Unexpected synthesis of N-Acyl indolines via a consecutive cyclization of iminophosphorane

Article abstract of DOI:10.1055/s-0030-1259280

N-Acyl indolines were obtained unexpectedly from a consecutive cyclization of iminophosphorane in refluxing xylene or 1,2-dichlorobenzene in good yields. This new approach provides an efficient and direct access to the biologically important indolines which are further oxidizable to indoles and oxindoles. Georg Thieme Verlag Stuttgart.

Full text of DOI:10.1055/s-0030-1259280

Accounts and
Rapid Communications in
Synthetic Organic Chemistry
SYNLETT
SUPPORTING INFORMATION
Supporting Information
for DOI: 10.1055/s-0030-1259280
© Georg Thieme Verlag KG Stuttgart · New York 2010
Thieme

Supporting Information
Unexpected Synthesis of N-Acyl Indolines via A Consecutive
Cyclization of iminophosphorane
Wen-Jing Li, Fen-Fen Zhao, Ming-Wu Ding*
Key Laboratory of Pesticide and Chemical Biology of Ministry of Education, Central China
Normal University, Wuhan 430079, People’s Republic of China
Fax +86(27)67862041; E-mail: mwding@mail.ccnu.edu.cn
Table of Contents
General Methods………………………………………………….S2
Preparations and Characterization data of Compounds 2………...S2-S4
Preparations and Characterization data of Compounds 4 and 5.…S4-S7
1H NMR and 13C NMR Spectrums for All Compounds……...…..S8-S27
S1

General Methods:
Reactions were generally carried out in an appropriate round bottom flask with magnetic stirring. Thin
layer chromatography (TLC) was performed on a silica gel. All melting points were taken on a Digital
1
Melting Point without correction. H, and 13C spectra were recorded on a 400 MHz or 600 MHz
l
spectrometer. Chemical shifts for H NMR spectra are reported in ppm downfield from TMS, chemical
shifts for 13C NMR spectra are reported in ppm relative to internal chloroform (δ 77.0 ppm for 13C), and
chemical shifts. The terms m, s, d, t, q refer to multiplet, singlet, doublet, triplet, quartlet; br refers to a
broad signal.
General Procedure for the Synthesis of Iminophosphorane 2:
