A new route to N-aryl 2-alkenamides, N-allyl N-aryl 2-alkenamides, and N-aryl α,β-unsaturated γ-lactams from N-aryl 3-(phenylsulfonyl)propanamides

Article abstract of DOI:10.1002/jccs.200100016

A series of N-aryl 2-alkenamides were produced efficiently by treating N-aryl 3-(phenylsulfonyl)-propanamides with potassium tert-butoxide in THF at 0°C. Without isolation, it was further treated with an additional equivalent of potassium tert-butoxide and allyl bromide to give N-allyl N-aryl 2-alkenamides in one pot in good yields. Followed by a ring-closing metathesis reaction, these N-allyl N-aryl 2-alkenamides were respectively converted into corresponding N-aryl α,β-unsaturated γ-lactams in moderate yields.

Full text of DOI:10.1002/jccs.200100016

JournaloftheChineseChemicalSociety, 2001, 48, 83-90
83
A New Route to N-Aryl 2-Alkenamides, N-Allyl N-Aryl 2-Alkenamides, and
N-Aryl , -Unsaturated -Lac tams fromN-Aryl
3-(Phenylsulfonyl)propanamides
Eng-Chi Wang* ( 王英基 ), Keng-Shiang Huang (
), Gwo-Woei Lin ( 林國偉 ),
黃耿祥
Jia-Ruei Lin (
) and Ming-Kun Hsu (
)
林佳叡
許明坤
SchoolofChemistry,KaohsiungMedicalUniversity,Kaohsiung,Taiwan807,R.O.C.
A se ries of N-aryl 2-alkenamides were pro duced ef fi ciently by treat ingN-aryl3-(phenylsulfonyl)-
propanamideswithpotassiumtert-butoxide in THF at 0 C. With out iso la tion, it was fur ther treated with an
additionalequivalentofpotassium tert-butoxide and allyl bro mide to give N-allyl N-aryl 2-alkenamides in
one pot in good yields. Fol lowed by a ring-closing me tath e sis re ac tion, these N-allyl N-aryl 2-alkenamides
wererespectivelyconvertedintocorrespondingN-aryl
-unsaturated -lactamsinmoderateyields.
INTRODUCTION
re port a new, sim ple, ef fi cient and less toxic method to pre-
pare N-aryl alkenamides by debenzenesulfonation of 3-
(phenylsulfonyl)propanamides with one equiv a lent of po tas-
sium tert-butoxide (Scheme I). On the other hand N-allyl
N-aryl alkenamides, an im por tant build ing block for some
-lac tams, pre pared for merly from a cor re spond ing amine
andtoxicacryloylchloride,weredisadvantageous.
2-Alkenamides or acrylamides, use ful mono mers for
polyacrylamides, have been known to chem ists for a long
time. In ad di tion, they are widely used as Mi chael ac cep tors
for sev eral nucleophiles such as organolithums,1 piperazine,2
an ion of malonate,3 thiourea, 4 etc.5 It also played as a start ing
ma te rial for pro duc ing 1-aza-2-cyano-1,3-butadiene, a key
intermediatetogiveazacyclohexenes,6 and also can be con-
verted to a chiral dienophiles for Diels-Alder re ac tion.7 Fur-
thermore, inrecentreportsN-substituted2-alkenamideshav-
ing N-allyl func tion, play an im por tant role to cer tain -lac-
Scheme I
O
OH
SO2Na
+
HO
SO2
tams viarad i cal cyclization8 and for
-unsaturated -lac-
O
3
1
2
tams by ring-closing me tath e sis re ac tion with Grubbs cat a-
lyst.9 The pres ent in dus trial prep a ra tion for acrylamides,
which cir cum vents the highly un sta ble and toxic acryloyl
chloride as key starting material,10 adopts the two-step
method. This strat egy in volves the Mi chael ad di tion and
amidation of acrylic es ter with 2 equiv a lents of amine and
fol lowed by deamination to give the de sired com pound at
180-300 C.11 Other meth od ol o gies in cluded the use of hy-
droxylgroup,12 chloride,13 bromide,14 amine,15 etc. as leav ing
group for the prep a ra tion of N-sub sti tuted acrylamidesvia
1,2-elimination. Their draw backs in clude low yield, long re-
actiontime,harshreactioncondition,andthereagent’scorro-
sive, vol a tile, and toxic na ture. De spite the avail abil ity of
many syn thetic meth ods, there still ex ists a need to de velop
more ef fi cient and less toxic pro ce dures than those cur rently
in ex is tence. To the best of our knowl edge, all pre vi ous re-
ports forN-aryl alkenamides have paid no at ten tion to the use
of phenylsulfonyl group as leav ing group. Herein we wish to
O
ArNH2
O
SOCl2
5
SO2
ArNH
SO2
Cl
Et3N
6
4
O
O
tert-BuO-K+
ArNH
7
tert-BuO-K+
i) 2
ii)
Grubbs cat.
O
Ar
N
Br
N
Ar
9
8
c. Ar = 4-CH3OC6H5
b. Ar = 4-CH3C6H5 d. Ar =4-FC6H5
e. Ar = 4-ClC6H5
a. Ar = C6H5
f. Ar= 4-BrC H
6
5
PCy3
Ph
H
Cl
Cl
Ru
Grubbs catalyst =
PCy3

84 J. Chin. Chem. Soc., Vol. 48, No. 1, 2001
Wang et al.
1
In this re ported pro cess, it can be pre pared in one pot by
treat ing N-aryl 3-(phenylsulfonyl)propanamide with two
equivalentsoftert-butoxideand1equivalentofallylbromide
to un dergo debenzenesulfonation and fol lowed by allylation.
