In Situ Generation of Oxazole Ylide and Interception with Sulfonamide: Construction of Amidines Using Two Diazo Molecules

Article abstract of DOI:10.1002/cjoc.201800208

A novel generation of oxazole ylide and interception with sulfonamide have been well developed to construct fully substituted amidines. This copper-catalyzed four-component reaction incorporates two diazo molecules to target amidines and shows broad substrate scope, excellent functional groups tolerance and good to excellent yields.

Full text of DOI:10.1002/cjoc.201800208

In Situ Generation of Oxazole Ylide and Interception with Sulfonamide:
Construction of Amidines Using Two Diazo Molecules
Jijun Chen,a Wenhao Long,a Yanwei Zhao,a Haiyan Li,a Yonggao Zheng,a Pengcheng Lian,a and Xiaobing Wan*,a
ABSTRACT A novel generation of oxazole ylide and interception with sulfonamide have been well developed to construct fully substituted amidines. This
copper-catalyzed four-component reaction incorporates two diazo molecules to target amidines and shows broad substrate scope, excellent functional
groups tolerance and good to excellent yields.
KEYWORDS oxazole ylide, sulfonamide, diazo compounds, amidines
generated by ring-opening of oxazole through tandem alkylation
and phenylsilane-induced reduction. To the best of our knowledge,
Introduction
The metal-catalyzed carbene transfer reactions of diazo
the in situ generation of oxazole ylide and subsequent
compounds have been one of the most essential transformations
interception by nucleophile were underexplored up to now. Very
in modern organic synthesis.[1] In this field, carbene dimerization
recently, our group reported that amide ylides and nitrile ylides
is a ubiquitous process, which is commonly considered as a
could be trapped by sulfonamides and carboxylic acids,
peculiarly worrisome side reaction.[1a] Several groups have
developed this reaction as an alternative approach for the
synthesis of olefin.[2] In general, incorporation of two diazo
molecules to target products constitute a challenge due to the
difficulty in controlling chemo-selectivity.[3] Recently, Dixneuf has
elegantly disclosed that ruthenium vinyl carbenes, generated in
situ from diazo compounds and alkynes, could couple with
another diazo compounds to deliver conjugated dienes (Scheme
1a).[4] Nevertheless, the multi-component reaction utilizing two
diazo molecules is still less well investigated.
respectively.[8] We thus conceived that oxazole ylides, generated
in situ from nitriles and diazo compounds in the presence of a
metal catalyst, could be intercepted by sulfonamides, thus leading
to amidines in high selectivity (Scheme 1c). This four-component
methodology install two diazo molecules to construct fully
substituted amidines in a "one-pot" fashion, which are ubiquitous
substructures in medicinal compounds and natural products.[9]
Results and Discussion
To validate the feasibility of our proposed transformation, we
first investigated the reaction using p-toluenesulfonamide 1a,
acetonitrile 2a, and EDA (ethyl diazoacetate) 3a as substrates. To
our delight, 11% yield of amidines 4a was obtained when CuI was
used as the catalyst (Table 1, entry 1). Encouraged by this result,
other copper sources were then evaluated and Cu(OTf)2 turned
out to be the optimal catalyst (Table 1, entries 2−4). Next, we
found the yield of 4a could be increased by decreasing the
amount of Cu(OTf)2 (Table 1, entry 5). As expected, increasing
EDA loading promoted the formation of 4a (Table 1, entries 5-8).
To maximize the conversion of this reaction, addition of EDA with
a batchwise mode (3.0 equiv./30 min for 2 times) was attempted
and afforded product 4a in a better yield of 85% (Table 1, entry 9).
The yield of 4a could be further improved to 94% yield by using
6.0 equiv. of EDA (1.0 equiv./6 min for 6 times (Table 1, entry 11).
The reaction temperature was found to be a key parameter for
this amidines formation reaction (entries 12−13). Finally, control
experiment indicted that this reaction hardly proceeded in the
absence of Cu(OTf)2 (entry 14).
Scheme 1 Research background
After a receivable optimal reaction condition established, we
turned to evaluate the scope of sulfonamides. As summarized in
Table 2, both electron-rich and electron-poor sulfonamides were
compatible in this reaction, furnishing the desired products 4a−4n
with moderate to high yields. Remarkably, various synthetically
useful functional groups, such as halides (4c−4f, 4k, and 4n) and
ester (4l) were conserved under this transformation, thus
supplying the potential for further derivatization. Substitution in
the ortho, meta, and para position of arene all gave the
5-Alkoxyoxazoles are a class of useful building blocks for various
organic transformations.[5] In pioneering works, Vedejs has
demonstrated that they are convenient azomethine ylide
corresponding
amidines
in
satisfactory
yields.
The
naphthyl-substituted sulfonamide worked well to afford amidine
4o in 89% yield. Moreover, heteroaryl-substituted sulfonamides
proceeded smoothly to deliver medicinally important amidines
4p−4q. Reaction with alkyl sulfonamides were also feasible,
precursors in 1,3-dipolar cycloadditions with alkynes or alkenes
[6],[7]
(Scheme 1b).[6] In these reactions,
azomethine ylide was
a Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry,
Chemical Engineering and Mate-rials Science, Soochow University, Suzhou,
Jiangsu 215123, China
E-mail: wanxb@suda.edu.cn
Dedicated to Professor Xiyan Lu on the occasion of his 90th birthday.
This article has been accepted for publication and undergone full peer review but has not
been through the copyediting, typesetting, pagination and proofreading process, which
may lead to differences between this version and the Version of Record. Please cite this
article as doi: 10.1002/cjoc.201800208
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leading to amidines 4r−4u in remarkable yields. The exact
structure of 4a was further confirmed by single-crystal X-ray
analysis.
Table 3 Scope of nitrilesa
Table 1 Optimization of reaction conditionsa
entry
1
catalyst (mol %) Temp./oC 3a/equiv.
yieldb/%
11
CuI (5)
80
80
80
80
80
80
80
80
80
80
80
60
70
80
4
4
Cu (5)
23
2
CuCl2 (5)
4
19
3
Cu(OTf)2 (5)
Cu(OTf)2 (2)
Cu(OTf)2 (2)
Cu(OTf)2 (2)
Cu(OTf)2 (2)
Cu(OTf)2 (2)
Cu(OTf)2 (2)
Cu(OTf)2 (2)
Cu(OTf)2 (2)
Cu(OTf)2 (2)
—
4
37
4
4
42
5
6
61
6
7
8
71
10
6c
6d
6e
6e
6e
6e
74
8
a Reaction conditions: 1a (0.5 mmol), 2 (10.0 mmol), 3a (6.0 equiv.), and
Cu(OTf)2 (2.0 mol%) at 80 oC under air for 2 h. 3a was added at 1.0
equiv./6 min for 6 times.
85
9
90
10
11
12
13
14
94
To highlight the substrate scope of this process, a variety of
nitriles were investigated as shown in Table 3. It was found that
alkyl nitriles were competent reactants, leading to fully
substituted amidines 5a−5g in satisfactory yields. Sterically
hindered isobutyronitrile afforded 5f in lower yield. Next, aryl
nitriles were also proved to be amenable to this transformation
and gave 5h−5j in modest yields. In addition, benzyl nitriles
bearing various substituents were smoothly converted to 5k−5s in
moderate yields.
59
74
< 5
a Reaction conditions: 1a (0.5 mmol), 2a (2.0 mL), 3a, and catalyst at T
under air for 2h, unless otherwise noted. b Isolated yields. c 3a was added
at 3 equiv./30 min for 2 times. d 3a was added at 1.5 equiv./10 min for 4
times. e 3a was added at 1 equiv./6 min for 6 times.
Table 2 Scope of sulfonamidesa
Table 4 Scope of diazo compoundsa
a
Reaction conditions: 1a (0.5 mmol), 2a (2.0 mL), 3 (6.0 equiv.), and
Cu(OTf)2 (2.0 mol%) at 80 oC under air for 2 h. 3 was added at 1.0 equiv./6
min for 6 times.
a
Reaction conditions: 1 (0.5 mmol), 2a (2.0 mL), 3a (6.0 equiv.), and
The substrate scope was further extended by assessment of
different diazo compounds (Table 4). In most cases, α-diazo ester
bearing different lengths of alkyl groups were well tolerated,
providing amidines 6a–6c and 6e–6i in moderate to good yields.
Meanwhile, various functional groups such as halides (6e–6f),
Cu(OTf)2 (2.0 mol%) at 80 oC under air for 2 h. 3a was added at 1.0
equiv./6 min for 6 times.
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trimethylsilyl (6g), ester (6i, 6p), and carbonyl (6n–6o) survived in
this transformation. In addition, α-diazo esters containing aryl and
heteroaryl groups also afforded the corresponding amidines in
satisfactory yields (6d, 6j–6m, 6q, and 6r).
Scheme 2 was the plausible catalytic cycle for this amidines
formation reaction.
Scheme 3 Mechanistic studies
Scheme 2 Proposed mechanism
path I
N
[Cu]
O
OEt
O
D
N
A
OEt
C
[Cu]
EtO
O
O
N
N
[Cu]
N
OEt
O
OEt
OEt
[Cu]
O
A
B
E
TsNH2
TsNH2
path II
O
N2
[Cu]
EtO
OEt
Ts
NH2 [Cu]
N
N
O
OEt
OEt
O
H2N
Ts
O
I
Conclusions
F
EtO
Ts
NH
[Cu]
N
O
In summary, we have successfully achieved in situ generation
of oxazole ylide and subsequent interception with sulfonamide,
leading to amidines in high selectivity. This Cu-catalyzed
four-component reaction utilizes two diazo molecules and
exhibits good tolerance for diverse functional groups. Further
investigations on interception of oxazole ylides with other
nucleophiles are ongoing in our laboratory.
O
OEt
N
OEt
OEt
HN
O
J
Ts
G
1,3-H shfit
ring-opening
Ts
Ts
Ts
OEt
N
N
O
N
1,4-H shfit
N
H
O
N
A
OEt
O
O
O
N
N-H insertion
H
OEt
OEt
K
H
Experimental
General procedure for the synthesis of fully substituted
amidines 4–6: Sulfonamide (0.5 mmol) and Cu(OTf)2 (0.01 mmol)
were added to a 20 mL test tube with a stirring bar. Acetonitrile
(2.0 mL or 10 mmol) were added via syringe. The reaction mixture
was heated in an oil bath at 80 oC. Next, diazo compound was
added through a batchwise mode (0.5 mmol/6 min for 6 times)
(total 30 min). The reaction mixture was stirred for additional 1.5
h under air. After, the solvent was removed under reduced
pressure and the residue was purified by silica gel column
chromatography using petroleum ether/ethylacetate to give the
desired products.
