Synthesis of selenol esters using acyl halides and a novel selenating reagent, LiAlHSeH

Article abstract of DOI:10.1080/10426500490422254

Several selenol esters were synthesized by the reaction of acyl chlorides with LiAlHSeH then with alkyl halides in moderate to good yields.

Full text of DOI:10.1080/10426500490422254

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Phosphorus, Sulfur, and Silicon and the Related
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SYNTHESIS OF SELENOL ESTERS USING ACYL HALIDES
AND A NOVEL SELENATING REAGENT, LiAlHSeH
Mamoru Koketsu a , Hiroshi Asada a & Hideharu Ishihara a
a Gifu University , Gifu, Japan
Published online: 12 Aug 2010.
To cite this article: Mamoru Koketsu , Hiroshi Asada & Hideharu Ishihara (2004) SYNTHESIS OF SELENOL ESTERS USING ACYL
HALIDES AND A NOVEL SELENATING REAGENT, LiAlHSeH, Phosphorus, Sulfur, and Silicon and the Related Elements, 179:3,
591-595, DOI: 10.1080/10426500490422254
To link to this article: http://dx.doi.org/10.1080/10426500490422254
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Phosphorus, Sulfur, and Silicon, 179:591–595, 2004
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Copyright Taylor & Francis Inc.
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500490422254
SYNTHESIS OF SELENOL ESTERS USING ACYL
HALIDES AND A NOVEL SELENATING
REAGENT, LiAlHSeH
Mamoru Koketsu, Hiroshi Asada, and Hideharu Ishihara
Gifu University, Gifu, Japan
(Received April 25, 2003; accepted September 25, 2003)
Several selenol esters were synthesized by the reaction of acyl chlorides
with LiAlHSeH then with alkyl halides in moderate to good yields.
Keywords: Acyl chloride; lithium aluminium halide; selenium; selenol
ester
Selenol esters are important key intermediates in organic synthesis.
They have been used as precursors of acyl radicals,1 as acyl transfer
reagents,2 and for radical addition-cyclization reactions.3 In spite of the
growing interest in new organic transformations of these compounds,
preparative methods available for their synthesis are still limited.4 A
facile method for the preparation of selenol esters would certainly be
very useful. Recently, we developed a novel selenating reagent,5 LiAlH-
SeH. This reagent is useful for preparing a variety of different selenium
containing compounds.6 Previously, we presented a possible method for
the preparation of selenol esters.6c However, since the reaction condi-
tions were not optimal, the yields were low and only two examples were
presented. Herein, we report an optimal procedure for preparation of
selenol esters using the novel reagent, LiAlHSeH.
RESULTS AND DISCUSSION
Optimal conditions for the preparation of Se-alkyl selenocarboxylates
(4) from the corresponding acyl chlorides (1) were determined by trial
This work was supported by a Grant-in-Aid for Science Research from the Ministry
of Education, Culture, Sports, Science and Technology of Japan (No. 14540490) to which
we are grateful.
Address correspondence to Mamoru Koketsu, Division of Instrumental Analysis,
Life Science Research Center, Gifu University, Gifu 501-1193, Japan. E-mail: koketsu@
cc.gifu-u.ac.jp
591

592
M. Koketsu et al.
SCHEME 1
and error. When the reaction of acyl chlorides (1) with LiAlHSeH (2)5
and then with alkyl halides (3) was carried out at 0◦C for 2 h, the yields
of (4a) and (4c) were 38% and 46% respectively. We found that the re-
action at room temperature and a longer reaction time, 15 h, gave the
highest yields of (4). The optimal reaction conditions leading to Se-alkyl
selenocarboxylates (4) is shown in Scheme 1. 4-Methylbenzoyl chloride
(1a) was added to an anhydrous THF solution of LiAlHSeH (2).5 The
reaction mixture was stirred at 0◦C for 30 min under an argon atmo-
sphere. A solution of methyl iodide (3a) in THF was added to the reac-
tion mixture at room temperature. The reaction mixture was stirred for
an additional 15 h. After work-up, Se-methyl 4-methylselenobenzoate
(4a) was obtained in a 71% yield. Reactions of four different acyl chlo-
rides (1) with four alkyl halides (3) also gave the corresponding Se-alkyl
selenocarboxylates (4) in moderate to good yields (Table I). The reaction
with aryl halides and secondary halides did not give desired products.
In conclusion, we report here a new synthesis procedure for prepara-
tion of various Se-alkyl selenocarboxylates by reaction of acyl halides
(1) with LiAlHSeH (2) and then with alkyl halides (3).
Experimental
Melting points were determined by use of a Yanagimoto micromelt-
ing point apparatus and are uncorrected. IR spectra were measured
on Perkin-Elmer 1600 spectrometer. 1H, 13C, and 77Se spectra were
recorded on a JEOL-JNM-α400 (400 MHz) spectrometer. Mass spectra
were obtained on a Shimadzu 9020-DF mass spectrometer. Tetrahy-
drofuran was distilled from sodium-benzophenone immediately prior
to use.
Se-Methyl 4-methylselenobenzoate (4a). p-Toluoyl chloride 1a
(0.13 mL, 1.0 mmol) was added to a THF solution (25 mL) of LiAlH-
SeH (2) (1.0 mmol). The reaction mixture was stirred at 0◦C for 0.5 h.
Methyl iodide 3a (0.076 mL, 1.2 mmol) was added to the reaction mix-
ture. The resulting reaction mixture was stirred at room temperature
for 15 h. The mixture was extracted with diethyl ether and washed
with saturated NaCl solution. The organic layer was dried over sodium
sulfate and evaporated to dryness. The residue was purified by flash

