DE1140567B - Process for the preparation of oximes - Google Patents
Process for the preparation of oximesInfo
- Publication number
- DE1140567B DE1140567B DEF33303A DEF0033303A DE1140567B DE 1140567 B DE1140567 B DE 1140567B DE F33303 A DEF33303 A DE F33303A DE F0033303 A DEF0033303 A DE F0033303A DE 1140567 B DE1140567 B DE 1140567B
- Authority
- DE
- Germany
- Prior art keywords
- parts
- sulfur dioxide
- oximes
- oxime
- salts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims description 11
- 150000002923 oximes Chemical class 0.000 title claims description 10
- 238000002360 preparation method Methods 0.000 title claims 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 36
- -1 organic acid halides Chemical class 0.000 claims description 9
- 150000002828 nitro derivatives Chemical class 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 239000012442 inert solvent Substances 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 18
- 230000008018 melting Effects 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 8
- 159000000000 sodium salts Chemical class 0.000 description 6
- NJNQUTDUIPVROZ-UHFFFAOYSA-N nitrocyclohexane Chemical compound [O-][N+](=O)C1CCCCC1 NJNQUTDUIPVROZ-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- FGLBSLMDCBOPQK-UHFFFAOYSA-N 2-nitropropane Chemical compound CC(C)[N+]([O-])=O FGLBSLMDCBOPQK-UHFFFAOYSA-N 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 2
- 239000012346 acetyl chloride Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- WGQSPSMCVCWUDO-UHFFFAOYSA-N nitrocyclododecane Chemical compound [O-][N+](=O)C1CCCCCCCCCCC1 WGQSPSMCVCWUDO-UHFFFAOYSA-N 0.000 description 2
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 2
- FZENGILVLUJGJX-IHWYPQMZSA-N (Z)-acetaldehyde oxime Chemical compound C\C=N/O FZENGILVLUJGJX-IHWYPQMZSA-N 0.000 description 1
- WFMBIXFCBWYGBZ-UHFFFAOYSA-N 1-methyl-3-nitrocyclohexane Chemical compound CC1CCCC([N+]([O-])=O)C1 WFMBIXFCBWYGBZ-UHFFFAOYSA-N 0.000 description 1
- AEVGGWPGNZOUEP-UHFFFAOYSA-N 1-nitrobutane Chemical compound [CH2]CCC[N+]([O-])=O AEVGGWPGNZOUEP-UHFFFAOYSA-N 0.000 description 1
- JUZHDRZOQVECPH-UHFFFAOYSA-N 1-nitropropane Chemical compound [CH2]CC[N+]([O-])=O JUZHDRZOQVECPH-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- SUGZATOHBPXTDV-UHFFFAOYSA-N 2-nitrobutane Chemical compound CCC(C)[N+]([O-])=O SUGZATOHBPXTDV-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 229910004373 HOAc Inorganic materials 0.000 description 1
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical compound CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- CJSZWOGCKKDSJG-UHFFFAOYSA-N nitrocyclopentane Chemical compound [O-][N+](=O)C1CCCC1 CJSZWOGCKKDSJG-UHFFFAOYSA-N 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- VLZLOWPYUQHHCG-UHFFFAOYSA-N nitromethylbenzene Chemical compound [O-][N+](=O)CC1=CC=CC=C1 VLZLOWPYUQHHCG-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 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
-
- 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
- C07C251/44—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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
DEUTSCHESGERMAN
PATENTAMTPATENT OFFICE
F 33303 IVb/12οF 33303 IVb / 12ο
ANMELDETAG: 27. FEBRUAR 1961REGISTRATION DATE: FEBRUARY 27, 1961
BEKANNTMACHUNG
DER ANMELDUNG
UNDAUSGABE DER
AUSLEGESCHRIiT: «· DEZEMBER 1962 NOTICE
THE REGISTRATION
AND ISSUE OF
EXPOSURE STEP: «· DECEMBER 1962
Es ist bekannt, aliphatische und cycloaliphatische Nitroverbindungen bzw. deren Salze oder freie Aciform mittels gewisser Reduktionsmittel, wie naszierendem Wasserstoff, Zinn(II)-chlorid, Natriumhydrosulfit, Schwefelwasserstoff, Thiosulfaten und Dithioniten, zu den entsprechenden Oximen zu reduzieren. Bei diesen Verfahren ist entweder die Oximausbeute nicht zufriedenstellend, oder das Oxim ist schwierig aus dem Reaktionsgemisch abzutrennen. Bei Verwendung schwefelhaltiger Reduktionsmittel enthält das Oxim meistens noch Schwefel. Bei manchen dieser Verfahren fallen außerdem größere Mengen an nicht verwertbaren Salzen an.It is known, aliphatic and cycloaliphatic nitro compounds or their salts or free Aciform using certain reducing agents such as nascent hydrogen, tin (II) chloride, sodium hydrosulfite, Hydrogen sulfide, thiosulfates, and dithionites, reduce to the corresponding oximes. With these procedures, either the oxime yield is unsatisfactory or the oxime is difficult to separate from the reaction mixture. When using sulfur-containing reducing agents, the oxime usually still contains sulfur. Some of these processes also produce large amounts of unusable salts.
