DE1793721B2 - PHENYLALLYL SULPHONES AND THE METHOD OF MANUFACTURING THEREOF - Google Patents
PHENYLALLYL SULPHONES AND THE METHOD OF MANUFACTURING THEREOFInfo
- Publication number
- DE1793721B2 DE1793721B2 DE19671793721 DE1793721A DE1793721B2 DE 1793721 B2 DE1793721 B2 DE 1793721B2 DE 19671793721 DE19671793721 DE 19671793721 DE 1793721 A DE1793721 A DE 1793721A DE 1793721 B2 DE1793721 B2 DE 1793721B2
- Authority
- DE
- Germany
- Prior art keywords
- bromo
- phenyl
- sodium
- product
- mixture
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C21/00—Acyclic unsaturated compounds containing halogen atoms
- C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
- C07C21/14—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds containing bromine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C22/00—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom
- C07C22/02—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings
- C07C22/04—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings containing six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C35/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring
- C07C35/02—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring monocyclic
- C07C35/04—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring monocyclic containing a three or four-membered rings
- C07C35/045—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring monocyclic containing a three or four-membered rings containing a four-membered ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/487—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
- C07C51/60—Preparation of carboxylic acid halides by conversion of carboxylic acids or their anhydrides or esters, lactones, salts into halides with the same carboxylic acid part
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C61/00—Compounds having carboxyl groups bound to carbon atoms of rings other than six-membered aromatic rings
- C07C61/16—Unsaturated compounds
- C07C61/35—Unsaturated compounds having unsaturation outside the rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C61/00—Compounds having carboxyl groups bound to carbon atoms of rings other than six-membered aromatic rings
- C07C61/16—Unsaturated compounds
- C07C61/40—Unsaturated compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/42—Singly bound oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D309/04—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D309/08—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D309/10—Oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/16—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D309/20—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hydrogen atoms and substituted hydrocarbon radicals directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12C—BEER; PREPARATION OF BEER BY FERMENTATION; PREPARATION OF MALT FOR MAKING BEER; PREPARATION OF HOPS FOR MAKING BEER
- C12C11/00—Fermentation processes for beer
- C12C11/02—Pitching yeast
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Genetics & Genomics (AREA)
- Health & Medical Sciences (AREA)
- Mycology (AREA)
- Bioinformatics & Cheminformatics (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Food Science & Technology (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Microbiology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
R,'R, '
bedeutet, worin Ri' einen Alkylrest mit 2 bis 6 Kohlenstoffatomen oder einen Phenylrest und R2' einen Alkylrest mit 1 bis 6 Kohlenstoffatomen oder einen Phenylrest bedeuten oder Ri' und R2' zusammen mit dem Kohlenstoffatom, an das sie gebunden sind, entweder einen gesättigten oder ungesättigten Kohlenstoffhomocyclus mit 5 oder 6 Kohlenstoffatomen, der durch einen oder mehrere Methylreste substituiert sein kann, oder einen gesättigten Heterocyclus, der ein Sauerstoffatom enthält, bilden.means in which Ri 'is an alkyl radical with 2 to 6 Carbon atoms or a phenyl radical and R2 'an alkyl radical having 1 to 6 carbon atoms or denote a phenyl radical or Ri 'and R2' together with the carbon atom to which they are attached are bonded, either a saturated or unsaturated carbon homocycle with 5 or 6 Carbon atoms, which can be substituted by one or more methyl radicals, or one saturated heterocycle containing one oxygen atom.
2. Verfahren zur Herstellung von Verbindungen der Formel V gemäß Anspruch 1, dadurch gekennzeichnet, daß man in an sich bekannter Weise ein Alkalimetallphenylsulfinat der Formel2. Process for the preparation of compounds of the formula V according to claim 1, characterized characterized in that an alkali metal phenylsulfinate of the formula is used in a manner known per se
SO2MSO 2 M
(Π)(Π)
worin M ein Alkalimetall, wie Natrium oder Kalium, bedeutet, mit einem halogenierten Allylderivat der Formelwherein M is an alkali metal such as sodium or potassium, with a halogenated allyl derivative of formula
H—A—X (HI)H — A — X (HI)
worin X ein Jod-, Brom-, Chloratom, die Mesyl- oder Tosylgruppe bedeutet und HA die in Anspruch 1 angegebene Bedeutung besitzt, umsetzt.wherein X is an iodine, bromine, chlorine atom, the mesyl or tosyl group and HA is the one in claim 1 has given meaning, implements.
