R. Huisgen et al. / Tetrahedron 61 (2005) 6143–6153
6151
C
152.144/152.144 (35) [C H N ], 137.133/137.133 (100)
10 18
contained, according to the IR spectrum, mainly 9C and
lactams 15 (hydration product of 9C).
C
C
[C H , 18], 136.125/136.124 (8) [C H ], 121.101/
0
1
17
10 16
C
C
1
21.101 (12) [C H ], 96.081/96.083 (12) [C H N ],
9 13 6 10
95.086/95.085 (14) [C H11; methylcyclohexenyl or
7
dimethylcyclopentyl ], 82.078/82.076 (42) [C H10],
6
71.073/71.074 (34) [C H N ], 69.070/69.070 (47)
4 9
C
C
3.3.5. 11-Methoxy-1,1,5,5-tetramethyl-9,10-bis(trifluoro-
methyl)-7-thia-12-azaspiro[5.6]dodec-11-ene-9-carboni-
C
C
C
trile (14). Ketene imine 9C (1.0 mmol) was dissolved in
CHCl (5 mL) and MeOH (0.1 mL). After one hour at rt, the
C
C
C
[C
68.995/68.995 (8) [CF
H , dimethylallyl ], 69.058/69.057 (33) [C H N ],
5 9 4 7
3
1
solvent was removed and H NMR analysis indicated 67%
C
3
C
], 55.055/55.055 (22) [C
H F N
22 6 2
H ,
4 7
C
methallyl ]. Anal. Calcd for C17 OS (416.43): C,
of 14. The colorless lactim ether (46%) crystallized from
MeOH. Mp 106–108 8C. IR (KBr): n 983m cm ; 1167s,
K1
49.03; H, 5.33; N, 6.73. Found: C, 49.24; H, 5.30; N, 6.50.
1
207s, 1249s, 1279s (C–F), 1690s (C]N). H NMR
80 MHz): d 1.04, 1.10, 1.21, 1.30 (4s, 4Me), 1.0 – 2.1
1
(
3.4. Reactions of thiocarbonyl ylide 1C with
ethenetetracarbonitrile (TCNE)
2
(
m, 3CH ), 3.22, 3.55 (AB, JZ15.4 Hz, 8-H ), 3.83 (s,
2
2
13
3
OMe), 5.24 (q, J(F,H)Z8.2 Hz, 10-H).
C NMR
(
4
20.2 MHz): d 18.9(t, C-3), 24.7, 26.0, 29.6, 29.8 (4q,
3.4.1. 6,6,10,10-Tetramethyl-1-thiaspiro[4,5]decane-
3,3,4,4-tetracarbonitrile (3C). Dihydrothiadiazole 7C
(425 mg, 2.00 mmol) and TCNE (282 mg, 2.20 mmol) in
C H (10 mL) were refluxed for 20 h. After removal of the
3
Me), 37.0 (tq, J(C,F)Z2.4 Hz, C-8), 37.2, 37.9 (2t, C-2,
2
C-4), 43.1, 46.6 (2s, C-1, C-5), 45.4 (q, J(C,F)Z31.7 Hz,
C-9), 48.5 (dq, J(C,F)Z30.5 Hz, C-10), 54.3 (s, OMe),
2
6
6
3
1
8
1.9 (s, C-6), 113.7 (q, J(C,F)Z2.0 Hz, CN), 122.7 (q,
solvent, the H NMR analysis in CDCl with trichloroethene
3
1
1
J(C,F)Z285.6 Hz, CF ), 123.2 (q, J(C,F)Z280.8 Hz,
indicated quantitative formation of 3C. From MeOH, 3C
(330 mg, 54%) was isolated as yellow plates, mp 181 8C
(dec.). IR (KBr): n 980m cm , 1398m, 1404m, 1433m,
3
9
1
CF ), 148.2 (s, C-11). F NMR (376 MHz): d K61.9 (dq,
3
3
5
5
K1
J(F,H)w8 Hz, J(F,F)Z9.1 Hz, 10-CF ), K69.0 (q,
3
1
J(F,F)Z9.2 Hz, 9-CF ). MS (MAT 90, CMass), m/z (%):
1465m, 2250vw (C^N). H NMR (80 MHz): d 1.60 (s,
