Reactions of β-ethylsulfanylpropionyl tetrafluoroborate with electron-rich aromatics: A novel synthesis of aryl vinyl ketones

Article abstract of DOI:10.1055/s-1998-1993

A new synthesis of aryl vinyl ketones is described. The acylation of active aromatics with the complex of β-ethylsulfanylpropionyl fluoride 1 and boron trifluoride leads to formation of 1-aryl-3-(ethylsulfanyl)propan-1-ones. Subsequent methylation with methyl triflate and elimination with an aqueous solution of KHCO₃ results in formation of aryl vinyl ketones in 86-99% yield.

Full text of DOI:10.1055/s-1998-1993

January 1998
SYNTHESIS
89
b
Reactionsof -EthylsulfanylpropionylTetrafluoroboratewithElectron-RichAromatics:
A Novel Synthesis of Aryl Vinyl Ketones
Mikhail V. Lebedev, Valentine G. Nenajdenko,* Elizabeth S. Balenkova*
Department of Chemistry, Moscow State University, 119899 Moscow, Russia
Fax +7(095)9328846; E-mail: Nen@ acylium.chem.msu.su
Received 30 April 1997; revised 14 July 1997
A new synthesis of aryl vinyl ketones is described. The acylation of
active aromatics with the complex of b-ethylsulfanylpropionyl fluo-
ride 1 and boron trifluoride leads to formation of 1-aryl-3-
(ethylsulfanyl)propan-1-ones. Subsequent methylation with methyl
triflate and elimination with an aqueous solution of KHCO3 results in
formation of aryl vinyl ketones in 86–99 % yield.
Vinyl ketones have been widely used in synthesis as excel-
lent Michael acceptors, dienophiles and monomers.1 Differ-
ent aryl vinyl ketones and their derivatives such as
ArC(O)CH2CH2R, R = Cl, Me2N, MeS, Me2S+, Ph3P+, are ef-
fective as microbiocides with good environmental pro-
perties.2
ones 4a–n in high yields. We have found that the reaction
There are different methods of synthesis of aryl vinyl ke- proceeds regioselectively and it is very sensitive to elec-
tones including pyrolysis of b-dialkylaminocarbonyl tronic and steric factors. This can be illustrated by the re-
compounds and their quaternary salts, oxidation of allylic actions of anisole and para-methylanisole: the reaction
alcohols, base-induced elimination of HHal from b-halo- with anisole afforded 83% of para-substituted anisole 4a
propenones, and oxidative decarboxylation of g-oxo car- and no ortho-substituted product was observed, in the
boxylic acids with lead tetraacetate in the presence of case of para-methylanisole the only product was ortho-
cupric acetate.3 Nevertheless, the direct acylation of aro- (3-ethylsulfanylpropionyl)-para-methylanisole (4e), but
matics with acryloyl chloride leading to aryl vinyl ketones it was obtained in 30% yield. Analogously, the reaction
is not described.
with 1,2- and 1,3-dimethoxybenzene proceeds in high
yields whereas the reaction with 1,4-dimethoxybenzene,
which has a similar structure and nucleophilicity, leads to
formation of the corresponding ketone 4d only in 18%
yield. We believe that the reaction is regiospecific due to
complex 2 being in the form of four-membered cyclic
Now we report a new efficient method of synthesis of aryl
vinyl ketones. Recently we have proposed a new reagent,
the complex of b-ethylsulfanylpropionyl fluoride and bo-
ron trifluoride, which is supposed to exist in the form of
acylsulfonium salt (Scheme 1).4,5
¢
acylsulfonium salt 2 , and therefore there are considerable
When studying the properties of complex 2, we have steric requirements for the acylation transition state to oc-
found that it reacts with different electron-rich aromatic cur.
compounds. We have performed the reaction of 2 with
Recently it has been found that acylsulfonium salts are ef-
various aromatic and heteroaromatic compounds (Scheme
ficient reagents for acylation6 and perfluoroacylation7 of
2).
various unsaturated hydrocarbons including the aromatic
ones. It was reported that acetylsulfonium and trifluoro-
acetylsulfonium tetrafluoroborates react mildly with aro-
The acylation takes place under mild conditions to give
the corresponding 1-(2-aryl)-3-(ethylsulfanyl)propan-1-

90
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SYNTHESIS
fluoromethanesulfonic acid (Merck). b-(Ethylsulfanyl)propionyl flu-
oride was prepared according to the literature procedure4 from 3-sulf-
anylpropionic acid (Aldrich).
matic compounds to give the corresponding acetyl and
trifluoroacetyl arenes and hetarenes. However, the
authors8 failed to introduce acetyl or trifluoroacetyl func-
tions into anisole. The complex 2 is slightly more active
than dimethylacylsulfonium salts, it reacts with anisole
and para-methylanisole. Attempts to perform the acyla-
tion of less active aromatics such as toluene, xylenes,
mesitylene and anthracene were unsuccessful. Perhaps in
the last case the reaction does not take place because of
steric reasons.