dem Kohlenstoffatom, an das sie gebunden sind, entweder einen |esf ttigten oder ungesättigten Kohlensbffhomocyclu§ mit'5 oder 6 Kohlenstoffatomen, der durch einen oder mehrere Methylreste substituiert seinthe carbon atom to which they are attached, either a saturated or unsaturated carbon homocycle having 5 or 6 carbon atoms, which may be substituted by one or more methyl radicals
kann, oder einen gesättigten Heterocyclus, der ein Sauerstoffatom enthält, bilden.can, or a saturated heterocycle, which is a Containing oxygen atom.
Des weiteren betrifft die Erfindung ein Verfahren zur Herstellung von Verbindungen der vorstehenden Formel V das dadurch gekennzeichnet ist, daß man inThe invention also relates to a method for Preparation of compounds of the above formula V which is characterized in that in
.„ an sich bekannter Weise ein Alkalimetallphenylsulfinat der Formel. “In a manner known per se, an alkali metal phenyl sulfinate the formula
-SO2M-SO 2 M
worin M ein Alkalimetall, wie Natrium oder Kalium, bedeutet, mit einem halogenierten Allylderivat der Formelwherein M is an alkali metal such as sodium or potassium, with a halogenated allyl derivative of formula
20 Η—Α—Χ 20 Η — Α — Χ
worin X ein Jod-, Brom-, Chloratom, die Mesyl- oder Tosylgruppe bedeutet und HA die in Anspruch 1 angegebene Bedeutung besitzt, umsetztwherein X is an iodine, bromine, chlorine atom, the mesyl or Is tosyl group and HA has the meaning given in claim 1, converts
Die zur Herstellung der Sulfone der allgemeinen Formel I durchgeführte Umsetzung wird yorteilhafterweise in Gegenwart eines Lösungsmittels insbesondere in methanolischem oder äthanolischem Milieu und in Gegenwart eines basischen Mittels, wie eines Alkalimew tallcarbonats oder -acetats, durchgeführt Man arbeitet vorzugsweise in Methanol, wobei man als basisches Reagens Natrium- oder Kaliumcarbonat verwendetThe processing performed to prepare the sulfones of the general formula I reaction is yorteilhafterweise in the presence of a solvent, in particular in methanolic or ethanolic medium and in the presence of a basic agent such as an Alkalime w tallcarbonats or -acetate, carried out is preferably carried out in methanol to give as a basic Sodium or potassium carbonate reagent used
Alternativ können die Sulfone der allgemeinen Formel I durch Umsetzung des Alkalimetallphenylsulfinats der Formel II in Gegenwart von Ameisensäure mit einem Alkohol HA-OH hergestellt werden.Alternatively, the sulfones of the general formula I can be obtained by reacting the alkali metal phenyl sulfinate of formula II in the presence of formic acid with an alcohol HA-OH.
Die Sulfone der allgemeinen Formel I können auch durch Anwendung des in der französischen Patentschrift 14 83 715 beschriebenen Verfahrens erhalten werden.The sulfones of the general formula I can also be prepared by using the in the French patent 14 83 715 described method can be obtained.
