46ꢀMembered P,N,Oꢀcontaining cyclophanes
Russ.Chem.Bull., Int.Ed., Vol. 65, No. 5, May, 2016
1323
Then, the reaction mixture was dissolved in anhydrous degassed
DMF (3 mL), followed by the addition of a solution of 4,4´ꢀbisꢀ
(4´ꢀaminophenoxy)biphenyl (0.82 g, 2.22 mmol) in anhydrous
degassed DMF (13 mL). The reaction mixture was stirred for
1.5 days at 110 °C. A precipitate formed was filtered, washed
once with DMF and three times with acetonitrile, and dried for
4 h at 0.1 Torr. The filtrate of the reaction mixture was concenꢀ
trated in vacuo approximately to 1/4 of the initial volume.
A precipitate formed subsequently was allowed to stand for 1 day
at –20 °C, filtered, washed thrice with acetonitrile, recrystalꢀ
lized from DMF, and washed with acetonitrile. After drying, the
powder obtained was combined with the first portion. The yield
of compound 1 was 0.21 g (15%), m.p. 231 °C. Found (%): C, 75.13;
H, 5.68; N, 4.51; P, 9.46. C80H68N4O4P4. M = 1273.32. Calcuꢀ
lated (%): C, 75.46; H, 5.38; N, 4.40; P, 9.73. MS FABpos, m/z
(Irel (%)): 1273 [M + H]+ (96), 1289 [M + O + H]+ (100), 1305
{13,17,83,87ꢀTetra(lꢀmenthyl)ꢀ3,6,10,13ꢀtetraoxaꢀ1,8(1,5)ꢀdiꢀ
(1,5ꢀdiazaꢀ3,7ꢀdiphosphacyclooctana)ꢀ2,4,5,7,9,11,12,14(1,4)ꢀ
octabenzenacyclotetradecaphane}bis(dichloroplatinum)(II) (3).
A solution of (cyclooctadiene)dichloroplatinum(II) (0.0507 g,
0.135 mmol) in anhydrous degassed chloroform (4 mL) was added
to a solution of compound 2 (0.1032 g, 0.067 mmol) in anhyꢀ
drous degassed chloroform (5 mL). The reaction mixture was
stirred for 2.5 h at ~20 °C, then concentrated in vacuo virtually
to dryness. The crystals formed were filtered, thoroughly washed
with acetonitrile and dried for 4 h at 0.1 Torr. The yield of
compound 3 was 0.1012 g (84%), m.p. > 300 °C. Found (%):
C, 55.81; H, 5.88; N, 2.61; P, 6.23; Cl, 6.75. C96H124N4O4P4Pt2Cl4.
M = 2053.90. Calculated (%): C, 56.14; H, 6.09; N, 2.73; P, 6.03;
Cl, 6.90. 1H NMR (CDCl3, δ: 0.70—1.05 (m, Hment, H(18,19));
0.92 (d, H(17), 3JHH = 6.2 Hz) (a total intensity 52 H); 1.40—1.59
(m, 12 H, Hment); 1.70—1.81 (m, 8 H, Hment); 1.97—2.10 (m, 4 H,
H(16)); 3.60—3.88 (m, 16 H, H(1,1´)); 7.00—7.06 (m, 24 H,
1
[M + 2 O + H]+ (76), 1321 [M + 3 O + H]+ (38). H NMR
(DMSOꢀd6), δ: 4.19 (dd, 8 H, H(1,1´)eq, 2JHH = 13.7 Hz, 2JPH
=
3
H(3,4,7)); 7.49 (d, 8 H, H(8), JHH = 8.5 Hz). 31P{1H} NMR
= 11.2 Hz); 4.59 (br.d, 8 H, H(1,1´)ax, 2JHH = 13.7 Hz); 6.71 (d,
8 H, H(3), 3JHH = 7.8 Hz); 6.96 (d, 4 H, H(7), 3JHH = 7.8 Hz);
(CDCl3), δ: –5.72 (s, 1JPtP = 3178.8 Hz). [α]D20 –44 (c 0.3243,
CH2Cl2).