1-(2-Aryl)-3-(ethylsulfanyl)propan-1-ones; General Procedure:
A well-stirred solution of b-(ethylsulfanyl)propionyl fluoride (1)
(2.72 g, 0.02 mol) in CH2Cl2 (40 mL) was saturated by gaseous BF3
at –60°C. A solution of aromatic compound 3a–n (0.02 mol) in
CH2Cl2 (10 mL) was added dropwise. After stirring for 15 min at
–40°C the temperature was allowed to rise to 0°C and the mixture
was stirred for 2 h at this temperature. Sat. aq KHCO3 (40 mL) was
then added. The organic layer was separated, the aqueous layer was
extracted with Et2O (2 × 50 mL). The combined organic phases were
dried (Na2SO4), filtered and concentrated at reduced pressure. The
crude product was purified by passing through a short column with
silica gel in hexane/EtOAc (9/1).
Our attempts to carry out the reaction with different pyr-
roles and indoles failed. The complex 2 quickly decom-
poses even at –60°C in the presence of nitrogen-
containing heteroaromatic compounds. We suppose that
the recoordination of boron trifluoride from the complex
2 to nitrogen of the substrate occurs.
3-(Ethylsulfanyl)-1-(4-methoxyphenyl)propan-1-one (4a): colorless
oil, yield; 3.72 g (83%).
IR (Nujol): n = 1690 (CO).
We have investigated the transformation of the obtained
1-aryl 3-(ethylsulfanyl)propan-1-ones 4a–n into the aryl
vinyl ketones 5a–n. As a result we elaborated the two-step
synthesis of aryl vinyl ketones from the corresponding ar-
omatics: the first step: acylation with b-ethylsulfanylpro-
pionyl fluoride and boron trifluoride complex 2; the
second step: S-methylation of 1-aryl-3-(ethylsulfanyl)-
propan-1-ones 4a–n and elimination of ethyl methyl sul-
fide by treatment with an aqueous solution of KHCO3.
1H NMR: d = 1.27 (t, 3H, J = 7.2 Hz, CH2CH3), 2.58 (q, 2H, J =
7.2 Hz, CH2CH3), 2.90 (t, 2H, J = 7.2 Hz, CH2CH2S), 3.21 (t, 2H, J
= 7.2 Hz, COCH2), 3.85 (s, 3H, CH3O), 6.92 (d, 2H, J = 8.8 Hz,
Harom-3, 5), 7.93 (d, 2H, J = 8.8 Hz, Harom-2, 6).
13C NMR: d = 14.58, 25.87, 26.12, 38.43, 55.28, 113.59, 129.54,
l30.11, 163.39, 196.76.
C12H16O2S: Calc. C 64.25, H 7.19; Found: C 64.68, H 7.12.
1-(3,4-Dimethoxyphenyl)-3-(ethylsulfanyl)propan-1-one (4b): color-
It was found that yields of aryl vinyl ketones depended on
the nature of the methylating reagent used. We have stud-
ied the methylation with methyl triflate, methyl sulfate
and methyl iodide. The highest yields of aryl vinyl ke-
tones were obtained when methyl triflate was used. In this
case the target products were easily isolated after stirring
with aqueous KHCO3 (the products were purified by pass-
ing through a short column with silica gel). Methyl sulfate
and methyl iodide also gave good yields, but reactions
proceeded more slowly (two days) and the purification of
products required column chromatography since the vinyl
ketones had some impurities.
less needles, yield; 4.37 g (86%), mp 75–76 °C (hexane).
IR (Nujol): n = 1690 (CO).