Die erfindungsgemäßen Sulfone stellen wichtige Verbindungen zur Herstellung der Säure- und Esterderivate des Cyclopropans gemäß der Stammanmeldung dar. Dabei wird das Phenylallylsulfon mit einer Verbindung der allgemeinen FormelThe sulfones according to the invention are important compounds for the preparation of the acid and ester derivatives of the cyclopropane according to the parent application. The phenylallylsulfone with a Compound of the general formula
CH3 CH 3
Die Erfindung betrifft Phenylallylsulfone der augemeinen FormelThe invention relates in particular to phenylallylsulfones formula
CH3 CH 3
C=CH-CO2R'"C = CH-CO 2 R '"
m worin R" einen gegebenenfalls substituierten niederenm wherein R "is an optionally substituted lower one
Alkylrest bedeutet, umgesetzt und der erhaltene Ester der allgemeinen FormelAlkyl radical means converted and the ester obtained the general formula
worin HA die Allylgruppewhere HA is the allyl group
6060
C=CH-CH2 C = CH-CH 2
OR"OR "
bedeutet, worin Ri' einen Alkylrest mit 2 bis 6 Kohlenstoffatomen oder einen Phenylrest und R2' einen Alkylrest mit 1 bis 6 Kohlenstoffatomen oder einen Phenvlrest bedeuten oder Ri' und R2' zusammen mit 65 denotes where Ri 'denotes an alkyl radical having 2 to 6 carbon atoms or a phenyl radical and R2' denotes an alkyl radical having 1 to 6 carbon atoms or a phenyl radical, or Ri 'and R2' together with 65
einer üblichen alkalischen Hydrolyse unterworfen und die Säure gegebenenfalls in ihre optisch aktiven Isomeren aufgetrennt. Demnach erlauben es diesubjected to a customary alkaline hydrolysis and the acid optionally converted to its optically active Isomers separated. So they allow it
erfüidungsgemäöen Verbindungen, in einer einzigen Stufe und somit in vorteilhafter Weise zu sehr wichtigen Cyclopropancarbonsäuren mit großer Variation der Substituenten in 2- und 3-Steüung zu gelangen, wobei viele dieser neuen Säuren zu Estern mit Insektiziden s Eigenschaften führen, z. B.compliant connections, in a single Stage and thus advantageously to very important cyclopropanecarboxylic acids with great variation in the To get substituents in 2- and 3-Steüung, with many of these new acids lead to esters with insecticidal properties, e.g. B.
dl-Allethrolon-di-trans-33-dimethyl-dl-allethrolone-di-trans-33-dimethyl-
2-{2"-äthyH'-butenyl)-cyclopropan-2- {2 "-äthyH'-butenyl) -cyclopropane-
carboxylat,carboxylate,
m-Cinerolon-dl-trans-33-dimethyl-2-cyclopentylidenmethyl-l-cyclopropan- m-Cinerolon-dl-trans-33-dimethyl-2-cyclopentylidenemethyl-l-cyclopropane-
carboxylatundcarboxylate and
S-Benzyl-S-iurylmethyl-dl- und -d-trans-S-Benzyl-S-iurylmethyl-dl- and -d-trans-
Sß-dimethyl^-cyclopentylidenmethyl-Sß-dimethyl ^ -cyclopentylidenemethyl-
1-cydopropancarboxylat1-cydopropane carboxylate
Die ei-findtragsgemäßen Sulfone eröffnen somit einen neuen Weg zur Herstellung der verschiedenartigen Cyclopropancarbonsäuren, von denen viele sehr ausgeprägte insektizide Wirkung aufweisen.The sulfones according to the present invention thus open up one new way of producing the various types of cyclopropanecarboxylic acids, many of which are very pronounced have insecticidal effects.
Das erfindungsgemäße Verfahren besitzt den Vorteil der sehr allgemeinen Anwendbarkeit Man erhält ein Sulfon der allgemeinen Formel I, bei dem die Allylgruppe H-A die verschiedensten Strukturen aufweisen kann.The process according to the invention has the advantage that it can be used very generally Sulphone of the general formula I, in which the allyl group H-A has a wide variety of structures may have.
