CONCLUSIONS

i. The reaction of benzoyl peroxide with thioacetals leads to substitution of the ace-
tal hydrogen atom by the benzoyloxy group.
2. On the basis of spectral and kinetic data, a structure for the intermediate complex
for this reaction is proposed.

LITERATURE CITED
1, G. Sosnovsky, Tetrahedron, 18, 15 (1962).
2. S.-O. Lawesson and C. Berglund, Acta Chem. Scand., 15, 36 (1961).
3. KI. Gollmer and H. Ringsdorf, Makromol. Chem., 121, 227 (1969).
4. W. A. Pryor and H. T. Bickley, J. Org. Chem., 37, 2885 (1972).
5. Weygand and Hilgetag, Experimental Methods in Organic Chemistry [Russian translation],
Khimiya, Moscow (1968), p. 596.
. A. J. Gordon and R. A. Ford, Chemist's Companion: A Handbook of Practical Data, Tech-
niques, and References, Wiley (1973).

NITRATION OF THE CONDENSATION PRODUCTS OF MONOETHANOLAMINE

AND FORMALDEHYDE

L. N. Punegova, G. A. Marchenko, UDC 542.958.1:542.953:547.435.1:547.281oi

V. A. Al'fonsov, A. V. Ii'yasov,
A. N. Chernov, A. A. Nafikova,
and L. S. Egorova

It has previously been shown [i] that condensation of monoethanolamine and formaldehyde,
depending on the ratios of the starting reagents, leads to various products: N,N'-methylene-
bisoxazolidine (I), 1,3,5-tris(2-hydroxyethyl)-l,3,5-triazacyclohexane (s-triazine) (II), and
1,7-dihydroxy-3,5-diazaheptane (III). On study of the nitration of these compounds it was
found that in the case of oxazolidine (I) l-acetoxy-2-nitro-2-aza-4-nitroxybutane (IV) [2]
is formed as the main product. On nitration of s-triazine (II) the formation of 1,7-dinitroxy-
3,5-dinitro-3,5-diazaheptane (V) was found along with the acetoxynitrate (IV). The dinitrate
(V) was obtained in maximal yield on nitrating compound (III) [3].

~HOC]-I~GIi2NH2 -y mCfizO
=2 [
CHe--C}toh
! " ,rl CH2--CH2i
; CH2Cif20It HOCH2CH~N
CH~
0 N--CH2--N 0 /
./ ~ / Clt2 CIJ2 I {OCt~[2(.]}{2N
(-;Ha CI-I2 i
(i) H
HOCU~CH2--N N--CH.zCt [x()II
"\\ 1/ (i~i)
Ct{~ (II)
I
~ I-INOa/Ac~O
CHaCOOCI-t~NCH2CIt~ONO~ ,~ 02NOCH2CHzNCH~NCI%L;H2ONO~
I (iv) F I (v)
N0~ NO2 NO2

In contrast to works [4-6] in which a preprepared mixture of HNO3 and Ac20 was used for
the nitration of s-triazine compounds, we carried out nitrations of compounds (I)-(III) by
means of consecutive introductions of HN03 and Ac20 into the reaction mixture, i.e., the first
step of the nitration reaction is the interaction of (I)-(III) with the acid. In conjunction

A. E. Arbuzov Institute of Organic Chemistry, Kazan Branch, Academy of Sciences of the

USSR. Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2076-
2082, September, 1984. Original article submitted June 29, 1983.

0568-5230/84/3309-1895508~ 9 1985 Plenum Publishing Corporation 1895

with this it became necessary to study the introduction of the condensation products of mono-
ethanolamine and formaldehyde into the acid medium.
In the present work we undertook an investigation by the IH and ~gF NMR methods of com-
pounds (I)-(III) in the course of their reaction with trifluoroacetic acid (TFAA). TFAA is
convenient in that it has no resonance signals in the region of the spectrum of interest to us,
and furthermore it makes it possible to observe the fate of the acid residue (trifluoroace-
tate group) with the aid of 19F NMR. For the proper designation of the NMR spectra of prod-
ucts (I)-(III) compounds containing the NHCH2CH20H fragment were studied: monoethanolamine
(VI), N-methylethanolamine (VII) and the trifluoroacetate of monoethanolamine (VIII). The
spectra of solutions of (VI) and (VIII) in TFAA are identical. The PMR spectral parameters
of these compounds are shown in Table i.
The PMR spectra of the ethane fragments of compounds (VI) and (VII) dissolved in MeCN or
PhCN do not show any splitting caused by vicinal spin--spin splitting interactions with the
protons of the amino group because of rapid exchange of the latter. The multiplet character
of the signals differs from the spectra of A2B2 systems and is closer to slightly degenerate
AA'BB' spectra with the value 3JAB + 3JAB, = i0 Hz. The nonequivalent protons may be caused
by the lack of free rotation around the C--C bond. The protons of the OH and NH groups give
one shift signal as a result of rapid exchange.
The spectrum of the solution of (VI) in TFAA is evidence of the presence of two protona-
ted forms of (VIII) and (IX) (see Table i)