1H NMR: d = 1.28 (t, 3H, J = 7.2 Hz, CH2CH3), 2.59 (q, 2H, J =
7.2 Hz, CH2CH3), 2.92 (t, 2H, J = 7.2 Hz, CH2CH2S), 3.23 (t, 2H, J
= 7.2 Hz, COCH2), 3.93 (s, 3H, CH3O), 3.94 (s, 3H, CH3O), 6.89 (d,
1H, J = 8.4 Hz, Harom-5), 7.52 (d, 1H, J = 2.0 Hz, Harom-2), 7.56 (dd,
1H, J = 8.4 Hz, J = 2.0 Hz, Harom-6).
13C NMR: d = 14.78, 26.17, 26.35, 38.49, 56.00, 56.05, 110.05,
122.70, 129.90, 149.07, 153.40, 196.97.
C13H18O3S: Calc. C 61.39, H 7.13; Found: C 61.45, H 7.27.
1-(2,4-Dimethoxyphenyl)-3-(ethylsulfanyl)propan-1-one (4c):
colorless oil, yield; 4.62 g (91%).
We have also investigated the possibility of one-pot syn-
thesis of aryl vinyl ketones. Yield in the reaction with
thiophene was 72% – close to that of the two-step synthe-
sis. Therefore, the complex of b-(ethylsulfanyl)propionyl
fluoride with boron trifluoride 2 can be considered as an
acryloyl cation synthetic equivalent.
IR (Nujol): n = 1680 (CO).
1H NMR: d = 1.25 (t, 3H, J = 7.2 Hz, CH2CH3), 2.55 (q, 2H, J =
7.2 Hz, CH2CH3), 2.84 (t, 2H, J = 7.2 Hz, CH2CH2S), 3.23 (t, 2H, J
= 7.2 Hz, COCH2), 3.78 (s, 3H, CH3O), 3.80 (s, 3H, CH3O), 6.42 (d,
1H, J = 2.0 Hz, Harom-3), 6.51 (dd, 1H, J = 8.4, 2.0 Hz, Harom-5), 7.80
(d, 1H, J = 8.4 Hz, Harom-6).
Inconclusion,wehaveinvestigatedtheacylationofvarious
aromatics with the complex of b-(ethylsulfanyl)propionyl
fluoride/ boron trifluoride. This reaction leads to formation
of 1-aryl-3-(ethylsulfanyl)propan-1-ones 4a–n in good
yields.Thesubsequentmethylationwithmethyltriflateand
elimination with aqueous KHCO3 allows the synthesis of
aryl vinyl ketones 5a–n in excellent yields. The possibility
of one-pot synthesis of aryl vinyl ketones was shown.
13C NMR: d = 14.82, 26.23, 26.38, 43.99, 55.51, 55.53, 98.33,
105.37, 120.72, 132.78, 160.91, 164.62, 198.21.
C13H18O3S: Calc, C 61.39, H 7.13; Found: C 61.17, H 7.57.
1-(2,5-Dimethoxyphenyl)-3-(ethylsulfanyl)propan-1-one (4d):
yellow oil, yield; 0.91 g (18%).
IR (Nujol): n = 1690 (CO).
1H NMR: d = 1.26 (t, 3H, J = 7.3 Hz, CH2CH3), 2.56 (q, 2H, J =
7.3 Hz, CH2CH3), 2.90 (t, 2H, J = 7.2 Hz, CH2CH2S), 3.27 (t, 2H, J
= 7.2 Hz, COCH2), 3.75 (s, 3H, CH3O), 3.79 (s, 3H, CH3O), 6.92 (d,
1H, J = 8,9 Hz, Harom-3), 7.11 (dd, 1H, J = 8.9, 2.9 Hz, Harom-4), 7. 16
(d, 1H, J = 2.9 Hz, Harom-6).
Melting points were determined in sealed capillaries and are uncor-
rected. All yields refer to pure isolated products. NMR spectra were
recorded on Varian VXR-400 and Bruker AM 400C spectrometers in
CDCl3 with TMS as an internal standard. The IR spectra were ob-
tained with UR-20 spectrometer. Column chromatography was per-
formed on silica gel (63-200 mesh, Merck). All solvents used were
dried and distilled according to the standard procedures. Methyl tri-
flate was prepared according to the literature procedure9 from tri-
13C NMR: d = 14.63, 25.54, 26.34, 38.66, 55.89, 112.26, 114.52,
119.35, 124.25, 151.68, 156.71, 203.82.
C13H18O3S: Calc. C 61.39, H 7.13; Found: C 61.01, H 7.44.