4Me), 1.28 – 1.75 (m, 6 ring-H), 3.58 (s, 2-H2). C NMR
3
C C
30.151/430.151 (10) [M ], 415.127/415.124 (8) [M K
13
4
Me], 372.176/372.176 (32) [C H F NO ], M KSKCN,
C
C
(20.2 MHz): d 17.5 (t, C-8), 25.9, 32.3 (2s, 2!2 Me), 41.3
(t, C-2), 42.1 (t, C-7CC-9), 42.6 (s, C-6CC-10), 51.6, 55.0
(2s, C-3, C-4), 84.2 (s, C-5), 111.1, 112.7 (2s, 2!2 CN). MS
1
7 24 6
1
3
C
C 6.1/7.0], 348.073/348.071 (10) [C H F N OS ,
1
2
14
6
2
C
M KC H ], 346.057/346.058 (10) [348K2H], 305.018/
6
10
C
C
05.018 (12) [C H F N OS , M KC H ], 278.007/
C
C
3
2
8
1
(80 8C), m/z (%): 297 (3) [M KMe], 285 (3) [M KHCN],
13 34
9
7
6
2
9 17
C C
78.008 (100) [C H F NOS , M KHCNKC H ,
13
C
C
.9/9.0], 152.144/152.143 (31) [C H N ], 141 (23),
259 (8) [M KHCNKCN; C C S 0.44/0.49], 234 (8)
2
13 13 34
[C H N S , M KH C]C(CN) ; C 1.1/1.1; C C S
13 18 2 2 2 2
0.42/0.48], 228 (32) [C H N S , M KC H ; HR
11 8 4 6 12
8
6
6
9
17
C
C
C
1
0
18
C
17
C
C
37.133/137.134 (15) [C H , 18], 136.037/136.039 (18)
1
0
C
3
C
C
S , 234KMe;
[
C H NF ], 107 (23), 105 (10), 95.086/95.086 (9) [C H ],
5
228.0469/228.0474], 219 (20) [C12
H
15
N
C 2.6/2.3], 201 (28) [C H N S , 228KHCN; HR
2
5
7 11
C
C
13
C
8
7
6
5
(
5
9.039/89.042 (26) [C H S ], 79.053/79.053 (9) [C H ],
4 9 6 7
7.039/77.040 (45) [C H ], 69.070/69.070 (37) [C H ],
8.995/68.995 (5) [CF ], 68.050/68.057 (11) [C H N ],
5.055/55.054 (37) [C H ]. Anal. Calcd for C H F N OS
4
10 7 3
C
C
9
C
C
201.036/201.019], 187 (31) [C H N , possibly dicyano-
2
methylene-trimethylcyclohexyl ; C 4.1/4.3], 174 (11),
152 (13), 150 (33), 149 (13), 147 (16), 146 (13), 145 (15),
6
C
5
5
12 15
13
C
3
4 6
C
7
18 24 6 2
C
13
430.45): C, 50.22; H, 5.62; N, 6.51. Found: C, 50.29; H,
.59; N, 6.58.
134 (33) [C H ; C 3.5/3.8; HR 134.109/134.096], 133
10 14
C
C
(78) [C H ], 119 (17), 106 (18), 91 (11) [tropylium ], 83
10 13
C
C
C
(
57) [C H , trimethylallyl ], 78 (54) [C H N , methyl-
6 11 4 2 2
C
C
3.3.6. 1,1,5,5-Tetramethyl-11-oxo-9,10-bis(trifluoro-
methyl)-7-thia-12-azaspiro[5.6] dodecane-9-carbonitrile
(
enemalononitrile ; HR 78.022/78.023], 77 (35) [C H ], 70
6 5
C
10
13
C
(100) [C C 5.6/5.9], 69 (65) [dimethylallyl ], 55
(77) [methylallyl ]. Anal. Calcd for C17H N S (312.43):
20 4
H
,
5
C
15). Ketene imine 9C (1.0 mmol) was reacted with H O
2
(
MeOH. Mp 192–193 8C (green, gas evol.). IR (KBr): n
0.25 mL) in THF (20 mL) 1 h at rt and gave 15 (48%) from
C, 65.35; H, 6.45; N, 17.93. Found: C, 64.94; H, 6.60; N,
17.84.
