Helvetica Chimica Acta ± Vol. 82 (1999)
2361
Si ( H, 13C) and NH
1
NO
�
(15N). Mass spectra were obtained
300WB spectrometer. NMR References are Me
4
4
with a VG-ZAB-E mass spectrometer. M.p. were obtained on a Thomas-Hoover capillary apparatus or on a
Laboratory Devices Mel-Temp II apparatus, and were not corrected. Elemental analyses were performed by
Micro-Analyses Inc., Wilmington, Delaware, or Oneida Research Services, Whitesboro, NY.
1,3-Bis(2,4,6-trimethylphenyl)-2-(ethynyl)imidazolidine (2). To a soln. of 1.0 g (3.26 mmol) of 1,3-bis(2,4,6-
trimethylphenyl)-4,5-dihydroimidazol-2-ylidene (1) in 10 ml of THF were condensed 93 mg (3.59 mmol) of
acetylene at � 1968.The colorless mixture was allowed to warm to 238 and was stirred for 16 h, during which
time it became yellow. The solvent and all volatiles were removed in vacuo, and the resulting oil was
recrystallized from THF at � 258to afford 2 as colorless crystals, which were suitable for X-ray diffraction. Yield:
1
4
1
(
.016 g (93%). M.p. 140 ± 38. H-NMR ((D
s, 4 o-Me); 3.42 (m, NCH ); 3.73 (m, NCH
NMR ((D
8
)THF): 2.22 (s, p-Me); 2.33 (d, J(H,H) 1.62, CꢀCH); 2.41
4
13
1
2
2
); 5.37 (d, J(H,H) 1.62, H� C(2)); 6.84 (s, 2m-CH). C{ H}-
8
)THF): 19.74 (s, o-Me); 20.97 (s, p-Me); 50.54 (s, NCH
2
); 68.96 (s, C(2)); 72.38 (s, CꢀCH); 84.87
(
(
s, CꢀCH); 130.23 (s, C ); 135.95 (s, C ); 139.18 (br. s, Cipso); 139.72 (s, C
m
p
o
). 13C-NMR ((D
8
)THF): 19.74
1
1
3
1
qm, J(C,H) 126.34, o-Me); 20.97 (tq, J(C,H) 125.73, J(C,H) 4.58, p-Me); 50.54 (t, J(C,H) 140.23,
1
1
3
NCH
(
C
(
(
(
(
(
2
); 68.96 (dm, J(C,H) 150.15, C(2)); 72.37 (dd, J(C,H) 148.42, J(C,H) 3.66, CꢀCH); 84.87
2
2
1
2
dd, J(C,H) 47.61, J(C,H) 2.45, CꢀCH); 130.23 (dm, J(C,H) 153.82, C
m
); 135.95 (q, J(C,H) 5.49,
1
5
1
p
); 139.18 (m, Cipso); 139.72 (m, C
o
). N-NMR ((D
8
)THF): � 328.38 (s). H-NMR ((D
8
)THF, � 808): 2.364
4
s, 2 o-Me); 2.438 (s, 2 o-Me); 2.23 (s, 2 p-Me); 2.75 (d, J(H,H) 1.20, CꢀCH); 3.36 (m,NCH
2
); 3.74
13
1
m,NCH
s, o-Me); 21.071 (s, p-Me); 50.697 (s, NCH
s, C ); 130.237 (s, C ); 135.779 (s, C ); 139.463 (s, Cipso); 137.912 (s, C
332.49): C 83.09, H 8.49, N 8.43; found: C 83.21, H 8.50, N 8.21.
,2-Bis[1,3-bis(2,4,6-trimethylphenyl)imidazolidin-2-yl]ethyne (3). A soln. of 100 mg (0.301 mmol) of 2
2
); 5.29 (br. s, H� C(2)); 6.86 (s, 4 m-CH). C{ H}-NMR ((D
); 74.500 (s, C(2)); 72.642 (s, CꢀCH); 85.517 (s, CꢀCH); 130.231
28 2
); 139.624 (s, C ). Anal. calc. for C23H N
8
)THF, � 808): 19.383 (s, o-Me); 20.772
2
m
m
p
o
o
1
and 92 mg (0.301 mmol) of 1 in 10 ml of THF was stirred for 3 d at 238. The solvent volume was reduced in vacuo
and the clear yellow solution stored at � 258 to induce crystallization of 3 as colorless crystals. Yield: 165 mg
1
(
3
86%). M.p. 233 ± 58 (2258 dec.). H-NMR ((D
8
)THF): 2.03 (s, 8 o-Me); 2.29 (s, 4 p-Me); 3.20 (m, 2 NCH
2
);
13
1
.50 (m, 2 NCH
Me); 50.62 (s, NCH
s, C ). Anal. calc. for C44
,3-Bis(2,4,6-trimethylphenyl)-2-[(phenylsulfonyl)methyl]imidazolidine (4). A soln. of 102 mg (0.33 mmol)
of 1 and 55 mg (0.33 mmol) of MeSO Ph in 30 ml of toluene was stirred for 20 h at 238. Evaporation of the
2
); 5.28 (s, 2 H� C(2)); 6.69 (s, 8 m-CH). C{ H}-NMR ((D
); 68.53 (s, C(2)); 84.52 (s, CꢀC); 130.35 (s, C ); 135.21 (s, C
(638.94): C 82.71, H 8.52, N 8.77; found: C 82.83, H 8.54, N 8.66.
