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CF2-Bridged Metal Complexes.

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Finally, y-elimination of dimethyl sulfide leads to the compounds 13a-c in 42-84% yie1d.l'' In all cases the trans-configuration predominates, to the extent of ca. 90-95%.
_ 13
I
R
10, 1 1 , 13
1 3 a ~ l b -l a
13b
-3a
7b
1 3 ~
a
-
b
C
Alkaline hydrolysis of the ester 13a (= 2b) leads to formation of 2a (yield 94%); in the same way, the ester 13b
furnishes the carboxylic acid 3a (yield 91Yo) in a one pot
reaction under alkaline conditions. Cleavage of acetal
from 13c with acid furnishes the hexafluorocaronaldehyde
7b in 93% yield.
7b is the central intermediate in the synthesis of substituted ethyl 3-(1-alkenyl)-2,2-bis(trifluoromethyl)cyclopropanecarboxylates. Reaction of 7b with the phosphoranes
14,''3115,['] and 16['41affords the pyrethroid esters 4b, 5b,
and 6b, respectively, in 43-95% yield;[51these can be converted by acid hydrolysis into the pyrethroid acids 4a, 5a,
and 6a, respectively.
7b
4b,5b,6b
R'
Received: October 4, 1985;
revised: November 25, 1985 [Z 1485 IE]
German version: Angew Chem. 98 (1986) 181
CAS Registry numbers:
trans-la, 99903-45-4; l d , 82224-37-1 : rrans-3a, 99903-46-5; 3d, 99903-55-6;
rrans-4a, 99903-52-3; trans4b, 99903-49-8; trans-5a, 99903-53-4; trans-5b,
99903-50.1 ; transBa, 99903-54-5; trans-6b. 99903-51-2; trans-7c, 99903-47-6:
8a, 99903-58-9; 8b, 82224-38-2; ma, 2648-51-3: lob, 53394-32-4; lOc, 534423-0; l l a , 99903-40-9: l l b , 99903-41-0; llc, 99903-42-1 ; trans-13a, 9990343-2; 13b, 99923-35-0; rrans-l3c, 99903-44-3; 14a, 42867-45-8: 14b, 7360710-0; 1 4 ~ 99903-48-7;
,
17,+99903-56-7; 18, 99903-57-8; (FiC)ZCCIZ, 1652-808; PPh,, 603-35-0; Me2SCHC02Et, 7380-81-6; PhO-3-C,H4CH(CN)OH.
39515-47-4; 4-CIChH,CH0, 104-88.1.
9
11
8d. All the new compounds were unequivocally characterized by 'H-, I3C-NMR, IR, and MS spectroscopy.[l6I
[I] J. E. Casida (Ed.): Pyrethrum. The Natural Insecticrde. Academic Press,
New York 1973.
[2] M. Elliott: Synrherrc Pyrethroids. Am. Chem. Sac.. Washington 1977.
[3] R. Wegler (Ed.): Chernie der PfTanzenschurz- und Schadlinysbekarnpfirngsmittel, Vol. 7, Springer, Berlin 1981: D. Arlt, M. Jautelat, R.
Lantzsch, Angew. Chem. 93 (1981) 719: Angew. Chem. In:. Ed. Engl. 20
(1981) 703.
141 M. Elliott, N. F. Janes, Chem. SOC.Rev. 7 (1978) 473.
[ S ] H. Mack, Disserfalion. Universitat Tiibingen 1985.
161 The derivatives 2-4 and 8 are in fact mentioned in a Japanese patent,
but without any description of the synthesis and without any physical
data. See Y . Katsuda, J. P. 8240440, Japan Kokai, Tokyo Koho: Chem.
Absrr. 97 (1982) 38559.
[7] D. J. Burton, Y. Inouye, Tetrahedron Lett. 1979. 3397.
[8] J. T. Maynard, J . Org. Chem. 28 (1963) 112: B. S . Farah, E. E. Gilbert,
ibid 30 (1965) 1241.
[9] M. Levas, E. Levas, Bull. SOC.Chim. Fr. 26 (1959) 1800.
[lo] A. Reinink, J. Grendelman, DOS 2641356: Shell Internationale Research Maatschappij B.V.; Chem. Abstr. 87 (1977) 5398: C . L. Stevens, B.
T. Gillis, J. Am. Chem. SOC.79 (1957) 3448; analogous procedure for the
preparation of 2-chloro-2-methylpropanal.
