B. Huras et al.
O
CH3
Cl
O
CHBr2
Cl
Results and discussion
Br
[2H15]Triethyl phosphite 3b was obtained in 57% yield from
ethanol-d6 and phosphorus trichloride in the presence of
N,N-diethylaniline in hexane.13,14 3b was condensed with 2,4-
dichlorophenacylidene bromide (2) in the Perkow reaction.
After elimination of [2H5]ethyl bromide, the labelled target
compound – [2H10]bromfenvinphos (1b) was obtained in 79%
yield (Scheme 1).
(i)
O
C2X5O
C2X5O
(iii )
H
P
O
Cl
Cl
2 Cl
- C2X5Cl
1a:X=H
Cl 1b:X=D
(ii)
(C2X5O)3P
C H OX+
3a:X=H,3b:X=D
PCl 3
2
5
Scheme 1. Synthesis of bromfenvinphos (1a,b). (i) Br2, 401C, 3 h, 51% (ii) PhNEt2,
hexane, reflux, 1 h, 57% (3b, X = D) (iii) Br2, 501C, 1 h, 63% (1a, X = H), 79%
(1b, X = D).
The structures of synthesized compounds and the location
of deuterium-labelled sites were confirmed using spectral
methods.
Acknowledgements
with a crystal of 2. The crystallizing 2 was kept at 01C for
30 min. The crystals were rapidly filtered off, washed with
small amount of chilled hexane, and dried to afford 2 (44 g).
The above crystallization procedure was repeated (175mL of
hexane) to afford colorless, crystalline 2,4-dichlorophenacylidene
bromide (2), yield 35.5g, (51%), purity (GC): 99.3%, mp 27–301C;
(28.5–29.51C6).
The work was supported by the Polish Ministry of Science and
Higher Education, 429/E-142/S/2009.
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´
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0.02 Torr. Purity (GC): 94% (sum of
E and Z isomers),
Rt = 17.26 min (E, 3.52%,), 17.56 min (Z, 90.44%). 1H NMR dH
(CDCl3): 6.06 (d, 1H, JPH = 1 Hz, CHBr), 7.28 (dd, 1H, J = 2.0, 8.3 Hz,
Har), 7.42 (d, 1H, J = 8.3 Hz, Har), 7.44 (d, 1H, J = 2 Hz, Har); 13C NMR
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(quintet of doublets, JCD = 22.9 Hz, JCP = 5.9 Hz, OCD2CD3), 97.7
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Copyright r 2011 John Wiley & Sons, Ltd.
J. Label Compd. Radiopharm 2011, 54 399–400