DE1793721A1 - New Arylallylsulfones and Process for Their Preparation - Google Patents

New Arylallylsulfones and Process for Their Preparation

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Publication number
DE1793721A1
DE1793721A1 DE19671793721 DE1793721A DE1793721A1 DE 1793721 A1 DE1793721 A1 DE 1793721A1 DE 19671793721 DE19671793721 DE 19671793721 DE 1793721 A DE1793721 A DE 1793721A DE 1793721 A1 DE1793721 A1 DE 1793721A1
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radical
aryl
formula
alkali metal
substituents
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DE19671793721
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DE1793721C3 (en
DE1793721B2 (en
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Chanh Huynh
Jacques Martel
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Sanofi Aventis France
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Roussel Uclaf SA
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    • 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
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    • C07C317/00—Sulfones; Sulfoxides
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    • 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
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    • C07C51/41—Preparation of salts of carboxylic acids
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • 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
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C61/00—Compounds having carboxyl groups bound to carbon atoms of rings other than six-membered aromatic rings
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    • 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
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    • C07D307/42—Singly bound oxygen atoms
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    • 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
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    • 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
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    • 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
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    • 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
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Description

Dr. F. Zumstc-fr» sen. - Dr. E. Assrricinn Dr. R. Koenigsbevoer - Dlpi.-Phys. R. Holzbauer - Dr. F. Zumoiein jun.Dr. F. Zumstc-fr »sen. - Dr. E. Assrricinn Dr. R. Koenigsbevoer - Dlpi.-Phys. R. Holzbauer - Dr. F. Zumoiein jun.

PATENTANWÄLTEPATENT LAWYERS

TELEFON: SAMMEL-NR. 225341TELEPHONE: COLLECTIVE NO. 225341

TEtEX 52997aTEtEX 52997a

TELEGRAMME; ZUMPATTELEGRAMS; ZUMPAT

POSTSCHECKKONTO: MÜNCHEN 91139CHECK ACCOUNT: MUNICH 91139

BANKKONTO": BANKHAUS H. AUFHÄUSERBANK ACCOUNT ": BANKHAUS H. AUFHÄUSER

8MUNCHENa, E3RÄUHAUSSTRASSE 4/III8MUNCHENa, E3RÄUHAUSSTRASSE 4 / III

Oane 11«?4 F-DAU Oane 11 "? 4 F-DAU

ROU^fJTSL-UOTi.* T?, Pa-pi.r/SrEvniTe 1.ohROU ^ fJTSL-UOTi. * T ?, Pa-pi.r / SrEvniTe 1st oh

.fnne -und Vp 7; fahr en f.ii ihre"11 He tf, ^ β "1Ii 1 .fnne and Vp 7; drive en f.ii their " 11 He tf, ^ β" 1 Ii 1

Patent (Pat.Anrn. P 16 6hPatent (Pat.Anrn. P 16 6h

Die vorclie^enrle "Rr.findunp; betrifft Arj^laTTvl al I f cera e .i η en l?o rra ß 1The vorclie ^ enrle "Rr.findunp; concerns Arj ^ laTTvl al I f cera e .i η en l ? O rra ß 1

eiereggs

H-A-S-ArH-A-S-Ar

CJCJ

worin Ar einen aur» einem oder ßwei arornatisehen Kernen bestehenden Aryl rest, der einen oder mehrere SiiDptituenten trafen konn, ' aun^ev/fiblt insbesondere nnter Mi edri,^alkyl-, A Halogenmethyl"-, Halogen- und iiitro^Tinpen, und.in which Ar has a single or two aromatic nucleus Aryl radical that met one or more Si-ptituenten Konn, 'aun ^ ev / fiblt especially nnter Mi edri, ^ alkyl-, A Halomethyl "-, halo and iiitro ^ Tinpen, and.

IiA die AlIyIgruppe HAaIiA the AlIyI group HAa

R1 R 1

'O=CiH-GH'O = CiH-GH

209 8 A3/1132209 8 A3 / 1132

R1^ ein Wasserstoffatom oder einen Niedrigalkylrest,R 1 ^ is a hydrogen atom or a lower alkyl radical,

R'2 einen Alkyl-, Aralkyl-, Aryl-, Alkenyl-, Alkinyl-f Cycloalkyl-, Cycloalkenylrest oder einen heterocyclischen Rest,,R'2 is an alkyl, aralkyl, aryl, alkenyl, alkynyl f cycloalkyl, cycloalkenyl or a heterocyclic radical ,,

R1, einen Alkylrest rait mindestens 2 Kohlenstoffatomen, einen Aralkyl-, Aryl-, Alkenyl-, Alkinyl-, Cycloalkyl-, Cycloalkenylrest oder einen heterocyclischen Reat "bedeuten, oderR 1 , an alkyl radical having at least 2 carbon atoms, an aralkyl, aryl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl radical or a heterocyclic radical "are, or