Gegenstand der vorliegenden Erfindung ist ein neuartiges, technisch vorteilhaftes Verfahren zur Herstellung von Oximen aus Salzen oder der freien Aciform aliphatischer und cycloaliphatischer Nitroverbindungen, das darin besteht, diese Verbindungen mit etwa äquimolaren Mengen anorganischer oder organischer Säurehalogenide in Gegenwart mindestens äquimolarer Mengen Schwefeldioxyd, gegebenenfalls überschüssigem, flüssigem Schwefeldioxyd Verfahren zur Herstellung von OximenThe present invention is a novel, technically advantageous process for Production of oximes from salts or the free aciform of aliphatic and cycloaliphatic nitro compounds, that consists in these compounds with approximately equimolar amounts of inorganic or organic acid halides in the presence of at least equimolar amounts of sulfur dioxide, if appropriate excess liquid sulfur dioxide Process for the production of oximes
Anmelder:Applicant:
Farbenfabriken Bayer Aktiengesellschaft,
LeverkusenPaint factories Bayer Aktiengesellschaft,
Leverkusen
Dr. Walter Müller, Krefeld-Bockum,Dr. Walter Müller, Krefeld-Bockum,
und Dr. Hermann Schnell, Krefeld-Uerdingen,and Dr. Hermann Schnell, Krefeld-Uerdingen,
sind als Erfinder genannt wordenhave been named as inventors
oder/und unter Zusatz eines inerten Lösungsmittels, umzusetzen und die Reaktionsprodukte, gegebenenfalls nach dem Verdampfen des überschüssigen Schwefeldioxyds bzw. des Lösungsmittels, mit Wasser zu behandeln.and / or with the addition of an inert solvent to implement and the reaction products, if appropriate after evaporation of the excess sulfur dioxide or the solvent, with water to treat.
Dieses Verfahren entspricht vermutlich folgendem Reaktionsverlauf:This procedure probably corresponds to the following course of the reaction:
C = NC = N
OHOH
SO2 + XAcSO 2 + XAc
RiRi
RaRa
RiRi
C = N- OAc HX±Jfe°_C = N- OAc HX ± Jfe ° _
NOH+ HOAcNOH + HOAc
R2 R 2
Darin bedeuten Ri und R2 aliphatische Reste bzw. Ri — R2 die Ergänzungsglieder eines cycloaliphatischen Ringes, X Halogen und Ac einen anorganischen oder organischen Säurerest!Here, Ri and R2 mean aliphatic radicals or Ri - R2 the supplementary members of a cycloaliphatic Ring, X halogen and Ac an inorganic or organic acid radical!
Die Oxime fallen in guten Ausbeuten und in beachtlicher Reinheit an.The oximes are obtained in good yields and in considerable purity.
