Method to yield ketones , Hive Chemistry Discourse


		politoxicomania (Hive Bee) 11-06-03 19:54 No 469180				Method to yield ketones
						An old reaktion to yield ketones is like this : (R-COO)2Ca + (R´-COO)2Ca --> R-CO-R´ + CaCO3 Anyone tried this with Phenylaceticacid or MD-Phenylaceticacid ?? The source of this reaktion says that not all Carbonacidsalts will react and the yields are low. If someone wants to try it i can also generate an attempt guidance but bees should know whats meant. Thanks in advance.



		lugh (Moderator) 11-06-03 22:04 No 469197				Temperature (Rated as: good read)
						You forgot to mention the temperature at which this reaction generally takes place, about 400°C, and the references Ber 3 198 (1870) & JCS 59 621 (1891) See Post 358531 (moo: "P2P from phenylacetic acid and calcium acetate", Methods Discourse), Post 302647 (mysterious: "piperonal", Newbee Forum), Post 297386 (Elementary: "P2P from Acetone and Phenylacetic Acid", Chemistry Discourse), Post 256203 (WizardX: "Re: Propiophenone OTC route", Chemistry Discourse), Post 244672 (PrimoPyro: "Re: IS THIS THE BEST OTC P2P Route", Stimulants), Post 98406 (Torch: "R'CH2COCH3 via R'CH2COOH destructive distillation?", Chemistry Discourse) and Post 172207 (not existing) for previous in depth discussions The tube furnace method from Organic Synthesis and Vogel's is closely related, since they react the vapor of the two acids with a heated metallic carbonate catalyst Chemistry is our Covalent Bond



		politoxicomania (Hive Bee) 11-06-03 22:27 No 469206				UTFSE
						I should UTFSE. Its possible ok. As it is possible there are further questions. How differs the yield with other Metalions. The first i would try to compare the yields of this reaktion with Ba, Sr, or Ca salts. What is about other Katalysts? Ill try some katalysts i use every day but it would help if someone out there could help me. I have plenty of ideas about this reaktion which seems to be very interesting.



		GC_MS (Hive Addict) 11-06-03 23:22 No 469211				JFS (Rated as: good read)
						AC Allen et al. Differentiation of illicit phenyl-2-propanone synthesized from phenylacetic acid with acetic anhydride versus lead(II) acetate. J Forensic Sci 37(1) (1992) 301-322. The illicit synthesis of phenyl-2-propanone (P2P) in clandestine drug laboratories from phenylacetic acid and acetic anhydride in the presence of sodium acetate or pyridine, or from the dry distillation of phenylacetic acid and lead (II) acetate is examined. These two routes are investigated using capillary gas chromatography (GC) combined with vapor-phase Fourier transform infrared (FTIR) spectroscopy and electron impact mass spectrometry (EIMS) detection (GC-FTIR-EIMS), and using nuclear magnetic resonance (NMR) spectroscopy to identify 21 reaction by-products. The mechanisms of the two reactions producing P2P are presented, along with the mechanisms giving rise to these by-products. This investigation has identified 4 reaction-specific compounds which can be used to differentiate the two synthetic methods. Advanced clitoris massage specialist. 32 years of experience. PM me for a "sample".



		lugh (Moderator) 11-07-03 01:03 No 469230				Limited Yields
						Yields are limited by the nature of the reaction, the mixed ketone is formed along with the two simple ketones, in the case of methyl benzyl ketone; dibenzyl ketone and dimethyl ketone are also formed As has been pointed out before, the methylenedioxy ring is unlikely to survive such conditions, perhaps you should rethink your course of research, other routes have higher yields and less destructive conditions for such substituents Chemistry is our Covalent Bond



		politoxicomania (Hive Bee) 11-07-03 01:55 No 469242				Thats the reason why
						Thats the reason why i want to find a better katalysator for this reaktion. The problem that also Dibenzylketone will form is soluted by using excess CH3Coo. With the right katalyst this reaktion could be more mildly. Is it neccesary for this reaktion to be a solid-phase reaktion ? Never say never. Whats about generating a BaM(R-COO)2(R´-COO)2 or a M(R-COO)(R´-COO) intermediate in aprotic, anhydrous polar conditions ?? Or M(R-COO)(R´-COO)(Cl2) ? Ziegler Natter ?



