Comments on a Conversion of Epoxides to Halohydrins with Elemental Halogen Catalyzed by Phenylhydrazine: Tandem Electrophilic Halogenation of Aromatic Compounds and Epoxide Ring Opening to Halohydrins

Synthesis

Volumn , Issue 15, 2003, Pages 2341-2344

  Soroka, Mirosław ^a   Goldeman, Waldemar ^a   Małysa, Piotr ^a   Stochaj, Monika ^a  

^a WROCLAW UNIVERSITY OF TECHNOLOGY   (Poland)

Author keywords

Arenes; Bromine; Bromohydrins; Chlorohydrins; Epoxides; Halogenation

Indexed keywords

AROMATIC COMPOUNDS; BROMINE; CHLORINE;

HALOHYDRINS;

HALOGENATION;

AROMATIC COMPOUND; BROMINE; CHLORINE; EPOXIDE; HALOGEN; PHENYLHYDRAZINE;

ARTICLE; CATALYSIS; CHEMICAL MODIFICATION; HALOGENATION; QUANTUM YIELD; REACTION ANALYSIS; REACTION OPTIMIZATION; RING OPENING;

EID: 0242656273     PISSN: 00397881     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-2003-42424     Document Type: Article

References (36)

1. Since citation of more than 50 papers in this short article is not appropriate, we are ready to send a copy of a text file with the citations to interested readers.
2. Sharghi, H.; Eskandari, M. M. Synthesis 2002, 1519.
3. For concluding that the phenylhydrazine is a catalyst, it is necessary to find it, or better to isolate it, or much better to use it again, after reaction.
4. (4) There are two possibilities: electrophilic halogenation of phenylhydrazine, and the oxidation of phenylhydrazine by halogen. Both reactions give hydrogen halogenide as a side product. Therefore, the reaction of arylhydrazines with chlorine or bromine gave a mixture of chlorination/ bromination and oxidation products, mainly aryldiazonium salts, and the products thereof. We found some precedents in the literature. For examples, see: (a) Chattaway, F. D.; Hodgson, G. D. J. Chem. Soc. 1916, 583. (b) Chattaway, F. D. J. Chem. Soc. 1908, 852. Chattaway, F. D. J. Chem. Soc. 1909, 862. Michaelis, L. Ber. Dtsch. Chem. Ges. 1893, 26, 2190. (e) Vaubel, W. J. Prakt. Chem. 1894, 49, 540.
5. There are two possibilities: electrophilic halogenation of phenylhydrazine, and the oxidation of phenylhydrazine by halogen. Both reactions give hydrogen halogenide as a side product. Therefore, the reaction of arylhydrazines with chlorine or bromine gave a mixture of chlorination/ bromination and oxidation products, mainly aryldiazonium salts, and the products thereof. We found some precedents in the literature. For examples, see: (a) Chattaway, F. D.; Hodgson, G. D. J. Chem. Soc. 1916, 583. (b) Chattaway, F. D. J. Chem. Soc. 1908, 852. Chattaway, F. D. J. Chem. Soc. 1909, 862. Michaelis, L. Ber. Dtsch. Chem. Ges. 1893, 26, 2190. (e) Vaubel, W. J. Prakt. Chem. 1894, 49, 540.
