One-pot preparation of o-xylylene diamine and its related amines

Article abstract of DOI:10.1515/znb-2000-1017

A method for one-pot preparation of o-xylylene diamine, 1,8-diaminomethylnaphthalene, and 1,2,4,5-tetrakis(aminomethyl)benzene has been developed. The procedure is simpler and the yield of the reaction is higher than by the conventional method.

Full text of DOI:10.1515/znb-2000-1017

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985
the other hand, Saady et al. used it as two benzyl
protected am ino groups in characteristic nucleotide
analogue synthesis [2]. The G abriel reaction is fre-
quently used for the preparation of o-xylylene di-
amine. W hile it is an effective m ethod, the operation
is com plex; for exam ple, diphthalim idate, which is
an interm ediate of o-xylylene diam ine, is heated in
refluxed aqueous hydrazine in a sealed tube [1,3].
T here are som e o th er m ethods for preparation
of o-xylylene diam ine: hydrogenolysis [4] or elec-
trolysis [5] of phthalazine, hydrogenolysis of
phthalonitrile [6], acidic cleavage of tert-butoxy-
carbonyl derivatives [7], and alkylation of urea fol-
lowed by hydrolysis [8]. H ow ever, each m ethod
described above has inherent shortcom ings, in
term s of yield, com plex operation, generality for
the preparation of sim ilar com pounds, availability
of the starting m aterials, and so on. N ot only o-
xylylene diam ine, but also in general, arom atic
com pounds having tw o or m ore closely located
am inom ethyl groups w ould be im portant and use-
ful as a starting m aterial of ligand. Thus, a new
m ethod for easy and efficient preparation of such
arom atic am ines has been highly dem anded.
One-Pot Preparation of o-Xylylene
Diamine and its Related Amines
Shun-ichi K aw ahara and Tadafum i
U chim aru*
Department of Physical Chemistry, National
Institute of Materials and Chemical Research,
Agency of Industrial Science and Technology,
MITI, Tsukuba Science City 305-8565, Japan
Reprint request to Dr. T. Uchimaru.
Fax: +81-298-61-4487.
E-mail: t_uchimaru@home.nimc.go.jp
Z. Naturforsch. 55 b, 985-987 (2000);
received May 18, 2000
Amines, Halides, Staudinger Reaction
A method for one-pot preparation of o-xyly-
lene diamine, 1,8-diaminomethylnaphthalene, and
l,2,4,5-tetrakis(aminomethyl)benzene has been
developed. The procedure is simpler and the yield
of the reaction is higher than by the conven-
tional method.
o-X ylylene diam ine is an im portant com pound as
a ligand and the starting m aterial of ligands [1]. O n
NaNq
PPh,
Br
Br
N,
2.0
N3
2.0 equiv
2HCI
equiv
^PPh3
N
cone. HCI
PPh,
as above
2HBr
as above
H2N ^ ' T T
Br'
n h 2
, n h 2
Br
f Y
h 2n ^
Br>
•4HBr
8
(71 %)
Scheme 1.
0932- 0776/2000/1000- 0985 $06.00 © 1999 Verlag der Zeitschrift für Naturforschung, Tübingen • www.znaturforsch.com
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986
H ere, we report a m ethod for one-pot p rep ara-
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o-Xylylene diam ine (4, free form ): ’H N M R (300
M Hz, CD C I3): d = 1.65 (s, 4H , C H 2N //2), 3.91 (s,
4H, C H 2N H 2), 7.23-7.33 (m, 4H . A r). - 13C N M R
(75 M Hz. D 20 ): (3 = 44.0 (C H 2), 127.4 (A r, 3 and
6 ), 128.6 (A r, 4 and 5), 141.1 (A r. 1 and 2). The !H
N M R chem ical shifts of N H 2 protons are highly
dependent on the conditions, i. e., tem perature,
concentration, trace am ount of w ater in solution,
and so on.
