Synthesis of advanced fluorescent probes
Russ.Chem.Bull., Int.Ed., Vol. 65, No. 11, November, 2016 2727
=
CH); 7.2—8.15 (m, 16 H, =CH and arom.). 13C NMR
6.32—6.35, 6.57—6.63, 6.99—7.02, 7.26—7.30, 7.43—7.46 (all
m, 1 H each, HC=CH); 7.68—7.83 (m, 2 H, arom., =CH);
7.94—8.32 (m, 10 H, arom., =CH); 8.59 (t, 2 H, arom., J = 7.7 Hz);
3
(
DMSOꢀd ), δ: 16.5 (d, OCH CH , J = 5.1 Hz); 20.1, 21.3,
6
2
3
CP
1
3
(
1
both s, C(CH ) ); 26.0 (d, CH P, J = 144.1 Hz); 26.2 (d, CH P,
JCP = 136.1 Hz); 27.5, 27.6 (both s, CH ); 53.5 (s, N CH );
3
2
2
CP
2
+
2
2
9.01 (d, 3 H, POH, J = 5.7 Hz); 9.24 (d, 1 H, POH, J
=
2
2
HP
HP
2
13
5
3.9 (s, C(CH ) ); 56.06 (s, C(CH ) ); 61.7 (d, OCH , J
=
= 5.7 Hz). C NMR (CD OD), δ: 19.72 (s, CH ); 20.42
(s, CH ); 21.00 (s, C(CH ) ); 25.53 (d, CH P, J = 142.7 Hz);
2 3 2 2 CP
25.77 (d, CH P, J = 137.6 Hz); 26.24 (s, C(CH ) ); 27.16
2 CP 3 2
3
2
3 2
2
CP
3
2
1
=
5.1 Hz); 94.78, 103.5, 110.3, 122.1, 122.2, 122.3, 124.9, 127.7,
1
1
1
28.3, 130.0, 130.6, 131.7, 133.9 (all s, arom.); 154.3, 154.7,
55.5 (all s, =CH); 175.9 (s, NC=); 183.6 (s, N=C). P NMR
31
(s, CH ); 28.29(s, CH ); 31.61 (s, C(CH ) ); 31.76 (s, C(CH ) );
2 2 3 2 3 2
–
1
+
(
DMSOꢀd ), δ: 31.50, 31.63, 31.68. IR, ν/cm : 1065 (P—O—
56.63 (s, C(CH ) ); 58.07 (s, N CH ); 61.24 (s, C(CH ) ); 63.43
3 2 2 3 2
6
+
+
C H ), 1215 (P=O). Found: m/z 837.4132 [M – Br] .
(s, N CH ); 108.92 (s, arom.); 112.49, 118.82 (both s, =CH);
2
5
2
C H N O P . Calculated: M = 837.4154.
123.01, 124.15 (both s, arom.); 127.28 (s, =CH); 128.15, 128.30,
129.33, 129.65, 130.35, 131.07, 131.07 (all s, arom.); 135.80,
144.62, 145.48 (all s, =CH); 174.43 (s, NC=); 183.86 (s, N=C).
4
9
63
2
6 2
2
ꢀ((1E,3E,5E,7Z)ꢀ1,7ꢀBis[4ꢀ(diethoxyphosphoryl)butyl]ꢀ
3
,3ꢀdimethylꢀ3Hꢀbenzo[e]indolꢀ2(3H)ꢀylidene)heptaꢀ1,3,5ꢀtriꢀ
31
–1
2–
enyl)ꢀ3,3ꢀdimethylꢀ1Hꢀbenzo[e]indolium bromide (7b). The yield
P NMR (CD OD), δ: 28.66. IR, ν/cm : 1088 (PO3) . Found:
3
1
–
was 20%. H NMR (CD OD), δ: 1.23—1.32 (m, 12 H,
m/z 751.3086 [M – Br – 2 H] . C H N O P . Calculated:
3
43 51
2
6 2
OCH CH ); 1.75—1.90 (m, 8 H, CH ); 2.00 (s, 12 H C(CH ) );
M = 751.3071.
2
3
2
3 2
2
.02—2.25, 2.10—2.15 (both m, 4 H, CH P); 3.97—4.07 (m, 4 H,
2ꢀ((1E,3E,5E,7Z)ꢀ1,7ꢀBis{3,3ꢀdimethylꢀ3ꢀ[5ꢀ(dihydroxyꢀ
phosphoryl]pentyl}ꢀ3Hꢀbenzo[e]indolꢀ2(3H)ꢀylidene)heptaꢀ1,3,5ꢀ
trienyl)ꢀ3Hꢀbenzo[e]indolium bromide (7e). The yield was 12%.
