close

Вход

Забыли?

вход по аккаунту

?

Methyltrioxorhenium as Catalyst of a Novel Aldehyde Olefination.

код для вставкиСкачать
107-18-6;crotyl aldehyde, 4170-30-3; 1,4-naphthoquinone, 130-15-4; pentafluorophenylethene, 653-34-9; propene oxide, 75-56-9; 1.2-propanediol, 57-55-6 ;
2.3-butanediol, 513-85-9; 2,3-pentanediol, 42027-23-6; cis-2,3-epoxypentane,
76-09-5; truns-4,5-epoxyoctane, 16893203-99-4; 2,3-dimethyl-2,3-butanediol,
70-9; (runs-I .2-cyclohexanediol, 1460-57-7; 1,2-epoxycyclohexane, 286-20-4,
1,2-epoxy-4-vinylcyclohexane, 106-86-5; 1,2-dihydroxy-4-vinylcyclohexane,
31646-64-7; 1-methyI-l,2-~yclohexanediol,
6296-84-0; 1,2,4,5-tetrdhydroxycyclohexdne, 35652-37-0; 4-cyclohexene-l,2-diol, 117919-55-8 ; 5.6-epoxycyclooctene, 637-90-1; 12-epoxycyclododecane,286-99-7; /?-pinene oxide, 693154-0; P-pinane-2.10-diol. 2005-76-7; methyl 9.10-dihydroxyoctadecanoate,
1115-01-1 : 2.3-epoxy-1-propanol. 556-52-5; 2.3-epoxybutana1, 52788-68-8;
2,3-epoxy-1,4-naphthoquinone, 15448-58-5; 1.2-epoxy(pentafluoropheny1)ethane. 13561-85-8; cis-1,4-dichloro-2-butene,1476-11-5; 1,4-dichloro-2,3epoxybutane, 3583-47-9.
[I] Summaries: a) R. A. Sheldon, J. K. Kochi: Metal-Cutulyzed Oxidation of
Orgunic Compounds, New York 1981; b) W. J. Mijs, C. R. H. I. de Jonge
(Eds.): Organic Syntheses by Oxidation wifh Metal Compounds, Plenum
Press. New York 1986; c) R. A. Sheldon in R. Ugo (Eds.): Aspects of
Homogeneous Carulysis. Vol. 4, Reidel, Dordrecht 1981. S. 3ff; d) H. A.
Jerrgensen, Chem. Rev. 89 (1989) 431.
[2] a) R. Criegee, B. Marchand, H. Wannowius, Liebigs Ann. Chem. 550
(1942) 99; b) Summary: M. Schroder. Chem. Rev. 80 (1980) 187.
[3] Recently described Re"-porphyrin complexes are active oxidizing agents:
J. W. Buchler. S. Kruppa, M. Schmidt, G. Prescher, DOS-DE 3731 689
(March 30. 1989) and DE 3731 690 (January 19, 1989) DEGUSSA AG.
[4] Up-to date reviews: a) W. A. Herrmann, Angew. Chem. 100 (1988) 1269;
Angew. Chem. Inr. Ed. Engl. 27 (1988) 1297; b) W. A. Herrmann, J.
Organomel. Chem. 382 (1990) 1.
[51 W. A. Herrmann, DOS-DE 3902357 (January 27, 1989/August 2, 1990)
Hoechst AG.
[6] W. A. Herrmann, J. G. Kuchler, G. Weichselbaumer, E. Herdtweck, P.
Kiprof. J. Organomet. Chem. 372 (1989) 351.
[7] W. A. Herrmann, R. W. Fischer, W. Scherer, unpublished results from
1991.
[8] W. A. Herrmann, R. Alberto, P. Kiprof, E Baumgartner, Angew. Chem.
102 (1990) 188; Angew. Chem. Inf. Ed. Engl. 29 (1990) 189.
[9] W. A. Herrmann, G. Weichselbaumer, E. Herdtweck, J. Orgunornet.
Chem. 372 (1989) 371.