Beispiel 1
(3-Äthyl-2-pentenyl)-phenylsulfonexample 1
(3-ethyl-2-pentenyl) phenyl sulfone
In 60 cm3 Methanol suspendiert man 1,85 g Natriumcarbonat und 18,5 g Natriumphenylsuifinat und gibt zu der erhaltenen Suspension im Verlauf von etwa 30 Minuten bei Raumtemperatur 20 g l-Brom-3-äthyl-2-penten. Man rührt noch eine Stunde und 30 Minuten bei Raumtemperatur, gießt die Reaktionsmischung in Eiswasser, trennt die organische Phase durch Dekantieren ab, extrahiert die wäßrige Phase mit Ätiiyläther, vereinigt die Ätherextrakte mit der organischen Hauptlösung, trocknet die erhaltene Lösung über Magnesiumsulfat, entfernt das Lösungsmittel bei vermindertem Druck und erhält 21,665 g (3-Äthyl-2-pentenyl)-phenylsulfon. 1.85 g of sodium carbonate and 18.5 g of sodium phenyl sulfinate are suspended in 60 cm 3 of methanol, and 20 g of 1-bromo-3-ethyl-2-pentene are added to the suspension obtained in the course of about 30 minutes at room temperature. The mixture is stirred for an hour and 30 minutes at room temperature, the reaction mixture is poured into ice water, the organic phase is separated off by decanting, the aqueous phase is extracted with ethyl ether, the ether extracts are combined with the main organic solution, the resulting solution is dried over magnesium sulfate and the solvent is removed at reduced pressure and receives 21.665 g (3-ethyl-2-pentenyl) -phenylsulfone.
Eine Probe dieses Produkts wird bei vermindertem Druck rektifiziert: Kp.=125° C bei 0,02 mm Hg, π 2=1,530.A sample of this product is rectified under reduced pressure: b.p. = 125 ° C at 0.02 mm Hg, π 2 = 1.530.
Analyse:Ci3 Hi8 SO2 (23834)
Berechnet:C65,53, H 7,61, S 13,46%;
gefunden: C 65,4, H 7,6, S 13,2%.Analysis: Ci3 Hi 8 SO 2 (23834)
Calculated: C65.53, H 7.61, S 13.46%;
found: C 65.4, H 7.6, S 13.2%.
Dieses Produkt ist in der Literatur nicht beschrieben.This product is not described in the literature.
Beispiel 2
(3-Isobutyl-5-methyl-2-hexenyl)-phenylsulfonExample 2
(3-Isobutyl-5-methyl-2-hexenyl) phenyl sulfone
In 500 cm3 Methanol löst man 55 g Natriumphenylsuifinat, fügt 8 g Kaliumcarbonat, 1 g Natriumiodid und dann 71 g l-Brom-3-isobutyl-5-methyl-2-hexen zu und rührt 15 Stunden bei Raumtemperatur. Dann verdampft man bei vermindertem Druck zur Trockne, fügt Wasser zu, extrahiert die wäßrige Phase mit Methylenchlorid, vereinigt die Methylenchloridextrakte, wäscht die erhaltene organische Lösung mit Wasser, trocknet diese und verdampft bei vermindertem Druck zur Trockne.55 g of sodium phenyl sulfinate are dissolved in 500 cm 3 of methanol, 8 g of potassium carbonate, 1 g of sodium iodide and then 71 g of 1-bromo-3-isobutyl-5-methyl-2-hexene are added and the mixture is stirred for 15 hours at room temperature. The mixture is then evaporated to dryness under reduced pressure, water is added, the aqueous phase is extracted with methylene chloride, the methylene chloride extracts are combined, the organic solution obtained is washed with water, dried and evaporated to dryness under reduced pressure.
Der Rückstand wird an einer Aluminiumoxydsäule Chromatographien, man erhält 62,32 g (3-Isobutyl-5-methyl-2-hexenyl)-phenylsulfon. The residue is chromatographed on an aluminum oxide column, 62.32 g of (3-isobutyl-5-methyl-2-hexenyl) -phenylsulfone are obtained.
n« Produkt ist in der Literatur nicht beschrieben.n «The product is not described in the literature.