To a stirred solution of 2-(2-azidophenyl)ethanol (0.33 g, 2.0 mmol) and Et3N (0.60 g, 6.0 mmol) in CH2Cl2
(15 mL) was added a solution of acyl chloride (2.0 mmol) in CH2Cl2 (10 mL) at r.t. The reaction mixture
was stirred for 30 min. It was then pour into water to remove the Et3NHCl, and extracted with CH2Cl2 three
times. The organic phase was combined and dried with anhydrous Na2SO4. The crude product was purified
by flash chromatography (15:1, PE–Et2O) to yield azide 1. To a stirred solution of azide 1 (2 mmol) in
CH2Cl2 (15 mL) was added a solution of Ph3P (0.52 g, 2 mmol) in dry CH2Cl2 (10 mL). After the reaction
mixture was stirred for 1 h, the solvent was removed under reduced pressure, and the residue was
recrystallized from Et2O and CH2Cl2 (2:1; v/v) to give the iminophosphorane 2.
2-(Triphenylphosphoranylideneamino)phenethyl benzoate (2a):
1
yield 93%, white solid, mp: 140-141 °C. H NMR (600 MHz, CDCl3): δ =
8.07 (d, 2H, J = 7.8 Hz, Ar-H), 7.78-6.46 (m, 22H, Ar-H), 4.68 (t, 2H, J = 6.6
Hz, OCH2), 3.39 (t, 2H, J = 6.6 Hz, CH2). MS: m/z (%) = 501 (8) [M+], 396
O
O
(38), 380 (29), 262 (42), 183 (100), 108 (36), 105 (45), 77 (48). Anal. Calcd
for C33H28NO2P: C, 79.02; H, 5.63; N, 2.79. Found: C, 79.24; H, 5.74; N,
PPh3
N
2.61.
2-(Triphenylphosphoranylideneamino)phenethyl 4-methylbenzoate (2b):
yield 81%, white solid, mp: 118-119 °C. 1H NMR (600 MHz, CDCl3): δ =
7.96-6.47 (m, 23H, Ar-H), 4.66 (m, 2H, OCH2), 3.38 (m, 2H, CH2), 2.41 (s,
3H, CH3). MS: m/z (%) = 515 (8) [M+], 396 (44), 380 (37), 262 (59), 183
(100), 119 (50), 108 (40), 91 (60). Anal. Calcd for C34H30NO2P: C, 79.20;
O
O
PPh3
N
H, 5.86; N, 2.72. Found: C, 79.02; H, 5.68; N, 2.78.
2-(Triphenylphosphoranylideneamino)phenethyl 4-chlorobenzoate (2c):
yield 85%, yellow solid, mp: 127-128 °C. 1H NMR (600 MHz, CDCl3): δ
Cl
= 7.98 (d, 2H, J = 7.8 Hz, Ar-H), 7.77-6.46 (m, 21H, Ar-H), 4.67 (t, 2H, J
= 6.6 Hz, OCH2), 3.37 (t, 2H, J = 6.6 Hz, CH2). MS: m/z (%) = 535 (5)
[M+], 396 (36), 380 (32), 262 (44), 184 (17), 183 (100). Anal. Calcd for
C33H27ClNO2P: C, 73.95; H, 5.08; N, 2.61. Found: C, 73.84; H, 5.29; N,
O
O
PPh3
N
2.35.
S2

