1.

Acetoacetic Ester Synthesis
Base-catalyzed alkylation or arylation of β-ketoesters. Subsequent mild hydrolysis and decarboxylation yield substituted acetones. Alternately, treatment with concentrated base produces substituted esters:

Synthetic applications: R. Kluger, M. Brandl, J. Org. Chem. 51, 3964 (1986); T. Yamamitsu et al., J. Chem. Soc. Perkin Trans. I 1989, 1811.
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2. Acyloin Condensation
L. Bouveault, R. Loquin, Compt. Rend. 140, 1593 (1905). Reductive coupling of esters by sodium to yield acyloins (α-hydroxyketones). Yields are greatly improved in the presence of trimethylchlorosilane:

K. T. Finley, Chem. Rev. 64, 573 (1964); K. Ziegler, Houben-Weyl 4/2, 729-822 (1955); S. M. McElvain, Org. React. 4, 256 (1948); J. J. Bloomfield et al., ibid. 23, 259 (1976); R. Brettle, Comp. Org. Syn. 3, 613-632 (1991). Cf. Benzoin Condensation.
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3. Akabori Amino Acid Reactions
S. Akabori, J. Chem. Soc. Japan 52, 606 (1931); Ber. 66, 143, 151 (1933); J. Chem. Soc. 64, 608 (1943). 1. Formation of aldehydes by oxidative decomposition of α-amino acids when heated with sugars according to the equation:

2. Reduction of α-amino acids and esters by sodium amalgam and ethanolic hydrogen chloride to the corresponding α-amino aldehydes:

3. Formation of alkamines by heating mixtures of aromatic aldehydes and amino acids. No reaction was observed with tertiary amino groups. E. Takagi et al., J. Pharm. Soc. Japan 71, 648 (1951); 72, 812 (1952); A. Lawson, H. V. Morley, J. Chem. Soc. 1955, 1695; A. Lawson, ibid. 1956, 307; K. Dose, Ber. 90, 1251 (1957); V. N. Belikov et al., Izv. Akad. Nauk SSSR, Ser. Khim. 1969, 2536.
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4. Aldol Reaction (Condensation)
R. Kane, Ann. Phys. Chem., Ser. 2, 44, 475 (1838); idem, J. Prakt. Chem. 15, 129 (1838). Traditionally, it is the acid- or base-catalyzed condensation of one carbonyl compound with the enolate/enol of another, which may or may not be the same, to generate a β-hydroxy carbonyl compound—an aldol. The method is compromised by selfcondensation, polycondensation, generation of regioisomeric enols/enolates, and dehydration of the aldol followed by Michael addition, q.v. The development of methods for the preparation and use of preformed enolates or enol derivatives, that dictate specific carbon-carbon bond formation, have revolutionized the coupling of carbonyl compounds:

Historical perspective: C. H. Heathcock, Comp. Org. Syn. 2, 133-179 (1991). General review: T. Mukaiyama, Org. React. 28, 203-331 (1982). Application of lithium and magnesium enolates: C. H. Heathcock, Comp. Org. Syn. 2, 181-238 (1991); of boron enolates: B. M. Kim et al., ibid. 239-275; of transition metal enolates: I. Paterson, ibid. 301-319. Stereoselective reactions of ester and thioester enolates: M. Braun, H. Sacha, J. Prakt. Chem. 335, 653-668 (1993). Review of asymmetric methodology: A. S. Franklin, I. Paterson, Contemp. Org. Syn. 1, 317-338 (1994). Cf. Claisen-Schmidt Condensation; Henry Reaction; Ivanov Reaction; Knoevenagel Condensation; Reformatsky Reaction; Robinson Annulation.

5. Algar-Flynn-Oyamada Reaction
J. Algar, J. P. Flynn, Proc. Roy. Irish Acad. 42B, 1 (1934); B. Oyamada, J. Chem. Soc. Japan 55, 1256 (1934). Alkaline hydrogen peroxide oxidation of o-hydroxyphenyl styryl ketones (chalcones) to flavonols via the intermediate dihydroflavonols:

T. S. Wheeler, Record Chem. Progr. 18, 133 (1957); W. P. Cullen et al., J. Chem. Soc. C 1971, 2848. Mechanism: T. R. Gormley, et al., Tetrahedron 29, 369 (1973); M. Bennett et al., ibid. 54, 9911 (1998). Synthetic applications: H. Wagner et al., ibid. 33, 1405 (1977); A. C. Jain et al., Bull. Chem. Soc. Japan 56, 1267 (1983). Cf. Auwers Synthesis.
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6. Allan-Robinson Reaction
J. Allan, R. Robinson, J. Chem. Soc. 125, 2192 (1924). Preparation of flavones or isoflavones by condensing o-hydroxyaryl ketones with anhydrides of aromatic acids and their sodium salts:

S. F. Dyke et al., J. Org. Chem. 26, 2453 (1961); Seshandri in The Chemistry of Flavonoid Compounds, T. A. Geissman, Ed. (New York, 1962) p 182; Gripenberg, ibid. p 411; W. Rahman, K. T. Nasim, J. Org. Chem. 27, 4215 (1962); D. L. Dreyer et al., Tetrahedron 20, 2977 (1964). Synthesis applications: P. K. Dutta et al., Indian J. Chem. 21B, 1037 (1982); T. Horie et al., Chem. Pharm. Bull. 37, 1216 (1989); J. K. Makrandi et al., Synth. Commn. 19, 1919 (1989); E. J. Corey et al., Tetrahedron Letters 37, 7162 (1996); B. P. Reddy et al., J. Heterocyclic Chem. 33, 1561 (1996). Cf. Baker-Venkataraman Rearrangement; Kostanecki Acylation.
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7. Allylic Rearrangements
L. Claisen, Ber. 45, 3157 (1912). Migration of a carbon-carbon double bond in a three carbon (allylic) system on treatment with nucleophiles under SN1 conditions (or under SN2 conditions when the nucleophilic attack takes place at the γ-carbon):

Reviews: J. R. DeWolfe, W. G. Young, Chem. Rev. 56, 753 (1956); W. G. Young, J. Chem. Ed. 39, 455 (1962); P. de la Mare in Molecular Rearrangements Part 1, P. de Mayo, Ed. (Wiley-Interscience, New York, 1963) pp 27-110; K. Mackenzie in The Chemistry of Alkenes, S. Patai, Ed. (Interscience, New York, 1964) pp 436-453; R. H. DeWolfe, W. G. Young in ibid. pp 681738; J. March, Advanced Organic Chemistry (Wiley-Interscience, New York, 4th ed., 1992) pp 327-330.
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8. Amadori Rearrangement
M. Amadori, Atti Accad. Nazl. Lincei 2(6), 337 (1925), C.A. 20, 902 (1926); ibid. 9(6), 68, 226 (1929), C.A. 23, 3211, 3443 (1929). Conversion of N-glycosides of aldoses to N-glycosides of the corresponding ketoses by acid or base catalysis:

J. E. Hodge, Advan. Carbohyd. Chem. 10, 169 (1955); R. U. Lemieux in Molecular Rearrangements Part 2, P. de Mayo, Ed. 13 (Wiley-Interscience, New York, 1964) p 753. C-NMR studies: W. Funcke, Ann. 1978, 2099. Review: K. Maruoka, H. Yamamoto, Comp. Org. Syn. 6, 789-791 (1991).
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2. Nef Synthesis. Helv. Houben-Weyl 6/3. 259 (1956). Arens et al. O. Arens. Chim. Isler Modification D. Favorskii-Babayan Synthesis. Org. All rights reserved. 189 (1965). H. Copyright © 2001 by Merck & Co. NJ. Heusser et al. Inc. Advan. 609 (1949). Helv. 189 (1947).9. Arens. which is then condensed with the ketone: H. Nature 160. Chem. J. Isler et al. van Dorp. Whitehouse Station. 117-212 (1960). F. Rec. In the Isler modification the tedious preparation of ethoxyacetylene is obviated by treating β-chlorovinyl ether with lithium amide to yield lithium ethoxyacetylene. 68. Trav. F. Acta 33.. 604. .. Arens-van Dorp Synthesis. Cf. Chim. A.. Chim. 370 (1950). Meerwein. The preparation of alkoxyethynyl alcohols from ketones and ethoxyacetylene. USA. F. J. Acta 39.. J..

B. Syn... 6145 (1997).. Whitehouse Station. E. K. Application to synthesis of unsaturated diazoketones: T. 38. Org. NJ. Ed. Bachmann. Hudlicky et al. 38. Gademann et al.10. DeVita et al. Comp.. Gill. 2667. 888-889 (1991). Cf. Tetrahedron Letters 37. 1781 (1996). Bioorg. Reviews: W. 1979. R.. Struve. Copyright © 2001 by Merck & Co. 200 (1935). Arndt-Eistert Synthesis F. Angew. Letters 9. Eistert in Newer Methods in Preparative Organic Chemistry vol. Homologation of carboxylic acids: Alternative reagent for diazomethane: T. Wolff Rearrangement. G. Tetrahedron Letters 21. ibid. Arndt. J. B. React. New York. W. Chem. Ber. Eistert. 1223 (1999). 1. 2621 (1999). E. Org. 38-62 (1942).. . Winum et al. Marti et al. Aoyama. 4461 (1980). All rights reserved. 3. via ultrasonic activation: J-Y.. Chem. 68. USA. S. Inc. 1948) pp 513570. Int. B. 1 (Interscience. of amino acids: R. Med. ibid.

ibid. 49. 1968 (1925). Ber.. Heterocyclic Compounds 2. Robinson.. R.11. B.. Wawzonek. All rights reserved. Copyright © 2001 by Merck & Co. S. Auwers. 243 (1914). H. Kalff. . USA. Acharya et al. ibid. v. Pohl. 1598 (1922). 85 (1915). Cf. ibid. Ann.. 121. B. 895. P. J. 48. K. Whitehouse Station. Minton. Ingham et al. H. Auwers et al. 809 (1916).. 4233 (1908). 817. Stephen. AlgarFlynn-Oyamada Reaction. 245 (1951). Auwers Synthesis K. 1931. 1940. v. Soc. Expansion of coumarones to flavonols by treatment of 2-bromo-2-(α-bromobenzyl)coumarones with alcoholic alkali: T. H. G. Chem. 127. NJ. 405. J. 41. Inc.

. V. Baeyer. pyruvic acid or acetaldehyde. Ber. Mckee et al. J. of o-nitrobenzaldehydes to acetone. Fitjer et al. Rodd's Chemistry of Carbon Compounds IVB. Baeyer-Drewson Indigo Synthesis A. 14421 (1999). 15. q. L. 353 (1977).. M. Chemistry of Synthetic Dyes 2.. Chem. Synthetic applications: J. Sainsbury. 68. 346. Venkataraman. Drewson. Tetrahedron 55.v. R. 2856 (1882).12. A242 (1991). Inc. 1008 (New York. Formation of indigos by an aldol reaction. of interest mainly as a method of protecting o-nitrobenzaldehydes: K. Whitehouse Station. Ed. USA. NJ.... Copyright © 2001 by Merck & Co. All rights reserved. 1952).

251-798 (1993). A. Baeyer. Villiger. Baeyer-Villiger Reaction A. Rev. B. 32. Copyright © 2001 by Merck & Co. 671-688 (1991). 73 (1957). Org. P. Ed. Whitehouse Station. Hassall. Soc. J.13.. 33.. 3625 (1899). 21. Inc. 429-457 (1967). idem. Ber. 43. Chem. S. New York. Quart. Smith in Molecular Rearrangements Part 1. H. 1963) pp 577-591. Lee. R. de Mayo. The oxidation of ketones to esters or lactones by peracids: Reviews: P. B. USA. Org. V. C. Uff. C. 858 (1900). 7. Krow. Syn. G. React. ibid. (Wiley-Interscience. NJ. All rights reserved. 9. Comp. .

C. Kalinin et al. New J. 1767. J. J. 85 (2000). II 1986. 221. All rights reserved. Allan-Robinson Reaction. 1381. Kostanecki Acylation.. D. 1988. USA. Tetrahedron Letters 39. Baker. Cf. J. Copyright © 2001 by Merck & Co.. V. Jain et al. S. G. Pinto et al. 1934. 1962) p 410. important intermediates in the synthesis of chromones and flavones: Gripenberg in The Chemistry of Flavonoid Compounds. Perkin Trans. Soc.14. A. 24. . Zhu et al. Whitehouse Station. Chem.. Bowden. Chehel-Amiran.. K. Mahal. Geissman. Inc. NJ. (New York. Ed. ibid. M. K. Chem. Base-catalyzed rearrangement of o-acyloxyketones to β-diketones. Mechanistic studies: K. Soc.. 2039. Commun. Venkataraman. Chem. 4995 (1998).. Baker-Venkataraman Rearrangement W. Synthesis 1982. H. Chem. 1933. Synthetic applications: P. 1549.

Zoran et al. Commun. Bamberger. 2239. J. Labelled Compd. Kinetic and mechanistic study: G. 1347. J. 1315 (1988). NJ. 1548 (1894).. Fluorine Chem. Modified conditions: A. Intermolecular rearrangement of N-phenylhydroxylamines in aqueous acid to give the corresponding 4-aminophenols: Early review: H. 74. D. 25. Whitehouse Station. Tordeux.. Kohnstam et al. USA.15. J. New York. Perkin Trans. Elder. M. Synthetic application: D. 251 (1995). Ber. Chem. C. J. 1994. Inc. 1967) pp 182-190.. Wakselman. II 1984. 27. Radiopharm.. Copyright © 2001 by Merck & Co. Bamberger Rearrangement E. Shine. All rights reserved. 423. . Soc. Aromatic Rearrangements (Elsevier. Johnston. Chem.

Formation of olefins by base-promoted decomposition of p-toluenesulfonylhydrazones of aldehydes and ketones: The formation of unrearranged alkenes. H. by treatment of ketone derived ptoluenesulfonylhydrazones with alkyl lithium reagents is known as the Shapiro reaction: R. 55-59 (1983).16. M. Stevens. H. Copyright © 2001 by Merck & Co. 1952. Reviews: R. 4735. J. J. Comp. H. M. Sall. Am. Ghorai. R. Shapiro. Soc. Res. D. R. Bamford. 944-949. A. B. USA. Maruka. Bamford-Stevens Reaction. Shapiro Reaction W. Use of N. Inc.. NJ. Commun. Org. All rights reserved. Sarkar. R. J. .N-diethylaminosulfonylhydrazones: J. 16. A. Barrett. Bull. K. Kang et al. 1992. Org. Syn. 6. K. M. G. Soc. 13. Whitehouse Station. Adlington. Silicon directing effect: T. S. 23. Accts. T. generally the less substituted isomers. Shapiro. 89. Chamberlin. 8. 1184. Korean Chem. React. 5734 (1967). Yamamoto. Heath. J.. 192 (1992). Chem. K. 405-507 (1976). Chem. ibid. 776-779 (1991). Chem.. Chem.

Hong et al. Eds. 67 (1992). P. C. Barbier. Tetrahedron 48.. All rights reserved. 289. One-step procedure for the preparation of alcohols from organic halides and aldehydes or ketones: Review of mechanistic studies of Sm-mediated coupling: D. Whitehouse Station.. Grignard Reaction. (Springer-Verlag. Sm-mediated coupling: M. Curran et al. Commun. New York.17. Chem.. Pharm. 2190 (1994). Acad. Copyright © 2001 by Merck & Co. K.. Chem. NJ. USA. 128. 110 (1899).. Synlett 1992. Znpromoted coupling: F. Kihara et al. 1994. Inc. 943-961. Blomberg. Kunishima et al. The Barbier Reaction and Related One-Step Processes.. Comparison with Ni(0) insertion chemistry for intramolecular cyclization: M. . Hafner et al. Sci. Bull. 1993) 183 pp. R. Cf.. Barbier(-type) Reaction P. Book: C. 42.

and the olefin oxidized with chromic acid to a lower homologous carboxylic acid: H. 29. (Chem. Am. 1958.. C. R. P. . J. Chem. Cf. Barbier-Wieland Degradation H. Wilcox. Copyright © 2001 by Merck & Co. W. Krafft Degradation. 1387 (1988). 3102 (1986). 156. 184 (1947). W. Synthetic applications: S. Inc. A. R. Hofmann. J.. Schteingart. J. 3685. C. Physiol.. Whitehouse Station. The ester is converted to a tertiary alcohol that is dehydrated with acetic anhydride. All rights reserved. Dias. NJ. Lipid Res. Tetrahedron Letters 1976. 1007. Ann. Chem.. Soc. Barbier. USA. Soc. Ber. London) 44. 45. Guadino. Chem. Rend. Miescher Degradation. J. Wieland. D. Z. C. 484 (1912). Soc. 108. Stepwise carboxylic acid degradation of aliphatic acids (particularly in sterol side chains) to the next lower homolog. E. R. 161. 80 (1926).. Ramachandra. Repts. Wieland et al.18. 1443 (1913). Baker et al. Compt. J. J. Locquin. Shoppee.

All rights reserved. J. Soc. Saunders. Soc.. Hamilton. DE 254092 (1910). Whitehouse Station. Cowdry. D. F. 55 (1922). Formation of aromatic arsonic acids by treating aromatic diazonium compounds with alkali arsenites in the presence of cupric salts or powdered silver or copper. G. Ann. Morgan. Ruddy et al. W. K. A. Bart.19.. 1949) p 330. in the Scheller modification primary aromatic amines are diazotized in the presence of arsenious chloride and a trace of cuprous chloride: The modified Bart reaction can be applied to the formation of arylstibonic acids: C. Scheller Modification H. USA. Chem. Inc. 828 (1942). NJ. GB 261026. Am. W. Davies. Quart. Am. 6. J. G. DE 264924 (1910). . H. 1987 (1946). Chem. H. Copyright © 2001 by Merck & Co. 429. Scheller. Doak. S. Rev. A. E. Bart Reaction. Aromatic Diazo-Compounds and Their Technical Applications (London. 363 (1952). React.. 2. Steinman. J. DE 268172 (1912). DE 250264 (1910). 64. 415 (1944). Org. 68. F. O.

1083 (1997). Ziegler. Org. H. Copyright © 2001 by Merck & Co. NJ. Whitehouse Station. E. 62. Belema. eidem. All rights reserved. USA. Radical decarboxylation of organic acids to the corresponding noralkane with tri-n-butyltin hydride or t-butylmercaptan: Synthetic application: F. Chem. Inc. J.. Tetrahedron 41. Barton et al. M. . Barton Decarboxylation D. Chem.. Commun.. 939. R. 1983. 3901 (1985).20.