[I I ] H. Stetter, K. H. Mohrmann, Synthesis 1981. 129
[I21 G. B. Payne, J. Org. Chem. 32 (1967) 3351.
[I31 E. J. Corey, P. L. Fuchs, Terrahedron Lett. 1972. 3769.
[I41 H. Havant, Re.r. Disc/. 219 (1982) 239, No. 21 903.
[IS] D.A. Pulman, Pestrc. Sci. 14 (1983) 182.
1161 Note added in proof (January 21, 1986): After completion of this work,
Y. Kobayashi et al. (Chem. Pharm. Bull. 33 (1985) 4085) reported the
preparation of bis(trifluoromethyl)cyclopropane derivatives from hexafluorosenecioic acid ethyl ester.
R2
CF,-Bridged Metal Complexes**
By Wolfgang Schulze, Hans Hartl, and Konrad Seppelt*
CH,-bridged metal complexes have been investigated
extensively; they are of interest with regard to the mechaThe acid chlorides 2a and 3c, generated by reaction of
nism of catalytic processes such as the Fischer-Tropsch
sulfinyl chloride with 2a and 3a, respectively, are allowed
to react with 2-hydro~y-2-(3-phenoxyphenyl)acetonitrile~'~~ synthesis."' In spite of the well-known analogy between
C H - and CF-compounds very little is known about CF,to give the pyrethroids 2d and 3d.
bridged metal complexes, since the methods currently in
A simple route was also found for the synthesis of the
use for the preparation of their CH,-bridged counterparts
hexafluorofenvalerate 8d. 4-Chlorobenzaldehyde reacts
are
not suitable for CFZ-bridged complexes. See1 et al.
with the phosphorane 915] to give the bis(trifluoromehave already described the complexes [Co,(CF,)(CO),],
thyl)olefin 17. Addition of hydrocyanic acid under basic
[CO,(CF~)~(CO),],and [Fe2(CF2)z(CO),],1z~31
but without
conditions then leads to formation of the nitrile 18 (68%
giving structural data. We report here, with two examples,
a synthetic route which affords direct access to CF2F7C CF-,
bridged complexes, and the structural properties of such
complexes.
C d
17
18
yield referred to overall conversion). 2-Hydroxyisobutyronitrile is a suitable reagent for supplying the HCN. Subsequent acid hydrolysis of 18 leads, via the carboxylic acid
8a (94%) and in analogy to 2d, to the fenvalerate analogue
Angew. Chem. I n t . Ed. En@. 25 (1986) No. 2
["I Prof. Dr. K. Seppelt, Dr. W. Schulze, Prof. Dr. H. Hartl
Institut fur Anorganische und Analytische Chemie der
Freien Universitat
Fabeckstr. 34-36, D-1000 Berlin 33
[*'I This work was sponsored by the Fonds der Chemischen Industrie. We
thank Dr.D . Lentz for kindly supplying a sample of trifluoromethyl isocyanide.
0 VCH VerlaysgesellschaJ? mbH. 0-6940 Weinheim. 1986
0570-0833/86/0202-0185 $ 02.50/0
18.5
2 Na[Mn(CO)5]
+ CIOC-CF2-COCI
I
- 78 o c
d
- 2 NaCi
6
97 o c
2
co
hv
Mn (CO)5]
+
(CO),Mn
- co
>
- 30 "C
-
7
3
n- CO- CF,-
>-
[(CO)~CO-CO-CF~-CO-CO(CO)~]
d
-
30 "C
- 2 NoCl
L
[(C0)5Mn-CO-CF,-CO-Mn(C0)5]
[(CO),M
-
+
2 N ~ [ C O ( C O ) ~ ] CIOC-CF,-COCI
ICF2\
,-\
Mn(C0)4
[(CO),+Co - CO -CF2- CO(CO)4]
>-
25
8
-2
OC,
co
30 min
- co
5
4
p
0
Sodium pentacarbonylmanganate 1 reacts with difluoromalonyl dichloride 2 to give the malonyl compound
3, which decomposes almost completely upon heating, undergoing extrusion of one molecule of C O to give the difluoroacetyl complex 4. Further heating leads only to the
known complex [(C0)5MnCF3]. UV irradiation, however,
gives Mn2(CO)loand the doubly CF,-bridged complex 5 .
According to an X-ray structure analysis, 5 is highly symmetric (Fig. 1). The C O ligands trans to the CF2 bridges are
more tightly bound than the cis ligands.
