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W.D. Habicher and I. Bauer University of Technology Dresden Institute of Organic Chemistry. Phosphorus Bridgehead Macrobicycles Synthesis, Structures, Isomerism. HAS-Phosphites as Antioxidants for Synthetic Polymers. processing stabilizer. - PowerPoint PPT Presentation
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Phosphorus Bridgehead MacrobicyclesSynthesis, Structures, Isomerism
W.D. Habicher and I. Bauer University of Technology Dresden
Institute of Organic Chemistry
HAS-Phosphites as Antioxidants for Synthetic Polymers
long term thermo stabilizer
light and long term thermo stabilizer
processing stabilizer
O
O
PO
NH
NH
Oligomeric Hindered Amine Phosphites as Polymer Stabilizers-Phosphorous Amide Method-
neat,160°C, 5 h
OH
OH+
NEt2
NEt2NHOP
O
NH
OP
O
n
neat,160°C, 5 h
OH
OH+
NEt2
NEt2NOP Me
O
N
OP
O
Me
n
Oligomeric Hindered Amine Phosphites as Polymer Stabilizers -Phosphorous Chloride Method-
Cl
ClNHOPNHOH
Cl
ClClP
N
+
toluene,r.t., 2 h
22%
Unexpected Result: Formation of Macrocyclic Byproducts !!!
OH
OH
Cl
ClNHOP
O
ONHOPNH O P
O
O
O
NH
OP
O
n
N
toluene,60°C, 10 h
+
+
mixture of cis- and trans-product31P NMR: 138.3 (br., cis, trans)
31P NMR: 139.7
Phosphorus Containing Macrocycles in Synthetic Organic and Supramolecular Chemistry
Tricoordinated phosphorus containing macrocycles
• can function as ligands for transition metal catalyzed reactions (Heck reaction, hydroformylation, homogenous catalytic hydration, Suzuki coupling, Sonogashira coupling etc.)
Pentavalent phosphoryl macrocycles
• can be used for metal complexation and for molecular recognition of H donating substrates also of biologically interesting compounds such as amino acids
Principles of Macrocycle Formation
Cyclization
Closure(capping)
Condensation1 +1 A B Symmetrical (A = B) or
unsymmetrical (A B) rings
Condensation2 + 2 A
BA
B
Rings with 4 sites:2 identical (A B)4 identical (A = B)
A A
B
B
BA
B. Dietrich, P. Viout, J.-M. Lehn, "Macrocyclic Chemistry: Aspects of Organic and Inorganic Supramolecular Chemistry", VCH, Weinheim, New York, Basel, Cambridge, 1992.
Doublecapping
Synthesis of Macrocycles with P(III) and P(V) Acid Derivatives
P RX
Y
OH - HXP R
O
YCyclization
P RX
X Y
- 2 HX
OH
OH
- 4 HXP R
X
X YPR
X
XY
P RO
O
Y
P RO
O
YPR
O
OY
Closure(capping)
Double Capping
OHHO
OHHO
X = Cl, NR2 Y = lone pair, O, SP chloride method P amidite method
Reaction of Phosphorous Dichlorides with Bisphenols I
OH
OH
NOPCl
Cl
+
N
O
ONOPN O P
O
O
toluene (~ 5 x 10-3 M),60°C, 10 h
56%mixture of cis- and trans-product (1:1)31P NMR: 138.3
Reaction of Phosphorous Dichlorides with Bisphenols II
O
OOPO P
O
O
OH
OH
Cl
ClOP
TEA, toluene, r.t., 24 h
+
66%cis/trans-mixture (1:1)31P NMR: 137.2, 137.0 (cis, trans)
Reaction of Phosphorous Dichlorides with Bisphenols III
OHOH
O O
OONOPN O P
NOPCl
Cl
N
+
toluene, r.t., 3 d
28%mixture of cis- and trans-product (1:1.7)31P NMR: 136.8, 137.2 (cis, trans)
Reaction of Phosphorous Dichlorides with Bisphenols IV
O
O O
O
OP
OP
OP
OOPO
O
O
O
OP
O
Cl
ClOP
OHOH
+
TEA, toluene, r.t., 3 d
23%mixture of cis- and trans-product31P NMR: 141.5, 141.2 (cis, trans)
+
43%mixture of rcc- and rct-product31P NMR: 137.2, 137.1, 137.0
OO PO
PO
OOOO PP
O O
OO
Cl
ClOP
OHOH
+TEA, toluene, r.t., 24 h
20%four possible isomers (rccc, rcct, rctt, rtct)31P NMR: 138.4
Reaction of Phosphorous Dichlorides with Bisphenols V
Oxidation of Phosphorus Macrocycles
OO
N
OP
N
OP
O OX
XOO
N
OP
N
OP
O O
OOH
S8
X = O 65% 31P NMR: = -12.4, -12.2 (cis, trans)X = S 76% 31P NMR: = 54.1, 54.0 (cis, trans)
cis,trans-mixture
+ 2 toluene, r.t., 2 h
+ 1/4 toluene,90°C, 8 h
P-Containing Macrobicycles - Principles of Formation I -
B. Dietrich, P. Viout, J.-M. Lehn, "Macrocyclic Chemistry: Aspects of Organic and Inorganic Supramolecular Chemistry", VCH, Weinheim, New York, Basel, Cambridge, 1992.
