Synthesis of 1-tetralone derivatives using a Stille cross coupling/friedel crafts acylation sequence

Article abstract of DOI:10.1081/SCC-200032474

An efficient method of synthesis of 1-tetralones has been achieved featuring a Stille cross-coupling reaction as the key step.

Full text of DOI:10.1081/SCC-200032474

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Synthesis of 1‐Tetralone
Derivatives Using a Stille
Cross Coupling/Friedel Crafts
Acylation Sequence
Johnny Vercouillie a , Mohamed Abarbri a ,
Jean‐Luc Parrain b , Alain Duchêne a & Jérôme
Thibonnet a
a Laboratoire de Physicochimie des Interfaces et
des Milieux Réactionnels, Faculté des Sciences et
Techniques de Tours, Parc de Grandmont, 37200,
Tours, France
b Laboratoire SYMBIO, Equipe Synthèse par voie
Organométallique, associé au CNRS (UMR 6178),
Faculté des Sciences et Techniques de Saint
Jérôme, Avenue Escadrille Normandie‐Niemen,
13397, Marseille Cedex 20, France
Published online: 19 Apr 2010.
To cite this article: Johnny Vercouillie , Mohamed Abarbri , Jean‐Luc Parrain , Alain
Duchêne & Jérôme Thibonnet (2004) Synthesis of 1‐Tetralone Derivatives Using a
Stille Cross Coupling/Friedel Crafts Acylation Sequence, Synthetic Communications:
An International Journal for Rapid Communication of Synthetic Organic Chemistry,
34:20, 3751-3762, DOI: 10.1081/SCC-200032474
To link to this article: http://dx.doi.org/10.1081/SCC-200032474

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SYNTHETIC COMMUNICATIONSw
Vol. 34, No. 20, pp. 3751–3762, 2004
Synthesis of 1-Tetralone Derivatives Using
a Stille Cross Coupling/Friedel Crafts
Acylation Sequence
Johnny Vercouillie,1 Mohamed Abarbri,1 Jean-Luc Parrain,2
1
Alain Duchene, and Jerome Thibonnet
1,
*
ˆ
´ ˆ
1Laboratoire de Physicochimie des Interfaces et des Milieux
´ ´
Reactionnels, Faculte des Sciences et Techniques de Tours, Parc de
Grandmont, 37200, Tours, France
`
2
´
Laboratoire SYMBIO, Equipe Synthese par voie Organometallique,
´
associe au CNRS (UMR 6178), Faculte des Sciences et Techniques de
´
´ ˆ
Saint Jerome, Avenue Escadrille Normandie-Niemen, 13397, Marseille
Cedex 20, France
ABSTRACT
An efficient method of synthesis of 1-tetralones has been achieved
featuring a Stille cross-coupling reaction as the key step.
Key Words: Friedel–Crafts acylation; Stille cross-coupling reaction;
1-Tetralone.
*
´ ˆ
Correspondence: Jerome Thibonnet, Laboratoire de Physicochimie des Interfaces et
´
´
des Milieux Reactionnels, Faculte des Sciences et Techniques de Tours, Parc de Grand-
mont, 37200, Tours, France; Tel.: 33 (0)2 47 36 73 59; Fax: 33 (0)2 47 36 70 40;
E-mail: jerome.thibonnet@univ-tours.fr.
3751
DOI: 10.1081/SCC-200032474
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com
Copyright # 2004 by Marcel Dekker, Inc.