Diethyl 2,2'-((1-(tosylimino)ethyl)azanediyl)(E)-diacetate (4a).
Petroleum ether/ ethylacetate = 2:1, light yellow solid, 180.8 mg,
94% yield, mp: 74−75 °C. 1H NMR (400 MHz, CDCl3) δ 7.76–7.74
(m, 2H), 7.25–7.23 (m, 2H), 4.25–4.18 (m, 6H), 4.06 (q, J = 7.1 Hz,
2H), 2.50 (s, 3H), 2.39 (s, 2H), 1.28 (t, J = 7.1 Hz, 3H), 1.16 (t, J =
7.1 Hz, 3H). 13C NMR (101 MHz, CDCl3) δ 167.8, 167.6, 166.6,
142.1, 140.3, 128.9, 126.1, 62.0, 61.2, 51.5, 51.2, 21.3, 17.3, 13.9,
13.8. HRMS (ESI-TOF): Anal. Calcd. For C17H24N2O6S+Na+: 407.1247,
Found: 407.1248; IR (neat, cm-1): υ 2985, 1737, 1537, 1020, 683.
Diethyl
The plausible mechanism of above transformation is
illustrated as shown in Scheme 2. Initially, Cu salt decomposes
diazo compounds to generate electrophilic Cu-carbenoid A,[1,10]
which is then attacked by acetonitrile to produce nitrile ylide
intermediate B or its enolate counterparts C.[8a,11] Amidine 4a may
be obtained through either path I or path II. In path I, enolate C
undergo intramolecular [3+2] cycloaddition to produce oxazole
D.[8a,11h] Then, oxazole D interacts with A to generate ylide E,[12]
which can be intercepted by sulfonamide to furnish F.[8,11e] Next,
intermediate F releases the Cu catalyst and affords G. Finally,
intermediate G undergoes ring-opening[6,7] and 1,4-H shift to
access the desired product 4a. On the other hand, intermediate B
might be trapped by sulfonamide to furnish I,[8,11e] which then
decomposes into J and regenerate the Cu catalyst (path II).
Subsequently, intermediate
J undergo 1,3-H shift to afford
intermediate K. Finally, further N−H inserꢀon of
K by
Cu-carbenoid A to give the desired amidine 4a.[1,13]
To further clarify the reaction mechanism, several
experiments were performed as shown in Scheme 3. When
4-tert-butylstyrene, a carbene scavenger, was subjected to the
reaction, the cyclopropanation product 7 could be detected by GC
(Scheme 3a), which indicated that a carbene intermediate was
2,2'-((1-((phenylsulfonyl)imino)ethyl)azanediyl)(E)-diacetate (4b).
Petroleum ether/ ethylacetate = 2:1, yellow solid, 160.1 mg, 87%
yield, mp: 60−61 °C. 1H NMR (400 MHz, CDCl3) δ 7.89– 7.86 (m,
2H), 7.53–7.43 (m, 3H), 4.2 –4.18 (m, 6H), 4.04 (q, J = 7.1 Hz, 2H),
involved
in
this
transformation.
Subsequently,
3-nitrobenzenesulfonamide was used as reaction partner for this
transformation, the desired amidine 4m was obtained in 54%
yield accompanied by by-product 8 in 30% yield (Scheme 3b).
Moreover, compound 8 could not produce amidine 4m under
standard conditions (Scheme 3c). These results rule out the
possibility of intermediate J was involved in this transformation.
Notably, nitrile ylide [3+2] cycloaddition product 9 was observed
in our reaction. Treatment of 9 under the standard condition
delivered products 4a and 5h in 65% and 31%, respectively
(Scheme 3d). Based upon above results, we preferred the path I in
2.52 (s, 3H), 1.27 (t, J = 7.1 Hz, 3H), 1.14 (t, J = 7.1 Hz, 3H). 13
C
NMR (101 MHz, CDCl3) δ 167.7, 167.5, 166.8, 143.0, 131.5, 128.3,
126.0, 62.0, 61.2, 51.6, 51.3, 17.4, 13.9, 13.8. HRMS (ESI-TOF):
Anal. Calcd. For C16H22N2O6S+Na+: 393.1091, Found: 393.1093; IR
(neat, cm-1): υ 2982, 1744, 1545, 1141, 731, 630.
Diethyl
2,2'-((1-(((4-fluorophenyl)sulfonyl)imino)ethyl)azanediyl)(E)-diac
etate (4c). Petroleum ether/ ethylacetate = 2:1, light yellow solid,
161.3 mg, 83% yield, mp: 125−127 °C. 1H NMR (400 MHz, CDCl3) δ
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7.91–7.86 (m, 2H), 7.16–7.10 (m, 2H), 4.26–4.17 (m, 6H), 4.06 (q, J
CDCl3) δ 7.81–7.77 (m, 2H), 6.94–6.90 (m, 2H), 4.24–4.19 (m, 6H),
= 7.1 Hz, 2H), 2.53 (s, 3H), 1.29 (t, J = 7.1 Hz, 3H), 1.16 (t, J = 7.1 Hz, 4.06 (q, J = 7.1 Hz, 2H), 3.84 (s, 3H), 2.49 (s, 3H), 1.27 (t, J = 7.1 Hz,
3H). 13C NMR (101 MHz, CDCl3) δ 167.7, 167.5, 166.8, 164.3 (J =
251 Hz), 139.3 (J = 3 Hz), 128.7 (J = 9 Hz), 115.4 (J = 22 Hz), 62.0,
61.3, 51.6, 51.3, 17.5, 13.9, 13.8. HRMS (ESI-TOF): Anal. Calcd. For
4H), 1.16 (t, J = 7.1 Hz, 3H). 13C NMR (101 MHz, CDCl3) δ 167.8,
167.5, 166.5, 161.9, 135.0, 128.0, 113.4, 61.8, 61.1, 55.3, 51.4,
51.1, 17.1, 13.8, 13.7. HRMS (ESI-TOF): Anal. Calcd. For
C
16H21FN2O6S+Na+: 411.0997, Found: 411.1011; IR (neat, cm-1): υ
C
17H24N2O7S +Na+: 423.1196, Found: 423.1205; IR (neat, cm-1): υ
2975, 1743, 1551, 1143, 840, 685.
2987, 1736, 1186, 1140, 687.
Diethyl
Diethyl
2,2'-((1-(((4-chlorophenyl)sulfonyl)imino)ethyl)azanediyl)(E)-diac
etate (4d). Petroleum ether/ ethylacetate = 2:1, light yellow solid,
161.3 mg, 80% yield, mp: 102−103 °C. 1H NMR (400 MHz, CDCl3) δ
7.83–7.80 (m, 2H), 7.45–7.41 (m, 2H), 4.26–4.21 (m, 6H), 4.09–
4.03 (q, J = 7.1 Hz, 2H), 2.53 (s, 3H), 1.29 (t, J = 7.1 Hz, 3H), 1.16 (t,
J = 7.1 Hz, 3H). 13C NMR (101 MHz, CDCl3) δ 167.7, 167.4, 166.9,
141.6, 137.8, 128.6, 127.6, 62.0, 61.3, 51.6, 51.4, 17.5, 13.9, 13.8.
HRMS (ESI-TOF): Anal. Calcd. For C16H2135ClN2O6S+Na+: 427.0701,
2,2'-((1-((o-tolylsulfonyl)imino)ethyl)azanediyl)(E)-diacetate (4j).
Petroleum ether/ ethylacetate = 2:1, light yellow solid, 182.4 mg,
95% yield, mp: 130−132 °C. 1H NMR (400 MHz, CDCl3) δ 8.00–7.98
(m, 1H), 7.41–7.37 (m, 1H), 7.28–7.24 (m, 2H), 4.24–4.19 (m, 6H),
4.02 (q, J = 7.1 Hz, 2H), 2.61 (s, 3H), 2.50 (s, 3H), 1.27 (t, J = 7.1 Hz,
3H), 1.13 (t, J = 7.1 Hz, 3H). 13C NMR (101 MHz, CDCl3) δ 167.9,
167.5, 166.9, 140.8, 137.1, 131.8, 131.7, 127.3, 125.3, 61.9, 61.2,
51.4, 50.9, 20.0, 17.4, 13.9, 13.8. HRMS (ESI-TOF): Anal. Calcd. For
C
16H2137ClN2O6S+Na+: 429.0672, Found: 427.0714, 429.0714; IR
C
17H24N2O6S+Na+: 407.1247, Found: 407.1256; IR (neat, cm-1): υ
(neat, cm-1): υ 2975, 1548, 1205, 759, 655.
Diethyl
2,2'-((1-(((4-bromophenyl)sulfonyl)imino)ethyl)azanediyl)(E)-dia
2968, 1741, 1213, 1025, 630.
Diethyl
2,2'-((1-(((2-bromophenyl)sulfonyl)imino)ethyl)azanediyl)(E)-dia
cetate (4e). Petroleum ether/ ethylacetate = 2:1, light yellow solid, cetateMethyl (4k). Petroleum ether/ ethylacetate = 2:1, light
169.5 mg, 76% yield, mp: 104−105 °C. 1H NMR (400 MHz, CDCl3) δ
7.76–7.73 (m, 2H), 7.61–7.58 (m, 2H), 4.26–4.17 (m, 6H), 4.06 (q, J
yellow solid, 134.8 mg, 60% yield, mp: 140−141 °C. 1H NMR (400
MHz, CDCl3) δ 8.16–8.14 (m, 1H), 7.70–7.68 (m, 1H), 7.44–7.39 (m,
= 7.1 Hz, 2H), 2.53 (s, 3H), 1.29 (t, J = 7.1 Hz, 3H), 1.16 (t, J = 7.1 Hz, 1H), 7.36–7.32 (m, 1H), 4.27–4.21 (m, 6H), 4.03 (q, J = 7.1 Hz, 2H),
3H). 13C NMR (101 MHz, CDCl3) δ 167.7, 167.4, 166.9, 142.2, 131.5, 2.57 (s, 3H), 1.29 (t, J = 7.1 Hz, 3H), 1.12 (t, J = 7.1 Hz, 3H). 13
127.8, 126.2, 62.1, 61.3, 51.6, 51.4, 17.6, 13.9, 13.8. HRMS NMR (101 MHz, CDCl3) δ 167.8, 167.4, 167.0, 141.7, 134.8, 132.6,
(ESI-TOF): Anal. Calcd. For 129.3, 127.0, 120.4, 62.0, 61.2, 51.4, 50.9, 18.0, 13.9, 13.8. HRMS
16H2179BrN2O6S+Na+: 471.0196,
16H2181BrN2O6S+Na+: 473.0175, Found: 471.0197, 473.0184; IR 16H2179BrN2O6S+Na+: 471.0196,
(ESI-TOF): Anal. Calcd. For
16H2181BrN2O6S+Na+: 373.0175, Found: 471.0198, 473.0197; IR
C
C
C
C
(neat, cm-1): υ 2975, 1739, 1548, 746, 646.
