CA1102817A - Process for the production of 1,3-dichloroacetone oxime and its acetate derivatives - Google Patents
Process for the production of 1,3-dichloroacetone oxime and its acetate derivativesInfo
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- CA1102817A CA1102817A CA270,498A CA270498A CA1102817A CA 1102817 A CA1102817 A CA 1102817A CA 270498 A CA270498 A CA 270498A CA 1102817 A CA1102817 A CA 1102817A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
- A01N33/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds containing nitrogen-to-oxygen bonds
- A01N33/24—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds containing nitrogen-to-oxygen bonds only one oxygen atom attached to the nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
- C07C249/08—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes by reaction of hydroxylamines with carbonyl compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/32—Oximes
- C07C251/34—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
- C07C251/36—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atoms of the oxyimino groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C251/38—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atoms of the oxyimino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of a saturated carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/32—Oximes
- C07C251/34—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
- C07C251/44—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atom of at least one of the oxyimino groups being part of a ring other than a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/32—Oximes
- C07C251/62—Oximes having oxygen atoms of oxyimino groups esterified
- C07C251/64—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids
- C07C251/66—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids with the esterifying carboxyl groups bound to hydrogen atoms, to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Abstract
Abstract of the Disclosure 1,3-dichloroacetone oxime is prepared from 1,3-dichloropropanone by reaction with a hydroxyl-amine salt in a strongly acidic medium in the presence of a base selected from the group consisting of ter-tiary amines, lower alkyl amides, alkali metal bicar-bonates, alkali metal carbonates and alkaline earth metal carbonates. 1,3-dichloroacetone oxime acetate is advantageously prepared by reaction of the oxime with acetic anhydride. The acetate is obtained in high purity.
Description
Z~
Bacl~round and Prior Art This application relates to an improved process for production of 1,3-dichloroacetone oxime and 1,3-dichloroacetone oxime acetate.
1,3-dichloroacetone oxime, as illustrated in U.S.
patent 3,733,419 of Arnold D. Gutman, is an intermediate for the production of a number of compounds useful in controlling fungi and bacteria. Among these compounds is 1,3-dichloro-acetone oxime acetate (compound 5 of the said patent.) Accord-ing to this patent, the oxi.~e was prepared by reacting ~,3-dichloropropanone with hydroxylamine hydrochloride in the presence of ethanol and water. The oxime was obtained from the reaction products by extraction with chloroform.
Examples of conversion of the oxime to its deriva-tives, for instance, the trichloroacetate and the crotonate, show that the reaction was conducted between the oxime and an acyl chloride in the presence of benzene and the product recovered fro~ the benzene phase.
T~hen processes of this type were applied to the production o 1,3-dichloroacetone oxi~e acetate, however,
Bacl~round and Prior Art This application relates to an improved process for production of 1,3-dichloroacetone oxime and 1,3-dichloroacetone oxime acetate.
1,3-dichloroacetone oxime, as illustrated in U.S.
patent 3,733,419 of Arnold D. Gutman, is an intermediate for the production of a number of compounds useful in controlling fungi and bacteria. Among these compounds is 1,3-dichloro-acetone oxime acetate (compound 5 of the said patent.) Accord-ing to this patent, the oxi.~e was prepared by reacting ~,3-dichloropropanone with hydroxylamine hydrochloride in the presence of ethanol and water. The oxime was obtained from the reaction products by extraction with chloroform.
Examples of conversion of the oxime to its deriva-tives, for instance, the trichloroacetate and the crotonate, show that the reaction was conducted between the oxime and an acyl chloride in the presence of benzene and the product recovered fro~ the benzene phase.
T~hen processes of this type were applied to the production o 1,3-dichloroacetone oxi~e acetate, however,
2~ the product turned black either during recovery or subsequently on standing.
It is an object of the present invention to pro-vide an i~proved process for the production of 1,3-dichloro-acetone oxime.
It is a further object of this invention to provide an improved process for the preparation of 1,3-dichloroacetone oxime acetate through the oxime inter~ediate.
Another object of the present invention is to provide a process for the produc~ion of 1,3-dichloroacetone oxime ".,~
12~L7 aceta~e ~hich is co~Dara~-iv21y s able and does not ~iscolor on s,anding.
Summary of the Invention In one aspec " this inventloll comprises a process for the production of 1,3-dichloroacetone o~;~e comprising reacting 1,3-dichloropropanone with a hydroxylamine salt in the presenee of a base seleeted from the group eonsisting of tertiary amines, lower alkyl amides, alkali metal bi-earbonates, alkali metal earbonates and alkaline earth metal earbonates, establishing the pH of the reaetion system at a value of 2 or less and therear,er malntaining the pH of the reaction system at a value of 2 or less throughout the re~ainder of the reaction.
