High-yielding synthesis of 1-carboxamido-3,4-dihydronaphthalenes via palladium-catalyzed aminocarbonylation

Article abstract of DOI:10.1016/j.tet.2012.11.033

1-Iodo-3,4-dihydronaphthalene, an iodoalkene substrate obtained from α-tetralon, has been carbonylated in the presence of palladiumephosphine precatalysts. Systematic investigations have revealed that the 1-carboxamido-3,4-dihydronaphthalenes and 1-methox

Full text of DOI:10.1016/j.tet.2012.11.033

Tetrahedron 69 (2013) 500e504
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Tetrahedron
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High-yielding synthesis of 1-carboxamido-3,4-dihydronaphthalenes
via palladium-catalyzed aminocarbonylation
a
a
a
b
a,b,
ꢀ
*
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
Roland Farkas , Erik A. Molnar , Peter Acs , Attila Takacs , Laszlo Kollar
a
ꢀ
ꢀ
ꢀ
Department of Inorganic Chemistry, University of Pecs and Szentagothai Research Center, H-7624 Pecs, PO Box 266, Hungary
MTA-PTE Research Group for Selective Chemical Syntheses, H-7624 Pecs, Ifjusag u. 6., Hungary
b
ꢀ
ꢀ ꢀ
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 17 July 2012
Received in revised form 19 October 2012
Accepted 7 November 2012
Available online 15 November 2012
1-Iodo-3,4-dihydronaphthalene, an iodoalkene substrate obtained from a-tetralon, has been carbony-
lated in the presence of palladiumephosphine precatalysts. Systematic investigations have revealed that
the 1-carboxamido-3,4-dihydronaphthalenes and 1-methoxycarbonyl-3,4-dihydronaphthalene have
been formed in exceptionally high isolated yields (up to 96%) in chemospecific reaction. The influence of
the amine nucleophile and that of the reaction conditions (carbon monoxide pressure, reaction tem-
perature) on the reactivity of the substrate have been investigated.
Keywords:
Carbonylation
Ó 2012 Elsevier Ltd. All rights reserved.
Palladium
Homogeneous catalysis
Amine nucleophile
Carbon monoxide
1. Introduction
The synthesis of key intermediates, such as 1-amino-2-cyano-3,4-
dihydronaphthalene derivatives,14 1-amino-2-formyl-3,4-dihydro-
The discovery of the carbonylation of aryl halides in the pres-
ence of O- and N-nucleophiles1 initiated various synthetic routes
for the synthesis of esters and amides. The synthetic potential of
this carbonylation reaction was illustrated using several aryl halide
models and substrates of practical importance as well.2e6 The
intramolecular alkoxy- and aminocarbonylation resulted in the
formation of lactones and lactams, respectively.7 The palladium-
catalyzed alkoxy- and aminocarbonylation of aryl halides proved to
be of industrial importance and has been reviewed recently.8,9
As synthetic analogues to aryl halides, iodo- and bromo-alkenes
of various structures have also been synthesized and widely used as
naphthalene,15 1-chloro-2-formyl-3,4-dihydronaphthalene,16 3,4-
dihydronaphthalene-2-carboxylic acid17 was reported. 3,4-
Dihydronaphthalene derivatives have been used in the synthesis of
dibenzonaphthyridines,18 demethoxydaunomycinones,19 phenan-
trenones,20 chromenones,21 secopseudopterosin aglycone,22 optically
active anthracyliones.23 The regioselectivity of nucleophilic additions
on dihydronaphthalene has been controlled by the chromium-
tricarbonyl moiety coordinated to the aromatic ring.24 Rhodium
nanoparticles served as efficient catalysts in the selective hydroge-
nation of 2-acetyl-5,8-dimethoxy-3,4-dihydronaphthalene to the
corresponding 1,2,3,4-tetrahydronaphthalene, a precursor of anti-
tumour anthracyclinic compounds.25
substrates in the synthesis of a,b-unsaturated esters and carbox-
amides in palladium-catalyzed alkoxy- and aminocarbonylations,
Compounds with 3,4-dihydronaphthalene moiety were used as
substrates also in various homogeneous catalytic reactions. 1-
Bromo-3,4-dihydronaphthalene and its triflate analogue have
been used as substrate in Suzuki-26 and Negishi-reaction,27 re-
spectively. 6-Aryl- and 1-aryl-substituted 3,4-dihydronaphthalenes
were synthesized in the cross-coupling reaction of the corre-
sponding 6-triflate28 and 1-bromo-3,4-dihydronaphthalene,29 re-
spectively. Enantioselective Sharpless-dihydroxylation30 and
Jacobsen-epoxidation31 of functionalized 3,4-dihydronaphthalenes
led to the corresponding 1,2-substituted chiral building blocks.
