938
A. V. Ivachtchenko, D. V. Kravchenko, V. I. Zheludeva, D. G. Pershin
Vol. 41
279.21243. Calculated for C
–0.6.
H
BN O , 279.21179; dm (mmu)
Anal. Calcd. for C H BN O : C, 62.41; H, 9.27; B, 4.32; N,
13 23 2 2
11.19. Found: C, 62.42; H, 9.42; B, 4.41; N, 11.40.
14 26
3
2
Anal. Calcd. for C
15.05. Found: C, 60.28; H, 9.57; B, 3.51; N, 15.43.
H BN O : C, 60.22; H, 9.39; B, 3.87; N,
14 26 3 2
1-Propyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-
pyrazole (18c).
1-(3,3-Diethoxypropyl)-4-(4,4,5,5-tetramethyl-1,3,2-diox-
aborolan-2-yl)-1H-pyrazole (10g).
D
This compound was obtained in 82% yield as an oil; n
20
11
1.4739; bp 78-80 °C/0.02 mm Hg; B NMR (CDCl , ppm):
δ+27.8; H NMR (DMSO-d , ppm): δ 0.75 (t, 3H, CH CH , J =
3
1
D
This compound was obtained in 70% yield as an oil; n
6
3
2
20
11
1
7.4 Hz), 1.26 (s, 12H, (CH ) C-O), 1.70-1.80 (m, 2H, CH CH ),
1.4695; B NMR (CDCl , ppm): δ+29.5; H NMR (DMSO-d ,
3 2
2
3
3
6
4
4.28 (t, 2H, CH N, J = 6.3 Hz), 6.60 (s, 1H, C H), 7.40 (s, 1H,
C H); C NMR (DMSO-d , ppm): δ 10.8 (CH CH ), 24.1
ppm): δ 1.07 (t, 6H, CH , J = 6.2 Hz), 1.18 (s, 12H, (CH ) C-O),
2
3
3 2
3
13
2.08 (m, 2H, CH CH), 3.42-3.66 (m, 4H, CH O), 4.10 (t, 2H,
6
3
2
2
2
(CH CH ), 24.5 ((CH ) C-O), 52.6 (CH N), 83.8 ((CH ) C-O),
CH N, J = 6.8 Hz), 4.22 (t, 1H,O-CH-O, J = 5.8 Hz), 7.63 (s, 1H,
2
3
3 2
2
3 2
2
4
3
+
+
3
5
13
115.2 (C ), 137.9 (C ); MS, m/z: 236 ([M] ), 221 ([M-CH ] ),
C H), 7.77 (s, 1H, C H); C NMR (DMSO-d , ppm): δ 15.2
3
6
+
+
208 ([M-C H ] ). HRMS: Found, [M] , 236.16839. Calculated
(CH CH ), 24.6 ((CH ) C-O), 34.0 (CH CH), 47.0 (CH N), 60.7
2
4
3
2
3 2
2
2
3
for C
H BN O , 236.16960; dm (mmu) +1.2.
(CH O), 82.5 ((CH ) C-O), 99.7 (O-CH-O), 136.3 (C ), 140.0
12 21 2 2
2
3 2
5
+
+
+
(C ); MS, m/z: 324 ([M] ), 309 ([M-CH ] ), 295 ([M-C H ] ),
279 ([M-C H O] ), 251 ([M-C H O] ), 207 ([M-C H O ] ).
HRMS: Found, [M-C H ] , 295.18372. Calculated for
Anal. Calcd. for C H BN O : C, 61.04; H, 8.96; B, 4.58; N,
3
2
5
12 21 2 2
+
+
+
11.86. Found: C, 61.09; H, 9.13; B, 4.54; N, 12.08.
2
5
4
9
5 11 2
+
2
5
1-(3-Methylbutyl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-
yl)-1H-pyrazole (18d).
C
H BN O , 295.18290; dm (mmu) –0.8.
