专利号:US-3836544-A 优先权日:1972-04-25 标 题:Synthesis of zearalanes ii and related compounds and intermediates useful in the syntheses thereof 发明人:URRY W; MULLENBACH G 权利人:COMMERCIAL SOLVENTS CORP 摘要:THIS INVENTION PROVIDES A NEW SYNTHESIS FOR NORZEARALANE II AND RELATED COMPOUNDS WHICH RELATED COMPOUNDS AND NORZEARALANE II ARE REPRESENTED BY THE FORMULA 1,5-DI(HO-),2,3-(-CO-O-CH2-(CH2)X-)-BENZENE WHERE X IS AN INTEGER HAVING A VALUE FROM 1 TO 13 INCLUSIVE. THE ANABOLIC AGENT NORZEARALANE II, IN WHICH X=9 IN THEFOREGOING FORMULA, IS PREPARED BY A TOTAL CHEMICAL SYNTHESIS INVOLVING THE REACTION OF 10-UNDECENAL WITH MALONIC ACID TO PRODUCE TRANS-2,12-TRIDECADIENOIC ACID; TREATING THE ACID SO FORMED WITH DIAZOMSTHANE TO YIELD METHYL TRANS-2,12-TRIDECADIENOATE; REACTING THE METHYL ESTER WITH ETHYL ACETOACETATE AND SODIUM ETHOXIDE TO FORM THE SODIUM SALT OF ETHYL 6-(9-DECENYL)-B-DIHYDRORESORCYLATE; BROMINATING THE DIHYDRORESORCYLATE TO PREPARE ETHYL 3-BROMO- 6 - (9-DECENYL)-B-DIHYDRORESOCRYLATE; DE-HYDROBROMINATING THE FOREGOING BROMO DERIVATIVE TO GIVE ETHYL 6-(9-DECENYL)-B-RESORCYLATE; REACTING THE RESORCYLATE ESTER WITH BENZYL CHLORIDE TO PRODUCE ETHYL 6-(9-DECENYL)-BRESORCYLATE DIBENZYL ETHER; SUBJECTING THE BENZYLATED ESTER TO THE ACTION OF DIBORANE, WATER AND HYDROGEN PEROXIDE TO FORM ETHYL 2,4-BIS (BENZYLOXY)-6-(10-HYDROXYDECYL)BENZOATE; TREATING THE FOREGOING BENZOATE WITH SODIUM ETHOXIDE TO PREPARE NORZEARALANE II DIBENZYL ETHER, ONE ALSO TO PREPARE AS A BY-PRODUCT THE DIMERIC DILACTONE OF 2,4-BIS(BENZYLOXY)-6-(10-HYDROXYDECYL)-BENZOIC ACID; HYDROGENATING NORZEARALANE II DIBENZYL ETHER TO FORM NORZEARALANE II. IN GENERAL, A HOMOLOGUE OF NORZEARALANE II AND/OR OF THE CORRESPONDING DIMERIC DILACTONE IS PREPARED BY SUBSTITUTING FOOR 10-UNDECENAL IN THE FOREGOING SEQUENCE OF REACTIONS AN UNSATURATED ALDEHYDE HAVING THE FORMULA CH2=CH-(CH2)X-1-CHO WHERE X IS AN INTEGER WHICH MAY HAVE THE VALUE 1,2,3,4, 5, 6, 7, 8, 9, 10, 11, 12 OR 13 SPECIFICALLY ZEARALANE II (WHERE X=10) IS PREPARED STARTING WITH 11-DODECENAL AND THE DIMERIC DILACTONE FROM 6-(5-HYDROXYPENTYL-B-RESORCYCLIC ACID DIBENZYL ETHER IS PREPARED WHEN THE STARTING ALDEHYDE IS 5-HEXENAL (WHERE X= 4) THE INVENTION ALSO COVERS PHYSIOLOGICALLY ACTIVE COMPOUNDS RELATED TO THE ZEARALANES II AND KNOW AS DIMERIC DILACTONES HAVING THE FORMULA, 1,5-DI(RO-),2,3-(-CO-O-CH2-(CH2)X-(3,5-DI(RO-)-1,6-PHENYL ENE)-CO-O-CH2-(CH2)X-)-BENZENE X IS AN INTEGER WHICH MAY HAVE THE VALUE 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 OR 13 AND WHERE R IS EITHE HYDROGEN OR A BENZYL RADICAL (C6H5CH2-). MORE PARTICULARLY, THIS INVENTION RELATES TO NOVEL INTERMEDIATES PRODUCED IN THE SYNTHESIS OF THE ABOVE COMPOUNDS AND TO PROCESSES FOR MAKING THESE INTERMEDIATES.