HOCH2CH2NH2 + CF~COOH --~ HOCH2CH2~Ha. CFaCOO - CF~COOH> CFaCOOCH2CH2NHa.

+ CFaCO0-
(VI) (VIII) (IX)

In the freshly prepared solution there is observed principally the salt (VIII) for which all
proton signals are shifted in a weak field in comparison with the spectra of solutions of
(VI) in MeCN and PhCN as a result of appearance of the positive ion on the N atom. In this
instance the NCH2C multiplet (6, 3.47 ppm) is shifted to a greater extent than the OCH2C mul-
tiplet (6, 4.15 ppm). Methylene protons near the N atom in compound (VIII) have a great mul-
tiplicity as a result of spin--spin interactions with the protons of the amino groupl which
is evidence of a slowing down of the rate of intramolecular proton exchange in the NH3 groups.
Signals of the protons of the substituted ammonium ion (6, 7.24 ppm) are widened because of
quadrupole interactions with the N atom [7]. Integral intensities of signals of the NH3, OCH2,
and CH2N groups are in the ratio 3:2:2, but the signal of the OH group is not individually
detectable since because of exchange with the TFAA it is either greatly widened or displaced
to the region of resonance of the OH of TFAA 16,.10.26 ppm) . On letting the monoethanolamine
stand for a long time (up to 18 h) in TFAA or on heating to 100~ acylation of the OH group
occurs with the formation of (IX). The PMR spectrum of compound (IX) is similar to the spec-
trum of (VIII) but it has a greater downfield shift of the signals of the protons of OCH2-
CH2N because of the influence of the ~QF3CO0- group (4.76 and 3.67, respectively). A widened
signal at 6 7.54 ppm belongs to the NHs protons. A signal at 0.56 ppm in the 19F N-MR spec-
trum of compound (VI) in TFAA is ascribed to the trifluoroaeetate ion of form (VIII) parti-
cipating in exchange with the TFAA in which the position of the signal changes somewhat de-
pending on the concentration. Moreover, on long standing or heating of compound (VI) with
TFAA in TFAA a signal at 1.62 ppm appears in the ~gF NMR spectrum, the intensity of which
increases along with the increased intensities of signals of the acylated form (IX) in the
PMR spectrum. This fact allows us to assign the signal at 1.62 ppm to the covalent bonded
CF3COO group of compound (IX) not participating in the rapid exchange with TFAA.
We found analogous regularities in the changes in the nature of the spectrum on going
from MeCN to TFAA (see Table i) and on study of the interaction of N-methylethanolamine (VII)
with TFAA.
The PMR spectra of the OCH2CHaN fragment of solution of (VII) in MeCN, PhCN, and TFAAare
similar to the PMR spectrum of (VI) in these solvents and are also evidence for the presence
in TFAA of two protonated forms (X) and (XI). Protons of the CHs group give triplet reso-
nance signals in TFAA with 6 2.99 ppm (X), 3.01 (XI) and SJHH = 5.5 Hz. For compound (VII),
just as with monoethanolamine increase in the concentration of the form acylated on the OH
group (compound (Xl)) is observed on standing or heating the solution

CHaNCH~CH20H + CFsCOOH --~ CHsNCH~CH~OHCF3C00- CF3COOH ---, CHaNCH2CH20CO

+ CFaCFaCO0-
I /\ /\
H (VII) H H (X) H H . (XI)

