Synthesis of dibenzodiazepinones via tandem copper(I)-catalyzed C-N bond formation

Article abstract of DOI:10.1002/adsc.201301020

An efficient, one-pot method for the synthesis of dibenzodiazepinone derivatives involving copper-catalyzed tandem C-N bond formation is reported. The use of various halo amide and 2-iodoaniline derivatives permitted the synthesis of an array of dibenzodiazepinone derivatives in moderate to good yields. Moreover, a dibenzodiazepinone derivative {2-(11-oxo-5H-dibenzo[b,e][1, 4]diazepin-10(11H)-yl)benzonitrile} was utilized to synthesize the triazapentacyclic ring derivative {12-chloro- 8,15,22-triazapentacyclo[13.7.0. 0^2,7.0^9,14.0^16,21]docosa-1(22),2,4,6,9(14),10, 12,16(21),17,19-decaene}.

Full text of DOI:10.1002/adsc.201301020

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DOI: 10.1002/adsc.201301020
Synthesis of Dibenzodiazepinones via Tandem Copper(I)-
À
Catalyzed C N Bond Formation
Sachin D. Gawande,a Veerababurao Kavala,a Manoj R. Zanwar,a Chun-Wei Kuo,a
Wen-Chang Huang,a,* Ting-Shen Kuo,a Hsiu-Ni Huang,a Chiu-Hui He,a
and Ching-Fa Yaoa,*
a
Department of Chemistry, National Taiwan Normal University, 88, Sec. 4, Tingchow Road, Taipei, Taiwan 116, R.O.C.
E-mail: cheyaocf@ntnu.edu.tw
Received: November 15, 2013; Revised: January 15, 2014; Published online: && &&, 0000
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201301020.
Abstract: An efficient, one-pot method for the syn- 10ACTHNUTRGNEUGN(11H)-yl)benzonitrile} was utilized to synthesize
thesis of dibenzodiazepinone derivatives involving the triazapentacyclic ring derivative {12-chloro-
copper-catalyzed tandem C N bond formation is re- 8,15,22-triazapentacyclo[13.7.0.02,7.09,14.016,21]docosa-
À
ported. The use of various halo amide and 2-iodoani- 1(22),2,4,6,9(14),10,12,16(21),17,19-decaene}.
line derivatives permitted the synthesis of an array
À
of dibenzodiazepinone derivatives in moderate to Keywords: C N bond formation; copper catalysts;
good yields. Moreover,
a
dibenzodiazepinone dibenzodiazepinones; tandem processes; Ullmann
derivative {2-(11-oxo-5H-dibenzoACTHNUGRTNENUG[b,e]ACHTUNGTRENN[UGN 1,4]diazepin- coupling
Introduction
and co-workers reported on the synthesis of dibenzo-
diazepinone from 2-bromo-N-(2-bromophenyl)benz-
The synthesis of seven-membered fused N-heterocy-
ACHTUNGTRENaNGNU mide and various primary amines using a Cu(I) cata-
cles is an area of considerable interest for synthetic lyst.[6] However, in our recent publication, we found
organic chemists. Fused N-heterocycles such as diben- that the product formed is, in fact, the N-substituted-
zoxazepinone, dibenzothiazepin, dibenzoazepine de- 2-(benzo[d]oxazol-2-yl) (B), as confirmed by
rivatives are ubiquitous structures that are found in 1H NMR, 13C NMR, LRMS, HR-MS and single crys-
numerous natural products as well as in the core tal X-ray analysis data (Scheme 1)[7] and is not the di-
structures of many best selling drugs.[1] In particular, benzodiazepinone derivative (A). Thus, an efficient,
1,4-dibenzodiazepinone derivatives are ideal scaffolds one-pot protocol for the synthesis of dibenzodiazepi-
due to their diverse curative properties. The dibenzo- none derivatives continues to be highly desirable.
diazepinone nucleus is a component of many pharma-
2-Iodobenzamide is very useful substrate in organic
ceutical drugs that possess antithrombotic, antitumor, synthesis. Smart structural manipulation at the amidic
antibiotics, anxiolytic, anticonvulsant, hypnotic, seda- position leads to the formation of numerous interest-
tive, amnestic, antidepressant properties.[2] Further, ing compounds.[8] In recent years, our group has been
they are also used in the treatment of diabetic nephr- interested in exploring copper-catalyzed transforma-
opathy, the central nervous system and can function tions and the synthesis of seven-membered rings.[9] In
as novel inhibitors of HIV protease.[3] Despite several a continuation of our interest in copper-catalyzed
advances in the synthesis of seven-membered hetero- transformations, we were prompted to investigate the
cycles, the synthesis of dibenzodiazepinone continues reaction of N-(2-cyanophenyl)-2-iodobenzamide de-
to be a cumbersome task. Recently, Buchwald and co- rivatives and 2-iodoaniline derivatives in the presence
workers reported on the synthesis of dibenzodiaze- of a copper catalyst. We envisioned that the reaction
pines and dibenzooxazepines using a 2-aminoaryl of 1a with 2-iodoaniline in the presence of copper
ketone with 1,2-dihaloarenes in the presence of iodide and a base would initially generate the Ull-
a Pd(0) or Cu(I) catalyst in a step wise process.[4a] Fur- mann coupled product 3a. Furthermore, it may form
ther, the limited available protocols for the synthesis the fused benzoimidazole derivative (4a), via pathway
of dibenzodiazepinone derivatives are either multi- a or the dibenzodiazepinone (5a), via pathway
step or are lacking in selectivity.[5] Very recently, Ma b (Scheme 2).
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Sachin D. Gawande et al.
Scheme 1. Reaction of 2-halo-N-(2-halophenyl)benzamide and various primary amines.
Scheme 2. Plausible pathway for the formation of the products.
Results and Discussion
30 mol% failed to show any further improvement in
the yield (entry 5). Next, in an attempt to improve
To test our hypothesis, in an initial experiment, we re- product yield, several copper catalysts, including
acted N-(2-cyanophenyl)-2-iodobenzamide (1a) and CuCl, CuBr, Cu2O, CuOAc2 and CuSO4 were em-
2-iodoaniline (2a) in the presence of a catalytic ployed, but no improvement in yield was observed
amount of copper iodide (10 mol%) with K2CO3 as (entries 6–10).
a base and DMSO as a solvent at 1208C. The reaction
Screening the reaction using various inorganic and
afforded compound 3a in 72% yield (Table 1, entry 1) organic bases either resulted in the formation of the
along with trace amounts of a polar compound. This intermediate 3a or a lower yield of compound 5a (en-
polar compound was isolated and analyzed by tries 11–17). Besides DMSO, the reaction proceeded
1H NMR, 13C NMR, LR-MS, and HR-MS. Single crys- in DMF but afford a lower yield of compound 5a
tal X-ray analysis data revealed that the compound (entry 18). Finally, from the optimization studies, we
formed was 5a (dibenzodiazepinone) instead of com- found that, the reaction with 20 mol% copper iodide
pound 4a (Figure 1).