In the present study, a high-yielding palladium-catalyzed che-
mospecific synthesis of 2-carboxamido- and 2-methoxycarbonyl-
3,4-dihydronaphthalene derivatives is reported.
respectively.5,6
As a part of our continuing research in the carbonylation and
coupling reactions of iodoalkenes, the synthesis of various building
blocks was carried out. Recently, we turned our attention towards
the synthesis of compounds with dihydronaphthalene backbone.
The pharmacological importance of these derivatives as key moi-
eties has been shown in the synthesis of benzoquinazoline de-
rivatives,10 tetrahydrobenzoisoquinolines,11 azasteroids obtained in
DielseAlder reaction12 and estrane derivatives in diene additions.13
ꢀ
* Corresponding author. E-mail address: kollar@ttk.pte.hu (L. Kollar).
0040-4020/$ e see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.tet.2012.11.033

R. Farkas et al. / Tetrahedron 69 (2013) 500e504
501
Table 1
2. Results and discussion
-Tetralone (1) was transformed to the corresponding hydra-
zone (2), which was treated with iodine in the presence of a strong
base, TMG (N,N,N0,N0-tetramethylguanidine) (Scheme 1). The
iodoalkenyl derivative (3) was obtained in good yields based on the
starting material (1). Although a general methodology for pre-
paring iodoalkenes from ketones is known,32,33 due to the opti-
Aminocarbonylation of 1-iodo-3,4-dihydronaphthalene (3) in the presence of pal-
ladiumePPh3 in situ catalystsa
a
Entry
Amine
p (CO)
[bar]
R. Time
[h]
Conv.b
[%]
Isolated yield
of 4
1
2
3
4
a
a
a
a
a
a
a
a
1
1
1
1
1
0.5
1
2
75
85
92
96
>99.8
78
n.d.
n.d.
n.d.
90 (4a)
96 (4a)
n.d.
5
mization of the procedure
a complete description of the
5
24
24
5
5
5
5
1
24
5
1
24
5
1
24
5
1
24
4
1
24
5
6c
7
1
preparation of 3 is given in the Section Experimental.
20
40
60
60
1
1
40
1
1
40
1
1
40
1
99
n.d.
8
9
>99.8
>99.8
89
72
>99.8
99
80
>99.8
99
85
>99.8
99
81
>99.8
98
70
>99.8
98
95 (4a)
96 (4a)
n.d.
a
a
I
NNH2
O
10c
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
bd
bd
bd
ce
ce
ce
df
df
df
ef
ef
ef
ff
n.d.
N2H4.H2O
Et3N
TMG, I2
86 (4b)
82 (4b)
n.d.
90 (4c)
n.d.
1
2
3
Scheme 1. The synthesis of 1-iodo-3,4-dihydronaphthalene (3).
n.d.
91 (4d)
88 (4d)
n.d.
92 (4e)
85 (4e)
n.d.
1-Iodo-3,4-dihydronaphthalene (3) was aminocarbonylated in
the presence of palladium catalysts formed in situ by the reaction of
palladium(II) acetate and two molar equiv of triphenylphosphine.
tert-Butylamine (a), aniline (b), piperidine (c), methyl glycinate (d),
methyl alaninate (e) and methyl prolinate (f) were used as N-nu-
cleophiles (Scheme 2).