6.98 (d, 4 H, H(7´), 3JHH = 7.8 Hz); 7.04 (d, 8 H, H(4), 3JHH
=
[13,17,83,87ꢀTetra(lꢀmenthyl)ꢀ3,6,10,13ꢀtetraoxaꢀ1,8(1,5)ꢀdiꢀ
(1,5ꢀdiazaꢀ3,7ꢀdiphosphacyclooctana)ꢀ2,4,5,7,9,11,12,14(1,4)ꢀ
octabenzenacyclotetradecaphane]bis(dichloropalladium)(II) (4)
was obtained similarly to compound 3 from compound 2 (0.1057 g,
0.069 mmol) and (cyclooctadiene)dichloropalladium(II). After
completion of the reaction, the mixture was concentrated to
dryness, the residue was crystallized from acetonitrile, the crysꢀ
tals formed were filtered, thoroughly washed with acetonitrile,
and dried for 4 h at 0.1 Torr. The yield of compound 4 was
0.0929 g (78 %), m.p. > 300 °C. Found (%): C, 60.97; H, 6.34;
N, 2.72; P, 6.86; Cl, 7.22. C96H124N4O4P4Pd2Cl4. M = 1876.58.
Calculated (%): C, 61.44; H, 6.66; N, 2.99; P, 6.60; Cl, 7.56.
1H NMR (CDCl3), δ: 0.70—1.00 (m, Hment); 0.97 (d, H(17),
3JHH = 6.2 Hz) (a total intensity 56 H); 1.02—1.25 (m, 4 H,
Hment); 1.45—1.60 (m, 4 H, Hment); 1.61—1.79 (m, 8 H, Hment);
1.90—2.05 (m, 4 H, H(16)); 3.39—3.82 (m, 16 H, H (1,1´));
6.97—7.10 (m, 24 H, H (3,4,7)); 7.50 (d, 8 H, H(8), 3JHH = 8.9 Hz).
31P NMR (CDCl3), δ: 16.51 (s). [α]D20 –55 (c 0.3629, CH2Cl2).
[13,17,83,87ꢀTetra(lꢀmenthyl)ꢀ3,6,10,13ꢀtetraoxaꢀ1,8(1,5)ꢀdiꢀ
(1,5ꢀdiazaꢀ3,7ꢀdiphosphacyclooctana)ꢀ2,4,5,7,9,11,12,14(1,4)ꢀ
octabenzenacyclotetradecaphane]bis(tetracarbonyltungsten)(0)
(5). A 0.0426 M solution of (THF)W(CO)5 in THF (0.289 mmol,
6.8 mL) was added to a solution of compound 2 (0.1002 g,
0.066 mmol) in anhydrous degassed THF (20 mL). The reaction
mixture was stirred for 56 h at 50 °C, then another portion of
0.0426 M solution of (THF)W(CO)5 in THF (0.119 mmol,
2.8 mL) was added, and the stirring was continued for another 44 h
at 50 °C. A dark precipitate formed was filtered, the filtrate of
the reaction mixture was concentrated in vacuo to dryness, the
residue was crystallized from acetonitrile. A powdered precipiꢀ
tate formed was filtered, twice thoroughly washed with acetoꢀ
nitrile, and dried for 4 h at 0.1 Torr. The yield of compound 5 was
0.049 g (35 %), m.p. > 300 °C. Found (%): C, 58.86; H, 6.04; N, 2.53;
P, 5.64. C104H124N4O12P4W2. M = 2113.69. Calculated (%):
= 7.8 Hz); 7.40—7.55 (m, 12 H, H(11,13)); 7.57 (d, 8 H, H(8,8´),
3JHH = 7.8 Hz); 7.61—7.70 (m, 8 H, H(12)). 31P{1H} NMR
(DMSOꢀd6), δ: –51.20 (s). 31P{1H} NMR (DMF), δ: –50.18 (s).
13,17,83,87ꢀTetra(lꢀmenthyl)ꢀ3,6,10,13ꢀtetraoxaꢀ1,8(1,5)ꢀdiꢀ
(1,5ꢀdiazaꢀ3,7ꢀdiphosphacyclooctana)ꢀ2,4,5,7,9,11,12,14(1,4)ꢀ
octabenzenacyclotetradecaphane (2). A mixture of menthylphosꢀ
phine (1.01 g, 5.87 mmol) and paraformaldehyde (0.35 g,
11.66 mmol) was heated at 110—115 °C until homogenization.
Then, the dense liquid obtained was dissolved in anhydrous deꢀ
gassed toluene (5 mL). 4,4´ꢀBis(4´ꢀaminophenoxy)biphenyl
(1.08 g, 2.93 mmol) in toluene (28 mL) was added to the warmedꢀ
up suspension, the reaction mixture was stirred for 2.5 days at
100 °C. A precipitate formed was filtered, washed once with
toluene, then thrice with acetonitrile, and dried for 4 h at 0.1 Torr.