In another aspect, this invention co~prises a process for the product-on of 1,3-dichloroacetone oxi~e acetate com-prlsinga) producing 1,3-dichloroacetone oxi~e by: reacting 1,3-dichloropropanone with a hydroxyla~ine salt, in the presenee of a base selected from the group eonsisting of tertiary amines, lower alkyl amides, al~ali metal biearbonates, alkali metal earbonates and alkaline earth metal earbonates, establishing the pH of the reaetion system at a value of 2 or less and thereafter maintaining the pH of the reaction system at a value of 2 or less throughout the remainder of the reaction; and b) reacting the 1,3-dichloroacetone oxime from step (a) ~ith acetic anh7drlde.
~ J~7 Detailed Description of the Invention In producing an oxi~e by reaction of a l;etone with a hydroxylamine salt, it has hitherto been considered that the preferred p~. of the system should be between about 4 and 5.
See, for instance, Sid~wick, The Or~anic Chemistry of Nitro~en, Clarendon Press (Oxford)~ 1945, P. 170. Operation at lower pH
was felt to result in hydrolysis of the oxime. However~ we have now found that~ at least for the production of dichloro-acetone oxi~e, optimum and ~uite ur.expected results are obtained by establi.ching the reaction svstem in a highly acidic condition, -3a-.~
1~1Z~ 7 at a pH of 2 or less, and then maintaining the reaction system at a pH of 2 or less throughout the remainder of the reaction.
Operation of the reaction at pX values higher than 2 for the entire reaction time generally results in the formation of a gum or slime.
The hydroxylamine salt may be any of those commonly employed such as hydroxylamine hydrochloride and hydroxylamine sulfate.
In the present process, as well as those heretofore used, it is preferred to conduct the reaction in the presence of an added base. If a sufficient excess of hydroxylamine salt is utilized, this can serve as the base; however, such a practice represents an unnecessary waste of comparatively expensive mate-rials. In general, any suitable base can be used provided it can be readily dispersed throughout the reaction medium without forming undesirable high localized pH values. The alkali metal carbonates and bicarbonates and alkaline earth metal carbonates, particularly calcium carbonate, are the preferred bases for this process. Other members of these groups such as sodium, magnesium, barium, strontium carbonates and sodium and potassium bicarbonates are also suitable. Tertiary amines such as triethylamine, pyridine, substituted pyridines such as the lutidines and dimethylaniline, may also be used Lower alkyl amides such as acetamide, formamide and di-methylformamide are also suitable bases for this reaction. ~owever, these are less preferable because although the oxime product can be produced in good yield, it may contain unreacted 1,3-dichloro-propanone in a sufficient amount to create problems because of its irritant properites. T'nis compound therefore, must be removed from the oxime product, thereby requiring additional purification steps and equipment.
In general, strong bases such as sodium and potassium hydroxides are not desirable for use in this process as their addition may cause the formation of localized pH values above 2.
The pH may be established at a value of 2 or less by any of several expedients, and may be done by active or passive measures. In general, the pH of the starting reaction mixture of 1,3-dichloropropanone and hydroxylamine salt will be between about 3.7 and about 4. As the reaction proceeds, the pH will drop due to the formation of hydrogen ions as the hydroxylamine salt reacts. Thus, in one embodiment of the process, 1,3-dichloropropanone and the hydroxylamine salt are caused to react and, when the pH drops to below about 2 (generally within 15 - 45 minutes), addition of the base is commenced. Thereafter, the pH of the reaction mixture is monitored and addition of the base is controlled to maintain the pH at a value no higher than 2 The overall reaction time is generally about 2 - 4 hours and it is not detrimental to the conduct of the process for the pH of the system to be above 2 for the first 15 - 45 minutes or so .
In some cases, as was the case in Example 2 which follows, the pH of the initial reaction system may actually be less than about 3.7-4 This is believed to be caused by acidic impurities in the reactants or solvents used in the process, most likely in the hydroxylamine salt. In such a case, the base may be added earlier in the course of the reaction, with pH monitoring and controlled addition of base as above.
An alternate method of operation is to add part of the base at the commencement of the reaction. In such case, there is also added at that time a sufficient quantity of a mineral acid such as hydrochloric, sulfuric, phosphoric or nitric acid to bring the pH o~ the reaction system down to an initial value of 2 or less. The remainder of the base is subsequently added with pH monitoring and controlled addition to maintain the p~
at a value of 2 or less.
