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Diaryl Alkylphosphonates and Methods for Preparing

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Diaryl Alkylphosphonates and Methods for Preparing (19) TZZ_Z_T (11) EP 1 940 855 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.: of the grant of the patent: C07F 9/12 (2006.01) C07F 9/145 (2006.01) 01.07.2015 Bulletin 2015/27 C07F 9/40 (2006.01) (21) Application number: 06849055.6 (86) International application number: PCT/US2006/060035 (22) Date of filing: 17.10.2006 (87) International publication number: WO 2007/079272 (12.07.2007 Gazette 2007/28) (54) DIARYL ALKYLPHOSPHONATES AND METHODS FOR PREPARING SAME DIARYL-ALKYLPHOSPHONATE UND HERSTELLUNGSVERFAHREN DAFÜR ALKYLPHOSPHONATES DE DIARYLE ET LEURS MÉTHODES DE SYNTHÈSE (84) Designated Contracting States: • YAO ET AL: "A concise method for the synthesis AT BE BG CH CY CZ DE DK EE ES FI FR GB GR of diaryl aryl- or alkylphosphonates" HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI TETRAHEDRON LETT., vol. 47, 22 November SK TR 2005 (2005-11-22), pages 277-281, XP002495388 Designated Extension States: • DATABASECA [Online] CHEMICAL ABSTRACTS AL BA HR MK RS SERVICE, COLUMBUS, OHIO, US HUDSON, HARRY R. ET AL: ’Quasiphosphonium (30) Priority: 18.10.2005 US 727619 P intermediates. I. Preparation, structure, and 18.10.2005 US 727680 P nuclear magnetic resonance spectroscopy of triphenyl and trineopentyl phosphite- alkyl halide (43) Date of publication of application: adducts’ Retrieved from STN Database 09.07.2008 Bulletin 2008/28 accession no. 1974:449742 & JOURNAL OF THE CHEMICAL SOCIETY, PERKIN TRANSACTIONS (60) Divisional application: 1: ORGANIC AND BIO-ORGANIC CHEMISTRY 11169075.6 / 2 395 011 (1972-1999) , (9), 982-5 CODEN: JCPRB4; ISSN: 0300-922X, 1974, (73) Proprietor: FRX Polymers, Inc. • LANDAUER S R ET AL: "458. The organic Chelmsford, MA 01824 (US) chemistry of phosphorus. Part I. Some new methods for the preparation of alkyl halides", (72) Inventors: JOURNAL OF THE CHEMICAL SOCIETY, • FREITAG, Dieter CHEMICAL SOCIETY, LETCHWORTH; GB LNKD- Chelmsford, Massachusetts 01824 (US) DOI:10.1039/JR9530002224, 1 January 1953 • HADJIKYRIACOU, Savvas (1953-01-01), pages 2224-2234, XP008096397, Chelmsford, MA 01824 (US) ISSN: 0368-1769 • PHILLIPS, DON I. ET AL: "Rates of ionization of (74) Representative: Müllejans, Inge et al phosphoranes", 1976, JOURNAL OF THE Murgitroyd & Company AMERICAN CHEMICAL SOCIETY , 98(1), 184-9 Scotland House CODEN: JACSAT; ISSN: 0002-7863 165-169 Scotland Street • HONIG, MILTON L. ET AL: "A convenient Glasgow G5 8PL (GB) synthesis of diaryl methylphosphonates and transesterification products therefrom", (56) References cited: JOURNAL OF ORGANIC CHEMISTRY , 42(2), EP-A- 0 034 239 DE-A1- 2 747 554 379-81 CODEN: JOCEAH; ISSN: 0022-3263, 1977, DE-C1- 4 302 958 US-A- 4 642 366 US-A- 4 736 052 Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). EP 1 940 855 B1 Printed by Jouve, 75001 PARIS (FR) (Cont. next page) EP 1 940 855 B1 Remarks: Thefile contains technical information submitted after the application was filed and not included in this specification 2 EP 1 940 855 B1 Description [0001] Various methods for the synthesis of diaromatic alkylphosphonates are known. Methods for making diaromatic alkylphosphonates aredescribed inU.S. Patent Nos. 4,152,373 and 4,377,537, for example.In U.S. PatentNo. 4,152,373, 5 diaromatic alkylphosphonates are prepared by the reaction of a triaromaticphosphite specifically triphenylphosphite and methanol in the presence of a catalytic amount of methyl iodide. The reaction temperatures are higher than the boiling point of methanol (~65 °C), and consequently require a relatively slow addition of methanol in order to keep it from boiling out of the reactor. In this reaction, phenol is a by-product that is distilled from the product in a separate step. [0002] U.S. Patent No. 4,377,537 describes a method of synthesizing diaromatic methylphosphonates by the reaction 10 of a triarylphosphite (specifically triphenylphosphite) and trialkylphosphite (specifically trimethylphosphite) in the pres- ence of a catalytic amount of methyl iodide. The reaction typically involves heating the components to a final temperature of about 230 °C for up to 1 hour. Exothermic reactions for this process occur in two temperature regions, the first around 100 °C, and the second near 210 °C. Due to the exothermic (even explosive) nature of these reactions when used in a batch process, the reaction scheme described in U.S. Patent No. 4,377,537 is limited to small scale production of 15 diaromatic alkylphosphonates. [0003] DE 274755 describes a method for preparing alkylphosphonates by combining triarylphosphite with a perfluor- inated suphonic acid at a defined temperature and reacting the combination with methanol. [0004] DE 4302958 describes a method for recovering methyl iodine by absorbing the methyl iodine onto triphenyl- phosphite in the presence of nitrogen gas. The absorbed methyl iodine is then used to catalyse a subsequent reaction. 