This method led a new route to N-allyl N-aryl alkenamides
and cir cum vented the use of the toxic and vol a tile start ing
material,acryloylchloride.Furthermorethering-closureme-
tath e sis (RCM) ofN-allyl N-aryl alkenamides with Grubbs
8c, the H-NMR (400 MHz, CDCl3) spectrum showed a
three- proton sin glet sig nal at 3.83 ppm in di cat ing the pres-
ence of one methoxyl group; a two-proton dou blet trip let at
4.34ppmcorrespondingtothemethyleneoftheallylgroupin
the struc ture. In ad di tion, a three one-proton dou blet dou blet
at 5.51 ppm (J = 2.0 Hz, and 10.4 Hz), 6.04 ppm (J = 10.4 Hz,
and 16.8 Hz), and 6.36 ppm (J = 2.0, and 16.8 Hz) were in di-
cated, re spec tively, to the three vi nyl pro tons by gem-cis,
cis-trans, and gem-trans coupling. Fur ther more the three
olefinic pro tons of the allyl group were shown, re spec tively,
at 5.07 ppm (d, J = 1.2 Hz, 1H), 5.11-5.14 ppm (m, 1H), and
5.83-5.93 ppm (m, 1H). The re main ing two two-proton ar o-
matic multiplet sig nals were in di cated, re spec tively, at 6.89-
6.92 ppm, and 7.05-7.09 ppm. The EI-MS spec trum showed
themolecularionatm/z 217,correspondingtothemolecular
formulaC13H15NO2. The high-resolution mass of 8c, C13H15NO2
found for 217.1103, matched with the cal cu lated one. These
re sults proved the cor rect ness of the struc ture of 8c. 8a-f was
a col or less liq uid, and dif fi cult to pu rify by dis til la tion be-
cause part of it was poly mer ized dur ing the pro cess of vac-
uumdistillation. Itspurificationwassubjectedtochromato-
graphicsilica-gelcolumnusingethylacetate/n-hexane(1/5)
as eluent. Our one-pot method has suc cess fully af forded a
newandefficientroutetoprepareN-allyl N-aryl acrylamides,
and suc cess fully cir cum vented the use of toxic and vol a tile
startingmaterial,acryloylchloride.Furthermorecyclization
catalyst16a was achieved to give a se ries of N-aryl
-unsatu-
rated -lactams, akeyintermediateformitomycin.17 Mean-
while the phys i cal data, such as 1H-NMR,13C-NMR, and EI-
MS of some new N-aryl
-unsaturated -lac tams are de-
scribed.
RESULTSANDDISCUSSION
3-(Phenylsulfonyl)propanoic acid (3), pur chased from
Aldrich Co. or pre pared from so dium benzenesulfinate (1),
and acrylic acid (2), as gen eral method in 65% yields, was
treated with excess thionyl chlo ride un der re flux to give
3-(phenylsulfonyl)propanoyl chlo ride (4).Afterremoving
excessthionylchloride, andwithoutfurtherpurification, it
was al lowed to re act with cor re spond ing pri mary amines in
the pres ence of an hy drous triethylamine to af ford N-aryl
3-(phenylsulfonyl)propanamides (5a-f) in high yields. When
compound5 wasreactedwithpotassiumtert-butoxide at 0 C
in THF, no cyclization or dimerization, but high yield of elim-
inationproducts 6 was ob served. But the re ac tion of 5 with
potassiumtert-butoxidewascarriedoutatroomtemperature
in THF, gave a lower yield of 6to gether with its dimer. For in-
stance, in the case of com pound 5b, its dimer was given in
10% yields, and showed two sin glet methyl sig nals at 2.30
and 2.37; and three dou blet dou blet olefinic pro tons at 5.54,
6.01, and 6.37 in 1H-NMR spec trum. By our method run ning
at 0 C in THF, it gave N-phenylacrylamide (7a) in 90%
yield, N-(4-methylphenyl)acrylamide (7b) in 95% yield,
N-(4-methoxyphenyl) acrylamide (7c) in 96% yield,
N-(4-fluorophenyl)acrylamide (7d) in 90% yield, N-(4-chlo-
ro phenyl)acrylamide (7e ) in 93% yield, and N-(4-bromo-
phenyl)acrylamide (7f) in 96% yield. Their struc tures are co-
in ci dent with the pre vi ous re ports by com par ing with MP,
EI-MSandNMRspectradataifavailable.Furthermorethese
acrylamides, with out iso la tion or pu ri fi ca tion, can be ex-
tended to the one-pot method for the prep a ra tion ofN-allyl
N-aryl acrylamides (8a-f) in good yields by re act ing it with
anadditionalequivalentofpotassiumtert-butoxide and allyl
bro mide. Their struc tures were elu ci dated by spec tral data
such as NMR, EI-MS, and HRMS. For in stance, in the case of
of N-allyl N-aryl acrylamides (8a-f) to N-aryl
-unsatu-
rated -lactams (9a-f) was ac com plished by oleifin ring-
closure me tath e sis in the pres ence of Grubbs cat a lyst. As in
the gen eral pro ce dure de scribed by Grubbs et al., 8a-f were
cyclized, re spec tively, to give 9a-f within 20 hours in 50-
65%yieldsinanhydrousdichloromethane,evenprolonging
the re ac tion time to 2-3 days. Re cently Furstner, A. et al.,16b
usingmodifiedGrubbscatalysttocyclize 8a in anhydrousto-
lu ene at 80 C to give 9a in 82% yield was re ported. Un der
the same con di tions, in our case us ing Grubbs cat a lyst to
cyclize 8a in anhydrous to lu ene at 80 C gave 9a in 55%
yields which al most gave the same yield to com pare with the
reactionrunningindrieddichloromethaneatroomtempera-
ture. But the de crease of the re ac tion time from 2 days to 3
hours was ob served. The struc ture of 9a-fwas elu ci dated by
their phys i cal data such as 1H-NMR, 13C-NMR, HETCOR,
and HRMS. In the 1H-NMR spec trum (400 MHz, CDCl3), a
typ i cal pat tern was found in this se ries of com pounds. The
case of 9d showed a two-proton trip let at 4.34 ppm (J = 2.0
Hz)correspondingtoH-5,andtwoone-protondoublettriplet
(J = 6.0 Hz, J = 2.0 Hz) at 6.19 and 7.10 ppm in di cat ing the
pres ence of ole fin pro tons, H-3 and H-4, re spec tively. The
13C-NMR spec trum (100 MHz, CDCl3) of 9d showed one

2-Alkenamides and , -Unsaturated -Lactams
J. Chin. Chem. Soc., Vol. 48, No. 1, 2001 85
sp3-car bon at 53.42 ppm cor re spond ing to C-5, two olefinic
carbonsat129.11ppmand142.17ppm,respectively,indicat-
ing C-3 and C-4, four ar o matic car bon at 115.69 (J = 21.3
Hz), 120.70 (J = 9.1 Hz), 135.17 (J = 0 Hz), and 159.31 (J =
242.7Hz)respectivelyindicatingC’-3,C’-2,C’-1,andC’-4,
andonecarbonylcarbonat168.98ppm.Furthermorebesides
the mo lec u lar ion, some char ac ter is tic frag ments such as
[m+-29], [m+-55], and [m+-82] in the EI/MS spec tra were
commonly found in 9a-f. The detailed studies about the
(n-hexane/ethyl acetate = 1/1). The results obtained are
shownasfollows:
N-Phenyl-3-(phenylsulfonyl)propanamide (6a)
Pure ( 6a) (1.37 g, 95%) was ob tained as col or less crys-
tals; mp 116-117 C (EtOAc + n-hexane);R f = 0.56 (EtOAc :
n-hex ane = 1 : 1);1H-NMR (CDCl3, 400 MHz) : 2.93 (t, J =
8.0 Hz, 2H, SO2CH2CH2), 3.57 (t,J = 8.0 Hz, 2H, SO2CH2CH2),
7.08 (t, J = 7.6 Hz, 1H, Ar-H), 7.26 (t, J = 8.0 Hz, 2H, Ar-H),
7.43 (t, J = 8.0 Hz, 2H, Ar-H), 7.56 (t, J = 7.6 Hz, 2H, Ar-H),
7.66 (m, 1H, Ar-H), 7.94 (d,J = 7.6 Hz, 2H, Ar-H), 8.04 (br s,
1H, NH); 13C-NMR (CDCl3, 100 MHz) : 29.80 (CH2), 51.89
(CH2), 119.87, 124.48, 127.96 128.92, 129.47, 134.10, 137.55,
138.63 (Ar-C), 167.01 (C=O); MS (EI, 70 eV), m/z 289 (M+,
54.30), 197 (7.26), 148 (2.95), 125 (41.02), 93 (100), 77
(19.07), 55 (34.67). Anal. Calcd for C15H15NO3S: C, 62.26;
H, 5.23; N, 4.84. Found: C, 62.20; H, 5.28; N, 4.71.