with K2CO3 as a base in DMSO solvent at 1358C
Delighted by our initial results, we investigated the were found to be the best conditions for the reaction,
optimum conditions for this reaction. The yield of the these conditions were used in further experiments.
product 5a was improved to 30% when reaction was
With optimized reaction conditions in hand, we fo-
conducted at 1358C (entry 2). However, further in- cused our attention on the scope and limitations of
creases in temperature failed to result in further im- this protocol. In this regard, we initially investigated
provements in yield (entry 3). To examine the efficacy the scope of the reaction with respect to 2-iodoaniline
of the catalyst, we conducted the reaction with differ- derivatives with 1a as a model substrate (Table 2).
ent quantities of copper catalyst. The use of 20 mol% The reaction of an unsubstituted 2-iodoaniline with 1a
CuI gave a better yield of compound 5a (entry 4). furnished the corresponding dibenzodiazepinone de-
However, a further increase in the amount of CuI to rivative in 74% yield (entry 1). Moreover, moderately
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Synthesis of Dibenzodiazepinones
Table 1. Optimization of the reaction conditions.
Table 2. Synthesis of dibenzodiazepinone from 1a and differ-
ent 2-iodoanilines.
[a]
[a]
All reactions were performed on 0.5 mmol of 1a and
0.5 mmol of 2a–g with CuI (20 mol%) and K2CO3
(2.5 equiv.) in DMSO at 1358C.
Yields refer to isolated and purified compound.
10–15% of 2 is recovered.
Reactions were performed on a 0.5-mmol scale.
[b]
Yields refer to the isolated and purified compound..
[c]
Reaction was performed in DMF as the solvent.
[b]
[c]
electron-donating substitutions on 2-iodoaniline such
as methyl and isopropyl groups resulted in the forma-
tion of the corresponding compounds 5b and 5c in
good yields, respectively (entries 2 and 3). Further-
more, the reaction of 2-iodoaniline bearing a strong
electron-donating group (OMe) afforded the corre-
sponding compound 5d in 59% yield (entry 4). How-
ever, 2-iodoanilines possessing electron-withdrawing
substituents, such as fluoro and chloro groups, provid-
ed 48% and 55% yields of the corresponding com-
pounds with a longer reaction time (entries 5 and 6).
In both these cases about 10–15% unreacted 2-iodo-
Figure 1. ORTEP diagram of 5a.
ACHTUNGERTNaNUNG niline was recovered.
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Scheme 3. Smiles rearrangement during the synthesis of dibenzoxaazepinone.[10]
Recently, Snieckus and co-workers observed 2-iodoaniline (Scheme 4). Under the present reaction
a Smiles rearrangement during the synthesis of diben- conditions, 1p underwent decomposition and 1q yield-
zoxaazepinone (Scheme 3).[10] Based on literature re- ed the N-arylated compound (3y). Furthermore, when
ports, N-hetrocycles also can undergo a Smiles rear- 2-bromo-N-(2-bromophenyl)benzamide was used as
rangement.[11] However, in our reactions, no evidence substrate, we obtained 2-(benzo[d]oxazol-2-yl)-N-(2-
was found for such a rearranged product, which is evi- iodophenyl)aniline (6a) as a sole product.[7]
dent from the single crystal X-ray analysis of com-
Finally, the synthesis of the nitro-substituted diben-
pound 5g (see the Supporting Information).
zodiazepinone (5n) provided us with the opportunity
To extend the scope of this methodology, we subse- to carry out a reductive cyclization (Scheme 5). The
quently utilized various 2-halo-N-phenylbenzamides triaza-pentacyclic compound 7a was obtained in ex-
and 2-iodoanilines using the developed optimal reac- cellent yield, which was confirmed by single crystal
tion conditions and the results are shown in Table 3. X-ray analysis (Figure 2).
The reaction of unsubstituted phenyl-2-iodobenza-
mide (1b) with the 2-iodoanilines 2a and 2c resulted
in the production of their corresponding compounds Conclusions
(5h and 5i) in good yields within a shorter reaction
time (entries 1 and 2). Further, the amides derived In conclusion, we report herein on an efficient,
from 2-iodobenzoic acid and ortho-substituted ani- copper-catalyzed, one-pot protocol for the synthesis
lines reacted smoothly with 2-iodoanilines (2a and 2c) of phenyl-substituted dibenzodiazepinone derivatives
to furnish the corresponding dibenzodiazepinone de- in moderate to good yields from 2-halo-N-
rivatives in moderate to good yields. It is worth phenylbenzACTHNUTRGNEaNUG mides and 2-iodoaniline via a cascade
noting that the 2-halo-N-phenylbenzamides derived process. Interestingly, no evidence was found for the
from electron-withdrawing ortho-substituted anilines compounds undergoing a Smiles rearrangement, as
such as F, Cl, NO2 required a longer reaction time reported in the case of dibenzoxaazepinone. More-
than for those with electron-donating groups (en- over, the nitro-substituted dibenzodiazepinone deriva-
tries 3–9). Moreover, 2-iodobenzamides derived from tive 5n was utilized to synthesize compound 7a in ex-
m-methoxyaniline and p-isopropylaniline produce cellent yield by reductive cyclization.
compounds 5q and 5r in moderate yields (entries 10
and 11). However, the yield dropped considerably to
44% when the electron-withdrawing N-(4-chlorophen-
yl)-2-iodobenzamide (1k) was treated with 2-iodoani-
Experimental Section
line (entry 12). Furthermore, the reactions of 2-iodo-
N-phenylbenzamides generated from 2-iodo-5-me-
General Information
All chemicals were purchased from various sources and
were used directly without further purification. Analytical
thin-layer chromatography was performed using silica gel
60F glass plates and silica gel 60 (230–400 mesh) was used in
flash chromatographic separations. NMR spectra were re-
corded in DMSO-d6 with DMSO and CDCl3 with CHCl3 as
the internal standards for 1H NMR (400 MHz) and
13C NMR (100 MHz). Coupling constants are expressed in
Hertz. HR-MS were recorded using MALDI, ESIÀ or ESI+
mode. Melting points were recorded using an electro ther-
thoxybenzoic acid and 6-iodobenzo[d]ACHTNUTRGNEUNG[1,3]dioxole-5-
carboxylic acid formed the corresponding compounds
5t and 5u in moderate yields (entries 13 and 14).
However, electron-withdrawing substitution on 2-io-
dobenzoic acid such as Cl and F increased the product
yield as well as reduced the reaction time (entries 15
and 16).
We next investigated the reactions of 2-iodobenz-
ACHTUNGTRENNUNGamides having less ortho effect such as 2-iodobenz-
ACHTUNGTRENNUNGamide (1p) and 2-iodo-N-methylbenzamide (1q) with mal capillary melting point apparatus and are uncorrected.
