DOCSLIB.ORG

(12) United States Patent (10) Patent No.: US 7,927,613 B2 Almarsson Et Al

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
(12) United States Patent (10) Patent No.: US 7,927,613 B2 Almarsson Et Al USOO7927613B2 (12) United States Patent (10) Patent No.: US 7,927,613 B2 Almarsson et al. (45) Date of Patent: *Apr. 19, 2011 (54) PHARMACEUTICAL CO-CRYSTAL (58) Field of Classification Search .................. 424/400; COMPOSITIONS 514/217,403 (75) Inventors: Örn Almarsson, Shrewsbury, MA (US); See application file for complete search history. Magali Bourghol Hickey, Medford, MA (US); Matthew L. Peterson, (56) References Cited Framingham, MA (US); Michael J. Zaworotko, Tampa, FL (US); Brian U.S. PATENT DOCUMENTS Moulton, Providence, RI (US); Nair 2,665,277 A 1/1954 Homeyer et al. Rodriguez-Hornedo, Ann Arbor, MI 2,711,411 A 6, 1955 Holbert etal. 3,028,420 A 4, 1962 Petrow et al. (US) 3,598,123 A 8, 1971 Zaffaroni (73) Assignees: University of South Florida, Tampa, FL 3,845,770 A 11/1974 Theeuwes etal. 3,916,899 A 11/1975 Theeuwes etal. (US); The Regents of the University of 3,970,651 A 7/1976 Kaplanet al. Michigan, Ann Arbor, MI (US); 4,008,321 A 2f1977 Kamishita et al. Transform Pharmaceuticals, Inc., 4,008,719 A 2f1977 Theeuwes et al. Lexington, MA (US) 4,198,507 A 4/1980 Barry et al. 4,267,179 A 5/1981 Heeres et al. (*) Notice: Subject to any disclaimer, the term of this 4,368, 197 A 1/1983. Shefter et al. patent is extended or adjusted under 35 4.513,006 A 4/1985 Maryanoffetal. U.S.C. 154(b) by 1101 days. 4,764,604. A 8, 1988 Muller 4,853,379 A 8, 1989 Shroot et al. This patent is Subject to a terminal dis 4,916,134 A 4, 1990 Heeres et al. claimer. 4,925,674. A 5/1990 Giannini et al. 4,927,855 A 5, 1990 Lafon (21) Appl. No.: 10/660,202 4,994,604. A 2/1991 Tung et al. (22) Filed: Sep. 11, 2003 3,536,809 A 4, 1991 Schaller et al. (65) Prior Publication Data (Continued) US 2007/OO26O78A1 Feb. 1, 2007 FOREIGN PATENT DOCUMENTS Related U.S. Application Data EP O310.122 B1 4, 1989 (60) Continuation-in-part of application No. (Continued) PCT/US03/27772, filed on Sep. 4, 2003, which is a continuation-in-part of application No. 10/378.956, OTHER PUBLICATIONS filed on Mar. 1, 2003, application No. 10/660,022, Angelo Gavezzotti, Are Crystal Structures Predictable?, 1994. Acc. which is a continuation-in-part of application No. Chem. Res., vol. 27, pp. 309-314.* 10/637,829, filed on Aug. 8, 2003, now abandoned, which is a division of application No. 10/295,995, filed (Continued) on Nov. 18, 2002, now Pat. No. 6,699,840, which is a continuation of application No. 10/232,589, filed on Primary Examiner — Sreeni Padmanabhan Sep. 3, 2002, now Pat. No. 6,559,293, application No. Assistant Examiner — Renee Claytor 10/660.202, which is a continuation-in-part of (74) Attorney, Agent, or Firm — Saliwanchik, Lloyd & application No. 10/601,092, filed on Jun. 20, 2003, Saliwanchik now abandoned, and a continuation-in-part of application No. 10/449,307, filed on May 30, 2003, now Pat. No. 7,078,526. (57) ABSTRACT (60) Provisional application No. 60/360,768, filed on Mar. A pharmaceutical composition comprising a co-crystal of an 1, 2002, provisional application No. 60/451,213, filed API and a co-crystal former; wherein