2-(Triphenylphosphoranylideneamino)phenethyl 2-chlorobenzoate (2d):
1
yield 83%, white solid, mp: 121-122 °C. H NMR (600 MHz, CDCl3): δ =
7.81-6.46 (m, 23H, Ar-H), 4.70 (t, 2H, J = 6.6 Hz, OCH2), 3.39 (t, 2H, J = 6.6
Hz, CH2). MS: m/z (%) = 535 (4) [M+], 396 (38), 380 (28), 262 (36), 184 (16),
183 (100). Anal. Calcd for C33H27ClNO2P: C, 73.95; H, 5.08; N, 2.61. Found:
C, 73.67; H, 5.26; N, 2.52.
O
O
Cl
PPh3
N
2-(Triphenylphosphoranylideneamino)phenethyl 3-chlorobenzoate (2e):
yield 87%, white solid, mp: 125-126 °C. 1H NMR (600 MHz, CDCl3): δ
= 8.04 (s, 1H, Ar-H), 7.93 (d, 1H, J = 7.8 Hz, Ar-H), 7.77-6.47 (m, 21H,
Ar-H), 4.68 (t, 2H, J = 7.2 Hz, OCH2), 3.38 (t, 2H, J = 7.2 Hz, CH2). MS:
m/z (%) = 535 (8) [M+], 396 (27), 380 (27), 277 (30), 262 (42), 184 (19),
183 (100). Anal. Calcd for C33H27ClNO2P: C, 73.95; H, 5.08; N, 2.61.
O
Cl
O
PPh3
N
Found: C, 74.17; H, 5.22; N, 2.35.
2-(Triphenylphosphoranylideneamino)phenethyl 4-nitrobenzoate (2f):
yield 85%, orange solid, mp: 146-147 °C. 1H NMR (600 MHz, CDCl3):
NO2
δ = 8.23 (d, 2H, J = 9.0 Hz, Ar-H), 8.18 (d, 2H, J = 9.0 Hz, Ar-H),
7.76-6.47 (m, 19H, J = 7.8 Hz, Ar-H), 4.74 (t, 2H, J = 6.6 Hz, OCH2),
3.40 (t, 2H, J = 6.6 Hz, CH2). MS: m/z (%) = 546 (13) [M+], 277 (26),
183 (25), 119 (58), 118 (100), 117 (30). Anal. Calcd for C33H27N2O4P:
O
O
PPh3
N
C, 72.52; H, 4.98; N, 5.13. Found: C, 72.23; H, 4.74; N, 5.38.
2-(Triphenylphosphoranylideneamino)phenethyl 4-fluorobenzoate (2g):
1
yield 91%, white solid, mp: 150-151 °C. H NMR (600 MHz, CDCl3): δ
= 8.07 (t, 2H, J = 7.2 Hz, Ar-H), 7.77-6.46 (m, 21H, Ar-H), 4.67 (t, 2H, J
= 6.6 Hz, OCH2), 3.37 (t, 2H, J = 6.6 Hz, CH2). MS: m/z (%) = 519 (8)
[M+], 396 (36), 380 (34), 262 (48), 184 (18), 183 (100). Anal. Calcd for
C33H27FNO2P: C, 76.29; H, 5.24; N, 2.70. Found: C, 76.46; H, 5.05; N,
F
O
O
PPh3
N
2.85.
2-(Triphenylphosphoranylideneamino)phenethyl 2-fluorobenzoate (2h):
1
yield 90%, white solid, mp: 131-132 °C. H NMR (600 MHz, CDCl3): δ =
7.95 (t, 1H, J = 7.2 Hz, Ar-H), 7.78-6.46 (m, 22H, Ar-H), 4.69 (t, 2H, J = 6.6
Hz, OCH2), 3.39 (t, 2H, J = 6.6 Hz, CH2). MS: m/z (%) = 519 (7) [M+], 396
(35), 380 (33), 262 (41), 184 (18), 183 (100). Anal. Calcd for C33H27FNO2P:
C, 76.29; H, 5.24; N, 2.70. Found: C, 76.55; H, 5.52; N, 2.56.
O
O
F
PPh3
N
5-Bromo-2-(triphenylphosphoranylideneamino)phenethyl 4-chlorobenzoate (2i):
1
yield 84%, white solid, mp: 158-159 °C. H NMR (400 MHz,
CDCl3): δ = 7.97 (d, 2H, J = 8.4 Hz, Ar-H), 7.74-6.28 (m, 20H,
Ar-H), 4.63 (t, 2H, J = 6.8 Hz, OCH2), 3.31 (t, 2H, J = 6.8 Hz,
CH2). MS: m/z (%) = 613 (10) [M+], 476 (21), 277 (21), 262 (51),
189 (18), 183 (100). Anal. Calcd for C33H26BrClNO2P: C, 64.46;
H, 4.26; N, 2.28. Found: C, 64.19; H, 4.47; N, 2.15.
Cl
Br
O
O
PPh3
N
S3

