Patent US4334073A successfully refreshed from Google Patents.
US4334073A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Process for the preparation of alpha-hydroxycarboxylic acid amide compounds
Assignee: Bayer AG
•
Filing: 1980-12-01
•
Granted: 1982-06-08
•
Expires: 2000-12-01
Abstract
Abstract Process for the preparation of an alpha-hydroxycarboxylic acid amide compound of the formula ##STR1## wherein R 1 is hydrogen or alkyl; and R 2 and R 3 are individually selected from hydrogen, alkyl, alkenyl, alkynyl, aralkyl, cycloalkyl or aryl, each of which may be optionally substituted, or a nitrogen-containing heterocyclic radical; or R 2 and R 3 , together with the nitrogen atom to which they are bonded, represent an optionally benzo-fused monocyclic or bicyclic ring, which ring may be substituted and may be partially unsaturated, which process comprises reacting in a first stage an alpha-halocarboxylic acid amide of the formula ##STR2## wherein R 1 , R 2 and R 3 are identified as above; and Hal is chlorine or bromine, with an alkali metal acetate or alkaline earth metal acetate in the presence of a quaternary ammonium salt at a temperature between 20° and 200° C., and, in a second stage, deacylating the alpha-acetoxycarboxylic acid amide produced, having the general formula ##STR3## in which R 1 , R 2 and R 3 , are identified as above by reacting said amide III with an alcohol of the general formula R.sup.4 --OH (IV) in which R 4 is alkyl in the presence of a catalytic amount of a catalyst selected from alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal carbonates, and alkaline earth metal carbonates, at a temperature between 20° and 150° C., these compounds are useful as intermediates in the preparation of herbicides, e.g., substituted sulfonyl glycol amides and anilides.
Inventors
- 👤 Hans-Joachim Diehr
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-08 10:46
CPC Classifications
C; C07; C07D; C07D295/00; C07D295/16; C07D295/18; C07D295/182; C07D295/185; C07D209/00; C07D209/02; C07D209/04; C07D209/08; C07D215/00; C07D215/02; C07D215/04; C07D215/08
Claims Analysis
Total Claims: 17
Claim 1
Independent Claim
266 words
Process for the preparation of an alpha-hydrocarboxylic acid amide compound of the formula ##STR42## wherein R 1 is hydrogen or alkyl; and R 2 and R 3 are individually selected from hydrogen, alkyl, alkenyl, alkynyl, aralkyl, cycloalkyl or aryl, each of which may be optionally substituted, or a nitrogen-containing heterocyclic radical; or R 2 and R 3 , together with the nitrogen atom to which they are bonded, represent an optionally benzo-fused monocyclic or bicyclic ring, which ring may be substituted and may be partially unsaturated, which process comprises reacting in a first stage an alpha-halocarboxylic acid amide of the formula ##STR43## wherein R 1 , R 2 and R 3 are identified as above with the proviso that R 1 , R 2 and R 3 are not all hydrogen; and Hal is chlorine or bromine, with an alkali metal acetate or alkaline earth metal acetate in the presence of a quaternary ammonium salt and as a diluent wherein the reactants are suspended, an aliphatic or aromatic optionally chlorinated hydrocarbon, at a temperature between 20° and 200° C., and, in a second stage, deacylating the alpha-acetoxycarboxylic acid amide produced, having the general formula ##STR44## in which R 1 , R 2 and R 3 , are identified as above by reacting said amide III with an alcohol of the general formula R.sup.4 -OH (IV), in which R 4 is alkyl in the presence of a catalytic amount of a catalyst selected from alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal carbonates, and alkaline earth metal carbonates, at a temperature between 20° and 150° C.
