TABLE 3. 1H NMR Chemical Shifts and 1H-1H Coupling Constants of the Synthesized PBDEs
PBDE no.
δ (from TMS)
BDE-1
7.63 (H3, dd, J ) 7.9, 1.6 Hz), 7.34 (H3′, H5′, t, J ) 8.6, 7.5 Hz), 7.25 (H5, dt, J ) 8.6, 7.5, 1.6 Hz), 7.11 (H4′, t,
J ) 7.5 Hz), 7.01 (H4, t, J ) 7.9, 7.5, 1.5 Hz), 6.97 (H2′, H6′ d, J ) 8.6 Hz), 6.96 (H6, d, J ) 8.6, 1.5 Hz)
7.36 (H3′, H5′, t, J ) 8.3, 7.5 Hz), 7.22 (H4, dt, J ) 7.9, 2.2 Hz), 7.18 (H5, t, J ) 7.9, 7.7 Hz), 7.15 (H4′, t,
J ) 7.5 Hz), 7.14 (H2, t, J ) 2.2 Hz), 7.02 (H2′, H6′, d, J ) 8.3 Hz), 6.93 (H6, dt, J ) 7.7, 2.2 Hz)
7.43 (H3, H5, d, J ) 9.2 Hz), 7.35 (H3′, H5′, t, J ) 8.1, 7.6 Hz), 7.12 (H4′, t, J ) 7.6 Hz), 7.00 (H2′, H6′, d,
J ) 8.1 Hz), 6.88 (H2, H6, d, J ) 9.2 Hz)
BDE-2
BDE-3
BDE-7
BDE-8
BDE-10
BDE-12
BDE-13
7.77 (H3, d, J ) 2.2 Hz), 7.36 (H5, dd, J ) 8.8, 2,2 Hz), 7.35 (H3′, H5′, t, J ) 8.3, 7.6 Hz), 7.13 (H4′, t, J ) 7.6 Hz),
6.96 (H2′, H6′, d, J ) 8.3 Hz), 6.81 (H6, d, J ) 8.8 Hz)
7.64 (H3, dd, J ) 7.9, 1.6 Hz), 7.43 (H3′, H5′, d, J ) 9.2 Hz), 7.28 (H5, dt, J ) 8.1, 7.7, 1.6 Hz), 7.05 (H4, dt,
J ) 7.9, 7.7, 1.5 Hz), 6.98 (H6, dd, J ) 8.1, 1.5 Hz), 6.83 (H2′, H6′, d, J ) 9.2 Hz)
7.61 (H3, H5, d, J ) 8.1 Hz), 7.30 (H3′, H5′, t, J ) 8.3, 7.5 Hz), 7.05 (H4′, t, J ) 7.5 Hz), 7.01 (H4, t, J ) 8.1 Hz),
6.81 (H2′, H6′, d, J ) 8.3 Hz)
7.53 (H5, d, J ) 8.8 Hz), 7.38 (H3′, H5′, t, J ) 8.5, 7.3 Hz), 7.25 (H2, d, J ) 2.9 Hz), 7.17 (H4′, t, J ) 7.3 Hz),
7.01 (H2′, H6′, d, J ) 8.5 Hz), 6.83 (H6, dd, J ) 8.8, 2.9 Hz)
7.46 (H3′, H5′, d, J ) 9.0 Hz), 7.24 (H4, dt, J ) 7.7, 1.8 Hz), 7.19 (H5, t, J ) 7.7 Hz), 7.13 (H2, t, J ) 1.8 Hz),
6.93 (H6, dt, J ) 7.7, 1.8 Hz), 6.90 (H2′, H6′, d, J ) 9.0 Hz)
BDE-15
BDE-17
7.44 (H3, H5, H3′, H5′, d, J ) 9.0 Hz), 6.88 (H2, H6, H2′, H6′, d, J ) 9.0 Hz)
7.78 (H3, d, J ) 2.2 Hz), 7.64 (H3′, dd, J ) 7.9, 1.8 Hz), 7.34 (H5, dd, J ) 8.8, 2.2 Hz), 7.28 (H5′, dt, J ) 8.1,
7.3, 1.8 Hz), 7.06 (H4′, dt, J ) 7.9, 7.3, 1.5 Hz), 6.89 (H6′, dd, J ) 8.1, 1.5 Hz), 6.66 (H6, d, J ) 8.8 Hz)
7.79 (H3, d, J ) 2.2 Hz) 7.41 (H5, dd, J ) 8.8, 2.2 Hz), 7.25 (H4′, dt, J ) 8.1, 2.2, 1.8 Hz), 7.19 (H5′, t,
J ) 8.1, 8.0 Hz), 7.09 (H2′, t, J ) 2.2, 1.8 Hz), 6.88 (H6′, dt, J ) 8.0, 2.2, 1.8 Hz), 6.87 (H6, d, J ) 8.8 Hz)
7.78 (H3, d, J ) 2.3 Hz), 7.44 (H3′, H5′, d, J ) 8.8 Hz), 7.39 (H5, dd, J ) 8.5, 2.3 Hz), 6.84 (H6, d, J ) 8.5 Hz),
6.83 (H2′, H6′, d, J ) 8.8 Hz)
BDE-25
BDE-28
BDE-30
BDE-32
BDE-33