In a preferred embodiment, the oxime production step is conducted in the presence of an inert organic solvent, such as benzene, toluene, xylene, chlorinated hydrocarbons such as chloroform, methylene chloride, perchloroethylene, 1,2-dichloro-ethane and others.
L0 In general, the oxime production step is conducted at temperatures of between about 5C and about 85C, depending on the base and solvent, if used. When using a tertiary amine, lower temperatures are preferred, preferably between about 5C
and about 40C, most preferably between about 15C and about 25C. When using an alkaline earth metal carbonate or alkali metal carbonate, the reaction proceeds best at a temperature of between about 35C and about 45C, though higher temperatures up to about 85C may be utilized, depending on the boiling point of the solvent.
The reaction of the 1,3-dichloroacetone oxime with acetic anhydride is conducted in the presence of an inert sol-vent such as those previously mentioned. Small amounts of water may be tolerated so long as a separate a~ueous phase is not formed, as the reaction will not proceed to completion in a two-phase system. This step is conducted at a temperature of between about 5C and about 40C. For a complete reaction, acetic anhydride should be used in a slight excess such as about 1.4-1.5 moles per mole of oxime. A smaller excess can be utilized ir the organic solution of the oxime is dried prior to _~, _ ~ u~
its use in the acetate production step.
The oxime may be separated ;~ m the reaction mixture before reacting with acetic anhydride. However, in a preferred embodiment, both the oxime production and acetate production reactions are carried out in the presence of the same inert solvent, Since the oxime will be contained in the organic layer from the first reaction, it may be utilized for the next as a solution of oxime in the solvent. Separation of the or-ganic phase of the Gxime production step from the a~ueous phase should be done careul~y to preclude introduction OL an undesi-rable amount of water into the acetate formation system.
The oxime may undergo decomposition if it isallowed to reach a pH of above about 3 or to stand for long periods of time.
In ~ further embodiment the 1,3-dichloropropanone can be prepared by oxidation of 1,3-dichloropropanol with an oxidizing agent such as sodium dichromate and concentrated sulfuric acid. The 1,3-dichloropropanone can be recovered from the reaction products by extraction with toluene or another suitable solvent and the solution of this compound can be used as one of the starting materials for the oxime production re-action without separation of the l~etone. In all steps o~ the process removal of solvent from a reaction product by evapo-ration should be performed carefully as all the desired pro-ducts are guite volatile and substantial amounts ~ay be carried off with the solJents, The ollowing Examples are presented as illustrative of the invention; however~ the invention may comprise conditions and/or variations of the processes not mentioned or outside the ran~es of the Examples; thererore, the invention is not t ~Z~7 intended to be limited thereby, but only by the claims which ollow.
~xample 1 Into a 12-liter flask was introduced 2.5 kg (8.8 mole) sodium dichromate dihydrate and 1 liter of water. The mixture was stirred to dissolve the salt. There was then added 1.94 lcg (15.0 mole) of 1,3-d-chloro-2-propanol, followed by 2.95 kg (30 mole) of concentrated sulfuric acid dissolved in 0.75 liter of water. The reaction temperature was main-tained at about 20 during the course of the reaction and stirring was continued at a moderate rate. Caution was taken as the addition of sulfurlc acid to this mixture is quite exo-thermic. A~ the end of the reaction, the reaction mixture was viscous and blaclc.
It is an object of the present invention to pro-vide an i~proved process for the production of 1,3-dichloro-acetone oxime.
It is a further object of this invention to provide an improved process for the preparation of 1,3-dichloroacetone oxime acetate through the oxime inter~ediate.
Another object of the present invention is to provide a process for the produc~ion of 1,3-dichloroacetone oxime ".,~
12~L7 aceta~e ~hich is co~Dara~-iv21y s able and does not ~iscolor on s,anding.
Summary of the Invention In one aspec " this inventloll comprises a process for the production of 1,3-dichloroacetone o~;~e comprising reacting 1,3-dichloropropanone with a hydroxylamine salt in the presenee of a base seleeted from the group eonsisting of tertiary amines, lower alkyl amides, alkali metal bi-earbonates, alkali metal earbonates and alkaline earth metal earbonates, establishing the pH of the reaetion system at a value of 2 or less and therear,er malntaining the pH of the reaction system at a value of 2 or less throughout the re~ainder of the reaction.
In another aspect, this invention co~prises a process for the product-on of 1,3-dichloroacetone oxi~e acetate com-prlsinga) producing 1,3-dichloroacetone oxi~e by: reacting 1,3-dichloropropanone with a hydroxyla~ine salt, in the presenee of a base selected from the group eonsisting of tertiary amines, lower alkyl amides, al~ali metal biearbonates, alkali metal earbonates and alkaline earth metal earbonates, establishing the pH of the reaetion system at a value of 2 or less and thereafter maintaining the pH of the reaction system at a value of 2 or less throughout the remainder of the reaction; and b) reacting the 1,3-dichloroacetone oxime from step (a) ~ith acetic anh7drlde.
