an argon atmosphere for 5 days. The solution was washed
p-tert-Butyl-calix[4]arene-25-benzyloxy-26,27,28-phosphite
twice with water, dried over MgSO , filtered and the solvent
(up-up-out-up) (4). Method B and BЈ. Crystals suitable for X-ray
4
evaporated. The crude mixture was purified by column chrom-
atography with toluene/light petroleum (PE, bp 40–60 ЊC) as
eluent.
analysis were grown from a CH Cl /pentane solution. Yield
0.11 g (0.14 mmol, 29%); mp = 265 ЊC; H NMR: δ = 0.99
2
2
1
(s, 9H; t-Bu), 1.20 (s, 9H; t-Bu), 1.36 (s, 18H; t-Bu), 3.44
2
2
Method B: starting from monoalkylated p-tert-butyl-calix-
(d, J = 14.4 Hz, 2H; CH eq), 3.50 (d, J = 14.2 Hz, 2H;
HH
2
HH
2
[
4]arenes. 2.5 mmol of the calix[4]arene was azeotropically
CH eq), 4.40 (d, JHH = 14.4 Hz, 2H; CH2 ax), 4.64 (d,
2
2
dried twice with dry toluene (5 ml) and dissolved in 30 ml of
dry toluene. This solution was dropwise added to a solution of
JHH = 14.2 Hz, 2H; CH ax), 4.95 (s, 2H; OCH Ph), 6.81 (s, 2H;
2
2
4
ArH), 7.06 (s, 2H; ArH), 7.10 (d, J = 2.3 Hz, 2H; ArH), 7.15
HH
4
3
mmol of HMPT (0.64 ml) and a catalytic amount of 1H-
(d, JHH = 2.3 Hz, 2H; ArH), 7.38 (m, 4H; ArH), 7.57 (d,
13
tetrazole in 25 ml of dry toluene under an argon atmosphere
at 50 ЊC and under stirring. After a night of stirring at 50 ЊC
the temperature was raised to reflux temperature and heated
for 20 hours. Toluene and excess of HMPT were evaporated
under vacuum and the resulting solid was subjected to column
chromatography. An excess of phosphite with conformation
a was produced in this way. Addition of the HMPT and
JHH = 7 Hz, 1H; ArH); C NMR: δ = 31.0, 31.3 (s; CH ), 33.5,
3
36.4 (s; CH ), 33.5, 33.9, 34.1 (s; C(CH ) ), 76.6 (s; OCH C H ),
2
3
3
2
6
5
124.3, 124.4, 126.0, 126.5, 126.9, 127.3, 128.1 (s; ArCH), 129.8,
131.9, 132.2, 133.8, 133.8, 137.8, 144.7, 144.7, 145.7, 146.5,
31
147.1, 147.7, 147.9, 152.1 (s; ArC); P NMR: δ = 107 (s, 1P;
Ϫ1
P(OR) ); IR(KBr): ν(cm ) >3000 (C–H arom.); 2961, 2869
3
(C–H aliph.); 1486, 1465 (C᎐C); 1207, 1193.94, 1173 (C–O–P);
ϩ
1
5
H-tetrazole to a solution of the monoalkylated calix[4]arene at
0 ЊC resulted in the formation of an excess of phosphite with
1106 (C–O); FAB: m/z (%) 767(100) [MH ]; Anal. Calcd. for
C H O Pؒ1.5H O: C, 77.15; H, 7.87. Found: C, 77.60; H,
51
59
4
2
conformation e.
7.80%.
Method BЈ: synthesis with PCl . 0.5 mmol of the monoalkyl-
3
ated calix[4]arene phosphite was azeotropically dried with dry
toluene and then dissolved in 30 ml of dry THF. Distilled
triethylamine was added and the solution was cooled to Ϫ78 ЊC
p-tert-Butyl-calix[4]arene-25-benzyloxy-26,27,28-phosphite
(up-out-up-up) (5). Method B and BЈ. Crystals suitable for X-ray
analysis were grown from a toluene solution. Yield 1.26 g (1.6
1
in an acetone/dry ice bath. 0.5 mmol PCl , dissolved in 10 ml of
mmol, 36%); mp = 180 ЊC; H NMR: δ = 1.16 (s, 9H; t-Bu), 1.28
3
2
dry THF, was then added dropwise and the solution was
allowed to come to room temperature whilst stirring under an
argon atmosphere. The solid pyridine salts were removed by
filtration and the solvent was evaporated. The resulting solid
was seperated by column chromatography over silica with
CH Cl /PE (ratio 1/2) as eluent.