5-Bromo-2-(triphenylphosphoranylideneamino)phenethyl 2-fluorobenzoate (2j):
yield 81%, white solid, mp: 166-167 °C. 1H NMR (600 MHz, CDCl3):
δ = 7.94-7.13 (m, 20H, Ar-H), 6.86 (d, 1H, J = 8.0 Hz, Ar-H), 6.28 (d,
1H, J = 8.4 Hz, Ar-H), 4.65 (t, 2H, J = 7.2 Hz, OCH2), 3.32 (t, 2H, J =
7.2 Hz, CH2). MS: m/z (%) = 597 (10) [M+], 476 (22), 458 (15), 262
(49), 183 (100), 123 (51). Anal. Calcd for C33H26BrFNO2P: C, 66.23;
H, 4.38; N, 2.34. Found: C, 66.12; H, 4.58; N, 2.12.
Br
O
O
F
PPh3
N
5-Bromo-2-(triphenylphosphoranylideneamino)phenethyl 4-nitrobenzoate (2k):
1
yield 87%, red solid, mp: 174-175 °C. H NMR (400 MHz,
CDCl3): δ = 8.25-7.27 (m, 20H, Ar-H), 6.86 (d, 1H, J = 8.0 Hz,
Ar-H), 6.29 (d, 1H, J = 8.4 Hz, Ar-H), 4.70 (t, 2H, J = 6.8 Hz,
OCH2), 3.34 (t, 2H, J = 6.8 Hz, CH2). MS: m/z (%) = 624 (9)
[M+], 474 (18), 277 (43), 262 (57), 199 (20), 183 (100). Anal.
NO2
Br
O
O
PPh3
N
Calcd for C33H26BrN2O4P: C, 63.37; H, 4.19; N, 4.48. Found: C, 63.15; H, 4.31; N, 4.64.
2-(triphenylphosphoranylideneamino)phenethyl acetate (2l):
yield 86%, yellow solid, mp: 76-78 °C. 1H NMR (600 MHz, CDCl3): δ = 7.76-6.44
(m, 19H, Ar-H), 4.42 (t, 2H, J = 6.6 Hz, OCH2), 3.24 (t, 2H, J = 6.6 Hz, CH2), 2.04
(s, 3H, CH3). MS: m/z (%) = 439 (10) [M+], 396 (25), 380 (39), 262 (34), 183 (100),
O
O
PPh3
N
152 (15), 108 (34). Anal. Calcd for C28H26NO2P: C, 76.52; H, 5.96; N, 3.19. Found:
C, 76.27; H, 5.74; N, 3.38.
2-(triphenylphosphoranylideneamino)phenethyl propionate (2m):
1
yield 87%, white solid, mp: 101-102 °C. H NMR (600 MHz, CDCl3): δ =
7.77-6.44 (m, 19H, Ar-H), 4.43 (t, 2H, J = 6.6 Hz, OCH2), 3.24 (t, 2H, J = 7.2
Hz, CH2), 2.33 (q, 2H, J = 7.2 Hz, CH2), 1.14 (t, 3H, J = 7.2 Hz, CH3). MS: m/z
(%) = 453 (8) [M+], 396 (31), 380 (40), 262 (34), 184 (17), 183 (100), 152 (13).
O
O
PPh3
N
Anal. Calcd for C29H28NO2P: C, 76.80; H, 6.22; N, 3.09. Found: C, 76.94; H, 6.01; N, 3.23.
2-(triphenylphosphoranylideneamino)phenethyl 2-chloropropanoate (2n):
1
yield 88%, yellow solid, mp: 121-124 °C. H NMR (600 MHz, CDCl3): δ =
7.76-6.45 (m, 19H, Ar-H), 4.54 (t, 2H, J = 7.2 Hz, OCH2), 4.40 (q, 1H, J = 4.8
Cl
O
Hz, CHCl), 3.30-3.24 (m, 2H, CH2), 1.67 (d, 3H, J = 7.2 Hz, CH3). MS: m/z (%)
= 487 (6) [M+], 397 (7), 380 (42), 277 (35), 183.1 (100). Anal. Calcd for
O
PPh3
N
C29H27ClNO2P: C, 71.38; H, 5.58; N, 2.87. Found: C, 71.15; H, 5.65; N, 2.99.
General Procedure for the Synthesis of N-Acyl indolines 4 and 5:
The solution of iminophosphorane 2 (2 mmol) in xylene or 1,2-dichlorobenzene was heated to reflux for
1-24 h. The crude product was purified by flash chromatography to yield N-acyl indolines 4 and 5.
1-Benzoylindoline (4a):
1
white solid, mp: 121-123 °C. H NMR (600 MHz, CDCl3): δ = 8.31-7.03 (m, 9H),
4.06 (br, 2H ), 3.12 (t, J = 8.4 Hz, 2H). 13C NMR (150 MHz, CDCl3): δ = 168.8,
N
142.4, 136.8, 132.1, 130.1, 128.4, 126.9, 124.7, 123.9, 123.8, 117.3, 50.7, 28.1. MS:
m/z (%) = 223 (66) [M+], 105 (100), 77 (33). Anal. Calcd for C15H13NO: C, 80.69;
O
H, 5.87; N, 6.27. Found: C, 80.53; H, 5.85; N, 6.42.
S4

