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Helvetica Chimica Acta – Vol. 92 (2009)
5-Methyl-3-oxazolidine-1’-spiropyrrolidinium Bis[(trifluoromethyl)sulfonyl]azanide (¼4-Methyl-2-
oxa-5-azoniaspiro[4.4]nonane Bis[(trifluoromethyl)sulfonyl]azanide; 5MOP NTf2). 5MOP NTf2 was
synthesized using metathesis of 5MOP BF4 and LiNTf2 in the same manner as the synthesis of 2MOP
NTf2 in 91% yield, and the product was further recrystallized from MeOH at ꢀ 808, in the same manner
as 2MOP BF4. 1H-NMR: 5.04 (d, J ¼ 5.6, HꢀC(1)); 4.79 (d, J ¼ 6.1, HꢀC(1)); 4.59 (qdd, J ¼ 6.9,
HꢀC(4)); 3.95 (dd, J ¼ 7.1, 11.6, HꢀC(3)); 3.79 – 3.58 (m, 4 H); 3.35 (dd, J ¼ 8.6, 11.6, HꢀC(3)); 2.30 –
2.14 (m, 4 H); 1.45 (d, J ¼ 6.6, Me). 13C-NMR: 121.2 (q, J ¼ 320.5, 1 H); 92.3 (br.); 76.4; 66.6 (m); 64.3
(m); 62.6 (m); 23.0; 23.0; 18.6; 18.6. 19F-NMR: ꢀ 81.1 (s).
Synthesis of 3,3’-Spirobioxazolidinium Tetrafluoroborate (¼2,7-Dioxa-5-azoniaspiro[4.4]nonane
Tetrafluoroborate; SBO BF4). 1,3-Oxazolidine was synthesized from paraformaldehyde (15.02 g,
0.50 mol) and 2-aminoethanol (30.54 g, 0.50 mol) [44]. The reaction between paraformaldehyde and
aminoethanol yielded 1,3,5-tris(2-hydroxyethyl)hexahydro-1,3,5-triazine [45], which was thermally
cracked to yield 1,3-oxazolidine. The crude distillate (34.4 g, 94%) was collected in a trap chilled at ꢀ
788 and was used without further purification. Crude 1,3-oxazolidine (34.4 g, 0.47 mol) was added to
paraformaldehyde (14.11 g, 0.47 mol) and 2-chloroethanol (37.8 g, 0.47 mol) in Et2O (120 ml) at ꢀ 788.
The temp. was raised to 08 and then slowly to r.t. overnight while stirring continuously. The volatile
materials were removed by evaporation, and the residue was dissolved in H2O. The insoluble material
was filtered, and the filtrate was washed three times with CH2Cl2, and then applied to a column of Hþ-
form cation exchange resin (250 ml). The column was washed with H2O to neutralize the eluent, and
subsequently eluted with 1 to 2m HCl. Solvent evaporation yielded a crude SBO Cl (51.04 g, 66%,
0.31 mol), which was converted to SBO BF4 with 50% HBF4 (54.17 g, 0.31 mol) in MeOH (100 ml) to
immediately generate a white precipitate. The product was filtered and subsequently recrystallized from
H2O, and dried in vacuo at 1008 to yield SBO BF4 (23.55 g, 35%). 1H-NMR ((D6)DMSO): 5.27 (d, J ¼
5.6, 2 H); 5.13 (d, J ¼ 5.6, 2 H); 4.50 (t, J ¼ 7.1, 4 H); 4.19 – 4.07 (m, 4 H). 13C-NMR ((D6)DMSO): 90.0
(m); 66.1 (m); 56.6 (m). 19F-NMR: ꢀ 148.7; ꢀ 148.7.
We would like to thank the Chemistry Department for providing processing and characterization
facilities.
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