		lugh (Moderator) 11-09-03 02:54 No 469698				References (Rated as: excellent)
						The references from Allen's JFS article: [1] Allen, A. C. and Cantrell, T. S., "Synthetic Reductions in Clandestine Amphetamine and Methamphetamine Laboratories: A Review," Forensic Science International, Vol. 42, 1989, pp. 183-199. [2] King, J. A. and McMillan, F. H., "The Decarboxylative Acylation of Arylacetic Acids," Journal of the American Chemical Society, Vol. 73, 1951, pp. 4911-4915. [3] Magidson, O. Y. and Garkusha, G.IA., "Synthesis of (3-Phenylisopropylamines (Phenamine)," Journal of General Chemistry (USSR), Vol. 11, 1941, pp. 339-343 [CA 35:58685 (1941)]. [4] Rubstov, M. V. and Baichikov, A. G., Synthetic Chemicopharmaceutical Preparations, Moscow, 1971, pp. 38-39. [5] Hurd, C. D. and Thomas, C. L., "Preparation of Dibenzylketone and Phenylacetone," Journal of the American Chemical Society, 'Vol. 58, 1936, p. 1240. [6] Tsutsumi, M., "Illegal Preparation of an Amphetamine-Like Compound," Science and Crime Detection (Japan), Vol. 6, 1953, pp. 50-52 [CA 47:11661h (1953)]. Senderens, J. B., "Catalytic Preparation of Aromatic Ketones," Comptes Rendus Hebdomadaires des Seances de 1'Academie des Sciences, Vol. 150, 1910, pp. 111-113 [CA 4:1479 (1910)]. Senderens, J. B., "Ketones Derived from Benzoic Acid and Phenylacetic Acids," Comptes Rendus Hebdomadaires des Seances' de l'Academie des Sciences, Vol. 150, 1910, pp. 1336-1338 [CA 4:2101 (1910)]. Herbst, R. M. and Manske, R. H., "Methyl Benzyl Ketone (Phenylacetone)," Organic Syntheses, Vol. 16, 1936, pp. 47-50 (Organic Syntheses, Collective Vol. II, Wiley, New York, 1943, pp. 389-391). [10] Pickard, R. H. and Kenyon, J., "Investigations on the Dependence of Rotatory Power on Chemical Constitution: Part VI. The Optical Rotatory Power of Methyl-tert-butyl-, Methylbenzyl-, Methylphenylethyl-, and Methyl-a-Naphthyl-Carbonols," Journal of the Chemical Society, Vol. 105, 1914, pp. 1115-1131. [11] Radiszewski, B., `i Zur Geschichte der Phenylessigsaure," Berichte der Deutschen Chemischen Gesellsehaft, Vol. 13, 1870, pp. 198-199. [12] Young, S., "Dibenzyl Ketone," Journal of the Chemical Society, Vol. 59, 1891, pp. 621-626. [13] Potapov, V. M. and Terent'ev, A. P., "Stereochemical Studies: IV. Schiff Bases from Optically Active a-Benzylethylamines," Zhurnal Obshchei Khimii, Vol. 28, 1958, pp. 3323-3328 [CA 53:14028h (1959)], [14] Cowan, D. M., Jeffery, G. H., and Vogel, A. I., "Physical Properties and Chemical Constitution: V. Alkyl Ketone," Journal of the Chemical Society, Vol. 62, 1940, pp. 171-176. [15] Vogel, A. I., A Textbook of Practical Organic Chemistry, 1st ed., Longmens, Green and Co., London, 1948, pp.. 336-338. [16] Zaputrayaev, B. A., Velitskaya, O. Y., Glikina, L. S., and Khaletskii, A. M., "Improvement of Methylbenzyl Ketone Synthesis," Meditsinskaya Promyshlennost SSSR, Vol. 14, No. 1, 1960, pp. 48-51 [CA 54:22464c (1960)]. Bodranskii, B. R., and Drabik, Y. V., "A New Method of Preparing 1-Phenyl-2-Aminopropane," Journal of Applied Chemistry, (USSR), Vol. 14, 1941, pp. 410--414 [CA 36:2531g (1942)]. Julian, P. L., Oliver, J. J., Kimball, R. H., Pike, A. B., and Jefferson, G. D., "Methyl Benzyl Ketone from a-Phenylacetoacetonitrile," Organic Syntheses, Vol. 18, 1948, pp. 54-55 and pp. 66-69 (Organic Syntheses, Collective Vol. II, Wiley, New York, 1943, pp. 391-392). [19] Murahashi, S., Ha.niwara, N., and Hirao, I., "Phenylacetone," Japanese Patent No. 3616, 