O ne-Pot Preparation o f o-Xylylene D iam ine and its Related Am ines

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Notizen 985

O ne-Pot Preparation o f o-Xylylene D iam ine and its Related Am ines

S h u n -ic h i K a w a h a r a a n d T a d a fu m i U c h im a ru *

D epartm ent of Physical Chemistry, National Institute of M aterials and Chemical Research, Agency of Industrial Science and Technology, M ITI, Tsukuba Science City 305-8565, Japan R eprint 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 m ethod for one-pot preparation of o-xylylene diamine, 1,8-diaminomethylnaphthalene, and l,2,4,5-tetrakis(am inom ethyl)benzene has been developed. The procedure is simpler and the yield of the reaction is higher than by the conven

tional m ethod.

o -X y ly le n e d ia m in e is a n im p o r ta n t c o m p o u n d as a lig a n d a n d th e s ta rtin g m a te r ia l o f lig a n d s [1]. O n

th e o th e r h a n d , S a a d y et al. u se d it as tw o b e n z y l p r o te c te d a m in o g ro u p s in c h a ra c te ris tic n u c le o tid e a n a lo g u e sy n th e sis [2]. T h e G a b rie l r e a c tio n is f r e q u e n tly u se d fo r th e p r e p a ra tio n o f o -x y ly le n e d i

am ine. W hile it is an e ffec tiv e m e th o d , th e o p e r a tio n is com p lex ; fo r e x a m p le , d ip h th a lim id a te , w h ich is an in te rm e d ia te o f o -x y ly le n e d ia m in e , is h e a te d in re flu x e d a q u e o u s h y d ra z in e in a se a le d tu b e [1,3].

T h e re a re so m e o th e r m e th o d s fo r p r e p a ra tio n o f o -x y ly le n e d ia m in e : h y d ro g e n o ly sis [4] o r e le c tro ly sis [5] o f p h th a la z in e , h y d ro g e n o ly sis o f p h th a lo n itrile [6], ac id ic c lea v ag e o f tert-b u to x y - c a rb o n y l d e riv a tiv e s [7], a n d a lk y la tio n o f u r e a fo l

lo w e d b y h y d ro ly sis [8]. H o w e v e r, e a c h m e th o d d e s c rib e d a b o v e h a s in h e re n t sh o rtc o m in g s, in te rm s o f yield , c o m p le x o p e r a tio n , g e n e ra lity fo r th e p r e p a r a tio n o f sim ila r c o m p o u n d s, a v a ila b ility o f th e s ta rtin g m a te ria ls, a n d so o n . N o t o n ly o- xyly len e d ia m in e , b u t also in g e n e ra l, a ro m a tic c o m p o u n d s h a v in g tw o o r m o re clo sely lo c a te d a m in o m e th y l g ro u p s w o u ld b e im p o r ta n t a n d u s e ful as a s ta rtin g m a te ria l o f lig a n d . T hus, a n e w m e th o d fo r ea sy a n d e ffic ie n t p r e p a ra tio n o f su c h a ro m a tic a m in e s h a s b e e n hig h ly d e m a n d e d .

Br NaNq

Br 2.0 equiv

N, PPh,

N3 2.0 equiv

^ P P h 3

N cone. HCI

PPh,

as above

2HCI

2HBr

Br' Br>

f Y

^Br ^{as above} ^{H2N ^ '}

T T

^{n h}²

h2n^ ,n h2

8 (71 %)

•4HBr

Scheme 1.

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986 Notizen H e re , w e r e p o r t a m e th o d fo r o n e - p o t p r e p a r a

tio n o f o -x y ly le n e d ia m in e , 1 ,8 -d ia m in o m e th y l- n a p h th a le n e , a n d l,2 ,4 ,5 -te tra k is (a m in o m e th y l)- b e n z e n e u sin g th e S ta u d in g e r r e a c tio n (S c h e m e 1) [9, 10], s ta rtin g fro m th e c o rre s p o n d in g b ro m o - m e th y l c o m p o u n d s. A n a n a ly tic a lly p u re c o m p o u n d as d ih y d ro h a lid e w as o b ta in e d a f te r re c ry s ta lliz a tio n . TTius, th is m e th o d is c o n v e n ie n t fo r p r e p a ra tio n o f a ro m a tic c o m p o u n d s, h a v in g closely lo c a te d a m in o m e th y l g ro u p s, o n a la b o r a to ry scale.