C
Diethyl
(neat, cm-1): υ 2992, 1739, 1209, 1184, 1023, 743.
2,2'-((1-(((4-iodophenyl)sulfonyl)imino)ethyl)azanediyl)(E)-diacet
ate (4f). Petroleum ether/ ethylacetate = 2:1, light yellow solid,
168.6 mg, 68% yield, mp: 119−120 °C. 1H NMR (400 MHz, CDCl3) δ
7.83– 7.79 (m, 2H), 7.61–7.58 (m, 2H), 4.26–4.20 (m, 4H), 4.17 (s,
2H), 4.05 (q, J = 7.1 Hz, 2H), 2.52 (s, 3H), 1.28 (t, J = 7.1 Hz, 3H),
1.16 (t, J = 7.1 Hz, 3H). 13C NMR (101 MHz, CDCl3) δ 167.6, 167.4,
Diethyl
2,2'-((1-(((2-(methoxycarbonyl)phenyl)sulfonyl)imino)ethyl)azan
ediyl)(E)-diacetate (4l). Petroleum ether/ ethylacetate = 2:1,
yellow solid, 155.6 mg, 73% yield, mp: 86−87 °C. 1H NMR (400
MHz, CDCl3) δ 8.05–8.02 (m, 1H), 7.56–7.53 (m, 3H), 4.26–4.20 (m,
6H), 4.03 (q, J = 7.1 Hz, 2H), 3.91 (s, 3H), 2.54 (s, 3H), 1.28 (t, J =
166.9, 142.8, 137.5, 127.6, 98.6, 77.32, 61.3, 51.6, 51.3, 17.5, 13.9, 7.2 Hz, 3H), 1.12 (t, J = 7.1 Hz, 3H). 13C NMR (101 MHz, CDCl3) δ
13.8. HRMS (ESI-TOF): Anal. Calcd. For C16H21IN2O6S +Na+:
519.0057, Found: 519.0071; IR (neat, cm-1): υ 2974, 1546, 1204,
1188, 738, 640.
168.0, 167.8, 167.5, 166.6, 140.8, 131.6, 131.4, 130.1, 128.6,
127.8, 62.0, 61.2, 52.6, 51.4, 50.9, 17.7, 13.9, 13.8. HRMS
(ESI-TOF): Anal. Calcd. For C18H24N2O8S+Na+: 451.1146, Found:
451.1145; IR (neat, cm-1): υ 2983, 1740, 1188, 1120, 1024, 742,
629.
Diethyl
2,2'-((1-(((4-(trifluoromethyl)phenyl)sulfonyl)imino)ethyl)azaned
iyl)(E)-diacetate (4g). Petroleum ether/ ethylacetate = 2:1, light
yellow solid, 150.5 mg, 69% yield, mp: 116−117 °C. 1H NMR (400
Diethyl
2,2'-((1-(((3-nitrophenyl)sulfonyl)imino)ethyl)azanediyl)(E)-diace
MHz, CDCl3) δ 8.03–8.01 (m, 2H), 7.74–7.72 (m, 2H), 4.27–4.22 (m, tate (4m). Petroleum ether/ ethylacetate = 2:1, light yellow solid,
4H), 4.17 (s, 2H), 4.04 (q, J = 7.1 Hz, 2H), 2.56 (s, 3H), 1.29 (t, J =
7.1 Hz, 3H), 1.13 (t, J = 7.1 Hz, 3H). 13C NMR (101 MHz, CDCl3) δ
167.6, 167.4, 167.1, 146.5, 133.2 (q, J = 33 Hz), 126.7, 125.5 (q, J =
4 Hz), 123.3 (q, J = 271 Hz), 62.1, 61.3, 51.7, 51.5, 17.8, 13.9, 13.8.
HRMS (ESI-TOF): Anal. Calcd. For C17H21F3N2O6S +Na+: 461.0965,
Found: 461.0954; IR (neat, cm-1): υ 2976, 1549, 1205, 1016, 721,
644.
116.2 mg, 54% yield, mp: 88−90 °C. 1H NMR (400 MHz, CDCl3) δ
8.72–8.71 (m, 1H), 8.39–8.36 (m, 1H), 8.24–8.21 (m, 1H), 7.72–
7.68 (m, 1H), 4.28–4.23 (m, 4H), 4.19 (s, 2H), 4.09 (d, J = 7.1 Hz,
2H), 2.59 (s, 3H), 1.30 (t, J = 7.2 Hz, 3H), 1.16 (t, J = 7.1 Hz, 3H). 13
C
NMR (101 MHz, CDCl3) δ 167.5, 167.4, 167.3, 147.8, 145.1, 131.8,
129.8, 126.1, 121.6, 62.2, 61.5, 51.8, 51.5, 17.9, 14.0, 13.9. HRMS
(ESI-TOF): Anal. Calcd. For C16H21N3O8S+Na+: 438.0942, Found:
438.0951; IR (neat, cm-1): υ 1745, 1528, 1211, 1183, 1026, 666.
Diethyl
Diethyl
2,2'-((1-(((4-(tert-butyl)phenyl)sulfonyl)imino)ethyl)azanediyl)(E)
-diacetate (4h). Petroleum ether/ ethylacetate = 2:1, light yellow
solid, 195.9 mg, 92% yield, mp: 68−69 °C. 1H NMR (400 MHz,
CDCl3) δ 7.80– 7.78 (m, 2H), 7.47–7.45 (m, 2H), 4.24–4.19 (m, 6H),
4.03 (q, J = 7.1 Hz, 2H), 2.51 (s, 3H), 1.32 (s, 9H), 1.26 (t, J = 7.1 Hz,
3H), 1.13 (t, J = 7.1 Hz, 3H). 13C NMR (101 MHz, CDCl3) δ 167.7,
167.5, 166.6, 154.9, 140.1, 125.8, 125.2, 61.8, 61.0, 51.5, 51.2,
34.7, 30.8, 17.2, 13.8, 13.7. HRMS (ESI-TOF): Anal. Calcd. For
2,2'-((1-(((3-bromophenyl)sulfonyl)imino)ethyl)azanediyl)(E)-dia
cetate (4n). Petroleum ether/ ethylacetate = 3:1, light yellow solid,
73% yield, 163.2 mg, mp: 97−98 °C. 1H NMR (400 MHz, CDCl3) δ
8.02–8.01 (m, 1H), 7.83–7.80 (m, 1H), 7.65–7.62 (m, 1H), 7.36–
7.32 (m, 1H), 4.27–4.21 (m, 4H), 4.18 (s, 2H), 4.09 (q, J = 7.1 Hz,
2H), 2.54 (s, 3H), 1.29 (t, J = 7.1 Hz, 3H), 1.17 (t, J = 7.1 Hz, 3H). 13
C
NMR (101 MHz, CDCl3) δ 167.6, 167.4, 167.0, 144.9, 134.6, 130.0,
C
20H30N2O6S +Na+: 449.1717, Found: 449.1729; IR (neat, cm-1): υ
129.1, 124.6, 122.2, 62.1, 61.4, 51.7, 51.4, 17.6, 13.9, 13.9. HRMS
2964, 1741, 1547, 1150, 659.
(ESI-TOF): Anal. Calcd. For
C
16H2181BrN2O6S+Na+: 473.0175, Found: 471.0188, 473.0187; IR
C
16H2179BrN2O6S+Na+: 471.0196,
Diethyl
2,2'-((1-(((4-methoxyphenyl)sulfonyl)imino)ethyl)azanediyl)(E)-d
iacetate (4i). Petroleum ether/ ethylacetate = 2:1, light yellow
solid, 189.5 mg, 95% yield, mp: 98−99 °C. H NMR (400 MHz,
(neat, cm-1): υ 2980, 1542, 1207, 1023, 661, 631.
Diethyl
2,2'-((1-((naphthalen-2-ylsulfonyl)imino)ethyl)azanediyl)(E)-diac
1
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etate (4o). Petroleum ether/ ethylacetate = 2:1, light yellow solid,
185.8 mg, 89% yield, mp: 113−114 °C. 1H NMR (400 MHz, CDCl3) δ
8.44 (s, 1H), 7.94–7.85 (m, 4H), 7.60–7.53 (m, 2H), 4.23–4.18 (m,
6H), 3.99 (q, J = 7.1 Hz, 2H), 2.56 (s, 3H), 1.25 (t, J = 7.1 Hz, 3H),
1.05 (t, J = 7.1 Hz, 3H). 13C NMR (101 MHz, CDCl3) δ 167.7, 167.5,
166.8, 140.0, 134.2, 131.8, 128.9, 128.5, 128.0, 127.5, 126.9,
126.4, 122.3, 61.9, 61.2, 51.5, 51.3, 17.4, 13.8, 13.7. HRMS
(ESI-TOF): Anal. Calcd. For C20H24N2O6S+Na+: 443.1247, Found:
443.1249; IR (neat, cm-1): υ 2976, 1548, 1210, 1020, 678.
Diethyl
cm-1): υ 2959, 1744, 1191, 1126, 892.
Diethyl
2,2'-((1-(tosylimino)pentyl)azanediyl)(E)-diacetate
(5a). Petroleum ether/ ethylacetate = 3:1, light yellow solid, 140.2
mg, 66% yield, mp: 48−49 °C. 1H NMR (400 MHz, CDCl3) δ 7.77–
7.75 (m, 2H), 7.25–7.23 (m, 2H), 4.26–4.20 (m, 4H), 4.13 (s, 2H),
4.03 (q, J = 7.2 Hz, 2H), 2.92–2.88 (m, 2H), 2.39 (s, 3H), 1.69–1.61
(m, 2H), 1.50–1.41 (m, 2H), 1.29 (t, J = 7.1 Hz, 3H), 1.15 (t, J = 7.1
Hz, 3H), 0.94 (t, J = 7.3 Hz, 3H). 13C NMR (101 MHz, CDCl3) δ 169.3,
167.9, 167.8, 141.9, 140.7, 128.9, 126.0, 62.0, 61.2, 51.1, 51.0,
30.1, 28.5, 22.7, 21.2, 14.0, 13.8, 13.4. HRMS (ESI-TOF): Anal.
