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DE1226562B - Process for the preparation of carbonyl compounds - Google Patents

Process for the preparation of carbonyl compounds

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Publication number
DE1226562B
DE1226562B DEB79138A DEB0079138A DE1226562B DE 1226562 B DE1226562 B DE 1226562B DE B79138 A DEB79138 A DE B79138A DE B0079138 A DEB0079138 A DE B0079138A DE 1226562 B DE1226562 B DE 1226562B
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Germany
Prior art keywords
radical
parts
aromatic
aralkyl
general formula
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
Application number
DEB79138A
Other languages
German (de)
Inventor
Dr Horst Koenig
Dr Horst Metzger
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to DEB87722A priority Critical patent/DE1239288B/en
Priority to DEB79138A priority patent/DE1226562B/en
Priority to DEB79140A priority patent/DE1238454B/en
Priority to DEB79139A priority patent/DE1226563B/en
Priority to CH1445765A priority patent/CH468970A/en
Priority to BE671693D priority patent/BE671693A/xx
Priority to NL6514088A priority patent/NL6514088A/xx
Priority to FR36755A priority patent/FR1461695A/en
Priority to GB45818/65A priority patent/GB1120737A/en
Publication of DE1226562B publication Critical patent/DE1226562B/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 Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

BUNDESREPUBLIK DEUTSCHLAND DEUTSCHES WWW PATENTAMTFEDERAL REPUBLIC OF GERMANY GERMAN WWW PATENT OFFICE

AUSLEGESCHRIFTEDITORIAL

Int. CL:Int. CL:

Nummer:
Aktenzeichen:
Anmeldetag:
Auslegetag:Number:
File number:
Registration date:
Display day:

C 07c C 07c

C07dC07d

Deutsehe "KL: 12 ο-16Deutsehe "KL: 12 ο-16

1226 562
B79138IVb/12o
30. Oktober 1964
13. Oktober 19661226 562
B79138IVb / 12o
October 30, 1964
October 13, 1966

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

O R2 OR 2

Il IIl I

R1-C-CHR 1 -C-CH

I
R3 I.
R 3

in der R1 einen Alkyl-, Aralkyl-, einen aromatischen oder heterocyclischen Rest oder den Rest — NHR4, worin R4 einen aliphatischen, araliphatischen, aromatischen oder heterocyclischen Rest bedeutet, R2 einen gegebenenfalls durch Chlor oder eine Äther-, Sulfon-, Nitro- oder Nitrilgruppe substituierten Alkyl- oder Aralkylrest und R3 Jod, Brom oder einen Benzolcarbonsäurerest bedeutet, in guten Ausbeuten erhält, wenn man Dimethyloxosulfurylene der allgemeinen Formel IIin which R 1 is an alkyl, aralkyl, an aromatic or heterocyclic radical or the radical - NHR 4 , in which R 4 is an aliphatic, araliphatic, aromatic or heterocyclic radical, R 2 is an optionally substituted by chlorine or an ether, sulfone , Nitro or nitrile group substituted alkyl or aralkyl radical and R 3 is iodine, bromine or a benzene carboxylic acid radical, obtained in good yields if dimethyloxosulfurylenes of the general formula II

OO

IlIl

R1C — CHR 1 C - CH

Verfahren zur Herstellung von
CarbonylverbindungenProcess for the production of
Carbonyl compounds

S=OS = O

CH3 CH3 CH 3 CH 3

worin R1 die vorstehend genannte Bedeutung hat, mit einem Alkylierungsmittel der Formel R2R3, worin R2 und R3 die vorstehend genannte Bedeutung haben, bei Temperaturen zwischen O und 1500C, gegebenenfalls in Gegenwart eines organischen Lösungsmittels, umsetzt.in which R 1 has the abovementioned meaning with an alkylating agent of the formula R 2 R 3 , in which R 2 and R 3 have the abovementioned meaning, at temperatures between 0 and 150 ° C., optionally in the presence of an organic solvent.

