Reactions of Isocyanates with Methyl N-(Cyanothioformyl)anthranilate

Article abstract of DOI:10.1002/jhet.5570400522

The triethylamine-catalyzed reactions of methyl N-(cyanothioformyl)anthranilate (1) with isocyanates result in cyclization involving the cyano group to form methyl 2-(4-imino-2-oxo-3-substituted-5-thioxoimidazolidin-1-yl)benzoates (4). Ring closure at the ester carbonyl to form 3-aryl-3,4-dihydro-4-oxoquinazoline-2-carbonitriles (8) is observed when the S-methyl derivative of 1 is allowed to react with aromatic amines.

Full text of DOI:10.1002/jhet.5570400522

885
Reactions of Isocyanates with Methyl
N-(Cyanothioformyl)anthranilate
Sep-Oct 2003
L. M. Deck*, E. P. Papadopoulos and K. A. Smith
Department of Chemistry, University of New Mexico
Albuquerque, New Mexico 87131
Received April 29, 2003
The triethylamine-catalyzed reactions of methyl N-(cyanothioformyl)anthranilate (1) with isocyanates
result in cyclization involving the cyano group to form methyl 2-(4-imino-2-oxo-3-substituted-5-thioxoimi-
dazolidin-1-yl)benzoates (4). Ring closure at the ester carbonyl to form 3-aryl-3,4-dihydro-4-oxoquinazo-
line-2-carbonitriles (8) is observed when the S-methyl derivative of 1 is allowed to react with aromatic
amines.
J. Heterocyclic Chem., 40, 885 (2003).
Esters of anthranilic acid react with isocyanates to yield
Both cleavage of the imino group and oxidation of the
thiocarbonyl group of 4 were observed when hydrogen
peroxide in acetic acid was used, but the methyl 2-(2,4,5-
trioxo-3-substituted-imidazolidin-1-yl)benzoates (6, Table
2) formed as products were isolated only in moderate
yields possibly due to side reactions involving hydrolysis
of the ester group. However, the structure of compounds 6
is confirmed by their formation in excellent yield from the
corresponding ureas (7), (readily obtainable from methyl
anthranilate and the appropriate isocyanate) and oxalyl
chloride [7]. The reaction of suitably substituted
thioamides with primary amines under mild conditions is
known to proceed with elimination of hydrogen sulfide
and formation of amidines [8]. This reaction is often facil-
itated by initial conversion of the thioamides to their more
reactive S-methyl derivatives [9]. In the present case the
proximity of the thioamide and ester groups in 1 suggested
the possibility that such an amidine formation could be fol-
lowed by a cyclization resulting from nucleophilic attack
on the ester carbonyl group. Indeed this was the observa-
tion when compounds 1 were treated first with methyl
iodide, in the presence of triethylamine and then with a pri-
mary aromatic amine. The products were 3-aryl-3,4-dihy-
dro-4-oxoquinazoline-2-carbonitriles (8, Table 3), as indi-
3-substituted 2,4(1H,3H)-quinazolinediones [1]. On the
other hand, the analogous reaction between 2- or
3-aminonitriles and isocyanates is known to lead to a wide
variety of heterocyclic compounds [2]. A variation of the
latter reaction involving 1-cyanothioformanilide results in
the formation of 1-substituted 5-imino-3-phenyl-4-thioxo-
2-imidazolidinones [3]. It was of interest to investigate the
behavior of methyl N-(cyanothioformyl)anthranilate (1)
toward isocyanates (2) since in this case the reaction may
in principle follow either (or both) of two pathways: after
initial nucleophilic attack by the thioamide nitrogen on the
isocyanate, further reaction and cyclization could involve
either the ester group to form an N-cyanothioformylquina-
zolinedione (3), or the cyano group to form a 4-imino-5-
thioxo-2-imidazolidinone (4). A literature method for
preparation of 1 involves the reaction of methyl anthrani-
late with 4,5-dichloro-1,2,3-dithiazolium chloride to form
an N-aryliminodithiazole, which is then treated with triph-
enylphosphine to yield 1 [4]. For our purposes 1 was pre-
pared in analogy with cyanothioformanilide from methyl
2-isothiocyanatobenzoate [5] by treatment with potassium
cyanide followed by acidification [6]. The results of the
present investigation showed that when 1 is treated with an
isocyanate in the presence of triethylamine the reaction
proceeds following exclusively the second of the two path-
ways shown in Scheme 1 to form the corresponding
methyl 2-(4-imino-2-oxo-3-substituted-5-thioxoimidazo-
lidin-1-yl)benzoates (4) in excellent yields (Table 1).