1-(4-Methylbenzoyl)indoline (4b):
1
white solid, mp: 102-104 °C. H NMR (600 MHz, CDCl3): δ = 7.45-6.99 (m,
8H), 4.06 (br, 2H ), 3.08 (t, J = 7.2 Hz, 2H). 13C NMR (150 MHz, CDCl3): δ =
169.0, 142.6, 140.4, 133.9, 132.4, 132.2, 129.0, 127.1, 124.7, 123.6, 117.4, 50.7,
28.1, 21.5. MS: m/z (%) = 237 (14) [M+], 119.1 (100), 91.1 (38), 65.1(16). Anal.
Calcd for C16H15NO: C, 80.98; H, 6.37; N, 5.90. Found: C, 80.81; H, 6.48; N,
N
O
5.72.
1-(4-Chlorobenzoyl)indoline (4c):
1
white solid, mp: 116-117 °C. H NMR (600 MHz, CDCl3): δ = 8.30-7.03 (m,
8H), 4.04 (br, 2H ), 3.11(t, J = 8.4 Hz, 2H). 13C NMR (150 MHz, CDCl3): δ =
167.0, 141.9, 135.6, 134.8, 131.7, 129.3, 128.1, 127.1, 126.6, 124.4, 123.6,
117.0, 50.3, 27.7. MS: m/z (%) = 257 (18) [M+], 141 (33), 139 (100), 111 (33),
75 (11). Anal. Calcd for C15H12ClNO: C, 69.91; H, 4.69; N, 5.43. Found: C,
N
O
Cl
69.64; H, 4.85; N, 5.31.
1-(2-Chlorobenzoyl)indoline (4d):
white solid, mp: 93-94 °C. 1H NMR (600 MHz, CDCl3): major rotamer (75:25) δ =
8.35 (d, J = 14.4 Hz, 0.75H), 7.43-6.81 (m, 7.54H), 5.71 (d, J = 8.4 Hz, 0.25H),
4.37-4.27 (m, 0.52H ), 3.84-3.75 (m, 1.47H ), 3.18-3.10 (m, 2H). 13C NMR (150
MHz, CDCl3): δ = 169.1, 142.7, 137.1, 132.5, 130.4, 128.7, 127.2, 125.0, 124.1,
117.5, 50.9, 28.3. MS: m/z (%) = 257 (19) [M+], 141 (34), 139 (100), 111 (29), 75
Cl
N
O
(12). Anal. Calcd for C15H12ClNO: C, 69.91; H, 4.69; N, 5.43. Found: C, 69.72; H, 4.58; N, 5.67.
1-(3-Chlorobenzoyl)indoline (4e):
white solid, mp: 158-159 °C. 1H NMR (600 MHz, CDCl3): δ = 8.24-7.06 (m, 8H),
4.03 (br, 2H ), 3.13 (t, J = 8.4 Hz, 2H). 13C NMR (150 MHz, CDCl3): δ = 167.1,
142.3, 138.5, 134.4, 132.0, 130.2, 129.8, 127.0, 125.0, 117.8, 51.2, 28.2. MS: m/z
(%) = 257 (20) [M+], 141 (33), 139 (100), 111 (37), 75 (11). Anal. Calcd for
C15H12ClNO: C, 69.91; H, 4.69; N, 5.43. Found: C, 70.15; H, 4.84; N, 5.27.
Cl
N
O
1-(4-Nitrobenzoyl)indoline (4f):
yellow solid, mp: 203-204 °C. 1H NMR (600 MHz, CDCl3): δ = 8.32-5.86 (m,
8H), 4.27-3.97 (m, 2H ), 3.16(t, J = 7.8 Hz, 2H). 13C NMR (150 MHz, CDCl3):
δ = 166.4, 148.4, 142.2, 131.8, 127.9, 127.5, 124.8, 123.8, 122.9, 117.7, 50.8,
28.4. MS: m/z (%) = 268 (35) [M+], 150 (100), 139 (18), 120 (58), 104 (34),
N
O
NO2
91 (27), 76 (21), 65 (22). Anal. Calcd for C15H12N2O3: C, 67.16; H, 4.51; N, 10.44. Found: C, 67.37; H,
4.75; N, 10.27.
1-(4-Fluorobenzoyl)indoline (4g):
1
white solid, mp: 104-105 °C. H NMR (600 MHz, CDCl3): δ = 8.24-7.03 (m,
8H), 4.08 (br, 2H ), 3.13 (t, J = 8.4 Hz, 2H). 13C NMR (150 MHz, CDCl3): δ =
N
167.3, 164.0, 162.4, 142.1, 132.6, 132.0, 129.1, 126.7, 124.5, 123.6, 117.0,
116.2, 115.1, 114.1, 50.4, 28.0. MS: m/z (%) = 241 (17) [M+], 123 (100), 95
O
F
(35). Anal. Calcd for C15H12FNO: C, 74.67; H, 5.01; N, 5.81. Found: C, 74.58;
S5

