CA1113936A - Catalytic oxidation of 3,3-dimethyl 2-hydroxybutyric acid to 2-oxo acid - Google Patents
Catalytic oxidation of 3,3-dimethyl 2-hydroxybutyric acid to 2-oxo acidInfo
- Publication number
- CA1113936A CA1113936A CA336,011A CA336011A CA1113936A CA 1113936 A CA1113936 A CA 1113936A CA 336011 A CA336011 A CA 336011A CA 1113936 A CA1113936 A CA 1113936A
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- Prior art keywords
- dimethyl
- acid
- ruthenium
- salt
- process according
- Prior art date
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-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/373—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in doubly bound form
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
Abstract of the Disclosure Sodium 3,3-dimethyl-2-hydroxybutyrate and ruthenium dioxide hydrate are added to water, the pH rendered alkaline, and sodium hypochlorite is slowly added to produce sodium 3,3-dimethyl-2-oxybutyrate in high yield and purity. The solid catalyst is filtered off and may be re-used while the filtrate can be directly used in further synthesis.
Description
I.I;J I~ I O ' 'J
CATALYTIC OXIDATION OF 3,3-~IMETHYL
CATALYTIC OXIDATION OF 3,3-~IMETHYL
2-HYDROXYBUTYRIC ~CID TO 2-OXO ACID
ihe present invention relates to the preparation of
ihe present invention relates to the preparation of
3,3-dimethyl-2-oxobutyric acid ancl its salts.
United States Patent 3,905,801 discloses the conclensation ~ of ~-oxo-alkanoic acids uith thiocarbohydraæide to produce 4-.. amino-6-(substituted)-3-thio-1,2,l~-triazin-5(4-H)-ones whici- can be methylated to give 4-amino-6-(substituted)-3-(methyl-thio)-1,2,4-triazin-5-(4-H)-ones of which the 6-tert. butyl derivative lO is an especially effectlve selective herbicide of special utilit;
in the cultivation of soybeans, tomatoes, potatoes, and the like It is disclosed in that patent that 2-oxoacids can be prepared from the 2-hydroxy counterpart.s by oxidation with potassium permanganate.
This process is quite acceptable and has been used success-fuliy in making millions of pounds of the 6-tert.butyl derivative but it is not inexpensive due to the high cost of potassium permanganate. In addition, it results in large quantities of by-product manganese dioxide which must be disposed oE, with 20 possible environmental impact.
It is accordingly an object of the present invention to provide an improved process for the preparation of 3,3-dime~.hyl-2-oxobutyric acid and/or its salts.
These and other objects and advantages are real;.zed in 25 accordance with the present invention pursuclnt to which a salt of 3,3-dimethyl-2-oxobutyric acid is prepared by reacting 3,3-dimethyl-2-hydroxybutyric acid with a hypochlorous salt under alkaline conditions in the presence o:E ruthenium as catalys~.
Advantageously the salts are soclium salts al~hougl~ othcr alkali metal and alkaline earth metal salts can be used provided they are soluble in the reaction medium, e.g. water.
- The reaction medium is preferably o~ a pH of abou~ 9 to 13, especially about 10 to 12. Since some hydroxyl ion appears to be consumed during the reaction, either it is init:ially sur)plied in excess or alkali is added durin~, oxidation to maintain the clesired p~l. rf the pM o~ the hydroxy salt so].uti.on is below about 6.0 or if the free caustic content of the hypochlorite lO solution is lowered to below about 1.3%, the desired oxidation does not proceed to any significant extent and further additlon ~;j of hypochlorite merely cleaves any keto acid which may be present.
'~ In add~ition, the Ru catalyst is converted to a water soluble form which is difficult to recover from the solution.
The hypochlorite is advantageously ~ISed in excess to e~ re complete conversion of the 2-hydroxyacid using about 5 to 15~
excess. The hypochlorite can be formed in situ, e.g. by bubbling chlorine gas into an aqueous caustic solution of the hydroxy acid containing the`catalyst.
The reaction proceeds even at room temperature but preferably is conducted at about 40C or higher to speed it up. ~'~bove about 60C pivalic acid is produced so advantageously the oxidation is carried out at or below 60C.
