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(12) United States Patent (10) Patent No.: US 6,541,659 B1 Chen (45) Date of Patent: Apr

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(12) United States Patent (10) Patent No.: US 6,541,659 B1 Chen (45) Date of Patent: Apr USOO6541659B1 (12) United States Patent (10) Patent No.: US 6,541,659 B1 Chen (45) Date of Patent: Apr. 1, 2003 (54) PROCESS FORACYL SUBSTITUTION OF (56) References Cited ANHYDRIDE BY WANADYL SALT CATALYST PUBLICATIONS (75) Inventor: Chien-Tien Chen, Taipei (TW) Klaseketal, Chemical Papers, (1997) 51 (2) pp. 111-116 as described in Chemical Abstract vol. 127 num 135436. (73) ASSignee: National Taiwan Normal University, Lee et al, Bull. Korean Chem. Soc. (1988) 9 (6) pp. Taipei (TW) 362-364, as described in Chemical Abstract, Vol. 110, No. - 204627.* (*) Notice: Subject to any disclaimer, the term of this Chem Abrst. vol. 110, No. 204627 Lee et al.* patent is extended or adjusted under 35 Chem. Abst. vol. 127 No. 135436 Klasek et al. U.S.C. 154(b) by 0 days. C. AOS. WO. O. SCK C. a. * cited by examiner (21) Appl. No.: 10/115,546 Primary Examiner Alan L. Rotman Assistant Examiner Hector M Reyes (22) Filed: Apr.a 2,49 2002 (74) Attorney, Agent, or Firm Morgan & Finnegan, LLP (57) ABSTRACT (51) Int. Cl." ........................... C07C 69/02; B01J 21/00 A proceSS for acyl Substitution of an anhydride with an active-hydrogen-containing compound includes reacting the (52) U.S. Cl 560/231; 502/100: 502/103; anhydride with the active-hydrogen-containing compound in the presence of a Vanadyl Salt catalyst to obtain a high 502/151; 502/153; 502/154 yield of acyl Substitution reaction product with high chemoSelectivity. (58) Field of Search .......................... 560/231; 502/100, 502/103, 151,153, 154 10 Claims, No Drawings US 6,541,659 B1 1 2 PROCESS FOR ACYL SUBSTITUTION OF SUMMARY OF THE INVENTION ANHYDRIDE BY WANADYL SALT CATALYST Therefore, the object of the present invention is to provide a process for acyl Substitution of an anhydride with an BACKGROUND OF THE INVENTION 5 active-hydrogen-containing compound that is devoid of the 1. Field of the Invention aforesaid drawbacks of the prior art. The invention relates to a proceSS for acyl Substitution of an anhydride with an active-hydrogen-containing Accordingly, the proceSS for acyl Substitution of an anhy compound, more particularly to a proceSS for acyl Substitu dride with an active-hydrogen-containing compound tion of an anhydride with an active-hydrogen-containing includes reacting the anhydride with the active-hydrogen compound in the presence of a Vanadyl Salt catalyst So as to containing compound in the presence of a Vanadyl Salt obtain a high yield of acyl Substitution reaction product with catalyst So as to obtain a high yield of acyl Substitution high chemoSelectivity. reaction product with high chemoSelectivity. 2. Description of the Related Art 15 The acylations of alcohols, amines and thiols are impor tant and commonly used transformations in organic Synthe DETAILED DESCRIPTION OF THE Sis. In these reactions, acid halides or anhydrides are often PREFERRED EMBODIMENTS employed as the acyl Source in basic media or in the presence of Lewis base or acid catalysts. In the past, trimethylsilyl (TMS) and metal triflates, such as indium, In the process according to this invention, the anhydride Scandium, copper, and bismuth triflates, have been found to is reacted with the active-hydrogen-containing compound in be effective in catalyzing the acylation of alcohols with the presence of a Vanadyl Salt catalyst. anhydrides. However, only a few of them have been studied with more extensive Species of anhydrides, and Substrates 25 The vanadyl salt catalyst has the following formula: bearing acid-Sensitive groups, Such as acetonide and allyl, might not be fully compatible. Moreover, most of these catalysts have encountered Some disadvantages. For example, the acylation of allyl alcohols (Such as cinnamyl (VO)X, alcohol) catalyzed by Scandium triflate would produce rear ranged by-products. The acylation catalyzed by trimethyl wherein X is selected from the group consisting of (OTf), silyl triflate should be operated at a temperature of O C. or SO-aryl, SO, (acac), (CH-CO), (F), (Cl), (Br), (I), less So as to Suppress the hydrolysis of the functional groups Al-O, (N), SbF6, HPO, MoC), (NbO), (NO), CO, on the Substrates. In addition, the actual role of the afore (CIO), SeO, Pt(CN), TiO, WO, and ZrO. mentioned catalysts in the catalytic pathway was not fully 35 understood. In this application triflate refers to trifluo The active-hydrogen-containing compound has the fol romethaneSulfonate. lowing formula: Notably, the preparation of metal triflates often require direct mixing of metal oxides with excess hot triflic acid (trifluoromethane sulfonic acid). The unavailability of com 40 plete removal of triflic