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(12) United States Patent (10) Patent No.: US 7,084,306 B2 Saito Et Al

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(12) United States Patent (10) Patent No.: US 7,084,306 B2 Saito Et Al USOO70843 06B2 (12) United States Patent (10) Patent No.: US 7,084,306 B2 Saito et al. (45) Date of Patent: Aug. 1, 2006 (54) PROCESS FOR PREPARING B-DIKETONE OTHER PUBLICATIONS COMPOUND AND PROCESS FOR Swaelens, G. et al: “NMR experiments on acetals. XXVI. PREPARING METAL COMPLEX THEREOF Influence of B-Substitution on geminal coupling values in 1,3-dioxanes'O Bulletin Des Societes Chimiques Belges (75) Inventors: Makoto Saito, Kanagawa (JP); Takashi (1970), 79(7-8), 441-50, p. 448, XP000983.130. Ueda, Kanagawa (JP); Takashi Tani, Chemical Abstracts, vol. 116, No. 19, May 11, 1992 Colum Kanagawa (JP) bus, Ohio, US; abstract No. 193677WU, Yuehuan et al, “Synthesis of 2.2.6,6-tetramethylheptane-3,5-dione (73) Assignee: Showa Denko K.K., Tokyo (JP) (dipivaloylmethane)” XP002248216 abstract & Huaxue Shiji (1991), 13(6), 379, 372. (*) Notice: Subject to any disclaimer, the term of this Chemical Abstracts, vol. 126, No. 7, Feb. 17, 1997 Colum patent is extended or adjusted under 35 bus, Ohio, US; abstract No. 98457 Rees, William S., Jr. et U.S.C. 154(b) by 33 days. al: “Tris (2.2.6,6-tetramethyl-3, 5-heptanedionato) yttrium’ XP00248217 abstract & Inorganic Syntheses (1997), 31, (21) Appl. No.: 10/500,963 3O2-306. Database WPI Section Ch, Week 200255 Derwent Publica (22) PCT Filed: Dec. 18, 2002 tions Ltd., London, GB: Class E12, AN 1994-124127, XP002248218 & JP 03307685 B (Nippon Sanso KK), Jul. (86). PCT No.: PCT/UP02/13238 24, 2002 abstract. Patent Abstracts of Japan vol. 18, No. 30 (C-1153), Jan. 17, S 371 (c)(1), 1994, abstract of JP 05255855A of Oct. 5, 1993. (2), (4) Date: Jul. 8, 2004 Joe T. Adams and Charles R. Hauser; The Acylation of Methyl Ketones with Aliphatic Esters by Means of Sodium (87) PCT Pub. No.: WO03/059858 Amide. Synthesis of B-Diketones of the Type ROCHCOR'; J. Am. Chemical Society, Vol. 66, pp. 1220-1222(1944). PCT Pub. Date: Jul. 24, 2003 Karl R. Kopecky, Derek Nonhebel, Gene Morris, and George S. Hammond; Preparation of Dipivaloylmethane, J. (65) Prior Publication Data Org. Chemical, vol. 27, pp. 1036-1037 (1962). Kent J. Eisentraut and Robert E. Sievers: Volatile Rare-Earth US 2005/01 19466 A1 Jun. 2, 2005 Chelates of 2.2.6,6-Tetramethylheptane-3,5-Dione, Inor Related U.S. Application Data ganic Synthesis, 11, pp. 94-98 (1968). William S. Rees, Jr. and Michael W. Carris; Bis(2.2.6,6- (60) Provisional application No. 60/384,393, filed on Jun. Tetramethyl-3,5-Heptanedionato) Copper, Inorganic 3, 2002. Synthsis, 31, pp. 286-288 (1997). (30) Foreign Application Priority Data * cited by examiner Jan. 9, 2002 (JP) ............................. 2002-002727 Primary Examiner Sikarl A. Witherspoon May 27, 2002 (JP) ............................. 20O2-151760 (74) Attorney, Agent, or Firm—Sughrue Mion, PLLC (51) Int. Cl. (57) ABSTRACT C07C 45/72 (2006.01) CD7C II/00 (2006.01) Disclosed is a process for preparing 2.2.6.6-tetramethyl-3, C07F 9/00 (2006.01) 5-heptanedione, comprising reacting a pivalic acid alkyl C07F 7/00 (2006.01) ester with pinacolone in the presence of an alkali metal (52) U.S. Cl. ...................... 568/385; 568/388: 568/391; alkoxide catalyst using a pivalic acid alkyl ester as a solvent 556/41; 556/42; 556/51; 556/57 but using no other solvent or reacting them in an amide type or urea type solvent in the presence of an alkali metal (58) Field of Classification Search ................ 568/385, alkoxide catalyst. Also disclosed is a process for preparing 568/388,391; 556/41, 42, 51, 57 a 2.2.6,6-tetramethyl-3,5-heptanesione metal complex using See application file for complete search history. the 2.2.6,6-tetramethyl-3,5-heptanedione obtained by the above process. The process for preparing 2.2.6.6-tetram (56) References Cited ethyl-3,5-heptanedione is an industrially advantageous pro U.S. PATENT DOCUMENTS cess in which an alkali metal alkoxide that is easy to handle 5,344.992 A * 9, 1994 Drewes et al. .............. 568.388 can be used as a catalyst for preparing 2.2.6.6-tetramethyl 6,143,935 A * 1 1/2000 Boaz et al. ................. 568,314 3.5-heptanedione from a pivalic acid alkyl ester and pina colone. FOREIGN PATENT DOCUMENTS EP 454.624 A 10, 1991 27 Claims, No Drawings US 7,084,306 B2 1. 