A B BA
A
B
C
C
StepwiseSynthesis
SingleCapping
TripodeCoupling
A
B
A
B
Doublecapping
O
OO
OP
P
O
O
O
OO
OP
PO
O
PCl3OH
OH
+
+
TEA, toluene, RT, 3 d
3% 15%out,out in,out
31P NMR 129.7 31P NMR 147.7 (in), 128.0 (out)
Double-Capping Method for Macrobicycle Formation I
diastereomers
In,Out-Isomerism
RRR R
RRR R
homeomorphic isomerisation
homeomorphic isomerisation
out,outin,in
in,out out,in
R.W. Alder, S.P. East, Chem. Rev. 1996, 96, 2097-2111
diastereomers
rela
tivel
y rig
id a
rms
R R RR
in,out intertwined out,out
flexi
ble
arm
s
Oxidation of in,out-Phosphite Macrobicycle
31P{1H} NMR: = 147.2 (in), 128.0 (out)
31P{1H} NMR: = 147.9 (in), -21.6 (out)
31P{1H} NMR: = -11.2 (in), -21.8 (out)
0 10 20 30 40 500,00
0,01
0,02
c [m
ol/l]
t [min]0 2 4 6 8 10 12 14 16
0,00
0,01
0,02
c [m
ol/l]
t [103min]
kox [s-1] (298 K)
out-P 2.7410-3
in-P 110-6
123
321
O
OO
OP
PO
O O
OO
OP
PO
O
O
O
OO
OP
PO
O
O
O
OOH
kox(out)
OOH
kox(in)
Double-Capping Method for Macrobicycle Formation II
in,in
in,out
out,out
macropolycycles
31P NMRafter roughchroma-tography
O
OO
OP
P
O
O
O
OO
OP
PO
OO
OO
OP
PO
O
PCl3OH
OH
+ +
+
TEA, toluene, RT, 3 d
5% 2.9% 4.4%out,out in,outin,in
31P NMR 121.6 31P NMR 142.3 31P NMR 143.1 (in), 121.6 (out)m.p. 289-292°C m.p. 313-316°C m.p. 290-294°C
X-Ray Structure of out,out-p,p,p-Phenylene Bridged Phosphite-Macrobicycle
view into the cavity view along the P-P-axis
O
OO
OP
P
O
O
10.5
Å
Conformer A
Conformer B
view into the cavity
view along P-P-axis
X-Ray Structure of in,in-p,p,p-Phenylene Bridged Phosphite-Macrobicycle
O
OO
OP
PO
O
8.5
Å
8.3
Å
Oxidation of Isomeric P-Macrobicycles
O
OO
OP
P
O
O
O
O
k1 k2
O
OO
OP
P
O
O
O
OO
OP
P
O
O
O
2 5 631P NMR: = 121.6 (out,out) 121.1 (out), -19.2 (out) -19.4
ROOHROOH
O
OO
OP
PO
O
O
O
k3
O
OO
OP
PO
OO
OO
OP
PO
O
O
31P NMR: = 143.1 (in), 121.6 (out)
4 7 8143.2 (in), -19.4 (out)
k4
-11.5 (in), -19.8 (out)
ROOH ROOH
O
OO
OP
PO
O
O
O
O
OO
OP
PO
O O
OO
OP
PO
O
O
ROOH
k5
ROOH
k6
31P NMR: = 142.3 (in,in) 142.0 (in), -12.2 (in)
3 9 10 -12.7 (in,in)
104 × kox /s-1
(298 K)