acid from the metal triflates will diminish the value of the metal triflate as a catalyst because wherein it might affect the overall catalytic activity in the acylation process. In this context, new mild and neutral catalysts, Y is selected from the group consisting of O, NH and S; which can achieve general nucleophilic acyl Substitution of 45 R is hydrocarbylene group; anhydrides with protic nucleophiles, remain in great each of R is independently selected from the group demand. consisting of alkene moiety, ester moiety, lactone The value of Vanadium-containing compounds as a cata moiety, ketone moiety, imide moiety, acetonide moiety, lyst in Synthesis has been widely Studied and assessed. and lactol moiety; Among them, oxovanadium (IV) (vanadyl) compounds were 50 normally treated as pre-catalysts of the corresponding Vana m is 0, 1, 2 or 3; dium (V) species. However, Synthetic reactions and path n is 0, 1, 2, or 3; and ways that are directly catalyzed by Vanadyl species were m+n=3 rarely Studied in contrast. Togni in organometallics, 1990 “OTf represents triflate or trifluoromethane sulfonate. reported the use of camphor-derived vanadyl bis (1,3- 55 diketonato) complexes as Lewis acid catalysts for asymmet The anhydride typically has the following formula: ric Diels-Alder reactions between Danishefsky dienes and aldehydes. Although a concerted pathway was Suggested in the report, the potential amphoteric characteristic of the V=O unit (i.e., "V-O) which could...be conducive to a 60 Stepwise, push-pull type mechanism was not taught. wherein each of R is independently selected from the Namely, the (partial) positively charged V in the V=O unit group consisting of acyclic aliphatic moiety, cyclic is a Lewis acid which is Sufficient to activate the carbonyl aliphatic moiety and aromatic moiety. oxygen of an aldehyde. In the meantime, the (partial) A proposed reaction mechanism between an amphoteric negatively charged O in the V=O unit serves as a Lewis 65 Vanadyl Salt catalyst and an anhydride in the catalytic base to activate an enol Silane and to permit dissociation of acylation of an alcohol is illustrated in the following the Silyl group concomitantly. Scheme 1: US 6,541,659 B1 4 Example 3 Scheme 1: C(O)R’ The Preparation of Vanadyl Chloride IV(O)Cl.-X O O o1 XSY X-Y, RC(O)IO ^ (HO) x1 x1 x1 YOC(OR In a dry 5-mL, two-necked, round-bottomed reaction flask, vanadylsulfate trihydrate (114.0 mg, 0.53 mmol) was placed, followed by addition of aqueous methanol (MeOH/ HO, 1/0.3 mL). A solution of BaCl-2H2O (122.1 mg, 0.50 O mmol) in methanol (1 mL) was added to the reaction flask L/N-K 9i us R at ambient temperature. After 30 min of Stirring, precipita R o1 tion of bariumsulfate was observed, which was filtered off over a short pad of dry Celite. The filtrate was concentrated and dried in vacuo at 120° C. for 4 hours, and 86.4 mg (90% yield) of Vanadyl chloride as pale purple Solids was obtained. AS shown in the above Scheme 1, a protic nucleophile Example 4 (e.g., the alcohol in the Scheme) may add to one of the two alkanoates in the adduct with concomitant elimination of an alkanoic acid to regenerate the Vanadyl Salt catalyst. The Preparation of Vanadyl Azide IV(O) (N)-X The most preferred Vanadyl triflate catalyst can be pro (HO) duced either by reacting vanadylsulfate with barium triflate In a dry 5-mL, two-necked, round-bottomed reaction or by reacting Vanadium oxide and an excess of triflic acid 25 in a Suitable Solvent. flask, vanadylsulfate trihydrate (114.0 mg, 0.53 mmol) was The process according this invention is useful for the placed, followed by addition of methanol (1 mL). A solution acylation required in the proceSS for preparing Sun-Screen of Ba(N) (112.5 mg, 0.51 mmol) in methanol (1 mL) was lotion and Surfactant, Such as the acylation of Sorbitol, added to the reaction flask at ambient temperature. After 30 glycerin, fatty acid or N,N-dimethyl benzoic acid. The min of Stirring, precipitation of barium Sulfate was observed, process according to this invention is also useful for the which was filtered off over a short pad of dry Celite. The acylation of Saccharides and the Synthesis of peptides. filtrate was concentrated and dried in vacuo at 120° C. for 2 The following examples further illustrate the preferred hours, and 91.5 mg (88% yield) of vanadyl azide as brown embodiments of the invention, but are not to be construed as ish Solids was obtained. limiting. 35 EXAMPLES: Example 5 Example 1 The Preparation of Vanadyl Hexafluoroantimonate V(O) (SbF)-x(HO) The Preparation of Vanadyl Triflate V(O) (OTf)-x 40 (HO) In a dry 5-mL, two-necked, round-bottomed reaction Vanadyl sulfate (V(O)SO3HO) (342 mg, 2.1 mmole) flask, vanadyl chloride trihydrate (88.0 mg, 0.50 mmol) was was added into a two-neck flask (50 ml, Vacuum-dried), and placed, followed by addition of THF (2 mL).
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