[lo] Compounds R-ReO,: a) W. A. Herrmann, C. C. Romao, R. W. Fischer,
C. de Meric de Bellefon, P. Kiprof, Angew. Chem. 103 (1991) 186; Angew.
Chem. Inr. Ed. Engl. 31 (1991) 185. b) Also the aryl derivatives Aryl-ReO,
are known: W. A. Herrmann, M. Ladwig, P. Kiprof, J. Riede, J. Organomef. Chem. 371 (1989) C13; C. de Meric de Bellefon, W. A. Herrmann,
P. Kiprof, C. Whitaker, Orgunometullics, in press. c) (C,H,)C(CH,)HCH,-ReO,: W. A. Herrmann, Wang Mei, unpublished.
(111 CH,ReO,(OR),: a) J. Takacs, P. Kiprof, J. Riede, W. A. Herrmann,
Organomerallics 9 (1990) 783; b) J. Takacs, P. Kiprof, J. G. Kuchler,
W. A. Herrmann, J. Orgunomet. Chem. 369 (1989) C 1.
(121 a) N. A. Milas, S. Sussaman, J. Am. Chem. SOC.58 (1936) 1302; ibid. 59
(1937) 2345; b) G. W. Parshall, US-Pat. 3646130 (February 29,1972) DuPont.
Methyltrioxorhenium as Catalyst of a
Novel Aldehyde Olefination**
By Worfgang A . Herrmann* and Mei Wang
Dedicated to Professor Karl Heinz Biichel
on the occasion of his 60th birthday
One of the most important syntheses for olefins is the
Wittig reaction.['] Although restricted to the preparation of
terminal double bonds, an organometallic variation that
[*] Prof. Dr. W. A. Herrmann, Dr. Mei Wang ['I
Anorganisch-chemisches Institut der Technischen Universitat Miinchen
Lichtenbergstrasse 4, W-8046Garching (FRG)
['I Visiting scientist (199011991) from the Dalian Institute of Chemical
Physics of the Academia Sinica (China).
[**I Multiple Bonds between Main-Group Elements and Transition Metals,
Part 100, third communication. (The first and second communications
precede this paper.) This work was supported by the Hoechst AG and the
Alexander von Humboldt Foundation (scholarship for M. W.). We thank
Dr. J. K . Fdixberger for experimental assistance. Part 99: W. A. Herrmann,
S. J. Eder, P. Kiprof, 1 Orgunomer. Chem. 412 (1991) 407-414.
Angew. Chem. In[. Ed. Engl. 30 (1991) No. 12
0 VCH
uses the organotitanium Tebbe-Grubbs reagent is a particularly efficient process for open-chain and cyclic en01
ethers.[21The driving force for this reaction is the high stability of the resulting T i 0 bond, which leads to drawbacks such
as the necessity of stoichiometric quantities of the reagent.
Here we describe the first aldehyde olefination catalyzed by
a structurally defined organometallic compound.
Aldehyde 2 treated with diazoalkane 3 in the presence of
an equimolar amount of a tertiary phosphane, preferably
triphenyl- or tri-n-butylphosphane (4 a or 4c), affords the
olefinic coupling product 5 according to Equation (a) if
methyltrioxorhenium (MTO, 1 a)[3a1is used as catalyst. Although the scope of the applications of this olefin synthesis
has not been exhaustively studied, the advantages of easily
accessible reagents, simple procedures, mild reaction conditions (room temperature), and good yields are apparent. In
particular, diazoacetates and -malonates may be transformed with saturated and unsaturated aliphatic and aromatic aldehydes into the olefins 5 containing terminal carboxyl groups. Neither by a Wittig reaction nor with
Tebbe-Grubbs reagents can this class of compound be synthesized. In contrast to MTO (la), the II: complexes I b , ~ [ ~ ~ ~
are not catalytically active.