the API has at least one on Feb. 28, 2003, provisional application No. functional group selected from ether, thioether, alcohol, thiol, 60/463,962, filed on Apr. 18, 2003, provisional aldehyde, ketone, thioketone, nitrate ester, phosphate ester, application No. 60/487,064, filed on Jul. 11, 2003, thiophosphate ester, ester, thioester, Sulfate ester, carboxylic provisional application No. 60/406,974, filed on Aug. acid, phosphonic acid, phosphinic acid, Sulfonic acid, amide, 30, 2002, provisional application No. 60/380,288, primary amine, secondary amine, ammonia, tertiary amine, filed on May 15, 2002, provisional application No. sp2 amine, thiocyanate, cyanamide, Oxime, nitrile diazo, 60/356,764, filed on Feb. 15, 2002, provisional organohalide, nitro, S-heterocyclic ring, thiophene, n-hetero application No. 60/444,315, filed on Jan. 31, 2003, cyclic ring, pyrrole, o-heterocyclic ring, furan, epoxide, per provisional application No. 60/439,282, filed on Jan. oxide, hydroxamic acid, imidazole, pyridine and the co-crys 10, 2003, provisional application No. 60/384,152, tal former has at least one functional group selected from amine, amide, pyridine, imidazole, indole, pyrrolidine, car filed on May 31, 2002. bonyl, carboxyl, hydroxyl, phenol, Sulfone, Sulfonyl, mer (51) Int. Cl. capto and methylthio, such that the API and co-crystal former A6 IK9/00 (2006.01) are capable of co-crystallizing from a solution phase under AOIN 43/46 (2006.01) crystallization conditions. AOIN 43/56 (2006.01) (52) U.S. Cl. ......................... 424/400: 514/217: 514/403 36 Claims, 66 Drawing Sheets US 7,927,613 B2 Page 2 U.S. PATENT DOCUMENTS 6,559,293 B1* 5/2003 Almarsson et al. .......... 536,187 5,006,513 A 4, 1991 Hector et al. 3.95 R 258 Real 5,023,092 A 6/1991 DuRoss. 6,613790 B2 92003 Carter 5,059,595 A 10/1991 Le Grazie 6,699,840 B2 3/2004 Almarsson et al. 5,073,543 A 12/1991 Marshall et al. 7,078.526 B2 7/2006 Remenar et al. .............. 544,336 5, 120,548 A 6, 1992 McClelland et al. 7,132,570aw sy B2 11/2006 Neckebrocket al. 5,177.262 A 1/1993 Taylor et al. T172.769 B2 2/2007 Kararlietal 5.242.942 A 9, 1993 Costanzo et al. J. 4 ararii et al. 5273.760 A 12/1993 Oshlack et all 7,205,413 B2 4/2007 Morissette et al. 4 - 7,446,107 B2 11/2008 Remenar et al. 5,286,493 A 2f1994 OShlack et al. 7,452,555 B2 11/2008 Childs 5,324,351 A 6, 1994 OShlack et al. 7459,449 B2 12/2008 Kelt 5,332,834. A 7/1994 Bhattacharya et al. 2003,666, Ki 1563 financial 5,338,644 A 8/1994 Taylor et al. 5,354,556. A 10/1994 Sparks et al. 2002fOO 13357 A1 1/2002 Nadkarni et al. 2002fOO15735 A1 2/2002 Hedden et al. 5.366.7385,356,467 A 110/1994 1/1994 OshlackRork et all et al. 2002/0034542 A1 3/2002 Thombre et al. 5.380,867 A 1, 1995 RA tal 2002/0037925 A1 3/2002 Dewey et al. 53.84.337 A 1, 1995 C al aC y a. 2002/0042446 A1 4/2002 Dewey et al. 542,094 A 5, 1995 AE 2002, 0071857 A1 6, 2002 Kararietal. 