3
N
I1
I1
co(co)3
9
CNCFJ
-3
-
co
(oc)3co-
10
gand, which strongly prefers the bridge positions14'
(9-10). The two fluorine atoms of the CF, group of 10
are not equivalent; the coupling constant of the geminal
fluorine atoms is quite small (12.2 Hz).
The method described here should, in principle, be of
general utility for the introduction of CF2 bridges.
Experimental
Fig. 1. Structure of [(CO),Mn(p-CF,),Mn(CO),] 5 in the crystal. Crystallo8=90.01(2),
graphic data: P2,/n, a=8.367(2), b = 10.613(3), c=7.996(2)
V=710.04A3, 2=2,p,,,,=2.03 g . c m - ) , p = 8 . 9 cm-', R=0.020, R,=0.033;
3024 measured reflections, 1248 crystallographically independent observations with I > 2 O c ( l ) , 110 refined parameters. The manganese atoms essentially remain in a n octahedral environment. Selected distances [A] and angles
["I: Mn-Mn 2.664(3), Mn-CI 2.026(4), Mn-C2 1.880(6), Mn-C3 1.846(4),
CI-Mn-CI 98.2(1), FI-CILF2 102.7(2). Further details of the crystal structure investigation are available on request from the Fachinformationszentrum Energie, Physik, Mathematik GmbH, D-7514 Eggenstein-Leopoldshafen 2, on quoting the depository number CSD-51697, the names of the
authors, and the full citation of the journal.
A,
If sodium tetracarbonylcobaltate 6 is allowed to react
with difluoromalonyl dichloride 2, multiple elimination of
C O already takes place at room temperature. The complexes 7 and 8 were only detected as intermediates by "FNMR spectroscopy (7: 6(F)= -92.3, 8 : S(F)= -32.2).
The Co2-complex 9 is formed as end product in high
yields ; the orange-yellow liquid is probably identical to the
compound [CO,(CF,)(CO)~]described by Seel et
The
I3C-NMR spectrum of 9 (up to -40°C) shows a singlet
for the time-averaged equivalent C O groups as well as a
triplet for the CF2 group. In the 19F-NMR spectrum the
singlet line of the CF, group (6=44.7) does not change on
lowering the temperature to - 100°C. The intramolecular
CO exchange of all C O ligands must therefore be still
rapid even at - 100°C.
The C O bridge, which obviously participates in the intramolecular exchange, can be replaced by the CNCF, li186
0 VCH Verlagsgesellschafi mbH. 0-6940 Weinheim. 1986
3 : 2 (2.2 mmol) was added to a stirred solution of 1 151 (4 mmol) in anhydrous oxygen-free tetrahydrofuran (THF) at - 78°C. After 2 hours' stirring,
slow warming to room temperature, and removal of the solvent in a high
vacuum, there remained a yellowish-orange greasy solid. The fraction soluble
in CH2C12 was chromatographed on silica gel ( 4 x 6 0 c m column) with
CH,Cl,/petroleum ether 40-60 ( I :3) at 0°C. 3 was eluted as an almost colorless zone. After crystallization from CHzC12/pentaneat -40°C. 3 was obtained as air-stable, pale yellow needles. Yield 445 mg (SSO/o). M.p. 97°C
(dec.).-MS: m / z 496 ( M e ) and fragments. IR (pentane) v(C0)=2122 (m),
2067 (w), 2039 (vs), 2013 (s), 1641 (m, br) c m - ' . "F-NMR (CH2Cl2,CFCI,
ext.): 6 = -96.5.
4 : 1 mmol of 3 was melted in an argon atmosphere for 15 min at 9 7 T , and
evolution of gas was observed. After cooling down, the yellow-brown melt
was dissolved in CHC12 and chromatographed at 0 ° C on silica gel (4 x 60 cm
column) with CH2CIZ/petroleumether 40-60 (1 :3). 4 was eluted as a yellow
zone; air-stable, yellow crystals were obtained upon crystallization from
CH2CI2/pentane. Yield 398 mg (85%) M.p. 99°C (dec.).-MS: m / z 468 (M')
and fragments. IR (pentane) @C0)=2113 (s), 2038 (vs, sh), 2022 (s), 2007
(vs), 1967 (w), 1641 (m, sh) c m - ' . I9F-NMR(CH2Cl2,CFCL ext.): 6= -41.7.