1
40
1
1
40
ff
88 (4f)
n.d.
ff
a
Reaction conditions (unless otherwise stated):
1 mmol of substrate (1);
0.025 mmol of Pd(OAc)2; 0.05 mmol of PPh3; 3 mmol of a; 0.5 mL of triethylamine;
O
NR'R"
solvent: 10 mL of DMF, reaction temperature: 50 ꢀC; n.d.: not determined.
I
b
Determined by GC and GCeMS (naphthalene as internal standard).
c
Reaction temperature: 30 ꢀC.
CO, R'R"NH
d
1.5 mmol of b.
2.0 mmol of c.
Pd(OAc)2 / PPh3
e
f
1.1 mmol of d, e or f. (as a hydrochloride salt).
3
4
R' R"
maintained (entry 7e9), (iii) the aminocarbonylation at high car-
bon monoxide pressure also needs a reaction temperature higher
than 30 ꢀC in order to achieve complete conversion (entry 10).
Screening the various amines in aminocarbonylation, efficient
synthesis of the corresponding carboxamides (4bef) was carried
out. In longer reaction times (24 h) practically complete conversion
was achieved in all cases (entries 12, 15, 18, 21 and 24). However,
decreasing the reaction time some differences in the reactivities
can be observed: (i) the aromatic primary amine (b) (entry 11) and
the more hindered amino acid-derived secondary amine (f) (entry
23) show slightly lower reactivity in aminocarbonylation than the
secondary amine (c) (entry 14) and the amino acid-derived primary
amines (d and e) (entry 17 and 20), (ii) the increase of the carbon
monoxide pressure lead to complete conversion in case of all
amines (bef) in reasonable reaction times (entries 13, 16, 19, 22 and
25).
a
b
c
d
e
f
H
tBu
H
Ph
-(CH2)5-
H
H
CH2COOCH3
CH(CH3)COOCH3
-CH(COOCH3)(CH2)3-
Scheme 2. Aminocarbonylation of 3 towards carboxamides (4).
It is worth mentioning, that the above Pd(OAc)2/2PR3-type
catalyst is widely used as
a precursor of ‘in situ’ formed
palladium(0)-tertiary phosphine systems. It has been proved that
palladium(II) is reduced to palladium(0) while one of the 2 equiv of
phosphine ligands is oxidized.34e36 In our case, the formation of
coordinatively highly unsaturated Pd(PPh3)(S)n (S stands for sol-
vent (DMF)) complex is supposed while the ‘second’ equivalent of
PPh3 is oxidized to triphenylphosphine oxide. Under the amino-
carbonylation conditions used (see below) the action of other
compounds (amine, carbon monoxide) as reducing agents cannot
be excluded.
A highly chemoselective reaction has been observed in the
presence of tert-butylamine (a) resulting in the formation of the
corresponding carboxamide derivative (4a). Yields of practical in-
terest were obtained under mild conditions (1 bar CO, 50 ꢀC).
Practically complete conversions can be achieved within a few
hours reaction time (Table 1, entry 1e5).
In addition to the N-nucleophiles specified above methanol as
O-nucleophile was also investigated.
3 as a substrate was
methoxycarbonylated in the presence of ‘in situ’ formed palla-
dium(0) catalysts. Mild reaction conditions (50 bar CO, 50 ꢀC) and
2.5% palladium catalyst precursor were used. The exclusive for-
mation of the corresponding methyl ester (5) was observed and
isolated in good yields (up to 78%) (Scheme 3).
For comparison, the reactivity of structurally analogous com-
pounds, such as
a a-iodoethenyl-naphtha-
-iodo-styrene37,38 and
lene isomers39 was related to that of 3 in carbonylation reactions. It
can be stated that the reactivity of the cyclic iodoalkene compound
3 proved to be definitely higher than that of the aforementioned
open chain 1-iodo-1-arylalkene type iodoalkenes both in amino-
and alkoxycarbonylation reactions.
