2,4-Dinitrophenylhydroxylamine: An efficient and more general reagent for iron-catalyzed allylic amination

Article abstract of DOI:10.1081/SCC-100105881

2,4-Dinitrophenylhydroxylamine (1) is an efficient reagent for the iron-catalyzed regioselective allylic amination of olefins. Moderate to excellent yields of N-DNP-N-allyl amines (2) are obtained resulting from introduction of the N-DNP group at the less

Full text of DOI:10.1081/SCC-100105881

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2,4-DINITROPHENYLHYDROXYLAMINE: AN EFFICIENT
AND MORE GENERAL REAGENT FOR IRON-CATALYZED
ALLYLIC AMINATION
Sumita Singh a & Kenneth M. Nicholas b
a Department of Chemistry and Biochemistry , University of Oklahoma , Norman, OK,
73019, U.S.A.
b Department of Chemistry and Biochemistry , University of Oklahoma , Norman, OK,
73019, U.S.A.
Published online: 16 Aug 2006.
To cite this article: Sumita Singh & Kenneth M. Nicholas (2001) 2,4-DINITROPHENYLHYDROXYLAMINE: AN EFFICIENT AND
MORE GENERAL REAGENT FOR IRON-CATALYZED ALLYLIC AMINATION, Synthetic Communications: An International Journal
for Rapid Communication of Synthetic Organic Chemistry, 31:20, 3087-3097, DOI: 10.1081/SCC-100105881
To link to this article: http://dx.doi.org/10.1081/SCC-100105881
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SYNTHETIC COMMUNICATIONS, 31(20), 3087–3097 (2001)
2,4-DINITROPHENYLHYDROXYLAMINE:
AN EFFICIENT AND MORE GENERAL
REAGENT FOR IRON-CATALYZED
ALLYLIC AMINATION
Sumita Singhand KennethM. Nicholas
*
Department of Chemistry and Biochemistry,
University of Oklahoma, Norman, OK 73019
ABSTRACT
2,4-Dinitrophenylhydroxylamine (1) is an efficient reagent for
the iron-catalyzed regioselective allylic amination of olefins.
Moderate to excellent yields of N-DNP-N-allyl amines (2) are
obtained resulting from introduction of the N-DNP group at
the less substituted vinylic carbon with accompanying double
bond transposition. N-alkylation of 2 and subsequent treat-
ment with MeNH2 affords secondary N-alkyl-N-allyl amines
(5) in good overall yield.
Allylamines are important both as synthetic intermediates1 and as end-
products,2 including numerous natural products.3 Although the synthesis of
allylamines is traditionally accomplished via functional group interconver-
sion,4 the direct allylic amination of olefins constitutes an attractive, but
relatively little developed, alternative route.5 Recently, allylic amination of
*Corresponding author. E-mail: knicholas@ou.edu
3087
Copyright & 2001 by Marcel Dekker, Inc.
www.dekker.com

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olefins by phenylhydroxylamine catalyzed by LnMo(VI)(O)2 (Ln ¼ dipic,
8
dedtc),6 LnFe(II, III)X7 and FeCl2,3 has been developed in our laboratory
and elsewhere (Scheme 1, Z ¼ Ph). These reactions provide secondary
N-phenyl-N-allyl amines in moderate yields and exhibit excellent ene
reaction-like regioselectivity.
In order to increase the synthetic scope of these direct amination
reactions, a new aminating agent, ZNHOH (1), was sought in which the
Z group could be cleaved from the amination product 2, providing general
access to primary and/or secondary allyl amines (3,5) (Scheme 1). Since
initial investigations in our laboratory had indicated that hydroxylamine
Scheme 1.
derivatives with conventional protecting groups, e.g. RCONHOH, were
ineffective as aminating agents because of metal chelate formation,9
we sought hydroxylamines devoid of potential coordinating groups. The
2,4-dinitrophenyl (DNP) group has been used for the protection of
amines10 and its electronic character was anticipated to provide a highly
electrophilic aminating agent. Herein we report our findings on the utiliza-
tion of 2,4-dinitrophenylhydroxylamine, DNP-NHOH (1, Z ¼ 2,4-dinitro-
phenyl), as a reagent for the amination of olefins catalyzed by Fe(II,
III)-chlorides and the subsequent deprotection of the DNP-allylamines
thus produced.
RESULTS AND DISCUSSION
The required reagent 1 was obtained efficiently from commercially
available 2,4-dinitroanisole11 as an orange solid which is stable in the

