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Catalytic Hydration of Acrylonitrile to Acrylamide under Mild Conditions.

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type reactions and from reactions which are unique for this
reagent, for example the one-pot synthesis of the biologically
interesting methylphosphonates of type 41"l (Scheme 3) and
phosphorofluoridates."21 The chemical and enzymatic properties of 4 compare with those of other dinucleoside
methylph~sphonates.[~*
mediates in nucleotide chemistry, can be readily obtained by
hydrolysis from 2 and 3 in a one-pot procedure.
Received: December 13, 1989;
revised: February 12, 1990 [Z 3684 IE]
German version: Angew. Chem. 102 (1990) 565
CAS Registry numbers:
1,114071-78-2; Za, 126256-30-2; 2b, 126256-31-3; 3 a pa isomer, 126256-32-4;
3a P, isomer, 126373-38-4; 3 b P, isomer, 126451-68-1; 3 b ps isomer, 12625640-4; 3c P, isomer, 126256-35-7; 3c P, isomer, 126373-40-8; 3d P, isomer,
126256-36-8; 3d P, isomer, 126373-41-9; 4 a P, isomer, 90865-75-1; 4 a P, isomer, 90865-76-2;5 a PRisomer, 126256-33-5; 5 a P, isomer, 126373-45-3; 5 b P,
isomer, 126256-31-9;5 b P,isomer, 126373-42-0;5 c P, isomer, 126256-39-1;5 c
P, isomer, 126373-442; 6 a P, isomer, 126256-34-6; 6a Ps isomer, 126373-39-5;
561836 b PRisomer, 126256-38-0; 6b P, isomer, 126373-43-1; [(IR)~N],PC~,
63-2; 3'-o-Ac-thymidine, 21090-30-2; 5'-0-DMT-thymidine. 40615-39-2;
3'-o-Ac-N6-benzoyl-2'-deoxyadenosine,
251 52-95-8; 5'-o-DMT-Nh-benzoyl-2'deoxyadenosine, 64325-78-6.
OAc
Scheme 3. Synthesis of 4 (2 h, 20°C) [Sb]. ,'P-NMR (CDCI,, 85% H,PO,
ext.): 6 = 32.7, 32.5.
Unique for reagents of type 3 is the reaction with oxalylazolides and anilides to form in excellent yields the dinucleotide azolides 5a, b and anilides 5 c (Scheme 4).
"MTrovThy
00
0
I
.N-C-C -NR.
7..
J
P
R L
' "=P-NR,
v-
5
~
-2 CO
-Me,SiNR,,
I
Thv
o
v
OAc
5a, R,NH
= imidazole;
5b, R,NH
=
triazole; 5c, R,NH
= aniline
Scheme 4. Synthesis of 5 from 3 a and (R,N-CO), (l/l); 3 h, 20°C. Yield.
NMR (CDCI,, 85%
(determined by ,'PNMR spectroscopy) 90-94%.
H,PO,ext.):&= -12.0, -11.5(5a); -10.6, -10.3(5b); f2.0, +1.6(5c).
In this way the anilides of type 5 c have become readily
accessible for the first time. Nucleotide anilides are of importance for the stereospecific synthesis of nucleoside phosphorothioates.1' 31
The reaction of 5 a leading to the anhydrides 6 a and 6 b
further illustrates the potential of this approach (Scheme 5).
DMTroYThy
0I
" " O Y T h Y
0
1
O=P-NJ
F N
y20
Jv
Thy
~
O=P-0-Y
J
OAc
6
5a
= CH,SO,;
Catalytic Hydration of Acrylonitrile to Acrylamide
under Mild Conditions **
By Jik Chin* and .
I
H . Kim
~-N^N
OAc
6a, Y
[l] R. L. Letsinger, W. B. Lunsford, 1 Am. Chem. Soc. 98(1976) 3655-3661.
[2] L. J. McBride, M. H. Caruthers, Tetrahedron Lect. 24 (1983) 245-248.
[3] S . A. Narang (Ed.): Synthesis and Applications of D N A and R N A , Academic Press, Orlando, FL 1987.
