1
042
M. Kitamura et al.
PAPER
6
l
fied by flash column chromatography (silica gel; hexane–EtOAc) to
give the pure 2-diazo-1,3-dicarbonyl compound.
5-Diazo-2,2-dimethyl-1,3-dioxane-4,6-dione (7h)
IR (Nujol): 2177, 1714, 1194, 1167 cm .
–
1
1
H NMR (400 MHz, CDCl ): d = 1.79 (s, 6 H).
6
l
3
2
-Diazo-1-phenylbutane-1,3-dione (7a)
1
3
–
1
C NMR (100 MHz, CDCl ): d = 158.2, 107.0, 64.9, 26.7.
3
IR (Nujol): 2114, 1651 cm .
1
Anal. Calcd for C H N O : C, 42.36; H, 3.55; N, 16.47. Found: C,
10 8 2 2
H NMR (400 MHz, CDCl ): d = 7.65 (m, 2 H), 7.58 (tt, J = 7.4,
3
4
2.34; H, 3.59; N, 16.43.
1
.6 Hz, 1 H), 7.50 (m, 2 H), 2.58 (s, 3 H).
1
3
C NMR (100 MHz, CDCl ): d = 190.7, 185.0, 137.3, 132.6, 128.9,
-Diazoindane-1,3-dione (7i)6g
IR (Nujol): 2127, 1682, 1545 cm .
3
2
1
27.3, 83.7, 29.2.
–1
Anal. Calcd for C H N O : C, 63.82; H, 4.28; N, 14.89. Found: C,
1
10
8
2
2
H NMR (400 MHz, CDCl ): d = 7.83–7.86 (m, 2 H), 7.75–7.77 (m,
3
6
3.81; H, 4.38; N, 14.81.
2
H).
1
3
C NMR (100 MHz, CDCl ): d = 182.1, 137.0, 134.7, 122.6, 70.1.
2
-Diazopentane-1,3-dione (7b)
3
–
1
IR (neat): 2368, 2268, 2125, 1666, 1225, 1136, 1049, 1024 cm .
6
k
Diethyl 1-Diazo-2-oxopropylphosphonate (12a)
IR (neat): 2987, 2119, 1659, 1269 cm .
1
H NMR (400 MHz, CDCl ): d = 2.44 (s, 6 H).
–1
3
1
3
C NMR (100 MHz, CDCl ): d = 188.2, 84.5, 28.4.
1
3
H NMR (400 MHz, CDCl ): d = 4.28–4.16 (m, 4 H), 2.29 (s, 3 H),
3
HRMS (EI): m/z calcd for C H N O :126.0429; found: 126.0435.
1.40 (dt, J = 7.1, 0.6 Hz, 6 H).
5
6
2
2
1
3
C NMR (100 MHz, CDCl ): d = 189.8 (d, J = 13.2 Hz), 63.2 (d,
-Diazo-1,3-diphenylpropane-1,3-dione (7c)6k
IR (Nujol): 2117, 1641, 1595, 1317, 1261, 1174 cm .
3
2
J = 5.6 Hz), 27.0, 15.9 (d, J = 6.7 Hz).
–
1
HRMS (EI): m/z calcd for C H N O P: 220.0613; found:
2
1
7
13
2
4
H NMR (400 MHz, CDCl ): d = 7.57 (d, J = 8.2 Hz, 4 H), 7.44 (t,
3
20.0595.
J = 7.4 Hz, 2 H), 7.31 (t, J = 7.8 Hz, 4 H).
1
3
Ethyl Diazo(diethoxyphosphoryl)acetate (12b)20a,b
IR (neat): 2133, 1705, 1479, 1446, 1392, 1369, 1306 cm .
C NMR (100 MHz, CDCl ): d = 186.4, 137.0, 132.6, 128.4, 128.3,
3
–
1
8
4.4.
1
Anal. Calcd for C H N O : C, 71.99; H, 4.03; N, 11.19. Found C,
H NMR (400 MHz, CDCl ): d = 4.17–4.30 (m, 6 H), 1.37 (t, J =
10
8
2
2
3
7
1.90; H, 4.17; N, 11.21.
7.1 Hz, 6 H), 1.31 (t, J = 7.1 Hz, 3 H).
1
3
C NMR (100 MHz, CDCl ): d = 163.4 (d, J = 48.8 Hz), 63.6 (d,
Ethyl 2-Diazo-3-oxobutyrate (7d)6l
3
J = 23.2 Hz), 61.6, 16.1 (d, J = 27.6 Hz), 14.3.
