DE1238454B - Process for the preparation of carbonyl compounds - Google Patents

Process for the preparation of carbonyl compounds

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Publication number
DE1238454B
DE1238454B DEB79140A DEB0079140A DE1238454B DE 1238454 B DE1238454 B DE 1238454B DE B79140 A DEB79140 A DE B79140A DE B0079140 A DEB0079140 A DE B0079140A DE 1238454 B DE1238454 B DE 1238454B
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Germany
Prior art keywords
parts
radical
extract
sodium hydroxide
hydroxide solution
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
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DEB79140A
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German (de)
Inventor
Dr Horst Koenig
Dr Horst Metzger
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BASF SE
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BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to DEB79138A priority Critical patent/DE1226562B/en
Priority to DEB79140A priority patent/DE1238454B/en
Priority to DEB87722A priority patent/DE1239288B/en
Priority to DEB79139A priority patent/DE1226563B/en
Priority to CH1445765A priority patent/CH468970A/en
Priority to FR36755A priority patent/FR1461695A/en
Priority to BE671693D priority patent/BE671693A/xx
Priority to GB45818/65A priority patent/GB1120737A/en
Priority to NL6514088A priority patent/NL6514088A/xx
Publication of DE1238454B publication Critical patent/DE1238454B/en
Priority to US00863770A priority patent/US3821277A/en
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/14—Preparation of nitro compounds by formation of nitro groups together with reactions not involving the formation of nitro groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/49—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups
    • C07C205/50—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups having nitro groups and carboxyl groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C205/51—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups having nitro groups and carboxyl groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C247/00—Compounds containing azido groups
    • C07C247/02—Compounds containing azido groups with azido groups bound to acyclic carbon atoms of a carbon skeleton
    • C07C247/12—Compounds containing azido groups with azido groups bound to acyclic carbon atoms of a carbon skeleton being further substituted by carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C315/00—Preparation of sulfones; Preparation of sulfoxides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C331/00—Derivatives of thiocyanic acid or of isothiocyanic acid
    • C07C331/02—Thiocyanates
    • C07C331/14—Thiocyanates having sulfur atoms of thiocyanate groups bound to carbon atoms of hydrocarbon radicals substituted by carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/673—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/20—Unsaturated compounds containing keto groups bound to acyclic carbon atoms
    • C07C49/255—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing ether groups, groups, groups, or groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
    • C07C69/734—Ethers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
    • C07D213/46—Oxygen atoms
    • C07D213/50—Ketonic radicals
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

BUNDESREPUBLIK DEUTSCHLANDFEDERAL REPUBLIC OF GERMANY

DEUTSCHESGERMAN

PATENTAMTPATENT OFFICE

AUSLEGESCHRIFTEDITORIAL

Int. Cl.:Int. Cl .:

C07cC07c

C07d
Deutsche Kl.: 12 ο -16C07d
German class: 12 ο -16

Nummer: 1238 454Number: 1238 454

Aktenzeichen: B 79140IV b/12 οFile number: B 79140IV b / 12 ο

Anmeldetag: 30. Oktober 1964Filing date: October 30, 1964

Auslegetag: 13. April 1967Opened on: April 13, 1967

Es wurde gefunden, daß man Carbonylverbindungen der allgemeinen FormelIt has been found that carbonyl compounds of the general formula

O HO H

R1-C-C-R2 R 1 -CCR 2

in der R1 einen Alkyl-, Aralkyl-, aromatischen oder heterocyclischen Rest oder den Rest — NHR3 bedeutet, worin R3 für einen aliphatischen, araliphatischen, aromatischen oder heterocyclischen Rest steht, R2 ein Wasserstoffatom oder den Rest — CO — R1 bedeutet, worin R1 die vorstehende Bedeutung hat, und B einen geradkettigen niedermolekularen Alkoxy-, Alkylthio-, Aryloxy- oder Arylthiorest bedeutet, erhält, wenn man Dimethyloxosulfurylene der allgemeinen Formelin which R 1 is an alkyl, aralkyl, aromatic or heterocyclic radical or the radical - NHR 3 , in which R 3 is an aliphatic, araliphatic, aromatic or heterocyclic radical, R 2 is a hydrogen atom or the radical - CO - R 1 denotes in which R 1 has the above meaning and B denotes a straight-chain, low molecular weight alkoxy, alkylthio, aryloxy or arylthio radical, is obtained when dimethyloxosulfurylenes of the general formula are obtained

