A facile synthesis of N-aryl aziridines

Article abstract of DOI:10.1081/SCC-100103544

Reaction of N-aryl-β-amino alcohols with p-toluenesulphonyl chloride under phase transfer catalytic condition gave the corresponding N-aryl aziridines in good yields, whereas N-alkyl-β-amino alcohol [for e.g., L-ephedrine] gave the corresponding N-tosyl derivative as the major product, along with the expected N-alkyl aziridines in lower yield.

Full text of DOI:10.1081/SCC-100103544

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A FACILE SYNTHESIS OF N-
ARYL AZIRIDINES
Kamaraj Sriraghavan a & Vayalakkavoor T.
Ramakrishnan b
a Department of Organic Chemistry, University of
Madras, Guindy Campus, Chennai, 600 025, India
b Department of Organic Chemistry, University of
Madras, Guindy Campus, Chennai, 600 025, India
Published online: 09 Nov 2006.
To cite this article: Kamaraj Sriraghavan & Vayalakkavoor T. Ramakrishnan
(2001): A FACILE SYNTHESIS OF N-ARYL AZIRIDINES, Synthetic Communications: An
International Journal for Rapid Communication of Synthetic Organic Chemistry,
31:7, 1105-1121
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SYNTHETIC COMMUNICATIONS, 31(7), 1105–1121 (2001)
A FACILE SYNTHESIS OF
N-ARYL AZIRIDINES
Kamaraj Sriraghavan and Vayalakkavoor
T. Ramakrishnan*
Department of Organic Chemistry, University of Madras,
Guindy Campus, Chennai 600 025, India
ABSTRACT
Reaction of N-aryl-ꢀ-amino alcohols with p-toluenesul-
phonyl chloride under phase transfer catalytic condition gave
the corresponding N-aryl aziridines in good yields, whereas
N-alkyl-ꢀ-amino alcohol [for e.g., L-ephedrine] gave the cor-
responding N-tosyl derivative as the major product, along
with the expected N-alkyl aziridines in lower yield.
The aziridine ring is a versatile building block for organic synthesis,
not only because the ring opening of aziridines provides a convenient entry
to the stereoselective preparation of functionalized amino compounds, but
also because the exocyclic N-substituent modulates the properties and reac-
tivity of the three membered ring.1–4 The growing importance of function-
alized aziridines in organic synthesis and its presence in numerous
biomolecules suggest that a general synthetic procedure leading to -C- and
-N- substituted aziridines under essentially neutral conditions would be
attractive. So far reported classical methods for the synthesis of N-aryl
aziridines are: (a) ring closure of N-aryl ꢀ-amino alcohol by Gabriel
* Corresponding author. Fax: þ91-44-2352494; E-mail: vtr@unimad.ernet.in
1105
Copyright & 2001 by Marcel Dekker, Inc.
www.dekker.com

1106
SRIRAGHAVAN AND RAMAKRISHNAN
and Wenker synthesis, which suffers from side reactions like dimerization,
polymerization, elimination; further, it requires strongly acidic or basic
conditions,5–7 (b) addition of carbenoids to imines or addition of nitrenoids
to electron deficient alkenes catalyzed either by Lewis acid or transition
metal complexes,8–11 (c) the cyclodehydration of N-alkyl-ꢀ-amino alcohol
using triphenylphosphine dihalide, diethoxytriphenylphosphorane wherein
triphenylphosphine oxide and 1,4-diphenylpiperazine formed as side prod-
ucts complicate the isolation of the expected products; moreover, applica-
tion of this method to N-aryl aziridines has received scant attention.12,13
Although the Lewis-acid catalyzed addition of aryl azides to alkenes gave
the expected N-aryl aziridines, it undergoes subsequent ring opening,
furnishing either amino alkenes or ꢀ-chloro amines as a major product if
AlCl3 is used as a Lewis acid.14
In continuation of our effort on the synthesis of bioactive heterocyclic
compounds,15–19 we have developed a mild and convenient method of
cyclizing N-aryl-ꢀ-amino alcohol to N-aryl aziridines under phase transfer
catalytic conditions in fairly good yields, which is herein reported.
The Pechmann reaction of 5,8-dihydro-1-naphthol, which was
obtained by the Birch reduction of 1-naphthol,20 with ethyl acetoacetate
in the presence of POCl3, furnished the expected 4-methyl-7,10-dihydro-
benzo[h]coumarin 2. Epoxidation of 2 with m-CPBA furnished the
anticipated 4-methyl-7,8,9,10-tetrahydro-8,9-epoxybenzo[h]coumarin 3.
Treatment of the epoxide 3 with 2-bromo-4-methylaniline furnished
two regioisomeric N-aryl-ꢀ-amino alcohols (ꢀ50:50) viz., 9-(2-bromo-4-
methylanilino)-8-hydroxy-4-methyl-7,8,9,10-tetrahydro-7,8-benzo[h]coumarin
4a, 8-(2-bromo-4-methylanilino)-9-hydroxy-4-methyl-7,8,9,10-tetrahydro-7,
8-benzo[h]coumarin 5a in an overall yield of >80% along with 8,9-
dihydroxy-4-methyl-7,8,9,10-tetrahydro-7,8-benzo[h]coumarin 6 (<10%)
as a minor product. The two regioisomers and the diol were separated by
column chromatography. The structures of the two regioisomers and the
diol were assigned by spectral, analytical data and further the structure of
the regioisomer 5a has been confirmed by XRD.21
Treatment of 4a with 1.2 equiv. of p-toluenesulphonyl chloride,
50% NaOH, and 0.2 equiv. of n-Bu4NHSO4 in benzene furnished the
expected aziridine 7a in less than half an hour. Similarly, the reaction
with regioisomeric alcohol 5a under the same condition furnished the
same aziridine 7a. Hence, the later experiments were carried out with
a mixture of regioisomeric alcohols. A blank reaction was also carried out
in the absence of PTC, which resulted only in the recovery of the starting
material. Extension of the reaction to the mixture of N-aryl-ꢀ-amino
alcohols 4b and 5b, as well as 4c and 5c, under the aforesaid condition
furnished the expected N-aryl aziridines 7b and 7c, respectively, in good