Calcd. For C20H30N2O6S+Na+: 449.1717, Found: 449.1710; IR (neat,
2,2'-((1-((thiophen-2-ylsulfonyl)imino)ethyl)azanediyl)(E)-diaceta
te (4p). Petroleum ether/ ethylacetate = 2:1, light yellow solid, 70% cm-1): υ 2961, 1538, 1145, 1087, 684.
yield, mp: 66−68 °C. 1H NMR (400 MHz, CDCl3) δ 7.58–7.57 (m, 1H),
7.51–7.49 (m, 1H), 7.02–7.00 (m, 1H), 4.26–4.21 (m, 6H), 4.13 (q, J
Diethyl
2,2'-((4-chloro-1-(tosylimino)butyl)azanediyl)(E)-diacetate (5b).
= 7.2 Hz, 2H), 2.52 (s, 3H), 1.29 (t, J = 7.1 Hz, 3H), 1.22 (t, J = 7.1 Hz, Petroleum ether/ ethylacetate = 4:1, light yellow solid, 146.2 mg,
3H). 13C NMR (101 MHz, CDCl3) δ 167.7, 167.4, 167.0, 144.5, 130.4, 66% yield, mp: 95−96 °C. 1H NMR (400 MHz, CDCl3) δ 7.76–7.74
130.0, 126.5, 62.1, 61.4, 51.6, 51.3, 17.3, 13.9, 13.9. HRMS
(ESI-TOF): Anal. Calcd. For C14H20N2O6S2+Na+: 399.0655, Found:
399.0666; IR (neat, cm-1): υ 2983, 1741, 1140, 1015, 724, 623.
Diethyl
(m, 2H), 7.25–7.23 (m, 2H), 4.29 (s, 2H), 4.24 (q, J = 7.1 Hz, 2H),
4.11 (s, 2H), 4.02 (q, J = 7.1 Hz, 2H), 3.67 (t, J = 5.8 Hz, 2H), 3.13–
3.06 (m, 2H), 2.39 (s, 3H), 2.27–2.20 (m, 2H), 1.29 (t, J = 7.1 Hz,
3H), 1.14 (t, J = 7.1 Hz, 3H). 13C NMR (101 MHz, CDCl3) δ 168.0,
167.8, 167.7, 142.1, 140.3, 128.9, 126.0, 62.0, 61.2, 51.3, 51.1,
44.4, 29.5, 27.7, 21.3, 14.0, 13.8. HRMS (ESI-TOF): Anal. Calcd. For
2,2'-((1-((quinolin-8-ylsulfonyl)imino)ethyl)azanediyl)(E)-diacetat
e (4q). Petroleum ether/ ethylacetate = 1:3, light yellow solid,
176.7 mg, 84% yield, mp: 113−114 °C. 1H NMR (400 MHz, CDCl3) δ
9.05–9.03 (m, 1H), 8.50–8.48 (m, 1H), 8.21–8.18 (m, 1H), 7.99–
7.97 (m, 1H), 7.58–7.55 (m, 1H), 7.49–7.45 (m, 1H), 4.25–4.20 (m,
4H), 4.14 (s, 2H), 3.73 (q, J = 7.1 Hz, 2H), 2.75 (s, 3H), 1.27 (t, J =
7.1 Hz, 3H), 0.89 (t, J = 7.1 Hz, 3H). 13C NMR (101 MHz, CDCl3) δ
167.7, 167.6, 167.3, 150.7, 143.7, 139.1, 135.9, 132.5, 129.4,
128.5, 124.9, 121.4, 61.8, 60.7, 51.2, 50.8, 17.4, 13.9, 13.5. HRMS
(ESI-TOF): Anal. Calcd. For C19H23N3O6S+Na+: 444.1200, Found:
444.1213; IR (neat, cm-1): υ 2995, 1749, 1543, 1125, 1020, 678.
Diethyl
C
19H2735ClN2O6S+Na+: 469.1171, C19H2737ClN2O6S+Na+: 471.1141,
Found: 469.1158, 471.1127; IR (neat, cm-1): υ 2978, 1736, 1536,
1217, 1139, 685.
Diethyl
2,2'-((4-phenyl-1-(tosylimino)butyl)azanediyl)(E)-diacetate (5c).
Petroleum ether/ ethylacetate = 4:1, light yellow liquid, 168.5 mg,
69% yield. 1H NMR (400 MHz, CDCl3) δ 7.76–7.74 (m, 2H), 7.30–
7.16 (m, 7H), 4.14 (q, J = 7.2 Hz, 2H), 4.07 (s, 2H), 4.01 (q, J = 7.1
Hz, 2H), 3.92 (s, 2H), 2.87–2.83 (m, 2H), 2.73 (t, J = 7.2 Hz, 2H),
2.38 (s, 3H), 2.03–1.95 (m, 2H), 1.23 (t, J = 7.1 Hz, 3H), 1.12 (t, J =
7.1 Hz, 3H). 13C NMR (101 MHz, CDCl3) δ 169.1, 167.8, 167.6,
142.0, 140.6, 140.5, 128.9, 128.4, 128.3, 126.1, 126.0, 61.9, 61.2,
51.0, 50.7, 35.2, 29.4, 28.1, 21.2, 13.9, 13.8. HRMS (ESI-TOF): Anal.
2,2'-((1-((benzylsulfonyl)imino)ethyl)azanediyl)(E)-diacetate (4r).
Petroleum ether/ ethylacetate = 2:1, light yellow solid, 186.4 mg,
97% yield, mp: 80−81 °C. 1H NMR (400 MHz, CDCl3) δ 7.41–7.30
(m, 5H), 4.23–4.17 (m, 8H), 4.12 (s, 2H), 2.28 (s, 3H), 1.32–1.25 (m, Calcd. For C25H32N2O6S+Na+: 511.1873, Found: 511.1866; IR (neat,
6H). 13C NMR (101 MHz, CDCl3) δ 167.8, 167.4, 167.1, 130.7, 130.0, cm-1): υ 2982, 1741, 1539, 1140, 685.
128.2, 127.9, 61.8, 61.3, 60.6, 51.1, 50.7, 17.2, 14.0, 13.8. HRMS
(ESI-TOF): Anal. Calcd. For C17H24N2O6S+Na+: 407.1247, Found:
407.1257; IR (neat, cm-1): υ 2980, 1746, 1557, 1189, 1026, 792.
Diethyl
2,2'-((1-((cyclopropylsulfonyl)imino)ethyl)azanediyl)(E)-diacetate
(4s). Petroleum ether/ ethylacetate = 2:1, light yellow solid, 160.4
mg, 96% yield, mp: 61−62 °C. 1H NMR (400 MHz, CDCl3) δ 4.28–
4.18 (m, 8H), 2.55–2.48 (m, 4H), 1.33–1.27 (m, 6H), 1.14–1.09 (m,
2H), 0.95–0.90 (m, 2H). 13C NMR (101 MHz, CDCl3) δ 167.9, 167.7,
166.2, 61.9, 61.2, 51.3, 51.0, 32.1, 17.5, 13.9, 13.9, 4.9. HRMS
(ESI-TOF): Anal. Calcd. For C13H22N2O6S+Na+: 357.1091, Found:
357.1078; IR (neat, cm-1): υ 2991, 1551, 1188, 1125, 1024, 723.
Diethyl
Diethyl
2,2'-((3-methoxy-1-(tosylimino)propyl)azanediyl)(E)-diacetate
(5d). Petroleum ether/ ethylacetate = 2:1, light yellow solid, 141.4
mg, 66% yield, mp: 153−154 °C. 1H NMR (400 MHz, CDCl3) δ 7.77–
7.75 (m, 2H), 7.25–7.23 (m, 2H), 4.43 (s, 2H), 4.21 (q, J = 7.1 Hz,
2H), 4.14 (s, 2H), 4.02 (q, J = 7.1 Hz, 2H), 3.82 (t, J = 5.9 Hz, 2H),
3.31 (s, 3H), 3.26 (t, J = 5.9 Hz, 2H), 2.39 (s, 3H), 1.29 (t, J = 7.1 Hz,
3H), 1.14 (t, J = 7.1 Hz, 3H). 13C NMR (101 MHz, CDCl3) δ 168.2,
167.8, 167.5, 142.0, 140.6, 128.9, 126.0, 69.9, 61.7, 61.1, 58.7,
51.7, 51.6, 31.1, 21.3, 14.0, 13.8. HRMS (ESI-TOF): Anal. Calcd. For
C
19H28N2O7S+Na+: 451.1509, Found: 451.1506; IR (neat, cm-1): υ
2918, 1748, 1544, 1206, 1186, 686.
Diethyl
2,2'-((1-((methylsulfonyl)imino)ethyl)azanediyl)(E)-diacetate (4t)
Petroleum ether/ ethylacetate = 2:1, light yellow solid, 146.1 mg,
95% yield, mp: 65−66 °C. 1H NMR (400 MHz, CDCl3) δ 4.27–4.18
(m, 8H), 2.97 (s, 3H), 2.50 (s, 3H), 1.32–1.27 (m, 6H). 13C NMR
(101 MHz, CDCl3) δ 167.9, 167.6, 166.3, 61.9, 61.2, 51.3, 51.0,
42.9, 17.4, 14.0, 13.9. HRMS (ESI-TOF): Anal. Calcd. For
2,2'-((3-phenyl-1-(tosylimino)propyl)azanediyl)(E)-diacetate (5e).
Petroleum ether/ ethylacetate = 3.5:1, light yellow solid, 189.1 mg,
80% yield, mp: 100−101 °C. 1H NMR (400 MHz, CDCl3) δ 7.80–7.78
(m, 2H), 7.31–7.30 (m, 4H), 7.25–7.22 (m, 3H), 4.21 (d, J = 7.1 Hz,
2H), 4.14 (d, J = 5.2 Hz, 4H), 4.03 (q, J = 7.1 Hz, 2H), 3.21–3.17 (m,
2H), 3.06–3.02 (m, 2H), 2.38 (s, 3H), 1.26 (t, J = 7.2 Hz, 3H), 1.15 (t,
J = 7.1 Hz, 3H). 13C NMR (101 MHz, CDCl3) δ 168.2, 167.8, 167.7,
142.0, 140.5, 139.5, 128.9, 128.6, 128.2, 126.5, 126.0, 62.0, 61.2,
51.4, 51.1, 32.6, 32.4, 21.3, 13.9, 13.8. HRMS (ESI-TOF): Anal.