5.414997 A 5, 1995 As et al. 2002/0107250 A1 8/2002 Hariharan et al. I k l 2002/01 19193 A1 8, 2002 Le et al. 5,466,823. A 1 1/1995 Talley et al. 2003/0069 190 A1 4/2003. Abdel-Magid et al. 5,472,712 A 12/1995 Oshlack et al. 2003, OO728O2 A1 4, 2003 Cutler 5,474,997 A 12/1995 Gray et al. 2003/0096014 A1 5.2003 Sherman 5,521.2075,510,496 A 4/19965, 1996 TalleyG et al. 2003/0162226 A1 8/2003 Cima et al. - 4 J. raneto 2003/0166581 A1 9, 2003 Almarsson et al. 5,523,090 A 6/1996 Znaiden et al. 2003/0224006 A1 12/2003 Zaworotko et all 5,563,165 A 10/1996 Talley et al. 2004/00 19211 A1 1/2004 Remenar et al. S.E. A 58. Metal 1 2004/002994.6 A1 2/2004 Arora et al. wk I Olare et al. 2004/005.3853 A1 3/2004 Almarsson et al. 5,631,250 A 5, 1997 Bunnell et al. 5.633,015 A 5, 1997 Gilis etal 2004/0106052 A1 6, 2004 Molaire w - - S C a. 2004/0106053 A1 6/2004 Molaire et al. 5,633,272 A 5/1997 Talley et al. 2004/0106055 A1 6/2004 Molaire et al. 5,639,476 A 6/1997 Oshlack et al. 2004/O154890 A1 8, 2004 Liu : A 88. SE 1 2004/0171062 A1 9, 2004 Hirth et al. ww. Sena et al. 2004/0176335 A1 9, 2004 Childs ........................... 514,165 SE A 1992 RVNS al 2004/0242640 A1 12/2004 Desai et al. 5.707,975 A 1, 1998 E. 2005/0070551 A1 3/2005 Remenar et al. ......... 514,254.07 5,733,566 A 3, 1998 toise a. 2005, 0169982 A1 8/2005 Almarsson et al. 5,736,54. A 4, 1998 Bunnell et al. 2005/02526492005/0181041 A1 11/20058/2005 ChiuGoldman et al. 5.753,693.5,753,688 A 5,5/1998 1998 TalleyShank et al. 2005/0256127 A1 11/2005 Ku et al. - - al 2006/0223794 A1* 10/2006 Bourghol Hickey et al. , 514/220 5,760,007 A 6, 1998 Shank et al. 2007, OO15841 A1 1/2007 Tawa et all 5,932,5985,760,068 A 6/19988/1999 Talley et al. 2007/0021510f A.* 1/20071? HickeyRival et al. ................. 514,618f 5,935,933 A 8, 1999 Shank et al. 2007/0059356 A1 3/2007 Almarsson et al. ........... 424/464 5,952,187 A 9/1999 Stenglein et al. 2007/0293674 Al 12/2007 Scoppettuolo et al. 5,972,986 A 10/1999 Seibert et al. 5,985,902 A 1 1/1999 Talley et al. FOREIGN PATENT DOCUMENTS 5,994,365 A 1 1/1999 Zaworotko et al. EP 0283992 B1 9, 1992 5.998,380 A 12/1999 Ehrenberg et al.
Load more

Recommended publications
  • Hans Renata – Strategic Redox Relay Enables a Scalable Synthesis Of
    Strategic Redox Relay Enables A Scalable Synthesis of Ouabagenin, A Bioactive Cardenolide A thesis presented by Hans Renata to The Scripps Research Institute Graduate Program in partial fulfillment of the requirements for the degree of Doctor of Philosophy in the subject of Chemistry for The Scripps Research Institute La Jolla, California February 2013 UMI Number: 3569793 All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. UMI 3569793 Published by ProQuest LLC (2013). Copyright in the Dissertation held by the Author. Microform Edition © ProQuest LLC. All rights reserved. This work is protected against unauthorized copying under Title 17, United States Code ProQuest LLC. 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, MI 48106 - 1346 © 2013 by Hans Renata All rights reserved ! ii! ACKNOWLEDGEMENTS To Phil, thank you for taking me under your wing, the past five years have been a wonderful learning experience. You truly are a fantastic teacher, both in and out of the fumehood and your unbridled enthusiasm, fearlessness and passion for chemistry are second to none. In the words of Kurt Cobain, I am “forever indebted to your priceless advice.” To the members of the Baran lab, in the words of Kurt Cobain, “Our little (?) group has always been and always will until the end.” See what I did there? Oh well, whatever, nevermind.