1987) pp 84-96. C. Barton Deoxygenation (Barton-McCombie Reaction) D.. Intermed. S. W. Chatgilialoglu. Res. Forbes. 1574. S. McCombie. Whitehouse Station. . NJ. Copyright © 2001 by Merck & Co.21. particularly the replacement of trin-butyltin hydride with silicon hydrides: C. Pereyre et al. USA. Tetrahedron Letters 30. E. Review: M. 4367 (1989).. Perkin Trans. Boston. 755-775 (1993). Review of methodological improvements. Zard. Ferreri. Deoxygenation of alcohols via their thiocarbonyl derivatives which undergo free radical scission upon treatment with tri-nbutyltin hydride: Mechanistic study: J. Chem. Inc.. I 1975. 19. All rights reserved. Z. R. Barton. Tin in Organic Synthesis (Butterworths. H.

Copyright © 2001 by Merck & Co. Particularly applicable to the synthesis of moderately hindered tetra-substituted ethylenes: 3 Scope and limitations: D. Barton et al. ibid. Hoogesteger et al. 40. R. K. R. Bachi et al. McMurry Reaction. R. Wassenaar. Olefin synthesis by two-fold extrusion of nitrogen and sulfur from a ∆ -1. Soc. 1226. J. Tetrahedron Letters 1978.. 5018 (1984).. Chem. Org. Cf. M. Schaap. F. J. ibid. S. Chem. Org.. NJ. J. Soc. All rights reserved.22. G. Tetrahedron Letters 1970. Kellogg. J. Synthetic applications: A. 106. Whitehouse Station. E. 2212 (1975). 4375 (1995). 3061 (1973).3. Barton Olefin Synthesis (Barton-Kellogg Reaction) D.. USA. Perkin Trans. McMurry et al. J.. P.. Barton et al. Inc. R. Faler. R. Chem. I 1974. 4689. Am.. 1970. M.4-thiadiazoline intermediate. Chem. Bee et al. J.. H. H. 1987. M. L. 38.. Chem. 60. Kellogg et al. Commun. 4167. . D. 1794.

Soc. Photochem. Synthetic application: A. R. Chem. 2640 (1960). H.. Inc. 263 (1964). USA. Chem. 1552 (1998). 8. Angew. Advan. All rights reserved.23. R. Angew.. Free Radical Chem. J. Barton et al. Ed. 1159. Akhtar. Soc. I 1979. Int. Copyright © 2001 by Merck & Co. Chem. 3. NJ. Kalvoda. 525 (1964). Hesse. R. 82. Advan. Ed. Mechanism: D. Int. 4076 (1961). H. Perkin Trans. Barton Reaction D. Conversion of a nitrite ester to a γ-oximino alcohol by photolysis involving the homolytic cleavage of a nitrogen-oxygen bond followed by hydrogen abstraction: M. 83 (1969). Barton et al.. 37. 2.. 83. Herzog et al. Chem. H.. Am. J. J. Whitehouse Station. .

All rights reserved. 1909.24.. E. D. Pelkey et al. 1996. 7587 (1990). Tetrahedron Letters 35. idem. Commun... 2493 (1994). Formation of a pyrrole by condensation of a substituted nitroso-alkene with an isocyanoester: Synthetic applications: T. Barton-Zard Reaction D. H. Chem.. Barton et al. R. 2031 (1997). 38. . Tetrahedron 46. USA. Copyright © 2001 by Merck & Co. Whitehouse Station. Inc. T. et al. ibid.. Lash et al.. NJ.

769 (1939). NJ.. USA. 1025. W. Maruyama et al. 5889. 63. 3120 (1971). Chem. Chem. 768. J. Whitehouse Station.. 32. hydroxylamine and hydrogen peroxide in the presence of copper salts: K. Am. Chem. Soc. 336 (1940). Tetrahedron Letters 1966. Baudisch Reaction O. Org. Japan 44. Bull. 1027 (1971). . J. 622 (1941). 27. 2516 (1967). Seidenfaden.25. Houben-Weyl 10/1.. Inc. Science 92. Baudisch et al. Naturwiss.. All rights reserved. Copyright © 2001 by Merck & Co. Synthesis of o-nitrosophenols from benzene or substituted benzenes. Soc.

7947 (1994). 1973 both to Celanese). L. Tetrahedron 48. H. J. US 3743669 (1972. 6931 (1993). Inc. Baylis. Chem. Tetrahedron Letters 35.4-diazabicyclo[2.. eidem. E.. Synthetic applications: idem et al.2]octane (DABCO). Drewes et al. DE 2155113. 46. 49. Synth. D. T. E. 2807. Coupling of activated vinyl systems with aldehydes. Fort et al. Rate enhancement study: J. Use of chiral auxillary: S. Augé et al. 253 (1993). 4653-4670 (1988).. Hillman. Tetrahedron 44. E. ibid. P. Copyright © 2001 by Merck & Co. Commun. . E.. catalyzed by 1. 1215 (1993). Baylis-Hillman Reaction A.26. B. M. 23. Aust. 6371 (1992). to yield αhydroxyalkylated or -arylated products: Scope and limitations/mechanistic studies: Y. ibid. NJ. Roos. All rights reserved. Drewes. Perlmutter. USA. Whitehouse Station. D. McCarthy. G.. M. Review: S.. P.2.. van Rozendaal et al.

USA. 2. Inc. 40. React. Helv. 1841 (1949). Yagi et al. Chem. 42(3). F. Reviews: C. R. Bull.. Whitehouse Station. S. J. Acta 62. Reduction of aromatic nitro compounds to the corresponding amines by iron. Hamilton. Morgan. ferrous salts or iron catalysts in aqueous acid: J. A. Copyright © 2001 by Merck & Co. Ann. J. Soc. Houben-Weyl 11/1. All rights reserved.. Chim. Chim. Courtin. 186. Org. . 428 (1944). 194 (1956).27. Béchamp. 1575 (1948). Béchamp Reduction A.. Phys. Ind. 394-409 (1957). Japan 29. (1854). NJ. S. Chem. Schröter. Werner. Eng. 2280 (1980). 41.

Acid-mediated isomerization of oximes to amides. (Interscience. H. Oximes of cyclic ketones give ring enlargements: Certain oximes. Maruoka. NJ. G. Syn. Gawley. are likely to undergo the Beckmann fragmentation to form nitriles instead of amides: Application to steroidal oximes: P. Beckmann. New York. S. 19. Tiemann Rearrangement. Patai. particularly those having a quarternary carbon anti to the hydroxyl. Comp. D. 689-702. Ed. 35. Donaruma. C. E. Z. 1. 6. Catsoulacos. R. Inc. ibid. Beckmann Fragmentation E. . 1 (1993). J. Yamamoto. 30. R. J. Heldt. Org. 988 (1886).. React. 1970) pp 408-439. ibid. Whitehouse Station.28. Reviews: L. Ber. McCarty in The Chemistry of the Carbon-Nitrogen Double Bond. Hauske. USA. Heterocyclic Chem.. K. ibid. Catsoulacos. G. Copyright © 2001 by Merck & Co. 763-775. Org. Schmidt Reaction. 1-156 (1960). 1-420 (1988). Beckmann Rearrangement. D. 11. All rights reserved. 98-100 (1991). Craig. W. 7. Cf.

Normant. Soc. Pasteur et al. 91. Chim... Cuvigny. H. Ber. 1867 (1958). Action of Grignard reagents on enamino ketones or aldehydes yields β-substituted α.29. Bénary Reaction E. Chim. Bull. Soc. Jutz. All rights reserved. Ber. NJ. 1573 (1930).. Bull. . France 1960. France 1965. Whitehouse Station. 64. 2543 (1931). Mechanism: A. 515. Copyright © 2001 by Merck & Co. 2328. USA. Inc. 63.β-unsaturated ketones or aldehydes: T. Bénary. Use of lithio derivatives instead of Grignard reagents: C.

Chem.30. 3230 (1955). Synlett 1993. 475. Comparative review: E. Benkeser et al. I 1975. Birch Reduction. USA.. Am.. Eaborn et al. A. 2796 (1983). 5699 (1952). J. Org. 48. A. 74. All rights reserved. Copyright © 2001 by Merck & Co. .. Benkeser Reduction R. Eckrich.. M. Cf. as well as the fully reduced products. Reduction of aromatic and olefinic compounds with lithium or calcium and low molecular weight amines to monounsaturated olefins. Scope and limitations: R. 344. Kaiser. Soc. Whitehouse Station. Benkeser et al. J. A.. 16. Chem. Perkin Trans. 1 (1960). 391-415 passim.. The extent of reduction and selectivity can be controlled by varying the reaction conditions: Selectivity study: R. Synthesis 1972. Kuck. D. Soc. J. R. Synthetic applications: C. Inc. NJ. Tetrahedron Letters no. Benkeser et al. Chem. 77.

then the favored product is p-aminodiphenylamine (Semidine rearrangement): D. Jacobson et al.4′-diaminobiphenyls. 7077 (1984). Synthetic applications: T. H. All rights reserved. Chem. 576 (1863). Soc. Am. 106. E. Tipper. Inc. Mechanistic studies: H. 26. 62. Nozoe et al. C. F. Azo and Azoxy Groups. Buncel. H. K. 13. Copyright © 2001 by Merck & Co. Cox. London 12. 103. 2. Eds. New York. Kang.31. Roy. S. H. (Wiley. Ed. 955 (1981). C. 5184 (1982).. Ber.. (Elsevier. Letters 1986. H. Chem.. USA. Proc. A. Semidine Rearrangement A. 1975) pp 775-807. J. L. Park. J. Chem. 3794 (1997). . Comprehensive Chemical Kinetics vol. Org.. Williams. Patai. 1577. 1972) pp 437-448. Acid-catalyzed rearrangement of hydrazobenzenes to 4. J. J. New York.. Shine et al. Whitehouse Station. Bamford. 688 (1893). The Chemistry of Hydrazo. If the hydrazobenzene contains a para substituent. P. Hofmann. Soc. pt. R. W. S. Benzidine Rearrangement. 104. NJ.

Rai. . J. 653 (1973). Ber. Whitehouse Station.33. 3535 (1913). USA. Inc. Copyright © 2001 by Merck & Co. S. Buck. Comp. K. 85. H. 46. J. Cf. 4. Benzoin Condensation A. A. M.. Ide. Herlinger. Chem. 995 (1903). NJ. L. Syn.. 1. 1206 (1904). W. 269 (1948). Lapworth. 541-577 (1991). React. Staudinger. J. Cyanide-catalyzed condensation of aromatic aldehydes to give benzoins (acyloins): H. Org. Acyloin Condensation. Org. All rights reserved. Soc. 83. 3530. Hassner. Houben-Weyl 7/2a. S.

1965) pp 238-243. Eastham. N. 25. More commonly perceived to include the migrations of other groups in α-dicarbonyl compounds: Reviews: S. Cram. Org. USA. B. G. Base-induced rearrangement of benzil to benzylic acid via phenyl group migration. J. Ann. 31. Whitehouse Station. NJ. Fundamentals of Carbanion Chemistry (Academic Press. Gill. J. Quart. Liebig. D. Benzilic Acid Rearrangement (Benzil-Benzilic Acid Rearrangement) J. . Inc. Syn. 3.. ibid. Copyright © 2001 by Merck & Co. 221 (1960). 821-838 (1991). 329 (1939). All rights reserved. Rev. F. Selman. Comp. Zinin.32.. 14. 27 (1838).

4th ed. M. NJ.g. Gas World 58. Bergius Process F. 2 (New York. All rights reserved. Fischer-Tropsch Syntheses. Copyright © 2001 by Merck & Co. 490 (1913).. Cf. GB 18232 (1914). Bergius. USA. T. Baldwin in Kirk-Othmer Encyclopedia of Chemical Technology vol..34. . 6 (Wiley. 1950) p 115. New York. Brooks. Inc. 1960) p 166. B.. Formation of petroleum-like hydrocarbons by hydrogenation of coal at high temperatures and pressures (e. The Chemistry of the Nonbenzenoid Hydrocarbons (New York. 1993) p 569. Whitehouse Station. R. 450°C and 300 atm) with or without catalysts. production of toluene by subjecting aromatic naphthas to cracking temperatures at 100 atm with a low partial pressure of hydrogen in the presence of a catalyst.. McGraw-Hill Encyclopedia of Science and Technology vol.

. 33-36. C. Bergman. Chem. Kinetic study: idem et al.. Res. Chem. Grissom et al. . Tetrahedron 50. Chem. Cremer. G. Sci. Proc. (1994). 94.. Inc. R. All rights reserved.. Reaction energetics: E. The cyclization of enediynes to generate 1. Soc. K. Acad.. Copyright © 2001 by Merck & Co. Bergman. 5881-5888 (1993). 5833 (1994).4-benzenoid diradicals: Application to ring annulation: J. J. Soc. Nicolaou et al. Jones. Nat. 6. 4635 (1994). Chem. R. Bergman Reaction R. Reviews of enediyne chemistry and its application to the development of antitumor agents: K. USA 90. 4929 (1994). Kraka. 660 (1972). USA. NJ. Am. G. J. Accts.35. Org. J. Am. D. Nicolaou. Chem. 41. R. 116. 59. Whitehouse Station. Brit. 25 (1973). W.

Whitehouse Station. Copyright © 2001 by Merck & Co. S. 1951) p 181. M. Archer in Amino Acids and Proteins. Inc. Bergmann Azlactone Peptide Synthesis M. Bergmann et al. Conversion of an acetylated amino acid and an aldehyde into an azlactone with an alkylene side chain. followed by catalytic hydrogenation and hydrolysis to the dipeptide: J. Quart. Ed. Erlenmeyer-Plöchl Azlactone and Amino Acid Synthesis. Advan. 15 (1949). IL... 277 (1926). . Fruton. Baltazzi. Ann. 235 (1956). S. reaction with a second amino acid with ring opening and formation of an acylated unsaturated dipeptide. Rev. D. E. All rights reserved. Springfield. (London) 10. USA.36. D. V. 1954) p 29. H. 449.. Greenberg. Cf. Springall. NJ. (Thomas. Protein Chem. The Structural Chemistry of Proteins (New York.

439 (1934). Stepwise degradation of polypeptides involving benzoylation.37. Cf. J. Bergmann. Chem. Science 79. via rearrangement to isocyanates. 1954) p 321. Springall.. Inc. . Copyright © 2001 by Merck & Co. NJ. Biol. USA. Bergmann Degradation M. D. The Structural Chemistry of Proteins (New York. 113. L. Zervas. All rights reserved. 341 (1936).. this treatment yields. Whitehouse Station. Curtius Rearrangement. Bergmann. H. conversion to azides and treatment of the azides with benzyl alcohol. carbobenzoxy compounds which undergo catalytic hydrogenation and hydrolysis to the amide of the degraded peptide: M.

Formation of the N-carbobenzoxy derivative of an amino acid for use in peptide synthesis and liberation of the amino group at an appropriate stage of synthesis by hydrogenolysis of the labile carbon-oxygen bond: C. Archer in Amino Acids and Proteins. M. NJ. Chem. The Chemistry of the Amino Acids and Proteins (Thomas. Inc. 1951) p 177. Soc. A. (Charles C. Fischer Peptide Synthesis. Cf. Greene. Greenberg. G. Ber. 1944) p 262. USA.. 65. Protective Groups in Organic Synthesis (Wiley. Springfield. All rights reserved. W. 3689. L. Kenner. . IL. New York. Thomas. IL. J.38. S. Bergmann. Ed. Springfield. Bergmann-Zervas Carbobenzoxy Method M.. 1956. W. Whitehouse Station. 1981) p 239. L. Zervas. Schmidt. D. Copyright © 2001 by Merck & Co. 1192 (1932). T.

Soc.. usually in the presence of zinc chloride: A. 1 (1884). Buu-Hoi et al. 571 (1992). Formation of 5-substituted acridines by heating diarylamines in organic acids or anhydrides. Acridines (Interscience. NJ. Whitehouse Station. 1955. Popp.39. A. USA. Albert. 1082. F. J. Bernthsen Acridine Synthesis A. . 29. R. Org. New York. 1951) p 67. Alkyl migration: L. 502 (1952). Klemm et al. Ann. Albert... J. Copyright © 2001 by Merck & Co. H. M. 192. 1 (1878). Bernthsen. 1956) pp 19-25. P. D. Chem. Heterocyclic Chem. Weissberger.. 224. The Acridines (London.. 2658 (1962). All rights reserved. Heterocyclic Compounds 4. N. Ed. 27. A. Chem. Inc. Acheson in The Chemistry of Heterocyclic Compounds.

