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Chemiluminescent Paracyclophanes.

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In such circumstances ( 2 ) exists in a particularly reactive
form, being converted completely into ( 3 u ) by further
reaction with ( I a) according to the first mechanism above.
The compounds (3) are intensely
oily liquids that
distil unchanged under reduced pressure and react with
halides"!
In its 'H-NMR spectrum, ( 3 U ) shows the expected two
singlets, with intensity ratio 3 :2, at 6(Ctl,),Si=-0.33 and
6(CH,),N= -2.93 ppm relative to (CH,),Si (external). The
IR spectrumcontainsabsorptions at 2990w, 2980s, 2890w,
1452s, 1255 vs, 1 I87 vs, 1037 w, 962 vs, 850 vs, 760 s, 673 s,
633 s, and 471 w cm- ' (capillary between KBr disks). The
bands at 2900 are assigned to the C-H stretching and
those at 1452cm- to the corresponding deformation
vibration. The strong bands at 1255 and 1187 cm- ' belong
to S=N stretching vibrations.
Insertion reactions of S4N4 with other organometallic derivatives are at present under study.
Genorul i~xperimentalprocedwo.
S,N,CI, (0.05 mol) or S4N4(0.1 mol) is suspended or partly
dissolved, respectively, in CH2CI, contained in a twonecked flask with an attached dropping funnel and reflux
condenser. (CH,),SiNR2 (0.2mol) is added dropwise to
this mixture at a rate such that the methylene chloride
just boils. At the end of the reaction the solvent is removed
and the product distilled at oil-pump vacuum. The reaction
gives an almost quantitative yield of (3)c7I.
Rcccivcd: March 9. I973 [Z X15a IE]
German version: Angew. Chem. A'S. 453 (1973)
[I]
0. J . Sc herrr. Organometal. Chem Rev. A 3, 28 I (1968)
[2] H . W R o c d v and 0. P r t r r s m . Angew. Chem. 84, 946 11972): Angew.
Chem. internat. Edit. / I . 91X (1972)
[3] H . W Rouskv and H . W i c w . unpublished
[4] M . ~ c c k r - G o d i r i n gand E.
/ = / i d
in C. 5 Colhiruiir Developments
heterocycles of type ( 3 ) are formed quantitatively from
trimethylsilyl azide (2) and ( I ) .
The removal of sulfur and nitrogen begins already at room
temperature and no further nitrogen is evolved if an excess
of ( 2 ) is used.
( J a ) is colorless, sublimes, and can be unambiguously
identified by means of its 'H-NMR and mass spectrum['l.
For the (CH,),Si group the 'H-NMR spectrum shows
a singlet at 6 = -0.53 ppm and for the CH3P groups a
doublet at 6= -2.52ppm with JHcp= 14.5Hz [relative to
(CH,),Si, external; solution in CH,CI,]. In the mass spectrum the following characteristic fragments can be seen
as well as the molecular ion 275 (58Y0):m/e=260 [67%;
M-CH,], 245 [ I % ; M-2CH,],228 [3%; M-SCH,],
211 [7%; M-2S], 196 [lo%; M-SZCH,],
182 [ 5 % ;
(CH,),SiNPS,], 170 112%; (CH3)2P,S2N], 164 [lo%;
(CH,),SiNP,CH,], 150 [loo%; (CH,),SiNPS], 138 [lOoA1;
(CH,),P,SN],
I18 [26%; (CH,),SiNP],
73 [62%:
(CH,),Si] 63 [I1 %; PSI, 45 [20%; PN], and 32 [65"/,; S].
The IR spectrum of ( 3 a ) (KBr disk) shows bands at 2970w,
29 10 w, 1398vs, I300 vs, 1295 vs, I286 s, 1255 vs, 985 vs,
9 10vs, 845 vs, 770 vs, 758 vs, 700 vs, 620 vs, 541 s, 430 VS,
412vs, 340s, and 320wcm-'. It differs from the spectrum
of ( I a ) particularly in the region of the (HCSi) deformation
vibration.