Das Verfahren läßt sich z. B. für die Umsetzung von Dimethyloxosulfurylen-acetanilid mit Methyljodid durch folgende Reaktionsgleichung wiedergegeben :The method can be z. B. for the implementation of Dimethyloxosulfurylen-acetanilid with methyl iodide represented by the following reaction equation:

IlIl

C6H5NH — C — CH + CH3JC 6 H 5 NH-C-CH + CH 3 J

Il s =0Il s = 0

/ \/ \

CH3 CH3
OCH 3 CH 3
O

-v C6H5-NH-C-CH-CH3 + CH3-SO-CH3 J-v C 6 H 5 -NH-C-CH-CH 3 + CH 3 -SO-CH 3 J

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

Die als Ausgangsstoffe der Formel II verwendeten Dimethyloxosulfurylene lassen sich 1. B. durch Umsetzung von 1 Mol Dimethyloxosulfoniumylid mit 1 Mol eines Isocyanats, Ketens, Carbonsäurehalogenide oder Carbonsäureanhydrids herstellen (vgl. die deutsche Auslegeschrift 1 207 379 und die französische Patentschrift 1 408 203). Für die Umsetzung nach dem Verfahren der Erfindung ist es nicht unbedingt erforderlich, die Dimethyloxosulfurylene der Formel II aus deren Herstellungsgemisch zu isolieren. Als Ausgangsstoffe kann man z. B. Dimethyloxosulfurylenacetanilid, Dimethyloxosulfurylenacettoluidid, Dimethyloxosulfurylenessigsäuremethylamid, Dimethyloxosulfurylenaceton, Dimethyloxosulfurylenacetophenon und Dimethyloxosulfurylen-N-phenyläthylacetamid verwenden.The Dimethyloxosulfurylene used as starting materials of the formula II can be 1, by reacting 1 mol of Dimethyloxosulfoniumylid with 1 mole of an isocyanate, ketene, carboxylic acid halides or carboxylic acid anhydride to produce (see. The German Auslegeschrift 1,207,379 and French Patent 1,408,203). For the reaction according to the process of the invention it is not absolutely necessary to isolate the dimethyloxosulfurylenes of the formula II from their preparation mixture. As starting materials you can, for. B. Dimethyloxosulfurylenacetanilid, Dimethyloxosulfurylenacettoluidid, Dimethyloxosulfurylenessigsäuremethylamid, Dimethyloxosulfurylenaceton, Dimethyloxosulfurylenacetophenon and Dimethyloxosulfurylen-N-phenyläthylacetamid use.

Als Alkylierungsmittel der Formel R2R3 kann man z. B. Methyljodid, Benzylbromid, Butylbromid, Benzoesäuremethylester, p-Nitrobenzoesäureäthylester, p-Methoxybenzoesäurebenzylester, Terephthalsäuredimethylester oder Phthalsäuredimethylester verwenden.The alkylating agent of the formula R 2 R 3 can be, for. B. use methyl iodide, benzyl bromide, butyl bromide, methyl benzoate, ethyl p-nitrobenzoate, benzyl p-methoxybenzoate, dimethyl terephthalate or dimethyl phthalate.

Das Verfahren läßt sich ohne Lösungsmittel durchführen. Man kann aber auch in Gegenwart von Lösungsmitteln arbeiten. Als Lösungsmittel eignen sich Kohlenwasserstoffe, wie Hexan, Heptan, Cyclohexan oder Benzol, ferner Äther, wie Diäthyläther oder Dibutyläther, Ν,Ν-disubstituierte Carbonsäureamide, wie Dimethylformamid oder N-Methylpyrrolidon. Ferner kann man als Lösungsmittel auch Alkanole mit niederer Kohlenstoffzahl verwenden, wie Methanol, Äthanol oder Butanol.The process can be carried out without a solvent. But you can also do it in the presence of Solvents work. Hydrocarbons such as hexane, heptane and cyclohexane are suitable solvents or benzene, also ethers, such as diethyl ether or dibutyl ether, Ν, Ν-disubstituted carboxamides, such as dimethylformamide or N-methylpyrrolidone. Alkanols can also be used as solvents Use with a lower carbon number such as methanol, ethanol or butanol.

Die Umsetzungsteilnehmer 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 reaction participants can be used in a stoichiometric amount. Advantageously one uses the Dimethyloxosulfurylen in a deficiency. This ensures that the Implementation in terms of the valuable Dimethyloxosulfurylenes is quantitative.

609 670/427609 670/427

Zur Abtrennung der gewünschten Verfahrensprodukte destilliert man im allgemeinen das Lösungsmittel und den überschüssigen Umsetzungsteilnehmer 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 implementation participants. From the residue you can then get the pure ones Substances, e.g. B. by distillation or recrystallization, win. But you can also use the process products by adding another solvent, e.g. B. water, precipitate from the reaction mixture and then detach.

Die nach dem Verfahren der Erfindung herstellbaren Stoffe sind wertvolle Zwischenprodukte für die Herstellung von Arznei- und Schädlingsbekämpfungsmitteln. The substances which can be prepared by the process of the invention are valuable intermediates for Manufacture of medicines and pesticides.

