close

Вход

Забыли?

вход по аккаунту

?

Homogeneous Catalytic Vinylation of Cyclic Imides and Lactams for the Synthesis of N-Vinyl Monomers.

код для вставкиСкачать
*
Experimental
Synthesis of (46). route A ' " ' : Compound ( l a ) , X=Br15'
(1.5 g, 5 mmol) in acetonitrile (10 ml) is added dropwise to a
stirred suspension of (26) (1.0 g, 3 mmol)['l in acetonitrile (10
ml) at 0 ° C under nitrogen. After 3 h at 20°C and addition of
ether (30 ml). the mixture is filtered and evaporated down in
racuo. Chromatography of the crude product (1.3 g, m.p.
96 " C ) over Woelm 0.05-0.2 mm silica gel (100 g, column
dimensions 50 x 3 cm) with ethyl acetate (200 ml) gives (4b)
(0.9 g. 68%) as yellow crystals of m.p. 114 "C.
Synthesis of (lUa)litl:A solution of (4h) (700 mg) in toluene (30 ml) is heated under reflux for 30 min (decoloration) and evaporated. Digestion of the residue with a small
volume of ether and cooling gives compound (fUa) (550 mg,
78%) of m.p. 161 'C (from ether).
Convenient and general methods for the synthesis of N-vinyl
compounds, however, were hitherto unknown.
There are two important methods for the synthesis of cyclodliphatic N-vinylimides and -1actams: Reaction of imides
and lactams according to Reppe's method['' with acetylene at
high pressure and elimination of alcohol from the N - ( l-alkoxyethyl) derivatives'''. Procedures involving high pressures
and elevated temperatures lead to formation of byproducts,
and necessitate special safety precautions; the elimination
process has the particular disadvantage that the starting compounds are accessible only by multistep synthesis.
The transvinylation of nitrogen-containing heterocycles
with vinyl acetate in the presence of mercury salts has been
described" 'I: in this method addition of oleum is essential.
Moreover. this procedure has the disadvantage that the product must be isolated by column chromatography" ''.
Attempts by Hopff et al. to synthesize N-vinylimides by
transvinylation with vinyl acetate at room temperaturel'l or
at 72"CI4I gave negative results in the case of phthalimide
and some other imides.
We have now found that cyclic N-vinyl compounds (2) are
formed in one step and in high yields on reaction of imides
and lactams with vinyl acetate in the homogeneous phase if
+
($CH=CH,
Receired: March 22. 1979:
supplemented: April 5. 1979 (Z 23X IF]
German version: Angew. Chem V / . 566 (IY79)
OH
(i
CAS Regi\tr\ nurnher\.
/ / o J ( X = Br ).70562-64-0. / / o ) ( X = CIO; ).64hX5-YX-9: ( I h) ( X = Br I.I ~ I Y O - I X 0: ( l h ) ( X = C I O , ) . >1778-20-2: ( ? a ) . 70550-75-3. / ? h i , 70550-76-4 (.la). 2749170-9. / . i h i . 53q.L(1(>-2: /Jif). 70550-77-5: / 4 h ) . 70550-78-6: ( 4 r ) . 70550-79-7: ( 4 d / .
70550-XU-0. /I'. 5376-03-4: /6).70550-81-1: (71. 2522-21-6: (8).27006-49-1, /IOU).
7055(1-X2-2. (/Oh). 70550-83-3. IIf1c.j. 70550-84-4. ItiIdJ. 7055045-5: 11 I ) . 3650973-6: ( / ? I . 70550-X6-6: (1.)) 501-65-5; 1/41, 7608-IX-0: //.i).
70250-87-7. l l h ) .
70~50-~4-~
i
Table I . Data for N-vinyl monomer\ ( 2)
R=CH
CH,
[ I1 F ,Ir11dr. B Cf.\rerr. W. Purrdr. Ber. Dtsch. Chem. Ges MI. 1364 (1927)
[ 21 Ke\it.w M R q r r z Diamalkane Thieme. Stuttgart 1977. pp. 2 3 5 l l .
