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Catalyzed Acetal Reduction with BH BoranesЧ1-O-Alkyl(aryl)alditols Anhydroalditols and 1-O-Alditylalditols from O-Glycopyranosides.

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An attempt to displace the two monodentate ligands at
the platinum atom Pt2 in 8- 11 by a second chelating diphosphane led to an unexpected result. On treatment of 8,
10, and 11 with diphos or dpmb, the complexes 12-14
are formed, which, according to the IR spectra, contain a
bridging CS, or CSSe ligand.[Iz1 The position of the CS
stretching frequency at ca. 900 c m - ' is very similar to that
of the compound [Pt2Cl,(y-Ph2P-CH2- PPh,),(y-CS,)], the
structure of which has been determined by X-ray structural
analysis.['31The 3'P-NMR spectrum of 13 consists of two
AB pairs which correspond to two pairs of phosphorus
atoms (PA, PB and Px, Py) located in a similar chemical environment."2h1
8 , 10, 11
8, 12
10, 13
11, 14
12-14
M
E
P^P
Pt
Pt
S
Se
Se
diphos
dpmb
diphos
Pd
The reaction of 9 with diphos does not lead to the formation of a product comparable to 12 - 14. Although displacement of PPh, by the chelating ligand occurs, a band
at 1055 cm-' in the IR spectrum corresponding to a v(CS)
stretching frequency points to the presence of a C S bridge
in the binuclear complex. Thus, the tendency of the two
fragments C S and S or C S and Se to reform the corresponding heteroallene depends both on the metals and on
the ligands.
Received: February 21, 1985 [ Z 1182 IE]
German version: Angew. Chem. 97 (1985) 522
CAS Registry numbers:
4, 96482-93-8; 5, 89606-43-9; 6, 89606-44-0; 7, 85318-47-4: 8, 85897-25-2; 9,
96482-94-9: 10, 96482-95-0; 11, 96482-96-1 ; 12, 85698-24-4; 13, 96502-47-5;
14, 96482-97-2 ; [Pt(PPh,),], I422 1-02-4; [Pt(PPh,)2C2H4], 12120-15-9: SeCS,
5951-19-9: C S 2 , 75-15-0; S2-, 18496-25-8; Se2-, 22541-48-6; CS, 2944-05-0;
Pt, 7440-06-4; Pd, 7440-05-3.
[ I ] H. Werner, 0. Kolb, Cbem. Ber. 118 (1985) 880.
[2] I. S . Butler, Acc. Chem. Res. 10 (1977) 359, and references therein.
[ 3 ] a) H. Werner, K. Leonhard, Angew. Chem. 91 (1979) 663; Angew. Chem.
Int. Ed. Engl. 18 (1979) 627: b) H. Werner, K. Leonhard, 0. Kolb, E.
Rottinger, H. Vahrenkamp, Chem. Ber. 113 (1980) 1654.
[4] Preparation from [M(q2-CSE)(PPh3),] ( E = S , Se) and diphos o r dpmb.
4 : M. Ebner, Dissertation. Universitat Wurzburg 1985; 5 , 6 : H. Werner,
M. Ebner, J. Organomer. Chem. 258 (1983) C52; 7 : H. Werner, M. Ebner. W. Bertleff, U. Schubert, Organometallics 2 (1983) 891.
