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Oxidation of Amines with Benzyl(triethyl)ammonium Permanganate.

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Oxidation of Amines with Benzyl(triethy1)ammonium
Permanganate
By H.-Jiirgen Schmidt and Hans J. Schaferr["
Dedicated to Professor Wilhelm Klemm on the occasion
of his 85th birthday
Tertiary amines can be heterogeneously oxidized with potassium permanganate only with difficulty, and even then to
a mixture of products of little preparative use[']. In contrast,
the homogeneous oxidation with benzyl(triethy1)ammonium
permanganate in dichloromethane affords an N,N-dialkylamide as single product in high yield. In the case of secondary and primary amines the oxidation is less selective (see
Table 1).
Table 1. Products of the oxidation of amines with benzyl(triethyl)ammonium
permanganate
[%I)
Amine [a]
Oxidation products (yield isolated
n-Decylamine [b]
Decanonitrile ( 1 I). decanamide (6). decanoic N-decylamide (35)
Decanonitrile (54). decanamide (13). N-decylformamide
(4). decanoic N-decylamide (IS), decanoic acid (10) [d]
Butyric N-butylamide (44),methylene dibutyrate (14).
butyric acid (30) [el
Octanoic N-octylamide (49). methylene dioctanoate ( 1 1 ).
octanoic acid (20) [fl
N-Benzylbenzamide (36), dibenzamide (6). benzamide
(20), benzaldehyde (7). benzoic acid (25)
N-Methylbenzamide (36). benzaldehyde (33), benzoic
acid (27)
N-Phenylformamide ( < 10)
N-Phenylacetamide ( < 10)
N,N-Dibutylbutyramide (93), butyric acid (5)
N-Methyl-N-phenylformamide(78)
n-Decylamine [c]
Di(n-butyl)amine
Di(n-octyl)amine
Dibenzylamine
N-Methylbenzylamine
N-Methylaniline
N-Ethylaniline
Tributylamine
N,N-Dimethylaniline
N, N-Diethylaniline
N,N-Dimethyldodecylamine
N-Methy1-N.Ndioctylamine
N,N-Dimethylbenzy lamine
N-Ethylpiperidine
N-Ethyl-N-phenylacetamide (63)
N,N-Dimethyldodecanoylamide (30). N-dodecyl-N-methylformamide (42)
N-Methyl-N-octyl-octanoylamide(51 ), N,N-dioctylformamide (21)
N,N-Dimethylbenzamide (70). N-benzyl-N-methylformamide (7). benzaldehyde (3). benzoic acid (14)
I -Ethyi-2-piperidone (72). N-acetylpiperidine ( I 3)
[a] General reaction conditions: 5 mmol amine, 10 mmol benzyl(triethyl)ammonium permanganate in 75 cm' dichloromethane. 0.5 to 2 d at 0 to 40 "C: isolation
of the product HPLC separation. [b] At 20°C and I equiv. benzyl(triethy1)ammonium permanganate. [cl At 40 "C and 2 equiv. benzyl(triethy1)ammonium
permanganate [d] Additional lower homologs. [el Mixture of 80% C - , 2016 C,acids. [q Mixture of 7516 C8-, 20% C7-, and 5% C,-acids.
The formation of the products can be explained (in part
analogously to I*]) according to Scheme 1.
The amine ( 1 ) is oxidized with permanganate to (2) or (3).
For example, n-decylamine reacts (i) via (2) to give the imine
(5), which with decylamine and after secondary oxidation
yields decanoic N-decylamide, or (ii) via (3) to give the nitrile
(6); under milder reaction conditions the former pathway
predominates, on more rapid oxidation the latter. Secondary
amines furnish the amides (4) in yields between 35-50%.
Side reactions are markedly reduced in comparison to the
oxidation of primary amines; secondary amines give carboxylic acids and esters, presumably by oxidation of the imine
(5). Tertiary amines afford the amides (4) in 75-98% yield,
practically without formation of byproducts. The different
CH bonds react with about the following chemoselectivities:
benzyl: CH2:CH3= 24: 2: 1.
[*] Prof. Dr. H. J. Schafer, DiplLChem. H.-J. Schmidt
Organisch-Chemisches Institut der Universitat
Orleans-Ring 23, D-4400 Mhnster (Germany)
Angew. Chem. Inf. Ed. Engl. 20 (19x1) No. I
R
=
Phenyl, Alkyl;
R-CII-:KR'
R-C E N
(5)
16)
H'= H , A l k y l ; Y
= H , RiIn03H0
Scheme I .