Für das Verfahren geeignete aliphatische Nitroverbindungen sind primäre und sekundäre Nitroverbindungen, wie Nitromethan, Nitroäthan, 1- bzw. 2-Nitropropan, 1- bzw. 2-Nitrobutan und Phenylnitromethan, sowie cycloaliphatische Nitroverbindungen, wie Nitrocyclopentan, Nitrocyclohexan, Nitrocyclododecan und substituierte Nitrocyclohexane, wie 3-Nitro-l-methyl-cyclohexan.Aliphatic nitro compounds suitable for the process are primary and secondary nitro compounds, such as nitromethane, nitroethane, 1- or 2-nitropropane, 1- or 2-nitrobutane and phenylnitromethane, as well as cycloaliphatic nitro compounds such as nitrocyclopentane, nitrocyclohexane, Nitrocyclododecane and substituted nitrocyclohexanes, such as 3-nitro-1-methyl-cyclohexane.
Diese Verbindungen verwendet man in Form ihrer Salze, z. B. ihrer Alkali-, Ammonium- oder Erdalkalisalze. Bei Nitroverbindungen, deren Aciform verhältnismäßig beständig ist, so z. B. bei Nitrocyclododecan, kann man auch durch Einwirkung von Säuren auf ihre Salze die freie Aciform herstellen und diese einsetzen.These compounds are used in the form of their salts, e.g. B. their alkali, ammonium or Alkaline earth salts. In the case of nitro compounds, the aciform of which is relatively stable, e.g. B. at Nitrocyclododecane, one can also get the free aciform through the action of acids on their salts manufacture and use them.
An geeigneten Säurehalogeniden seien beispielsweise genannt: Phosphortrichlorid, Phosphoroxychlorid, Phosphorpentachlorid, Thionylchlorid, Sulfurylchlorid, Phosgen, Acetylchlorid, Benzoylchlorid und die entsprechenden Bromide.Examples of suitable acid halides are: phosphorus trichloride, phosphorus oxychloride, Phosphorus pentachloride, thionyl chloride, sulfuryl chloride, phosgene, acetyl chloride, benzoyl chloride and the corresponding bromides.
Man trägt zweckmäßig das Salz der Nitroverbindung oder die Nitroverbindung in der Aciform in ein Gemisch des Säurechlorids in flüssigem Schwefeldioxyd bei Temperaturen unterhalb etwa + 1O0C, vorzugsweise unterhalb 00C, unter Normaldruck oder bei höheren Temperaturen unter einem entsprechend höheren Druck unter Rühren ein.One carries suitably the salt of the nitro compound or the nitro compound in the Aciform in a mixture of the acid chloride in liquid sulfur dioxide at temperatures below about + 1O 0 C, preferably below 0 0 C, under atmospheric pressure or at higher temperatures under a correspondingly higher pressure with stirring .
Gegebenenfalls kann man an Stelle von flüssigem Schwefeldioxyd eine Lösung von Schwefeldioxyd in einem inerten Lösungsmittel, z. B. Aceton oder Tetrachlorkohlenstoff, verwenden. Alsdann läßt man gegebenenfalls das überschüssige Schwefeldioxyd bzw. das Lösungsmittel verdampfen und versetzt den Rückstand mit wenig Wasser. Dabei fällt das Oxim, gegebenenfalls nach dem Neutralisieren, aus.If necessary, instead of liquid sulfur dioxide, a solution of sulfur dioxide in an inert solvent, e.g. B. acetone or carbon tetrachloride, use. Then one lets if necessary, the excess sulfur dioxide or the solvent evaporate and mixed the residue with a little water. The oxime precipitates, if necessary after neutralization.
so z. B. in das entsprechende Lactam umgelagert so werden.so z. B. be rearranged into the corresponding lactam.
Die in den folgenden Beispielen genannten Teile sind Gewichtsteile.The parts mentioned in the following examples are parts by weight.