k1 (out) 137
k2 (out) 75
k3 (out) 90
k4 (in) 8
k5 (in) 15
k6 (in) 3
Double-Capping Method for the Formation of p,m,p-Phenylene Bridged Phosphorus Brigdehead Macrobicycles III
+ PCl3OH OH
TEA, toluene, RT, 3 d
in,in
in,out
out,out31P NMRof the crudeproduct
OP
O
O
X
OP
O
O
X
mixture of atropisomers; cis,cis-isomer isolated
OOP
O
OOP
O O
OO
OP
PO
OO
OO
OP
PO
O
1.5% 0.9% 1.9%
out,out in,outin,in31P NMR 123.4 31P NMR 133.1 31P NMR 131.3 (in), 124.6 (out)
+ +
view into the cavity view along P-P-axis
X-Ray Structure of out,out-p,m,p-Phenylene Bridged Phosphite-Macrobicycle
OOP
O
OOP
O
view into the cavity
view along P-P-axis
Conformer A
Conformer B
X-Ray Structure of in,in-p,m,p-Phenylene Bridged Phosphite-Macrobicycle
O
OO
OP
PO
O
Reaction of in,in-P-Macrobicycle with a Bisazide
O
OO
OP
PO
O
N
O
OO
OP
PO
O
N
N3 N3 N
O
OO
OP
PO
O
N3
toluene, 75°C,2d
+
31P NMR: -27.7MALDI (m/z): 1275 [M+H]+
31P NMR: 143.0, -20.0MALDI (m/z): 1303 [M+H]+
O
OO
OP
PO
O
Cu
Cl
Cu
Cl
+O
OO
OP
PO
O
CuClCH2Cl2/CH3CN
31P NMR: 112 br.MALDI (m/z): 1254 [M - Cl-]+
Complexation of Cu(I) with the in,in-P-Cryptand
Extraction of Metal Cations from Aqueous Solution with Macrocyclic P(III)- and P(V) compounds
Ag(I) Cu(I) Hg(II) Co(II) Yb(III) Eu(III)
85
86
84
91, 92
01020304050
6070
80
90
Extra
hier
bark
eit [
%]
1,23
4
5
O
OO
OP
P
O
Oout,out
O
OO
OP
PO
O
in,out
3 X = lone pair4 X = S5 X = O
1
2
O
ONOPN O P
O
O
X X
E
xtra
ctab
ility
[%]
Acknowledgement
Dr. I. Bauer
Dr. M. Gruner
G. Theumer
(TU Dresden)
Prof. I. Antipin
Dr. I. I. Stoikov
Dr. S. Solovieva
(Kazan State University)
Prof. R. Schmutzler, Prof. P.G. Jones, Dr. H. Thönnessen (TU Braunschweig)
Dr. R. Fröhlich (University Münster)
Financial support
DFG: Graduiertenkolleg ”Struktur-Eigenschafts-Beziehungen bei Heterocyclen”
DFG + RFFI: Projekt 2133/3-1: „Synthese neuer phosphorhaltiger Makrocyclen
und Kryptanden“
Fonds der Chemischen Industrie
Prof. E. Kazakova
Dr. A. Prosvirkin
Dr. A. Ziganshina
(A.E. Arbuzov Institute Kazan)
„Pyrocatechol phosphites“
O
OP O
P.A. Kirpichnikov et al.