[ 31 / 2 a i . / h i . D. Sevfwrh. R. S. Murmor. P. Hflherr. J. Org Cheni. 36. 1379
(197 I).(2hJ.(.lh): M . Rr~Rilz.A. L r i d h e p w r . U. Ech ~ 1 ~ M.
1 .Morrirz. W. A I I \ r / z r i / : , Justus Liehigs Ann. Chem. 748. 207 (1971).
14)J <'Ri~hiirioi~i,
E. C. Nurhun. J . Am. Cheni. Soc Oi. 4766 (1969).
[ 51 R. Hrc,\lnii.. 1.. J. .A/rmrrn. A. Krrhc. E. Muhocrr. 1. Mirrura. R. A P<w,-jofi.J.
Power. J. Am. Chem. Soc. 87. 1326 (1965).
(61 Hitherto. methyl (tri-ri~rr-butylcyclopropen~I)dia7.oacetate
wa\ the only
k n o w n representative of this c l a w it was prepared from / l o ) and methyl
(diaiolithiomethyl)acetate: S. Musamrmr. N . Nokumurrr. M . Sudrr. N. OIIU.
.I.Am. Cheni Soc. VS. 84x1 (1973) T h e reaction can he greatly improved by
.ilk!lation 0 1 the Hg derivaiive.
71 Z Yu,hidu. Y 7unirru. J. Am. Chem. Soc. 9.). 2574 (1471)
[ X i 1.' hmirurh. FortEeschrittenenarheIt. Universitdt K a i s e r h u t e r n 1979
191 Such a rearrangement has been mentioned lor (tri-rerr-hutylcyclopropen ~ l i i i i r t h o x y c d r h o i ~ ~ l c a r h e161:
n e we found that acetylene5 are a l w formed
0 1 hud. I [rrtgeschrittenenarheit. Universitat Kaiserslautern 1979).
[ 101 (;. W m r . rortge\chrittcnenarheii. Universitat KaiserYldutern 1979.
I 1 I]Anhydrous solvent\ m u j t be used.
Homogeneous Catalytic Vinylation of Cyclic h i d e s
and Lactams for the Synthesis of N-Vinyl Monomers
0
CH,-C, 4
X2
20
46
47
4x
15
I2
x4
x4 121
X5
20
I2X/2I
81
12
II 7
79
7
131
[a]
1 II/lO [7]
I31
132 131
sodium tetrachloropalladate is employed as catalyst (Table
1). The compounds (2) thus prepared were identified by
N MR and IR spectroscopy and by thin-layer chromatography.
By Ernsf Baver and Kuri Geckeler"]
N-Vinyl compounds are starting substances for the synthesis o f important polymers, e. g . poly(vinylpyrro1idinone)~'I.
[ ' 1 Prof, D r E. Bayer. D r K. Geckeler
lnstitut tur Organische Chemie der Univenit&t
A u l der Morgenstelle 18. D-7400 Tbhingen I (Germany)
A n w u ('hc.m. Inr. Ed. Oigl I 8 ( 1 9 7 V ) No. 7
0 Verlug
General procedure
T o a stirred solution of the imide or lactam (1) (20 mmol)
in vinyl acetate (50 ml) is added 50 mg of NaJPdCl,] and the
mixture heated under reflux for 4-20 h with exclusion of
moisture. After addition of 200 mg of activated charcoal the
solution is shaken for 10 min, filtered free of solids, and the
Chemir. GmbH. 6940 Wrinhrrm. IY7Y
03 70- OX3/ 70/0707-015.31 $ 02.50/0
533
solvent removed by distillation in a high vacuum. The same
amount of catalyst and reagent is then added again and the
procedure repeated. For isolation of the vinyl compound, the
solid is extracted with ether or petroleum ether, the solvent
removed in a vacuum and the product recrystallized or distilled.