January 1998
SYNTHESIS
91
1H NMR: d = 1.27 (t, 3H, J = 7.2 Hz, CH2CH3), 2.60 (br s, 2H,
CH2CH3), 2.71 (br s, 2H, CH2CH2S), 3.42 (t, 2H, J = 7.2 Hz,
3-(Ethylsulfanyl)-1-(2-methoxy-5-methylphenyl)propan-1-one (4e):
colorless oil, yield; 1.43 g (30%).
COCH2), 8.20–7.73 (m, 8H, C16H9), 8.89 (d, 1H, J = 9.4 Hz, Harom
2).
13C NMR: d = 14.85, 26.37, 26.53, 42.51, 123.87, 124.08, 124.70,
124.80, 125.96, 126.09, 126.21, 126.28, 126.90, 129.35, 129.46,
129.57, 130.37, 130.91, 131.62, 133.73, 202.58.
-
IR (Nujol): n = 1690 (CO).
1H NMR: d = 1.26 (t, 3H, J = 7.6 Hz, CH2CH3), 2.28 (s, 3H, CH3),
2.56 (q, 2H, J = 7.6 Hz, CH2CH3), 2.86 (t, 2H, J = 7.2 Hz,
CH2CCH2S), 3.26 (t, 2H, J = 7.2 Hz, COCH2), 3.86 (s, 3H, CH3O),
6.84 (d, 1H, J = 8.4 Hz, Harom-3), 7.24 (dd, 1H, J = 8.4, 2.4 Hz, Harom
4), 7.51 (d, 1H, J = 2.4 Hz, Harom-6).
13C NMR: d = 14.76, 20.22, 26.14, 44.08, 55.58, 111.54, 127.42,
129.92, 130.60, 134.16, 156.68, 200.62.
-
C21H18OS: Calc. C 79.21, H 5.70; Found: C 79.24, H 5.66.
3-(Ethylsulfanyl)-1-(2-thienyl)propan-1-one (4k), colorless oil, yield;
3.45 g (86%).
C13H18O2S: Calc. C 65.61, H 7.61; Found: C 65.34, H 7.71.
IR (Nujol): n = 1700 (CO).
1H NMR: d = 1.22 (t, 3H, J = 7.2 Hz, CH2CH3), 2.51 (q, 2H, J =
7.2 Hz, CH2CH3), 2.88 (t, 2H, J = 7.2 Hz, CH2CH2S), 3.23 (t, 2H, J
= 7.2 Hz, COCH2), 7.08 (dd, 1H, J = 4.9, 3.8 Hz, Harom-4), 7.59 (dd,
1H, J = 4.9, 1.1 Hz, Harom-5), 7.68 (dd, 1H, J = 3.8, 1.1 Hz, Harom-3).
13C NMR: d = 14.66, 26.85, 26,15, 39.51, 128.14, 132.02, 133.83,
143.80, 191.14.
3-(Ethylsulfanyl)-1-(4-methoxy-1-naphthyl)propan-1-one (4f):
colorless oil, yield; 3.68 g (67%).
IR (Nujol): n = 1680 (CO).
1H NMR: d = 1.29 (t, 3H, J = 7.2 Hz, CH2CH3) 2.60 (q, 2H, J = 7.2
Hz, CH2CH3), 2.95 (t, 2H, J = 7.2 Hz, CH2CH2S), 3.28 (t, 2H, J = 7.2
Hz, COCH3), 4.04 (s, 3H, CH3O), 6.76 (d, 1H, J = 8.2 Hz, C10H6),
7.64–7.46 (m, 2H, C10H6), 7.96 (d, 1H, J = 8.2 Hz, C10H6), 8.30 (d,
1H, J = 8.2 Hz, C10H6), 8.91 (d, 1H, J = 8.2 Hz, C10H6).
C9H12OS2: Calc. C 53.97, H 6.04; Found: C 54.14, H 6.08.
1-(5-Bromo-2-thienyl)-3-(ethylsulfanyl)propan-1-one (41): pale
yellow oil, yield; 4.19 g (75%).
13C NMR: d = 14.76, 26.33, 26.68, 41.26, 55.77, 102.0, 122.08,
125.78, 125.81, 125.98, 127.13, 128.66, 130.82, 131.95, 159.16,
200.44.
IR (Nujol): n = 1670 (CO).