~ J~7 Detailed Description of the Invention In producing an oxi~e by reaction of a l;etone with a hydroxylamine salt, it has hitherto been considered that the preferred p~. of the system should be between about 4 and 5.
See, for instance, Sid~wick, The Or~anic Chemistry of Nitro~en, Clarendon Press (Oxford)~ 1945, P. 170. Operation at lower pH
was felt to result in hydrolysis of the oxime. However~ we have now found that~ at least for the production of dichloro-acetone oxi~e, optimum and ~uite ur.expected results are obtained by establi.ching the reaction svstem in a highly acidic condition, -3a-.~
1~1Z~ 7 at a pH of 2 or less, and then maintaining the reaction system at a pH of 2 or less throughout the remainder of the reaction.
Operation of the reaction at pX values higher than 2 for the entire reaction time generally results in the formation of a gum or slime.
The hydroxylamine salt may be any of those commonly employed such as hydroxylamine hydrochloride and hydroxylamine sulfate.
In the present process, as well as those heretofore used, it is preferred to conduct the reaction in the presence of an added base. If a sufficient excess of hydroxylamine salt is utilized, this can serve as the base; however, such a practice represents an unnecessary waste of comparatively expensive mate-rials. In general, any suitable base can be used provided it can be readily dispersed throughout the reaction medium without forming undesirable high localized pH values. The alkali metal carbonates and bicarbonates and alkaline earth metal carbonates, particularly calcium carbonate, are the preferred bases for this process. Other members of these groups such as sodium, magnesium, barium, strontium carbonates and sodium and potassium bicarbonates are also suitable. Tertiary amines such as triethylamine, pyridine, substituted pyridines such as the lutidines and dimethylaniline, may also be used Lower alkyl amides such as acetamide, formamide and di-methylformamide are also suitable bases for this reaction. ~owever, these are less preferable because although the oxime product can be produced in good yield, it may contain unreacted 1,3-dichloro-propanone in a sufficient amount to create problems because of its irritant properites. T'nis compound therefore, must be removed from the oxime product, thereby requiring additional purification steps and equipment.
In general, strong bases such as sodium and potassium hydroxides are not desirable for use in this process as their addition may cause the formation of localized pH values above 2.
The pH may be established at a value of 2 or less by any of several expedients, and may be done by active or passive measures. In general, the pH of the starting reaction mixture of 1,3-dichloropropanone and hydroxylamine salt will be between about 3.7 and about 4. As the reaction proceeds, the pH will drop due to the formation of hydrogen ions as the hydroxylamine salt reacts. Thus, in one embodiment of the process, 1,3-dichloropropanone and the hydroxylamine salt are caused to react and, when the pH drops to below about 2 (generally within 15 - 45 minutes), addition of the base is commenced. Thereafter, the pH of the reaction mixture is monitored and addition of the base is controlled to maintain the pH at a value no higher than 2 The overall reaction time is generally about 2 - 4 hours and it is not detrimental to the conduct of the process for the pH of the system to be above 2 for the first 15 - 45 minutes or so .
In some cases, as was the case in Example 2 which follows, the pH of the initial reaction system may actually be less than about 3.7-4 This is believed to be caused by acidic impurities in the reactants or solvents used in the process, most likely in the hydroxylamine salt. In such a case, the base may be added earlier in the course of the reaction, with pH monitoring and controlled addition of base as above.
An alternate method of operation is to add part of the base at the commencement of the reaction. In such case, there is also added at that time a sufficient quantity of a mineral acid such as hydrochloric, sulfuric, phosphoric or nitric acid to bring the pH o~ the reaction system down to an initial value of 2 or less. The remainder of the base is subsequently added with pH monitoring and controlled addition to maintain the p~
at a value of 2 or less.
In a preferred embodiment, the oxime production step is conducted in the presence of an inert organic solvent, such as benzene, toluene, xylene, chlorinated hydrocarbons such as chloroform, methylene chloride, perchloroethylene, 1,2-dichloro-ethane and others.
L0 In general, the oxime production step is conducted at temperatures of between about 5C and about 85C, depending on the base and solvent, if used. When using a tertiary amine, lower temperatures are preferred, preferably between about 5C
and about 40C, most preferably between about 15C and about 25C. When using an alkaline earth metal carbonate or alkali metal carbonate, the reaction proceeds best at a temperature of between about 35C and about 45C, though higher temperatures up to about 85C may be utilized, depending on the boiling point of the solvent.
