NO143941B - PROCEDURE FOR PREPARING 1,3-DICHLOR-ACETON-OXIM - Google Patents
PROCEDURE FOR PREPARING 1,3-DICHLOR-ACETON-OXIM Download PDFInfo
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- NO143941B NO143941B NO770280A NO770280A NO143941B NO 143941 B NO143941 B NO 143941B NO 770280 A NO770280 A NO 770280A NO 770280 A NO770280 A NO 770280A NO 143941 B NO143941 B NO 143941B
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- Prior art keywords
- reaction
- oxime
- value
- reaction system
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- 238000000034 method Methods 0.000 title claims description 20
- YWXYBQXZYIIPSM-UHFFFAOYSA-N n-(1,3-dichloropropan-2-ylidene)hydroxylamine Chemical compound ON=C(CCl)CCl YWXYBQXZYIIPSM-UHFFFAOYSA-N 0.000 title claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 38
- SUNMBRGCANLOEG-UHFFFAOYSA-N 1,3-dichloroacetone Chemical compound ClCC(=O)CCl SUNMBRGCANLOEG-UHFFFAOYSA-N 0.000 claims description 22
- 239000002585 base Substances 0.000 claims description 19
- -1 alkyl amides Chemical class 0.000 claims description 10
- 150000002443 hydroxylamines Chemical class 0.000 claims description 9
- 230000007306 turnover Effects 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 150000003512 tertiary amines Chemical class 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 3
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 150000002923 oximes Chemical class 0.000 description 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- MQRDNTHUNXTMLF-UHFFFAOYSA-N acetic acid;n-(1,3-dichloropropan-2-ylidene)hydroxylamine Chemical compound CC(O)=O.ON=C(CCl)CCl MQRDNTHUNXTMLF-UHFFFAOYSA-N 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- ZNBNBTIDJSKEAM-UHFFFAOYSA-N 4-[7-hydroxy-2-[5-[5-[6-hydroxy-6-(hydroxymethyl)-3,5-dimethyloxan-2-yl]-3-methyloxolan-2-yl]-5-methyloxolan-2-yl]-2,8-dimethyl-1,10-dioxaspiro[4.5]decan-9-yl]-2-methyl-3-propanoyloxypentanoic acid Chemical compound C1C(O)C(C)C(C(C)C(OC(=O)CC)C(C)C(O)=O)OC11OC(C)(C2OC(C)(CC2)C2C(CC(O2)C2C(CC(C)C(O)(CO)O2)C)C)CC1 ZNBNBTIDJSKEAM-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- 229940051269 1,3-dichloro-2-propanol Drugs 0.000 description 2
- DEWLEGDTCGBNGU-UHFFFAOYSA-N 1,3-dichloropropan-2-ol Chemical compound ClCC(O)CCl DEWLEGDTCGBNGU-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- IFDLXKQSUOWIBO-UHFFFAOYSA-N 1,3-dichloropropan-1-ol Chemical compound OC(Cl)CCCl IFDLXKQSUOWIBO-UHFFFAOYSA-N 0.000 description 1
- YHRUOJUYPBUZOS-UHFFFAOYSA-N 1,3-dichloropropane Chemical compound ClCCCCl YHRUOJUYPBUZOS-UHFFFAOYSA-N 0.000 description 1
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical class CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 1
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical class [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- HFTNNOZFRQLFQB-UHFFFAOYSA-N ethenoxy(trimethyl)silane Chemical compound C[Si](C)(C)OC=C HFTNNOZFRQLFQB-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- NXPHCVPFHOVZBC-UHFFFAOYSA-N hydroxylamine;sulfuric acid Chemical compound ON.OS(O)(=O)=O NXPHCVPFHOVZBC-UHFFFAOYSA-N 0.000 description 1
- 230000000622 irritating effect Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- MENKEXRMFOBKST-UHFFFAOYSA-N n-(1,1-dichloropropan-2-ylidene)hydroxylamine Chemical compound ON=C(C)C(Cl)Cl MENKEXRMFOBKST-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical class [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical class [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 229940066528 trichloroacetate Drugs 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
Denne oppfinnelse vedrører en forbedret fremgangsmåte for fremstilling av 1,3-dikloraceton-oksim. This invention relates to an improved process for the production of 1,3-dichloroacetone oxime.