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2,4-DINITROPHENYLHYDROXYLAMINE
3089
solid state but which slowly degrades in solution. Olefins were found to
react with 1 in the presence of catalytic amounts of Fe(II, III)-chlorides
in refluxing dioxane to produce secondary N-(2,4-dinitrophenyl)-N-allyl-
amines (2) (Scheme 1, Table 1). The products 2 were isolated as air-stable
yellow solids and conveniently purified by column chromatography or
sublimation. The highest yields were obtained when the solution of 1 was
added to the reaction mixture containing a ten-fold excess of the olefin and
10 mol% of the catalyst over a period of 10–15 minutes. A mixture of nine
parts FeCl2 and one part FeCl3 was found to be optimum; both anhydrous
and hydrated Fe(II, III)-chlorides catalyze the reaction, but the rate is
higher using anhydrous salts. The only by-product detected in these
reactions is 2,4-dinitroaniline, presumably formed by decomposition of 1
in solution.
Table 1. Iron-Catalyzed Amination of Olefins Using
DNP-NHOH (6)
aisolated yield after chromatography; (yield based on
NMR of crude product).

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SINGH AND NICHOLAS
The yields of allyl amines using 1 are generally superior to those
obtained using PhNHOH.8a–c Unsymmetrical alkenes (e.g. entries 1, 3, 4, 5)
react with complete ene-like regioselectivity, i.e. nitrogen is introduced at the
less substituted vinylic carbon with transposition of the double bond.
Carbonyl and hydroxyl-containing substrates are also selectively aminated
at the C-C double bond (entries 4, 5). Although we have not yet investigated
the catalytic mechanism with this new aminating agent, we believe that the
remarkable regioselectivity derives from an intermediate iron-complexed
azodioxide species.8b,c
Considering the previously cited precedents10 for amine protection
by the DNP group, our attempts to cleave the 2,4-DNP group from the
secondary allylamines 2 to produce the corresponding primary N-allyl-
amines 3 were surprisingly unsuccessful (Scheme 1). Various reaction con-
ditions, employing either basic, nucleophilic or acidic reagents, were
investigated. DNP-derivative 2b was unreactive towards Ba(OH)2, NaOH,
KSPh, MeNH2, and NaOCH3 as well as several acidic reagents including
TFA/MeOH, TFA/PhSH or TsOH/H2O; product mixtures (apparently
including the deprotected amine) were obtained from 2b upon treatment
with the basic resin Amberlite 400(OH).
In contrast, net conversion of the N-(2,4-dinitrophenyl)-allylamines 2
to secondary allyl amines 5 can be accomplished by N-alkylation of 2 and
subsequent deprotection (Scheme 1). N-methylation occurs efficiently upon
treatment of 2 with base (NaH or K2CO3) and methyl iodide (Table 2), affor-
ding good yields of the corresponding N-methyl-N-(2,4-dinitrophenyl)-allyl-
amines (4a, b, c). Similarly, N-benzylation can be effected with BnBr/
Bu4NI.11 The 2,4-DNP group could then be cleaved from 4b, c by reaction
with excess MeNH2 or BuNH2 in DMSO to produce the corresponding
secondary N-methyl-N-allylamines (5b, c) in moderate yields (Scheme 1,
Table 2). That these reactions involve nucleophilic displacement at the DNP
group (rather than at the allylic carbon) was indicated by the formation of
the N-methyl amine 5a (and DNP-NHBu) when 4a was treated with BuNH2.
Dinitrophenyl hydroxylamine 1 thus provides an efficient reagent for
the direct, regioselective amination of olefins. General entry to secondary
N-alkyl-N-allyl amines is provided via subsequent alkylation/deprotection.
The development of other, still more general aminating agents to produce
primary allylic amines from olefins is currently under investigation.
EXPERIMENTAL
All reactions were conducted under nitrogen. 2,4-Dinitroanisole was
obtained from Pfaltz and Bauer. NMR spectra were obtained at 400 MHz