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Synthesis of Dibenzodiazepinones
Table 3. Synthesis of dibenzodiazepinone from various 2-ha-
lobenzamides and different 2-iodoanilines.
Table 3. (Continued)
[a]
All reactions were performed on 0.5 mmol of 1b–o and
0.5 mmol of 2 a, c with CuI (20 mol%) and K2CO3
(2.5 equiv.) in DMSO at 1358C.
Yields refer to isolated and purified compound.
[b]
[c]
10–15% of 2 is recovered.
General Procedure for the Synthesis of 2-(11-Oxo-
5H-dibenzo
ACHTUNGTNER[UNGN b,e]ACHTUNRTEGG[NNUN 1,4]diazepin-10ACHTNUGTNER(NUGN 11H)-yl)benzo-
nitriles (5a–5x)
In an oven-dried, 10-mL round-bottom flask equipped with
magnetic stirrer was added 1a (0.5 mmol), 2a (0.5 mmol),
CuI (20 mol%), K2CO3 (1.25 mmol) in anhydrous DMSO
(1.5 mL). The reaction mixture was then stirred at 1358C
under a nitrogen atmosphere. After completion of the reac-
tion, as determined by TLC, the reaction mixture was al-
lowed to cool to room temperature. The crude reaction mix-
ture was then purified by column chromatography without
work-up using hexane-ethyl acetate as the eluent to yield
compound 5a.
12-Chloro-8,15,22-triazapentacyclo-
[13.7.0.02,7.09,14.016,21]docosa-
1(22),2,4,6,9(14),10,12,16(21),17,19-decaene (7a)
In a stir-bar-equipped, flame-dried, 50-mL round-bottom
flask, 5n (1 mmol) in acetic acid (20 mL) was added, fol-
lowed by the addition of iron powder (5 mmol). The reac-
tion mixture was then stirred at 808C for 6 h. After comple-
tion of the reaction as determined by TLC, the reaction mix-
ture was allowed to cool to room temperature. The crude re-
action mixture was then evaporated under reduced pressure
and then basified by adding aqueous Na2CO3 to pH 10. The
resulting solution was then extracted with ethyl acetate
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Scheme 4. Reaction with different amides.
Spectral Data of Prepared Compounds
N-(2-Cyanophenyl)-2-iodobenzamide (1a): Yield: 78%;
white solid; mp 181–1838C; FT-IR (KBr): n=3468, 2283,
1590 cmÀ1 1H NMR (400 MHz, CDCl3): d=8.57 (d, J=
;
8.5 Hz, 1H), 7.96–7.97 (m, 2H), 7.64–7.71 (m, 2H), 7.57 (d,
J=7.5 Hz, 1H), 7.49 (t, J=7.5 Hz, 1H), 7.25–7.29 (m, 1H),
7.22 (t, J=7.8 Hz, 1H); 13C NMR (100 MHz, CDCl3): d=
167.6, 141.2, 140.6, 140.3, 134.5, 132.7, 132.3, 128.8, 128.7,
125.0, 121.8, 116.4, 108.9, 92.5; LR-MS (EI): m/z (relative in-
tensity)=348 (100) [M]+, 322 (40); HR-MS: m/z=347.9765,
calcd. for C14H9IN2O [M]+: 347.9760.
Scheme 5. Synthesis of 7a ring by reductive cyclization.
N-(2-Cyanophenyl)-2-(2-iodophenylamino)benzamide
(3a): Yield: 84%; white solid; mp 157–1598C; FT-IR (KBr):
1
n=3431, 2305, 1560 cmÀ1; H NMR (400 MHz, CDCl3): d=
9.09 (brs, 1H), 8.55 (d, J=8.4 Hz, 1H), 8.48 (brs, 1H), 7.87
(d, J=7.9 Hz, 1H), 7.73 (d, J=7.5 Hz, 1H), 7.63–7.67 (m,
2H), 7.37–7.40 (m, 2H), 7.21–7.31 (m, 3H), 6.96 (t, J=
7.5 Hz, 1H), 6.79 (t, J=7.5 Hz, 1H); 13C NMR (100 MHz,
CDCl3): d=167.3, 145.6, 142.8, 140.7, 140.1, 134.4, 133.5,
132.5, 129.1, 127.9, 124.9, 124.5, 121.8, 121.3, 119.8, 118.6,
117.1, 116.7, 102.7, 93.6; LR-MS (EI): m/z (relative intensi-
ty)=440 (95) [M+H]+, 314 (100); HR-MS: m/z=440.0257,
calcd. for C20H15IN3O [M+H]+: 440.0260.
2-{11-Oxo-5H-dibenzo
zonitrile (5a): Yield: 74%; yellow solid; mp 213–2158C; FT-
IR (KBr): n=3478, 2305, 1590 cmÀ1 1H NMR (400 MHz,
ACHTUNGTNER[UNGN b,e]ACHTUNRTEGG[NNUN 1,4]diazepin-10ACHTNUGERTN(NUGN 11H)-yl]ben-
;
DMSO-d6): d=8.12 (brs, 1H), 7.98 (d, J=7.52 Hz, 1H), 7.82
(t, J=7.9 Hz, 1H), 7.66 (d, J=7.6 Hz, 1H), 7.56–7.61 (m,
2H), 7.42 (t, J=7.7 Hz, 1H), 7.23 (d, J=8.0 Hz, 1H), 7.14
(d, J=8.0 Hz, 1H), 7.08 (t, J=7.3 Hz, 1H), 7.02 (t, J=
7.5 Hz, 1H), 6.90 (t, J=7.6 Hz, 1H), 6.58 (d, J=8.0 Hz,
1H); 13C NMR (100 MHz, DMSO-d6): d=167.9, 151.8,
145.4, 144.6, 134.7, 133.8, 133.4, 133.0, 132.2, 130.9, 128.8,
126.4, 124.8, 123.9, 123.6, 121.9, 121.2, 119.4, 116.4, 113.0;
LR-MS (ESI): m/z (relative intensity)=334 (100) [M+
Na]+, 323 (40); HR-MS: m/z=334.0964, calcd. for
C20H13N3NaO [M+Na]+: 334.0956.
Figure 2. ORTEP diagram of 7a.
(100 mL). The ethyl acetate layer was dried over MgSO4, fil-
tered and evaporated under reduced pressure. The crude
compound was then purified by column chromatography
using hexane-ethyl acetate as the eluent to afford compound
7a.
2-{8-Methyl-11-oxo-5H-dibenzo
ACHTUGTNREN[UNG b,e]ACHUTTGNREN[NUGN 1,4]diazepin-10-
AHCTUNGTREG(NNNU 11H)-yl}benzonitrile (5b): Yield: 67%; yellow solid; mp
6
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Synthesis of Dibenzodiazepinones
216–2188C; FT-IR (KBr): n=3310, 2280, 1560 cmÀ1
;
150.5, 145.4, 143.0, 134.6, 134.1, 133.9, 133.6, 133.2, 131.6,
129.0, 128.6, 126.6, 125.3, 124.2, 123.2, 122.2, 119.2, 116.2,
113.4; LR-MS (EI): m/z (relative intensity)=345 (100)
[M]+, 311 (30); HR-MS: m/z=345.0665, calcd. for
C20H12ClN3O [M]+: 345.0669.