5: A solution of 4 (0.1 mmol) in pentane (250mL) was irradiated with a
Phillips immersion lamp (HPK 125 W) for 30 mins at 0°C under inert gas in a
circulated photolyzer. After removal of the solvent in a high vacuum, the
yellowish orange residue was taken up in a few mL of CH2C12.The solution
wds chromatographed on silica gel in a medium-pressure column with pentane (column: 2.5 x 60 cm, Merck silica gel 0.015-0.040 mm). The second
orange zone contained 5. The pentane solution was evaporated down to ca.
10 mL; upon slow cooling of the solution to -50°C. 5 was obtained as airstable yellow crystals. Yield 5 mg (12%). M.p. 118°C.-MS: m / z 434 (M')
and fragments. IR (pentane): @C0)=2084 ( s ) , 2035 (vs), 2028 (vs), 1985 (w)
cm-'. Raman (solid) v(C0): 2121 (s)* 2038 (vs), 2020 (vs), 2004 (m) c m - ' .
"F-NMR (pentane, CFCli ext.): &=71.6.
9: 2 ( 1 . 1 mmol) was added to a stirred solution of 6 151 (2 mmol) in anhydrous oxygen-free diethyl ether (60 mL) at -30°C. The solution turned yellowish-orange in color. After warming and 30 minutes' stirring, the solution
was fractionally distilled under high vacuum. 9 was collected at - 30°C as a
yellow, air-stable solid, m.p. -2°C. 9 i s thermally stable (up to 8 0 T ) and
photochemically stable. Yield 325 mg (90°/o). - The spectroscopic data ("FNMR, IR, and MS) were identical with the values given in the literature 121.
"C-NMR (CD2C12,TMS ext.): 6=200.5 (CO), 194.1 (CF2, J(CF)=390 Hz).
'"F-NMR (CD,CI2, CFCli ext.): S=44.7.
10: CNCF3 (2 mmol) was condensed under high vacuum into a solution of 9
(2 mmol) in pentane (10 mL). The stirred solution was warmed to room temperature. Fractional distillation under high vacuum afforded 10 in the collector cooled at -60°C; air-stable yellow crystals, m.p. - 18°C. Yield quantitative.-MS: m / z 431 ( M e )and fragments. IR (pentane) @ C 0 ) = 2 1 4 0 ( s ) ,
21 I0 (vs). 1990 (vs), 2038 (m), v(CN)= 1720 (s, br) cm-'. "F-NMR (pentane.
CFCI? ext.): S=43.3, 26.1 (CF2, J = 12.2 Hz), -58.8 (CF,). "C-NMR
0570-0833/86/0202-0186 $ 02.50/0
Angew. Chem. Int. Ed. Engl. 25 13986) No. 2
(CD-CI,, TMS ext., -25°C): 6=196.0 (CO), 192.3 (CFA 'J(CF)=395 Hz),
236 (CN), 116.5 (CF,, 'J(CF)=263 Hz.
the reaction solution) upon unsensitized irradiation
(A>300nm, CDCI3, -20°C). As expected, 9 and 10 d o
Received: October 9, 1985:
revised: December 2, 1985 [Z 1491 IE]
German version: Angew. Chem. 98 (1986) 189
[ I ] W. A. Herrmann. Adu. Organomef. Chem. 20 (1982) 159: Angew. Chern. 94
(1982) 118: Angew. Chem. Inr. Ed. Engl. 21 (1982) 117.
12) F. Seel, R D. Flaccus, J. Fluorine Chem. I2 (1978) 81.
131 F. Seel, G. V. Roschenthaler, Z . Anorg. Allg. Chem. 386 (1971) 297.
14) 1. Brudgam, H. Hart], D. Lentz, Z . Nafurforch. 8 3 9 (1984) 721.
[ 5 ] R. B. King, Adu. Organomef. Chem. 2 (1964) 158ff.
Laticyclic 1,5-Conjugation between
Parallel, Neighboring
Azo-Groups and Phenyl Groups**
By Karin Beck and Siegfried Hiinig*
Since the discovery of the first system 1, with parallel
oriented C = C / N = N bonds['] with analyzed[*] laticyclic
I ,5-~onjugation,[~~
general methods have been developed
for the synthesis of related systems by [4 21-Cycloadditions with cyclic azines as electron-deficient dienes.!"] It
emerged thereby that the size of the ring (five-membered
ring (9,six-membered ring (6)), which the n-bridges span,
has no influence on the smooth [2+2]-photocyclization to
diazetidines with a cage
This is valid in the
case of C=C(5)/N=N(6) (e.g. l), C=C(6)/N=N(6),
C=C(S)/N=N(5), and, as shown by 7 , also in the case of
C=C(6)/N=N(5) (for further examples see ref. [6]). We
have now checked whether a hitherto unknown [6+2]-photocyclization takes place upon replacement of the ethenobridge by an o-phenylene bridge in these systems.
