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Butadienedimethylaluminate Complexes.

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New Synthesis of Derivatives of Isoquinoline and
By Dr. G. Simchen
Institut fur Organische Chemie und Organisch-Chemische
Technologie der Technischen Hochschule Stuttgart
When o-cyanomethylbenzoic acid ( I ) is treated with phosphorus pentachloride, 3-chloro-1-isoquinolinol(2) is at
once obtained. If the reaction is carried out with 2 moles of
phosphorus pentachloride in phosphorus oxide chloride as
solvent, 1,3-dichloroisoquinoline(3) is formed by chlorination of the intermediate (2).
vacuum, and the solid residue is taken up in benzene and
precipitated with light petroleum. Yield: 7.8 g (92 %), m.p.
104-106 OC.
A solution of 0.7 g (0.0035 mole) of o-thiocyanatobenzoyl
chloride in 3 ml of dibutyl ether is treated with a saturated
solution of HC1 in diethyl ether. The mixture is heated for
4 hr at 6OoC. The product crystallizes on cooling. Yield:
0.5 g (71 %), m.p. 115-117°C.
Received: February 17th. 1966
[Z 164/996 IE]
German version: Angew. Chem. 78, 614 (1966)
Publication delayed at the author's request
[l] M . Rensonand J. L. Pietfe,Bull. SOC.chim. belges 73,507 (1964).
[21 E. Allensrein and P.Quis, Chem. Ber. 97, 3162 (1964).
[3] F. Kluges and W. Grill, Liebigs Ann. Chem. 594, 21 (1955).
[4] S. Gabriel, Ber. dtsch. chem. Ges. 19, 2354 (1886).
Butadienedimethylaluinate Complexes
By Dr. H. Lehmkuhl
2 POC1,
2 HC1
In order to determine the course of reaction we treated othiocyanatobenzoic acid (4) with phosphorus pentachloride
under mild conditions. The o-thiocyanatobenzoyl chloride
first formed then was cyclized to 2-chloro-1,3-benzothiazin-4-one (6) in the presence of hydrogen chloride a t
60 "C. However, cyclization does not occur in the absence of
hydrogen chloride. It seems to follow that cyclization of ocyanocarbonyl chlorides depends on acylation of the unstable imide chlorides formed as intermediates [2,31.
Max-Planck-Institut fur Kohlenforschung,
Mulheim/Ruhr (Germany)
Butadiene and its homologues react with alkali metals (M =
Li or Na) with formation of salts Mz@[C4H6]20, which
immediately add further diolefin stepwise [I]. The butadiene
dianion can be trapped as 2-butene by sufficiently acidic
reagents, e.g. N-methylaniline.
On reaction of butadiene with alkali metal in an ether
[(CH&O, THF, (C2Hs)zOI in the presence of an amount
of trimethylaluminurn-ether adduct equivalent to the metal,
the butadiene dianion C4Hs2@probably forms an adduct ( I )
with the dimethylaluminum cation present in the dissociationequilibrium mixture from trimethylaluminum [?-,31. Suitable
reaction conditions are alkali metal: Al(CH3)3:C4Hs = 2:2: 1,
-30 to +2OoC.
3-Chloro-l-isoquinolinol(q) [41
6.8 g (0.033 mole) of Pc15 is added to 4.8 g (0.03 mole) of
o-cyanomethylbenzoic acid in 25 ml of methylene chloride
and the mixture is stirred for 2-3 hr first at O°C and then
at room temperature, then kept overnight. The methylene
chloride is distilled off and the residue recrystallized from
water. Yield: 5.0 g (94 %), m.p. 218 "C.