209 710/338209 710/338
In eine Lösung von 11,9 Teilen Thionylchlorid in 64 Teilen Sehwefeldioxyd trägt man bei —20 bis —400C portionsweise 23,5 Teile des Natriumsalzes des Nitrocyclododecans ein. Hierauf läßt man das überschüssige Schwefeldioxyd verdampfen und versetzt den Rückstand mit wenig Wasser. Das ausgefallene Cyclododecanoxim wird abgesaugt. Ausbeute: 18,9 Teile = 96% der Theorie; Schmelzpunkt: 128 bis 1310C. Aus Petroläther oder Cyclohexan umkristallisiert hat das Oxim den Schmelzpunkt von 1310C.In a solution of 11.9 parts of thionyl chloride in 64 parts Sehwefeldioxyd one carries at -20 to -40 0 C portionwise 23.5 parts of the sodium salt of a Nitrocyclododecans. The excess sulfur dioxide is then allowed to evaporate and a little water is added to the residue. The precipitated cyclododecane oxime is filtered off with suction. Yield: 18.9 parts = 96% of theory; Melting point: 131 0 C. recrystallized bis From 128 petroleum ether or cyclohexane oxime has the melting point of 131 0 C.
Man verfährt wie im Beispiel 1, verwendet jedoch an Stelle von Thionylchlorid 20,8 Teile Phosphorpentachlorid. Rohprodukt: 15,8 Teile; Schmelzpunkt: 120 bis 125°C.The procedure is as in Example 1, except that 20.8 parts of phosphorus pentachloride are used instead of thionyl chloride. Crude product: 15.8 parts; Melting point: 120 to 125 ° C.
2020th
Man verfährt wie im Beispiel 1, verwendet jedoch an Stelle von Thionylchlorid 13,4 Teile Sulfurylchlorid. Rohprodukt: 15,8 Teile; Schmelzpunkt: 119 bis 126° C. ' The procedure is as in Example 1, except that 13.4 parts of sulfuryl chloride are used instead of thionyl chloride. Crude product: 15.8 parts; Melting point: 119 to 126 ° C. '
Man verfährt wie im Beispiel 1, verwendet jedoch an Stelle von Thionylchlorid 9,9 Teile Phosgen. Rohprodukt: 17,5 Teile; Schmelzpunkt: 119 bis 125° C.The procedure is as in Example 1, but 9.9 parts of phosgene are used instead of thionyl chloride. Crude product: 17.5 parts; Melting point: 119 to 125 ° C.
23,5 Teile des Natriumsalzes des Nitrocyclododecans werden bei -4O0C in eine Lösung von 7,9 Teilen Acetylchlorid in 64 Teilen Schwefeldioxyd eingetragen. Nach dem Verdampfen des Schwefeldioxyds und der Zugabe von Wasser zum Rückstand erhält man 15,4 Teile Cyclododecanoxim. Schmelzpunkt: 118 bis 124°C.23.5 parts of the sodium salt of Nitrocyclododecans be entered at -4o 0 C in a solution of 7.9 parts of acetyl chloride in 64 parts of sulfur dioxide. After evaporation of the sulfur dioxide and the addition of water to the residue, 15.4 parts of cyclododecane oxime are obtained. Melting point: 118 to 124 ° C.
In eine Lösung von 11,9 Teilen Thionylchlorid in 79 Teilen Aceton und 64 Teilen Schwefeldioxyd trägt man portionsweise bei —20 bis — 400C 23,5 Teile des Natriumsalzes des Nitrocyclododecans ein. Nach Beendigung der Umsetzung läßt man das Lösungsmittel verdampfen, gibt Wasser zu und isoliert 16,3 Teile Cyclododecanoxim. Schmelzpunkt: 116 bis 120°C.In a solution of 11.9 parts of thionyl chloride in 79 parts acetone and 64 parts of sulfur dioxide to wear in portions at -20 to - 40 0 C 23.5 parts of the sodium salt of a Nitrocyclododecans. After the reaction has ended, the solvent is allowed to evaporate, water is added and 16.3 parts of cyclododecane oxime are isolated. Melting point: 116 to 120 ° C.