9
+
3
1
4
We report here on the first positive r e s ~ 1 t . IThe
~ ~ desired
o-phenylene bridge can be incorporated with one of the
cycloaddends (here benzobarrelene 6 ) or by subsequent
conversion of the double bond in a benzene ring.
The trimeric 4,4-dimethyl-4H-pyrazole 5 reacts under
proton catalysis conditions[41with 6 to give a 4 : 1 mixture
of the adducts 7 and 8 (phenylene (6)/N=N(S)), which
can be separated chromatographically.~81The expected
cycloadducts 9 and 10 are formed almost quantitatively
(no by-products recognizable in the 'H-NMR spectrum of
[*] Prof. Dr. S. Hiinig, DipLChem. K. Beck
lnstitut fur Organische Chemie der Universitat
[**I
Am Hubland, D-8700 Wurzburg (FRG)
This work was supported by the Deutsche Forschungsgeineinschaft, the
Fonds der Chemischen Industrie, and BASF AG, Ludwigshafen
(FRG).
Anyew. Chem. Inr. Ed. Engl. 25 (19861 No. 2
10
not show any absorptions UV for the azo group. In the 'HN M R spectrum (CDC13, 6 values) the signals of the etheno
bridge (5.93 (dd)) migrate into the region typical for diazetidines (4.08 (mc)) during the transition 7 + 9 , whilst those
of the arene remain virtually stationary (7.06-7.25). Conversely, in the reaction 8-10 the signals of the olefinic
protons of 10 (5.64, 5.88) appear in place of those of the
arene (7.08), whereas those of the additional double bond
remain virtually stationary (6.65 (dd)-6.23 (dd)). In addition, the signals of the protons on the bridgeheads of the
azo bridges experience a typical upfield shift of = 1.2 pm
upon closure of the diazetidine ring: 7 (4.64 (bs))-9 (3.42
(bs)); 8 (4.45 (bs))+ 10 (3.19 (bs)). That is, both the interaction with the etheno bridge (cf. [2]) as well as that with
the phenylene residue is so strong upon n-n*- and/or 71n*-excitation of the azo group that the extraordinarily efficient photoextrusion from the 2,3-diazabicyclof2.2.I]heptene (aN2=
l.00[91)present in 7 and 8 is completely overshadowed.""' Interestingly, compound 4, in which the
bridges are, as it were, interchanged (phenylene(S)/
N=N(6)), is not cyclized under the same irradiation conditions.L1olIt remains unchanged, since it contains the photostable 2,3-diazabicyclo[2.2.2]octene~keleton.'~,'~
The different interaction between the parallel 7c systems observable in the UV spectrum (in each case in hexane) corresponds to the difference in photochemical behavior. The
bathochromic shift in 1 (A,,,=396
nm ( E = 15S))L'1of
15 nm compared to that in the same system with an ethano
bridge 1 [2 HI (A,,, =381 nm ( E = 155))[4h]is only 6 nm in
the case of the benzo derivative 4 (Amax= 387 nm (E = 185)).
In contrast, the bathochromic shift of 9 nm in the transi= 354
tion from 7 [2 HI (hydrogenated etheno bridge
( ~ = 3 6 6 ) )to 7 (ilm,,=363 nm ( ~ = 3 7 0 ) )stays the same in
the case of the benzo derivative 8 (Amdx = 364 nm ( E = 64 I)),
while the intensity almost d o ~ b l e s . - 4 ~ " ]is formed by addition of tetrachlorothiophene dioxide 2[l2]to 1 via the
readily interceptable intermediate 3, which, after smooth
dehydrogenation,'"] is dehalogenated"'l in the conventional
to 4.
Of the systems with laticyclic 1,5-conjugation still to be
examined, namely o-phenylene(6)/N=N(6) (which in the
meantime has also attracted interest from another point of
view"") and o-phenylene(5)/N=N(5), at least the latter is
expected to photocyclize upon direct excitation. A photo-
0 VCH Verlagsgesellschaft mbH. D-6940 Weinheim, 1986
0570-0833/86/0202-0187 $ 02.50/0
187
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