fragmental be hav iors of N-aryl
-unsaturated -lactam in
EI/MS will be re ported else where. The ap pli ca tion of acryl-
amides to synthesize some other interestingheterocyclic
compoundsnowiscurrentlyinprogress.
EXPERIMENTAL
Meltingpoints(Yanacomicromelting-pointapparatus)
are un cor rected.1H-NMR and 13C-NMR spec tra were ob-
tained on a Varian Gem ini-200 or Varian Unity Plus 400 spec-
trom e ter. Chem i cal shifts are mea sured in parts per mil lion
withrespecttoTMS. Elementalanalyseswererecordedona
HeraeusCHN-ORapidanalyzer.Massspectrawererecorded
onChem/hp/middleinstrument,andHRMSwererecordedon
JEOL, JMSD-200 or on JEOL, JMS-SX. Sil ica gel (230-400
mesh)forcolumnchromatography, andprecoatedsilicagel
plates (60F-254) for TLC were pur chased from E. Merck. UV
light (254 nm) was used to de tect spots on TLC plates af ter
development.
N-(4-Methylphenyl)-3-(phenylsulfonyl)propanamide (6b)
Pure ( 6b) (1.45 g, 96%) was ob tained as col or less crys-
tals; mp 136-137 C (EtOAc + hex ane); Rf = 0.41 (EtOAc :
n-hex ane = 1 : 1);1H-NMR (CDCl3, 400 MHz) : 2.29 (s, 3H,
CH3), 2.89 (t, J = 8.0 Hz, 2H, SO2CH2CH2), 3.55 (t, J = 8.0
Hz, 2H, SO2CH2CH2), 7.07 (d, J = 8.0 Hz, 2H, Ar-H), 7.30 (d,
J = 8.0 Hz, 2H, Ar-H), 7.57 (t,J = 7.6 Hz, 2H, Ar-H), 7.66 (t,J
= 7.6 Hz, 1H, Ar-H), 7.81 (br s, 1H, NH), 7.94 (d, J = 7.6 Hz,
2H, Ar-H); 13C-NMR (CDCl3, 100 MHz) : 20.82, 29.84,
51.92, 119.99, 127.99, 129.44 134.06, 134.20, 134.92, 138.70,
(Ar-C), 166.81 (C=O); MS (EI, 70 eV), m/z 303 (M+, 67.34),
197 (1.35), 162 (6.97), 125 (26.80), 107 (100), 106 (20.76),
77 (16.19), 55 (27.12). Anal. Calcd for C16H17NO3S: C,
63.34; H, 5.65; N, 4.62. Found: C, 63.32; H, 5.72; N, 4.53.
General procedure for the preparation of N-aryl 3-
(phenylsulfonyl)propanamide (6a-f)
3-(phenylsulfonyl)propanoic acid ( 4a-f) (5 mmol), pre-
pared from so dium benzenesulfinate and acrylic acid, or pur-
chased from Aldrich Co., was re acted with ex cess thionyl
chlo ride (20 mmol) un der re flux for 12 hr. Then the re ac tion
mixturewasconcentratedunderreducedpressuretoremove
excess thionyl chloride to afford 3-(phenylsulfonyl)pro-
panoyl chlo ride (5a-f).Withoutfurtherpurification,it(5a-f)
was dis solved in an hy drous di chloro methane (100 mL), and
cooled with ice bath. To this cooled so lu tion, it was added
dropwisewiththecorrespondingamine(3a-f) (5 mmol), and
fol lowed with triethylamine (5.5 mmol). The mix ture was
stirred at 0 C for 2 h, and then it was washed with 2% HCl
(10 mL 2), and with brine (10 mL 2). Finally the or ganic
layer was dried with an hy drous mag ne sium sul fate, and fil-
tered.Thefiltratewasconcentratedunderareducedpressure
to give crude N-aryl 3-(phenylsulfonyl)propanamide (6a-f)
which was pu ri fied by sil ica gel chro mato graphic col umn
N-(4-Methoxyphenyl)-3-(phenylsulfonyl)propanamide (6c)
Pure (6c) (1.52 g, 95%) was ob tained as col or less crys-
tals; mp 118-119 C (EtOAc + hex ane); R = 0.24 (EtOAc :
f
n-hex ane = 1 : 2);1H-NMR (CDCl3, 200 MHz) : 2.85 (t, J =
7.8 Hz, 2H, SO2CH2CH2), 3.55 (t,J = 7.8 Hz, 2H, SO2CH2CH2),
3.78 (s, 3H, OCH3), 6.84 (d,J = 9.1 Hz, 2H, Ar-H), 7.33 (d, J
= 9.1 Hz, 2H, Ar-H), 7.42 (br s, 1H, NH), 7.54-7.68 (m, 3H,
Ar-H), 7.92-7.96 (m, 2H, Ar-H);13C-NMR (CDCl3, 50 MHz)
: 29.77, 52.00, 55.46, 114.13, 121.85, 128.03, 129.48,
130.58, 134.09, 138.75, 156.62, 166.82 (C=O); MS (EI, 70
eV), m/z 319 (M+, 100), 125 (15.74), 123 (98.01), 108
(26.44), 77 (7.13), 55 (23.66). Anal. Calcd for C16H17NO4S:
C, 60.17; H, 5.37; N, 4.39. Found: C, 59.99; H, 5.38; N, 4.30.