19 Oct. 1950 [CA 47:3347h (1953)]. [20] Hamada, K., et al., "Phenylacetone," Japanese Patent No. 4367, 16 Dec. 1950 [CA 47:3347i (1953)]. [21] Bruce, W. F., "Cholestanone," Organic Syntheses, Collective Vol. 11, Wiley, New York, 1943, pp. 139-140. [22] Walker, H. G. and Hauser, C. R., "Synthesis of Methyl Ketones from Diethylacylmalonates," Journal of the American Chemical Society, Vol. 68, 1946, pp. 1386-1388. [23] Wilson, J. W. III, "Synthesis of d,l-Amphetamine Sulfate Labeled with 14C," Journal of the American Pharmaceutical Association, Vol. 39, 1950, pp. 687-688. [24] Popoff, A., "Oxydationsprodukte der Benzylketone," Berichte der Deutschen Chemischen Gesellschaft, Vol. 5, 1872, pp. 500-501. [25] Sund, E. H. and Henze, H. R., "Alkyl Benzyl Ketones and Hydantoin Derivatives," Journal of Chemical and Engineering Data, Vol. 15, No. 1, 1970, pp. 200-201 [CA 66:89969e (1972)]. [26] McKillop, A., Hunt, J. D., Taylor, E. C., and Kienzle, F., "Thallium in Organic Synthesis: XX. Oxidative Rearrangement of Olefins with Thallium (III) Nitrate-A Simple One-Step Synthesis of Aldehydes and Ketones," Tetrahedron Letters, No. 60, 1970, pp. 5275-5280. [27] Gajac, J. and Fioramonti, M., "Hydrogenation of Nitro Derivatives," Memorial des Poudres, Vol. 33, 1951, pp. 515-520 [CA 49:1537a (1955)]. [28] Hass, H. B., Susie, A. G., and Heider, R. L., "Nitroalkene Derivatives," Journal of Organic Chemistry, Vol. 15, 1950, pp. 8-14. [29] Heinzelmann, R. V., "Physiologically Active Secondary Amines: (3-(o-Methoxyphenyl)-Isopropyl-N-Methylamine and Related Compounds," Journal of the American Chemical Society, Vol. 75, 1953, p. 921. [30] Heinzelmann, R. V., "Alkyl Aralkyl Ketones," U.S. Patent No. 2,557,051, 12 June 1951 [CA 46:531g (1952)]. [31] Tindall, J. B., "1-Aryl-2-Oxoalkanes," U.S. Patent No. 2,427,822, 23 Sept. 1947 [CA 42:602d (1955)]. [32] Monti, D., Gramatica, P., Speranza, GI., and Manitto, P., "Reaction of Nitroolefins with Raney Nickel and Sodium Hypophosphite, a Mild Method for Converting Nitroolefins into Ketones (or Aldehydes)," Tetrahedron Letters, Vol. 24, No. 4, 1983, pp. 417-418. [33] Kirchhoff, R., "The Conversion of Nitro Groups to Carbonyls with Vanadium (II) Chloride," Tetrahedron Letters, No. 29, 1976, pp. 2533-2534. [34] Fujisawa, T., Okada, M., and Deguchi, Y., "1-((3-Diethylaminoethoxyphenyl)-3-Methyl-3,4Dihydro-6,7-Methylenedioxyisoquinoline, Japanese Patent, No. 8573, 5 Oct. 1956 [CA 52:11965b (1958)]. [35] Tiffeneau, M., "Benzene Hydrocarbons 'with a Pseudo Allyl Side Chain: Methovinylbenzene and Its Homologues-Study of Certain Molecule Migrations: Second Part. Study of Molecular Transpositions Which Accompany the Transformation of a-Glycols and Their Derivatives into Aldehydes and Ketones," Annales de Chimie et de Physique, Paris, Vol. 10, 1908, pp. 322378 [CA 2:265 (1908)]. [36] Coulson, D. R., "A New Synthesis of N)ethyl Ketones," Tetrahedron Letters, No. 45, 1964, pp. 3323-3326. [37] Instituto de Biologia y Sueroterapia, "1-Phenyl-2-Aminopropane," Spanish Patent No. 193,150, 20 May 1951 [CA 46:11237g (19:52)]. [38] Mason, J. P. and Terry, L. I.