1H NMR (400 MHz, CDCl3): d=7.92 (d, J=7.5 Hz, 1H),
7.68–7.76 (m, 2H), 7.62 (d, J=7.80 Hz, 1H), 7.45 (t, J=
7.5 Hz, 1H), 7.34 (t, J=7.0 Hz, 1H), 7.06 (t, J=7.4 Hz, 1H),
6.82–6.86 (m, 2H), 6.71 (d, J=7.8 Hz, 1H), 6.54 (d, J=
8.1 Hz, 1H), 5.57 (brs, 1H), 2.26 (s, 3H); 13C NMR
(100 MHz, CDCl3): d=168.3, 150.9, 146.1, 144.1, 136.8,
133.9, 133.7, 133.3, 133.2, 131.4, 131.3, 128.1, 125.5, 125.0,
124.7, 122.9, 121.5, 119.1, 116.4, 113.8, 20.8; LR-MS (ESI):
m/z (relative intensity)=348 (100) [M+Na]+, 286 (60); HR-
MS: m/z=348.1120, calcd. for C21H15N3NaO [M+Na]+:
348.1113.
2-{8-Bromo-11-oxo-5H-dibenzo
ACHTUGTNREN[UNG b,e]ACHUTTGNREN[NUGN 1,4]diazepin-10-
AHCTUNGTREG(NNNU 11H)-yl}benzonitrile (5g): Yield: 63%; yellow solid; mp
230–2328C; FT-IR (KBr): n=3500, 3455, 1650 cmÀ1
;
1H NMR (400 MHz, CDCl3): d=7.90 (d, J=7.8 Hz, 1H),
7.73–7.79 (m, 2H), 7.66 (d, J=7.9 Hz, 1H), 7.51 (d, J=
7.6 Hz, 1H), 7.34 (t, J=7.4 Hz, 1H), 7.13 (d, J=8.3 Hz,
1H), 7.06 (t, J=7.5 Hz, 1H), 6.84–6.90 (m, 2H), 6.76 (s,
2-{8-Isopropyl-11-oxo-5H-dibenzo
(11H)-yl}benzonitrile (5c): Yield: 79%; grey solid; mp 196–
1988C; FT-IR (KBr): n=3500, 2305, 1650 cmÀ1 1H NMR
A
N
1H), 5.83ACTHNGUTERNNUG
(brs, 1H); 13C NMR (100 MHz, CDCl3): d=168.0,
150.4, 145.4, 143.5, 134.9, 134.2, 133.9, 133.6, 133.3, 131.6,
129.5, 128.6, 128.3, 124.3, 123.3, 122.5, 119.2, 116.3, 116.1,
113.5; LR-MS (EI): m/z (relative intensity)=389 (100)
[M]+, 310 (65); HR-MS: m/z=389.0168, calcd. for
C20H12BrN3O [M]+: 389.0164.
;
(400 MHz, CDCl3): d=7.92 (d, J=7.8 Hz, 1H), 7.77 (d, J=
8.6 Hz, 1H), 7.71 (t, J=7.9 Hz, 1H), 7.63 (d, J=7.9 Hz,
1H), 7.46 (t, J=7.5 Hz, 1H), 7.33 (t, J=7.8 Hz, 1H), 7.04 (t,
J=7.60 Hz, 1H), 6.89–6.94 (m, 2H), 6.85 (d, J=8.0 Hz,
1H), 6.48 (s, 1H), 5.64 (brs, 1H), 2.66 (m, 1H), 1.05 (m,
10-Phenyl-5H-dibenzoACTHUNGTREN[UNNG b,e]ACHTNUGTREG[NNUN 1,4]diazepin-11CAHTNUGTRENUN(GN 10H)-one
(5h): Yield: 74%; white solid; mp 236–2388C; FT-IR (KBr):
1
3H), 1.03
N
n=3525, 3425, 1635, 746 cmÀ1; H NMR (400 MHz, CDCl3):
151.1, 146.1, 145.1, 142.0, 133.8, 133.6, 133.5, 133.23, 133.20,
131.4, 128.1, 124.7, 124.4, 123.7, 122.8, 120.9, 119.0, 116.4,
113.9, 33.4, 23.9; LR-MS (ESI): m/z (relative intensity)=376
(100) [M+Na]+, 354 (80); HR-MS: m/z=376.1419, calcd.
for C23H19N3NaO [M+Na]+: 376.1426.
d=7.93 (d, J=7.6 Hz, 1H), 7.40–7.47 (m, 4H), 7.29–7.35 (m,
2H), 7.06 (t, J=7.5 Hz, 1H), 6.98–7.01 (m, 1H), 6.94–6.96
(m, 1H), 6.89 (t, J=8.0 Hz, 1H), 6.79–6.84 (m, 2H), 5.61
(brs, 1H); 13C NMR (100 MHz, CDCl3): d=168.3, 150.9,
144.0, 143.6, 135.3, 133.2, 132.8, 129.3, 129.2, 127.4, 126.8,
125.9, 125.6, 124.1, 122.9, 120.7, 118.8; LR-MS (EI): m/z
(relative intensity)=286 (100) [M]+; HR-MS: m/z=
286.1106, calcd. for C19H14N2O [M]+: 286.1106.
2-{8-Methoxy-11-oxo-5H-dibenzo
(11H)-yl}benzonitrile (3d): Yield: 59%; white solid; mp 216–
2188C; FT-IR (KBr): n=3480, 3494, 2280, 650 cmÀ1
1H NMR (400 MHz, DMSO-d6): d=7.92 (d, J=7.6 Hz, 1H),
7.75 (d, J=7.6 Hz, 1H), 7.68–7.71(m, 1H), 7.63 (d, J=
ACHTUGTNREN[UNG b,e]ACHUTTGNREN[NUGN 1,4]diazepin-10-
ACHTUNGTRENNUNG
;
8-Chloro-10-phenyl-5H-dibenzo
(10H)-one (5i): Yield: 83%; red solid; mp 223–2258C; FT-
IR (KBr): n=3439, 3400, 1530, 1360 cmÀ1 1H NMR
ACHTUGTNREN[UNG b,e]ACHUTTGNREN[NUGN 1,4]diazepin-11-
G
ACHTUNGTRENNUNG
7.9 Hz, 1H), 7.44 (t, J=7.5 Hz, 1H), 7.32 (t, J=7.5 Hz, 1H),
7.06 (t, J=7.4 Hz, 1H), 6.85 (d, J=7.9 Hz, 1H), 6.56–6.59
(m, 2H), 6.45 (dd, J=2.2 Hz, 8.8 Hz, 1H), 5.79 (brs, 1H),
;
(400 MHz, CDCl3): d=7.90 (d, J=8.0 Hz, 1H), 7.45–7.49
(m, 2H), 7.34–7.39 (m, 3H), 7.30–7.34 (m, 1H), 7.07 (t, J=
7.5 Hz, 1H), 6.96 (dd, J=2.2 Hz, 8.4 Hz, 1H), 6.81–6.89 (m,
2H), 6.77 (d, J=2.2 Hz, 1H), 5.56 (brs, 1H); 13C NMR
(100 MHz, CDCl3): d=168.0, 150.5, 143.1, 142.6, 136.4,
133.3, 133.0, 129.6, 129.2, 129.1, 127.9, 126.6, 125.8, 125.3,
123.3, 121.7, 118.8; LR-MS (EI): m/z (relative intensity)=
320 (100) [M]+; HR-MS: m/z=320.0719, calcd for
C19H13ClN2O [M]+: 320.0716.