R
la
R2
0
R'-C
//
\
+N,=C
H
2
/
\
+PR3
cat.MT0
RZ
/
R'wCH=C
R3
3
2a,
2 b,
R' = (CH,),CH
2e,
R' = C,H,
lb, R = H
I C , R = CH,
\
+Nz+O=PR3
R3
4
5
R' = C,H,CH=CH (rruns)
ZC, R' = (CH,),C=CH(CH,),CH(CH,)CH,
Zd, R' = (CH,),C=CH(CH,),C(CH,)=CH
Zf, R' = 4-BrC6H,
2 g, R' = 4-NOzC6H4
3a, R2 = H, R3 = C 0 2 C 2 H ,
3b, RZ = COzCH3, R 3 = CO,CH,
4a, R = (C,H,)
4 b, R = (rn-C,H,SO;Na+)3
4c, R = (n-C4H,)
The reaction is generally carried out at room temperature
by adding the diazoalkane dissolved in benzene or tetrahydrofuran dropwise to a solution of stoichiometric amounts
of aldehyde and triphenylphosphane and a catalytic amount
of MTO (1 - 10 mol%) in the same solvent.141The reaction
temperature (- 20- 80 "C) has little effect on the product
distribution. Minor products are formed in metal-catalyzed
side reactions of the diazoalkane (formation of ketazines and
olefins). Table 1 provides a preliminary summary of the
scope of the new reaction. Existing double bonds or those
being formed remain intact, because MTO does not catalyze
cyclopropanati~n.[~]
If the molybdenum complex [MoO,{S,CN(C,H,),},] is
used in place of MTO, the olefins derived from diazomalonate according to Equation (a) are not obtained; instead
stable phosphorus ylides are formed, which do not react with
the aldehyde.[61
Verlugsgeseilschafi mbH. W-6940 Weinheim, 1991
+
0570-0833~9l/l212-1641
$3.50+.25/0
1641
(a)
Table 1. MTO-catalyzed aldehyde olefination [a].
no.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
R'CHO
N,=CRZR3 phosphane R'-CH=CR2R3 ( 5 )
yield [%I
2a
2a
2b
2c [bl
2d [cl
2d [cl
3a
3b
3a
3a
3a
3b
3a
3b
3a
3b
3a
3a
3a
3a
3a
2e
2e
2f
2g
2g
2g
2g
2g
2g
(@:(a
4a
4a
4a
4a
4a
4a
413
4a
4a
4a
4a
4a
4b
4c
4c
82
85:15
79
97
89
91
75
80
90
96
87
93
78 [dl
76 [el
98
16
-
60 :40
45: 55
43:57
89:11
-
42: 58
-
92:s
92:s
60 :40
97: 3
91.9
[a] Reaction conditions: 2 0 T , 20 min, benzene, 10 mol% CH,ReO,; see [4].
[b] (R)-(+)-citronellal. [c] Citral. [d] 3 mol% CH,ReO,, 120min. [el Twophase system C,H,/H,O.
Both saturated and o$unsaturated
aldehydes react, as
well as benzaldehyde and its derivatives. Electron-withdrawing substituents on the aldehyde favor the olefination
(Table 1). Some cycloketones undergo the reaction as well,
although the yields and catalyst activities still need improvement: the olefin (CH,),C=CHCO,C,H,
is formed in ca.
45 YOyield from cyclobutanone and MTO/P(C,H,), (20 "C,
2 h, 8 mol% MTO). The predominant side reaction here is a
metal-catalyzed olefin formation from diazoalkane. An interesting variation with a two-phase water/benzene solvent
system is possible for applications with the water-soluble
phosphane 4b; the workup then is limited to a simple phase
separation, and phosphane and the rhenium catalyst remain
in the aqueous phase. Tri(n-buty1)phosphine (4) is also suitable as cocatalyst.
The following has been established about the reaction
mechanism of the new olefin synthesis:
MTO first forms the adduc; CH,ReO, . OP(C,H,), (A')
with the phosphane as formulated in Scheme 3. The adduct is known to afford complexes of the type
CH,ReO,L (L = alkyne, for instance) under mild conditions.['J
The isolated phosphane oxide adduct A' reacts with diazoalkanes to yield olefins. In the presence of aldehydes
the formation of the symmetrical olefins (from diazoalkane) is suppressed in favor of the desired unsymmetrical
olefins. Thus intermediate A functions as a C-C coupling
catalyst; in other words, the phosphane is necessary
chiefly for aldehyde deoxygenation.