Structure 4 is consistent with an N-H band at 3210-3275
-1
cated by the nitrile band at 2236-2260 cm in their
infrared spectra (Table 3) and the absence of the methoxy
protons signal from their proton nmr spectra (Table 6). As
expected, the cyano group in compounds 8, is readily dis-
placed by nucleophiles [10]. Thus treatment with sodium
hydroxide in methanol converts 8 to the corresponding
3-aryl-2-methoxy-4(3H)-quinazolinones (9, Table 3), as
indicated by the removal of the nitrile band from the
infrared spectra (Table 3) and the appearance of a three
proton singlet at 3.89-3.90 ppm for the methoxy protons in
the proton nmr spectra (Table 6).
-1
-1
cm and a relatively high wavenumber (1750-1790 cm )
band for the imidazolidinone carbonyl in the infrared
spectra of the products (Table 1), whereas for compounds
of structure 3 the carbonyl bands would be expected to
-1
appear at 1630-1730 cm [1c]. In addition, structure 4 is
supported by the presence of a 3-proton singlet at 3.7-3.8
ppm for the methyl protons of the ester group in the proton
nmr spectra of the products (Table 4). Treatment of 4 with
hydrochloric acid in ethanol cleaves the imino group with
formation of brightly colored methyl 2-(2,4-dioxo-3-sub-
stituted-5-thioxoimidazolidin-1-yl)benzoates (5, Table 2).
Table 4 contains proton nmr spectroscopic data of com-
pounds 4a-4h in dimethyl-d sulfoxide solutions. It is
6
interesting to note that for compounds 4b and 4d addi-
tional signals for some resonances are seen which are
attributed to rotational isomers. Since compound 4g would
also be expected to exhibit rotational isomerism, proton

886
L. M. Deck, E. P. Papadopoulos and K. A. Smith
Vol. 40
nmr spectra were taken in hexadeuteriobenzene and deu-
teriochloroform. Unlike the dimethyl-d sulfoxide spec-
and 5g exist as mixtures of rotational isomers. Table 5 con-
tains proton nmr spectroscopic data of compounds 6a-6h
6
trum, shown in Table 4, the spectra in CDCl and C D do
taken in dimethyl-d sulfoxide. Since compounds 6b and
3
6
6
6
show additional signals. Additional spectra taken above
room temperature for compounds 4b, 4d and 4g confirmed
rotational isomerism. Sets of peaks converged and often
coalesced as the temperature was increased. Table 5 con-
tains proton nmr spectroscopic data for compounds 5a-5h
6g would be expected to exhibit rotational isomerism,
spectra were also taken in deuteriochloroform. Both com-
pounds exhibit a broad singlet for the methyl protons.
However this signal splits into a doublet when the spectra
are taken below room temperature thus indicating the pres-
ence of rotational isomers. As shown in Table 4, com-
pound 4f exhibits a doublet of doublets for the methylene
protons alpha to the substituent carbonyl, probably due to
the overall chirality of the molecule. Similarly, the proton
in dimethyl-d sulfoxide solutions. In this case additional
6
signals are seen for 5b and 5g but not 5d. However spectra
of 5d taken in C D do show additional resonances. Again
6
6
spectra taken above room temperature confirmed rota-
tional isomerism because signals converged or coalesced.
