Patai S., Rappoport Z. 1996 The chemistry of functional groups. The chemistry of amino, nitroso, nitro and related groups. Part 2 / 0857 891

19. Rearrangement reactions involving the amino, nitro and nitroso groups 887

HNO2

GC6H4NHNHCOR ! GC6H4N(NO)NHCOR ! GC6H4NHN(NO)COR

SCHEME 18

				N
			O	O
RCONHR′		HNO2

RC

+

NH

R′

		N
	O	O
	NO
RCON	RC
	R′	NR′
	SCHEME 19
R		R	NO
	HNO2
N			+N
H			H
		−H+
R		R	NO
N			N
NO

SCHEME 20

buffers. Under these conditions the nitroso group rearrangement is the rate-limiting step. There is also evidence104 that the nitrosation of nitronic acids to give nitroso introalkanes (pseudonitroles) or nitro oximes (nitrolic acids) also occurs by initial attack at an oxygen atom followed by an O to C rearrangement of the NO group (Scheme 21).

Nitrosation at one site in a molecule (usually the most nucleophilic site) followed by NO rearrangement to give the final stable nitroso compound seems to be quite widespread.

888	D. Lyn H. Williams
	OH		HNO2			O−
+						+
Me2 C N	O−				Me2 C	N
						O

ON

Me2 CNO2

NO

SCHEME 21

Final examples of this report rearrangements from S to N. The diazotisation of amino acids containing the SR group appears to involve initial nitrosation at the very nucleophilic sulphur site, followed by a 1,4-rearrangement of the NO group, finally to give the alcohol product of deamination (Scheme 22)105. Again the evidence here is kinetic, the reaction being ca 100 times faster than the corresponding reaction in the absence of the sulphur group. Similar S to N rearrangements have been proposed in the nitrosation reactions of thioproline106 and thiomorpholine107.

				Me
				+
	CH2 SMe	HNO2		CH2 S
	C		C	NO
	NH2			NH2

CH2 SMe	CH2 SMe
C	C
	+
OH	NH2 NO
	SCHEME 22

A large number of NO group rearrangements can also be brought about photochemically. These are not within the scope of this chapter and are discussed elsewhere in this volume.

VIII. REFERENCES

1.A. W. Murray, in Organic Reaction Mechanisms (Eds. A. C. Knipe and W. E. Watts), Wiley, Chichester, 1993, pp. 437 559 and earlier volumes.

2.L. M. Harwood, Polar Rearrangements, Oxford University Press, Oxford, 1992.

3.C. J. Davies, B. T. Heaton and C. Jacob, J. Chem. Soc., Chem. Commun., 1177 (1995).

4.D. V. Banthorpe, in The Chemistry of the Amino Group (Ed. S. Patai), Wiley-Interscience, London, 1968, pp. 642 649.

5.R. A. Cox and E. Buncel, in The Chemistry of the Hydrazo, Azo and Azoxy Groups (Ed. S. Patai), Wiley, London, 1975, pp. 775 805.

6.H. J. Shine, in Aromatic Rearrangements, Elsevier, New York, 1967, pp. 126 179.

19. Rearrangement reactions involving the amino, nitro and nitroso groups 889

7.D. V. Banthorpe, Top, Carbocyclic Chem., 1, 1 (1969); Chem. Rev., 70, 295 (1970).

8.M. J. S. Dewar, in Molecular Rearrangements, Part 1 (Ed. P. de Mayo), Interscience, New York, 1963, pp. 295 344.

9.H. J. Shine, J. Chem. Educ., 66, 793 (1989).

10.M. J. S. Dewar, The Electronic Theory of Organic Chemistry, Oxford University Press, Oxford, 1949, pp. 233 240.

11.D. V. Banthorpe, E. D. Hughes and C. K. Ingold, J. Chem. Soc., 2864 (1964).

12.L. Melander and W. H. Saunders, Reaction Rates of Isotopic Molecules, Wiley-Interscience, New

York, 1980, p. 124.

13.S. M. Husain, J. McKenna and J. M. McKenna, J. Chem. Res. (S), 280 (1980); J. McKenna,

J.M. McKenna and P. S. Taylor, J. Chem. Res. (S), 281 (1980).

14.P. Paneth, Talanta, 34, 877 (1987); Isot. Org. Chem., 41 (1992).

15.H. Kwart and J. Stanulonis, J. Am. Chem. Soc., 98, 4009 (1976); H. J. Shine, Isot. Org. Chem., 1 (1992).

