close

Вход

Забыли?

вход по аккаунту

?

Bicyclo[2.2.2]octa-5 7-diene-2-carboxylic Acid and 7-Methylenebicyclo[2.2

код для вставкиСкачать
fails to undergo further reaction with phosgene. Temporary
appearance of a precipitate during this reaction prompted us
to undertake a detailed study, especially since Becher and
Langer['I had already obtained carbonyl bis(dipheny1phosphide) as an unstable product from phosgene and diphenyl(trimethy1silyl)phosphane at - 110 "C.
We found that (1) reacts stepwise with COCI, via several
isolable intermediates: at a molar ratio of 2: 1 in pentane,
these reactants first give a yellow oil shown by elemental
analysis, molecular weight (cryoscopy and mass spectrometry), "P- and I3C-NMR, to be phenyl[(phenyltrimethylsilylphosphino)trimethylsiloxymethylene]phosphane (2). Evidence for migration of a silyl group to oxygen and for a
methylenephosphane structure comes from the doublets at
6= + 164 and - 37 in the "P-NMR spectrum and the double
doublet at 6= 205 in the I3C-NMR spectrum[41.
- + COCl*
PhP(SilVIe3)z
(1)
PhPC12
- Me,SiCI
+ coal
0-1
- co
(PhP),
+ coc12
- Me3SiCI
- co
( 4 ) , n = 4,5
Me,SiO
SiMes
I
/
Ph-P=C-P,
Ph
(2)
[(PhP)z(COSiMe,~2
Phosgene (4.95 g, 50 mmol) is condensed under similar
conditions into a solution of (2) (39.0 g, 100 mmol) in n-pentane (400 ml). Since CO is liberated the reaction vessel must
be equipped via a reflux condenser ( - 60 "C, cryostat cooling) with a Hg safety valve. The solution is concentrated to
ca. 100 ml, whereupon (3) precipitates. Filtration over a
sealed frit, washing with a small volume of n-pentane, and
vacuum drying affords 15 g (47%) of spectroscopically pure
product, m.p. 148-150 "C, which can be recrystallized from
(3)
CH,Cl,/n-pentane or CH,Cl,/CH,CN.-Alternatively,
can be prepared directly from (1) and COCI, in the molar ratio 4:3.
Received: February 12. 1979 [ Z 215 IE]
German version: Angew. Chem. 91. 497 (1979)
[ l ] Phosphorus-Carbon-Halogen Compounds. Part 17.-Part
16. R. Appel.
M . Huppertz. Z . Anorg. Allg. Chem.. in press.
121 R. Appel. B. Eluser, G. Siegemund, Z.Anorg. Allg. Chem. 363, 176 (IS6X): R.
Appel. W. Heinzelmann, DBP 1 192205 (1966). BASF AG.
[3] H. J. Becher, E. Langer, Angew. Chem. 85. 910 (1973): Angew. Chem. Int.
Ed. Engl. 12, 842 (1973).
[4] a) G. Becker. Z . Anorg. Allg. Chem. 423, 242 (1976); b ) T. C. Kleebuch, R.
Loureus, F. Bickelhaupt, J. Am. Chem. Soc. IOU, 4886 (1978).
[5] Cf. M . Boudler. B. Carlsohn. W Bohm, G. Reuschenbach, Z . Naturforsch. B
31. 558 (1976).
[6] K . Issleib, H. Schmidr, H. Meyer, J. Organomet. Chem. 160, 47 (1978).
[7] R. Appel, K. Geisler, J . Organomet. Chem. 112, 61 (1976).
(3)
Addition of COCI, to a pentane solution of (2) (1 :2) leads
to precipitation of a colorless solid substance of composition
(3). The signal of dicoordinate phosphorus is absent from the
3'P-NMR spectrum of (3);a temperature-dependent AA'BB'
spin system is observed which is interpretable in terms of
various proposed structures. An X-ray structure determination is still in progress.
Further action of COCI, leads to dissolution of the fine
precipitate of (3), with simultaneous production of chlorotrimethylsilane and CO gas. The two new "P-NMR signals at
6= - 5.9 and - 49.5 were previously observed on reaction of
(1) with phosgene by Baudler et al.l5],and assigned to the cyclophosphanes (4). The intermediates (4) are chlorinated by