N-ARYL AZIRIDINES
1107
Scheme 1.
yields (Scheme 1). The new N-arylaziridines 7a–c were characterized well
by spectral, analytical data and further the aziridine 7a has been confirmed
by x-ray studies.22
Since a systematic literature survey revealed that this method is new
and facile, we extended this method to the synthesis of several known and
new N-aryl aziridines for generalisation. Cyclohexene oxide was opened
with p-nitroaniline and p-toluidine to afford the respective ring-opened
compounds 8 and 9. Then the treatment of 8 and 9 under our experimental
condition furnished the expected N-arylaziridines 10 and 11 in good yields.
The cyclodehydration of 4a, 5a, 8, and 9 using triphenylphosphine dihalide/
Et3N or triphenylphosphine-diethyl azodicarboxylate (Mitsunobu reagent)
did not give the expected aziridines; to our surprise, only the starting
materials were recovered. The structures of 10 and 11 have been determined
by the spectral, analytical data and further the structure of 10 has been
confirmed by XRD23 (Scheme 2).
Scheme 2.

1108
SRIRAGHAVAN AND RAMAKRISHNAN
Next, styrene oxide was opened with p-nitroaniline to afford 2-
hydroxy-N-(4-nitrophenyl) phenethylamine 12a as the major product and
2-(4-nitroanilino)-phenethylalcohol 13a as the minor product. The struc-
tures of these two regioisomers were duly characterized by spectral and
analytical data and further evidenced by XRD.24,25 Treatment of either
12a or 13a under our reaction condition gave the expected aziridine 14.
The structure of 14 is in accordance with literature data.26 Similarly, the
regioisomeric mixture of N-p-tolyl-ꢀ-amino alcohols 12b and 13b, which
were obtained from the reaction of styrene oxide and p-toluidine under
our experimental condition, gave the expected N-aryl aziridine 15 (80%)
along with trans-1,4-di(4-methylphenyl)-2,5-diphenyl-piperazine 16 (15%).
The structures of 1527 and 16 were confirmed by spectral and analytical
data (Scheme 3).
Scheme 3.
Next we were very much interested to synthesize polycyclic imines by
our method because of their biological relevance and the reports
of unsuccessful attempts in the literature.28 Phenanthrene-9,10-oxide was
opened by p-nitroaniline and p-toluidine to give the ring-opened com-
pounds 17 and 18, respectively. Treatment of 17 under the aforesaid con-
dition furnished N(-4-nitrophenyl)-9-aminophenanthrene 20 in 30% yield
instead of the expected N-aryl aziridine 19. During the course of the reac-
tion, TLC analysis showed the complete disappearance of the starting
materials with the appearance of a new spot. However, during work-up
the new spot completely disappeared with the appearance of another spot
on TLC. It was separated and identified as 20. It has been reported that
polycyclic imino compounds, which have electron-withdrawing groups
attached to the nitrogen atom, rearranged readily at ambient temperature
to aromatic amines. For example, the rearrangement of 1-acetyl-1a, 9c-
dihydrophenanthr[9,10-b]azirine to N-acetyl-9-amino phenanthrene is well
known.29 Hence, the isolation of the compound 20 indirectly confirms the

N-ARYL AZIRIDINES
1109
formation of N-(4-nitrophenyl)-phenanthr[9,10-b]aziridine 19 (which would
have readily rearranged to 20 as a stable product). Treatment of 18 under
our reaction condition gave no characterizable product (Scheme 4). So far,
we have witnessed that the reaction of N-aryl-ꢀ-aminoalcohols with p-TsCl
under phase transfer condition gave the corresponding N-aryl aziridines in
good yields.
Scheme 4.
As a further application of our method to synthesize N-alkyl aziri-
dines, we took L-ephedrine as the starting material. The reaction of
L-ephedrine furnished two products under the aforesaid condition and
were identified as the expected (þ) trans-1,2-dimethyl-3-phenylaziridine 21
(20%) and the corresponding N-tosylated product 22 (78%). Our effort to
improve the yield of aziridine by changing the condition such as base
concentration, catalyst variation, and solvent variation (CHCl3, CH2Cl2,
and toluene), gave no fruitful results (Scheme 5).
Scheme 5.
In conclusion, this method provides a mild and convenient way of
cyclizing (N-aryl-ꢀ-aminoalcohol to the corresponding N-aryl aziridines
and has some advantages over the known classical method because of the
mild reaction condition, simplicity of performance, and good yields, which
make this method a useful addition to the existing methodology.