6. There are two possibilities: electrophilic halogenation of phenylhydrazine, and the oxidation of phenylhydrazine by halogen. Both reactions give hydrogen halogenide as a side product. Therefore, the reaction of arylhydrazines with chlorine or bromine gave a mixture of chlorination/ bromination and oxidation products, mainly aryldiazonium salts, and the products thereof. We found some precedents in the literature. For examples, see: (a) Chattaway, F. D.; Hodgson, G. D. J. Chem. Soc. 1916, 583. (b) Chattaway, F. D. J. Chem. Soc. 1908, 852. (c) Chattaway, F. D. J. Chem. Soc. 1909, 862. Michaelis, L. Ber. Dtsch. Chem. Ges. 1893, 26, 2190. (e) Vaubel, W. J. Prakt. Chem. 1894, 49, 540.
7. There are two possibilities: electrophilic halogenation of phenylhydrazine, and the oxidation of phenylhydrazine by halogen. Both reactions give hydrogen halogenide as a side product. Therefore, the reaction of arylhydrazines with chlorine or bromine gave a mixture of chlorination/ bromination and oxidation products, mainly aryldiazonium salts, and the products thereof. We found some precedents in the literature. For examples, see: (a) Chattaway, F. D.; Hodgson, G. D. J. Chem. Soc. 1916, 583. (b) Chattaway, F. D. J. Chem. Soc. 1908, 852. (c) Chattaway, F. D. J. Chem. Soc. 1909, 862. (d) Michaelis, L. Ber. Dtsch. Chem. Ges. 1893, 26, 2190. (e) Vaubel, W. J. Prakt. Chem. 1894, 49, 540.
8. There are two possibilities: electrophilic halogenation of phenylhydrazine, and the oxidation of phenylhydrazine by halogen. Both reactions give hydrogen halogenide as a side product. Therefore, the reaction of arylhydrazines with chlorine or bromine gave a mixture of chlorination/ bromination and oxidation products, mainly aryldiazonium salts, and the products thereof. We found some precedents in the literature. For examples, see: (a) Chattaway, F. D.; Hodgson, G. D. J. Chem. Soc. 1916, 583. (b) Chattaway, F. D. J. Chem. Soc. 1908, 852. (c) Chattaway, F. D. J. Chem. Soc. 1909, 862. (d) Michaelis, L. Ber. Dtsch. Chem. Ges. 1893, 26, 2190. (e) Vaubel, W. J. Prakt. Chem. 1894, 49, 540.
9. 2 moiety by bromine. For examples, see: (a) Callander, D. D.; Coe, P. L.; Tatlow, J. C. Tetrahedron 1966, 22, 419. (b) Field, L. D.; Hambley, T. W.; Pierens, G. K. Tetrahedron 1990, 46, 7069. Joshi, S. S.; Deorha, D. S. J. Chem. Soc. 1957, 2414.
10. 2 moiety by bromine. For examples, see: (a) Callander, D. D.; Coe, P. L.; Tatlow, J. C. Tetrahedron 1966, 22, 419. (b) Field, L. D.; Hambley, T. W.; Pierens, G. K. Tetrahedron 1990, 46, 7069. Joshi, S. S.; Deorha, D. S. J. Chem. Soc. 1957, 2414.
11. 2 moiety by bromine. For examples, see: (a) Callander, D. D.; Coe, P. L.; Tatlow, J. C. Tetrahedron 1966, 22, 419. (b) Field, L. D.; Hambley, T. W.; Pierens, G. K. Tetrahedron 1990, 46, 7069. (c) Joshi, S. S.; Deorha, D. S. J. Chem. Soc. 1957, 2414.
12. 5c as well as by: (a) Brady, O. L.; Bowman, J. H. J. Chem. Soc. 1921, 119, 896. (b) Meyer, E. J. Prakt. Chem. 1887, 36, 115.
13. 5c as well as by: (a) Brady, O. L.; Bowman, J. H. J. Chem. Soc. 1921, 119, 896. (b) Meyer, E. J. Prakt. Chem. 1887, 36, 115.
14. Also, the application of halogens for the oxidation of N,N′-disubstituted hydrazines to azo compounds is a well-documented fact. See for example: (a) Overberger, C. G.; Pao-Tung, H.; Berenbaum, M, B. Org. Synth. Coll. Vol. IV; Wiley: London, 1966, 66. (b) Rabjohn, N. Org. Synth. Coll. Vol. III; Wiley: London, 1966, 375.