1896
The ~gF NMR spectra also testify to presence of two types of CFsCOO groups: those exchanging
with TFAA (6 0.53 ppm), and the covalent bonded in (XI) (6 1.53 ppm).
Results of analysis of the PMR spectra of model compounds allow us to interpret the spec-
tra of the monoethanolamine--formaldehyde condensation products (I)-(III) and to formulate con-
clusions about the nature of their transformations in TFAA. Characteristically all spectra
have groups of signals, differing in relative intensities, but alike in their chemical shift
values and identical in their multiplet structures. This fact indicates that as a result of
interaction of (I)-(III) with TFAA compounds are formed containing similar proton fragments.
In all spectra there are signals at 6 3.59 (quintet), 4.29 (triplet), 5.0 ppm triplet; sing-
lets at ~ 4.46, 5.56, and 8.43 ppm, and also wide resonance bands in the range from 7 to 9 ppm.
On irradiation at the resonance frequency of the band ~8.30 ppm widening of the structure of
the signals at ~ 5.01 (triplet) and 3.39 ppm (quintet) to singlet and triplet, respectively, is
observed in the homonuclear double resonance spectrum. Considering this result and also the
fact that the group of signals at ~ 3.69 and 4.29 are similar in structure to the spectra of
the protonated forms (IX) and (XI) (see Table i) we suggest that these signals belong to the
protons of a single molecule, namely substituted ammonium+(6 8.30 ppm), methylene (~ 5.01 ppm),
and ethane (6 4.29 and 3.69 ppm) proton fragments of OCH2NCH2CH20. Evidently in all three in-
~/\H
stances practically complete rupture of one of the C--N ~onds of the NCH2N fragment (in the
case of oxazolidine (I) the C--O bond of the OCH2N fragment) takes place with formation of the
compound XCH2~CH2CH=Y as the main product of the reaction CF3CO0-; X, Y = CF3CO0, OH (XII).
H/ \H
Attention is drawn to the fact that the relative intensities of the signals indicated
above at 6 4.46, 5.56, and 8.43 ppm decrease on going from the spectrum of structure (I) to
that of structure (II) and practically disappear in the spectrum of structure (III). For that
reason the potential for bonding with formaldehyde also decreases from (I) to (III) which
provides a basis for the supposition that the singlets in question belong to various polymer
forms of formaldehyde. However, on intermittent heating the appearance of these singlets in
the spectrum of (III) and the intensification of these same signals in the spectra of (I) and
(II) was observed. This indicates that partial splitting of the C--N bond of the OCH2N frag-
ment of compound (xII) occurs in all three instances.
CF, COOH +
XCH2~CH2CH~Y' CFaCOOv - - "~"HsNCH2CH2OCOCF3. CFaCOO-
H/ \ !t (xu) (ix)

Actually, in the case of compound (I) in view of the insufficient concentration of mono-
ethanolamine, signals o f t h e p r o t o n s o f i t s two f o r m s ( V I I I ) and ( I X ) ( s e e T a b l e 1) a r e f o u n d
at the noise level, then in the spectrum of the solution of s-triazine (II) in TFAA there is
a small proportion of the signals of (IX). On going over to (III) intensities of the signals
of salt (IX) increase.
In the ~gF NMR spectra of condensation products of (I) and (II) there is only one signal
at 6 0.6-0.9 ppm, which belongs to the CF3COOH participating in proton exchange with the tri-
fluoroacetate anion. Other signals were not found in the ~gF NMR spectrum. This makes it
possible to suggest that the terminal substituent of the ethane fragment of compound (XII)
is the OH group which does not enter into reaction with excess TFAA like that which occurred
in the case of the model (VI).
The signal of the covalent bonded CF3CO0 group in the 1.6-ppm region does not appear eith-
er on long standing at 20~ or on 4 h heating of the sample in TFAA at 100~ but by analogy
with monoethanolamine acylation of the OH group of the ethanol fragment should have been facil-
itated. The fact that the end OH group of the HOCH2CH= in (XII) is not acylated is verified
by the :H NMR spectral data. Chemical shifts of the methylene protons of CCH20 are equal to
4.27 and 4.25 ppm, i.e., close in magnitude to the chemical shifts of analogous protons in the
unacylated form of monoethanolamine (VIII) (4.14-4.24 ppm), and substantially different from
the chemical shifts in the acylated from (IX) (4.78-4.82 ppm). Resolution of the question
about the presence of the CF3COO group on the methylene fragment of (XII) is not possible at
the present stage of the investigation. It could be either the hydroxy group OH or the CFa-
COO group participating in the rapid intramolecular exchange by an SN~ mechanism [8].
Thus, based on the investigations carried out it can be proposed that on reaction of the
condensation products of monoethanolamine and formaldehyde with TFAA practically complete de-
composition of these compounds is observed according to the scheme