3.71ACHTUNGTRENNUNG
(s, 3H); 13C NMR (100 MHz, DMSO-d6): d=168.2,
158.2, 150.5, 146.2, 145.7, 133.9, 133.6, 133.2, 133.1, 131.3,
127.9, 126.9, 126.7, 124.8, 123.1, 119.1, 116.4, 113.6, 109.9,
106.2, 55.7; LR-MS (ESI): m/z (relative intensity)=340
(100) [MÀH]À, 386 (65); HR-MS: m/z=340.1082, calcd. for
C21H14N3O2 [MÀH]À: 340.1086.
2-{7,8-Difluoro-11-oxo-5H-dibenzoACTHNUTRGENN[UG b,e]AHCTUNGTRNEN[UGN 1,4]diazepin-10-
A
10-(2-Chlorophenyl)-5H-dibenzoACTHNGUTREN[UNG b,e]ACTHUNGTRENN[UNG 1,4]diazepin-11-
;
(10H)-one (5j): Yield: 59%; yellow solid; mp 180–1818C;
1H NMR (400 MHz, CDCl3): d=7.92 (d, J=7.9 Hz, 1H),
7.74–7.80 (m, 2H), 7.65 (d, J=8.0 Hz, 1H), 7.52 (t, J=
7.6 Hz, 1H), 7.38 (t, J=7.8 Hz, 1H), 7.10 (t, J=7.6 Hz, 1H),
6.84–6.88 (m, 2H), 6.50 (dd, J=7.7 Hz, 11.1 Hz, 1H), 5.67
(brs, 1H); 13C NMR (100 MHz, DMSO-d6); d=167.2, 150.6,
144.5, 141.58 (d, J=2.3 Hz), 141.51 (d, J=2.1 Hz), 134.5,
133.9, 133.4, 132.1, 130.9, 129.14 (d, J=2.2 Hz), 129.07 (d,
J=2.3 Hz), 128.8, 123.5, 122.2, 119.2, 115.9, 113.5, 113.3,
112.4, 109.2, 109.0; LR-MS (ESI): m/z (relative intensity)=
347 (100) [M]+, 318 (80); HR-MS: m/z=347.0863, calcd. for
C20H11F2N3O [M]+: 347.0870.
FT-IR (KBr): n=3468, 1636, 339 cmÀ1; H NMR (400 MHz,
1
DMSO-d6): d=8.01 (brs, 1H), 7.61–7.65 (m, 2H), 7.38–7.49
(m, 4H), 7.19 (d, J=7.1 Hz, 1H), 7.12 (d, J=7.6 Hz, 1H),
6.98–7.06 (m, 2H), 6.87 (t, J=6.9 Hz, 1H), 6.62 (d, J=
7.7 Hz, 1H); 13C NMR (100 MHz, DMSO): d=167.4, 151.6,
144.2, 140.4, 132.9, 132.8, 132.3, 132.1, 131.8, 130.2, 129.6,
128.2, 125.8, 124.3, 124.1, 123.3, 121.7, 120.9, 119.1; LR-MS
(ESI): m/z (relative intensity)=321 (100) [M+H]+, 323
(95); HR-MS: m/z=321.0792, calcd. for C19H14ClN2O [M+
H]+: 321.0795.
8-(2-Chlorophenyl)-8,13-dihydro-7H-benzo[b]naphtho-
2-{8-Chloro-11-oxo-5H-dibenzo
[b,e]
E
N
ACHTUNGTRENNUNG
A
;
2488C; FT-IR (KBr): n=3446, 3422, 1620, 745 cmÀ1
;
(400 MHz, CDCl3): d=7.90 (d, J=8.6 Hz, 1H), 7.85–7.91
(m, 2H), 7.51–7.64 (m, 5H), 7.33–7.41 (m, 2H), 7.12 (d, J=
7.7 Hz, 1H), 7.04 (t, J=7.4 Hz, 1H), 6.93 (t, J=7.9 Hz, 1H),
6.78 (d, J=8.0 Hz, 1H)„ 6.44 (brs, 1H); 13C NMR
(100 MHz, CDCl3): d=168.8, 146.9, 143.4, 140.8, 136.1,
135.1, 133.7, 131.7, 130.8, 129.4, 129.3, 128.3, 128.0, 127.9,
1H NMR (400 MHz, CDCl3): d=7.91 (d, J=7.6 Hz, 1H),
7.73–7.79 (m, 2H), 7.66 (d, J=7.9 Hz, 1H), 7.51 (d, J=
7.6 Hz, 1H), 7.32 (d, J=7.4 Hz, 1H), 7.06 (d, J=7.5 Hz,
1H), 6.93–6.98 (m, 2H), 6.85 (d, J=8.0 Hz, 1H), 6.62 (s,
1H), 5.86 (brs, 1H); 13C NMR (100 MHz, CDCl3): d=168.1,
Adv. Synth. Catal. 0000, 000, 0 – 0
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FULL PAPERS
Sachin D. Gawande et al.
126.9, 125.8, 124.9, 124.7, 124.6, 122.8, 121.8, 121.4, 120.5;
LR-MS (EI): m/z (relative intensity)=370 (100) [M]+, 337
(55); HR-MS: m/z=370.0875, calcd. for C23H15ClN2O [M]+:
370.0873.
CDCl3): d=168.1, 155.9, 150.3, 141.9, 135.8, 133.0, 132.9,
132.0, 130.3, 129.9, 128.7, 125.5, 125.4, 124.9, 122.9, 121.6,
121.5,
118.9,
112.8,
56.2;
LR-MS
(EI):
m/z (relative intensity)=350 (100) [M+], 315 (60); HR-MS:
10-(2-Fluorophenyl)-5H-dibenzo
(10H)-one (5l): Yield: 78%; violet solid; mp 230–2328C; FT-
IR (KBr): n=3461, 1636, 551 cmÀ1 1H NMR (400 MHz,
ACHTUGTNREN[UNG b,e]ACHUTTGNREN[NUGN 1,4]diazepin-11-
m/z=350.0819, calcd. for C20H15ClN2O2 (M+): 350.0822.