Received March 5. 1979 [ Z 239 IE]
German version: Angew. Chem. 01. 56X (1979)
CAS Registry numbers:
f l u ) . 123-56-X: I l h ) . 85-41-6: I I c ) . 105-60-2: ( l d ) . 91-56-5: f / P J , 81-07-3: ( ? < I ) .
2372-96-5: ( Z h j . 3485-X4-5: ( 7 c ) . 2235-00-9: ( ? d ) . 69564-74-5: (?el. 20583-3X-4.
vinyl acetate. IOX-05-4: sodiuni tetrachloropalladate. 13820-53-6
( I1 W R q y e et u l . Juhtua Liebigs Ann. Chcm. 601. 135 (lY5h).
[ 21 J. I:uru!,uxu. A . O n i \ / i i . T. 7~\1iru1o.
J . Org Chrm. 23. 672 (1958)
[ 3 ] H Hop]/. U. WI,.>\,//. /A\.W. Helv Chim. Acta 4.1. 135 (1960).
[ 4 ] H /lop{(, 6' He&rr. Makromol. Chem. 133. I (lY70).
[ S J G. M u n ~ k i (~I . Ruhl. Makromol. Chem. /XO. 103 (1479)
[ h ] W. E. Hut!/ord. H B. Slei?nwil. US-Pal 2231 905 (1941). d u Pant.
17) W. Reppr. / I . Kri:ku/lu, 0 I)onlhcLn. R Suiierhri,r. US-Pal. 2 31 7 X04 ( I 943).
Chrm. Ah\tr. 37. 6057 (1943):0. t: Sulonion. D S. Vuule\cii. V 7firuriwii. J
Appl Polymer Sci. 12. 1x43 ( IYhX)
tlond lengths [pnil
Angle\ [ ]
Mn- CI
Mn -C4
S -CI -Mn
C h -CI --Mn
C h - -C
~ I- -s
R'-CI-Mn
R2 -CI -S
R2-C I-Ch
C I -s- .P
Mn- -C5
Mn-Ch
C I C(t
C6- -C5
CS- c 4
C4-P
Manganese-Containing Heterocycles Having a
X4-Thia-Xs-phosphanorbornadiene
Skeleton[''
P
s
-s
-CI
213. I(2)
2 I5.0(3)
208 l(2)
207.2(2)
145 013)
I41.0(3)
146.I(3)
I7Y. I ( 2 )
203 X( I )
IK3.2(3)
s-
P-c4
C& -CS- C6
c5-- Ch- I
Cl-Mn- C4
-c
12231)
67.7( I )
II X O ( 2 )
I 16.412)
I10.0(2)
I17.1(2)
97 7( I)
104. I(I)
1190(2)
I Ih.O(?)
xo I(1)
By Ekkehard Lindner, A x e l Rau, and Sigurd Hoehne"'
Metal-containing heterocycles are of interest in connection
with organic syntheses, and especially with catalytic processesI''. While looking for new pathways leading to metallacycles containing metal-carbon u bonds, we obtained the manganacycles (2) having a thiaphosphanorbornadiene skeleton
for the first time by reaction of the inorganic heterocycles
(l)"!with acetylene derivatives.
(214 pm) and that for a double bond (194 pm). The positive
charge in the PS part of (2) is manifested in a strong downfield shift ( = 74 ppm) of the "P-NMR signal (in CH2ClZ,rel.
to 85% H3P04ext.).
Heating of (Za) in tetrahydrofuran (THF) to 100 "C under
a CO pressure of 200 bar leads to elimination of the
Mn(C0)3 and the P(CH,)' group, yielding the thiophene
derivative (3).
ICOL
Procedure
(2a). R' =
(2b), R' =
(ZC), R1 =
(Zd), R' =
CH,,
CH,,
CBHS,
CsHs,
R~ = CO~CH,
R2 = C 0 2 C z H ~
R2 = C02CH3
R2 = COzCzHs
The yellow compounds (2) are readily soluble in polar solvents and melt with decomposition above 125 "C. They were
characterized by complete elemental analysis, IR [each with
three intense bands at ca. 2025. 1955, 1948 cm I (in CCI,)].
