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Synthesis Structure and Thermolysis of an Unusual Azaphosphasiliridine.

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'H NMR (600 MHz. CDCI,): [I21 6 = 0.96 (t. 3J(H,H) = 6.9 Hz, 6 H ; CH,),
1.40 (m. 4 H ; CH,CH,CH,), 1.45 (m, 4 H ; CH,CH,CH,), 1.94 (m, 2H ; H7),
2.05 (m, 4H ; H2), 2.26 (m, 4H; H3, H7), 2.63 (m. 4H; ArCH,nPr), 2.79 (ddd,
'J(H,H) =17.2 Hz, '4H.H) = 9.8 Hz, 'J(H.H) = 4.9 Hz, 2H; Hl), 2.94 (m,
IOH; H I , H6, H8), 3.34 (ddd, 'J(H,H) =17.5 Hz, 'J(H,H) = 4.8 Hz,
'J(H,H) = 4.8 Hz, 2H, H3); "C NMR (75 MHz, CDCI,): 6 =159.1, 157.6,
153.0, 144.6, 144.3. 139.1, 136.3, 33.6, 29.8, 28.5, 26.3. 25.2, 25.0, 23.1, 22.4.
20.3,13.6. FT-IR (KBr): [cm-'1 = 3370 br (H,O), 2942 s (CH), 2860 s (CH),
1619m (C = N). FAB-MS (Xe', 6-8 kV): m / i 620 (M-NO,, loo), 557
(M-HN,O,, 21.2%). UVjVIS (CH,CI,): A,,,[nm] ( E ) = 238 (ZSOOO), 296
(16000). Correct C,H,N-analysis for C,,H,,N,O,Mg(H,O), 5 .
Received: December 9, 1991 [Z 5061 IE]
German version: Angew. Chem. 1992, 104, 792
Whereas beginning from A, compounds of the type C are
readily accessible by N, elimination, starting from B (R' =
aryl) the analogous formation of D is not observed."] However, a disilirane D (R' = H) is accessible from the reaction of
CH,N, with tetrakis(2,6-dimethylphenyl)di~ilene,[~]
although
an intermediate could not be observed. Recently we described
a simple, high-yield access to stable phosphanylidensilanes
(phosphasilene~),[~I
so that it is now possible to investigate
the reaction pathways of such compounds with diazoalkanes
and other cycloaddition partners. Herein we report the synthesis and structure of the first azaphosphasiliridine 1 and its
stepwise conversion to the thermolysis products 2-4.
CAS Registry numbers:
1 b, 140926-56-3;2, 140926-54-1;3, 140926-55-2.
[I] T. W. Bell, S. K. Sahni in Inclusion Compounds, Vol. 4, Key Organic Hosr
Systems (Eds.: J L. Atwood, J. E. D. Davies, D. D. MacNicol), Oxford
University Press, Oxford. 1991, p. 325.
(21 T. W. Bell, A. Firestone, R. Ludwig, J. Chem. Soc. Chem. Commun. 1989,
1902; T. W Bell, P. J. Cragg, M. G. B. Drew, A. Firestone, D.-I. A. Kwok.
AngeM,. Chem. 1992,104, 319; Angew. Chem. I n t . Ed. Engl. 1992,31,345;
ibid. 1992, 104, 321 and 1992, 31, 348.
[3] M. F. Marshalkin, L. N . Yakhontov, Zl7. Org. Khim. 1978, 14, 1729; J.
Org. Chem. U S S R (Engl. Trans/.) 1978, 14, 1610.
[4] A. Kumar, E. Chapoteau, B. P. Czech, C. R. Gebauer, M. Z. Chimenti, 0.
Raimondo, Clin. Chern. ( Winsrun-Salem, N C ) 1988, 34, 1709; M. Takagi
in Calion Binding by Macrocycles, (Eds.: Y. Inoue, G. W Gokel), Dekker.
New York. 1990,465; F. Vogtle, M. Bauer, C. Thilgen, P. Knops, Chimia
1991, 45, 319.
[S] T. W. Bell, A. Firestone, J. Am. Chem. SOC.1986, 108, 8109; T. W. Bell,
Y-M. Cho. A. Firestone, K. Healy. J. Liu, R. Ludwig, S. D. Rothenberger,
Org. S w t h . 1990, 69, 226.