5555
6060
65 Beispiel 3
33-Diphenyl-(2-propenyl)-phenylsulfon 65 Example 3
33-diphenyl (2-propenyl) phenyl sulfone
In 80 cm3 Methanol suspendiert man 15,5 g Natriumphenylsuifinat und 1,5 g Natriumcarbonat ein, fügt bei Raumtemperatur unter einer Stickstoffatmosphäre 25,6 g l-Brom-33-diphenyl-2-propen zu und rührt eine Stunde und 30 Minuten. Dann gießt man in kaltes Wasser, extrahiert mit Methylenchlorid, vereinigt die Methylenchloridextrakte, wäscht die erhaltene organische Lösung mit Wasser, trocknet sie und verdampft zur Trockne. Der Rückstand kristallisiert teilweise. Man isoliert den gebildeten Niederschlag durch Absaugen, trocknet und erhält 25,48 g 33-Diphenyl-(2-propenyl)-phenylsulfon mit einem F= 1040C.15.5 g of sodium phenyl sulfinate and 1.5 g of sodium carbonate are suspended in 80 cm 3 of methanol, 25.6 g of 1-bromo-33-diphenyl-2-propene are added at room temperature under a nitrogen atmosphere and the mixture is stirred for one hour and 30 minutes. It is then poured into cold water, extracted with methylene chloride, the methylene chloride extracts are combined, the organic solution obtained is washed with water, dried and evaporated to dryness. The residue partially crystallizes. Isolating the precipitate formed by filtration with suction, and dried to give 25.48 g of 33-diphenyl (2-propenyl) -phenylsulfon with an F = 104 0 C.
Eine Probe wird in Isopropyläther kristallisiert: F= 1060CA sample is crystallized in isopropyl ether: F = 106 ° C
Analyse: C21 Hi8SO2 (334,43)
Berechnete 75,41, H 5,42, S 9,58%;
gefunden: C 75,3, H 5,4, S 9,4%.Analysis: C21 Hi 8 SO 2 (334.43)
Calculated 75.41, H 5.42, S 9.58%;
found: C 75.3, H 5.4, S 9.4%.
Das Produkt ist in der Literatur nicht beschrieben.The product is not described in the literature.
Beispiel 4
(2-Cyclopentylidenäthyl)-phenylsulfonExample 4
(2-Cyclopentylidenethyl) phenyl sulfone
In 50 cm3 Methanol suspendiert man 223 g Natriumphenylsuifinat, 2,2 g Kaliumcarbonat, 0,2 g Natriumjodid ein und fügt bei etwa +100C unter Rühren 23,6. g l-Brom-2-cyclopentylidenäthan zu und rührt 2 Stunden bei 200C. Man gießt die Reaktionsmischung in Eiswasser, kühlt auf 00C isoliert den gebildeten Niederschlag durch Absaugen und trocknet im Vakuum in Gegenwart von Kaliumhydroxyd.Suspended in 50 cm 3 of methanol, 223 g Natriumphenylsuifinat, 2.2 g of potassium carbonate, 0.2 g of sodium iodide and added at about +10 0 C with stirring 23.6. g of 1-bromo-2-cyclopentylidenethane are added and the mixture is stirred for 2 hours at 20 ° C. The reaction mixture is poured into ice water, cooled to 0 ° C., the precipitate formed is isolated by suction and dried in vacuo in the presence of potassium hydroxide.
Man erhält 15 g (2-Cyclopentylidenäthyl)-phenylsulfon mit einem F=68° C15 g of (2-cyclopentylidene ethyl) phenyl sulfone are obtained with an F = 68 ° C
Eine Probe dieses Produkts wird in Isopropyläther kristallisiert: F=68° CA sample of this product is crystallized from isopropyl ether: F = 68 ° C
Analyse: CuHi6SO2 (236,33)
Berechnet: C 66,06, H 6,82, S 13,57%;
gefunden: C 65,8, H 6,8, S 13,2%.Analysis: CuHi 6 SO 2 (236.33)
Calculated: C 66.06, H 6.82, S 13.57%;
found: C 65.8, H 6.8, S 13.2%.
Das Produkt ist in der Literatur nicht beschrieben.The product is not described in the literature.
Das l-Brom-2-cyclopentylidenäthan kann nach dem in Bull. Soc. Chim, 1964,2618, beschriebenen Verfahren hergestellt werden.The l-bromo-2-cyclopentylidenethane can be prepared according to the in Bull. Soc. Chim, 1964, 2618 getting produced.