20 Honig, Milton L.et al"A ConvenientSynthesis of Diaryl Methylphosphonatesand Transesterification Products Therefrom", Journal of Organic Chemistry, 42(2), 379-381, 1977 describes a method in which methanol and methyl iodide are added to heated triarylphosphite. [0005] Although some diaromatic alkylphosphonates (e.g. diphenyl methylphosphonate) (Registry number 7526-26-3) are commercially available, they are relatively expensive. 25 SUMMARY [0006] Embodiments of the invention described herein include a method for preparing diaryl alkylphosphonate as defined in claim 1. The method can provide optionally substituted diarylalkylphosphonate containing substantially no 30 triarylphosphite. In some embodiments, the optionally substituted trialkylphosphite, or optionally substituted alkanol, may be from at least 20 % to 40 % molar excess in relation to the optionally substituted triarylphosphite, and in others, the optionally substituted trialkylphosphite or optionally substituted alkanol may be in a 13 % molar excess in relation to the optionally substituted triarylphosphite. [0007] In some embodiments, the optionally substituted triarylphosphite may be of general formula (III): 35 40 wherein R1 may be of general formula (II): 45 50 55 wherein R3, R4, R5, R6 and R 7, independently may be selected from hydrogen, trifluoromethyl, nitro, cyano, C 1-C20 alkyl, an aromatic, a halide, C 1-C20 alkyl ether, benzyl halide, benzylether, aromatic ether and combinations thereof. In certain embodiments, the optionally substituted triarylphosphite may be triphenylphosphite. 3 EP 1 940 855 B1 [0008] In some embodiments, the optionally substituted trialkylphosphite may be of general formula (IV): 5 wherein R2 may be a C1-C20 alkyl. In certain embodiments, the optionally substituted trialkylphosphite may be trimeth- 10 ylphosphite. [0009] In embodiments, the optionally substituted alkanol may be of general formula (V): 15 where R8 and R 9 may independently be hydrogen or C 1-C20 alkyl, and in certain embodiments, the optionally substituted 20 alkanol may be methanol. [0010] In embodiments, the mixture comprising optionally substituted trialkylphosphite or optionally substituted alkanol and the catalyst may be added under a surface of the heated optionally substituted triarylphosphite, and in some em- bodiments, the optionally substituted trialkylphosphite or optionally substituted alkanol and the catalyst may be added on top of a surface of the heated optionally substituted triarylphosphite. 25 [0011] The catalyst of embodiments may be an alkylating catalyst, and in certain embodiments may be CH 3I. [0012] In some embodiments, the defined reaction temperature may be at least greater than the temperature of the highest exotherm of those exotherms created when the reactants are mixed together at room temperature and heated up, and in other embodiments, the defined reaction temperature may be from 210 °C to 260 °C. In alternative embodi- ments, the defined reaction temperature may be maintained during the addition of the optionally substituted trialkylphos- 30 phite or optionally substituted alkanol and a catalyst. [0013] In embodiments, substantially no toxic by-products may be formed when the optionally substituted diaryl alkyl- phosphonate prepared using the methods described above are used in subsequent reactions. [0014] Other embodiments of the invention may include methods for preparing optionally substituted diaryl alkylphos- phonate including heating optionally substituted triarylphosphite with a catalyst as defined in claim 1 to a reaction tem- 35 perature from 210 to 260 °C, adding a mixture including optionally substituted trialkylphosphite in molar excess of from at least 10 % to 50 % in relation to the optionally substituted triarylphosphite and a catalyst to the heated optionally substituted triarylphosphite, or adding a mixture comprising optionally substituted alkanol in a molar excess of from at least 10 % to 50 % in relation to the optionally substituted triarylphosphite and a catalyst to the heated optionally substitut ed triarylphosphite, maintaining the reaction temperature during the addition of the optionally substituted trialkylphosphite 40 or optionally substituted alkanol and a catalyst, reacting with the optionally substituted triarylphosphite and optionally substituted trialkylphosphite
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