Chemiluminescence of Phosphonate Carbanions
C17H18NO3P: C, 64.76; H, 5.75; N, 4.44. Found: C, 64.54; H,
5.76; N, 4.32.
(29), 206 (51). Anal. Calcd for C15H14NO3P: C, 62.72; H, 4.88;
N, 4.88. Found: C, 62.60; H, 4.91; N, 5.27.
9-(5′,5′-Dim eth yl-2′-oxo-2′λ5-[1′,3′,2′]dioxaph osph or in an -
2′-yl)-10-h yd r oa cr id a n e (3e). This was prepared similarly
to the above procedure using N-hydroacridinium bromide (2.00
g, 7.68 mmol) and 5,5-dimethyl-2-methoxy-1,3,2-dioxaphos-
phorinane (1.89 g, 11.5 mmol), obtained from the reaction of
methyl dichlorophosphite and 2,2-dimethyl-1,3-propnediol in
the presence of triethylamine in benzene. The product was
recrystallized from acetonitrile (1.68 g, 67%): mp 187-188 °C;
1H NMR δ 0.53, 0.93 (s, 6H), 3.48-3.53, 3.92-3.97 (m, 4H),
4.70 (d, 1H, J PH ) 26 Hz), 6.69-6.71, 6.89-6.91, 7.10-7.14,
7.29-7.31 (m, 8H); 13C NMR δ 18.83, 19.73 (J PC ) 7 Hz), 41.36
(d, J PC ) 137 Hz), 74.51 (d, J PC ) 8 Hz), 112.05, 112.51, 119.13,
126.54, 128.57, 138.34; 31P NMR δ 16.71; MS (m/z) 329 [M+]
(2.5), 59 (100). Anal. Calcd for C18H20NO3P: C, 65.65; H, 6.12;
N, 4.25. Found: C, 65.72; H, 6.08; N, 4.07.
9-Dim eth ylp h osp h on o-10-m eth yla cr id a n e (4a ), 9-d i-
eth ylp h osp h on o-10-m eth yla cr id a n e (4b), 9-bis(2′,2′,2′-
t r iflu or oet h yl)p h osp h on o-10-m et h yla cr id a n e (4c), and
9-d ip h en ylp h osp h on o-10-m eth yla cr id a n e (4f) are known
compounds and were prepared by the established procedure.4b
9-(4′,5′-Dim eth yl-2′-oxo-2′λ5-[1′,3′,2′]d ioxa p h osp h ola n -
2′-yl)-10-m eth yla cr id a n e (4d ). This was prepared similarly
to the above procedure using N-methylacridinium iodide (1.60
g, 5.00 mmol) and 4,5-dimethyl-2-methoxy-1,3,2-dioxaphos-
pholane (1.60 g, 5.00 mmol, mixture of stereoisomers). The
product was recrystallized from benzene/hexane (0.37 g,
49%): mp 201-202 °C; 1H NMR δ 0.66, 0.85, 1.17 (d, 6H, J )
6 Hz), 2.85-2.92, 4.02-4.08, 4.61-4.68 (m, 2H), 3.35 (s, 3H),
4.78 (d, 1H, J PH ) 22 Hz), 6.86-6.98, 7.22-7.35 (m, 8H); 13C
NMR δ 15.11, 17.49, 18.05, 33.54, 43.92, 45.20 (d, J PC ) 129
Hz), 80.41, 83.66, 112.89, 118.50, 121.28, 128.84, 130.40,
143.25; 31P NMR δ 39.49, 39.71, 40.42 (mixture of stereoiso-
mers); MS. m/z 329 [M+] (4.3), 180 (100). Anal. Calcd for
9-Dieth ylp h osp h on oa cr id in e (7b). This was prepared
similarly to the above procedure using 3b (1.72 g, 5.42 mmol)
and chloranil (1.60 g, 6.51 mmol). The crude product was
recrystallized from ether (0.70 g, 41%): mp 82-84 °C; 1H NMR
(60 MHz) δ 1.28 (t, 6H, J ) 7.2 Hz), 4.18 (dq, 4H, J ) 7.2 Hz,
J PH ) 14.4 Hz), 7.41-7.86 (m, 4H), 9.11-9.27 (m, 4H); MS
(m/z) 315 [M+] (100), 286 (29), 206 (51). Anal. Calcd for C17H18
-
NO3P: C, 64.76; H, 5.75; N, 4.44. Found: C, 64.64; H, 5.66;
N, 4.81.