Calcd. For C24H30N2O6S+Na+: 497.1717, Found: 497.1705; IR (neat,
cm-1): υ 2987, 1736, 1537, 1209, 1190, 689.
C
11H20N2O6S+Na+: 331.0934, Found: 331.0946; IR (neat, cm-1): υ
2980, 1556, 1190, 1021, 844.
Diethyl
2,2'-((1-((butylsulfonyl)imino)ethyl)azanediyl)(E)-diacetate (4u).
Petroleum ether/ ethylacetate = 23:1, light yellow solid, 173.7 mg,
99% yield, mp: 65−66 °C. 1H NMR (400 MHz, CDCl3) δ 4.27–4.17
(m, 8H), 3.01–2.97 (m, 2H), 2.51 (s, 3H), 1.83–1.75 (m, 2H), 1.49–
1.39 (m, 2H), 1.32–1.26 (m, 6H), 0.94 (t, J = 7.4 Hz, 3H). 13C NMR
(101 MHz, CDCl3) δ 167.9, 167.6, 166.5, 61.9, 61.2, 54.6, 51.3,
51.0, 25.5, 21.3, 17.6, 13.94, 13.90, 13.4. HRMS (ESI-TOF): Anal.
Calcd. For C14H26N2O6S+Na+: 373.1404, Found: 373.1416; IR (neat,
Diethyl
2,2'-((2-methyl-1-(tosylimino)propyl)azanediyl)(E)-diacetate (5f).
Petroleum ether/ ethylacetate = 3:1, light yellow solid, 82.2 mg,
40% yield, mp: 68−70 °C. 1H NMR (400 MHz, CDCl3) δ 7.77–7.74
(m, 2H), 7.25–7.23 (m, 2H), 4.29–4.20 (m, 4H), 4.02–3.96 (m, 4H),
2.39 (s, 3H), 1.36 (d, J = 7.3 Hz, 6H), 1.29 (t, J = 6.8 Hz, 3H), 1.17 (d,
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J = 6.9 Hz, 1H), 1.11 (t, J = 6.9 Hz, 3H). 13C NMR (101 MHz, CDCl3) δ
172.1, 168.0, 168.0, 141.8, 141.0, 128.8, 126.0, 62.0, 61.1, 52.4,
51.5, 31.8, 21.3, 19.4, 18.3, 14.0, 13.8. HRMS (ESI-TOF): Anal.
Calcd. For C19H28N2O6S+Na+: 435.1560, Found: 435.1564; IR (neat,
cm-1): υ 2978, 1744, 1542, 1142, 1086, 675.
1.21–1.16 (m, 6H). 13C NMR (101 MHz, CDCl3) δ 167.8, 167.4,
165.8, 142.3, 139.9, 132.9, 131.2, 129.5, 128.92, 128.91, 126.2,
62.0, 61.4, 51.4, 51.1, 35.4, 21.3, 13.9, 13.9. HRMS (ESI-TOF): Anal.
Calcd. For C23H2735ClN2O6S+Na+: 517.1171, C23H2737ClN2O6S+Na+:
519.1141, Found: 517.1166, 519.1140; IR (neat, cm-1): υ 2980,
1737, 1550, 1194, 1146, 1089, 677.
Diethyl
2,2'-((cyclopropyl(tosylimino)methyl)azanediyl)(E)-diacetate (5g).
Petroleum ether/ ethylacetate = 3:1, light yellow solid, 174. Mg,
85% yield, mp: 95−96 °C. 1H NMR (400 MHz, CDCl3) δ 7.77–7.75
(m, 2H), 7.24–7.22 (m, 2H), 4.52–3.91 (m, 8H), 2.38 (s, 3H), 1.93–
1.86 (m, 1H), 1.29–1.07 (m, 10H). 13C NMR (101 MHz, CDCl3) δ
168.2, 168.0, 168.0, 141.6, 141.2, 128.7, 125.9, 61.7, 61.1, 51.7,
51.0, 21.2, 13.9, 13.8, 8.4, 7.2. HRMS (ESI-TOF): Anal. Calcd. For
Diethyl
2,2'-((2-(4-bromophenyl)-1-(tosylimino)ethyl)azanediyl)(E)-diace
tate (5m). Petroleum ether/ ethylacetate = 3:1, light yellow solid,
202.4 mg, 76% yield, mp: 125−126 °C. 1H NMR (400 MHz, CDCl3) δ
7.69–7.67 (m, 2H), 7.41–7.38 (m, 2H), 7.19–7.17 (m, 2H), 7.11–
7.09 (m, 2H), 4.36 (s, 2H), 4.19 (s, 2H), 4.06 (q, J = 7.1 Hz, 4H), 4.02
(s, 2H), 2.38 (s, 3H), 1.21–1.16 (m, 6H). 13C NMR (101 MHz, CDCl3)
δ 167.7, 167.3, 165.6, 142.3, 139.9, 131.8, 131.7, 129.8, 128.9,
126.2, 120.9, 61.9, 61.3, 51.3, 51.0, 35.4, 21.3, 13.9, 13.8. HRMS
C
19H26N2O6S+Na+: 433.1404, Found: 433.1409; IR (neat, cm-1): υ
2938, 1743, 1540, 1147, 681.
Diethyl
(ESI-TOF): Anal. Calcd. For
C
23H2781BrN2O6S+Na+: 563.0645, Found: 561.0676, 563.0630; IR
C
23H2779BrN2O6S+Na+: 561.0665,
2,2'-((phenyl(tosylimino)methyl)azanediyl)(E)-diacetate
(5h).
Petroleum ether/ ethylacetate = 3:1, light yellow solid, 115.0 mg,
52% yield, mp: 114−115 °C. 1H NMR (400 MHz, CDCl3) δ 7.52–7.50
(m, 2H), 7.46–7.42 (m, 1H), 7.38–7.34 (m, 2H), 7.21–7.19 (m, 2H),
7.14–7.12 (m, 2H), 4.35 (s, 2H), 4.19–4.09 (m, 4H), 3.87 (s, 2H),
(neat, cm-1): υ 2978, 1737, 1550, 1193, 1146, 673.
Diethyl
2,2'-((2-(4-methoxyphenyl)-1-(tosylimino)ethyl)azanediyl)(E)-dia
cetate (5n). Petroleum ether/ ethylacetate = 2:1, light yellow solid,
143.8 mg, 59% yield, mp: 105−106 °C. 1H NMR (400 MHz, CDCl3) δ
7.73–7.71 (m, 2H), 7.20–7.18 (m, 2H), 7.14–7.12 (m, 2H), 6.83–
2.36 (s, 3H), 1.26 (t, J = 7.1 Hz, 3H), 1.19 (t, J = 7.1 Hz, 3H). 13
C
NMR (101 MHz, CDCl3) δ 168.0, 167.7, 167.4, 141.9, 140.1, 130.8,
130.3, 128.8, 128.3, 127.2, 126.4, 61.7, 61.5, 52.0, 50.1, 21.3, 14.0, 6.80 (m, 2H), 4.34 (s, 2H), 4.18 (s, 2H), 4.09–4.03 (m, 6H), 3.76 (s,
13.9. HRMS (ESI-TOF): Anal. Calcd. For C22H26N2O6S+Na+: 469.1404, 3H), 2.37 (s, 3H), 1.21–1.16 (m, 6H). 13C NMR (101 MHz, CDCl3) δ
Found: 469.1397; IR (neat, cm-1): υ 2979, 1743, 1522, 1209, 1144,
731, 661.
167.9, 167.5, 166.6, 158.5, 142.1, 140.2, 129.2, 128.8, 126.2,
124.6, 114.2, 61.8, 61.2, 55.1, 51.4, 51.0, 35.4, 21.3, 13.9, 13.9.
HRMS (ESI-TOF): Anal. Calcd. For C24H30N2O7S+Na+: 513.1666,
Found: 513.1680; IR (neat, cm-1): υ 2986, 1743, 1556, 1185, 1143,
684.
Diethyl
2,2'-((p-tolyl(tosylimino)methyl)azanediyl)(E)-diacetate
(5i).
Petroleum ether/ ethylacetate = 3:1, light yellow solid, 134.6 mg,
59% yield, mp: 104−105 °C. 1H NMR (400 MHz, CDCl3) δ 7.55–7.53
Diethyl
(m, 2H), 7.18–7.10 (m, 6H), 4.32 (s, 2H), 4.17–4.10 (m, 4H), 3.90 (s, 2,2'-((2-(2-chlorophenyl)-1-(tosylimino)ethyl)azanediyl)(E)-diacet
2H), 2.37 (d, J = 4.8 Hz, 6H), 1.24 (t, J = 7.1 Hz, 3H), 1.20 (t, J = 7.1
Hz, 3H). 13C NMR (101 MHz, CDCl3) δ 168.0, 167.7, 167.6, 141.8,
140.5, 140.2, 129.0, 128.6, 127.9, 127.0, 126.3, 61.6, 61.4, 52.0,
50.1, 21.4, 21.2, 13.9, 13.9. HRMS (ESI-TOF): Anal. Calcd. For
ateMethyl (5o). Petroleum ether/ ethylacetate = 3.5:1, light
yellow solid, 166.2 mg, 68% yield, mp: 91−92 °C. 1H NMR (400
MHz, CDCl3) δ 7.73–7.71 (m, 2H), 7.38–7.34 (m, 1H), 7.30–7.27 (m,
1H), 7.21–7.15 (m, 4H), 4.46 (s, 2H), 4.21 (s, 2H), 4.11–4.04 (m,
4H), 3.94 (s, 2H), 2.36 (s, 3H), 1.19 (t, J = 7.1 Hz, 6H). 13C NMR (101
MHz, CDCl3) δ 167.8, 167.4, 166.0, 142.3, 139.9, 133.2, 130.7,
129.3, 129.2, 128.9, 128.5, 127.3, 126.3, 61.9, 61.4, 51.3, 50.8,
33.6, 21.3, 13.9, 13.9. HRMS (ESI-TOF): Anal. Calcd. For
C
23H28N2O6S+Na+: 483.1560, Found: 483.1571; IR (neat, cm-1): υ
2980, 1742, 1546, 1146, 885, 683.