1.8 -D iam inom ethylnaphthalene dihydrobrom -
ide (6 ) was prepared from 1,8 -dibrom om ethyl-
naphthalene (5) by the sam e procedure, except
that 47% aq. hydrobrom ic acid was used instead
of hydrochloric acid, because the resulting dihy-
drobrom ide was m uch easier to crystallize, com -
pared with the corresponding dihydrochloride.
tion of o-xylylene diam ine, 1,8-diam inom ethyl-
naphthalene, and l,2,4,5-tetrakis(am inom ethyl)-
benzene using the S taudinger reaction (Schem e 1)
[9, 10], starting from the corresponding brom o-
m ethyl com pounds. A n analytically pure com -
pound as dihydrohalide was obtained after recrys-
tallization. TTius, this m ethod is convenient for
preparation of arom atic com pounds, having
closely located am inom ethyl groups, on a labora-
tory scale.
E xperim ental Section
o-X ylylene diam ine (4): o-X ylylene dibrom ide
(1, 2.63 g, 10 m m ol) was dissolved in T H F -E tO H -
w ater (40 + 30 + 10 ml). Sodium azide (1.39 g,
20 m m ol) in w ater (20 m l) was added, then the so-
lution was refluxed for 1 h [11]. It was not neces-
sary to carry out the reaction in the dark on this
tim e scale. A fter cooling the solution to r. t., tri-
phenylphosphine (5.25 g, 20 m m ol) was gradually
added to the solution. E xotherm ic nitrogen evolu-
tion started instantly. A fter the nitrogen evolution
finished, the solution was heated to reflux for 0.5
h. Then 35% aq. hydrochloric acid (20 ml) was
added, then heated to reflux for 2 h. The reaction
m ixture was concentrated to about 20 ml in vacuo.
The precipitate of triphenylphosphine oxide was
rem oved by filtration. The filtrate was w ashed
with CHC13 (20 ml) th ree tim es to rem ove the re-
m aining phosphine oxide. Then, the aqueous layer
was concentrated to about 5 ml in vacuo, w ith a
hot-w ater bath (about 5 0 -6 0 °C). Cooling to r. t.
gave colorless needles of 4. R ecrystallization from
hot w ater gave colorless prism s of 4 (1.89 g, 84% ).
Free o-xylylene diam ine was prep ared as follows:
4 (1.05 g, 5 m m ol) was dissolved in aq. sodium hy-
doxide (5 mol/1, 5 ml). The residue was extracted
with eth er (5 x 10 m l). The organic layer was dried
over sodium sulfate, then evaporation in vacuo
gave a colorless oil of 4 (0.84 g, 62% ). Spectral
data for o-xylylene diam ine in this procedure was
in good agreem ent w ith the literature [2].
Starting from 500 mg of
5 (1.6 m m ol), 440 mg
(79% ) colorless needles of 6 w ere obtained.
1.8-D iam inom ethylnaphthalene dihydrobrom ide
(6 ): IR (KBr): v = 3100-2000, 1579, 1477, 1375
c m -1. - lH N M R (300 M H z, D 20 ): <3 = 4.72 (s,
4H, C H 2N H 3+), 4.75 (s, 6 H, C H 2N H 3+), 7.56-7.65,
8.02-8.05 (m, 6H , A r).
-
13C N M R (75 M H z,
D 20 ): (3 = 43.8 (C H 2), 126.0 (A r, 3 and 6 ), 127.8
(Ar, 2 and 7), 130.5 (A r, 4 and 5), 131.9 (A r, 1 and
8 ), 133.6 (A r, 10), 135.7 (A r, 9). - C 12H 16B r2N 2
(348.08): calcd. C 41.41, H 4.63, N 8.05; found C
41.22, H 4.60, N 7.94.
