09

0.10

0.11

0.12

0.13

Nor

mal

ized

Inte

nsity

170.

8317

0.29

169.

6716

9.54

161.

41

144.

47

125.

52

100.

20

81.2

6

72.7

772

.10

71.4

568

.45

62.6

561

.91

41.1

0

28.5

224

.12

20.8

820

.80

20.7

1

42

n

HN

O

O

HNN

NNNNN 8d

43


0

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

0.60

0.65

0.70

Nor

mal

ized

Inte

nsity

11.922.434.404.454.124.004.171.78

8.51

3.42

3.40

3.39

2.88

2.24

1.72

1.67

1.66

1.64

1.46

1.44

1.37


0

0.005

0.010

0.015

0.020

0.025

0.030

0.035

0.040

0.045

0.050

0.055

0.060

0.065

0.070

0.075

0.080

0.085

0.090

0.095

Nor

mal

ized

Inte

nsity

161.

83

146.

13

137.

07

83.2

0

41.3

1

28.6

928

.09

25.9

324

.95

24.5

624

.41

22.2

1

44


0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

0.60

0.65

0.70

0.75

0.80

0.85

0.90

0.95

Nor

mal

ized

Inte

nsity

6.2011.456.196.042.022.142.003.831.803.881.992.111.991.71

8.20

5.16

5.13

5.08

5.05

4.99

4.97

4.95

4.86

4.80

4.61

4.59

4.49

4.48

4.21

4.12

4.11

3.70

3.70

3.68

2.07

1.99

1.96

1.96

1.35

1.33

1.32

O O

N NNN N

N

O O

O

O

O

OO O

O

O

O

OO

O

O OO

OO O

OO

11

45


0

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

0.60

0.65

0.70

0.75

0.80

0.85

0.90

0.95

Nor

mal

ized

Inte

nsity

170.

7417

0.28

169.

44

160.

37

144.

64

124.

29

99.8

8

79.3

3

72.8

372

.04

71.1

668

.37

65.2

262

.42

61.9

4

20.8

020

.64

13.7

9

46


0

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

0.60

0.65

0.70

0.75

0.80

0.85

0.90

0.95

Nor

mal

ized

Inte

nsity

6.192.993.012.833.231.142.174.081.022.082.091.041.022.042.020.970.98

8.45

8.25

7.82

7.82

7.80

7.42

7.40

7.34

5.17

5.14

5.07

4.99

4.88

4.83

4.64

4.62

4.56

4.55

4.54

4.53

4.52

4.23

4.22

4.13

3.71

3.68

3.67

2.09

2.01

1.98

1.94

1.41

1.40

1.39

1.38

1.37

1.37

O O

N NNN N

NPh

O O

O

O

O OO

OO O

OO

10

47


0

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

Nor

mal

ized

Inte

nsity

170.

7817

0.29

169.

47

160.

54

148.

26

144.

68

129.

5512

9.04

128.

8912

6.02

124.

3612

0.61

99.7

9

79.5

5

72.9

272

.10

71.2

268

.45

65.2

462

.28

61.9

8

20.8

320

.68

20.5

9

13.8

6

48


0

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

0.60

0.65

0.70

0.75

0.80

0.85

0.90

0.95

Nor

mal

ized

Inte

nsity

2.393.9012.323.721.002.163.761.381.012.565.03

8.00

7.86

7.69

7.50

7.32

5.17

5.05

4.97

4.89

4.81

4.73

4.65

4.19

4.12

4.04

3.69

3.39

2.03

1.99

1.96

1.89

1.73

1.61

1.40

1.25

R =

O OO

O

O

O

O

O

OO

R' =

O

n

NN

NN

NN

ONH

R

R

NH

O

n

NN

NN

NN

ONH

R'

R'

NH

O

n

NN

NN

NN

ONH

R'

R

NH

8e

49


0.01

0.02

0.03

0.04

0.05

0.06

0.07

0.08

0.09

0.10

0.11

0.12

0.13

0.14

0.15

0.16

0.17

0.18

0.19

Nor

mal

ized

Inte

nsity

170.

8017

0.25

169.

6616

9.51

161.

6616

1.51

161.

41

147.

66

144.

31

129.

2012

9.01

125.

8912

5.57

122.

00

100.

0999

.99

81.4

881

.34

81.2

2

72.7

272

.00

71.3

868

.38

62.5

362

.40

61.8

5

40.9

8

28.3

923

.95

20.8

120

.73

20.6

4

50

R =

O OO

O

O

O

O

O

OO

R' =

O

n

NN

NN

NN

ONH

R

R

NH

O

n

NN

NN

NN

ONH

R'

R'

NH

8f

51


0

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

0.60

0.65

0.70

0.75

0.80

0.85

0.90

0.95

Nor

mal

ized

Inte

nsity

2.273.7912.583.711.002.063.761.210.963.214.35

8.01

7.72

7.26

5.19

5.17

5.06

5.04

4.97

4.91

4.89

4.77

4.67

4.20

4.14

4.11

3.72

3.37

2.05

2.00

1.97

1.59

1.42

1.38

1.24


0.005

0.010

0.015

0.020

0.025

0.030

0.035

0.040

0.045

0.050

0.055

0.060

0.065

0.070

0.075

0.080

0.085

0.090

0.095

Nor

mal

ized

Inte

nsity

170.

8017

0.26

169.

6416

9.51

161.

7516

1.37

147.

6514

4.44

128.

9912

8.54

125.

8512

5.48

122.

01

100.

12

81.4

081

.26

72.7

472

.05

71.4

068

.41

62.5

761

.87

40.9

7

28.4

323

.98

20.8

520

.77

20.6

8

52

53

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 -0.5Chemical Shift (ppm)

0

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

Nor

mal

ized

Inte

nsity

11.994.094.003.560.491.481.00

DMSO-d6

8.78

6.36

4.32

3.06

3.04

1.44

1.42

1.40

0.49

0.47

0.45

0.02

O

NH

O

nSiO

SiNH NH2

15

54

176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 -8Chemical Shift (ppm)

0.01

0.02

0.03

0.04

0.05

0.06

0.07

0.08

0.09

0.10

0.11

0.12

0.13

0.14

0.15

0.16

0.17

0.18

0.19

Nor

mal

ized

Inte

nsity

169.

50

58.4

1

44.0

6

24.5

1

16.6

1

0.74

Documents

Functional Polyamides with gem-Diazido Units: Synthesis ... · Functional Polyamides with gem-Diazido Units: Synthesis and Diversification . Phillip Biallas. a, Janina Heider and