2
+
OCH ); 4.21—4.30 (m, 4 H, CH N ); 6.35—6.40 (m, 1 H,
2
2
=
7
CH); 6.57—6.67 (m, 2 H, =CH); 7.47—7.49 (m, 2 H, =CH);
.59—7.65 (m, 4 H, arom.); 7.74—7.77 (m, 2 H, arom.); 7.82—7.84
m, 2 H, =CH); 7.95—8.10, 8.22—8.31 (both m, 6 H, arom.).
1
H NMR (CD OD), δ: 0.70—1.00, 1.02—1.48 (both m, 4 H,
3
(
7 H, CH , C(CH ) ); 1.50—1.78 (m, 10 H, C(CH ) , CH );
2
3 2
3 2
2
1
3
3
C NMR (CD OD), δ: 16.18 (d, OCH CH , J = 5.8 Hz);
1.82 (s, 3 H, C(CH ) ); 1.97—2.07 (m, 4 H, CH P); 4.63 (t, 4 H,
3 2 2
3
2
3
CP
3
+
3
1
6.39 (d, OCH CH , JCP = 5.1 Hz); 21.78, 21.82, (both s,
CH N , J = 7.7 Hz); 6.30—6.35, 6.56—6.67, 6.76—6.83,
2
3
2
1
C(CH ) ); 22.64 (s, CH ); 23.12 (d, CH P, J = 139.8 Hz);
2
7.11—7.20, 7.39—7.48 (all m, 1 H each, HC=CH); 7.55—7.66
(m, 1 H, =CH); 7.68—7.83 (m, 3 H, arom., =CH); 7.95—8.04
(m, 2 H, arom.); 8.07—8.34 (m, 6 H, arom.); 8.58 (t, 2 H, arom.,
3
2
2
2
CP
1
6.95 (d, CH P, J = 151.5 Hz); 29.67, 30.20 (both s, CH );
2 CP 2
0.23, 50.33 (both s, N CH ); 61.70, 62.68 (both d, OCH ,
2 2
+
5
2
3
2
JCP = 7.32 Hz); 62.25 (s, C(CH ) ); 108.02, 110.85, 111.22,
J = 7.7 Hz); 9.01 (d, 3 H, POH, J = 5.7 Hz); 9.24 (d, 1 H,
3 2
HP
2
13
1
1
27.83, 127.86, 128.16, 128.18, 129.90, 129.98, 130.70, 130.78,
35.86, 142.06, (all s, arom.); 147.77, 157.75, 158.74, 159.79 (all
POH, J = 5.7 Hz). C NMR (CD OD), δ: 18.81 (s, CH );
HP 3 2
19.48 (s, CH ); 22.51 (s, CH ); 24.02 (s, CH ); 24.09
2 2 2
31
1
s, =CH); 174.00 (s, NC=); 184.74 (s, N=C). P NMR (CD OD),
δ: 30.29. IR, ν/cm–1: 1055 (P—O—C H ), 1210 (P=O).
Found: m/z 865.4467 [M – Br] . C H N O P . Calculated:
(s, C(CH ) ); 27.74 (d, CH P, J = 141.4 Hz); 27.78 (d, CH P,
3 2 2 CP 2
3
1
JCP = 137.3 Hz); 28.82 (s, C(CH ) ); 29.89 (s, C(CH ) ); 30.67
2
5
3 2
3 2
+
+
(s, C(CH ) ); 30.98 (s, CH ); 31.35 (s, CH ); 42.69 (s, N CH );
3 2 2 2 2
43.40 (s, N CH ); 57.79 (s, C(CH ) ); 62.99 (s, C(CH ) );
51
67
2
6
2
+
M = 865.4469.
ꢀ(5ꢀ(Ethoxy(hydroxy)phosphoryl)pentyl)ꢀ2ꢀ((1E,3E,5E,7Z)ꢀ
ꢀ(3ꢀ(5ꢀ(diethoxyphosphoryl)pentyl)ꢀ1,1ꢀdimethylꢀ1Hꢀbenzoꢀ
e]indolꢀ2(3H)ꢀylidene)heptaꢀ1,3,5ꢀtrienyl)ꢀ1,1ꢀdimethylꢀ1Hꢀ
2 3 2 3 2
3
109.20 (s, arom.); 114.60, 122.81 (both s, =CH); 126.03 (s, arom.);
127.70 (s, =CH); 127.86, 129.63, 130.35, 130.02, 132.59, 132.69,
138.08, 139.65 (all s, arom.); 135.80, 144.73,146.15, 153.82 (all s,
7
[
1
31
benzo[e]indolium bromide (7´c). The yield was 25%. H NMR
=CH); 168.53 (s, NC=); 189.50 (s, N=C). P NMR (CD OD),
3
–
1
2–
(
(
DMSOꢀd ), δ: 0.81—1.0 (br.m, 3 H, OCH CH ); 1.0—2.00
br.m, 26 H); 3.75—4.10 (br.m, 6 H, OCH ); 4.15—4.40 (br.m,
δ: 28.41. IR, ν/cm : 1088 (PO3) . Found: m/z 779.3419. [M –
– Br – 2 H] . C H N O P . Calculated: M = 779.3384.