1110
SRIRAGHAVAN AND RAMAKRISHNAN
EXPERIMENTAL
Melting points were determined by using a Toshniwal melting point
apparatus in an open capillary tube and are uncorrected. IRspectra were
recorded in Nicolet Impact 400 FT-IRspectrophotometer. 1H NMRand
13C NMRwere recorded on Jeol 400 MHz, Brucker 300 MHz, Bruker
ARX 200 MHz, and Jeol FX 90Q spectrometers, using TMS as internal
standard. GC/MS data were obtained from a Jeol-DX-303 spectrometer.
Microanalyses were performed in a Perkin-Elmer 240B element analyzer.
Chromatography was performed on silica gel (ACME, 100–200 mesh), and
purified according to the reported procedure.30 Phenanthrene oxide was
prepared by the literature method.31
4-Methyl-7,10-dihydrobenzo[h]coumarin (2)
A mixture of 5,8-dihydro-1-naphthol7 (1.46 g, 0.01 mol), ethyl aceto-
acetate (1.56 g, 0.012 mol), and phosphoryl chloride (1.53 g, 0.01 mol) was
refluxed in dry benzene (30 mL) for 12 h. Then solvent was removed under
vacuum and to the residue was added 30 mL of ice-water and 50 mL of
CH2Cl2, neutralized with saturated aqueous NaHCO3 to pH ¼ 7, and
extracted with CH2Cl2 (3ꢁ50 mL). The combined extracts were washed
with water, brine, and dried (MgSO4). After removal of the solvent under
vacuum, the residue was chromatographed over silica gel using a mixture of
hexane-EtOAc (9:1) as eluant to afford 2, (1.48 g, 70%).
M.p. 150ꢂ–152ꢂC. IR(KBr): ꢁ ¼ 2900, 2800, 2760, 1720, 1600 cmꢃ1
.
1H NMR(90 MHz, CDCl 3): ꢂ ¼ 2.3 (s, 3H, CH3), 3.4 (bs, 4H, 2CH2),
5.8–5.9 (m, 2H, 2CH), 6.2 (s, 1H, H3), 6.90 (d, 1H, J ¼ 9 Hz, Ar-H5), 7.3
(d, 1H, J ¼ 9 Hz, Ar-H6). MS (EI) m/z (%) ¼ 212 (100), 204 (48), 184 (36),
183 (28), 169 (34), 167 (86), 165 (62), 155 (20), 144 (22), 143 (38), 142 (24),
132 (42), 130 (60), 119 (24), 98 (16), 97 (22), 95 (52). Anal. calc. for
C14H12O2: C, 79.23; H, 5.70. Found: C, 79.00; H, 5.59. Further, the struc-
ture of 2 has been confirmed by XRD.32
4-Methyl-7,8,9,10-tetrahydro-8,9-epoxybenzo[h]coumarin (3)
A mixture of the compound 2 (2.12 g, 0.01 mol) and m-CPBA (1.725 g,
0.01 mol) in anhydrous chloroform (50 mL) was stirred overnight at room
temperature. After the disappearance of the starting material on TLC, dil.
aqueous NaHCO3 was added to the reaction mixture while stirring at 0ꢂC.
The organic layer was separated, washed several times with water, and dried
(MgSO4). The solvent was removed under reduced pressure and the

N-ARYL AZIRIDINES
1111
concentrate on crystallization from CHCl3 furnished 3 as colorless
needless (1.93 g, 85%).
M.p. 198ꢂ–200ꢂC. IR(KBr): ꢁ ¼ 3100, 3000, 2900, 2850, 1710, 1600,
1
1400, 1190, 1000 cmꢃ1. H NMR(90 MHz, CDCl ): ꢂ ¼ 2.4 (s, 3H, CH3),
3
2.8–3.8 (m, 6H, 2CH2 and 2CH), 6.2 (s, 1H, H3), 6.90 (d, 1H, J ¼ 9 Hz,
Ar-H5), 7.40 (d, 1H, J ¼ 9 Hz, Ar-H6). MS (EI): m/z (%) ¼ 228 (100), 213
(10), 199 (40), 185 (5), 171 (20), 128 (38), 115 (30), 102 (5), 91 (5), 77 (5).
HRMS (positive FAB): m/z ¼ Mþ calculated for C14H12O3: 228.078644.
Found: 228.079200. Further, the structure of the compound 3 has been
confirmed by XRD.32
General Procedure for Ring Opening of the Epoxide
A mixture of the activated alumina (7.5 g per 1 g epoxide), aniline (1.3
equiv.), and epoxide in anhydrous benzene (50 mL) was refluxed under
nitrogen atmosphere, until the TLC analysis showed the complete dis-
appearance of the epoxide. The reaction mixture was cooled and filtered
through a sintered funnel under vacuum; the alumina was repeatedly
washed with dry methanol. Removal of the solvent under vacuum gave a
viscous oil, which was purified by column chromatography using silica gel
and eluted with hexane-ethyl acetate (8:2) to get the respective ring-opened
compound.
9-(2-Bromo-4-methylanilino)-8-hydroxy-4-methyl-7,8,9,10-
tetrahydro-7,8-benzocoumarin (4a), 8-(2-bromo-4-methylanilino)-
9-hydroxy-4-methyl-7,8,9,10-tetrahydro-7,8-benzocoumarin (5a), and
8,9-dihydroxy-4-methyl-7,8,9,10-tetrahydro-7,8-benzocoumarin (6)
Compound 4a, 5a, and 6 were obtained from the reaction of 4-methyl-
7, 8, 9, 10-tetrahydro-8, 9-epoxybenzo[h]coumarin 4 (1.14 g, 5 mmol),
2-bromo-4-methylaniline and activated alumina (7.5 g) using the above
general procedure. The reason for the formation of dihydroxy compound
6 may be due to the traces of moisture present in the reaction medium and it
could be avoided if the alumina is dried at 120ꢂC in a vacuum oven.
Compound 4a
Yield: 0.93 g (45%), m.p. 128ꢂ–130ꢂC IR(KBr): ꢁ ¼ 3450, 3350, 2900,
1720, 1600, 1510 cmꢃ1. 1H NMR(200 MHz, CDCl 3): ꢂ ¼ 2.19 (s, 3H, ArCH3),
2.37 (d, 3H, J ¼ 0.93 Hz, 4CH3), 2.65 (dd, 1H, J ¼ 8.5, 7.0 Hz, 10CH2), 3.00