R1-C-C-R2 R 1 -CCR 2

IIII

S = OS = O

CH,CH,

CH3 CH 3

in der R1 und R2 die vorstehende Bedeutung haben, in Gegenwart von vorzugsweise äquivalenten Mengen, bezogen auf umzusetzendes Dimethyloxosulfurylen, starker Säuren mit geradkettigen Alkanolen oder Mercaptanen mit 1 bis 8 Kohlenstoffatomen, Phenolen oder Thiophenolen, gegebenenfalls in Gegenwart eines Lösungsmittels, bei Temperaturen zwischen —20 und +15O0C umsetzt.in which R 1 and R 2 have the above meaning, in the presence of preferably equivalent amounts, based on dimethyloxosulfurylene to be reacted, strong acids with straight-chain alkanols or mercaptans with 1 to 8 carbon atoms, phenols or thiophenols, optionally in the presence of a solvent, at temperatures between -20 and + 15O 0 C converts.

Die neuen Ausgangsstoffe der Formel II lassen sich z. B. durch Umsetzung von Dimethyloxosulfoniumyliden mit Isocyanaten, Ketenen, Säurechloriden oder Anhydriden herstellen. Für die Umsetzung gemäß vorliegender Erfindung ist es nicht unbedingt erforderlich, die Dimethyloxosulfurylene der Formel II aus deren Herstellungsgemisch abzutrennen. Man kann vielmehr das Herstellungsgemisch unmittelbar im Rahmen des Verfahrens dieser Erfindung weiterverwenden. Als Ausgangsstoffe kann man z. B. Dimethyloxosulfurylen-malondianilid, Dimethyloxosulfurylenmalonsäure - N,N' - cyclohexyldiamid, Dimethyloxosulfurylenacetanilid, Dimethyloxosulfurylenacettoluidid oder Dimethyloxosulfurylenessigsäuremethylamid verwenden.The new starting materials of formula II can be z. B. by reacting Dimethyloxosulfoniumyliden with isocyanates, ketenes, acid chlorides or anhydrides. For implementation according to In the present invention, it is not absolutely necessary to use the dimethyloxosulfurylenes of the formula II to separate their preparation mixture. Rather, you can use the preparation mixture directly in the Continue to use the method of this invention. As starting materials you can, for. B. Dimethyloxosulfurylenemalondianilide, dimethyloxosulfurylenmalonic acid - N, N '- cyclohexyldiamide, dimethyloxosulfurylene acetanilide, dimethyloxosulfurylene acetoluidide or use dimethyloxosulfuryleneacetic acid methylamide.

Die Dimethyloxosulfurylene der Formel II lassen sich mit geradkettigen Alkoholen oder Mercaptanen, mit 1 bis 8 Kohlenstoffatomen, Phenolen oder Thio-Verfahren zur Herstellung von
CarbonylverbindungenThe Dimethyloxosulfurylen of the formula II can be with straight-chain alcohols or mercaptans, with 1 to 8 carbon atoms, phenols or thio process for the preparation of
Carbonyl compounds

Anmelder:Applicant:

Badische Anilin- & Soda-FabrikAniline & Soda Factory in Baden

Aktiengesellschaft, Ludwigshafen/RheinAktiengesellschaft, Ludwigshafen / Rhein

Als Erfinder benannt:Named as inventor:

Dr. Horst König,Dr. Horst König,

Dr. Horst Metzger, Ludwigshafen/RheinDr. Horst Metzger, Ludwigshafen / Rhine

phenolen in Gegenwart von starken Mineralsäuren, wie Schwefelsäure, Phosphorsäure, Borfluorwasserstoffsäure, oder Sulfonsäuren, wie Benzol- oder Toluolsulfonsäuren, umsetzen. Man kann katalytische oder stöchiometrische Mengen Säure, bezogen auf umzusetzendes Dimethyloxosulfurylen, oder aber einen Überschuß an Säure, z. B. bis zu 10 Äquivalente, anwenden.phenols in the presence of strong mineral acids such as sulfuric acid, phosphoric acid, hydrofluoric acid, or sulfonic acids, such as benzene or toluenesulfonic acids. One can be catalytic or stoichiometric amounts of acid, based on dimethyloxosulfurylene to be converted, or one Excess of acid, e.g. B. apply up to 10 equivalents.