40. Betti Reaction
M. Betti, Gazz. Chim. Ital. 30 II, 301 (1900); 33 II, 2 (1903); F. Pirrone, ibid. 66, 518 (1936); 67, 529 (1937). The reaction of aromatic aldehydes, primary aromatic or heterocyclic amines and phenols leading to α-aminobenzylphenols:

J. P. Phillips, Chem. Rev. 56, 286 (1956); J. P. Phillips, E. M. Barrall, J. Org. Chem. 21, 692 (1956). Early review: J. P. Phillips, Leach, Trans. Kentucky Acad. Sci. 24(3-4), 95 (1964). Mechanistic study: H. Möhrle et al., Chem. Ber. 107, 2675 (1974). Stereoselectivity: C. Cardellicchio et al., Tetrahedron Asymmetry 9, 3667 (1998). Cf. Mannich Reaction.
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41. Biginelli Reaction
P. Biginelli, Ber. 24, 1317, 2962 (1891); 26, 447 (1893). Synthesis of tetrahydropyrimidinones by the acid-catalyzed condensation of an aldehyde, a β-keto ester and urea:

H. E. Zaugg, W. B. Martin, Org. React. 14, 88 (1965); D. J. Brown, The Pyrimidines (Wiley, New York, 1962) p 440; ibid., Suppl. I, 1970, p 326, F. Sweet, Y. Fissekis, J. Am. Chem. Soc. 95, 8741 (1973). Synthetic applications: M. V. Fernandez et al., Heterocycles 27, 2133 (1988); K. Singh et al., Tetrahedron 55, 12873 (1999); A. S. Franklin et al., J. Org. Chem. 64, 1512 (1999). Modified conditions: C. O. Kappe et al., Synthesis 1999, 1799; J. Lu, H. Ma. Synlett 2000, 63.
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42. Birch Reduction
A. J. Birch, J. Chem. Soc. 1944, 430; 1945, 809; 1946, 593; 1947, 102, 1642, 1949, 2531. Reduction of aromatic rings by means of alkali metals in liquid ammonia to give mainly unconjugated dihydro derivatives:

Reviews: A. J. Birch, H. Smith, Quart. Rev. (London) 12, 17 (1958); D. Caine, Org. React. 23, 1-258 (1976); P. W. Rabideau, Z. Marcinow, ibid. 42, 1-334 (1992); J. M. Hook, L. N. Mander, Nat. Prod. Rep. 3, 35-85 (1986); L. N. Mander, Comp. Org. Syn. 8, 489-521 (1991). Cf. Benkeser Reduction.
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43. Bischler-Möhlau Indole Synthesis
A. Bischler et al., Ber. 25, 2860 (1892); 26, 1336 (1893); R. Möhlau, ibid. 14, 171 (1881); 15, 2480 (1882); E. Fischer, T. Schmitt, ibid. 21, 1071 (1888). Formation of 2-substituted indoles by heating ω-halogeno- or ω-hydroxy- ketones with excess aniline via cyclization of the intermediate 2-arylaminoketone:

P. L. Julian et al., Heterocyclic Compounds 3, 22 (1952); R. J. Sundberg, The Chemistry of Indoles (Academic Press, New York, 1970) p 164; R. K. Brown in The Chemistry of Heterocyclic Compounds, A. Weissberger, E. C. Taylor, Eds., Indoles, Part I, W. J. Houlihan, Ed. (Wiley, New York, 1972) p 317; J. R. Henry, J. H. Dodd, Tetrahedron Letters 38, 8763 (1998).
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44. Bischler-Napieralski Reaction
A. Bischler, B. Napieralski, Ber. 26, 1903 (1893). Cyclodehydration of β-phenethylamides to 3,4-dihydroisoquinoline derivatives by means of condensing agents such as phosphorous pentoxide or zinc chloride:

W. M. Whaley, T. R. Govindachari, Org. React. 6, 74 (1951); T. Kametani et al., Tetrahedron 27, 5367 (1971); G. Fodor et al., Angew. Chem. Int. Ed. 11, 919 (1972); G. Fodor, S. Nagubandi, Tetrahedron 36, 1279 (1980); eidem, Heterocycles 15, 165 (1981). Review of enantioselective modifications: M. O. Rozwadowska, ibid. 39, 903-931 (1994). Cf. Bradsher Reaction; Pechmann Condensation; Pictet-Gams Isoquinoline Synthesis; Pictet-Hubert Reaction; Skraup Reaction.
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45. Blaise Ketone Synthesis; Blaise-Maire Reaction
E. E. Blaise, A. Koehler, Bull. Soc. Chim. [4] 7, 215 (1910); E. E. Blaise, M. Maire, Compt. Rend. 145, 73 (1907); E. E. Blaise, Bull. Soc. Chim. [4] 9, 1 (1911). Formation of ketones by treatment of acid halides with organozinc compounds; the use of β-hydroxy carbonyl chlorides to give β-hydroxy ketones, convertible into α,β-unsaturated ketones in boiling dilute sulfuric acid, is known as the Blaise-Maire reaction:

J. Cason, Chem. Rev. 40, 17 (1947); D. A. Shirley, Org. React. 8, 29 (1954).
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46. Blaise Reaction
E. E. Blaise, Compt. Rend. 132, 478 (1901). Formation of β-oxoesters by treatment of α-bromocarboxylic esters with zinc in the presence of nitriles. The intermediate organozinc compound reacts with the nitrile and the complex is hydrolyzed with 30% potassium hydroxide:

A. Horeau, J. Jacques, Bull. Soc. Chim. 1947, Mem. 58; J. Cason et al., J. Org. Chem. 18, 1594 (1953); H. Henecka, Houben-Weyl 7/2a, 518 (1973); K. Nützel, ibid. 13/2a, 829. Modified conditions: S. M. Hannick, Y. Kishi, J. Org. Chem. 48, 3833 (1983); N. Zylber et al., J. Organometal. Chem. 444, 1 (1993); K. Narkunan, B.-J. Uang, Synthesis 1998, 1713. Stereoselectivity: J. J. Duffield, A. C. Regan, Tetrahedron Asymmetry 7, 663 (1996); A. S.-Y. Lee et al., Tetrahedron Letters 38, 443 (1997); J. Syed et al., Tetrahedron Asymmetry 9, 805 (1998). Cf. Reformatsky Reaction.
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47. Blanc Reaction (Chloromethylation)
G. Blanc, Bull. Soc. Chim. France [4], 33, 313 (1923). Introduction of the chloromethyl group into aromatic rings on treatment with formaldehyde and hydrogen chloride in the presence of zinc chloride:

Reviews: R. C. Fuson, C. H. McKeever, Org. React. 1, 63 (1942); G. Olah, W. S. Tolgyesi, in Friedel-Crafts and Related Reactions vol. II, Part 2, G. Olah, Ed. (Interscience, New York, 1963) pp 659-784. Cf. Quelet Reaction.
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Cyclization of dicarboxylic acids on heating with acetic anhydride to give either cyclic anhydrides or ketones depending on the respective positions of the carboxyl groups.4.. Rend.5-diacids yield anhydrides. while diacids in which the carboxy groups are in 1. Copyright © 2001 by Merck & Co. . Blanc Reaction-Blanc Rule H. K. Ed. Kwart.48. Whitehouse Station. London. USA. King in The Chemistry of Carboxylic Acids and Esters. 640 (1973). 1. Blanc.and 1. K. Bode. All rights reserved. NJ. Inc. Houben-Weyl 7/2. Ruzicka Large Ring Synthesis. Cf.. 1356 (1907). Patai. G. (Interscience. 144. 1969) p 362. D. J.6 or further removed positions yield ketones: H. Compt.

138. DeWolfe. 37. All rights reserved. NJ. USA. H. 186. Rend. H. Smith et al. Copyright © 2001 by Merck & Co. Meerwein. I. A. Org. Bodroux. 489 (1941). Houben-Weyl 6/3. . J.49. 437. Formation of aldehydes by treatment of orthoformates with Grignard reagents: L. New York. Inc. 850 (1904). The Chemistry of the Aliphatic Orthoesters (New York. Ber.. 6. 1970) p 224.. E. Compt. Post. 1943) p 96. Bouveault Aldehyde Synthesis. R. Cf. Carboxylic Orthoacid Derivatives (Academic Press. W. Chichibabin. Whitehouse Station. 92 (1904). H.. Bodroux-Chichibabin Aldehyde Synthesis F. Chem. 243 (1965).

1188. Bodroux. 142. Compt. Houben-Weyl 13/2a. Soc. 1954. Bassett. 1427 (1904). 138. . NJ. Bull. France 33. J. Bodroux Reaction F. 401 (1906). 35. Formation of substituted amides by reaction of a simple aliphatic or aromatic ester with an aminomagnesium halide obtained by treatment of a primary or secondary amine with a Grignard reagent at room temperature: H. 519 (1906)..50. 1108 (1905). C. 912 (1907). K. 278 (1973).. Rend. Thomas. R. L. 831 (1905). Soc. All rights reserved. Chim. Copyright © 2001 by Merck & Co. Inc. Chem. USA. Whitehouse Station. 1. Nützel. 140.

51. Copyright © 2001 by Merck & Co. Science 77. see D. Hewett. W. J. Evans et al. F. J. USA. Fieser. J.. Whitehouse Station. M. Am. Bogert-Cook Synthesis M. Soc. 1098. 1933. A. 3620 (1973). Schmidt et al. For a general approach to the synthesis of phenanthrenoid compounds... 289 (1933). J. 1949) p 90. L. C. T. Cook. All rights reserved. C. Inc. Natural Products Related to Phenanthrene (New York. 99. Chem. .. Condensation of β-phenylethylmagnesium bromide with cyclohexanones followed by cyclodehydration of the tertiary alcohol with concentrated sulfuric acid with formation of octahydrophenanthrene derivatives and a small amount of spiran: L. Soc. Fieser. 51. Chem. Chem. 7083 (1977). Can. Bogert. NJ.

Chem.. Chim. R. Organic Chemistry (New York. . Rev. Copyright © 2001 by Merck & Co. Indian J. Dhruva et al. 168 (1929). Fieser.. Bohn. Helv. Phillips. B. 14 (B). Studies and proposed mechanism: J. Hydroxylation of anthraquinones containing at least one hydroxyl group by treatment with fuming sulfuric acid or sulfuric acid and boric acid in the presence of a catalyst such as mercury: Reviews: M. R. All rights reserved. E. Inc. DE 60855 (1891). Fieser. DE 46654 (1889). Acta 48.52. 1956) p 903. Chem. USA. Jenny.. Winkler. W. 6. Whitehouse Station. 622 (1976). 119 (1965). Bohn-Schmidt Reaction R. Schmidt. NJ.

55. Swallen. Org. NJ. H. J. 3396 (1930). Boord Olefin Synthesis L. 52. Chem.. USA.. Soc. Application to taxanes: J. 227 (1942). Inc. Tetrahedron Letters 35. 53. (London) 6. P. Chim. 131 (1952). Schlosser. 52. J. Wagner. Beusker et al. 3617 (1994). 11. Dykstra et al. J. L. Crombie. ibid. All rights reserved. Org. Bandart. 3293 (1933).. C. D. Chem. Boord. Whitehouse Station. Chem. 1998. 7. M. P. Yadav et al. Eur. 1505 (1931). Houben-Weyl 5/1b. Regiospecific synthesis of olefins from aldehydes and Grignard reagents by zinc induced reductive elimination of halogen and alkoxy groups: C. . Quart. 336 (1944). 651 (1930).. S.53. E. H. Copyright © 2001 by Merck & Co. 213 (1972). Am. C. Bull. Rev. Soc. 2483. C. B. Niemann.

Chem. 361 (1947). 40. Barclay. 20. Chem. B. M. 378 (1904). Drechsel. Ber. Whitehouse Station. Rev. 2222 (1970). Prakt. Feise. . 38(2). Heterocyclic Compounds 3. Copyright © 2001 by Merck & Co. NJ. Borsche. Campbell.54. P. 298 (1952). J.. Borsche-Drechsel Cyclization E. Org. Fischer Indole Synthesis. 35. All rights reserved. J. W. Formation of carbazole by acid-catalyzed rearrangement of cyclohexanone phenylhydrazone to tetrahydrocarbazole followed by oxidation: N.. Cf. Bruck. Piloty-Robinson Synthesis. Freudenberg. Inc. W. Chem. M. Bucherer Carbazole Synthesis. 69 (1858). USA.

NJ. 75. E. USA. Bull. J. Action of Grignard or organic lithium reagents on N. France 31. . (London) 1957. Chem. Prakt. 1322 (1904). Org. J. Chem. & Ind. L. Bouveault Aldehyde Synthesis L. 1306. 1596. Bouveault. Smith. J. 1958. Evans. J. 466 (1999). Luche. Chem. Sicé J. Jones et al. Whitehouse Station.55. 3697 (1953). Cf. Einhorn. All rights reserved. Aust.N-disubstituted formamides yields the homologous aldehydes: L. J.. J. Chem. 1791 (1986). 489 (1941). H. Synthetic applications using modified conditions: C. 27.. I. 3361 (1982). R. H. Am. 341. Inc. Tetrahedron Letters 23. Soc. Meier. Copyright © 2001 by Merck & Co. 6. 1054. A. ibid. H. Chim.. Pétrier et al. Use of lithio derivatives instead of Grignard reagents: E. Bodroux-Chichibabin Aldehyde Synthesis. Nichols. Soc. J. Chem. Soc..

666 (1904). Benjamin.. Compt. 2nd ed. Bouveault.56. Formation of alcohols by reduction of esters with sodium and an alcohol: H. USA. O. 1972) p 150.. Rend. Whitehouse Station. All rights reserved. Bouveault-Blanc Reduction L. G. France [3] 31. A. Chim.. Modern Synthetic Reactions (W. 1676 (1903). NJ. Copyright © 2001 by Merck & Co. California. Blanc. Soc. House. 136. . Inc. Bull. Menlo Park.

Alkaline persulfate oxidation of aromatic amines to yield predominantly the o-amino aryl sulfates. 421-511 (1988). J. Org. Org. 57. E. P. 3623..57. 2266 (1992). J. Behrman. Cf. Copyright © 2001 by Merck & Co. USA. Sims. Boyland. Chem. Chem. 35. Review: idem. Whitehouse Station. Acid-catalyzed hydrolysis generates the o-hydroxy aryl amines: Regioselectivity/mechanistic study: E. All rights reserved. Elbs Persulfate Oxidation. Boyland-Sims Oxidation E. 1953. React.. . Inc. 1954. J. 980. Soc.. NJ. ibid. Boyland et al.

Solomons. M. NJ. T. K. Stone. . Whitehouse Station. [4 + 2] addition of a common dienophile with cationic aromatic azadienes such as acridizinium or isoquinolinium: Mechanistic study: C. J. 6904 (1995). A. Chem. Nicolas. 69.58. Copyright © 2001 by Merck & Co.. Chem. E. Inc. J. R. Org. Soc. 519 (1968). Hetero Diels-Alder Methodology in Organic Synthesis (Academic Press.. H. G. W. Bradsher. USA. K. Am. ibid. Soc. S. 644 (1992). 33. Review: D. J. Chem. 57. Boger. 1987) pp 239-299. Bolitt et al. T. 80. NY. Bradsher. 6320 (1991). Org. Chem. Weinreb. Franck. 113. J. Am. J. L... Yin et al. W. 933 (1958). Synthetic applications: V. All rights reserved. Bradsher Cyclization (Bradsher Cycloaddition) C.

Bischler-Napieralski Reaction. Inc. Bradsher Reaction C. Soc.. 87. Whitehouse Station. Cf. Chem. USA. Bradsher. . J. J. K. Perkins Trans. Rev. Application: T. All rights reserved. 1 1997. Acid-catalyzed cyclodehydration of o-acyldiarylmethanes to anthracene derivatives: Extension to an o-acyldiaryl ether: H. Chem. 1277-1297 (1987). 1193.. 486 (1940). Chem. Tetrahedron 50.59.. Soc. K. Copyright © 2001 by Merck & Co. Review: C. NJ.. Bradsher. Ishibashi et al. 10215 (1994). 62. Yamato et al. Am.

G. 1886 (1958). 257. Brook. Reich et al. Am. NJ. Takeda et al.. Base-catalyzed silicon migration from carbon to oxygen in α-. Accts. Chem. 81. Chem. Synthetic applications: H. Brook. . Chem. Chem. J. Soc.. Whitehouse Station. β.. Brook Rearrangement A. I 1994. Soc. All rights reserved. Synlett 1993. 80. 77-84 (1974). J. Copyright © 2001 by Merck & Co. U. 7.and γ-silyl alcohols. Inc. G.60. 981 (1959). 5609 (1990). ibid. Fleming. Ghosh et al. Am. 112.. idem et al. USA. yielding silyl ethers: Early review: A. K. I. J... Perkin Trans. J. Res. Soc. 841.

Tetrahedron 36. Bergs. J. H. 69 (1934).-I. Tetrahedron Asymmetry 6. Copyright © 2001 by Merck & Co. Med. ibid. ibid. Strecker Amino Acid Synthesis. Bucherer-Bergs Reaction H. 33. Chem. Pharmazie 52. Chem. Cf. or from the corresponding cyanohydrin and ammonium carbonate: E. Ware. Knabe. 511 (1997). Fischbeck... . DE 566094 (1929). W. A. NJ. Prakt. Rev. USA. 1641. Preparation of hydantoin from carbonyl compounds by reaction with potassium cyanide and ammonium carbonate. Whitehouse Station.. 8. H. J. All rights reserved. Chem. 422 (1950). T. 912 (1997). Domínguez et al. 2271 (1995). Bucherer. 291. Urech Cyanohydrin Method. C. Sarges et al. Steiner. Modified conditions: R.61.. T. H. T. 1859 (1990). J. Bucherer. Synthetic applications to excitatory amino acids: K. Tanaka et al. 140. Inc.. 2649 (1980). 46.. Rousset et al.

Houben-Weyl 10/2. aryl hydrazines and sodium bisulfite: Reviews: N. L. Enders. Org. 114 (1942).. 1. J. T.62. 403 (1908). . Borsche-Drechsel Cyclization. F. React. Chem. Seyde. Prakt. 250 (1967). 77(2). Formation of carbazoles from naphthols or naphthylamines. Bucherer Carbazole Synthesis H. Whitehouse Station. E.. NJ. Cf. USA. All rights reserved. Inc. Drake. Bucherer. Copyright © 2001 by Merck & Co.

Tetrahedron Letters 1969. R. J. Mulhouse 1903. Chem. 102 (1986).. Drake. J. T. Int. Bucherer Reaction H. Ind. USA. All rights reserved. 1968) p 37. Org. Ed. London. Org. M. 307 (1967). Allan et al.. Lepetit. 4855. Soc. . Angew. Tetrahedron 48. Whitehouse Station. 326. React. Copyright © 2001 by Merck & Co. 49 (1904). S. H. Chem. Ed.. T. 9207 (1992). H.63. Pochapsky. W. Bendig et al. Pirkle. Inc. (Interscience. Patai. 1. NJ. 51. Seeboth. L. Reversible formation of β-naphthylamine from β-naphthol and aqueous ammonium sulfite or bisulfite via intermediate formation of tetralonesulfonic and tetraloneiminosulfonic acids: N. Prakt. C. Z. Bull. Gibson in The Chemistry of the Amino Group. S. Bucherer. 6. Chem. [2] 69. J. 105 (1942)..

Buchner. J.. 2559 (1909). NJ. Bastus. 2371 (1885). Eistert in Newer Methods of Preparative Organic Chemistry. Tetrahedron Letters 1963. Inc. ethylene oxides may also be formed: B. . Gutsche. Whitehouse Station.64. 955. 479 (1907).. F. Ber. 40. B. 18. T. 364 (1954). 8. React. Buchner-Curtius-Schlotterbeck Reaction E. Ber. Schlotterbeck. English Ed. USA. D. C. Copyright © 2001 by Merck & Co. 42. 1948) p 521. Curtius. Org. All rights reserved. (New York. Formation of ketones from aldehydes and aliphatic diazo compounds.

NJ. All rights reserved. Soc. J. Pfau-Plattner Azulene Synthesis. H. Inc. Diazoacetic acid ester reacts with benzene and homologs to give the corresponding esters of noncaradienic acid.. von F. transformed at high temperatures to derivatives of cycloheptatriene and phenylacetic acid: W.. Buchner Method of Ring Enlargement E. Org. A. 873 (1981). Knox.. New York. E.. Carbene Chemistry (Academic Press. Schottenhammer. Chem. 106 (1896). . Buchner. 79. Chem. K. Ber. Kirmse. 53. Noels et al. Whitehouse Station. L. F. 2nd ed. Ber. Buchner. 865 (1920). 1971). Cf.65. Copyright © 2001 by Merck & Co. 352 (1957). Doering. Am. W. 46. USA. 29. J.

