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Preparation and Properties of the Diastereoisomeric 1 3 5-Triglycidyl-s-triazinetriones.

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+ C,H,-N=C=O
sodium methoxide/methanol or ( 9 ) and diazomethane gave
the methyl" ester (10): m.p. = 142-143 "C, C = O 1650 and
1730 cm-1; N M R (CDC13) T = 7.21 (NCHS), S;6.43 (OCHd,
S; 5.09 (benzhydryl H ) , S. (7): 93% yield, m.p. = 146 to
148 "C, C - 0 and C-C 1635 and 1758 cm-1; N M R (CDC13):
+ (C,H,),C=C=o
y y c(c
I 71
~ N y C ( C & ) ~
the 1: I : 1 adduct ( 8 ) were isolated [8J [**I. Thus the second
ketene molecule can be replaced in its role as the dipola
rophile and the intermediate 1,4-dipole (6) is intercepted by
phenyl isocyanate.
Gonzes and JoulliC 191 recently reacted benzylideneaniline
with ketene in SO2 and obtained a thiazolidone 1,l-dioxide
stoppas a five-membered cycloadduct. Kagan and Luche
ed the reaction of (1)with benzylideneaniline by the addition
of methanol. and isolated 10% of a n open-chain methanol
adduct of the 1,4-dipole.
Properties and proof of structures of new compounds[lll:
( 4 ) , m.p. = 118 O C ,
c = o 1752cm-l; N M R (CDC13*6o MHz): = 7.17 (CH3)*
S;4.73 (tert.H), S.3-Methyl-4,5,5-triphenyl-2-diphenylmethy( 5 ):m.p. = 208-209 *c(dec.1,
C = O and C = C 1757 and 1630 cm-1; N M R (CDCI3): 7 = 7.67
(CH3), s; 5.08 ( f e r t . H ) , s. When shortly boiled in 80%
dioxane, ( 5 ) was converted into ( 9 ) : m.p. = 201-203 "C,
amide-1 1616, acid c-0 1727 cm-'. ( 9 ) is insoluble in
aqueous sodium hydroxide solution, but can be titrated in
dimethyl sulfoxide with NaOH.
N M R (CD3SOCW: T =17.31 (CH3), s.The singlet at T = 4.82
corresponds to the benzhydryl proton, since this signal is
absent in the case of the Product from ( 5 ) + D2O; the signal
of the second tert.H lies below the phenyl signals. ( 5 ) and
4.98 (tert.H), S. (7) does not react with aqueous dioxane;
it is hydrolyzed by dioxanejaqueous hydrochloric acid to
give diphenylacetic acid and isoquinoline.
Received: July 31, 1968
[Z 859 IE]
German version: Angew. Chem. 80, 802 (1968)
[*I Prof. Dr. R. Huisgen
Institut fur Organische Chemie der Universitst
8 Munchen 2, Karlstrasse 23 (Germany)
Dr. B. A. Davis (A.-v.-Humboldt Fellow, 1967)
University Chemical Laboratory
Lensfield Road, Cambridge (England)
Dr. M. Morikawa
Toyo Rayon Co., Ltd.
Sonoyama 3, Otsu (Japan)
H . Stnuclinger, Liebigs Ann. Chem, 356, 51 (1907).
121 Review: J. C. Sheehan and E. J. Corey, Org. Reactions 9, 388
[3] H . Srrrudingerand H . W. Klever, Ber, dtsch, (-hem. Ges. 39,
968 (1906); H . Staudinger, H. W. Klever, and P . Kober, Liebigs
Ann. Chem. 374, 1 (1910).
[4] J . C.Martin, V . A . Hoyle, and K . C. Brannock, Tetrahedron
Letters 1965, 3589.
[5] R . N . Pratt, G . A . Taylor, and S . A . Proctor, J. &em. Soc.
(London) C 1967, 1569.
[6] Yields based on the reactant present in the smaller quantity.
[71 For definition see: R . Hujsgen and K . Herbig, Liebigs Ann,
Chem. 688, 98 (1965); R. Huisgen, M . Morikawa, K. Herbig, and
E. Brunn, Chem. Ber. 100, 1094 (1967).
[8] R . Huisgen, K . Herbig, and M. Morikawa, Chem. Ber. 100,
1107 (1967).
[**I It is not yet certain whether this is (8a) or (86). No decision
can be reached from the IR and NMR spectra.
[9] A . Comes and M . M . Joullid, Chem. Commun. 1967, 935.
[lo] H . B. Kagan and J. L . Luche, Tetrahedron Letters 1968,
[11] Correct elementary analyses and molecular weight determinations have been carried out for all the new compounds.
Preparation and Properties of the Diastereoisomeric 1,3,5-Triglycidyl-s-triazinetriones
By M. Budnowski[*]
Interaction of epichlorohydrin ( 2 ) and cyanuric acid ( I )
above 60 "C leads to the N-alkyl compounds ( 3 ) in a thermodynamically controlled reaction. A relatively small excess of
(2) favors formation of the addition product ( 3 ~ 1whereas
large excess converts (3c) to the desired (3f). Thus epichlorohydrin functions as both alkylating agent and base. The
intermediates (3dl and ( 3 e ) were detected by thin-layer
Fractional crystallization of the product ( 3 f ) gives two
stereoisomers a-(3f) and p-(3f), which were considered, o n
Angew. Chem. internat. Edit.
Vol. 7 (1968)/ No. 10
account of the chirality of the glycidyl group, toebe'racernates
with the configurations (R,R,R/S,S,S) or (R,R,S/S,S,R)
[m.p. 105 "C(a), 156 "C(P)].