1,3-dikloraceton-oksim er, som belyst i US-patentskrift nr. 3.733.419 til Arnold D. Gutman, et mellomprodukt for fremstilling av en rekke forbindelser som er nyttige til å regulere sopper og bakterier. Blant disse forbindelser er 1,3-dikloraceton-oksim-acetat (forbindelse 5 i nevnte patentskrift). 1,3-Dichloroacetone oxime is, as disclosed in US Patent No. 3,733,419 to Arnold D. Gutman, an intermediate for the preparation of a variety of compounds useful in controlling fungi and bacteria. Among these compounds is 1,3-dichloroacetone-oxime-acetate (compound 5 in the aforementioned patent document).
I henhold til dette patentskrift ble oksimet fremstilt ved omsetning av 1,3-diklorpropanon med hydroksylamin-hydroklorid i nærvær av etanol og vann. Man fikk oksimet fra reaksjonsproduktene ved ekstraksjon med kloroform. According to this patent, the oxime was prepared by reacting 1,3-dichloropropanone with hydroxylamine hydrochloride in the presence of ethanol and water. The oxime was obtained from the reaction products by extraction with chloroform.
Eksempler på omdannelse av oksimet til dets derivater, f.eks. trikloracetatet og krotonatet, viser at omsetningen ble utført mellom oksimet og et acylklorid i nærvær av benzen, og produktet ble utvunnet fra benzen-fasen. -Når imidlertid fremgangsmåter av denne type ble benyttet for fremstilling av 1,3-dikloraceton-oksim-acetat, ble produktet svart enten under utvinningen eller ved efterfølgende hensettelse. Examples of conversion of the oxime to its derivatives, e.g. the trichloroacetate and the crotonate, show that the reaction was carried out between the oxime and an acyl chloride in the presence of benzene, and the product was recovered from the benzene phase. - However, when methods of this type were used for the production of 1,3-dichloroacetone-oxime-acetate, the product turned black either during recovery or during subsequent storage.
Det er et formål med foreliggende oppfinnelse å til-veiebringe en forbedret fremgangsmåte for fremstilling av 1,3-dikloraceton-oksim. It is an object of the present invention to provide an improved process for the production of 1,3-dichloroacetone oxime.
I henhold til oppfinnelsen tilveiebringes en fremgangsmåte for fremstilling av 1,3-dikloraceton-oksim ved å omsette 1,3-diklorpropanon med et hydroksylaminsalt, ved en temperatur mellom 5 og 85°C og i nærvær av et inert organisk oppløsnings-middel. Fremgangsmåten karakteriseres ved at omsetningen utføres i nærvær av en base valgt fra gruppen bestående av tertiære aminer, lavere alkylamider, alkalimetallbikarbonater, alkalimetal1-karbonater og jordalkalimetallkarbonater, slik at det opprettes en pH i reaksjonssystemet på 2 eller lavere, og derefter opprettholdes pH i reaksjonssystemet ved en verdi på 2 eller lavere gjennom resten av omsetningen. According to the invention, a method for the production of 1,3-dichloroacetone oxime is provided by reacting 1,3-dichloropropanone with a hydroxylamine salt, at a temperature between 5 and 85°C and in the presence of an inert organic solvent. The process is characterized in that the reaction is carried out in the presence of a base selected from the group consisting of tertiary amines, lower alkyl amides, alkali metal bicarbonates, alkali metal 1 carbonates and alkaline earth metal carbonates, so that a pH in the reaction system of 2 or lower is established, and then the pH in the reaction system is maintained by a value of 2 or lower throughout the rest of the turnover.
Hvis man ønsker å fremstille 1,3-dikloraceton-oksim-acetat, kan dette gjøres ved at 1,3-dikloraceton-oksimet fremstilt ifølge oppfinnelsen, omsettes med eddiksyreanhydrid. If one wishes to prepare 1,3-dichloroacetone oxime acetate, this can be done by reacting the 1,3-dichloroacetone oxime prepared according to the invention with acetic anhydride.
Ved fremstilling av et oksim ved omsetning mellom et keton og et hydroksylaminsalt har man hittil antatt at den foretrukne pH-verdi i systemet bør være mellom 4 og 5. Se f.eks. When producing an oxime by reaction between a ketone and a hydroxylamine salt, it has so far been assumed that the preferred pH value in the system should be between 4 and 5. See e.g.