7.76 (H3, H5, s), 7.30 (H3′, H5′, t, J ) 8.6, 7.5 Hz), 7.06 (H4′, t, J ) 7.5 Hz), 6.80 (H2′, H6′, d, J ) 8.6 Hz)
7.61 (H3, H5, d, J ) 8.1 Hz), 7.40 (H3′, H5′, d, J ) 9.2 Hz), 7.03 (H4, t, J ) 8.1 Hz), 6.70 (H2′, H6′, d, J ) 9.2 Hz)
7.65 (H3′, dd, J ) 7.9, 1.8 Hz), 7.53 (H5, d, J ) 8.8 Hz), 7.32 (H5′, dt, J ) 8.1, 7.7, 1.8 Hz), 7.19 (H2, d, J ) 2.6 Hz),
7.10 (H4′, dt, J ) 7.9, 7.7, 1.5 Hz), 7.03 (H6′, dd, J ) 8.1, 1.5 Hz), 6.77 (H6, dd, J ) 8.8, 2.6 Hz)
7.57 (H5, d, J ) 8.8 Hz), 7.29 (H4′, dt, J ) 8.1, 1.8 Hz), 7.27 (H2, d, J ) 2.9 Hz), 7.22 (H5′, t, J ) 8.1, 7.7 Hz),
7.16 (H2′, t, J ) 2.2, 1.8 Hz), 6.94 (H6′, ddd, J ) 7.7, 2.2, 1.8 Hz), 6.84 (H6, dd, J ) 8.8, 2.9 Hz)
7.55 (H5, d, J ) 8.8 Hz), 7.47 (H3′, H5′, d, J ) 8.8 Hz), 7.24 (H2, d, J ) 2.6 Hz), 6.90 (H2′, H6′, d, J ) 8.8 Hz),
6.82 (H6, dd, J ) 8.8, 2.6 Hz)
BDE-35
BDE-37
BDE-47
BDE-49
7.79 (H3, H3′ d, J ) 2.2 Hz), 7.38 (H5, H5′, dd, J ) 8.8, 2.2 Hz), 6.71 (H6, H6′, d, J ) 8.8 Hz)
7.80 (H3, d, J ) 2.2 Hz), 7.50 (H3′, d, J ) 8.8 Hz), 7.41 (H5, dd, J ) 8.8, 2.2 Hz), 7.17 (H4′, dd, J ) 8.8, 2.2 Hz),
6.91 (H6′, d, J ) 2.2 Hz), 6.78 (H6, d, J ) 8.4 Hz)
BDE-51
BDE-66
BDE-71
7.78 (H3, d, J ) 2.2 Hz), 7.62 (H3′, H5′, d, J ) 8.1 Hz), 7.25 (H5, dd, J ) 8.8, 2.2 Hz), 7.05 (H4′, t, J ) 8.1 Hz),
6.26 (H6, d, J ) 8.8 Hz)
7.80 (H3, d, J ) 2.2 Hz), 7.55 (H5′, d, J ) 8.8 Hz), 7.43 (H5, dd, J ) 8.8, 2.2 Hz), 7.19 (H2′, d, J ) 2.9 Hz),
6.89 (H6, d, J ) 8.8 Hz), 6.77 (H6′, dd, J ) 8.8, 2.9 Hz)
7.62 (H3, H5, d, J ) 8.1 Hz), 7.51 (H5′, d, J ) 8.8 Hz), 7.09 (H2′, d, J ) 2.9 Hz), 7.05 (H4, t, J ) 8.1 Hz), 6.65
(H6′, dd, J ) 8.8, 2.9 Hz)
BDE-75
BDE-77
7.76 (H3, H5, s), 7.40 (H3′, H5′, d, J ) 9.2 Hz), 6.69 (H2′, H6′, d, J ) 9.2 Hz)
7.58 (H5, H5′, d, J ) 8.8 Hz), 7.27 (H2, H2′, d, J ) 2.9 Hz), 6.84 (H6, H6′, dd, J ) 8.8, 2.9 Hz)
7.78 (H3′, d, J ) 2.2 Hz), 7.77 (H3, H5, s), 7.26 (H5′, dd, J ) 8.8, 2.2 Hz), 6.27 (H6′, d, J ) 8.8 Hz)
7.32 (H3′, H5′, t, J ) 8.1, 7.4 Hz), 7.09 (H4′, t, J ) 7.4 Hz), 6.79 (H2′, H6′, d, J ) 8.1 Hz)
7.77 (H3, H5, s), 7.52 (H5′, d, J ) 8.8 Hz), 7.08 (H2′, d, J ) 2.9 Hz), 6.64 (H6′, dd, J ) 8.8, 2.9 Hz)
7.78 (H3′, H5′, s), 7.45 (H5, d, J ) 8.8 Hz), 6.24 (H6, d, J ) 8.8 Hz)
BDE-100
BDE-116
BDE-119
BDE-140
BDE-154
BDE-166
BDE-181
BDE-190
7.88 (H3, s), 7.79 (H3′, H5′, s), 6.58 (H6, s)
7.42 (H3′, H5′, d, J ) 9.2 Hz), 6.68 (H2′, H6′, d, J ) 9.2 Hz)
7.80 (H3′, d, J ) 2.2 Hz), 7.27 (H5′, dd, J ) 8.8, 2.2 Hz), 6.25 (H6′, d, J ) 8.8 Hz)