1H NMR: d = 1.26 (t, 3H, J = 7.2 Hz, CH2CH3), 2.57 (q, 2H, J =
7.2 Hz, CH2CH3), 2.89 (t, 2H, J = 6.8 Hz, CH2CH2S), 3.12 (t, 2H, J
= 6.8 Hz, COCH2), 7.11 (d, 1H, J = 4.0 Hz, Harom-4), 7.46 (d, 1H, J
= 4.0 Hz, Harom-3).
13C NMR: d = 14.55, 25.71, 26.17, 38.83, 122.72, 131.12, 131.95,
145.18, 189.99.
C16H18O2S: Calc. C 70.04, H 6.61; Found: C 69.86, H 6.59.
1-(2,3-Dihydro-1,4-benzodioxin-6-yl)-3-(ethylsulfanyl)propan-1-
one (4g): colorless oil, yield; 4.14 g (82%).
IR (Nujol): n = 1690 (CO).
1H NMR: d = 1.21 (t, 3H, J = 7.4 Hz, CH2CH3), 2.59 (br s, 2H,
CH2CH3), 2.92 (br s, 2H, CH2CH2S), 3.12 (t, 2H, J = 7.2 Hz,
COCH2), 4.30–4.15 (m, 4H, OCH2CH2O), 6.84 (d, 1H, J = 9.1 Hz,
Harom-5), 7.42 (d, 1H, J = 9.1 Hz, Harom-6), 7.44 (s, 1H, Harom-2).
C9H11BrOS2: Calc. C 38.72, H 3.97; Found: C 38.69, H 3.81.
3-(Ethylsulfanyl)-1-(2-selenophenyl)propan-1-one (4m): colorless
oil, yield; 3.56 g (72%).
13C NMR: d = 14.74, 25.99, 26.25, 38.63, 64.07, 64.65, 117.21,
117.49, 122.05, 130.45, 143.32, 148.10, 196.83.
IR (Nujol): n = 1690 (CO).
1H NMR: d = 1.24 (t, 3H, J = 7.2 Hz, CH2CH3), 2.55 (q, 2H, J =
7.2 Hz, CH2CH3), 2.89 (t, 2H, J = 7.2 Hz, CH2CH2S), 3.20 (t, 2H, J
= 7.2 Hz, COCH2), 7.38 (dd, 1H, J = 5.5, 3.9 Hz, Harom-4), 7.93 (dd,
1H, J = 5.5, 1.2 Hz, Harom-5), 8.38 (dd, 1H, J = 3.9, 1.2 Hz, Harom-3).
13C NMR: d = 14.73, 26.17, 26.27, 39.01, 130.78, 134.37, 140.13,
l50.81, 192.19.
C13H16O3S: Calc. C 61.88, H 6.39; Found: C 62.03, H 6.17.
3-(Ethylsulfanyl)-1-(4-phenoxyphenyl)propan-1-one (4h): colorless
oil, yield; 3.72 g (65%).
IR (Nujol): n = 1690 (CO).
1H NMR: d = 1.25 (t, 3H, J = 7.4 Hz, CH2CH3), 2.56 (q, 2H, J = 7.4
Hz, CH2CH3), 2.89 (t, 2H, J = 7.2 Hz, CH2CH2S), 3.20 (t, 2H, J = 7.2
Hz, COCH2), 7.39–6.96 (m, 7H, C6H5 and Harom-3, 5), 7.91 (d, 2H, J
= 8.9 Hz, Harom-2, 6).
C9H12OSSe: Calc. C 43.47, H 4.89; Found: C 43.52, H 5.01.
3-(Ethylsulfanyl)-1-(ferrocenyl)propan-1-one (4n): brown viscous
oil, yield; 4.84 g (80%).
13C NMR: d = 14.54, 25.71, 26.07, 38.51, 117.05, 119.93, 124.41,
l29.81, 130.08, 131.04, 155.13, 161.81, 196.70.
C17H18O2S: Calc. C 71.30, H 6.33; Found: C 71.16, H 6.43.
IR (Nujol): n = 1680 (CO).
1H NMR: d = 1.24 (t, 3H, J = 7.4 Hz, CH2CH3), 2.55 (q, 2H, J =
7.4 Hz, CH2CH3), 2.85 (t, 2H, J = 7.2 Hz, CH2CH2S), 2.95 (t, 2H, J
= 7.2 Hz, COCH2), 4.17 (s, 5H, C5H5), 4.46 (s, 2H, Harom-3, 4), 4.75
(s, 2H, Harom-2, 5).