"P-NMR. and mass spectra [nz/e ( M ' ): (Za) 516, (2hl 572.
( 2 0 640. (2d) 6961; (2a) was further characterized by X-ray
crystal s!ructure determinati~nl~l
(Fig. 1) and by its "C ' H j NMR spectrum [CDCI,, rel. to TMS: S = 44.9 (d. J = 72 Hz;
C-4), 53.6 (s; (2-1). 101.6, 103.1 (s; C-5, C-6)]'5'.
The angle between the planes through the atoms C1, C4,
C5, C6 and C1, S, P, C4 is 46.9". The ester groups (R') attached to C1 and C4 are twisted by 10 and 13". respectively,
out of the plane, and those attached to C5 and C6 by 3.5 and
2", respectively; in a limiting structure the manganese is
therefore linked by two u bonds and one T bond to C1 and
C4 and to C5 and C6, respectively1"].In accord with the IR
band v(P S) at 530 cm
(in polyethylene). the P S distance corresponds to a value lying between that for a single
['I Prof. Dr. E Lindner. 1)ipl:Chem.
A . Rau. Uipl.-Chern S. Hoehne
Institiit fur Anorgani\che Chemie der Universitat
Auf der Morgenstelle 1X. D-7400 Tuhingen 1 (Germany)
Compound ( I ) (0.5 mmol) and R2C-CR2 (4 mmol) are
heated with stirring in T H F (100 ml) within 1 h to 66 " C .The
reflux temperature is maintained for 30 min. After stripping
off the solvent, chromatography with benzene/ethyl acetate
on A1207(activity V) or silica gel (activity 11) gives the organometallic compounds (2a) and (Zb) and ( 2 4 and (Zd). respectively in yields of 10 to 60% as oils which crystallize at
- 30 " C or on addition of diethyl ether.
A solution of (Za) (0.2 mmol) in T H F (50 ml) is subjected
to a CO pressure of 200 bar at 100°C in an autoclave. After
12 h the solvent is stripped off and the residue chromatographed with benzene/ethyl acetate on silica gel. The thiophene (3) is obtained in ca. 80% yield.
Keceivzd. January 30. 1979 [ Z 245a IF.]
German version. Angew Chcm. O f . 5hX (1479)
Publication delayed ;it authors' rrqur\l
[ I ] Preparation and Propertie\ of. and Keactions with. Metal-Containing He-
terocycles. Part 2 . This work was supported hy the Ueutsche Forschungsgemeincch,ilt and the Fonds der Chemischrn Industrir Part I : E. Liiidner. G.
i'on Air. H.-J. Eberk. Z. Naturlbrsch. B 11. I2Yh (lY7K).
[ 2 ] M. I Bruie. Angew. Chem 80.75 (lY77): Angew. Chern. int. Ed. t n g l . / 6 . 7 3
(1977).
131 E. Lindner. B. S<hil/ing.Chenl. Ber 110. 38x9 (1977)
I41 12u) is obtained a? triciinic crystals lrom cyclohexane/dichlor[~meth~ne
(space group Pi). ri=YO2.3(2). h = I692 t(3). c = X h 7 0 ( 2 ) pm. e = 102.01(2).
p=Y4.X7(2). y=YO.hX(Z) . L= 2. ( P ~ , , =
, ~ I439 g - c n ? 1 T h e strucltire wa,
solved hy Pattenon and dil'f'erence-Fourier hyntheses: anisotropic refinement
for 5914 independent rellections with program syilem S H E L - 7 6 (except HI
Документ
Категория
Без категории
Просмотров
1
Размер файла
225 Кб
Теги
monomerl, synthesis, cyclic, vinylation, homogeneous, catalytic, vinyl, lactam, imide
1/--страниц
Пожаловаться на содержимое документа