[4] a) M. J. Nemer, K. K. Ogilvie, Tetrahedron Lett. 21 (1980) 4149-4252;
b) S. A. Noble, E. F. Fisher, M. H. Caruthers, Nucleic Acids Res. 12(1984)
3387-3404; c) W J. Stec, G. Zon, W. Egan, R. A. Byrd, L. R. Philips.
K. A. Gallo, J. Org. Chem. 50 (1985) 3908-3913; d) A. Wilk, W. J. Stec,
Nucleic Acids Res. Symp. Ser. 18 (1987) 289-292.
[5] a) K. Imai, T. Ito, S. Kondo, T. Takaku, Nucleosides& Nucleatides 4 (1985)
669-679; b) W. Dgbkowski, F. Cramer, J. Michalski, Tetrahedron Lett. 28
(1987) 3559-3560.
[6] E. S. Batyeva, V. A. Alfonsov, A. N. Pudovik, Izv. Akad. Nauk SSSR. Ser.
Khim. 1976,463-466.
[7] a) R. B. King, P. M. Sundaram, 1 Org. Chem. 49 (1984) 1784- 1789; b) S .
Hamamoto, H. Takaku, Chem. Lett. 1986, 1401-1404.
[S] a ) A . Kurne, M. Fujii, M. SekinqT. Hata, J. Org. Chem. 49(1984) 21392143; b) E. de Vroom, M. L. Spierenburg, C. E. Dreef, G. A. van der
Marel, J. H. van Boom, Red. Eav. Chim. Pays-Bas 106 (1987) 65-66.
[9] a ) R . H. Hall, A. Todd, R. F. Webb, J. Chem. Sac. 1957. 3291-3296;
b) P. J. Garegg, T. Regberg, J. Stawinski, R. Stromberg, Chem. Srr. 25
(1985) 280-282; c) B. C. Froehler, M. D. Matteucci, Tetrahedron Lelt. 27
(1986) 469-472; d) J. E. Marugg, M. Tromp, E. Kuyl-Yeheskiely, G. A.
van der Marel, J. H. van Boom, ibid. 27 (1986) 2661 -2664; e) M. Fujii, K.
Ozaki, M. Sekine, T. Hata, Tetrahedron 43 (1987) 3395-3407. and references cited therein.
[lo] a) A. Lopusinski, J. Michalski, M. Potrzebowski, Phosphorus Suljiur 28
(1986) 299-305; b) W. Dgbkowski, J. Michalski, 1 Chem. Sac. Chem.
Commun. 1987, 755-756; c) W. Dqbkowski, F. Cramer, J. Michalski, Tecrahedron Lett. 28 (1987) 3559-3560; d) A. Skowronska, R. Dembinski,
R. Kaminski, J. Michalski, 1 Chem. Sac., Perkin Trans. 1 1988, 21972201.
[Ill P. S . Miller, P. 0. P. Ts'o, Annu. Rep. Med. Chem. 23(1988)295-304, and
references cited therein.
[12] W. Dgbkowski, F. Cramer, J. Michalski, Tetrahedron Left.29 (1988) 3301 3302.
[13] Z. J. Lesnikowski, M! Niewiarowski, W. S . Zielinski, W J. Stec, Tetrahedren
40 (1984) 15-32.
6b, Y
= CF,CO
Scheme 5. Synthesis of 6 (15min, 2 0 T , CH,CN). Yield (determined by
"PNMR spectroscopy) 95-97%. " P NMR (CDCl,, 85% H,PO, ext.):
6 = -15.6, -15.3 (6a); -9.8, -9.5 (6b).
All compounds 3-6 are mixtures of diastereoisomers.
Phosphonates with P-H bonding, which are versatile interAngew. Chem. Int. Ed. Engl. 29 (1990) No. 5
Numerous articles have been written on the development
of catalysts that hydrolyze amides, esters and nitnles. Due to
the stability of these substrates, most studies have been focused on model systems involving activated substrates"] or
intramolecular catalysis.r21Perhaps it is now time to exploit
[*] Prof. J. Chin, J. H. Kim
Department of Chemistry, McGill University
801 Sherbrooke Street West, Montreal, Quebec H3A 2K6 (Canada)
[**I Support by the National Science and Engineering Research Council of
Canada is gratefully acknowledged.