1112
SRIRAGHAVAN AND RAMAKRISHNAN
(dd, 1H, J ¼ 8.8, 17.20 Hz, 7CH2), 3.3 (dd, 1H, J ¼ 5.25, 17.30 Hz, 7CH2),
3.6 (dd, 1H, J ¼ 5.3, 17.20 Hz, 10CH2), 3.7–3.75 (m, 1H, 9CH), 3.9–4.12 (m,
1H, 8CH), 6.20 (d, 1H, J ¼ 1.03 Hz, 3-H), 6.77 (d, 1H, J ¼ 8.3 Hz, Ar-Hf),
6.92 (dd, 1H, J ¼ 1.4, 8.3 Hz, ArHe), 7.04 (d, 1H, J ¼ 8.2 Hz, Ar-5H), 7.21 (d,
1H, J ¼ 1.4 Hz, Ar-Hc), 7.37 (d, 1H, J ¼ 8.2 Hz, Ar-6H). 13C NMR(50 MHz,
CDCl3): ꢂ ¼ 18.59, 19.89, 28.74, 36.46, 55.43, 69.34, 110.83, 113.04, 113.80,
117.53, 122.37, 122.37, 124.63, 128.17, 128.52, 129.00, 132.77, 138.72,
141.85, 151.03, 152.66, 160.70. Anal. calc. for C21H20NO3Br: C, 60.88; H,
4.87; N, 3.38. Found: C, 61.02; H, 4.88; N, 3.40.
Compound 5a
Yield: 0.820 g (40%), m.p. 196ꢂ–198ꢂC. IR(KBr): ꢁ ¼ 3470, 3350, 3000,
2950,2900,1720,1600,1520,1450,1400,1300,1190,1100,1090,1040,880,800,
770, 690, 590 cmꢃ1. 1H NMR(300 MHz, CDCl 3): ꢂ ¼ 2.24 (s, 3H, Ar-CH3),
2.43 (d, 3H, J ¼ 1.1 Hz, 4-CH3), 2.70 (d, 1H, J ¼ 1.65 Hz, OH), 2.81 (dd, 1H,
J ¼ 9.15, 7.2 Hz, 7-CH2), 2.95 (dd, 1H, J ¼ 8.42, 17.90 Hz, 10-CH2), 3.40 (dd,
1H, J ¼ 5.12, 17.2 Hz, 7-CH2), 3.6 (dd, 1H, J ¼ 5.67, 17.76 Hz, 10-CH2),
3.71–3.77 (m, 1H, 8-CH), 4.03–4.16 (m, 1H, 9-CH), 6.26 (d, 1H, J ¼ 0.78 Hz,
3-H), 6.81 (d, 1H, J ¼ 8.42 Hz, Ar-Hf), 6.99–7.11 (m, 2H, Ar-He&Ar-5H),
7.24–7.26 (m, 1H, Ar-He), 7.40 (d, 1H, J ¼ 8.24 Hz, Ar-6H). 13C NMR
(50 MHz, CDCl3): 18.70, 20.01, 30.15, 34.72, 55.28, 69.23, 110.98, 113.27,
114.10, 117.82, 122.11, 122.45, 124.47, 128.72, 129.12, 132.89, 138.64, 141.91,
151.42,152.63,160.79.Anal.calc.forC21H20NO3Br:C,60.88;H,4.87;N,3.38.
Found: C, 60.80; H, 4.79; N, 3.35.
Compound (6)
Yield: 0.062 g (5%), m.p. 190ꢂ–192ꢂC. IR(KBr): ꢁ ¼ 3330, 3225, 1721,
1610, 1500, 1470, 1100, 980, 920 cmꢃ1. 1HNMR(90 MHz, CDCl 3):ꢂ ¼ 2.41(d,
3H, J ¼ 1.0 Hz,CH3),2.58–2.60(m,1H,CH),2.78–2.91(m,1H,CH),3.40–3.48
(m, 4H, 2CH2), 3.80–3.92 (m, 1H, OH). MS (EI): m/z (%); 246 (100), 228 (85),
210(30),199(82),187(35),171(18),158(40),145(22),128(45),105(18),91(25),
77 (30). Anal. calc. for C14H14O4: C, 68.28; H, 5.73. Found: C, 68.35; H, 5.79.
9-(2,6-Diethylanilino)-8-hydroxy-4-methyl-7,8,9,10-tetrahydro-7,8-
benzocoumarin (4b) and 8-(2,6-diethylanilino)-9-hydroxy-4-methyl-
7,8,9,10-tetrahydro-7,8-benzocoumarin (5b)
Following the general procedure, treatment of epoxide 3 (1.14 g,
5 mmol) with 2,6-diethylaniline (0.968 g, 6.5 mmol) gave 1.602 g (85%) of
an inseparable mixture of 4b and 5b.

N-ARYL AZIRIDINES
1113
8-Hydroxy-4-methyl-9-(4-nitroanilino)-7,8,9,10-tetrahydro-7,8-benzo-
coumarin (4c) and 8-(4-nitroanilino)-9-hydroxy-4-methyl-7,8,9,10-
tetrahydro-7,8-benzocoumarin (5c)
Following the general procedure epoxide 3 (1.14 g, 5 mmol) and
4-nitroaniline (0.897 g, 6.5 mmol), gave 1.885 g (85%) of an inseparable
mixture of 4c and 5c.
trans-2-(4-Nitroanilino)cyclohexanol (8)
Following the general procedure, use of cyclohexene oxide (0.45 g,
5 mmol) and 4-Nitroaniline (0.897 g, 6.5 mmol), gave 1.12 g (95%) of 8 as
yellow-colored crystalline compound.
M.p. 118ꢂ–120ꢂC. IR(KBr): ꢁ ¼ 3400, 2975, 2870, 1500, 1600, 1420,
1350, 1340, 1320, 1400 cmꢃ1. 1H NMR(90 MHz, CDCl 3): ꢂ ¼ 1.30–1.39 (m,
4H, -CH2), 1.70–2.18 (m, 4H, CH2), 3.2–3.4 (m, 2H, 2CH), 4.80 (bs, 2H,
NH&OH, D2O-exchangeable), 6.65 (d, 2H, J ¼ 9.3 Hz, ArH), 7.98 (d, 2H,
J ¼ 9.3 Hz). 13C NMR(90 MHz, CDCl ): ꢂ ¼ 25.30, 25.0, 32.0, 35.10, 59.01,
3
75.0, 112.50, 127.29, 137.05, 156.16.
trans-2-(4-Methylanilino)cyclohexanol (9)
Following the general procedure, reaction of cyclohexene oxide
(0.45 g, 5 mmol) and p-toluidine (0.700 g, 6.5 mmol) gave 0.943 g (92%) of
9 as a viscous liquid.
IR(KBr): ꢁ ¼ 3400, 3000, 1510, 1500, 1200, 890 cmꢃ1
.
1H NMR
(90 MHz, CDCl3): ꢂ ¼ 1.25–1.40 (m, 4H, 2CH2), 1.75–2.09 (m, 4H, 2CH2),
2.12 (s, 3H, CH3), 3.0–3.35 (m, 2H, 2CH), 4.75 (bs, 2H, NH&OH), 6.60 (d,
2H, J ¼ 9.3 Hz, ArH), 7.38 (d, 2H, J ¼ 9.3 Hz, Ar-H). 13C NMR(90 MHz,
CDCl3): ꢂ ¼ 20.5, 25.3, 32.0, 35.20, 59.05, 69.0, 115.50, 127.0, 135.5, 145.
ꢀ-Hydroxy-N(4-nitrophenyl)phenethylamine (12a) and 2-(4-nitroanilino)-
2-phenylethanol (13a)
Following the general procedure, treatment of styrene oxide (0.6 g,
5 mmol) with 4-Nitroaniline (0.897 g, 6.5 mmol), gave 1.03 g (80%) of 12a
and 0.125 g (10%) of 13a.

