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Dimerization of Oxaallyl Azaallyl Oxaphosphaallyl and Oxathiaallyl Groups by Way of Organocopper Compounds.

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(S)-(-)-a-Methylbenzylamine
(S)-(-)-a-Methylbenzylamine
(R)-(+)-a-Methylbenzylamine
(S)-(-)-2-Methylbutan-l-ol
(S)-Ethyl (-)-lactate
(R)-Dibutyl (+)-tartrate
+ AgNOl
+ AgNO,
I
170
80
80
10.002
+0.039
-0.057
0.002
-0.040
+0.082
*
120
145
170
Dehydrodimerization of heteroarylated alkanes [41 is a
particular case of this reaction principle.
Continuing these investigations we have now observed dimerization of the I-oxaallyl group on treatment of (2) [5,61
with one molar equivalent of CuCl in ether at 35°C. The
yield of dimerization product (3) of only 11% for this case increases to 42% if the I-azaallyl compound ( 4 ) is used and
dimerization (treatment with CuI in ether at 35 "C) is followed
by hydrolysis with 2 N HCl[71; compound ( 4 ) is formed by
the action of NaNHz on acetophenone anil in ether at 35 "C.
Yields are still better [52% for (7), 84% for (9)l in the
analogous reaction (treatment with CuCl at -60 t o +20 "C,
then with 0 2 at 20-65°C; solvent tetrahydrofuran) of ( 6 )
and (8), which were obtained on treatment of the corresponding ketazines with lithium diisopropylamide in tetrahydrofuran at 10 ' C . The dehydrodimerization of ketazines
thus disclosed may open a convenient route t o long-chain
azapolyenes.
(2), X = 0; A = N a
(4), X = N-C6H5; A = N a
(6), X
(3).
(7), X = N - N = C (C,H,)CH,
( 9 ) , X = N-N=C(C6H5),
= N-N=C (C,H,)CH3;
A = Li
(8). X
A
[*] Prof. Dr. W. Kirmse and Dip1.-Chem. H. Arold
Institut fur Organische Chemie der Universitat
355 Marburg, Bahnhofstr. 7 (Germany)
[l] W. Kirnise and G . Wachtershauser,Tetrahedron 22,73 (1966).
[2] W. Kirmse and K . Horn, Chem. Ber. 100, 2698 (1967).
I31 W . Kirmse, H. D. Y . Scholz, and H . AroZd, Liebigs Ann.
Chem. 711, 22 (1968).
[4] Prepared from the lithium salt of 2-ethylbutanal tosylhydrazone, m.p. 104 "C,by dry pyrolysis in a vacuum at 80-125 "C [ 5 ] .
[ S ] G. M . Kaufman, J. A . Smith, G . G. van der Strouw, and H .
Shechter, J. Amer. chem. SOC.87,935 (1965).
[6] W . v. E. Doering and W . Kirmse, Tetrahedron 11,272 (1960).
[7] 2-Methyl-1-diazobutane is not suitable for series of experiments because of its poor accessibility and the difficulty of separating its reaction products; cf. W. Kirmse and G . Wachtershauser,
Tetrahedron 22, 63 (1966).
[ 8 ] For similar results on carbenoid addition of diazoacetic ester
to styrene see H . Nozaki, S . Moriuti, H . Takaya, and R. Noyori,
Tetrahedron Letters 1966, 5239.
Dimerization of Oxaallyl, Azaallyl, Oxaphosphaallyl, and Oxathiaallyl Groups by Way of
Organocopper Compounds111
x=0
(
j
)
,X = N-CcHs
= N-N=C(C~HS)Z;
=
Li
The I-oxa-2-phosphaailyl group of (ZU) 181 can be dimerized.
giving (11) (4373, by treatment with 1 molar equivalent of
CuCl at -40 t o +20 "C in tetrahydrofuran and subsequently
with 0 2 at 20 "C.
0
(C6H5)2(
A'
CH2
-
0
(CIZH5)2(
%
/p (C6H5) 2
CHz-CHz
(10)
(11)
The I-oxa-2-thiaallyl group of compound (12) [9J,whicharises
o n reaction of phenylmagnesium bromide with methyl
phenyl sulfone in benzene at 2OOC. was dimerized on
treatment with 1 molar equivalent of CuCl at -68 t o +20 'C
in ether/benzene/tetrahydrofuran (ca. 1:3:4), yielding (13)
(20-25 %).
C6H5\
C6H5,
S"
0" 'CH:
M g B r -+
S
/p
o+ ,C6H5
/
S\
0' \ C H ~ - C H ~o
Surprisingly, the 2-azaallyl group of (14), which can be dimerized by use of CuI131, was cyclized on treatment with
1 molar equivalent of CuBrz in ether at 35 "C, affording (15)
in 18 % yield (presumably not optimal).
By Th. Kauffmann, G. Beissner, H. Berg, E . Koppelmann,
J. Legler, and M. Schonfelder [*I
Compounds of type ( I ) are formally derived from allyl compounds by replacement of allyl-carbon atoms by hetero
atoms and may thus b e termed heteroaliyl compounds. In
several cases they can be dehydrodimerized in accord with
the following scheme [ 2 , 3 ] :
Received: May 14, 1968
[Z 786a IE]
German version: Angew. Chem. 80, 565 (1968)
[*] Prof. Dr. Th. Kauffmann, Dip1.-Chem. G. Beissner, H. Berg,
1
(A = alkali metal; Cu = CuI or CuII)
E. Koppelmann, Dip1.-Chem. J. Legler, and Dip1.-Chem.
M. Schonfelder
Organisch-Chemisches Institut der Universitat
44 Miinster, Gievenbecker Weg 1 -7/Orleansring 23 (Germany)
[l] Activation of Organic Compounds by Introduction of Transition Metal Atoms. Part 5. This work was supported by the
Deutsche Forschungsgemeinschaft and the Fonds der Chemischen Industrie. - Part 4: Th. Kauffmann and D. Berger, Chem.
Ber., in press.
Angew. Chem. internat. Edit.
Val. 7 (1968)1 No. 7
[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
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organocopper, azaallyl, compounds, dimerization, group, oxathiaallyl, oxaallyl, oxaphosphaallyl, way
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