B e i s ρ i e 1 5
(2-Cyclohexylidenäthyl)-phenylsulfonB is ρ ie 1 5
(2-Cyclohexylidenäthyl) -phenylsulfon
In 116 cm3 Methanol suspendiert man 384 g Natriumphenylsuifinat und dann 3,85 g Natriumcarbonat ein und fügt tropfenweise unter Rühren im Verlauf von etwa 30 Minuten bei Raumtemperatur 44 g frisch hergestelltes l-Brom-2-cyclohexylidenäthan zu. Man rührt noch eine Stunde und 30 Minuten bei Raumtemperatur und gießt dann die Reaktionsmischung in 400 cm3 Eiswasser. Man saugt den gebildeten Niederschlag ab, wäscht ihn mit Wasser und trocknet Das so erhaltene Rohprodukt wird in der Wärme in einer Mischung von Methylenchlorid und Methanol gelöst Die erhaltene Lösung wird über Magnesiumsulfat getrocknet, auf ein geringes Volumen konzentriert und zu Isopropyläther gegeben. Der gebildete Niederschlag wird abgesaugt und getrocknet, und man erhält 36,4 g (2-Cyclohexylidenäthyl)-phenylsu!fon mit einem F=70° C.384 g of sodium phenyl sulfinate and then 3.85 g of sodium carbonate are suspended in 116 cm 3 of methanol and 44 g of freshly prepared 1-bromo-2-cyclohexylidene ethane are added dropwise with stirring over the course of about 30 minutes at room temperature. The mixture is stirred for a further hour and 30 minutes at room temperature and the reaction mixture is then poured into 400 cm 3 of ice water. The precipitate formed is filtered off with suction, washed with water and dried. The crude product obtained in this way is dissolved in a warm mixture of methylene chloride and methanol. The solution obtained is dried over magnesium sulfate, concentrated to a small volume and added to isopropyl ether. The precipitate formed is filtered off with suction and dried, and 36.4 g of (2-cyclohexylideneethyl) phenylsulfone with an F = 70 ° C. are obtained.
Eine Probe dieses Produkts wird in Isopropyläther für die Analyse gereinigt: F=70° CA sample of this product is purified in isopropyl ether for analysis: F = 70 ° C
Analyse:Ci4H,8SO2(25035)Analysis: Ci4H, 8SO2 (25035)
Berechnete 67,16, H 7,24, S 12,81%;
gefunden: C 67, H 7,1, S 12,5%.Calculated 67.16, H 7.24, S 12.81%;
found: C 67, H 7.1, S 12.5%.
Das Produkt ist in der Literatur nicht beschrieben.The product is not described in the literature.
Das l-Brom-2-Cydohexylidenäthan kann nach dem in Helvetica 25 {1942) 29 beschriebenen Verfahren hergestellt werden.The l-bromo-2-Cydohexylidenäthan can after in Helvetica 25 (1942) 29 described processes.
Geht man gleichermaßen von verschiedenen haiogenierten AUylderivaten aus, so erhält man in analoger Weise, wie in den vorstehenden Beispielen, verschiedene Arylallylsulfone:If one equally starts from different halogenated AUyl derivatives, one obtains an analogous one As in the examples above, various aryl allyl sulfones:
Beispiel 6example 6th
Ausgangsprodukt Starting product
1 -Brom-S-propyW-hexen1 -Bromo-S-propyW-hexen
(3-Propyl-2-hexenyl)-phenylsulfon (3-propyl-2-hexenyl) phenyl sulfone
1 -Brom-3-(isopropyl)-4-methyl-2-penten 1 -Bromo-3- (isopropyl) -4-methyl-2-pentene
p-IsoprapyM-methyl-2-pentenyl)-phenylsulfon, F = 500Cp-IsoprapyM-methyl-2-pentenyl) -phenylsulfon, F = 50 0 C
1 -Brom-2 -(2',6'-dimethylcyclohexyliden)-äthan 1 -Bromo-2 - (2 ', 6'-dimethylcyclohexylidene) ethane
[2-{2',6'-Dimethylcyclohexyliden)-athy^phenylsulfon, F = 96°C[2- {2 ', 6'-Dimethylcyclohexylidene) -athy ^ phenylsulfon, F = 96 ° C
Beispiel 9example 9
1010
1111th
1212th
Ausgangs- 1 -Brom-2-(4',4'-dimethylprodukt cyclohexylidenj-äthanStarting 1-bromo-2- (4 ', 4'-dimethyl product cyclohexylidenj-ethane
[2-(4',4'-Dimethyl-cyclohexyüden)-äthyl]phenylsulfon,F = 1100C[2- (4 ', 4'-dimethyl-cyclohexyüden) ethyl] phenyl sulfone, F = 110 0 C.
