Back to results
US 8,569,523 B2Granted
Method of making ketals and acetals
AssigneeSegetis, Inc.
InventorsSergey Selifonov, Scott D. Rothstein, Brian D. Mullen
Life of this patent
Estimating the term…
Abstract
The reaction of alcohols with oxocarboxylates to form acetals or ketals is catalyzed by unexpectedly low levels of protic acids. By employing low acid catalyst levels compared to amounts conventionally used, rapid formation of acetal or ketal is facilitated while the formation of oxocarboxylate esters is minimized. Further employing a significant molar excess of oxocarboxylate in conjunction with low acid catalyst level gives rise to the rapid and clean formation of acetals and ketals from oxocarboxylates and alcohols.
Claims46
A method of preparing a compound of formula (3)
- wherein
- R1, R2, and R3 are independently hydrogen, a linear alkyl group, a branched alkyl group, a cyclic alkyl group, a linear alkenyl group, a branched alkenyl group, a cyclic alkenyl group, an aryl group, or alkaryl group, each of which groups optionally comprises one or more heteroatoms independently chosen from oxygen, nitrogen, halogen atoms, sulfur, silicon, and phosphorus;
- R4 is a linear alkyl group, a branched alkyl group, a cyclic alkyl group, a linear alkenyl group, a branched alkenyl group, a cyclic alkenyl group, an aryl group, or alkaryl group, each of which groups optionally comprises one or more heteroatoms independently chosen from oxygen, nitrogen, halogen atoms, sulfur, silicon, and phosphorus;
- a is 0 or an integer from 1 to 12;
- b is 0 or an integer;
- and
- R5 is a residue of a polymeric polyol, a hydroxyl functionalized surface, a silane, a siloxane, a silanol, or a hydrocarbon group having the formula:
- wherein c is 0 or 1 and R6, R7, R8, R9, R10, and R11 are independently hydrogen, a linear alkyl group, a branched alkyl group, a cyclic alkyl group, a linear alkenyl group, a branched alkenyl group, a cyclic alkenyl group, an aryl group, or an alkaryl group, each of which groups optionally comprises one or more heteroatoms;
- the method comprising:
- a) providing a reaction mixture comprising
- i. a compound of formula (2)
- wherein R1, R2, R3, R4, and a are as defined above,
- ii. a compound of formula (4)
- wherein R5 and b are as defined above, and
- iii. 1×10−6 to 1×10−3 molar equivalents, based on moles of compound (4), of an acid catalyst;
- and
- b) reacting compounds (2) and (4);
- wherein less than 5% of compound (2) undergoes an esterification or transesterification reaction, as measured by GC-MS.
15 more elements
A method of preparing a compound of formula (3)
- wherein
- R1, R2, R3, and R4 are independently hydrogen, a linear alkyl group, a branched alkyl group, a cyclic alkyl group, a linear alkenyl group, a branched alkenyl group, a cyclic alkenyl group, an aryl group, or an alkaryl group, each of which groups optionally comprises one or more heteroatoms independently chosen from oxygen, nitrogen, halogen atoms, sulfur, silicon, and phosphorus;
- a is 0 or an integer from 1 to 12;
- b is 0 or an integer;
- and
- R5 is a residue of a polymeric polyol, a hydroxyl functionalized surface, a silane, a siloxane, a silanol, or a hydrocarbon group having the formula
- wherein c is 0 or 1, and R6, R7, R8, R9, R10, and R11 are independently hydrogen, a linear alkyl group, a branched alkyl group, a cyclic alkyl group, a linear alkenyl group, a branched alkenyl group, a cyclic alkenyl group, an aryl group, or an alkaryl group, each of which groups optionally comprises one or more heteroatoms independently chosen from oxygen, nitrogen, halogen atoms, sulfur, silicon, and phosphorus;
- the method comprising:
- a) providing a reaction mixture comprising
- i. about 2.5 molar equivalents or greater, based on moles of compound (4), of a compound of formula (2)
- wherein R1, R2, R3, R4, and a are as defined above, and
- ii. about 1 molar equivalent of a compound of formula (4)
- wherein R5 and b are as defined above, and
- iii. 1×10−6 to 5×10−3 molar equivalents of an acid catalyst based on moles of compound (4);
- and
- b) reacting compounds (2) and (4),
- wherein less than 5% of compound (2) undergoes an esterification or transesterification reaction as measured by GC-MS.
14 more elements
A method of preparing a cyclic ketal of levulinic acid or an ester thereof, the method comprising:
- a. providing a reaction mixture comprising
- i. glycerol,
- ii. about 2.5 to 5 molar equivalents, based on moles of glycerol, of an alkyl levulinate selected from the group consisting of ethyl levulinate and butyl levulinate, and
- iii. 1×10−6 to 1×10−3 molar equivalents, based on moles of glycerol, of an acid catalyst selected from sulfuric acid, sulfamic acid, and a sulfonic acid;
- and
- b. collecting a cyclic ketal of levulinic acid or ester thereof;
- wherein less than 5% of the alkyl levulinate undergoes an esterification or transesterification reaction, as determined by GC-MS.
4 more elements
A method of preparing a cyclic ketal of levulinic acid or an ester thereof with a polyol, the method comprising:
- a. providing a reaction mixture comprising
- i. 1,2-propanediol;
- ii. about 2.5 to 5 molar equivalents, based on moles of 1,2-propanediol, of an alkyl levulinate selected from the group consisting of ethyl levulinate and butyl levulinate, and
- iii. 1×10−6 to 1×10−3 molar equivalents, based on moles of 1,2-propanediol, of an acid catalyst selected from sulfuric acid, sulfamic acid, and a sulfonic acid;
- and
- b. collecting a cyclic ketal of levulinic acid or ester thereof;
- wherein less than 5% of the alkyl levulinate undergoes an esterification or transesterification reaction, as determined by GC-MS.
4 more elements
Dependencies are inferred from the claim text.