The stable phosphorus ylide (C,H,),P=C(CO,CH,),
does not even react with aldehydes in boiling benzene. At
room temperature, but only in the presence of stoichiometric amounts of MTO, the olefins R'CH=C(CO,CH,),
are formed (e.g., R' = 4-NO,C6H,; ca. SOY0).MTO (in
benzene at 20 "C) does not catalyze olefin formation from
ylides and phosphazines [Eq. (b) or (c)].
4) In the absence of phosphanes MTO acts as catalyst for
diazoalkane decomposition: diazoacetate is transformed
into fumarate and maleate at 20 "C without formation of
any sideproducts [Eq. (d)]. If aldehydes are added to such
reactions, the product spectrum remains unchanged.
5 ) Stable five- and six-coordinate amine adducts of the type
CH,ReO,L (L' = quinuclidine; 2,2'-bipyridine)I8l react
neither with aldehydes nor diazoalkanes. This shows that
other complexes cannot be used instead of MTO.
Apparently the Lewis acidity of MTO and its reactivity
with phosphanes is the determining factor for the olefin synthesis described here [Eq. (a)]. The phosphane-induced deoxygenation of MTO possibly enables a C-C bond to be
formed between a metal-stabilized carbene species and the
aldehyde, while the metal is oxidized back from ReVto ReV1'.
Although we have not yet isolated carbene complexes of type
B, the nucleophilicity of the carbene ligands attached to
metals in high oxidation states has been d o c ~ m e n t e d . ~ ~ ~ ' ~ ~
The C-C coupling step via metallaoxetane C formulated in
Scheme 1 is not only plausible, but is also in accord with the
observation that increasing the C-electrophilicity of the aldehyde employed increases the reaction rate and the yield. The
c
A'
t
I
CH3Re02(=CR2R3)
B
Scheme 1. Proposed mechanism of the olefination reaction according to Equation (a).
metalkarbene species B results from the displacement of the
phosphane oxide by the diazoalkane, which thereby loses
nitrogen (Scheme 1). Phosphorus ylides can be disregarded
as carbene precursors, because carbenes do not even form
from 3a and 3 b under the reaction conditions. The reaction
mechanism in Scheme 1 could be extended, however, if phosphazines are rapidly formed according to Equation (e) ; they
also afford olefins 5 under the reaction conditions of Equation (a).
Thus rhenium-containing species are involved in every
step of the catalytic cycle. Moreover, MTO implements the
cat. CH,ReO,
2 (C6H,),P=C(C02CH3),
2 (C,H,),P=N-N=C(CO,CH,),
cat. CH,ReO,
__7*_j
cat.
P(C,H,),
1642
0 VCH
+ N,=C(C,H,),
+ C,H,CHO + CH,ReO,
Verlagsgesellschafi mbH, W-6940 Weinheim, 1991
+ 2 p(c6H5)3
fC(C02CH3),],
+ 2P(C6H&
+CH(C0,C,H,)]2
+ 2N,
CH,ReO,
2N,=CH(CO,C,H,)
(C6H5)3P=C(C0,CH,),
fCH(CO,C,H,)],
-
0570-0833/91/1212-1642 $3.50+.25/0
(b)
f
~ N (C)
z
(C,H,),P=N-N=C(C,H,),
C,H,CH=C(CO,CH,),
(a
(e)
+ O=P(C,H,),
(f)
Angew. Chem. Int. Ed. Engl. 30 (1991) No. 12
Wittig olefination of aldehydes with otherwise unreactive
phosphorus ylides. Herein lies a potential extension of this
important reaction [Eq. (f)] . Furthermore, a generalization
of the catalytic diazoalkane decomposition according to
Equation (d) is conceivable. Only the ketazine formation
from aldehydes and diazoalkane, which can play a role with
components other than 3a, b, restricts the scope of the conversion formulated in Equation (a); ketazines are inert to
MTO.
MTO is the first organometallic compound that enables
catalytic olefin synthesis from easily accessible precursors.
