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Diamino-tert-butylphosphine. Ц Synthesis and Conversion into N-Silylated Aminophosphine Imines with Non-equivalent Replaceability of the Hydrogen Atoms

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[2] Th. Kauffmann, J . Albrecht, D. Berger, and J. Legler, Angew.
Chem. 79,620 (1967); Angew. Chem. internat. Edit. 6,633 (1967).
[3] Th. Kauffmann, G. Beissner, E. Koppelmann, D. Kuhlmann,
A . Schott, and H . Schrecken, Angew. Chem. 80, 117 (1968);
Angew. Chem. internat. Edit. 7, 131 (1968).
[4] Th. Kauffmann, D. Kuhlmann, W. Sahm, and H . Schrecken,
Angew. Chem. 80,566 (1968); Angew. Chem. internat. Edit. 7,541
(1968).
[S] L. Claisen, Ber. dtsch. chem. Ges. 38, 697 (1905).
161 It is considered unnecessary to formulate the individual
metal compounds realistically here. Yields quoted refer to the
metal-free compound brought into reaction.
[7] The dianil (S), which was detected indirectly, was not
isolated.
[8] L. Horner, H . Hoffmann, and V. C. Toscano, Chem. Ber. 95,
536 (1962).
[9] L. Field, J. Amer. chem. SOC.74, 3919 (1952).
73%; ratio racemic:meso-form = cn. l:l), and the product
from 2,3-dimethylquinoxaline (see Table) can be converted
into the pentacyclic compound (2) (yield 25 %) if the dilution
method is used. On the other hand, attempts t o convert the
dehydrodimer of 2,6-dimethylpyridine (see Table) into the
known compound ( 3 ) [31 failed.
Dehydrodimerization of Heteroarylated Alkanes
by Way of Organocopper Compounds
(3)
By Th. Kauffniann, D . Kuhlrnann, W. Sahm, and
H. Srhrecken 1*I
[*I Prof. Dr. Th. Kauffmann, Dipl.-Chem. D. Kuhlmann,
We recently reported the dehydrodimerization of 2-methylpyridine (78 % yield) [21. Analogously the heteroarylated
alkanes listed in the Table can be converted into the corresponding dehydrodimers according to the scheme indicated.
Since the yields are mostly satisfactory this seems t o be a
useful method for preparation of bis(heteroary1)ethanes and
thus of bis(heteroary1)ethylenes and -acetylenes.
?
Ar-CHZ
-[
LiCbH,
?
Ar-CH-Li
] E*
[
]
Ar-hH-Cu
'12
Received: May 14, 1968
[Z 78Gb IE]
German version: Angew. Chem. 80, 566 (1968)
Dipl.-Chem. W. Sahm, and H. Schrecken
Organisch-Chemisches Institut der Universitat
44 Miinster, Gievenbecker Weg 1-7/Orltansring 23 (Germany)
[l] Activation of Organic Compounds by Introduction of Transition Metal Atoms. Part 6. This work was supported by the
Deutsche Forschungsgemeinschaft and by the Fonds der Chemischen Industrie. - Part 5: Th. Kauffmann, C. Beissner, H . Berg,
E. Koppelmann, J . Legler, and M. Schonfelder, Angew. Chem.
80, 565 (1968); Angew. Chem. internat. Edit. 7, 540 (1968).
121 Th. Kaufmann, G. Beissner, E. Koppelmann, D. Kuhlmann,
A . Schott, and H . Schrecken, Angew. Chem. 80, 117 (1968);
Angew. Chem. internat. Edit. 7, 131 (1968).
131 W. Baker, K. M . Buggle, J . F . W. McOmie, and D. A. M .
Watkins, J. chem. SOC.(London) 1958, 3594.
B B
Diamino-teut-butylphosphine.-
Ar-CH-CH-Ar
Synthesis and Conversion into N-Silylated
Aminophosphine Imines with Non-equivalent
Replaceability of the Hydrogen Atoms
-
I
CuHal
Dehydrodimers,
yield ( %)
2-Pyridyl Ial
CuCl
63
65
6-Methyl-2-pyridyl [a]
4-Pyridyl [a]
CuCl(CuBr2)
CuCl
71 (77)
54
40
34
2-Quinolyl [bl
4-Quinolyl [bl
2-Phenyl-4-quinolyl Ib]
3-Methyl-2quinoxalinyl [bl
CuCl(CuBr)
CuCl
CuCl
CuC1(CuBr2)
65
IH
67 (69)
58
74
61 (65)
By 0. J. Scherer and P. Klusmann[*I
AIkyl diaminophosphines and diaminoarylphosphines
have
not been described previously, and phosphorodiamidous
acid derivatives 121 are polymeric substances.