IR (neat): 2985, 2937, 2393, 2134, 1726, 1660, 1651, 1373, 1319,
–1
HRMS (EI): m/z calcd for C H N O P: 250.0719; found:
2
1
176, 1074, 1022 cm .
8
15
2
5
50.0707.
1
H NMR (400 MHz, CDCl ): d = 4.31 (q, J = 7.1 Hz, 2 H), 2.48 (s,
3
3
H), 1.34 (t, J = 7.1 Hz, 3 H).
20c
Dimethyl 1-Diazo-2-oxopropylphosphonate (12c)
IR (neat): 2854, 2123, 1660, 1363, 1273, 1028 cm .
1
3
–1
C NMR (100 MHz, CDCl ): d = 190.1, 161.3, 76.3, 61.3, 28.1,
3
1
4.2.
1
H NMR (400 MHz, CDCl ): d = 3.86 (d, J = 11.9 Hz, 6 H), 2.28 (s,
3
HRMS (EI): m/z calcd for C H N O :156.0535; found: 156.0523.
3 H).
6
8
2
3
1
3
C NMR (100 MHz, CDCl ): d = 189.6 (d, J = 12.9 Hz), 53.4 (d,
3
2
-Diazo-3-oxobutyric Acid N,N-Dimethyl Amide (7e)
J = 5.6 Hz), 26.9.
–
1
IR (neat): 3473, 2112, 1633, 1497, 1398, 1298, 1057 cm .
HRMS (EI): m/z calcd for C H N O P: 192.0300; found: 192.0270.
1
5
9
2
4
H NMR (400 MHz, CDCl ): d = 3.02 (s, 6 H), 2.36 (s, 3 H).
3
1
3
C NMR (100 MHz, CDCl ): d = 189.3, 161.1, 73.1, 37.3, 27.0.
2-Chloro-1,3-dimethylimidazolinium Hexafluorophosphate
3
1
7b
+
(5b)
To a solution of 2-chloro-1,3-dimethylimidazolinium chloride (5a;
.24 g, 7.3 mmol) in MeCN (2 mL) was added potassium hexafluo-
HRMS (FAB): m/z [M + H] calcd for C H N O :156.0773; found:
1
6
9
3
2
56.0800.
1
Diethyl 2-Diazomalonate (7f)6l
IR (neat): 2985, 2141, 1765, 1373, 1323, 1095 cm .
rophosphate (1.32 g, 7.2 mmol) in MeCN (5 mL), and the mixture
was stirred for 10 min at r.t. The mixture was filtered through a
Celite pad and the filtrate was concentrated in vacuo. The residue
was dissolved with a small amount of MeCN (ca. 2 mL) and the so-
–
1
1
H NMR (400 MHz, CDCl ): d = 4.31 (q, J = 7.1 Hz, 4 H), 1.32 (t,
3
J = 7.1 Hz, 6 H).
lution was poured into Et O to form a precipitate, which was col-
2
1
3
lected by suction filtration to afford chloroimidazolinium
hexafluorophosphate 5b.
C NMR (100 MHz, CDCl ): d = 160.9, 65.3, 61.5, 14.2.
3
HRMS (EI): m/z calcd for C H N O :186.0641; found: 186.0659.
7
10
2
4
Yield: 1.91 g (94%); mp 230–231 °C.
IR (Nujol): 2362, 2320, 1641, 1551, 1338, 1308 cm–1.
2
-Diazo-5,5-dimethylcyclohexane-1,3-dione (7g)6g
IR (Nujol): 2359, 2341, 2189, 2137, 1660, 1633, 1306, 1277, 1265
1H NMR (400 MHz, CD
13C NMR (100 MHz, CD
Anal. Calcd for C
C, 21.29; H, 3.48; N, 9.73.
CN): d = 3.89 (s, 4 H), 3.08 (s, 6 H).
CN): d = 35.2, 50.9.
H10ClF N P: C, 21.56; H, 3.62; N, 10.06. Found:
5 6 2
–
1
3
cm .
1
3
H NMR (400 MHz, CDCl ): d = 2.45 (s, 4 H), 1.13 (s, 6 H).
3
1
3
C NMR (100 MHz, CDCl ): d = 189.8, 83.7, 50.5, 31.1, 28.3.
3
Anal. Calcd for C H N O : C, 57.82; H, 6.07; N, 16.86. Found C,
10
8
2
2
5
7.84; H, 6.06; N, 16.74.
Synthesis 2011, No. 7, 1037–1044 © Thieme Stuttgart · New York