Poly(3-cyclopropyl-3-hydroxypropionate) and processes for its preparation and derivatives thereof
OwnerJohn Clark Hubbs, Theresa Sims Barnette +1inventors
InventorsJohn Clark Hubbs, Theresa Sims Barnette, Neil Warren Boaz
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Abstract
Poly(3-cyclopropyl-3-hydroxypropionates) (I) which are useful for the preparation of vinylcyclopropane and cyclopropylacetylene are disclosed. Methods for the preparation of a variety of intermediates obtained from (I) such as 3-cyclopropyl-3-hydroxypropionic acid and esters and salts thereof, 3-cyclopropylacrylic acid, and vinylcyclopropane also are disclosed.
Claims45
A composition having the formula
- 12
- wherein n is greater than 1.
Process for the preparation of a composition having the formula
- 13
- wherein n is greater than 1 which comprises reacting cyclopropanecarboxaldehyde and ketene in the presence of a catalyst selected from Lewis acids and tertiary amines.
Process for the preparation of 3-cyclopropyl-3-hydroxypropionic acid which comprises contacting poly(3-cyclopropyl-3-hydroxypropionate) having the formula
- 14
- wherein n is greater than 1, with water in the presence of an acid catalyst.
Process for the preparation of a metal 3-cyclopropyl-3-hydroxypropionate salt which comprises contacting poly(3-cyclopropyl-3-hydroxypropionate) having the formula
- 15
- wherein n is greater than 1, with water in the presence of a base selected from the hydroxides, carbonates, and bicarbonates of the alkali metals and alkaline earth metals.
Process for the preparation of an alkyl 3-cyclopropyl-3-hydroxypropionate ester which comprises contacting poly(3-cyclopropyl-3-hydroxypropionate) having the formula
- 16
- wherein n is greater than 1, with an alcohol in the presence of an acid or base catalyst.
Process for the preparation of 3-cyclopropyl acrylic acid which comprises heating poly(3-cyclopropyl-3-hydroxypropionafe) having the formula
- 17
- wherein n is greater than 1.
Process for the preparation of vinylcyclopropane which comprises heating poly(3-cyclopropyl-3-hydroxypropionate) having the formula
- 18
- wherein n is greater than 1.
Process for the preparation of a mixture of 3-cyclopropylacrylic acid and vinylcyclopropane which comprises heating poly(3-cyclopropyl-3-hydroxypropionate) having the formula
- 19
- wherein n is greater than 1.
Process for the preparation of vinylcyclopropane which comprises heating 3-cyclopropylacrylic acid at a temperature of about 100 to 300° C. in the presence of an acidic catalyst.
Process for the preparation of vinylcyclopropane which comprises heating 3-hydroxy-3-cyclopropylpropionic acid at a temperature of about 100 to 400° C.
Process for the preparation of vinylcyclopropane which comprises the steps of (1) contacting 3-cyclopropyl-3-hydroxypropionic acid with a C2-C14 carboxylic acid anhydride to produce a mixed anhydride of 3-cyclo-propyl-3-acyloxypropionic acid;
- (2) contacting the anhydride from step (1) with water to form a 3-cyclopropyl-3-acyloxypropionic acid;
- and (3) treating the 3-cyclopropyl-3-acyloxypropionic acid from step (2) with acid, base or heat to form vinylcyclopropane.
A mixed carboxylic anhydride comprising a 3-cyclopropyl-3-acyloxy-propionyl residue and the acyl residue of a C2-C14 carboxylic acid wherein the acyloxy group is the residue of the C2-C14 carboxylic acid.
Process for the preparation of 3-cyclopropyl-3-hydroxy-propionic acid which comprises contacting 3-cyclopropylacrylic acid with water in the presence of an acidic or basic catalyst.
An alkyl 3-cyclopropyl-3-alkoxypropionate comprising methyl 3-cyclopropyl-3-methoxypropionate, ethyl 3-cyclopropyl-3-ethoxypropionate, and n-propyl 3-cyclopropyl-3-n-propoxypropionate.
Methyl 3-cyclopropyl-3-methoxypropionate.
3-Cyclopropyl-β-propiolactone.
Process for the preparation of vinylcyclopropane which comprises heating 3-cyclopropyl-β-propiolactone.
Process for the preparation of a metal salt of cyclopropylacrylic acid which comprises contacting poly(3-cyclopropyl-3-hydroxypropionate) having the formula
- 20
- wherein n is greater than 1, with water in the presence of a base selected from the hydroxides, carbonates, and bicarbonates of the alkali metals and alkaline earth metals.
Process for the preparation of trans-3-cyclopropylacrylic acid which comprises the steps of 1) contacting poly(3-cyclopropyl-3-hydroxypropionate) having the formula
- 21
- wherein n is greater than 1, with water in the presence of a base selected from the hydroxides, carbonates, and bicarbonates of the alkali metals and alkaline earth metals and 2) neutralization of the solution resulting from step one with an acid selected from hydrogen halide, sulfuric acid, phosphoric acid or a sulfonic acid and 3) isolation of the formed solid trans-3-cyclopropylacrylic acid by filtration.
Process for the preparation of a mixture of a metal salt of cyclopropylacrylic acid and a metal salt of 3-cyclopropyl-3-hydroxypropionic acid which comprises contacting poly(3-cyclopropyl-3-hydroxypropionate) having the formula
- 22
- wherein n is greater than 1, with water in the presence of a base selected from the hydroxides, carbonates, and bicarbonates of the alkali metals and alkaline earth metals.
Dependencies are inferred from the claim text.