3-(Ethylsulfanyl)-1-[4-(phenylsulfanyl)phenyl]propan-1-one
colorless oil, yield; 2.84 g (47%).
(4i):
13C NMR: d = 14.59, 26.68. 26.20, 39.58, 69.00, 69.58, 72.10, 78.41,
IR (Nujol): n = 1690 (CO).
1H NMR: d = 1.25 (t, 3H, J = 7.2 Hz, CH2CH3), 2.57 (q, 2H, J =
7.2 Hz, CH2CH3), 2.89 (t, 2H, J = 7.2 Hz, CH2CH2S), 3.19 (t, 2H. J
= 7.2 Hz, COCH2), 7.19 (d, 2H, J = 8.40 Hz, Harom-3, 5), 7.51–7.37
(m, 5H, C6H5), 7.81 (d, 2H, J = 8.40 Hz, Harom-2, 6).
201.98.
C15H18FeOS: Calc. C 59.62, H 6.00; Found: C 59.55, H 6.02.
1-Arylprop-2-en-1-ones; General Procedure:
13C NMR: d = 14.75, 25.89, 26.35, 38.83, 127.43, 128.59, 128.82,
129.68, 131.95, 133.91, 145.16, 197.35.
A
solution of l-(2-aryl)-3-(ethylsulfanyl)propan-1-one 4a–n
(0.01 mol) in CH2Cl2 (15 mL) was cooled to 0°C. Methyl triflate
(1.64 g, 0.01 mol) dissolved in CH2Cl2 (5 mL) was added dropwise.
The mixture was stirred at r.t. until the starting 4a–n disappeared
(controlled by TLC). Then sat. aq KHCO3 (20 mL) was added and
the mixture was stirred for an additional 2 h. The organic layer was
separated, the aqueous layer was extracted with CH2Cl2 (2 × 10 mL).
The combined organic phases were dried (Na2SO4), filtered and
C17H18OS2: Calc. C 67.51, H 6.00; Found: C 67.87, H 5.58.
3-(Ethylsulfanyl)-1-(1-pyrenyl)propan-1-one (4j): yellow powder,
yield; 2.87 g (45%), mp 90–93 °C (hexane).
IR (Nujol): n = 1680 (Co).

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Papers
SYNTHESIS
13C NMR: d = 123.71, 124.12, 124.49. 124.68, 125.84, 126.02,
l26.21, 126.44, 126.92, 129.04, 129.16, 129.44, 130.40, 130.88,
131.10, 132.24, 133.30, 137.05, 195.78.
concentrated at reduced pressure. The crude product was purified by
passing through a short column with silica gel in hexane/EtOAc,
(9/1).
C19H12O: Calc. C 89.04, H 4.72; Found: C 89.14, H 4.69.
1-(4-Methoxyphenyl)prop-2-en-1-one (5a): colorless oil, yield; 1.61 g
(99%).
1-(2-Thienyl)prop-2-en-1-one (5k): colorless oil, yield; 1.37 g (99%).
IR (Neat): n = 1660 (CO).
1H NMR: d = 5.86 (dd, 1H, J = 10.4, 1.6 Hz, H-3), 6.48 (dd, 1H, J =
16.9, 1.6 Hz, H-3), 7.08 (dd, 1H, J = 16.9, 10.4 Hz, H-2), 7.16 (dd,
1H, J = 4.9, 3.7 Hz, Harom-4), 7.68 (dd, 1H, J = 4.9, 1.1 Hz, Harom-5),
7.78 (dd, 1H, J = 3.7, 1.1 Hz, Harom-3).
IR spectrum was identical to lit.10
1H NMR: d = 3.83 (s, 3H, CH3O), 5.84 (dd, 1H, J = 10.5, 1.6 Hz, H-
3), 6.39 (dd, 1H, J = 17.0, 1.6 Hz, H-3), 6.94 (d, 2H, J = 8.7 Hz, Harom
3, 5), 7.16 (dd, 1H, J = 17.0, 10.5 Hz, H-2), 7.92 (d, 2H, J = 8.7 Hz,
Harom-2, 6).
13C NMR: d = 55.36, 113.77, 129.03, 130.89, 132.03, 163.48, 188.97.
-
13C NMR: d = 128.13, 129.19, 131.69, 132.30, 134.17, 144.39,
182.20.
1-(3,4-Dimethoxyphenyl)prop-2-en-1-one (5b): colorless oil, yield;
1.91 g (99%).