~ "Preparation of Phenylacetone," Journal of the American Chemical Society, Vol. 62, 1940 p. 1622. [39] Vinogradov, M. G., Verenchikov, S. P., and Nikishin, U. I., "Radical Reaction of Acetone with Benzene Initiated by Manganese (III) Acetate," Izvesitya Akademii Nauk SSSR Seriya Khimicheskaya, Vol. 7, 1972, pp. 1674-1.675 [CA 77:151620t (1983)]. [40] Heiba, E. I. and Dessau, R. M., "Oxidation by Metal Salts: VII. Synthesis Bases on the Selective Oxidation of Organic Free Radicals," Journal of the American Chemical Society, Vol. 93, No. 2, 1971, pp. 524-526. [41] Okabe, K., Ohwada, T., Ohta, IT., and Shudo, K., "Novel Electrophilic Species Equivalent to a-Keto Cations: Reactions of, O,O-Diprotonated Nitro Olefins with Benzenes Yield Arylmethyl Ketones," Journal of Organic Chemistry, Vol. 54., No. 4, 1989, pp. 733-734. [42] Walshe, N. D. A., Goodwin, G. B. T., and Woodward, F. E., "Acetone Trimethylsilyl Enol Ether," Organic Syntheses, Vol., 65, 1987, pp. 1-5. [43] Mukaiyama, T. and Narasaka, K., "3-I-)ydroxy-3-Methyl-l-Butanone by Crossed Aldol Reaction," Organic Syntheses, Vol; 65, 1987, pp. 6-11. i [44] Augustine, R. L., Carbon-Carbon Bond Formation, Marcel Dekker, New York, 1979, p. 112. [45] Solomon, T. W. G., Organic Chemistry, Wiley, New York, 1976, p. 693. [46] Allinger, N. L., Wang, G. L., and Dewhurst, B. B., "Kinetic and Mechanistic Studies of the Dakin-West Reaction," Journal of Organic Chemistry, Vol. 39, No. 12, 1974, pp. 1730-1735. [47] Buchanan, G. L., "The Dakin-West Reaction," Chemical Society Reviews, Vol. 17, 1988, pp. 91-109. I 1 [48] Breslow, D. S. and Hauser, C.,R., "Condensations Brought About by Bases: V. The Condensation of the Anhydride with the Aldehyde in the Perkin Synthesis," Journal of the American Chemical Society, Vol. 61, 1939, pp. 786-792. [49] Hauser, C. R. and Breslow, D. S., "Condensations Brought About by Bases: VI. The Mechanism of the Perkin Synthesis," Journal of the American Chemical Society, Vol. 61, 1939, pp. 793-798. [50] House, H. 0., Modern Synthetic Reactions, 2nd ed., Benjamin Publishing, Menlo Park, CA, 1972, pp. 660-663. [51] Augustine, R. L., Carbon-Carbon Bond Formation, Marcel Dekker, New York, 1979, pp. 179. [52] Davies, D. I. and Waring, C., "Cyclization Reactions Involving the Oxidation of Carboxylic Acids with Lead Tetra-acetate: Part III. Oxidation of Phenyl- and o-Biphenylyl-Substituted Acetic and Propionic Acids, and of o-Biphenylylmethylmalonic Acid," Journal of the Chemical Society, Vol. 18, 1968, pp. 2333-2336. [53] Rudbottom, G. M., Oxidation in Organic Chemistry, Vol. 5-D, W. S. Trahanovsky, Ed., Academic Press, New York, 1982, pp. 1-145. [54] House, H. 0., Modern Synthetic Reactions, 2nd ed., Benjamin Publishing, Menlo Park, CA, 1972, pp. 374-375. The references in bold are the p2p syntheses, 2-26 start with phenylacetic acid, 27-33 from betamethylbetanitrostyrene, 24 from allylbenzene, 35 from phenylmagnesium bromide, 36 from benzaldehyde and 37-41 from benzene Chemistry is our Covalent Bond



		SPISSHAK (Hive Addict) 11-11-03 02:19 No 470040				Lugh
						IF I may say I have never seen a reference post that long before that deserves a record for the longest list of refs.



		Rhodium (Chief Bee) 11-11-03 09:30 No 470135				1377
						How about this list of references then: ../rhodium /forensic.references.html



		Rhodium (Chief Bee) 11-11-03 23:03 No 470276				P2P Synthesized from Phenylacetic Acid (Rated as: excellent)
						So there, now available in its entirety, the article from Post 469211 (GC_MS: "JFS", Chemistry Discourse) Differentiation of Illicit Phenyl-2-Propanone Synthesized from Phenylacetic Acid with Acetic Anhydride Versus Lead(II)Acetate AC Allen, ML Stevensen, SM Nakamura, RA Ely Journal of Forensic Sciences 37(1), 301-322 (1992) (../rhodium /p2p.phenylacetic.html)