E
D. Dar’in et al.
Paper
Synthesis
Yield: 222 mg (84%); yellow viscous liquid (lit.14 mp 2–3 °C).
1Н NMR (400 MHz, СDCl3): = 5.43 (s, 1 H), 1.15 (s, 9 H).
1Н NMR (400 MHz, СDCl3): = 7.92 (br. s, 1 H), 7.45 (ddd, J = 8.4, 7.3,
1.9 Hz, 1 H), 7.04 (ddd, J = 7.8, 7.3, 1.0 Hz, 1 H), 6.96 (dd, J = 8.4,
1.0 Hz, 1 H), 6.33 (br. s, 1 H, НС=N2), 3.90 (s, 3 H, ОСН3).
13С NMR (101 MHz, СDCl3): = 201.2 (С=О), 51.7 (С=N2), 42.5
[С(СН3)3], 27.02 [С(СН3)3].
13С NMR (101 MHz, СDCl3): = 185.2 (С=О), 158.2, 133.4, 130.3,
126.1, 120.8, 111.6, 57.9 (С=N2), 55.7 (ОСН3).
Ethyl 2-Diazo-2-phenylacetate (4a)
The title compound was synthesized according to GP2 from ethyl 2-
phenylacetate.
Yield: 208 mg (73%); orange viscous liquid (lit.18 orange oil).
2-Diazo-1-(3-methoxyphenyl)ethanone (3m)
The title compound was synthesized according to GP1 from 3′-me-
thoxyacetophenone; the crude substance was purified by flash chro-
matography on silica gel eluting with CH2Cl2.
Yield: 201 mg (76%); yellow viscous liquid (lit.10 yellow oil).
1Н NMR (400 MHz, СDCl3): = 7.38–7.33 (m, 2 H), 7.29 (dt, J = 7.6,
1.2 Hz, 1 H), 7.09 (ddd, J = 8.1, 2.7, 1.0 Hz, 1 H), 5.91 (s, 1 H, НС=N2),
3.86 (s, 3 H, ОСН3).
1Н NMR (400 MHz, СDCl3): = 7.54–7.49 (m, 2 H), 7.44–7.37 (m, 2 H),
7.24–7.17 (m, 1 H), 4.36 (q, J = 7.1 Hz, 2 H, СН2СН3), 1.37 (t, J = 7.1 Hz,
3 H, СН2СН3).
13С NMR (101 MHz, СDCl3): = 165.2 (СО2), 128.9, 125.8, 125.7, 124.0,
63.3 (С=N2), 61.0 (СН2СН3), 14.5 (СН2СН3).
Methyl 2-Diazo-2-(3,4-dichlorophenyl)acetate (4b)19
13С NMR (101 MHz, СDCl3): = 186.1 (С=О), 159.9, 138.1, 129.6,
118.9, 111.5, 55.4 (ОСН3), 54.3 (С=N2).
The title compound was synthesized according to GP2 from methyl 2-
(3,4-dichlorophenyl)acetate.
Yield: 272 mg (74%); light-orange solid; mp 95.4–97.0 °C (decomp.).
1Н NMR (400 MHz, СDCl3): = 7.66 (d, J = 2.3 Hz, 1 H), 7.45 (d,
J = 8.6 Hz, 1 H), 7.31 (dd, J = 8.6, 2.3 Hz, 1 H), 3.90 (s, 3 H, СН3).
13С NMR (101 MHz, СDCl3): = 164.8 (СО2), 133.3, 130.7, 129.4, 126.0,
125.3, 122.7, 62.9 (С=N2), 52.2 (СН3).
2-Diazo-1-(thiophen-2-yl)ethanone (3n)
The title compound was synthesized according to GP1 from 2-acet-
ylthiophene.
Yield: 217 mg (95%); yellow solid; mp 62.4–64.4 °C (lit.10 mp 59–
60 °C).
1Н NMR (400 MHz, СDCl3): = 7.60 (dd, J = 5.0, 1.0 Hz, 1 H), 7.53 (dd,
J = 3.8, 1.0 Hz, 1 H), 7.12 (dd, J = 4.9, 3.9 Hz, 1 H), 5.84 (s, 1 H, НС=N2).
13С NMR (101 MHz, СDCl3): = 178.9 (С=О), 142.5, 132.2, 129.0,
128.0, 54.2 (С=N2).
Ethyl 2-Diazo-2-(3,4-dimethoxyphenyl)acetate (4c)
The title compound was synthesized according to GP2 from ethyl 2-
(3,4-dimethoxyphenyl)acetate.
