Q. Guo et al. / Tetrahedron 58 (2002) 7327–7334
7333
obtained in 78% yield (465 mg) from trimethylene oxide
3 mmol) and benzoic acid chloride (3 mmol) as a colorless
liquid (flash chromatography with a mixture of hexane/
chloride (1 mmol) as a colorless oil (flash chromatography
1
(
with a mixture of hexane/Et O, 30/1). H NMR (CDCl ,
2
3
Me Si) d 1.71 (tt, J¼6.2, 7.2 Hz, 4H), 1.86 (tt, J¼6.8,
4
1
Et O, 30/1). H NMR (CDCl , Me Si) d 2.24 (tt, J¼6.3,
7.2 Hz, 4H), 3.43 (t, J¼6.1 Hz, 4H), 3.57 (t, J¼6.6 Hz, 4H);
2
3
4
1
3
6
7
7
6
.6 Hz, 2H), 3.70 (t, J¼6.5 Hz, 2H), 4.48 (t, J¼6.0 Hz, 2H),
C NMR (CDCl , Me Si) d 27.11, 29.58, 44.97, 69.98.
3 4
.44 (t, J¼7.5 Hz, 2H), 7.52–7.58 (m, 1H), 8.04 (d, J¼
1
3
38
.2 Hz, 2H); C NMR (CDCl , Me Si) d 31.77, 41.29,
3
4.1.13. Bis(4-bromobutyl) ether (26). Ether 26 was
obtained in 25% yield (72 mg, the yield is based on WBr5
4
1.69, 128.43, 129.59, 130.06, 133.08, 166.42.
(1 mmol)) from THF (4 mmol) as a colorless oil (flash
chromatography with a mixture of hexane/Et O, 30/1). H
1
4
.1.8. 4-(4-Chlorobutoxy)butyl benzoate (19). Ester 19
2
was obtained in 32% yield (46 mg, the yield is based on
PhCOCl) from THF (25 mmol) benzoic acid chloride
NMR (CDCl , Me Si) d 1.68–1.75 (m, 4H), 1.91–1.98 (m,
4
3
1
3
4H), 3.42–3.46 (m, 8H); C NMR (CDCl , Me Si) d 28.29,
3
4
(
(
5 mmol) and MoCl5 (0.5 mmol) as a colorless liquid
flash chromatography with a mixture of hexane/Et O, 30/1
29.67, 33.77, 69.81.
2
1
and 20/1). H NMR (CDCl , Me Si) d 1.63–1.91 (m, 8H),
3
4.2. Stoichiometric reaction of dioctyl ether with MoCl5
4
3
6
8
2
1
2
.42–3.50 (m, 4H), 3.57 (t, J¼6.5 Hz, 2H), 4.35 (t, J¼
.5 Hz, 2H), 7.41–7.46 (m, 2H), 7.53–7.58 (m, 1H), 8.03–
.06 (m, 2H); C NMR (CDCl , Me Si) d 25.65, 26.37,
To a mixture of molybdenum chloride (1.0 mmol, 270 mg)
and DCE (5 ml) was added dioctyl ether (1 mmol, 242 mg).
The reaction mixture was stirred at 808C for 3 h. GC
analysis of the resulting mixture sample after hydrolysis
showed the formation of 1-chlorooctane in 93% GC yield.
And then benzoyl chloride (1 mmol, 141 mg) was added, it
was stirred for additional 3 h at 808C. After that, the reaction
mixture was quenched and extracted. The extraction was
treated as shown in the representative procedure above,
column chromatography on silica gel afforded the octyl
benzoate ester (106 mg, 45%; GC yield: 49%) and
1-chlorooctane (97 mg, 65%; GC yield: 93%) as colorless
liquid.
1
3
3
4
7.09, 29.54, 45.00, 64.80, 70.00, 70.31, 128.34, 129.55,
þ
84.1179, found 284.1190.
30.40, 132.87, 166.65; HRMS calcd for C H ClO (M )
1
5
21
3
9
4.1.9. 5-Chloropentyl benzoate (21). Ester 21 was
obtained in 82% yield (186 mg) from THP (1 mmol) and
benzoic acid chloride (1 mmol) as a colorless oil (flash
1
chromatography with a mixture of hexane/Et O, 20/1). H
2
NMR (CDCl , Me Si) d 1.54–1.65 (m, 2H), 1.78–1.93 (m,
3
4
4
H), 3.57 (t, J¼6.6 Hz, 2H), 4.34 (t, J¼6.5 Hz, 2H), 7.44 (t,
1
3
J¼7.7 Hz, 2H), 7.54–7.61 (m, 1H), 8.04–8.06 (m, 2H); C
NMR (CDCl , Me Si) d 23.47, 28.06, 32.18, 44.78, 64.66,
3
4
1
28.37, 129.55, 130.35, 132.91, 166.62.