0 VCH Verlagsgesellschajt mbH, 0-6940 Weinheim. !990
0570-0833190j0505-0523$02.50/0
523
the knowledge gained from extensive model studies to the
development of true catalysts that hydrolyze unactivated
substrates.[31We recently showedr4]that 1 is highly efficient
at catalyzing the hydrolysis of unactivated esters such as
methyl acetate. The hydrolysis of amides and nitriles poses
an even greater challenge than the hydrolysis of esters, since
amides and nitriles are thousands of times more stable than
esters. For example, the second-order rate constants
for hydroxide-catalyzed hydrolysis of methyl acetate,"] acetonitrileI6I and acetamide"] are 1.5 x lo-' M s-', 1.6 x
M s-', and 7.4 x
M s-', respectively. Herein we
report on the hydrolysis of acetonitrile under mild conditions using 1, 2 and 3 as catalysts.
1
2
3
In a typical kinetically controlled experiment, acetonitrile
(0.1-0.5 M) was added to a D,O solution of 2 (0.01 M,
perchlorate salt) at pD 7.0 and 40 "C. Figure 1 shows that, as
the reaction proceeds, the 'H-NMR signal of acetonitrile
Cu2@,Ni2* and Zn2* have all been shown to catalyze the
hydration of nitriles when the nitrile function is covalently
linked to metal-coordinating functional groups.[*,91 For example, 2-cyanopyridine and 2-cyano-1,lO-phenanthroline
are rapidly hydrated to the corresponding amides when
Cu2* is added to the aqueous reaction mixture under mild
conditions. It has been shown that, under reflux conditions,
Pt2@-complexescatalyze the hydrolysis of simple nitriles that
do not contain any additional metal-coordinating functionalities.['O1Simple nitriles directly coordinated to CO'"-,[~]
and Ir"'[' ''-complexes can be easily hyRh"'-,[' Ru"'-['~~
drolyzed to the corresponding amido complexes at ambient
temperature. However, there is no catalytic turnover with
the substitutionally inert Co'"-, Rh"'-, Ru"'- and Ir"'-complexes. Interestingly, ten turnovers can be easily detected for
the hydrolysis of acetonitrile by 2 in neutral water (pH 7) at
40 "C (Fig. 1). The turnover time is approximately 3 x lo3 s.
This represents the first example of turnover for a Co"'-complex-catalyzed hydrolysis of a nitrile. Although Co"'-complexes are generally substitutionally inert the coordinated
water molecules in 2 can be rapidly displaced under mild
conditions." 31
There are three possible mechanisms for the hydrolysis of
acetonitrile when catalyzed by 2. The first mechanism involves intermolecular attack of the metal hydroxide on acetonitrile (A). The second involves coordination of acetonitrile followed by intermolecular hydroxide-attack (B).r6IThe
third involves coordination of acetonitrile followed by intramolecular attack of the metal hydroxide (C). Mechanism
A
U
U
B
C
A can be ruled out on the basis that 3 is much less reactive
than 2. If mechanism A were correct, 2 and 3 would be
2.0
1.5
-6
Fig. 1. 'H-NMR chemical shift of the a proton of acetonitrile (0.1 M) after
addition of 2 (0.01 M) at pD 7.0 and 40°C. fert-Butyl alcohot as standard
(6 = 1.22). Measurements after a) 0 h, b) 5.5 h, c) 23 h.
(6 = 2.04) decreases while that of acetamide (6 = 1.96) increases. The reaction is zero order with respect to acetonitrile
concentration and first order with respect to the catalyst
concentration. Under the above conditions, the rate of the
M s- I . 3 is about 20 times less reachydrolysis is 3.2 x
tive than 2. 1 is active but deligates to give free tris(3aminopropy1)amine after initial production of acetamide.