L.. Ed. J. . 34. MacNeil et al.66. Hartwig. Angew. Tetrahedron Letters 36.. Buchwald-Hartwig Cross Coupling Reaction J.. USA. Chem. 3609 (1995). F. 2046-2067 (1998). All rights reserved. Hartwig. Louie. 419. Whitehouse Station. 37. A. Angew. 1348 (1995). Chem. Metal catalyzed formation of an arylamine by a reaction of aryl halide of triflate with primary or secondary amine: Application: S. Inc.. Review: J. Synlett 1998. NJ. Ed. S. Int. Int. Guram et al. F. Copyright © 2001 by Merck & Co.

Formation of hydroxyquinolines from o-acylaminoacetophenones in alcoholic sodium hydroxide. Chem. H. B. Pharm. 2641 (1951). Bull. Pharm. R. 73. 2760 (1954). Two isomers are produced. Copyright © 2001 by Merck & Co. Ber. 3228 (1899). 76. NJ. C. Camps Quinoline Synthesis R. J. 1080 (1973). Rev. H. Chem.67. Whitehouse Station. All rights reserved. 30. Camps.. .. Am. Heterocyclic Compounds 4. F. Witkop et al.... 127 (1942). Yanagisawa et al. 22. Inc. Arch. USA. 21. 237. the relative proportions are mainly determined by the residue on the amino nitrogen: R. ibid. Bornstein et al. J. 239. 60 (1952). Elderfield. 591 (1901). Manske. Soc. 659 (1899). Chem..

Inc. A. Geissman. 90. Whitehouse Station. K. USA. 1061 (1981). Limpricht. Am. 1998) p 40-42. Meerwein-Ponndorf-Verley Reduction.. NJ. Sibley. J. G. Swain et al. F. E. Soc. Van der Maeden et al. 129 (1853). J. H. C. 101. Cannizzaro. Copyright © 2001 by Merck & Co. Ann. 180 (1854). the reaction is called the “crossed Cannizarro reaction”: T. . Ann. Cannizzaro Reaction S. Cf. Tishchenko Reaction. 88. Can. 2. Chichester.. 94 (1944). Chem. Pays-Bas 91(2). 59. S. McDonald. All rights reserved. A. Plagens. If the aldehydes are different. Trav. Lane. Rec.. Chim. P. Review: T. 221 (1972).68. Oppenauer Oxidation. Named Organic Reactions (John Wiley & Sons. React. 3576 (1979). List. C.. Org. Chem. R. Base-catalyzed disproportionation reaction of aromatic or aliphatic aldehydes with no α-hydrogen to corresponding acid and alcohol. B.

Wilson.. Echavarren et al. 34. 1992 (1943). Carroll. C. V. Cope. Claisen Rearrangement. Chem. N. 1940. 68. 65. 6421 (1991). Soc. 704. C.69. 1149 (1993). Inc. A. Kimel. Synthetic applications: A. Preparation of γ. 507. Whitehouse Station. 1941. . Am. Tetrahedron Letters 32. E. Soc. Carroll Rearrangement M.. W. J. F. J. USA. R.. Ouvrard et al. Syn. ibid. NJ. Chem. Augelli. All rights reserved. Org.δ-unsaturated ketones by base-catalyzed reaction of allylic alcohols with β-ketoesters or thermal rearrangement of allyl acetoacetates: Detailed experimental: S. Cf. 210 (1990). Copyright © 2001 by Merck & Co..

Castro-Stephens Coupling (Stephens-Castro Coupling. Div. 299. Stephens. R. Glaser Coupling. Org. Org. C. Whitehouse Station. R.. 868-896 (1979). Stephens. Castro. Castro Reaction) C. Synthesis 1995. . Rev. E. Sci. R. Early reviews: G.. D. Kabbara et al. M. Castro. Tetrahedron Letters 39. Sladkov et al. ibid. Posner. USA. D. Yu et al. Inc. NJ. Chem. Sladkov. Cf. 1963. 2043. 9347 (1998).70. S. Bull.. 253-400 passim (1975). All rights reserved. E.. A. Synlett 1993. React. Sci. M. 28. 3313. The coupling of cuprous acetylides with aryl halides to yield arylacetylenes: Synthetic applications: J. USSR. H.. 2163 (1963). M. Russ. J. J. Copyright © 2001 by Merck & Co.. D. Kinder et al. A. Chem. 22. Chem. 48. 149. Acad. I. Gol'ding.

Soc. H. USA.. Chim. Mumm et al. 1992 (1925). Dubau-Assibat et al. 132. Inc. J. Bull. Soc. McCarty. Patai. 569. Soc. 1927. Copyright © 2001 by Merck & Co. 48. Chapman-like rearrangements: F. Suttle. J. (Interscience. Schulenberg et al. Dessolin et al. Esser et al.. 1139 (1995). Whitehouse Station. Perkin Trans. 18. Org. Heterocyclic Chem. Mechanistic study: N. 1975) p 189. Garner in The Chemistry of Amidines and Imidates S. Commun. J. Perkin Trans. A. 3311. Chem. 174. A.. 1 (1965). C. A. Thermal rearrangement of aryl imidates to N. Ber.. 659 (1981). Fr. Chem. 127. 1929.. Chapman. 1992. 379 (1915). All rights reserved. G. Peterson et al. NJ. 1369. Williams. W. L. II 1983. .. N.. New York. J. Soc. W. M. 132. React. 14. Chem. Synthetic applications: L. Chem. Chapman Rearrangement O.N-diaryl amides: J..71. I 1988. Ed.

Soc. H. M. Chem. Mosher.. 16. Soc. J. T. Heterocyclic Compounds 1. Phys. P. 26. Cf. the reaction is reversible and produces different pyridine derivatives along with byproducts: M. E. Renault. 588. 456 (1950). Chim. Chem. 3477 (1956). Soc. J. Copyright © 2001 by Merck & Co. J. A. Kröhnke Pyridine Synthesis. 301 (1940). 37. Sprung. Inc. Soc. P. 122 (1924). Prakt. Soldatenkov. NJ. Chem. Chem. 78. E. Russ. Rev. Frank. Eliel. Chem. Chichibabin. 1229 (1906). Whitehouse Station. Am. A. France 1955. Khim. USA.. J. R. Zh. 2629 (1949). J. Farley. Seven. Bull. S. Chichibabin Pyridine Synthesis A. Am. R. . Org. J. C. Hantzsch (Dihydro)Pyridine Synthesis. 107. Gautier. All rights reserved. 188 (1980). Condensation of carbonyl compounds with ammonia or amines under pressure to form pyridine derivatives.72. L. L. 71.

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56. Garratt. 266-322 (1942). All rights reserved. React. House. . 2. 651 (1887). Benjamin. 721 (1979). Comp. Claisen. Ed. A. Claisen Condensation (Acetoacetic Ester Condensation) L. J. Dieckmann Reaction. J. Am. P. J. 795-805 (1991). Cf. Ber. 103. Garst.. Hauser. Chem. Soc. Org. Lowman. 1972) pp 734-746. Bartmess et al. B. Base-catalyzed condensation of an ester containing an α-hydrogen atom with a molecule of the same ester or a different one to give β-keto esters: C. F. Org. 1. B. Menlo Park. NJ. R.. Whitehouse Station. O. USA.76. E. Chem.. 1338 (1981). 2nd ed.. R. Hudson. Syn. E. J. Copyright © 2001 by Merck & Co. California. O. J. 20. Davis. H. Modern Synthetic Reactions (W. Inc.

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Rev. Haaf. Inc.. Am. 110. Ann. H. Copyright © 2001 by Merck & Co. Olah. 21B. 618. Extension to amides: C. Möller. Olah in Friedel-Crafts and Related Reactions vol. J. Koch. Formation of tertiary carboxylic acids by treating alcohols with carbon monoxide in strong acid: H. J. Brennstoff Chem. 47. C. Reviews: K. Chem. E. Y. 405 (1982). ibid. G. 1241 (1989). 10 (1966). Bahrmann. Eidus. W. 1964) pp 1272-1296. USA. (Interscience. . Rev. H.. Rev. Falbe. Part 2. Olah. 20B. Chem. 321 (1955). 864 (1988). Langhals et al. R. R. 34. et al. Extension to olefins: G. 36. (Springer-Verlag. Chem. Indian J. Ed. Russ. 251 (1958). Soc. Carp. 283 (1962). eidem.. T. Tetrahedron Letters 22. Bird. Farooq et al. Chim. “Koch Reactions” in New Syntheses with Carbon Monoxide. J. O. E. 1980) pp 372-413. Koch-Haaf Carboxylations H. 207 (1981). Whitehouse Station. New York. 2365 (1981). Ed. All rights reserved. Leonte. New York. W. Brennstoff Chem. NJ. Chem. 199 (1973).. Rao. Bhattacharya.218. Roum. 62.. Koch. A. J. 3. 42.

A. Chem. Org. 1257 (1979). Sheldon. 19. P. 57. Inc.. J. Kochi Reaction J. Kochi. M. Soc.. Synthesis of organic chlorides by decarboxylation of carboxylic acids in the presence of lead tetraacetate and lithium chloride: R. USA. Can. K. Whitehouse Station. 2500 (1965). NJ. Aycard.219. J. K. React. All rights reserved. Copyright © 2001 by Merck & Co. Hunsdiecker Reaction. 87. Cf. Kochi. Mannier. 279 (1972). . Am. J. Chem. J.

J. Chem. 6. Koenigs-Knorr Synthesis W. 41-52 (1951). Chem.. Laszlo et al. E. 337 (1991). The reaction proceeds with inversion of configuration: Reviews: Evans et al. 34. 6. R. 957 (1901).. 474-480 (1972). 33-64 (1991). Carbohyd. Lichtenthaler. Stereoselectivity: J. Carbohyd. F. Ber. 15. Whitehouse Station. S. M. 1999. Advan. R. W.-I.220. 12. Methods Carbohyd. Chem. 893 (1993). Copyright © 2001 by Merck & Co. NJ. . 591.. W.. Schmidt. Milius et al. Chem. USA. Tetrahedron Letters 38. Commun. Igarashi. Knorr. 34. Applications: A. 6. Flowers. Tamaru et al.. 5477 (1997). K. Org. 243 (1977). All rights reserved. H. Formation of glycosides from acetylated glycosyl halides and alcohols or phenols in the presence of silver salts. Comp. New J. Inc. Chem. Metz. ibid. Koenigs. Syn.. T.

Syn. M. Japan. K. Hiebl et al. Crum Brown. Org. 257 (1849). 67. Reviews: B. L. J.. L. Soc. Ann.221. Sugiya. Schäfer. Vijh. Weedon.. Crum Brown-Walker Reaction H. Noshira. E. Tetrahedron 54. J. 73. Nuding et al. J. 6. Weiguny. C. Ann. 623 (1967). Letters 1998. A. Chem. The coupling of two distinct carboxylates yields unsymmetrical products: The dimerization of half-esters is known as the Crum Brown-Walker reaction: A. 1994.. eidem. Schäfer. Copyright © 2001 by Merck & Co. Rev. USA. 1973) pp 469-507. Inc. ibid. 705 (2000).. 71. Synthesis 1996. H. J. 479. 261. . J. 3. (M. G. Baizer. H. M. Quart. 2059 (1998). H. NJ. Walker. B. Comp. New York. 69. M. Whitehouse Station. 633-658 (1991). Dekker. Bull. Chem. 225. Formation of symmetrical dimers by the electrolysis of carboxylates (decarboxylative dimerization). Rev. Conway. Kolbe. Kolbe Electrolytic Synthesis. Eberson in Organic Electrochemistry. Ed. All rights reserved. Chem. 107 (1891). 380 (1952).

Whitehouse Station. Chem. S. 1954. [2] 31. Carbanions in Synthesis 1966. 57. Jeskey.. March. Rev. Ayres. . 4th ed.. Kolbe. USA. 397 (1885). New York. NJ. R. by carbon dioxide: Reviews: A. Kolbe-Schmitt Reaction H. 113. 3145. J. mostly in the ortho position.222. Advanced Organic Chemistry (Wiley-Interscience. 168-173. J. Inc. All rights reserved. Ann.. Formation of aromatic hydroxy acids by carboxylation of phenolates. Schmitt. H. Chem. J. Copyright © 2001 by Merck & Co. C. D. 1992) p 546. J. Soc. 125 (1860).. Prakt. 583 (1957). Chem. Hales et al. L. Lindsey.

All rights reserved. T. R. 1381. React. Cf.. J. Trivedi.. A. Ber. R. Y. R. Inc. Kostanecki Acylation S. C. Szell et al. 49. USA.223. 713 (1972). Tetrahedron 25. 8. S. 49.. followed by cyclization: W. 34. Rozycki. 715 (1969). 2636 (1969). idem et al. Allan-Robinson Reaction. Formation of chromones or coumarins by acylation of o-hydroxyaryl ketones with aliphatic acid anhydrides. Acta 52. J. 25 (1972). Shaikh. K. Hauser. N. ibid. Org.. ibid. S. Save et al.. 599. 91 (1954). 102 (1901). NJ. Soc. Chim. von Kostanecki. Indian Chem. Chem. Baker-Venkataraman Rearrangement. 675 (1971). Save et al. Copyright © 2001 by Merck & Co.. Helv. 1933. Whitehouse Station. Soc. 48. . A. Baker.

224. Krafft Degradation
F. Krafft, Ber. 12, 1664 (1879). Conversion of carboxylic acids, especially of high molecular weight, into the next lower homolog by dry distillation of the alkaline earth salt with the corresponding acetate, followed by chromic acid oxidation of the methyl ketone:

F. C. Whitmore, Organic Chemistry (New York, 1951) p 255; F. Klages, Lehrbuch der organischen Chemie I (Berlin, 1952) pp 262, 266, 368. Cf. Barbier-Wieland Degradation.
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225. Krapcho Decarbalkoxylation
A. P. Krapcho et al., Tetrahedron Letters 1967, 215. The decarbalkoxylation of malonate esters, β-keto esters, α-cyano esters and α-sulfonyl esters in dipolar aprotic solvents, at high temperatures, in the presence of water and/or salt, to yield esters, ketones, nitriles and sulfonyl derivatives, respectively:

Scope and limitations: A. P. Krapcho et al., J. Org. Chem. 43, 138 (1978). Mechanistic studies: A. M. Bernard et al., Tetrahedron 46, 3929 (1990); P. J. Gilligan, P. J. Krenitsky, Tetrahedron Letters 35, 3441 (1994). Review of synthetic applications: A. P. Krapcho, Synthesis 1982, 805-822, 893-914.
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226. Kröhnke Oxidation
F. Kröhnke et al., Ber. 69, 2006 (1936); 71, 2583 (1938); 72, 440 (1939). Transformation of activated halides into aldehydes via their pyridinium salts, which yield nitrones upon treatment with pnitrosodimethylaniline. Aldehydes or ketones are generated upon hydrolysis:

A. A. Goldberg, H. A. Walker, J. Chem. Soc. 1954, 2540; F. Kröhnke, Angew. Chem. Int. Ed. 2, 380 (1963); A. Markovac et al., Heterocyclic Chem. 14, 19 (1977); I. Maeba et al., J. Chem. Soc. Perkin Trans. I 1991, 939; S. N. Kilenyi, Comp. Org. Syn. 7, 657-659 (1991). Cf. Sommelet Reaction.
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227. Kröhnke Pyridine Synthesis
W. Zecher, F. Kröhnke, Ber. 94, 690, 698 (1961); eidem, Angew. Chem. Int. Ed. 1, 626 (1962). 1,4-Michael addition, q.v., of α-pyridinium methyl ketone salts to α,β-unsaturated ketones, generating the 1,5-dicarbonyl compounds which undergo ammonium acetate-promoted ring closure, to yield substituted pyridines:

Early review: F. Kröhnke, Synthesis 1976, 1-24. Synthetic applications: J. N. Chatterjea et al., Indian J. Chem. 15B, 430 (1977); G. R. Newkome et al., J. Org. Chem. 51, 850 (1986); P. Lhoták, A. Kurfürst, Coll. Czech. Chem. Commun. 57, 1937 (1992); T. R. Kelly et al., J. Org. Chem. 62, 2774 (1997). Cf. Chichibabin Pyridine Synthesis; Guareschi-Thorpe Condensation; Hantzsh (Dihydro)Pyridine Synthesis.
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228. Kucherov Reaction
M. Kucherov, Ber. 14, 1540 (1881). Hydration of acetylenic hydrocarbons with dilute sulfuric acid in the presence of mercuric sulfate or boron trifluoride as catalyst:

Reviews: A. D. Petrov. Usp. Khim. 21, 250 (1952); M. Miocque et al., Ann. Chim. (Paris) 8, 157 (1963); M. M. Khan, A. E. Martell, Homogeneous Catalysis by Metal Complexes vol. 2 (Academic Press, New York, 1974) p 1974; B. S. Krupin, A. A. Petrov, J. Gen. Chem. USSR 33, 3799 (1963); W. L. Budde, R. E. Dessy, Tetrahedron Letters 1963, 651; J. Am. Chem. Soc. 85, 3964 (1963); K. G. Golodova, S. I. Yakimovich, Zh. Org. Khim. 8, 2015 (1972). Extension to allenes: A. V. Fedorova, A. A. Petrov, J. Gen. Chem. USSR 32, 1740 (1962).
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229. Kuhn-Winterstein Reaction
R. Kuhn, A. Winterstein, Helv. Chim. Acta 11, 87 (1928). Conversion of 1,2-glycols into trans olefins by reaction with diphosphotetraiodide (P2I4) or other halogenated reagents. This reaction is useful in the preparation of polyenes:

Kuhn et al., Ber. 71, 1510 (1938); 84, 566 (1961); 88, 309 (1965); Inhoffen et al., Ann. 684, 24 (1965); H. Kessler, W. Ott, Tetrahedron Letters 1974, 1383; W. W. Win et al., J. Org. Chem. 59, 2803 (1994).
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230. Ladenburg Rearrangement
A. Ladenburg, Ber. 16, 410 (1883); Ann. 247, 1 (1888). Thermal rearrangement of an alkyl- or benzylpyridinium halide to an alkyl- or benzylpyridine:

J. H. Brewster, E. L. Eliel, Org. React. 7, 135 (1953); L. E. Tenenbau in Pyridine and Its Derivatives, Pt. 2, E. Klingsberg, Ed. (Interscience, New York, 1961) p 163.
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231. Lebedev Process
S. V. Lebedev, Zh. Obshch. Khim. 3, 698 (1933). Formation of butadiene from ethanol by catalytic pyrolysis. The catalysts used are mixtures of sililcates and aluminum and zinc oxides:

S. V. Lebedev, FR 665917 (1928); GB 331482 (1929); RU 24393 (1931); C. Ellis, The Chemistry of Petroleum Derivatives II (New York, 1937) p 173; G. Egloff, G. Hulla, Chem. Rev. 36, 67 (1945); Y. A. Gorin, Zh. Obshch. Khim. 20, 1596 (1950); Kirk-Othmer Encyclopedia of Chemical Technology vol. 4 (New York, 3rd ed., 1978) p 322.
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693. 65. 528 (1927).. 1960. Chim. . USA. Whitehouse Station. Tanasescu. Z. Lehmstedt. Frenkel. Copyright © 2001 by Merck & Co. 834 (1932). Roumaine Chim. Bull. Lehmstedt-Tanasescu Reaction K. ibid. NJ. 1035 (1965). Ber. Frenkel.232. France 41. Inc. Soc. Preparation of acridones (and 10-hydroxyacridones) from o-nitrobenzaldehyde and a halobenzene in the presence of concentrated sulfuric acid containing nitrous acid as catalyst: I. All rights reserved. Tanasescu. 10. Rev.. I. Mechanism: Silberg.