3
6
4
2
5
.1.10. 2-(2-Chloroethoxy)ethyl benzoate (22) and
3
References
7
-chloroethyl benzoate (17). Ester 22 was obtained in
2% yield (357 mg) from 1,4-dioxane (3 mmol) and
benzoic acid chloride (3 mmol) as a colorless oil (flash
chromatography with a mixture of hexane/Et O, 10/1), at
1. Bhatt, M. V.; Kulkarni, S. U. Synthesis 1983, 249.
2. Larock, R. C. Ether Cleavage in Comprehensive Organic
Transformations. 2nd ed. Wiley-VCH: Wienheim, 1999.
3. Burwell, Jr. R. L. Chem. Rev. 1954, 54, 615.
4. For Lewis acid catalyzed acylative cleavage of ethers please
see: Mimero, P.; Saluzzo, C.; Amouroux, R. Tetrahedron Lett.
1994, 35, 1553.
2
the same time, ester 17 was isolated as a byproduct (55 mg,
1
1
0%). Data of 22: H NMR (CDCl , Me Si) d 3.65 (t,
3
4
J¼5.8 Hz, 2H), 3.81 (t, J¼5.7 Hz, 2H), 3.87 (t, J¼4.8 Hz,
2
H), 4.49 (t, J¼4.8 Hz, 2H), 7.45 (t, J¼7.2 Hz, 2H), 7.54–
1
3
7
Me Si) d 42.71, 63.95, 69.25, 71.30 128.37, 129.68, 129.98,
.61 (m, 1H), 8.07 (d, J¼7.8 Hz, 2H); C NMR (CDCl ,
5. Ganem, B.; Small, Jr. V. R. J. Org. Chem. 1974, 39, 3728.
6. Oriyama, T.; Kimura, M.; Oda, M.; Koga, G. Synlett 1993,
437.
3
4
1
1
3
7
33.06, 166.53. Data of 17: H NMR (CDCl , Me Si) d
3 4
.80–3.83 (m, 2H), 4.55–4.58 (m, 2H), 7.43–7.47 (m, 2H),
3
7. Ahmad, S.; Iqbal, J. Chem. Lett. 1987, 953.
8. Iqbal, J.; Khan, M. A.; Srivastava, R. R. Tetrahedron Lett.
1988, 29, 4985.
1
.55–7.59 (m, 1H), 8.07 (d, J¼8.1 Hz, 2H); C NMR
(
CDCl , Me Si) d 41.70, 64.46, 128.45, 129.61, 129.74,
3
4
1
33.28, 166.17.
9. Iqbal, J.; Srivastava, R. R. Tetrahedron 1991, 47, 3155.
0. Green, L.; Hemeon, I.; Singer, R. D. Tetrahedron Lett. 2000,
41, 1343.
1
4.1.11. 6-Chlorohexyl benzoate (23). Ester 23 was
obtained in 52% yield (125 mg) from oxepane (1 mmol)
11. Qian, C.; Qiu, A.; Huang, Y.; Chen, W. J. Organomet. Chem.
1991, 412, 53.
and benzoic acid chloride (1 mmol) as a colorless oil (flash
1
chromatography with a mixture of hexane/Et O, 30/1). H
2
12. Qian, C.; Qiu, A.; Zhu, D.; Yang, X. J. Mol. Catal. 1994, 87,
357.
NMR (CDCl , Me Si) d 1.46–1.57 (m, 4H), 1.78 (tt, J¼6.3,
3
4
7
7
.1 Hz, 4H), 3.55 (t, J¼6.7 Hz, 2H), 4.33 (t, J¼6.6 Hz, 2H),
.43–7.46 (m, 2H), 7.54–7.58 (m, 1H), 8.03–8.06 (m, 2H);
C NMR (CDCl , Me Si) d 25.42, 26.57, 28.59, 32.46,
13. For metal catalyzed acylative cleavage of ethers, please see:
Luzzio, F. A.; Bobb, R. A. Tetrahedron 1999, 55, 1851.
14. Bhar, S.; Ranu, B. C. J. Org. Chem. 1995, 60, 745.
15. For low-valent group 5 and 6 metal carbonyl catalyzed
acylative cleavage of ethers, please see: Alper, H.; Huang,
C.-C. J. Org. Chem. 1973, 38, 64.
1
3
3
4
44.98, 64.85, 128.35, 129.53, 130.38, 132.87, 166.66.
HRMS calcd for C H ClO 240.0917, found 240.0928.
1
3
17
2
3
8
4.1.12. Bis(4-chlorobutyl) ether (24). Ether 24 was
obtained in 70% yield (139 mg, the yield is based on
MoCl (1 mmol)) from THF (5 mmol) and benzoic acid
5
16. Tsonis, C. P. J. Mol. Catal. 1988, 45, 145.
17. Preliminary result has been reported, see Guo, Q.; Miyaji, T.;
Gao, G.; Hara, R.; Takahashi, T. Chem. Commun. 2001, 1018.