G
10-(3-Methoxyphenyl)-5H-dibenzo
(10H)-one (5q): Yield: 74%; yellow solid; mp 199–2018C;
FT-IR (KBr): n=3472, 3431, 1590, 1379 cmÀ1 1H NMR
ACHTUGTNREN[UNG b,e]ACHUTTGNREN[NUGN 1,4]diazepin-11-
;
ACHTUNGTRENNUNG
CDCl3): d=7.97 (d, J=7.7 Hz, 1H), 7.35–7.46 (m, 3H),
7.24–7.31 (m, 2H), 7.10 (d, J=7.5 Hz, 1H), 7.06 (t, J=
7.5 Hz, 1H), 6.99 (t, J=7.3 Hz, 1H), 6.95 (t, J=8.0 Hz, 1H),
6.88 (d, J=8.0 Hz, 1H), 6.84 (d, J=8.0 Hz, 1H), 5.66 (brs,
1H); 13C NMR (100 MHz, CDCl3): d=168.1, 160.3, 157.8,
150.8, 143.5, 134.4, 133.3, 133.0, 131.1, 129.7 (d, J=7.8 Hz),
126.1, 125.5, 125.0 (d, J=8.5 Hz), 124.9, 124.2, 122.9, 120.8,
118.9, 116.8, 116.6; LR-MS (ESI): m/z (relative intensity)=
305 (100) [M+H]+, 383 (20); HR-MS (ESI): m/z=305.1091,
calcd. for C19H14FN2O [M+H]+: 305.1090.
;
(400 MHz, CDCl3): d=7.92 (dd, J=1.5 Hz, 7.8 Hz, 1H),
7.35 (t, J=8.0 Hz, 1H), 7.28–7.32 (m, 1H), 7.01–7.07 (m,
2H), 6.97–7.00 (m, 2H), 6.93–6.97 (m, 1H), 6.85–6.91 (m,
3H), 6.83 (d, J=8.0 Hz, 1H), 5.67 (brs, 1H), 3.80 (s, 3H);
13C NMR (100 MHz, CDCl3): d=168.3, 160.5, 151.0, 144.7,
143.9, 135.1, 133.1, 132.8, 129.9, 126.6, 125.9, 125.6, 124.1,
122.9, 121.7, 120.8, 118.9, 115.1, 113.3, 55.6; LR-MS (EI):
m/z (relative intensity)=316 (100) [M]+, 243 (30); HR-MS:
m/z=316.1219, calcd. for C20H16N2O2 [M]+: 316.1212.
10-(2-Nitrophenyl)-5H-dibenzo
[b,e]
E
10-(4-Isopropylphenyl)-5H-dibenzo
(10H)-one (5r): Yield: 66%; pink solid; mp 188–1908C; FT-
IR (KBr): n=3530, 3470, 1635, 540 cmÀ1 1H NMR
ACHTUGTNREN[UNG b,e]ACHUTTGNREN[NUGN 1,4]diazepin-11-
(10H)-one (5m): Yield: 57%; yellow solid; mp 238–2408C;
ACHTUNGTRENNUNG
FT-IR (KBr): n=3350, 1537, 1357 cmÀ1; H NMR (400 MHz,
;
CDCl3): d=8.07 (d, J=7.9 Hz, 1H), 7.87 (d, J=7.6 Hz, 1H),
7.61 (d, J=7.4 Hz, 1H), 7.48 (t, J=7.6 Hz, 1H), 7.29–7.34
(m, 2H), 6.96–7.09 (m, 3H), 6.89–6.95 (m, 2H), 6.84 (d, J=
7.8 Hz, 1H), 5.65 (brs, 1H); 13C NMR (100 MHz, CDCl3):
d=167.8, 150.6, 148.1, 143.9, 136.8, 134.2, 134.1, 133.4, 133.3,
131.4, 128.4, 126.6, 126.5, 124.9, 124.5, 124.45, 123.1, 120.7,
118.9; LR-MS (ESI): m/z (relative intensity)=354 (100)
[M+Na]+, 535 (20); HR-MS: m/z=354.0855, calcd. for
C19H13N3NaO3 [M+Na]+: 354.0855.
(400 MHz, CDCl3): d=7.93 (d, J=7.7 Hz, 1H), 7.28–7.34
(m, 5H), 7.04 (t, J=7.5 Hz, 1H), 6.93 (m, 2H), 6.89 (t, J=
7.9 Hz, 1H), 6.83 (d, J=7.8 Hz, 2H), 5.64 (brs, 1H), 2.95
(m, 1H), 1.29 (s, 3H), 1.27 (s, 3H); 13C NMR (100 MHz,
CDCl3): d=168.5, 151.2, 147.9, 144.1, 141.2, 135.3, 133.0,
132.6, 128.8, 127.2, 126.7, 125.7, 125.5, 123.8, 122.7, 120.7,
118.9, 33.9, 24.1; LR-MS (EI): m/z (relative intensity)=328
(100) [M]+, 313 (80); HR-MS: m/z=328.1572, calcd. for
C22H20N2O [M]+: 328.1576.
8-Chloro-10-(2-nitrophenyl)-5H-dibenzo
G
G
10-(4-Chlorophenyl)-5H-dibenzo
(10H)-one (5s): Yield: 44%; light red solid; mp 193–1958C;
FT-IR (KBr): n =3490, 1580, 1360 cmÀ1 1H NMR
ACHTUGTNREN[UNG b,e]ACHUTTGNREN[NUGN 1,4]diazepin-11-
pin-11(10H)-one (5n): Yield: 65%; white solid; mp 219–
T
ACHTUNGTRENNUNG
2128C; FT-IR (KBr): n=3480, 1545, 1378, 719 cmÀ1
;
;
1H NMR (400 MHz, CDCl3): d=8.06 (d, J=8.0 Hz, 1H),
7.80 (d, J=7.7 Hz, 1H), 7.61 (d, J=7.6 Hz, 1H), 7.48 (t, J=
(400 MHz, CDCl3): d=7.92 (d, J=7.8 Hz, 1H), 7.39–7.41 (d,
J=8.7 Hz, 2H), 7.34–7.36 (m, 2H), 7.30–7.32 (m, 1H), 7.00–
7.08 (m, 2H), 6.95 (d, J=7.0 Hz, 1H), 6.91 (t, J=8.1 Hz,
1H), 6.84 (d, J=8.0 Hz, 1H), 6.77 (d, J=8.0 Hz, 1H), 5.63
(brs, 1H); 13C NMR (100 MHz, CDCl3): d=168.2, 150.9,
144.1, 142.1, 134.9, 133.2, 133.1, 132.9, 130.5, 129.5, 126.8,
126.2, 125.2, 124.2, 123.0, 120.8, 118.9; LR-MS (EI): m/z
(relative intensity)=320 (100) [M]+; HR-MS: m/z=
320.0710, calcd. for C19H13ClN2O [M]+: 320.0716.