Exprrimmtal:
(CH,),SiN3 ( I 1.5 g,O.I mol) is added dropwise with stirring
to a suspension of (CH,PS2), (22g, 0.1 mol) in CH2C12
(300ml). Vigorous gas evolution sets in at once. At the
end of the reaction the mixture is warmed for a short
time and then filtered from the deposited sulfur under
nitrogen. The solvent is removed in a vacuum and the
residue is either recrystallized from CCI, or sublimed at
oil-pump vacuum. The yield is quantitative (27g).
in Inorganic Nitrogen Chemistry. Elsevier, Amsterdam 1966, pp. 150 to
240.
Received: March 9. I973 [Z Xl5b 11.1
German version: Angew. Chem. 35. 454 119731
151
W Frrrs, Dissertation, UnivcrsitZt Heidelberg 1962.
[6] H . W R(J&I. and G . R ~ w i i i i r r s .unpublished work
[7] The composition of the compounds ( 3 ) was proved by complete
elemental analysis.
A Novel Covalent Azide Reaction in Phosphorus
Chemistry [**I
[I]
H . Sruudingrr and J . M r y r . Helv. Chim. Acta 2. 675 11919).
[2] H . S t u d i n g e r and E . Huusrr, Helv. Chim. Acta 4. 861 (1921).
131 L H c m w r and A. Gross, Licbigs Ann. Chcm. 5YI. I17 (1955).
[4] W K c s t i n g , J. Prakt. Chem. /05, 242 (1923).
151 G. Schrodw, DBP I104506 (1961): Chem. Abstr. 56, 1482h (1962).
[6] E . FIm k and H . Binder, Z. Anorg. Allg. Chem. 354, I13 (1967).
By Herbert W Roesky and Michael Dietli"]
The best known reaction of azides for preparation of phosphazenes is connected with the names Stairdinger and
Horner : it consists in treating phosphane derivatives with
alkyl, aryl, or acyl azides['-41. Reaction of cyclic alkyldithiophosphonic anhydrides ( I ) with sodium azide leads to
complete cleavage of the ring"], but in contrast thereto
[*I
Prof Dr. H. W. Roesky and Dipl.-Chem M . Diet1
Anorganisch~chcmischesInstitul I dcr I:nivcrsitdt
6 Frankfurt. Robert-Mayer-Strdssc 7 9 IGermany)
[**I Thi:. work was supported by f h c Fonds der Chemischen lndiistrie
and the Deiitschc Forschiiiigs~cmeinschaft
Chemiluminescent Paracyclophanes[**l
By Karl-Dirtrich Gundrrmann and
K[uus-Dirter Riiker[*]
Some time ago, White et a/."] synthesized chemiluminescent compounds of type ( I ) containing a hydrazide group
in a part of the molecule that is not itself luminescent
or at most slightly so; the electronic excitation energy
produced by their oxidation is transferred to another part
of the same molecule that fluoresces strongly in the visible
region; ( I ) chemiluminesces with the fluorescence emission
of N-methylacridone. That the energy transfer is intramolecular is shown, inter alia, by the fact that a mixture of
["I
[**I
Prof. Dr. K:D. Gundermann and DipLChem. K:D. Riikcr
Organisch-Chcmisches Instittit der Tcchnischen L!niversitiit
Clausthal
3392 C'laust hal-Zcllcrfeld. Leibnizstrassc 6 (Germany)
('onstittition and Chcmilumincsccncc, Part 5. Part 4: [ 5 ] .
~
425
phthalhydrazide and N-methylacridone does not emit
under the same conditions.
1,4-bis(mercaptomethyl)anthracene ( 9 ) acts as a group
that fluoresces in the visible region.
( 4 ) (5.1 x
mol/l) chemiluminesces on oxidation by
oxygen/potassium tert-butoxide (2.3 x
mol/l) in
dimethyl sulfoxide at hm,,=450nm [fluorescence of (10):
423nml with about double the amount of light emitted
by 2,3-anthracenedicarboxylichydrazide[']. A mixture of
( 1 0 ) and the hydrazide (7) emits only about 1/25 as
much light as ( 4 ) under the same conditions.
The paracyclophane derivative (2) fluoresces although
formally only a p-xylene residue that cannot fluoresce
(2). -R R - = -NH-NHis present as acceptor of excitation energy: Vulu, Haebig,
(3), R = OCH,
and Ricec2]previously noted the ability of unsubstituted
[2.2]paracyclophane to fluoresce (X,,,,,, = 355 nm). The emission of (2) in the system DMSO/tert-butoxideloxygen
R'
(X,,,,,=395nm) is considerably weaker than that of ( 4 )
but nevertheless exceeds that of (7) in the same system
by an order of magnitude.