    [Show full text]
  • (12) Patent Application Publication (10) Pub. No.: US 2005/0044778A1 Orr (43) Pub
    US 20050044778A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2005/0044778A1 Orr (43) Pub. Date: Mar. 3, 2005 (54) FUEL COMPOSITIONS EMPLOYING Publication Classification CATALYST COMBUSTION STRUCTURE (51) Int. CI.' ........ C10L 1/28; C1OL 1/24; C1OL 1/18; (76) Inventor: William C. Orr, Denver, CO (US) C1OL 1/12; C1OL 1/26 Correspondence Address: (52) U.S. Cl. ................. 44/320; 44/435; 44/378; 44/388; HOGAN & HARTSON LLP 44/385; 44/444; 44/443 ONE TABOR CENTER, SUITE 1500 1200 SEVENTEENTH ST DENVER, CO 80202 (US) (57) ABSTRACT (21) Appl. No.: 10/722,127 Metallic vapor phase fuel compositions relating to a broad (22) Filed: Nov. 24, 2003 Spectrum of pollution reducing, improved combustion per Related U.S. Application Data formance, and enhanced Stability fuel compositions for use in jet, aviation, turbine, diesel, gasoline, and other combus (63) Continuation-in-part of application No. 08/986,891, tion applications include co-combustion agents preferably filed on Dec. 8, 1997, now Pat. No. 6,652,608. including trimethoxymethylsilane. Patent Application Publication Mar. 3, 2005 US 2005/0044778A1 FIGURE 1 CALCULATING BUNSEN BURNER LAMINAR FLAME VELOCITY (LFV) OR BURNING VELOCITY (BV) CONVENTIONAL FLAME LUMINOUS FLAME Method For Calculating Bunsen Burner Laminar Flame Velocity (LHV) or Burning Velocity Requires Inside Laminar Cone Angle (0) and The Gas Velocity (Vg). LFV = A, SIN 2 x VG US 2005/0044778A1 Mar. 3, 2005 FUEL COMPOSITIONS EMPLOYING CATALYST Chart of Elements (CAS version), and mixture, wherein said COMBUSTION STRUCTURE element or derivative compound, is combustible, and option 0001) The present invention is a CIP of my U.S.
    [Show full text]
  • US5169929.Pdf
    |||||||||||| USOO5169929A United States Patent (19) 11) Patent Number: 5,169,929 Tour et al. 45 Date of Patent: Dec. 8, 1992 (54) LITHIUM/HMPA-PROMOTED SYNTHESIS Noren, et al. Macromolecular Reviews (1971) 5. pp. OF POLY(PHENYLENES) 386-431. Yamamoto, et al. Bulletin Che. Soc. of Japan (1978) 51. 75 Inventors: James M. Tour; Eric B. Stephens, (7) pp. 2091-2097. both of Columbia, S.C. Shacklette, et al. J. Chem. Soc., Chem. Commun. (1982) 73 Assignee: University of South Carolina, pp. 361-362. Columbia, S.C. Ivory, et al. J. Chem. Phys. (1979) 71. (3) pp. 1506-1507. Shacklette, et al. J. Chem. Phys. (1980) 73. (8) pp. 21 Appl. No.: 543,673 4098-4102. 22 Filed: Jun. 25, 1990 Kovacic, et al. J. Org. Chem. (1963) 28. pp. 968-972, 1864-1867. I51) Int. Cl. .............................................. CO8G 61/00 Kovacic, et al. J. Org. Chem. (1964) 29. pp. 100-104, 52 U.S.C. .................................................... 528/397 2416-2420. 58 Field of Search ......................................... 528/397 Kovacic et al. J. Org. Chem. (1966) 31. pp. 2467-2470. (56) References Cited Primary Examiner-John Kight, II U.S. PATENT DOCUMENTS Assistant Examiner-Terressa M. Mosley Attorney, Agent, or Firm-Brumbaugh, Graves, 4,576,688 3/1966 David .................................. 528/397 Donohue & Raymond OTHER PUBLICATIONS 57 ABSTRACT Kovacic, et al. Chem. Rev. (1987) 87, pp. 357-379. Poly(phenylene) that is substantially free of insoluble Elsenbaumer, et al. Handbook of Conducting Polymers material is prepared by the polymerization of a lithi (1986), T. A. Skotheime ed. pp. 213-263. oarylhalide compound in the presence of a polar aprotic Perlstein, Angew.