The reaction conditions were optimized towards the formation
of 4a. The following effects are worth mentioning: (i) the use of
even lower reaction temperature (30 ꢀC) resulted in lower activity
(entry 6), (ii) the increase of the carbon monoxide pressure lead to
higher conversion, while the high chemoselectivity was still
The increased reactivity of the substrate (3) could be explained
by the sterically less congested arrangement of the alkenyl-group,

502
R. Farkas et al. / Tetrahedron 69 (2013) 500e504
Elemental analyses were measured on a 1108 Carlo Erba apparatus.
O
OMe
I
Samples of the catalytic reactions were analyzed with a Hewlett
Packard 5830A gas chromatograph fitted with a capillary column
coated with OV-1 (internal standard: naphthalene; injector temp
250 ꢀC; oven: starting temp 50 ꢀC (hold-time 11 min), heating rate
15 ꢀC minꢂ1, final temp 320 ꢀC; detector temp 280 ꢀC; carrier gas:
helium (rate: 1 mL minꢂ1)). The FT-IR spectra were taken in KBr
pellets using an IMPACT 400 spectrometer (Nicolet) applying
a DTGS detector in the region of 400e4000 cmꢂ1, the resolution
was 4 cmꢂ1. The amount of the samples was ca. 0.5 mg.
The substrate (3) was synthesized by the modified Barton-
procedure (See Section 4.2).32,33 The amine nucleophiles were
purchased from SigmaeAldrich and were used without further
purification. It is worth noting that all carboxamides (4aef) and the
ester (5) can be isolated in nearly quantitative yields (up to 96%)
being the only products under mild reaction conditions.
CO, MeOH
Pd(OAc)2 / PPh3
3
5
Scheme 3. Methoxycarbonylation of 3 in the presence of palladium catalysts.
and consequently, its facile oxidative addition to palladium(0)
resulting in the palladium(II)-alkenyl intermediate (A) (Scheme 4).
Furthermore, the iodoecarbon bond of 3 has higher polarizability
than the corresponding C(sp2)eX bonds in its structural analogues,
such as chloro- and bromo-alkenes. (In general, in line with the
decreasing carbonehalide bond energy, the rate of the oxidative
addition to palladium(0), and consequently, the efficiency of car-
bonylations decrease in the order CeI>C(OTf)ꢁCeBr[CeCl
[CeF.2,9) The formation of the terminal carbonyl complex (B) is
followed by carbon monoxide insertion. The highly reactive acyl
intermediate (C) gives the amide in the product forming step while
the coordinatively unsaturated intermediate is formed.
4.2. Synthesis of 1-iodo-3,4-dihydronaphthalene (3)
a-Tetralone (1) (29.2 g, 0.2 mol), freshly distilled hydrazine hydrate
(98%, 60 g, 1.2 mol) and triethylamine (50 g, 0.49 mol) were heated in
refluxing methanol (150mL) for 2.5h. Aftercompletion of thereaction
the mixture was poured onto water and extracted with hexane
(2ꢃ120 mL). Thenthecombined organic phasewas washed withbrine
(3ꢃ70 mL) and water (70 mL), and dried over molecular sieve. After
the evaporation of the solvent the crude hydrazone derivative (2) was
obtained and used in the next step without further purification.