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2,4-DINITROPHENYLHYDROXYLAMINE
3091
Table 2. Alkylation and Deprotection of DNP-Allyl Amines
(1H) or 100 MHz (13C) in CDCl3 (unless noted otherwise) and less than 2%
impurites were detected in purified products.
2,4-Dinitrophenyl hydroxylamine (1)
This compound was prepared by a modification of the reported
method.11 Under a nitrogen atmosphere sodium (0.223 g, 9.70 mmol) was
added to anhydrous methanol (5 mL) with cooling in an ice bath. When the
exothermic reaction had subsided and the hydrogen gas evolution ceased,
the solution was stirred at room temperature for 15 min. To this was then
added a solution of NH2OHEHCl (0.682 g, 9.82 mmol) in hot methanol
(10 mL) with stirring. Immediate formation of a white solid (NaCl)
was observed. This suspension was stirred at room temperature for 30 min
and then added to a solution of 2,4-dinitroanisole (1.62 g, 8.18 mmol) in
hot methanol (15 mL) upon which the clear yellow solution of the anisole
derivative turned green. The reaction mixture was then refluxed and mon-
itored by analytical TLC for the disappearance of 2,4-dinitroanisole. When
all the starting material had been consumed (19h), the reaction mixture

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SINGH AND NICHOLAS
was cooled and then filtered. Solvent was removed from the filtrate by
rotary evaporation. The residue obtained was dissolved in ether and
extracted with H2O (3 Â 25 mL), the organic phase was dried with Na2SO4
and then the solvent was evaporꢀated to afford 1 as an orange solid in 91%
yield (1.49g, 7.49mmol). mp 79 C (dec) (lit mp 80ꢀC, dec); H NMR 7.61
1
(d, J ¼ 9.6 Hz, 1H), 8.38 (dd, J ¼ 9.4, 2.4 Hz, 1H), 9.09 (d, J ¼ 2.8 Hz, 1H);
IR (KBr) 819, 1320, 1518, 1623, 3089, 3305, 3450 cmÀ1; MS (EI, 12 eV DIP,
m/z, rel intensity) 199 (Mþ, 50), 200 (M þ 1, 2) 197 (21), 183 (100), 181 (99),
168 (34), 153 (18), 107 (2).
Amination of Olefins with1
Anhydrous FeCl2 (0.011 g, 0.090 mmol) and FeCl3 (0.002 g,
0.010 mmol) were weighed out in the dry box into a dry three-necked
flask. To this dry 1,4-dioxane (4 mL) and the olefin (10 mmol) were
added. The reaction mixture was stirred at 80–85ꢀC and to this was added
a solution of 2,4-dinitrophenylhydroxylamine (0.20 g, 1.0 mmol) in 1,4-diox-
ane (15 mL) over 10 min. The reaction mixture was then heated and mon-
itored by TLC for the disappearance of the hydroxylamine. After the
reaction was complete, the mixture was cooled and filtered. Solvent was
rotary evaporated from the filtrate and the residue was dried under
vacuum in a hot water bath to remove excess olefin. The residue was then
purified by flash column chromatography over silica gel with 60:40 petro-
leum ether/ether as the eluent. The first yellow band was collected and
solvent was removed to give the DNP-allylamines 2 as yellow–orange
solids. The second yellow band off the column was 2,4-dinitroaniline. The
allylamines obtained were characterized spectroscopically. Crystals of allyl-
amine 2b suitable for X-ray diffraction were obtained by dissolving a small
quantity in a minimum volume of ether and allowing it to stand in the
freezer for two days. X-ray data for 2b, which confirm its assigned structure,
are provided in the Supporting Information.
2a. Yield 76%; mp 68–69ꢀC; H NMR 1.02 (t, J ¼ 7.6 Hz, 3H), 1.70
1
(s, 3H), 1.76–1.88 (m, 2H), 3.93 (dd, J ¼ 13.2, 6.8 Hz, 1H), 4.98 (br s, 1H),
5.02 (br s, 1H), 6.86 (d, J ¼ 9.6 Hz, 1H), 8.20 (dd, J ¼ 9.6, 2.8 Hz, 1H), 8.64
(br, 1H), 9.11 (d, J ¼ 2.8 Hz, 1H); 13C NMR 10.4, 17.8, 26.8, 61.3, 114.1,
115.1, 124.2, 130.0, 142.4, 148.0; IR (KBr) 823, 1341, 1540, 1591, 1627, 1884,
1950, 1977, 3122, 3374 cmÀ1; MS (EI, 12 eV DIP, m/z, rel. intensity) 265
(Mþ, 23), 266 (Mþ þ 1, 1), 236 (100); High resolution FAB for C12H16N3O4
266.1148 (Mþ þ 1), calc. 266.2745.
2b. Yield 87%; mp 105–108ꢀC; 1H NMR 4.45 (d, J ¼ 5.6 Hz, 2H), 5.28
(br s, 1H), 5.56 (br s, 1H), 6.91 (d, J ¼ 9.2 Hz, 1H), 7.34–7.46 (m, 5H), 8.25