42. 5. Reid. 162 (1910). Soc. Chem.233. J. Inc. Rev. F. Lehrbuch der organischen Chemie I (Berlin. J. T. All rights reserved. 38. D.. E. Letts Nitrile Synthesis E. 669 (1872). 43. Chem. E. Letts. Krüss. . 1959) p 362. Copyright © 2001 by Merck & Co. Ber. G. Formation of nitriles by heating aromatic carboxylic acids with metal thiocyanates: G. NJ. Reid. Klages. 1766 (1884).. Am. USA. A. E. Chem. E. Ber. 2120 (1916). van Epps. Mowry. 17. Whitehouse Station. D. Am. 264 (1948).

Wallach. et al. C. Org. Synth. Soc. Tetrahedron Asymmetry 10. Sunman. All rights reserved. J. 99 (1892). Ber. 611 (1999). Whitehouse Station. Schröter. Agwada. 1046 (1993). Pharm. J. 18. 301-330 (1949). 2341 (1885). Casanova. J. Copyright © 2001 by Merck & Co. 63. Inc. E. USA. 19 (1974). J. Leuckart-Wallach Reaction. Steroids 56. 648-664 (1957). T. Scand. G.. F. R. Farkas. 38. J. Heterocycles 24. I. Helland. 5. 8177 (1996). 47. Synthetic applications: E. Doorenbos. M. I. The reductive methylation of primary or secondary amines employing formaldehyde and formic acid is known as the Eschweiler-Clarke reaction: W. Optimized procedure: R. 1899 (1990). . Heterocycles 51. Acta Chem.. Clarke. Martinez et al. Lejon.. 4571 (1933). NJ. J. 880 (1905). Villa et al.234. Ber.. L. Early reviews: M. J.. Eschweiler. Modified conditions: A. Commun. 1943 (1986). N. React.. Application to deoxybenzoins: M. 1110 (1985). Am. Tetrahedron Letters 37. A. Awachie. H. Devi. Bellini et al. Org. Houben-Weyl 11/1. Chem. P. 1499 (1999). C. Sci. Loupy et al. Möller. Chem. Eschweiler-Clarke Reaction R. Leuckart (Leukart) Reaction. Ann. Leuckart. Application to steroids: W. T. 55. Reductive alkylation of ammonium (or amine) salts of formic acid or formamides by aldehydes or ketones: When the reaction is performed in the presence of excess formic acid it is referred to as the Leuckart-Wallach reaction: O. Moore. A. 23. Mechanistic study: P. Carlson et al. Solomons. 245 (1993).. 50. 395 (1991).. Tetrahedron 46. 272. V.

Rodd's Chemistry of Carbon Compounds IIIA. Am. R. 179 (1890). J. 809 (1955).235. A. III. A. 48 (1952). USA.. J. Chem. D. Saunders. M. L. 1949) p 325. Leuckart Thiophenol Reaction R. Schöberl. Copyright © 2001 by Merck & Co. Forrester. 74. . vol. Chem. The Aromatic Diazo-Compounds and Their Technical Applications (London. NJ. to the corresponding aryl xanthates which afford aryl thiols on alkaline hydrolysis and aryl thioethers on warming: D.. Leuckart. 422 (1971). Fukushima. H. Houben-Weyl 9. Soc. 12 (1955). Wardell. D. A. [2] 41. McCall. A. S. J. by warming gently in faintly acidic cuprous media. Prakt. Tarbell. Syn. K. Org. Wagner. Tarbell. All rights reserved. S. Whitehouse Station. Decomposition of diazoxanthates. coll. K. Inc.

4th ed. Seelye. Copyright © 2001 by Merck & Co. Rev..) 7. A. . H. Fuson. J. Whitehouse Station. 1972) pp 464-465. Cleavage of methyl ketones with halogens (mostly iodine) and base to carboxylic acids and haloform: R. T. J Chem. R. Lieben. 15. Bull. Benjamin. A. March. 218 (1870). 275 (1934). Ed. House.236. Lieben Iodoform Reaction (Haloform Reaction) A. 572 (1959). All rights reserved. Inc... California. 36. New York. B. N. 1992) p 632. 2nd ed. Ann. Chem. Modern Synthetic Reactions (W. O. (Suppl. A. Menlo Park. Turney. C. Advanced Organic Chemistry (Wiley-Interscience. NJ.. USA.

38. Res. P. Chem. 151 (1976). G. Rev. Inc. J. 14. 1568. A.237. Whitehouse Station. 13. Carbohydr. Trav. 1473 (1964). Lobry de Bruyn-van Ekenstein Transformation C. Papert. 150 (1895). Sedmera et al. ibid. Schaffer. The Carbohydrates (Academic Press. Advan. Advan. Carbohyd. Mechanistic study: B. 29. Org. Chem. . 16. Lobry de Bruyn. 195. 9. Scr. van Ekenstein. H. USA. A. Sauerbrei et al. 2888 (1999).. Chem. Ind. New York. Johansson. 1957) p 60. Res. M. Rec. Lobry de Bruyn. 203.. Ann. Sattler. A. J.. NJ. 262 (1897). Chem. Carbohyd. 63 (1958). C. Synthetic applications: P Köll. considered to embrace both epimerization of aldoses and ketoses and aldose-ketose interconversion: Reviews: Evans. Chim. 1351 (1998). W. 113 (1948). Speck. Carbohydr. 280. 3. Chem.. 17. Copyright © 2001 by Merck & Co. Isomerization of carbohydrates in alkaline media. 31.. Eng. All rights reserved. 223 (1996). 1986. Kabyemela et al. 544 (1942). Samuelson. Pigman. O. Chem. Chem. M. B.

Org. Anilkumar et al. 13. A. are generated: Reviews: H. Fawcett et al. J. Lossen Rearrangement W. ureas are formed. Lossen. Bauer. 3858 (1997). 5291 (2000). USA. Ann. Yale. L. 271. 485 (1993). In the presence of amines.. Angew. Cf. 1992. Chem. Exner. Commun. Chem. Int. Bauer. Schmidt Reaction. R. 209 (1943). 61. 376 (1974). 10040 (1998). amines containing one less carbon than the starting material. A. to sulfonyloxy imides: D. Org. 161. 227. in the presence of water. All rights reserved. Modifications: J. Curtius Rearrangement. T. Casteel et al. Shiori. NJ. Ed. Rev. 347 (1872). Pihuleac. Inc.. O.. 6. Copyright © 2001 by Merck & Co. 33. L. 175. 62. Synthesis 1989. Reaction conditions leading to the formation of ureas: J. 821-825 (1991).. Chem. Whitehouse Station. Syn. Chem. extention to N-phosphinoylhydroxylamines: J. Salomon. Conversion of a hydroxamic acid to an isocyanate via the intermediacy of its O-acyl. 313 (1874). or phosphoryl derivative. C.. Stafford et al. . Tetrahedron Letters 41. E. sulfonyl. Comp. Chem. Org. L. J. Hofmann Reaction. Heterocycles 36.. J. Breuer.238. 63.

Heterocyclic Chem. Chem. McFadyen. H. J. Chem. 584. Dudman et al.. .. Synth. 793. All rights reserved. Org. 1225 (1975). Copyright © 2001 by Merck & Co. USA. M. Mosettig. Commun. Stevens. 8. 28. R. Siddappa. Soc. K. Chem. J. Base-catalyzed thermal decomposition of acylbenzenesulfonylhydrazines to aldehydes: E. 178. Alternative hydrazide reagent: C.. Org. McFadyen-Stevens Reaction J. 9 (1998). NJ. React. Graboyes et al. Nair. Commun. Synthetic applications: H. S. T. C. 39. S. Soc. A. 2285 (1974)..239. S. Tetrahedron Letters 1980. Shechter. 1978. 4645. S. Manna et al. G. 12... Chem. C 1971. Matin et al. Inc. J. Whitehouse Station. J. Bhat. 1936. 232-240 (1954). B.

McLafferty Rearrangement F. Chem. Chem.. All rights reserved. Mass Spectrom. . Soc.. 15. 82 (1959). 215 (1974). K. Am. McLafferty. Biemann. W. G. J. Djerassi et al.. Lacey et al. Cf. NJ. 8 (1980). Norrish Type Cleavage.240. Mass Spectrometry (New York. 91. Electron-impact-induced cleavage of carbonyl compounds having a hydrogen in the γ-position. 74. 87. 8938 (1972). Am. Kingston et al. Eadon. M. USA. 2069 (1969). Chem. J. 473 (1972). V. Copyright © 2001 by Merck & Co. F. Org. J. 31.. Hanus. 5. Inc. Rev. to an enolic fragment and an olefin: D. 94. Chem. Whitehouse Station. Mass Spectrom. 94. I. Anal. 1391 (1971). Turecek. G. 817 (1965). 1962) p 119. Org. Soc..

2147. T.. M.. USA. D. N.. Bull. Letters 1973. A. 2549-2554 (1998). Tetrahedron Letters 38. 63. Chim. Met. Tetrahedron 48. Deoxygenative coupling of carbonyl compounds to alkenes induced by low-valent titanium: Synthetic application: A. 1041. 5991 (1992). Am. Chem. 1513-1524 (1989). 62. Act. Talukdar et al. Fürstner. 7353 (1997). 4925 (1998). Lectka. McMurry. M. 89. ibid. 1996. Brückner. Tyrlik. G. Fleming. Soc.. 4566 (1997). Rucker. Jumbam. Ephritikhine. 3.241. 4708 (1974). M. Chem. P. S. All rights reserved. 96.. Robertson. Mukaiyama et al. Reviews: J. Barton Olefin Synthesis. Soc. 23. Chem. E. Cf. R. P. McMurry Coupling Reaction J. Inc.. McMurry. 85-131. E. Rev. Org. J. M. I. J. Wolochowicz. Lipski et al. NJ. 1141 (1998). Syn. Polyhedron 17. Copyright © 2001 by Merck & Co. Harter et al. 583-595 (1991). Whitehouse Station. Comp. France 1973. Org. T. Chem. Commun. Modified conditions: T. S. . Chem.

Verboom et al. Indoles. Madelung.. A. Copyright © 2001 by Merck & Co.. Brown in The Chemistry of Heterocyclic Compounds. Ed. E. (Wiley. New York. 4515 (1981). 5053 (1986). Chem. Ed. 3817 (1987). M.. ibid. Whitehouse Station. USA. J. 46. eidem. Orlemans et al. Madelung Synthesis W. 4511. J. O. Ber. W. Houlihan et al... 1128 (1912). Tetrahedron Letters 26. Inc. All rights reserved. Weissberger.242. Under mild conditions: W.. NJ. K. W. . 45. 685 (1985). Org. 1972) pp 385-396. 43. Tetrahedron 42. Part I. Houlihan. Formation of indole derivatives by intramolecular cyclization of an N-(2-alkylphenyl)alkanamide by a strong base at high temperature: R. J.

. J. 2499 (1999). 258 (1916). 14. Chim. Klaiber. 2818 (1995). 60. P. 1998) 464 pp. Ann. 19. Maillard. Lederer. Mechanism: M. U. Whitehouse Station. J. F. Chem. N. II 1999. M. Org. Rend. high pressure effects: M. Cambridge.. (Royal Soc. 5. S..K. J. G. Eriksson. Copyright © 2001 by Merck & Co. C. Chem. Reviews: C. Soc. Food Nutr. Prog.. O. Isaacs. All rights reserved. 6246 (1995). Eds. Anet. NJ. 63 (1959). 7. Amrani-Hemaimi et al. 43. Med. 66 (1912). Chem. Bioorg. G. Maillard Reaction (“Browning”Reaction) L. Sci. USA. Crosslinking in proteins: K.. Perkin Trans.. L. peptides or proteins with the “glycosidic” hydroxyl group of sugars ultimately resulting in the formation of brown pigments. Chem. O'Brien et al. R. Bristow. Inc. O. 5. 9. 154. The Maillard Reaction in Foods and Medicine.243. 181 (1964). Ellis. J. Advan. Agr. E. . 159-176 (1981). J. Wells-Knecht et al. The reactions of amino groups of amino acids. Chem.. Food Chem. ibid. 221. Carbohyd. Compt.

2nd ed. 382 (1928). Compt. All rights reserved. K. Kirby. 683 (1928). Eds. Whitehouse Station. France [4] 43. Malaprade Reaction (Periodic Acid Oxidation) L. Menlo Park. Malaprade. Rend. K. O. Bentley in Elucidation of Organic Structures by Physical and Chemical Methods. House.. undergo cleavage of the carbon-carbon bond when treated with periodic acid to yield aldehydes: H. Bull. NJ. W. attached to adjacent carbon atoms. Soc.. Inc. A. New York. Benjamin. Compounds containing two hydroxyl groups. 1972) pp 353-359.244. USA. Pt. 186. (Wiley. Criegee Reaction. or a hydroxyl and an amino group. Cf. Chim. W. 2. 2nd ed. G. Modern Synthetic Reactions (W. Bentley.. California. 1973) pp 177-185. W.. Copyright © 2001 by Merck & Co. .

After hydrolysis. NJ. A. Malonic Ester Syntheses Syntheses based on the strongly activated methylene group of malonic esters which on reaction with sodium ethoxide form a resonance-stabilized ion that can be alkylated or acylated. Stereoselectivity: T. Synth.. All rights reserved. J. 37. 1972) pp 510-518. A. Tetrahedron Asymmetry 8. Sato. Copyright © 2001 by Merck & Co. 2627 (1995). 3127 (1981). Use of crown ethers as catalysts: D. 26. Hunter. 1821 (1997). the free alkylmalonic acids readily decarboxylate to mono. Whitehouse Station. 756-761. . Modern Synthetic Reactions (W. Cf.. Casadei et al. B.. Inc. Modified conditions: M. Perkin Alicyclic Synthesis. Menlo Park. House. Klotz-Berendes et al. K. Benjamin. Org. B.245. Synthesis 1977. J. H... 60. 46. Chem. Commun.. et al. Chem. Org.or disubstituted monocarboxylic acids: H. 2nd ed. Otera. O. USA. 3859 (1996). Wilk. California. J.

Inc. Cf. 7153 (1997). Menlo Park. Ed. Leigh. 5639 (1993). Mannich. Linnane. 3504 (1999). Blicke. Chem. Robinson-Schöpf Reaction. Krawezyk. Am. 250. O. C. 647 (1912). 303 (1942). 1791-1837 (1990). Pharm. Mannich Reaction C. Org. K. 58. eidem. Org. Tetrahedron Letters 34.246. Angew. In synthesis of vinylphosphonates: H. Synth. Chem. Arend et al. H. Ricca. Whitehouse Station.. 1007-1046. Betti Reaction. Arch. P. p-Substituted phenols as substrates: D. Copyright © 2001 by Merck & Co. F. et al. 37. D. B.. Org. J. J. Tetrahedron 46. 6902 (1993). Tramontini. React. Soc. Overman. Modern Synthetic Reactions (W. Syn. All rights reserved. enantioselectivity: H. 38. Int. NJ. 1044-1070 (1998). 119. Chem. 893-951 (1991). A. Yamada. 953-973. Kleinman. House. H. Tetrahedron Letters 40. W. Int. 24.. Chem. 2nd ed. Reaction of compounds having an active hydrogen with non-enolizable aldehydes and ammonia or primary or secondary amines to give aminomethylated products (Mannich bases): Early reviews: F. Heane. 2. Ed. 2161 (1999).. Krosche.. Commun. Ishitani et al. F.. 2263 (1994). 1972) pp 654-660. Comp. L. E. USA. Diastereoselectivity: P. M. ibid. . Benjamin. A. E. 1.. Angew. California. ibid. Reviews: M. Page et al. J.

Chim. S. Synthetic applications: F. 340. Bull. Chem. et al.. M. Whitehouse Station. Chem. Indian J. Ayyangar et al. M. Soc. Bernhard. Synth. Baltus. Am. 1545 (1936).. 3 (1992). Sodium dithionite reduction of 1-hydroxy. 31B. 26 (1998). Krohn.. Can.. N. Chem. Krohn. Prakt.247. 2691 (1990).. Soc. Inc. All rights reserved. 100. 2-Hydroxyanthraquinones yield 1-alkylated products: Scope and limitations: K. J. NJ. K. R. followed by condensation with aldehydes to yield the 2-alkylated anthraquinones. France 3. Marschalk et al. 62. T. USA. Commun. Chem. Tetrahedron 44. W. Copyright © 2001 by Merck & Co.. 2272 (1978). 20. . 49 (1988). Suzuki. Furlong et al. L. J. Harwood et al.. Marschalk Reaction C. 1922 (1984). J.or aminoanthraquinones to their leuco-forms.

201 (1932).. .. Martinet. ibid. W. Langenbeck et al. Chim. Guyot. Rend. Compt. Formation of derivatives of dioxindole from esters of mesoxalic acid and aromatic amines or amino quinolines: J. P. 998 (1918). USA. Martinet Dioxindole Synthesis A. Ann. 156. Whitehouse Station. 239 (1952). Ann. W. 276 (1934). Chem. [9] 11. 1625 (1913). Sumpter. 37. All rights reserved.. Inc. Martinet. 472 (1945).. L. Heterocyclic Compounds 3. C. 166. 85 (1919). J. Copyright © 2001 by Merck & Co. Julian et al. Rev. NJ. 499.248. 851. 512.