,~
, -2-The ruthe~ m catalys~ is oxidize(ll)y t:lle hyp0ch1ori ~-e to produce a mixture o:E ruthenate, perruthena.te ancl ruthenium tetroxide, the ruthenate predominatin~,. At the end oE the reaction the ruthenium oxide is an insoluble solid present in substantially the same amount as initially so it can be filterecl off an.d reused, even without treatment, in another cycle The ruthenium can be supplied to the reaction solution in -the Eorm of a salt or an oxide, ruthenium dioxide and especially ruthenium dioxide hydrate being preferred. The oxide, for example, could be formed in situ commencing with a salt such as ruthenium trichloride.
The ruthenium oxide is employed in catalytic amounts, e.g.
from between 0.01g to about 1.0g per mole of hydroxyacid, preferably between about 0.lg to 0.5g per mole.
.
The catalyst and hydroxacid salt aqueous ~luLion is adjusted to the desired pH and the temperature brought to the desired value. Then caustic soda and ch]orine or pre-formed NaOCl can be added dropwise or incrementally. After all the oxidizing agent is added the mass is maintained to ensure 20 completion of the reaction and then it is filtered to separate the catalyst from the solution containing the product in high yield and purity.
.
Tlle oxidation proceeds rapi~1y allcl a~l~iLion oL ~lle llyl)o-" chlorite within only 5 minutes results in very high yields.
Advantageously, somewhat longer reactlon times are employed, e.g. about 30 minutes or an hour, to permit the ruthenium 5 catalyst to be returned to suitable insoluble form for filtration and then re-use in a further cycle. The resulting solution can then be used directly for reaction with thiocarbohydrazide to form 4-amino-6-(1~1-dimethylethyl)-3-thio-1~3~4-5(4-1~)-one In Chemical Communi.cationsl420 (1970) it is taught that : 10 compounds containing the grouping-CHOH-CO- undergo carbon-carbon cleavage under ruthenium-catalyzed oxidation rather than con-version to -CO-CO-, e.g.
-CHQH-CO ~ -CHO ~ OHC--CHOH-CO ~ -CO-CO-Surprisingly, however, witll the i.nstant s~arting materia].s and conditions of alkalinity oxidation proceeds herein by con-version of the hydroxy group to a carbony] wlthout cleavage between the hydroxy-bearing and carbonyl-bearing carbon atoms.
The invention will be further described in the following 20 illustrative examples wherein all parts are by weight unless otherwise expressed: --Example 1 (a) A 2 liter Morton flask equipped with a mechanical stirrer, thermometer, condenser, and dropping funnel was charged with 559 g of an 11.8% aqueous solution of 3,3-dimethyl-2-hydroxybutyric acid ("hydroxy acid") as the sodium salt (0.5 mole) and 0.2 g of ruthenium dioxide hydrate (RuO2 H2O). The pH was raised to 12 and the temperature to 40C. With rapid stirriny, 330.5 g of 12.1~ NaOCl (0.5 mole + 7.5% excess) in water was added dropwise over about 1~2 hour while the temperature was maintained at 40C with an ice bath. When the addition was complete the ice bath was removed and the solution was stirred for one hour, then filtered to remove catalyst to give 879 g of a 7.5% aqueous solution of 3,3-dimethyl-2-oxobutyric acid ("keto acid") as the sodium salt;
approximate yield 100%.
(b) At the end of ,the oxidation the Ru catalyst was in the form of the black, water-insoluble ruthenium dioxide hydrate. It was removed by filtration employing Celite filter aid. The wet filter cake of catalyst plus filter aid was added directly into a furtherbatch of hydroxy acid salt solution and another oxidation conducted as before by addition of hypochlorite.
(c) To 956 g of a 15.8% thiocarbohydrazide solution in dilute HCl at 70 there were added over a 10-minute period 2682 g of 7.27% keko acid filtrate produced as in (a) (temperature = 70C) with rapid stirring. After heating at 70C (pH 1.3) for 4 hours the solution was cooled to room temperature and filkered. The solid was washed with water and air dried to give 272.2 g of 99.3% pure 4-amino-6-tert.-butyl-3-mercapto-1,2,4-triazin-5-(4-H)-one.
, ~$~
xample 2 A 1 liter 4-neck round bot~om ~lask equipped ~7itl~
a stirrer, thermometer, ancI addltion funIlel was charge~
with 524 g of aqueous solution containing 0.5 mole of "hydroxy acid" and 100 mg oE ruthenium dioxide hydrate.