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2,4-DINITROPHENYLHYDROXYLAMINE
3093
(dd, J ¼ 9.4, 2.8 Hz, 1H), 8.79 (br, 1H), 9.13 (d, J ¼ 2.8 Hz, 1H); 13C NMR
47.2, 114.3, 114.6, 124.2, 125.9, 128.6, 128.8, 130.3, 137.8, 141.8, 148.2; IR
(KBr) 813, 1315, 1340, 1523, 1540, 1523, 1620, 2927, 2971, 3110, 3395 cmÀ1
;
MS (EI, 12 eV DIP, m/z, rel. intensity) 299 (Mþ, 45), 253 (100), 207 (6), 163
(10), 103 (30); High resolution FAB for C15H14N3O4 300.0998 (Mþ þ 1),
calc. 300.2917.
2c. Yield 63%; mp 100–101ꢀC; H NMR (acetone-d6) 0.84 (s, 3H),
1
1.16 (d, J ¼ 8.4 Hz, 1H), 1.27 (s, 3H), 2.08–2.13 (m, 1H), 2.18–2.22 (m,
1H), 2.23–2.30 (m, 2H), 2.40–2.46 (m, 1H), 4.14 (br s, 2H), 5.55 (br s,
1H), 7.20 (d, J ¼ 9.6 Hz, 1H), 8.27 (dd, J ¼ 9.6, 2.6 Hz, 1H), 8.90 (br, 1H),
8.97 (d, J ¼ 2.8 Hz, 1H); 13C NMR (acetone-d6) 21.3, 26.3, 31.7, 32.1, 38.7,
41.5, 44.5, 48.3, 116.3, 119.9, 124.2, 130.4, 143.9, 149.6; IR (KBr) 808, 1311,
1339, 1526, 1592, 1621, 2898, 2884, 2927, 2998, 3106, 3376 cmÀ1; MS (EI,
12 eV DIP, m/z, rel. intensity) 316 (MþÀ1, 19), 282 (28), 271 (100), 196 (27),
134 (24), 133 (55), 119 (24), 105 (59), 91 (62); High resolution FAB for
C16H20N3O4 318.1445 (Mþ þ 1), calc. 318.3501.
1
2d. Yield 30%; H NMR (acetone-d6) 1.85 (s, 3H), 3.94 (br s, 2H),
4.35 (dd, J ¼ 11.0, 5.0 Hz, 1H), 4.45 (br s, 1H), 5.02 (br s, 1H), 5.05 (br s,
1H), 7.07 (d, J ¼ 9.6 Hz, 1H), 8.25 (dd, J ¼ 9.6, 2.8 Hz, 1H), 8.98 (d,
J ¼ 2.8 Hz, 1H), 9.11 (br, 1H); 13C NMR (acetone-d6) 19.7, 61.3, 63.5,
113.9, 114.1, 116.8, 124.2, 130.6, 142.5, 149.1; IR (KBr) 830, 1335, 1528,
1594, 1630, 2878, 2932, 3094, 3353, 3465 cmÀ1; MS (EI, 12 eV DIP, m/z, rel.
intensity) 267 (Mþ, 11), 237 (4), 236 (100), 183 (4).
2e. Yield 30%; 1H NMR (acetone-d6) 1.78 (s, 3H), 2.03–2.05 (m, 2H),
2.15 (s, 3H), 2.69(t, J ¼ 7.0 Hz, 2H), 4.33 (dd, J ¼ 13.6, 6.8 Hz, 1H), 5.03 (br
s, 1H), 5.07 (br s, 1H), 7.16 (d, J ¼ 9.6 Hz, 1H), 8.26 (dd, J ¼ 9.6, 2.8 Hz, 1H),
8.64 (br, 1H), 8.97 (d, J ¼ 2.8 Hz, 1H); 13C NMR (acetone-d6) 18.0, 27.7,
30.4, 39.8, 59.7, 114.2, 116.5, 116.6, 124.2, 130.6, 144.2, 148.4; IR (KBr) 800,
1261, 1334, 1522, 1591, 1618, 1717, 2851, 2927, 2965, 3110, 3363 cmÀ1; MS
(EI, 12 eV DIP, m/z, rel. intensity) 307 (Mþ, 6), 259(12), 246 (10), 236 (100),
219 (10), 183 (11), 167 (93), 140 (32), 99 (38).
Reaction of Secondary N-(2,4-Dinitrophenyl)-N-allyl
Amine 2b withNucleophilic and Acidic Reagents
Amine 2b (0.10 g, 0.33 mmol) was dissolved in the given solvent system
(THF, MeOH, or acetone, 10 mL) at room temperature. To this was added
the required reagent. The reaction mixture was stirred for 6–24 h at room
temperature and (if no reaction was observed) then heated at reflux for
an additional 10–30 h. After this, the mixture was cooled to room tempera-
ture and the solvent was removed by rotary evaporation. The residue was