Ammonolysis of tert-butyldichlorophosphine [31 in ether at
-50 "C gives the diamino-tert-butylphosphine ( I ) i n ca. 60%
yield.
[a] Reaction in tetrahrdrofuran/diethyl ether (ca. 1: 1).
[b] Reaction in dimethoxyethane/diethyl ether (ca. I: 1). To obtain a
higher boiling point the diethyl ether was distilled off o n decomposition
of the organocopper compounds.
For preparation of the necessary lithium compounds the
heteroarylated alkanes were treated with 1 to 1.1 molar
equivalents of phenyllithium in the solvents listed, a t -10 t o
0 ° C under Nz. Then 1 molar equivalent of CuCl or CuBrz
was added at -60 to -40°C and the mixture was warmed
slowly to 60 t o 80°C. whereupon the organocopper compounds (brown or red; not isolated) which were formed as
intermediates decomposed with precipitation of elemental
copper or of CuBr according t o whether CuCl or CuBrZ had
been used.
I t is remarkable that the compounds formed by this process
are mostly susceptible t o further reactions of the same type.
For instance, the dehydrodimer of 2-methylpyridine [21 can
be converted into the two isomers of constitution ( I ) (yield
Angew. Chem. internat. Edit. / Vol. 7 (1968) / No. 7
$.
2 NH4Cl
( I ) : colorless crystals, subliming at 75-85 'C/12 torr, extremely sensitive to oxygen and hydrolysis, m.p. 77-79 "C,
readily soluble in ether or benzene. 'H-NMR: J3IPCCH =
12.5 Hz (6NH2, broad signal, observable only o n integration). Treatment of ( I ) with chlorotrimethylsilane gives
tert-butylbis(trimethylsily1amino)phosphine (2) in 70 % yield.
(2): b.p. 51-55 "Cj0.1 torr, J31PCCH = 12.7 Hz, J31PNSiCH
0.75 Hz, very sensitive t o oxygen and hydrolysis, readily
soluble in ether o r benzene. Reaction of compound (2) with
=
54 I
CC14 gives P-tert-butyl-P-chloro-N-(trimethylsily1)-P-(trimethylsily1amino)phosphine imine (3) [41, which with dimethylamine affords compound (4).This can be metalated
by n-butyllithium, affording the lithium amide derivative ( 5 )
in good yield.
+ CCI,
+ z (CH,),NH
C i ,m-Si(CH3)3
P+
N-Si(CH3I3
(CH3l3C
- (CH,)pH
. HC1-
imine ( 9 ) , b.p. 70-74 'C,'O.l torr, m.p. 4-6 OC, is obtained
in 10% yield.
As in metalorganic amidines 161 the non-equivalent trimethylsilyl groups of ( 9 ) appear in the 1H-NMR spectrum at 35 "C
only as a single, broadened signal, which splits into two
signals at ca. -20°C (separation NN 20 I-iz in CDC13; area
ratio 2: 1).
Received: May 8, 1968
[Z 785 IE]
German version: Angew. Chem. 80, 560 (1968)
(3)
[*] Doz. Dr. 0. J. Scherer and P. Klusmann
Institut fur Anorganische Chemie der Universitat
87 Wurzburg, Rontgenring 11 (Germany)
[ l ] Cf. C&P(NHR)2 compounds: A . P . Lane, D . A . MortonBlake, and D. S . Payne, J. chern. SOC.(London) A 1967, 1492.