1,3-Dichloroisoquinoline(3) [41
A solution of 42.0 g (0.20 mole) of PCls in 80 ml of POC13
is treated slowly with 16.1 g (0.1 mole) of o-cyanomethylbenzoic acid. The mixture is stirred for 2 hr at room temperature and 2 hr at the boiling point. The POC13 is distilled off
at atmospheric pressure and the residue recrystallized from
alcohol. Yield: 18.5 g (94 %), m.p. 120°C.
o-Thiocyanatobenzoyl chloride (5)
T o a slurry of 7.7 g (0.043 mole) of o-thiocyanatobenzoic
acid in 50 ml of CCl4, is added 9.0 g (0.043 mole) of PC15 and
the mixture is stirred for 2 hr at 0 "C and 6 hr at room temperature. The Cc14 and the POc13 formed are distilled off in a
Angew. Chem. internat. Edit.
i Vol. 5 (1966) / No. 7
This complex formation protects the dianion C4H628 from
further reaction with butadiene. When the experiment is
conducted in tetrahydrofuran with Li or Na, the product ( I )
is precipitated as large colorless crystals and can be purified
by recrystallization from a small quantity of THF. The alkali
tetramethylaluminate (2) formed in equivalent amount can
be isolated by distillation of the solvent from the first filtrate,
finally at 100°C/10-3 mm. The reaction with butadiene
derivatives resembles the formation of alkali metal naphthalenedialkylaluminate and tetraalkylaluminate from alkali
metal, naphthalene, and trialkylaluminum in ethers [41.
The compound ( I ) . 4 T H F readily loses 3 moles of T H F in
vacuum (10-3 mm); a t 90°C under the same sonditions all
the bound T H F is lost. Compound ( I ) is insoluble in aliphatic hydrocarbons and benzene; it decomposes above
15OoC without melting. Its infrared spectrum includes a
sharp C = C stretching band at 1580 cm-1, this being at longer
wavelength than for butadiene (1597 cm-1) and indicating a
strongly polarized double bond. The 1H-NMR spectrum of a
solution of ( I ) in T H F renders the proposed structure very
probablersl: it contains a well resolved triplet at T = 4.86 for
the two olefinic protions (a), a moderately split doublet at
T = 9.46 for the CH2 protons (b) (intensity ratio a : b = 2: 3.9),
and a singlet at T = 11.21 for the CH3 protons (c) (intensity
6.5). For the analogous compounds to ( I ) from 2,3-dimethyl1,3-butadiene the signal for (b) changes to a singlet at T = 9.81
[Si(CH3)4 as internal standard: T = 101.
Preparation of Bis(dialkylcarbamoy1)mercury
Compounds by Carbonylation in Amines
The bonds[*] between the dianion C4H629 and the
[(CH3)2AI]@cation are very reactive; o n oxidation with dry
0 2 they are preponderatingly attacked before the Al-CH3
bonds, butadiene being regenerated :
1/2 0 2
By Prof. U. Schollkopf and F. Gerhart
+ [:O+Al(CH3)2]@Na@
Organisch-Chemisches Institut
der Universitat Gottingen (Germany)
The structure of the oxidation product ( 3 ) has not been
conclusively elucidated. On alcoholysis of the N a compound
( I ) , I-butene and at most 1 to 4 % of 2-butene are formed
alongside methane; the proportion of 2-butene rises to 15 %
for the Li compound. Hoberg"J has recently reported an
Although carbamoylmetal compounds containing a-bonded
carbonyl groups may play a decisive role in metal-catalysed
carbonylation of amines [I], it has hitherto not been possible
to isolate such compounds 121. We have now found that stable
6.72 (s), 6.10 (s)
6.29, (4). 6.58 (4)
6.83,6.98,7.17,7.22, 5.12,
5.26, 5.40, 5.43 (each s)
6.20, (t), 6.62 (t)
6.26 (t), 6.47 (t)
6.26 (m), 6.38 (m)
allylic rearrangement of aluminum compounds of the type
to RR"Al-CHR-CH=CHz;
a n apparently analogous rearrangement by way of (4a) and
(46) evidently occurs o n alcoholysis of compounds ( I ) :
bis(dialkylcarbamoy1)mercury compounds (see table) are
formed in accordance with Equation (a) when mercury(I1)
acetate and a tenfold amount (by weight) of a secondary
amine are shaken with carbon monoxide for several days
at room temperature. The excess of amine is removed in a
vacuum and the residue is crystallized from benzene, ether,
or tetrahydrofuran.
