(12) United States Patent (10) Patent No.: US 6,429,329 B1 Aarons0n Et Al
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USOO6429329B1 (12) United States Patent (10) Patent No.: US 6,429,329 B1 Aarons0n et al. (45) Date of Patent: Aug. 6, 2002 (54) SYNTHESIS OFA T. Hirao et al., “Palladium-Catalyzed New Carbon-Phos HYDROCARBYLVINYLPHOSPHONCACID phorus Bond Formation', Bull. Chem. Soc. Jpn., 55, HYDROCARBYLESTER 909–913 Mar. (1982). W.E. Krueger et al., “Additions of Trialkyl Phosphites to (75) Inventors: Alan M. Aaronson, Fresh Meadows; Nitroalkenes”, J. Org. Chem., vol. 43, No. 14, pp. John Tomko, Dobbs Ferry; Jeffrey E. 2877–2879 (Month not available) (1978). F. Texier-Boullet et al., “An Unexpected Reactivity of Telschow, Tarrrytown; Johannes Simple Heterogeneous Mixture of Y-Alumina and Potas Hermanus Boelee, Irvington; Fred sium Fluoride: 1-Hydroxyalkane Phosphonic Esters Syn Jaffe, Ossining, all of NY (US) thesis From Non-Activated Ketones in Dry Media”, Tet rahedron Letters, vol. 27, No. 30, pp. 3515–3516 (Month not (73) Assignee: Akzo Nobel NV, Arnhem (NL) available) (1986). R. Engel, ed., Handbook of Organophosphorus Chemistry (*) Notice: Subject to any disclaimer, the term of this (Marcel Dekker, New York, (Month not available) (1992), patent is extended or adjusted under 35 pp. 301 and 355. U.S.C. 154(b) by 1359 days. V.S. Abramov, “The Reaction of Dialkylphosphorus Acids With Aldehydes and Ketones: A New Method of Synthesiz (21) Appl. No.: 08/711,135 ing Esters of Alpha Hydroxyalkylphosphinic Acids”, Zh. Obshch. Khim., 22, pp. 709–713 (Month not available) (22) Filed: Sep. 9, 1996 (1952). F. Texier-Boullet et al., “A Convenient Synthesis of Dialkyl Related U.S. Application Data 1-Hydroxyalkanephosphonates. Using Potassium or Cae sium Fluoride Without Solvent”, Synthesis (Communica (63) Continuation of application No. 08/386,392, filed on Feb. tions), Feb. 1982, pp. 165-166. 10, 1995, now abandoned. Chemical Abstracts, vol. 45, Abstract 2855h (Month not available) (1951). (51) Int. Cl.................................................... C07F 9/40 Chemical Abstracts, vol. 46, Abstract 6140h (Month not (52) U.S. Cl. ....................................................... 558/142 available) (1952). (58) Field of Search .......................................... 558/142 Chemical Abstracts, vol. 60, Abstract 10718f (Month not available) (1964). (56) References Cited Chemical Abstracts, vol. 61, Abstract 9524d (Month not available) (1964). U.S. PATENT DOCUMENTS Chemical Abstracts, vol. 73, Abstract 77387w (Month not 2.254,124 A 8/1941 Stevens et al. ...... ... 260/500 available) (1970). 2,365,466 A 12/1944 Hamilton ... ... 260/543 Chemical Abstracts, vol. 73, Abstract 88024b (Month not 2.579810 A * 12/1951 Fields ....... 260/.461.1 available) (1970). 3,493,639 A 2/1970 Tavs ........................... 260/969 Chemical Abstracts, vol. 74, Abstract 64277f (Month not 4,388.252 A * 6/1983 Dursch et al. .............. 558/142 4,427,602 A 1/1984 Kleiner ................... 260/543 P available) (1971). 4,486.357 A 12/1984 Krause et al. ........ 260/502.4 R * cited by examiner 4,507,249 A 3/1985 Pieper et al. ......... 260/502.4 R 4,529,559 A 7/1985 Pieper ................. 