Ca libr a tion of P h otom u ltip lier . It is known23 that au-
toxidation of a luminol solution having an absorbance of 1.0
produces photons of 1.62 × 10-6 mol/L in the reaction with
excess t-BuOK in t-BuOH; therefore, the correction value (G)
for the photomultiplier is defined by
Vlumi
G ) (1.62 × 10-6)Abslumi
Nlumi
where Abslumi is the absorbance, Vlumi is the volume of the
luminol solution, and Nlumi is the count number determined
by an average of at least five measurements. Because a luminol
solution of a certain concentration suitable for the capacity of
the photomultiplier used in this study was required, the
absorbance at 359.5 nm of a stock luminol solution (1.6 × 10-7
M) in distilled DMSO was determined to be 1.22 × 10-3 from
a calibration curve of the luminol solution. To this luminol
solution (2.0 mL) in a quartz cell was added t-BuOK solution
(0.3 mL, 2.0 × 10-2 M) in t-BuOH, and the photons generated
immediately were counted. The G value was calculated ac-
cording to the above equation.
Mea su r em en t of CL Qu a n tu m Yield s. The total CL
quantum yields (ΦCL) were calculated according to
Rphoto
ΦCL) GN
C
18H20NO3P: C, 65.65; H, 6.12; N, 4.25. Found: C, 65.63; H,
(
)
M
6.31; N, 4.48.
9-(5′,5′-Dim eth yl-2′-oxo-2′λ5-[1′,3′,2′]d ioxa p h osp h or a n -
2′-yl)-10-m eth yla cr id a n e (4e). This was prepared similarly
to the above procedure using N-methylacridinium iodide (1.12
g, 3.50 mmol) and 5,5-dimethyl-2-methoxy-1,3,2-dioxaphos-
phorinane (2.22 g, 12.5 mmol). The product was recrystallized
from benzene/hexane (0.90 g, 75%): mp 242-243 °C; 1H NMR
δ 0.52, 0.95 (s, 6H), 3.38 (s, 3H), 3.39-3.43, 3.89-3.94 (m, 4H),
4.67 (d, 1H, J PH ) 26 Hz), 6.87-6.98, 7.23-7.36 (m, 8H); 13C
NMR δ 21.06, 21.95, 32.60 (d, J PC ) 7 Hz), 33.58, 44.92 (d,
J PC ) 136 Hz), 76.71-76.99 (m), 112.77, 118.63, 121.31, 128.76,
130.37, 143,23; 31P NMR δ 16.20; MS (m/z) 343 [M+] (3.6), 194
(100). Anal. Calcd for C19H22NO3P: C, 66.46; H, 6.46; N, 4.08.
Found: C, 66.51; H, 6.48; N, 4.28.
where N is the average number of the counts, Rphoto the
correction factor given by the manufacturer for the fluores-
cence emission maximum of the fluorophores, and M is the
moles of phosphonoacridanes. For a typical run, a solution (1.0
mL) containing 3 or 4 (1.00 × 10-3 M) in distilled DMSO was
placed in a 1 × 1 cm2 quartz cuvette in front of the photomul-
tiplier in exactly the same geometry. Photon-counting was
initiated simultaneously with the injection of a solution (0.5
mL) of t-BuOK (2.00 × 10-1 M) in DMSO into the cuvette, and
the data collection was continued for 512 s. The total CL
quantum yields were calculated according to the above equa-
tion.
Ack n ow led gm en t. This work was partially sup-
ported by a Grant-in-Aid for the 21st Century COE
Research (14B1-30) by the Ministry of Education,
Culture, Sports, Science and Technology of J apan.
9-Dim et h ylp h osp h on oa cr id in e (7a ). A solution of 3a
(3.80 g, 13.1 mmol) and chloranil (3.88 g, 15.8 mmol) in
benzene (150 mL) was heated under reflux for 4 h. After
removal of the solvent, purification by column chromatography
(eluant hexane/AcOEt ) 6/1) gave the product, which was
recrystallized from chloroform/hexane (2.44 g, 65%): mp 164-
J O030046L
1
166; H NMR (60 MHz) δ 3.85 (d, 6H, J PH ) 11.4 Hz), 7.27-
(23) Lee, J .; Seliger, H. H. Photochem. Photobiol. 1965, 4, 1015-
1048.
7.94 (m, 4H), 8.18-8.40 (m, 4H); MS (m/z) 315 [M+] (100), 286
J . Org. Chem, Vol. 68, No. 15, 2003 5955