The yield of compound 2 was 0.57 g (24%), m.p. 200—204 °C.
Found (%): C, 75.41; H, 8.37; N, 3.81; P, 8.25. C96H124N4O4P4.
M = 1521.93. Calculated (%): C, 75.76; H, 8.21; N, 3.68;
P, 8.14. MS ESIpos, m/z (Irel. (%)): 1521 [M + H]+ (100). 1H NMR
3
(CDCl3), δ: 0.75 (d, 12 H, H(18), JHH = 5.9 Hz); 0.86—1.08
(m, 32 H, Hment + H(17,19)); 1.09—1.20 (m, 4 H, Hment);
1.32—1.48 (m, 8 H, Hment); 1.58—1.88 (m, 16 H, Hment); 2.66—2.79
2
(m, 4 H, H(16)); 3.62 (d, 4 H, H(1)ax, JHH = 15.6 Hz); 3.77
2
(d, 4 H, H(1´)ax, JHH = 15.7 Hz); 4.30 (br.d, 4 H, H(1)eq,
2
2JHH = 15.6 Hz); 4.47 (dd, 4 H, H(1´)eq, JHH = 15.7 Hz,
2JPH = 4.1 Hz); 6.55 (d, 8 H, H(3), 3JHH = 8.3 Hz); 6.96 (d, 8 H,
3
3
H(4), JHH = 8.3 Hz); 7.02 (d, 8 H, H(7,7´), JHH = 8.3 Hz);
7.52 (d, 8 H, H(8,8´), JHH = 8.3 Hz). 1H NMR (CDCl3—
3
3
DMSOꢀd6, 9 : 1), δ: 0.76 (d, 12 H, H(18), JHH = 6.8 Hz);
0.90—0.99 (m, 8 H, Hment); 0.92 (d, 12 H, H(19), 3JHH = 6.3 Hz);
3
0.94 (d, 12 H, H(17), JHH = 6.8 Hz); 1.00—1.08 (m, 4 H,
Hment); 1.10—1.20 (m, 4 H, Hment); 1.35—1.46 (m, 8 H, Hment);
1.67—1.75 (m, 4 H, Hment); 1.75—1.84 (m, 8 H, Hment); 2.66—2.74
(m, 4 H, H(16)); 3.66 (dd, 4 H, H(1)ax, 2JHH = 15.7 Hz, 2JPH
=
= 3.2 Hz); 3.82 (br.d, 4 H, H(1´)ax,2JHH = 15.3 Hz); 4.27 (dd, 4 H,
H(1´)eq, 2JHH = 15.3 Hz, 2JPH = 5.9 Hz); 4.44 (dd, 4 H, H(1)eq,
2JHH = 15.7 Hz, 2JPH = 6.8 Hz); 6.53 (d, 8 H, H(3), 3JHH = 9.0 Hz);
C, 59.10; H, 5.91; N, 2.65; P, 5.86. H NMR (C6D6), δ: 0.61
1
3
(d, 12 H, H(18), JHH = 6.4 Hz); 0.78—0.90 (m, Hment); 0.82
(d, H(19), 3JHH = 5.9 Hz) (a total intensity 16 H); 1.12 (d, 12 H,
H(17), 3JHH = 5.9 Hz); 1.17—1.29 (m, 4 H, Hment); 1.31—1.41
(m, 4 H, Hment); 1.42—1.51 (m, 4 H, Hment); 1.58—1.75 (m, 16 H,
Hment); 2.01—2.13 (m, 8 H, Hment, H(16)); 3.44—3.58 (m, 12 H,
H(1)B, H(1´)); 3.64 (br.d, 4 H, H(1)A, 2JHH = 11.2 Hz); 6.99 (d,
3
6.93 (d, 8 H, H(4), JHH = 9.0 Hz); 7.01 (d, 8 H, H(7,7´),
3JHH = 8.6 Hz); 7.52 (d, 8 H, H(8,8´), 3JHH = 8.6 Hz). 31P{1H}
NMR (CDCl3), δ: –46.54 (s). 31P{1H} NMR (toluene), δ: –50.48
(s). [α]D20 –63 (c 0.3677, CHCl3).