    [Show full text]
  • Front Matter
    Towards the Total Synthesis of 1!,25-dihydroxylumisterol A. Simon Partridge Julia Laboratory, Department of Chemistry, Imperial College London, South Kensington Campus, London SW7 2AZ, United Kingdom September 2012 A thesis submitted as partial fulfilment of the requirements for the degree of Doctor of Philosophy, Imperial College London. Abstract This thesis is divided into three chapters. The first chapter provides a brief review on recent work in the application of cascade cyclisations to the total synthesis of natural products. This is followed by a review of the decarboxylative Claisen rearrangement (dCr), a novel variant of the Ireland-Claisen reaction in which tosylacetic esters of allylic alcohols are transformed into homoallylic sulfones using BSA and potassium acetate, and its applications. The second chapter discusses the results of our studies towards the total synthesis of 1!,25-dihydroxylumisterol via a proposed route containing two key steps; a cascade-inspired, Lewis-acid mediated cyclisation to form the steroid B-ring in I, and the dCr reaction of tosylacetic ester IV to give diene III. Successful syntheses, as well as problems encountered along this route will be discussed, as well as the measures taken to adapt the synthesis to circumvent these problems. OH PGO H O OH H H H H H PGO PGO H H HO Ts Ts 1!,25-dihydroxylumisterol I II OH O H + O H O H HO Ts PGO OPG H Ts Ts OPG VI V IV III The third and final chapter contains experimental procedures and characterisation data for the prepared compounds. Declaration I certify that all work in this thesis is solely my own, except where explicitly stated and appropriately referenced.
    [Show full text]
  • Hexamethylphosphoramide for Jet Fuels
    Report on Carcinogens, Fourteenth Edition For Table of Contents, see home page: http://ntp.niehs.nih.gov/go/roc Hexamethylphosphoramide for jet fuels. It also can be used as a flame­retarding additive in lith­ ium­ion batteries; however, it reduces the performance of the bat­ CAS No. 680-31-9 tery (Izquierdo­Gonzales et al. 2004). Reasonably anticipated to be a human carcinogen Production First listed in the Fourth Annual Report on Carcinogens (1985) In 2009, hexamethylphosphoramide was produced by one manufac­ Also known as HMPA or hexamethylphosphoric triamide turer worldwide, in the United States (SRI 2009), and was available from 21 suppliers, including 14 U.S. suppliers (ChemSources 2009). H3C CH3 No data on U.S. production, import, or export volumes were found. N H3C CH3 NP N Exposure H C CH 3 O 3 The routes of potential human exposure to hexamethylphosphoramide Carcinogenicity are inhalation, ingestion, and dermal contact (HSDB 2009). The ma­ jor source of exposure is probably occupational; however, the general Hexamethylphosphoramide is reasonably anticipated to be a human population potentially could be exposed through release of hexameth­ carcinogen based on sufficient evidence of carcinogenicity from stud­ ylphosphoramide to the environment. No environmental releases of ies in experimental animals. hexamethylphosphoramide were reported in the U.S. Environmental Protection Agency’s Toxics Release Inventory (TRI 2009). Hexameth­ Cancer Studies in Experimental Animals ylphosphoramide exists in the air solely in the vapor phase and will Exposure of rats to hexamethylphosphoramide by inhalation caused be degraded by photochemically produced hydroxyl radicals, with a nasal tumors, which are rare in this species.
