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Bis(trimethylsilyl)aminodimethylarsine and Tris(dimethylarsino)amine.

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is simply treated with the alkyne in acetic anhydride. Thus,
dimethyl 5-methyl-l,2-trimethylenepyrrole-3,4-dicarboxylate
is obtained in 76 % yield by merely warming proline with dimethyl acetylenedicarboxylate in acetic anhydride at 130 "C
for 1 hr.
The kinetics of the release of carbon dioxide indicate that
the acetylenic dipolarophile first combines with (31, presumably to form the bicyclic adduct (4) ; the elimination of CO:!
from (4) is a rapid subsequent reaction. Compound ( 3 ) belongs to the azomethine-ylide class of 1,3-dipoles [4], cf. the
sextet structure (20); here the 1,3-dipole system is part
of an aromatic ring. H: Staudinger [5] has proposed the
term "nitrenes" for azomethine ylides. The first representatives have recently been described [6].
Received, December 20th, 1963 [Z 642/469 IE]
German version: Angew. Chem. 76, 1 8 5 (1964)
[I] 1. C. Earland A . W . Mackney, J. chem. SOC.(London) 1935,
899.
[2] Mesoionic compounds: W. Buker and W. f). Ollis, Quart.
Reviews (chem. SOC.,London) 11, 15 (1957).
[3] H . D. Dakirz and R. Wesf, J. biol. Chemistry 78, 91, 757
(1928); R . H . Wiley and 0 . H . Borum, J. Amer. chem. SOC.72,
1626 (1950); A . Lnwson and C . E. Searlc, J. chem. SOC.(London)
1957, 1556.
[4] Classification: R. Huisgen, Angew. Chem. 75, 604 (1963);
Angew. Chem. internat. Edit. 2, 565 (1963).
[5] H . Staudinger and K . Miescher, Helv. chim. Acta2, 554 (1919).
[6] R . Huisgen, R . Grashey, and E. Steingruber, Tetrahedron
Letters 1963, 1441.
Tris(biphenyleneviny1)methane i l l
Institut fur Chemie, Max-Planck-Institut fur Medizinische
Forschung, Heidelberg (Germany)
Bis(bipheny1ene)pentadienone (1) reacts with iodomethylenetriphenylphosphorane to give yellow needles of (2), m.p.
152-153 OC. Condensation of (2) with fluorene in dimethylformaniide in the presence of sodium hydroxide yields
a hydrocarbon which crystallizes in colorless prisms, m. p.
235-237 'C (decomp.), molecdar weight 540. This is
tris(biphenyleneviny1)methane ( 3 u ) , somewhat contaminated
by its structural isomer ( 3 b ) , judging by its ultraviolet spectrum [2]. The new hydrocarbon is about 300 times more
acidic than the bis(bipheny1ene)pentadielie ( 4 ) described in
our third communication [l] (pK of (3u) [*I in a 1: 1 acetone,/pyridine mixture: 6.2; p K of (4):8.8). The anion of
(3a) has a n absorption maximum at 645 m p (E = lO5), i.e.
at only slightly longer wavelength than that of the anion of
(4)
= 633 mp). The high acidity of the hydrocarbon
and the absorption band of the anion are in agreement with
the predictions of the molecular orbital theory [3] (delocalization energy of ( 4 ) : 2.22 9,delocalization energy of (3a):
2.50 p; calculated absorption band for the anion of ( 3 ~ ) :
ca. 630 mp).
+ Ph,P=CHI
---f
(1)
BiphCH2
~
_
_4
_
(BiphC = CH),CH
DMF/OHa
+
CHs-CBiph
--f
(BiphC=CH)zCH-Ph
(7)
OH
The hydrocarbon (3u) is a n analogue of tris-($,P-diphenylvinyl)methane, which requires treatment with phenylisopropylpotnssiiim to convert it into an anion [6!.
Received, January 2nd, 1964
[Z 639/467 IE]
German version: Angew. Chem. 76, 146 (1964)
[l] Communication No. 4 on Highly Acidic Hydrocarbons;
Communication No. 3 : R . Kuhn, H . Fischer, F. A . Neirgebaurr,
and H . Fischer, Liebigs Ann. Chem. 654, 64 (1962).