(s, 9H; t-Bu), 1.36 (s, 18H; t-Bu), 3.33 (d, J = 14.6 Hz, 2H;
HH
2
CH eq), 3.68 (d, JHH = 16.9 Hz, 2H; CH2 eq), 4.29 (d,
JHH = 16.9 Hz, 2H; CH ax), 4.45 (d, J = 14.6 Hz, 2H; CH2
2
2
2
2
HH
ax), 4.86 (s, 2H; OCH Ph), 7.00 (s, 2H; ArH), 7.12 (s, 4H; ArH),
2
13
7.16 (s, 2H; ArH), 7.26 (m, 5H; ArH); C NMR: δ = 31.2, 31.3,
31.4 (s; CH ), 33.4, 37.2 (s; CH ), 33.9, 34.0, 34.1 (s; C(CH ) ),
2
2
3
2
3 3
7
6.4 (s; OCH C H ), 125.7, 126.0, 126.1, 127.7, 127.9, 128.9
2 6 5
(
1
(
2
s; ArCH), 130.0, 133.0, 133.1, 133.1, 134.8, 134.9, 136.6, 144.0,
Characterisation
31
45.0, 145.1, 146.2, 146.5, 154.0 (s; ArC); P NMR: δ = 116
Ϫ1
p-tert-Butyl-calix[4]arene-25-methoxy-26,27,28-phosphite
up-up-out-up) (2). Method B. Yield 0.06 g (0.087 mmol, 17%);
s, 1P; P(OR) ); IR(KBr): ν(cm ) 3038 (C–H arom.); 2963,
3
(
907, 2865 (C–H aliph.); 1477 (C᎐C); 1290, 1184 (C–O–P); 1117,
᎐
ϩ ϩ
because the product contained 1–2% of the intermediate phos-
phorus amidite 12 no correct microanalytical data could
be obtained; mp = 310 ЊC; H NMR: δ = 0.98 (s, 9H; t-Bu), 1.19
1
100 (C–O); FAB: m/z (%) 57(100) [C(CH ) ], 767(48) [MH ];
3
3
Anal. Calcd. for C H O P: C, 79.86; H, 7.75. Found: C, 79.24;
H, 7.90%.
51
59
4
1
2
(
s, 9H; t-Bu), 1.36 (s, 18H; t-Bu), 3.45 (d, J = 14.4 Hz, 2H;
HH
2
CH eq), 3.55 (d, J = 14.2 Hz, 2H; CH eq), 3.82 (s, 3H;
2
HH
2
p-tert-Butyl-calix[4]arene-25-isopropoxy-26,27,28-phosphite
(up-up-out-up) (6). Method B. Yield 0.57 g (0.80 mmol, 42%);
mp = 270 ЊC; H NMR (benzene-d ): δ = 0.83 (s, 9H; t-Bu), 1.01
(s, 9H; t-Bu), 1.37 (d,
(s, 18H; t-Bu), 3.39 (d, JHH = 14 Hz, 2H; CH eq), 3.59
2
OCH ), 4.40 (d, JHH = 14.4 Hz, 2H; CH2 ax), 4.62 (d,
3
2
JHH = 14.2 Hz, 2H; CH ax), 6.80 (s, 2H; ArH), 7.06 (s, 2H;
1
2
6
2
ArH), 7.11 (d, J = 2.3 Hz, 2H; ArH), 7.18 (d, JHH = 2.3 Hz,
2
HH
J
= 6.1 Hz, 6H; -CH(CH )), 1.41
HH 3
1
3
2
3
1
1
1
H; ArH); C NMR: δ = 30.1, 30.4 (s; CH ), 32.5, 35.5 (s; CH ),
2
3
2
2
2.9, 33.0, 33.2 (s; C(CH ) ), 61.1 (s; OCH ), 123.5, 123.6,
25.1, 125.6 (s; ArCH), 129.0, 131.4 (d, JPC = 2.3 Hz; ArC),
31.3 (d, JPC = 3.0 Hz; ArC), 130.8, 143.8, 143.8, 144.8, 145.4,
46.2, 146.7, 146.9, 152.6 (s; ArC); P NMR: δ = 107 (s, 1P;
2
2
3
3
3
(d, J = 13 Hz, 2H; CH eq), 4.09 (septet, J = 6.1 Hz, 1H;
HH 2 HH
2
CH(CH ) ), 4.63 (d, JHH = 14 Hz, 2H; CH2 ax), 4.94
3
2
2
(d, J = 14 Hz, 2H; CH ax), 4.95 (s, 2H; OCH Ph), 7.02
HH
2
2
3
1
2
(
s, 2H; ArH), 7.06 (s, 2H; ArH), 7.18 (d, J = 2.5 Hz, 2H;
HH
13
Ϫ1
P(OR) ); IR(KBr): ν(cm ) 3051 (C–H arom.); 2962, 2906, 2868
3
ArH), 7.34 (d, JHH = 2.5 Hz, 2H; ArH); C NMR: δ = 22.1
(
(
C–H aliph.); 1480, 1465 (C᎐C); 1212, 1173 (C–O–P); 1108
᎐
ϩ
(s; CH(CH ) ), 31.2, 30.9 (s; C(CH ) ), 34.0, 36.3 (s; CH ), 33.7,
33.8, 34.1 (s; C(CH ) ), 77.0 (s; OCH(CH ) ), 123.9, 124.3,
3 3 3 2
3
2
3
3
2
C–O); FAB: m/z (%) 57(100) [C(CH ) ], 691(78) [MH ].
