Patent US40838374
Process for production of allylamines from Pi-allyl palladium complexesAbstract:The present invention provides a process for the production of allylic amines which comprises reacting a pi-allyl palladium complex with ammonia or an amine having a reactive hydrogen attached to the nitrogen atom and a cupric salt, the reaction taking place at a temperature below the decomposition temperature of the complex and in solution in a solvent for the pi-allyl palladium complex.
References Cited:Patent US3584020
Patent US3642902
Patent US3719701
Patent US3855321
Other References:
Akermark et al., "Tetrahedron Letters", No. 43, pp. 3733-3736, (1975).
Kuran et al., "Journal of Organometallic Chemistry", vol. 40, pp. 647-648, (1972).Example 1:This Example describes the effect of a copper salt on the formation of triallylamine by the process of the invention.
Allyl palladium chloride was placed in a reaction vessel provided with means for heating and for the introduction of gases.
15 Ml of dimethylacetamide were then introduced into the reaction vessel which was then pressurized to a pressure of between 6.7 and 9.5 kg/cm.sup.2 of ammonia at the reaction temperature. The reaction was conducted at the temperature indicated for an hour after which the contents of the reaction vessel were analyzed. The results are indicated below in Table I:
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Moles Moles Relative Amounts
CuX.sub.2
C.sub.3 H.sub.5 PdX
(C.sub.3 H.sub.5) .sub.3 N*
Temp. .degree. C.
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0 0.004 C.sub.3 H.sub.5 PdCl
1 100
0.008 CuCl.sub.2
0.002 C.sub.3 H.sub.5 PdCl
71 100
0.008 CuBr.sub.2
0.004 C.sub.3 H.sub.5 PdBr
78 100
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*This column is a measure of the amount of the triallylamine formed in the reaction and hence a measure of the completeness of the reaction. The figure quoted is the height of a chromatogram registering the amount of the triallylamine.
The information presented in the table shows that the addition of cupric chloride or cupric bromide greatly increases the amount of triallylamine registered by the chromatograph and by inference since the tri-allylamine is formed along with diallylamine and monoallylamine, the total amount of allylamine produced.
A similar reaction but of course without the presence of cupric chloride gives a yield of only 28% of triallylamine under comparable conditions.
Example 2: Ammonia (200 Millimoles) was added at 25.degree. C. to a solution of 3.66g (20 millimoles) of pi-allyl palladium chloride and 2.69g (20 millimoles) of cupric chloride in 80 ml of pyridine contained in an autoclave. The mixture was heated at 100.degree. C for 11/4 hours.
A total yield of 61% of allylamines was obtained and of this 7 millimoles (35% of the total) was monoallylamine. Example 3: Example II was repeated with the solvent changed from pyridine to a mixture of N-methylpyrrolidone (45ml) and benzonitrile (35 ml).
The total yield of allylamines was 47%. Example 4: Example III was repeated with the difference that the amount of CuCl.sub.2 was increased to 40 millimoles.
The total yield of allylamines was 75%. Example 5: A flask was charged with 0.92g (5 millimoles) of C.sub.3 H.sub.5 PdCl.sub.2, 1.49g (11 millimoles) CuCl.sub.2 and 11 ml of N-methylpyrrolidone and 9 ml of benzonitrile. After stirring 20 minutes at room temperature, 6.5 ml (75 millimoles) of morpholine were added.
In ten minutes the yield of allylmorpholene was 87%. Examples 6-10: The following Examples show the effect various solvents, all run under similar conditions. An autoclave was charged with 20 millimoles of C.sub.3 H.sub.5 PdCl.sub.2, 40 millimoles cupric chloride and 80 ml of solvent. After charging with ammonia the autoclave was brought to 100.degree. and samples at intervals. "Time zero" is taken to be the time when the autoclave reaches 100.degree.EXAMPLES C. and is in fact several minutes after the reactants were first mixed.
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NH.sub.3 pressure
Yield of total allylamines
Example
solvent kg/cu.sub.2
Time Zero
One Hour
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VI N-methylpyrrolidone
10.6 27% 77%
VII dimethylsulfoxide
11.5 20% 89%
VIII hexamethylphosphoramide
10.9 4% 69%
IX phenylacetontrile
8.08 23% 49%
X dimethylacetamide
10.8 17% 67%
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Examples 11-24: The following Examples show the effect of the addition of ligands to the system. The autoclave was charged with 20 millimoles of C.sub.3 H.sub.5 PdCl.sub.2, 20 millimoles of the ligand, 40 millimoles cupric chloride and 80 ml N-methylpyrrolidone. After charging with NH.sub.3 the reactor was heated to 100.degree.. Sampling was done as in Examples VI to X.
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NH.sub.3 pressure
Yield of total allylamines
Example
Ligand kg/cm.sub.2
Time One Hoar
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I none 10.6 27% 77%
XII triphenylphosphine
11.4 95% same
XIII triphenylphsophine oxide
10.6 10% 78%
XIV DIPHOS* 11.25 76% 68%
XV tributylphosphite
10.6 100% same
XVI tributylphosphate 10.9
14% 80%
XVII triphenylphosphite
9.5 83% 89%
XVIII
triphenylphosphate
10.8 10% 76%
XIX tributylphosphine oxide
11.4 13% 78%
XX triphenylarsine
10.8 66% 55%
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The remaining ligands were used at a level only 1/10 the above (i.e. 2 millimoles)
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XXI triphenylbismarsine
10.7 46% 71%
XXII triphenylbismuthene
10.3 41% 53%
XXIII triphenylstibine 10.9 74% 71%
XXIV tributoxystibene 10.4 34% 80%
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* bis (1,2-diphenylphosphine) ethane
Example 25: A run similar to Example II was made with the temperature at 76.degree. C.
After 4 hours the yield of allylamines was 21%. A similar run made at 164.degree. C. for 20 minutes gave a yield of 64%. These results indicate that the reaction is enhanced by elevated temperatures.