To a stirred solution of iodine (22.6 g, 0.089 mol) in ether (100 mL)
N,N,N0,N0-tetramethylguanidine (46.3 g, 0.4 mol) was added at ice-
bath cooling. To this solution the ethereal solution (30 mL) of 2 (5 g,
0.031 mol) was added dropwise at room temperature. The reaction
mixturewasstirredfor 0.5 hand theprecipitated saltwasfiltered. The
solvent was evaporated and the residue was heated at 90 ꢀC under
argon atmosphere for 2 h. The mixture was poured onto iced water
(250 mL) and extracted with hexane (3ꢃ100 mL). The combined or-
ganic layer was washed with 1 N aqueous hydrochloric acid
(3ꢃ50 mL), water (2ꢃ50 mL), 5% aqueous sodium hydrogen carbon-
ate(2ꢃ50mL), thenwithwater(2ꢃ50mL), saturatedaqueoussodium
thiosulfate (3ꢃ5 mL) and water (3ꢃ5 mL) again. The hexane solution
was dried on molecular sieve overnight. The hexane was distilled off
and the crude product was distilled under vacuum. The highly pure
product(3)wasusedinfurtherexperimentsasobtained.Yield:21.5g;
42% (based on 1). (In order to avoid its oxidative and photochemical
decomposition,3has tobekeptunderargoninrefrigerator. Byusingit
in carbonylation reactions, reproducible results can be obtained even
after two months. No changes in its colour and analytical character-
istics were observed within this time interval.)
NR1R2
I
O
PdL
n
+ 2L - 2L
PdLn-2
Et3NHI
Et3N
HNR1R2
PdLn-2
I
O
PdLn-2I
A
C
CO
B
PdLn-2(CO)I
Scheme 4. The simplified catalytic cycle of the aminocarbonylation of 3.
3. Conclusions
4.3. Aminocarbonylation of 1-iodo-3,4-dihydronaphthalene
(3) in the presence N-nucleophiles under high carbon mon-
oxide pressure
The aminocarbonylation of 1-iodo-3,4-dihydronaphthalene
provides an easy access to 1-carboxamido-3,4-dihydronaphtha-
lenes, the regioisomers of 2-substituted 3,4-dihydronaphthalenes
(e.g., 2-carbonitrile/2-carboxaldehyde/2-carboxylic acid-3,4-dihy-
dronaphthalene) with wide pharmacological interest. The above
methodology resulted in the highly selective formation of
In a typical experiment Pd(OAc)2 (5.6 mg, 0.025 mmol), triphe-
nylphosphine (13.2 mg, 0.05 mmol), 1-iodo-3,4-dihydronaphthalene
(256 mg, 1 mmol), amine nucleophile (3 mmol of a/1.5 mmol of b/
2 mmol of c/1.1 mmol of d, e or f) and triethylamine (0.5 mL) were
dissolved in DMF (10 mL) under argon in a 100 mL autoclave. The
atmosphere was changed to carbon monoxide and the autoclave was
pressurized to the given pressure by carbon monoxide. The reaction
was conducted for the given reaction time upon stirring at 50 ꢀC (or
30 ꢀC) and analyzed by GCeMS. The mixture was then concentrated
and evaporated to dryness. The residue was dissolved in chloroform
(20 mL) and washed with water (3ꢃ20 mL). The organic phase was
dried over Na2SO4, filtered and evaporated to a crystalline material or
to a waxy residue. All compounds were subjected to column chro-
matography (Silicagel 60 (Merck), 0.063e0.200 mm), EtOAc/CHCl3
dihydronaphthalene-based a,b-unsaturated amides and esters. All
products were isolated in yields of synthetic interest.
4. Experimental
4.1. General procedures
1H and 13C NMR spectra were recorded in CDCl3 on a Varian
Inova 400 spectrometer at 400.13 MHz and 100.62 MHz, re-
spectively. Chemical shifts
d are reported in parts per million rela-
tive to CHCl3 (7.26 and 77.00 ppm for 1H and 13C, respectively).

R. Farkas et al. / Tetrahedron 69 (2013) 500e504
503
(the exact ratios are specified in Section Characterization (4.6) for
each compound).
3231 (NH); 1651 (CON); MS m/z (rel int.): 249 (80, Mþ),157 (100),102
(7), 77 (11). MS (m/z/rel.int.): 249/80 (Mþ), 77/11, 102/7, 157/100.