Sidgwick, The Organic Chemistry of Nitrogen, Clarendon Press (Oxford), 1945, s. 170. Utførelse ved lavere pH-verdier kom til Sidgwick, The Organic Chemistry of Nitrogen, Clarendon Press (Oxford), 1945, p. 170. Execution at lower pH values came to
å resultere i hydrolyse av oksimet. Vi har imidlertid nå to result in hydrolysis of the oxime. However, we have now
funnet at det i det minste for fremstillingen av dikloraceton-oksim, erholdes optimale og ganske uventede resultater ved å opprette en sterkt sur tilstand i reaksjonssystemet, ved en pH-verdi på 2 eller lavere, og så opprettholde pH-verdien ved 2 eller lavere i reaksjonssystemet gjennom resten av omsetningen. found that, at least for the preparation of dichloroacetone oxime, optimal and rather unexpected results are obtained by creating a strongly acidic condition in the reaction system, at a pH value of 2 or lower, and then maintaining the pH value at 2 or lower in the reaction system through the rest of the turnover.
Utførelse av omsetningen ved pH-verdier høyere enn 2 under hele reaksjonstiden resulterer vanligvis i dannelse av en gummi eller et slam. Carrying out the reaction at pH values higher than 2 during the entire reaction time usually results in the formation of a gum or a sludge.
Hydroksylaminsaltet kan være hvilket som helst av slike som vanligvis blir benyttet, så som hydroksylamin-hydroklorid og hydroksylamin-sulfat. The hydroxylamine salt can be any of those commonly used, such as hydroxylamine hydrochloride and hydroxylamine sulfate.
Ved foreliggende fremgangsmåte, og også for de fremgangsmåter som hittil er anvendt, foretrekkes det å utføre omsetningen i nærvær av en tilsatt base. Dersom det benyttes et tilstrekkelig overskudd med hydroksylaminsalt, kan dette tjene som base. En slik praksis medfører imidlertid et unød-vendig tap av forholdsvis dyre materialer. Vanligvis kan man anvende hvilken som helst egnet base, forutsatt at den lett kan dispergeres gjennom hele reaksjonsmediet uten å danne uønskede høye lokale pH-verdier. Alkalimetallkarbonatene og -bikarbonatene og jordalkalimetallkarbonatene, spesielt kalsiumkarbonat, er de foretrukne baser for denne fremgangsmåte. Andre medlemmer av denne gruppe, så som natrium-, magnesium-, barium- og strontium-karbonater og natrium- og kalium-bikarbonater, er også egnet. Tertiære aminer så som trietylamin, pyridin, substituerte pyridiner så som lutidinene og dimetylanilin, kan også anvendes. In the present method, and also for the methods used so far, it is preferred to carry out the reaction in the presence of an added base. If a sufficient excess of hydroxylamine salt is used, this can serve as a base. However, such a practice entails an unnecessary loss of relatively expensive materials. In general, any suitable base can be used, provided that it can be readily dispersed throughout the reaction medium without forming undesirably high local pH values. The alkali metal carbonates and bicarbonates and the alkaline earth metal carbonates, especially calcium carbonate, are the preferred bases for this process. Other members of this group, such as sodium, magnesium, barium and strontium carbonates and sodium and potassium bicarbonates, are also suitable. Tertiary amines such as triethylamine, pyridine, substituted pyridines such as the lutidines and dimethylaniline can also be used.
Lavere alkylamider så som acetamid, formamid og di-metylformamid er også egnede baser for denne omsetning. Disse er imidlertid mindre foretrukket på grunn av at selv om oksim-produktet kan dannes med godt utbytte, så kan det inneholde uomsatt 1,3-diklorpropan i en tilstrekkelig mengde til at det skapes problemer på grunn av dets irriterende egenskaper. Denne forbindelse må derfor fjernes fra oksim-produktet, og til dette er det nødvendig med ytterligere rensetrinn og utstyr. Lower alkyl amides such as acetamide, formamide and dimethylformamide are also suitable bases for this reaction. However, these are less preferred because, although the oxime product can be formed in good yield, it may contain unreacted 1,3-dichloropropane in sufficient quantity to cause problems due to its irritating properties. This compound must therefore be removed from the oxime product, and for this further purification steps and equipment are required.