16.H. J. Shine, J. Phys. Org. Chem., 2, 491 (1989).

17.H. J. Shine, H. Zmuda, K. H. Park, H. Kwart, A. G. Horgan and M. Breichbiel, J. Am. Chem. Soc., 104, 2501 (1982); L. Kupezyk-Subotkowska, H. J. Shine, W. Subotkowski and J. Zygmunt,

Gazz. Chim. Ital., 117, 513 (1987).

18.G. Frater¨ and H. Schmid, Helv. Chim. Acta, 53, 269 (1970).

19.H. J. Shine, H. Zmuda, H. Kwart, A. G. Horgan and M. Brechbiel, J. Am. Chem. Soc., 104, 5181 (1982).

20.E. S. Rhee and H. J. Shine, J. Am. Chem. Soc., 108, 1000 (1986); 109, 5052 (1987); J. Org. Chem., 52, 5633 (1987).

21.H. J. Shine, E. Gruszecka, W. Subotkowski, M. L. Brownawell and J. San Filippo, J. Am. Chem. Soc., 107, 3218 (1985).

22.W. Subotkowski, L. Kupezyk-Subotkowska and H. J. Shine, J. Am. Chem. Soc., 115, 5073 (1993).

23.H. J. Shine, J. Habdas, H. Kwart, M. Breichbiel, A. G. Horgan and J. San Filippo, J. Am. Chem. Soc., 105, 2823 (1983).

24.B. C. Auman and A. E. Feiring, U.S. Patent, US 5 175 367; Chem. Abstr., 119, 9319 (1993).

25.T. Nozoe, K. Takase, H. Saito, H. Yamamoto and K. Imafuku, Chem. Lett., 1577 (1986).

26.B. Miller, in Mechanisms of Molecular Migrations (Ed. B. Thyagarajan), Interscience, New York, 1968, p. 306.

27.B. Boduszek and H. J. Shine, J. Am. Chem. Soc., 110, 3247 (1988).

28.H. J. Shine, Aromatic Rearrangements, Elsevier, Amsterdam, 1967, pp. 272 284.

29.E. Buncel, Acc. Chem. Res., 8, 132 (1975).

30.D. L. H. Williams and E. Buncel, in Isotopes in Organic Chemistry, Vol. 5 (Eds. E. Buncel and

C.C. Lee), Elsevier, Amsterdam, 1980, pp. 184 197.

31.I. Shimao and S. Oae, Bull. Chem. Soc. Jpn., 56, 643 (1983).

32.I. Shimao and S. Matsumura, Bull. Chem. Soc. Jpn., 49, 2294 (1976).

33.I. Shimao, K. Fujimori and S. Oae, Bull. Chem. Soc. Jpn., 55, 546 (1982).

34.J. Yamamoto, H. Aimi, Y. Masuda, T. Sumida, M. Umezu and T. Matuura, J. Chem. Soc., Perkin Trans. 2, 1565 (1982).

35.E. Buncel, S. R. Kuem, M. Cygler, K. I. Varaghese and G. I. Birnbaum, Can. J. Chem., 62, 1628 (1984).

36.G. G. Furin, O. I. Andreevskaya, A. I. Rezvukhin and G. G. Yakobson, J. Fluorine Chem., 28, 1 (1985).

37.H. J. Shine, W. Subotkowski and E. Gruszecka, Can. J. Chem., 64, 1108 (1986).

38.E. Bamberger, Chem. Ber., 27, 1347, 1548 (1894) and later papers.

39.H. J. Shine, Aromatic Rearrangements, Elsevier, Amsterdam, 1967, pp. 182 190.

40.H. E. Heller, E. D. Hughes and C. K. Ingold, Nature, 168, 909 (1951).

41.J. C. Fishbein and R. A. McClelland, J. Am. Chem. Soc., 109, 2824 (1987).

42. S. Okazaki and M. Okumura, unpublished work, cited by S. Oae, T. Fukumoto and

M. Yamagami, Bull. Chem. Soc. Jpn., 34, 1873 (1961); 36, 601 (1963).

43.T. Sone, Y. Tokuda, T. Sakai, S. Shinkai and O. Manabe, J. Chem. Soc., Perkin Trans. 2, 298 (1981).

44.G. Kohnstam, W. A. Petch and D. L. H. Williams, J. Chem. Soc., Perkin Trans. 2, 423 (1984).

45.M. Heyrovsky, S. Vavricka, L. Holleck and B. Katening, J. Electroanal. Chem. Interfacial Electrochem., 26, 399 (1970).