524
0 VCH
Verlagsgesellschaft m b H , 0-6940 Weinhelm, 1990
expected to have comparable reactivities, since the basicities
of the metal hydroxides are about the same.[161Mechanism
B can also be ruled out. The pseudo-first-order rate constant
for the hydrolysis of [(NH,),CO(NCCH,)]~@in water to
give the acetamide-bound cobalt complex is 3.4 x
s-'
at pH 7.0 and 25 oC.[61Hence, if mechanism B is correct, the
expected maximum rate constant for hydrolysis of acetonitrile (0.5 M) catalyzed by 2 (0.01 M) would be
M s-'. This is too slow to account for the ob3.4 x
M s-'). Furthermore,
served rate of hydrolysis (3.2 x
hydroxide-catalyzed hydrolysis of [(NH,),Co(NCCH,)] is
accompanied by a proton exchange for the methyl group.r61
In sharp contrast, the hydrolysis of acetonitrile catalyzed by
2 does not show any proton exchange for the methyl group.
Mechanism C is consistent with the observed rate-enhancement as well as the lack of any proton exchange for the
methyl group. Related mechanisms involving intramolecular
metal-hydroxide attack on metal-coordinated substrates
have been proposed for the Co"' complex-promoted hydrolysis of phosphate esters and carboxylate ester^."^'
There has been considerable industrial interest in developing catalysts for the hydrolysis of acrylonitrile to acrylamide
without hydrolyzing the carbonxarbon double bond. Intramolecular metal-hydroxide attack on coordinated acrylo-
0570-0833~90/OSOS-0524
$02.50/0
Angew. Chem. Inr Ed. Engl. 29 (1990)No. S
nitrile according to mechanism C should result in clean hydrolysis of the cyano group with retention of the C-C double
bond. Indeed acrylonitrile is quantitatively converted into
acrylamide by 2 (Fig. 2).
[3] a) D. Kahn, W C. Still, J. Am. Chem. SOC.110 (1988) 7529; b) F. M.
Menger, M. Ladika, ibid. 109 (1987) 3145.
[4] J. Chin, M. Banaszczyk, J. Am. Chem. Soc. I l l (1989) 2724.
[5] J. P. Guthrie, P. A. Cullimore. Can. J. Chem. S8 (1980) 1281
161 D. A. Buckingham, F. R. Keene, A. M. Sargeson, 1 Am. Chem. Soc. 95
(1973) 5649.
171 T. Yamana, Y. Mizukami, A. Tsuji, Y. Yasuda, K. Masuda, Chem. Pharm.
Bull. 20 (1972) 881-891.
[8] P. F. B. Barnard, J. Chem. SOC.A 1969,2140.
[9] R. Breslow, R. Fairweather, J. Keana, J. Am. Chem. SOC.
89 (1969) 2135.
[lo] a) M. A. Bennett, G. B. Robertson, P. 0. Whimp, T. Yoshida, J. Am.
Chem. Soc. 9S (1973) 5649; b) C. M. Jensen, W. C. Trogler, ibid. 108 (1986)
723.
Ill1 N. J. Curtis, A. M. Sargeson, J. Am. Chem. Soc. 106 (1984) 625.
1121 a)A. W. Zanella, P. C. Ford, J. Chem. Soc. Chem. Commun. 1974, 795;
b) A. W. Zanella, P. C. Ford, Inorg. Chem. 14 (1975) 42.
[13] J. Chin, M. Banaszczyk, V. Jubian, X. Zou, J. Am. Chem. Soc. 111 (1989)
186.
[14] a) J. Chin, M. Banaszczyk, J. Am. Chem. SOC.111 (1989) 4103; b) J. Chin.
V. Jubian, J. Chem. SOC.Chem. Commun. 1989, 839.
Oligorylene as a Model for
“Poly(perinaphtha1ene)”**
By Angelika Bohnen, Karl-Heinz Koch, Worfgang Liittke,
and Klaus Miillen *
Dedicated to Professor Wolfgang Roth on the occasion
of his 60th birthday
-6
Fig. 2. ‘H-NMR chemical shift of the u proton of acrylonitrile (0.1 M) after
addition of 2’ (0.01 M) at pD 6.3 and 40°C. Measurements after a) 0 h, b) 3.5 h,
c) 20 h.