[*] Somewhat contaminated with ( 3 b ) .
121 Starting from bis(bipheny1ene)pentadiene and biphenylenevinyl bromide, both (3a) and (3b) have been obtained: m.p.
(decomp.) 268-270 "C and 229-230 "C, respectively; Amax in
tetrahydrofuran 319 mv (E = 53x 103) and 342 mv (E = 35x iO3),
respectively. Both give the same anion ( R . Kuhn and D.Rewicki).
[3] J. N . Murrel and H . Fischer, in preparation.
[4] S. Wairzonelc and E. Dufek, J. Amer. chem. SOC. 78, 3530
(195 6).
[5] On ozonolysis, 1.4 molar equivalents of fluorenone and some
phenylacetic acid were obtained.
[6] G. Wirrigand H . Kosack, Liebigs Ann. Chem. 529, 167 (1937).
Tris(dimethy1arsino)amine
By Dr. 0. J. Scherer and Prof. Dr. Max Schmidt
Institut fur Anorganische Chemie der Universitlt Marburg/L.
(Germany)
In connection with studies of hetero-tris(trimethy1silyl)amines
[l], we have prepared bis(trimethylsilyl)aminodimethylarsine(1) in 75 %yield from dimethylchloroarsine and sodium
bis(trimethylsily1)amide [2] in dry ether according to the
equation:
The product is a liquid (m.p. -46 to -44 OC, b.p. 45-46 "C/
1 mm) which is colorless, sensitive toward oxygen and moisture, and is cleaved at the As-N bond by methyl-lithium with
formation of [(CH3)3Si]2NLi and As(CH&. The NMR
spectrum of ( I ) [two signals, area ratio l ( 8 = -77.8 cps) : 3
(6 = -10.0 cps)] shows that there is no migration of the silyl
group from the nitrogen to the arsenic. Compound ( I ) is
not cleaved even at 120 "C by excess chloroarsine.
+ (BiphC = CH)2C= CH-CHBiph
(36)
(BiphC=CH)zCHr
14)
Biph = Biphenylene
The preparation of 1,1,5,5-bis(biphenylene)-3-(diphenyIvinyl)pentadiene (6) from 1,I-diphenyl-5,5-biphenylenepentadienone (5) was achieved similarly. In addition t o (6), two structural isomers are possible, one of which can also be expected
to have geometric isomers. The anion of (6) absorbs a t
675 mp.
(5)
OH
(BiphC=CH)zC=CHI
(2)
(34
(Ph)K=CH-CO-CH=CBiph
BiphC-CH=CH-Ph
Bis(trimethylsily1)aminodimethylarsine and
By Prof. Dr. Richard Kuhn and Dr. Herbert Fischer
(BiphC=CH)zCO
1,1,5,5-Bis(biphenylene)-3-phenylpentadiene
(7) was prepared
by condensation of styrylfluorenol and methylfluorenol by
the method of Wawzonek [4, 11 as colorless rods [5], m.p.
192-193"C, and is at least 100 times less acidic than the
pentadiene ( 4 ) (pK of (7) in a 1: 1 acetone/pyridine mixture co. I l j . Its anion absorbs at 686 m!.r (E = 82x103).
as above
----+ (BiphC=CH)2CH-CH=CPh
f 6)
Angew. Chem. internat. Edit. / Vol. 3 (1964) / No. 2
We obtained tris(dimethy1arsino)amine in 50 :d yield as
colorless prisms, m.p. 22-25 "C, b.p. 57-58 O C / l mm, by
heating bis(trimethylsily1)amine with dimethylchloroarsine
without solvent for 6 hours at 100-120 "C. Its N M R spectrum shows only one signal (6 = -69.0 cps). Compound (2)
is extremely sensitive towards oxygen and moisture.
Received, January 2nd, 1964
[Z 636/463 IE]
German version: Angew. Chem. 76, 144 (1964)
111 0. J. Scherer and M . Schmidt, Angew. Chem. 75, 642 (1963);
Angew. Chem. internat. Edit. 2, 478 (1963); J. organometall.
Chem., in the press.
[Z] U.Wannagat and H . Niederpruem, Chem. Ber. 94,1540 (1961).
137
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trimethylsilyl, aminodimethylarsine, dimethylarsino, amin, bis, trish
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