898
M. Limbeck and D. Gündisch
Vol. 40
+
2
7
:24 min, ms (EI): m/z (%) = 155 (30) [M+H] , 112 (8), 84 (100),
The synthesis was done according to method A with
tetrahydrofuran-2-methylchloride 4 (1.206 g, 10 mmol) and mor-
pholine 5d (4.356 g, 50 mmol). Distillation afforded 1d (1.174 g,
1
0 (4), 56 (7); H nmr (500 MHz, CDCl , 25 °C): δ = 1.48 (m, 1
H), 1.75 (m, 4 H), 1.84 (m, 2 H), 1.97 (m, 1 H), 2.48 (dd, J = 4.1
and 12.3 Hz, 1 H), 2.56 (m, 5 H), 3.69 (m, 1 H), 3.84 (m, 1 H),
.98 (m, 1 H); 13C nmr (125 MHz, CDCl , 25 °C): δ = 23.4, 25.5,
0.3, 54.6, 61.0, 67.9, 77.8; ir (CHCl ): = 2920, 2845, 2770,
440, 1130, 1070, 1045, 865 cm . HRMS calcd. for C H NO,
3
2
0
68%) as a colourless oil, bp 115 °C (20 mbar), nD = 1.4704.
+
3
3
1
1
GC: R = 3:01 min, ms (EI): m/z (%) = 172 (14) [M+H] , 100
3
t
1
(100), 73 (13), 70 (23), 56 (11); H nmr (500 MHz, CDCl , 25
3
3
-1
°C): δ = 1.46 (m, 1 H), 1.82 (m, 2 H), 1.95 (m, 1 H), 2.36 (dd, J =
9
17
55.1310. Found: 155.1311.
3.5 and 12.9 Hz, 1 H), 2.46 (m, 5 H), 3.70 (m, 5 H), 3.84 (m, 1
1
3
H), 4.00 (m, 1 H); C nmr (125 MHz, CDCl , 25 °C): δ = 25.4,
3
1
-(Tetrahydrofuran-2-ylmethyl)pyrrolidine (1a).
3
0.3, 54.3, 63.8, 66.9, 68.1, 76.4; ir (CHCl ): = 2940, 2860, 2820,
3
The synthesis was done according to method B with 1,4-dibro-
1452, 1298, 1270, 1115, 1065, 1017, 915, 865 cm-1. HRMS
calcd. for C H NO , 171.1259. Found: 171.1257.
mobutane 3a (2.591 g, 12 mmol), triethylamine (2.529 g, 25
mmol) and tetrahydrofuran-2-methylamine 2 (1.112 g, 11 mmol).
Distillation afforded 1a (0.634 g, 37%) as a colourless oil.
Analytical data correspond with 1a, method A.
9
17
2
1-Ethyl-4-(tetrahydrofuran-2-ylmethyl)piperazine (1e).
The synthesis was done according to method A with tetrahy-
drofuran-2-methylchloride 4 (1.206 g, 10 mmol) and 1-ethyl-
piperazine 5e (5.709 g, 50 mmol). Distillation and column chro-
matography afforded 1e (1.412 g, 71%) as a colourless oil, bp
1
-(Tetrahydrofuran-2-ylmethyl)piperidine (1b).
The synthesis was done according to method A with tetrahy-
drofuran-2-methylchloride 4 (1.206 g, 10 mmol) and piperidine
b (4.258 g, 50 mmol). Distillation afforded 1b (0.842 g, 50%) as
20
1
28-129 °C (14 mbar), nD = 1.4683. GC: R = 4:09 min, ms
t
5
+•
(EI): m/z (%) = 198 (4) [M] , 127 (71), 112 (12), 98 (30), 84
2
0
a colourless oil, bp 110 °C (22 mbar), nD = 1.4749. GC: R =
2
5
H), 1.55 (m, 4 H), 1.81 (m, 2 H), 1.94 (m, 1 H), 2.33 (dd, J = 3.8
and 12.9 Hz, 1 H), 2.41 (m, 5 H), 3.69 (m, 1 H), 3.83 (m, 1 H),
3
2
1
1
t
(100), 70 (88), 56 (33), 42 (65); H nmr (500 MHz, CDCl ,
3
+
:48 min, ms (EI): m/z (%) = 170 (18) [M+H] , 98 (100), 70 (27),
25 °C): δ = 1.05 (t, J = 7.3 Hz, 3 H), 1.46 (m, 1 H), 1.82 (m, 2 H),
1
5 (4), 42 (13); H nmr (500 MHz, CDCl , 25 °C): δ = 1.41 (m, 3
3
1.95 (m, 1 H), 2.35-2.74 (m, 12 H), 3.68 (m, 1 H), 3.82 (m, 1 H),
13
4
.00 (m, 1 H); C nmr (125 MHz, CDCl , 25 °C): δ = 11.9, 25.4,
3
3
0.4, 52.3, 52.7, 53.8, 63.4, 68.1, 76.7; ir (CHCl ): = 2940, 2860,
3
.99 (m, 1 H); 13C nmr (125 MHz, CDCl , 25 °C): δ = 24.3, 25.4,
-1
3
2820, 1450, 1380, 1305, 1160, 1015, 930 cm . HRMS calcd. for
5.9, 30.5, 55.1, 64.2, 68.0, 77.3; ir (CHCl ): = 2920, 2850, 2780,
3
C H N O, 198.1733. Found: 198.1741.
11 22 2
-1
435, 1295, 1150, 1070, 1050, 980, 855 cm . HRMS calcd. for
Anal. Calcd. for C H N O (198.3): C, 66.62; H, 11.18; N,
11 22 2
C H NO, 169.1467. Found: 169.1464.