15. Also, the application of halogens for the oxidation of N,N′-disubstituted hydrazines to azo compounds is a well-documented fact. See for example: (a) Overberger, C. G.; Pao-Tung, H.; Berenbaum, M, B. Org. Synth. Coll. Vol. IV; Wiley: London, 1966, 66. (b) Rabjohn, N. Org. Synth. Coll. Vol. III; Wiley: London, 1966, 375.
16. 2 + 8 HBr). However, we did not observe more than tetrabrominated products in the reaction mixture. Since the main product is 2,4,6- tribromophenylhydrazine, the proper stoichiometry should be at least one mole of phenylhydrazine per three moles of bromine (and respectively 3 mol of epoxide).
17. 2 are hard to understand, since in many cases the regioselectivities recorded are opposite to those indicated by the mechanism of the ring opening reaction of epoxides and, therefore, should be re-analysed.
18. There are many examples of using epoxides as hydrogen halogenide scavengers or a specific kind of 'terminating' base. The side products of those reactions are usually halohydrins. For example, epoxides were extensively used for the precipitation of amino acids from their hydrochlorides or hydrobromides, see: (a) Gmeiner, P.; Feldman, P. L.; Chu-Moyer, M. Y.; Rapoport, H. J. Org. Chem. 1990, 55, 3068. (b) Jackson, R. F. W.; Turner, D.; Block, M. H. J. Chem. Soc., Chem. Commun. 1995, 2207. Chambers, J. R.; Isbell, A. F. J. Org. Chem. 1964, 29, 832.
19. There are many examples of using epoxides as hydrogen halogenide scavengers or a specific kind of 'terminating' base. The side products of those reactions are usually halohydrins. For example, epoxides were extensively used for the precipitation of amino acids from their hydrochlorides or hydrobromides, see: (a) Gmeiner, P.; Feldman, P. L.; Chu-Moyer, M. Y.; Rapoport, H. J. Org. Chem. 1990, 55, 3068. (b) Jackson, R. F. W.; Turner, D.; Block, M. H. J. Chem. Soc., Chem. Commun. 1995, 2207. Chambers, J. R.; Isbell, A. F. J. Org. Chem. 1964, 29, 832.
20. There are many examples of using epoxides as hydrogen halogenide scavengers or a specific kind of 'terminating' base. The side products of those reactions are usually halohydrins. For example, epoxides were extensively used for the precipitation of amino acids from their hydrochlorides or hydrobromides, see: (a) Gmeiner, P.; Feldman, P. L.; Chu-Moyer, M. Y.; Rapoport, H. J. Org. Chem. 1990, 55, 3068. (b) Jackson, R. F. W.; Turner, D.; Block, M. H. J. Chem. Soc., Chem. Commun. 1995, 2207. (c) Chambers, J. R.; Isbell, A. F. J. Org. Chem. 1964, 29, 832.
21. For other, more sophisticated examples, see: (a) Sato, K.; Kojima, Y.; Sato, H. J. Org. Chem. 1970, 35, 2374. (b) Isaacs, N. S.; Kirkpatrick, D. Tetrahedron Lett. 1972, 3869. Hartshorn, M. P.; Jones, E. R. H. J. Chem. Soc. 1962, 1312. Kirk, D. N.; Patel, D. K.; Petrow, V. J. Chem. Soc. 1956, 627. (e) Hunsberger, I. M.; Tien, J. M. Chem. Ind. 1959, 88. (f) Buddrus, J. Angew. Chem., Int. Ed. Engl. 1968, 7, 536; Angew. Chem. 1968, 80, 535. (g) Buddrus, J. Angew. Chem., Int. Ed. Engl. 1972, 11, 1041; Angew. Chem. 1972, 84, 1173. (h) Weyerstahl, P.; Klamann, D.; Finger, C.; Nerdel, F.; Buddrus, J. Chem. Ber. 1967, 100, 1858.