The reaction of the 1,3-dichloroacetone oxime with acetic anhydride is conducted in the presence of an inert sol-vent such as those previously mentioned. Small amounts of water may be tolerated so long as a separate a~ueous phase is not formed, as the reaction will not proceed to completion in a two-phase system. This step is conducted at a temperature of between about 5C and about 40C. For a complete reaction, acetic anhydride should be used in a slight excess such as about 1.4-1.5 moles per mole of oxime. A smaller excess can be utilized ir the organic solution of the oxime is dried prior to _~, _ ~ u~
its use in the acetate production step.
The oxime may be separated ;~ m the reaction mixture before reacting with acetic anhydride. However, in a preferred embodiment, both the oxime production and acetate production reactions are carried out in the presence of the same inert solvent, Since the oxime will be contained in the organic layer from the first reaction, it may be utilized for the next as a solution of oxime in the solvent. Separation of the or-ganic phase of the Gxime production step from the a~ueous phase should be done careul~y to preclude introduction OL an undesi-rable amount of water into the acetate formation system.
The oxime may undergo decomposition if it isallowed to reach a pH of above about 3 or to stand for long periods of time.
In ~ further embodiment the 1,3-dichloropropanone can be prepared by oxidation of 1,3-dichloropropanol with an oxidizing agent such as sodium dichromate and concentrated sulfuric acid. The 1,3-dichloropropanone can be recovered from the reaction products by extraction with toluene or another suitable solvent and the solution of this compound can be used as one of the starting materials for the oxime production re-action without separation of the l~etone. In all steps o~ the process removal of solvent from a reaction product by evapo-ration should be performed carefully as all the desired pro-ducts are guite volatile and substantial amounts ~ay be carried off with the solJents, The ollowing Examples are presented as illustrative of the invention; however~ the invention may comprise conditions and/or variations of the processes not mentioned or outside the ran~es of the Examples; thererore, the invention is not t ~Z~7 intended to be limited thereby, but only by the claims which ollow.
~xample 1 Into a 12-liter flask was introduced 2.5 kg (8.8 mole) sodium dichromate dihydrate and 1 liter of water. The mixture was stirred to dissolve the salt. There was then added 1.94 lcg (15.0 mole) of 1,3-d-chloro-2-propanol, followed by 2.95 kg (30 mole) of concentrated sulfuric acid dissolved in 0.75 liter of water. The reaction temperature was main-tained at about 20 during the course of the reaction and stirring was continued at a moderate rate. Caution was taken as the addition of sulfurlc acid to this mixture is quite exo-thermic. A~ the end of the reaction, the reaction mixture was viscous and blaclc.
3.3 liters of water and 5.2 liters of toluene were then added to the reaction mixture and the resulting mixture was phase separated. The lower aqueous layer was back extrac~ed with toluene and the combined toluene solutions washed with a small amount of water. The yield of 1,3-dichloropropanone was about 93%.
Into a 12-liter flask was placed the 1,3-dichloro-propanone solution in toluene prepared in the previous step, 1.43 kg (8.7 ~ole) of hydroxylamine sulfate, (HONH2)2 . H2S04, dissolved in 3 liters of water, and 48 ml of concentrated hydrochloric acid. There was then slowly added while stirring, 1.19 kg (15 mole) pyridine with pH monitoring. The reaction temperature was maintained at 20-25C. The pH was maintained at a value of below 2 throughout the addition of the base.
~?Z~17 The addition was completed in about 2-2.5 hours and the re-action was stirred for 0.5 hours after that time. Gas chromato-graphic analysis showed that the ketone was completely con-verted to the corresponding oxime. The reaction products were phase separated, with the oxime being contained in the toluene layer.
The toluene-oxime solution from the previous step was introduced to a 12-liter flask and there was slowly added to it 2.2 l~g (21.6 moLes) of acetic anhyd-ride. The reaction mixture was maintained at about 20C. Addition of the anhydride was complete in about 2 hours. After the reaction had been com-pleted 0.5 liters of water were added, the solution was stirred and then phase separated. The toluene layer was washed with saturated sodium bicarbonate solution, dried over magnesium sulfate, filtered and evaporated. The liquid was concentra.ed in vacuo for 1.5 to 2 hours at about 50C. There was obtained 2,041 g of 1,3-dichloroacetone oxime acetate, b.p. 80-82C at 4mm Hg pressure. The purity was 95 wt. %; the yield was 74%
based on starting 1,3-dichloro-2-propanol and on the intermediate ketone.