4.6.4. 1-(N,N-(Pentan-1,5-diyl)carboxamido)-3,4-dihydronaphthalene
(4c). Yield:217 mg(90%); white solid, mp 84e85ꢀC;[found: C, 79.54;
H, 8.11; N, 5.60; C16H19NO requires C, 79.63; H, 7.94; N, 5.80%]; Rf (10%
EtOAc/CHCl3)0.69;dH (400MHz,CDCl3)7.25e7.10(3H,m, AreH);7.05
(1H, d, 3.7 Hz, AreH); 6.05 (1H, t, 4.6 Hz, ]CH); 3.7 (2H, br s, NCH2);
3.25 (2H, br s, NCH2); 2.8 (2H, t, 7.7 Hz, CH2); 2.42e2.30 (2H, m, ]
CHCH2);1.6(4H, brs,2ꢃCH2); 1,4(2H, br s, CH2), dC (100.6MHz,CDCl3)
168.9; 136.1; 135.2; 131.4; 127.9; 127.7; 127.0; 126.7; 124.1; 48.1; 42.4;
4.4. Aminocarbonylation of 1-iodo-3,4-dihydronaphthalene
(3) in the presence N-nucleophiles under atmospheric carbon
monoxide pressure
In a typical experiment Pd(OAc)2, triphenylphosphine, 1-iodo-
3,4-dihydronaphthalene, amine nucleophile and triethylamine
were dissolved in DMF (for the quantity of the reagents See Section
4.3) under argon in a 100 mL three-necked flask equipped with
a gas inlet, reflux condenser with a balloon (filled with argon) at the
top. The atmosphere was changed to carbon monoxide. The re-
action was conducted for the given reaction time upon stirring at
50 ꢀC and analyzed by GCeMS (internal standard: naphthalene).
The mixture was then concentrated and evaporated to dryness and
worked-up as described in Section 4.3.
27.4; 26.6; 25.7; 24.6; 22.7; IR (KBr n
(cmꢂ1)) 1636 (CON); MS m/z (rel
int.): 241 (100, Mþ), 158 (43), 128 (84), 84 (22).
4.6.5. 1-((N-Methoxycarbonylmethyl)carboxamido)-3,4-dihydronaph-
thalene (4d). Yield: 223 mg (91%); off-white solid, mp 94e95 ꢀC;
[found: C, 68.40; H, 6.29; N, 5.55; C14H15NO3 requires C, 68.56; H,
6.16; N, 5.71%]; Rf (30% EtOAc/CHCl3) 0.70; dH (400 MHz, CDCl3) 7.45
(1H, d, 7.4 Hz, AreH); 7.15 (3H, m, AreH); 6.5 (2H, br s, ]CHþNH);
4.1 (2H, s, CH2); 3.75 (3H, s, OCH3); 2.75 (2H, t, 7.8 Hz, CH2); 2.3 (2H,
m, ]CHCH2). dC (100.6 MHz, CDCl3) 170.4; 168.9; 136.1; 135.6; 132.1;
4.5. Methoxycarbonylation of 1-iodo-3,4-
dihydronaphthalene
131.0; 127.8; 127.8; 126.7; 125.2; 52.3; 41.3; 27.5; 22.9. IR (KBr
n
(cmꢂ1)) 3321 (NH); 1752 (COO); 1656 (CON).
In a typical experiment Pd(OAc)2 (5.6 mg, 0.025 mmol), tri-
phenylphosphine
(13.2
mg,
0.05
mmol),
1-iodo-3,4-
4.6.6. 1-(N-(1-(Methoxycarbonyl)-ethyl)carboxamido)-3,4-dihydrona-
phthalene (4e). Yield: 238 mg (92%); yellow solid, mp 89e90 ꢀC;
[found: C, 69.41; H, 6.69; N, 5.19; C15H17NO3 requires C, 69.48; H,
6.61; N, 5.40%]; Rf (5% EtOAc/CHCl3) 0.63; dH (400 MHz, CDCl3) 7.45
(1H, d, 6.8 Hz, AreH); 7.18 (3H, m, AreH); 6.55 (1H, t, 4.7 Hz, ]CH);
6.5 (1H, br s, NH); 4.72 (1H, quint, 7.3 Hz, CHCH3); 3.75 (3H, s, OCH3);
2.75 (2H, t, 7.7 Hz, CH2); 2.3 (2H, m, ]CHCH2); 2.05 (3H, d, 7.3 Hz,
CHCH3). dC (100.6 MHz, CDCl3) 173.5; 168.2; 136.1; 135.8; 131.9;
dihydronaphthalene (256 mg, 1 mmol), methanol (0.202 mL,
5 mmol) and triethylamine (0.5 mL) were dissolved in DMF (10 mL)
under argon in a 100 mL three-necked flask equipped with a gas
inlet, reflux condenser with a balloon (filled with argon) at the top.