This nonequivalence of protons should be attributed to
restricted rotation about the o-substituted aryl-nitrogen
bond, as a result of which compounds 4b, 4d, 4g, 5b, 5d
nmr spectrum of compound 5f taken in dimethyl-d sul-
6
foxide shows a singlet for the methylene protons, but when
taken in deuteriochloroform a doublet of doublets is
observed. There are many reports of axially twisted

Sep-Oct 2003
Reactions of Isocyanates with Methyl N-(Cyanothioformyl)anthranilate
887
Table 1
Methyl 2-(4-Imino-2-oxo-3-substituted-5-thioxoimidazolidin-1-yl)benzoates (4)
–1
Yield [a]
(%)
Mp [b]
(°C)
Elemental Analysis
Calcd. (Found)
H
IR (cm )
R
C=N
N-H
C=O
C
N
4a
4b
4c
4d
4e
4f
C H
93%
92%
95%
76%
92%
91%
87%
94%
140–141.5
147–148
166–167
176-177
60.17
(60.39)
61.18
(61.12)
61.18
(61.40)
54.62
(54.65)
54.62
(54.76)
51.57
(51.38)
62.11
(62.14)
57.14
3.86
(3.92)
4.28
(4.37)
4.28
(4.35)
3.24
(3.44)
3.24
(3.40)
4.33
(4.55)
4.66
(4.76)
3.38
12.38
(12.32)
11.89
(11.95)
11.89
(11.84)
11.24
(11.12)
11.24
(11.25)
12.03
(12.23)
11.44
(11.28)
11.76
1640
1665
1640
1660
1675
1668
1655
1660
3235
3260
3210
3240
3270
3275
3260
3245
1700,1760
1730,1775
1700,1750
1720,1770
1735,1780
6
5
2-CH C H
3
6
4
4-CH C H
3
6
4
2-ClC H
6
4
4
4-ClC H
187–189
119–120[c]
170–171.5
170-171
6
EtOOCCH
1728,1755
1773
1722,1790
2
4g
4h
2,6-(CH ) C H
6 3
3 2
4-FC H
1728,1775
6
4
(57.01)
(3.42)
(11.82)
[a] Crude or recrystallized product with melting point within 10° of the analytically pure compound; [b] Recrystallized from ethanol; [c]
Recrystallized from benzene/ligroine.
Table 2
Methyl 2-(2,4-Dioxo-3-substituted-5-thioxoimidazolidin-1-yl)benzoates (5) and Methyl 2-(2,4,5-Trioxo-3-substi-
tuted-imidazolidin-1-yl)benzoates (6)
–1
Yield [a]
(%)
Mp [b]
(°C)
Elemental Analysis
Calcd. (Found)
IR (cm
C=O
)
R
C
H
N
5a
5b
5c
5d
5e
5f
C H
90%
90%
91%
90%
89%
90%
90%
144–146
176-177
156-157
159-161
172–174
92-93.5
176-178
59.99
(60.08)
61.01
(61.17)
61.01
(60.98)
54.48
(54.56)
54.48
(54.63)
51.42
(51.61)
61.94
3.55
(3.62)
3.98
(4.08)
3.98
(4.13)
2.96
(3.29)
2.96
(3.15)
4.03
(4.18)
4.38
8.23
(8.23)
7.90
(7.89)
7.90
(8.00)
7.47
(7.50)
7.47
(7.47)
8.00
(8.22)
7.60
1760,1740
1750, 1725
6
5
2-CH C H
3
6
4
4-CH C H
1750, 1728
3
6
4
2-ClC H
1755, 1725
6
4
4
4-ClC H
1750, 1725
6
EtOOCCH
1770, 1755,1729
1755, 1730
2
5g
2,6-(CH ) C H
3 2 6 3
(61.83)
(4.26)
(7.68)

888
L. M. Deck, E. P. Papadopoulos and K. A. Smith
Vol. 40
Table 2 (continued)
–1
Yield [a]
(%)
Mp [b]
(°C)
Elemental Analysis
Calcd. (Found)
IR (cm
C=O
)
R
C
H
N
5h
6a
6b
6c
6d
6e
6g
6h
4-FC H
81%
146-147
138-139
56.98)
(56.91)
62.96
(62.66)
63.90
(63.66)
63.90
(63.65)
56.92
(56.64)
56.92
(56.62)
64.77
(64.61)
59.65
3.09
(3.15)
3.73
(3.64)
4.17
(4.12)
4.17
(4.13)
3.09
(3.03)
3.09
(3.07)
4.58
(4.58)
3.24
7.82
(7.93)
8.64
(8.53)
8.28
(8.24)
8.28
(8.24)
7.81
(7.69)
7.81)
(7.71)
7.95
(7.84)
8.18
1770, 1730
1747, 1735, 1725, 1716
1748, 1718
6
4
C H
65%[c]
85% [d]
63%[c]
90% [d]
91%[d]
6
5
2-CH C H
126-127
3
6
4
4-CH C H
159.5-160.5
177.5-179
159-160
1747,1712, 1709
1747, 1725, 1715
1746, 1716
3
6
4
2-ClC H
66%[c]
90% [d]
90%[d]
6
4
4
4-ClC H
6
2,6-(CH ) C H 85%[d]
163.5-165
154-155.5
1744, 1715
3 2
6 3
4-FC H
91%[d]
1743, 1725
6
4
(59.41)
(3.16)
(8.02)
[a] Crude or recrystallized product with melting point within 10° of the analytically pure compound; [b] Recrystallized
from ethanol; [c] Method A; [d] Method B.