Yield: 128 mg (34%); orange solid; mp 69.7–71.4 °C (lit.20 mp 81 °C).
1Н NMR (400 MHz, СDCl3): = 7.22 (d, J = 1.9 Hz, 1 H), 6.91 (d,
J = 8.5 Hz, 1 H), 6.88 (dd, J = 8.5, 1.9 Hz, 1 H), 4.34 (q, J = 7.1 Hz, 2 H,
СН2СН3), 3.92 (s, 3 H), 3.90 (s, 3 H), 1.36 (t, J = 7.1 Hz, 3 H, СН2СН3).
13С NMR (101 MHz, СDCl3): = 165.7 (СО2), 149.5, 147.4, 117.6, 116.4,
111.7, 108.4, 62.6 (С=N2), 60.9 (СН2СН3), 56.0, 55.9, 14.5 (СН2СН3).
2-Diazo-1-(pyridin-3-yl)ethanone (3o)
The title compound was synthesized according to GP1 from 3-
acetylpyridine; the crude substance was purified by flash chromatog-
raphy on silica gel eluting with CHCl3.
Yield 161 mg (73%); yellow solid; mp 47.8–48.6 °C (lit.15 mp 71–
73 °C).
1Н NMR (400 MHz, СDCl3): = 8.93 (dd, J = 2.3, 0.8 Hz, 1 H), 8.74 (dd,
J = 4.8, 1.8 Hz, 1 H), 8.08 (ddd, J = 8.0, 2.3, 1.8 Hz, 1 H), 7.39 (ddd,
J = 8.0, 4.8, 0.8 Hz, 1 H), 5.97 (s, 1 H, НС=N2).
13С NMR (101 MHz, СDCl3): = 184.3 (С=О), 153.2, 147.9, 134.3,
132.0, 123.6, 54.9 (С=N2).
2-Diazocyclooctanone (4d)
The title compound was synthesized according to GP2 from cyclooc-
tanone.
Yield: 125 mg (55%); yellow liquid.
1Н NMR (400 MHz, СDCl3): = 2.61–2.57 (m, 2 H), 2.56–2.51 (m, 2 H),
1.81–1.74 (m, 2 H), 1.73–1.67 (m, 2 H), 1.64–1.58 (m, 4 H).
13С NMR (101 MHz, СDCl3): = 198.7 (С=О), 66.3 (С=N2), 43.9, 37.9,
29.7, 28.4, 25.8, 25.7, 24.5.
2-Diazo-1-(1-methyl-1H-pyrrol-2-yl)ethanone (3p)
The title compound was synthesized according to GP1 from 2-acetyl-
1-methylpyrrole.
IR (KBr): 2083, 1627 cm–1
.
HRMS (ESI, +ve): m/z [M + Na]+ calcd for C8H12N2NaO: 175.0842;
found: 175.0840.
Yield: 181 mg (81%); yellow solid; mp 91.5–92.6 °C (lit.16 mp 91–
95 °C).
1Н NMR (400 MHz, СDCl3): = 6.83 (t, J = 2.0 Hz, 1 H), 6.65 (dd, J = 4.1,
1.6 Hz, 1 H), 6.11 (dd, J = 4.0, 2.6 Hz, 1 H), 5.69 (s, 1 H, НС=N2), 3.99 (s,
3 H, СН3).
2-Diazo-3,4-dihydronaphthalen-1(2H)-one (4e)
The title compound was synthesized according to GP2 from -te-
tralone.
13С NMR (101 MHz, СDCl3): = 177.7 (С=О), 130.4, 129.0, 115.3,
108.0, 53.6 (С=N2), 37.3 (СН3).
Yield: 163 mg (63%); brown solid; mp 43.6–45.4 °C (lit.10 mp 47–
49 °C).
1Н NMR (400 MHz, СDCl3): = 8.04–8.00 (m, 1 H), 7.44 (td, J = 7.5,
1.5 Hz, 1 H), 7.39–7.32 (m, 1 H), 7.22 (ddq, J = 7.5, 1.3, 0.8 Hz, 1 H),
3.07–3.02 (m, 2 H), 3.02–2.97 (m, 2 H).
1-Diazo-3,3-dimethylbutan-2-one (3q)
The title compound was synthesized according to GP1 from pina-
colone.
13С NMR (101 MHz, СDCl3): = 183.6 (С=О), 140.1, 133.3, 132.5,
128.2, 127.1, 126.0, 62.7 (С=N2), 27.8, 20.8.
Yield: 181 mg (96%); orange liquid (lit.17 bp 31–34 °C/1 Torr).
© 2019. Thieme. All rights reserved. — Synthesis 2019, 51, A–G