1.2.4.5-Tetrakis(am inom ethyl)benzene tetrahy-
drochloride (8)was prepared from 1,2,4,5-tetrakis-
(brom om ethyl)benzene (7) by the sam e p ro -
cedure, except that i) equivalent am ounts of
sodium azide and triphenylphosphine (4.0 equiv)
were applied, and ii) hydrobrom ic acid was used
instead of hydrochloric acid. A fter acidic hydroly-
sis of the phosphazene, the reaction m ixture was
darkly colored. Thus, using the p ro p er quantity of
charcoal is recom m ended for decoloration. S tart-
ing from 900 mg of
7 (2.0 m m ol) gave 735 mg
(71% ) colorless prism s of 8. Free 1,2,4,5-tetrakis-
(am inom ethyl)benzene was not extracted from al-
kaline (pH >14) w ater by CHC13.
1.2.4.5-Tetrakis (am inom ethyl) benzene
drobrom ide (8): IR (KBr): v = 3100-2000, 1993,
1578, 1508, 1484 cm " 1 *H N M R (300 M H z,
tetrahy-
o-X ylylene diam ine dihydrochloride hem ihy-
drate (4 -2 H C l-0 .5 H 20 ): M. p. 261-267 °C
-
(dec.).
- IR (K B r): v = 3100-2000, 1935, 1641,
D 20 ): (3 = 4.39 (s, 8 H, C H 2N H 3+), 4.72 (s, 12H,
C H 2N H 3+), 7.68 (m, 2H ). - 13C N M R (75 M H z,
D zO): <3 = 39.1 (C H 2), 132.0 (A r, 3 and 6 ), 133.6
(A r, 1, 2, 4 and 5). - C 10H 22B r4N 4 (517.93): calcd.
C 23.19, H 4.28, N 10.82; found C 23.49, H 4.35,
N 11.06.
1585,1495 c m -1. - *H N M R (300 M H z, D 20 ): (3 =
4.35 (s, 4H , C //2N H 3+), 4.82 (s, 6H , C H 2N H 3+),
7.50-7.60 (m. 4H, A r).
D 20 ): (5 = 39.4 (C H 2), 130.2, 130.3 (A r, 3, 4, 5 and
6), 131.4 (A r, 1 and 2). - C8H 15Cl2N 2O 0 5 (218.13):
calcd. C 44.05, H 6.93, N 12.84; found C 44.24, H
6.91, N 12.57.
-
13C N M R (75 M Hz,
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[9] Y. G. Gololobov, I. N. Zhmurova, L. F. Kasukhin,
Tetrahedron 37, 437 (1981); L. Horner, A. Gross,
Liebigs Ann. Chem. 591, 117 (1955); A. Deeb, H.
Sterk, T. Kappe, Liebigs Ann. Chem. 1225 (1991).
[10] Catalytic hydrogenolysis of azides is an alternative
method for preparation of the amines: J. H. Boyer,
F. C. Canter, Chem. Rev. 54, 1 (1954).
[11] o-Xylylene diazide (2) can be isolated, but it is bet-
ter to treat the reaction mixture with phosphine
without isolation and purification of o-xylylene di-
azide, considering the stability of azide compounds.
o-Xylylene diazide (2): JH NMR (300 MHz,
CDC13): d = 4.23 (s, 4H, CH2N3), 7.25-7.35 (m, 4H,
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[5] P. Knowles, K. R. H. Wooldridge, J. Chem. Soc. Per-
kin Trans. 1 975 (1972).
[6] H. Lund, E. T. Jensen, Acta. Chem. Scand. 24,
Ar).
-
13 CNMR (75 MHz, CDC13): ö = 52.2
1867 (1970).
(CH2N3), 129.1, 130.2 (Ar, 3, 4, 5 and 6) 133.9 (Ar,
1 and 2).
[7] L. A. Carpino, J. Org. Chem. 29, 2820 (1964).
[8] C. Dauth, H. G. O. Becker, J. Prakt. Chem. 313,
686 (1971).
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