Table 3
3-Aryl-3,4-dihydro-4-oxoquinazoline-2-carbonitriles (8) and 3-Aryl-2-methoxy-4(3H)-quinazolinones (9)
–1
Yield [a]
(%)
Mp [b]
(°C)
Elemental Analysis
Calcd. (Found)
IR (cm
)
R
C=O
1690
1700
1695
1698
1700
1705
1694
1694
1690
C≡N
2238
2236
2260
2238
2238
8a
8b
8c
8d
8e
8h
9a
9e
9h
C H
60%
59%
65%
16%
56%
69%
93%
86%
95%
196–197[c]
179-180
72.87
(72.85)
73.55
(73.42)
73.55
(73.55)
63.96
(63.80)
63.96
(64.04)
67.92
(67.77)
71.42
(71.32)
62.84
3.67
(3.90)
4.24
(4.29)
4.24
(4.43)
2.86
(2.89)
2.86
(2.98)
3.04
(3.02)
4.79
(4.68)
3.87
16.99
(17.11)
16.08
(16.04)
16.08
(16.15)
14.92
(14.83)
14.92
(14.57)
15.84
(15.76)
11.10
(11.01)
9.77
6
5
2-CH C H
3
6
4
4-CH C H
179–180.5
198–200
181-182
3
6
4
2-ClC H
6
4
4
4-ClC H
6
4-FC H
182-183
6
4
C H
135-136
6
5
4-ClC H
145-146.5
156-157
6
4
(62.84)
66.66
(66.56)
(3.88)
4.10
(4.21)
(9.79)
10.37)
(10.21)
4-FC H
6
4
[a] Crude or recrystallized product with melting point within 10°of the analytically pure compound; [b] Recrystallized from
ethanol; [c] Lit [11] mp 198°C.
amides and imides exhibiting chirality due to a high rota-
tional barrier [2g,12]. Tables 7 and 8 contain carbon-13
nmr spectra of compounds 4a-4h and 5a-5h. The carbon
spectra of compounds 4b, 4d, 4g, 5b, 5d and 5g all exhibit
additional resonances due to rotational isomerism.
Assignments of carbon resonances was facilitated by
DEPT, HMQC and HMBC experiments in addition to
literature data on structurally related compounds [13].

Sep-Oct 2003
Reactions of Isocyanates with Methyl N-(Cyanothioformyl)anthranilate
889
Table 4
1
H-nmr Chemical Shifts (δ) of Compounds 4 in Dimethyl-d Sulfoxide
6
H-5(dd)
H-4(dt) H-3(dt) H-2(dd) OCH (s)
=NH(s)
9.85
Ar-H(m)
CH (dd) CH (s)
OCH (q) CH (t)
3
2
3
2
3
4a 8.13
7.89
7.74
7.75
7.72
7.75
7.73
7.72
7.73
7.77
7.71
7.70
7.70
7.71
7.68
7.61
7.81
7.73
3.78
7.45–7.60
4b 8.13, 8.11[a] 7.89
4c 8.12 7.88
4d 8.11, 8.15[a] 7.88
4e 8.13
4f 8.10
4g 8.12
4h 8.18
3.77, 3.80[a] 9.71, 9.82[a] 7.27–7.49
3.78 9.80 7.41[b], 7.35[b]
3.75, 3.82[a] 9.86, 10.1[a] 7.54–7.73
2.26, 2.29[a]
2.37
7.89
7.86
7.88
7.94
3.78
3.74
3.78
3.83
9.93
9.85
9.80
9.93
7.65[b], 7.58[b]
4.56
4.19
1.24
7.24[b], 7.32[d]
7.43-7.67
2.24[c]
[a] Due to rotational isomers; [b] doublet; [c] six protons; [d] triplet.