Example 2 Into a 300 ml flask were introduced a solution of 12.7 g (0.10 ~ole) 1,3-dichloro-2-propanone in 29.5 ml 1,2-dichloroethane and a solution of 9.5 g (0.058 mole) hydroxyl-amine sulfate in 20 ml water. The flask was placed in a water bath maintained at 40C. The initial pH was about. 1.5, pre-sumably due to acidic impurities in a reagent or the dichloro-ethane. A.ter 60 minutes the p~. had decreased to a negative value. There was added 2.50 g (0.025 mole) calcium carbonate with another 2.50 g af~er 30 additional minutes. The pX then LU ht,~
increased to a~out 1.5. The reaction proceeded for a total of 195 minutes, at which point the p~ was about 0.8. rne reaction product was cooled, filtered and phase separated.
The organic phase was placed in a 100 ml flask, to which was added 14.7 g (0.144 mole) acetic anhydride. Temperature was maintained at 40C. The reaction was 96% complete after 180 mlnutes: the mixture was then allowed to cool and stand. The resulting solution was stripped under vacuum at 50C. There was obtained 16.8 g of a light yellow liquid which contained 95.2 weight % (91.3% of theoretical yield) 1,3-dichloroacetone oxime acetate, and 1.3% 1,3-dichloro-2-propanone.
Example 3 The oxime was prepared by the process of Example 2 and was isolated. The yield of oxime was 98%; the purity 85-9%.
Example 4 The oxime was prepared as in Example 2, with the reaction temperature being maintained at 22C. The oxime was obtained in 80% yield and 85.1% purity.
Example 5 The oxime was prepared as in Example 2 but using only one addition of 2.50 g (0.025 mole) calcium carbonate (about 0.5 mole equivalents per mole-equivalent of hydroxylamine sulfate).
The yield of oxime was 73%; the purity 74.1%.
_xample 6 The oxime was prepared as in Example 2 but a total of 7.50 g (0.075 mole) calcium carbonate was added (about 1.5 mole-equivalents per mole-equivalent of hydroxylamine sulfate).
The yield of oxime was 74%; the purity was 79.4%.
Into a 12-liter flask was placed the 1,3-dichloro-propanone solution in toluene prepared in the previous step, 1.43 kg (8.7 ~ole) of hydroxylamine sulfate, (HONH2)2 . H2S04, dissolved in 3 liters of water, and 48 ml of concentrated hydrochloric acid. There was then slowly added while stirring, 1.19 kg (15 mole) pyridine with pH monitoring. The reaction temperature was maintained at 20-25C. The pH was maintained at a value of below 2 throughout the addition of the base.
~?Z~17 The addition was completed in about 2-2.5 hours and the re-action was stirred for 0.5 hours after that time. Gas chromato-graphic analysis showed that the ketone was completely con-verted to the corresponding oxime. The reaction products were phase separated, with the oxime being contained in the toluene layer.
The toluene-oxime solution from the previous step was introduced to a 12-liter flask and there was slowly added to it 2.2 l~g (21.6 moLes) of acetic anhyd-ride. The reaction mixture was maintained at about 20C. Addition of the anhydride was complete in about 2 hours. After the reaction had been com-pleted 0.5 liters of water were added, the solution was stirred and then phase separated. The toluene layer was washed with saturated sodium bicarbonate solution, dried over magnesium sulfate, filtered and evaporated. The liquid was concentra.ed in vacuo for 1.5 to 2 hours at about 50C. There was obtained 2,041 g of 1,3-dichloroacetone oxime acetate, b.p. 80-82C at 4mm Hg pressure. The purity was 95 wt. %; the yield was 74%
based on starting 1,3-dichloro-2-propanol and on the intermediate ketone.
Example 2 Into a 300 ml flask were introduced a solution of 12.7 g (0.10 ~ole) 1,3-dichloro-2-propanone in 29.5 ml 1,2-dichloroethane and a solution of 9.5 g (0.058 mole) hydroxyl-amine sulfate in 20 ml water. The flask was placed in a water bath maintained at 40C. The initial pH was about. 1.5, pre-sumably due to acidic impurities in a reagent or the dichloro-ethane. A.ter 60 minutes the p~. had decreased to a negative value. There was added 2.50 g (0.025 mole) calcium carbonate with another 2.50 g af~er 30 additional minutes. The pX then LU ht,~
increased to a~out 1.5. The reaction proceeded for a total of 195 minutes, at which point the p~ was about 0.8. rne reaction product was cooled, filtered and phase separated.
The organic phase was placed in a 100 ml flask, to which was added 14.7 g (0.144 mole) acetic anhydride. Temperature was maintained at 40C. The reaction was 96% complete after 180 mlnutes: the mixture was then allowed to cool and stand. The resulting solution was stripped under vacuum at 50C. There was obtained 16.8 g of a light yellow liquid which contained 95.2 weight % (91.3% of theoretical yield) 1,3-dichloroacetone oxime acetate, and 1.3% 1,3-dichloro-2-propanone.
