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Cycloaddition of Azosulfones and Sulfonylimines.

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When kept with I mole of ethyl acetoacetate in the four-fold
volume of concentrated H 2 S O 4 at room temperature (24 h) or
when heated with malic acid and concentrated H 2 S O 4 until gas
evolution ceases [molar ratio (2) :malic acid: HzSO4 = 1 :1 : 151,
compound (2) affords 3',4'-dihydro-4-methylseselin (3n),
needles, m.p. 164.5-165 "C (from 2-propanol/water; ca.
60 % yield), or 3'4'-dihydroseselin (3b), m.p. 104-105 "C
(from light petroleum; cn. 50 % yield), respectively.
Received: January 31d, 1966
[Z 142/975 IEI
German version: Angew. Chem. 78, 389 (1966)
[l] Part I1 of Experiments in the Coumarin Series.-Part. I:
K.-H. Boltze and H.-D. Dell, Angew. Chem. 78, 114 (1966);
Angew. chem. internat. Edit. 5, 125 (1966).
[2] E. Spath, K . Eiter, and T. Meinhardt, Ber. dtsch. chem. Ges.
75, 1623 (1942); T. 0. Soine, J. Pharmac. Sci. 53, 231 (1964).
[3] E. Spath and H . Holzen, Ber. dtsch. chem. Ges. 67, 264 (1934).
[4] Neuere Methoden der praparativen organischen Chemie.
Verlag Chemie, Weinheim 1963, Vol. I, p. 476.
Synthesis of 1'-Methylspiro[3H-naphtho12,1411pyran-3,2'( lY2-dihydroquinoline)]
Cycloaddition of Azosulfones and Sulfonylimines
By Doz. Dr. F. Effenberger and Dip1.-Chem. R. Maier
Institut fur Organische Chemie der Technischen Hochschule
Stuttgart (Germany)
Ketene N,N-acetals ( I ) and ketene 0,N-acetals (2) containing hydrogen in the 2-position afford P-substitution products
when treated with compounds such as isocyanates and isothiocyanates that contain an electrophilic double bond
However, azosulfones (3) [31 and N-sulfonylimines (7) [41
react with ketene N,N-acetals ( I ) by cycloaddition, affording
(5) (Table 1)
the hitherto unknown 1,2-dihydro-1,2-diazetes
and 1,2-dihydroazetes ( 9 ) (Table 2), respectively. Ketene
0,N-acetals (2) and azosulfones (3), under comparable con(5).
ditions, also give 1,2-dihydro-1,2-diazetes
By Dr. C. Schiele and H. 0. Kalinowski
Forschungsinstitut der Telefunken AG., Ulm (Germany)
It has hitherto been assumed that l'-methylspiro[3H-naphtho[2,1-b]pyran-3,2'(1,2-dihydroquinoline)J (3) can be isolated
only in a n intramolecularly ionised form, as "spirain" [ I ] .
We have found that compound (3) is obtained as spiran if
quinaldine and 2-hydroxy- 1-naphthaldehyde are heated with
anhydrous ZnClz at 150°C for 1.5 hr and the resulting compound ( I ) is then treated in ethanolic suspension with methyl
sulfate. The product, 2-[2-(2-hydroxy-l-naphthyl)vinyI]-lmethylquinolinium methyl sulfate (2), can be cyclized to the
spiran (3) by means of a basic ion-exchange resin (Merck 111)
in methanol. Yields amount to ca. 80 % calculated o n ( I ) .
Table I . 1,2-Dihydro-1,2-diazedes(5) obtained from (Z) or (2) and (3)
in benzene.
Compound (3) forms yellow needles, m.p. 205-206 "C, from
methanol; it is converted by acid into salts corresponding to
(2). Its infrared spectrum includes the vCspiro-O stretching
, is
vibration at 970 cm-1, characteristic of spiropyrans [I]
absent from the spectra of compounds (2) and (4). Compound (3) is, to the best of our knowledge, the first spiran
of pyran and quinoline.
Table 2. 1,2-Dihydroazetes (9) from ( I ) and (7) in benzene at 80 "C.
Received: January 191h, 1966; revised: February 4th, 1966
[Z 152/985 IE]
German version: Angew. Chem. 78, 389 (1966)
111 R. Wizinger and H . Wenning, Helv. chim. Acta 23,247( 1940);
C. F. Koelsch, J. org. Chemistry 16, 1362 (1951); E. B. Knott, J.
chem. SOC.(London) 1951,3038; 0. Chaude, Cahiers de Physique
50, 17 (1954); 51, 6 (1954); 52, 3 (1954).
I21 G. Arnold, 2. Naturforsch. 2Ib, in press.
Angew. Chem. ititernat. Edit.
179- 181
/ Vol. 5 (1966) / No. 4
Equimolar quantities of the ketene derivative ( I ) or (2) and
the sulfonyl derivative ( 3 ) or (7), separately dissolved in
anhydrous benzene, are mixed and, depending o n the reactivity of the sulfonyl derivative, are kept at room temperature
for 2 days or heated under reflux for 2 hr. After removal of
the benzene by distillation, the products, which mostly separate as oils, crystallize when rubbed with ether or petroleum
ether and can be obtained analytically pure by recrystallization from acetonitrile or ethyl acetate. Elemental analysis,
molecular weight determinations, as well as infrared and
N M R spectra show these to be 1,2-dihydro-1,2-diazetes
-azetes, respectively. The 1 : 1 adducts ( 4 ) and ( 8 ) that are
presumably formed as primary p:oducts could not be isolated under the conditions used.