R'RZNH+ Hg(0Ac)z
-NR1R2+ 2 HOAC
The bis(dialkylcarbamoy1) structure and a-bonded carbon
monoxide are indicated by the result of the bromine cleavage
(see below), by the carbonyl infrared bands, and by the
N M R signals of the N-CH-protons (see table).
The compounds are stable towards concentrated sulfuric
acid but decompose in dilute mineral acids:
The following considerations are also in favor of a reaction
via (la) and (4b) :
(a) On the basis of structure ( I ) (which is strongly indicated
by the N M R spectra), only I-butene can be formed if a
rearrangement intervenes o n hydrolysis. 2-Butene does not
rearrange to I-butene under the reaction conditions.
(b) Hydrolysis of compounds ( I ) with D 2 0 affords
CHZ=CH-CHD-CH~D. The CHzD group can be identified
mass-spectroscopically, and the C H D group infraredspectroscopically. The N M R spectrum confirms the appearance of [3,4-D&l-butene.
Received: March 22nd, 1966
[Z 191/26 IE]
German version: Angew. Chem. 78, 675 (1966)
[l] K. Ziegler, L. Jakob, H. Wollthan, and A . Wenz, Liebigs Ann.
Chem. 511, 64 (1934).
[2] E. Bonitz, Chem. Ber. 88, 742 (1955); Angew. Chem. 67, 525
[3]H. Lehmkuh1andH.D. Kobs,Tetrahedron Letters29,2505(1965).
[4] H. Lehmkuhl, Angew. Chem. 77, 623 (1965), Angew. Chem.
internat. Edit. 4, 600 (1965).
[5]WethankDr. E.G.Hoffmannfordeterminingthe NMRspectrum.
[*I The ionic structure seems justified because groups R (e.g.
CH3) that certainly are covalently bound to Al react with insertion of oxygen, yielding >AI-O-R, and, on the other hand,
compounds such as naphthalenesodium that are certainly to be
formulated as ionic are cleaved by oxygen with regeneration of
the original hydrocarbon.
[6] H. Hoberg, Angew. Chem. 78, 492 (1966), Angew. Chem.
internat. Edit. 5 , 513 (1966).
The rate of decomposition (TI/*) depends o n the nucleophilicity of the anion. Thus if RI=RZ=CzHs (0.03 M ; p H
4.75), ~ 1 1 2in the presence of 0.56 M CIQ, BrO, or 1 0 ions
amounts to 26, 4.2, and 0.4 min, respectively.
As shown by experiments with bis(dimethylcarbamoyI)mercury and bis(diethylcarbamoyl)mercury, the amino or
carbamoyl group can be transferred to other atoms. For
instance, with acetyl chloride we obtained N,N-diethylacetamide (59 %), with benzyl chloride, N,N-dimethylbenzylamine (23 %), and with bromine, N,N-diethylcarbamoyl bromide (72 %) 131.
Received: April 26th, 1966
[Z 209 IE]
German version: Angew. Chem. 78, 675 (1966)
[I] H. W. Sternberg and I. Wender, International Conference on
Co-ordination Chemistry. Special Publications No. 13, The
Chemical Society, London 1959, p. 35. R . F. Heck: Insertion
Reactions of Metal Complexes, Mechanisms of Inorganic
Rextions. Advances i n Chsmistry Series No. 49, American
Chemical Society, Washington, D.C.. 1955, and literature cited
[2] See, however, the synthesis of R2NCOFe(CO)&H5 from
NaFe(C0)2CSHS and carbamoyl chloride derivatives: R . B. King,
J . Amer. chem. SOC.85, 1918 (1963).
[3] Isolated as tetraethylurea after treatment with diethylamine.
Angew. Chem. internat. Edit.
1 Vol. 5 (I966) 1 No. 7
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butadienedimethylaluminate, complexes
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