COCI, via CO elimination to give dichloro(pheny1)phosphane (S) as the stable final product.
Preliminary investigations show that phosgene analogues
react similarly with (1) and that acyclic compounds having
P-=C bond^'^.^] are no longer mere curiosa.
Bicyclo[2.2.2]octa-5,7-diene-2-carboxylic Acid
7-Methylenebicycl0[2.2.2]octa-2,5-diene[''~
and
By Rudolf Gompper and Karl-Heinz Etzbach[*]
Dedicated to Professor Hellmut Bredereck on the occasion of
his 75th birthday
In the alkylation of the alkali-metal salts of bicyclo[2.2.2]octanone derivatives, e. g. those of barrelenone (1),
it can be calculated from the O/C-product ratio that an antiaromatic effect prevails, e. g . in the anion of (2)['].It can be
expected that similar electronic circumstances are present in
the anions of (2) and (4) (cf. [21). 7-Methylenebicyclo[2.2.2]octadiene (3),the potential starting material for (4),
Experimental
Phosgene (10.7 g, 108 mmol; slight excess) is condensed at
0 ° C within 6 h into a stirred solution of (I)['] (50.8 g, 200
mmol) inp-pentane (400 ml) in an evacuated vessel. After 12
h at room temperature, the solution is evaporated down to
ca. 100 ml and stirred for another 12 h. Filtration and stripping off the solvent gives (2) almost quantitatively as a yellow oil which cannot be distilled without decomposition. The
compound can be stored for several weeks at 0 "C in the absence of oxygen and moisture. 3 ' P ( 1 H J - N M R(C,D,, 85%
H,P04 ext.): 6= + 164.0 [d, 'J(P"Pb)=72.8 Hz, Pa=C],
- 37.0 [d, 2J(PbP")= 72.8 Hz, P b -Si].--'3C [ IHj -NMR
(CD,C12, TMS int.): 6= - 1.0 [dd, 'J(PhC)= 12.4,
4J(P"C) = 6.3 Hz, P'SiC],
+ 0.3 [dd, 4J(PbC)=2.9,
4J(P"C) = 0.3 Hz, OSiC], + 205.3 [dd, J(P"C) = 78.9,
J(PbC) = 37.7 Hz, P T ] ; the complex spectrum of the phenyl
groups was not e~aluated.-'~Si ( ' H ) -NMR (CD,CI,, TMS
int.): 6= + 3.7 [dd, J(PbSi)= 21.0, 3J(P"Si)= 12.2 Hz, PbSi],
+ 23.6 [d, 3J(PbSi)= 5.0 Hz, OSi].
470
0 Verlag Chemie, GmbH, 6940 Wriiiheim, 1979
has been obtained in "very low yields" together with other
products on irradiation of a solution of allene in benzeneL3'.
The methods developed for the synthesis of barrelenone (1)[']
should enable the synthesis of (3) on a preparative scale and,
moreover, provide general access to 7-substituted bicyclo[2.2.2]octadienes.
Diels-Alder reaction of dihydrophthalic acid and methyl
acrylate (cf. 141) affords the anhydride (S), subsequent electrolysis of which (10 mmol anhydride: 180 ml pyridine, 30 nrl
water, 5 ml triethylamine; cf. [ ' 'I) gives methyl bicyclo[2.2.2]octa-5,7-diene-2-carboxylate
(6) and the tetracyclic
[*I Prof. Dr. R. Gompper, Dip1.-Chem. K.-H. Etabach
Institut fur Organische Chemie der Universitat
Karlstrasse 23. D-8000 Munchen 2 (Germany)
[**I This work was supported by the Fonds der Chemischen Industrie. We are
grateful to BASF for supplying the dihydrophthalic acid.
05 70-0833/79/0606-0470 $ 02.50/0
Anyew Chein. I n t . Ed. Engi. 18 (2979) N o . 6
(6) delactone (7) (consistent with the proposed
composes above 80°C into benzene and acrylic ester.
-4:
COzMe
A, AczO
+
0
90 %
MeS
X
1
COzR
EleCtrolyslS
lLleS C 0 2 H o
(6) can be reduced with lithium tetrahydroaluminate to
the alcohol (81, which without purification reacts with toluenesulfonyl chloride to give the tosylate (9) (chromatographic workup; silica gel, chloroform). On treatment with
potassium tert-butoxide in dimethyl sulfoxide, (9) is converted into (3), a colorless mobile liquid.