7.8 Hz, 1H), 7.23–7.29 (m, 2H), 6.97–7.01ACTHNUGRTENUNG(m, 2H), 6.89 (d,
J=8.5 Hz, 1H), 6.85 (s, 1H), 6.78 (d, J=7.92 Hz, 1H), 5.79
(brs, 1H); 13C NMR (100 MHz, CDCl3): d=167.7, 150.4,
147.9, 142.6, 136.2, 135.0, 134.5, 133.6, 133.3, 131.2, 129.2,
128.9, 126.5, 126.1, 124.9, 124.1, 123.2, 121.8, 119.1; LR-MS
(ESI): m/z (relative intensity)=366 (93) [M+H]+, 331 (67);
HR-MS: m/z=366.0641, calcd. for C19H13ClN3O3 [M+H]+:
366.0645.
2-Methoxy-10-phenyl-5H-dibenzoACHTUNTRGENN[GU b,e]ACHUTNGTRENN[GUN 1,4]diazepin-11-
9-(2-Methylphenyl)-2,9-diazatricyclo[9.4.0.03,8]pentadeca-
1(15),3(8),4,6,11,13-hexaen-10-one (5o): Yield: 78%; red
solid; mp 208–2108C; FT-IR (KBr): n=3445, 1580,
A
1
IR (KBr): n=3490, 3410 cmÀ1; H NMR (400 MHz, CDCl3):
d=7.39–7.46 (m, 5H), 7.31–7.35 (m, 1H), 6.98–7.01 (m,
1H), 6.93–6.95 (m, 1H), 6.85–6.91 (m, 2H), 6.76–6.80 (m,
2H), 5.46 (brs, 1H), 3.78 (s, 3H); 13C NMR (100 MHz,
CDCl3): d=168.2, 155.5, 144.9, 144.7, 143.7, 135.7, 129.3,
129.2, 127.4, 126.8, 126.2, 125.9, 123.9, 120.9, 120.5, 120.2,
115.8, 55.9; LR-MS (EI): m/z (relative intensity)=316 (100)
[M]+, 314 (55); HR-MS (EI): m/z=316.1215, calcd. for
C20H16N2O2 [M]+: 316.1212.
1385 cmÀ1 1H NMR (400 MHz, CDCl3): d=7.90 (dd, J=
;
1.2 Hz, 7.8 Hz, 1H), 7.42–7.44 (m, 1H), 7.28–7.35 (m, 4H),
7.06 (t, J=7.5 Hz, 1H), 6.98–7.01 (m, 1H), 6.93–6.94 (m,
1H), 6.84–6.90 (m, 2H), 6.75 (dd, J=0.9 Hz, 8.0 Hz, 1H),
5.55 (brs, 1H), 2.22 (s, 3H); 13C NMR (100 MHz, CDCl3):
d=168.2, 150.8, 143.5, 142.2, 136.1, 134.3, 133.1, 132.8, 131.6,
130.2, 128.1, 126.9, 125.9, 125.8, 125.5, 124.1, 123.0, 120.7,
118.8, 17.9; LR-MS (EI): m/z (relative intensity)=300 (100)
[M+]; HR-MS: m/z=300.1268, calcd. for C20H16N2O [M+]:
300.1263.
9-Phenyl-14,16-dioxa-2,9-diazatetracyclo[9.7.0.03,8.013,17]-
octadeca-1(18),3(8),4,6,11,13(17)-hexaen-10-one (5u): Yield:
48%; yellow solid; mp 210–2128C; FT-IR (KBr): n=3477,
8-Chloro-10-(2-methoxyphenyl)-5H-dibenzo
azepin-11(10H)-one (5p): Yield: 75%; yellow solid; mp 167–
1698C; FT-IR (KBr): n=3520, 3489, 670 cmÀ1 1H NMR
3410, 599 cmÀ1 1H NMR (400 MHz, DMSO-d6): d=7.81
;
G
(brs, 1H), 7.41–7.45 (m, 2H), 7.28–7.34 (m, 3H), 7.16 (d, J=
7.8 Hz, 1H), 7.10 (s, 1H), 7.03 (t, J=7.3 Hz, 1H), 6.89 (t,
J=7.7 Hz, 1H), 6.72 (s, 1H), 6.67 (d, J=8.0 Hz, 1H), 6.01
(s, 2H); 13C NMR (100 MHz, DMSO-d6): d=166.7, 150.9,
148.3, 145.2, 143.3, 142.4, 134.7, 128.94, 128.92, 126.9, 125.9,
125.6, 123.2, 120.5, 116.7, 109.9, 101.7, 99.4; LR-MS (EI): m/
(400 MHz, CDCl3): d=7.88 (d, J=8.0 Hz, 1H), 7.38 (t, J=
7.1 Hz, 1H), 7.29–7.31 (m, 2H), 7.02–7.08 (m, 3H), 6.91 (dd,
J=2.2 Hz, 8.4 Hz, 1H), 6.83 (d, J=8.4 Hz, 1H), 6.76–6.80
(m, 2H), 5.76 (brs, 1H), 3.86 (s, 3H); 13C NMR (100 MHz,
8
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Adv. Synth. Catal. 0000, 000, 0 – 0
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FULL PAPERS
Synthesis of Dibenzodiazepinones
z
(relative intensity)=330 (100) [M]+; HR-MS: m/z=
330.1008, calcd. for C20H14N2O3 [M]+: 330.1004.
3-Chloro-10-phenyl-5H-dibenzo[b,e][1,4]diazepin-11-
Acknowledgements
G
E
Financial support for this work by the National Science
Council of the Republic of China (NSC 100-2113M-003-008-
MY3), National Taiwan Normal University (99T3030-2, 99-
D, 100-D-06) and Instrumentation Centre at National Taiwan
Normal University are gratefully acknowledged.
(10H)-one (5v): Yield: 62%; white solid; mp 243–2458C;
1
DMSO-d6): d=8.21 (brs, 1H), 7.70 (d, J=8.4 Hz, 1H), 7.43–
7.47 (m, 2H), 7.31–7.36 (m, 3H), 7.19–7.24 (m, 2H), 7.05–
7.09 (m, 2H), 6.91 (t, J=7.6 Hz, 1H), 6.70 (d, J=8.0 Hz,
1H); 13C NMR (100 MHz, CDCl3): d=166.3, 152.9, 143.7,
143.0, 136.8, 134.2, 134.2, 129.0, 128.9, 127.2, 126.2, 125.8,
123.6, 123.2, 121.6, 120.8, 118.3; LR-MS (EI):
m/z (relative intensity)=320 (100) [M]+; 319 (75); HR-MS:
m/z=320.0708, calcd. for C19H13N2OCl35 [M]+: 320.0716.