The temperature was held at 15C with an ice bath and stirred while 294 g of 11.9% NaCCl solution was added dropwise over abou~ 1.5 hours. The solution was then stirred for one hour while it was allowed to come to room temperature. Filtration through GI~A glass fiber filter paper and washing the RuO2 with a small amount oE
dilute caustic gave 829 g of 7.25% keto acid. Notwith-standing the low temperature and small amount of catalyst, the yield was 94.4%.
; 15 Exam~le 3 The reaction was run as Example l except that the temperature was Icept at 80C. Thus, 427.4 g (3.5%
ex,cess) of 9.0~/~ NaOCl was added over about l/2 hour to 555 g of 11.7% "hydroxy acid" containing 0.4 ~ of Ru2.H2O. Filtration gave 982 g of product containing 5.82% "keto acid" (87.9%), 0.44% unreacted "hydroxy acid"
(6.5%), and 0.32% (6.6% yield) oE pivalic acid, as salt.
Thus, the higher temperature results in small amounts of undesired pivalic acid by-product.
25 Examp 1 e 4 ~ s in ~xample 1, the NaOCl was adcled at a constant rate over 5 minutes while the temperature o.E the reaction mixture was kept at 40C. This gave 982 ~, of product with 6.36% keto (96.1% yield) and no unreacted "hydroxy acid".
o . 3 g O r Ru2 . il~o was used. The lower tempera~ure avoided pivali.c aci.d formation but the :Castcr ~-lddition, compared with Example 1, resulted in a small clrop in yield.
5 Example 5 Repeating Example 4 except that the NaOCl solution was aclded over two hours, gave 9&3 g of product of which 6.55~o was "keto acid" (yield 99%).
Example 6 Example 1 was re-run using glass and platinum ; electrodes attached to a Sargent-Welch Model LS pH meter and a 10 mv recorder. The NaOCl was added at a constant rate with a metering pump. The potential of the solution was kept at 330-400 mv. ~Jear the end of the reaction the 15 reading climbed up to 500 mv at which point the NaOCl addition was stopped. There were obtained from 559 g of 11.8% hydroxy acid solution 921 g of 6.7% "keto acid", yield 95%.
Example 7 To a mixture of 120 ml of water, 100 ml of 50%
sodium hydroxide solution, 1 g of Ru02. hydrate, and 0.5 mole of "hydroxy acid" (559.3 g of an ll. 8% sol.uLion) was added chlorine gas at about 0.5 g/min. The temperature was maintained at 0-5Cand when approxima~ely 0.7 moles 25 of C12 had been added the solution was allowed to warm to room temperature and was filtered to give 839 g of product containing 7.05% keto acid (91% yi.elcl) and 0.38% hydroxy acid (4.8% yield).
., .
~$ ~ 3 Examplc 8 .
: As in Example 1 except ruthenium trichloride hy~rate was used. 350.5 g of 1l.4% NaOCl was added dropwise to a solution of 511.6 g o 12.9% hydroxy acicl containing 0.3 g of RuC13:l~20. This gave 818.7 g of 7.25% keto acid solution with a yield of 91.3%.
Example 9 As in Example 1 279.7 g of ].1.8% hydroxy acid was charged to the flask and the pH was adjusted to 12. 0.3 g of ~Uo2 H2o was added and 76.8 g of 26% NaOCl solution was added dropwise. This gave 34l g of 9.53% ke~o acid solution with a yield of 100Ø
It will be appreciated that the instant specification and examples are set forth by way of illustration and not limitation, 15 and that various modifcations and changes may be made without departing from the spirit and scope of the present invention.
United States Patent 3,905,801 discloses the conclensation ~ of ~-oxo-alkanoic acids uith thiocarbohydraæide to produce 4-.. amino-6-(substituted)-3-thio-1,2,l~-triazin-5(4-H)-ones whici- can be methylated to give 4-amino-6-(substituted)-3-(methyl-thio)-1,2,4-triazin-5-(4-H)-ones of which the 6-tert. butyl derivative lO is an especially effectlve selective herbicide of special utilit;
in the cultivation of soybeans, tomatoes, potatoes, and the like It is disclosed in that patent that 2-oxoacids can be prepared from the 2-hydroxy counterpart.s by oxidation with potassium permanganate.