2 PROCESS FOR PREPARING B-DIKETONE prepared by simple and easy operations at a low cost has COMPOUND AND PROCESS FOR been unknown so far, and further improvement has been PREPARING METAL COMPLEX THEREOF desired. CROSS REFERENCES OF RELATED OBJECT OF THE INVENTION APPLICATION It is an object of the present invention to provide an This application is the national stage application of PCT/ industrially advantageous process wherein a B-diketone JP02/13238 filed Dec. 18, 2002, and published as WO compound represented by the following formula (3) can be 03/059858 on Jul. 24, 2003, and claiming benefit pursuant to 10 obtained. 35 U.S.C. 119(e) (1) of the filing date of Provisional Application 60/384,393 filed on Jun. 3, 2002 pursuant to 35 CRIR2R3COCHRSCOCRR6R7 (3) U.S.C. 111(b). wherein R' to R and R to R7 are each independently an alkyl group of 1 to 3 carbon atoms, and R is hydrogen or an FIELD OF THE INVENTION 15 alkyl group of 1 to 4 carbon atoms. The present invention relates to a process for preparing a Particularly, it is an object of the present invention to 3-diketone compound that is useful as a ligand of a volatile provide an industrially advantageous process wherein 2.2, organometallic complex used as, for example, a starting 6,6-tetramethyl-3,5-heptanedione can be obtained easily and material of MOCVD (metal organic chemical vapor depo at a low cost. sition), and more particularly to a process for preparing More specifically, it is an object of the invention to 2.2.6,6-tetramethyl-3,5-heptanedione. provide a process wherein an alkali metal alkoxide catalyst The present invention also relates to a process for pre can be used for the reaction of an ester compound repre paring a 2.2.6.6-tetramethyl-3,5-heptanedione metal com sented by the formula (1): plex using the 2.2.6.6-tetramethyl-3,5-heptanedione. 25 CRIR2R3COOR4 (1) BACKGROUND OF THE INVENTION wherein R' to R are each independently an alkyl group of 1 to 3 carbon atoms, and R is an alkyl group, As a process for the production of inorganic or metal thin with a ketone compound represented by the formula (2): films, MOCVD has been widely applied, and as MOCVD 30 materials, metal alkoxides, B-diketone complexes, etc. have CRR'R''COCHR8 (2) been developed. Of these, 2.2.6,6-tetramethyl-3,5-hep wherein R to R are each independently an alkyl group of tanedione is known to form volatile complexes together with 1 to 3 carbon atoms, and R is hydrogen or an alkyl group relatively many kinds of metals, but this compound has not of 1 to 4 carbon atoms, become so widespread industrially because it is expensive. 35 A process using Claisen condensation is well known as a to prepare the B-diketone compound represented by the process for preparing the 2.2.6.6-tetramethyl-3,5-heptanedi formula (3). one. For example, in J. Am. Chem. Soc., 66, 1220 (1944), That is to say, it is an object of the invention to provide ethyl pivalate is reacted with pinacolone (3.3-dimethyl-2- a process wherein an alkali metal alkoxide can be used as a catalyst for preparing 2.2.6.6-tetramethyl-3,5-heptanedione butanone, tert-butyl methyl ketone) using a sodium amide 40 catalyst to synthesize 2.2.6,6-tetramethyl-3,5-heptanedione from a pivalic acid alkyl ester and pinacolone which are in a yield of 28%. In this report, acylation reaction of methyl starting materials. ketone with an ester using sodium ethoxide is also described, It is another object of the invention to provide a process and it is reported that the reactivity is inferior when a higher for preparing a 2.2.6,6-tetramethyl-3,5-heptanedione metal ester is used. 45 complex by reacting the 2.2.6.6-tetramethyl-3,5-heptanedi In J. Org. Chem..., 27, 1036 (1962), methyl pivalate is one prepared as above with a metal salt. reacted with pinacolone using a sodium hydride catalyst to The present inventors have earnestly studied to solve such synthesize 2.2.6,6-tetramethyl-3,5-heptanedione in a yield problems associated with the prior art as described above, of 60 to 70%. and as a result, they have found that 2.2.6,6-tetramethyl-3, Other examples of the process for preparing 2.2.6.6- 50 5-heptanedione can be synthesized in the presence of an tetramethyl-3,5-heptanedione using Claisen condensation alkali metal alkoxide catalyst that is easy to handle by reaction have also been reported. In any of these processes, reacting a pivalic acid alkyl ester with pinacolone using a however, sodium hydride or sodium amide that is difficult to pivalic acid alkyl ester as a solvent but using no other handle similarly to the metallic sodium is used, and there Solvent in the beginning of the reaction or by reacting them resides a problem of safety. Moreover, safety countermea 55 in an amide type or urea type solvent. Based on the finding, Sures thereto are necessary, and hence, it is difficult to use the present invention has been accomplished.
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