Claim 2
Dependent Claim
266 words
Process for the preparation of an alpha-hydrocarboxylic acid amide compound of the formula ##STR42## wherein R 1 is hydrogen or alkyl; and R 2 and R 3 are individually selected from hydrogen, alkyl, alkenyl, alkynyl, aralkyl, cycloalkyl or aryl, each of which may be optionally substituted, or a nitrogen-containing heterocyclic radical; or R 2 and R 3 , together with the nitrogen atom to which they are bonded, represent an optionally benzo-fused monocyclic or bicyclic ring, which ring may be substituted and may be partially unsaturated, which process comprises reacting in a first stage an alpha-halocarboxylic acid amide of the formula ##STR43## wherein R 1 , R 2 and R 3 are identified as above with the proviso that R 1 , R 2 and R 3 are not all hydrogen; and Hal is chlorine or bromine, with an alkali metal acetate or alkaline earth metal acetate in the presence of a quaternary ammonium salt and as a diluent wherein the reactants are suspended, an aliphatic or aromatic optionally chlorinated hydrocarbon, at a temperature between 20° and 200° C., and, in a second stage, deacylating the alpha-acetoxycarboxylic acid amide produced, having the general formula ##STR44## in which R 1 , R 2 and R 3 , are identified as above by reacting said amide III with an alcohol of the general formula R.sup.4 -OH (IV), in which R 4 is alkyl in the presence of a catalytic amount of a catalyst selected from alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal carbonates, and alkaline earth metal carbonates, at a temperature between 20° and 150° C.
Claim 3
Dependent Claim
27 words
Process as claimed in claim 1 in which the said first stage of the reaction is carried out at a temperature between 50° C. and 150° C.
Claim 4
Dependent Claim
27 words
Process as claimed in claim 1 in which the said second stage of the reaction is carried out at a temperature between 50° C. and 120° C.
Claim 5
Dependent Claim
68 words
Process as claimed in claim 1 wherein a tetraalkylammonium salt with 1 to 4 carbon atoms per alkyl radical or a trialkyl-aralkylammonium salt with 1 to 4 carbon atoms per alkyl radical and with 1 or 2 carbon atoms in the alkyl part of the aralkyl radical and 6 or 10 carbon atoms in the aryl part of the aralkyl radical is employed as the quaternary ammonium salt.
Claim 6
Dependent Claim
20 words
Process as claimed in claim 1 wherein a tetra-n-butylammonium bromide or benzyltrimethylammonium chloride is employed as the quaternary ammonium salt.
Claim 7
Dependent Claim
35 words
Process as claimed in claim 1 wherein, in the first stage, 0.9 to 1.5 moles of acetate (anhydrous) and 1 to 20 mmoles of the quaternary ammonium salt are employed per mole of amide (II).
Claim 8
Dependent Claim
30 words
Process as claimed in claim 6 wherein 0.95 to 1.2 moles of acetate (anhydrous) and 2 to 15 mmoles of quaternary ammonium salt are employed per mole of amide (II).
Claim 9
Dependent Claim
62 words
Process as claimed in claim 1 wherein, in the second stage, 2 to 5 mol equivalents of alcohol (IV) and 1 to 100 mmoles of an alkali metal hydroxide or alkaline earth metal hydroxide or of an alkali metal carbonate or alkaline earth metal carbonate are employed with the alpha-acetoxycarboxylic acid amide (III) obtained per mole of the alpha-halocarboxylic acid amide (II).
Claim 10
Dependent Claim
48 words
Process as claimed in claim 8 wherein 5 to 50 mmoles of an alkali metal hydroxide or alkaline earth metal hydroxide or of an alkali metal carbonate or alkaline earth metal carbonate are employed with the alpha-acetoxycarboxylic acid amide (III) obtained per mole of the alpha-halocarboxylic acid (II).
Claim 11
Dependent Claim
221 words
Process as claimed in claim 1 wherein a compound of formula (II) is used wherein R 1 is hydrogen or methyl, R 2 and R 3 are individually selected from hydrogen, alkyl with 1 to 20 carbon atoms, cyanoalkyl with 2 to 5 carbon atoms, alkoxyalkyl with 2 to 8 carbon atoms, alkylthioalkyl with 2 to 8 carbon atoms, alkenyl with 3 to 10 carbon atoms, alkynyl with 3 to 10 carbon atoms, cycloalkyl with 3 to 12 carbon atoms, aralkyl with 1 to 2 carbon atoms in the alkyl part and 6 or 10 carbon atoms in the aryl part, aryl with 6 or 10 carbon atoms, it being possible for the last two mentioned radicals to carry one or more substituents selected from 1 to 3 halogen atoms, 1 to 3 alkyl radicals with, in each case, 1 to 4 carbon atoms, nitro and cyano; morpholinyl or tetrahydrofurfuryl, or R 2 and R 3 , together with the nitrogen atom to which they are bonded, represent an optionally benzo-fused monocyclic or bicyclic ring with 3 to 15 carbon atoms which is optionally substituted by 1 to 3 alkyl groups with, in each case, 1 to 5 carbon atoms (spiro-linked substituents with up to 4 carbon atoms and up to 2 oxygen atoms also being possible), and Hal is chlorine.
