O. Sharon, A. A. Frimer / Tetrahedron 59 (2003) 8153–8162
8161
carboxylic acid 43 (21 mg, 1.2 mmol, 14% yield) as a
white solid (mp 878C).
which was identified as alcohol 47 (41 mg, 0.245 mmol,
58% yield based on 60% conversion). The latter rearranges
upon standing at room temperature to a mixture of cis and
trans 44b.
Compound 41: d (300 MHz, CDCl ) 7.32–7.21 (5H, aryl),
H
3
6
.99 (1H, s, H ), 6.79 (1H, dd, J¼17.0, 12.0 Hz, H
0
), 6.39
), 5.83 (1H, dd, J¼12.0, 1.5 Hz,
2
2
(
H
1H, dd, J¼17.0, 1.5 Hz, H
0
Compound 16b: d (600 MHz, CDCl ) 7.28 (2H, t, J¼7 Hz,
3
H
3
0
), 4.00 (1H, dd, J¼4.5, 1.5 Hz, H ), 3.27 (1H, dd,
meta), 7.26 (2H, m, ortho), 7.20 (1H, bt, J¼7.0 Hz, para),
6.16 (1H, s, H ), 3.81 (1H, bd, J¼4.0 Hz, H ), 2.81 (1H, dd,
3
3
J¼13.0, 4.5 Hz, H ), 2.65 (1H, dd, J¼13.0, 1.5 Hz, H ); d
4
4
C
2
3
(
75.5 MHz, CDCl ) 185.8 (C
3
0
), 147.5 (C ), 146.8 (C ),
1
J¼12.0, 4.0 Hz, H ), 2.16 (1H, dd, J¼12.0, 2.0 Hz, H
0
),
4
1
2
4
1
(
3
40.6 (ipso), 131.8 (C2
para), 126.8 (ortho), 43.8 (C ), 38.4 (C ); n
0
), 128.7 (C3
0
), 128.6 (meta), 126.9
(KBr) 3057,
1.03 (2H, m, H
0
and H
0
), 0.87 (2H, m, H
0
and H
0
); d
(150 MHz, CDCl ) 151.3 (C ), 143.9 (ipso), 128.5 (C ),
2
3
2
3
C
3
4
max
3
1
2
2
1
027, 2959, 2933, 1728, 1661, 1599, 1403, 751, 697 cm
;
m/z (EI) 184 (M , 22%), 128 (M2C H O, 100%), 104
128.3 (meta), 126.7 (ortho), 126.2 (para), 54.9 (C1
(C ), 37.8 (C ), 14.6 and 14.2 (C and C3 ); n (KBr)
max
0
), 41.9
þ
M2C H O, 44%), 92 (M2C H O, 49%), 77 (M2C H O,
0
0
3
4
3
4
2
2
1
(
3454, 3360, 2955, 2925, 2853, 1602 cm ; m/z (CI,
i-butane) 187 (MH , 12%), 186 (M, 13%), 168 (M2H O,
5
3
6
4
7 7
þ
þ
25%), 129 (M2C H O, 35%), 105 (MH 2C H O, 100%),
4
requires 184.0888.
1%); HRMS (CI, i-butane): M , found 184.0880. C H O
12
13
2
þ
04 (M2C H O, 61%); HRMS (CI, i-butane): MH , found
3
5
5 6
þ
1
187.1120. C H O requires 187.1123.
5
6
Compound 42: dH (600 MHz, CDCl ) 7.33–7.30 (4H,
3
13 15
meta), 7.25–7.21 (6H, ortho and para), 7.11 (1H, s, H2),
.99 (1H, s, H200), 3.98 (1H, dd, J¼4.0, 2.0 Hz, H 00), 3.97
6
3
(
3
4
1H, dd, J¼4.0, 2.0 Hz, H ), 3.96 (2H, t, J¼5.0 Hz, H
0
),
3
3
.25 (1H, dd, J¼14.0, 4.0 Hz, H ), 3.19 (1H, dd, J¼14.0,
References
4
.0 Hz, H 00), 2.92 (2H, t, J¼5.0 Hz, H
0
), 2.63 (1H, dd,
4
4
J¼14.0, 2.0 Hz, H ), 2.57 (1H, dd, J¼14.0, 2.0 Hz, H 00); dC
4
4
1. (a) Frimer, A. A.; Roth, D.; Sprecher, M. Tetrahedron Lett.
1977, 33, 1927–1930. (b) Frimer, A. A.; Farkash, T.;
Sprecher, M. J. Org. Chem. 1979, 44, 989–995. (c) Frimer,
A. A.; Roth, D. J. Org. Chem. 1979, 44, 3882–3887.
(d) Frimer, A. A.; Antebi, A. J. Org. Chem. 1980, 45,
2334–2340. (e) Frimer, A. A. Isr. J. Chem. 1981, 21,
194–202. (f) Frimer, A. A. J. Photochem. 1984, 25,
211–226. (g) Frimer, A. A.; Weiss, J. J. Org. Chem. 1993,
58, 3660–3667. (h) Frimer, A. A.; Weiss, J.; Gottlieb, H. E.;
Wolk, J. L. J. Org. Chem. 1994, 59, 780–792. (i) Frimer, A. A.;
Pizem, H. Tetrahedron 1999, 55, 12175–12186. (j) Frimer,
A. A.; Afri, M.; Baumel, S. D.; Gilinsky-Sharon, P.;
Rosenthal, Z.; Gottlieb, H. E. J. Org. Chem. 2000, 65,
1807–1817. (k) Pizem, H.; Sharon, O.; Frimer, A. A.