    [Show full text]
  • Federal Register/Vol. 84, No. 230/Friday, November 29, 2019
    Federal Register / Vol. 84, No. 230 / Friday, November 29, 2019 / Proposed Rules 65739 are operated by a government LIBRARY OF CONGRESS 49966 (Sept. 24, 2019). The Office overseeing a population below 50,000. solicited public comments on a broad Of the impacts we estimate accruing U.S. Copyright Office range of subjects concerning the to grantees or eligible entities, all are administration of the new blanket voluntary and related mostly to an 37 CFR Part 210 compulsory license for digital uses of increase in the number of applications [Docket No. 2019–5] musical works that was created by the prepared and submitted annually for MMA, including regulations regarding competitive grant competitions. Music Modernization Act Implementing notices of license, notices of nonblanket Therefore, we do not believe that the Regulations for the Blanket License for activity, usage reports and adjustments, proposed priorities would significantly Digital Uses and Mechanical Licensing information to be included in the impact small entities beyond the Collective: Extension of Comment mechanical licensing collective’s potential for increasing the likelihood of Period database, database usability, their applying for, and receiving, interoperability, and usage restrictions, competitive grants from the Department. AGENCY: U.S. Copyright Office, Library and the handling of confidential of Congress. information. Paperwork Reduction Act ACTION: Notification of inquiry; To ensure that members of the public The proposed priorities do not extension of comment period. have sufficient time to respond, and to contain any information collection ensure that the Office has the benefit of SUMMARY: The U.S. Copyright Office is requirements. a complete record, the Office is extending the deadline for the extending the deadline for the Intergovernmental Review: This submission of written reply comments program is subject to Executive Order submission of written reply comments in response to its September 24, 2019 to no later than 5:00 p.m.
    [Show full text]
  • Synthesis and Properties of Diorganomagnesium Compounds
    University of Tennessee, Knoxville TRACE: Tennessee Research and Creative Exchange Doctoral Dissertations Graduate School 12-1967 Synthesis and Properties of Diorganomagnesium Compounds Conrad William Kamienski University of Tennessee - Knoxville Follow this and additional works at: https://trace.tennessee.edu/utk_graddiss Part of the Chemistry Commons Recommended Citation Kamienski, Conrad William, "Synthesis and Properties of Diorganomagnesium Compounds. " PhD diss., University of Tennessee, 1967. https://trace.tennessee.edu/utk_graddiss/3077 This Dissertation is brought to you for free and open access by the Graduate School at TRACE: Tennessee Research and Creative Exchange. It has been accepted for inclusion in Doctoral Dissertations by an authorized administrator of TRACE: Tennessee Research and Creative Exchange. For more information, please contact [email protected]. To the Graduate Council: I am submitting herewith a dissertation written by Conrad William Kamienski entitled "Synthesis and Properties of Diorganomagnesium Compounds." I have examined the final electronic copy of this dissertation for form and content and recommend that it be accepted in partial fulfillment of the equirr ements for the degree of Doctor of Philosophy, with a major in Chemistry. Jerome F. Eastham, Major Professor We have read this dissertation and recommend its acceptance: Bruce M. Anderson, George K. Schwitzer, David A. Shirley Accepted for the Council: Carolyn R. Hodges Vice Provost and Dean of the Graduate School (Original signatures are on file with official studentecor r ds.) Novemb er 27, 1967 To the Graduate Council: I am submitting herewith a dissertation written by Conrad Wiliiam Kamienski entitled "Synthesis and Properties of Diorgano­ magnesium Compounds." I recommend that it be accepted in partial fulfillment of the requirements for the degree of Doctor of Philosophy, with a maj or in Chemistry .