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SINGH AND NICHOLAS
dissolved in Et2O or CH2Cl2 and thoroughly washed with deionized
water. The organic portion was dried (MgSO4) and the solvent was evapo-
rated. The residue was dried under vacuum and analyzed by 1H NMR
spectroscopy.
N-Alkyl-N-(2,4-Dinitrophenyl)-N-allylamines (4)
(Method A) In a dry flask 95% NaH (0.026 g, 1.04 mmol) was weighed
out in the dry box and to this anhydrous DMF (20 mL) was added.
The suspension thus obtained was stirred at room temperature and the
2,4-DNP-allylamine 2a or c (0.94 mmol) was added. The color of the reac-
tion mixture immediately became deep red. This solution was stirred at rt
for 30 min and then MeI (0.40 g, 0.18 mL, 2.8 mmol) was added; the mixture
was then stirred for an additional 2 h, during which time the color changed
to brown. Deionized H2O (25 mL) was added to the reaction mixture and
the resulting yellow turbid solution was stirred for 15 min. This was then
extracted with Et2O (2 Â 20 mL) and the organic layer was washed with H2O
(3 Â 15 mL). The combined organic layer was dried (MgSO4) and the solvent
was removed by rotary evaporation to produce the products 4.
4a. Yield 81% (0.21 g, 0.76 mmol). mp 93–94ꢀC; 1H NMR 1.01
(t, J ¼ 7.2 Hz, 3H), 1.77 (s, 3H), 1.93–2.00 (m, 2H), 2.67 (s, 3H), 4.04
(m, 1H), 4.81 (br s, 1H), 5.06 (br s, 1H),7.05 (d, J ¼ 9.6 Hz, 1H), 8.15
(dd, J ¼ 10.0, 2.4 Hz, 1H), 8.65 (d, J ¼ 2.8 Hz, 1H); 13C NMR 10.7, 11.7,
35.0, 67.9, 113.6, 114.1, 118.2, 123.5, 124.8, 128.0, 141.0, 149.9; IR (KBr)
801, 1024, 1097, 1338, 1523, 1577, 1605, 2966, 3089, 3122 cmÀ1; MS (EI,
12 eV DIP, m/z, rel. intensity) 279(M, 8), 280 (M þ 1, 1), 250 (100), 236 (22).
4c. Yield 76% (0.081 g, 0.25 mmol). 1H NMR 0.81 (s, 3H), 1.11
(d, J ¼ 8.4 Hz, 1H), 1.26 (s, 3H), 1.95 (m, 1H), 2.12 (m, 1H), 2.18, 2.35
(m, 2H), 2.36–2.45 (m, 1H), 2.90 (s, 3H), 3.86 (m, 2H), 5.35 (br s, 1H),
6.97 (d, J ¼ 9.6 Hz, 1H), 8.14 (dd, J ¼ 9.2, 2.8 Hz, 1H), 8.66 (d, J ¼ 2.8 Hz,
1H); 13C NMR 20.9, 26.0, 31.2, 31.5, 38.2, 40.7, 41.0, 43.4, 58.7, 117.8,
120.4, 124.1, 127.4, 141.4, 148.9; MS (EI, 12 eV DIP, m/z, rel. intensity)
331 (Mþ, 2), 314 (10), 285 (100), 282 (21), 270 (14), 239(9), 217 (13), 215
(24), 210 (47), 194 (16), 189(22), 178 (12), 133 (27), 119(18), 91 (43).
(Method B) To a solution of 2,4-DNP-allylamine 2b (0.10 g,
0.33 mmol) and K2CO3 (0.23 g, 1.67 mmol) in anhydrous DMF (5 mL)
was added MeI (0.070 g, 0.030 mL, 0.50 mmol) under nitrogen. The dark
red reaction mixture was stirred for 19h. Deionized H 2O was added to the
reaction mixture and then extracted with Et2O. The organic layer was
washed with water, dried (Na2SO4), and the solvent was removed by
rotary evaporation to yield an orange solid. This solid was triturated with

