C. Clausen, I. Weidner, H. Butenschön
FULL PAPER
Treatment of Phthaloyl Dichloride (35) with SmI2/Sm: a) Anhydrous
NiI2 (0.060 g, 0.2 mmol) was added to a solution of SmI2, which
had been obtained from samarium (3.308 g, 22.0 mmol), diiodome-
thane (1.339 g, 5.0 mmol)[15] and THF (50 mL). Phthaloyl dichlor-
ide (35) (3.0 mL, 2.144 g, 20.8 mmol) was added dropwise at 25 °C.
The mixture was stirred for 2 h at 25 °C and then cooled to 0 °C.
After addition of 50 mL of 2N HCl, the mixture was extracted six
times, each time with 50 mL of trichloromethane. The combined
organic layers were washed with satd aq solutions of NaHCO3,
Na2S2O3 and brine, and dried over Na2SO4. The solvents were re-
moved at reduced pressure, and the residue was dissolved in acet-
one. The insoluble material was separated by filtration and washed
with acetone to give 0.050 g (0.2 mmol, 2%) of an unseparated mix-
ture of 37 and 38 (1:4).[46,47]
by filtration, and the TBME was removed to afford 0.605 g of the
same unidentified orange-yellow solid that had also been obtained
in a).
Treatment of 3,3-Dimethylbutanoyl Chloride (39) with SmI2/Sm:
Anhydrous NiI2 (0.030 g, 0.10 mmol) was added to a solution of
SmI2, which had been obtained from samarium (1.654 g,
11.0 mmol), diiodomethane (1.339 g, 5.0 mmol) and THP (10 mL).
3,3-Dimethylbutanoyl chloride (1.50 mL, 1.454 g, 10.8 mmol) was
added dropwise at 25 °C. The mixture was stirred for 2 h at 25 °C
and then cooled to 0 °C. After addition of 50 mL of a satd. aqueous
solution of NH4Cl, the mixture was extracted six times, each time
with 50 mL of TBME. The collected organic layers were washed
with a satd aq solution of NaHCO3, Na2S2O3 and NaCl and then
dried over Na2SO4. Column chromatography (length 90 cm, л
3 cm, petroleum ether, then petroleum ether/TBME 20:1) gave
315 mg (1.1 mmol, 31%) of 2,2,8,8-tetramethyl-5-(2,2-dimethylpro-
pyl)-nonane-4,6-dione (40), colorless solid (m.p. 93 °C).
Compound 37: 13C NMR (100.6 MHz, Cl2CDCDCl2, APT): δ ϭ
164.7 [ϩ, C-1(1Ј)], 135.8 [ϩ, C-1a(1aЈ)], 135.1 [Ϫ, C-6(6Ј) ], 133.2
[ϩ, C-2(2Ј)], 130.9 [ϩ, C-5(5Ј)], 126.9 [Ϫ, C-3(3Ј)], 125.3 [Ϫ, C-
4(4Ј)].
Compound 40: enol form 4:1. Ϫ IR (ATR): ν˜ ϭ 3150 cmϪ1 (very
weak, br, enol -OH), 2953 (s, CH), 2906 (m, CH), 2869 (m, CH),
1726 (s, β-diketone), 1699 (m, CϭO), 1477 (m, CH), 1466 (m, CH),
1388 (m), 1364 (m), 1242 (m), 1091 (m), 1021 (m). Ϫ 1H NMR
(400.1 MHz, TMS, C6D6): δ ϭ 0.76 (s, 9 H, 12-H), 1.01 [s, 18 H,
Compound 38: 13C NMR (100.6 MHz, Cl2CDCDCl2, APT): δ ϭ
166.0 [ϩ, C-1(1Ј)], 137.0 [ϩ, C-1a(1aЈ)], 135.3 [Ϫ, C-6(6Ј) ], 133.5
[ϩ, C-2(2Ј)], 130.7 [ϩ, C-5(5Ј)], 125.9 [Ϫ, C-3(3Ј)], 123.3 [Ϫ, C-
4(4Ј)].