Selenol Esters
593
TABLE I Synthesis of Se-Alkyl Selenocarboxylates (4)
Products (4)
Yield (%)a
71
Products (4)
Yield (%)a
46
4ab
4bc
4cd
4fe
4gb
4hd
68
77
64
78
4db
4ed
67
75
4ib
4jd
46
65
aIsolated yield.
bMethyl iodide (3a) was used.
cEthyl iodide (3b) was used.
dBenzyl bromide (3c) was used.
eOctyl bromide (3d) was used.
chromatography on silica gel with dichloromethane:n-hexane (1:2) to
give 4a 0.15g (71%) as pale yellow liquid; IR (neat): 1681, 1662 cm−1
,
1H NMR (400 MHz, CDCl3): δ 2.37 (3H, s, CH3, 2 J(77Se-1H) = 10.7 Hz),
2.39 (3H, s, CH3), 7.24 (2H, d, J= 7.6 Hz, Ar), 7.81 (2H, d, J= 8.0
Hz, Ar),13C NMR (100 MHz, CDCl3): δ 4.9, 21.7, 127.1, 129.4, 136.5,
144.4 (Ar), 194.3 (C O), 77Se NMR (76 MHz, CDCl3): δ 438.0, MS (CI):
m/z = 215 (M++1), lit.6c
Se-Ethyl 4-methylselenobenzoate (4b). Yellow liquid, IR (neat): 1683,
1662 cm−1, 1H NMR (400 MHz, CDCl3): δ 1.49 (3H, t, J= 7.4 Hz, CH3),
2.39 (3H, s, CH3), 3.07 (2H, q, J= 7.6 Hz, CH2), 7.23 (2H, d, J= 8.4 Hz,
Ar), 7.79 (2H, d, J= 8.0 Hz, Ar), 13C NMR (100 MHz, CDCl3): δ 15.9,
19.3, 21.7, 127.2, 129.4, 136.7, 144.4 (Ar), 194.4 (C O), 77Se NMR (76
MHz, CDCl3): δ 550.7, MS (CI): m/z = 229 (M+ + 1), lit.7
Se-Benzyl 4-methylselenobenzoate (4c). White crystals, m.p.: 55.2–
56.0◦C, IR (KBr): 1681, 1661 cm−1, 1H NMR (400 MHz, CDCl3): δ 2.38
(3H, s, CH3), 4.33 (2H, s, CH2), 7.20–7.30 (5H, m, Ar), 7.35–7.37 (2H,
m, Ar), 7.79 (2H, d, J= 8.4 Hz, Ar), 13C NMR (100 MHz, CDCl3): δ 21.7,
28.9, 126.9, 127.3, 128.6, 129.0, 129.4, 136.3, 144.7 (Ar), 193.9 (C O),
77Se NMR (76 MHz, CDCl3): δ 595.5, MS (CI): m/z = 291 (M+ + 1),
lit.6c