1114
SRIRAGHAVAN AND RAMAKRISHNAN
Compound 12a
M.p. 138ꢂ–140ꢂC. IR(KBr): ꢁ ¼ 3400, 2950, 1500, 1460, 1340, 1320,
1150, 1200 cmꢃ1. 1H NMR(400 MHz, CDCl 3): ꢂ ¼ 3.69–3.75 (m, 1H, CH2),
3.88–3.93 (m, 1H, CH2), 4.10 (t, 1H, OH, D2O-exchangeable), 4.50–4.54 (m,
1H, CH), 6.14 (bs, 1H, NH, D2O-exchangeable), 6.46 (d, 2H, J¼9.28 Hz,
Ar-H), 7.30–7.35 (m, 5H, Ar-H, 7.95 (d, 2H, J ¼ 9.28 Hz, Ar-H). 13C NMR
(100 MHz, CDCl3): ꢂ ¼ 59.98 (d), 66.67 (t), 112.06 (d), 126.12 (d), 126.58 (d),
127.76 (d), 128.86 (d), 137.72 (s), 139.15 (s), 153.31 (s). Anal. calc. for
C14H14N2O3: C, 65.10; H, 5.46; N, 10.85. Found: C, 65.0; H, 5.37; N, 10.20.
Compound 13a
M.p. 96ꢂ–98ꢂC. IR(KBr): ꢁ ¼ 3410, 2960, 1500, 1450, 1350, 1310,
1290, 1255, 1175 cmꢃ1
.
1H NMR(400 MHz, CDCl 3): ꢂ ¼ 3.30–3.45 (m,
2H, CH2), 4.25 (bs, 1H, NH, D2O-exchangeable), 4.86–4.90 (m, 1H, CH),
5.46 (t, 1H, OH, D2O-exchangeable), 6.50 (d, 2H, J ¼ 9.32 Hz, Ar-H),
7.27–7.40 (m, 5H, Ar-H), 7.99 (d, 2H, J ¼ 9.28 Hz, Ar-H). 13C NMR
(100 MHz, CDCl3): ꢂ ¼ 50.69 (t), 71.99 (d), 111.20 (d), 125.93 (d), 126.38
(d), 128.05 (d), 128.59 (d), 137.57 (s), 141.89 (s), 153.61 (s). Anal. calc.
for C14H14N2O3: C, 65.10; H, 5.46; N, 10.85. Found: C, 65.50; H, 5.52;
N, 10.98.
2-Hydroxy-N (4-methylphenyl)phenethylamine (12b) and
2-(4-Methylanilino)-2-phenylethanol (13b)
Following the general procedure, use of styrene oxide (0.6 g, 5 mmol)
and p-toluidine (0.7 g, 6.5 mmol) gave 0.930 g (82%) of an inseparable
mixture of 12b and 13b as a viscous liquid.
trans-10-(4-nitroanilino)-9,10-dihydrophenanthren-9-ol (17)
Following the general procedure reaction of 9,10-phenanthrene oxide
(0.97 g, 5 mmol) and 4-nitroaniline (0.897 g, 6.5 mmol) gave 1.162 g (70%) of
17 as a yellow crystalline solid.
M.p. 108ꢂ–110ꢂC. IR(KBr): ꢁ ¼ 3400, 3300, 3050, 3020, 1600, 1490,
1
1300, 1120 cmꢃ1. H NMR(90 MHz, CDCl ): ꢂ ¼ 3.75 (bs, 1H, OH), 4.74
3
(d, 1H, Ar-CH), 6.53 (d, 1H, Ar-CH), 7.27–7.60 (m, 8H, ArH), 7.71–7.93
(m, 4H, ArH).