[6] V. L. Goedken, Y Park, S.-M. Peng, J. M. Norris, J. A m . Chern. SOC.1974,
96, 7693.
[7] W. Radecka-Paryzek, Inorg. Chim. Acta 1979, 34, 5.
[8] F. De Jong. D. N. Reinhoudt, Stuhilily und Reactivity of Crown Ether
Coniplexa. Academic Press, New York, 1981, 30.
[9] S. Ogawa, R. Narushimd, Y. A m , J. Am. Chem. Soc. 1984, 106, 5760.
[lo] A. T. Balaban, M. Banciu, V. Ciorba, Annulenes. Benio-Hetero-HomoDerivatives und Their Valence Isomers, CRC Press, Boca Raton, FI, USA,
1987, 142-143.
[11] C. Thilgen, F. Vogtle, Chem. Ber. 1991. 121, 671.
[12] The spin systems were identified according to results of a COSY experiment.
B
A
C
D
The reaction of the phosphasilene Is2Si=P-Si(r'Pr)3
(Is = 2,4,6-rF'r3C,H,) with diphenyldiazomethane led to the
[2 + I] cycloadduct lL4]
in 87 % yield, which was isolated in
the form of yellow crystals (Scheme 1). The composition of
Is
\
/si=7
Is
PhZCN,
Si(i Pr),
IS/,,
1s'
\/
,Si(i Pr),
si-p"
N
I
N
1 \CPh,
Is = 2.4.6-iPr3CBH2
J*
Synthesis, Structure, and Thermolysis
of an Unusual Azaphosphasiliridine**
llPC
- N2
By Matthius Driess* and Huns Pritzkow
Dedicated to Professor Friedrich Bickelhuupt
on the occasion of his 60th birthday
The reactivity of disilenes, phosphaalkenes, and diphosphenes towards organoazides and diorganodiazomethanes
leads to new five- and three-membered heterocycles, in which
the bonding is of particular interest."] It was observed that
disilenes can react with organoazides and diazomethanes by a
[2 + 31 or [2 + 11 cycloaddition depending on electronic and
steric factors. In contrast, phosphaalkenes only react by
[3 + 21 cycloaddition, and diphosphenes react with diazoalkanes to give stable diphosphiranes. Of particular interest is
the [2 + I] cycloaddition of disilenes, which for the reaction
with alkylazides and aryldiazomethane derivatives leads to A
and B, respectively; however, for the reaction with alkenes
there are no examples.
[*I Dr. M. Driess. Dr. H. Pritzkow
Anorganisch-chemisches Institut der Universitit
Im Neuenheimer Feld 270, D-W-6900 Heidelberg (FRG)
[**I This work was supported by the Deutsche Forschungsgemeinschaft (SFB
247). We also thank Prof. Dr. W. Siebert (Heidelberg) for his support.
Angew. Chem. Int. Ed. Engl. 31 (1992) No. 6
0 VCH
4
Scheme 1. Synthesis of the heterocycles 1-4.
1 was deduced from the mass spectrum141and a correct elemental analysis. The 31PNMR spectrum shows a singlet at
6 = - 25.6. In the 29Sispectrum a I4N/"N relaxation-broadened doublet is observed for the Si atom in the three-membered ring at extremely high field (6 = - 86.0) and with an
unusually small
coupling constant ( J = 3.9 Hz). In contrast, the corresponding coupling constant for the "Si nucleus
of the Si(Pr), group (99.5 Hz) is very large. In cyclic, threemembered phosphasilanes the 29Sichemical shifts of the ring
atoms lie between 6 = - 31.3 and 6 = -75.3 and show values of 72.5 to 121.7 Hz for the lJp,sicoupling constants.[51
Verlugsgesellschuft mbH, W-6940 Weinheim, 1992
0570-0833/92/0606-0751$3.50+.25/0
751
The 29Sichemical shifts for compounds of the type A-C are
typically found at around 6 = - 53.['] Since the constitution
of 1 could not be unequivocally proved from the NMR data,
an X-ray structure determination was carried out (Fig.