EtO
OEt
1
The dilithium salt of (f4)can be smoothly sulfenylated to
(15) [(i) 2 LiN(iPr), in THF/HMPT at 0°C;(ii) MeSSMe].
of (15) leads to a mixture of (16)
Oxidative decarbo~ylation[~~
and (1). Acid hydrolysis finally yields barrelenone (1). The
physical data of a few compounds are given in Table 1.
IBuOK
(61, R = CO,n,le
( S ) , R CHzOH(82yo)
(91, R = C H Z O T O S ( ~ ~ T U )
( I 3 ) , R = lLle (76%)
(151, R = 11 (7770)
(fj),R = Me
(14), R = H
COzMe
13/, 60%
Table I . Physical data of compounds (3). (5). (7). (9). (1.3). (14)
1
(3) is difficult to deprotonate. It reacts with n-butyllithium/potassium tert-butoxide['I to give, at least partially,
(4); further reaction with methyl fluorosulfonate affords a
mixture of products which contains 7-methyl-8-methylenebicyclo[2.2.2]octadiene, together with (3) and an unidentified
compound. More understandable is the behavior of the dibenzo derivativel'l of (3). Here, reaction with n-butyllithium/
potassium tert-butoxide in tetrahydrofuran (THF) at - 78 "C
furnishes quantitatively the deep-red salt (lo), which reacts
(3): m.p. 50-60"C/lS mbar (Kugelrohr)
(5): m.p. 121 " C (from chloroform-ligroin)
(6): colorless, sweet-smelling oil, b.p. 52"C/10 ' mbar: IR (film): 1735. 1538
cm-l. , IH-NMR (CDCI,): 6= 1.67 (mc, 2H). 2.55 (mc, lH), 3.60 (s. 3H). 3 70
(mc, 1H), 4.00 (mc. IH), 6.40 (mc, 4H)
17): m.p. 74-XS"C (from ether); IR (KBr): 1780. 1735 cm I : 'H-NMR
(CDC1,)- S= 1.43-3.13 (m. 8H), 3.73 (s, 3H). 4.80 (m. 1H)
(9): m . p 4 6 ° C (from hexane): IR (KBr)- 1603 cm '
(131. m.p. 48°C (from penlane): IR (KBr): 1720, 1625, 1590 cm I ; 'H-NMR
(CDCI,): 6= 1.37 (dd, J , = 13 Hz, J2=2.S Hz; IH), 2.13 (s, 3H). 2.40 (dd. J , = 13
Hr. J 2 = 3 Hz; lH), 3.73 (s. 3H), 3.73 (mc. IH). 4.17 (mc. IH), 6.43 (mc. 4H)
(14): m.p. 5 3 ° C (from pentane): 1R (KBr): 1702 c m - ' ; 'H-NMR (CDCI,):
6= 1.70 (mc, 2H): 2.57 (mc. IH). 3 67 (mc, 1H). 4.00 (mc. 1H). 6.43 (mc. 4H).
10.90 (mc, 1H)
.A
Received: February 12, 1979 [ Z 219 IE]
German version: Angew. Chem. 91. 500 (1979)
with methyl fluorosulfonate to give a 9: 1 mixture of (11) and
(12). Alkylation of (4) and (10) proceeds similarly to that of
(2) and related salts.
Sulfenylati~nl~l
of (6) with (i) lithium diisopropylamide in
THF/hexamethylphosphoric triamide (HMPT) at - 78 "C
A i ~ y r u . Chtvn.
.
lnr. Ed. Enql. I 8 (1979) N o . 6
0 Vrrlag
[ I ] R. Gompper, KGH. Elzbach. Angew. Chem. 90, 630 (1978); Angew. Chem.
Int. Ed. Engl. 17, 603 (197X).
121 R. Gompper, H.-U. Wagner, Angew. Chem. 88. 389 (1976); Angew. Chem.
Int. Ed. Engl. 15, 321 (1976).
(31 D. Bryce-Smirh, B. E. Foulger, A . Gilbert, J. Chem. Soc. Chem. Commun.
1972, 664.
141 Neth Pat. Appl. 6409347 (1965). BASF: Chem. Abstr. 63. P 113X9d
( I 965).
(51 P. Radlick. R. Klem, S. Spurlock. J. J. Sims, E. E. ran Tamelen, T. Whitesides.
Tetrahedron Lett. 1968, 51 17.
(61 L. H Zuldow. D. R. Brannon, J. Chem. Sac. Suppl. I IY64, 5497.
[7] J. Hartmann, M. Schlosser, Helv. Chim. Acta 59, 453 (1976).
(81 a ) P. F. Hudrlik. A . M. Hudrlik. Chung-Nan Wan. J . Org. Chem. 40, 1116
(1975): b) S. J. Cristol, C. 0. Mavo. ihrd. 34, 2363 (1969).
(91 B. M Trost. Chem. Rev. 78. 363 (1978).
Chonir. G m b H , 6940 Weiiiheini. I Y79
o.r7o-08~.~/7Y/l)6I~n-O471
5 02 50/0
47 1
Документ
Категория
Без категории
Просмотров
0
Размер файла
213 Кб
Теги
acid, bicycle, diener, methylenebicyclo, carboxylic, octa
1/--страниц
Пожаловаться на содержимое документа