N-ARYL AZIRIDINES
1115
trans-2-(4-Methylphenylamino)-9,10-dihydrophenanthren-1-ol (18)
Following the general procedure, reaction of 9,10-phenanthrene oxide
(0.97 g, 5 mmol) and p-toluidine (0.7 g, 6.5 mmol) gave 1.05 g (70%) of 18 as
a brown-colored crystalline solid.
M.p. 154ꢂ–156ꢂC. IR(KBr): ꢁ ¼ 3420, 3200, 3000, 1590, 1520, 1420,
1200, 1150 cmꢃ1. 1H NMR(90 MHz, CDCl 3): ꢂ ¼ 2.14 (s, 3H, Ar-CH3), 3.05
(bs, 1H, NH), 5.14 (d, 1H, J ¼ 3.8 Hz, Ar-CH), 5.79 (d, 1H, J ¼ 3.56 Hz, Ar-
CH), 7.20–7.50 (m, 8H, Ar-H), 7.6–7.8 (m, 4H, Ar-H).
General Procedure for Cyclizing N-aryl-ꢀ-Aminoalcohol to N-Aryl
Aziridines Under PTC Condition
To a mixture of N-aryl-ꢀ-aminoalcohol (0.05 m), p-toluenesulfonyl
chloride (0.06 m) and 0.2 equiv. of tetrabutylammonium hydrogensul-
phate in 50 mL of benzene, was added 5 mL of 50% NaOH. Then the
reaction mixture was stirred at room temperature for half an hour. After
completion of the reaction, the organic layer was separated and the aqueous
layer was extracted twice with ethyl acetate (2ꢁ25 mL). The organic layers
were combined and washed several times with water, brine, and dried
(MgSO4). After removal of the solvent under vacuum, the N-aryl aziridines
were obtained either by crystallization or by chromatographic purification
using purified silica gel. It was found that the use of commercially available
silica gel (which is slightly acidic) gives lower yield of N-aryl aziridines along
with respective ring-opened compound. But the use of purified silica gel
furnished the N-aryl aziridines in fairly good yields and without any trace
of ring-opened compound.
N-(2-bromo-4-methylphenyl)-4-methyl-7,8,9,10-tetrahydro-7,8-benzo-
coumarin-8,9-aziridine (7a)
Following the general procedure using 4a/5a or a mixture of 4a and 5a
(0.5 g, 1.20 mmol) and p-toluenesulphonyl chloride (0.276 g, 1.45 mmol)
gave 0.391 g (82%) of 7a as a colorless solid.
M.p. 208ꢂ–210ꢂC. IR(KBr): ꢁ ¼ 2890, 1720, 1600, 1490, 1380, 1370,
1
1210, 1090, 830, 800 cmꢃ1. H NMR(300 MHz, CDCl ): ꢂ ¼ 2.22 (s, 3H,
3
Ar-CH3), 2.37 (d, 3H, J ¼ 1 Hz, 4-CH3), 2.70 (ddd, 1H, J ¼ 6.59, 3.23,
1.46 Hz, 9-CH), 2.80 (ddd, 1H, J ¼ 6.58, 3.29, 1.64 Hz, 8-CH), 3.05 (dd,
1H, J ¼ 2.74, 18.0 Hz, 10-CH2), 3.26 (dd, 1H, J ¼ 2.53, 17.6 Hz, 7-CH2),
3.70 (d, 1H, J ¼ 17.6 Hz, 7-CH2), 4.10 (d, 1H, J ¼ 18.0 Hz, 10-CH2),

1116
SRIRAGHAVAN AND RAMAKRISHNAN
6.20 (d, 1H, J ¼ 1.0 Hz, 3-CH), 6.85 (d, 1H, J ¼ 8.2 Hz, Ar-Hf), 6.97 (dd, 1H,
J ¼ 1.4, 8.2 Hz, Ar-He), 7.05 (d, 1H, J ¼ 8.2 Hz, Ar-5H), 7.26 (d, 1H,
J ¼ 4.8 Hz, Ar-Hc), 7.37 (d, 1H, J ¼ 8.3 Hz, Ar-6H). 13C NMR(100 MHz,
CDCl3): ꢂ ¼ 18.65 (q), 20.21 (q), 22.69 (splitt. t, 10-CH2), 29.88 (t, 7-CH2),
38.91 (d, 8-CH), 39.54 (d, 9-CH), 113.73 (d), 116.26 (s), 117.93 (s), 121.40
(s), 121.44 (d), 121.97 (d), 125.11 (d), 128.45 (d), 133.17 (s), 133.31 (d),
137.83 (s), 148.70 (s), 151.50 (s), 152.77 (s), 160.97 (s). MS (EI): m/z
(%) ¼ 395 (100), 379 (65), 361 (35), 348 (10), 316 (20), 297 (30), 288 (15),
255 (10), 219 (30), 210 (45), 198 (60), 182 (30), 152 (25), 127 (35), 110 (30), 95
(25), 85 (25), 73 (42), 67 (30). Anal. calc. for C21H18NO2Br: C, 63.65; H,
4.58; N, 3.53. Found: C, 63.67; H, 4.48, N, 3.14.
N-(2,6-diethylphenyl)-4-methyl-7,8,9,10-tetrahydro-7,8-benzo-
coumarin-8,9-aziridine (7b)
Following the general procedure, reaction of a mixture of regioisomers
of 4b and 5b (0.5 g, 1.32 mmol) and p-toluenesulphonyl chloride (0.303 g,
1.59 mmol) gave 0.415 g (90%) of 7b as a colorless solid.
M.p. 158ꢂ–160ꢂC. IR(KBr): ꢁ ¼ 2970, 2910, 2870, 1720, 1600, 1450,
1
1400, 900 cmꢃ1. H NMR(400 MHz, CDCl ): ꢂ ¼ 1.26 (t, 6H, 2CH3), 2.40
3
(d, 3H, J ¼ 0.96 Hz, 4-CH3), 2.67–2.80 (m, 6H, 8-CH, 9-CH&2Ar-CH2),
3.02 (dd, 1H, J ¼ 18.08 Hz, 10CH2), 3.28 (dd, 1H, J ¼ 15.6 Hz, 7-CH2),
3.59 (d, 1H, J ¼ 17.6 Hz, 7-CH2), 4.07 (d, 1H, J ¼ 18.08, 10-CH2), 6.23 (d,
1H, J ¼ 1 Hz, 3-CH), 6.84–6.88 (m, 1H, Ar-Hc), 6.98 (d, 2H, J ¼ 7.8 Hz,
Ar-Hb&Hd), 7.08 (d, 1H, J ¼ 8.32 Hz, Ar-H5), 7.39 (d, 1H, J ¼ 8.28 Hz,
Ar-H6). 13C NMR(100 MHz, CDCl 3): ꢂ ¼ 14.05 (q), 18.70 (q), 22.61
(splitt. t), 25.03 (t), 29.96 (t), 38.96 (d), 113.89 (d), 118.09 (s), 121.64 (s),
121.95 (d), 120.05 (d), 125.0 (d), 126.53 (d), 135.01 (d), 138.04 (s), 138.03 (s),
150.03 (s), 151.56 (s), 152.73 (s), 160.99 (s). MS (EI): m/z (%) ¼ 359 (100),
358 (85), 343 (25), 316 (65), 256 (40), 199 (60), 182 (45), 171 (55), 153 (50),
101 (15), 56 (70). Anal. calc. for C24H25NO2: C, 80.19; H, 7.01; N, 3.90.
Found: C, 80.50; H, 6.95; N, 3.70.
N-(4-nitrophenyl)-4-methyl-7,8,9,10-tetrahydro-7,8-benzocoumarin-
8,9-aziridine (7c)
Following the general procedure, use of a mixture of regioisomers 4c
and 5c (0.5 g, 1.36 mmol) and p-toluenesulphonyl chloride (0.312 g, 1.64
mmol) gave 0.420 g (85%) of 7c as a colorless compound.