Diethyl
2,2'-(((4-acetylphenyl)(tosylimino)methyl)azanediyl)(E)-diacetat
e (5j). Petroleum ether/ ethylacetate = 2:1, light yellow liquid,
C
23H2735ClN2O6S+Na+: 517.1171, C23H2737ClN2O6S+Na+: 519.1141,
71.3 mg, 32% yield. 1H NMR (400 MHz, CDCl3) δ 7.98–7.96 (m, 2H), Found: 517.1175, 519.1155; IR (neat, cm-1): υ 2989, 1748, 1546,
7.57–7.55 (m, 2H), 7.39–7.37 (m, 2H), 7.18–7.16 (m, 2H), 4.34 (s,
2H), 4.19–4.11 (m, 4H), 3.86 (s, 2H), 2.63 (s, 3H), 2.38 (s, 3H), 1.25
1139, 683.
Diethyl
(t, J = 7.1 Hz, 3H), 1.20 (t, J = 7.1 Hz, 3H). 13C NMR (101 MHz, CDCl3) 2,2'-((1-(tosylimino)-2-(3-(trifluoromethyl)phenyl)ethyl)azanediy
δ 197.2, 167.8, 167.6, 166.1, 142.3, 140.0, 138.3, 135.4, 128.9,
128.3, 127.7, 126.4, 62.0, 61.6, 51.9, 50.2, 26.6, 21.4, 14.0, 14.0.
HRMS (ESI-TOF): Anal. Calcd. For C24H28N2O7S+Na+: 511.1509,
Found: 511.1495; IR (neat, cm-1): υ 2983, 1741, 1535, 1146, 886,
677.
l)(E)-diacetate (5p). Petroleum ether/ ethylacetate = 3.5:1, light
yellow solid, 105.9 mg, 67% yield, mp: 161−163 °C. 1H NMR (400
MHz, CDCl3) δ 7.70–7.68 (m, 2H), 7.51–7.43 (m, 4H), 7.18–7.16 (m,
2H), 4.49 (s, 2H), 4.21 (s, 2H), 4.11–4.04 (m, 4H), 4.02 (s, 2H), 2.36
(s, 3H), 1.21–1.17 (m, 6H). 13C NMR (101 MHz, CDCl3) δ 167.8,
167.3, 165.3, 142.5, 139.8, 133.9, 131.6 (d, J = 1 Hz), 131.1 (d, J =
32 Hz), 129.5, 129.0, 126.3, 124.8 (d, J = 4 Hz), 124.0 (d, J = 4 Hz),
123.8 (d, J = 271 Hz), 62.1, 61.5, 51.5, 51.1, 35.7, 21.3, 14.0, 13.9.
HRMS (ESI-TOF): Anal. Calcd. For C24H27F3N2O6S+Na+: 551.1434,
Diethyl
2,2'-((2-phenyl-1-(tosylimino)ethyl)azanediyl)(E)-diacetate (5k).
Petroleum ether/ ethylacetate = 2:1, light yellow solid, 138.5 mg,
61% yield, mp: 145−147 °C. 1H NMR (400 MHz, CDCl3) δ 7.73–7.71
(m, 2H), 7.30–7.26 (m, 2H), 7.23–7.17 (m, 5H), 4.42 (s, 2H), 4.18 (s, Found: 551.1438; IR (neat, cm-1): υ 2982, 1744, 1541, 1120, 674.
2H), 4.09–4.01 (m, 6H), 2.37 (s, 3H), 1.20–1.15 (m, 6H). 13C NMR
Diethyl
(101 MHz, CDCl3) δ 167.8, 167.5, 166.2, 142.1, 140.2, 132.8, 128.9, 2,2'-((2-(3,4-dichlorophenyl)-1-(tosylimino)ethyl)azanediyl)(E)-di
128.8, 128.0, 126.9, 126.2, 61.8, 61.3, 51.4, 51.1, 36.2, 21.3, 13.9, acetate (5q). Petroleum ether/ ethylacetate = 3:1, light yellow
13.8. HRMS (ESI-TOF): Anal. Calcd. For C23H28N2O6S+Na+: 483.1560, solid, 202.8 mg, 77% yield, mp: 141−142 °C. 1H NMR (400 MHz,
Found: 483.1555; IR (neat, cm-1): υ 2985, 1745, 1543, 1189, 1140,
686.
CDCl3) δ 7.68–7.66 (m, 2H), 7.36–7.34 (m, 1H), 7.261–7.256 (m,
1H), 7.19–7.17 (m, 2H), 7.11–7.09 (m, 1H), 4.38 (s, 2H), 4.21 (s,
2H), 4.13–4.07 (m, 4H), 4.02 (s, 2H), 2.38 (s, 3H), 1.23–1.18 (m,
6H). 13C NMR (101 MHz, CDCl3) δ 167.7, 167.3, 165.1, 142.5, 139.7,
132.9, 132.8, 131.3, 130.7, 130.0, 129.0, 127.6, 126.3, 62.2, 61.5,
51.4, 51.2, 34.9, 21.4, 14.0, 13.9. HRMS (ESI-TOF): Anal. Calcd. For
Diethyl
2,2'-((2-(4-chlorophenyl)-1-(tosylimino)ethyl)azanediyl)(E)-diacet
ate (5l). Petroleum ether/ ethylacetate = 3:1, light yellow solid,
170.6 mg, 69% yield, mp: 108−109 °C. 1H NMR (400 MHz, CDCl3) δ
7.70–7.68 (m, 2H), 7.29–7.23 (m, 2H), 7.20–7.15 (m, 4H), 4.39 (s,
2H), 4.19 (s, 2H), 4.07 (q, J = 7.2 Hz, 4H), 4.02 (s, 2H), 2.38 (s, 3H),
C
23H2635Cl2N2O6S+H+: 551.0781, C23H2637Cl2N2O6S+H+: 553.0751,
Found: 551.0783, 553.0795; IR (neat, cm-1): υ 2982, 1736, 1550,
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1144, 1088, 682.
Bis(2-fluoroethyl)
Diethyl
2,2'-((1-(tosylimino)ethyl)azanediyl)(E)-diacetate (6e). Petroleum
ether/ ethylacetate = 1.5:1, light yellow solid, 228.6 mg, 99% yield,
mp: 136−137 °C. 1H NMR (400 MHz, DMSO) δ 7.67–7.65 (m, 2H),
7.35–7.33 (m, 2H), 4.71–4.69 (m, 1H), 4.62–4.57 (m, 4H), 4.50–
4.48 (m, 1H), 4.44–4.42 (m, 1H), 4.36–4.34 (m, 1H), 4.30–4.27 (m,
3H), 4.22–4.20 (m, 1H), 2.43 (s, 3H), 2.37 (s, 3H). 13C NMR (101
MHz, DMSO) δ 168.4, 167.9, 167.8, 142.1, 140.6, 129.3, 125.8,
82.3 (d, J = 7.7 Hz), 80.6 (d, J = 7.9 Hz), 64.5 (d, J = 18.9 Hz), 64.0 (d,
J = 19.2 Hz), 51.5, 51.5, 20.9, 17.1. HRMS (ESI-TOF): Anal. Calcd.
For C17H22F2N2O6S+Na+: 443.1059, Found: 443.1061; IR (neat,
cm-1): υ 2920, 1747, 1546, 1184, 1142, 683.
2,2'-((2-(3,4-dimethoxyphenyl)-1-(tosylimino)ethyl)azanediyl)(E)
-diacetate (5r). Petroleum ether/ ethylacetate = 2:1, light yellow
solid, 101.5 mg, 39% yield, mp: 132−133 °C. 1H NMR (400 MHz,
CDCl3) δ 7.72–7.71 (m, 2H), 7.19–7.17 (m, 2H), 6.79–6.73 (m, 3H),
4.36 (s, 2H), 4.20 (s, 2H), 4.11–4.04 (m, 6H), 3.85 (s, 3H), 3.82 (s,
3H), 2.37 (s, 3H), 1.22–1.17 (m, 6H). 13C NMR (101 MHz, CDCl3) δ
167.9, 167.6, 166.6, 149.2, 147.9, 142.1, 140.2, 128.8, 126.3,
125.0, 120.2, 111.31, 111.28, 61.9, 61.3, 55.8, 55.7, 51.4, 51.1,
35.5, 21.3, 13.9, 13.9. HRMS (ESI-TOF): Anal. Calcd. For
C
25H32N2O8S+Na+: 543.1772, Found: 543.1761; IR (neat, cm-1): υ
2936, 1748, 1538, 1136, 1022, 683.
Bis(2-bromoethyl)
Diethyl
2,2'-((1-(tosylimino)ethyl)azanediyl)(E)-diacetate (6f). Petroleum
ether/ ethylacetate = 2:1, light yellow solid, 237.2 mg, 88% yield,
mp: 110−112 °C. 1H NMR (400 MHz, CDCl3) δ 7.74–7.72 (m, 2H),
7.27–7.25 (m, 2H), 4.47 (t, J = 5.8 Hz, 2H), 4.29 (s, 2H), 4.25 (t, J =
6.3 Hz, 2H), 4.21 (s, 2H), 3.52 (t, J = 5.8 Hz, 2H), 3.31 (t, J = 6.3 Hz,
2H), 2.52 (s, 3H), 2.40 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 167.2,
2,2'-((2-(naphthalen-1-yl)-1-(tosylimino)ethyl)azanediyl)(E)-diace
tate (5s). Petroleum ether/ ethylacetate = 3:1, light yellow solid,
148.9 mg, 59% yield, mp: 120−122 °C. 1H NMR (400 MHz, CDCl3) δ
7.89–7.85 (m, 2H), 7.73–7.71 (m, 1H), 7.62–7.60 (m, 2H), 7.59–
7.50 (m, 2H), 7.31–7.26 (m, 2H), 7.02–7.00 (m, 2H), 4.78 (s, 2H),
4.31 (s, 2H), 4.14 (q, J = 7.2 Hz, 2H), 4.05 (q, J = 7.2 Hz, 2H), 3.96 (s, 167.1, 166.6, 142.3, 140.0, 129.0, 126.0, 64.8, 64.1, 51.4, 51.3,
2H), 2.29 (s, 3H), 1.25 (t, J = 7.1 Hz, 3H), 1.13 (t, J = 7.1 Hz, 3H). 13
28.3, 27.9, 21.3, 17.2. HRMS (ESI-TOF): Anal. Calcd. For
17H2279Br2N2O6S+Na+: 562.9458, C17H2281Br2N2O6S+Na+: 564.9437,
C
NMR (101 MHz, CDCl3) δ 168.1, 167.6, 167.2, 142.1, 139.8, 133.6,
130.9, 128.80, 128.75, 128.2, 127.6, 126.6, 126.4, 125.9, 125.6,
124.9, 122.5, 61.9, 61.5, 51.2, 51.1, 32.8, 21.2, 14.0, 13.8. HRMS
(ESI-TOF): Anal. Calcd. For C27H30N2O6S+Na+: 533.1717, Found:
533.1725; IR (neat, cm-1): υ 2979, 1743, 1537, 1147, 674.