The atmosphere was changed to carbon monoxide. The reaction
was conducted for 24 h upon stirring at 50 ꢀC and analyzed by
GCeMS (internal standard: naphthalene). The mixture was then
concentrated and evaporated to dryness and worked-up as de-
scribed in Section 4.3.
131.1; 127.8; 127.8, 126.7; 125.1; 52.4; 48.1; 27.5; 23.0; 18.3. IR (KBr
n
(cmꢂ1)) 3292 (NH); 1743 (COO); 1647 (CON). MS (m/z/rel.int.): 259
(28, Mþ), 128 (55), 157 (100), 200 (14).
4.6. Characterization of the products
4.6.7. 1-((N,N-1-Methoxycarbonylbutan-1,4-diyl)carboxamido)-3,4-
dihydronaphthalene (4f, 3/1 mixture of two rotational isomers). Yield:
251 mg (88%); yellow solid, mp 101e102 ꢀC; [found: C, 71.40; H, 6.88;
N, 4.79; C17H19NO3 requires C, 71.56; H, 6.71; N, 4.91%]; Rf (20% EtOAc/
CHCl3) 0.56; dH (400 MHz, CDCl3) 7.3 (1H, t, 7.4 Hz, AreH); 7.15e7.05
(3H, m, AreH); 6.2/6.05 (major/minor) (1H, t, 4.6 Hz, ]CH); 4.6 (1H,
m, NCH); 3.75 (3H, s, OCH3); 3.4 (2H, m, NCH2); 2.75 (2H, t, 8.1 Hz,
CH2); 2.35 (2H, m, ]CHCH2); 1.85e2.00 (4H, m, (CH2)2). dC
(100.6 MHz, CDCl3) 172.9/172.7 (minor/major); 169.2/169.0 (minor/
major); 136.4/136.3 (major/minor); 135.5/135.3 (minor/major);
130.9/130.5 (major/minor); 128.7/128.4 (major/minor); 127.83/
127.72 (minor/major); 127.8/127.67 (minor/major); 126.9/126.7
(major/minor); 124.4/124.0 (major/minor); 60.5/58.4 (minor/major);
52.2/52.0 (major/minor); 48.6/46.0 (major/minor); 31.2/29.5 (minor/
major); 27.4/27.1 (major/minor); 24.9/22.9 (major/minor); 22.7/22.5
4.6.1. 1-Iodo-3,4-dihydronaphthalene (3). Yield: 21.5 mg (42%);
highly viscous yellow material; [found: C, 46.65; H, 3.61; C10H9I
requires C, 46.90; H, 3.54%]; Rf (10% EtOAc/CHCl3) 0.90; dH
(400 MHz, CDCl3) 7.45 (1H, d, 7.6 Hz, AreH), 7.2 (1H, t, 7.4 Hz,
AreH), 7.15 (1H, t, 7.5 Hz, AreH), 7.0 (1H, d, 7.2 Hz, AreH), 6.8 (1H, t,
4.8 Hz, ]CH), 2.85 (2H, t, 7.9 Hz, CH2), 2.4 (2H, m, ]CHCH2). dC
(100.6 MHz, CDCl3) 140.0, 135.8, 134.3, 130.8, 128.2, 127.2, 126.9,
98.0, 27.8, 27.1; IR (KBr n
(cmꢂ1)): 1604 (C]C); MS m/z (rel int.): 256
(63, Mþ), 128 (100), 102 (11).