Tetrahedron 2002, 58, 3199–3205. (l) Frimer, A. A. The
Spectrum 2000, 13(2), 9–16.
(
150 MHz, CDCl ) 196.8 (C
3
0
), 166.2 (C
0
), 150.8 (C ),
2
5
1
1
(
(
47.9 (C200), 146.4 (C100), 140.7 (both the ipso carbon), 139.5
C ), 128.7–126.8 (other aromatic carbons), 57.9 (C3
1
0
), 43.8
), 38.4 (C ), 37.3 (C 00); nmax (KBr)
C ), 43.4 (C 00), 39.6 (C4
0
3
3
4
4
2
1
3
m/z (CI, i-butane) 359 (MH , 24%), 203 (MH 2C H O,
060, 3027, 2931, 1712, 1666, 1599, 1490, 1129, 699 cm
þ
;
þ
1
1 8
1
1
5%), 157 (M2C H O , 21%), 129 (M2C H O ,
13 13 2 14 13 3
þ
00%); HRMS (CI, i-butane): MH , found 359.1620.
C H O requires 359.1647.
24 23 3
Compound 43: dH (600 MHz, CDCl ) 7.32 (2H, t,
3
J¼7.0 Hz, meta), 7.23 (3H, m, ortho and para), 7.14 (1H,
dd, J¼1.5, 0.5 Hz, H ), 3.98 (1H, ddd, J¼5.0, 2.0, 1.5 Hz,
2
H ), 3.25 (1H, dd, J¼13.5, 5.0 Hz, H ), 2.65 (1H, ddd,
0
),
1
3
4
J¼13.5, 2.0, 0.5 Hz, H ); d (150 MHz, CDCl ) 167.2 (C
4
C
3
1
(
1
3
51.4 (C ), 140.6 (ipso), 138.2 (C ), 128.6 (meta), 126.9
2
2. (a) Koch, E. Tetrahedron 1968, 24, 6295–6318. (b) Ashford,
R. D.; Ogryzlo, E. A. J. Am. Chem. Soc. 1975, 97, 3604–3607.
3. (a) Denny, R. W.; Nickon, A. Org. React. 1973, 20, 133–336.
(b) Gollnick, K.; Kuhn, H. J. In Singlet Oxygen; Wasserman,
A. A., Murray, R. W., Eds.; Academic: New York, 1979;
pp 287–427. (c) Frimer, A. A. Chem. Rev. 1979, 79, 359–387.
(d) Frimer, A. A. In The Chemistry of Peroxides; Patai, S., Ed.;
Wiley: Chichester, 1983; pp 201–234. (e) Frimer, A. A.;
1
ortho), 126.8 (para), 43.8 (C ), 38.4 (C ); m/z (CI, NH )
3 4 3
þ
74 (M , 16%), 129 (M2CHO , 100%), 84 (M2C H ,
2 7 6
þ
2%); HRMS (CI, i-butane): M , found 174.0674.
C H O requires 174.0681.
11 10 2
3
1
.4.3. Low temperature photooxidation of cyclobutane
6b; formation of 1-(1 -hydroxycyclopropyl)-3-phenyl-1-
0
cyclobutene (47). 1-Cyclopropylidene-3-phenylcyclobutane
6b (120 mg, 0.71 mmol) was dissolved in CDCl (3 mL)
Stephenson, L. M. Singlet O : Reaction Modes and Products,
2
1
Part I; Frimer, A. A., Ed.; Chemical Rubber Company: Boca
3
along with a spatula tipful of methylene blue and cooled to
ca. 2508C (dry-ice/acetone). The reaction mixture was
photooxygenated for 3.5 h until oxygen uptake essentially
ceased (0.5 equiv.). Triphenylphosphine (185 mg, 0.71 mmol)
Raton, Florida, 1985; Vol. II, p 3 Chapter 3. (f) Singlet O2;
Frimer, A. A., Ed.; Chemical Rubber Company: Boca Raton,
Florida, 1984–1985; Vols. 1–4.
4. Allen, F. H. Tetrahedron 1982, 38, 645–655.
5. Laurie, V. W.; Stiglani, W. M. J. Am. Chem. Soc. 1970, 92,
1485–1488.
dissolved in CDCl (1 mL) was syringed into the reaction
3
vessel. The latter was then removed from the dry-ice/
acetone bath and stored overnight in the freezer (2188C).
6. Lau, K. S. Y. Chemistry, characterization and processing of
IMC curing polymers; Technical Report # AFWAL-TR-83-
4063; US Air Force Wright Aeronautical Laboratories, July
1983, pp 55–60.
1
H NMR spectroscopy of the crude reaction mixture
revealed the presence of only two components, unreacted
starting material 16b and a new product, in a 1:1 ratio. Silica
column chromatography, eluting with a solvent gradient
ranging from 5–50% ethyl acetate in petroleum ether,
yielded two fractions. The first was the starting material 16b
7. Utimoto, K.; Tamura, M.; Sisido, K. Tetrahedron 1973, 29,
1169–1171.
8. Low, C. M. R. Synth. Lett. 1991, 123–124.
9. (a) Foote, C. S. Tetrahedron Lett. 1963, 9, 579–583.
(
48 mg), while the second was a white solid (mp 1038C)