14 24 2 4
Anal. Calcd. for C
H BN O : C, 59.27; H, 9.02; B, 3.34; N,
16 29 2 4
D
This compound was obtained in 90% yield as an oil; n
8.64. Found: C, 59.31; H, 9.14; B, 3.51; N, 8.68.
20
11
1
1.4718; B NMR (CDCl , ppm): δ+27.7; H NMR (DMSO-d ,
3
6
1,3,5-Trimethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-
1H-pyrazole (15).
ppm): δ 0.87 (d, 6H, CH , J = 7.2 Hz), 1.30 (s, 12H, (CH ) C-O),
3
3 2
1.40-1.50 (m, 1H, (CH ) CH), 1.60-1.68 (m, 2H,CH CH N),
3 2
2
2
4
This compound was obtained in 65% yield as a solid; mp 98-
4.34 (t, 2H, CH N, J = 7.2 Hz), 6.60 (s, 1H, C H), 7.45 (s, 1H,
C H); C NMR (DMSO-d , ppm): δ 22.2 ((CH ) CH), 24.5
6 3 2
2
11
1
3
13
100 °C; B NMR (CDCl , ppm): δ+29.7; H NMR (DMSO-d ,
3
6
3
ppm): δ 1.25 (s, 12H, (CH ) C-O), 2.15 (s, 3H, CH -C ), 2.28 (s,
((CH ) C-O), 25.1 (,(CH ) CH), 39.8 (CH CH N), 49.6
3 2
3
3 2 3 2 2 2
5
13
4
3
3H, CH -C ), 3.60 (s, 3H, CH N); C NMR (DMSO-d , ppm):
(CH N), 83.7 ((CH ) C-O), 114.9 (C ), 137.4 (C ); MS, m/z: 264
2 3 2
3
3
6
3
5
+
+
+
δ 10.8 (CH -C ), 13.7 (CH -C ), 24.6 ((CH ) C-O), 35.1
(CH N), 82.0 ((CH ) C-O), 146.6 (C ), 152.2 (C ); MS, m/z: 236
([M] ), 221 ([M-CH ] ), 108 ([M-C H O] ). HRMS: Found,
[M] , 236.17063. Calculated for C
(mmu) –1.0.
([M] ), 249 ([M-CH ] ), 207 ([M-C H ] ). HRMS: Found,
3
3
3 2
3 4 9
3
5
+
[M] , 264.20232. Calculated for C
(mmu) –1.4.
H BN O , 264.20090; dm
14 25 2 2
3
3 2
+
+
+
3
6 12
+
H
BN O , 236.16960; dm
Anal. Calcd. for C H BN O : C, 63.65; H, 9.54; B, 4.09; N,
12 21
2
2
14 25 2 2
10.60. Found: C, 63.40; H, 9.62; B, 3.73; N, 10.88.
Anal. Calcd. for C
11.86. Found: C, 61.18; H, 9.27; B, 4.66; N, 11.84.
H BN O : C, 61.04; H, 8.96; B, 4.58; N,
12 21 2 2
1-(3,3-Diethoxypropyl)-5-(4,4,5,5-tetramethyl-1,3,2-diox-
aborolan-2-yl)-1H-pyrazole (18e).
1-Methyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-
pyrazole (18a).