N-(4-Fluorophenyl)-3-(phenylsulfonyl)propanamide (6d)
Pure ( 6d) (1.49 g, 97%) was ob tained as col or less crys-

86 J. Chin. Chem. Soc., Vol. 48, No. 1, 2001
Wang et al.
tals; mp 117-118 C (EtOAc + hex ane); Rf = 0.32 (EtOAc :
n-hex ane = 1 : 1);1H-NMR (DMSO-d6 + CDCl3, 200 MHz) :
2.94 (t, J = 7.22 Hz, 2H, SO2CH2CH2), 3.57 (t, J = 7.22 Hz,
2H, SO2CH2CH2), 6.88-6.96 (m, 2H, Ar-H), 7.35-7.42 (m,
2H, Ar-H), 7.51-7.71 (m, 3H, ArH), 7.91-7.95 (m, 2H, Ar-H),
8.33 (br s, 1H, NH); 13C-NMR (DMSO-d6 + CDCl3, 50 MHz)
: 29.49, 51.87, 115.47 (d, JC-C-F = 22.25 Hz), 121.65 (d,
JC-C-C-F = 7.80 Hz), 127.88, 129.48, 133.66 (d, JC-C-C-C-F = 2.65
Hz), 134.17, 138.53, 159.31 (d, JC-F = 242.20 Hz), 167.13
(C=O); MS (EI, 70 eV), m/z 307 (M+, 15.69), 125 (63.20),
111 (100), 110 (10.02), 77 (16.42), 55 (32.63). Anal. Calcd
for C15H14FNO3S: C, 58.62; H, 4.59; N, 4.56. Found: C,
58.96; H, 4.85; N, 4.27.
THF (50 mL) at 0 C for 1 h. At the end of the re ac tion, which
was mon i tored by silical gel TLC (n-hexane:ethylacetate=
2 : 1), the mix ture was poured into a sep a rat ing fun nel and
mixed with EtOAc (100 mL). The so lu tion was washed with
brine (10 mL 5), then the or ganic layer was sep a rated, and
dried with an hy drous mag ne sium sul fate, and fil tered. The
filtratewasconcentratedunderareducedpressuretogivethe
de sired com pound (7a-f), which was pu ri fied by sil ica gel
chromatographiccolumn(n-hexane/ethylacetate=2/1).The
re sults ob tained are shown as fol lows:
N-Phenylacrylamide (7a)
Pure ( 7a) (0.66 g, 90%) was ob tained as col or less crys-
tals; mp 103-105 C (EtOAc + n-hex ane) [lit.13b mp 101-
1
N-(4-Chlorophenyl)-3-(phenylsulfonyl)propanamide (6e)
Pure ( 6e) (1.59 g, 98%) was ob tained as col or less crys-
tals; mp 160-161 C (EtOAc +n-hexane);Rf = 0.42 (EtOAc :
n-hex ane = 1 : 1);1H-NMR (DMSO-d6 + CDCl3, 200 MHz) :
2.78 (t, J = 7.30 Hz, 2H, SO2CH2CH2), 3.53 (t, J = 7.30 Hz,
2H, SO2CH2CH2), 7.20, 7.92 (each d, J = 8.0 Hz, 4H, Ar-H),
7.49-7.70 (m, 5H, ArH), 10.03 (br s, 1H, NH); 13C-NMR
(DMSO-d6 +CDCl3, 50 MHz) : 29.24, 51.01, 120.34, 127.33,
127.40, 127.95, 128.86, 133.38, 137.08, 138.35, 166.89
(C=O); MS (EI, 70 eV),m/z 325 (M+2 , 4.68), 323 (M+, 14.32),
197 (10.13), 129 (29.09), 127 (100), 126 (12.53), 125
(90.66), 105 (10.94), 99 (7.21), 77 (28.95), 55 (41.46). Anal.
Calcd for C 15H14 Cl NO3S: C, 55.64; H, 4.36; N, 4.33. Found:
C, 55.86; H, 4.51; N, 4.27.
103]; Rf = 0.42 (EtOAc : n-hexane = 1 : 1.5); H-NMR
(CDCl3, 400 MHz) : 5.72 (dd, J = 2.0 Hz; 10.0 Hz, 1H,
olefinic H), 6.30 (dd, J = 10.0 Hz; 17.0 Hz, 1H, olefinic H),
6.42 (dd, J = 2.0 Hz; 17.0 Hz, 1H, olefinic H), 7.11 (t,J = 7.6
Hz, 1H, Ar-H), 7.31 (t,J = 8.4 Hz, 2H, Ar-H), 7.60 (d, J = 7.6
Hz, 1H, Ar-H), 8.00 (br s, 1H, NH); 13C-NMR (CDCl3, 100
MHz) : 120.13 (olefinic), 124.47 (olefinic), 127.59, 128.93,
131.24, 137.79 (Ar-C), 163.82 (C=O); MS (EI, 70 eV), m/z
147 (M+, 38.12), 93 (100), 55 (77.04).
N-(4-Methylphenyl)acrylamide (7b)
Pure ( 7b) (0.76 g, 95%) was ob tained as col or less crys-
tals; mp 139-140 C (EtOAc + n-hexane)[lit.18 mp 138-139];
Rf = 0.66 (EtOAc :n-hex ane = 1 : 1.5);1H-NMR (CDCl3, 200
MHz) : 2.31 (s, 3H, CH3), 5.72 (dd,J = 2.0 Hz; 10.0 Hz, 1H,
olefinic H), 6.25 (dd, J = 10.0 Hz; 17.0 Hz, 1H, olefinic H),
6.41 (dd, J = 2.0 Hz; 17.0 Hz, 1H, olefinic H), 7.12, 7.46 (d, J
= 8.3 Hz, each 2H, Ar-H), 7.64 (br s, 1H, NH); 13C-NMR
(CDCl3, 100 MHz) : 20.90 (CH3), 120.15 (olefinic), 127.47
(olefinic), 129.52, 131.30, 134.20, 135.20 (Ar-C), 163.82
(C=O); MS (EI, 70 eV), m/z 161 (M+, 74.48), 107 (100), 106
(37.99), 55 (77.04).
N-(4-Bromophenyl)-3-(phenylsulfonyl)propanamide (6f)
Pure ( 6e) (1.80 g, 97%) was ob tained as col or less crys-
tals; mp 169-170 C (EtOAc +n-hexane);Rf = 0.33 (EtOAc :
n-hex ane = 1 : 1);1H-NMR (DMSO-d6 + CDCl3, 200 MHz) :
2.86 (t, J = 7.30 Hz, 2H, SO2CH2CH2), 3.52 (t,J = 7.3 Hz, 2H,
SO2CH2CH2), 7.35, 7.43 (each d, J = 9.1 Hz, 4H, Ar-H),
7.52- 7.66 (m, 3H, ArH), 7.92 (dd,J = 1.7 Hz, 2H, ArH), 9.63
(br s, 1H, NH); 13C-NMR (DMSO-d6 + CDCl3, 50 MHz) :
29.44, 51.52, 115.95, 121.05, 127.67, 129.07, 131.30, 133.66,
137.34, 138.53, 167.21 (C=O); MS (EI, 70 eV),m/z 369 (M+2,
37.67), 367 (M+, 29.52), 197 (12.77), 173 (91.58), 171
(98.32), 125 (100), 55 (47.33). Anal. Calcd for C15H14 Br
NO3S: C, 48.92; H, 3.83; N, 3.80. Found: C, 49.12; H, 3.51;
N, 3.97.
