Migration of methyl groups between aliphatic amines in water

Journal of the American Chemical Society

Volumn 125, Issue 2, 2003, Pages 310-311

  Callahan, Brian P ^a   Wolfenden, Richard ^a  

^a UNIVERSITY OF NORTH CAROLINA SCHOOL OF MEDICINE   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALIPHATIC AMINE; METHYL GROUP; SULFONIUM DERIVATIVE; TETRAMETHYLAMMONIUM; WATER;

AQUEOUS SOLUTION; ARTICLE; CHEMICAL REACTION KINETICS; DECARBOXYLATION; PH; REACTION ANALYSIS;

AMINES; DIMETHYLAMINES; KINETICS; METHYLATION; QUATERNARY AMMONIUM COMPOUNDS; WATER;

EID: 0037438506     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja021212u     Document Type: Article

References (20)

1. Snider, M. J.; Wolfenden, R. J. Am. Chem. Soc. 2000, 122, 11507.
2. Under driving conditions, in the absence of water, Raney nickel catalyzes alkyl transfer between primary amines at temperatures between 130 and 200 °C (Winans, C. F.; Adkins, H. T. J. Am. Chem. Soc. 1932, 54, 306), and the anion of benzylamine displaces ammonia from neat benzylamine at 88 °C (Baltzly, R.; Blackman, S. W. J. Org. Chem. 1963, 28, 2405).
3. Under driving conditions, in the absence of water, Raney nickel catalyzes alkyl transfer between primary amines at temperatures between 130 and 200 °C (Winans, C. F.; Adkins, H. T. J. Am. Chem. Soc. 1932, 54, 306), and the anion of benzylamine displaces ammonia from neat benzylamine at 88 °C (Baltzly, R.; Blackman, S. W. J. Org. Chem. 1963, 28, 2405).
4. The horizontal coordinate of Figure 1, b and c, shows pH values determined at room temperature with a glass electrode. The theoretical lines in Figure 1 are based on the fraction of titratable amine that was present in protonated format the outset of the experiment. In no case did the pH value of the reaction mixture, measured at room temperature before and after the reaction, change by more than 0.4 units during the interval over which the initial rate of reaction was determined.
5. Swain, C. G.; Kuh, D. A.; Schowen, R. L. J. Am. Chem. Soc. 1965, 87, 1553.
6. Mihel, I.; Knipe, R. G.; Coward, J. K.; Schowen, R. L. J. Am. Chem. Soc. 1979, 101, 4349.
7. For a discussion of methyl transfer in larger ring systems, see King, J. F.; McGarrity, M. J. J. Chem. Soc., Chem. Commum. 1982, 175.
8. Wolfenden, R.; Snider, M. J. Acc. Chem. Res, 2001, 34, 938.
9. Tang, K.-C.; Pegg, A. E.; Coward, J. K. Biochem. Biophys. Res. Commun. 1980, 96, 1371.
10. Craig, S. L.; Brauman, J. I. J. Am. Chem. Soc. 1999, 121, 6690. In the biosynthesis of methionine, the methyl donor may be either betaine (Garrow, T. A. J. Biol. Chem. 1996, 271, 41)
11. 5-tetrahydrofolate (for a recent review, see Matthews, R. G. Acc. Chem. Res. 2001 34, 681).
12. 5-tetrahydrofolate (for a recent review, see Matthews, R. G. Acc. Chem. Res. 2001 34, 681).
13. Cantoni, G. Annu. Rev. Biochem. 1975, 44, 435.
14. For reactions of the trimethylsulfonium ion with trimethylamine see Hughes, E. D.; Wittingham, D. J. J. Chem. Soc. 1960, 806; with oxygen nucleophiles see: Swain, C. G.; Taylor, L. J. J. Am. Chem. Soc. 1962, 84, 2456; Coward, J. K.; Sweet, W. D. J. Org. Chem. 1971, 36, 2337; Knipe, J. A.; Coward, J. K. J. Am. Chem. Soc. 1979, 101, 4339).
15. For reactions of the trimethylsulfonium ion with trimethylamine see Hughes, E. D.; Wittingham, D. J. J. Chem. Soc. 1960, 806; with oxygen nucleophiles see: Swain, C. G.; Taylor, L. J. J. Am. Chem. Soc. 1962, 84, 2456; Coward, J. K.; Sweet, W. D. J. Org. Chem. 1971, 36, 2337; Knipe, J. A.; Coward, J. K. J. Am. Chem. Soc. 1979, 101, 4339).
16. For reactions of the trimethylsulfonium ion with trimethylamine see Hughes, E. D.; Wittingham, D. J. J. Chem. Soc. 1960, 806; with oxygen nucleophiles see: Swain, C. G.; Taylor, L. J. J. Am. Chem. Soc. 1962, 84, 2456; Coward, J. K.; Sweet, W. D. J. Org. Chem. 1971, 36, 2337; Knipe, J. A.; Coward, J. K. J. Am. Chem. Soc. 1979, 101, 4339).
17. For reactions of the trimethylsulfonium ion with trimethylamine see Hughes, E. D.; Wittingham, D. J. J. Chem. Soc. 1960, 806; with oxygen nucleophiles see: Swain, C. G.; Taylor, L. J. J. Am. Chem. Soc. 1962, 84, 2456; Coward, J. K.; Sweet, W. D. J. Org. Chem. 1971, 36, 2337; Knipe, J. A.; Coward, J. K. J. Am. Chem. Soc. 1979, 101, 4339).
18. m value of histamine reported for guinea pig histamine N-methyltransferase (Brown, D. D.; Tomchick, R.; Axelrod, J. J. Biol. Chem. 1959, 234, 2948) and a molecular mass of 29 000 reported for the monomeric enzyme (Matuzewska, B.; Borchardt, R. T. J. Neurochem. 1983, 271, 37, 22831), assuming that the monomer contains a single active site.
19. m value of histamine reported for guinea pig histamine N-methyltransferase (Brown, D. D.; Tomchick, R.; Axelrod, J. J. Biol. Chem. 1959, 234, 2948) and a molecular mass of 29 000 reported for the monomeric enzyme (Matuzewska, B.; Borchardt, R. T. J. Neurochem. 1983, 271, 37, 22831), assuming that the monomer contains a single active site.
20. It may be worth noting that the rate enhancement produced by histamine N-methyltransferase is similar, both numerically and in its detailed thermodynamic origins, to the rate enhancement produced by yeast hexokinase, whose action is probably based on similar principles (Sigmon, K. A.; Wolfenden, R., unpublished observations).