N-ARYL AZIRIDINES
1117
M.p. 210ꢂ–212ꢂC. IR(KBr): ꢁ ¼ 3100, 2950, 2970, 1720, 1600,
1500, 1350 cmꢃ1
.
1H NMR(200 MHz, CDCl 3): ꢂ ¼ 2.40 (d, 3H,
J ¼ 1.16 Hz, 4-CH3), 2.86–2.95 (m, 2H, 8-CH&9-CH), 3.05 (d, 1H,
J ¼ 18.64 Hz, 10-CH2), 3.29 (d, 1H, J ¼ 17.7 Hz, 7-CH2), 3.55 (d,
1H, J ¼ 17.5 Hz, 7-CH2), 3.99 (d, 1H, J ¼ 18.10 Hz, 10-CH2), 6.24 (d, 1H,
J ¼ 1.08 Hz, 3-CH), 7.04–7.10 (m, 3H, Ar-H), 7.35–7.44 (m, 1H, Ar-H),
8.08–8.13 (m, 2H, Ar-H). 13C NMR(50 MHz, CDCl 3); ꢂ ¼ 18.67,
22.88, 30.11, 38.72, 38.99, 114.09, 118.22, 120.52, 120.97, 122.34,
125.07, 128.29, 137.17, 142.56, 151.48, 152.64, 160.68, 160.60. Anal. calc.
for C20H16N2O4: C, 68.97; H, 4.63; N, 8.04. Found: C, 69.50; H, 4.49;
N, 7.95.
7-(4-Nitrophenyl)-7-azabicyclo[4.1.0]-heptane (10)
Following the general procedure, reaction of 8 (0.5 g, 2.12 mmol) with
p-toluenesulphonyl chloride (0.485 g, 2.54 mmol) gave 0.450 g (99%) of 10
as a yellow crystalline compound.
M.p. 90ꢂ–92ꢂC. IR(KBr): ꢁ ¼ 3100, 3050, 3000, 2970, 2870, 1590,
1500, 1400, 1340, 1280, 1100, 1090 cmꢃ1 1H NMR(200 MHz, CDCl 3):
.
ꢂ ¼ 1.23–1.46 (m, 4H, 2CH2), 1.49–1.59 (m, 4H, 2CH2), 1.88–2.33 (m, 2H,
2-CH), 7.00 (d, 2H, J ¼ 9.02 Hz, Ar-H), 8.08 (d, 2H, J ¼ 9.04 Hz, Ar-H).
13C NMR(50 MHz, CDCl 3); ꢂ ¼ 20.07, 24.29, 39.42, 120.22, 125.03,
142.11, 162.06, Anal. calc. for C12H14N2O2: C, 66.04; H, 6.47; N, 12.84.
Found: C, 65.70; H, 6.60; N, 12.70.
7-(4-Methylphenyl)-7-azabicyclo[4.1.0]-heptane (11)
Following the general procedure, reaction of 9 (0.5 g, 2.43 mmol) with
p-toluene sulphonylchloride (0.558 g, 2.93 mmol) gave 0.350 g (75%) of 11
as a viscous liquid.
IR(KBr): ꢁ ¼ 3000, 2950, 2950, 1520, 1500, 1420 cmꢃ1
.
1H NMR
(200 MHz, CDCl3): ꢂ ¼ 1.20–1.40 (m, 4H, 2CH2), 1.35–1.45 (m, 4H,
2CH2), 1.80–2.20 (m, 2H, 2CH), 2.30 (s, 3H, CH3), 6.65 (d, 2H,
J ¼ 9.2 Hz, Ar-H), 7.25 (d, 2H, J ¼ 9.2 Hz, Ar-H). 13C NMR(50 MHz,
CDCl3); ꢂ ¼ 20.60, 20.05, 24.0, 39.0, 120.18, 125.60, 140.50, 152.8. Anal.
calc. for C13H17N: C, 83.37; H, 9.15; N, 7.48. Found: C, 83.28; H, 9.10;
N, 7.39.