Das Verfahren läßt sich ohne besondere Lösungsmittel durchführen. Es ist jedoch zweckmäßig, in Gegenwart eines Lösungsmittels zu arbeiten. Als Lösungsmittel kann man Kohlenwasserstoffe, wie Hexan, Heptan, Cyclohexan oder Benzol, chlorierte Kohlenwasserstoffe, wie Chloroform, Tetrachlorkohlenstoff oder Trichloräthylen, oder Äther, wie Diäthyl- oder Dibutyläther, Ν,Ν-disubstituierte Carbonsäureamide, ζ. B. Dimethylformamid oder N-Methylpyrrolidon, oder Dimethylsulfoxyd verwenden. Man kann aber auch z. B. den an der Umsetzung beteiligten Alkohol, sofern er im Überschuß angewandt wird, als Lösungsmittel verwenden.The process can be carried out without special solvents. However, it is convenient to use in Presence of a solvent to work. The solvent can be hydrocarbons, such as Hexane, heptane, cyclohexane or benzene, chlorinated hydrocarbons such as chloroform, carbon tetrachloride or trichlorethylene, or ethers, such as diethyl or dibutyl ether, Ν, Ν-disubstituted carboxamides, ζ. B. use dimethylformamide or N-methylpyrrolidone, or dimethyl sulfoxide. Man but can also z. B. the alcohol involved in the implementation, if it is used in excess, as Use solvents.

Die Reaktionsteilnehmer können in stöchiometrischer Menge angewandt werden. Vorteilhafterweise verwendet man die Dimethyloxosulfurylene in einem Unterschuß. Dadurch wird erreicht, daß die Umsetzung im Hinblick auf die wertvollen Dimethyloxosulfurylene quantitativ ist.The reactants can be used in a stoichiometric amount. Advantageously one uses the Dimethyloxosulfurylen in a deficiency. This ensures that the implementation is quantitative with regard to the valuable dimethyloxosulfurylenes.

Zur Abtrennung der gewünschten Verfahrensprodukte destilliert man im allgemeinen das Lösungsmittel und den überschüssigen Reaktionsteilnehmer ab. Aus dem Rückstand kann man dann die reinen Stoffe z. B. durch Destillation oder Umkristallisieren gewinnen. Man kann aber auch die Verfahrensprodukte durch Zugabe eines weiteren Lösungsmittels, z. B. Wasser, aus dem Umsetzungsgemisch ausfällen und dann abtrennen.To separate off the desired process products, the solvent is generally distilled off and the excess reactant. From the residue you can then get the pure ones Substances e.g. B. win by distillation or recrystallization. But you can also the process products by adding another solvent, z. B. water, precipitate from the reaction mixture and then separate.

709 549/429709 549/429

Die nach dem Verfahren herstellbaren Stoffe sind wertvolle Zwischenprodukte für die Herstellung von Arznei- und Schädlingsbekämpfungsmitteln.The substances that can be produced by the process are valuable intermediate products for the production of Medicines and pesticides.

Die in den Beispielen angeführten Teile bedeuten Gewichtsteile.The parts given in the examples are parts by weight.

Beispiel 1example 1

4 Teile Dimethyloxosulfurylen-acetanilid, 2,10 Teile Thiophenol und 10 Teile Dimethylformamid ergeben nach Zugabe von 0,1 Teil p-Toluolsulfonsäure eine klare Lösung. Nach 10 Stunden bei 25 0C wird in Eiswasser eingerührt, abgesaugt, gewaschen und getrocknet. Man erhält 3,73 Teile Phenylmercaptoacetanilid 4 parts of dimethyloxosulfurylene acetanilide, 2.10 parts of thiophenol and 10 parts of dimethylformamide give a clear solution after adding 0.1 part of p-toluenesulfonic acid. After 10 hours at 25 ° C., the mixture is stirred into ice water, filtered off with suction, washed and dried. 3.73 parts of phenyl mercaptoacetanilide are obtained

O \ !5O \! 5

der Theorie, Phenoxyacetophenon als leicht gefärbte, halbfeste Masse. Durch Umlösen aus Alkohol erhält man farblose Prismen vom Schmelzpunkt 69 bis 70° C.theory, phenoxyacetophenone as a lightly colored, semi-solid mass. Obtained by dissolving from alcohol colorless prisms with a melting point of 69 to 70 ° C.