3
3
1
25.7, 126.3 (s; ArCH), 129.9, 132.1, 132.4, 134.2, 144.8, 145.6,
31
p-tert-Butyl-calix[4]arene-25-methoxy-26,27,28-phosphite
147.0, 147.7, 147.9, 150.9 (s; ArC); P NMR (benzene-d ):
δ = 105 (s, 1P; P(OR) ); IR(KBr): ν(cm ) >3000 (C–H arom.);
6
Ϫ1
(
up-out-up-up) (3). Method B. Yield 0.83 g (1.2 mmol, 10%);
3
1
mp = 325 ЊC; H NMR: δ = 1.17 (s, 9H; t-Bu), 1.28 (s, 9H; t-Bu),
2954, 2897, 2862 (C–H aliph.); 1474 (C᎐C); 1275, 1154 (C–O–P);
2
ϩ
1
.39 (s, 18H; t-Bu), 3.60 (d, J = 14.4 Hz, 2H; CH eq), 3.70
1104 (C–O); FD: m/z (%) 718(100) [M ]; Anal. Calcd. for
HH
2
2
(
d, J = 16.9 Hz, 2H; CH eq), 3.71 (s, 3H; OCH ), 4.30 (d,
C H O P: C, 78.52; H, 8.27. Found: C, 78.25; H, 8.35%.
HH
2
3
47 59
4
2
2
JHH = 16.9 Hz, 2H; CH ax), 4.57 (d, J = 14.4 Hz, 2H; CH2
ax), 7.06 (s, 2H; ArH), 7.14 (d, J = 2.3 Hz, 2H; ArH), 7.16
2
HH
4
p-tert-Butyl-calix[4]arene-25-n-butoxy-26,27,28-phosphite
HH
4
13
(
s, 2H; ArH), 7.21 (d, J
=2.3 Hz, 2H; ArH); C NMR:
(up-up-out-up) (7). Method B. Because the product contained
up to 5% of hydrolytic side products (phosphate and H-
HH
1
δ = 31.2, 31.3, 31.5 (s; CH ), 33.1, 37.3 (s; CH ), 34.0, 34.1, 34.1
3
2
(
s; C(CH ) ), 61.9 (s; OCH ), 125.9, 126.2, 126.2 (s; ArCH),
phosphonate) no correct microanalytical data could be
3
3
3
1
1
1
29.9, 130.0, 132.7, 132.7, 133.2, 133.2, 134.7, 134.7, 144.0,
obtained; H NMR: δ = 0.99 (s, 9H; t-Bu), 0.99 (t, 3H; CH -
2
31
45.0, 145.1, 146.2, 146.4, 147.2 (s; ArC); P NMR: δ = 116
CH CH CH ), 1.20 (s, 9H; t-Bu), 1.36 (s, 18H; t-Bu), 1.63 (m,
2
2
3
Ϫ1
3
3
(
s, 1P; P(OR) ); IR(KBr): ν(cm ) 3040 (C–H arom.); 2962,
JHH = 7.7 Hz, 2H; CH CH CH CH ), 1.85 (m, J = 7.7 Hz,
2H; CH CH CH CH ), 3.44 (d, J = 14 Hz, 2H; CH eq),
3.50 (d, J = 14 Hz, 2H; CH eq), 3.85 (t, J = 6.3 Hz, 1H;
3
2
2
2
3
HH
2
2
1
904, 2867 (C–H aliph.); 1478 (C᎐C); 1290, 1183 (C–O–P); 1113,
᎐
2
2
2
2
3
HH
2
ϩ
3
100 (C–O); FAB: m/z (%) 57(100) [C(CH ) ], 691(35) [MH ];
3
3
HH
2
HH
2
Anal. Calcd. for C H O Pؒ1.5H O: C, 75.29; H, 8.14. Found:
CH CH CH CH ), 4.41 (d, J = 14 Hz, 2H; CH ax), 4.61
45
55
4
2
2
2
2
2
3
HH
2
C, 75.36; H, 8.10%.
(d, J = 14 Hz, 2H; CH ax), 6.80 (s, 2H; ArH), 7.06 (s, 2H;
HH
2
1
120
J. Chem. Soc., Dalton Trans., 2000, 1113–1122