H, 5.24; N, 5.61.
1-(2-Fluorobenzoyl)indoline (4h):
white solid, mp: 96-97 °C. 1H NMR (600 MHz, CDCl3): major rotamer (79:21) δ =
8.31 (d, J = 7.8 Hz, 0.79H), 7.48-6.83 (m, 7.34H), 5.92 (d, J = 6.6 Hz, 0.21H),
4.38-4.28 (m, 0.42H ), 3.92 (t, J = 7.8 Hz, 1.57H ), 3.12 (t, J = 7.8 Hz, 2H ). 13C
NMR (150 MHz, CDCl3): δ = 163.7, 162.7, 158.8, 158.3, 157.2, 156.6, 141.8, 140.6,
132.9, 131.7, 131.0, 128.5, 128.1, 126.8, 126.4, 125.0, 124.3, 123.9, 116.8, 115.5,
F
N
O
112.6, 48.7, 47.9, 27.4, 26.2. MS: m/z (%) = 241 (17) [M+], 123 (100), 95 (35). Anal. Calcd for C15H12FNO:
C, 74.67; H, 5.01; N, 5.81. Found: C, 74.42; H, 4.87; N, 5.97.
5-Bromo-1-(4-chlorobenzoyl)indoline (4i):
white solid, mp: 142-143 °C. 1H NMR (400 MHz, CDCl3): δ = 7.51-7.26
Br
(m, 7H, Ar-H), 4.07 (br, 2H, OCH2), 3.12 (t, J = 8.0 Hz, 2H, CH2). MS:
m/z (%) = 335 (11) [M+], 139 (100), 111 (27). Anal. Calcd for
N
C15H11BrClNO: C, 53.52; H, 3.29; N, 4.16. Found: C, 53.74; H, 3.43; N,
O
Cl
4.04.
5-Bromo-1-(2-fluorobenzoyl)indoline (4j):
1
white solid, mp: 149-150 °C. H NMR (400 MHz, CDCl3): major rotamer
(75:25) δ = 8.19 (d, J = 8.4 Hz, 0.72H, Ar-H), 7.49-6.95 (m, 6.42H, Ar-H),
5.77 (br, 0.25H, Ar-H), 4.39-4.22 (m, 0.47H, OCH2), 3.95 (t, J = 8.4 Hz,
1.49H, OCH2), 3.12 (t, J = 8.0 Hz, 2H, CH2). 13C NMR (100 MHz, CDCl3): δ
= 164.4, 159.2, 156.8, 141.5, 134.3, 131.8, 131.7, 130.3, 128.7, 127.7, 124.8,
Br
F
N
O
118.8, 116.9, 116.1, 115.9, 49.2, 27.8. MS: m/z (%) = 319 (12) [M+], 123 (100), 95 (20). Anal. Calcd for
C15H11BrFNO: C, 56.27; H, 3.46; N, 4.37. Found: C, 56.13; H, 3.58; N, 4.51.
5-Bromo-1-(4-nitrobenzoyl)indoline (4k):
1
yellow solid, mp: 215-216 °C. H NMR (400 MHz, CDCl3): =
Br
8.35-7.29 (m, 7H, Ar-H), 4.00 (br, 2H, OCH2), 3.16 (t, J = 8.0 Hz, 2H,
CH2). MS: m/z (%) = 346 (17) [M+], 150 (100), 117 (24), 104 (32).
N
Anal. Calcd for C15H11BrN2O3: C, 51.90; H, 3.19; N, 8.07. Found: C,
O
NO2
51.67; H, 3.11; N, 8.26.
1-Acetylindoline (4l):
1
white solid, mp: 98-100 °C. H NMR (600 MHz, CDCl3): δ = 8.20 (d, J = 7.8 Hz, 1H),
7.17 (q, J = 7.8 Hz, 2H), 7.00 (t, J = 7.8 Hz, 1H), 4.12 (t, J = 7.8 Hz, 0.29H), 4.01 (t, J =
8.4 Hz, 1.71H), 3.17 (t, J = 7.8 Hz, 1.72H), 3.05 (t, J = 7.8 Hz, 0.29H), 2.43 (s, 0.43H),
2.20 (s, 2.67H). 13C NMR (150 MHz, CDCl3): δ = 168.2, 142.4, 130.8, 126.8, 125.3, 124.1,
N
O
122.9, 122.5, 116.1, 113.5, 48.1, 47.4, 27.3, 26.2, 24.1, 23.6. MS: m/z (%) = 161 (32) [M+], 119 (67), 118
(100), 91 (17). Anal. Calcd for C10H11NO: C, 74.51; H, 6.88; N, 8.69. Found: C, 74.58; H, 6.63; N, 8.94.
1-Propionylindoline (4m):
white solid, mp: 101-102 °C. 1H NMR (600 MHz, CDCl3): δ = 8.24 (d, J = 7.8 Hz, 1H),
7.18 (q, J = 7.8 Hz, 2H), 6.99 (t, J = 7.8 Hz, 1H), 4.14 (s, 0.29H), 4.01 (t, J = 8.4 Hz,
N
1.71H), 3.18 (t, J = 8.4 Hz, 1.71H), 3.05 (s, 0.29H), 2.68 (s, 0.29H), 2.43 (q, J = 7.8 Hz,
O
S6