The direction of cycloaddition of the sulfonylimines (7) is
proved by N M R investigations (AB spectrum at 8 rn 6.7 ppm,
JAB = 17 cps). However, formation of the isomeric compound (6) in reactions of azosulfones (3) could not be excluded, although we consider formation of compounds (5)
more probable because of the electronic influence of the sulfonyl group on the N=N double bond.
N-Sulfonylimines (7) react also with 4-(cyclohexen-l-yl)morpholine (10) (molar ratio 1 : 1 , in boiling benzene), although the latter is less reactive than compounds ( I ) and (2) ;
cycloaddition affords compounds (11) (elemental analysis,
molecular weight determination, infrared and N M R spectra).
Compounds (11) are hydrolysed to ketones (12) in acidic
For instance, N-t-butoxycarbonyl-mono- or -bis-(6-aminohexanoic acid), m.p. 41 "C or 66 "C, respectively, was converted by o-phenylene chlorophosphite (PCP) into a mixed
anhydride, and this was treated o n a shaker at 100 "C with 6aminohexanoic acid ( I ) bound as benzyl ester to the carrier
of di(chloromethylated polystyrene, cross-linked with 2
vinylbenzene, particle size 200-400 mesh). The mode of
linkage of the monomer to the carrier and removal of the
butoxycarbonyl protecting group and, after several repetitions
of the process, of the whole oligomer chain, will be evident
from the reaction scheme below and is performed under
standardized conditions [21.
Excess of starting material and by-products can be easily removed by means of diethyl phosphite (DEP) as solvent, even
when higher butoxycarbonyl-oligoamides are used as "carboxyl components" in the chain extension.
The molecular homogeneity of the oligoamides obtained was
established by thin-layer electrophoresis at pH 1.9 and 0.3.
The products were identified by comparison with authentic
specimens [4 51.
Yields were in excess of 90 :i for the lower, water-soluble
oligoamides and 60 to 70 % for the higher oligoamides that
were more difficult to isolate.
The prospects for synthesis of much longer, monodisperse
chains by this procedure appear to be good, since solubility
difficulties that have so far precluded the preparation of
homogeneous macromolecules d o not occur.
Received: J a n u a r y 27th, 1966
[ Z 153/986 IE]
G e r m a n version: Angevv. C h em . 78, 3x9 (1966)
[ I ] D.H . Clemens, J . A . Bell, and J . L . O'Brien, J. org. Chemistry
29, 2932 (1964).
[2] R. Cleiter, Dissertation, Technische Hochschule Stuttgart
1964; G. Kiefer, Diploma Thesis, Technische Hochschule Stutt-
gart 1964.
[3] W. Konigs, Ber. dtsch. chern. Gcs. 10, 1533 (1877).
[4] R. Albreckt, 6. Kresze, and B. M l ~ k ~ rChem.
Rer. 97, 483
( I 964).
Synthesis of Monodisperse Oligoamides
on Macromolecular Carrierdl1
By Priv.-Doz. Dr. M. Rothe and Dipl.-Chem. Hj. Schneider
Received: J a n u a r y 28 th, 1966; revised: February 7th, 1966
[Z 150/983 IE]
G e r m a n version: Angew. Chem. 78, 390 (1966)
[ l ] Part XVI of Linear and Cyclic Oligomers. - Part X V :
M . Rotlie et nl., Makromolekulare Chern. 91, 23 (1966).
I21 R. B. Merrifield, J. Amer. chern. Soc. 85, 2149 (1963).
[3] M . Rotlie, Lecture at Marl (Germany) on June 16th, 1965.
[4] G. W. Anderson et nl., J. Arner. chern. Soc. 74, 5304, 5307
(1952); M . Rotlie etal., Makromolekulare Chem. 75, 122 (1964).
[5] M . Rothe et ul., Liebigs Ann. Chem. 609, 88 (1957).
Organisch-Chemisches Institut de; Universitit
Mainz (Germany)
We have worked out a synthesis of molecularly homogeneous
linear oligomers H[NH(CH2)5CO],OH of 6-aminohexanoic
acid with a degree of polymerization up to n = 11 by using
Merrifield's procedure [21 for the synthesis of peptides (covalent bonding to a n insoluble macromolecular carrier of the
oligoamide chain that is to be extended stepwise)[31. For
formation of the amide linkage we have used phosphorous
ester chlorides '41, which have not bccn previously used for
this puipose; they give quantitative conversions, even in
heterogeneous reaction with the oligomers bound on the
carrier, which is a prerequisitz for homogeneity of the products.
Airgew. Citein. iirtcriiat. Edit.
Vol. 5 (1966) 1 No. 4
Preparation and Crystallographic Data of
Vanadium Chlorimide Trichloride, Cl3VNC1
By Dr. J. Strahle and Dr. H. Barnighausen
Chemisches Laboratorium der Universitat Freiburg
The compound CIjVNCI is remarkable in that it contains a
metal-nitrogen multiple bond and is a metal derivative of
chloramine. It was first obtained on reaction of chlorazide
with vanadium tetrachloriderll. We have now found a more
cxpdicnt p x i n x t i o n of CI3VNC1, which eliminntcs the
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cycloadditions, azosulfones, sulfonylimines
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