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Tatu

1. The document provides supporting information for an NMR study of the conversion of TATD to TATU, including reaction mixtures and experimental methods. 2. NMR data is given for intermediates TABO and AETABO observed in the reaction, including 1H and 13C spectra. 3. A 15N NMR spectrum shows peaks for products containing 15N from 15N-NH4Cl in the reaction mixture. 4. The EI/MS spectrum of one reaction product, TATU-15N2, is shown.

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Liliana Muñoz
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87 views

Tatu

1. The document provides supporting information for an NMR study of the conversion of TATD to TATU, including reaction mixtures and experimental methods. 2. NMR data is given for intermediates TABO and AETABO observed in the reaction, including 1H and 13C spectra. 3. A 15N NMR spectrum shows peaks for products containing 15N from 15N-NH4Cl in the reaction mixture. 4. The EI/MS spectrum of one reaction product, TATU-15N2, is shown.

Uploaded by

Liliana Muñoz
Copyright
© Attribution Non-Commercial (BY-NC)
We take content rights seriously. If you suspect this is your content, claim it here.
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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: [email protected]

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

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