l-Brom-2-(3',3',5',5'-te-l-bromo-2- (3 ', 3', 5 ', 5'-te-
tramethyl-cyclohexyl-tramethyl-cyclohexyl-
iden)-äthaniden) -ethane
[2-(3',3',5',5'-Tetrame-[2- (3 ', 3', 5 ', 5'-tetram-
thyl-cyclohexyliden)-ethyl cyclohexylidene) -
äthyl]-phenylsulfon.ethyl] phenyl sulfone.
l-Brom-2-(2',3',5',6'-te- l-Brom-2-cyclotrahydro-4'-pyranyliden)-butylidenäthan
äthan1-bromo-2- (2 ', 3', 5 ', 6'-te- 1-bromo-2-cyclotrahydro-4'-pyranylidene) butylidene ethane
ethane
55°C55 ° C
[2-(2',3',5',6'-Tetrahydro-4'-pyranyliden)-äthyl]-
phenylsulfon, F = 68° C[2- (2 ', 3', 5 ', 6'-tetrahydro-4'-pyranylidene) ethyl] -
phenyl sulfone, m.p. 68 ° C
(2-Cyclobutyliden)-phenylsulfon
F = 76 bis 78° C(2-cyclobutylidene) phenyl sulfone
F = 76 to 78 ° C
Die erhaltenen Sulfone sind in der Literatur nicht beschrieben.The sulfones obtained are not described in the literature.
Beispiel 13
(3-Methyl-2-cyclohexenyl)-phenylsulfonExample 13
(3-methyl-2-cyclohexenyl) phenyl sulfone
in 400 cm3 Ameisensäure bringt man 34,2 g rohes 3-Methyl-2-cyclohexen-l-ol ein, fügt 68 g Natriumphenylsulfinat zu und rührt etwa 15 Minuten bei Raumtemperatur. Man gießt in eine Mischung von Wasser und Eis, extrahiert mit Methylenchlorid, vereinigt die Methylenchloridextrakte, wäscht die erhaltene Lösung mit Wasser, dann mit einer wäßrigen Natnumbicarbonatlösung und schließlich mit Wasser,34.2 g of crude 3-methyl-2-cyclohexen-1-ol are introduced into 400 cm 3 of formic acid, 68 g of sodium phenylsulfinate are added and the mixture is stirred at room temperature for about 15 minutes. It is poured into a mixture of water and ice, extracted with methylene chloride, the methylene chloride extracts are combined, the resulting solution is washed with water, then with an aqueous sodium bicarbonate solution and finally with water,
trocknet und verdampft zur Trockne.
Der Rückstand wird zu einer Mischung vondries and evaporates to dryness.
The residue becomes a mixture of
Isopropyläther und Petroläther gegeben. Man isoliert den gebildeten Niederschlag durch Filtrieren, wäscht, trocknet und erhält 47 g (3-Methyl-2-cyclohexenyl)-phe-Given isopropyl ether and petroleum ether. The precipitate formed is isolated by filtering, washing, dries and receives 47 g (3-methyl-2-cyclohexenyl) -phe-
nylsulfon.
Eine Probe dieses Produkts wird durch Auflösen innylsulfone.
A sample of this product is prepared by dissolving in
Methylenchlorid, Konzentrieren und Zugabe von Isopropyläther gereinigt: F= 700C.Methylene chloride, concentrating and adding isopropyl ether, purified: F = 70 0 C.
Analyse: CuHi6O2S (236,33)Analysis: CuHi 6 O 2 S (236.33)
Berechnete 66,06, H 6,82, S 13,57%;
gefunden: C 66,3, H 6,8, S 13,3%.Calculated 66.06, H 6.82, S 13.57%;
found: C 66.3, H 6.8, S 13.3%.
Das Produkt ist in der Literatur nicht beschrieben.The product is not described in the literature.