We have shown that 2 forms four-membered ring intermediates much more readily than does 3.[14’Since mechanism
C involves the formation of a four-membered ring intermediate, it is not surprising that 2 is so much more reactive than
3 in hydrolyzing acetonitrile. Although 1 also catalyzes the
hydrolysis of acetonitrile, it starts to decompose after initial
reaction due to acetamide-promoted deligation of the tetraamine ligand. Amide-promoted deligation of Co”’-amine
complexes is a known phenomenon.“ ‘1 Deligation does not
take place with 2, apparently because the cyclic tetraamine
ligand binds very tightly to the cobalt atom.
The three most important criteria in developing a “perfect” catalyst are reactivity, selectivity, and turnover number. Unlike enzymes, simple catalysts are far from being
perfect. Nevertheless, 2 is an excellent catalyst for the hydrolysis of nitriles. The catalytic mechanism involving intramolecular metal-hydroxide-attack on the Co”’-complexcoordinated nitrile allows for unprecedented reactivity and
selectivity. Furthermore, rapid dissociation of the product
from the metal complex allows for catalytic turnover to take
place for the first time using a Co”‘-complex.
Received: November 24, 1989 [Z 3644 IE]
German version: Angew. Chem. 102 (1990) 580
[l] a) R. Breslow, G. Trainor, A. Ueno, J. Am. Chem. SOC.10s (1983) 2739;
b) D. J. Cram, P. Y. Lam, S . P. Ho, ibid. 108 (1986) 839; c) J. M. Lehn, C.
Sirlin, J. Chem. Soc. Chem. Commun. 1978,949; d) J. Chin, X. Zou, J. Am.
Chem. SOC.106 (1984) 3687.
[21 a) H. Kroll, J. Am. Chem. SOC.74 (1952) 2036; b) M. L. Bender, B. W.
Turnquist, i b d 79 (1957) 1889; c) P. A. Sutton, D. A. Buckingham, Arc.
Chem. Res. 20 (1987) 357, and references cited therein; d) P. Nanjappan,
T. Czarnik, J. Am. Chem. Soc. 109 (1987) 1826; e) A. J. Kirby, P. W. Lancaster, J Chem. SOC.Perkin Trans. 2 1972, 1206; 0 R. Kluger, J. Chin, J.
Am. Chem. Soc. 104 (1982) 2891.
Angew. Chem. In!. Ed. Engl. 29 (1990) No. 5
0 VCH
The annelated arenes derived formally by connecting all
the peri-positions of naphthalene have been designated by
Clar as ‘‘rylenes”.l’l Although chemical and physical properties of the first member of this series of naphthalene
oligomers, perylene 2 a, have been thoroughly investigated,[’ -41 the higher homologues terrylene 3a and quaterrylene 4 a have resisted all attempts at characterization even
though they are known compounds. This is primarily due to
the fact that they are difficult to synthesize and extremely
insoluble in organic solvents.[51
1:
2a:
3a:
Ca:
2b:
3b:
Cb
R=H
R = H,n = 0
R = H,n = 1
R = H,n = 2
R=tBu.n=O
R = tBu.n = 1
R=tBu.n=2
Theoretical studies suggest that these higher rylenes
should be of considerable interest, however. Thus, a low-lying energy gap has been predicted for polyberi-naphthalene)
1, which might give rise to intrinsic conductivity.[6*
As part of an attempt to extrapolate from existing experimental data to the properties of 1, we have succeeded
[‘I Prof. Dr. K. Mullen, DipLChem. A. Bohnen, DipLChem. K.-H. Koch
Max-Planck-Institut fur Polymerforschung
Ackermannweg 10, D-6500 Maim 1 (FRG)
Prof. Dr. W. Luttke
Institut fur Organische Chemie der Universitat Gottingen
[**I Polyarylenes and Polyarylenevinylenes, Part 2. This work was supported
by the Volkswagen Stiftung and the Bundesministerium fur Forschung
und Technologie. Part 1: [lo].
Verlagsgesellschaft mbH, 0-6940 Weinheim, 1990
0570-0833~9O/OSOS-O52SSO2.SOjO
525
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