3752
Vercouillie et al.
The efficient preparation of functionalized cyclic structures is important in
the search for small bioactive molecules. In particular, 1-tetralones constitute an
important class of starting materials and intermediates for the synthesis of bio-
logically active substances,[1] and they are also found in natural products.[2]
Numerous methods have been reported over a period of time for the syn-
thesis of these structures. Classical means for the synthesis of 1-tetralones
include intramolecular Friedel–Crafts reaction of 4-arylbutyric acids and its
variants.[3] 1-Tetralones can also be prepared by radical cyclization, in the
presence of stoichiometric amounts of lauryl peroxide,[4] or by palladium-
catalyzedcyclizationofappropriatelysubstitutedv-(2-iodoaryl)alkanenitriles.[5]
We previously described the synthesis of 2 and demonstrated its efficiency
in transferring but-3-enoic-d4 acid synthons onto miscellaneous substrates.[6]
To broaden the use of 2 in synthesis, we planned to prepare 1-tetralones
from aryl halides using Stille and intramolecular Friedel–Crafts acylation.
The required organotin precursor 2 was easily obtained by radical hydro-
stannation[7] of but-3-ynoic acid 1 (prepared via carbonation of the correspond-
ing allenylmagnesium bromide)[8] as a thermodynamic mixture (E/Z ¼ 85/15)
with 83% yield (Sch. 1). It should be noted that the radical hydrostannation con-
ducted at a lower temperature (e.g., in benzene) led to a 50/50 mixture of 2 and
its internal isomer 3. Our investigation began with the coupling of 2 with
organic halides under standard Stille conditions (Sch. 2).[9]
Various catalysts were tested in order to find optimal experimental con-
ditions, and we found that tetrakis(triphenylphosphine)palladium was the
most efficient for 2. Good yields of homocinnamic acids (4a–m) were
obtained with aryl halides (55–92%). When the thermodynamic mixture of
E/Z ¼ 85/15 was used for cross-coupling with organic halides, the crude
mixture was found to contain a small amount of Z (,12%) that was eliminated
during the crystallization process. The temporary protection of the carboxylic
acid function was removed by simple hydrolysis at room temperature with 1 M
HCl/water or by stirring on silica gel. These results demonstrate the efficiency
of 2 to obtain the homocinnamyl skeleton cleanly.
Taking into account the numerous applications of compounds 4, we
decided to report an alternative and fairly general route to substituted 1-tetra-
lones involving intramolecular Friedel–Crafts acylation (Sch. 3). Selective
reduction of the double bond of the crude products 4 was accomplished
Scheme 1.

Synthesis of 1-Tetralone Derivatives
3753
Scheme 2.
under catalytic hydrogenation conditions using 10% Pd-C[10] at 14.7 psi of
hydrogen at room temperature. 4-Phenylbutyric acids 5 were converted to
1-tetralones 6 by Friedel–Crafts acylation using trifluoroacetic anhydride[11]
(2.0 mole equivalent) in 1,2-dichloroethane (DCE) or methanesulfonic acid
and P2O5.[12] The results are summarized in Table 1.
Finally, 6,7-methylenedioxy-1-tetralone 6h, which is a key intermediate
in the synthesis of ABT 200 f(+) 10Rꢀ, 3Rꢀ)-3-phenyl-1-[10, 20, 30, 40-tetra-
hydro-50,60-methylene-dioxy-10-naphthalenyl-methyl]-pyrrolidineg, an a-2
antagonist and a norepinephrine uptake inhibitor (3e), was synthesized by
this procedure (Fig. 1).
In conclusion, a convenient procedure has been developed for the synthesis
of 1-tetralones using the Stille cross-coupling between a functional vinyltin
reagent and aryl halides as key step. The method appears to be general and
compatible with different substitution patterns in the aromatic moiety.
EXPERIMENTAL SECTION
General Methods
All reactions were performed in oven-dried glassware under positive
argon pressure. Toluene was dried and freshly distilled from sodium.
1H-NMR spectra were recorded at 200 MHz or at 300 MHz using CDCl3
Scheme 3.