IS] a) 8- I 1 are prepared by stirring a suspension of 0.4 mmol 4-7 with a
molar equivalent amount of [F't(PPh,),] or [Pt(C2H4)(PPh3)2]in 20 mL of
acetone for 60-90 min. The orange precipitate is filtered off, washed
with acetone and ether, dissolved in 5 m L of CH2C12, and chromatographed on alumina (Woelm, activity 111) with CH2C12(8, 9 , 11) o r benzene (10). Removal of the solvent gives a fairly air-stable solid which is
washed with hexane and dried in vacuo. Yield 70-90%; correct C, H,
Pt, Pd analyses.-b) Decomposition temperature determined by differential thermal analysis; 1R in Nujol; "P-NMR (90 MHz, ext. 85%
H,PO,) in CH,CI,/C,D, ( I : 10) with 1% Cr(acac),, all signals dd.-8:
Decomp. temp. 197°C; I R : v(CS)= 1305 c m - ' :
"P-NMR:
&(PA)=58.79, S(P~)=27.56, S(Px)=47.83, &PAP.)= 147, J(P,Px)=3,
J(P,Px)= 27, J ( P t ' P A ) = 3200, J(Pt'P,)= 3160, J(R2PR)= 2330 Hr.- 9 :
"P-NMR:
Decomp. temp. 178°C; 1R: v(CS)= I305 cm-I:
& ( P A ) = 59.87, S ( PR)= 28.13, S(Px) = 42.97, J(PAPR)= 148, J(P,Px) = 5,
J(P,Py) = 25, ./(RIP,) = 3180, J(Pt'Px) = 3280, J(Pt2Pe)= 2400 Hz.- 10 :
Decomp. temp. 162°C; I R : v(CS)= I305 c m - ' :
"P-NMR:
S(P,)= 22.47, &(Pa)= 7.18, S(P,y)= 1.22, J(PAPB)=184, J(PaPx)= 24,
Angew. Chem. Inr. Ed. Enql. 24 (1985) No. 6
J(PBPx) = 18, J( Pt ' PB)= 3 100, J(Pt ' Px) = 3640, J( Pt'Ph)
= 2060 Hz.- I 1 :
Decomp. temp. 135°C; IR: v(CS)=I300 c m - ' :
"P-NMR:
6(PA)=59.14, fi(P~)=28.32, 6(Px)=42.03, J(PAPH)= 148, J(P,Px)=S,
J(P,Px) =26, J(Pt'P8) =2360 Hz.
[6] W. P. Fehlhammer, H. Stolzenberg, Inorg. Chim. Acta 44 (1980) L I 5 I .
[7] W. M. Hawling, A. Walker, M. A. Woitzik, J . Chem. Soc. Chern. Cornmun. 1983. 11.
[XI 0. J . Scherer, R. Konrad, E. Guggolz, M. L. Ziegler, Chem. Ber. 116
(1983) 2676.
(91 P. E. Garrou, Chem. Reu. 81 (1981) 229.
[lo] Crystals from acetone. Triclinic, space group PI, Z = 4 ; a = 1434.7(3),
b = 1452.8(1), c=2522.3(3) pm. n=89.0(2), p1=88.8(1), y=70.8(2)",
V=5257. 10b pm'; pLalCd=
1.67 g/cm3: 5 " < 2 8 < 3 2 " ( M o ~ , , .1=71.069
pm); 5038 independent reflections; position of the platinum atoms by
Multan-80, position of the other atoms from difference Fourier synthesis: R , =0.098, R2=0.113 for 4228 structure factors (F,,22.96u(F,,)). Further details of the crystal structure analysis can be obtained from the
Fachinformationszentrum Energie Physik Mathematik, 0-75 14 Eggenstein-Leopoldshafen 2, by quoting the depository number CSD 51 355,
the names of the authors, and the journal citation.
[ I I ] Example: [Cl(PPh3)Pt(p-CO)Pt(PPh3)2CI]:264.3 pm; R. Bender, P.
Braunstein, A. Tiripicchio, M. Tiripicchio-Camellini, J . Chem. Soc.
Chem. Commun. 1984, 42; [(PPh,),Pt(p-S)F't(CO)PPh,]: 264.7 pm: A.
Skapski, P. Traughton, J. Cbem. SOC.Chem. Commun. 1969, 170.
[12] a) Complexes 12-14 are prepared by stirring a suspension of
0.15 mmol 8 , 10, 11 with a molar equivalent amount of diphos or dpmb
in 10 mL of acetone for 60-90 min. The yellow precipitate is filtered
off, washed repeatedly with ether, and dried in vacuo. Yield 92% (12).
65% (13), 77% (14); correct C, H, Pt, Pd analyses.-b) Decomposition
temperature, IR, and "P-NMR as for 8-11 [ 5 ] . - 1 2 : Decomp. temp.
251°C; IR: v(CS)=SSS cm-I; "P-NMR could not be completely analyzed; the spectrum consists of two A B parts which overlap.-- 13: Decamp. temp. 226°C; 1R: v(CS)=920 c m - ' : "P-NMR: 6(PA)=39.78,
S(Ps) = 37.73, ~ ( P X=)33.47, S(P,) = 32.83, J(PAPR)= 46, J(P,Py) = 16,
J(PAPx)= 7, J(PBPY)=6, J(PtP,) = 4 120, J(PtPs) = 2600, J(PtPx) = 4400,
J(PtPy)=2380 Hz.-14: Decomp. temp. 198°C: IR: v(CS)=905 c m - ' .
