548 Bull. Chem. Soc. Jpn., 74, No. 3 (2001)
ones, (97 atom% D) and
Solvolysis of 1-Decenyliodonium Salt
(93 atom% D) prepared
1-βD
ed by K.-y. Akiba, Wiley-VCH, New York (1999), Chap. 12. b) T.
Okuyama, Rev. Heteroatom Chem., 21, 257 (1999).
T. Okuyama, T. Takino, T. Sueda, and M. Ochiai, J. Am.
Chem. Soc., 117, 3360 (1995).
a) M. Ochiai, K. Oshima, and Y. Masaki, J. Am. Chem. Soc.,
1-αD
previously3b and stored at –20 °C were used. Iodobenzene (4), 1-
decyne (3), and decanal (2c) were obtained commercially. Metha-
nol was distilled before use. Salts and other organic additives were
used as received.
2
3
E/Z mixtures of 1-methoxy- and 1-ethoxy-1-decene (2e(Me)
and 2e(Et)) were prepared by phosphoric acid-catalyzed dealkoxy-
lation of the corresponding 1,1-dialkoxydecane (2a)19 which were
obtained from 2c by a standard method.20
113, 7059 (1991). b) T. Okuyama, T. Takino, K. Sato, K. Oshima,
S. Imamura, H. Yamataka, T. Asano, and M. Ochiai, Bull. Chem.
Soc. Jpn., 71, 243 (1998).
4
a) M. Ochiai, Y. Takaoka, and Y. Nagao, J. Am. Chem. Soc.,
(Z)-1-Acetoxy-1-decene (2e(Ac)) was isolated from the aceto-
lysis products of 1 by preparative gas chromatography. H NMR
110, 6565 (1988). b) M. Ochiai, M. Kunishima, S. Tani, and Y.
Nagao, J. Am. Chem. Soc., 113, 3135 (1991). c) M. Ochiai, K.
Uemura, and Y. Masaki, J. Am. Chem. Soc., 115, 2528 (1993). d)
M. Ochiai, T. Sueda, K. Uemura, and Y. Masaki, J. Org. Chem., 60,
2624 (1995).
1
(CDCl3) δ 0.88 (t, J = 6.6 Hz, 3H), 1.3 (m, 12H), 1.5 (m, 2H), 2.14
(s, 3H), 4.86 (dt, J = 6.4, 8.5 Hz, 1H), 6.98 (dt, J = 6.4, 1.6 Hz, 1H).
From the coupling constant of 6.4 Hz for olefinic protons, the ge-
ometry is assigned as Z compared with Jcis = 6.3 and Jtrans = 12.4 Hz
for 1-methoxy-1-decene. MS m/z (relative intensity) 198 (M+;
10.5), 156 (9.5), 138 (25), 110 (17), 96 (41), 82 (49), 68 (20), 57
(38), 43 (100). HRMS Found: m/z 198.1615. Calcd for C12H22O2
M, 198.1620.
5
T. Okuyama, Y. Ishida, and M. Ochiai, Bull. Chem. Soc.
Jpn., 72, 163 (1999).
6
T. Okuyama, H.Yamataka, and M. Ochiai, Bull. Chem. Soc.
Jpn., 72, 2761 (1999).
7
M. C. Caserio, D. L. Glusker, and J. D. Roberts, J. Am.
[1-2H]-1-Decyne (97 atom% D) was obtained by quenching the
lithium acetylide of 3 with D2O.
Chem. Soc., 81, 336 (1959); F. M. Beringer, E. M. Gindler, M.
Rapoport, and R. J. Taylor, J. Am. Chem. Soc., 81, 351 (1959).
Product Determination. Reaction products were extracted
with pentane and determined by gas chromatography, as described
previously.2,3b
8
(1999).
9
T. Okuyama and H. Yamataka, Can. J. Chem., 77, 577
T. Okuyama, T. Takino, K. Sato, and M. Ochiai, J. Am.
The products from the deuterated substrates were obtained in a
larger scale and analyzed by H NMR spectroscopy at 400 MHz
(JEOL EXcalibur 400) and GC MS (JEOL JMS-DX303HF). A
Chem. Soc., 120, 2275 (1998).