Example 3 The oxime was prepared by the process of Example 2 and was isolated. The yield of oxime was 98%; the purity 85-9%.
Example 4 The oxime was prepared as in Example 2, with the reaction temperature being maintained at 22C. The oxime was obtained in 80% yield and 85.1% purity.
Example 5 The oxime was prepared as in Example 2 but using only one addition of 2.50 g (0.025 mole) calcium carbonate (about 0.5 mole equivalents per mole-equivalent of hydroxylamine sulfate).
The yield of oxime was 73%; the purity 74.1%.
_xample 6 The oxime was prepared as in Example 2 but a total of 7.50 g (0.075 mole) calcium carbonate was added (about 1.5 mole-equivalents per mole-equivalent of hydroxylamine sulfate).
The yield of oxime was 74%; the purity was 79.4%.
Claims (23)
1. A process for the production of 1,3-dichloroacetone oxime comprising reacting 1,3-dichloropropanone with a hydrolyl-amine salt in the presence of a base selected from the group consisting of tertiary amines, lower alkyl amides, alkali metal bicarbonates, alkali metal carbonates, and alkaline earth metal carbonates, establishing the pH of the reaction system at a value of 2 or less and thereafter maintaining the pH of the reaction system at a value of 2 or less throughout the remainder of the reaction.
2. A process according to Claim 1 in which the base is pyridine.
3. A process according to Claim 1 in which the base is sodium carbonate.
4. A process according to Claim 1 in which the base is an alkaline earth metal carbonate.
5. A process accroding to Claim 4 in which the base is calcium carbonate.
6. A process according to Claim 1 in which the base is an alkali metal bicarbonate.
7. A process according to Claim 1 in which the base is added to the reaction system at a time subsequent to the com-mencement of the reaction and at which the pH of the reaction system is at a value of 2 or less, and the addition of the base is controlled so as to thereafter maintain the pH of the reaction system at a value of 2 or less.
8. A process according to Claim l in which a portion of the base is added to the reaction system at the commencement of the reaction and the remainder is subsequently added in a controlled fashion so as to maintain the pH of the reaction system at a value of 2 or less, and further comprising simultaneously adding a suf-ficient quantity of a mineral acid to maintain the pH of the re-action system at a value of 2 or less.
9. A process according to Claim 1 in which the tem-perature is between about 5°C and about 85°C.
10. A process according to Claim 1 in which the reaction is carried out in the presence of an inert organic solvent.
11. A process according to Claim 10 in which the solvent is toluene.
12. A process for the production of 1,3-dichloroacetone oxime acetate comprising:
a) producing dichloroacetone oxime by a process comprising: reacting 1,3-dichloropropanone with a hydroxylamine salt in the presence of a base selected from the group consisting of tertiary amines, lower alkyl amides, alkali metal bicarbonates, alkali metal carbonates, and alkaline earth metal carbonates, establishing the pH of the reaction system at a value of 2 or less and thereafter maintaining the pH of the reaction system at a value of 2 or less throughout the remainder of the reaction; and b) reacting the 1,3-dichloroacetone oxime from step (a) with acetic anhydride.
a) producing dichloroacetone oxime by a process comprising: reacting 1,3-dichloropropanone with a hydroxylamine salt in the presence of a base selected from the group consisting of tertiary amines, lower alkyl amides, alkali metal bicarbonates, alkali metal carbonates, and alkaline earth metal carbonates, establishing the pH of the reaction system at a value of 2 or less and thereafter maintaining the pH of the reaction system at a value of 2 or less throughout the remainder of the reaction; and b) reacting the 1,3-dichloroacetone oxime from step (a) with acetic anhydride.
13. A process according to Claim 12 in which the base is pyridine.
14. A process according to Claim 12 in which the base is sodium carbonate.
15. A process according to Claim 12 in which the base is an alkaline earth metal carbonate.
16. A process according to Claim 15 in which the base is calcium carbonate.
17. A process according to Claim 12 in which the base is an alkali metal bicarbonate.
18. A process according to Claim 12 in which the base is added to the reaction system at a time subsequent to the commencement of the reaction and at which the pH of the reaction system is at a value of 2 or less, and the addition of the base is controlled so as to thereafter maintain the pH of the system at a value of 2 or less.
19. A process according to claim 12 in which at least a portion of the base is added to the reaction system at the commencement of the reaction and the remainder is subsequently added in a controlled manner so as to maintain the pH of the sys-tem at a value of 2 or less, and further comprising simultaneously adding a sufficient quantity of a mineral acid to maintain the pH of the reaction system at a value of 2 or less.