Claims (1)
1. Phenylallylsulfonedev-allgemeinen FormelPatent claims:
1. Phenylallylsulfonedev-general formula
Applications Claiming Priority (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR74405A FR1505423A (en) | 1966-08-26 | 1966-08-26 | New derivatives of cyclopropane and method of preparation |
| FR74405 | 1966-08-26 | ||
| FR74404A FR1507192A (en) | 1966-08-26 | 1966-08-26 | Novel aryl allylsulfones and method of preparation |
| FR96425A FR1527844A (en) | 1966-08-26 | 1967-02-24 | New acids and esters derived from cyclopropane and method of preparation |
| FR96425 | 1967-02-24 | ||
| FR110719A FR93112E (en) | 1966-08-26 | 1967-06-16 | New derivatives of cyclopropane and method of preparation. |
| FR110719 | 1967-06-16 | ||
| FR114833A FR94309E (en) | 1966-08-26 | 1967-07-19 | New cyclopropane derivatives and method of preparation. |
| FR114833 | 1967-07-19 | ||
| FR74404 | 1975-12-16 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DE1793721A1 DE1793721A1 (en) | 1972-10-19 |
| DE1793721B2 true DE1793721B2 (en) | 1976-12-23 |
| DE1793721C3 DE1793721C3 (en) | 1977-08-25 |
Family
ID=
Also Published As
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE1289046B (en) | Process for the production of trans-chrysanthemum monocarboxylic acid or their functional derivatives | |
| DE2715080A1 (en) | PROCESS FOR THE PRODUCTION OF CYCLOPENTENONE DERIVATIVES | |
| DE2241680C2 (en) | 17-Hydroxy-7-alkoxycarbonyl-3-oxo-17α-prepregn-4-ene-21-carboxylic acid-γ-lactones and processes and intermediates for their preparation | |
| DE1793721C3 (en) | Phenylallylsulfones and process for their preparation | |
| DE1793721B2 (en) | PHENYLALLYL SULPHONES AND THE METHOD OF MANUFACTURING THEREOF | |
| DE2415765C2 (en) | ||
| DE906222C (en) | Process for the preparation of trioxo compounds | |
| DE2029043A1 (en) | New cyclopropanecarboxylic acid derivatives and processes for their preparation | |
| DE1443278A1 (en) | Process for the production of spirocyclic keto alcohols | |
| DE957123C (en) | Process for the production of colchicine thioabules | |
| DE2702370C2 (en) | Prostaglandin analogues, processes for their preparation and medicaments containing them | |
| DE962256C (en) | Process for the production of serines from glycocolla and aldehydes | |
| AT267493B (en) | Process for the preparation of d, 1-trans-chrysanthemum acid and its functional derivatives | |
| DE838140C (en) | Process for the preparation of amino-aryl-pyridlyl-alkanols and their esters | |
| DE804563C (en) | Process for the preparation of esters of butanediol-1, 4-one-2 and its homologues | |
| DE1668631C3 (en) | ||
| AT217994B (en) | Process for the preparation of new derivatives of polyhydroxy alcohols | |
| DE900935C (en) | Process for the preparation of 12-bromo-3-acyloxy-5,7,9 (11) -pregnatrien-20-one addition products | |
| DE1142595B (en) | Process for the preparation of 4- (2,6,6-trimethyl-cyclohexen- (1) -yl) -2-methylbutene- (3) -al- (1) | |
| EP0181409A1 (en) | 15(r+s)-fluorine-11,15-didesoxyprostaglandin e 1? derivatives | |
| DE1468333C (en) | 17alpha-Chloräthinyl-19-nor-5 (10> androstan-17beta-ol-3on, 17alpha-Chloräthinyl-19-nor-4-androsten-17beta-ol-3on and a process for their preparation | |
| DE1050765B (en) | Process for the preparation of testan-3a-ol-II-one and its esters | |
| CH303086A (en) | Process for the production of a coumarin derivative. | |
| DE1817881B2 (en) | ||
| DE3742437A1 (en) | 5-HYDROXI-PGF (DOWN ARROW) 1 (DOWN ARROW) (DOWN ARROW) (ALPHA) (DOWN ARROW) -1,5-LACTONE DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND PHARMACEUTICAL PRODUCTS CONTAINING THESE COMPOUNDS |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C3 | Grant after two publication steps (3rd publication) | ||
| E77 | Valid patent as to the heymanns-index 1977 |