This process is quite acceptable and has been used success-fuliy in making millions of pounds of the 6-tert.butyl derivative but it is not inexpensive due to the high cost of potassium permanganate. In addition, it results in large quantities of by-product manganese dioxide which must be disposed oE, with 20 possible environmental impact.
It is accordingly an object of the present invention to provide an improved process for the preparation of 3,3-dime~.hyl-2-oxobutyric acid and/or its salts.
These and other objects and advantages are real;.zed in 25 accordance with the present invention pursuclnt to which a salt of 3,3-dimethyl-2-oxobutyric acid is prepared by reacting 3,3-dimethyl-2-hydroxybutyric acid with a hypochlorous salt under alkaline conditions in the presence o:E ruthenium as catalys~.
Advantageously the salts are soclium salts al~hougl~ othcr alkali metal and alkaline earth metal salts can be used provided they are soluble in the reaction medium, e.g. water.
- The reaction medium is preferably o~ a pH of abou~ 9 to 13, especially about 10 to 12. Since some hydroxyl ion appears to be consumed during the reaction, either it is init:ially sur)plied in excess or alkali is added durin~, oxidation to maintain the clesired p~l. rf the pM o~ the hydroxy salt so].uti.on is below about 6.0 or if the free caustic content of the hypochlorite lO solution is lowered to below about 1.3%, the desired oxidation does not proceed to any significant extent and further additlon ~;j of hypochlorite merely cleaves any keto acid which may be present.
'~ In add~ition, the Ru catalyst is converted to a water soluble form which is difficult to recover from the solution.
The hypochlorite is advantageously ~ISed in excess to e~ re complete conversion of the 2-hydroxyacid using about 5 to 15~
excess. The hypochlorite can be formed in situ, e.g. by bubbling chlorine gas into an aqueous caustic solution of the hydroxy acid containing the`catalyst.
The reaction proceeds even at room temperature but preferably is conducted at about 40C or higher to speed it up. ~'~bove about 60C pivalic acid is produced so advantageously the oxidation is carried out at or below 60C.
,~
, -2-The ruthe~ m catalys~ is oxidize(ll)y t:lle hyp0ch1ori ~-e to produce a mixture o:E ruthenate, perruthena.te ancl ruthenium tetroxide, the ruthenate predominatin~,. At the end oE the reaction the ruthenium oxide is an insoluble solid present in substantially the same amount as initially so it can be filterecl off an.d reused, even without treatment, in another cycle The ruthenium can be supplied to the reaction solution in -the Eorm of a salt or an oxide, ruthenium dioxide and especially ruthenium dioxide hydrate being preferred. The oxide, for example, could be formed in situ commencing with a salt such as ruthenium trichloride.
The ruthenium oxide is employed in catalytic amounts, e.g.
from between 0.01g to about 1.0g per mole of hydroxyacid, preferably between about 0.lg to 0.5g per mole.
.
The catalyst and hydroxacid salt aqueous ~luLion is adjusted to the desired pH and the temperature brought to the desired value. Then caustic soda and ch]orine or pre-formed NaOCl can be added dropwise or incrementally. After all the oxidizing agent is added the mass is maintained to ensure 20 completion of the reaction and then it is filtered to separate the catalyst from the solution containing the product in high yield and purity.
.
Tlle oxidation proceeds rapi~1y allcl a~l~iLion oL ~lle llyl)o-" chlorite within only 5 minutes results in very high yields.
Advantageously, somewhat longer reactlon times are employed, e.g. about 30 minutes or an hour, to permit the ruthenium 5 catalyst to be returned to suitable insoluble form for filtration and then re-use in a further cycle. The resulting solution can then be used directly for reaction with thiocarbohydrazide to form 4-amino-6-(1~1-dimethylethyl)-3-thio-1~3~4-5(4-1~)-one In Chemical Communi.cationsl420 (1970) it is taught that : 10 compounds containing the grouping-CHOH-CO- undergo carbon-carbon cleavage under ruthenium-catalyzed oxidation rather than con-version to -CO-CO-, e.g.
-CHQH-CO ~ -CHO ~ OHC--CHOH-CO ~ -CO-CO-Surprisingly, however, witll the i.nstant s~arting materia].s and conditions of alkalinity oxidation proceeds herein by con-version of the hydroxy group to a carbony] wlthout cleavage between the hydroxy-bearing and carbonyl-bearing carbon atoms.