Die in den Beispielen angeführten Teile sind Gewichtsteile. X5The parts given in the examples are parts by weight. X5

Beispiel 1example 1

4,22 Teile Dimethyloxosulfurylen-acetanilid, 5 Teile Methyljodid und 500 Teile Methanol werden 100 Stunden bei 20° C gehalten. Das Methanol wird unter ver- ao mindertem Druck abdestilliert (20°C/10Torr). Der Rückstand wird aus mit Wasser verdünntem Methanol kristallisiert. Man erhält 2,15 Teile «-Jodpropionanilid vom F. = 131° C. Die Ausbeute beträgt 39% der Theorie, bezogen auf angewandtes Dimethyloxosulfurylen-acetanilid. 4.22 parts of dimethyloxosulfurylene acetanilide, 5 parts of methyl iodide and 500 parts of methanol are 100 hours held at 20 ° C. The methanol is distilled off under reduced pressure (20 ° C./10 Torr). Of the The residue is crystallized from methanol diluted with water. 2.15 parts of α-iodopropionic anilide are obtained from the F. = 131 ° C. The yield is 39% of theory, based on the dimethyloxosulfurylene acetanilide used.

Beispiel 2Example 2

44 Teile Trimethyloxosulfoniumjodid und 5,34 Teile 90%iges Natriumhydrid werden in 400 Teilen Di- 3u methylsulfoxyd gelöst. Man erhält so eine Lösung des Dimethyloxosulfomummethylids, die schnell mit 29,2 Teilen Benzoesäuremethylester versetzt wird.Man rührt 80 Stunden bei 25° C. Das jetzt neutrale Reaktionsgemisch wird durch Absaugen vom Natriumbenzoat befreit. Aus dem Filtrat fällt man mit Aceton und Essigester 14,5 Teile Trimethyloxosulfoniumjodid aus und filtriert es ab. Unter vermindertem Druck destilliert man aus dem Filtrat die Lösungsmittel ab und gewinnt durch Extraktion des Rückstandes mit Äthanol 5,05 Teile a-Benzoyloxy-äthyl-phenylketon; F. = 1060C. Die Ausbeute beträgt 40% der Theorie, bezogen auf angewandtes Trimethyloxosulfoniumjodid. 44 parts of trimethyloxosulfonium iodide and 5.34 parts of 90% sodium hydride are dissolved in 400 parts of dimethyl sulfoxide. This gives a solution of dimethyloxosulfomum methylide to which 29.2 parts of methyl benzoate are quickly added. The mixture is stirred for 80 hours at 25 ° C. The now neutral reaction mixture is freed from sodium benzoate by suction. 14.5 parts of trimethyloxosulfonium iodide are precipitated from the filtrate with acetone and ethyl acetate and filtered off. The solvent is distilled off from the filtrate under reduced pressure and 5.05 parts of α-benzoyloxy-ethyl-phenyl ketone are obtained by extracting the residue with ethanol; F. = 106 ° C. The yield is 40% of theory, based on the trimethyloxosulfonium iodide used.

Bei dieser Reaktion entsteht als nicht isoliertes Zwischenprodukt aus Dimethyloxo-sulfoniummethylid und Benzoesäuremethylester- zunächst Dimethyloxosulfurylen-acetophenon, das dann erfindungsgemäß die Methylgruppe und den Benzoatrest eines weiteren ' Moleküls Benzoesäuremethylesters unter Eliminierung von Dimethylsulf oxyd anlagert.In this reaction, dimethyloxosulfonium methylide is formed as a non-isolated intermediate and methyl benzoate- initially dimethyloxosulfurylene-acetophenone, which then according to the invention the methyl group and the benzoate radical of a further 'molecule of methyl benzoate with elimination of dimethyl sulfoxide is deposited.

Beispiel 3Example 3

Teile Dimethyloxosulfurylen-acetanilid und Teile Methyljodid werden 200 Stunden bei 25° C gehalten. Man digeriert den Rückstand mit Äther, destilliert das Lösungsmittel und überschüssiges Methyljodid ab und kristallisiert den Rückstand der Ätherschicht aus verdünntem Methanol um. Man erhält 102 Teile (37% der Theorie) a-Jodpropiananilid vom F. = 1310C.Parts of dimethyloxosulfurylene acetanilide and parts of methyl iodide are kept at 25 ° C. for 200 hours. The residue is digested with ether, the solvent and excess methyl iodide are distilled off and the residue of the ether layer is recrystallized from dilute methanol. To obtain 102 parts (37% of theory) of a-Jodpropiananilid mp = 131 0 C.