3754
Vercouillie et al.
Table 1. Synthesis of 1-tetralones.
Organic Halide 1-Tetralone
Entry
1
Number
Yield (%)
90a
Ph-I
6a
6b
6c
6d
6e
6fa
6g
2
3
4
5
6
7
p-F-Ph-Br
89a
94a
90a
87b
75b
85a
p-MeO-Ph-Br
p-Acetyl-Ph-Br
p-CF3-Ph-Br
p-Br-Ph-Br
8
6h
78a
9
6i
6j
80b
10
83b
(continued)

Synthesis of 1-Tetralone Derivatives
Table 1. Continued.
1-Tetralone
3755
Entry
11
Organic Halide
Number
Yield (%)
72b
6k
12
13
1-Bromonaphthalene
2-Bromobiphenyl
6l
82b
70b
6m
a(CF3CO)2O, DCE, 0 8C, 2 h.
bP2O5, MeSO3H, rt, 2 h.
as solvent. Results, reported using the residual proton resonance of CDCl3
(dH ¼ 7.25 ppm) as the internal reference, were as follows (in order):
chemical shift (d in ppm relative to Me4Si), multiplicity (s, d, t, q, quint, m,
b for singlet, doublet, triplet, quartet, quintuplet, multiplet and broad), and
coupling constants (J in Hz). 13C-NMR spectra were recorded at 50 MHz or
75 MHz using CDCl3 solvent peak at dC ¼ 77.0 ppm as the reference. Electron
impact mass spectra were measured at 70 eV by gas chromatography-mass
spectrometry (GC-MS) or direct introduction mode. Raman spectra were
recorded on a Bruker RFS 100 and excitation with a laser Nd: YAG
Figure 1. Structure of ABT-200: an alpha-2 antagonist and a norepinephrine uptake
inhibitor.

3756
Vercouillie et al.
(1064nm, 130 mW). Infrared (IR) spectra were recorded on a Perkin Elmer
Spectrum One Fourier transform infrared (FT-IR) spectrophotometer. Melting
points were taken on a Bu¨chi B-540 and are uncorrected. Standard column
˚
chromatography was performed on Merck silica gel (60A, 230–400 mesh
silica gel) by flash column chromatography techniques. Analytical thin-layer
chromatography (TLC) was conducted on Merck precoated silica gel 60 F254
plates. Tributyltin hydride was commercialy available (from Aldrich). Acid 1
was prepared by a previously reported procedure.[8] The preparation of tributyl-
stannyl-4-tributylstannylbut-3-enoate 2 has already been described.[6c]
General Procedure for the Preparation of Substituted
Homocinnamic Acids 3a–m
Toluene (20 mL), 2 (7 mmol), aryl bromide (5.8 mmol), and tetrakis(triphe-
nylphosphine)palladium (3 mol%) were introduced into a 50 mL flask. The
mixture was degassed under vacuum and stirred overnight at 1008C. After
cooling, the stannyl ester was hydrolyzed with 10 mL of 1 M HCl solution.
After extraction with diethylether, the organic layer was treated with 1 M NaOH
solution. The aqueous layer was washed with Et2O and then acidified with 1 M
HCl solution and extracted with Et2O. After removal of the solvents under
reduced pressure, compounds 4 were obtained by crystallization from petroleum
ether/Et2O (95/5) or by column chromatography on silica gel with first petroleum
ether/Et2O (99/1) as eluent, then elution with petroleum ether/Et2O (80/20).
(E)-4-[(8,9-Methylenedioxy)phenyl]but-3-enoic acid (4g)
Mp: 1158C. IR (KBr): 3018, 1689, 1604, 1257, 1230. RAMAN: 1617, 1603.
1H-NMR (d ppm): 3.30 (d, J ¼ 7 Hz, 2H), 6.00 (s, 2H), 6.14 (dt, J ¼ 15.8 Hz,
J ¼ 7 Hz, 1H), 6.46 (d, J ¼ 15.8 Hz, 1H), 6.76–6.86 (m, 2H), 6.96–7.00
(m, 1H), 8.55 (bs, 1H). 13C-NMR (d ppm): 38.3, 101.5, 106, 108.7, 119.4,
121.4, 131.5, 133.9, 147.7, 148.4, 178.4. MS (70 eV, EI) m/z: 206 (Mþ, 91),
161 (32), 132 (11), 131 (100), 104 (10), 103 (85), 102 (15), 77 (32), 51 (15), 45 (12).
(E)-4-[(6,7-Methylenedioxy)phenyl]but-3-enoic acid (4h)
IR: 3018, 1711, 1655, 1288. 1H-NMR (d ppm): 3.35 (d, J ¼ 4.8 Hz, 2H),
6.03 (s, 2H), 6.48–6.55 (m, 2H), 6.75–6.85 (m, 3H), 11.52 (bs, 1H).
13C-NMR (d ppm): 38.4, 100.8, 107.4, 120.6, 121.5, 123.8, 128.3, 119,
144.5, 147.6, 177.9. MS (70 eV, EI) m/z: 206 (Mþ, 100), 161 (40), 132
(14), 131 (91), 104 (14), 103 (94), 102 (17), 78 (10), 77 (42), 76 (12), 75
(11), 63 (14), 51 (21), 50 (10), 45 (18).