[I31 T. S. Cameron, P. A. Gardner, K. R. Grundy, J. Organornet. Chem. 212
(1981) C 19.
Catalyzed Acetal Reduction with >BH Boranes 1-0-Alkyl(aryl)alditols, Anhydroalditols, and
1-0-Alditylalditols from 0-Glycopyranosides""
By Roland Koster,* SoIedad Penadb-Ullate, and
Wilhelrn Volker Dahlhoff
In contrast to semiacetals, acetals are completely stable
towards >BH-boranes and fBH-borates up to 2 130°C.
In the course of our investigations on the analytical uses of
organoboron reagents we found that open-chain and cyclic
0,O-acetals can be quantitatively reduced with aliphaticsubstituted >BH boranes in the presence of certain electrophiles, e.g. ether-trifluoroboranes or alkane- and arenesulfonyloxy(diorgano)boranes, respectively."' We report
here on the preparation of open-chain and cyclic polyhydroxyethers from 0-gluco- and O-galactopyranosides[2'
with alkyldiboranes(6) in the presence of the activator
9-methanesulfonyloxy-9-borabicyclo[3.3.
llnonane
(MSBBN).I3' Apart from 1-0-methylalditols, 1-0-phenylgalactitol and various anhydroalditols, also 1-0-alditylalditols can now be prepared from disaccharides.
The per-0-diethylboryl derivatives l a to l0al4' of the 0glycopyranosides 1 to 10 (cf. Scheme 1 and Table 1) are
especially suitable for the reduction with alkyldiboranes(6)
(alkyl= ethyl, p r ~ p y l ) [ ~in" ~the presence of MSBB"']
at
[I'
Prof. Dr. R. Koster, Dr. S. Penades-Ullate ['I, Dr. W. V. Dahlhoff
Max-Planck-Institut fur Kohlenforschung
Kaiser-Wilhelm-Platz 1, D-4330 Mulheim a. d. Ruhr (FRG)
['I
Present address: Instituto de Quimica Organica General C.S.I.C.
Juan de la Cierva 3, Madrid-6 (Spain)
Boron Compounds, Part 66.-Part 65: R. Koster, G. Seidel, B. Wrackmeyer, Angew. Chem. 97 (1985) 317; Angew. Chem. Inr. Ed. Engl. 24
(1985) 326.
[**I
0 VCH Verlagsgesellschafl mbH. 0-6940 Weinheim. 1985
0570-0833/85/0606-0519 $ 02.50/0
5 19
la-5a
l l b , 12b
13b
13'b
14b
15 b
15' b
exocyclic
hyd rob o r a t i o n
endocyclic
hyd r o b o r a ti on
hydroboration
LOR
6a-10a
= HLabl; a,
- R
b, R
16 b- 19b
exocyclic
hyd rob0 r a t i on
= B E t z L41;
= Ac[8al
2Ob
Scheme I . Catalytic hydroboration of per-0-diethylboryl-substituted a- and 0-glucopyranosides l a -5a
1).
14 b
endocyclic
hydroboration
and a- and P-galactopyranosides 6a - 10a (see Table
Table I . Products l l b - 2 0 b of the catalytic hydroboration after deborylation and subsequent acetylation of the pyranosides l a - 10a (see Scheme 1) [a, b]. Prod12b ; per-0-acetylated 1,5-anhydro-u-glucitol 13b. 1,4-anhydro-n-glucitol 13'b.
ucts: Per-0-acetylated I-0-methyl-D-glucitol I l b and l-O-(4-~-glucityl)-~-glucitol
n-glucitol 14b, 2,5-anhydro-~-mannitol15b and 2,5-anhydro-~-glucitol15'b ; per-0-acetylated I-0-methyl-u-galactitol 16b, I-0-phenyl-n-galactitol 17b, 1-0-(4n-glucitylj-u-galactitol ISb, I-O-(~-glucityl)-u-galactitol
18'b and 1-0-(6-D-glUCityl)-D-galaCtitOI 19b ; per-U-acetylated I ,5-anhydro-u-galactitol 20b.