This property does not necessarily apply to other metal oxides: with the Mo"' complex, [MoO,{S,CN(C,H,),},], as
catalyst the benzaldehyde/diazomalonate/triphenylphosphane
affords predominantly the phosphorus ylide
(C6H,),P=C(C0,R), (R = C,H,, 67%) even in boiling
benzene, whereas MTO yields 90% of the desired olefin
already at room temperature. The scope of the olefin synthesis described here should be able to be extended through
designed exchange of the methyl groups of MTO for functionalized residues.13c1
In addition the search for analogous
complexes of other cheaper metals with low coordination
numbers and in high oxidation states will be worthwhile.
Received: July 19, 1991 [24807 IE]
German version: Angew. Chem. 103 (1991) 1709
CAS Registry numbers:
l a , 70197-13-6; 2a, 78-84-2; 2b. 14371-10-9; t c , 2385-77-5; 2d, 5392-40-5; 2e,
100-52-7; 2f, 1122-91-4; t g , 555-16-8; 3a, 623-73-4; 3b, 6773-29-1; 7a, 60335-0;4b. 63995-70-0; 4c, 798-40-3; (E)-5aa, 15790-86-0; (Z)-5aa, 15790-85-9;
5ab, 36825-11-3; (E,E)-5 ba, 39806-16-1 ; (E,Z)-5 ba, 38447-06-2; (R,E)Jca,
137172-05-5; (R,Z)-Sca, 137170-91-3; (E,X)-5da, 137057-25-1; (Z,X)-Sda,
137057.26-2; 5db, 132549-07-6; (E)-5ea, 4192-77-2; (Z)-5ea, 4610-69-9; 5eb,
6626-84-2; (E)-Sfa, 24393-53-1 ; (Z)dfa, 136265-11-7; (E)bga, 24393-61-1;
(Z)-5ga. 51507-21-2; 5gb, 6626-84-2; (CH,),C=CHC02Et, 27741-65-7;
cyclobutanone. t191-95-3.
Review: a) H.-J. Bestmann, 0. Vostrowsky, Top. Curr. Chem. 109 (1983)
8 5 ; H. Pommer, P. C. Thieme, ibid. 109 (1983) 165; b) H.-J. Bestmann,
R. Zimmermann in Houben- Weyl, Methoden der Organischen Chemie,
Vol. E l , 4th. ed., Thieme, Stuttgart 1982, p. 616ff.
a) K. A. Brown-Wensley, S. L. Buchwald, L. Canniuo, L. Clawson,
S. Ho. D. Meinhardt, J.-R. Stille, D. Straus, R. H. Grubbs, Pure Appl.
Chem. 55(1983) 1733; b) J. Mulzer, H.-J. Altenbach, M. Braun, K. Krohn,
H . 4 . ReiOig: Organic Synthesis Highlights, VCH Verlagsgesellschaft,
Weinheim 1991, p. 192ff.
a) W. A. Herrmann, J. G . Kuchler, G. Weichselbaumer, E. Herdtweck,
P. Kiprof, J. Organomet. Chem. 372 (1989) 351; b) W. A. Herrmann,
R. Serrrano. H. Bock, Angew. Chem. 96 (1984) 364; Angew. Chem. l n f .Ed.
Engl. 23 (1984) 383; W. A. Herrmann, M. Taillefer, C. de Meric de Bellefon, F. Behn, Inorg. Chem. 30 (1991) 3247; c) W. A. Herrmann, C. C.
Romao, R. W. Fischer, P. Kiprof, C. de Meric de Bellefon, Angew. Chem.
103 (1991) 183; Angew. Chem. Int. Ed. Engl. 30 (1991) 185.
Example (11 in Table 1): Ethyl diazoacetate (3a, 3.15 mL, 30 mmol) was
added dropwise at room temperature to a solution of 4-nitrobenzaldehyde
(2g. 4.53 g. 30 mmol), P(C,H,), (4a, 7.90 g, 30.1 mmol), and MTO (1,
250 mg. 1 mmol) in 100 mL benzene. The mixture was stirred for 2 h,
whereupon the solvent was removed under reduced pressure. The brown
residue was taken up in n-hexanelethyl acetate (6:l) and filtered over a
SiO, column. The product precipitated from the yellow filtrate, and after
recrystallizing it from dichloromethane/n-hexane we obtained 6.72 g
(93%) of analytically pure R'CH=CHCO,C,H, (R1 = 4-N0,C6H,) as a
mixture of E/Z isomers (92%).