Table 5
H-nmr Chemical Shifts (δ) of Compounds 5 and 6 in Dimethyl-d Sulfoxide
1
6
H-5(dd) H-4(dt)
H-3(dt) H-2(dd)
OCH (s)
Ar-H(m)
CH (s)
CH (s)
OCH (q)
CH (t)
3
2
3
2
3
5a 8.15
5b 8.14
5c 8.14
5d 8.13
7.91
7.91
7.90
7.91
7.91
7.87
7.91
7.74
7.77
7.74
7.78
7.75
7.73
7.82
7.66
7.67
7.64
7.67
7.65
7.60
7.74
3.80
3.79, 3.82[a]
3.80
7.50–7.61
7.27–7.50
7.39[b]
7.57-7.73
7.56[c],7.68[c]
2.29, 2.28[a]
2.38
3.77
3.80
3.75
3.79
5e
5f
8.15
8.12
4.58
4.20
1.24
5g 8.14
7.37[c],
7.27[e]
2.25, 2.28[a]
5h 8.15
7.91
7.89
7.88
7.88
7.88
7.88
7.88
7.88
7.75
7.72
7.72
7.72
7.73
7.74
7.72
7.72
7.64
7.60
7.62
7.59
7.59
7.58
7.73
7.59
3.80
3.82
3.83
3.82
3.81
3.82
3.81
3.82
7.41-7.63
7.46-7.59
7.47-7.37
7.38[c],7.34[c]
7.57-7.70
7.67[c], 7.51[c]
7.25[c], 7.35[e]
7.61-7.40
6a
6b 8.11
6c 8.12
6d 8.11
8.11
2.31
2.37
6e
6g
8.11
8.11
2.27[d]
6h 8.11
[a] Due to rotational isomers; [b] singlet; [c] doublet; [d] six protons; [e] triplet.

890
L. M. Deck, E. P. Papadopoulos and K. A. Smith
Vol. 40
Table 6
A solution of 0.5 g of the substituted imidazolidinone 4 in 5
mL of ethanol and 5 mL of concentrated hydrochloric acid was
stirred at room temperature for one to six hours, the reaction
progress being followed by thin layer chromatography. The solu-
tion was then diluted with water and the precipitated solid was
collected by filtration. Yields and physical properties of com-
pounds 5 are shown in Table 2.
1
H-nmr Chemical Shifts (δ) of Compounds 8 and 9
in Dimethyl-d Sulfoxide
6
Methyl 2-(2,4,5-Trioxo-3-substituted-imidazolidin-1-yl)ben-
zoates (6).
Method A.
To an ice cold solution of 0.5 g of 4 in 5 mL of acetic acid was
added 3 mL of 30% hydrogen peroxide and the resulting mixture
was stirred at room temperature until its yellow color had essen-
tially been discharged (1-4 h). The product was isolated by dilu-
tion with water and filtration.
H-8(dd) H-7(dt) H-6(dt) H-5(dd) CH (s)
Ar-H(m)
3
8a
8b
8c
8d
8e
8h
9a
9e
9h
7.90
7.92
7.88
7.94
7.90
7.90
7.54
7.44
7.54
8.00
8.02
7.99
8.05
8.00
8.00
7.78
7.78
7.77
7.76
7.78
7.75
7.81
7.76
7.76
7.48
7.38
7.47
8.23
8.26
8.22
8.26
8.22
8.22
8.03
8.03
8.03
7.58-7.70
7.40–7.56
7.53[a], 7.41[a]
7.91[b], 7.70-7.84
7.72[c]
7.76[b], 7.47[b]
7.36-7.51
7.57[a], 7.54[a]
7.31-7.46
2.14
2.42
Method B.
A solution of equal weights (5-10 g) of oxalyl chloride and the
corresponding urea (7) in an adequate volume of benzene (25-50
mL) was refluxed for 1-6 h (the reaction progress being followed
by thin layer chromatography). The reaction was then cooled,
diluted with petroleum ether (bp 63-75° C) and filtered to give
the product. Yields and physical properties of compounds 6 are
shown in Table 2.
3.89
3.89
3.90
[a] Doublet; [b] doublet of doublets; [c] singlet.
3-Aryl-3,4-dihydro-4-oxoquinazoline-2-carbonitriles (8).
EXPERIMENTAL
To 0.0050 mole of methyl N-(cyanothioformyl)anthranilate (1)
in 10 ml of benzene was added 0.0055 mole of triethylamine
dropwise with stirring. After five minutes, 0.0055 mole of methyl
iodide was added dropwise and the solution was stirred for thirty
minutes, after which time 0.0050 mole of the appropriate amine
was added. The resulting mixture was then refluxed for 24 hours.