10
19
14.13. Found: C, 66.35; H, 11.11; N, 14.02.
1-(Tetrahydrofuran-2-ylmethyl)piperidine (1b).
1-Methyl-4-(tetrahydrofuran-2-ylmethyl)piperazine (1f).
The synthesis was done according to method B with 1,5-dibro-
The synthesis was done according to method A with tetrahy-
mopentane 3b (5.518 g, 24 mmol), triethylamine (5.060 g, 50
mmol) and tetrahydrofuran-2-methylamine 2 (2.225 g, 22 mmol).
Distillation afforded 1b (1.283 g, 34%) as a colourless oil.
Analytical data correspond with 1b, method A.
drofuran-2-methylchloride 4 (1.206 g, 10 mmol) and 1-methyl-
piperazine 5f (5.709 g, 50 mmol). Distillation and column chro-
matography afforded 1f (1.345 g, 73%) as a colourless oil, bp
20
1
20-121 °C (20 mbar), nD = 1.4793; GC: R = 3:27 min, ms
t
+
•
(
(
(
(
EI): m/z (%) = 184 (8) [M] , 113(48), 98 (15), 70 (100), 42
45); H nmr (500 MHz, CDCl , 25 °C): δ = 1.46 (m, 1 H), 1.82
m, 2 H), 1.95 (m, 1 H), 2.25 (s, 3 H), 2.31-2.75 (m, 9 H), 3.71
m, 1 H), 3.84 (m, 1 H), 3.99 (m, 1 H); C nmr (125 MHz,
1-(Tetrahydrofuran-2-ylmethyl)azepane (1c).
1
3
The synthesis was done according to method A with tetrahy-
drofuran-2-methylchloride 4 (1.206 g, 10 mmol) and azepane 5c
4.959 g, 50 mmol). Distillation afforded 1c (1.631 g, 89%) as a
1
3
(
CDCl , 25 °C): δ = 25.4, 30.4, 46.0, 53.8, 55.0, 63.3, 68.1, 76.7;
3
2
0
colourless oil, bp 109 °C (15 mbar), nD = 1.4797. GC: R = 3:38
min, ms (EI): m/z (%) = 184 (6) [M+H] , 112 (100), 84 (4), 58
(
t
ir (CHCl ): = 2920, 2800, 2780, 1455, 1282, 1160, 1010, 920
3
+
-
1
cm . HRMS calcd. for C10H20N O, 184.1576. Found:
2
1
86), 44 (8); H nmr (500 MHz, CDCl , 25 °C): δ = 1.49 (m, 1H),
3
1
84.1579.
1
.54-1.61 (m, 8 H), 1.82 (m, 2 H), 1.95 (m, 1 H), 2.51 (dd, J = 4.6
and 13.1 Hz, 1 H), 2.61 (dd, J = 6.9 and 13.1 Hz, 1 H), 2.70 (m, 4
4-(Tetrahydrofuran-2-ylmethyl)piperazine-1-carboxylic Acid
Ethylester (1g).
1
3
H), 3.70 (m, 1 H), 3.84 (m, 1 H), 3.96 (m, 1 H); C nmr (125
MHz, CDCl , 25 °C): δ = 25.4, 27.1, 27.8, 30.3, 56.0, 62.1, 68.0,
3
The synthesis was done according to method A with tetrahy-
drofuran-2-methylchloride 4 (1.206 g, 10 mmol) and ethyl 1-
piperazinecarboxylate 5g (7.997 g, 33 mmol). Distillation and
column chromatography afforded 1g (1.965 g, 81%) as a light
7
1
7.7; ir (CHCl ): = 2910, 2850, 1445, 1355, 1335, 1132, 1065,
020, 955, 910 cm . HRMS calcd. for C H NO, 183.1230.
11 21
3
-
1
Found: 183.1230.
Anal. Calcd. for C H NO (183.3): C, 72.08; H, 11.55; N,
20
11
21
yellow oil, bp 132-135 °C (12 mbar), nD = 1.4858; GC: R =
t
7
1
.64. Found: C, 71.69; H, 11.31; N, 7.51.
+•
7
9
:38 min, ms (EI): m/z (%) = 242 (4) [M] , 171 (100), 143 (40),
7 (53), 70 (12), 56 (14), 42 (12); H nmr (500 MHz, CDCl , 25
1
-(Tetrahydrofuran-2-ylmethyl)azepane (1c).
3
°C): δ = 1.22 (t, J = 7.1 Hz, 3 H), 1.46 (m, 1 H), 1.83 (m, 2 H),
The synthesis was done according to method B with 1,6-dibro-
1
3
.95 (m, 1 H), 2.36-2.48 (m, 6 H), 3.46 (m, 4 H), 3.71 (m, 1 H),
.85 (m, 1 H), 4.00 (m, 1 H), 4.09 (q, J = 7.1 Hz, 2 H); 13C nmr
mohexane 3c (5.367 g, 22 mmol), triethylamine (5.060 g, 50
mmol) and tetrahydrofuran-2-methylamine 2 (2.023 g, 20 mmol).
Distillation afforded 1c (1.129 g, 31%) as a colourless oil.
Analytical data correspond with 1c, method A.
(
125 MHz, CDCl , 25 °C): δ = 14.7, 25.4, 30.3, 43.6, 53.5, 61.2,
3
6
1
3.4, 68.2, 76.6, 155.5; ir (CHCl ): = 2975, 2900, 2850, 1700,
3
472, 1445, 1300, 1258, 1150, 1115, 840 cm . HRMS calcd. for
-1
4-(Tetrahydrofuran-2-ylmethyl)morpholine (1d).
C H N O , 242.1630. Found, 242.1635.
12 22 2 3