Cooperative Ratiometric Chemosensors
J . Org. Chem., Vol. 66, No. 20, 2001 6511
removed in vacuo. Flash chromatography (EtOAc/Hex, 35:65)
1349, 1282, 1256, 1163, 1072, 911, 816, 650 cm-1. HRMS for
M + Na+ calcd for C72H56N2O12S2Na: 1227.1372. Found:
1227.3120.
afforded compound 5 as a white solid (37.6 g, 69.7 mmol, 94%
1
yield). Mp 61-62 °C; H NMR (400 MHz) δ 2.61 (s, 1H), 3.14
(s, 3H), 3.76 (s, 6H), 6.71 (d, J ) 8.9 Hz, 4H), 6.87 (t, J ) 1.9
Hz, 1H), 7.01 (d, J ) 8.8 Hz, 4H),7.17-7.28 (m, 3H), 7.39 (dd,
J ) 1.8, 6.0 Hz, 1H), 7.58-7.64 (m, 2H), 7.74 (d, J ) 8.7 Hz,
1H), 7.84 (d, J ) 8.1 Hz, 1H), 7.88 (d, J ) 8.1 Hz, 1H), 8.12 (s,
1H); 13C NMR (100 MHz) δ 38.6, 55.7, 81.4, 113.6, 123.4, 125.4,
126.4, 127.1, 127.6, 128.1, 128.6, 129.0, 129.0, 129.1, 129.3,
129.5, 132.4, 134.0, 135.2, 139.2, 141.5, 148.7, 159.1; IR (neat)
3507, 3058, 3001, 2954, 2836, 1607, 1508, 1347, 1250, 1175,
1033, 828, 734 cm-1; HRMS calcd for C32H29NO5SNa (M +
Na+): 562.1664. Found: 562.1676.
Com p ou n d 6. A solution of compound 5 (18 g, 33.4 mmol)
and acetyl chloride (180 mL) was stirred at room temperature
for 2 h. The acetyl chloride was removed in vacuo, and the
resulting solid was carefully dried under high vacuum. The
solid was dissolved in benzene (1 L). The solution was sparged
with a steady stream of argon for 15 min. Ethynylmagnesium
bromide (334 mL, 167 mmol, 0.5M in THF) was added to the
reaction and stirred at room temperature for 1.5 h. The
reaction was quenched with saturated NH4Cl, and the aqueous
layer was extracted with CH2Cl2 (3 × 125 mL). The organic
layer was then dried over MgSO4, and the solvent was removed
in vacuo. Flash chromatography (EtOAc/Hex, 30:70) afforded
compound 6 as an amorphous solid (15.5 g, 28.3 mmol, 85%
yield). 1H NMR (400 MHz) δ 2.39 (s, 1H), 3.12 (s, 3H), 3.75 (s,
6H), 6.68 (d, J ) 8.9 Hz, 4H), 6.75 (t, J ) 1.8 Hz, 1H), 6.98 (d,
J ) 8.8 Hz, 4H), 7.18 (dt, J ) 1.8, 7.1 Hz, 1H), 7.22-7.28 (m,
2H), 7.43 (dd, J ) 1.7, 8.6 Hz, 1H), 7.56-7.66 (m, 2H), 7.78
(d, J ) 8.7 Hz, 1H), 7.87 (t, J ) 8.8 Hz, 2H), 8.12 (s, 1H); 13C
NMR (100 MHz) δ 38.7, 54.3, 55.6, 73.6, 89.8, 113.7, 123.6,
126.5, 126.8, 127.8, 128.3, 128.5, 128.9, 129.2, 129.3, 129.5,
129.8, 130.3, 132.4, 134.0, 135.2, 136.9, 141.6, 146.8, 158.8;
IR (neat) 3289, 3057, 2932, 2835, 1605, 1507, 1347, 1251, 1177,
1033, 826 cm-1; HRMS calcd for C34H29NO4SNa (M + Na+):