After cooling of the solution and removal of benzene by distilla-
tion, addition of ethanol caused precipitation of a buff solid.
Yields and physical properties of compounds 8 are shown in
Table 3.
Reagent-grade solvents were used without further purification.
Tetrahydrofuran was distilled over calcium hydride. Melting
points were determined in capillaries with a Thomas-Hoover
Uni-Melt apparatus and are uncorrected. Infrared spectra were
recorded on a Beckman IR-33 spectrophotometer using mineral
oil mulls. Proton and carbon-13 nmr spectra were obtained on
Bruker AC250 and AC500 nmr spectrometers. Chemical shifts
are given in ppm (δ).
Methyl N-(Cyanothioformyl)anthranilate (1).
3-Aryl-2-methoxy-4(3H)-quinazolinones (9).
To a solution of 7.5 g (0.115 mol) of potassium cyanide in 75
mL of water was gradually added with stirring 19.3 g (0.100 mol)
of methyl 2-isothiocyanatobenzoate in 60 mL of ethanol. The
resulting mixture was stirred at room temperature for one half
hour. After 150 mL of water was added, the solution was acidi-
fied by dropwise addition of concentrated hydrochloric acid
(Caution: Possible HCN evolution!). The resulting solid was fil-
tered and washed several times with water to give 21.7 g (98%)
of 1, mp 121-122° C. Recrystallization from ethyl acetate gave
the pure compound, mp 122-123 °C (lit [4] mp 118 °C).
To a solution of 30 mg of sodium hydroxide in 30 ml of
methanol was added 0.38 mmole of 3-aryl-3,4-dihydro-4-
oxoquinazoline-2-carbonitrile (8). The mixture was stirred for
one hour at room temperature and then neutralized with 10%
hydrochloric acid. The solvent was removed by distillation and
the residue was extracted repeatedly with dichloromethane. The
combined extracts were dried over magnesium sulfate, filtered
and the solvent was removed by distillation to yield a solid,
which was recrystallized from hexane. Yields and physical
properties of compounds 9 are shown in Table 3.
Methyl 2-(4-Imino-2-oxo-3-substituted-5-thioxoimidazolidin-1-
yl)benzoates (4).
REFERENCES AND NOTES
To 0.0050 mole of methyl N-(cyanothioformyl)anthranilate (1)
in 10 mL of benzene was added 0.0051 mole of the isocyanate (2)
and 5 drops of triethylamine. An exothermic reaction took place
and the solution was allowed to stand for 10 hours. Petroleum
ether (bp 63-75 °C) was added to the resulting mixture and the
precipitate was collected by filtration. Yields and physical prop-
erties of compounds 4 are shown in Table 1.
*
Author to whom correspondence should be addressed.
[1a] M. T. Bogert and G. Scatchard, J. Am. Chem. Soc., 41, 2052
(1919); [b] H. Wamhoff and L. Lichtenthäler, Chem. Ber., 111, 2297
(1978); [c] E. P. Papadopoulos and C. D. Torres, J. Heterocyclic Chem.,
19, 269 (1982).
[2a] K. W. Breukink and P. E. Verkade, Rec. Trav. Chim., 79, 443
(1960); [b] E. C. Taylor and R. V. Ravintranathan, J. Org. Chem., 27,
2622 (1962); [c] E. P. Papadopoulos, J. Heterocyclic Chem., 17, 1553
(1980); [d] E. P. Papadopoulos, J. Heterocyclic Chem., 18, 515 (1981);
Methyl 2-(2,4-Dioxo-3-substituted-5-thioxoimidazolidin-1-
yl)benzoates (5).