In 320 Teilen Tetrachlorkohlenstoff werden 72 Teile Schwefeldioxyd und 23,8 Teile Thionylchlorid gelöst. Hierzu gibt man bei —20° C innerhalb 60 Minuten 30,4 Teile des Natriumsalzes des Nitrocyclohexans. Nach dem Verdampfen des Schwefeldioxyds und Abdestillieren des Tetrachlorkohlenstoffes versetzt man den Rückstand mit wenig Wasser. Durch Extrahieren mit Äther werden 12 Teile Nitrocyclohexan zurückgewonnen. Nach dem Neutralisieren mit verdünntem Ammoniak erhält man 9,5 Teile Cyclohexanonoxim = 79% der Theorie, berechnet auf das umgesetzte Nitrocyclohexan.72 parts of sulfur dioxide and 23.8 parts of thionyl chloride are dissolved in 320 parts of carbon tetrachloride. To this end, 30.4 parts of the sodium salt of nitrocyclohexane are added at -20 ° C. within 60 minutes. After the sulfur dioxide has evaporated and the carbon tetrachloride has been distilled off the residue with a little water. Extraction with ether gives 12 parts of nitrocyclohexane recovered. After neutralization with dilute ammonia, 9.5 parts are obtained Cyclohexanone oxime = 79% of theory, calculated on the converted nitrocyclohexane.
29,1 Teile des Natriumsalzes des Nitroäthans, das mit wenig Tetrachlorkohlenstoff angefeuchtet wurde, werden bei -6O0C in eine Lösung von 110 Teilen Sehwefeldioxyd in 21,8 Teilen Thionylchlorid eingetragen. Neben nichtumgesetztem Nitroäthan werden 3 Teile Acetaldehydoxim erhalten.29.1 parts of the sodium salt of nitroethane, which has been moistened with a little carbon tetrachloride, are introduced into a solution of 110 parts of sulfur dioxide in 21.8 parts of thionyl chloride at -6O 0 C. In addition to unreacted nitroethane, 3 parts of acetaldehyde oxime are obtained.
44,4 Teile des Natriumsalzes des 2-Nitropropans werden bei -4O0C in eine Lösung von 47,5 Teilen Thionylchlorid in 195 Teilen Sehwefeldioxyd eingetragen. Nach dem Verdampfen des Schwefeldioxyds gibt man wenig Eis zum Reaktionsgemisch. Man erhält 11 Teile Acetonoxim vom Schmelzpunkt 60 bis 62° C und 9,8 Teile nicht umgesetztes 2-Nitropropan. 44.4 parts of the sodium salt of 2-nitro propane are introduced at 0 -4o C in a solution of 47.5 parts of thionyl chloride in 195 parts Sehwefeldioxyd. After the sulfur dioxide has evaporated, a little ice is added to the reaction mixture. 11 parts of acetone oxime with a melting point of 60 to 62 ° C. and 9.8 parts of unconverted 2-nitropropane are obtained.
Claims (1)
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF33303A DE1140567B (en) | 1961-02-27 | 1961-02-27 | Process for the preparation of oximes |
| CH1214561A CH396882A (en) | 1961-02-27 | 1961-10-20 | Process for the preparation of oximes |
| GB44094/61A GB931369A (en) | 1961-02-27 | 1961-12-08 | Process for the production of oximes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF33303A DE1140567B (en) | 1961-02-27 | 1961-02-27 | Process for the preparation of oximes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1140567B true DE1140567B (en) | 1962-12-06 |
Family
ID=7095041
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEF33303A Pending DE1140567B (en) | 1961-02-27 | 1961-02-27 | Process for the preparation of oximes |
Country Status (3)
| Country | Link |
|---|---|
| CH (1) | CH396882A (en) |
| DE (1) | DE1140567B (en) |
| GB (1) | GB931369A (en) |
-
1961
- 1961-02-27 DE DEF33303A patent/DE1140567B/en active Pending
- 1961-10-20 CH CH1214561A patent/CH396882A/en unknown
- 1961-12-08 GB GB44094/61A patent/GB931369A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CH396882A (en) | 1965-08-15 |
| GB931369A (en) | 1963-07-17 |
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