    [Show full text]
  • Chemicals Subject to TSCA Section 12(B) Export Notification Requirements (January 16, 2020)
    Chemicals Subject to TSCA Section 12(b) Export Notification Requirements (January 16, 2020) All of the chemical substances appearing on this list are subject to the Toxic Substances Control Act (TSCA) section 12(b) export notification requirements delineated at 40 CFR part 707, subpart D. The chemicals in the following tables are listed under three (3) sections: Substances to be reported by Notification Name; Substances to be reported by Mixture and Notification Name; and Category Tables. TSCA Regulatory Actions Triggering Section 12(b) Export Notification TSCA section 12(b) requires any person who exports or intends to export a chemical substance or mixture to notify the Environmental Protection Agency (EPA) of such exportation if any of the following actions have been taken under TSCA with respect to that chemical substance or mixture: (1) data are required under section 4 or 5(b), (2) an order has been issued under section 5, (3) a rule has been proposed or promulgated under section 5 or 6, or (4) an action is pending, or relief has been granted under section 5 or 7. Other Section 12(b) Export Notification Considerations The following additional provisions are included in the Agency's regulations implementing section 12(b) of TSCA (i.e. 40 CFR part 707, subpart D): (a) No notice of export will be required for articles, except PCB articles, unless the Agency so requires in the context of individual section 5, 6, or 7 actions. (b) Any person who exports or intends to export polychlorinated biphenyls (PCBs) or PCB articles, for any purpose other than disposal, shall notify EPA of such intent or exportation under section 12(b).
    [Show full text]
  • The Action of Tetramethylurea and Hexamethylphosphoramide
    The action of tetramethylurea and hexamethylphosphoramide blended with other solvents on the dissolution of coal by Timothy Lee Ward A thesis submitted in partial fulfillment of the requirements for the degree of Master of Science in Chemical Engineering Montana State University © Copyright by Timothy Lee Ward (1984) Abstract: Tetramethylurea (TMU) and hexamethylphosphoramide (HMPA) were blended with a number of other solvents to determine the solvent action and effectiveness of the blends on extraction of coal as compared with that of unblended TMU/HMPA (TMU and HMPA In a 50/50 mixture). Dissolution to more than 41% was observed using 33% tetralin blended with 67% TMU/HMPA on Kittaning coal at 320°F, compared to a maximum of 40.7% dissolution observed with unblended TMU/HMPA. It was found that aromatic/hydroaromatic solvents such as tetralin, napthalene, and l-me-napthaIene, which are relatively inert toward coal at temperatures below 350°F, could be blended up to 80% by volume with TMU/HMPA without significantly reducing the ultimate dissolving power below that of unblended TMU/HMPA. Use of 80% decalin and 80% limonene blended with TMU/HMPA resulted in substantially lower extraction than unblended TMU/HMPA. Isopropyl alcohol, when blended with TMU/HMPA in amounts greater than 10%, was found to result in a substantial decrease in dissolving ability. The apparent dissolution rate for a blend of 80% tetralin and 20% TMU/HMPA is lower than for unblended TMU/HMPA, however the ultimate dissolution attained is approximately equal. At 320°F much of the ultimately attainable dissolution with TMU/HMPA and 80% tetralin blended with TMU/HMPA occurs within 5 minutes, with slow or even retrogressive dissolution after that.
    [Show full text]
  • Oxides Affording Phosphines(III) and Their Metal Catalysts
    pubs.acs.org/Organometallics Article A Mild One-Pot Reduction of Phosphine(V) Oxides Affording Phosphines(III) and Their Metal Catalysts Łukasz Kapusniak,́ Philipp N. Plessow, Damian Trzybinski,́ Krzysztof Wozniak,́ Peter Hofmann, and Phillip Iain Jolly* Cite This: Organometallics 2021, 40, 693−701 Read Online ACCESS Metrics & More Article Recommendations *sı Supporting Information ABSTRACT: The metal-free reduction of a range of phosphine(V) oxides employing oxalyl chloride as an activating agent and hexachlorodisilane as reducing reagent has been achieved under mild reaction conditions. The method was successfully applied to the reduction of industrial waste byproduct triphenylphosphine(V) oxide, closing the phosphorus cycle to cleanly regenerate triphenylphosphine(III). Mechanistic studies and quantum chemical calculations support the attack of the dissociated chloride anion of intermediated phosphonium salt at the silicon of the disilane as the rate-limiting step for deprotection. The exquisite purity of the resultant phosphine(III) ligands after the simple removal of volatiles under reduced pressure circumvents laborious purification prior to metalation and has permitted the facile formation of important transition metal catalysts. ■ INTRODUCTION Scheme 1. Phosphine Synthesis: Background and This a Applications of Phosphine(III) Ligands and Synthesis. Work Phosphines and their derivatives are of significant importance to both academic and industrial chemistry. In particular, within organic chemistry phosphine(III) compounds have a distin- guished history, mediating classical transformations such as the Appel,1 Mitsunobu,2 and Wittig3,4 reactions. Additionally, the ready modulation of electronic and steric properties of phosphine(III) has made them excellent ligands for the formation of well-defined transition metal complexes,5 although recalcitrant phosphine(V) oxides arise, when 6 Downloaded via KIT BIBLIOTHEK on April 16, 2021 at 16:05:05 (UTC).
