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United States Patent (19) 11 Patent Number: 5,410,094 Babler 45 Date of Patent: Apr

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United States Patent (19) 11 Patent Number: 5,410,094 Babler 45 Date of Patent: Apr US005410094A United States Patent (19) 11 Patent Number: 5,410,094 Babler 45 Date of Patent: Apr. 25, 1995 54 TERTARY ALKYNOLS 2R,4R,8R-a-Tocopherol Vitamin E. Construction of 75) Inventor: James H. Babler, Chicago, Ill. Chiral Chromans from an Optically Active, Nonaromatic Precursor, Journal of the American Chemical Society, 73 Assignee: Loyola University of Chicago, 1979, pp. 6710-6716. Chicago, Ill. Chan, et al., Synthesis of 2R,4R, 8R-a-Tocopheryl Ace 21 Appl. No.: 255,369 tate Vitamin E Acetate Using 3,3 Sigmatropic Rear 22 Filed: Jun. 8, 1994 rangement, The Journal of Organic Chemistry, vol. 43, No. 18, 1978, pp. 3435-3440. Russell, A. and Kenyon, R. L., Pseudoionone, Organic Related U.S. Application Data Syntheses Collective vol. 3, pp. 747-750 1955. 62) Division of Ser. No. 976,219, Nov. 25, 1992, Pat. No. Haynes, L.J. and Jones, E. R. H., Unsaturated Lactones, 5,349,071. Part I J. Chem. Soc., 1946, pp. 954-957. 51 Int. Cl.' .................... C07C33/042; CO7C 43/14; Sato, K., et al., Japanese Patent Application 26,656('63) C07C 43/166; C07C 43/178 6,10,14-Trimethylpentadeca-6-en-yn-2-ol, Chem. (52) U.S.C. .................................... 568/662; 556/449; Abstr., 1964, p. 6746(e). 568/675; 568/855 Acetylene-Alcohol, Compendium of Organic Synthetic 58) Field of Search ....................... 568/855, 675, 662; Methods, vol. 2, Section 302, pp. 218–220 1974. 556/449 Acetylene-Alcohol, Compendium of Organic Synthetic 56 References Cited Methods, vol. 3, Section 302, p. 337 1977. U.S. PATENT DOCUMENTS (List continued on next page.) 2,529,498 11/1950 Isler ..................................... 568/662 2,555,362 6/1951 Newman ............................. 568/675 Primary. Examiner-Joseph E. Evans 2,824,041 2/1958 Bavley et al. ....................... 568/874 Attorney, Agent, or Firm-Marshall, O'Toole, Gerstein, 3,082,260 3/1963 Tedeschi et al. .................... 568/874 Murray & Borun 3,709,946 1/1973 Tedeschi et al..................... 568/874 3,755,469 8/1973 Pasedach ............................. 568/874 57 ABSTRACT 3,801,611 4/1974 Henricket al. ..................... 568/675 Processes for synthesizing tertiary alkynols by reacting 4,179,579 12/1979 Fujita et al.......................... 568/675 carbonyl-group-containing compounds with alkynes in 4,191,842 3/1980 Cohen et al. ........................ 556/449 the presence of a basic catalyst are disclosed. Preferred OTHER PUBLICATIONS products are 6,10,14-trimethyl-4-pentadecyn-6-ol com Isler, et al., Vitamins and Hormones-Chemistry of Vita pounds having the structure: min E, vol. 20, 1962, pp. 389-405. Fischer, F. G. and Löwenberg, Kurt, Die Synthese des Phytols, Ann., 475, 1929, pp. 183-204. Burrell, et al., Carotenoids and Related Compounds. Part fH, ph pR XIV. Stereochemistry and Synthesis of Geraniol, Ne (CH),CHCH2CHCH-C= CCH2CHCH3 rol, Farnesol and Phytol, J. Chem. Soc. C, 1966, pp. CH3 244-2154. Sato, et al., A Total Synthesis of Phytol, vol. 32, Jan., 1967, pp. 177-180. A preferred, novel compound, 6,10,14-trimethyl-4-pen Fujisawa, et al., A Stereocontrolled Total Synthesis of tadecyne-2,6-diol, can be used in the synthesis of Vita Optically Active R, R-Phytol, Tetrahedron Letters, vol. min E or Vitamin K1. 