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AssigneeE. I. Du Pont de Nemours and Company
InventorDavid R. Brittelli
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Process for preparing the substituted phosphonoalkanoic acid of the formula ##STR1## wherein: R.sup.1 is alkyl of 1-8 carbon atoms, aralkyl of 7-10 carbon atoms, phenyl, or substituted phenyl of 6-10 carbon atoms; R.sup.2 is H, hydrocarbyl of 1-18 carbon atoms, or substituted hydrocarbyl of 1-18 carbon atoms, wherein in said hydrocarbyl groups the carbon atom attached to the ##STR2## moiety is substituted with two or three hydrogen atoms or is a carbon atom of an aromatic ring; and Y is oxygen or sulfur, which process comprises contacting and reacting, at a temperature of about -70.degree. C. to about 125.degree. C., a pressure of about 1-100 atmospheres (0.1-10 MPa), and for a time sufficient to effect reaction, the phosphite ester of the formula ##STR3## wherein R.sup.1 and Y are as defined above, with the .alpha.-halocarboxylic acid of the formula R.sup.2 CHXCO.sub.2 H, wherein X is Cl, Br, or I and R.sup.2 is as defined above, in the presence of at least two moles of base per mole of limiting reagent, said base having a pKa greater than about 15, to produce the substituted phosphonoalkanoic acid, and process for preparing the substituted acrylic acid of the formula R.sup.3 R.sup.4 C.dbd.CR.sup.2 COOH wherein: R.sup.2 is as defined above; and R.sup.3 and R.sup.4 are the same or different and are selected from H, hydrocarbyl of 1-18 carbon atoms, and substituted hydrocarbyl of 1-18 carbon atoms or R.sup.3 and R.sup.4 taken together are cycloalkylene or substituted cycloalkylene of 4-18 carbon atoms, which process comprises: (a) carrying out the aforesaid reaction to produce the substituted phosphonoalkanoic acid except that at least three moles of base are present; and (b) contacting and reacting, at a temperature of about -70.degree. to about 125.degree. C., a pressure of about 1-100 atmospheres (0.1-10 MPa), and for a time sufficient to effect reaction, the substituted phosphonoalkanoic acid produced in step (a) with the carbonyl compound of the formula R.sup.3 R.sup.4 C.dbd.O, wherein R.sup.3 and R.sup.4 are as defined above, to produce the substituted acrylic acid.
Process for preparing the substituted acrylic acid of the formula R.sup.3 R.sup.4 C=R.sup.2 COOH, wherein R.sup.3 and R.sup.4 are the same or different and are selected from H, hydrocarbyl of 1-18 carbon atoms, and substituted hydrocarbyl of 1-18 carbon atoms or R.sup.3 and R.sup.4 taken together are cycloalkylene or substituted cycloalkylene of 4-18 carbon atoms, and R.sup.2 is H, hydrocarbyl of of 1-18 carbon atoms, or substituted hydrocarbyl of 1-18 carbon atoms, wherein said hydrocarbyl groups the carbon atom attached to the ##STR11## moiety is substituted with two or three hydrogen atoms or is a carbon atom of an aromatic ring, which process comprises:
Dependencies are inferred from the claim text.
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No related US applications are recorded in the indexed filing history.
With only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to atoms of the carbocyclic ring: radicals…
By reactions not involving formation of carboxyl groups: by isomerisation; by change of size of the carbon skeleton
The acid moiety containing a substituent or a structure which is considered as characteristic: esters of acyclic acids which can have further…
Heterocyclic compounds
Term ended 21 Mar 2000 (estimated)
USPTO file history isn’t available for this patent, so only indexed dates are shown.
1. Technical Field
This invention relates to the preparation of dialkyl- and diarylphosphonoalkanoic acids and to the use thereof in the preparation of substituted acrylic acids.
2. Background
The following examples are illustrative of the invention; all parts and percentages are by weight and all temperatures are degrees Celsius.
To 4.0 ml (0.031 mole) of diethyl phosphite and 6.5 g (0.093 mole) of 97% sodium ethoxide in 100 ml of absolute ethanol was added dropwise a solution of 4.32 g (0.031 mole) of bromoacetic acid in 25 ml of absolute ethanol. The mixture was stirred for 15 min, then heated to 50.degree. for 20 min, at which time the mixture became homogenous. Then 3.29 g (0.031 mole) of benzaldehyde was added and the mixture was stirred for 1.5 h. The solution was then poured into 500 ml of water, acidified to pH 3 with conc hydrochloric acid, and extracted with ethyl acetate. The extracts were dried (over MgSO.sub.4) and evaporated in vacuo to yield 3.0 g (67%) of E-(trans)-cinnamic acid; .sup.1 H NMR (CDCl.sub.3) .delta. 6.43 (1, d (J=16 Hz), .dbd.CHCO.sub.2 H), 7.2-7.6 (s, m, aromatic), 7.80 (1, d (J=16 Hz), PhCH.dbd.), and 11.90 (1, s, --CO.sub.2 H).
To 20.35 ml (0.093 mole) of a 24.7% solution of sodium methoxide in methanol and 25 ml of dry methanol was added 4.0 ml (0.031 mole) of diethyl phosphite. Then 4.32 g (0.031 mole) of bromoacetic acid was added. The temperature of the mixture rose to 50.degree. autogenously. After stirring for 1.0 h at ambient temperature, 3.15 ml (0.031 mole) of benzaldehyde was added. The mixture was stirred 1.5 h and then processed as in Example 1 to yield, after recrystallizaton from n-butyl chloride, 2.4 g (48%) of E-(trans)-cinnamic acid; mp 132.degree.-133.5.degree. (literature mp reported in Merck Index, Eighth Edition, p 265: 133.degree.); .sup.1 H NMR identical to the product of Example 1.