Synthesis of Macrocycles with P(III) and P(V) Acid Derivatives
- 2 HX
- 2 HX
- 4 HX
HO
HO
P XRY
P XY R
PXYR
P XY R
OHHO
OHHO
P XRY
P XY R
PXR Y
PXR Y
P ORY
P OY R
POR Y
POR Y
PORY
P ORY
P ORY
P ORY
Condensation1 +1
Condensation1 +1
Condensation2 +2
HO
OH
X = Cl, NR2 Y = lone pair, OP chloride method P amidite method
Stereoisomerism of Tetracoordinated P(III)- and P(V)-Macrocycles
PR
XP
R
XP
R
XP
R
X
trans cis
PR
XP
R
X
PR X
PRX
PR
XP
R
X
PRX
PRX
PR
XP
R
X
PRX
PRX
PR
XP
R
X
PRX
PR X
rccc rcct rctt rtct
2 Phosphorus Centers
4 Phosphorus Centers
3 Phosphorus Centers
PR
XP
R
X
PR X
PR
XP
R
X
PRX
cis,cis (rcc) cis,trans (rct)P
X
R
P
R
X
P
R
X
P
R
X
X = lone pair, O
O
O
NOPN O PO
O
O
OPP
O
OO O
O O
OP
N
N
OO
OP
N
N
O
O OO
NN
O
O
N
N
OP
O
O
N
N
P P
+
O
O O
O
OP
OP
OP
OOPO
O
O
O
OP
O
+
OO P
OP
O
OOOO PP
O O
OO
Dimers Dimers + Trimers
Tetramer
Different Ring Sizes of P-Macrocycles
O
OO
O
N
OP
N
OP
P-Containing Macrocycles from Bisphenols and Naphthols by Phosphorous Amide Method – Literature examples
O O
OOPP
OHOH
PNEt2
NEt2
+
OH
OH
PNEt2
NEt2
O
OO
O P
P
+
P OO
OO P P
OO
P
OO
Y. I. Blokhin, D. V. Gusev, V. K. Belsky, A. I. Stash, E. E. Nifantev, Phosphorus, Sulfur and Silicon 1995, 102, 143.
Y. I. Blokhin, F. M. Galiaskarova, D. V. Gusev, M. Y. Ergashov, V. K. Belsky and E. E. Nifantev, Phosphorus, Sulfur and Silicon 1996, 111, 170.
Phosphorous Amide Method I-Asymmetric P-Macrocycles as Unstable Intermediates-
- Formation of Symmetric P-Macrocycles and Open Chain Products-
OPNEt2
O
NEt2
PNEt2
N
O O
OONEt2PNEt2 P
ONEt2PEt2N P
O
OO
OHOH
OPNEt2
OH
O OP
O OH
NEt2
OPNEt2
OH
O OH
OH
OH
Et2
toluene, reflux, 24 h
+
+
+ more open chain products
1 2
+ 2
3
4
5
6
7
a)
b) + 2
5%cis,trans-mixture
+
X-Ray Structure of trans-4
Phosphorous Amide Method II-Asymmetric P-Macrocycles as Unstable Intermediates-
- Formation of Symmetric P-Macrocycles and Open Chain Products-
OH
OH
OPNEt2
O
NEt2
PNEt2
NEt2
O
ONEt2PP
O
ONEt2
OH
OH
+
+
toluene, reflux, 24 h
5%cis,trans-mixture
+
open chain products
31P NMR: 140.0, 140.1 (cis, trans)
Selective Oxidation of a P-Macrocycle II
OOP
PO O
O
OO
OOP
PO O
O
O
H2O2/urea, r.t.,12 h
31P NMR: 137.7, -18.5MALDI (m/z): 1205 [M+H]+
43%
Selective Oxidation of a Tetrameric Phosphorus Macrocycle
OO PO
PO
OOOO PP
O O
OO
OO PO
PO
OOOO PP
O O
OO O
O
O
H2O2/urea, CH2Cl2, 12 h
47%
P-Containing Macrobicycles - Principles of Formation II -
B. Dietrich, P. Viout, J.-M. Lehn, "Macrocyclic Chemistry: Aspects of Organic and Inorganic Supramolecular Chemistry", VCH, Weinheim, New York, Basel, Cambridge, 1992.