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2,4-DINITROPHENYLHYDROXYLAMINE
3095
hexane to give 4b as a brown solid in 77% yield (0.080 g, 0.26 mmol). mp
124–126ꢀC; H NMR (acetone-d6) 3.0 (s, 3H), 4.62 (br s, 2H), 5.22 (br s,
1
1H), 5.57 (br s, 1H), 7.25 (d, J ¼ 9.6 Hz, 1H), 7.32–7.38 (m, 3H), 7.47 (d,
J ¼ 7.8 Hz, 2H), 8.20 (dd, J ¼ 9.6, 2.8 Hz, 1H), 8.61 (d, J ¼ 3.2 Hz, 1H);
13C NMR (acetone-d6) 41.1, 58.1, 114.4, 119.4, 124.2, 126.9, 128.0, 129.0,
129.3, 139.3, 142.4.
(Method C) The 2,4-DNP-allylamine 2b (0.12 g, 0.40 mmol), benzyl
bromide (0.082 g, 0.06 mL, 0.48 mmol) and tetrabutylammonium iodide
(0.015 g, 0.040 mmol) were dissolved in THF (10 mL) under nitrogen. To
this was added 95% NaH (0.014 g, 0.44 mmol) resulting in a very dark red
color. This solution was stirred at room temperature for 20 h, by which time
the color had become brown. Saturated NH4Cl (20 mL) was added and the
reaction mixture was stirred for 10 min. The aqueous layer was separated
and then washed with Et2O (3 Â 20 mL). The combined organic layer was
washed with brine (2 Â 25 mL), dried over MgSO4, and the solvent was
removed by rotary evaporation. The residue was dried under vacuum in a
hot water bath to give 4d in 91% yield (0.142 g, 0.364 mmol) as an orange
oil. 1H NMR (acetone-d6) 4.43 (s, 3H), 4.59(br s, 2H), 5.30 (br s, 1H), 5.48
(br s, 1H), 7.19(d, J ¼ 9.6 Hz, 1H), 7.25–7.37 (m, 10H), 8.09 (dd, J ¼ 8.8,
2.8 Hz, 1H), 8.64 (d, J ¼ 3.2 Hz, 1H); 13C NMR (acetone-d6) 56.3, 57.9,
117.3, 122.0, 13.9, 127.1, 127.9, 128.5, 128.7, 128.9, 129.2, 129.4, 137.2,
139.4, 144.3, 149.9; IR (KBr) 802, 1029, 1261, 1334, 1522, 1602, 2855,
2923, 2967, 3033, 3096 cmÀ1; MS (EI, 12 eV DIP, m/z, rel. intensity) 389
(Mþ, 3), 372 (16), 343 (85), 270 (14), 118 (34), 105 (12), 91 (100).
Deprotection of N-(2,4-Dinitrophenyl)-N-alkyl-N-allylamines (4)