Brunner et al. Chem. 541. J.. Meerwein et al. Sutter. C. G.. NJ. D. Prakt. 9567 (1998). 237 (1939). Weis. USA. Meerwein Arylation H.249. 24. J. Obushak et al. J. Gurka. S.. Tetrahedron Letters 39. Heterocyclic Chem. Weis. 24. 225-259 (1976). 739 (1997). Pschorr Reaction. 1-20 (1988). ibid. Inc. . All rights reserved.. D. C. Reviews: C. 69 (1987). Wurm. Formation of arylated olefins on treatment of olefins with diazonium salts in the presence of cupric salts: Synthetic applications: P. 89 (1997). Organometal. Dyes Pigment 9. 189 (1960).. Whitehouse Station. D. enhanced stereoselectivity: H. J. H. Modified conditions: M. Cf. Org. Pharmazie 52. 11. Jr. Copyright © 2001 by Merck & Co. React. Chem.. 152. Rondestvedt.

537. Comp. 115. T. Y. R. Nakano et al. 1998. ibid. Enantioselectivity: D. A. 122. Verley. NJ. 221 (1925). Copyright © 2001 by Merck & Co. France 37. Schmidt. M.): Reviews: A. Chem. Inc. J. Chem.250. Synthesis 10. All rights reserved. L. S. 39.. 444. Meerwein-Ponndorf-Verley Reduction (Aluminum Alkoxide Reduction) H. Kellogg. Whitehouse Station. Org. Angew. Ponndorf. USA. Evans et al. Org.. Tischenko Reaction.. . Tetrahedron Letters 41. 10790 (1998). 88-91 (1991). 138 (1926). 178-202 (1944).v. Commun. 8. Am. Kumbhar et al. 120. 2. 9800 (1993). R. C. q. 871 (1925). Node et al. Bull. 1007-1017 (1994). Ooi et al.. J. Soc. Modified conditions: P... Chim. Chem. Reduction of aldehydes or ketones to the corresponding alcohols with aluminum alkoxides (the reverse of the Oppenauer oxidation. Soc. Am. React. Wilds. F. Chem. 1927 (2000). Cf. M. A. Cannizzaro Reaction... Soc. 1565 (2000). Meerwein. 535. de Graauw et al.. Syn. Ann. W.

R. N-trisubstituted hydroxylamines from tertiary amine oxides via [1. 303 (1976). 3749 (1994).2]-R group migration.. Helv. et al. NJ. Inc. J.3]-Rearrangements: V. Mislow-Evans Rearrangement. 1994. [2. [2. H. Jr. Meisenheimer Rearrangements J. ibid. 1667 (1919).2]: T.3]sigmatropic rearrangement when R′ = allyl: [1. Synlett.251. 969. Chem. Aust. Tetrahedron 26. Sommelet-Hauser Rearrangement. Whitehouse Station. Ber. or [2. J. Chem. or [1. 293 (1988). Davies. 41. Buston et al. Tetrahedron Asymmetry 7. 2492 (1973). Asymmetric syntheses: D.3]-Wittig Rearrangement. Bremner et al. B.. 4319 (1970). Smyth. J. Kempen. G. Rautenstrauch. N. Stevens Rearrangement. D. Copyright © 2001 by Merck & Co. All rights reserved. Acta 56.2]-Wittig Rearrangement. 475 (1994). 42. Yoneda et al. Meisenheimer. H. Enders. S. Cf. 1001 (1996). Chim.. 1995 (1998). Yamamato et al. Castagnoli. 41. 9. Pharm.. Org. J. Formation of O.. eidem. Kurihara et al. Tetrahedron 52.2]-Rearrangements: N. Cf. Y. Chem. USA. Bull. . 14563 (1996).. E. [1. Tetrahedron Letters 35. G... 52.

NJ. Whitehouse Station. Reaction of tertiary amines with alkyl halides to form quaternary salts: Mechanistic studies: C. E. Solvent effects: J. Am. Phys. Chem. 2nd ed. Reich. M. H. Menschutkin. 589 (1890). Shaik et al. Chem. Physik... Bull.. K. Chem. Org. Kang et al.. Structure and Mechanism in Organic Chemistry (Cornell Univ. Chem. 254 (1998). S. 11. Org. 5892 (1980). S. New York. Menschutkin Reaction N. Arnett. Chem. Progr. ibid. J. Inc. 116. M.252. Phys. H. 66. 1969) p 435. M. 262 (1994). 1 (1974). Soc. 972 (1993). 214 (1989). S. Z. 11. J.-G. Chem. Kim et al. R. USA. Ingold. Phys. All rights reserved. 93.-L. Copyright © 2001 by Merck & Co. 102.. 41 (1890).. Abboud et al. Japan.. Press. Soc. J. 5. Abraham. . 6.

. J. Soc... Chem. G. I. Life During a Golden Age of Peptide Chemistry. New York. Merrifield. Synthetic applications: D. Soc. D. Review: C. Copyright © 2001 by Merck & Co. Smith et al. K. Washington.. 1978) pp 102. Am. Synthesis of long peptides involving the following steps: (1) attachment of the C-terminal amino acid to an insoluble polymeric support resin. Peptide Antigens (Oxford University Press. Léger et al. All rights reserved. (Springer-Verlag. Am. J. Chem. Merrifield. NJ. Science 232. Seeman. Inc. Whitehouse Station.. B. O'Donnell et al. . Am. 1993) pp 54-118. and (3) cleavage of the peptide from the resin: Method for monitoring synthesis: B.253. 85. 341-347 (1986). J. 44. D. Birr. B. Larsen et al. Peptide Protein Res. D. Chem. Autobiographical account: B. 4171 (1998). 118.. 6070 (1996). Wisdom et al.. Eds. M.. Merrifield Solid-Phase Peptide Synthesis (SPPS) R. (2) elongation of the peptide chain. J.. 115. (ACS. B. Tetrahedron Letters 39. Hafner et al. 1994) pp 27-81.C. USA. 2149 (1963). 183 (1994). J. Ed. 6247 (1993). Merrifield. R. Soc. Aspects of Merrifield Peptide Synthesis. J.

Meyer. Copyright © 2001 by Merck & Co. R.. NJ. respectively: W. Advan. 148 (1966). Inc. Chem.. 1439 (1883). Meyer Reaction G. Organometal. . All rights reserved. 4. Ber. Cullen. When applied to alkali arsenites or plumbites the reaction yields alkylarsonic and alkylplumbonic acids. 16. Preparation of alkylstannonic acids by reacting alkali stannite with an alkyl iodide.254. Whitehouse Station. USA.

Early reviews: R. Omar et al. NJ. Chem. Mechanism studies: M. A.. A. K. 4798 (1995). Heilmann. Meyer. Chim. . Ann. 672 (1926).. Applications: E. Org. Yoshimatsu et al. Rupe Rearrangement K. Rupe. Lorber. Glenat. Acid-catalyzed rearrangement of secondary and tertiary α-acetylenic alcohols to α. Chem. 819 (1922). 71. 3403 (1977). H. Kambli. Heterocyclic Chem. Andres et al.. 947 (1992). M. J. 60. is referred to as the Rupe rearrangement: Metal-based catalysis: P. Chem. Chim. Tetrahedron Letters 29. Acta 9. All rights reserved. Org. Ber. R. Schuster.β-unsaturated ketones and not the expected aldehydes. Soc. Chem. Inc. J. Rev.. Copyright © 2001 by Merck & Co. J. ketones when it is internal: The conversion of tertiary alkylacetylenic carbinols with a terminal acetylenic group to predominantly α. Chabardes. 178 (1963). Whitehouse Station.. 429 (1971). 853 (1996). H. 6253 (1988). C. V. ibid. 37.β-unsaturated carbonyl compounds: aldehydes result when the acetylenic group is terminal. Am. Edens et al. J. S. USA. 55. 42. Osborn. Y. 666 (1988). (Paris) 8. J.255. Narayanan. K. Helv. Meyer-Schuster Rearrangement. Swaminathan. 29. 110.. E. J.

B. 368 (1963). J. J. 279 (1929). Vessel. Syn. Formation of aliphatic nitrites and nitro derivatives by the reaction of aliphatic halides with metal nitrites: R. Chem. Application to the synthesis of α. 12. Org. G. 32. All rights reserved. Riley. React. E. Reynolds. Copyright © 2001 by Merck & Co. Meyer. 51. . 373 (1943). Meyer Synthesis (Victor Meyer Synthesis) V. D. 5. Org.256. NJ. Chem. Ber. Stille.. B. Soc. E. 25. Stuber. USA. H. Leston.. 478 (1960). Whitehouse Station. F. 203 (1872). K. 101-156 (1962). Chem. Adkins. Reviews: H. 4. N. Hass. Inc. Am.ω-dinitroalkanes: J. Kornblum. Org. Rev. O.

J. USA. 36 (1973). All rights reserved. 4th ed. Inc.. 783 (1981). Synthesis of aldehydes from alkylhalides and 2-lithiomethyltetrahydro-3-oxazine: J. 91. Advanced Organic Chemistry (Wiley-Interscience. March. Copyright © 2001 by Merck & Co. Chem. J. NJ. 46. Org. . Chem.. Org. Meyers et al. 38. eidem. Soc. Meyers et al.. J.. I. 1992) pp 478-479. Meyers Aldehyde Synthesis A. Whitehouse Station. New York. 763 (1969). A. Chem. Am..257. I.

Modern Synthetic Reactions (W. Schmalz.258. USA. 2nd ed. Top. Reviews of stereoselective synthesis: H. A. NJ. California. Review of organometallic nucleophiles: D. Benjamin. Proced. Comp.-G. Prep.. Eur. Int.. M.. A. 69137. 199-236. Base-promoted conjugate addition of carbon nucleophiles (donors) to activated unsaturated systems (acceptors): Reviews: E. [2] 35. Copyright © 2001 by Merck & Co. Robinson Annulation. J. Leonard et al. E. Org. 20. ibid. Menlo Park. Inc. Condensation) A.. 139-168 (1991). Org. 4. Chem. React. J. . Oare. Org. 21. J. Tetrahedron Asymmetry 3. 4.. Whitehouse Station. Prakt. D. 705-749 (1989). H. C. A. Nagata Hydrocyanation.. Syn. Org. Org. H. 1-67 (1991). Cf. D. Stereochem. V. Heathcock. Jung. Hunt et al. J. A. Michael Reaction (Addition. 179-555 (1959). Kozlowski.. ibid. 349 (1887). Michael. 1998. 10. Lee. d'Angelo et al. 2051-2061. 87-170 (1991). 169-198. All rights reserved. Bergmann et al. Chem. 459-505 (1992). 1972) pp 595-623. J. Syn. O. House. J. Comp.

Phys. Houben-Weyl 12/1. A. Faure et al. Yadav. E. II. 71. Chem. J. 433 (1963). All rights reserved. Inc. Rev. 307 (1964). G. 20. Angew. Commun. G. Chem. Arbuzov. Pure Appl.. React. . Ed. Chem. 1048 (1898). Sasse. 31. Copyright © 2001 by Merck & Co. 317 (1971). 1989. 239 (1990). 6. 805. M. D. Whitehouse Station. USA. Commun. Soc. Thyagarajan. R. 16. Bauer. Redmore. NJ. Zentr.. 1906. Haegele. K. G. Bhattacharya. Arbuzov. via the intermediate phosphonium salt: K. Chem.. Michaelis-Arbuzov Reaction A. K. A. 1639. Kaehne. Chem. Ber. Chem. 38. Kosolapoff. 415 (1981). G. Org. A.259. 9. Rev. 477 (1977). 687 (1906). Formation of monoalkylphosphonic esters from alkyl halides and trialkyl phosphites. B. B. V. Synth. 276 (1951). Int. 81. Chem. Michaelis. Russ.

3355. Copyright © 2001 by Merck & Co. Helv. G. 1950. W. Chim. followed by dehydration. q. to permit simultaneous elimination of three carbon atoms. 26 (1970). as in degradation of the bile acid side chain to the methyl ketone stage.. 407. F. Acta 27. Spring. 233. Ann. Marshall. . London) 44. Adaptation of the Barbier-Wieland degradation. Experientia 1954. 184 (1947). NJ.v. All rights reserved. J. Wettstein. P. Brooks. Miescher Degradation C. dehydrohalogenation and oxidation of the diene yields the chain-shortened ketone: C.. Whitehouse Station. 1815 (1944). 323. C. Anner. Soc. Chem. Soc. ibid. J. G.. bromination. Rodd's Chemistry of Carbon Compounds IID. Conversion of the methyl ester of the bile acid to the tertiary alcohol. Shoppee. (Chem. USA. W.260.. Repts. S. A. Inc. Meystre et al. 253.

Copyright © 2001 by Merck & Co. Randvere. All rights reserved. 81 (1948). Anales farm.. Inc. Compt. Formation of amines by catalytic hydrogenation of aldehydes or ketones in liquid ammonia and absolute ethanol in the presence of a nickel catalyst: F. bioquim. 51 (1955). NJ. USA. Rend. Houben-Weyl 4/2. Whitehouse Station. 172. Mignonac. 223 (1921).. (Buenos Aires) 18.261. . Mignonac Reaction G.

1841 (1940). Gunstone. USA. Cf. 1302 (1936). 2345 (1937). Organic Syntheses with Noble Metal Catalysts (Academic Press. Chem.. or chromium oxide: F. Whitehouse Station. . P.262. Inc. J. 1844 (1939). Formation of cis-glycols by reaction of alkenes with hydrogen peroxide and either ultraviolet light or a catalytic amount of osmium. 543. 2342. 1973) p 60. N. 58. Sharpless Dihydroxylation. NJ. D. 59. 62. Advan.. 115 (1960). Rylander. Milas et al. Milas Hydroxylation of Olefins N. Soc. 1. 61.. vanadium. New York. A. All rights reserved. Org. Chem. Copyright © 2001 by Merck & Co. Am.

52. Chem. Accts. H. Meisenheimer Rearrangements. Mechanistic studies: D. Acid-catalyzed modification: Y. 7.. 4869 (1968). eidem. All rights reserved. The reverse process is accomplished by treating the alcohol with arylsulfenyl chloride. 93. ibid. NJ. W. [2. 56. Inc. 90. . 9077 (1995). 7051 (1982). A. J. 33. G. followed by thermal rearrangement of the sulfenate to generate the allylic sulfoxide: Early review: D. Res. 4836 (1987). Am. Chem.. Am. Posner et al. Jorgensen. Chem. G. Bickart et al. Chem. J. Am. thereby effecting the 1.3]-Wittig Rearrangement. Soc. Chem... A. Reich. Bull. 104. Synthetic applications: H. Whitehouse Station. D. A. C. 60. J. Cf. Wollowitz. Padwa et al. L. ibid.. Masaki et al. Jones-Hertzog. S. Soc. USA. Chem. 4252 (1991).263.3-transposition of sulfoxide and alcohol functions. 4956 (1971). K. Mislow-Evans Rearrangement P. Evans et al. 2531 (1985). Copyright © 2001 by Merck & Co. Pharm. Org. 6682 (1995). J. ibid. Soc.3]-Sigmatropic rearrangement of allylic sulfoxides to allylic sulfenates which are captured by thiophiles to generate the allylic alcohols. 117.. Evans.. Andrews. J. [2. 147 (1974).

D. Trav. Solid-phase synthesis: S. Mechanism: T. J. Jones. Chem. 1-162 (1983). Chhabra et al. Tetrahedron Letters 40. Chem. 41.. L. Hughes. Watanabe et al. Yamada. Mitsunobu. R. Rec. J. Pelletier. Bull. A. Mitsunobu. L. Hughes. ibid.or triarylphosphines occurring primarily with inversion of configuration via the proposed intermediary oxyphosphonium salts: Methods development: R. Schedel et al. All rights reserved. F. 346 (2000). H. Tetrahedron Letters 41. Copyright © 2001 by Merck & Co. 40.. Tetrahedron 50. NJ. 5469 (1994). 935 (1967). 2015. ibid.. Zaragoza. 1. Swayze. Tsunoda et al. O. Poelert et al. 407 (2000). 355 (1994). 797 (2000). A. 273-283 (1997). A.-P. ibid.264. T. Kincaid. 29. Mitsunobu et al. Stephensen.. Brown et al.. C. USA. 1099 (2000). 28. 2125 (2000). 7355 (1999). Organic Preparations and Procedures Int. A. E. Inc. 113. Y. 5651 (1999). F. Japan 40. Org. Chim. Tetrahedron Asymmetry 11. 2380. . Synthesis 1981. Soc. H. Chirality 12. S. Reviews: O. ibid. Dodge. Synthetic applications: M. Recent Res. Condensation of alcohols and acidic components (NuH) on treatment with dialkyl azodicarboxylates and trialkyl. Whitehouse Station. Tetrahedron Letters 41. S. React. C. Dev. D. Mitsunobu Reaction O. 1-28. Viso et al. P.. Org..... Kung. 127-164 (1996).

4995 (1989).. 13-26. Chem. ibid. J. Tetrahedron Letters 30. Moore. Soc. B. W. Karlsson et al. Wang. A. W. Copyright © 2001 by Merck & Co. 8057 (1989). Wulff. O. Chem. USA. NJ. 96. Maier. M. Am. Am. Rahm. Whitehouse Station. Nagata et al. All rights reserved. 1807 (1996). R. Cf.265. 273313.. Soc. Bergman Reaction. J. Myers Cyclization J. Inc. Chemtracts 1992.. D. Synlett 1995. Myers et al. 3392 (1985). K. . E. Thermal generation of a biradical by cyclization of enyne-ketenes (Moore) or of enyene-allenes (Myers): A. 111. Moore Myers Cyclization. K. Rev.. 207-222 (1996). Moore Cyclization.. 107. R. G. Yerxa. Reviews: H. Chem. 118.

Carreira et al. . (Springer-Verlag. Mukaiyama et al. Whitehouse Station. Germany. 38-51 (2000). idem et al.266. Am. 1011. Carreira in Comprehensive Asymmetric Catalysis I-III vol.. tin tetrachloride or boron trifluoride etherate: Enantioselectivity: E. K. Soc. Tetrahedron 54. E. Copyright © 2001 by Merck & Co. Evans Aldol Reaction. eidem. Reviews: H.. 96. All rights reserved.. E. Cf. 1973. Inc. Iseki. 4. E.. Am. 746. Soc. J. 1974.. ibid. Berlin. 8837 (1994). 116. 1999) 9971065. 3. Eds. Gröger et al. Chem. N.. USA. M. NJ. Ser.. Eur. 10389 (1998). such as titanium tetrachloride. M. Chem Lett. Formation of β-hydroxy ketones via reaction of silyl enol ethers or ketene silyl acetals with aldehydes in presence of a Lewis acid. 7503 (1974). Diastereoselectivity: S. Chem. ACS Symp. Aldol Reaction. Chem.. J. Mukaiyama Aldol Reaction T. 323. Denmark et al. J. 1137-1141 (1998). Jacobsen et al.