D
This compound was obtained in 70% yield as an oil; n
20
11
1
1.4670; B NMR (CDCl , ppm): δ+27.9; H NMR (DMSO-d ,
3
6
This compound was obtained in 84% yield as a solid; mp 74-
ppm): δ 1.05 (t, 6H, CH , J = 6.2 Hz), 1.18 (s, 12H, (CH ) C-O),
1.98-2.10 (m, 2H, CH CH), 3.42-3.58 (m, 4H, CH O), 4.18 (t,
2 2
3 3 2
11
1
75 °C; B NMR (CDCl , ppm): δ+27.7; H NMR (DMSO-d ,
3
6
ppm): δ 1.30 (s, 12H, (CH ) C-O), 3.93 (s, 3H, CH N), 6.60 (s,
2H, CH N, J =6.9 Hz), 4.22 (t, 1H, O-CH-O, J = 5.4 Hz), 6.60 (s,
1H, C H), 7.46 (s, 1H, C H); C NMR (DMSO-d , ppm): δ 15.2
6
3 2
13
3
2
4
3
4
3
13
1H, C H), 7.42 (s, 1H, C H); C NMR (DMSO-d , ppm): δ 24.5
6
4
((CH ) C-O), 39.0 (CH N), 84.0 ((CH ) C-O), 115.4 (C ), 137.8
(CH CH ), 24.5 ((CH ) C-O), 34.8 (CH CH), 47.4 (CH N), 60.5
3 2
3
3 2
3 2 3 2 2 2
3
+
+
4
(C ); MS, m/z: 208 ([M] ), 193 ([M-CH ] ), 109 ([M-
(CH O), 83.9 ((CH ) C-O), 100.0 (O-CH-O), 115.4 (C ), 138.0
2 3 2
3
+
+
3
+
+
C H O] ). HRMS: Found, [M] , 208.13957. Calculated for
(C ); MS, m/z: 324 ([M] ), 295 ([M-C H ] ), 279 ([M-
6
11
2 5
+
+
+
C
H
BN O , 208.13830; dm (mmu) –1.3.
C H O] ), 251 ([M-C H O] ). HRMS: Found, [M-C H ] ,
2 5 4 9 2 5
10 17
2
2
Anal. Calcd. for C
H
BN O : C, 57.72; H, 8.24; B, 5.20; N,
295.18118. Calculated for C
H BN O , 295.18290; dm (mmu)
10 17
2
2
14 24 2 4
+1.7.
13.46. Found: C, 58.00; H, 8.38; B, 5.26; N, 13.40.
Anal. Calcd. for C
8.64. Found: C, 59.36; H, 9.23; B, 2.99; N, 8.84.
H BN O : C, 59.27; H, 9.02; B, 3.34; N,
16 29 2 4
1-Isobutyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-
pyrazole (18b).
1,3-Dimethyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-
1H-pyrazole (24a).
This compound was obtained in 88% yield as a solid; mp 40-
11
1
42 °C; B NMR (CDCl , ppm): δ+27.8; H NMR (DMSO-d ,
3
6
D
ppm): δ 0.80 (d, 6H, (CH ) CH, J = 5.4 Hz), 1.28 (s, 12H,
This compound was obtained in 80% yield as an oil; n
3 2
20
11
1
(CH ) C-O), 2.00-2.10 (m, 1H, CH(CH ) ), 4.15 (d, 2H, CH N,
1.4782; B NMR (CDCl , ppm): δ+27.6; H NMR (DMSO-d ,
3 2
3 2
2
3
6
4
3
13
3
J = 6.2 Hz), 6.60 (s, 1H, C H), 7.45 (c, 1H, C H); C NMR
(DMSO-d , ppm): δ 19.6 ((CH ) CH), 24.5 ((CH ) C-O), 30.1
(CH(CH ) ), 58.1 (CH N), 83.9 ((CH ) C-O), 115.2 (C ), 137.9
(C ); MS, m/z: 250 ([M] ), 235 ([M-CH ] ), 203 ([M-C H ] ).
HRMS: Found, [M] , 250.18680. Calculated for C
250.18525; dm (mmu) –6.2.
ppm): δ 1.27 (s, 12H, (CH ) C-O), 2.12 (s, 3H, CH -C ), 3.86 (s,
3 2 3
3H, CH N), 6.35 (s, 1H, C H); C NMR (DMSO-d , ppm): δ
4
13
6
3 2
3 2
3
6
4
3
12.7 (CH -C ), 24.5 ((CH ) C-O), 38.5 (CH N), 83.6 ((CH ) C-
3 2
2
3 2
3 3 2 3 3 2
3
+
+
+
4
3
+
O), 114.4 (C ), 145.7 (C ); MS, m/z: 222 ([M] ), 207 ([M-
CH ] ), 122 ([M-C H O] ). HRMS: Found, [M] , 222.15251.
3
3 7
+
+
+
+
H
BN O ,
13 23
2
2
3 6 12
Calculated for C H BN O , 222.15395; dm (mmu) +1.4.
11 19
2 2