1897
b~
O0
kO
OO

TABLE i. NMR Spectra of the Compounds Under Investigation

•'H, p p m

Solvent proton groups

CompouM
5,9F, ppm
a* b* c d e

e c b a
CH3COOCH2NCH2CH2ON02 (IV) CHCI3 4,75 4,22 5,70 2,12
I
NO~
d a b c
HOCH2CH2NH2 (VI) MeCN 3,45 2,65 2,63 2,63
PhCN 3,75 2,86 3,36 3,36
d a b c e
HOCH2CH2NHCHs (VII) MeCN 3,54 2,60 3,34 3,34 2,35
PhCN 3,77 2,74 3,96 3,96 2~47
+
HOCH~CH2NH3"CF3CO0- (VII) TFAA 4'i5 3,47 7,24 0,56
+
CF~COOCH2CH2NH3 9CF3COO- (IX) TFAA 4'78 3,70 %54 i,62
+
HOCH2CH2NH2CH3 .CFaCO0- (X) TFAA 4,14 3,42 7,56 2,99 0,53
+
CFaCOOCH2CH~NH~CH3 9CF~COO- (XI) TFAA 4'78 3,67 7,96 3,0i t,53
e c b a d e
CHaCOOCH2NCH2CH2OCH2OCOCH~ (XIV) CHC]3 4'07 3,91 5,67 5,24 2,10; 2,08
I
NO2

*Chemical shift data give the central line of the multiplet signal.
 (I)--~ CFtCOOtt
(II) ] > (vnI) + (ix) + (xli)
(Ill) L

Based on the model reactions carried out it would be expected that in the nitration reac-
tion the same processes would occur at the stage of addition of HN03 to the condensation prod-
ucts (I)-(III) as by the action of TFAA. The subsequent introduction of Ac20 into the reac-
tion mixture should make possible on the one hand condensation of the decomposition products
formed and their acylation, on the other hand occurrence of the O and N nitration processes.

(I), (II), (Ili)

HO _ NO3-
~+ HNOs
+
(02NO)CH2NCH~CH20H + H3NCH~CH2ON02 + HsNCH2CH20H + (CH20)n
/ \ NO~- NO3-
H H (XIII) 1 (CH,CO)20
Y
CH3COOCH2NCH~CHzON02+ 02NOCH2CHsNCH2NCH~CH2ON02
I
NO2 NlO~ NO~
I
(IV) (v)

As is evident from the above scheme, increasing the concentration of the mono or dinitrate
of monoethanolamine should lead to an increased yield of the dinitrate (V), formed as a re-
sult of the condensation of (XIII) with monoethanolamine. Actually, we have shown that ad-
dition to a mixture of s-triazine with HNO3 of an equivalent amount of a solution of mono-
ethanolamine in HNOs with subsequent introduction of Ac20 leads to an approximate doubling
of the yield of dinitrate (V) compared with direct nitration of the s-triazine. We obtained
analogous yields of the dinitrate (V) by adding monoethanolamine dinitrate to the reaction
mixture at the protonization stage.
In the case of the oxazolidine (I) containing a potential excess of formaldehyde, in our
opinion, compound (XIII) and the decomposition products containing bonded formaldehyde parti-
cipate in the condensation reaction. Thus on nitration of oxazolidine (I) in addition to the
main reaction product, acetate (IV), 1,6-diacetoxy-2-nitro-2-aza-5-oxaheptane (XIV) is formed.
PMR spectral parameters of compounds (IV) and (XIV) are shown in Table 1.

(CH3CO)~O
(I) + HNO3 ~ (XIII) -I- (CH20)n >' (IV) + CH3COOCH~NCH2CH~0CH~0COCHs
I
N02 (xlv~

With the aim of establishing the possibility of the condensation of monoethanolamine

with products formed after the introduction of Ac20 into the reaction mixture we investigated
the reaction of monoethanolamine and its dinitrate with acetate (IV). We were not able to
find any evidence of the formation of dinitrate (V). Probably condensation of the decomposi-
tion products of compounds (I), (II), and (III) in acid medium takes place in the steps pre-
ceding N-nitration. The introduction of Ac20 into the reaction mixture in the final analysis
leads to the formation of N-acetoxymethylnitramines, which under the conditions of the nitra-
tion reaction are not capable of further transformation.

