PAPER
Synthesis of Hydrazines with Aromatic Substituents Using Triarylbismuth Reagents
1595
Table 2 Selected Data for N-Aryl Substituted Hydrazines made with Ar3Bi in the Presence of Cu(OAc)2 and Et3N
Cmpd Structure
Yield
(%); Mp d, J (Hz)
(∞C)
1H NMR (400 MHz, CDCl3/TMS)
13C NMR (100 MHz, CDCl3/TMS)
d, J (Hz)
FT-IR
(cm–1)
3ba
4-Me-C6H4/
Boc/Boc/ Boc 99-100
98;
1.50 and 1.51 (2 ¥ s, 27 H, Me), 2.32 (s, 3 20.9 (MeAr), 27.9 (Me, NBoc2), 28.1 (Me,
H, MeAr), 7.10 and 7.22, and 7.10 and 7.32 NBoc), 81.9 (Cq, NBoc), 83.6 (Cq, NBoc2),
1725, 1746
and 1766
(2 ¥ ABq, J = 8.1, 4 H, Ar)
123.2, 124.7, 129.0, 135.6, 138.2 (Ar), 150.3 (CO), 2935
(CO, NBoc), 152.2 (CO, NBoc2)
and 2977
(CH)
3cb
4-MeO-C6H4/ 97;
Boc/Boc/Boc 69-70
1.52/1.51/1.44 (3 ¥ s, together 27 H, 3 ¥
Boc), 3.79/3.80 (2 ¥ s, 3 H, OMe), 6.85/
28.0 and 28.2 (Boc), 55.4 (OMe), 81.8/82.0 1724, 1741
(Cq, NBoc), 83.6/83.5 (Cq, NBoc2), 113.7/ and 1769
6.83 (2 ¥ d, J = 9.2, together 2 H, Ar-H2,6), 113.4, 125.9/126.9, 133.8/134.4, 157.8/158.0 (CO), 2937
7.38/7.30 (2 ¥ d, J = 9.2, together 2 H,
Ar-H3,5
(Ar), 150.4/150.6 (CO, NBoc), 152.5 (CO,
NBoc2
and 2984
(CH)
)
6a
6b
Ph/Boc/Z/Boc 98; oil
See 6a from 7
See 6a from 7
See 6a from
7
4-Me-C6H4/
Boc/Z/Boc
98; oil
1.38/1.42 (2 ¥ s, together 9 H, BocNAr),
1.49 (s, 9 H, BocNZ), 2.31 (s, 3 H, MeAr), (CH2Ph), 82.2/82.5 (Cq, BocNAr), 84.2 (Cq, and 1805
20.9 (MeAr), 27.9/28.0 (2 ¥ Boc), 68.9
1732, 1766
5.21 and 5.32 (ABq, J = 12.2, together 2 H, BocNZ), 123.5, 125.0, 128.1, 128.5, 129.0, (CO), 2979
CH2Ph), 7.08–7.34 (m, 9 H, Ar)
129.1, 135.1, 135.9, 136.3, 137.9, 138.5 (Ar), (CH)
149.9/150.1 (CO, BocNAr), 152.1/152.2
(2¥CO, BocNZ+Z)
6c
4-MeO-C6H4/ 97; oil
Boc/Z/Boc
1.38/1.41 (2 ¥ s, together 9 H, BocNAr),
27.9/28.0/28.1 (2¥Boc), 55.4 (OMe), 69.0
1732, 1766
1.51/1.50 (2 ¥ s, 9 H, BocNZ), 3.78 (s, 3 H, (CH2Ph), 82.2/82.3 (Cq, BocNAr), 82.4 (Cq, and 1805
OMe), 5.23 and 5.32/5.23 and 5.29 (2 ¥
ABq, J = 12.1, together 2 H, CH2Ph), 6.82/ 128.3, 128.4, 128.5, 133.5, 134.1, 135.0,
6.78 (d, J = 8.8, 2 H, Ar), 7.23-7.37 (compl. 158.0, 158.2 (Ar), 150.0/150.2 (CO, Boc),