C7H6OS: Calc. C 60.84, H 4.38; Found: C 60.99, H 4.42.
IR spectrum was identical to lit.10
1-(5-Bromo-2-thienyl)prop-2-en-1-one (5l): pale yellow oil, yield;
1H NMR: d = 3.90 (s, 6H, 2xCH3O), 5.86 (dd, 1H, J = 10.5, 1.8 Hz,
H-3), 6.38 (dd, 1H, J = 17.0, 1.8 Hz, H-3), 6.85 (d, 1H, J = 9.2 Hz,
Harom-5), 7.14 (dd, 1H, J = 17.0, 10.5 Hz, H-2), 7.52 (s, 1H, Harom-2),
7.56 (d, 1H, J = 9.2 Hz, Harom-6).
13C NMR: d = 55.82, 55.91, 109.84, 110.59, 123.25, 129.01, 130.22,
l31.75, 149.07, 153.26, 188.86.
2.08 g (96%).
IR (Nujol): n = 1660 (CO).
1H NMR: d = 5.86 (dd, 1H, J = 10.4, 1.6 Hz, H-3), 6.48 (dd, 1H, J =
16.4, 1.6 Hz, H-3), 7.04 (dd, 1H, J = 16.8, 10.4 Hz, H-2), 7.08 (d, 1H,
J = 3.6 Hz, Harom-4), 7.46 (d, 1H, J = 3.6 Hz, Harom-3).
13C NMR: d = 123.19, 129.82, 130.73, 131.32, 132.40, 145.96,
181.08.
1-(2,4-Dimethoxyphenyl)prop-2-en-1-one (5c): colorless oil, yield;
l.88 g (98%).
C7H5BrOS: Calc. C 38.73, H 2.32; Found: C 38.61, H 2.16.
IR spectrum was identical to lit.10
1-(2-Selenophenyl)prop-2-en-1-one (5m): colorless oil, yield; 1.81 g
(98%).
1H NMR: d = 3.80 (s, 3H, CH3O), 3.82 (s, 3H, CH3O), 5.68 (dd, 1H,
J = 10.4, 2.0 Hz, H-3), 6.30 (dd, 1H, J = 17.2, 2.0 Hz, H-3), 6.44 (d,
1H, J = 2.4 Hz, Harom-3), 6.52 (dd, 1H, J = 8.4, 2.4 Hz, Harom-5), 7.12
(dd, 1H, J = 17.2, 10.4 Hz, H-2), 7.60 (d, 1H, J = 8.4 Hz, Harom-6).
13C NMR: d = 55.46, 55.51, 98.37, 102.24, 121.18, 126.94, 132.87,
136.64, 160.57, 164.36, 190.54.
IR (Nujol): n = 1660 (CO).
1H NMR: d = 5.86 (dd, 1H, J = 10.4, 1.6 Hz, H-3), 6.48 (dd, 1H, J =
18.2, 1.6 Hz, H-3), 7.04 (dd, 1H, J = 18.2, 10.4 Hz, H-2), 7.37 (dd,
1H, J = 4.0, 5.2 Hz, Harom-4), 7.95 (d, 1H, J = 4.0 Hz, Harom-5), 8.36
(d, 1H, J = 5.2 Hz, Harom-3).
13C NMR: d = 129.12, 130.78, 131.07, 134.64, 140.51, 151.43,
183.32.
1-(4-Methoxy-1-naphthyl)prop-2-en-1-one (5f): colorless oil, yield;
2.10 g (99%).
C7H6OSe: Calc. C 45.44, H 3.27; Found: C 45.72, H 3.39.
IR (Nujol): n = 1650 (CO).
1H NMR: d = 4.02 (s, 3H, CH3O), 5.90 (dd, 1H, J = 9.0, 2.4 Hz, H-
3), 6.38 (dd, 1H, J = 17.2, 2.4, H-3), 6.74 (d, 1H, J = 8.1), 7.08 (dd,
1H, J = 17.2, 9.0 Hz, H-2), 7.68–7.52 (m, 2H, C10H6), 7.85 (d, 1H, J =
8.1 Hz, C10H6), 8.38 (d, 1H, J = 8.6 Hz, C10H6), 8.72 (d, 1H, J =
8.6 Hz, C10H6).
13C NMR: d = 55.71, 102.06, 122.23, 125.78, 125.83, 127.71, 128.27,
l29.49, 131.02, 132.19, 136.45, 158.79, 193.62.