3
1(9)-H], 1.82 (d, 2 H, J10,5 ϭ 5.7 Hz, 10-H), 2.27 ϩ 2.28 [2s, 4 H,
3
3(7)-H], 3.56 (t, 1 H, J10,5 ϭ 5.7 Hz, 5-H). Ϫ 13C NMR
Acetone was removed from the filtrate under reduced pressure, and
the residue was dissolved in TBME. Insoluble material was re-
moved by filtration, and the filtrate was purified by column chro-
matography (length 14 cm, л ϭ 5 cm, petroleum ether/TBME 2:1).
(100.6 MHz, C6D6, TMS, APT): δ ϭ 29.4 (Ϫ, C-12), 29.5 [Ϫ, C-
1(9)], 30.4 [ϩ, C-2(8)], 30.8 (ϩ, C-11), 40.7 (ϩ, C-10), 53.3 [ϩ, C-
3(7)], 67.9 (Ϫ, C-5), 204.5 [ϩ, C-4(6)]. The constitution of 40 was
confirmed by a C,H COSY spectrum. Ϫ MS (70 eV, 25 °C): m/z
(%) ϭ 284 (2) [Mϩ ϩ 1], 283 (7) [Mϩ], 211 (3) [Mϩ Ϫ C5H11ϩ],
184 (39), 167 (1), 127 (43), 99 (100) [C6H11Oϩ], 71 (19) [C5H11ϩ].
Ϫ HRMS (C18H34O2): calcd. 282.255881, found 282.255829.
Fraction I: Di(4-iodobutyl) phthalate (39) (2.105 g, 4.0 mmol, 19%)
as a viscous yellow oil. IR (CHCl3): ν˜ ϭ 3033 (w) cmϪ1, 2961 (m),
1723 (s, CϭO), 1601 (w), 1287 (s, CϪO), 1131 (m, CϪO), 1074
1
(m), 994 (w). Ϫ H NMR (200.1 MHz): δ ϭ 1.7Ϫ2.1 [m, 8 H, 2Ј-
3
3
Enol Form:[33] 1H NMR (400.1 MHz, TMS, C6D6): δ ϭ 0.86 (s, 9
H), 0.89 (s, 9 H), 1.07 (s, 9 H), 2.16 (d, 2 H, J ϭ 10.3 Hz), 2.20 (s,
2 H), 5.07 (dd, 1 H, J ϭ 10.4, 2.0 Hz), 6.13 (s, 1 H). Ϫ 13C NMR
(100.6 MHz, C6D6, TMS, APT): δ ϭ 29.4 (Ϫ), 29.7 (Ϫ), 29.8 (Ϫ),
30.5 (ϩ), 30.9 (ϩ), 31.8 (ϩ), 47.6 (ϩ), 55.3 (ϩ), 77.1 (Ϫ), 138.5
(Ϫ), 171.5 (ϩ), 204.6 (ϩ).
H, 3Ј-H)], 3.24 (t, J ϭ 6.7 Hz, 4 H, 4Ј-H), 4.35 (t, J ϭ 6.2 Hz, 4
H, 1Ј-H), 7.63 [m, AAЈBBЈ, 4 H, 3-H, 4-H)]. Ϫ MS (70 eV, 140
°C): m/z (%) ϭ 530 (1) [Mϩ], 404 (43) [Mϩ Ϫ I], 332 (1), 264 (14),
183 (100), 167 (82), 149 (68) [C8H5O3ϩ], 132 (4) [C8H4O2], 76
(15) [C6H4ϩ].