C
Found: 562.9451, 564.9443; IR (neat, cm-1): υ 2957, 1744, 1543,
1143, 1080, 685.
Bis(2-(trimethylsilyl)ethyl)
2,2'-((1-(tosylimino)ethyl)azanediyl)(E)-diacetate (6g). Petroleum
ether/ ethylacetate = 5:1, light yellow solid, 134.7 mg, 51% yield,
mp: 82−83 °C. 1H NMR (400 MHz, CDCl3) δ 7.73–7.71 (m, 2H),
7.20–7.18 (m, 2H), 4.24–4.19 (m, 2H), 4.13 (d, J = 3.5 Hz, 4H),
4.08–4.04 (m, 2H), 2.47 (s, 3H), 2.35 (s, 3H), 0.99–0.95 (m, 2H),
0.87–0.82 (m, 2H), 0.01 (s, 9H), -0.02 (s, 9H). 13C NMR (101 MHz,
CDCl3) δ 168.0, 167.7, 166.6, 142.0, 140.3, 128.9, 126.2, 64.5, 63.6,
Diisopropyl 2,2'-((1-(tosylimino)ethyl)azanediyl)(E)-diacetate
(6a). Petroleum ether/ ethylacetate = 2.5:1, light yellow solid,
188.7 mg, 92% yield, mp: 101−102 °C. 1H NMR (400 MHz, CDCl3) δ
7.76–7.74 (m, 2H), 7.25–7.23 (m, 2H), 5.11–5.02 (m, 1H), 4.97–
4.88 (m, 1H), 4.16 (d, J = 6.8 Hz, 4H), 2.50 (s, 3H), 2.39 (s, 3H), 1.26
(d, J = 6.3 Hz, 6H), 1.14 (d, J = 6.3 Hz, 6H). 13C NMR (101 MHz,
CDCl3) δ 167.2, 167.0, 166.6, 141.9, 140.3, 128.8, 126.0, 69.9, 69.0, 51.6, 51.3, 21.3, 17.4, 17.3, 17.1, -1.71. HRMS (ESI-TOF): Anal.
51.7, 51.4, 21.45, 21.36, 21.2, 17.3. HRMS (ESI-TOF): Anal. Calcd.
For C19H28N2O6S+Na+: 435.1560, Found: 435.1561; IR (neat, cm-1):
υ 2981, 1737, 1554, 1141, 1102, 685.
Calcd. For C23H40N2O6SSi2 +Na+: 551.2038, Found: 551.2045; IR
(neat, cm-1): υ 2954, 1738, 1555, 1178, 832, 692.
Bis(3-methoxypropyl)
Di-tert-butyl
2,2'-((1-(tosylimino)ethyl)azanediyl)(E)-diacetate (6h). Petroleum
ether/ ethylacetate = 1:1, light yellow liquid, 159.3 mg, 68% yield.
1H NMR (400 MHz, CDCl3) δ 7.75–7.73 (m, 2H), 7.26–7.24 (m, 2H),
4.27 (t, J = 6.5 Hz, 2H), 4.20 (d, J = 3.4 Hz, 4H), 4.11 (t, J = 6.5 Hz,
2H), 3.42 (t, J = 6.0 Hz, 2H), 3.35 (t, J = 6.1 Hz, 2H), 3.31 (s, 3H),
3.29 (s, 3H), 2.50 (s, 3H), 2.39 (s, 3H), 1.93–1.87 (m, 2H), 1.81–
1.75 (m, 2H). 13C NMR (101 MHz, CDCl3) δ 167.8, 167.5, 166.6,
142.1, 140.2, 128.9, 126.1, 68.7, 68.6, 63.3, 62.5, 58.5, 58.4, 51.4,
51.1, 28.53, 28.52, 21.2, 17.2. HRMS (ESI-TOF): Anal. Calcd. For
2,2'-((1-(tosylimino)ethyl)azanediyl)(E)-diacetate (6b). Petroleum
ether/ ethylacetate = 4:1, yellow solid, 114.1 mg, 52% yield, mp:
85−86 °C. 1H NMR (400 MHz, CDCl3) δ 7.78–7.76 (m, 2H), 7.24–
7.22 (m, 2H), 4.08 (d, J = 2.1 Hz, 4H), 2.48 (s, 3H), 2.38 (s, 3H), 1.46
(s, 9H), 1.36 (s, 9H). 13C NMR (101 MHz, CDCl3) δ 166.9, 166.63,
166.60, 141.9, 140.4, 128.8, 126.1, 83.1, 82.0, 52.4, 52.0, 27.7,
27.6, 21.2, 17.2. HRMS (ESI-TOF): Anal. Calcd. For
C
21H32N2O6S+Na+: 463.1873, Found: 463.1863; IR (neat, cm-1): υ
2978, 1741, 1555, 1227, 1142, 681.
C
21H32N2O8S +Na+: 495.1772, Found: 495.1785; IR (neat, cm-1): υ
Dicyclohexyl
2926, 1741, 1547, 1145, 1081, 684.
2,2'-((1-(tosylimino)ethyl)azanediyl)(E)-diacetate (6c). Petroleum
ether/ ethylacetate = 2:1, light yellow solid, 199.0 mg, 81% yield,
mp: 118−119 °C. 1H NMR (400 MHz, CDCl3) δ 7.76–7.74 (m, 2H),
7.24–7.22 (m, 2H), 4.86–4.80 (m, 1H), 4.69–4.64 (m, 1H), 4.17 (d, J
= 9.1 Hz, 4H), 2.50 (s, 3H), 2.38 (s, 3H), 1.85–1.82 (m, 2H), 1.71–
1.63 (m, 5H), 1.55–1.23 (m, 13H). 13C NMR (101 MHz, CDCl3) δ
167.1, 166.9, 166.5, 141.9, 140.3, 128.8, 126.0, 74.6, 73.7, 51.8,
51.4, 31.14, 31.05, 25.0, 24.8, 23.32, 23.29, 21.2, 17.2. HRMS
(ESI-TOF): Anal. Calcd. For C25H36N2O6S+Na+: 515.2186, Found:
515.2190; IR (neat, cm-1): υ 2933, 1739, 1553, 1188, 1145, 687.
Diphenyl 2,2'-((1-(tosylimino)ethyl)azanediyl)(E)-diacetate
(6d). Petroleum ether/ ethylacetate = 2.5:1, light yellow solid,
241.3 mg, 99% yield, mp: 116−118 °C. 1H NMR (400 MHz, CDCl3) δ
7.79–7.76 (m, 2H), 7.36–7.32 (m, 2H), 7.28–7.14 (m, 6H), 7.09–
7.07 (m, 2H), 6.88–6.85 (m, 2H), 4.47 (s, 2H), 4.42 (s, 2H), 2.54 (s,
3H), 2.31 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 166.8, 166.5, 166.3,
150.0, 149.8, 142.3, 139.9, 129.4, 129.2, 129.0, 126.3, 126.1,
125.9, 121.1, 120.9, 51.81, 51.78, 21.2, 17.3. HRMS (ESI-TOF):
Anal. Calcd. For C25H24N2O6S+Na+: 503.1247, Found: 503.1235; IR
(neat, cm-1): υ 2924, 1764, 1547, 1143, 686.
Bis(2-acetoxyethyl)
2,2'-((1-(tosylimino)ethyl)azanediyl)(E)-diacetate (6i). Petroleum
ether/ ethylacetate = 1:1, light yellow liquid, 233.8 mg, 94% yield.
1H NMR (400 MHz, CDCl3) δ 7.74–7.72 (m, 2H), 7.27–7.25 (m, 2H),
4.38–4.35 (m, 2H), 4.29–4.26 (m, 4H), 4.22 (s, 2H), 4.19–4.17 (m,
4H), 2.50 (s, 3H), 2.40 (s, 3H), 2.05 (s, 3H), 2.04 (s, 3H). 13C NMR
(101 MHz, CDCl3) δ 170.44, 170.42, 167.5, 167.4, 166.7, 142.1,
140.0, 128.8, 125.9, 63.4, 62.8, 61.33, 61.31, 51.2, 51.0, 21.1,
20.40, 20.39, 17.0. HRMS (ESI-TOF): Anal. Calcd. For
C
21H28N2O10S+Na+: 523.1357, Found: 523.1351; IR (neat, cm-1): υ
2921, 1735, 1546, 1180, 1145, 685.
Dibenzyl
2,2'-((1-(tosylimino)ethyl)azanediyl)(E)-diacetate
(6j). Petroleum ether/ ethylacetate = 3:1, light yellow solid, 245.2
mg, 97% yield, mp: 115−117 °C. 1H NMR (400 MHz, CDCl3) δ 7.72–
7.70 (m, 2H), 7.32–7.29 (m, 8H), 7.24–7.20 (m, 2H), 7.15–7.13 (m,
2H), 5.14 (s, 2H), 4.98 (s, 2H), 4.21 (s, 4H), 2.45 (s, 3H), 2.33 (s, 3H).
13C NMR (101 MHz, CDCl3) δ 167.7, 167.4, 166.7, 142.0, 140.1,
134.8, 134.5, 128.9, 128.5, 128.5, 128.4, 128.3, 128.2, 127.9,
126.0, 67.5, 66.8, 51.5, 51.3, 21.2, 17.3. HRMS (ESI-TOF): Anal.
Calcd. For C27H28N2O6S+Na+: 531.1560, Found: 531.1566; IR (neat,
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cm-1): υ 2919, 1747, 1558, 1192, 1150, 681.
(neat, cm-1): υ 2957, 1746, 1547, 1167, 1144, 1082, 686.