[2] M . Becke-Goehring and J . Schulze, Chem. Ber. 91, 1188
( 3 ) : b.p. 55-59°C/0.1 torr, m.p. ll-l2OC,
20.4 Hz, yield 70%.
J31PCCH
=
(4): b.p. 54-58 "Cj0.1 torr, m.p. -26 "C,
16.3 Hz, J31PNCH = 9.1 Hz, yield 70%.
31JPCCH
=
( 5 ) : m.p. 137-140 "C, sublimes at 190-200°C/0.1 torr,
J31PCCH = 14.9 Hz, J31PNCH = 8.8 Hz.
methylsilyl signals appear (separation ca. 9 Hz), which combine to a single one on warming or on addition of ca. 5 mg of
methanol (alcoholysis is observable only at higher concentration). This finding is best interpreted by assuming that in (4)
transfer of the proton (that becomes stationary on strong
dilution) is effected ( a ) intermolecularly within one molecule
[cf. formula (7); in the IR spectrum, (4)gives no indication
(strong dilution) of bonding by fixed hydrogen bridges] and
( b ) by the alcohol molecule as in ( 6 ) .
I
Si(CH313
(6)
&(CH3)3
In contrast to the monomeric ( 4 ) , the "lithium sak" ( 5 ) .
which is readily soluble in ether, CC14, or benzene, is dimeric
in the last-mentioned solvent (cryoscopic determination).
The IH-NMR spectrum of (5) shows only one sharp signal
for the trimethylsilyl groups (even on strong dilution). These
facts are best accounted for by the suggested formula (7).
Attempts to convert ( 3 ) into a "phosphine diimine" by
elimination of HCI and to substitute ( 5 ) by chlorotrimethylsilane were unsuccessful.
If impure dimethylbis[(trimethylsilyl)amino]phosphine (8J151
[prepared from ((CH3)sSi)zNNa and (CH&PCI] is treated
with trimethylsilyl azide, the thrice-silylated aminophosphine
(1958).
[3] W. Voskuil and J . F. Arens, Recueil Trav. chim. Pays-Bas 82,
302 (1963).
[4] ( C ~ H S ) ~ P [ = N S ~ ( C ~ H ~ ) ~ ] [ N H S ~the
( C ~first
H ~ )represent~],
ative of this class, was prepared from (C6H&PH and
(C&s),SiN3: K . L. Paciorek and R . H. Kratzer, J . org. Chemistry 31, 2426 (1966). No indication of proton transfer was
reported.
Preparation of Single Crystals of Chromium
Thiospinels by Means of Transport Reactions
By H . D . Lutz and Cs. von Lovdsz[*1
Nitsche et al. 111 prepared single crystals of thiospinels - in
particular of indium and gallium thiospinels - by using
iodine as transport agent in transport reactions. Single crystals of chromium thiospinel, which we required for electrical
studies of thiospinel semiconductors 121, cannot be prepared
in this way since, in contrast to chromium chloride, chromium
sulfides are not transported by halogens - apparently the
entropy of reaction of the corresponding gas-phase reaction
is negative.
Chromium sulfides and chromium thiospinels can, however,
be transported by anhydrous aluminum chloride:
+
Cr2SqS) 4 AIC13(,)
4 AlCI(,)
t 2 CrC1qg)
+ 312 S2fg)
We obtained the following chromium thiospinels as black
octahedra (sides of length 1 mm) as well as various modifications of chromium sulfide such as Cr2S3 as hexagonal
leaflets of 10 mm size:
MnCrzS4 1000+900 "C
ZnCrzS4 1000+850 "C
CdCr2S4 1000+800 "C
FeCr2S4, CoCrzS4, CuCr2S4. and HgCrzS4 could not be
transported by AIC13.
2 g of the substance was transferred, together with 0.2 g of
anhydrous AICl3, to a 10 cm long, evacuated quartz ampoule
in a dry box and then heated for about 80 hours in a temperature gradient oven.
Received: May 20, 1968
[Z 788 IE]
German version: Angew. Chem 80, 562 (1968)
[*I Priv.-Doz. Dr. H. D. Lutz and Dip].-Chem. Cs. v. Lovasz
lnstitut fur Anorganische Chemie der Universitat
5 Koln, Ziilpicher Strasse 47 (Germany)
[l] R. Nitsche, Physics Chem. Solids 17, 163 (1960); J. A. Beun,
R. Nitsche, and M . Lichtensteiger, Physica 26, 647 (1960).
[2] H. D . Lutz and K . Grendel, Z. anorg. allg. Chem. 337, 30
ii(CH3)~
542
(1965).
Angew. Chem. internat. Edit. 1 Vol. 7 (1968) 1 No. 7
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hydrogen, imine, non, silylated, tert, equivalence, synthesis, replaceability, butylphosphinic, atom, conversion, diamine, aminophosphine
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