6
2
3
–
2
45 53
2
6 2
+
4
1
H, CH N ); 6.44—6.41 (br.m, 1 H, =CH); 7.40—8.32 (br.m,
8 H, =CH and arom.). C NMR (DMSOꢀd ), δ: 16.33
2
1
3
The work was carried out using equipment purchased
at the expense of the Moscow State University Developꢀ
ment Program.
6
3
3
(
d, OCH CH , J = 5.8 Hz); 16.50 (d, OCH CH , J
=
CP
2
3
CP
2
3
3
=
2
5.8 Hz); 16.57 (d, OCH CH , J = 6.6 Hz); 22.93 (s, CH );
2 3 CP 2
2.96 (s, CH ); 24.78 (d, CH P, JCP = 144.9 Hz); 26.37
1
2
2
1
(
d, CH P, J = 139.0 Hz); 26.98 (s, CH ); 27.15 (s, CH ); 26.70,
This work was financially supported by the Russian
Science Foundation (Program "Carrying out Fundamenꢀ
tal Scientific Studies and Pioneering Scientific Studies by
Scientific Groups", Project No. 14ꢀ13ꢀ00698).
2
CP
2
2
2
6.78 (both s, C(CH ) ); 27.40, 27.51 (both s, CH ); 44.71, 45.15
3 2 2
+
(
(
(
both s, N CH ); 51.58, 52.86 (both s, C(CH ) ); 61.04, 61.52,
both s, OCH ); 63.70 (d, OCH , JCP = 7.32 Hz); 93.07
s, =CH); 101.96 (s, =CH); 112.03, 122.66, 124.77, 127.63, 128.16,
30.21, 130.32, 131.00, 131.23, 131.65, 133.49, 136.37 (all s,
arom.); 142.83, 144.97, 146.62, 155.37, 156.36 (all s, =CH);
2
3
2
2
2
2
1
Reference
3
1
1
3
71.22 (s, NC=); 183.54 (s, N=C). P NMR (DMSOꢀd ), δ:
6
1.87, 22.69. IR, ν/cm–1: 1078 (P—O—C H ), 1194 (P=O).
1. H. A. Shindy, MiniꢀRev. Org. Chem., 2012, 9, 352.
2. A. Mishra, R. K. Behera, B. K Mishra, G. B. Behera, Chem.
Rev., 2000, 100, 1973.
3. M. Panigrahi, S. Dash, S. Patel, B. K. Mishra, Tetrahedron,
2012, 68, 781.
2
5
+
Found: m/z 865.4453 [M – Br] . C H N O P . Calculated:
M = 865.4469.
ꢀ((1E,3E,5E,7Z)ꢀ7ꢀ[3,3ꢀDimethylꢀ1ꢀ(4ꢀ(dihydroxyphosꢀ
5
1
67
2
6 2
2
phoryl)butyl]ꢀ1Hꢀbenzo[e]indolꢀ2(3H)ꢀylidene)heptaꢀ1,3,5ꢀtriꢀ
enyl)ꢀ3,3ꢀdimethylꢀ1ꢀ(4ꢀ(dihydroxyphosphoryl)butyl)ꢀ3Hꢀbenzoꢀ
4. J. Yin, Y. Kwon, D. Kim, D. Lee, G. Kim, Y. Hu, J.ꢀH. Ryu,
J. Yoon, J. Am. Chem. Soc., 2014, 136, 5351.
5. A. Gorka, R. Nani, M. Schnermann, Org. Biomol. Chem.,
2015, 13, 7584.
1
[
e]indolium bromide (7d). The yield was 13%. H NMR (CD OD),
3
δ: 1.68—1.86 (m, 16 H, C(CH ) , CH ); 1.90—2.01 (m, 4 H,
3
2
2
+
CH ); 2.07—2.14 (m, 4 H, CH P); 4.62—4.68 (m, 4 H, CH N );
2
2
2