Claims (1)

Patentanspruch:Claim: Verfahren zur Herstellung von Carbonylverbindungen der allgemeinen FormelProcess for the preparation of carbonyl compounds of the general formula O HO H C6H5NH- C— CH2- SC6H.C 6 H 5 NH- C- CH 2 - SC 6 H. in einer Ausbeute von 81% der Theorie; F. = 79°C. Nach dem Umlösen aus Cyclohexan steigt der Schmelzpimkt auf 81: C.in a yield of 81% of theory; M.p. = 79 ° C. After dissolving from cyclohexane, the melting peak rises to 81 : C. Beispiel 2Example 2 20 Teile Dimethyloxosulfurylen-aceton und 40 Teile Λ-Naphthol werden mit 0,1 Teil Phosphorsäure 48 Stunden auf HO0C erwärmt. Man läßt das Reaktionsgemisch abkühlen, extrahiert es mit Äther, wäscht den Extrakt mit verdünnter kalter Natronlauge und destilliert das \-Naphthoxyaceton als farblose Flüssigkeit vom Kp.14 = 205°C ab. Man erhält 11,8 Teile ^-Naphthoxyaceton, entsprechend einer Ausbeute von 39 % der Theorie.20 parts of dimethyloxosulfurylene acetone and 40 parts of Λ-naphthol are heated to HO 0 C with 0.1 part of phosphoric acid for 48 hours. The reaction mixture is allowed to cool, it is extracted with ether, the extract is washed with dilute, cold sodium hydroxide solution and the naphthoxyacetone is distilled off as a colorless liquid with a boiling point of 14 = 205 ° C. This gives 11.8 parts -Naphthoxyaceton ^, corresponding to a yield of 39% of theory it. Beispiel 3Example 3 30 Teile Phenol und 10 Teile Dimethyloxosulfurylenacetophenon werden mit 0,1 Teil konzentrierter Salzsäure 60 Stunden auf 9O0C erwärmt. Man gießt das Gemisch auf eine Mischung von Eis und Natronlauge, extrahiert das Ganze mit Methylenchlorid, wäscht den Extrakt mit verdünnter Natronlauge und dann mit Wasser nach. Nach dem Einengen des Extraktes hinterbleiben 14,8 Teile, entsprechend 70 % R1-C-C-R2 30 parts of phenol and 10 parts Dimethyloxosulfurylenacetophenon are heated for 60 hours 9O 0 C with 0.1 part of concentrated hydrochloric acid. The mixture is poured onto a mixture of ice and sodium hydroxide solution, the whole is extracted with methylene chloride, and the extract is washed with dilute sodium hydroxide solution and then with water. After concentrating the extract, 14.8 parts remain , corresponding to 70% R 1 -CCR 2 in der R1 einen Alkyl-, Aralkyl-, aromatischen oder heterocyclischen Rest oder den Rest — NHR3 bedeutet, worin R3 für einen aliphatischen, araliphatischen, aromatischen oder heterocyclischen Rest steht, R2 ein Wasserstoffatom oder den Rest — CO — R1 bezeichnet, worin R1 die vorstehende Bedeutung hat, und B einen geradkettigen niedermolekularen Alkoxy-, Alkylthio-, Aryloxy- oder Arylthiorest bedeutet, dadurch gekennzeichnet, daß man Dimethyloxosulfurylene der allgemeinen Formelin which R 1 is an alkyl, aralkyl, aromatic or heterocyclic radical or the radical - NHR 3 , in which R 3 is an aliphatic, araliphatic, aromatic or heterocyclic radical, R 2 is a hydrogen atom or the radical - CO - R 1 denotes in which R 1 has the above meaning and B denotes a straight-chain, low molecular weight alkoxy, alkylthio, aryloxy or arylthio radical, characterized in that dimethyloxosulfurylenes of the general formula R1-C-C-R2 IIR 1 -CCR 2 II S = OS = O //
CtI3 CH3 CtI 3 CH 3 in der R1 und R2 die vorstehende Bedeutung haben, in Gegenwart von vorzugsweise äquivalenten Mengen, bezogen auf umzusetzendes Dimethyloxosulfurylen, starker Säuren mit geradkettigen Alkanolen oder Mercaptanen mit 1 bis 8 Kohlenstoffatomen, Phenolen oder Thiophenolen, gegebenenfalls in Gegenwart eines Lösungsmittels, bei Temperaturen zwischen —20 und +1500C umsetzt. in which R 1 and R 2 have the above meaning, in the presence of preferably equivalent amounts, based on dimethyloxosulfurylene to be reacted, strong acids with straight-chain alkanols or mercaptans with 1 to 8 carbon atoms, phenols or thiophenols, optionally in the presence of a solvent, at temperatures between -20 and +150 0 C converts.
DEB79140A 1964-10-30 1964-10-30 Process for the preparation of carbonyl compounds Pending DE1238454B (en)