890	D. Lyn H. Williams

46.I. I. Kukhtenko, Russ. J. Org. Chem. (Engl. Transl.), 7, 324 (1971).

47.T. Sone, K. Hamamoto, Y. Seiji, S. Shinkai and O. Manabe, J. Chem. Soc., Perkin Trans. 2, 1596 (1981).

48.H. Landsheidt, A. Klausener and H. U. Blank, Eur. Pat-Appl. EP 569, 792; Chem. Abstr., 120, 163725 (1994).

49.L. Cerveny and J. Toman, Chem. Prum., 42, 85 (1992); Chem. Abstr., 117, 236179 (1992).

50.K. Miura, T. Kuvihara, K. Yanagida, Jpn. Kokai Tokkyo Koho JP 04 149, 160; Chem. Abstr., 117, 170969 (1992).

51.L. A. Sternson, A. S. Dixit and A. R. Becker, J. Org. Chem., 48, 57 (1983).

52.E. C. Miller, Cancer Res., 38, 1479 (1978).

53.Y. Kikugawa and K. Mitsui, Chem. Lett., 1369 (1993).

54.D. Gutshke and A Heesing, Chem. Ber., 106, 2379 (1973).

55.M. A. Carter and B. Robinson, Chem. Ind., 304 (1974).

56.N. Haga, Y. Endo, K. Kataoka, K. Yamaguchi and K. Shudo, J. Am. Chem. Soc., 114, 9795 (1992).

57.Y. Endo, K. Kataoka, N. Haga and K. Shudo, Tetrahedron Lett., 33, 3339 (1992).

58.H. J. Shine, Aromatic Rearrangements, Elsevier, Amsterdam, 1967, pp. 221 230.

59.R. Onoda and H. Kawaguchi, Kagaku Kyoiky, 29, 220 (1981); Chem. Abstr., 95, 203032 (1981).

60.M. D. Patwardhan, A. S. Mishra, S. S. Ghai and A. K. Mishra, J. Indian Chem. Soc., 58, 1084 (1981).

61.G. R. Underwood and P. E. Dietze, J. Org. Chem., 49, 5225 (1984).

62.M. De Rosa and J. L. Alonso Triana, J. Org. Chem., 43, 2639 (1978).

63.M. De Rosa, J. Org. Chem., 47, 1008 (1982).

64.M. De Rosa, A. Quesada and D. J. Dodsworth, J. Org. Chem., 52, 173 (1987).

65.P. G. Gassman, Acc. Chem. Res., 3, 26 (1970).

66.P. G. Gassman, G. A. Campbell and R. C. Frederick, J. Am. Chem. Soc., 94, 3884 (1972).

67.P. G. Gassman and G. A. Campbell, J. Am. Chem. Soc., 94, 3891 (1972).

68.K. U. B. Rao, R. K. Bhongle and S. Yoganarasimhan, Org. Prep. Proced. Int., 22, 113 (1990).

69.R. L. Atkins and W. S. Wilson, J. Org. Chem., 51, 2572 (1986).

70.W. N. White, J. R. Klink, D. Lazdins, C. Hathaway, J. T. Golden and H. S. White, J. Am. Chem. Soc., 83, 2024 (1961) and later papers.

71.J. H. Ridd and J. P. B. Sandall, J. Chem. Soc., Chem. Commun., 261 (1982); A. M. A. AbuNamous, J. H. Ridd and J. P. B. Sandall, Can. J. Chem., 64, 1124 (1986).

72.H. J. Shine, J. Zygmunt, M. L. Brownawell and J. S. Filippo, J. Am. Chem. Soc., 106, 3610 (1984).

73.S. Brownstein, C. A. Bunton and E. D. Hughes, J. Chem. Soc., 4354 (1958).

74.L. W. Deady, O. L. Korytsky and J. E. Rowe, Aust. J. Chem., 35, 2025 (1982).

75.J. P. H. Juffermans and C. L. Habraken, J. Org. Chem., 51, 4656 (1986).

76.J. B. Kyziol and Z. Daszkiewicz, Tetrahedron, 40, 1857 (1984).

77.P. Barrow, J. V. Bullen, A. Dent, T. Murphy, J. H. Ridd and O. Sabek, J. Chem. Soc., Chem. Commun., 1649 (1986).

78.J. V. Bullen, J. H. Ridd and O. Sabek, J. Chem. Soc., Perkin Trans. 2, 1681 (1990).

79.J. V. Bullen and J. H. Ridd, J. Chem. Soc., Perkin Trans. 2, 1675 (1990).