1-(Ferrocenyl)prop-2-en-1-one (5n): red powder, yield; 2.28 g (95%),
mp 72–73°C (hexane), lit.12 71–74°C.
IR (Nujol): n = 1660 (CO).
1H NMR: d = 4.11 (s, 5H, C5H5), 4.48 (t, 2H, J = 2.0 Hz, Harom-3, 4),
4.76 (t, 2H, J = 2.0 Hz, Harom-2, 5), 5.64 (dd, 1H, J = 10.4, 2.0 Hz, H-
3), 6.36 (dd, 1H, J = 17.2, 2.0 Hz, H-3), 6.74 (dd, 1H, J = 17.2, 10.4
Hz, H-2).
C14H12O2: Calc. C 79.23, H 5.70; Found: C 79.05, H 5.63.
13C NMR: d = 69.44, 69.49, 68.80, 72.59, 72.70, 79.38, 125.98,
l32.77, 192.68.
1-(2,3-Dihydro-1,4-benzodioxin-6-yl)prop-2-en-1-one (5g): pale
yellow oil, yield; 1.61 g (90%).
IR (Neat): n = 1660 (CO).
Financial support from the Russian Fundamental Investigation
Foundation (Grant N 97-03-33006a) is gratefully acknowledged.
M. L. thanks the CHEVRON Company as well as the International
Science Foundation (Grant N a97-26) for financial support.
1H NMR: d = 4.30–4.10 (m, 4H, OCH2CH2O), 5.86 (dd, 1H, J = 10.5,
1.7 Hz, H-3), 6.48 (dd, 1H, J = 17.1, 1.7 Hz, H-3), 6.83 (d, 1H, J = 8.2
Hz, Harom-5), 7.30 (dd, 1H, J = 17.1, 10.5 Hz, H-2), 7.46–7.42 (m, 2H,
Harom-2, 6).
13C NMR: d = 64.07, 64.66, 117.25, 118.14, 122.80, 129.28, 130.94,
131.98, 143.40, 148.09, 188.95.
(1) Denys, G.; Steponavicius, J.; Jasinskaite, R. Zh. Org. Khim.
1970, 6, 2503.
Maruoka, K.; Imoto, H.; Yamamoto, H. J. Am. Chem. Soc.
1994, 116, 12115.
C11H10O3: Calc. C 69.47, H 5.30; Found: C 69.51, H 5.35.
Pogosyan, G. M.; Avanesyan, E. S.; Matsoyan, S. G. Arm.
Khim. Zh. 1971, 24, 694; Chem. Abstr. 1972, 76, 46552.
(2) Paulus, W. Proc. Int. Biodegradation Symp. 3rd Meeting, 1975,
1063; Chem. Abst. 1977, 87, 112821.
(3) Sane, P.; Divakar, K.; Rao, A. Synthesis 1973, 9, 541.
Denys, G.; Steponavicius, J. Zh. Org. Khim. 1967, 4, 1691.
Toma, S. Collect. Czech. Chem. Commun, 1969, 34, 2771.
1-(1-Pyrenyl)propan-1-one (5j): yellow powder, yield; 2.21 g (86%).
mp 52–54°C (toluene), lit.11 yellow oil.
IR (Nujol): n = 1650 (CO).
1H NMR: d = 5.86 (dd, 1H, J = 10.4, 1.2 Hz, H-3), 6.48 (dd, 1H, J =
17.2, 1.2 Hz, H-3), 7.04 (dd, 1H, J = 17.2 Hz, J = 10.4 Hz, H-2), 8.20–
7.89 (m, 8H, C16H9), 8.61 (d, 1H, J – 9.2 Hz, Harom-2).

January 1998
SYNTHESIS
93
(4) Nenajdenko, V. G.; Lebedev, M. V.; Balenkova, E. S.
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(6) Vertelezkij, P. V.; Balenkova, E. S. Zh. Org. Khim. 1990, 26, (10) Setter, H.; Nienhaus, J. Chem. Ber. 1978, 111, 2825.
2446. (11) Profft, E.; Doehler, I. J. Prakt.Chem. 1962, 17, 219.
(7) Nenajdenko, V. G.; Leshcheva, I. F.; Balenkova, E. S. (12) Kaluz, S.; Toma, S. Collect. Czech. Chem. Commun. 1986, 51,
Tetrahedron 1994, 50, 775. Nenajdenko, V. G.; Gridnev, I. D.;
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2199.