8
)THF): 19.34 (s, o-Me); 21.10 (s, p-
2
m
p
); 139.03 (br. s, Cipso); 139.67
(
o
54 4
H N
1
2
volatiles gave a brown oil, which upon recrystallization from hexane furnished a colorless solid. Yield: 100 mg
1
(
3
(
(
65%). M.p. 189 ± 948. Solns. in CD
2
Cl
2
decomposed. H-NMR (C
6
D
6
): 2.12 (s, 2 p-Me); 2.20, 2.24 (s, 2 o-Me);
3
3
.09 (m, NCH ); 3.29 (m, NCH
m, 5 H, Ph); 6.72 (s, 4 m-CH). C-NMR (C
2
2
); 3.43 (d, J(H,H) 6.6, CH
2
SO
2
Ph); 5.55 (t, J(H,H) 6.6, H� C(2)); 6.5 ± 7.7
1
3
6 6 2
D ): 19.64 (br. s, o-Me); 20.88 (s, p-Me); 50.27 (s, NCH ); 62.03
s, CH SO Ph); 72.16 (s, C(2)); 127.62, 128.70, 132.31, 135.46, 136.66, 137.90, 139.07, 140.68 (8s, arom. C). EI-
2
2
MS (70 eV): 463.2414 (5, [M H] ; calc.: 463.2419), 462.2340 (5), M ; calc. for C28
H
34
N
2
O
2
S: 462.2341),
3
[
24.2184 (15, [M � C
7
H
6
OS] ; calc.: 324.2201], 305.1938 (40, [M � C
7 9 2
H O S] ; calc.: 305.2018), 148.1119 (100,
C
10
H
14N] ; calc.: 148.1126).
1,3-Bis(2,4,6-trimethylphenyl)-2-(cyanomethyl)imidazolidine (5). A soln. of 0.275 g (0.900 mmol) of 1 in a
mixture of 5 ml of toluene and 5 ml of MeCN was stirred for 2 h at 238. The mixture was concentrated in vacuo
to give a yellow oily soln. that did not crystallize upon storage at � 258. A few drops of hexane were added,
whereupon storage at � 258 led to the formation of a colorless solid, which was collected by filtration and dried
1
3
in vacuo. Yield: 0.22 g (70%). M.p. 1038. H-NMR (C
6
D
6
): 1.65 (d, J(H,H) 3.3, CH
2
CN); 2.13 (s, 4 o-Me);
3
2
.53 (br. s, 2 p-Me); 3.0 (m, NCH
2
); 3.5 (m, NCH
): 19.80 (br. s, CH
); 130.39 (br., CN); 135.68 (s, C
: 347.2362), 307.2182 (100, [M � CH
2
); 4.83 (t, J(H,H) 3.3, H� C(2)); 6.7 ± 7.0 (m, 4 m-CH).
1
3
C-NMR (C
29.93 (s, C
6
D
6
2
CN); 20.79 (s, o-Me); 23.37 (s, p-Me); 51.03 (s, NCH
); 139.04 (s, C ); 142.91 (s, Cipso). EI-MS (70 eV): 347.2360 (10, M;
CN] ; calc.: 307.2174), 148.1124 (50, C10H14N ; calc.:
2
); 74.34 (s, C(2));
1
p
m
o
calc. for C23
48.1126).
H
29
N
3
2
1
1,3-Bis(2,4,6-trimethylphenyl)-2-(trichloromethyl)imidazolidine (7). To a soln. of 0.153 g (0.500 mmol) of 1
in 20 ml of hexane was added a soln. of 3.60 g (3.00 mmol) of CHCl in 5 ml of hexane. The mixture was stirred
3
for 80 h at 238. Evaporation of the volatiles yielded 7 as a colorless solid which was recrystallized from hexane/
1
Et
.8 (m, NCH
Me); 21.43 (s, p-Me); 51.81 (s, NCH
2s, C ); 138.20 (s, C
); 141.77 (s, Cipso). EI-MS (70 eV): 353.1846 (5, [M � 2 Cl � H] ; calc. for C22
2
O at � 208. Yield: 0.194 g (91%). M.p. 1728 (dec.). H-NMR (C
6 6
D ): 2.14 (s, 2 p-Me); 2.34, 2.49 (2s, 4 o-Me);
13
2
2
); 3.7 (m, NCH
2
); 5.66 (s, H� C(2)); 6.76, 6.84 (2s, 4 m-CH). C-NMR (C
6
D
6
): 20.17, 20.76 (2s, o-
); 133.95, 134.83
2
); 86.46 (s, C(2)); 108.57 (s, Cl C); 130.17, 130.46 (2s, C
3
m
(
o
p
2
H26ClN :