Fraction II: 0.265 g of an unidentified orange-yellow solid. IR
(KBr): ν˜ ϭ 3041 (w) cmϪ1, 2958 (w), 1784 (s), 1725 (s, CϭO), 1599
(s), 1467 (s), 1285 (s, CϪO), 1073 (m), 991 (m), 761 (m), 735 (m),
Treatment of Benzoyl Chloride with 1,2-Diiodoethane/Sm2Co7:
Sm2Co7 alloy (7.740 g, 10.8 mmol) and 1,2-diiodoethane (2.770 g,
9.8 mmol) in THF (100 mL) were heated at reflux for 72 h. After
cooling to 25 °C, the green-blue solution was separated from the
alloy. After dropwise addition of benzoyl chloride (0.57 mL,
0.690 g, 4.9 mmol), the resulting solution was stirred for 24 h at 25
°C. Then 25 mL of 2N HCl and 25 mL of a satd aq solution of
Na2S2O3 were added, and the mixture was extracted three times,
each time with 30 mL of diethyl ether. The combined organic layers
were washed with 50 mL of satd aq solutions of Na2CO3 and brine,
and dried over Na2SO4. Column chromatography (length 16 cm,
3.5 cm, petroleum ether/diethyl ether 6:1).
1
692(m). Ϫ H NMR (400.1 MHz, [D6]acetone): δ ϭ 1.29 (t, 4 H,
3J ϭ 7.2 Hz), 3.17 (q, 3 H, 3J ϭ 7.2 Hz), 4.30 (m, 2 H), 7.3Ϫ8.4
(m, br, 28 H). Ϫ 13C NMR (100.6 MHz, BB): δ ϭ 8.8, 27.2, 46.7,
49.3, 64.9, 65.2, 123Ϫ135 (m, br), 168.2, 168.6. Ϫ MS-FAB: m/z ϭ
832, 744, 678, 624, 570, 463, 399, 366, 327, 289, 249, 207 (100%).
b) Anhydrous NiI2 (0.030 g, 0.1 mmol) was added to a solution of
SmI2, which had been obtained from samarium (1.654 g,
11.0 mmol), diiodomethane[15] (1.339 g, 5.0 mmol) and THP
(40 mL). Phthaloyl dichloride (26) (1.5 mL, 2.114 g, 10.4 mmol)
was added dropwise at 25 °C. The mixture was stirred for 1 h at 25
°C and then cooled to 0 °C. After addition of 50 mL of 2 N HCl,
the mixture was extracted six times, each time with 50 mL of trich-
loromethane. The combined organic layers were washed with satd
aq solutions of NaHCO3, Na2S2O3 and brine, and dried over
Na2SO4. The solvents were removed under reduced pressure, and
the residue was dissolved in acetone. The insoluble material was
separated by filtration and washed with acetone to afford 0.080 g
(0.3 mmol, 6%) of a mixture of 37 and 38 as a yellow solid, identi-
fied by comparison with authentic material.
Fraction I: 4-Iodobutyl benzoate (1.210 g, 4.0 mmol, 81%), yellow
liquid.[31,48]
Fraction II: 4-(4-Iodobutoxy)butyl benzoate (0.248 g, 0.7 mmol,
13%) as a yellow oil. IR (KBr): ν˜ ϭ 3060 cmϪ1 (w, arom. CH),
2940 (m, CH), 2860 (m, CH), 2796 (w, CH), 1716 (s, CO), 1600 (w,
arom. CϭC), 1584 (w, arom. CϭC), 1448 (m), 1372 (w), 1312 (m),
1272 (s), 1224 (m), 1176 (m), 1112 (s, CϪO), 1068 (m), 1024 (m),
1
956 (w), 712 (s), 688 (w). Ϫ H NMR (400.1 MHz, CDCl3): δ ϭ
1.60Ϫ1.78 (m, 4 H, 13-H ϩ14-H), 1.82Ϫ1.96 (m, 4 H, 9-H ϩ 10-
3
3
Acetone was removed at reduced pressure from the filtrate, and the
residue was dissolved in TBME. Insoluble material was removed
H), 3.22 (t, J15,14 ϭ 6.9, Hz2 H, 15-H), 3.44 (t, J12,13 ϭ 6.3 Hz,
3
3
2 H, 12-H), 3.47 (t, J11,10 ϭ 6.3 Hz, 2 H, 11-H), 4.35 (t, J8,9
ϭ
3804
Eur. J. Org. Chem. 2000, 3799Ϫ3806