专利号:US-3903115-A 优先权日:1972-04-25 标 题 :Synthesis of zearalanes II and related compounds and intermediates useful in the syntheses thereof 发明人:URRY WILBERT H; MULLENBACH GUY TOWNS 权利人:COMMERCIAL SOLVENTS CORP 摘要:This invention provides a new synthesis for norzearalane II and related compounds which related compounds and norzearalane II are represented by the formula where X is an integer having a value from 1 to 13 inclusive. The anabolic agent norzearalane II, in which X 9 in the foregoing formula, is prepared by a total chemical synthesis involving the reaction of 10-undecenal with malonic acid to produce trans-2,12-tridecadienoic acid; treating the acid so formed with diazomethane to yield methyl trans-2,12tridecadienoate; reacting the methyl ester with ethyl acetoacetate and sodium ethoxide to form the sodium salt of ethyl 6-(9-decenyl)- Beta -dihydroresorcylate; brominating the dihydroresorcylate to prepare ethyl 3-bromo-6-(9-decenyl)- Beta dihydroresorcylate; de-hydrobrominating the foregoing bromo derivative to give ethyl 6-(9-decenyl)- Beta -resorcylate; reacting the resorcylate ester with benzyl chloride to produce ethyl 6-(9-decenyl)- Beta -resorcylate dibenzyl ether; subjecting the benzylated ester to the action of diborane, water and hydrogen peroxide to form ethyl 2,4-bis(benzyloxy)-6-(10hydroxydecyl)-benzoate; treating the foregoing benzoate with sodium ethoxide to prepare norzearalane II dibenzyl ether, and also to prepare as a by-product the dimeric dilactone of 2,4bis(benzyloxy)-6-(10-hydroxydecyl)-benzoic acid; hydrogenating norzearalane II dibenzyl ether to form norzearalane II.
专利号:US-4150236-A 优先权日:1976-05-26 标 题 :Steroidal intermediates from the condensation product of dimethyl-3-ketoglutarate and glyoxal 发明人:WEISS ULRICH; RICE KENNER C 权利人:US HEALTH EDUCATION & WELFARE 摘要:Tricyclic aromatic compounds of the formula ##STR1## including those wherein: (A) R 1 is H, R 2 is carbomethoxy, and R 3 is methyl; n (b) R 1 is acetyl, R 2 is carbomethoxy, and R 3 is methyl; n (c) R 1 and R 3 are methyl and R 2 is carbomethoxy; n (d) R 1 , R 2 , and R 3 are hydrogen; and n (e) R 1 and R 3 are methyl and R 2 is hydrogen n Are intermediates for the total synthesis of steroids.
专利号:DE-2315557-A1 优先权日:1972-04-25 标 题:SYNTHESIS OF ZEARALANEN II AND RELATED COMPOUNDS AND INTERMEDIATE PRODUCTS THAT CAN BE USED TO SYNTHESIS THEREOF
专利号:CA-2640585-A1 优先权日:2003-02-05 标题 :Synthesis of 2-butyl-3-(2'-(1-trityl-1h-tetrazol-5-yl)biphenyl-4-yl)-1,3-diazaspirol{4,4}-non-ene-4-one
专利号:CA-1120053-A 优先权日:1976-05-26 标题:Intermediate for the total synthesis of steroids
摘要:J. Sunkel and H. Staude, Ber. Bunsenges. Physik. Chem. 72, 567 (1968). 摘要:M. W. Whitehouse and P. D. G. Dean, Biochem. Pharmacol. 14, 557 (1965). 参考文献:10.1107/s1600536810024785 摘要:Fun HK, Goh JH, Rai S, Isloor AM, Shetty P. Methyl 2,6-bis-[(5-chloro-4,6-dimeth-oxy-pyrimidin-2-yl)-oxy]benzoate. Acta Crystallogr Sect E Struct Rep Online. 2010 Jun 30;66(Pt 7):o1869–70. 参考文献:10.1107/s1600536810024724 摘要:Fun HK, Goh JH, Rai S, Isloor AM, Shetty P. Methyl 2,6-bis-[(5-bromo-4,6-dimeth-oxy-pyrimidin-2-yl)-oxy]benzoate. Acta Crystallogr Sect E Struct Rep Online. 2010 Jun 30;66(Pt 7):o1871.