Paulsen et al... Int. Japan 49. Mukaiyama-Michael Reaction K.β-unsaturated ketones and esters: T. Formation of 1.. 3373 (1999). USA. Synthetic application: H. 9409 (1996). S. Kobayashi. Otera et al. Copyright © 2001 by Merck & Co. Angew. Bull. Ed. 245 (1987).. in tandem-aldol reaction: N. Giuseppone et al.. All rights reserved. NJ. Mukaiyama. Chem.5-dicarbonyl compounds by reaction of ketene silyl acetals with α. Soc. Whitehouse Station. Chem.. 38.267. Tetrahedron Letters 39. 7874 (1998). Enhanced diasteroselectivity: J. Narasaka et al. 779 (1976). . Heterocycles 25. Inc. Tetrahedron 52.

268. Nagata Hydrocyanation
W. Nagata et al., Tetrahedron Letters 1962, 461. Alkylaluminum-mediated 1,4-addition of hydrogen cyanide to α,β-unsaturated carbonyl compounds:

Early review: W. Nagata, M. Yoshioka, Org. React. 25, 255-476 (1977). Synthetic application: T. F. Gallagher, J. L. Adams, J. Org. Chem. 57, 3347 (1992). Cf. Michael Reaction.
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269. Nametkin Rearrangement
S. S. Nametkin, Ann. 432, 207 (1923). A special case of carbonium ion rearrangement in camphene hydrochloride derivatives involving the migration of a methyl group:

H. Henecka, Houben-Weyl 4/2, 16 (1955); P. S. Moervs et al., J. Am. Chem. Soc. 100, 260 (1978). Cf. Retropinacol Rearrangement; Wagner-Meerwein Rearrangement.
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270. Nazarov Cyclization Reaction
I. N. Nazarov et al., Izv. Akad. Nauk S.S.S.R., Otd. Khim. Nauk 1942, 200. Protic or Lewis acid-catalyzed electrocyclic ring closure of divinyl ketones, or their equivalents, to yield 2cyclopentenones:

Silicon-directed cyclizations to α-methylenecyclopentanones: H. T. Kang et al., Tetrahedron Letters 33, 3495 (1992). Diastereoselectivity of interrupted reaction: J. A. Bender et al., J. Org. Chem. 63, 2430 (1998); idem et al., J. Am. Chem. Soc. 121, 7443 (1999); H. Hu et al., ibid. 121, 9895 (1999). Lewis acid catalyzed reactions: C. Kuroda et al., Chem. Commun. 1997, 1177; H. A. Buchholz, A. de Meijere, Eur. J. Org. Chem. 1998, 2301. Reviews: S. E. Denmark, Comp. Org. Syn. 5, 751-784 (1991); K. L. Habermas et al., Org. React. 45, 1-158 (1994); S. Giese, F. G. West, Tetrahedron Letters 39, 8393 (1998); of interrupted reaction: D. Zuev, L. A. Paquette, Chemtracts 12, 1019-1025 (1999).
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271. Neber Rearrangement
P. W. Neber, A. v. Friedolsheim, Ann. 449, 109 (1926); P. W. Neber, G. Huh, ibid. 515, 283 (1935). Formation of α-amino ketones by treatment of sulfonic esters of ketoximes with potassium ethoxide, followed by hydrolysis:

Reviews: C. O'Brien, Chem. Rev. 64, 81 (1964); C. G. McCarty in The Chemistry of the Carbon-Nitrogen Double Bond, S. Patai, Ed. (Interscience, New York, 1970) p 447; Y. Tamura et al., Synthesis 1973, 215; R. F. Parcell, J. C. Sanchez, J. Org. Chem. 46, 5229 (1981); K. Maruoka, H. Yamamoto, Comp. Org. Syn. 6, 786-789 (1991). Synthetic applications: I. Moldvai et al., Heterocycles 43, 2377 (1996); M. J. Mphahlele, T. A. Modro, Phosphorus, Sulfur, Silicon Relat. Elem. 127, 131 (1997); J. Y. L. Chung et al., Tetrahedron Letters 40, 6739 (1999).
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272. Nef Reaction
J. U. Nef, Ann. 280, 263 (1894). Formation of aldehydes and ketones from primary and secondary nitroalkanes, respectively, by treatment of their salts with sulfuric acid:

Modified conditions: W. Adam et al., Synlett 1998, 1335; P. Ceccherelli et al., Synth. Commun. 28, 3057 (1998). Application to spiroketals: T. Capecchi et al., Tetrahedron Letters 39, 5429 (1998). Reviews: P. Salomaa in The Chemistry of the Carbonyl Group, S. Patai, Ed. (Interscience, N.Y., 1966) pp 177-210; H. W. Pinnick, Org. React. 38, 655-792 (1990); D. S. Grierson, H.-P. Husson, Comp. Org. Syn. 6, 937-944 (1991).
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273. Nef Synthesis
J. U. Nef, Ann. 308, 281 (1899). Addition of sodium acetylides to aldehydes and ketones to yield acetylenic carbinols; occasionally and erroneously referred to as the Nef reaction, q.v.:

Farbenfabriken Bayer, DE 280226; DE 285770 (1913); J. H. Saunders, Org. Syn. 20, 40 (1940); A. W. Johnson, The Chemistry of the Acetylenic Compounds (London, 1946) p 11; C. D. Hurd, W. D. McPhee, J. Am. Chem. Soc. 69, 239 (1947); W. Oroschnik, A. O. Mebane, ibid. 71, 2062 (1949); R. A. Raphael, Acetylenic Compounds in Organic Synthesis (London, 1955) p 10. Cf. Arens-van Dorp Synthesis; Favorskii-Babayan Synthesis.
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274. Negishi Cross Coupling
E. Negishi et al., J. Org. Chem. 42, 1821 (1977). Formation of unsymmetric biaryls by cross coupling arylhalides with arylzinc reagents in presence of catalytic Ni or Pd:

Synthetic application: S. Superchi et al., Tetrahedron Letters 37, 6057 (1996); J. A. Miller, R. P. Farrell, ibid. 39, 6441 (1998). Extension to additional functional groups: E. Negishi, Acc. Chem. Res. 15, 340 (1982). Review: P. Knochel, R. D. Singer, Chem. Rev. 93, 2117-2188 (1993); idem et al., Ber. 130, 1021-1027 (1997).
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275. Nencki Reaction
M. Nencki, N. Sieber, J. Prakt. Chem. (2) 23, 147 (1881). The ring acylation of phenols with acids in the presence of zinc chloride, or the modification of the Friedel-Crafts reaction, q.v., by substitution of ferric chloride for aluminum chloride. M. Nencki, W. Schmid, ibid. 546; M. Nencki, ibid. 25, 273 (1882); U. S. Chiema, K. Venkataraman, J. Chem. Soc. 1932, 918; C. W. Schellhammer, Houben-Weyl 7/2a, 284 (1973); A. S. Anjaneyulu et al., Indian J. Chem. 33B, 847 (1994). Cf. Darzens-Nenitzescu Synthesis of Ketones.
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M. Pawlak et al. 312. USA.. 46. J. 2677. 337 (1973). G. J. 37 (1929). P. J. W. Huehnermann. Chem. Kinugawa et al. Allen. Org. Soc. Synthesis of 5-hydroxyindole derivatives by condensation of p-benzoquinone with β-aminocrotonic esters: Reviews: R. J. Henichart. Org. Perkin Trans. (Wiley.. 4197 (1981). React.. R. Bernier. I 1995. J. Chim. Houlihan. Ed. 20. Romania 11. All rights reserved. Org. D... 61. Nenitzescu Indole Synthesis C. Bull. 515 (1979). Whitehouse Station. NJ. K. Kuecklander. Chem. Chem. . 1972) p 413. M.276. 9055 (1996). Inc.. Synthetic applications: U. W. Pharm. L. Brown in The Chemistry of Heterocyclic Compounds. J. Soc. Arch. Copyright © 2001 by Merck & Co. J. Nenitzescu. New York. Jr.

Ionescu. Part 2 (New York. USA. 491. R.. Ber. J. Chicos. Ann. D. Darzens-Nenitzescu Synthesis of Ketones. Ber. 189 (1931). Soc. C.and sixmembered rings no change in ring size occurs but with seven-membered rings rearrangement takes place with formation of a cyclohexane derivative: C.277. Cioranescu. Nenitzescu. 68. 69. E. Cf. C. J. 1584 (1935). Nenitzescu Reductive Acylation C. C. 510. Copyright © 2001 by Merck & Co. Nenitzescu. III. Nenitzescu. 1964) p 1069. Inc. Nenitzescu. Anhydrous Aluminum Chloride in Organic Chemistry (New York. Whitehouse Station. Am. Olah. All rights reserved. I. N. Pinson. Cantuniari. ibid. Chem. 73. Hydrogenative acylation of cycloolefins with acid chlorides in the presence of aluminum chloride. Friess. 3512 (1951). Thomas. . 1941) p 759. NJ. 269 (1934). D. C. with five. 1820 (1936). L. P. S. A. Friedel-Crafts and Related Reactions vol. D..

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Inc. A. Armarego. 1. Williamson. All rights reserved. 3029 (1980). Advan. Cuny et al. F. NJ. 331 (1957).. L.4-dihydroquinazolines by cyclization of the reaction products of anthranilic acid and amides: Reviews: T. Tetrahedron Letters 21. Heterocyclic Compounds 6.279. E. J. 564 (1895).. Heterocyclic Chem. v. 253 (1963). USA. . Prakt. Formation of 4-oxo-3. [2] 51. Copyright © 2001 by Merck & Co. Whitehouse Station. W. Chem.. Niementowski. Niementowski Quinazoline Synthesis S.

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1966) pp 619-641. Whitehouse Station. Inc. 39.. 2575 (1974). All rights reserved. usually zinc chloride or hydrogen chloride: Review: N. Piloty-Robinson Synthesis O.. NJ. Formation of pyrroles by heating azines of enolizable ketones with acid catalysts. Soc. 43. Chem. J. Sidgwick. 639 (1918). Chem. 489 (1910). V. Robinson. . Borsche-Drechsel Cyclization.311. Ber. 43. J. M. Robinson. 3rd ed. Organic Chemistry of Nitrogen Compounds (Oxford. H. G. Cf... Piloty. Copyright © 2001 by Merck & Co. R. Posvic et al. Fischer Indole Synthesis. USA. Org.

Syn. Pinacol Coupling Reaction R. Formation of pinacols by a reductive radical-radical coupling of carbonyl compounds. Whitehouse Station.. H. Cf. especially ketones: Reviews: G. Weinheim. Robertson. Copyright © 2001 by Merck & Co. Fittig. Comp..312. Org. 110. Ann. 403-417. Jendralla et al. in Transition Metals for Organic Synthesis (Wiley-VCH. USA. 3.. Inc. M. NJ. 1998) pp. 17 (1859). . 563 (1991). All rights reserved. McMurry Reaction.

721-732 (1991). Rickborn. Collins. Eastham in Chemistry of the Carbonyl Group. C. Pinacol Rearrangement R. Rev. Syn. B. Copyright © 2001 by Merck & Co. J. New York. Comp. Ann. J. Whitehouse Station. Quart. F.313. USA. NJ. 54 (1860). Inc. Fittig. S. . J.. Acid-catalyzed rearrangement of vicinal diols to aldehydes or ketones: Reviews: C. Cf. Patai. (Interscience. Org.. 357 (1960). 114. Ed. TiffeneauDemjanov Rearrangement. 3. Collins. 1966) pp 762-767. 14. All rights reserved.

Russ. All rights reserved. Formation of imino esters (alkyl imidates) by addition of dry hydrogen chloride to a mixture of a nitrile and an alcohol. 23 (1970). USA.. Compagnon.. 615 (1962). 1889 (1877).. F. Moeque. Treatment of alkyl imidates with ammonia or primary or secondary amines affords amidines. 1643 (1883). Chem. Inc. 1978. Roger. Ber. . Zil'berman. Res. 10. Whitehouse Station. Neilson. Ann. while treatment with alcohols yields ortho-esters: Reviews: R. M. 352. (Paris) 5. 16. 61. Pinner Reaction (Amidine and Ortho Ester Synthesis) A. Chem. D. Rev. Decroix et al.314. 1475 (1878). 179 (1961). 11. Rev. Pinner. J. NJ. P. 31. Chim. 134. Copyright © 2001 by Merck & Co. L. B. Chem. 4. N. Klein. E.

Pinner Triazine Synthesis A. M.. Copyright © 2001 by Merck & Co. New York. 2447 (1956). ibid. All rights reserved. Inc. s-Triazines and Derivatives (Interscience. 2919 (1890). Preparation of 2-hydroxy-4. 483 (1895). E. J. Ephraim. Grundmann. 1414 (1892). ibid. J. USA. Smolin. L. 30. Pinner. P. 78. 2006 (1897).6-diaryl-s-triazines by reaction of aryl amidines and phosgene. Rapoport. . C. ibid. Weissberger.. 34. The Chemistry of Heterocyclic Compounds. 28. Am. 1959) p 186.. 26. The reaction may be extended to halogenated aliphatic amidines: A. Flatow. H. Ber.315. Soc. Schroeder. A. T. Ber. 23. Whitehouse Station. 2226 (1893). 1990 (1901). Ed. 25. Pinner. NJ. Rappaport. Chem.

All rights reserved. Chem. USA. 398 (1951). & Ind. Houben-Weyl 11/1.. Ann. NJ. Schroter. R. Chem. R. 49. Budziarek.316. F. (London) 1978. Zahler. Inc. Piria. Rev. Bunnett. Copyright © 2001 by Merck & Co.. . 78. Formation of arylsulfamic acids or sulfonation products or both by refluxing aromatic nitro compounds with a metal sulfite and boiling the mixture with dilute acid to yield the amines and sulfamic acids: J. Whitehouse Station. Piria Reaction R. E. 31 (1851). R. 583. 457 (1957).

. 909-924 (1991). Chemistry of Heterocyclic N-Oxides (Academic Press. The reaction proceeds via an iminium ion intermediate which becomes the stable reaction product when trifluoroacetic anhydride is employed. All rights reserved. France 41. Tetrahedron 23. R. R. Tamminen et al. Polonovski Reaction. Copyright © 2001 by Merck & Co. Lagowski.317. S.. H. 45. USA. Husson. 39. Bull. Comp.. Cave et al. Grierson. NJ. This modified procedure is commonly referred to as the Potier-Polonovski reaction: A. React. ibid. Katritzky. Org. 1190 (1927). D. 1971) p 279. 362. 2683 (1989). Org. . T. Inc.-P.. D. Polonovski. Grierson. Sundberg. N. ibid. 277 (1992). Potier-Polonovski Reaction M. J. New York. 48. J. generating the N. Syn. Soc. Rearrangement of tertiary amine oxides upon treatment with acetic anhydride or acetyl chloride. 6. Chim. et al. 85-295 (1990).N-disubstituted acetamide and aldehyde: Reviews: A. M.. 4681 (1967). Polonovski. in which one of the alkyl groups attached to the nitrogen is cleaved. Whitehouse Station.

J. J. 6. 368 (1952). Pomeranz-Fritsch Reaction (Schlittler-Müller Modification) C. Org. 914. 191 (1951). P.318. in the Schlittler-Müller modification the starting materials are benzyl amines and glyoxal semiacetal: M. J. M. Tetrahedron Letters 32. Heterocyclic Compounds 4. NJ. Copyright © 2001 by Merck & Co. Bourque. 601-614 (1987). Inc. idem. 26. 1775 (1991). All rights reserved.. Brown. USA. Müller.. Reviews: W. 14. E. 419 (1893). Org. E. Bobbit. Heterocycles 25. Ber. 1253 (1971). A. . React. Chem. J. Helv. Hirsenkorn. Monatsh. Bevis et al. Gensler. Chim. Acta 31. Tetrahedron 27. 3208 (1977). Schlittler. 42. V. 1119 (1948). Pomeranz. Fritsch. 116 (1893). Whitehouse Station.. J. Formation of isoquinolines by the acid-catalyzed cyclization of benzalaminoacetals prepared from aromatic aldehydes and aminoacetal. J. R.

Japan 61. von E. 171 (1897). Houben-Weyl 10/1.. F. Chem. 1967) p 325.. H. Bull. Suzuki et al. Reagents for Organic Synthesis (New York. .. USA. Gazz. 27. 68. 183 (1945). 36. Soc. Inc. Fieser. Padeken et al. Ital. Formation of dinitrophenylmethanes from benzaldoximes by oxidation with nitrogen dioxide in ether: J. J. Chem. Whitehouse Station. Chem. NJ. Fieser.319. M. Soc. Copyright © 2001 by Merck & Co. All rights reserved. F. 113 (1971). W. G. L. Improved procedure: H. Ponzio. Chim. Ponzio Reaction G. 2252 (1946). Rev. I. Am. 2929 (1988). Doering. L.. Fieser. L. Riebsomer.

F. C. 196. . A. O. Chem. React. Amin et al. 27. 46. Modern Synthetic Reactions (W. Menlo Park. Inc. Gunstone. V. Compt. 350 (1957). House. Chem. 9. Org. NJ.. USA. Prévost. All rights reserved. 2nd ed. 1972) p 438. Org. Cf. J. Prévost Reaction C. D. 3195 (1933). Advan. Benjamin. Wilson.. Woodward cis-Hydroxylation. 1129 (1933).A. Whitehouse Station.. Copyright © 2001 by Merck & Co. H. Rend. Org..320. S. 1. 2573 (1981). 117 (1960). Hydroxylation of olefins with iodine and silver benzoate in an anhydrous solvent to give trans-glycols: Reviews: C. California.

321. D.. Russ. Modern Synthetic Reactions (W. D. 4811 (1909). React. 16 (1949). Prilezhaev (Prileschajew) Reaction N. Metelitra. Whitehouse Station. I. Chem. Swern. Inc. 2nd ed. House. 42. 807 (1972). Rev... California. Chem. 20. Schnurgfeil. Menlo Park. 7. 378 (1953). . 445 (1980). 1972) pp 302-319. A. Copyright © 2001 by Merck & Co. Ber. 45. Z. Prilezhaev. Chem. Formation of epoxides by the reaction of alkenes with peracids: Reviews: D. USA. 41. Rev. Benjamin. O. NJ. Org. H. All rights reserved.