1.71H), 1.22 (s, 3H). 13C NMR (150 MHz, CDCl3): δ = 171.4, 142.6, 130.7, 126.8, 124.0, 122.8, 116.1,
47.1, 29.1 28.4, 27.4, 26.2, 9.2, 8.1. MS: m/z (%) = 175 (29) [M+], 119 (100), 91 (18), 65 (9). Anal. Calcd
for C11H13NO: C, 75.40; H, 7.48; N, 7.99. Found: C, 75.67; H, 7.45; N, 7.78.
1-(2-Chloropropanoyl)indoline (4n):
1
yellow solid; m.p.: 110-112 °C; H NMR (600 MHz, CDCl3): δ = 8.24 (d, J = 8.4 Hz,
1H), 7.21 (q, J = 7.8 Hz, 2H), 7.06 (t, J = 7.8 Hz, 1H), 4.58 (q, J = 6.6 Hz, 1H), 4.39 (q,
N
J = 9.6 Hz, 1H), 4.09 (q, J = 10. 2 Hz, 1H), 3.27-3.20 (m, 2H), 1.75 (d, J = 6.6 Hz, 3H);
13C NMR (150 MHz, CDCl3): δ = 166.5, 142.5, 131.4, 127.4, 124.5, 124.2, 117.2, 51.9,
47.5 27.9, 20.4; MS: m/z (%) = 209 (31) [M+], 146 (32), 128 (18), 119 (100), 91 (33), 65
O
Cl
(15); Anal. Calcd for C11H12ClNO: C, 63.01; H, 5.77; N, 6.68. Found: C, 63.25; H, 5.58; N, 6.60.
S7