Vanligvis er det ikkeønskelig å anvende sterke baser Generally, it is undesirable to use strong bases
så som natrium- og kaliutn-hydroksyder ved denne fremgangsmåte, such as sodium and potassium hydroxides in this process,
da tilsetning av slike kan forårsake dannelse av lokale pH- as the addition of such can cause the formation of local pH-
verdier over 2. values above 2.
pH kan opprettes ved en verdi på 2 eller lavere ved hvilke som helst av flere midler, og dette kan gjøres ved aktive eller passive forføyninger. Vanligvis vil pH-verdien i utgangs-reaksjonsblandingen av 1,3-diklorpropanon og hydroksylaminsalt ligge mellom 3,7 og 4. Eftersom omsetningen skrider frem vil pH-verdien falle på grunn av dannelse av hydrogenioner når hydroksylaminsaltet omsettes. Ved en utførelse av fremgangsmåten blir således 1,3-diklorpropanon og hydroksylaminsaltet bragt til å omsettes, og når pH-verdien er falt til under ca. 2 (vanligvis i løpet av 15-45 minutter), begynner tilsetningen av basen. Derefter måles pH-verdien i reaksjonsblandingen og tilsetningen av base reguleres slik at pH opprettholdes ved en verdi som ikke er høyere enn 2. Den samlede reaksjonstid er vanligvis ca. The pH can be established at a value of 2 or lower by any of several means, and this can be done by active or passive injunctions. Generally, the pH value in the starting reaction mixture of 1,3-dichloropropanone and hydroxylamine salt will lie between 3.7 and 4. As the reaction progresses, the pH value will fall due to the formation of hydrogen ions when the hydroxylamine salt is reacted. In one embodiment of the method, 1,3-dichloropropanone and the hydroxylamine salt are thus brought to react, and when the pH value has fallen below approx. 2 (usually within 15-45 minutes), the addition of the base begins. The pH value in the reaction mixture is then measured and the addition of base is regulated so that the pH is maintained at a value that is not higher than 2. The overall reaction time is usually approx.
2-4 timer, og det er ikke skadelig å utføre fremgangsmåten slik at pH-verdien i systemet er over 2 de første 15-45 minutter. 2-4 hours, and it is not harmful to carry out the procedure so that the pH value in the system is above 2 for the first 15-45 minutes.
I noen tilfeller, så som i eksempel 2 som følger, kan In some cases, such as in example 2 below, can
i virkeligheten pH-verdien i det opprinnelige reaksjonssystem være lavere enn ca. 3,7-4. Dette antas å være forårsaket av sure forurensninger i reaktanter eller løsningsmidler som anvendes ved fremgangsmåten, og da mest sannsynlig i hydroksylaminsaltet. I et slikt tilfelle kan basen tilsettes tidligere under reaksjonsforløpet, idet pH måles og tilsetningen av base reguleres som ovenfor. in reality the pH value in the original reaction system be lower than approx. 3.7-4. This is believed to be caused by acidic impurities in reactants or solvents used in the process, and then most likely in the hydroxylamine salt. In such a case, the base can be added earlier during the course of the reaction, the pH being measured and the addition of base regulated as above.
En alternativ metode er å tilsette en del av basen ved begynnelsen av omsetningen. I et slikt tilfelle blir det også samtidig tilsatt en tilstrekkelig mengde av mineralsyre, så som saltsyre, svovelsyre, fosforsyre eller salpetersyre, til å An alternative method is to add part of the base at the beginning of the turnover. In such a case, a sufficient amount of mineral acid, such as hydrochloric acid, sulfuric acid, phosphoric acid or nitric acid, is also added at the same time to
bringe pH-verdien i reaksjonssystemet ned til en opprinnelig verdi på 2 eller lavere. Resten av basen blir tilsatt efterpå idet pH-verdien måles og tilsetningen reguleres for å holde pH-verdien på en verdi av 2 eller lavere. bring the pH value in the reaction system down to an initial value of 2 or lower. The rest of the base is added afterwards as the pH value is measured and the addition is regulated to keep the pH value at a value of 2 or lower.
Ved en foretrukket utførelse blir oksimfremstillings-trinnet utført i nærvær av et inert organisk løsningsmiddel, så som benzen, toluen, xylen, klorerte hydrokarboner så som kloroform, metylenklorid, perkloretylen og 1,2-dikloretan. In a preferred embodiment, the oxime preparation step is carried out in the presence of an inert organic solvent, such as benzene, toluene, xylene, chlorinated hydrocarbons such as chloroform, methylene chloride, perchloroethylene and 1,2-dichloroethane.