10 M. N. Glukhovtsev, A. Pross, and L. Radom, J. Am. Chem.
Soc., 116, 5961 (1994).
1
sample of
or
(ca. 10 mg) was dissolved in a methanol
1-βD
11 V. Lucchini, G. Modena, and L. Pasquato, J. Am. Chem.
Soc., 117, 2297 (1995).
12 C. K. Kim, K. H. Hyun, C. K. Kim, and I. Lee, J. Am. Chem.
Soc., 122, 2294 (2000).
13 T. Okuyama, K. Sato, and M. Ochiai, Bull. Chem. Soc. Jpn.,
73, 2341 (2000).
14 The transition state for the out-of-plane SN2 pathway is the
same as that for the ligand-coupling mechanism occurring within
an adduct of the substrate with the nucleophile (λ3-iodane).8 The
former is bimolecular while the latter is unimolecular. When there
is no evidence for formation of the adduct, the term “out-of-plane
SN2” is more general, since the overall reaction is kinetically of the
second order.
15 F. L. Schadt, T. W. Bentley, and P. v. R. Schleyer, J. Am.
Chem. Soc., 98, 7667 (1976); T. W. Bentley and G. Llewellyn,
Prog. Phys. Org. Chem., 17, 121 (1990).
1-αD
solution (5 mL) in a Pyrex tube, and the tube was immediately im-
mersed in a water bath controlled at 50 °C. After the specified reac-
tion time, the products were extracted with pentane and washed
with water. The product mixture obtained in the acetate solution
was directly subjected to analysis. Those obtained in neutral meth-
anol and the trifluoroacetate solution were treated with methanol
containing 0.05 mol dm–3 trifluoroacetic acid for 5 h at room tem-
perature to convert 2e to 2a. The products were extracted again
with pentane, washed with water, and analyzed.
Kinetic Measurements. Reaction rates were determined by
monitoring the decrease in UV absorbance (240 nm) as described
previously2,6 at 60 ( 0.1) °C for solvolysis (without added base)
and at 25 ( 0.1) °C in the presence of carboxylates. In the absence
of added salts, freshly distilled solvents containing 10–3 mol dm–3
of trifluoroacetic acid were used for kinetic runs. Various solutions
of carboxylates were prepared at 0.05 mol dm–3 by weighing and
were diluted to the required concentrations with a 0.05 mol dm–3
solution of Bu4NClO4. These solutions were treated with the Chel-
ex 100 resin (Bio-Rad) before use to remove heavy metal ions.
16 D. N. Kevill and S. W. Anderson, J. Org. Chem., 56, 1845
(1991); D. N. Kevill, in “Advances in Quantitative Structure-Prop-
erty Relationships,” ed by M. Charton, JAI Press, Greenwich, Con-
necticut (1996), Vol. 1, pp. 81–115.
17 The β deuterium isotope effects on βE induced by halide
ions were evaluated to be kH/kD ≈ 3,3b but this value gives inconsis-
We thank Professor Masahito Ochiai of the University of
Tokushima for the gift of the iodonium samples and for helpful
discussions. We are also grateful to Dr. Morifumi Fujita
(Himeji Institute of Technology) for the measurements of
NMR spectra and to Kazuo Fukuda (Osaka University) for MS
measurements.
tent results from the data obtained with
and
.
1-βD
1-αD
18 T. Okuyama, T. Takino, K. Sato, and M. Ochiai, Chem.
Lett., 1997, 955.
19 (a) T. Okuyama, T. Fueno, H. Nakatsuji, and J. Furukawa, J.
Am. Chem. Soc., 89, 5826 (1967). (b) E. Taskinen and P. Liukas,
Acta Chem. Scand., B28, 114 (1974).
20 R. N. Icke, C. E. Redemann, B. B. Wisegarver, and G. A.
Alles, Org. Syn. Coll. Vol. 3, 644 (1955).
References
1
a) M. Ochiai, in “Chemistry of Hypervalent Compounds,”