22, No. 48, 1981, pp. 4823-4826. Cohen, et al., A Novel Total Synthesis of 7 Claims, No Drawings 5,410,094 Page 2 OTHER PUBLICATIONS Saimoto, et al., Regiocontrolled Formation of 4,5-Dihy Solomons, T. W., Organic Chemistry, 5th Ed., p. 471 dro-3(2H) furanones from 2-Butyne-1,4-diol Deriva 1992. tives, Bull. Chem. Soc. Jpn., vol. 56, 1983, pp. March, J., Advanced Organic Chemistry: Reactions, 3078-3087. Mechanisms and Structure, 4th Ed., pp. 250-255, 1992. Miyashita, N., et al., Pyridinium p-Toluenesulfonate, A Solomons, T. W., Organic Chemistry, 5th Ed., p. 94 Mild and Efficient Catalyst for the Tetrahyropyranylation 1992. of Alcohols, J. Org. Chem., vol. 42, No. 23, 2977, pp. Tedeschi, R. J., et al., Base-Catalyzed Reaction of Acety 3772-3774. lene and Vinyl-Acetylenes with Carbonyl Compounds in Claesson, A. and Bogentoft, C., Formation of Conju Liquid Ammonia under Pressure, J. Org. Chem., vol. 28, gated Dienes on Lithium Aluminium Hydride Reduction 1963, pp. 1740-1743. of Allenic tert-Alcohols, Acta Chem. Scand. 26, No. 6, Tedeschi, R.J., The Mechanism of Base-Cataylzed Ethy 1972, pp. 2540-2542. nylation in Donor Solvents, J. Org. Chem., vol. 30, 1965, Redel, J., et al., Fr. 1,460,512 (Dec. 2, 1966), Chem. pp. 3045-3049. Abstr., 67, 1964, pp. 100, 2792. Viehe, H. G. and Reinstein, M., Dichlorimethan als. Lö Grimaldi, J. and Bertrand, M., Quelques aspects de la sungsmittel fir Grignard-Reagenzien, Chem. Ber., 95, reactivite des epoxydes a-alleniques, Bulletin De La So 1962, pp. 2557-2562. ciété Chimique De France, No. 3, 1971, pp. 973-979. d'Engeniéres, et al., Alcoylation selective des alcods Trofimov, B. A., et al., Production of Allenyl Ethers, acetyleniques dan lammoniac liquide Généralisation de Chen. Abstracts 1989, vol. 111, 25313c. la méthode (4 memoire, Bulletin De La Societe Chi Weiberth, F. J., et al., Tanden Alkylation-Reduction. mique De France, No. 1, 1968, pp. 201-204. Highly Steroselective Synthesis of (E)-1-Hydroxymethyl Papa, et al., A New Class of Hypnotics: Unsaturated Car Methyl Propenyl Ethers from Aldehydes Using 1-Lithi binols. Part I, J. Am. Chem. Soc., vol. 76, 1954, pp. -1-Methoxyallene, J. Org. Chem. 1985, 50, pp. 4446-4450. 5308-5314. 5,410,094 1. 2 However, all such examples (except for certain reac TERTARY ALKYNOLS tions involving acetylene, discussed below) teach that the use of one equivalent of strong base is required for This is a divisional of U.S. application Ser. No. a successful reaction. Specific examples can be found in 07/976,219, filed Nov. 25, 1992, now U.S. Pat. No. 5 the following references: 5,349,071. (a) Section 302 (pages 218-220) in COMPENDIUM OF ORGANIC SYNTHETIC METHODS, BACKGROUND OF THE INVENTION VOLUME 2, edited by I. T. Harrison, et al. (John A. Technical Field Wiley & Sons, Inc., 1974). The present invention relates generally to processes O (b) Section 302 (page 337) in COMPENDIUM OF for synthesizing tertiary alkynols, in particular, 6,10,14 ORGANIC SYNTHETIC