The amines 4b and 4c (0.32 mmol) were dissolved in DMSO (5 mL)
to give a dark red solution. An excess (10–20 equiv.) of 40 wt % aqueous
solution of MeNH2 or pure BuNH2 was added and the solution was heated
to 65–80ꢀC for 20 h. The reaction mixture was then cooled to room tem-
perature, poured into deionized H2O (50 mL) and stirred. Yellow N-methyl-
2,4-dinitroaniline precipitated as determined by 1H NMR. The aqueous
filtrate was extracted with CH2Cl2 (2 Â 20 mL). The separated organic
layer was then extracted with 1 N HCl (3 Â 50 mL). The resulting aqueous
layer was neutralized with 2M KOH and then extracted with Et2O
(3 Â 20 mL). The organic layer was dried (MgSO4) and the solvent was
removed by rotary evaporation to yield 5b, c.
1
5b. Yield 64% (0.030 g, 0.20 mmol); H NMR 2.41 (s, 3H), 3.61 (br s,
2H), 5.21 (br s, 1H), 5.38 (br s, 1H), 7.25–7.45 (m, 5H); 13C NMR 36.0, 56.2,
113.0, 124.3, 126.0, 126.9, 128.2, 129.0, 130.8.

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SINGH AND NICHOLAS
5c. Yield 47% (0.017 g, 0.10 mmol); 1H NMR 0.82 (s, 3H), 1.16
(d, J ¼ 8.4 Hz, 1H), 1.41 (s, 3H), 2.07–2.12 (m, 1H), 2.21–2.25 (m, 2H),
2.34–2.39(m, 2H), 3.47 (br s, 2H), 5.36 (br s, 1H); 13C NMR 21.1, 26.1,
29.7, 30.3, 31.2, 31.6, 40.8, 44.3, 56.4, 65.8, 119.1, 125.5; MS (12 eV GCMS,
m/z, rel. intensity) 165 (Mþ, 94), 166 (M þ 1, 10), 167 (M þ 2, 1), 164 (10),
150 (27), 137 (11), 136 (68), 134 (69), 122 (48), 120 (33), 119(100), 109(65),
97 (21), 96 (31), 94 (23), 93 (26), 92 (32), 91 (85), 81 (11), 44 (56).
ACKNOWLEDGMENTS
We thank Dr. Masood Khan (O. U. Analytical Services X-ray Unit)
for determination of the X-ray structure of 2b. We are grateful for support
of this project provided by the National Science Foundation.
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Received in the USA December 4, 2000

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