Claims (1)

Patentanspruch:Claim: Verfahren zur Herstellung von Caibonylver-X5 bindungen der allgemeinen FormelMethod of making Caibonylver-X5 bonds of the general formula O R2 OR 2 Il IIl I R1-C-CHR 1 -C-CH R3 R 3 in der R1 einen Alkyl-, Aralkyl-, einen aromatischen oder heterocyclischen Rest oder den Rest — NHR4, worin R4 einen aliphatischen, araliphatischen, aromatischen oder heterocyclischen Rest bedeutet, R2 einen gegebenenfalls durch Chlor oder eine Äther-, Sulfon-, Nitro- oder Nitrilgruppe substituierten Alkyl- oder Aralkylrest und R3 Jod, Brom oder einen Benzolcarbonsäurerest bedeutet, dadurch gekennzeichnet, daß man Dimethyloxosulfurylene der allgemeinen Formelin which R 1 is an alkyl, aralkyl, an aromatic or heterocyclic radical or the radical - NHR 4 , in which R 4 is an aliphatic, araliphatic, aromatic or heterocyclic radical, R 2 is an optionally substituted by chlorine or an ether, sulfone , Nitro or nitrile group substituted alkyl or aralkyl radical and R 3 is iodine, bromine or a benzene carboxylic acid radical, characterized in that dimethyloxosulfurylenes of the general formula IlIl R1-C-CHR 1 -C-CH IlIl CH3 CH3 CH 3 CH 3 worin R1 die vorstehend genannte Bedeutung hat, mit einem Alkylierungsmittel der Formel R2R3, worin R2 und R3 die vorstehend genannte Bedeutung haben, bei Temperaturen zwischen 0 und 150° C, gegebenenfalls in Gegenwart eines organischen Lösungsmittels, umsetzt.in which R 1 has the abovementioned meaning, is reacted with an alkylating agent of the formula R 2 R 3 , in which R 2 and R 3 have the abovementioned meaning, at temperatures between 0 and 150 ° C., optionally in the presence of an organic solvent. In Betracht gezogene Druckschriften:
Journal of the American Chemical Society, Bd. 84, 1962, S. 867.Considered publications:
Journal of the American Chemical Society, Vol. 84, 1962, p. 867. 609 670/427 10.66 © Bundesdruckerei Berlin609 670/427 10.66 © Bundesdruckerei Berlin
DEB79138A 1964-10-30 1964-10-30 Process for the preparation of carbonyl compounds Pending DE1226562B (en)

Priority Applications (10)

Application Number Priority Date Filing Date Title
DEB87722A DE1239288B (en) 1964-10-30 1964-10-30 Process for the preparation of carbonyl compounds
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
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
BE671693D BE671693A (en) 1964-10-30 1965-10-29
NL6514088A NL6514088A (en) 1964-10-30 1965-10-29
FR36755A FR1461695A (en) 1964-10-30 1965-10-29 Process for the production of alpha-substituted carbonyl compounds
GB45818/65A GB1120737A (en) 1964-10-30 1965-10-29 Production of carbonyl compounds substituted in ª‡-position
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
DEB87722A DE1239288B (en) 1964-10-30 1964-10-30 Process for the preparation of carbonyl compounds
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
DEB79139A DE1226563B (en) 1964-10-30 1964-10-30 Process for the preparation of carbonyl compounds

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DE1226562B true DE1226562B (en) 1966-10-13

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DEB79139A Pending DE1226563B (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
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

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DEB79139A Pending DE1226563B (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
DEB87722A Pending DE1239288B (en) 1964-10-30 1964-10-30 Process for the preparation of carbonyl compounds

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

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0122576A1 (en) * 1983-04-16 1984-10-24 BASF Aktiengesellschaft Process for the production of vicinal polycarbonyl compounds

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Publication number Priority date Publication date Assignee Title
CN115557865B (en) * 2022-10-17 2024-05-14 南京工业大学 A thioether-promoted cysteine-based bioconjugation method

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0122576A1 (en) * 1983-04-16 1984-10-24 BASF Aktiengesellschaft Process for the production of vicinal polycarbonyl compounds

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GB1120737A (en) 1968-07-24
DE1239288B (en) 1967-04-27
NL6514088A (en) 1966-05-02
BE671693A (en) 1966-04-29
CH468970A (en) 1969-02-28
DE1226563B (en) 1966-10-13
DE1238454B (en) 1967-04-13

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