There are only few preparatively useful methods for the
conversion of secondary and tertiary amines into amides. NMethylamines form formamides on oxidation with oxygen
on platinumf31;N-methylanilines are oxidized with manganese dioxide to N-phenylformamides, while in anilines with
longer-chain alkyl groups one residue is decomposed to
formamidef41.Other oxidizing agents such as benzoyl peroxide15], bromineC6J, N-bromosuc~inimide~~]
lead, similarly to
aqueous permanganate solutionl2l, to aldehydes. Benzyl(triethy1)ammonium permanganate extends these possibilities,
in particular, to the oxidation of tertiary amines.
Received: July 9, 1980 12 670b lE]
German version: Angew. Chem. 93. 124 (1981)
CAS Registry numbers:
Decylamine, 2016-57-1; di(n-butyl)amine. I 1 1-92-2; di(n-octy1)amine. 1120-48-5,
dibenzylamine, 103-49-1; N-methylbenzylamine. 103-67-3; N-methyl-N-ethylaniline, 613-97-8; tributylamine, 102-82-9; N,N-dimethylaniline, 121-69-7, N,Ndiethylaniline, 91-66-7; N,N-dimethyldodecylamine,11 2-18-5; N-methy1-N.Ndioctylamine, 4455-26-9 N,N-dimethylbenzylamine, 103-83-3; N-ethylpiperidine, 766-09-6; decanonitrile, 1975-78-6; decanoamide, 2319.29-1; decanoic-Ndecylamide, 33598-69-5; N-decylformamide. 424 14-94-8; decanoic acid. 334-485; butyro-N-butylamide. 10264-16-1; methylene dibutyrate. 55696-44-I ; butyric
acid. 107-92-6; octanoic-N-octylamide, 42886-89-5; methylene dioctanoate,
76058-01-0; octanoic acid, 112-05-0; N-benzylbenzamide. 1485-70-7; dibenzamide, 614-28-8; benzamide, 55-21-0; benzaldehyde, 100-52-7, benzoic acid. 65-850; N-methylbenzamide, 61 3-93-4; N-phenylformamide, 103-70-8; N-phenylacetamide. 103-84-4, N,N-dibutylhutyramide, 14287-95-7; N-methyl-N-phenylformamide. 93-61 -8; N-ethyl-N-phenylacetamide,5461-49-4; N,N-dimethyldodecanoylamide, 3007-53-2; N-dodecyl-N-methylformamide,76058-02-1: N-methylN-octyloctanoylamide, 76058-03-2; N,N-dioctylformamide, 6280.57-5: N,N-dimethylbenzamide, 61 1-74-5: N-benzyl-N-methylformamide,
17105-71-4; 1 -ethyl2-piperidone. 4789-07-5; N-acetylpiperidine, 61 8-42-8. benzyl(triethy1)ammonium permanganate, 68844-25-7
( I ] H. Shechrer. S. S. Rawalay, J. Am. Chem. SOC.86, 1706 (1964).
121 H. Shechler, S. S. Rawalay. M. Tubis. J. Am. Chem. SOC.86, 1701 (1964); M.M. Wei, R. Stewart, ibid. 88, 1974 (1966); S. S. Rawalay. H. Shechter. J . Org.
Chem. 32. 3129 (1967).
[3] G. T. Davis, D. H. Rosenblart. Tetrahedron Lett. 1968. 4085
141 H. E. Henbest, A. Thomas, J Chem. SOC.1957, 3032.
[ S ] D. Buckley. S. Dunsran, H. B Henbest. J. Chem. SOC.1957, 4901.
161 N . C Deno, R. E. Fruit, Jr., J . Am. Chem. SOC.YO. 3502 (1968).
[7] S. Dunstan, H. B. Henbest, J. Chem. SOC.IY57. 4905.
Topotactic Electron/Proton Transfer Reactions
of Transition Metal Complexes with Columnar and
Cluster Structures
By Robert Schollhorn, Klaus Wagner, and Hermann Jonke[*'
Considerable work has been devoted in recent years to the
investigation of reversible topotactic redox reactions, at ambient temperature, of electronically conducting solids with
layer, chain and framework structures of the host lattice ma[*] Prof. Dr. R. Schollhorn, K. Wagner. H. Jonke
Anorganisch-chemisches Institut der Universitat
Gievenbecker Weg 9, D-4400 Munster (Germany)
0 Verlag Chemie, GmbH, 6940 Weinheim. 1981
0570-0833/81/0101-0109
$ 02.50/0
109
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oxidation, benzyl, triethyl, permanganate, ammonium, amines
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