Synthesis of 1-Tetralone Derivatives
3757
(E)-4-(4-Fluoro-2-methylphenyl)but-3-enoic acid (4i)
Mp: 96–978C. IR (KBr): 3054, 1711, 1609, 1585, 1266. 1H-NMR (d ppm):
2.35 (s, 3H), 3.35 (dd, J ¼ 7.1 Hz, J ¼ 1.4 Hz, 2H), 6.14 (dt, J ¼ 15.7 Hz,
J ¼ 7.1 Hz, 1H), 6.69 (d, J ¼ 15.7 Hz, 1H), 6.85–6.95 (m, 2H), 7.44 (dd,
J ¼ 9.3 Hz, J ¼ 5.9 Hz, 1H), 9.70 (bs, 1H). 13C-NMR (d ppm): 19.8, 38.2, 112.9
(d, JC-F ¼ 22 Hz), 116.7 (d, JC-F ¼ 21 Hz), 122.0, 121.3 (d, JC-F ¼ 8.6 Hz),
130.8, 137.5 (d, JC-F ¼ 7.6 Hz), 162.1 (d, JC-F ¼ 246 Hz), 177.6. MS (70 eV, EI)
m/z: 194 (Mþ, 52), 150 (12), 149 (100), 147 (13), 134 (32), 133 (30), 109 (41).
(E)-4-(4-Cyano-3-methylphenyl)but-3-enoic acid (4j)
Mp: 95–978C. IR (KBr): 3056, 1713, 1606, 1266. 1H-NMR (d ppm): 2.57
(s, 3H), 3.38 (d, J ¼ 5.8 Hz, 2H), 5.42 (dt, J ¼ 16.0 Hz, J ¼ 6.3 Hz, 1H), 6.62
(d, J ¼ 16.0 z, 1H), 7.22–7.34 (m, 2H), 7.58 (d, J ¼ 8.0 Hz, 1H), 8.90 (bs,
1H). 13C-NMR (d ppm): 20.4, 37.9, 111.4, 118.1, 124.0, 124.6, 127.9,
132.5, 132.7, 140.8, 142.2, 173.3. MS (70 eV, EI) m/z: 201 (Mþ 49), 159
(27), 157 (13), 156 (100), 154 (12), 142 (15), 141 (17), 140 (24), 130 (13),
129 (49), 128 (19), 127 (20), 116 (22), 115 (18), 77 (18), 51 (14), 39 (17).
(E)-4-(3,4-Dichlorophenyl)but-3-enoic acid (4k)
1
Mp: 708C. IR (KBr): 3056, 1710, 1554, 1293. H-NMR (d ppm): 3.34
(d, J ¼ 6.6 Hz, 2H), 6.32 (dt, J ¼ 15.9 Hz, J ¼ 6.6 Hz, 1H), 6.47
(d, J ¼ 15.9 Hz, 1H), 7.23 (dd, J ¼ 8.3 Hz, J ¼ 1.8 Hz, 1H), 7.41
(d, J ¼ 8.3 Hz, 1H), 7.49 (d, J ¼ 1.8 Hz, 1H), 9.25 (bs, 1H). 13C-NMR (d
ppm): 37.8, 122.9, 125.5, 128.0, 130.5, 131.4, 131.7, 132.7, 136.7, 177.4.
MS (70 eV, EI) m/z: 234 (Mþ, 7), 232 (Mþ, 39), 230 (Mþ, 61), 188 (20),
187 (59), 186 (11), 185 (93), 152 (25), 151 (78), 149 (59), 116 (15), 115
(100), 114 (19), 75 (18), 74 (14), 63 (19), 39 (19).
General Procedure for the Hydrogenation Acids 4a–m
Pd/C (0.24 mmol, 10% mol) was added to a solution of 4 (2.4 mmol) in
dry tetrahydrofuran (THF) (20 mL) in a dried, two-necked, 50 mL round-
bottomed flask equipped with a magnetic stir bar, rubber septum cap, and H2-
filled balloon. The resulting suspension was stirred at room temperature for 3 h
under a current of hydrogen. Insoluble materials were removed by filtration,
and the filtrate was concentrated in vacuo to give a residue that was purified
by column chromatography (silica gel, petroleum ether/Et2O ¼ 90/10) to give 5.