The invention will be further described in the following 20 illustrative examples wherein all parts are by weight unless otherwise expressed: --Example 1 (a) A 2 liter Morton flask equipped with a mechanical stirrer, thermometer, condenser, and dropping funnel was charged with 559 g of an 11.8% aqueous solution of 3,3-dimethyl-2-hydroxybutyric acid ("hydroxy acid") as the sodium salt (0.5 mole) and 0.2 g of ruthenium dioxide hydrate (RuO2 H2O). The pH was raised to 12 and the temperature to 40C. With rapid stirriny, 330.5 g of 12.1~ NaOCl (0.5 mole + 7.5% excess) in water was added dropwise over about 1~2 hour while the temperature was maintained at 40C with an ice bath. When the addition was complete the ice bath was removed and the solution was stirred for one hour, then filtered to remove catalyst to give 879 g of a 7.5% aqueous solution of 3,3-dimethyl-2-oxobutyric acid ("keto acid") as the sodium salt;
approximate yield 100%.
(b) At the end of ,the oxidation the Ru catalyst was in the form of the black, water-insoluble ruthenium dioxide hydrate. It was removed by filtration employing Celite filter aid. The wet filter cake of catalyst plus filter aid was added directly into a furtherbatch of hydroxy acid salt solution and another oxidation conducted as before by addition of hypochlorite.
(c) To 956 g of a 15.8% thiocarbohydrazide solution in dilute HCl at 70 there were added over a 10-minute period 2682 g of 7.27% keko acid filtrate produced as in (a) (temperature = 70C) with rapid stirring. After heating at 70C (pH 1.3) for 4 hours the solution was cooled to room temperature and filkered. The solid was washed with water and air dried to give 272.2 g of 99.3% pure 4-amino-6-tert.-butyl-3-mercapto-1,2,4-triazin-5-(4-H)-one.
, ~$~
xample 2 A 1 liter 4-neck round bot~om ~lask equipped ~7itl~
a stirrer, thermometer, ancI addltion funIlel was charge~
with 524 g of aqueous solution containing 0.5 mole of "hydroxy acid" and 100 mg oE ruthenium dioxide hydrate.
The temperature was held at 15C with an ice bath and stirred while 294 g of 11.9% NaCCl solution was added dropwise over abou~ 1.5 hours. The solution was then stirred for one hour while it was allowed to come to room temperature. Filtration through GI~A glass fiber filter paper and washing the RuO2 with a small amount oE
dilute caustic gave 829 g of 7.25% keto acid. Notwith-standing the low temperature and small amount of catalyst, the yield was 94.4%.
; 15 Exam~le 3 The reaction was run as Example l except that the temperature was Icept at 80C. Thus, 427.4 g (3.5%
ex,cess) of 9.0~/~ NaOCl was added over about l/2 hour to 555 g of 11.7% "hydroxy acid" containing 0.4 ~ of Ru2.H2O. Filtration gave 982 g of product containing 5.82% "keto acid" (87.9%), 0.44% unreacted "hydroxy acid"
(6.5%), and 0.32% (6.6% yield) oE pivalic acid, as salt.
Thus, the higher temperature results in small amounts of undesired pivalic acid by-product.
25 Examp 1 e 4 ~ s in ~xample 1, the NaOCl was adcled at a constant rate over 5 minutes while the temperature o.E the reaction mixture was kept at 40C. This gave 982 ~, of product with 6.36% keto (96.1% yield) and no unreacted "hydroxy acid".
o . 3 g O r Ru2 . il~o was used. The lower tempera~ure avoided pivali.c aci.d formation but the :Castcr ~-lddition, compared with Example 1, resulted in a small clrop in yield.
5 Example 5 Repeating Example 4 except that the NaOCl solution was aclded over two hours, gave 9&3 g of product of which 6.55~o was "keto acid" (yield 99%).
Example 6 Example 1 was re-run using glass and platinum ; electrodes attached to a Sargent-Welch Model LS pH meter and a 10 mv recorder. The NaOCl was added at a constant rate with a metering pump. The potential of the solution was kept at 330-400 mv. ~Jear the end of the reaction the 15 reading climbed up to 500 mv at which point the NaOCl addition was stopped. There were obtained from 559 g of 11.8% hydroxy acid solution 921 g of 6.7% "keto acid", yield 95%.