260/502.4 R Primary Examiner-Laura L. Stockton FOREIGN PATENT DOCUMENTS (74) Attorney, Agent, or Firm-Richard P. Fennelly (57) ABSTRACT GB 974.988 11/1964 A process for the synthesis of a hydrocarbylvinyl-1- OTHER PUBLICATIONS phosphonic acid hydrocarbyl ester, Such as a Morrison and Boyd, Organic Chemistry, 2" Ed., Allyn and 1-phenylvinylphosphonic acid dialkyl ester, which utilizes: Bacon, Inc., Boston (1966), p. 669.* (a) the base catalyzed addition (preferably using a nonnu M. Yamashita et al. “New Synthesis and Hydroboration of cleophilic strong organic base) of a hydrocarbyl phosphite, Vinylphosphonates’, Bull. Chem. Soc. Jpn., 53, 1625–1628 Such as a dialkyl phosphite containing no more than about Jun. (1980). eight carbon atoms in either of its alkyl groups, to an G. Maas et al., “Substituentenabhängigkeit des Norcaradien/ aldehyde or methyl ketone, Such as a phenyl ketone, as Cycloheptatrien-Gleichgewichtes-unterSucht an 7-phos exemplified by acetophenone, to form a hydrocarbyl phoryl-und 7-carbonylsubstituierten Systemen”, Chem. 1-hydroxy-1-hydrocarbylphosphonate, Such as a dialkyl Ber, 109, 2039–2063 (Month not available) (1976). P. Tavs et al., “Herstellung und KMR-Spektren Einiger 1-hydroxy-1-phenylalkylphosphonate compound; (b) the C.f3-Ungesättigter Phosphonsäureester, Tetrahedron, Vol. acid-catalyzed esterification (preferably acetylation) of the 26, pp. 5229 to 5534 (Month not available) (1970). compound from (a) with an acid anhydride to form an C. Li et al., “Studies on Organophosphorus Compounds: 68. acylated intermediate; and (c) the removal of carboxylic acid A New and Facile Synthetic Approach to Alkylidenebispho (preferably at a temperature of from about 50° C. to about nates”, Tetrahedron Letters, vol. 34, No. 9, pp. 1515-1516 215 C. under reduced or atmospheric pressure) from the (month not available) (1993). intermediate from (b) to form the desired hydrocarbylvii J.B. Conant et al., “Addition Reactions of the Phosphorus nylphosphonic acid hydrocarbyl ester, Such as a Halides: V. The Formation of an Unsaturated Phosphonic 1-phenylvinylphosphonic acid dialkyl ester. Acid”, J. Amer. Chem. Soc., 44, 2530–2536 (Month not available) (1922). 25 Claims, No Drawings US 6,429,329 B1 1 2 SYNTHESIS OFA acetophenone, to form a dihydrocarbyl 1-hydroxy hydrocar HYDROCARBYLVINYLPHOSPHONCACD bylphosphonate compound, Such as a dialkyl 1-hydroxy-1- HYDROCARBYL ESTER phenylethyl-phosphonate; (b) the acid-catalyzed esterification, e.g., acetylation, of the compound from (a) This is a continuation of application Ser. No. 08/386,392 with an acid anhydride, Such as acetic anhydride, to form an filed Feb. 10, 1995, now abandoned. esterified, e.g., acylated intermediate; and (c) the elimination of acid, e.g., by deacetylation, from the intermediate from BACKGROUND OF THE INVENTION (b) to form the desired hydrocarbylvinylphosphonic acid The known ester compounds of the type encompassed by hydrocarbyl ester, Such as a 1-phenylvinylphosphonic acid the terminology used in the title, Such as those of dialkyl ester. 1-phenylvinylphosphonic acid, are useful as intermediates Another embodiment of the present invention involves for further chemical Synthesis of, for example, plasticizers, Step (c) of the forgoing process in which carboxylic acid is flame retardants, and the like. Such compounds are also removed from the intermediate to form the desired dialkyl useful as comonomers, in minor amount, with a predominant ester product. amount of other vinylic monomers to impart flame retar 15 Still another embodiment of this invention is the base dancy and to alter the Surface