O
O
PPh3
N
2a
10.0
ppm (f1)
9.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
O
O
PPh3
N
2b
9.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
-1.0
ppm (f1)
S8

Cl
O
O
PPh3
N
2c
10.0
ppm (f1)
9.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
-1.0
O
O
Cl
PPh3
N
2d
9.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
ppm (f1)
S9

O
Cl
O
PPh3
N
2e
10.0
9.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
-1.0
-2.0
ppm (f1)
NO2
O
O
PPh3
N
2f
10.0
ppm (f1)
9.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
-1.0
S10

F
O
O
PPh3
N
2g
9.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
-1.0
ppm (f1)
O
O
F
PPh3
N
2h
9.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
-1.0
ppm (f1)
S11

Cl
Br
O
O
PPh3
N
2i
10.0
9.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
-1.0
ppm (f1)
Br
O
O
F
PPh3
N
2j
10.0
9.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
-1.0
-2.0
ppm (f1)
S12

NO2
Br
O
O
PPh3
N
2k
10.0
ppm (t1)
9.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
-1.0
O
O
PPh3
N
2l
9.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
-1.0
ppm (f1)
S13

O
O
PPh3
N
2m
10.0
ppm (f1)
9.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
-1.0
Cl
O
O
PPh3
N
2n
9.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
-1.0
ppm (f1)
S14

N
O
4a
10.0
ppm (f1)
9.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
-1.0
N
O
4a
190
ppm (f1)
180
170
160
150
140
130
120
110
100
90
80
70
60
50
40
30
20
10
0
S15

N
O
4b
10.0
ppm (f1)
9.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
-1.0
N
O
4b
180
ppm (f1)
170
160
150
140
130
120
110
100
90
80
70
60
50
40
30
20
10
S16

N
O
Cl
4c
10.0
ppm (f1)
9.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
-1.0
N
O
Cl
4c
190
ppm (f1)
180
170
160
150
140
130
120
110
100
90
80
70
60
50
40
30
20
10
S17

Cl
N
O
4d
11.0
ppm (f1)
10.0
9.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
-1.0
Cl
N
O
4e
11.0
ppm (f1)
10.0
9.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
-1.0
S18

Cl
N
O
4e
180
ppm (f1)
170
160
150
140
130
120
110
100
90
80
70
60
50
40
30
20
10
N
O
NO2
4f
10.0
9.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
-1.0
ppm (f1)
S19

N
O
NO2
4f
190
ppm (f1)
180
170
160
150
140
130
120
110
100
90
80
70
60
50
40
30
20
10
0
N
O
F
4g
10.0
ppm (f1)
9.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
-1.0
S20

N
O
F
4g
190
ppm (f1)
180
170
160
150
140
130
120
110
100
90
80
70
60
50
40
30
20
10
0
F
N
O
4h
11.0
ppm (f1)
10.0
9.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
-1.0
S21

F
N
O
4h
180
ppm (f1)
170
160
150
140
130
120
110
100
90
80
70
60
50
40
30
20
10
Br
N
O
Cl
4i
10.0
ppm (f1)
9.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
S22

Br
F
N
O
4j
10.0
9.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
ppm (f1)
Br
F
N
O
4j
190
180
170
160
150
140
130
120
110
100
90
80
70
60
50
40
30
20
10
ppm (f1)
S23

Br
N
O
NO2
4k
10.0
9.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
ppm (f1)
N
O
4l
10.0
9.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
-1.0
ppm (f1)
S24

N
O
4l
210 200 190 180 170 160 150 140 130 120 110 100 90
ppm (f1)
80
70
60
50
40
30
20
10
0
-10 -20
N
O
4m
9.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
-1.0
ppm (f1)
S25

N
O
4m
210 200 190 180 170 160 150 140 130 120 110 100 90
ppm (f1)
80
70
60
50
40
30
20
10
0
-10 -20
N
O
Cl
4n
10.0
9.0
8.0
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
-1.0
ppm (f1)
S26

N
O
Cl
4n
210 200 190 180 170 160 150 140 130 120 110 100
ppm (f1)
90
80
70
60
50
40
30
20
10
0
-10 -20
S27