1118
SRIRAGHAVAN AND RAMAKRISHNAN
N-(4-nitrophenyl)-2-phenyl-aziridine (14)
Following the general procedure using 12a/13a or a mixture of 12a and
13a (0.5 g, 1.93 mmol) and p-toluenesulphonyl chloride (0.443 g, 2.32 mmol),
14 was obtained 0.372 g (80%), as a yellow solid.
M.p. 132ꢂ–134ꢂC. Lit: 135ꢂC.26 IR(KBr): ꢁ ¼ 3100, 3080, 2950, 1620,
1530, 1450, 1320, 1280 cmꢃ1
.
1H NMR(90 MHz, CDCl 3): ꢂ¼3.68 (dd,
J ¼ 14.0, 9.8 Hz, CH2), 4.01 (dd, 1H, J ¼ 14.6, 4.9 Hz, CH2), 4.85 (dd, 1H,
J ¼ 9.8, 4.9 Hz, benzylic-H), 7.00 (d, 2H, J ¼ 9.0 Hz, Ar-H), 7.30–7.52 (m,
5H, Ar-H), 8.05 (d, 2H, J¼9.0 Hz, Ar-H).
N-(4-methylphenyl)-2-phenyl-aziridine (15) and trans-1,4-di(4-methylphe-
nyl)-2,5-diphenylpiperazine (16)
Treatment of a mixture 12b and 13b (0.5 g, 2.20 mmol) with
p-toluenesulphonyl chloride (0.50 g, 2.64 mmol) gave 0.322 g (70%) of 15
as a colorless solid and 0.135 g (15%) of 16.
Compound 15
M.p. 162ꢂ–164ꢂC. IR(KBr): ꢁ ¼ 3000, 3070, 2970, 2900, 1620, 1520,
1
1450, 1370, 810, 700 cmꢃ1. H NMR(400 MHz, CDCl ): ꢂ ¼ 2.17 (s, 3H,
3
Ar-CH3), 3.70 (dd, J ¼ 14.2, 9.80 Hz, CH2), 4.05 (dd, 1H, J ¼ 14.64, 4.88 Hz,
CH2), 4.80 (dd, 1H, J ¼ 9.8, 4.88, benzylic-H), 6.67 (d, 2H, J ¼ 8.32 Hz,
Ar-H), 6.93 (d, 2H, J ¼ 8.32 Hz, Ar-H), 7.20–7.40 (m, 5H, Ar-H).
13C NMR(100 MHz, CDCl 3): ꢂ ¼ 20.23 (q), 50.86 (t), 61.05 (d), 114.55
(d), 126.42 (d), 127.19 (s, d), 128.70 (d), 129.63 (d), 141.42 (s), 146.73 (s),
MS (EI): m/z (%) ¼ 209 (25), 208 (100), 194 (85), 193 (90), 118 (85), 91 (45).
Anal. calc. for C15H15N: C, 86.08; H, 7.22; N, 6.69. Found: C, 85.90; H,
7.30; N, 7.02.
Compound 16
M.p. 256ꢂ–258ꢂC. IR(KBr): ꢁ ¼ 3040, 2950, 2900, 2840, 2800, 1600,
1
1510, 1220, 1120, 920, 810, 740, 680 cmꢃ1. H NMR(400 MHz, CDCl ):
3
ꢂ ¼ 2.16 (s, 6H, 2Ar-CH3), 3.30 (dd, 2H, J ¼ 9.28, 12.68 Hz, 2-CH2), 3.77
(dd, 2H, J ¼ 3.4, 12.68 Hz, 2-CH2), 4.59 (dd, 2H, J ¼ 3.4, 9.28 Hz,
2-Benzylic-H), 6.74 (d, 4H, J ¼ 8.32 Hz, 4-Ar-H), 6.86 (d, 4H, J ¼ 8.32 Hz,
4-Ar-H), 7.10–7.37 (m, 10H, Ar-H). MS (EI): m/z (%) ¼ 418 (65), 298 (40),

N-ARYL AZIRIDINES
1119
222 (50), 208 (7), 195 (90), 119 (100), 104 (80), 103 (50), 91 (45). Anal.
calc. for C30H30N2: C, 86.08; H, 7.22; N, 6.69. Found: C, 86.00; H, 7.20;
N, 6.65.
9-Amino-N-(4-Nitrophenyl)phenanthrene (20)
Reaction of 17 (0.5 g, 1.506 mmol) with p-toluenesulphonyl chloride
(0.345 g, 1.80 mmol) gave 0.140 g (30%) of 20 as an orange-red solid.
M.p. 180ꢂ–182ꢂC. IR(KBr): ꢁ ¼ 3400, 3000, 1500, 1450, 1390, 1320,
1100 cmꢃ1
.
1H NMR(200 MHz, CDCl 3): ꢂ ¼ 6.57 (s, 1H, NH, D2O
exchangeable), 6.80 (d, 2H, J ¼ 9.16 Hz, Ar-H), 7.59–7.86 (m, 6H, Ar-H),
8.0–8.12 (m, 3H, Ar-H), 8.69–8.80 (m, 2H, Ar-H). 13C NMR(50 MHz,
CDCl3, DEPT-90): ꢂ ¼ 128.32, 127.48, 127.29, 127.18, 126.92, 126.33,
123.48, 123.04, 122.74, 122.55, 113.64. Anal. calc. for C20H14N2O2: C,
76.41; H, 4.49; N, 8.91. Found: C, 76.0; H, 4.80; N, 9.01.
(þ)trans-1,2-Dimethyl-3-phenylaziridine (21) and (1R,2S)-
2-[N-Methyl-(4-toluenesulphonyl)-amino]-1-phenylpropan-1-ol (22)
Following the general procedure, treatment of L-ephedrine (0.5 g,
3 mmol) with p-toluene sulphonylchloride (0.690 g, 3.63 mmol) gave the
expected (þ)trans 1,2-dimethyl-3-phenyl aziridine 21 0.090 g (20%) as a
viscous liquid, along with 0.675 g (70%) of 22 as the major product. The
IRand NMRdata of 21 agreed with the reported data.33
Compound 22
M.p. 124ꢂ–126ꢂC. IR(KBr): ꢁ ¼ 3550, 3090, 3020, 3000, 2950, 1590,
1370, 1320, 1150, 1120, 1100, 890 cmꢃ1 1H NMR(400 MHz, CDCl 3):
.
ꢂ ¼ 0.87 (d, 3H, N-CH3), 2.38 (s, 3H, Ar-CH3), 2.68 (s, 3H, Ar-CH3), 4.14
(dq, 1H, -CH-), 4.80 (d, 1H, Ar-CH), 7.25 (d, 2H, J ¼ 7.8 Hz, Ar-H),
7.30–7.35 (m, 5H, Ar-H), 7.55 (d, 2H, J ¼ 8.3 Hz, Ar-H). 13C NMR
(100 MHz, CDCl3): ꢂ ¼ 10.85 (q), 21.45 (q), 30.42 (q), 57.88 (d), 76.74 (d),
126.20 (d), 127.0 (d), 127.60 (s), 128.25 (s), 129.61 (d), 136.29 (d), 141.60 (s),
143.12 (s). Anal calc. for C17H21NO3S: C, 63.92; H, 6.63; N, 4.38. Found: C,
63.50; H, 6.59; N, 4.42. Further the structure of the compound 22 has been
confirmed by XRD.34

1120
SRIRAGHAVAN AND RAMAKRISHNAN
ACKNOWLEDGMENTS
The authors thank the UGC, New Delhi, for Special Assistance
Programme; C.S.I.R., New Delhi, for Senior Research Fellowship (KS),
R.S.I.C., I.I.T., Chennai; and Spic Science Foundation, Chennai, for
NMRfacilities.
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Received in Japan April 13, 2000