Reactions of Isocyanates with Methyl N-(Cyanothioformyl)anthranilate
891
Sep-Oct 2003

892
L. M. Deck, E. P. Papadopoulos and K. A. Smith
Vol. 40
Table 8
13
C-nmr Chemical Shifts (δ) of Compounds 5 and 6 in Dimethyl-d Sulfoxide
6
6
5
4
3
2
1
7
8
5'
4'
2'
1"
2"
3''
4''
5''
6''
7'
5a 132.3
5b 132.3
130.1 134.2 130.6 131.5
130.1 134.2 130.7 131.5
131.3 [a]
130.1 134.2 130.6 131.4
129.9 134.2 130.2 131.4
127.0 164.2 52.8
127.1 164.2 52.7
52.8 [a] 184.2 [a] 153.1 [a]
127.0 164.1 52.8
127.6 164.1 52.8
184.2
184.5
153.4
153.4
153.0 130.5 126.5
152.7 129.4 136.1
136.3 [a]
152.9 127.8 126.2
152.1 128.0 131.8
129.4
129.9
129.1
128.4
128.1 [a]
138.7
130.5
130.9
126.9 17.0
17.5 [a]
5c 132.2
5d 131.8
184.2
184.0
153.1
152.7
129.7
130.7
20.7
131.9
128.4
134.4 [a]
131.6 [a]
53.0 [a]
130.9 [a] 132.1 [a]
128.7 [a]
5e 132.1
5f 131.1
5g 132.2
130.0 134.1 130.6 131.3
130.0 134.1 130.7 131.4
130.5 134.2 130.7 131.2
126.9 164.1 52.7
127.3 164.0 52.7
126.9 164.1 52.7
183.8
184.0
184.1
152.9
153.5
152.8
152.6 130.2 128.0
153.1 138.5 166.3
152.3 128.8 136.8
129.3
61.7
128.4
133.8
13.9
129.9
17.4
136.3 [a] 128.5 [a]
17.6 [a]
5h 132.2
6a 129.4
6b 129.5
6c 129.4
6d 129.0
6e 128.9
6g 129.5
6h 129.3
130.0 134.2 130.6 131.4
129.8 133.9 130.2 131.2
129.8 133.8 130.2 131.1
129.6 133.8 130.1 131.1
129.7 133.9 130.2 131.2
129.4 133.9 130.3 131.2
130.2 133.9 130.3 131.0
129.6 133.8 130.2 131.2
127.0 164.2 52.8
127.1 164.5 52.7
127.1 164.5 52.5
127.0 164.5 52.6
127.3 164.4 52.7
127.1 164.5 52.6
127.1 164.5 52.5
127.1 164.5 52.6
184.0
155.7
156.0
155.7
155.5
155.6
155.8
155.6
153.2
155.6
155.9
155.7
155.1
155.4
155.5
155.5
152.8 126.6 128.7
116.3
129.2
129.8
129.6
130.3
129.4
128.4
116.3
161.7
129.0
128.1
138.6
130.1
133.6
129.8
161.6
151.9 130.0 126.4
151.8 129.0 136.2
152.0 127.3 126.1
151.0 127.5 131.7
151.7 129.7 128.1
151.4 127.8 136.6
151.8 126.1 128.7
130.9
20.7
131.8
126.8 17.1
128.4
17.5
[a] Due to rotational isomers.
Table 9
13
C-nmr Chemical Shifts (δ) of Compounds 8 and 9 in Dimethyl-d Sulfoxide
6
8a
8
7
6
5
4a
4
2
9
1''
2''
3''
4''
5''
6''
7''
8a
8b
8c
8d
8e
8h
9a
9e
9h
146.0 128.0 135.3 130.0 126.6 122.9 159.5 135.8 111.6 132.0 128.7 129.4 128.0
146.3 128.4 135.8 130.5 126.9 122.8 159.2 131.8 111.5 134.9 136.1 130.9 129.2 131.3 127.6 17.1
146.1 128.0 135.2 129.9 126.6 122.9 159.6 133.2 111.6 132.1 128.4 129.9 139.9 20.9
145.8 128.4 135.9 130.6 126.8 122.5 158.6 132.8 111.0 131.7 131.1 132.5 130.2 131.2 128.8
146.0 128.0 135.3 130.0 126.5 122.8 159.4 131.7 111.5 134.9 129.5 130.7 134.6
146.0 128.0 135.3 130.0 126.6 122.9 159.6 132.1 111.6 132.0 131.2 116.4 162.7
146.7 125.4 134.7 126.7 124.5 118.7 161.7 152.4 55.5
146.7 125.4 134.7 126.6 124.5 118.7 161.6 152.1 55.5
146.7 125.4 134.7 126.6 124.4 118.7 161.8 152.4 55.5
135.1 128.4 128.9 128.4
134.1 129.0 130.4 133.1
131.3 130.6

Sep-Oct 2003
Reactions of Isocyanates with Methyl N-(Cyanothioformyl)anthranilate
893
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