Per-0-(diethylbory1)u-glucopyranoside
xP
XI.
l a Methyl a-D-glucopyranoside
OCH,
X
[al?;'
53-55 1111
23.7 [Ill
(1.2)
H
OCH,
2a Methyl a-D-glucopyranoside
M.p.
I"C1
OCHs
H
Ilb
(c,CHC13]
Yield
1%)
13b
5
5
4
5
0
-
Y
O
1
0
0
-~~
0
5
13'b
Yield [oh]
14b
15b
-
15'b
-
3a Maltose
4a Cellobiose
5a Sucrose
Row
-
H
0
6
0
6
38
OR
bR
Per-0-(diethylboryl).
D-galactopyrdnoside
6a Methyl a-D-galactopyranoside
X,
XI3
X
1
M.p.
[dbo
Yield
I"Cl
(c, CHCI,)
[%I
117-1lX[II]
11.6[1l]
(0.6)
44
OCH,
H
H
OCH,
16b
16b
OCIHS
17b
0c.K~
18b
R
O
{
"
OCH3
7a Methyl fl-D-galactopyranoside
8a Phenyl P-~-galactopyranoside
9a Lactose
o a o R
RO
lS'blc1
10a Melibiose
133
19b
10
0
7
7
40
40
18.2
(0.55)
70
OR
LOR
[d]
Id1
= 16
2
20
97-98
~
99
82
0
OR
~
20
(0.3)
0
'aoR
Rt::
H
Yield [%I
2Ob
14b
-
(1)
[a] Standard conditions: 5-6 h heating of l a to 10a in boiling, neat ethyldiboranes(6) [12--15%0 He] [ 5 ] with addition of MSBBN 3 in the ratio educt:
>BH :MSBBN= I :4:0.1; in the case of 4a and 9a: 1 :4:0.8. [b] The mixtures of I l b to 2Ob [Xa] were separated gas-chromatographically: GC 1121: Siemens instrument glass capillary column (25-55m, OV-I), He (1.5 bar], column 100-320°C (IO/min); injection block: 250°C. [c] I-,2-, 3- or 5-u-glucityl-substituent. [dl
Not determined.
100°C. Hydroboration of the endocyclic acetalic C - 0
bond takes place, leading to open-chain O-ethylboron-protectedt5" polyhydroxy ethers, e.g. lla, 12a and 16a to
520
0 VCH Verlug.vgesellschufi mbH, 0-6940 Weinheim, 1985
19a.l6] Hydroboration of the exocyclic acetalic C - 0 bond
leads to cyclic 0-ethylboron-protected polyhydroxyether,
e.g. 13a and 20a. 0-Diethylboryl-, and the 0,O'-ethylbo-
0570-0833/85/0606-0520 $ 02.50/0
Angew. Chem. h i r . Ed. Engi. 24 (1985) No 6
-~
ranediyl-protective groups formed therefrom in the presence of ethyldiboranes(6) can readily be removed with met h a n ~ l / g l y c o l . The
[ ~ ~ per-0-acetyl derivatives[8"' l l b to 20b
are prepared from the product mixture and can be separated chromatographically and characterized spectroscopically (MS, NMR).Iah1
The 0-glycopyranosides la to 10a react with varying
rates on reduction with ethyldiboranes(6); 4a and 9a are
reduced especially slowly. By increasing the amount of
MSBNN (cf. Table 1, footnote [a]), the formation of pyranosylalditols in the product mixture can be avoided. The
composition of the polyhydroxyether mixtures is influenced by the anomeric configuration of the D-glUCOpyranosides 1 to 4 and the D-galactopyranosides 6 to 10. The
methyl [3-pyranosides 2a and 7a and the phenyl fl-D-galactopyrdnoside 8a afford highly selectively, via endocyclic
C - 0 hydroboration, 1-0-methyl-D-alditols (11, 16 with
80% selectivity) and 1-0-phenyl-D-galactitol (17, 98%), respectively. Octakis-0-(diethy1boryl)cellobiose 4a and octakis-0-(diethy1boryl)lactose 9a preferentially yield the 1-0aldityIalditol~[~~
12 (52%) and 18 and 18' (72%), respectively. In contrast, octakis-0-(diethylbory1)maltose 3a affords 12 and 13 practically non-selectively, while octakis0-(diethy1boryl)melibiose 10a gives only 20% 19, and
mainly 1,5-anhydro-~-galactitol
20 and D-glUCit01 14, both
of which are formed as a result of exocyclic C - 0 bond
cleavage (cf. Scheme 1 and Table 1).