K1
126 s cm , 1169s, 1213s, 1268s (C–F), 1636vs (C]O),
1
3
1
260m br (N–H). H NMR (80 MHz): d 1.11, 1.35 (2s,
3.4.2. Interception of ketene imine 4C. In a cursory
experiment, 7C (198 mmol) and TCNE (258 mmol) in C H
6 6
2
Me), 1.25 (s, 2Me), 1.3–1.8 (br s, 3CH ), 3.27, 3.66 (AB,
2
2
JZ16.5 Hz, right branch broadened, 8-H ), 5.20 (q,
J(C,F)Z6.8 Hz, 10-H), 6.70 (s, br, NH). C NMR
100.6 MHz, DEPT): d 17.9 (C-3), 24.8, 26.6, 28.4, 30.1
(5 mL)CMeOH (100 mL, 2.5 mmol) were heated to 80 8C
for 20 h. After evaporation of the solvent, the H NMR
2
3
13
1
(
(
(
(
signals (CDCl
3
) of MeO (s, d 3.83) and 8-H
AB, JZ16.2 Hz) are indicative of the lactim methyl ether
5C. Quantitative analysis with sym-C Cl pointed to 68%
2
(d 3.32, 3.56,
2
slightly broadened, 4Me), 36.35, 36.83 (C-2, C-4), 36.45
J(C,F)Z1.9 Hz, C-8), 43.8, 44.8 (C-1, C-5), 44.6
3
H
2
2
4
2
2
J(C,F)Z29.4 Hz, C-9), 49.4 ( J(C,F)Z29.4 Hz, C-10),
of 5C and 13% of thiolane 3C. During 20 h at 80 8C, part of
the TCNE probably reacted with the MeOH, before 1C was
completely set free.
3
1
7
7.2 (C-6), 112.7 ( J(C,F)Z1.9 Hz, CN), 122.51 ( J(C,F)Z
1
2
(
86.1 Hz, CF ), 122.76 ( J(C,F)Z280.6 Hz, CF ), 163.8
3
3
1
9
C]O). F NMR (376 MHz): d K61.9 (dq, 6 lines visible,
5
5
3
J(F,F)Z9.2 Hz, J(H,F)z9 Hz, 10-CF ), K69.0 (q,
J(F,F)Z9.2 Hz, 9-CF ). MS (MAT 95Q, CMass), m/z
3.5. Reactions of 1C with dimethyl 2,3-dicyanofumarate
((E)-26) and dimethyl 2,3-dicyanomaleate ((Z)-26)
3
3
C
%): 416.135/416.134 (0.8) [M ], 358.160/358.161 (6)
(
C
C
13
C H F NO , M KSKCN; C 2.8/2.4], 334.057/
[
3.5.1. Isolation of spirothiolanes. Dihydrothiadiazole 7C
(1.06 g, 5.0 mmol) and (Z)-26 (1.07 g, 5.5 mmol) in abs.
octane (10 mL) were reacted in the 130 8C bath for 10 min.
1
6
22 6
C
C
13
34
3
34.058 (29) [C H F N OS , M KC H ; C C S
11 12 6 2 6 10 2
C C
.3/4.4], 247.031/247.033 (13) [C H F N O , M K6CC
4
H], 224 (12), 211.028/211.029 (6) [C H F NOS ],
7
5 6 2
C
PLC (Et O/pentane 30:70, 2!) furnished trans-28C
2
7
8
3