"Ep
shows a sharp doublet at 6 = - 54.4 (lJp,si= 49.7 Hz). The
29SiNMR data assigned to compound 3 are identical with
that of comparable cyclophosphasilanes and other threemembered rings containing Si
s] The NMR spectroscopic assignment for 2 and 3 is also proved by the fact that
after the 3: 1 mixture was heated for two days at 80 "C, the
concentration of 3 significantly increases at the expense of
that of 2 (ca. 1 : 1 , 3 1 P NMR control), without the appearance of new signals or an increase in the small amount of 4.
If the thermolysis is now carried out at 1I0 "C for 48 h. the
31PNMR spectrum shows that compound 4['01 is the only
product. Compound 4 could be isolated in the form of analytically pure, colorless crystals by crystallization from hexane. The constitution of 4 was also completely established by
an X-ray crystal structure analysis (Fig. 2)."
Y
Fig. 1. Crystal structure of 1. Selected distances [A] and angles ["I: P1-SiI
2.237(2). P I 3 2 2.298(2), PI-Nl 1.817(3). Sil-N1 1.729(3), N1-N2 1.375(4).
N2-C1 1.287(5): Sil-Pl-Si2 112.9(1), Sil-P1-N1 49.2(1), SiZ-P1-N1 109.2(1),
PI-Sil-Nl 52.7(1), PI-N1-Si1 78.2(1), PI-Nl-N2 136.3(3), Sil-Nl-N2 133.2(2).
NZ-Cl-C2 114.6(4), N2-C1-CX 129.3(4).
The endocyclic P 1 -Si 1 distance (2.237(2) A) is significantly
shorter than the exocyclic P 1-Si 2 (2.298(2) A) distance;
however, it is typical for Si-P distances in three-membered
cycloph~sphasilanes.~~~
Notable differences were also found
for the N 1 -P 1 and N 1 -Si 1 distances. In comparison to
azadiphosphiridines,['] in which N-P distances of 1.698 and
1.710 A were observed, the N1-PI distance (1.817(3) A) in
1 is extremely long. In contrast to azadiphosphiridines (sum
of angles 359.9 "), the N 1 atom is not coordinated in a planar
fashion (347 "). Obviously, an ideal, planar conformation at
the N 1 atom in 1 is prevented as a result of the bulky substituents. Thus, no N-P bond strengthening is possible as was
previously discussed for azadiphosphiridines and 1,3,2,4-diazadiphosphetidines.['] The endocyclic angles at the phosphorus (49.2') and nitrogen atom (78.2") in 1 correspond
approximately to the values in the azadiphosphiridine derivatives. The sum of the exocyclic, basal bond angles at the Si 1
atom (359") is similar to that in three-membered rings with
two Si atoms and one heteroatom,[81in which the coordination geometry at the silicon and phosphorus atom could be
interpreted with the Dewar-Chatt-Duncanson model when
described as a n complex. The two planes Si2-P 1 -Si IjSi 1 C 29-C 14 are twisted into one another by 24", which would
be consistent with a description of 1 as a TC complex from
phosphasilene and the nitrene form of diphenyldiazomethane.
Thermolysis experiments have shown that 1, despite its
bulky substituents, can undergo rearrangement reactions
which can be controlled. After a yellow solution of 1 in toluene
was heated for 12h at 95 "C, a deep orange solution was
obtained whose 31PNMR spectrum showed that 1 had completely rearranged into a mixture consisting of 2 (6 =
- 101.9), 3 (6 = - 197.4), and a small quantity of 4 (6 =
- 100.7) in the ratio of approximately 3: I :0.5. Although so
far the isolation of 2 and 3 has not been successful, an unequivocal characterization is possible on the basis of the 31P
and 29Si NMR data. In the 29Si NMR spectrum (INEPT
pulse sequence) a relaxation-broadened doublet (as for 1) at
6 = - 6.1 ('JP,si = 3.6 Hz) is detected for the Si atom present
in the ring of 2, whereas the analogous 29Si nucleus in 3
752
('
VCH Verlugsge\ells<huft mbH. W-6940 Wernhrim, 1992
Fig. 2. Crystal structure of 4. Selected distances [A] and angles ['I: PI-CI
1.912(2), Sil-P1 2.267(1), Si2-Cl 1.973(2), Sil-C3 1.879(2), Cl-C2 1.544(3),
C2-C3 1.409(3); Sil-PI-Cl 95.8(1), Pl-Sil-C3 93.6(1), PI-Cl-C2 110.5(1). CIC2-C3 122.0(2), C2-C3-Sil 117.1(1).