The "trehalose" moiety of the octakis-0-(diethylbory1)sucrose 5a is not reduced at the endocyclic acetal
bonds. The quantitative reduction of 5a, however, takes
place regioselectively (88%), showing preference for the
exocyclic C - 0 bond of the furanoside ring. In each case,
44% glucitol 14 and a ca. 1 : 6 mixture of the 2,s-anhydroalditols 15 and 15' formed via an oxycarbenium intermediate are obtained. Reductive pyranoside-cleavage of
5a affords a further 6% of D-glucitol 14 and 6% of 1,5-anhydro-n-glucitol 13 (cf. Scheme 1).
Experimental
Penta-O-acetyl-I-O-phenyl-D-glucitol
17b: MSBBN [3] (0.1g, 0.38 mmol)
was added under protective gas at ii20°C to 1.94 g (3.67 mmol) 8a [prepared
from 1 g (3.9 mmol) of phenyl fi-D-galactopyranoside 8 and 4 m L
(28.4 mmolj of activated triethylborane [4]] and 1.27 g ethyldiboranes(6) [5a]
( I 1.86Oh H", i.e. 15.1 mmol >BH-borane) and the mixture stirred for 4 h at
120°C. After evaporation of the colorless solution in vacua (lo-' torr; bath:
70-80°C) the residue was treated with ii7 mL methanol/l,2-ethanediol
( ~ :2)5 and all volatile components were removed in vacua (lo-' torrj. The
procedure was repeated. The boron-free residue was then treated at 20°C
with 5 mL of acetic anhydride in 5 mL pyridine and, after stirring for 1 hour,
the mixture was evaporated t o dryness. The solid residue was washed with a
little ethanol, then with diethyl ether. The colorless, solid product (m.p.
129-131 " C ) was recrystallized from 20 m L diethyl ether/5 mL ethanol:
1.6g (93%) pure 17b: m.p. 133°C; [a]Z,"=20 ( c = 0 . 3 , CHCI,); H Z (Hydridzahl= hydride number) [8b, 10]=9.9.
I-O-Phenyl-~-galactitol17: A mixture of 17b (404.4 mg, 0.86 mmol) and
ethyldibordnes(6) (952.9 mg, 11.96 mmol >BH-borane) was heated for 2 h at
i
i 120°C. The excess >BH-borane
was destroyed by addition of 20 mL of
methanol (>BH-borane consumed: 8.53 mmol). After removal of volatile
components by distillation in vacua the residue was treated with a further
20 m L of methanol and the resulting solution evaporated to dryness, giving
225 mg (= 100%) 17: m.p. 2 0 2 T ; [alg=7.2 (c=0.4, (H;C),SO).
Received: January 18, 1985 [Z 1139 IE]
German version: Angew. Chem. 97 (1985) 508
CAS Registry numbers'
la, 61553-54-6; 2a, 96532-66-0; 3a, 83823-00-1; 4a, 96613-28-4; Sa, 50612.505: 6a, 96532-67-1; 7a, 96532-68-2; 8a, 96532-69-3; 9a, 96532-70-6; IOa,
96532-71-7. llb, 5139-25-3; 12b, 96532-72-8; 13b, 13137-69-4; 13'b, 5390578-5; 14b, 7208-47-1 ; 15b,65729-88-6; 15'b, 65729-86-4; 16b, 25678-3 1-3; 17,
96532-73-9; 17b, 96532-74-0; 18b, 96614-03-8; W b , 96532-78-4; 19b, 9653275-1; 20b, 13121-62-5.
Angen. Chrm Inr. Ed. Engl. 24 (1985) No. 6
~
[ I ] R. Koster, W. Schussler, unpublished.
[2] Cf. W. V. Dahlhoff, S. Penades-Ullate, R. Koster, 2nd European Symp.
on Carbohydrates and Glycoconjugates, Budapest, August 1983, Abstract S. A-32.