characteristics of the resulting catalyzed reaction (a) in which an aldehyde or ketone and polymer product. Various disclosures exist in regard to the dihydrocarbyl phosphite are reacted using a nonnucleophilic process of formation of Such compounds. Strong organic base as catalyst. U.S. Pat. No. 2,365,466 to L. A. Hamilton describes their formation by reaction of an alcohol or phenol with a DESCRIPTION OF PREFERRED phosphonic acid dichloride. EMBODIMENTS British Patent No. 974,988 describes the formation of The initial Step in the process of the present invention alpha, beta-unsaturated phosphonic acid esters, including comprises the reaction of a dialkyl phosphite of the formula certain 1-phenylvinyl phosphonic acid dialkyl ester 25 compounds, by the reaction of an O-hydroxyphosphonic acid ester with thionyl chloride. U.S. Abramov in Zh. Obshch. Khim, 22, pp. 709–712 P-H, (1952) discloses the reaction of aldehydes and ketones upon the Salts of dialkyl phosphorous acids to form diesters of RO alpha hydroxyalkylphosphonic acids. More recently, M. Yamashita et al. in Bull. Chem. Soc. where R and R are each as defined above with both, Japan, 53, 1625–1628 (1980) described the Arbuzov reac preferably, being an unsubstituted or Substituted alkyl group tion of trimethyl and triethyl phosphites with acyl chlorides of no more than eight carbon atoms, e.g., most preferably to give 1-Oxaalkylphosphonates which could be converted to 35 from C to C alkyl, with an aldehyde or ketone of the Vinylphosphonates by the Wittig reaction using methylen formula etriphenylphosphorane. T. Hirao et al. in Bull. Chem. Soc. Japan, 55,909–913 H (1982) describe the palladium catalyzed reaction of aryl bromides with dialkyl phosphites in the presence of triethy 40 lamine to form dialkyl arylphosphonates and the Similar R5 treatment of vinyl bromides to give dialkyl vinylphospho nateS. R. R., and Rs being defined as Set forth above, acetophe SUMMARY OF THE INVENTION 45 none being a preferred ketone, to form a dihydrocarbyl In its broadest embodiment the present invention relates 1-hydroxy-hydrocarbylphosphonate of the formula to the formation of hydrocarbylvinyl phosphonic acid hydro carbyl esters which can be represented by the formula 50 R1OP R4 \ M P-CEC / Q. / | \ Rs R4 RO R3 Rs 55 where each of the “R” groups depicted in the preceding where any of R through Rs can independently be hydrogen, formula is as defined before above. This step is practiced alkyl or aryl. Groups R and R can be joined together in a with base catalysis using, as a preferred class of catalyst, a Single cyclic Structure bonded at each end thereof to the nonnucleophilic strong organic base (Such as one where the oxygens attached to the phosphorus atom (such as when pKa of the conjugate acid is greater than about 10), Such as neopentylene glycol is used as a reactant as described and 60 1,1,3,3-tetramethylguanidine. If desired, an alkali metal claimed in U.S. Ser. No. 386,393, filed on even date alkoxide catalyst (Such as Sodium ethoxide in ethanol here with, and entitled “Neopentylene Phosphonate Solvent) in a Suitable hydrocarbon Solvent, Such as hexane Compounds”). may also be used but it is leSS preferred. The reaction can be The present invention can be defined as a proceSS for the carried out at slightly below to slightly above ambient Synthesis of a hydrocarbylvinylphosphonic acid hydrocarbyl 65 temperature (e.g., from 0° C.