(2) was obtained by conversion of disodium p-phenyleneR'
di(methanethio1ate) by (8) into (11) by the dilution
(6). R = OH, R' = H
(4). -R R - = -NH-NHmethod13] (yield ca. 30%; m.p. 147"C), oxidation of (11)
(7), - R R- = -NH-NH-, R' = H by acetic acid/perhydrol to the disulfone ( 1 2 ) [yield 65%;
(5). R = OCH,
m.p. 320°C (dec.)], pyrolysis of ( 1 2 ) to (3) (yield 25%;
(8);R = OCH,, R' = B r
m.p. l 0 O T ) and reaction of ( 3 ) with hydrazine hydrate
in methanol. When heated, ( 1 2 ) affords only traces of
(3) (cf. c41); only the addition of a 12-fold amount of
p-terphenyl, which clearly exerts a matrix-like short-range
\
ordering effect, leads to yields around 25% of ( 3 ) on
pyrolysis at 325 "C [ ( 3 ) : ' H-NMR (CDCI,), T = 6.5G7.20
SR
(m, benzyl-H) 3.32,3.43 (phenyl-H), and 2.92 (phthalyl-H)].
(11). x = s
(9)# R = H
We obtained ( 4 ) analogously. Simultaneous dropwise
(12). x = so,
(10). R = CH,
addition of (8), ( 9 ) , and sodium hydroxide to a large
volume of ethanol gave ( 5 ) (yield 31 YO;m.p. 230-C)
whose reaction with hydrazine led to ( 4 ) . We have not
yet succeeded in oxidizing ( 5 ) to the disulfone. ( 5 ) : 'HThe methylene group in (I) and similar compounds preNMR
(CDCI,), T = 5.69-6.05 (m, benzyl-H), 3.09, 2.23,
cludes mesomeric interaction between theenergy-producing
1.48 (anthracenyl-H), and 3.56 (phthalyl-H). This shift to
and the emitting parts of the molecule; the two partial
higher field in comparison with the phthalyl protons of
structures cannot assume the parallel positions particularly
(3) proves the presence of the anti-isomer (cf. I61).
favorable for energy transfer (cf. 1'1). Considerable parallel
fixation between the phthalhydrazide and the fluorescing
Received: March 6, 1972 [Z 816 I€]
German version: Angew. Chem. 85, 451 (1973)
group should, however, be present in the corresponding
paracyclophanes.
[ I ] E . H . White and D. F . Roswell, J. Amer. Chem. SOC. 89, 3944 (1967):
We have synthesized [2.2]paracyclophane4,5dicarboxylic
D. R. Roberts and E . H . White, ibid. 92. 4861 (1970).
hydrazide (2) and 2,15dithia[3.3](1,4)anthraceneparacy[2] M . T. Vala, J . Haebig, and S. A . Rice. J. Chem. Phys. 43, 886 (1965).
clophane-l8,19dicarboxylic hydrazide ( 4 ) by Vogtle's
[3] F. Irdgfle, Angew Chem. 81, 258 (1969); Angew. Chem. internat.
methodI3'. In both these compounds the hydrazide portion
Edit. 8, 274 (1969).
resembles an o,o'disubstituted derivative of 3,6-dimeth141 J . Bruhin and W Jenny, Chimia 26, 420 (1972).
ylphthalic acid (6), whose hydrazide (7) shows no chemi[5] K:D. Gundermann, H. Fwge, and G . Klockenbring, Liebigs Ann.
luminescence on hemin-catalyzed oxidation by aqueous
Chem. 738, 140 (1970).
alkaline hydrogen peroxide and extremely little in the
[6] D. S . Cram, C . K Dalton, and G. R. Knox, J. Amer. Chem. Soc.
85, 1088 (1963).
system DMSOltei-t-butoxideloxygen. In ( 4 ) a substituted
$+
(yJ$sR
426
Angew. Chrm. internal. Edit. / Vol. 12 ( 1 9 7 3 ) / No. 5
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