. El Gharbi et al. A. Comp. 2673 (1979). S. 2. 1510 (1919). V. H.. Arundale. Ed. Org.. 2. B.. Prins Reaction H.. Syn. P. Rev. Roberts in Friedel-Crafts and Related Reactions vol. B. allylic alcohols or meta-dioxanes: Reviews: R. Isagulyants et al. 505 (1952). A. Adams. 661. USA. G. Copyright © 2001 by Merck & Co. All rights reserved. NJ. L.3-diols. Chim. Synthesis 1977. Chem. 51. J. R. W. Helv. 361. Part 2. K. C. D. Acta 62. R. 13. Schulte-Elte et al. Olah. Chem. Mikeska. 3155 (1919). Russ. Synthesis 1981. Snider. 527-561 (1991). 64. Inc. 1964) pp 1175-1210. 17. . Bhatnagar. Whitehouse Station. Weekblad 16. Rev.A. Chem. 1968. Prins.322. C. Acid-catalyzed addition of olefins to formaldehyde to give 1. (Interscience. I. 1072.

G. Gadallah et al. Org. 3465 (1971). Kupchan et al. 27 (1956). 341 (1971). J. 49. All rights reserved. Synthesis of phenanthrene derivatives from diazotized α-aryl-o-aminocinnamic acids by intramolecular arylation: Reviews: P. Foldeak. Daidone et al. T. M. F. Hanson et al.. Cf.323. . Soc.. S. F. Tetrahedron 27. Mechanistic study: P. 27. Leake. K. React.. H. Kametani. Meerwein Arylation. J. J. Whitehouse Station. T. Advan. Rev. A. 56. Inc. 496 (1896). S. Free Rad. Pschorr Reaction R.. Perkin Trans II 1999. 88 (1967). NJ. F. 5367 (1971).. 9. Gomberg-Bachman Reaction. De Tar. USA. Abramovitch.. J. D. 38. 409 (1957). Heterocyclic Chem. Copyright © 2001 by Merck & Co. 29. Chem. 2386 (1973). Chem. Chem. Kametani et al.. R. 8. Fukumoto. 2. ibid. 1409 (1980). ibid. 405. Org. Pschorr. Chem. 17. Heterocyclic Chem. S. Ber.

Asymmetric synthesis: Y. Org. NJ. Application to vinyl sulfoxides (the additive Pummerer reaction): D. Copyright © 2001 by Merck & Co. 2603 (1993). All rights reserved. Su et al. Chem. DeLucchi et al. Husson. USA. Daniels. Majumdar.. Indian J. Pummerer Rearrangement R. Comp. 1401 (1910). Soc. Mal. K.-P. D. Tetrahedron 49.. H. Rearrangement of sulfoxides to α-acyloxythioethers in the presence of acyclic anhydrides. Bull. . 6. Tetrahedron Letters 35. 157-405 (1991).324. Syn. Inc. Org. 924-937 (1991). Whitehouse Station. When nucleophiles other than those derived from the anhydride are present... React. Grierson. Kita et al. 40. different functionalization is achieved: Diastereoselectivity in the preparation of 4-phenyl-4-butanolides: H. Pummerer. Craig.. 11263 (1993). 43. 33B. Chem. 700 (1994). Reviews: O. S. D. Regiospecific cyclization: G. Ber. 3575 (1994). Japan 66.

The Carbohydrates (New York. Chem. Pigman. Purdie Methylation (Irvine-Purdie Methylation) T. All rights reserved. Peat. 1021 (1903). W. Inc. ibid. Whitehouse Station. P. C. Purdie. Haworth Methylation. J. 753. Soc. 58.. S. J. V. 83. Exhaustive methylation of a methyl glycoside by repeated treatment with methyl iodide and silver oxide. Carbohyd. C. Bourne.325. . E. Chem. Carbohyd. Irvine. 327 (1977). 5. Copyright © 2001 by Merck & Co.. followed by hydrolysis of the pentamethyl ether with dilute acid to yield the anomeric hydroxyl group: C.. Kovac et al. 1957) p 370. Advan.. Res. Cf. NJ. 1946. et al. Barker. 146 (1950). J. USA.

Quelet Reaction R. 102 (1934). France 7. 195. 199. Rend. Neda. NJ.. R. Passage of dry hydrochloric acid through a solution in ligroin of a phenolic ether and an aliphatic aldehyde in the presence or absence of a dehydration catalyst to yield α-chloroalkyl derivatives by substitution in the para position to the ether group or in the ortho position in para-substituted phenolic ethers: R. Bull. Whitehouse Station. 198. Oda. 202. 155 (1932). Soc. J. Soc. 196. 956 (1936). 150 (1934). U. Japan 47.. Inc. 1411 (1933). Blanc (Chloromethylation) Reaction. 565 (1944). Copyright © 2001 by Merck & Co. ibid. All rights reserved. Quelet. Chim. Quelet. USA. Chem.326. 196 (1940). Ind. Compt. Cf. .

Arkiv Kemi Mineral Geol. Ramberg-Bäcklund Reaction L. 504. A. J. Reaction of α-halo sulfones with strong bases to yield alkenes: 5 Reviews: L. React. Synthesis 1982. Inc. Org. L. 34.327. All rights reserved. ibid. Res. M. Ramberg.. Comp. F. Hartman. G. 28 (1970). Org. Hartman. 3. 25.. NJ. Clough. 209-216 (1968). 13A(27). G. Bordwell. 50 (1940). Syn. USA. D. Whitehouse Station. 861-886 (1991). D. 1 (1977). Paquette. 3. R. Paquette. Accts. B. 4725 (1940). C. Bäcklund. 1. Copyright © 2001 by Merck & Co. . Chem.A.

1967) p 105. Industrial Chemistry (New York. J. Copyright © 2001 by Merck & Co. Kirk-Othmer Encyclopedia of Chemical Technology vol. 1962) p 339. 1982) p 378. US 1963761 (1934). A.328. 17 (New York. D... 25. Clark. 3012 (1931). 3rd ed. NJ. Kent. US 2156402 (1939). N. Shreve. USA. Chemical Process Industries (New York. H. Whitehouse Station. produced by the chlorination of benzene with hydrochloric acid and air: W.. 3rd ed. L. B. R. R. L.. FR 698341 (1930). All rights reserved. Keyes. 1965) p 586. Raschig Phenol Process F. C. W. Prahl. Commercial process for the production of phenol by the hydrolysis of chlorobenzene. . Riegel's Industrial Chemistry (New York. Raschig.A. Faith. Inc.

Eckoldt. Copyright © 2001 by Merck & Co.329. 34.. Sosnovsky. J. Houben-Weyl 9. 23 (1949). NJ. Reed Reaction C. Inc. USA. H. Schönberg.. 344 (1942). Asinger et al. . Präparative Organische Photochemie (Berlin. F. Free Radical Reactions in Preparative Organic Chemistry (New York. Reed. US 2174110 (1934).. H. Ann. 407427 (1955). All rights reserved. Whitehouse Station. G. A.. Photochemical sulfonation of paraffins and cycloparaffins by sulfur dioxide and chlorine under irradiation with ultraviolet light: F. 562. 1964) p 105. US 2174492 (1938). 42. US 2046090 (1933). 1958) p 201. Ber. 75. Helberger et al.

2nd ed. 2. Whitehouse Station. L. All rights reserved. J. Modern Synthetic Reactions (W. Application to the synthesis of β-keto esters: C. Menlo Park. Condensation of aldehydes or ketones with organozinc derivatives of α-halo esters to yield β-hydroxy esters: Early reviews: R... Rathke.330. Ber. 1. Schick et al. P. A. Cf. Tetrahedron Asymmetry 5. Syn. Copyright © 2001 by Merck & Co. M. NJ. Rathke. J. Reformatskii. 1972) pp 671-682. Weipert. Comp. 58. USA. Shriner. 6439 (1993). . Org. Benjamin. Org... Asymmetric synthesis: D. W. M. Reviews: A. Tetrahedron 51. 1210 (1887). 423 (1975). Org. Phys. 571-590. Pini et al. 22. Chandrasekharam et al. Use of thiocarbonyl electrophiles: M. Org. House. 2939 (1995). React. Russ. 793 (1993). 1 (1942). Inc.. Tetrahedron Letters 34.. Chem. H. 277-299 (1991). Aldol Reaction. W. 1875 (1994). O. Methods development for the synthesis of β-lactones: H. Kashima et al. California.. React. Blaise Reaction. 22. 20. Soc. Reformatsky (Reformatskii) Reaction S. 44 (1890). Synthesis 1989. Fürstner. Chem.

331. Reimer-Tiemann Reaction
K. Reimer, F. Tiemann, Ber. 9, 824, 1268, 1285 (1876). Formation of phenolic aldehydes from phenols, chloroform and alkali:

Review: H. Wynberg, Chem. Rev. 60, 169 (1960); H. Wynberg, E. W. Meijer, Org. React. 28, 2 (1982); H. Wynberg, Comp. Org. Syn. 2, 769-775 (1991). Cf. Duff Reaction; Gattermann Aldehyde Synthesis.
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332. Reissert Indole Synthesis
A. Reissert, Ber. 30, 1030 (1897). Condensation of an o-nitrotoluene with oxalic ester, reduction to the amine, and cyclization to the indole:

W. O. Kermack et al., J. Chem. Soc. 119, 1602 (1921); P. C. Julian et al., Heterocyclic Compounds 3, 18 (1962); J. G. Cannon et al., J. Med. Chem. 24, 238 (1981).
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333. Reissert Reaction (Grosheintz-Fischer-Reissert Aldehyde Synthesis)
A. Reissert, Ber. 38, 1603, 3415 (1905); J. M. Grosheintz, H. O. L. Fischer, J. Am. Chem. Soc. 63, 2021 (1941). Formation of 1-acyl-2-cyano-1,2-dihydroquinoline derivatives (Reissert compounds) by reaction of acid chlorides with quinoline and potassium cyanide; hydrolysis of these compounds yields aldehydes and quinaldic acid:

Reviews: E. Mosettig, Org. React. 8, 220 (1954); W. E. McEwen, R. L. Cobb, Chem. Rev. 55, 511 (1955); F. D. Popp, Advan. Heterocycl. Chem. 9, 1 (1968); idem, ibid. 24, 187 (1979); idem. Bull. Soc. Chim. Belg. 90, 609 (1981); idem in The Chemistry of Heterocyclic Compounds vol. 32, Part 2, G. Jones, Ed. (Wiley, New York, 1982) p 353.
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334. Reppe Chemistry
The term designates that phase of acetylene chemistry involving the use of acetylene at high pressures in the presence of suitable catalysts to carry out the fundamental reactions of vinylation, ethynylation, cyclopolymerization and carbonylation as developed from 1928 onward by Walter Reppe and associates in the I. G. Farbenindustrie laboratories in Ludwigshafen:

J. W. Copenhaver, M. H. Bigelow, Acetylene and Carbon Monoxide Chemistry (New York, 1949) p 246; W. Reppe, Acetylene Chemistry, U.S. Dept. Commerce PB 18852-S (1949); Neue Entwicklungen auf dem Gebiet des Acetylens und Kohlenoxyds (Berlin 1949); H. Kröper, Houben-Weyl 4/II, 413-422 (1955); D. W. F. Hardie, Acetylene, Manufacture and Uses (New York, 1965) p 67; L. F. Fieser, M. Fieser, Reagents for Organic Synthesis (New York, 1967) pp 61, 183, 185, 190, 519, 720, 722, 723. Review of carbonylations: A. Mullen, “Carbonylations Catalyzed by Metal Carbonyls-Reppe Reactions” in New Syntheses with Carbon Monoxide, J. Falbe, Ed. (Springer-Verlag, Berlin, 1980) pp 243-308. Mechanistic study of cyclooctatetraene synthesis: R. E. Colborn, K. P. C. Vollhardt, J. Am. Chem. Soc. 108, 5470 (1986); C. J. Lawrie et al., Organometallics 8, 2274 (1989).
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335. Retro-Diels-Alder Reaction
Thermal dissociation of Diels-Alder adducts, occurring most readily when one or both fragments are particularly stable:

Early review: H. Kwart, K. King, Chem. Rev. 68, 415-447 (1968). Acceleration by alkoxide substituent: O. Papies, W. Grimme, Tetrahedron Letters 21, 2799 (1980). Application to the synthesis of enethiols: Y. Vallée et al., Synth. Commun. 23, 1267 (1993); of cyclopentadienyl ligands: B. Y. Lee et al., J. Am. Chem. Soc. 116, 2163 (1994). Role in structure elucidation via mass spectrometry: F. Turecek, V. Hanus, Mass Spectrom. Rev. 3, 85-152 (1984). Application to natural product synthesis: A. Ichihara, Synthesis 1987, 207-222; R. W. Sweger, A. W. Czarnik, Comp. Org. Syn. 5, 551-592 (1991).
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336. Retropinacol Rearrangement
N. Zelinsky, J. Zelikow, Ber. 34, 3249 (1901). Conversion of an alcohol to the rearranged olefin on treatment with acid:

Application to sterols: W. F. Johns, J. Org. Chem. 26, 4583 (1961); L. M. Harrison, P. V. Fennessey, J. Steroid. Biochem. 36, 407 (1990); to cyclohexanols: W. Hueckel, S. K. Gupte, Ann. 685, 105 (1965). In conjunction with ring expansion: T. Kimura et al., J. Org. Chem. 43, 1247 (1978). Cf. Nametkin Rearrangement; Wagner-Meerwein Rearrangement.
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337. Reverdin Reaction
F. Reverdin, Ber. 29, 997, 2595 (1896). Migration of iodine during nitration of iodophenolic ethers:

F. Reverdin, Bull. Soc. Chim. France [4] 1, 618 (1907); G. M. Robinson, J. Chem. Soc. 109, 1078 (1916); D. V. Nightingale, Chem. Rev. 40, 128 (1947); M. J. S. Dewar, Electronic Theory of Organic Chemistry (Oxford, 1949) p 232.
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338. Riehm Quinoline Synthesis
P. Riehm et al., Ber. 18, 2245 (1885); 19, 1394 (1886); idem, Ann. 238, 9 (1887). Formation of quinoline derivatives by prolonged heating of arylamine hydrochlorides with ketones with or without use of aluminum chloride or phosphorus pentachloride:

E. Knoevenagel et al., Ann. 55, 1923, 1934 (1922); 56, 2414 (1923); C. Hollins, The Synthesis of Nitrogen Ring Compounds (London, 1924) p 263; D. J. Craig, J. Am. Chem. Soc. 60, 1458 (1938); R. C. Elderfield, J. R. McCarthy, ibid. 73, 975 (1951); R. C. Elderfield, Heterocyclic Compounds 4, 16 (1952).
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(Paris) 64. Riemschneider. Angew. Zentralhalle 89. Chem. 316 (1953).. idem et al. idem. Monatsh. Soc. Orlick. 7b. Riemschneider. R. K. Am. Ind. Inc. Ind. . Orlick. Riemschneider. R. All rights reserved. G. 73. Ind.. J. 277 (1952). 460 (1949). 64. J. 84. Naturforsch. Schmidt. Am. Riemschneider Thiocarbamate Synthesis R. 353 (1952). Copyright © 2001 by Merck & Co. Soc. 118 (1950). Pharm. F. NJ. (Milan) 33. Wojahn.339. Chim. Z. R. Chim. Chem. 483 (1951). Chem. (Milan) 34. Pharmazie 4. 5905 (1951). Riemschneider. 420 (1952). 75. 99 (1950). Kolleck-Bös. Riemschneider. USA.. Chim. 6067 (1953). Whitehouse Station. P. G. The action of concentrated sulfuric acid followed by treatment with ice-water serves to transform arylthiocyanates into the corresponding thiocarbamates: R.

Benjamin. L.g. O. 331 (1949). Chem. Rabjohn. J. All rights reserved. House. React. 1969) pp 119-187. Modern Synthetic Reactions (W. 5. R.. A. New York. . L. 1875.. Oxidations of organic compounds with selenium dioxide. N. Inc. 2nd ed. Menlo Park. NJ. e. Riley et al.. Eds. (Marcel Dekker. 1932. H. E. California... Org. Augustine. Riley Oxidations (Selenium Dioxide Oxidation) H. 1972) pp 407-411. Whitehouse Station. USA. Oxidation. Copyright © 2001 by Merck & Co. Soc. the oxidation of active methylene groups to carbonyl groups: N. Trachtenberg.340.

Synthesis of amides from nitriles and alcohols or alkenes in strongly acidic media: Reviews: L. Tetrahedron Letters 35. 6967 (1994). Fink. J. Am. G. Whitehouse Station. 213-325 (1969). Larock. Minieri.341. ibid. Syn. React. 2793 (1994). Synthetic applications: S. Org. D.. J. 6. Kalish. Chem. Jaouen. Commun. Effland. P. 292294 (1991). 17. Krimen. Ritter. Top. J. C. J. 4048. R. J. 261-300 (1991). Leong. Synth. USA. W. Inc. Samaniego et al. J. Comp. ibid. 78 (1981). 46.. 4045 (1948). W. Org. Cota. Soc. Copyright © 2001 by Merck & Co. Ritter.. 4. . J. R. W. I. Chem. D. P. R. C. M. 70. Org. All rights reserved. Ritter Reaction J. Bishop. NJ. M. 24.

NJ. Am.: Early review: R.. Gawley. 777-794. Soc. Sato et al. Kim. J. Michael Reaction. Robinson Annulation W.. J. Robinson. 1621 (1990).. USA. Chem.342. . 1285. S. Synthesis 1976. Synthetic applications: R. Chim. Soc. 5934 (1993). q. Chem. V. Cf. J. Stereochemical study: C.v. Inc. Chem. Copyright © 2001 by Merck & Co. Tetrahedron Letters 31. 1225. Rapson. 1581 (1990). Formation of six-membered ring α. All rights reserved. Nussbaumer. Improved methodology: T.β-unsaturated ketones by the addition of cyclohexanones to methyl vinyl ketone (or simple derivatives of methyl vinyl ketone) or its equivalents. E. Wichterle Reaction. 1935. I 1991. Whitehouse Station.. followed by an intramolecular aldol condensation. Soc. Perkin Trans. 115. Helv. Bonnert et al. Acta 73. Fuchs. P. R. L. S.

McCarthy. J. 101. 762. Commun. Synth. USA. Robinson-Schöpf Reaction R. C 1967. 876 (1917). J.. 1350 (1998). 22. Chem. Lee. 50. Soc. 3115 (1992). . R. Soc. A.. Whitehouse Station.343. Acta Chem. Inc. Angew. 62. Soc. 797 (1937). T. Cf. Chem. D. M. 601. 111. 779. 147 (1956).. Am. Langlois et al. NJ. Stevens. M. 7032 (1979). Robinson. R. V. J. Schöpf. Copyright © 2001 by Merck & Co. Guthrie. W. Mannich Reaction. Ann. F.. Synthesis of tropinones from a dialdehyde. Chem. Alder et al. 52. J.. Jarevang et al. All rights reserved. C. Petrenko-Kritschenko Piperidone Synthesis. Chem. methylamine and acetonedicarboxylic acid: K. Scand.

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