570.1715. Found: 570.1714.
Com p ou n d 1a . AcOH (1.5 mL, glacial) was added to a
stirred solution of EtOH (13.5 mL), compound 8 (241 mg, 0.20
mmol), and N,N,N′-trimethylethylenediamine (0.76 mL, 6.0
mmol). THF was added dropwise to the solution until all
reactants had dissolved. The reaction was stirred at ambient
temperature for 10 h. NaBH3CN (251 mg, 4.0 mmol) was added
to the solution, and the reaction was allowed to stir at ambient
temperatures for 14 h. The reaction mixture was added to 10%
HCl (25 mL) and allowed to stir for 15 min. The reaction was
then made basic (pH ∼10) with 10 M NaOH. The aqueous
layer was extracted with CH2Cl2. The organic layer was dried
over MgSO4 and removed in vacuo. The resulting residue was
purified via flash chromatography (NH3 sat. MeOH/CHCl3, 10:
90), and compound 1a was isolated as a yellow amorphous
solid (149 mg, 0.096 mmol, 48%). 1H NMR δ 2.07-2.13 (m,
36H), 2.33-2.44 (m, 16H), 3.06 (s, 6H), 3.42 (s, 8H), 3.75 (s,
12H), 6.54 (d, J ) 8.7 Hz, 4H), 6.74 (ft, J ) 1.6 Hz, 2H), 6.86
(dd, J ) 2.5, 8.6 Hz, 4H), 7.06 (d, J ) 2.4 Hz, 4H), 7.08-7.11
(m, 2H), 7.21-7.30 (m, 4H), 7.39 (dd, J ) 1.6, 8.6 Hz, 2H),
7.52-7.61 (m, 4H), 7.73-7.79 (m, 4H),7.86 (d, J ) 8.0 Hz, 2H),
8.15 (s, 2H). 13C NMR δ 38.3, 42.6, 55.0, 55.6, 55.9, 56.4, 57.5,
70.0, 84.6, 109.9, 123.5, 125.9, 126.4, 126.9, 127.5, 128.1, 128.5,
128.7, 128.9, 129.1, 129.3, 129.5, 131.9, 132.2, 133.9, 135.0,
135.7, 141.4, 146.5, 157.1. IR (neat) 3054, 2942, 2817, 2414,
1601, 1496, 1463, 1349, 1251, 1162, 1131, 1031, 810, 737, 652
cm-1. HRMS for M + H+ calcd for C92H113N10O8S2: 1549.8184.
Found: 1549.8210.
Com p ou n d 9. Compound 7 (4.0 g, 3.7 mmol) and Mg
turnings (17.8 g, 732 mmol) were added to a stirred solution
of CH2Cl2 (500 mL) and MeOH (500 mL). After 30 min, the
reaction began to reflux. The solution was then stirred at
ambient temperature for 24 h. The solvent was removed in
vacuo, and the residue was brought up in 50% AcOH (aq),
extracted with CH2Cl2 (3 × 200 mL), and dried over MgSO4.
After removal of the solvent in vacuo, the residue was purified
via flash chromatography (EtOAc/Hex, 40:60) and the resulting
bisaniline was isolated as a white solid (2.60 g, 3.7 mmol, 100%
yield). Mp 123-125 °C; 1H NMR (360 MHz) δ 2.77 (s, 6H),
3.79 (s, 12H),6.49-6.53 (m, 6H), 6.80 (d, J ) 8.5 Hz, 8H), 7.10
(t, J ) 7.8 Hz, 2H), 7.15 (d, J ) 9.1 Hz, 8H); 13C NMR (100
MHz) δ 31.1, 55.3, 55.7, 69.9, 84.9, 110.6, 113.6, 114.5, 118.8,
129.2, 130.6, 137.5, 146.3, 149.4, 158.7; IR (neat) 3416, 3000,
Com p ou n d 7. Copper (I) chloride (28.0 g, 283 mmol) was
added to a stirred solution of CH2Cl2 (290 mL) and compound
6 (15.5 g, 28.3 mmol). N-Methylpyrrolidine (59 mL, 566 mmol)
was added in a dropwise fashion. The solution was stirred at
ambient temperature for 2.5 h with a steady stream of
bubbling O2. The reaction mixture was filtered through a short
silica column with EtOAc, and the solvent was removed in
vacuo. The residue was purified via flash chromatography
(EtOAc/Hex, 40:60), and compound 7 was isolated as a white
amorphous solid (11.4 g, 20.9 mmol, 74% yield). 1H NMR (400
MHz) δ 3.09 (s, 6H), 3.74 (s, 12H),6.63-6.68 (m, 10H), 6.94
(d, J ) 8.8 Hz, 8H), 7.17-7.28 (m, 7H), 7.40 (dd, J ) 2.0, 8.5
Hz, 2H), 7.53-7.62 (m, 4H), 7.74 (d, J ) 8.5 Hz, 2H),7.79-
7.84 (m, 4H), 8.10 (s, 2H); 13C NMR (100 MHz) δ 36.2, 52.7,
53.3, 67.7, 82.3, 111.4, 121.1, 124.1, 124.2, 125.4, 125.9, 126.3,
126.7, 126.8, 126.9, 127.1, 127.3, 127.9, 130.0, 131.6, 132.8,
134.0, 139.2, 144.0, 156.5; IR (neat) 3010, 2932, 2836, 1605,
1057, 1348, 1177, 1072, 1033, 825 cm-1; HRMS calcd for
2953, 2835, 1605, 1507, 1298, 1251, 1177, 1033, 909, 828 cm-1
;
HRMS calcd for C48H45N2O4 (M + H+): 713.3379. Found:
713.3404.