20. A process according to Claim 12 in which the acetic anhydride is utilized in step (b) in an excess with res-pect to the oxime.
21. A process according to Claim 12 in which steps (a) and (b) are conducted in the presence of an inert organic solvent.
22. A process according to Claim 21 in which the sol-vent is toluene.
23. A process according to Claim 21 in which the oxime is introduced into step (b) as a solution of oxime in an organic solvent obtained from step (a).
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US65379776A | 1976-01-30 | 1976-01-30 | |
| US653,797 | 1976-01-30 | ||
| US05/751,491 US4128580A (en) | 1976-01-30 | 1976-12-21 | Process for the production of 1,3-dichloroacetone oxime and its acetate derivative |
| US751,491 | 1991-08-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1102817A true CA1102817A (en) | 1981-06-09 |
Family
ID=27096594
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA270,498A Expired CA1102817A (en) | 1976-01-30 | 1977-01-26 | Process for the production of 1,3-dichloroacetone oxime and its acetate derivatives |
Country Status (17)
| Country | Link |
|---|---|
| JP (1) | JPS52113910A (en) |
| AT (1) | AT354411B (en) |
| AU (1) | AU505546B2 (en) |
| CA (1) | CA1102817A (en) |
| CH (1) | CH623302A5 (en) |
| DD (1) | DD130783A5 (en) |
| DE (1) | DE2703370A1 (en) |
| DK (1) | DK32677A (en) |
| ES (1) | ES455423A1 (en) |
| FI (1) | FI770196A (en) |
| FR (1) | FR2339592A1 (en) |
| GB (1) | GB1525682A (en) |
| IL (1) | IL51353A (en) |
| IT (1) | IT1079462B (en) |
| NL (1) | NL7700914A (en) |
| NO (1) | NO143941C (en) |
| SE (1) | SE7700863L (en) |
-
1977
- 1977-01-21 FI FI770196A patent/FI770196A/fi not_active Application Discontinuation
- 1977-01-24 JP JP597677A patent/JPS52113910A/en active Pending
- 1977-01-25 AT AT43377A patent/AT354411B/en not_active IP Right Cessation
- 1977-01-26 CH CH94377A patent/CH623302A5/en not_active IP Right Cessation
- 1977-01-26 DK DK32677A patent/DK32677A/en not_active Application Discontinuation
- 1977-01-26 FR FR7702113A patent/FR2339592A1/en active Granted
- 1977-01-26 CA CA270,498A patent/CA1102817A/en not_active Expired
- 1977-01-27 GB GB3341/77A patent/GB1525682A/en not_active Expired
- 1977-01-27 SE SE7700863A patent/SE7700863L/en unknown
- 1977-01-27 DE DE19772703370 patent/DE2703370A1/en not_active Withdrawn
- 1977-01-28 NO NO770280A patent/NO143941C/en unknown
- 1977-01-28 IT IT47838/77A patent/IT1079462B/en active
- 1977-01-28 NL NL7700914A patent/NL7700914A/en not_active Application Discontinuation
- 1977-01-28 AU AU21761/77A patent/AU505546B2/en not_active Expired
- 1977-01-28 ES ES455423A patent/ES455423A1/en not_active Expired
- 1977-01-28 DD DD7700197144A patent/DD130783A5/en unknown
- 1977-01-28 IL IL51353A patent/IL51353A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| NL7700914A (en) | 1977-08-02 |
| ES455423A1 (en) | 1978-05-01 |
| DK32677A (en) | 1977-07-31 |
| NO770280L (en) | 1977-08-02 |
| DE2703370A1 (en) | 1977-08-04 |
| NO143941C (en) | 1981-05-13 |
| AT354411B (en) | 1979-01-10 |
| FI770196A (en) | 1977-07-31 |
| CH623302A5 (en) | 1981-05-29 |
| GB1525682A (en) | 1978-09-20 |
| FR2339592B1 (en) | 1980-08-29 |
| AU505546B2 (en) | 1979-11-22 |
| SE7700863L (en) | 1977-07-31 |
| ATA43377A (en) | 1979-06-15 |
| JPS52113910A (en) | 1977-09-24 |
| FR2339592A1 (en) | 1977-08-26 |
| IL51353A (en) | 1980-06-30 |
| IT1079462B (en) | 1985-05-13 |
| NO143941B (en) | 1981-02-02 |
| IL51353A0 (en) | 1977-03-31 |
| AU2176177A (en) | 1978-08-03 |
| DD130783A5 (en) | 1978-05-03 |
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