Fremgangsmåten utføres ved temperaturer mellom 5 og 85°C, i avhengighet av basen og løsningsmidlet, om anvendt. Når det anvendes et tertiært amin, er det foretrukket med lavere tempera turer, fortrinnsvis mellom 5 og 40°C, mest foretrukket mellom 15 og 25°C. Når det anvendes et jordalkalimetallkarbonat eller alkalimetallkarbonat, foregår omsetningen best ved en temperatur på mellom 35 og 45°C, selv om det kan benyttes høyere temperaturer på opptil 85°C, i avhengighet av kokepunktet til løsnings-midlet. The process is carried out at temperatures between 5 and 85°C, depending on the base and solvent, if used. When a tertiary amine is used, lower temperatures are preferred, preferably between 5 and 40°C, most preferably between 15 and 25°C. When an alkaline earth metal carbonate or alkali metal carbonate is used, the reaction takes place best at a temperature of between 35 and 45°C, although higher temperatures of up to 85°C can be used, depending on the boiling point of the solvent.
Omsetningen av 1,3-dikloraceton-oksimet og eddiksyre-anhydridet blir utført i nærvær av et inert løsningsmiddel, så som dem som tidligere er omtalt. Det kan tolereres små mengder med vann så lenge det ikke dannes en separat vandig fase, siden omsetningen ikke vil fullføres helt i et tofase-system. Dette trinn blir utført ved en temperatur mellom 5 og 40°C. For å oppnå en fullstendig omsetning bør eddiksyreanhydrid anvendes i et lite overskudd, så som 1,4-1,5 mol pr. mol oksim. Det kan benyttes et mindre overskudd dersom den organiske løsning av oksimet er tørket før den anvendes i acetatfremstiIlingstrinnet. The reaction of the 1,3-dichloroacetone oxime and the acetic anhydride is carried out in the presence of an inert solvent, such as those previously discussed. Small amounts of water can be tolerated as long as a separate aqueous phase is not formed, since the turnover will not be completely completed in a two-phase system. This step is carried out at a temperature between 5 and 40°C. To achieve complete conversion, acetic anhydride should be used in a small excess, such as 1.4-1.5 mol per moles of oxime. A smaller excess can be used if the organic solution of the oxime is dried before it is used in the acetate production step.
Oksimet kan separeres fra reaksjonsblandingen før omsetning med eddiksyreanhydrid. Imidlertid foretrekkes at både oksimfremstillingen ifølge oppfinnelsen og acetatfremstillingen utføres i nærvær av det samme inerte løsningsmiddel. Siden oksimet vil inneholdes i det organiske skikt fra den første omsetning, kan det benyttes i den neste som en løsning av oksim i løsningsmidlet. Separering av den organiske fase ved oksim-fremstillingstrinnet fra den vandige fase bør utføres omhyggelig for å utelukke innføring av en uønsket mengde vann i acetat-fremstillingssystemet. The oxime can be separated from the reaction mixture before reaction with acetic anhydride. However, it is preferred that both the oxime production according to the invention and the acetate production 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 can be used in the next as a solution of oxime in the solvent. Separation of the organic phase in the oxime preparation step from the aqueous phase should be carried out carefully to exclude the introduction of an undesired amount of water into the acetate preparation system.
Oksimet kan bli spaltet dersom det oppnår en pH-verdi The oxime can be split if it reaches a pH value
på over ca. 3 eller hensettes i lange tidsperioder. of over approx. 3 or set aside for long periods of time.
1,3-diklorpropanonet kan fremstilles ved oksydasjon av 1,3-diklorpropanol med et oksydasjonsmiddel så som natriumdikromat og konsentrert svovelsyre. 1,3-diklorpropanonet kan utvinnes fra reaksjonsproduktene ved ekstraksjon med toluen eller et annet egnet løsningsmiddel, og løsningen av denne forbindelse kan anvendes som et av utgangsmaterialene for omsetningen ved oksimfremstillingen uten fraskilling av ketonet. I alle trinn 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 reaction in the oxime production without separation of the ketone. In all steps
av fremgangsmåten bør fjerning av løsningsmiddel fra et reaksjons-produkt ved inndampning utføres omhyggelig, siden alle deønskede produkter er ganske flyktige og vesentlige mengder kan føres bort med løsningsmidlene. of the process, removal of solvent from a reaction product by evaporation should be carried out carefully, since all the desired products are quite volatile and significant amounts can be carried away with the solvents.