3758
Vercouillie et al.
4-[(7,8-Methylenedioxy)phenyl]butanoic acid (5g)
1
IR: 3034, 1706, 1602, 1257. H-NMR (d ppm): 1.96 (tt, J ¼ 7.2 Hz,
J ¼ 7.5 Hz, 2H), 2.40 (t, J ¼ 7.2 Hz, 2H), 2.63 (t, J ¼ 7.5 Hz, 2H), 5.96
(s, 2H), 6.69–6.79 (m, 3H), 10.15 (bs, 1H). 13C-NMR (d ppm): 26.3, 33.1,
34.6, 100.7, 108.1, 108.8, 121.2, 134.9, 145.7, 147.5, 180. MS (70 eV, EI)
m/z: 208 (Mþ, 36), 148 (58), 136 (11), 135 (100), 105 (10), 79 (12), 77
(42), 63 (10), 51 (33), 50 (10), 45 (12).
4-[(6,7-Methylenedioxy)phenyl]butanoic acid (5h)
1
IR: 3084, 3043, 1703, 1631, 1278, 1259. H-NMR (d ppm): 2.02 (tt,
J ¼ 7.3 Hz, J ¼ 7.4 Hz, 2H), 2.44 (t, J ¼ 7.3 Hz, 2H), 2.70 (t, J ¼ 7.4 Hz,
2H), 5.97 (s, 2H), 6.68–6.84 (m, 3H), 10.5 (bs, 1H). 13C-NMR (d ppm):
24.3, 28.5, 33.2, 100.4, 106.6, 121.4, 122.4, 128.2, 145.6, 145.9, 179.5. MS
(70 eV, EI) m/z: 208 (Mþ, 65), 149 (10), 148 (100), 136 (10), 135 (59), 105
(16), 91 (18), 79 (17), 78 (11), 77 (54), 51 (41), 50 (12), 45 (21).
4-(4-Fluoro-2-methylphenyl)butanoic acid (5i)
Mp: 548C. IR (KBr): 3055, 1709, 1612, 1591, 1266. 1H-NMR (d ppm): 1.94
(quint, J ¼ 7.3 Hz, 2H), 2.34(s, 3H), 2.46(t, J ¼ 7.3 Hz, 2H), 2.67(t, J ¼ 7.3 Hz,
2H), 6.78–6.96 (m, 2H), 7.11 (dd, J ¼ 6.1 Hz, J ¼ 7.8 Hz, 1H), 10.50 (bs, 1H).
13C-NMR (d ppm): 19.3, 25, 31.6, 33.5, 112.9 (d, JC-F ¼ 22Hz), 116.7 (d, JC-
¼ 21Hz), 122.0, 121.3 (d, JC-F ¼ 9 Hz), 130.8, 137.5 (d, JC-F ¼ 8 Hz), 162.1
F
(d, JC-F ¼ 246 Hz), 177.6. MS (70 eV, EI) m/z: 196 (Mþ, 27), 137 (13), 136
(81), 135 (22), 124 (11), 123 (100), 103 (15), 77 (16).
4-(4-Cyano-3-methylphenyl)butanoic acid (5j)
Mp: 61–628C. IR (KBr): 3056, 1710, 1611, 1209. 1H-NMR (d ppm): 2.00
(quint, J ¼ 7.3 Hz, 2H), 2.43 (t, J ¼ 7.3 Hz, 2H), 2.56 (s, 3H), 2.73
(t, J ¼ 7.3 Hz, 2H), 7.13 (d, J ¼ 7.9 Hz, 1H), 7.18 (s, 1H), 7.56
(d, J ¼ 7.9 Hz, 1H), 10.90 (bs, 1H). 13C-NMR (d ppm): 20.4, 25.6, 33.1,
35.0, 110.4, 118.3, 126.4, 130.4, 132.6, 142.1, 146.6, 179.0. MS (70 eV, EI)
m/z: 203 (Mþ, 16), 145 (12), 144 (100), 143 (51), 130 (23), 116 (13), 115
(13), 103 (24), 77 (31), 63 (13), 60 (45), 51 (17), 44 (28), 39 (22), 36 (18).
4-(3,4-Dichlorophenyl)butanoic acid (5k)
1
Mp: 71–728C. IR (KBr): 3056, 3034, 1708, 1563, 1212. H-NMR (d
ppm): 1.98 (quint, J ¼ 7.3 Hz, 2H), 2.42 (t, J ¼ 7.3 Hz, 2H), 2.68