EXPERIMENTAL
NMR spectra were taken on Varian T-60 (60 MHz) and Tesla BS-497 (i00 MHz) spectrometers.
Chemical shifts are given relative to TMS and to an external standard TFAA (internal C6F6).
Compound (I) was obtained according to the method of [i], compound (II) in accordance with
[9], (III) was synthesized like (II) by the condensation of 2 moles monoethanolamine and 1
mole formaldehyde. Nitration of s-triazine (II) was carried out as in [3]. Compound (III)
was nitrated analogously to (II) in the presence of three equivalents of monoethanolamine [3]
Trifluoroacetate of Monoethanolamine, (VIII). To a solution of 3 g monoethanolamine in
10 ml CH2C12 at 5~ 8 ml TFAA was added dropwise over 30 min, stirred at 30~ and concen-
trated by evaporation. Shining white needles of salt (VIII) were filtered off, washed with
methyl ethyl ketone and dried. The spectral data are shown in Table i.

1899
 Nitration of the Mixture of l-Acetoxy-2-nitro-2-aza-4-nitroxybutane (IV) with Monoethan-
olamine Dinitrate. To a suspension of 3 g of acetate (IV), 2.2 g of monoethanolamine dini-
trate in 20 ml dichloroethane (DCE) was added successively 0.5 ml 98% HN03, and 2.1 ml Ac=O.
after 1 h at 50~ the reaction mixture was cooled, the insoluble residue of the monoethanol-
amine dinitrate (2.15 g) was filtered, separated out, washed with alcohol and dried. After this
the dichloroethane solution was diluted with water to pH 6--7 and dried over MgS04. After re-
moval of the solvent in a vacuum 2.87 g of acetate (IV) was obtained.
Nitration of s-Triazine (II) in the Presence of Monoethanolamine. To a solution of 2 g
triazine (II) in i0 ml DCE at 12-15~ was added dropwise 3.6 ml of 96-98% HNO3, followed by
a solution of 1.65 g monoethanolamine in 3 ml 96"98% HNO3 in i0 ml DCE, and 20.8 ml Nc=O, The
reaction mixture was stirred 1 h at 22-25~ , diluted with water to pH 6-7, and dried. After
removal of the DCE in a vacuum the residue was diluted with 20 ml ethanol, the precipitate
formed was filtered off, washed with alcohol, and dried. There was obtained 1.22 g (30%) of
dinitrate (V), mp 32 ~ (from ethanol). Acetate (IV) was separated from the alcohol solution
in 33% yield.

CONCLUSIONS
1. By the IH NMR and 19F methods we have shown that in an acid medium there is practi-
cally complete decomposition of the condensation product of triethanolamine and formaldehyde
to a compound of a salt type containing the OCH2NCH2CH20 fragment.
2. The direction of nitration of the monoethanolamine--formaldehyde condensation products
on subsequent addition of HN03 and (CH3C0) 20 is determined by the ratio of the monoethanolam-
ine to the formaldehyde in the reaction mixture.

LITERATURE CITED
/
I. A.N. Gagarov, L. N. Punegova, E. I. Loginova, S. S. Novikov, and N. K. Titov, Izv. Akad.
Nauk SSSR, Ser. Khim., 2189 (1978).
2. A . N . Gafarov, L. N. Punegova, G. A. Marchenko, E. I. Loginova, and S. S. Novikov, Izv,
Akad. Nauk SSSR, Ser. Khim., 405 (1980).
3. A . N . Gafarov, L. N. Punegova, G. A. Marchenko, and S. S. Novikov, Zh. Org. Khim., 15,
1322 (1979).
4. I. Denkstein and V. Kaderabek, Collect. Czech. Chem. Commun., 26, 1373 (1961).
5. I. Denkstein and V. Kaderabek, Collect. Czech. Chem. Commun., 25, 2334 (1960).
6. V. Kaderabek and I. Denkstein, Collect. Czech. Chem. Commun., 42, 711 (1977).
7. R. Silverstein, G. Bassler, and T. Morril, Spectrometric Identification of Organic Com-
pounds, 4th ed., John Wiley and Sons, New York (1981), p. 198.
8. G. Becker, Introduction to Electronic Theories of Organic Reactions [Russian translation],
Mir, Moscow (1977), pp. 181-182.
9. P . A . Layrent, Bull. Soc. Chim. France, 2, 571 (1967).

1900