E x p e r im e n ta l S e c tio n

o -X y ly le n e d ia m in e (4): o -X y ly le n e d ib ro m id e (1, 2.63 g, 10 m m o l) w as d isso lv ed in T H F - E tO H - w a te r (40 + 30 + 10 m l). S o d iu m az id e (1.39 g, 20 m m o l) in w a te r (20 m l) w as a d d e d , th e n th e s o lu tio n w as re flu x e d fo r 1 h [11]. I t w as n o t n e c e s sa ry to c a rry o u t th e r e a c tio n in th e d a r k o n this tim e scale. A f te r c o o lin g th e s o lu tio n to r. t., tri- p h e n y lp h o s p h in e (5.25 g, 20 m m o l) w as g ra d u a lly a d d e d to th e so lu tio n . E x o th e rm ic n itro g e n e v o lu tio n s ta r te d instan tly . A f t e r th e n itro g e n e v o lu tio n fin ish e d , th e so lu tio n w as h e a te d to re flu x fo r 0.5 h. T h e n 3 5 % aq. h y d ro c h lo ric ac id (20 m l) w as a d d e d , th e n h e a te d to re flu x fo r 2 h. T h e r e a c tio n m ix tu re w as c o n c e n tr a te d to a b o u t 20 m l in vacuo.

T h e p r e c ip ita te o f tr ip h e n y lp h o s p h in e o x id e w as re m o v e d b y filtra tio n . T h e f iltr a te w as w a sh e d w ith C H C 13 (20 m l) th r e e tim e s to r e m o v e th e r e m a in in g p h o s p h in e o x id e. T h e n , th e a q u e o u s la y e r w as c o n c e n tra te d to a b o u t 5 m l in v a c u o, w ith a h o t-w a te r b a th (a b o u t 5 0 - 6 0 °C ). C o o lin g to r. t.

gave c o lo rle ss n e e d le s o f 4. R e c ry s ta lliz a tio n fro m h o t w a te r g av e c o lo rle ss p rism s o f 4 (1.89 g, 8 4 % ).

F re e o -x y ly le n e d ia m in e w as p r e p a r e d as follow s:

4 (1.05 g, 5 m m o l) w as d isso lv ed in aq . so d iu m hy- d o x id e (5 mol/1, 5 m l). T h e re s id u e w as e x tra c te d w ith e t h e r (5 x 10 m l). T h e o rg a n ic la y e r w as d rie d o v e r so d iu m su lfa te , th e n e v a p o r a tio n in va cu o gave a c o lo rle ss oil o f 4 (0.84 g, 6 2 % ). S p e c tra l d a ta fo r o -x y ly le n e d ia m in e in th is p r o c e d u re w as in g o o d a g re e m e n t w ith th e lit e r a tu r e [2].

o -X y ly le n e d ia m in e d ih y d r o c h lo r id e h e m ih y - drate ( 4 - 2 H C l - 0 .5 H 20 ) : M . p. 2 6 1 - 2 6 7 °C (dec.). - I R (K B r): v = 3 1 0 0 -2 0 0 0 , 1935, 1641, 1 5 8 5 ,1 4 9 5 c m - 1. - *H N M R (300 M H z , D 20 ) : (3 = 4.35 (s, 4 H , C / / 2N H 3+), 4.82 (s, 6 H , C H 2NH 3+), 7 .5 0 -7 .6 0 (m . 4 H , A r ) . - 13C N M R (75 M H z, D 20 ) : (5 = 39.4 ( C H 2), 130.2, 130.3 (A r, 3, 4, 5 a n d 6), 131.4 (A r, 1 a n d 2). - C 8H 15C l2N 2O 0 5 (218.13):

calcd. C 44.05, H 6.93, N 12.84; fo u n d C 44.24, H 6.91, N 12.57.

o -X y ly le n e d ia m in e (4, fr e e fo r m ): ’H N M R (300 M H z, C D C I3): d = 1.65 (s, 4 H , C H2N / / 2), 3.91 (s, 4 H , C H 2N H 2), 7 .2 3 -7 .3 3 (m , 4 H . A r). - 13C N M R (75 M H z. D20 ) : (3 = 44.0 ( C H 2), 127.4 (A r, 3 a n d 6), 128.6 (A r, 4 a n d 5), 141.1 (A r. 1 a n d 2). T h e !H N M R ch e m ic a l sh ifts o f N H2 p r o to n s a re hig h ly d e p e n d e n t o n th e c o n d itio n s, i. e., te m p e r a tu r e , c o n c e n tra tio n , tra c e a m o u n t o f w a te r in so lu tio n , a n d so on.

1.8- D ia m in o m e th y ln a p h th a le n e d ih y d r o b ro m ide (6) w as p r e p a re d fro m 1,8-d ib ro m o m e th y l- n a p h th a le n e (5) by th e s a m e p r o c e d u re , e x c e p t th a t 47% aq. h y d ro b ro m ic ac id w as u s e d in s te a d o f h y d ro c h lo ric acid, b e c a u s e th e re s u ltin g d ih y d r o b ro m id e w as m u c h e a s ie r to cry sta lliz e , c o m p a r e d w ith th e c o rre s p o n d in g d ih y d ro c h lo rid e . S ta rtin g fro m 500 m g o f 5 (1.6 m m o l), 440 m g (7 9 % ) c o lo rless n e e d le s o f 6 w e re o b ta in e d .