N-(4-Methoxyphenyl)acrylamide (7c)
Pure (7c) (0.85 g, 96%) was ob tained as col or less crys-
tals; mp 99-101 C (EtOAc + n-hexane)[lit.19 mp 95-96]; R f =
0.28 (EtOAc : n-hex ane = 1 : 1.5); 1H-NMR (CDCl3, 200
MHz) : 3.78 (s, 3H, OCH3), 5.69 (dd, J = 2.0 Hz; 10.0 Hz,
1H, olefinic H), 6.26 (dd, J = 10.0 Hz; 17.0 Hz, 1H, olefinic
H), 6.40 (dd, J = 2.0 Hz; 17.0 Hz, 1H, olefinic H), 6.83, 7.48
(d, J = 9.0 Hz, each 2H, Ar-H), 7.91 (br s, 1H, NH); 13C-NMR
(CDCl3, 100 MHz) : 43.58 (OCH3), 126.62 (olefinic),
127.47 (olefinic), 127.80, 128.63, 130.65, 138.02 (Ar-C),
165.43 (C=O); MS (EI, 70 eV), m/z 177 (M+, 100), 123
(80.28), 122 (27.65), 108 (46.37), 55 (53.01).
General procedure for the preparation of N-aryl
acrylamides (7a-f)
Un der dry ni tro gen, the mix ture ofN-aryl 3-(phenyl-
sulfonyl)propanamides (6a-f) (5 mmol) and po tas sium tert-
butoxide (0.57 g, 5.05 mmol) was sus pended in an hy drous

2-Alkenamides and , -Unsaturated -Lactams
J. Chin. Chem. Soc., Vol. 48, No. 1, 2001 87
N-(4-Fluorophenyl)acrylamide (7d)
mmol), and stirred con tin u ally at 0 C for 1 h. At the end of
the re ac tion, which was mon i tored by sil ica gel TLC (hex-
ane/ethyl ac e tate = 2/1), the mix ture was con cen trated to re-
move THF un der a re duced pres sure. The res i due was mixed
with EtOAc (100 mL), and washed with brine wa ter (10 mL
5). Then the so lu tion was dried with an hy drous mag ne sium
sulfate, andfiltered. Thefiltratewasconcentratedunderare-
duced pres sure to give the de sired com pound (8a-f), which
was pu ri fied by sil ica gel chro mato graphic col umn (n-hex-
ane/ethylacetate=2/1).
Pure (7d) (0.743 g, 90%) was ob tained as col or less
crys tals; mp 132-134 C (EtOAc + n-hex ane); Rf = 0.57
(EtOAc : n-hex ane = 1 : 2); 1H-NMR (DMSO-d6 + CDCl3,
400 MHz) : 5.68 (d, J = 10.0 Hz, 1H, olefinic H), 6.33 (d,J =
16.8 Hz, 1H, olefinic H), 6.43 (dd, J = 16.8 Hz, 10.0 Hz, 1H,
olefinic H), 6.98-7.02, 7.67-7.70 (m, each 2H, Ar-H), 9.94
(br s, 1H, NH); 13C-NMR (DMSO-d6 + CDCl3, 100 MHz) :
114.70 (d, Jc-c-F = 22 Hz), 120.99 (d, Jc-c-c-F = 7.6 Hz), 126.11
(olefinic C), 131.37 (olefinic C), 134.85 (d,Jc-c-c-c-F = 2.2 Hz),
158.20 (d, Jc-F = 240.5 Hz), 163.19 (C=O); MS (EI, 70 eV),
m/z 165 (M+, 41.99), 112 (4.96), 111 (100), 83 (13.41), 55
(50.29). Anal. Calcd for C9H8NFO: C, 65.45; H, 4.88; N,
8.48. Found: C, 65.67; H, 4.59; N, 8.76.
N-Allyl N-Phenylacrylamide (8a)8b
Pure (8a) (0.66 g, 70%) was ob tained as col or less liq-
uid; Rf = 0.45 (EtOAc : n-hex ane = 1 : 3);1H-NMR (CDCl3,
400 MHz) : 4.38 (dt, J = 6.4 Hz, 1.2 Hz, 2H, allyl H), 5.09
(dd, J = 1.2 Hz; 8.0 Hz, 1H, ole fin H), 5.12 (br s, 1H, ole fin
H), 5.50 (dd,J = 10.2 Hz; 1.6 Hz, 1H, ole fin H), 5.84-5.93 (m,
1H, ole fin H), 6.04 (dd, J = 10.4 Hz; 16.6 Hz, 1H, ole fin H),
6.37 (dd, J = 2.4 Hz; 16.6 Hz, 1H, ole fin H), 7.14-7.16 (m,
2H, Ar-H), 7.30-7.42 (m, 3H, Ar-H); 13C-NMR (CDCl3, 100
MHz) : 51.97, 117.44, 127.21, 127.38, 127.76, 128.34,
129.08, 132.59, 141.57, 164.79 (C=O); MS (EI, 70 eV), m/z
187 (M+, 24.18), 172 (19.51), 159 (12.40), 144 (7.66), 133
(29.07), 132 (50.04), 106 (23.14), 93 (22.18), 77 (35.68), 55
N-(4-Chlorophenyl)acrylamide (7e)
Pure ( 7e) (8.42 g, 93%) was ob tained as col or less crys-
tals; mp 174-176 C (EtOAc +n-hexane);[lit.20 mp 101-103];
Rf = 0.73 (EtOAc : n-hex ane = 1 : 2);1H-NMR (DMSO-d6 +
CDCl3, 400 MHz) : 5.71 (dd,J = 3.6 Hz; 8.6 Hz, 1H, olefinic
H), 6.39 (m, 2H, olefinic H), 7.23-7.27, 7.67-7.70 (m, each
2H, Ar-H), 9.85 (br s, 1H, NH); 13C-NMR (DMSO-d6 +
CDCl3, 100 MHz) : 120.24, 125.99, 127.26, 127.68, 130.76,
136.88 (Ar-C), 163.00 (C=O); MS (EI, 70 eV),m/z 183 (M+2,
13.36), 181 (M+, 42.52), 129 (33.54), 127 (100), 55 (70.31);
Anal. Calcd for C9H8NClO: C, 59.52; H, 4.44; N, 7.71.