Internal Template
Doublecapping
Tripode Capping
P-Containing Macrobicycles - Principles of Formation III -
B. Dietrich, P. Viout, J.-M. Lehn, "Macrocyclic Chemistry: Aspects of Organic and Inorganic Supramolecular Chemistry", VCH, Weinheim, New York, Basel, Cambridge, 1992.
External Template
„In-ness“ and “Out-ness“- of Bridgehead Substituents
R
R
in-CR 0° 90°out-CR 90°180°
R.W. Alder, S.P. East, Chem. Rev. 1996, 96, 2097-2111
Phosphorus Bridgehead Macrobicycles in Literature
P
O
P
O
O
O
O
O
O
OP
O
P
O
O
O
O
O
O
O
P
O
P
O
O
O
O
O
O
OP
O
P
O
O
O
O
O
O
O
B.P. Friedrichsen, R.P. Powell, H.W. Whitlock, J. Am. Chem. Soc. 1990, 112, 8931-8941.
Phosphorus Bridgehead Macrobicycles in Literature
ONP
O
NN
O
NN
ONN
ONN
O
NN
P
P O
PO
PO
O
O
OPO
OOO
OO
OOO
OOOPO
OO
O
OPOO
OO
O
OP O
H
A.A. Chaikovskaja, T.N. Kudrya, R.I. Yurchenko, O.M. Voitsekhovskaya, A.M. Pinchuk, Zh. Obshch. Khim. 1988, 58, 1925-1926.
Ch.B. Allen, L.O. Spreer, J. Org. Chem. 1994, 59, 7695-7700.
J. Mitjaville, A.-M. Caminade, J.-P. Majoral, J. Chem. Soc. Chem. Commun. 1994, 112, 2161.
Oxidation of Isomeric Phosphite Cryptands
0 2 4 6 8
0
20
40
60
80
100
2 5 6
conc
./mol
%
t/min 0 20 40 60 80 100
0
20
40
60
80
100
4 7 8
conc
./mol
%
t/min
0 20 40 60 80 100
0
20
40
60
80
100
3 9 10
conc
./mol
%
t/min
out,out-isomer in,out-isomer
in,in-isomer
Natural Products Showing in,out-Isomerism
AcO
OH
Hin
123
4
OH
H
OHin
123
4
Secotrinerviten-2,3-diol
3-Acetoxy-15-hydroxy-7,16-seco-trinervita-7,11-diene
in
OHOHOH
H
HO
H
OH
810
Ingenol
X-Ray Structure of a Novel Bisdioxaphospha[3.1.1.]p,m,p-Cyclophane
Podand Precursors for the Synthesis of Macrobicycles
OH
OH
OH
OSi
TBDMS, imidazol, CH2Cl2, RT, 24 h
36%
OH
OSi
1) PCl3, toluene2) cumene hydroperoxide3) TBAF, AcOH
O
OH
O
OH
O
OH
P
O
3%
Single-Capping Method for Macrobicycle Formation
O
OH
O
OH
O
OH
PO
+ + +
O
OO
OP
PO
O
O
O
OO
OP
P
O
O
O
PCl3, TEA, toluene,RT, 2 d, 8%
O
O
O
P
P
O
O
O O
O
O
O
O
P
P
O
O
O
PCl3, TEA, toluene,RT, 2 d, 12%
O
OO
OP
PO
O
O
O
OO
OP
PO
O
O
9 possible homeo-morphic isomers
Synthesis of a Thiophosphate Macrobicycle
OH
OH
O
OPS
ClCl
PCl
S
Cl
10 P(S)Cl3, TEA,toluene, r.t., 12 h
76%
O
OO
OP
P
O
O
S
S
+
TEA, toluene, 111°C, 3 d
O
OPS
ClCl
PCl
S
Cl
O
OPP
O
O
Cl
Cl
S
S
OH
OH2
+
30% 3%
Complexation of p-Nitrophenol with the in,in-Phosphate
O
O2N
H
O
O
OO
O
P
P
O
O
O
Novel Dioxaphospha[3.1.1.]p,m,p-Cyclophanes
31P NMR 121.3
OP
O
O
X
OP
O
O
X
mixture of atropisomers; cis,cis-isomer isolated
OP
O
OR
X
OP
O
OR
X
cis-isomer trans-isomer
X = lone pair, O
Recommended