The SiPC, five-membered ring is almost planar. The long
P 1-C 1 distance of 1.912(2) A is surely a result of the steric
hindrance of the substituents at the chiral C 1 atom. In the
crystal, as in solution (25 "C), only one of the two possible
diastereomers is found, that in which the H atom at the
phosphorus atom occupies a position trans to the phenyl
group at the C 1 atom. Although only tentative statements can
be made so far concerning the mechanism of the rearrangement of 3 into 4, the formation of 4 is worth consideration
regarding two aspects. On the one hand, the ring strain of 3
affects the cleavage of a C,,,-H bond at the phenyl ring under
simultaneous loss of the Si 1 -C 1 bond and a 1,2-silyl shift of
the Si(iPr), group from the phosphorus to the saturated C 1
atom, whereby the H atom, which was originally attached to
the C 3 atom, becomes attached to the phosphorus atom. On
the other hand, it should be noted that these processes probably occurring in a radical fashion, obviously proceed so
effectively that only 4 is obtained (31PNMRcontrol).
Experimen fa1 Procedure
1: Ph,CN, (311 mg. 1.60mmol) in hexane (2 mL) was added to a solution of
Is,Si=P-Si(iPr), (1 g, 1.60 mmol) in toluene (30 mL) at 0 " C . The reaction
solution immediately changed color from red-orange to bright yellow. After
removal of the solvent at lo-' Torr, the residue was taken up in hexane (ca.
2 mL) and left to stand for 12h at room temperature. Compound 1 was isolated
in the form ofair-stable, bright yellow crystals. More of 1 could be obtained by
0570-o833192jo6o6-0752$ 3 SO+ 2510
A n g m Chem lnt Ed Ennl 31 it9921 No 6
concentration of themother liquor. Yield: 1.13 g(1.38 mmol. 87%); m.p. 150153 C (decomp.).
4: I(435 mg. 0.53 mmol) was dissolved in toluene (1 mL) and heated at ll0'C
for cii.2.5d (3'P NMR control). Following the thermolysis only the presence
of 4 could be proven. The volatiles were removed at 25°C and
Torr, and
the residue was crystallized from hexane (ca. 1 mL). Yield: 372 mg (0.47 mmol,
89%) colorless crystals; m.p. 205-206 "C.
Received: January 17, 1992 [Z5131IE]
German version: Angew. Chem. 1992, 104. 775
CAS Registry numbers:
1. 140410-24-8; 2, 140437-96-3; 3, 140410-25-9; 4,
Is2Si=PSi(iPr),, 134456-72-7; Ph,CN,, 883-40-9.
140410-26-0;
[ l ] a) Disilene toward R,CN, and RN,: G. R. Gillette, R. West, J.
Orgunornet. Chem. 1990, 394. 45; H. Piana. U. Schubert, [bid.1988, 348,
C19: b) Phosphaalkene toward R,CN, and RN,: T. A. Van der Knaap,
T. C. Klebach, E Visser, R. Lourens, F. Bickelhaupt, Tetruhedron 1984.40,
991: T. Allspach, M. Regitz, G. Becker, W. Becker, Synthesis 1986, 31;
c) Diphosphene toward R,CN,: J. Bellan, G. Etemad-Moghadam, M.
Payard. M. Koenig. Tetruhedron Lett. 1986, 27, 1145: G. EtemadMoghadam. J. Bellan. C. Tachon, M. Koenig, Tetrahedron 1987,43, 1793;
M . Yoshifuji. S. Sasaki, T. Niitsu, N. Iuamoto, Tetrahedron Lett. 1989,30.
187
[2] S . Masamune, S. Murakami, H. Tobita, J. Am. Chem. Soc. 1983,105,7777.
131 M. Driess. Angm. Chem. 1991, 103, 979; Angrw. Chem. Int. Ed. Engi.
1991, 30. 1022.