594
M. Koketsu et al.
Se-Methyl selenobenzoate (4d). Yellow liquid, IR (neat): 1673 cm−1
,
1H NMR (400 MHz, CDCl3): δ 2.39 (3H, s, CH3, 2 J(77Se-1H) = 10.7 Hz),
7.43–7.47 (2H, m, Ar), 7.57–7.60 (1H, m, Ar), 7.9 (2H, dd, J= 1.6, 8.4 Hz,
Ar), 13C NMR (100 MHz, CDCl3): δ 5.1, 127.0, 128.7, 133.5, 139.0 (Ar),
194.9 (C O), 77Se NMR (76 MHz, CDCl3): δ 444.2, MS (CI): m/z = 201
(M+ + 1), lit.8
Se-Benzyl selenobenzoate (4e). Yellow liquid, IR (neat): 1671 cm−1
,
1H NMR (400 MHz, CDCl3): δ 4.34 (2H, s, CH2, 2 J(77Se-1H) = 11.2 Hz),
7.19–7.23 (1H, m, Ar), 7.27–7.30 (2H, m, Ar), 7.35–7.37 (2H, m, Ar),
7.41–7.45 (2H, m, Ar), 7.54–7.59 (1H, m, Ar), 7.89 (2H, dd, J= 1.6, 8.4
Hz, Ar), 13C NMR (100 MHz, CDCl3): δ 29.0, 127.0, 127.2, 128.8, 133.7,
138.8, 139.0 (Ar), 194.5 (C O), 77Se NMR (76 MHz, CDCl3): δ 600.8,
MS (CI): m/z = 277 (M+ + 1), lit.8,9
Se-Octyl selenobenzoate (4f). Yellow liquid, IR (neat): 1674 cm−1
,
1H NMR (400 MHz, CDCl3): δ 0.88 (3H, t, J= 6.8 Hz, CH3), 1.25–1.45
(10H, m, CH2), 1.71–1.79 (2H, m, CH2), 3.09 (2H, t, J= 7.6 Hz, CH2),
7.42–7.47 (2H, m, Ar), 7.55–7.59 (1H, m, Ar), 7.91 (2H, dd, J= 1.6, 8.4
Hz, Ar), 13C NMR (100 MHz, CDCl3): δ 14.1, 22.6, 25.8, 29.1, 29.2, 30.0,
30.5, 31.8, 127.1, 128.7, 133.4, 139.2 (Ar), 195.0 (C O), 77Se NMR (76
MHz, CDCl3): δ 524.7, MS (CI): m/z = 299 (M+ + 1); Anal. Calcd for
C15H22OSe: C, 60.60; H, 7.46. found: C, 60.48; H, 7.24%.
Se-Methyl phenylselenoacetate (4g). Yellow liquid, IR (neat): 1697
cm−1, 1H NMR (400 MHz, CDCl3): δ 2.17 (3H, s, CH3), 3.84 (2H, s, CH2),
7.27–7.35 (5H, m, Ar), 13C NMR (100 MHz, CDCl3): δ 5.34, 53.9, 127.6,
128.7, 129.9, 133.0 (Ar), 200.4 (C O), 77Se NMR (76 MHz, CDCl3): δ
474.6, MS (CI): m/z = 215 (M+ + 1), lit.4b
Se-Benzyl phenylselenoacetate (4h). White crystals, m.p.: 44.0–
45.0◦C, IR (KBr): 1686 cm−1, 1H NMR (400 MHz, CDCl3): δ 3.85 (2H, s,
CH2), 4.10 (2H, s, CH2), 7.15–7.34 (10H, m, Ar), 13C NMR (100 MHz,
CDCl3): δ 29.4, 53.8, 126.9, 127.7, 128.6, 128.9, 130.0, 132.8, 138.8 (Ar),
200.2 (C O), 77Se NMR (76 MHz, CDCl3): δ 632.8, MS (CI): m/z = 291
(M+ + 1), lit.10
Se-Methyl cyclohexanecarboselenoate (4i).Yellow liquid, IR (neat):
1700 cm−1, 1H NMR (400 MHz, CDCl3): δ 1.22–1.31 (3H, m), 1.44–1.48
(2H, m), 1.63–1.66 (1H, m), 1.77–1.79 (2H, m), 1.93–1.97 (2H, m), 2.18
(3H, s, CH3, 2 J
1
77Se− H) = 10.7 Hz), 2.53 (1H, tt, J= 3.6, 11.6 Hz, CH),
(
13C NMR (100 MHz, CDCl3): δ 4.34, 25.4, 25.6, 29.3, 56.1, 206.0 (C O),
77Se NMR (76 MHz, CDCl3): δ 440.8, MS (CI): m/z = 207 (M+ + 1),
lit.7
Se-Benzyl cyclohexanecarboselenoate (4j). Yellow liquid, IR (neat):
1695 cm−1, 1H NMR (400 MHz, CDCl3): δ 1.18–1.32 (3H, m), 1.41–1.51
(2H, m), 1.64–1.69 (1H, m), 1.76–1.80 (2H, m), 1.93–1.97 (2H, m), 2.53
(1H, tt, J= 3.6, 11.6 Hz, CH), 4.11 (2H, s, CH2), 7.16–7.27 (5H, m, Ar),

Selenol Esters
595
13C NMR (100 MHz, CDCl3): δ 25.3, 25.6, 28.3, 29.3, 56.0, 126.8, 128.5,
128.8, 139.4 (Ar), 205.5 (C O), 77Se NMR (76 MHz, CDCl3): δ 601.8,
(CI): m/z = 283 (M+ + 1); Anal. Calcd for C14H18OSe: C, 59.79; H, 6.45.
found: C, 60.01; H, 6.29%.
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