22. For other, more sophisticated examples, see: (a) Sato, K.; Kojima, Y.; Sato, H. J. Org. Chem. 1970, 35, 2374. (b) Isaacs, N. S.; Kirkpatrick, D. Tetrahedron Lett. 1972, 3869. Hartshorn, M. P.; Jones, E. R. H. J. Chem. Soc. 1962, 1312. Kirk, D. N.; Patel, D. K.; Petrow, V. J. Chem. Soc. 1956, 627. (e) Hunsberger, I. M.; Tien, J. M. Chem. Ind. 1959, 88. (f) Buddrus, J. Angew. Chem., Int. Ed. Engl. 1968, 7, 536; Angew. Chem. 1968, 80, 535. (g) Buddrus, J. Angew. Chem., Int. Ed. Engl. 1972, 11, 1041; Angew. Chem. 1972, 84, 1173. (h) Weyerstahl, P.; Klamann, D.; Finger, C.; Nerdel, F.; Buddrus, J. Chem. Ber. 1967, 100, 1858.
23. For other, more sophisticated examples, see: (a) Sato, K.; Kojima, Y.; Sato, H. J. Org. Chem. 1970, 35, 2374. (b) Isaacs, N. S.; Kirkpatrick, D. Tetrahedron Lett. 1972, 3869. (c) Hartshorn, M. P.; Jones, E. R. H. J. Chem. Soc. 1962, 1312. Kirk, D. N.; Patel, D. K.; Petrow, V. J. Chem. Soc. 1956, 627. (e) Hunsberger, I. M.; Tien, J. M. Chem. Ind. 1959, 88. (f) Buddrus, J. Angew. Chem., Int. Ed. Engl. 1968, 7, 536; Angew. Chem. 1968, 80, 535. (g) Buddrus, J. Angew. Chem., Int. Ed. Engl. 1972, 11, 1041; Angew. Chem. 1972, 84, 1173. (h) Weyerstahl, P.; Klamann, D.; Finger, C.; Nerdel, F.; Buddrus, J. Chem. Ber. 1967, 100, 1858.
24. For other, more sophisticated examples, see: (a) Sato, K.; Kojima, Y.; Sato, H. J. Org. Chem. 1970, 35, 2374. (b) Isaacs, N. S.; Kirkpatrick, D. Tetrahedron Lett. 1972, 3869. (c) Hartshorn, M. P.; Jones, E. R. H. J. Chem. Soc. 1962, 1312. (d) Kirk, D. N.; Patel, D. K.; Petrow, V. J. Chem. Soc. 1956, 627. (e) Hunsberger, I. M.; Tien, J. M. Chem. Ind. 1959, 88. (f) Buddrus, J. Angew. Chem., Int. Ed. Engl. 1968, 7, 536; Angew. Chem. 1968, 80, 535. (g) Buddrus, J. Angew. Chem., Int. Ed. Engl. 1972, 11, 1041; Angew. Chem. 1972, 84, 1173. (h) Weyerstahl, P.; Klamann, D.; Finger, C.; Nerdel, F.; Buddrus, J. Chem. Ber. 1967, 100, 1858.
25. For other, more sophisticated examples, see: (a) Sato, K.; Kojima, Y.; Sato, H. J. Org. Chem. 1970, 35, 2374. (b) Isaacs, N. S.; Kirkpatrick, D. Tetrahedron Lett. 1972, 3869. (c) Hartshorn, M. P.; Jones, E. R. H. J. Chem. Soc. 1962, 1312. (d) Kirk, D. N.; Patel, D. K.; Petrow, V. J. Chem. Soc. 1956, 627. (e) Hunsberger, I. M.; Tien, J. M. Chem. Ind. 1959, 88. (f) Buddrus, J. Angew. Chem., Int. Ed. Engl. 1968, 7, 536; Angew. Chem. 1968, 80, 535. (g) Buddrus, J. Angew. Chem., Int. Ed. Engl. 1972, 11, 1041; Angew. Chem. 1972, 84, 1173. (h) Weyerstahl, P.; Klamann, D.; Finger, C.; Nerdel, F.; Buddrus, J. Chem. Ber. 1967, 100, 1858.