BocNZ), 113.5, 113.8, 126.2, 127.2, 128.1, (CO), 2839,
2935 and
2981 (CH)
sign., 7 H, Ar)
152.1/152.3 (CO, Boc), 152.4/152.6 (CO, Z)
8
Ph/4-Me-
C6H4/Boc/Boc
96; oil
96; oil
1.51 (s, 9 H, Boc), 1.52 (s, 9 H, Boc), 2.29 20.9 (MeAr), 28.2 (Me, Boc), 82.1 and 82.2 1727 (CO),
(s, 3 H, Me), 7.08–7.38 (m, 9 H, Ar) (Cq, Boc), 122.7, 125.5, 128.5, 129.1, 135.4, 2932 and
138.6, 141.2 (Ar), 153.1 and 153.3 (CO)
2978 (CH)
9a
C3H5/Ph/Z/
Boc
1.36/1.48 (2 sign, together 9 H, Boc), 4.04 28.1/28.2 (Me, Boc), 51.8/53.8
1644 (allyl),
(compl. m, 1 H) and 4.20 (dd, J1 = 6.4, J2 = (CH2CH=CH2), 68.1 (CH2Ph), 81.7/81.9 (Cq, 1717 and
14.8, 1 H, CH2CH=CH2), 5.03-5.30 (com- Boc), 118.2, 118.8, 123.0, 126.0, 128.0, 1734 (CO),
pl. sign., 4 H, CH2Ph, =CH2), 5.79 (pert. m, 128.3, 128.4, 128.5, 128.59, 128.62, 132.7, 2932, 2978,
1 H, =CH-), 7.17–7.35 (m, 10 H, Ar)
133.1, 135.8, 135.9, 140.8, 141.1
3034 and
(Ar+CH=CH2), 154.3, 154.4 and 154.7 (CO) 3067 (CH)
9b
EtOCOCH2/
Ph/Z/Boc
97; oil
1.10/1.12 (2 ¥ t, J = 7, together 3 H,
CH3CH2), 1.35/1.45 (2 ¥ s, together 9 H,
Boc), 3.95–4.08 (m, 2 H, CH2CO), 3.84
13.9/14.0 (CH3CH2), 28.0/28.1 (Me, Boc), 1732 (CO),
52.6/54.0 (CH2CO), 61.1 (CH2CH3), 68.37/ 2936 and
68.40 (CH2Ph), 82.5/82.7 (Cq, Boc), 115.3, 2980 (CH)
and 4.63/3.86 and 4.51 (2 ¥ ABq, J = 17, 123.6/124.1, 126.2/126.4, 127.9, 128.2,
together 2 H, CH2CH3), 5.14–5.32 (m, 2 H, 128.3, 128.41, 128.45, 128.53, 128.59,
CH2Ph), 7.18–7.53 (m, 10 H, Ar)
135.62/135.71, 140.4/140.5 (Ar), 154.0/154.1
(CO, Boc), 154.7/154.3 (CO, Z), 168.3/168.4
(CO, CO2Et)
10a
Me/Bn/Z/4-
Me-C6H4
98; oil
2.26 (s, 3 H, MeAr ), 2.82 (pert. s, 3 H,
MeN), 4.26 and 4.30 (Abq, J = 14.6, NCH2, (OCH2), 112.0, 127.4, 127.7, 128.2, 128.5,
20.3 (MeAr), 40.1 (MeN), 52.9 (NCH2), 67.5 1706 (CO),
2924 and
1 H) and 5.11 (br sign., 3 H, OCH2 + 2 sign. 129.3, 129.7, 136.2, 137.4, 146.2 (Ar), 157.0 3032 (CH)
from previous ABq), 6.51 and 7.02 (ABq, (CO)
J ª 8, 2+2 H, Me-Ar),-7.0–7.36 (compl.
sign., ~10 H, Ar)
Synthesis 2000, No. 11, 1591–1597 ISSN 0039-7881 © Thieme Stuttgart · New York