4.6.2. 1-(N-tert-Butylcarboxamido)-3,4-dihydronaphthalene (4a).
Yield: 220 mg (96%); off-white solid, mp 94e95 ꢀC; [found: C,
78.41; H, 8.51; N, 8.20; C15H19NO requires C, 78.56; H, 8.35%]; Rf
(10% EtOAc/CHCl3) 0.82; dH (400 MHz, CDCl3) 7.41 (1H, d, 7.3 Hz,
AreH), 7.2 (3H, m, AreH), 6.4 (1H, t, 4.6 Hz, ]CH), 5.65 (1H, br s,
NH), 2.75 (2H, t, 7.9 Hz, CH2), 2.3 (2H, m, ]CHCH2), 2.45 (9H, s,
C(CH3)3); dC (100.6 MHz, CDCl3) 168.2; 137.4; 136.1; 131.5; 129.9;
(major/minor). IR (KBr
n
(cmꢂ1)) 1744 (COO); 1631 (CON). MS (m/z/
rel.int.): 285 (28, Mþ), 70 (16), 128 (56), 157 (100), 226 (28).
127.7; 127.6; 126.6; 124.9; 51.4; 28.8; 27.6; 22.8. IR (KBr
n
(cmꢂ1))
4.6.8. 1-Methoxycarbonyl-3,4-dihydronaphthalene (5). Yield: 147 mg
(78%); highly viscous yellow material, [found: C, 76.50; H, 6.64;
C12H12O2 requires C, 76.57; H, 6.43%]; Rf (10% EtOAc/CHCl3) 0.72; dH
(400 MHz, CDCl3) 7.8 (1H, d, 7.5 Hz, AreH); 7.12e7.28 (4H, m,
AreHþ]CH); 3.8 (3H, s, OCH3); 2.75 (2H, t, 7.7 Hz, CH2); 2.4 (2H, m,
]CHCH2). dC (100.6 MHz, CDCl3) 167.0; 139.7; 136.2; 130.9; 130.8;
3319 (NH), 1640 (CON); MS m/z (rel int.): 229 (63, Mþ), 214 (7), 172
(38), 157 (95), 129 (100).
4.6.3. 1-(N-Phenylcarboxamido)-3,4-dihydronaphthalene (4b). Yield:
209 mg (84%); off-white solid, mp 173e174 ꢀC; [found: C, 81.76; H,
6.21; N, 5.49; C17H15NO requires C, 81.90; H, 6.06; N, 5.62%]; Rf
(CHCl3) 0.56; dH (400 MHz, CDCl3) 7.7 (1H, br s, NH); 7.6 (2H, d,
7.8 Hz, Ph (ortho)); 7.45 (1H, d, 3.7 Hz, AreH); 7.32 (2H, t, 7.8 Hz, Ph
(meta)); 7.2 (3H, m, AreH); 7.15 (2H, t, 7.3 Hz, Ph (para)); 6.6 (1H, t,
4.6 Hz, ]CH); 2.8 (2H, t, 8.1 Hz, CH2); 2.4 (2H, m, ]CHCH2). dC
(100.6 MHz, CDCl3) 166.8; 138.0; 136.7; 136.3; 132.3; 131.0; 129.0;
127.6; 127.5; 126.6; 126.0; 51.8; 27.5; 23.5. IR (KBr
n
(cmꢂ1)) 1720
(COO). MS (m/z/rel.int.): 188 (39, Mþ), 129 (100), 157 (8).
Acknowledgements
The authors thank the Hungarian Research Fund (CK78553) and
Developing Competitiveness of Universities in the Transdanubian
128.1; 128.0; 126.9; 125.1; 124.4; 120.0; 27.5; 23.0; IR (KBr n
(cmꢂ1))

504
R. Farkas et al. / Tetrahedron 69 (2013) 500e504
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