Claim 12
Dependent Claim
223 words
Process as claimed in claim 1 wherein a compound of formula (II) is used wherein R 1 represents hydrogen, R 2 and R 3 , which can be identical or different, each represent straight-chain or branched alkyl with 1 to 10 carbon atoms, cyanoethyl, 2-alkoxyethyl with 1 to 5 carbon atoms in the alkoxy group, allyl, propargyl, 1-methylpropargyl, 1,1-dimethylpropargyl, cyclopentyl, cyclohexyl, phenyl, nitrophenyl, tolyl, nitrotolyl, chlorophenyl, naphthyl, benzyl, chlorobenzyl, chlorotolyl, morpholinyl or tetrahydrofurfuryl, or R 2 and R 3 together with the nitrogen atom to which they are bonded, represent pyrrolidyl, monoalkyl- or dialkyl-pyrrolidyl with 1 to 5 carbon atoms per alkyl group, morpholinyl, monoalkyl- or dialkylmorpholinyl with 1 to 5 carbon atoms per alkyl group, piperidyl, monoalkyl-, dialkyl- or trialkylpiperidyl with in each case 1 to 5 carbon atoms per alkyl group, spiro-substituted piperidyl, perhydroazepinyl, 1,2,3,4-tetrahydroindolyl, monoalkyl-, dialkyl- or trialkyl-1,2,3,4-tetrahydroindolyl with in each case 1 to 5 carbon atoms per alkyl group, perhydroindolyl, monoalkyl-, dialkyl- or trialkylperhydroindolyl with in each case 1 to 5 carbon atoms per alkyl group, 1,2,3,4-tetrahydro-quinolyl, 1,2,3,4-tetrahydro-iso-quinolyl, monoalkyl-, dialkyl- or trialkyl-1,2,3,4-tetrahydro-quinolyl or -isoquinolyl with in each case 1 to 5 carbon atoms per alkyl group, perhydroquinolyl or perhydroisoquinolyl, monoalkyl-, dialkyl- or trialkyl-perhydro-quinolyl or -isoquinolyl with in each case 1 to 5 carbon atoms per alkyl group, perhydrothiazolyl or the radical of the formula ##STR45## and Hal represents chlorine.
Claim 13
Dependent Claim
16 words
Process as claimed in claim 1 wherein hydroxyacetic acid N-methylanilide is produced from alpha-acetoxyacetic acid N-methylanilide.
Claim 14
Dependent Claim
16 words
Process as claimed in claim 1 wherein hydroxyacetic acid 2-methylpiperidide is produced from alpha-acetoxyacetic acid 2-methylpiperidide.
Claim 15
Dependent Claim
16 words
Process as claimed in claim 1 wherein hydroxyacetic acid N-methyl-N-cyclohexylamine is produced from alpha-acetoxyacetic acid N-methyl-N-cyclohexylamide.
Claim 16
Dependent Claim
16 words
Process as claimed in claim 1 wherein hydroxyacetic acid N-methyl-N-(1-methylpropargyl)-amide is produced from alpha-acetoxyacetic acid N-methyl-N-(1-methylpropargyl)-amide.
Claim 17
Dependent Claim
16 words
Process as claimed in claim 1 wherein hydroxyacetic acid N,N-di-(2-propenyl)amide is produced from alpha-acetoxyacetic acid N,N-di-(2-propenyl)amide.
References Cited (Backward Citations)
US3898262A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1985-06-07 | 1985-12-07 | 1986-06-08 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1989-06-07 | 1989-12-07 | 1990-06-08 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1993-06-07 | 1993-12-07 | 1994-06-08 | $7700.00 | Window Closed / Lapsed |