Synthesis of 1-Tetralone Derivatives
3759
(t, J ¼ 7.3 Hz, 2H), 7.06 (dd, J ¼ 7.4 Hz, J ¼ 2.0 Hz, 1H), 7.32 (d, J ¼ 2.0 Hz,
1H), 7.40 (d, J ¼ 7.4 Hz, 1H), 10.75 (bs, 1H). 13C-NMR (d ppm): 25.8, 30.1,
34.0, 127.9, 130.0, 130.3, 130.4, 132.3, 141.4, 179.7. MS (70 eV, EI) m/z: 234
(Mþ, 15), 232 (Mþ, 20), 174 (65), 173 (20), 172 (100), 161 (21), 159 (32), 89
(17), 60 (59).
Cyclization
1. A solution of (CF3CO)2O (1.92 mmol, 270 mL) in 1,2-dichlor-
oethane (4 mL) was added dropwise to
a solution of 5
(0.96 mmol) in dry 1,2-dichloroethane (2 mL) at 08C. The mixture
was stirred at room temperature for 2 h. The mixture was concen-
trated under reduced pressure on a rotary evaporator, and the
crude product was purified by column chromatography (petroleum
ether/Et2O ¼ 80/20) yielded 6.
2. Acid 5 (3 mmol) was added to a mixture of P2O5 (1.09 g, 7.56 mmol)
in CH3SO3H (10.95 g, 114 mmol). The solution was stirred at room
temperature for 12 h and then poured over 37 g of ice. The mixture
was extracted with CH2Cl2 (3 ꢁ 20 mL), and the combined organic
layers were dried over MgSO4, filtered, and concentrated under
reduced pressure to give 6.
6,7-Methylenedioxy-1-tetralone (6g)
1
Mp: 133–1348C. IR (KBr): 3080, 1676, 1620, 1584, 1283. H-NMR (d
ppm): 2.14 (quint, J ¼ 6.3 Hz, 2H), 2.64 (t, J ¼ 6.4 Hz, 2H), 2.87
(t, J ¼ 6 Hz, 2H), 6.08 (s, 2H), 6.80 (d, J ¼ 8.3 Hz, 1H), 7.72 (d, J ¼ 8.3 Hz,
1H). 13C-NMR (d ppm): 22.5, 22.7, 38.7, 101.8, 106.8, 123.0, 125.2, 127.5,
144.4, 151, 196. MS (70 eV, EI) m/z: 190 (Mþ, 82), 175 (13), 163 (10),
162 (100), 134 (49), 81 (11), 78 (14), 77 (14), 76 (13), 51 (12).
7,8-Methylenedioxy-1-tetralone (6h)
Mp: 74–758C. IR (KBr): 3067, 1672, 1620, 1500, 1265, 1248. 1H-NMR
(d ppm): 2.16 (quint, J ¼ 6.4 Hz, 2H), 2.68 (t, J ¼ 6.9 Hz, 2H), 2.96
(t, J ¼ 6.1 Hz, 2H), 5.92 (s, 2H), 6.57 (s, 1H), 7.35 (s, 1H). 13C-NMR (d
ppm): 23.3, 29.8, 38.4, 101.4, 105.8, 107.7, 127.1, 141.2, 146.6, 151.8,
196.4. MS (70 eV, EI) m/z: 190 (Mþ, 100), 175 (10), 162 (64), 148 (11),
134 (94), 104 (19), 77 (15), 76 (26), 51 (13).

