US4113767A
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Process for the preparation of alkali metal salts of 3,3-dimethyl-2-oxo-butyric acid
Assignee: Bayer AG
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Filing: 1975-12-15
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Granted: 1978-09-12
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Expires: 1995-12-15
Abstract
Abstract 6-Tert.-butyl-3-mercapto-4-amino-1,2,4-triazin-5(4H)-one is prepared by reacting pinacolone with a sulfur chloride at 0° to 80° C, optionally reacting the mixture with an aqueous amine solution, hydrolyzing the resulting product with an alkali metal hydroxide, heating the resulting mixture from 2 to 10 hours at 80° to 150° C, liberating a 3,3-dimethyl-2-oxo-butyric acid by acidifying with a mineral acid and reacting an aqueous solution of said 3,3-dimethyl-2-oxo-butyric acid with thiocarbohydrazide to yield the desired product.
Inventors
- 👤 Walter Merz
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-05 05:46
CPC Classifications
C; C07; C07D; C07D253/00; C07D253/02; C07D253/06; C07D253/065; C07D253/07; C07D253/075
Claims Analysis
Total Claims: 28
Claim 1
Independent Claim
214 words
A process which comprises (1) reacting pinacolone, of the formula (CH.sub.3).sub.3 C--CO---CH.sub.3 (IV), with a sulfur chloride of the general formula S.sub.n Cl.sub. 2 (XII), wherein n is 1 or 2, at a temperature between 0° and 80° C (2) reacting the reaction mixture directly, without further purification, with an aqueous solution of an amine of the general formula ##STR12## in which R and R' which may be identical or different, are each hydrogen, alkyl of from 1 to 8 carbon atoms, cycloalkyl of from 5 to 6 carbon atoms or aryl of from 6 to 10 carbon atoms and which is optionally substituted by methyl or chlorine, or R and R' conjointly form a radical --(CH 2 ) m -- (where m = 4, 5, or 6) or --(CH 2 ) 2 --O--(CH 2 ) 2 --, and (3) hydrolyzing the thus-formed tert.-butyl-glyoxylthioamide of the general formula ##STR13## wherein R and R' identified as above without intermediate isolation by adding at least 2 moles of alkali metal hydroxide of the formula MOH per mole of pinacolone (IV) and heating for from 2 to 10 hours at 80° to 150° C, to give an alkali metal salt of 3,3-dimethyl-2-oxo-butyric acid of the formula (CH.sub.3).sub.3 C-CO-COO.sup.⊖ M.sup.⊕ (I a), wherein M is an alkali metal.
Claim 2
Dependent Claim
214 words
A process which comprises (1) reacting pinacolone, of the formula (CH.sub.3).sub.3 C--CO---CH.sub.3 (IV), with a sulfur chloride of the general formula S.sub.n Cl.sub. 2 (XII), wherein n is 1 or 2, at a temperature between 0° and 80° C (2) reacting the reaction mixture directly, without further purification, with an aqueous solution of an amine of the general formula ##STR12## in which R and R' which may be identical or different, are each hydrogen, alkyl of from 1 to 8 carbon atoms, cycloalkyl of from 5 to 6 carbon atoms or aryl of from 6 to 10 carbon atoms and which is optionally substituted by methyl or chlorine, or R and R' conjointly form a radical --(CH 2 ) m -- (where m = 4, 5, or 6) or --(CH 2 ) 2 --O--(CH 2 ) 2 --, and (3) hydrolyzing the thus-formed tert.-butyl-glyoxylthioamide of the general formula ##STR13## wherein R and R' identified as above without intermediate isolation by adding at least 2 moles of alkali metal hydroxide of the formula MOH per mole of pinacolone (IV) and heating for from 2 to 10 hours at 80° to 150° C, to give an alkali metal salt of 3,3-dimethyl-2-oxo-butyric acid of the formula (CH.sub.3).sub.3 C-CO-COO.sup.⊖ M.sup.⊕ (I a), wherein M is an alkali metal.
Claim 3
Dependent Claim
21 words
A process as claimed in claim 1 wherein step (1) is effected at a temperature of from 20° to 60° C.
Claim 4
Dependent Claim
26 words
A process as claimed in claim 1 wherein the sulfur chloride is used in an amount of from 0.5 to 2 moles per mole of pinacolone.
Claim 5
Dependent Claim
16 words
A process as claimed in claim 1 wherein the sulfur chloride is S 2 Cl.sub. 2.
Claim 6
Dependent Claim
26 words
A process as claimed in claim 4 wherein the sulfur chloride is used in an amount of from 0.5 to 2 moles per mole of pinacolone.
Claim 7
Dependent Claim
26 words
A process as claimed in claim 4 wherein the sulfur chloride is used in an amount of from 1.0 to 1.2 moles per mole of pinacolone.
Claim 8
Dependent Claim
14 words
A process as claimed in claim 1 wherein the sulfur chloride is SCl.sub. 2.
Claim 9
Dependent Claim
26 words
A process as claimed in claim 7 wherein the sulfur chloride is used in an amount of from 0.5 to 3 moles per mole of pinacolone.
