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Organic Synteses vol 69 - Paquette L.A.

Paquette L.A., Boecman R.K. Organic Synteses vol 69 - John Wiley & Sons, 1990. - 174 p.
ISBN 0-471-54560-0
Download (direct link): organicsynthesesvol691990.pdf
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8. Filler, R. Isr. J. Chem. 1978, 17, 71.
138
9. Appelman, E. H.; Basile, L. J.;Thompson, R. C. J. Am. Chem. Soc. 1979, 101, 3384; Stavber, S.; Zupan, M. I Chem. Soc., Chem. Commun. 1981, 148.
10. Banks, R. E.; Williamson, G. E Chem. Ind. (London) 1964, 1864.
11. Purrington, S. T.; Jones, W. A J. Org. Chem. 1983, 48, 761; Purrington, S. T.; Jones, W. A. J. Fluorine Chen. 1984, 26, 43.
12. Barnette, W. E. J. Am. Chem. Soc. 1984, 106, 452.
13. Singh, S.; DesMarteau, D. D.; Zuberi, S. S.; Witz, M.; Huang, H.-N.. J. Am. Chem. Soc. 1987, 109, 7194.
14. Umemoto, T.; Tomita, K. Tetrahedron Lett. 1986, 27, 3271; Umemoto, T.; Kawada, K.; Tomita, K. Tetrahedron Lett. 1986, 27, 4465; Umemoto, T.; Tomizawa, G. Bull. Chem. Soc. Jpn. 1986, 59, 3625.
15. Umemoto, T., presented at the ACS 9th Winter Fluorine Conference, St. Petersburg, January 31, 1989. Triflate 5 was prepared in good yield by treatment of a solution of penlachloropyridine and an equimolar amount of triflic acid in trifluoroacetic acid at room temperature with 20% F2/N2.
16. Harasawa, K.; Tomita, K.; Umemoto, T., presented at the 52nd Symposium on Organic Synthesis, Tokyo, Novembers, 1987.
17. Kawada, K.; Onodera, K.; Uîiemoto, T., presented at the Japanese-United States Congress of Pharmaceutical Sciences, Honolulu, December 4,1987.
18. Barton, D. H. R. Pure Appl. Chem. 1977, 49, 1241; Hesse, R. H. Isr. J. Chem. 1978, 17, 60.
139
Appendix
Chemical Abstracts Nomenclature (Collective Index Number^ (Registry Number)
N-Fluoropyridinium triflate: Pyridinium, 1-fluoro-, salt with trifluoromethanesulfon«} acid (1:1) (12); (107263-95-6)
Pyridine (8,9); (110-86-1)
Sodium triflate: Methanesulfonic acid, trifluoro-, sodium salt (8,9); (2926-30-9) Trifluoromethanesulfonic acid: Methanesulfonic acid, trifluoro- (8,9); (1493-13-6) Fluorine (8,9); (7782-41-4)
140
TABLE I
ELECTROPHILIC FLUORINATIONS WITH N-FLUOROPYRIDINIUM TRIFLATES
Substrate
Reagent3
Conditions
n-Ci2H25MgCI
NaCH(COOEt)2
CH2(COOEt)2
P-CIC6H4SCH3
^ ^~OMe
O
2d
PAc
0°C, 30 min in Et20
0°C, 2 hr in THF
AICI3® 80°C
R.t., 8 hr in CH2CI2
1 ) -15°C, 1 hr in CH2CI2/CH3C
2) R.t., ca. 12 hr in c. HCI/DMF
R.t., 7 hr in CH2CI2
60°C, 30 min in CH2CICH2CI
Reflux, 7 hr in CH2C)2
Reflux, 10 hr in CH2CI2
Product Yield (%;
n-Ci 2H25F 75c
CHF(COOEt)2 42
CF2(COOEt)2 6
CF2(COOEt)2 761
CHF(COOEt)2 19*
p-CIC6H4SCH2F 76

54
F 46
F
87=
F
{ OMe 631
Cf 86h
O '°T<
r+'T
dP 71'
F
141
PhOH 3 Reflux, 5 hr in CH2CI2 f-c6h4oh (o:p) 57c (3.3:1
PhOMe 3 80°C, 18 hr in CH2CICH2CI F-CeH4OMe (o:p) 64° (1:1)
PhOMe 4 Reflux, 23 hr in CH2CI2 F-CeH4OMe (o:p) 65c (1:1)
PhNHCOOEt 3 80°C, 5 hr in CH2CICH2CI F-C6H4NHCOOEt (o:p) 54 (2.2:1)
a) Equimolar N-fluoropyridinium triflate unless noted otherwise, b) Isolated yields unless noted otherwise, c) GLPC yields, d) 2 Equivalents of 2. e) 0.4 Equivalents of AICI3. f) 19F NMR yields, g) 1.5 Equivalents of dihydropyran. h) cis/trans = 1/1.
i) a/p = 1/2.
142
Figure 1
H
A: Flowmeter (Matheson model 7825); B; Flowmeter (Hastings model CST); C: Alumina trap; D: Reactor system; E: Bubble counter containing perfluorotributylamine; F: Pressure regulator (Matheson model 63-5512); G, I, K, O, P: Stainless steel values; H: Pressure gauge (Matheson model 63-5512); J, N; Stainless steel filters; L: Pressure regulator for ntirogen; M, Q, R, S: Brass values; T: Viton tubing; U: Teflon corks; V: Pyrex Claisen adaptor; W: Pyrex flask; X: Pyrex tube; Y: Teflon-coated stirring bar; Z: -40°C Cooling bath.
143
1-CH LORO-1-(TRICHLOROETHENYL)CYCLOPROPANE (Cyclopropane, 1-chloro-1-(trichloroethenyl)-)
170°C
C2CI4
Submitted by Thomas Liese, Frank Jaekel, and Armin de Meijere.1 Checked by John R. Berry, James S. Piecara, and Bruce E. Smart.
1. Procedure
A 1-L Hastelloy C-276 shaker tube (Note 1) fitted with a temperature sensor, rupture-disk safety device, and a gas-inlet valve attached to an ethylene cylinder is charged with 120.0 g (0.675 mol) of freshly distilled tetrachlorocyclopropene (Note 2), 350 mL of dry tetrachloroethylene (Note 3), and 10 g of anhydrous sodium carbonate (Note 4). The tube is pressurized to 20 atm with ethylene and shaken for 3 hr. The ethylene cylinder is disconnected, the pressure vessel is gradually heated to 170°C over a 30-min period, and it is shaken at this temperature for 19.5 hr. The vessel is allowed to cool to room temperature, and the excess ethylene is slowly released and bubbled through a wash bottle containing methylene chloride (Note 5). The light brown liquid in the shaker tube is decanted and the remaining solid washed twice with 50 mL of methylene chloride. The organic phases are combined and the methylene chloride is removed by distillation. The residual liquid is distilled at water-aspirator vacuum through a 40-cm Vigreux column. The solvent tetrachloroethylene, bp 35°C (27 mm), is collected (Note 6), followed by 104.1-105.6 g (75-76%) of 1 -chloro-1-(trichloroethenyl)cyclopropane as a colorless liquid, bp 81-83°C (27 mm) (Note 7).
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