[4] I : ' H NMR (200 MHz, C,D,, 295 K): d = 0.615 (d, 3H, SiCHMe,, J
(H.H) = 6.5 Hz), 0.769-1.466 (m. 45H, SiCHMe, and o-, p-CHMe,),
1.553 (d, 3H. CHMe,, J (H,H) = 6.8 Hz), 1.804 (d, 3H, CHMe,, J
(H.H) = 6.8 Hz), 2.699 (sept, 2H, p-CHMe,, J (H,H) = 6.5 Hz). 3.515
(sept. 1 H, o-CHMe,, J(H,H) = 6.6 Hz), 3.914(br., 1 H, u-CHMe,), 4.620
(br., 1 H. o-CHMe,), 4.942 (sept. 1 H, u-CHMe,, J (H,H) = 6.5 Hr),
6.964-7.623(m, 14H.urom.H);MS(EI. 70eV):m/zS17(Mi,0.1 %),788
((M- N,)', 5), 632 ( ( M - N, - Si(iPr)3)+, 10). 623 ( ( M - N, CPh, + 1 H)', 32), 433 ((Is,Si - 1 H)', 100).
IS] M. Baudler, H. Jongebloed. Z. Anorg. Allg. Chem. 1979, 458, 9; K. F.
Tebbe, 2. Anorg. A&. Chem. 1980,468,202; M. Weidenbrnch, M. Herrnd o r t A. Schaefer, K. Peters, H. G. von Schnering, J. Organomrt. Chem.
1985,295. 7; M. Baudler. T. Pontzen, Z . Anorg. A&. Chem. 1982.491,27.
161 I : Space group P2,/n. u = 12.977(7), h = 18.066(9), c = 21.671(11) A,
a = 96.27(4)'. V = 5050 A3, Z = 4. 9231 measured reflections, 4898 observed. Non-hydrogen atoms were anisotropically refined, H atoms given
in calculated positions or as part of a rigid group (CH,) with groupwise
temperature factors. R = 0.061, R, = 0.063 (587 variables) 1121.
[7) E. Niecke, A. Nickloweit-Luke, R. Ruger, Angew. Chem. 1981, 93, 406;
Angeir. Chem. h i t . Ed. Enxi. 1981, 20,385; E. Niecke, A. Nickloweit-Luke,
R. Riiger, B. Krebs, H. Grewe, Z . Naturfbrsch. B 1981, 36, 1566; 1,3,2,4Diazadiphosphetidine: D. A. Harvey, R. Keat, A. N. Keith, K. W Muir,
D. R. Rycraft, Inorg. Chim. Acta 1979, 34, 201; M. L. Thomson, R. C .
Haltivanger. A. D. Norman, J. Chern. SOC.Chem. Commun. 1979. 647.
181 Si-Si-0: H. B. Yokelson, A. J. Millevolte, G. R. Gillette, R. West, J: Am.
Chem. SOC.1987, 109, 6865; Si-Si-S: R. West, D. J. Young, K. J. Haller.
[hid. 1985. 107, 4942, Si-Si-Se and Si-Si-Te: R. Peng-Koon Tan, G. R.
Gillette, D. R. Powell. R. West. Orgunometallics 1991, 10, 546; Si-C-C: D.
Seyferth. D. C. Annarelli, J: Am. Chem. Soc. 1975, 97, 2273; see also [l]
and 121.
191 R. S. Grev, H. F. Schaefer 111, J. Am. Chem. Soc. 1987, 109, 6577; D.
Cremer. E. Kraka, ibrd. 1985, 107, 3800; D. Cremer, J. Gauss, E. Cremer,
THEOCHEM 1988,46, 531.
[lo] 4: ' H N M R (200 MHz, C,D,, 295 K): 6 = 0.344 (br.. 6 H , SiCHMe,).
0.945 (d. 3H. CHMe,,J(H,H) = 6.6 Hz). 1.079-1.450 (m, 45H, CHMU,
and SiCHMe,). 2.698 (sept, 1 H. p-CHMe,, J (H,H) = 6.6 Hz), 2.709
(sept. 1 H. p-CHMe,, J (H,H) = 6.6 Hz), 3.543 (d, 1 H, PH, J (P,H) =
183.7 Hz). 3.571 (br., 2H, o-CHMe,), 3.814 (br., 2H, o-CHMe,), 6.8697.276 (m. 9H . urom.H), 7.753 (hr., 2 H , urom.H), 7.967 (m, 1H. ur0m.H).