Claim 10
Dependent Claim
26 words
A process as claimed in claim 7 wherein the sulfur chloride is used in an amount of from 1.5 to 2.0 moles per mole of pinacolone.
Claim 11
Dependent Claim
19 words
A process as claimed in claim 1 wherein step (1) is carried out in the presence of a diluent.
Claim 12
Dependent Claim
15 words
A process as claimed in claim 10 wherein said diluent is carbon tetrachloride or tetrachloroethylene.
Claim 13
Dependent Claim
13 words
A process as claimed in claim 10 wherein said diluent is excess pinacolone.
Claim 14
Dependent Claim
31 words
A process as claimed in claim 1 wherein the amine (XIII) as added in step (2) is an aqueous solution having an amine concentration of from 1 to 80% by weight.
Claim 15
Dependent Claim
30 words
A process as claimed in claim 13 wherein the amine (XIII) as added in step (2) is an aqueous solution having an amine concentration of 20 to 60% by weight.
Claim 16
Dependent Claim
25 words
A process as claimed in claim 1 wherein from 1 to 5 moles of the amine (XIII) are employed per mole of the reacted pinacolone.
Claim 17
Dependent Claim
25 words
A process as claimed in claim 15 wherein from 1.5 to 3 moles of the amine (XIII) are employed per mole of the reacted pinacolone.
Claim 18
Dependent Claim
25 words
A process as claimed in claim 15 wherein from 2.0 to 2.5 moles of the amine (XIII) are employed per mole of the reacted pinacolone.
Claim 19
Dependent Claim
41 words
A process as claimed in claim 1 wherein the amine (XIII) is selected from ammonia, methylamine, ethylamine, propylamine, isopropylamine, butylamine, pentylamine, hexylamine, octylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, dioctylamine, methylethylamine, methylbutylamine, methyloctylamine, cyclohexylamine, dicyclohexylamine, aniline, N-methylaniline, pyrrolidine, piperidene and morpholine.
Claim 20
Dependent Claim
29 words
A process as claimed in claim 1 wherein from 2 to 5 moles of the alkali metal hydroxide are used, in step (3), per mole of the tert.-butyl-glyoxyl-thioamide (XIV).
Claim 21
Dependent Claim
29 words
A process as claimed in claim 19 wherein from 3 to 4 moles of the alkali metal hydroxide are used, in step (3), per mole of the tert.-butyl-glyoxyl-thioamide (XIV).
Claim 22
Dependent Claim
17 words
A process as claimed in claim 1 wherein the alkali metal hydroxide is sodium or potassium hydroxide.
Claim 23
Dependent Claim
18 words
A process as claimed in claim 1 wherein step (3) is effected at from 100° to 130° C.
Claim 24
Dependent Claim
18 words
A process as claimed in claim 22 wherein step (3) is effected at from 110° to 120° C.
Claim 25
Dependent Claim
20 words
A process as claimed in claim 1 wherein step (3) is effected in the presence, as a diluent, of water.
Claim 26
Dependent Claim
16 words
A process as claimed in claim 1 wherein steps (1), (2), and (3) are effected continuously.
Claim 27
Dependent Claim
104 words
A process which comprises (a) reacting pinacolone, of the formula (CH.sub.3).sub.3 C--CO--CH.sub.3 (IV), with a sulfur chloride of the general formula S.sub.n Cl.sub. 2 (XII), wherein n is 1 or 2, at a temperature between 0° and 80° C, and (b) hydrolyzing the resulting reaction product without intermediate isolation by adding at least 2 moles of alkali metal hydroxide of the formula MOH per mole of pinacolone (IV) and heating for from 2 to 10 hours at 80° to 150° C to give an alkali metal salt of 3,3-dimethyl-2-oxo-butyric acid of the formula (CH.sub.3).sub.3 C-CO-COO.sup.⊖ M.sup.⊕ (I a), wherein M is an alkali metal.
Claim 28
Dependent Claim
104 words
A process which comprises (a) reacting pinacolone, of the formula (CH.sub.3).sub.3 C--CO--CH.sub.3 (IV), with a sulfur chloride of the general formula S.sub.n Cl.sub. 2 (XII), wherein n is 1 or 2, at a temperature between 0° and 80° C, and (b) hydrolyzing the resulting reaction product without intermediate isolation by adding at least 2 moles of alkali metal hydroxide of the formula MOH per mole of pinacolone (IV) and heating for from 2 to 10 hours at 80° to 150° C to give an alkali metal salt of 3,3-dimethyl-2-oxo-butyric acid of the formula (CH.sub.3).sub.3 C-CO-COO.sup.⊖ M.sup.⊕ (I a), wherein M is an alkali metal.
References Cited (Backward Citations)
No citation records indexed.
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1981-09-11 | 1982-03-13 | 1982-09-12 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1985-09-11 | 1986-03-13 | 1986-09-12 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1989-09-11 | 1990-03-13 | 1990-09-12 | $7700.00 | Window Closed / Lapsed |