Bis(2-(thiophen-2-yl)ethyl)
Bis(4-methylbenzyl)
2,2'-((1-(tosylimino)ethyl)azanediyl)(E)-diacetate (6k). Petroleum
ether/ ethylacetate = 3:1, light yellow solid, 212.3 mg, 80% yield,
mp: 108−109 °C. 1H NMR (400 MHz, CDCl3) δ 7.72–7.70 (m, 2H),
7.21–7.19 (m, 2H), 7.15–7.11 (m, 8H), 5.10 (s, 2H), 4.95 (s, 2H),
4.19 (s, 4H), 2.45 (s, 3H), 2.34–2.31 (m, 9H). 13C NMR (101 MHz,
CDCl3) δ 167.7, 167.4, 166.7, 141.9, 140.2, 138.4, 138.0, 131.8,
131.5, 129.2, 129.0, 128.9, 128.4, 128.1, 126.0, 67.5, 66.8, 51.5,
51.2, 21.2, 20.96, 20.95, 17.3. HRMS (ESI-TOF): Anal. Calcd. For
2,2'-((1-(tosylimino)ethyl)azanediyl)(E)-diacetate (6q). Petroleum
ether/ ethylacetate = 3:1, light yellow solid, 167.8 mg, 62% yield,
mp: 95−96 °C. 1H NMR (400 MHz, CDCl3) δ 7.75–7.73 (m, 2H),
7.21–7.19 (m, 2H), 7.15–7.12 (m, 2H), 6.93–6.90 (m, 2H), 6.83–
6.82 (m, 1H), 6.78–6.77 (m, 1H), 4.37 (t, J = 6.5 Hz, 2H), 4.17 (t, J =
6.8 Hz, 2H), 4.12 (s, 4H), 3.15 (t, J = 6.4 Hz, 2H), 2.98 (t, J = 6.8 Hz,
2H), 2.43 (s, 3H), 2.34 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 167.6,
167.4, 166.5, 142.1, 140.2, 139.2, 138.9, 128.9, 126.9, 126.8,
126.1, 125.7, 125.5, 124.2, 123.9, 65.8, 65.1, 51.4, 51.2, 28.9, 28.8,
21.2, 17.3. HRMS (ESI-TOF): Anal. Calcd. For C25H28N2O6S3+Na+:
571.1002, Found: 571.1004; IR (neat, cm-1): υ 2958, 1743, 1534,
1171, 1147, 707, 665.
C
29H32N2O6S+Na+: 559.1873, Found: 559.1888; IR (neat, cm-1): υ
2919, 1737, 1537, 1196, 1145, 871, 678.
Bis(4-nitrobenzyl)
2,2'-((1-(tosylimino)ethyl)azanediyl)(E)-diacetate (6l). Petroleum
ether/ ethylacetate = 1.5:1, light yellow solid, 297.2 mg, 99% yield,
mp: 149−150 °C. 1H NMR (400 MHz, DMSO) δ 8.24–8.22 (m, 2H),
8.16–8.13 (m, 2H), 7.67–7.65 (m, 2H), 7.61–7.59 (m, 2H), 7.56–
7.53 (m, 2H), 7.26–7.24 (m, 2H), 5.34 (s, 2H), 5.23 (s, 2H), 4.69 (s,
2H), 4.39 (s, 2H), 2.43 (s, 3H), 2.30 (s, 3H). 13C NMR (101 MHz,
DMSO) δ 168.3, 167.9, 167.8, 147.2, 147.0, 143.5, 143.2, 142.0,
140.4, 129.2, 128.6, 128.0, 125.7, 123.6, 123.4, 79.2, 65.4, 64.7,
51.7, 51.6, 20.8, 17.2. HRMS (ESI-TOF): Anal. Calcd. For
Bis(2-(naphthalen-1-yl)ethyl)
2,2'-((1-(tosylimino)ethyl)azanediyl)(E)-diacetate (6r). Petroleum
ether/ ethylacetate = 3:1, light yellow solid, 311.4 mg, 98% yield,
mp: 61−62 °C. 1H NMR (400 MHz, CDCl3) δ 8.06–8.01 (m, 2H),
7.88–7.81 (m, 4H), 7.78–7.76 (m, 2H), 7.57–7.47 (m, 4H), 7.45–
7.40 (m, 2H), 7.36–7.34 (m, 1H), 7.30–7.29 (m, 1H), 7.19–7.17 (m,
2H), 4.53 (t, J = 7.0 Hz, 2H), 4.33 (t, J = 7.4 Hz, 2H), 4.03 (s, 2H),
3.97 (s, 2H), 3.41 (t, J = 6.9 Hz, 2H), 3.24 (t, J = 7.4 Hz, 2H), 2.41 (s,
3H), 2.24 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 167.7, 167.3, 166.4,
142.1, 140.2, 133.60, 133.57, 133.0, 132.8, 131.7, 131.6, 128.9,
128.7, 128.6, 127.5, 127.3, 127.0, 126.8, 126.1, 126.0, 126.0,
125.52, 125.47, 125.3, 125.3, 123.2, 123.1, 65.6, 64.9, 51.2, 51.1,
C
27H26N4O10S +Na+: 621.1262, Found: 621.1264; IR (neat, cm-1): υ
3080, 1511, 1343, 1270, 734.
Bis(4-cyanobenzyl)
2,2'-((1-(tosylimino)ethyl)azanediyl)(E)-diacetate
(6m).
Petroleum ether/ ethylacetate = 1.5:1, light yellow solid, 244.9 mg, 31.6, 31.6, 21.0, 17.1. HRMS (ESI-TOF): Anal. Calcd. For
88% yield, mp: 157−159 °C. 1H NMR (400 MHz, CDCl3) δ 7.63–7.61
(m, 2H), 7.58–7.56 (m, 2H), 7.53–7.51 (m, 2H), 7.41–7.39 (m, 2H),
7.31–7.29 (m, 2H), 7.14–7.12 (m, 2H), 5.19 (s, 2H), 5.03 (s, 2H),
4.30 (s, 2H), 4.24 (s, 2H), 2.43 (s, 3H), 2.31 (s, 3H). 13C NMR (101
MHz, CDCl3) δ 167.4, 167.2, 166.9, 142.3, 140.2, 139.8, 139.7,
132.2, 132.1, 129.0, 128.3, 127.8, 125.9, 118.2, 118.1, 112.0,
111.6, 66.2, 65.4, 51.6, 51.4, 21.2, 17.2. HRMS (ESI-TOF): Anal.
Calcd. For C29H26N4O6S+Na+: 581.1465, Found: 581.1476; IR (neat,
cm-1): υ 3131, 2226, 1746, 1625, 1268, 818.
C
37H36N2O6S+Na+: 659.2186, Found: 659.2173; IR (neat, cm-1): υ
2958, 1742, 1546, 1145, 777, 733.
Ethyl
(E)-2-((1-((3-nitrophenyl)sulfonamido)ethylidene)amino)acetate
(8). Petroleum ether/ ethylacetate = 1.5:1, light yellow solid, 30%
yield, mp: 91−92 °C. 1H NMR (400 MHz, CDCl3) δ 8.76–8.75 (m,
1H), 8.39–8.37 (m, 1H), 8.27–8.24 (m, 1H), 7.72–7.68 (m, 1H),
6.62 (s, 1H), 4.21 (d, J = 7.1 Hz, 2H), 4.04 (d, J = 4.7 Hz, 2H), 2.54 (s,
3H), 1.26 (t, J = 7.1 Hz, 3H). 13C NMR (101 MHz, CDCl3) δ 168.6,
166.1, 148.0, 145.0, 132.0, 129.9, 126.3, 121.8, 62.1, 43.6, 21.2,
Bis(2-oxo-2-phenylethyl)
2,2'-((1-(tosylimino)ethyl)azanediyl)(E)-diacetate (6n). Petroleum
14.0. HRMS (ESI-TOF): Anal. Calcd. For C
12H15N3O6S +Na+:
ether/ ethylacetate = 1.5:1, light yellow solid, 277.9 mg, 99% yield, 352.0574, Found: 352.0583; IR (neat, cm-1): υ 3326, 1747, 1529,
mp: 135−137 °C. 1H NMR (400 MHz, CDCl3) δ 7.87–7.83 (m, 4H),
7.81–7.79 (m, 2H), 7.62–7.58 (m, 2H), 7.49–7.45 (m, 4H), 7.24–
7.22 (m, 2H), 5.43 (s, 2H), 5.23 (s, 2H), 4.49 (s, 4H), 2.61 (s, 3H),
2.33 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 191.2, 190.8, 167.5,
167.4, 167.2, 142.1, 140.2, 134.1, 134.0, 133.6, 133.4, 129.0,
128.82, 128.79, 127.58, 127.55, 126.2, 77.20, 67.1, 66.4, 51.2,
51.0, 21.2, 17.3. HRMS (ESI-TOF): Anal. Calcd. For
1111, 630.
Supporting Information
The supporting information for this article is available on the
WWW under https://doi.org/10.1002/cjoc.2018xxxxx.
C
29H28N2O8S+Na+: 587.1459, Found: 587.1446; IR (neat, cm-1): υ
Acknowledgement
2936, 1697, 1178, 963, 756, 687.
We are grateful for the financial support from the National
Natural Science Foundation of China (21572148, 51673141, and
21272165) and the Priority Academic Program Development of
Jiangsu Higher Education Institutions (PAPD).
Bis(2-oxopropyl)
2,2'-((1-(tosylimino)ethyl)azanediyl)(E)-diacetate (6o). Petroleum
ether/ ethylacetate = 1.5:1, light yellow liquid, 218.5 mg, 99%
yield. 1H NMR (400 MHz, CDCl3) δ 7.66–7.64 (m, 2H), 7.18–7.16 (m,
2H), 4.70 (s, 2H), 4.48 (s, 2H), 4.31 (s, 2H), 4.28 (s, 2H), 2.44 (s, 3H),
2.31 (s, 3H), 2.05 (s, 3H), 1.98 (s, 3H). 13C NMR (101 MHz, CDCl3) δ
201.0, 199.7, 167.2, 167.12, 167.08, 142.2, 139.9, 128.9, 126.0,
69.0, 68.5, 50.9, 50.7, 25.7, 25.5, 21.1, 17.1. HRMS (ESI-TOF): Anal.
Calcd. For C19H24N2O8S+Na+: 463.1146, Found: 463.1140; IR (neat,
cm-1): υ 2931, 1729, 1545, 1144, 1081, 688.
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(The following will be filled in by the editorial staff)
Manuscript received: XXXX, 2017
Revised manuscript received: XXXX, 2017
Accepted manuscript online: XXXX, 2017
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Entry for the Table of Contents
Page No.
In Situ Generation of Oxazole Ylide and
Interception
with
Sulfonamide:
Construction of Amidines Using Two Diazo
Molecules
A novel generation of oxazole ylide and interception with sulfonamide have been well developed
to construct fully substituted amidines. This copper-catalyzed four-component reaction
incorporates two diazo molecules to target amidines and shows broad substrate scope, excellent
functional groups tolerance and good to excellent yields.
Jijun Chen, Wenhao Long, Yanwei Zhao,
Haiyan Li, Yonggao Zheng, Pengcheng
Lian, and Xiaobing Wan*
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