Example 7 To a mixture of 120 ml of water, 100 ml of 50%
sodium hydroxide solution, 1 g of Ru02. hydrate, and 0.5 mole of "hydroxy acid" (559.3 g of an ll. 8% sol.uLion) was added chlorine gas at about 0.5 g/min. The temperature was maintained at 0-5Cand when approxima~ely 0.7 moles 25 of C12 had been added the solution was allowed to warm to room temperature and was filtered to give 839 g of product containing 7.05% keto acid (91% yi.elcl) and 0.38% hydroxy acid (4.8% yield).
., .
~$ ~ 3 Examplc 8 .
: As in Example 1 except ruthenium trichloride hy~rate was used. 350.5 g of 1l.4% NaOCl was added dropwise to a solution of 511.6 g o 12.9% hydroxy acicl containing 0.3 g of RuC13:l~20. This gave 818.7 g of 7.25% keto acid solution with a yield of 91.3%.
Example 9 As in Example 1 279.7 g of ].1.8% hydroxy acid was charged to the flask and the pH was adjusted to 12. 0.3 g of ~Uo2 H2o was added and 76.8 g of 26% NaOCl solution was added dropwise. This gave 34l g of 9.53% ke~o acid solution with a yield of 100Ø
It will be appreciated that the instant specification and examples are set forth by way of illustration and not limitation, 15 and that various modifcations and changes may be made without departing from the spirit and scope of the present invention.
Claims (9)
1. A process for the preparation of a salt of 3,3-dimethyl-2-oxo-butyric acid comprising reacting 3,3-dimethyl-2-hydroxybutyric acid with a hypochlorous acid salt under alkaline conditions in the presence of ruthenium as catalyst.
2. A process according to claim 1, wherein the salt of 3,3-dimethyl-2-hydroxybutyric acid and the ruthenium are first combined in water, and the hyprochlorous acid salt is then added to the water in at least stoichiometric amount.
3. A process according to claim 1, wherein the ruthenium is employed in the form of ruthenium dioxide hydrate or ruthenium trichloride hydrate.
4. A process according to claim 1, wherein the salt of 3,3-dimethyl-2-hydroxybutyric acid is the sodium salt, and the hypochlorous acid salt is the sodium salt.
5. A process according to claim 4, wherein the sodium 3,3-dimethyl-2-hydroxybutyric acid is first added to water along with ruthenium in the form of ruthenium dioxide hydrate the pH is maintained between about 9 and 13, the temperature is maintained between about 40 and 60°C, sodium hypochlorite is added to the water in at least stoichiometric amount, and the solution is thereafter filtered to separate the catalyst from the solution containing sodium 3,3-dimethyl-2-oxobutyrate.
6. A process according to claim 5, wherein the filtered off ruthenium catalyst is directly employed in oxidation of another quantity of 3,3-dimethyl-2-hydroxybutyric acid.
7. A process according to Claim 1, wherein the hypochlorous acid salt is formed in situ by addition of caustic and chlorine gas.
8. A process according to Claim 6, wherein the hypochlorous acid salt is formed in situ by addition of caustic and chlorine gas, and the solution containing sodium 3,3-di-methyl-2-oxobutyrate is directly condensed with thiocarbohydra-zide.