METHODS, VOL trimethyl-4-pentadecyn-6-ol compounds having the UME3, edited by L. S. Hegedus, et al. (John Wiley formula: & Sons, Inc., 1977). (c) T. W. G. Solomons, ORGANIC CHEMISTRY, 15 Fifth Edition, page 471 (John Wiley & Sons, Inc., H. ph pR 1992). (CH CHCHCHCH -C= CCH2CHCH3 The commonly-held notion that one equivalent of a CH3 strong base is required for alkylation is not surprising in view of the known acidities of a terminal alkyne and wherein "R" represents H, or an alkyl group which can 20 representative alcohols. For example, Table 8.1 on be aliphatic (e.g. tert-butyl), arylalkyl (e.g. benzyl) or pages 250-252 in ADVANCED ORGANIC CHEM part of a mixed acetal derivative ISTRY: REACTIONS, MECHANISMS AND STRUCTURE, Fourth Edition, by J. March (John Wiley & Sons, Inc., 1992) lists the following pKa values: (e.g., R = -HCH) 25 R2CHOH (a 2 alcohol, as found in 4-pentyn-2-ol: 16.5 OCH2CH3 R3COH (a 3° alcohol): 17 RCOCH2R (an enolizable ketone): 19-20 These 6,10,14-trimethyl-4-pentadecyn-6-ol compounds HCEC-H: 25 can be readily converted to 3,7,11,15-tetramethyl-l-hex NH3:38 adecen-3-ol (isophytol), an intermediate used in both 30 CH3CH2-H:50 the manufacture of alpha-tocopherol (the most active Similar pKa values are listed in a widely-used organic Vitamin E factor known to occur in nature) as well as in chemistry textbook: T. W. G. Solomons, ORGANIC the synthesis of Vitamin K1. CHEMISTRY, FIFTH EDITION, Table 3.1 on page The 6,10,14-trimethyl-4-pentadecyn-6-ol compounds 94 (John Wiley & Sons, Inc., 1992). Such data indicate 35 that strong bases such as NaNH2 or ethylmagnesium of the present invention can be prepared using the fol bromide can convert a terminal alkyne to an acetylide lowing novel alkylation reaction: salt, which can subsequently be treated with a ketone to give a 3 alkynol. On the other hand, alkoxides derived O from 2 and 3 alcohols are expected to be too weakly RCHCHR + Ric=CH catalytounte basic to convert (appreciably) a terminal alkyne to an acetylide anion. Indeed, under the reaction conditions OH utilized in the present invention, one would instead predict conversion of an enolizable ketone to its enolate RCH chir' anion. l=CR" 45 There are a number of patents, cited in R. J. Tede schi, et al., J. Org. Chen., 28, 1740 (1963), that at first R,R = alkyl and/or H and/or form part of an alicyc glance seem to suggest the alkynylation step of the lic ring (e.g., cyclohexanone). present invention. These patents relate to the use of R1 = an alkyl, alkenyl, aryl or arylalkyl group. potassium hydroxide (comparable in basicity to an alk The process can also be used to synthesize tertiary al 50 oxide) as a catalyst in the reaction of gaseous acetylene kynols in addition to 6,10,14-trimethyl-4-pentadecyn-6- or vinylacetylene with aldehydes and ketones in liquid olderivatives. ammonia-a process referred to as the Favorskii reac B. Technical Background tion. However, a subsequent article by R.J. Tedeschi, J. The addition of an acetylide anion to a ketone to yield Org. Chem., 30, 3045 (1965), confirmed that the Favor a 3 alkynol is not a novel process perse; however, the 55 skii conditions do not involve an acid-base reaction.
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