80.J. V. Bullen, J. H. Ridd, and O. Sabek, Gazz. Chim. Ital., 120, 291 (1990).

81.J. T. Murphy and J. H. Ridd, J. Chem. Soc., Perkin Trans. 2, 1767 (1987).

82.G. S. Bapat, A. Fischer, G. N. Henderson and S. Raymahasay, J. Chem. Soc., Chem. Commun., 119 (1983).

83.F. Al-Omran, K. Fujiwara, J. C. Giffney, J. H. Ridd and S. R. Robinson, J. Chem. Soc., Perkin Trans. 2, 518 (1981).

84.C. Bloomfield, A. K. Manglik, R. B. Moodie, K. Schofield and G. D. Tobin, J. Chem. Soc., Perkin Trans. 2, 75 (1983).

85.J. H. Ridd, J. P. B. Sandall and S. Trevellick, J. Chem. Soc., Chem. Commun., 1195 (1988).

86.E. Carvalho, J. Iley and E. Rosa, J. Chem. Soc., Chem. Commun., 1249 (1988).

87.R. P. Saxon and M. Yoshimine, Can. J. Chem., 70, 572 (1992).

88.E. S. Nigenda, D. F. McMillen and D. M. Golden, J. Phys. Chem., 93, 1124 (1989).

89.M. P. Hartshorn, W. T. Robinson, J. Vaughan and J. M. White, Aust. J. Chem., 38, 575 (1985) and earlier papers for other examples.

90.M. P. Hartshorn, H. T. Ing, K. E. Richards, K. H. Sulton and J. Vaughan, Aust. J. Chem., 35, 1635 (1982).

19. Rearrangement reactions involving the amino, nitro and nitroso groups 891

91.M. R. Amin, L. Dekker, D. B. Hibbert, J. H. Ridd and J. P. B. Sandall, J. Chem. Soc., Chem. Commun., 658 (1986).

92.L. Eberson, J. L. Calvert, M. P. Hartshorn and W. T. Robinson, Acta Chem. Scand., 47, 1025 (1993).

93.D. L. H. Williams, in The Chemistry of Amino, Nitroso and Nitro Compounds and Their Derivatives, Supplement F (Ed. S. Patai), Wiley, Chichester, 1982, pp. 133 140.

94.D. L. H. Williams, J. Chem. Soc., Perkin Trans. 2, 801 (1982).

95.L. P. Nikitenkova, S. D. Karaktov, Y. A. Strepikheev and I. I. Naumova, Zh. Obshch. Khim., 54, 1375 (1984); Chem. Abstr., 101, 110052 (1984).

96.S. P. Titova, A. K. Arinch and M. V. Gorelik, Zh. Org. Khim., 22, 1562 (1986); Chem. Abstr., 107, 39293 (1987).

97.R. N. Loeppky and H. Xiong, J. Org. Chem., 60, 5526 (1995).

98.R. E. Lyle, W. E. Krueger and V. E. Gunn, J. Org. Chem., 48, 3574 (1983).

99.J. C. Kim and S. H. Han, Bull. Korean Chem. Soc., 15, 173 (1994).

100.M. Tanno, S. Sueyoshi and S. Kamiga, Chem. Pharm. Bull., 38, 49 (1990).

101.A. Castro, E. Iglesias, J. R. Leis, M. E. Pena and J. V. Tato, J. Chem. Soc., Perkin Trans. 2, 1725 (1986).

102.A. Castro, M. Gonzalez, F. Meijide and M. Mosquera, J. Chem. Soc., Perkin Trans. 2, 2021 (1988).

103.A. Castro, E. Iglesias, J. R. Leis, M. E. Pena, J. V. Tato and D. L. H. Williams, J. Chem. Soc., Perkin Trans. 2, 1165 (1986).

104.E. Iglesias and D. L. H. Williams, J. Chem. Soc., Perkin Trans. 2, 1035 (1988).

105.T. A. Meyer and D. L. H. Williams, J. Chem. Soc., Chem. Commun., 1067 (1983).

106.	T. Tahira, M. Tsuda, K. Wakabayashi, M. Nugao and T. Sugimura, Gann, 75, 889 (1984);
	A. Castro, E. Iglesias, J. R. Leis, J. V. Tato, F. Meijide and M. E. Pena, J. Chem. Soc., Perkin
	Trans. 2, 651 (1987).
107.	A. Coello, F. Meijide and J. V. Tato, J. Chem. Soc., Perkin Trans. 2, 1677 (1989).