Found: C, 59.74; H, 4.68; N, 7.79.
(100); HRMS: Calcd for C H13NO: 187.0997. Found:
12
187.1027.
N-Allyl N-(4-Methylphenyl)acrylamide (8b)
N-(4-Bromophenyl)acrylamide (7f)
Pure (8b) (0.75 g, 75%) was ob tained as col or less liq-
uid; bp 135-145 C (2.5 mmHg); R f = 0.34 (EtOAc :n-hexane
= 1 : 3); H-NMR (CDCl3, 400 MHz) : 2.36 (s, 3H, CH3),
Pure (7f) (1.08 g, 96%) was ob tained as col or less crys-
tals; mp 179-181 C (EtOAc +n-hexane);[lit.18 mp 178-179];
Rf = 0.49 (EtOAc : n-hex ane = 1 : 2);1H-NMR (DMSO-d6 +
CDCl3, 400 MHz) : 5.70 (dd,J = 3.0 Hz; 8.6 Hz, 1H, olefinic
H), 6.39 (m, 2H, olefinic H), 7.37-7.41 (m, 1H, Ar-H), 7.63
(d, J = 8.8 Hz, 1H, Ar-H), 9.89 (br s, 1H, NH); 13C-NMR
(DMSO-d6 + CDCl3, 100 MHz) : 115.29, 120.94, 126.37,
130.96, 131.11, 137.72 (Ar-C), 163.33 (C=O); MS (EI, 70
eV), m/z 227 (M+2 , 14.09), 225 (M+, 14.05), 173 (34.02), 171
(34.64), 91 (10.54), 55 (100); Anal. Calcd for C9H8NBrO: C,
47.82; H, 3.57; N, 6.20. Found: C, 47.86; H, 3.51; N, 5.98.
1
4.36 (dt, J = 6.0 Hz, 1.2 Hz; 2H, allyl H), 5.08 (d, J = 7.6 Hz,
1H, allyl H), 5.11 (br s, 1H, allyl H), 5.48 (dd, Jgem-cis = 2.0
Hz; 10.4 Hz, 1H, vi nyl H), 5.83-5.92 (m, 1H, allyl H), 6.05
(dd, Jcis-trans = 10.4; 16.8 Hz, 1H, vi nyl H), 6.36 (dd, Jgem-trans
=
2.0 Hz; 16.8 Hz, 1H, vi nyl H), 7.04, 7.19 (d, J = 8.4 Hz, each
2H, Ar-H); 13C-NMR (CDCl3, 100 MHz) : 20.61 (CH3),
51.92 (CH2), 117.34, 126.93, 127.53, 128.37, 129.65, 132.64,
137.23, 138.89, 164.80; MS (EI, 70 eV),m/z 201 (M+, 27.43),
186 (13.22), 147 (28.38), 146 (35.74), 144 (10.01), 132
(20.70), 120 (24.31), 118 (18.98), 107 (37.34), 91 (39.19), 77
(16.36), 65 (31.14), 55 (100); HRMS: Calcd for C13H15NO:
201.1154. Found: 201.1152.
General procedure for one-pot preparation of N-Allyl
N-aryl acrylamide (8a-f)
Un der dry ni tro gen, the mix ture ofN-aryl 3-(phenyl-
sulfonyl)propanamides (7a-f) (5 mmol) and po tas sium tert-
butoxide (0.57 g, 5.01 mmol) was sus pended in a an hy drous
THF (100 mL) and stirred at 0 C for 1 h. Then the mix ture
was added with an additional tert-butoxide (0.57 g, 5.01
mmol), and sub se quently fol lowed with allyl bro mide (5.01
N-Allyl N-(4-methoxyphenyl)acrylamide (8c)
Pure (8c) (0.82 g, 76%) was ob tained as col or less liq-
uid; bp 165-170 C (3 mmHg); Rf = 0.54 (EtOAc : n-hexane=
1
1 : 3); H-NMR (CDCl3, 400 MHz) : 3.83 (s. 3H, OCH3),
4.34 (dt, J = 6.0 Hz, 1.2 Hz; 2H, al lyl ic H), 5.07 (d, J = 1.6

88 J. Chin. Chem. Soc., Vol. 48, No. 1, 2001
Wang et al.
Hz, 1H, allyl H), 5.11-5.14 (m, 1H, allyl H), 5.51 (dd, Jgem-cis
= 2.0 Hz; 10.4 Hz, 1H, vi nyl H), 5.83-5.93 (m, 1H, allyl H),
6.04 (dd, Jcis-trans = 10.4 Hz, 16.8 Hz, 1H, vi nyl H), 6.36 (dd,
Jgem-trans = 2.0 Hz; 16.8 Hz, 1H, vi nyl H), 7.89-6.92 (m, 2H,
Ar-H), 7.05-7.09 (m, 2H, Ar-H); 13C-NMR (CDCl3, 100
MHz) : 52.35 (CH2), 55.35 (OCH3), 114.47, 117.80, 127.35,
128.58, 129.24, 132.92, 134.49, 158.84, 165.41 (C=O); MS
(EI, 70 eV), m/z 217 (M+, 48.23), 163 (32.07), 148 (26.43),
147 (15.77), 134 (35.98), 130 (19.78), 123 (59.82), 120
(11.51), 108 (29.89), 94 (40.08), 77 (31.59), 64 (21.74), 55
400 MHz) : 4.32 (dt, J = 6.0 Hz, 1.2 Hz; 2H, allyl H), 5.04
(d, J = 1.2 Hz, 1H, allyl H), 5.10 (d, J = 10.4 Hz, 1H, allyl H),
5.53 (dd, Jgem-cis = 2.0 Hz, 10.2 Hz, 1H, vi nyl H), 5.78-5.82
(m, 1H, allyl H), 6.01 (dd,Jcis-trans = 10.2 Hz, 16.8 Hz, 1H, vi-
nyl H), 6.39 (dd, Jgem-trans = 2.0 Hz, 16.8 Hz, 1H, vi nyl H),
7.00-7.02 (m, 2H, Ar-H); 7.47-7.50 (m, 2H, Ar-H);13C-NMR
(CDCl3, 100 MHz) : 52.17, 118.13, 121.43, 128.18, 128.25,
129.69, 132.55, 140.87, 164.95; MS (EI, 70 eV), m/z 267
(M+2, 5.11), 266 (2.38), 265 (M+, 5.14), 211 (7.26), 184
(6.56), 171(6.51), 157 (4.99), 130 (13.53), 94 (9.24), 76
(9.21), 55 (100); HRMS: Calcd for C 12H12N Br79O: 265.0102.