De følgende eksempler er gitt for å illustrere oppfinnelsen. The following examples are given to illustrate the invention.
EK SEMPEL 1 OAK SAMPLE 1
I en kolbe på 12 liter ble det innført 2,5 kg (8,8 mol) natriumdikromat-dihydrat og 1 liter vann. Blandingen ble rørt for å oppløse saltet. Så ble det tilsatt 1,94 kg (15,0 mol) 1,3-diklor-2-propanol, fulgt av 2,95 kg (30 mol) konsentrert svovelsyre oppløst i 0,75 liter vann. Reaksjonstemperaturen ble holdt ved ca. 20°C under reaksjonsforløpet og røringen ble fort-satt med moderat hastighet. Man var forsiktig ettersom tilsetningen av svovelsyre til denne blanding er ganske eksotermisk. Ved slutten av omsetningenible reaksjonsblandingen viskøs og svart. 2.5 kg (8.8 mol) of sodium dichromate dihydrate and 1 liter of water were introduced into a 12 liter flask. The mixture was stirred to dissolve the salt. Then 1.94 kg (15.0 mol) of 1,3-dichloro-2-propanol was added, followed by 2.95 kg (30 mol) of concentrated sulfuric acid dissolved in 0.75 liters of water. The reaction temperature was maintained at approx. 20°C during the course of the reaction and stirring was continued at a moderate speed. Care was taken as the addition of sulfuric acid to this mixture is quite exothermic. At the end of the turnover, the reaction mixture is viscous and black.
3,3 liter vann og 5,2 liter toluen ble så satt til reaksjonsblandingen og den resulterende blanding ble fase-separert. Det lavere vandige sjikt ble ekstrahert tilbake med toluen og de kombinerte toluen-løsninger ble vasket med en liten mengde vann. Utbyttet av 1,3-diklorpropanon var ca. 98%. 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-extracted with toluene and the combined toluene solutions were washed with a small amount of water. The yield of 1,3-dichloropropanone was approx. 98%.
I en 12-liters kolbe innførte man 1,3-diklorpropanon-løsningen i toluen fremstilt i det foregående trinn, 1,4 3 kg (8,7 mol) hydroksylaminsulfat (HONH2)2• H2S04, oppløst i 3 liter vann, og 48 ml konsentrert saltsyre. Så ble det under omrøring sakte tilsatt 1,19 kg (15 mol) pyridin under pH-overvåking. Reaksjonstemperaturen ble holdt ved 20-25°C. pH ble holdt ved en verdi under 2 gjennom hele tilsetningen av basen. Tilsetningen var fullført i løpet av ca. 2-2,5 timer, og reaksjonsblandingen ble rørt i 1/2 time deretter. Gass-kromatografisk analyse viste at ketonet var fullstendig omdannet til det tilsvarende oksim. Reaksjonsproduktene ble fase-separert idet oksimet ble værende i toluen-sjiktet. Into a 12-liter flask was introduced the 1,3-dichloropropanone solution in toluene prepared in the previous step, 1.4 3 kg (8.7 mol) of hydroxylamine sulfate (HONH2)2• H2SO4, dissolved in 3 liters of water, and 48 ml of concentrated hydrochloric acid. Then, while stirring, 1.19 kg (15 mol) of pyridine was slowly added under pH monitoring. The reaction temperature was maintained at 20-25°C. The pH was maintained at a value below 2 throughout the addition of the base. The addition was completed within approx. 2-2.5 hours, and the reaction mixture was stirred for 1/2 hour thereafter. Gas chromatographic analysis showed that the ketone was completely converted to the corresponding oxime. The reaction products were phase-separated as the oxime remained in the toluene layer.