References
[1] a) N. Bhana, R. H. Foster, R. Olney, G. L. Plosker,
Drugs 2001, 61, 111–161; b) G. DeSarro, A. Chimirri,
A. DeSarro, R. Gitto, S. Grasso, M. Zappala, Eur. J.
Med. Chem. 1995, 30, 925–929; c) J. Gan, D. Ma, Org.
Lett. 2009, 11, 2788–2790; d) J. Sakaki, K. Konishi, M.
Kishida, H. Gunji, T. Kanazawa, H. Uchiyama, H.
Fukaya, H. Mitani, M. Kimura, Bioorg. Med. Chem.
Lett. 2007, 17, 4808–4811; e) S.-M. Lu, A. Howard, J.
Am. Chem. Soc. 2008, 130, 6451–6455; f) J. Hartwig, S.
Ceylan, L. Kupracz, L. Coutable, A. Kirschning,
Angew. Chem. 2013, 125, 9995–9999; Angew. Chem.
Int. Ed. 2013, 52, 9813–9817.
[2] a) R. D. Charan, G. Schlingmann, J. E. Janso, V.
Bernan, X. D. Feng, G. T. Carter, J. Nat. Prod. 2004, 67,
1431–1433; b) R. Mandrioli, L. Mercolini, M. A. Raggi,
Curr. Drug Metab. 2008, 9, 827–844; c) H.-Y. Zhao, G.
Liu, J. Comb. Chem. 2007, 9, 1164–1176; d) B. Petters-
son, V. Hasimbegovic, J. Bergman, J. Org. Chem. 2011,
76, 1554–1561.
3-Fluoro-10-phenyl-5H-dibenzoACHTUNTRGENN[GU b,e]ACHUTNGTRENN[GUN 1,4]diazepin-11-
A
FT-IR (KBr): n=3479, 1669, 545 cmÀ1 ; H NMR (400 MHz,
1
DMSO-d6): d=8.24 (brs, 1H), 7.74–7.78 (m, 1H), 7.42–7.46
(m, 2H), 7.31–7.35 (m, 3H), 7.20 (d, J=7.8 Hz, 1H), 7.06 (t,
J=7.5 Hz, 1H), 6.82–6.97 (m, 3H), 6.70 (d, J=8.0 Hz, 1H);
13C NMR (100 MHz, CDCl3): d=166.3, 165.6, 163.1, 153.8
(d, J=10.5 Hz), 143.8, 143.1, 135.1 (d, J=10.6 Hz), 134.3,
129.0, 128.9, 127.2, 126.1, 125.8, 123.6, 120.9 (d, J=2.4 Hz),
120.8, 109.0 (J=22.0 Hz), 105.1 (J=23.6 Hz); LR-MS (EI):
m/z (relative intensity)=304 (100) [M]+; 303 (80); HR-MS:
m/z=304.1013, calcd. for C19H13N2OF [M]+: 304.1012.
2-(2-Iodophenylamino)-N-methylbenzamide (3y): Yield:
83%; light yellow solid; mp 189–1918C; FT-IR (KBr): n=
3490, 3410, 1700 cmÀ1; H NMR (400 MHz, CDCl3): d=9.28
1
(brs, 1H), 7.85 (d, J=7.9 Hz, 1H), 7.46 (d, J=7.8 Hz, 1H),
7.34 (d, J=8.1 Hz, 1H), 7.23–7.30 (m, 3H), 6.83 (t, J=
7.6 Hz, 1H), 6.27 (t, J=7.7 Hz, 1H), 6.28 (brs, 1H), 3.00 (s,
3H); 13C NMR (100 MHz, CDCl3); d=169.9, 144.4, 143.3,
140.1, 132.1, 128.9, 127.8, 124.0, 120.0, 119.9, 119.3, 116.7,
92.8, 26.9; LR-MS (ESI): m/z (relative intensity)=352 (100)
[M]+, 226 (65); HR-MS: m/z=352.0068, calcd. for
C14H13IN2O [M]+: 352.0073.
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2-(Benzo[d]oxazol-2-yl)-N-(2-iodophenyl)aniline
Yield: 83%; white solid; mp 177–1798C; FT-IR (KBr): n=
3490, 3410, 2899, 1735 cmÀ1 1H NMR (400 MHz, CDCl3):
(6a):
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d=10.33 (brs, 1H), 8.22 (d, J=7.8 Hz, 1H), 7.97 (d, J=
7.9 Hz, 1H), 7.76–7.79 (m, 1H), 7.60–7.63 (m, 1H), 7.53 (d,
J=8.0 Hz, 1H), 7.32–7.40 (m, 4H), 7.23 (d, J=8.4 Hz, 1H),
6.95 (t, J=7.6 Hz, 1H), 6.86 (t, J=7.9 Hz, 1H); 13C NMR
(100 MHz, CDCl3): d=162.7, 149.5, 144.8, 143.2, 141.7,
140.3, 132.4, 129.4, 129.1, 125.4, 125.2, 124.7, 123.1, 119.8,
118.6, 114.7, 110.9, 110.5, 95.2; LR-MS (EI): m/z (relative in-
tensity)=412 (100) [M]+, 286 (60); HR-MS: m/z=412.0069,
calcd. for C19H13IN2O [M]+: 412.0073.
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12-Chloro-8,15,22-triazapentacyclo[13.7.0.02,7.09,14.016,21]do-
cosa-1(22),2,4,6,9(14),10,12,16(21),17,19-decaene (7a): Yield:
87%; light yellow solid; mp 238–2408C; FT-IR (KBr): n=
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3490, 550 cmÀ1; H NMR (400 MHz, CDCl3): d=8.17 (d, J=
7.6 Hz, 1H), 7.89 (d, J=7.3 Hz, 1H), 7.63–7.65 (m, 2H),
7.29–7.36 (m, 3H), 7.12–7.19 (m, 2H), 7.00 (d, J=8.4 Hz,
1H), 6.89 (d, J=7.8 Hz, 1H), 5.53 (brs, 1H); 13C NMR
(100 MHz, CDCl3): d=152.3, 149.0, 144.2, 142.0, 134.8,
131.8, 131.3, 130.2, 129.1, 127.7, 124.0, 123.9, 123.86, 123.81,
123.0, 121.6, 120.5, 119.8, 111.5; LR-MS (EI): m/z (relative
intensity)=317 (100) [M]+, 319 (31); HR-MS: m/z=
317.0715, calcd. for C19H12ClN3 [M]+: 317.0720.
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data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_request/cif.
10
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FULL PAPERS
Synthesis of Dibenzodiazepinones via Tandem Copper(I)-
11
À
Catalyzed C N Bond Formation
Adv. Synth. Catal. 2014, 356, 1 – 11
Sachin D. Gawande, Veerababurao Kavala,
Manoj R. Zanwar, Chun-Wei Kuo, Wen-Chang Huang,*
Ting-Shen Kuo, Hsiu-Ni Huang, Chiu-Hui He,
Ching-Fa Yao*
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