Found: 265.0103.
(100); HRMS: Calcd for C H15NO: 217.1103. Found:
13
217.1103.
N-Allyl N-(4-fluorolphenyl)acrylamide (8d)
General procedure for N-aryl
-unsaturated -lactams
Pure (8d) (0.80 g, 78%) was ob tained as col or less liq-
uid; Rf = 0.43 (EtOAc : n-hex ane = 1 : 3);1H-NMR (CDCl3,
400 MHz) : 4.36 (dt, J = 6.0 Hz, 1.2 Hz, 2H, allyl H), 5.08
(br s, 1H, allyl H), 5.14 (d,J = 10.8 Hz, 1H, allyl H), 5.55 (dd,
Jgem-cis = 2.0 Hz; 10.0 Hz, 1H, vi nyl H), 5.83-5.92 (m, 1H,
allyl H), 6.02 (dd, Jcis-trans = 10.0 Hz; 16.8 Hz, 1H, vi nyl H),
6.39 (dd, Jgem-trans = 2.0 Hz; 16.8 Hz, 1H, vi nyl H), 7.07-7.17
(m, 4H, Ar-H);13C-NMR (CDCl3, 100 MHz) : 52.16, 116.12
(9a-f)16b
Com pound9a-f (1 mmol) dis solved in an hy drous to lu-
ene (30 mL), was added with Grubbs cat a lyst (0.05 mmol).
The mix ture was stirred for 3 h at 80 Cunderdryargon. The
solventwasremovedundervacuum,andtheresiduewassub-
jected to a sil ica-gel col umn (n-hex ane/MTBE = 1/1) to give
9a-f inmoderateyields.
(d, Jc-c-c-F = 8.4 Hz), 117.92, 127.76, 128.17, 129.75 (d, Jc-c-F
=
N-Phenyl
-unsaturated -lactam (9a)
22.8 Hz), 132.54, 137.68, 161.52 (d,Jc-F = 246.5 Hz), 164.97;
MS (EI, 70 eV), m/z 205 (M+, 21.72), 190 (17.87), 177
(11.56), 151 (36.14), 150(44.70), 148 (11.09), 124 (17.08),
122 (18.68), 111 (25.51), 95 (34.66), 94 (14.18), 55 (100);
HRMS: Calcd for C 12H12NFO: 205.0903. Found: 205.0903.
Pure 9a (0.09g,57%)wasobtainedascolorlesscrystal,
mp 85-86 C (EtOAc + n-hexane)[lit.16a 86 C]; Rf = 0.53
(EtOAc : n-hex ane = 1 : 1); IR max (CH2Cl2) cm-1: 1692.11,
1596.95; 1H-NMR (400 MHz, CDCl3) : 4.39 (t, J = 2.0 Hz,
2H, H-5), 6.22 (dt,J = 6.0 Hz,J = 2.0 Hz, 1H, H-3), 7.14 (dt,J
= 6.0 Hz, J = 2.0 Hz, 1H, H-4), 7.11 (m, 1H, ArH), 7.35 (m,
2H, ArH), 7.68 (m, 2H, ArH);13C-NMR (100 MHz, CDCl) :
53.03 (C-5), 118.65, 123.97, 128.89 (C-3), 138.93, 142.26
(C-4), 169.99 (C=O); MS (EI, 70 eV): m/z 159 (M+, 100), 131
(13.16), 130 (60.69), 104 (41.53), 77 (43.44), 51 (12.08);
HRMS: Calcd for C9H9NO: 159.0684. Found: 159.0684.
N-Allyl N-(4-Chlorolphenyl)acrylamide (8e)
Pure (8e) (0.80 g, 72%) was ob tained as col or less liq-
uid; Rf = 0.49 (EtOAc : n-hex ane = 1 : 3);1H-NMR (CDCl3,
400 MHz) : 4.36 (dt,J = 6.0 Hz, 1.2 Hz, 2H, allyl H), 5.08 (d,
J = 1.2 Hz, 1H, allyl H), 5.14 (d, J = 10.4 Hz, 1H, allyl H),
5.56 (dd, Jgem-cis = 2.0 Hz, 10.2 Hz, 1H, vi nyl H), 5.82-5.92
(m, 1H, allyl H), 6.03 (dd, Jcis-trans = 10.2 Hz, 16.8 Hz, 1H, vi-
nyl H), 6.39 (dd, Jgem-trans = 2.0 Hz, 16.8 Hz, 1H, vi nyl H),
7.09-7.13 (m, 2H, Ar-H); 7.36-7.39 (m, 2H, Ar-H);13C-NMR
(CDCl3, 100 MHz) : 52.21, 118.11, 128.13, 128.27, 129.36,
129.54, 132.58, 133.48, 140.37, 165.01; MS (EI, 70 eV),m/z
223 (M+2 , 4.95), 221 (M+, 17.80), 206 (10.33), 178 (5.66),
167 (38.12), 166 (28.05), 140 (20.00), 130 (18.60), 127
(24.45), 111 (16.02), 94 (15.78), 75 (13.48), 55 (100); HRMS:
Calcd for C12H12NCl35O: 221.0607. Found: 221.0607.
N-(4-Methylphenyl)
-unsaturated -lactam (9b)
Pure 9b(0.11g, 64%)wasobtainedascolorlesscrystal,
mp 96-97 C (EtOAc + n-hexane)[lit.16a 95 C]; Rf = 0.56
(EtOAc : n-hex ane, 1 : 1); IR max (CH2Cl2) cm-1: 1694.00,
1598.15; 1H-NMR (400 MHz, CDCl3) : 2.33 (s, 3H, CH3),
4.42 (t, J = 2.0 Hz, 2H, H-5), 6.26 (dt, J = 6.0 Hz, J = 2.0 Hz,
1H, H-3), 7.15 (dt,J = 6.0 Hz,J = 2.0 Hz, 1H, H-4); 7.18, 7.57
(each d, J = 8.0 Hz, 2-H, ArH); 13C NMR (100 MHz, CDCl3)
: 20.77 (CH3), 53.38 (C-5), 119.12, 129.24, 129.59 (C-3),
133.91, 136.55, 141.95 (C-5), 170.04 (C=O); MS (EI, 70 eV):
m/z 173 (M+, 100), 145 (13.97),144 (64.39), 130 (24.74), 118
(22.53), 91 (28.87), 65 (11.51), HRMS: Calcd for C11H11NO:
173.0841. Found: 173.0841.
N-Allyl N-(4-Bromolphenyl)acrylamide (8f)
Pure (8f) (1.04 g, 78%) was ob tained as col or less liq-
uid; Rf = 0.41 (EtOAc : n-hex ane = 1 : 3);1H-NMR (CDCl3,

2-Alkenamides and , -Unsaturated -Lactams
J. Chin. Chem. Soc., Vol. 48, No. 1, 2001 89
N-(4-Methoxylphenyl)
-unsaturated -lactam (9c)
6.25 (dt, J = 6.0 Hz, J = 2.0 Hz, 1H, H-3), 7.19 (dt, J = 6.0 Hz,
J = 2.0 Hz, 1H, H-4); 7.44-7.48 (m, 2H, ArH), 7.60-7.63 (m,
2-H, ArH); 13C NMR (100 MHz, CDCl3) : 52.94 (C-5),
116.75 (Ar-C), 120.06 (Ar-C), 129.04 (C-3), 131.94 (Ar-C),
138.12 (Ar-C), 142.32 (C-4), 170.02 (C=O); MS (EI, 70 eV):
m/z 239 (M+2 , 100), 237 (M+, 99.52), 210 (35.74), 208
(35.92), 184 (49.99), 182 (48.75), 157 (34.38), 155 (33.24),
130 (64.68), 103 (7.84), 79 (14.63), 76 (20.45), 75 (17.56);
HRMS: Calcd for C10H8BrNO: 236.9798. Found: 236.9800.
Pure 9c(0.10g, 53%)wasobtainedascolorlesscrystal,
mp 103-104 C (EtOAc +n-hexane)[lit.16a 103 C]; R f = 0.40
(EtOAc : n-hex ane, 1 : 1); IR max (CH2Cl2) cm-1: 1681.30,
1609.21; 1H-NMR (400 MHz, CDCl3) : 3.81 (s, 3H, OCH3),
4.41 (t, J = 2.0 Hz, 2H, H-5), 6.27 (dt, J = 6.0 Hz, J = 2.0 Hz,
1H, H-3), 6.91-6.94 (m, 2H, ArH), 7.15 (dt,J = 6.0 Hz,J = 2.0
Hz, 1H, H-4), 7.57-7.60 (m, 2H, ArH); 13C NMR (100 MHz,
CDCl3) : 53.38 (C-5), 55.33 (OCH3), 114.16, 114.40 120.99,
129.24 (C-3), 141.70 (C-4), 156.37, and 169.81 (C=O); MS
(EI, 70 eV): m/z 189 (M+, 100), 174 (34.59),160 (18.77), 146
(27.44), 134 (23.34), 107(7.47), 92 (7.47), 77 (9.47); HRMS:
Calcd for C11H11NO2: 189.0790. Found: 189.0789.
ACKNOWLEDGEMENTS
This in ves ti ga tion was sup ported by a grant from the
Na tional Sci ence Coun cil, Tai wan. We are in debted to Prof.
Hiroki Takahata, Toyama Med i cal and Phar ma ceu ti cal Uni-
ver sity, Ja pan for a valu able dis cus sion and for mea sur ing
HRMS.
N-(4-Fluorophenyl)
-unsaturated -lactam (9d)
Pure 9d (0.11g, 62%)wasobtainedascolorlesscrystal,
mp 72-73 C (EtOAc + n-hexane),Rf = 0.47 (EtOAc :n-hex-
ane = 1 : 1); IR
(CH2Cl2) cm-1: 1680.59, 1594.80;
max
1H-NMR (400 MHz, CDCl3) : 4.34 (t, J = 2.0 Hz, 2H, H-5),
6.19 (dt, J = 6.0 Hz, J = 2.0 Hz, 1H, H-3), 6.96-7.02 (m, 2H,
ArH), 7.10 (dt,J = 6.0 Hz,J = 2.0 Hz, 1H, H-4); 7.55-7.61 (m,
2H, ArH), 13C NMR (100 MHz, CDCl3) : 53.42 (C-5),
115.69 (d,Jc-c-F = 21.3 Hz), 120.70 (d,Jc-c-c-F = 9.1 Hz), 129.11
(C-3), 135.17 (s, Jc-c-c-c-F = 0 Hz), 142.17 (C-4), 159.31 (d,Jc-F
= 242.7 Hz), 168.98 (C=O); MS (EI, 70 eV): m/z 177 (M+,
100), 149 (18.84), 148 (86.95), 122 (36.58), 95 (32.10), 75
(12.47); HRMS: Calcd for C10H8FNO: 177.0590. Found:
177.0592.
Received October 12, 2000.
Key Words
N-aryl 3-(phenylsulfonyl)propanamides; N-aryl
2-alkenamides; N-allyl N-aryl 2-alkenamides;
N-aryl
-unsaturated -lactams
REFERENCES
N-(4-Chlorophenyl)
-unsaturated -lactam (9e)
Pure 9e(0.11g, 57%)wasobtainedascolorlesscrystal,
mp 76-77 C (EtOAc + n-hexane),Rf = 0.53 (EtOAc :n-hex-
ane = 1 : 1); IR max (CH2Cl2) cm-1: 1690.68, 1594.47; 1H-
NMR (400 MHz, CDCl3) : 4.38 (t, J = 2.0 Hz, 2H, H-5),
6.22 (dt, J = 6.0 Hz, J = 2.0 Hz, 1H, H-3), 7.17 (dt, J = 6.0 Hz,
J = 2.0 Hz, 1H, H-4); 7.29-7.31 (m, 2H, ArH), and 7.63-7.65
(m, 2H, ArH); 13C NMR (100 MHz, CDCl3) : 52.97 (C-5),
119.70 (Ar-C), 126.95 (Ar-C), 128.79 (C-3), 134.12 (Ar-C),
137.51 (Ar-C), 142.41 (C-4), 169.99 (C=O); MS (EI, 70 eV):
m/z 195 (M+2 , 35.09), 193 (M+, 100), 166 (15.52), 164
(42.67), 140 (17.90), 138 (45.11), 130 (41.46), 113 (11.08),
1. Baldwin, J. E.; Dupont, W. A. TetrahedronLett. 1980, 21,
1881-1882.
2. Catto, A.; Motta, G. J. Med. Chem. 1987, 30(1), 13-19.
3. Honigberg, I. L.; Hartung, W. H. J. Org. Chem. 1960, 25,
1822-1824.
4. Bauer, L.; Welsh, T. L. J. Org. Chem. 1961, 26, 1443-
1445.
5. Rus sell, G. A.; Shi, B. Z.; Jiang, W.; Hu, S.; Kim, B. H.;
Baik, W. J. Am. Chem. Soc. 1995, 117(14), 3952-3962.
6. Sisti, N. J.; Motorina, I. A.; Dau, M. E. T. H.; Riche, C.;
Fowler, F. W.; Grierson, D. S. J. Org. Chem. 1996, 61,
3715-3728.
111 (32.99), 75 (15.48); HRMS: Calcd for C H8ClNO:
10
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