Toluen-oksim-løsningen fra det foregående trinn ble innført i en.12-liters kolbe, og til den ble det sakte satt 2,2 kg (21,6 mol) eddiksyreanhydrid. Reaksjonsblandingen ble holdt ved en temperatur på ca. 20°C. Tilsetningen av anhydridet var fullført i løpet av ca. 2 timer. Etter at omsetningen var fullstendig, ble det tilsatt 1/2 liter vann, løsningen ble rørt og den ble så fase-separert. Toluen-sjiktet ble vasket med mettet natriumbikarbonat-løsning, tørkét over magnesiumsulfat, filtrert og inndampet. Væsken ble konsentrert i vakuum i 1 1/2 time ved ca. 50°C. Man erholdt 2,041 g 1,3-dikloraceton-oksim-acetat, k.p. 80-82°C ved et trykk på 4 mm Hg. Renheten var 95 veku-% The toluene-oxime solution from the previous step was introduced into a 1.12-liter flask, and to it was slowly added 2.2 kg (21.6 moles) of acetic anhydride. The reaction mixture was kept at a temperature of approx. 20°C. The addition of the anhydride was completed within approx. 2 hours. After the reaction was complete, 1/2 liter of water was added, the solution was stirred and it was then phase-separated. The toluene layer was washed with saturated sodium bicarbonate solution, dried over magnesium sulfate, filtered and evaporated. The liquid was concentrated in vacuo for 1 1/2 hours at approx. 50°C. 2.041 g of 1,3-dichloroacetone oxime acetate were obtained, b.p. 80-82°C at a pressure of 4 mm Hg. Purity was 95%
og utbyttet var 74% basert på 1,3-diklor-2-propanol-utgangs-materialet og keton-mellomproduktet. and the yield was 74% based on the 1,3-dichloro-2-propanol starting material and the ketone intermediate.
EKSEMPEL 2 EXAMPLE 2
I en 300 ml's kolbe ble det innført en løsning av In a 300 ml flask, a solution of
12,7 g (0,10 mol) 1,3-diklor-2-propanon i 29,5 ml 1,2-dikloretan og en løsning av 9,5 g (0,058 mol) hydroksylamin-sulfat i 20 ml vann. Kolben ble anbragt i et vannbad som ble holdt ved 40°C. Den opprinnelige pH-verdi var ca. 1,5, sannsynligvis på grunn av sure forurensninger i et reagens eller dikloretanet. Etter 60 minutter var pH.avtatt til en negativ verdi. Det ble tilsatt 2,50 g (0,025 mol) kalsiumkarbonat og dessuten 2,50 g etter ytterligere 30 minutter. pH-verdien steg så til ca. 1,5. Omsetningen foregikk i tilsammen 195 minutter, og ved dette punktet var pH-verdien ca. 0,8. Reaksjonsproduktet ble avkjølt, filtrert og fase-separert. Den organiske fase ble anbragt i en 100 ml's kolbe, hvortil det ble satt 14,7 g (0,144 mol) eddiksyreanhydrid. Temperaturen ble holdt ved 40°C. Omsetningen var 96% fullstendig etter 180 minutter og blandingen ble så avkjølt og hensatt. Den resulterende løsning ble strippet under vakuum ved 50°C. Man erholdt 16,8 g av en lysegul væske som inneholdt 95,2 vekt-% 12.7 g (0.10 mol) of 1,3-dichloro-2-propanone in 29.5 ml of 1,2-dichloroethane and a solution of 9.5 g (0.058 mol) of hydroxylamine sulfate in 20 ml of water. The flask was placed in a water bath maintained at 40°C. The original pH value was approx. 1.5, probably due to acidic impurities in a reagent or the dichloroethane. After 60 minutes the pH had decreased to a negative value. 2.50 g (0.025 mol) of calcium carbonate was added and a further 2.50 g after a further 30 minutes. The pH then rose to approx. 1.5. The turnover took place for a total of 195 minutes, and at this point the pH value was approx. 0.8. The reaction product was cooled, filtered and phase-separated. The organic phase was placed in a 100 ml flask, to which 14.7 g (0.144 mol) of acetic anhydride was added. The temperature was maintained at 40°C. The conversion was 96% complete after 180 minutes and the mixture was then cooled and set aside. The resulting solution was stripped under vacuum at 50°C. 16.8 g of a pale yellow liquid containing 95.2% by weight was obtained
(91,3% av teoretisk utbytte) 1,3-dikloraceton-oksim-acetat og 1,3% 1,3-diklor-2-propanon. (91.3% of theoretical yield) 1,3-dichloroacetone oxime acetate and 1.3% 1,3-dichloro-2-propanone.
EKSEMPEL 3 EXAMPLE 3
Oksimet ble fremstilt ved fremgangsmåten fra eksempel 2, og ble isolert. Utbyttet av oksim var 98%, renheten 85-9%. The oxime was prepared by the method from example 2, and was isolated. The yield of oxime was 98%, the purity 85-9%.