9. In the production of 4-amino-6-tert.-butyl-3-thio-1,2,4-triazin-5(4-H)-one by oxidizing 3,3-dimethyl-2-hydroxy-butyric acid to 3,3-dimethyl-2-oxo-butyric acid and condensing the 3,3-dimethyl-2-oxo-butyric acid with thio-carbohydrazide, the improvement which comprises effecting the oxidation by adding sodium 3,3-dimethyl-2-hydroxybutyric acid to water along with ruthenium dioxide hydrate, maintaining the pH between about 9 and 13, maintaining the temperature between about 40 and 60°C, adding sodium hypochlorite to the water in at least stoichiometric amount, filtering the solution to separate the catalyst from the solution containing sodium 3,3-dimethyl-2-oxobutyrate, and directly condensing the solution with thiocarbohydrazide.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US96033078A | 1978-11-13 | 1978-11-13 | |
| US960,330 | 1978-11-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1113936A true CA1113936A (en) | 1981-12-08 |
Family
ID=25503053
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA336,011A Expired CA1113936A (en) | 1978-11-13 | 1979-09-20 | Catalytic oxidation of 3,3-dimethyl 2-hydroxybutyric acid to 2-oxo acid |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0011207B1 (en) |
| JP (1) | JPS5566536A (en) |
| AR (1) | AR222669A1 (en) |
| BR (1) | BR7906994A (en) |
| CA (1) | CA1113936A (en) |
| CS (1) | CS209941B2 (en) |
| DD (1) | DD146945A5 (en) |
| DE (1) | DE2961465D1 (en) |
| DK (1) | DK153539C (en) |
| HU (1) | HU182906B (en) |
| IL (1) | IL58678A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112592265A (en) * | 2020-12-21 | 2021-04-02 | 安达兰泽科技有限公司 | Preparation method of 3, 3-dimethyl-2-oxobutyric acid and sodium salt thereof |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1097917B1 (en) * | 1999-11-03 | 2003-02-12 | Korea Research Institute Of Chemical Technology | Preparing method of alpha-ketocarboxylic acid derivatives |
| DE10236919A1 (en) * | 2002-08-12 | 2004-02-26 | Bayer Ag | Process for the preparation of 3,3-dimethyl-2-oxobutyric acid |
| JP4650714B2 (en) * | 2003-09-01 | 2011-03-16 | ナガセケムテックス株式会社 | Method for producing carbonyl compound |
| CN113004141A (en) * | 2019-12-19 | 2021-06-22 | 北京颖泰嘉和生物科技股份有限公司 | Process for the preparation of 3, 3-dimethyl-2-oxobutanoic acid and triazinones |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1069955B (en) * | 1975-09-24 | 1985-03-25 | Air Prod & Chem | PROCEDURE FOR SELECTIVE CATALYTIC OXIDATION OF UNSATURATED ALCOHOLS TO FORM CARBONYL COMPOUNDS |
| US4052460A (en) * | 1976-01-20 | 1977-10-04 | Bayer Aktiengesellschaft | Production of 3,3-dimethyl-2-oxo-butyric acid salt |
-
1979
- 1979-09-20 CA CA336,011A patent/CA1113936A/en not_active Expired
- 1979-10-29 BR BR7906994A patent/BR7906994A/en not_active IP Right Cessation
- 1979-11-05 EP EP79104307A patent/EP0011207B1/en not_active Expired
- 1979-11-05 DE DE7979104307T patent/DE2961465D1/en not_active Expired
- 1979-11-09 DD DD79216802A patent/DD146945A5/en unknown
- 1979-11-09 IL IL58678A patent/IL58678A/en unknown
- 1979-11-12 DK DK477879A patent/DK153539C/en not_active IP Right Cessation
- 1979-11-13 AR AR278864A patent/AR222669A1/en active
- 1979-11-13 JP JP14611679A patent/JPS5566536A/en active Granted
- 1979-11-13 HU HU79MO1068A patent/HU182906B/en not_active IP Right Cessation
- 1979-11-13 CS CS797745A patent/CS209941B2/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112592265A (en) * | 2020-12-21 | 2021-04-02 | 安达兰泽科技有限公司 | Preparation method of 3, 3-dimethyl-2-oxobutyric acid and sodium salt thereof |
| CN112592265B (en) * | 2020-12-21 | 2023-09-01 | 安达兰泽科技有限公司 | Preparation method of 3, 3-dimethyl-2-oxo-butyric acid and sodium salt thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| DD146945A5 (en) | 1981-03-11 |
| DK153539B (en) | 1988-07-25 |
| BR7906994A (en) | 1980-07-15 |
| DE2961465D1 (en) | 1982-01-28 |
| JPS6239149B2 (en) | 1987-08-21 |
| JPS5566536A (en) | 1980-05-20 |
| CS209941B2 (en) | 1981-12-31 |
| AR222669A1 (en) | 1981-06-15 |
| DK477879A (en) | 1980-05-14 |
| EP0011207A1 (en) | 1980-05-28 |
| IL58678A0 (en) | 1980-02-29 |
| DK153539C (en) | 1989-01-02 |
| IL58678A (en) | 1982-11-30 |
| HU182906B (en) | 1984-03-28 |
| EP0011207B1 (en) | 1981-11-25 |
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