1.8 -D ia m in o m e th y ln a p h th a le n e d ih y d r o b r o m id e (6): I R (K B r): v = 3 1 0 0 -2 0 0 0 , 1579, 1477, 1375 c m - 1. - l H N M R (300 M H z , D20 ) : <3 = 4.72 (s, 4 H , C H 2N H 3+), 4.75 (s, 6H , C H 2NH 3+), 7 .5 6 -7 .6 5 , 8 .0 2 -8 .0 5 (m , 6H , A r) . - 13C N M R (75 M H z , D20 ) : (3 = 43.8 ( C H 2), 126.0 (A r , 3 a n d 6), 127.8 (A r, 2 a n d 7), 130.5 (A r, 4 a n d 5), 131.9 (A r, 1 a n d 8), 133.6 (A r, 10), 135.7 (A r, 9). - C12H16B r2N2 (348.08): calcd. C 41.41, H 4.63, N 8.05; fo u n d C 41.22, H 4.60, N 7.94.

1.2 .4 .5 -T e tra k is (a m in o m e th y l)b e n z e n e te tr a h y - d ro c h lo rid e (

8

) w as p r e p a re d fro m 1 ,2 ,4 ,5 -te trak is- (b ro m o m e th y l)b e n z e n e (7) b y th e sa m e p r o c e d u re , e x c e p t th a t i) e q u iv a le n t a m o u n ts o f so d iu m az id e a n d tr ip h e n y lp h o s p h in e (4.0 e q u iv ) w e re a p p lie d , a n d ii) h y d r o b ro m ic ac id w as u se d in ste a d o f h y d ro c h lo ric acid. A f t e r ac id ic h y d ro ly sis o f th e p h o s p h a z e n e , th e r e a c tio n m ix tu re w as d a rk ly c o lo re d . T hus, u sin g th e p r o p e r q u a n tity o f c h a rc o a l is r e c o m m e n d e d fo r d e c o lo ra tio n . S ta r t

ing fro m 900 m g o f 7 (2.0 m m o l) g av e 735 m g (7 1 % ) c o lo rless p rism s o f 8. F re e 1 ,2 ,4 ,5 -te trak is- (a m in o m e th y l)b e n z e n e w as n o t e x tra c te d fro m a l

k a lin e (p H >14) w a te r b y C H C 13.

1.2.4.5-T etrakis (a m in o m e th y l) b e n z e n e tetrahy- d ro b ro m id e (8): I R (K B r): v = 3 1 0 0 - 2 0 0 0 , 1993, 1578, 1508, 1484 c m" 1 - *H N M R (300 M H z , D20 ) : (3 = 4.39 (s, 8H , C H2N H 3+), 4.72 (s, 12H , C H2NH 3+), 7.68 (m , 2 H ). - 13C N M R (75 M H z , D zO ): <3 = 39.1 ( C H 2), 132.0 (A r, 3 a n d 6), 133.6 (A r, 1, 2, 4 a n d 5). - C10H22B r4N4 (517.93): calcd.

C 23.19, H 4.28, N 10.82; fo u n d C 23.49, H 4.35, N 11.06.

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N otizen 987 [1] R. C. Brasted, T. D. O ’Brien, W. L. Heino, Inorg.

Chem. 3, 503 (1964).

[2] M. Saady, A. Valleix, L. Llbeau, C. Mioskowski, J.

Org. Chem. 60, 3685 (1995); M. Saady, L. Llbeau, C. Mioskowski, Tetrahedron Lett. 36, 4237 (1995).

[3] H. Strassman, H. Ber. Dtsch. Chem. Ges. 21, 576 (1888); S. Gabriel, G. Pinkus, H. Ber. Dtsch. Chem.

Ges. 26, 2210 (1893); H. Ing, H. M anske, J. Chem.

Soc. 203 (1952); H. R. Rodriguez, B. Zitko, G. D e Stevens, J. Org. Chem. 33, 670 (1968).

[4] G. Lunn, J. Org. Chem. 52, 1043 (1987).

[5] P. Knowles, K. R. H. Wooldridge, J. Chem. Soc. P er

kin Trans. 1 975 (1972).

[6] H. Lund, E. T. Jensen, Acta. Chem. Scand. 24, 1867 (1970).

[7] L. A. Carpino, J. Org. Chem. 29, 2820 (1964).

[8] C. D auth, H. G. O. Becker, J. Prakt. Chem. 313, 686 (1971).

[9] Y. G. Gololobov, I. N. Zhmurova, L. F. Kasukhin, Tetrahedron 37, 437 (1981); L. H orner, 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 b et

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 NM R (300 MHz, CDC13): d = 4.23 (s, 4H, CH 2N3), 7.25-7.35 (m, 4H, Ar). - 13 CNMR (75 MHz, CDC13): ö = 52.2 (CH2N3), 129.1, 130.2 (Ar, 3, 4, 5 and 6) 133.9 (Ar, 1 and 2).