EKSEMPEL 4 EXAMPLE 4
Oksimet ble fremstilt som i eksempel 2, idet reaksjonstemperaturen ble holdt ved 22°C. Man erholdt oksimet med et utbytte på 80% og en renhet på 85,1%. The oxime was prepared as in example 2, the reaction temperature being kept at 22°C. The oxime was obtained with a yield of 80% and a purity of 85.1%.
EKSEMPEL 5 EXAMPLE 5
Oksimet ble fremstilt som i eksempel 2, men ved an-vendelse av bare en tilsetning av 2,50 g (0,025 mol) kalsiumkarbonat (ca. 0,5 mol-ekvivalenter pr. mol-ekvivalent hydroksylamin-sulfat). Utbyttet av oksim var 73%, renheten var 74,1%. The oxime was prepared as in Example 2, but using only an addition of 2.50 g (0.025 mol) of calcium carbonate (approx. 0.5 mol equivalents per mol equivalent of hydroxylamine sulphate). The yield of oxime was 73%, the purity was 74.1%.
EKSEMPEL 6 EXAMPLE 6
Oksimet ble fremstilt som i eksempel 2, men det ble tilsatt tilsammen 7,50 g (0,075 mol) kalsiumkarbonat (ca. 1,5 mol-ekvivalenter pr. mol-ekvivalent hydroksylamin-sulfat). Utbyttet av oksim var 74%, renheten var 79,4%. The oxime was prepared as in example 2, but a total of 7.50 g (0.075 mol) of calcium carbonate (approx. 1.5 mol equivalent per mol equivalent of hydroxylamine sulfate) was added. The yield of oxime was 74%, the purity was 79.4%.
Claims (3)
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US65379776A | 1976-01-30 | 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 |
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NO770280L NO770280L (en) | 1977-08-02 |
NO143941B true NO143941B (en) | 1981-02-02 |
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NO770280A NO143941C (en) | 1976-01-30 | 1977-01-28 | PROCEDURE FOR PREPARING 1,3-DICHLOR-ACETON-OXIM |
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AT (1) | AT354411B (en) |
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CA (1) | CA1102817A (en) |
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DD (1) | DD130783A5 (en) |
DE (1) | DE2703370A1 (en) |
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ES (1) | ES455423A1 (en) |
FI (1) | FI770196A (en) |
FR (1) | FR2339592A1 (en) |
GB (1) | GB1525682A (en) |
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IT (1) | IT1079462B (en) |
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NO (1) | NO143941C (en) |
SE (1) | SE7700863L (en) |
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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 FR FR7702113A patent/FR2339592A1/en active Granted
- 1977-01-26 CA CA270,498A patent/CA1102817A/en not_active Expired
- 1977-01-26 DK DK32677A patent/DK32677A/en not_active Application Discontinuation
- 1977-01-27 DE DE19772703370 patent/DE2703370A1/en not_active Withdrawn
- 1977-01-27 SE SE7700863A patent/SE7700863L/en unknown
- 1977-01-27 GB GB3341/77A patent/GB1525682A/en not_active Expired
- 1977-01-28 AU AU21761/77A patent/AU505546B2/en not_active Expired
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AU505546B2 (en) | 1979-11-22 |
AU2176177A (en) | 1978-08-03 |
AT354411B (en) | 1979-01-10 |
FR2339592A1 (en) | 1977-08-26 |
IL51353A (en) | 1980-06-30 |
NO770280L (en) | 1977-08-02 |
FI770196A (en) | 1977-07-31 |
GB1525682A (en) | 1978-09-20 |
NO143941C (en) | 1981-05-13 |
SE7700863L (en) | 1977-07-31 |
JPS52113910A (en) | 1977-09-24 |
ES455423A1 (en) | 1978-05-01 |
ATA43377A (en) | 1979-06-15 |
CH623302A5 (en) | 1981-05-29 |
CA1102817A (en) | 1981-06-09 |
DK32677A (en) | 1977-07-31 |
IL51353A0 (en) | 1977-03-31 |
FR2339592B1 (en) | 1980-08-29 |
NL7700914A (en) | 1977-08-02 |
DD130783A5 (en) | 1978-05-03 |
IT1079462B (en) | 1985-05-13 |
DE2703370A1 (en) | 1977-08-04 |
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