    [Show full text]
  • United States Patent Office Patented Aug
    3,524,846 United States Patent Office Patented Aug. 18, 1970 2. phosphonate esters under essentially neutral conditions 3,524,846 which is especially useful for sensitive molecules such as PROCESS FOR THE DIDEALKYLATION OF PHOSPHONATE ESTERS lipids, steroids, sugars, and nucleosides. Other objects and John G. Moffatt, Los Altos, and Gordon H. Jones, Palo advantages of the present invention will become apparent Alto, Calif.; said Moffatt assignor to Syntex Corpora as the invention is described hereinafter in detail and tion, Panama, Panama, a corporation of Panama from the appended claims. No Drawing. Filed June 2, 1967, Ser. No. 643,078 The term "lower alkyl,' as used herein, refers to a Int, C. C07f 9/40 straight or branched chain hydrocarbon group containing U.S. C. 260-211.5 22 Claims up to six carbon atoms inclusive and thus includes methyl, O ethyl, isopropyl, n-butyl, and the like. The term “alkoxy,' as used herein, means the group --OR wherein R is ABSTRACT OF THE DISCLOSURE lower alkyl as defined hereinabove. The term "dialkoxy Didealkylation of phosphonate esters is effected by phosphinyl' means the heating them with a soluble bromide or iodide salt in an aprotic dipolar solvent at a temperature in excess of 5 100° C. -P(OR) monumanomam group wherein R is lower alkyl as defined hereinabove. This invention relates to a novel process for the di Included in the term "monovalent cation' are lithium, dealkylation of phosphonate ester compounds. More par sodium, potassium, ammonium, tetramethylammonium, ticularly, this invention relates to a process for the di 20 tetraethylammonium, tetra-n-propylammonium, tetra-n- dealkylation of a dialkyl phosphonate ester by heating butylammonium, and the like.
    [Show full text]
  • 1 Draft Chemicals (Management and Safety)
    Draft Chemicals (Management and Safety) Rules, 20xx In exercise of the powers conferred by Sections 3, 6 and 25 of the Environment (Protection) Act, 1986 (29 of 1986), and in supersession of the Manufacture, Storage and Import of Hazardous Chemical Rules, 1989 and the Chemical Accidents (Emergency Planning. Preparedness and Response) Rules, 1996, except things done or omitted to be done before such supersession, the Central Government hereby makes the following Rules relating to the management and safety of chemicals, namely: 1. Short Title and Commencement (1) These Rules may be called the Chemicals (Management and Safety) Rules, 20xx. (2) These Rules shall come into force on the date of their publication in the Official Gazette. Chapter I Definitions, Objectives and Scope 2. Definitions (1) In these Rules, unless the context otherwise requires (a) “Act” means the Environment (Protection) Act, 1986 (29 of 1986) as amended from time to time; (b) “Article” means any object whose function is determined by its shape, surface or design to a greater degree than its chemical composition; (c) “Authorised Representative” means a natural or juristic person in India who is authorised by a foreign Manufacturer under Rule 6(2); (d) “Chemical Accident” means an accident involving a sudden or unintended occurrence while handling any Hazardous Chemical, resulting in exposure (continuous, intermittent or repeated) to the Hazardous Chemical causing death or injury to any person or damage to any property, but does not include an accident by reason only
    [Show full text]