W. A. Herrmann, U. N. Flessner, unpublished.
X. Lu, H. Fang, Z. Ni, J. Orgunomet. Chem. 373 (1989) 77.
W. A. Herrmann, J. K. Felixberger, J. G. Kuchler, E. Herdtweck, Z. Naturforsch. B 45 (1990) 876.
W. A. Herrmann, G. Weichselbaumer, E. Herdtweck, J. Organomet.
Chem. 372 (1989) 371.
Reviews: a ) R. R. Schrock, Pure Appl. Chem. f 9 (1986) 342; b) J.
Orgunomet. Chem. 300 (1986) 249; c) Acc. Chem. Res. 12 (1979) 98.
M. P. Doyle, Acc. Chem. Res. 19 (1986) 348.
Cf. deoxygenation of epoxides by organovanadium(u1) complexes: J. Ruiz,
M. Vivanco, C. Floriani, A. Chiesi-Villa, C. Guastini. J. Chem. SOC.Chem.
Commun. 1991. 762.
Anaew. Chem. Int. Ed. Enal. 30 (1991) No. 12
Salt-free Synthesis of Azo and Hydrazone Dyes
Under CO, Pressure
By Roderich Raue,* Alfred Brack, and Karl H. Lange
Dedicated to Professor Karl Heinz Biichel
on the occasion of his 60th birthday
We present here a new method for the preparation of azo
dyes in which the nitrous acid essential for the diazotization
is liberated from its salts or esters by carbon dioxide at a
pressure of 5 to 65 bar. Consequently, the amount of inorganic and organic salts produced as by-products is reduced
considerably compared to the conventional procedure. This
is of great ecological importance.
Azo dyes can be prepared in a two-step or single-step
procedure. In the two-step process treatment of an amine
with sodium nitrite in aqueous acidic solution leads to formation of a diazonium salt, which is subsequently treated
with the coupling component.['] In the one-step process diazotization in the presence of the coupling component provides the desired product.['] Active methylene compounds as
well as aromatics can be used as the nucleophilic coupling
c~mponent.'~*~J
A disadvantage of both methods is the large amount of
salts produced in the neutralization of the acid. Thus we
sought to improve the procedure, by avoiding the formation
of these by-products.
CO, is an inert, gaseous acid anhydride which can be
easily removed from the hydration equilibrium by change of
pressure or temperature. At atmospheric pressure an
aqueous solution of carbon dioxide is only weakly acidic.
Not unexpectedly, the passage of a vigorous CO, stream
through a mixture of the aromatic amine, the coupling component, and an aqueous solution of sodium nitrite did not
give even traces of an azo compound.
The apparent first dissociation equilibrium constant of
carbonic acid has a pK of 6.46. This value is composed of the
sum of the preceding hydration equilibrium constant of CO,
(pK = 3.16) and the equilibrium constant of the true first
dissociation step of carbonic acid (pK, = 3.3).['] It should be
possible to shift the preceding hydration equilibrium of carbon dioxide by application of pressure such that the true first
dissociation step of carbonic acid can be used for diazotization.
First we investigated the one-step synthesis of a precursor
of hydrazone dyes [Eq. (a)],
CH3
I
CH3
3
1
(4
2
['I
Dr. R. Raue
B. von Suttnerstrasse 48, W-5090 Leverkusen 1 (FRG)
Dr. A. Brack, Dr. K. H. Lange
Farbenforschung 1
Bayer AG
W-5090 Leverkusen (FRG)
0 VCH Verlaasaeseiischafi mbH. W-6940 Weinheim, 1991
0570-0833/9l~1212-1643$3.SO+ .2S/O
1643
Документ
Категория
Без категории
Просмотров
0
Размер файла
366 Кб
Теги
aldehyde, methyltrioxorhenium, novem, olefination, catalyst
1/--страниц
Пожаловаться на содержимое документа