7.53 (H5′, d, J ) 8.8 Hz), 7.09 (H2′, d, J ) 2.9 Hz), 6.62 (H6′, dd, J ) 8.8, 2.9 Hz)
2,5-dibromoaniline as previously described (20), but it was
isolated and purified differently.
wavelengths. Characteristic absorption bands were observed
for all PBDE congeners between 265 and 300 nm, with
ꢀ values that are 1 or 2 orders of magnitude lower than
ꢀ values at the largest absorption maxima.
BDE-77 was prepared in high yield by bromination of
BDE-35 using bromine as the bromination reagent, similar
to the way Tolstaya et al. (30) brominated 3,3′-diBDE (BDE-
11) leading to BDE-77. BDE-140 and BDE-154 were prepared
by bromination of BDE-119 using bromine as the bromination
reagent. BDE-140 and BDE-154 coeluted to some extent on
silica gel and were therefore only partly separated.
To our knowledge, 21 of the PBDEs and 2 of the iodonium
salts, 2,2′,4,4′-tetrabromodiphenyliodonium chloride and
3,3′,4,4′-tetrabrom odiphenyliodonium chloride, are de-
scribed here for the first time.
All monoBDEs, most of the di- and triBDEs, and two
tetraBDEs were oils at room temperature, whereas the
majority of the tetraBDEs and higher brominated PBDEs were
solids with melting points between 70 and 200 °C (Table 2).
The UV spectra of the PBDEs showed the largest maximum
absorbance between 200 and 230 nm. Highly brominated
PBDEs had the largest maximum absorbance at longer
In the case of mass spectra data only the most abundant
ions are given (Table 2). The major ions corresponded to the
molecular ion (M+) or the loss of one (for the monoBDEs)
or two bromine substituents (for the di-heptaBDEs). The
molecular ion was the base peak of PBDEs with no bromine
substituents in the ortho positions, whereas the base peak
of ortho-brominated PBDE congeners corresponded to m/ z
(M - 2Br)+. The only exception to this rule was 2,2′,4,4′,6-
pentaBDE (BDE-100), which had the molecular ion as the
base peak. Doubly charged ions were observed of an intensity
up to 60% of the base peak in some of the PBDE mass spectra.
1H chemical shifts for the PBDE protons occur in the shift
region δ 6.24-7.88 (Table 3). The 1H chemical shifts for ortho-
hydrogens of tri-ortho-substituted PBDEs were significantly
upfield. Similar observations have previously been reported
for PCDEs (17, 32). This diamagnetic shielding of the ortho-
9
3 0 3 6 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 33, NO. 17, 1999