26. For other, more sophisticated examples, see: (a) Sato, K.; Kojima, Y.; Sato, H. J. Org. Chem. 1970, 35, 2374. (b) Isaacs, N. S.; Kirkpatrick, D. Tetrahedron Lett. 1972, 3869. (c) Hartshorn, M. P.; Jones, E. R. H. J. Chem. Soc. 1962, 1312. (d) Kirk, D. N.; Patel, D. K.; Petrow, V. J. Chem. Soc. 1956, 627. (e) Hunsberger, I. M.; Tien, J. M. Chem. Ind. 1959, 88. (f) Buddrus, J. Angew. Chem., Int. Ed. Engl. 1968, 7, 536; Angew. Chem. 1968, 80, 535. (g) Buddrus, J. Angew. Chem., Int. Ed. Engl. 1972, 11, 1041; Angew. Chem. 1972, 84, 1173. (h) Weyerstahl, P.; Klamann, D.; Finger, C.; Nerdel, F.; Buddrus, J. Chem. Ber. 1967, 100, 1858.
27. For other, more sophisticated examples, see: (a) Sato, K.; Kojima, Y.; Sato, H. J. Org. Chem. 1970, 35, 2374. (b) Isaacs, N. S.; Kirkpatrick, D. Tetrahedron Lett. 1972, 3869. (c) Hartshorn, M. P.; Jones, E. R. H. J. Chem. Soc. 1962, 1312. (d) Kirk, D. N.; Patel, D. K.; Petrow, V. J. Chem. Soc. 1956, 627. (e) Hunsberger, I. M.; Tien, J. M. Chem. Ind. 1959, 88. (f) Buddrus, J. Angew. Chem., Int. Ed. Engl. 1968, 7, 536; Angew. Chem. 1968, 80, 535. (g) Buddrus, J. Angew. Chem., Int. Ed. Engl. 1972, 11, 1041; Angew. Chem. 1972, 84, 1173. (h) Weyerstahl, P.; Klamann, D.; Finger, C.; Nerdel, F.; Buddrus, J. Chem. Ber. 1967, 100, 1858.
28. For other, more sophisticated examples, see: (a) Sato, K.; Kojima, Y.; Sato, H. J. Org. Chem. 1970, 35, 2374. (b) Isaacs, N. S.; Kirkpatrick, D. Tetrahedron Lett. 1972, 3869. (c) Hartshorn, M. P.; Jones, E. R. H. J. Chem. Soc. 1962, 1312. (d) Kirk, D. N.; Patel, D. K.; Petrow, V. J. Chem. Soc. 1956, 627. (e) Hunsberger, I. M.; Tien, J. M. Chem. Ind. 1959, 88. (f) Buddrus, J. Angew. Chem., Int. Ed. Engl. 1968, 7, 536; Angew. Chem. 1968, 80, 535. (g) Buddrus, J. Angew. Chem., Int. Ed. Engl. 1972, 11, 1041; Angew. Chem. 1972, 84, 1173. (h) Weyerstahl, P.; Klamann, D.; Finger, C.; Nerdel, F.; Buddrus, J. Chem. Ber. 1967, 100, 1858.
29. For other, more sophisticated examples, see: (a) Sato, K.; Kojima, Y.; Sato, H. J. Org. Chem. 1970, 35, 2374. (b) Isaacs, N. S.; Kirkpatrick, D. Tetrahedron Lett. 1972, 3869. (c) Hartshorn, M. P.; Jones, E. R. H. J. Chem. Soc. 1962, 1312. (d) Kirk, D. N.; Patel, D. K.; Petrow, V. J. Chem. Soc. 1956, 627. (e) Hunsberger, I. M.; Tien, J. M. Chem. Ind. 1959, 88. (f) Buddrus, J. Angew. Chem., Int. Ed. Engl. 1968, 7, 536; Angew. Chem. 1968, 80, 535. (g) Buddrus, J. Angew. Chem., Int. Ed. Engl. 1972, 11, 1041; Angew. Chem. 1972, 84, 1173. (h) Weyerstahl, P.; Klamann, D.; Finger, C.; Nerdel, F.; Buddrus, J. Chem. Ber. 1967, 100, 1858.
30. For other, more sophisticated examples, see: (a) Sato, K.; Kojima, Y.; Sato, H. J. Org. Chem. 1970, 35, 2374. (b) Isaacs, N. S.; Kirkpatrick, D. Tetrahedron Lett. 1972, 3869. (c) Hartshorn, M. P.; Jones, E. R. H. J. Chem. Soc. 1962, 1312. (d) Kirk, D. N.; Patel, D. K.; Petrow, V. J. Chem. Soc. 1956, 627. (e) Hunsberger, I. M.; Tien, J. M. Chem. Ind. 1959, 88. (f) Buddrus, J. Angew. Chem., Int. Ed. Engl. 1968, 7, 536; Angew. Chem. 1968, 80, 535. (g) Buddrus, J. Angew. Chem., Int. Ed. Engl. 1972, 11, 1041; Angew. Chem. 1972, 84, 1173. (h) Weyerstahl, P.; Klamann, D.; Finger, C.; Nerdel, F.; Buddrus, J. Chem. Ber. 1967, 100, 1858.
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