8.373 (m. I H, urom.H); "PNMR (81 MHz): 6 = -100.68 (d. J(P,H) =
183.9 Hz: 2 9 SNMR
~
(INEPT): d = -0.74 (d, Is$-P, J(Si,P) = 23.5 Hz),
6.95(s.Si(rPr));MS(El,70eV):m/=788(M+,24%),745((M- iPr)+,12),
630 ((M- Si(iPr)3 -1 H)'. 100).
[Ill 4 : S p a c e g r o u p P 2 , ; n , a = 1 1 . 9 1 7 ( 6 ) . h = 1 7 . 4 8 7 ( 9 ) . c = 2 3 . 7 8 4 ( 1 2 ) ~ , ~ =
97.934) .. V = 4909 A3. 2 = 4. 8970 measured reflections (four-circle diffractometer, Mo,, radiation, w scan), 5753 observed ( I > 2al). Non-hydrogen atoms anisotropic. H atoms in observed positions isotropically refined, except protons of the methyl groups (rigid groups). R = 0.052,
R, = 0.059 (638 variables)[l2].
1121 Further details of the crystal structure investigations may be obtained
from the Fachinformationszentrum Karlsruhe, Gesellschaft fur wissenschaftlich-technische Information mbH. D-W-7514 Eggenstein-Leopoldshafen 2 (FRG) on quoting the depository number CSD-56208, the names
of the authors, and the journal citation.
Angeit. Cheni Int. Ed. Engl. 31 (1992) No. 6
0 VCH f+rlugsgesellschuft mbH,
Estradiols Modified by Metal Carbonyl Clusters
as Suicide Substrates for the Study of Receptor
Proteins: Application to the Estradiol Receptor**
By Anne EssiSres, Siden Top, Colette Vaillant,
Domenico Osella, Jean-Paul Mornon, and GPrard Juouen*
The intimate association of a hormone with its receptor is
known to be implicit in the triggering of hormone action;
however, mechanistic detail is largely unknown."] One approach to identifying the specific amino acids in the receptor
implicated in the binding of the hormone is affinity labeling,
that is, the use of molecules that will recognize the site of
association and bind irreversibly."' It is well known that
complexation by an organometallic moiety may dramatically alter the properties and reactivity of an organic substrate,
and make possible reactions that are difficult or impossible
by conventional procedures.['' Extrapolation of this concept
to the biological domain suggests that organometallic complexation of a bioligand may also alter its properties allowing access to information on the nature of recognition.
In studies of the estradiol-receptor complex, it has been
postulated that the association site is acidic in nature and
may contain an SH group.[31It also has been demonstrated
that the hydroxyl groups at C-3 and (2-17 of estradiol are
necessary for effective recognition.['] In addition, substitution studies show that the 17cr position can tolerate fairly
large substituents without severely diminishing recognition.14] We thus set about synthesizing the organometallic
hormone derivatives 1-5 with the aim of binding estradiol
OH
1
covalently to its receptor. We hoped to make use of the fact
that the transformation of alcohols to their corresponding
carbenium ions is facile when the C atom with the hydroxyl
group is stabilized by an organometallic moiety. These species may in turn demonstrate strong alkylating properties.[51
The preparation of 1 and 2 has been described previously.16] The trimetallic 0 s and Ru complexes 3 and 4 were
synthesized by reaction of ethynylestradiol with the activated clusters [M,(CO),,](MeCN), (M = Os, Ru) and display
characteristic chemical shifts in the 'H NMR spectra for the
[*] Prof. Dr. G. Jaouen, Dr. A. Vessieres, Dr. S. Top, Dr. C. Vaillant
Ecole Nationale Supkieure de Chimie de Paris
URA CNRS 403, 11 rue P. et M. Curie
F-75231 Paris Cedex 05 (France)
Prof. Dr. D. Osella
Dipartimento di Chimica Inorganica, Turin (Italy)
Dr. J.-P. Mornon
Universit6 Pierre et Marie Curie, Paris (France)
["*I This work was supported by the Centre National de la Recherche Scientifique, Pirmed, Inserm, MRT, and Medgenix. We thank J. Harrod for helpful discussions and Johnson Matthey for a generous loan of precious
metals.
W-6940 Weinheim. 1992
0570-0833f92~0606-07S3$" 3.50+.2510
753
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