Trifluoroacetic anhydride (1.29 mL, 9.1 mmol) was added
to a stirred solution of THF (20 mL) and the bisaniline (649
mg, 0.91 mmol) at 0 °C. The solution was warmed to ambient
temperature and quenched with water (20 mL). The aqueous
layer was extracted with CH2Cl2 (3 × 10 mL), and the collected
organic layers were dried over MgSO4. After removal of the
solvent in vacuo, the residue was filtered through a silica plug
(EtOAc/Hex, 40:60), and compound 9 was isolated as an
amorphous red solid (808 mg, 0.89 mmol, 98% yield). 1H NMR
(300 MHz) δ 3.30 (s, 6H), 3.80 (s, 12H), 6.84 (d, J ) 8.8 Hz,
8H), 7.08-7.16 (m, 12H), 7.32-7.40 (m, 4H); 13C NMR (75
MHz) δ 29.7, 54.8, 55.3, 69.7, 84.2, 113.6, 116.3 (q, J ) 285
Hz), 125.8, 128.0, 129.3, 129.7, 130.0, 135.9, 140.3, 147.2, 157.0
(q, J ) 35.8 Hz), 158.7; IR (neat) 3385, 3010, 2934, 1698, 1605,
1508, 1253, 1205, 1155, 1034, 910, 829 cm-1; HRMS calcd for
C
68H56N2O8S2Na (M + Na+): 1115.337. Found: 1115.3395.
Com p ou n d 8. 1,1-Dichloromethylmethyl ether (170 µL,
1.84 mmol) was added to a stirred solution of CH2Cl2 (10 mL),
and compound 7 at 0 °C. TiCl4 (2.53 mL, 2.53 mmol, 1 M in
CH2Cl2) was added in a dropwise fashion to the reaction. The
reaction was allowed to warm to ambient temperature over a
period of 30 min. The mixture was slowly poured over ice, and
the aqueous layer was extracted with CH2Cl2 (3 × 5 mL). The
organic layer was dried over MgSO4, and the solvent was
removed in vacuo. The resulting residue was purified via flash
chromatography (EtOAc/Hex, 70:30) and compound 8 was
isolated as a yellow amorphous solid (241 mg, 0.20 mmol, 87%).
1H NMR δ 3.16 (s, 6H), 3.88 (s, 12H), 6.82 (d, J ) 8.9 Hz, 4H),
6.96-7.00 (m, 4H), 7.16-7.26 (m, 4H), 7.39 (dd, J ) 2.6, 8.8
Hz, 4H), 7.43 (dd, J ) 1.8, 8.6 Hz, 2H), 7.54-7.62 (m, 8H),
7.81-7.84 (m, 4H),7.91 (d, J ) 8.0 Hz, 2H), 8.16 (s, 2H), 10.38
(s, 4H). 13C NMR δ 38.5, 55.1, 56.2, 70.9, 84.2, 112.3, 123.6,
124.6, 125.5, 127.6, 127.8, 128.2, 128.3, 128.8, 129.2, 129.4,
129.5, 129.7, 132.4, 133.7, 135.2, 136.2, 136.7, 141.9, 144.8,
161.4, 189.7. IR (neat) 3010, 2943, 2863, 1682, 1603, 1492,
C
52H42N2O6F6 (M + Na+): 927.2845. Found: 927.2874.
Com p ou n d 10. 1,1-Dichloromethylmethyl ether (0.74 mL,
8.16 mmol) was added to a stirred solution of CH2Cl2 (40 mL)
and compound 9 (923 mg, 0.33 mmol) at 0 °C. TiCl4 (11.2 mL,
1.0 M in CH2Cl2, 11.2 mmol) was added in a dropwise fashion
to the reaction. The reaction was allowed to warm to ambient
temperature over a period of 45 min. The mixture was slowly
poured over ice, and the aqueous layer was extracted with CH2-
Cl2 (3 × 20 mL). The organic layer was dried over MgSO4, and
the solvent was removed in vacuo. The resulting residue was
purified via flash chromatography (EtOAc/Hex, 70:30) to yield
the tetraaldehyde as a white amorphous solid (941 mg, 0.928