In order to assign configurations to a-(3f) and @-(3f)and to
the products therefrom suitable additive and degradative
reactions were performed.
Among reagents of the type HCA- used for addition, 0Aryl, S-Aryl, S-Alkyl, and NR2 act as anions. Treatment
with aequeous alkali leads to partial or total hydrolysis.
The adduct ( 4 ) is formed in almost quantitative yield on
addition of 3 moles of H A to 1 mole of (3f). Presence of a
base leads, again almost quantitatively, to the oxazolidone
(51, which is also accessible by heating ( 4 ) with bases. The
isomers or-(3f) and p-(3f) yield different adducts ( 4 ) but the
same oxazolidone ( 5 ) .
modified so as to open new possibilities for preparation of
derivatives of the above classes of compound which shall
have predetermined configurations.
Lecture at Hamburg (Germany) on July 12, 1968
[VB 165 IE]
German version: Angew. Chem. 80,851 (1968)
[*I Dr. M. Budnowski
Wissenschaftliche Laboratorien der Henkel & Cie GmbH
4 Diisseldorf 1, Postfach 1100 (Germany)
y CH2-CH-CH,
x >> 6
Hindered Rotation in Macromolecular Solids,
Investigated by Nuclear Magnetic Resonance
(a), R’ = RZ = H, R3 = CHz-CHOH-CH2C1
(b). R’ = H, R2 = R3 = CHZ-CHOH-CHZCl
(c), R’ = R2 =
R3 = C H ~ - C H O H - C H ~ C i
(d), R’ = R2 = CHz-CHOH-CH2C1,
R3 = C
(e), R’ = R~ = CH~T.
(f),R’ = R2 = R3 = CH
By R. KosfeldC*l
Nuclear magnetic resonance and nuclear magnetic relaxation
are used as well as the mechanical-dynamic and dielectric
methods for the study of molecular movements and their
relation with the structure of amorphous and semicrystalline
macromolecular solids.
The evaluation of investigations of this type are based on the
fact that thermal molecular motion always occurs above
absolute zero. These transpositions are strongly temperaturedependent. Owing to the complicated structure of high polymers, different types of movement can take place simultaneously or (depending on the temperature) successively. Thus
at low temperatures, smaller groups such as the CH3 group
are the first to exhibit recognizable mobility. With increasing
temperature larger parts of the molecule become mobile, and
the micro-Brownian movement begins only above the glass
temperature Tg.
We studied the freezing-in of the rotation of CH3 groups in
polycarbonate (PC) and poly-or-methylstyrene (PMSt).
Whereas the planar rotation of the CH3 groups in PC die
down between 216 and 64 “K, the rotation of the CH3 groups
in PMSt freezes at temperatures between 320 and 80 OK.
r N H
A = 0-Aryl. S-Aryl. S-Alkyl. NRz
Partial hydrolysis degrades the products ( 4 ) to the urea
derivatives ( 6 ) , a 4 4 ) giving a mixture of two isomers (6). but
@ ( 4 ) giving only one urea derivative (6). namely that formed
in lower yield from or-(4).
Total hydrolysis of ( 4 ) . ( 5 ) . and (6) leads to l-amino-2propanol derivatives (71, independently of the isomer (4)
or (6) used. Acylation of (7) with urea regenerates both
isomers (6) in approximately equal yield.
These results identify or-(3f) and @-(3f) as racemates with
the configurations (R,R,S/S,S,R) and (R,R,R/S,S,S) at
the asymmetric centers. The ring-opening reactions, which
occur with complete retention, require the same assignments
of configuration for the adducts ( 4 ) . For a - ( 4 ) the three
possibilities of ring fission lead to two moles of (R,S)-meso
and one mole of (R,S/S,S)-racemic urea derivative (6). @ - ( 4 )
can give only one racemate for ( 6 ) . Synthesis of ( 6 ) from
racemic (7) and urea yields the rneso-(4) and the rac-(4)
in about equal amounts.
Since the product distribution found for the diastereoisomers
approximates to that calculated statistically, intramolecular
interaction of the chiral groups is probably small. By variation of the anion in the reactant HA, this method can be
If a classical jump process is assumed for the rotation of the
CH3 groups, the activation energies for rotation as found
from N M R measurements are 1.2 kcal.mole-1 for P C and
1.5 kcal.mole-1 for PMSt. The limiting frequencies for this
process would then be in the MHz range, i.e. they would be
too low by a factor of 106.
Another model discussed instead of classical movement for
the CH3 groups is a quantum-mechanical rotator with a
three-fold axis of symmetry, which can overcome the potential opposing rotation by the tunnel effect. This model gives
a low-temperature potential barrier of 5.4-5.5 kcal.mole-1
for both polymers. At higher temperatures, the values of the
correlation frequencies vC, which are equal to the tunnel
frequencies for the quantum-mechanical rotator, differ considerably from those expected from the quantum-mechanical
model. This is understandable, in view of the fact that the
neighboring groups, which are responsible for the hindrance
of the CH3 rotation, also become more mobile with rising
temperature. As the temperature rises, therefore, the rotation
of the methyl groups approximate more closely to a rotation
diffusion capable of being described in the classical theory.
This result shows that the movement behavior of the methyl
groups on transition from the frozen-in to the “freely mobile”
state cannot be described merely by the model of a quantummechanical rotator, and points to a correlation spectrum.
Angew. Chem. internat. Edit.
1 Vol. 7 (1968) 1 No.
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preparation, properties, triglycidyl, diastereoisomers, triazinetriones
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