3760
Vercouillie et al.
5-Methyl-7-fluoro-1-tetralone (6i)
IR: 3055, 3022, 1686, 1606, 1266. 1H-NMR (d ppm): 2.17 (quint,
J ¼ 6.7 Hz, 2H), 2.34 (s, 3H), 2.70 (t, J ¼ 6.1 Hz, 2H), 2.85 (t, J ¼ 6.1 Hz,
2H), 7.12 (dd, J ¼ 9 Hz, J ¼ 2.8 Hz, 1H), 7.60 (dd, J ¼ 9 Hz, J ¼ 2.8 Hz,
1H). 13C-NMR (d ppm): 19.5, 22.4, 25.8, 38.2, 110.7 (d, JC-F ¼ 22 Hz),
122.1 (d, JC-F ¼ 22 Hz), 134.0 (d, JC-F ¼ 6.5 Hz), 139.0 (d, JC-F ¼ 7 Hz),
139.2, 160.9 (d, JC-F ¼ 246 Hz), 199. MS (70 eV, EI) m/z: 178 (Mþ, 56),
163 (26), 149 (54), 136 (21), 135 (18), 133 (20), 123 (12), 122 (11), 121
(21), 109 (12), 101 (22), 96 (30), 75 (19), 63 (14), 51 (23), 39 (23).
6-Methyl-7-cyano-1-tetralone (6j)
1
Mp: 131–1328C. IR (KBr): 3055, 2226, 1688, 1610, 1266. H-NMR (d
ppm): 2.17 (quint, J ¼ 6 Hz, 2H), 2.58 (s, 3H), 2.70 (t, J ¼ 6 Hz, 2H), 2.85
(t, J ¼ 6 Hz, 2H), 7.27 (s, 1H), 8.26 (s, 1H). 13C-NMR (d ppm): MS (70
eV, EI) m/z: 185 (Mþ, 41), 157 (100), 129 (51), 128 (19), 103 (16), 102
(25), 101 (11), 77 (19), 76 (14), 63 (20), 51 (26), 50 (14), 39 (30).
6,7-Dichloro-1-tetralone (6k)
1
Mp: 958C. IR (KBr): 3054, 1690, 1591, 1267. H-NMR (d ppm): 2.15
(quint, J ¼ 6.3 Hz, 2H), 2.65 (t, J ¼ 6.3 Hz, 2H), 2.93 (t, J ¼ 6.3 Hz, 2H),
7.37 (s, 1H), 8.05 (s, 1H). 13C- NMR (d ppm): 22.8, 28.8, 38.5, 128.9,
130.6, 131.2, 132, 137.5, 143.7, 196.1. MS (70 eV, EI) m/z: 218 (Mþ, 7),
216 (Mþ, 43), 214 (Mþ, 67), 201 (90), 199 (30), 188 (60), 187 (14), 186
(96), 79 (27), 160 (50), 158 (82), 151 (16), 149 (16), 125 (33), 123 (100),
116 (27), 115 (52), 114 (15), 99 (17), 97 (22), 89 (19), 88 (15), 87 (34), 86
(24), 85 (14), 75 (43), 74 (45), 73 (43), 63 (62), 62 (47), 57 (35), 56 (15),
55 (28), 51 (27), 50 (29), 39 (60).
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Received in the UK February 1, 2004