Supporting information for:

An NMR study of sequential intermediates and collateral products in the conversion of 1,3,6,8-tetraazatricyclo[4.4.1.13,8]dodecane (TATD) to 1,3,6,8tetraazatricyclo[4.3.1.13,8]-undecane (TATU)

Augusto Rivera,1* Martn E. Nez, Eliseo Avella,1 and Jaime Ros-Motta1

Departamento de Qumica, Universidad Nacional de Colombia, Ciudad Universitaria, Carrera 30 # 45-03, Bogot-D.C., Colombia. * To whom correspondence should be addressed. E-mail: ariverau@unal.edu.co

Contents 1. Experimental section 2. NMR Data for compounds 4 and 7 (100 and 400 MHz, D2O) 3. 15N-NMR spectra of a reaction mixture of 2 (1.41 M) and 15N-NH4Cl (4.50 M) in D2O. 4. EI/MS spectrum of TATU-15N2. 1 Experimental section:

1 2 3 4

For the NMR experiments we used 5 mm i.d. NMR tubes. 1H and 13C spectra were referenced to the residual solvent signals. All NMR measurements were performed on a Bruker Avance DRX 400 spectrometer operating at 400.13 MHz (1H) 100.0 MHz (13C) and 40.55 MHz (15N), equipped with a BBO probehead. Measurements were carried out at 23 C over a period of 8 h following the time evolution of 1H spectra. When required, COSY, 1-D TOCSY, GHSQC and GHMBC experiments were performed using standard pulse sequences and parameters available using the DRX-400 spectrometer. After this time, the mixture was extracted into chloroform (10 mLX2) and set aside.

The organic phases was then dried over sodium sulfate for a period of 4 h. The reaction mixtures were prepared directly in the NMR tube with a 2.112 M solution of TATD in D2O (0.4 mL, 0.84 mmol) and adding 0.2 mL of a 6.75 M solution of ammonium fluoride in D2O (1.35 mmol) with sodium benzenesulfonate (0.031, 0.175 mmol) as an internal standard. The reaction mixture was immediately inserted into the probehead. A residual signal of D2O ( 4.79) was set as an internal reference for spectrum calibration. For
15

N NMR experiments,

15

N-NH4Cl-98% (Sigma-Aldrich)

was used instead ammonium fluoride. Combined GCMS analysis was performed on a HewlettPackard 5973 mass spectrometer at 70 eV coupled to a Hewlett-Packard 6890 gas chromatograph. An HP5-MS column (0.25 m phase thickness, 30 m x 0.32 mm i.d.) programmed from 200 C (1 min) to 300 C (4 C/min) was used. The carrier gas was helium with a constant flow rate set close to 1.2 mL/min. The injector and detector temperatures were 200 C and 230 C respectively. An aliquot of 2 L of the respective reaction mixture was injected with split (1:4.9).

2. NMR Data for compounds 4 and 7 (100 and 400 MHz, D2O) 1,3,5-triazabicyclo[3.2.1]octane (TABO, 4), 1H NMR (400 MHz, D2O) ppm (J Hz): 2.71 (H6 and H7 , m); 2.97 (H6 and H7 , m); 3.18 (H8 , d; 10.4); 3.36 (H2 and H4 , dd: 12.9; 1.6); 3.84 (H2 and H4 , d; 12.9); 4.15 (H8 , d; 10.4). 13C NMR (100 MHz, D2O) ppm: 51.1 (C-6 and C-7); 69.1 (C-2 and C-4); 76.3 (C-8). 3-(2-aminoethyl)-1,3,5-triazabi-cyclo[3.2.1]octane (AETABO, 7), 1H NMR (400 MHz, D2O) ppm (J Hz): 2.50 (NCH2CH2NH2, m); 2.80 (H6 and H7 , m); 3.01 (NCH2CH2NH2, m); 3.21 (H6 and H7 , m); 3.30 (H8 , d; 10.4); 3.51 (H2 and H4 , d); 3.65 (H2 and H4 , d); 3.97 (H8 , d; 10.4). 13C NMR (100 MHz, D2O) ppm: 37.8. (NCH2CH2NH2); 49.7. (NCH2CH2NH2); 52.3 (C-6 and C-7); 76.3 (C-8); 76.6 (C-2 and C-4)

3. 15N-NMR spectra of a reaction mixture of 2 (1.41 M) and 15N-NH4Cl (4.50 M) in D2O.

30.0 ppm (t1)

25.0

20.0

15.0

10.0

5.0

0.0000 0.0

30.2

23.2

13.6

4. EI/MS spectrum of TATU-15N2