Priority Applications (10)

Application Number Priority Date Filing Date Title
DEB79138A DE1226562B (en) 1964-10-30 1964-10-30 Process for the preparation of carbonyl compounds
DEB79140A DE1238454B (en) 1964-10-30 1964-10-30 Process for the preparation of carbonyl compounds
DEB87722A DE1239288B (en) 1964-10-30 1964-10-30 Process for the preparation of carbonyl compounds
DEB79139A DE1226563B (en) 1964-10-30 1964-10-30 Process for the preparation of carbonyl compounds
CH1445765A CH468970A (en) 1964-10-30 1965-10-20 Process for the preparation of carbonyl compounds substituted in a-position
FR36755A FR1461695A (en) 1964-10-30 1965-10-29 Process for the production of alpha-substituted carbonyl compounds
BE671693D BE671693A (en) 1964-10-30 1965-10-29
GB45818/65A GB1120737A (en) 1964-10-30 1965-10-29 Production of carbonyl compounds substituted in ª‡-position
NL6514088A NL6514088A (en) 1964-10-30 1965-10-29
US00863770A US3821277A (en) 1964-10-30 1969-10-02 Ypsilon-methoxy-ypsilon-carbanilino-alpha,omega-dicyanopentane

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DEB79138A DE1226562B (en) 1964-10-30 1964-10-30 Process for the preparation of carbonyl compounds
DEB79140A DE1238454B (en) 1964-10-30 1964-10-30 Process for the preparation of carbonyl compounds
DEB87722A DE1239288B (en) 1964-10-30 1964-10-30 Process for the preparation of carbonyl compounds
DEB79139A DE1226563B (en) 1964-10-30 1964-10-30 Process for the preparation of carbonyl compounds

Publications (1)

Publication Number Publication Date
DE1238454B true DE1238454B (en) 1967-04-13

Family

ID=27436636

Family Applications (4)

Application Number Title Priority Date Filing Date
DEB79139A Pending DE1226563B (en) 1964-10-30 1964-10-30 Process for the preparation of carbonyl compounds
DEB87722A Pending DE1239288B (en) 1964-10-30 1964-10-30 Process for the preparation of carbonyl compounds
DEB79138A Pending DE1226562B (en) 1964-10-30 1964-10-30 Process for the preparation of carbonyl compounds
DEB79140A Pending DE1238454B (en) 1964-10-30 1964-10-30 Process for the preparation of carbonyl compounds

Family Applications Before (3)

Application Number Title Priority Date Filing Date
DEB79139A Pending DE1226563B (en) 1964-10-30 1964-10-30 Process for the preparation of carbonyl compounds
DEB87722A Pending DE1239288B (en) 1964-10-30 1964-10-30 Process for the preparation of carbonyl compounds
DEB79138A Pending DE1226562B (en) 1964-10-30 1964-10-30 Process for the preparation of carbonyl compounds

Country Status (5)

Country Link
BE (1) BE671693A (en)
CH (1) CH468970A (en)
DE (4) DE1226563B (en)
GB (1) GB1120737A (en)
NL (1) NL6514088A (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3313917A1 (en) * 1983-04-16 1984-10-25 Basf Ag, 6700 Ludwigshafen METHOD FOR PRODUCING VICINAL POLYCARBONYL COMPOUNDS
CN115557865B (en) * 2022-10-17 2024-05-14 南京工业大学 Thioether-promoted cysteine-based bioconjugate method

Also Published As

Publication number Publication date
CH468970A (en) 1969-02-28
NL6514088A (en) 1966-05-02
DE1226562B (en) 1966-10-13
GB1120737A (en) 1968-07-24
DE1239288B (en) 1967-04-27
BE671693A (en) 1966-04-29
DE1226563B (en) 1966-10-13

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