[3] Cf. Houben-Weyl: Methoden der orguni.fchen Chemie, 4th edit., Val.
X111/3a, Thieme, Stuttgart 1982, p. 590.
[4] R. Koster, K.-L. Amen, W. V. Dahlhoff, Liebigs Ann. Chem. 1975. 752.
(51 a) Ethyldiboranes(6) is a collective expression for mixtures of variously
highly ethylated boranes and diboranes(6); R. Koster, P. Binger, Inorg.
Svnth. 15 (1974) 141 : b j here, "0-ethylboron-protected" signifies the
presence of Et,B- and EtB< groups; for clarity, only the EtZBgroups
are shown in the formulas.
[6] Ethyldiboranes(6)-catalyzed reduction of tbe per-0-methyl-0-glycopyranosides of 1 and 2 leads predominantly (290%) to per-0-methylI,5-anhydro-~-glucitolof 13 with R = C H , (cf. Scheme I).
[7] R. Koster, P. Idelmann, W. V. Dahlhoff, Synthesis 1982. 650.
[S] a) Elemental analyses and spectroscopic data (MS, 'H-NMR, " C NMR) of per-0-acetyl derivatives llb to 20b are consistent with the calculated compositions and proposed structures. b) The polyhydroxy ethers 11 to 13 and 15-20, free of protective groups, are obtained from
llb to 13b and 15b to 2Ob by reaction with alkyldiboranes(6) at
2 1 0 0 ° C [cf. W. V. Dahlhoff, R. Koster, J . Org. Chem. 42 (1977) 31511 or
by Zemplen saponification.
[9] In analogy to the trivial names of the I-0-glycosidalditols (e.g. maltitol,
cellobiitol), for the new I-0-alditylalditols we propose the abbreviations
maltdiitol = cellobidiitol, lactdiitol, melibidiitol etc., which are formed
by adding the syllables "diitol" to the parent names.
[lo] R. Koster, L. Synoradzki, Chem. Ber. 117 (1984) 2850.
[ I I] Cf. H. Zinner, R. Kleeschatzky, R. Neels, Chem. Ber. 98 (1965) 1492.
[I21 G. Schomburg, F. Sagheh, unpublished work 1983/1984.
Bis(tricarbony1iron)-para-quinodimethanes :
Preparation and Molecular Structure
By Ali R . Koray, Claus Krieger, and Heinz A . Staab*
The stabilization of highly unstable organic molecules as
tricarbonyliron complexes is well-known in several cases
including cyclobutadiene, trimethylenemethane, and orrhoquinodimethane."] Other highly unstable molecules are
para-quinodimethanes like 1 and 2 which have attracted a
great deal of interest as intermediates in chemical reactions[21 and have been studied spectroscopically at low
temperature^.^^] In this paper we would like to report on
bis(tricarbony1iron) complexes of 1 and 2 , which, to our
knowledge, are the first examples of para-quinodimethanes stabilized as ligands in transition metal complexes.
l : R = H
3:R=H
2: R = CH,
4 : R = CH,
3 and 4 were obtained by rapid dropwise addition of solutions of 1,4-bis(bromomethyl)benzene and 1,4-bis(bromomethyl)-2,5-dimethylbenzene, respectively, in benzene
( = 0.01 mo1/250 mL) into a suspension of Fe,(CO), in benzene ( = 0.05 mo1/250 mL) at 40-45 " C .Evaporation of the
solution, rapid chromatography (silica/cyclohexane), sublimation and recrystallization from hexane yielded 314'
(orange microcrystals, dec. > 150"; 1.1% yield) and 4141
[*] Prof. Dr. H. A. Staab, Dr. A. R. Koray, C. Krieger
Abteilung Organische Chemie
Max-Planck-Institut fur medizinische Forschung
Jahnstrasse 29, D-6900 Heidelberg 1 (FRG)
0 VCH Verlugsgesellschafi mbH. 0-6940 Weinheim. 1985
0570-0833/8S/0606-0521 $ 02.50/0
52 1
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alkyl, boranesч1, alditylalditols, anhydroalditols, glycopyranosides, reduction, acetals, alditol, aryl, catalyzed
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