R1P und Rf~ zusammen einen Kqhlenstoffhoinocyclus, insbesondere mit 5 oder 6 Kohlenstoffatomen, einen ungesättigten Kohlenstoffhomocyclus, wie Cyclohexen, oder Cyclopentadien, ■ oder einen Heterocyclic bilden, wobei diese Ringe einen oder mehrere Substituenten tragen können, ausgewählt insbesondere unter den Hiedrigalkyl- und Hiedrigalkoxygruppen, oder R*2 und Rf, zusammen einen polycyclischen aromatischen Rest, wie den Fluorenrest,R 1 P and R f ~ together form a Kqhlenstoffhoinocyclus, in particular with 5 or 6 carbon atoms, an unsaturated carbon homocycle, such as cyclohexene, or cyclopentadiene, ■ or a heterocyclic, it being possible for these rings to carry one or more substituents, selected in particular from the lower alkyl and lower alkoxy groups, or R * 2 and R f , together a polycyclic aromatic radical, such as the fluorene radical,

bi3_den,bi3_den,

die Allylgruppe HAbthe allyl group HAb

CH R' -CH CH-CH R '-CH CH-

worin R1. einen liiedrigalkylrest, insbesondere Methyl, undwherein R 1 . a liiedrigalkylrest, especially methyl, and

R'c ein Wasnerstoffatom oder einen Niedrigalkylrest bedeuten, R'c is a hydrogen atom or a lower alkyl radical,

oder R14 und R',- zusammen einen gesättigten oder ungesättigberi Kohlenstoffhonjoc7fclus oder einen Haterocyclus bilden, und Y" eine Methylengruppe oder eine gesättigte oder ungesättigte Kohlenstoffkette bedeuten, oderor R 1 4 and R ', - together form a saturated or ungesättigberi Kohlenstoffhonjoc7fclus or Haterocyclus, and Y "represents a methyl group or a saturated or unsaturated carbon chain, or

die Allyl gruppe HActhe allyl group HAc

RI4 RI 4

0 - , f!II / \0 -, f! II / \

209843/17 32209843/17 32

bedeuten,.worinmean .worin

R1^ und R1 [-die oben angegebene Bedeutung "he Bit κ en, und Ύ u» pi η p. ilethingruprie oder eine gesättigte od?r ungesättigte fm «toff W-: te darstellt.R 1 ^ and R 1 [-the meaning given above "he bit κ en, and Ύ u» pi η p. Ilethingruprie or a saturated or unsaturated fm «toff W-: te represents.

^τΦΙη betrifft die Ti^fiiidiTnfr ein .Verfahren ?.ur Her stellung;" ■"■on "Ar? IaI J-TrI siilionen der l?ormel V, daß dadurch gekemise lehrt et ■int, ei a 9. man ein "Alkallmetaniarylstilfinat der Eormel^ τΦΙη concerns the Ti ^ fiiidiTnfr a .procedure? .ur production; "■" ■ on "Ar? IaI J-TrI siilionen der L ? ormel V, that thereby kemise teaches et ■ int, ei a 9. one a" Alkallmetaniarylstilfinate of the formula

ArSO2M IIIArSO 2 M III

v.'or.ln M ein Alkalimetall, "wie ITatrrum oder Kalium, Üfid^tp+, inxi Ar einen Ärylrest darstellt, der aus einem oder kv;ei ..-aromatischen Kcrnon besteht, der einen oder tnehrere Si.tbetitnenten tragen kann, ausgewählt unter liiedri^-* 8Χ)ζγ1-, Ai.lcoxy-, Halo^eninethyl-, Halogen- und Hitrorp-uppen, -reit einern halogenlerteii Allylderivat der Formelv.'or.ln M is an alkali metal, "such as ITatrrum or potassium, Üfid ^ tp +, inxi Ar represents an aryl radical, which consists of one or kv; ei ..- aromatic nucleus which can carry one or more Si.tbetitinenten, selected from liiedri ^ - * 8Χ) ζγ1-, Ai.lcoxy-, Halo ^ eninethyl-, halogen and Hitrorp-groups, -reit a halogenated allyl derivative of the formula

H-A-X IVH-A-X IV

umsetzt, v/orin X oin Jod-, I3rora-, Cliloratotn, die Me sy I- oderconverts, v / orin X oin iodine, I3rora-, Cliloratotn, the Me sy I- or

ionylgruppe bedeutet, undionyl group means, and

HA die in Anspruch 1 angegebene Bedeutung "besitzt, und da« erhaltene Arylallylsul.fon der allgemeinen iorrn°lHA has the meaning given in claim 1 ", and the arylallylsulfide obtained from the general standard

H - A ~ S - Ar V 0 0H - A ~ S - Ar V 0 0

viorin Ar u.ndHA. die oben ervrVhnte B°deutung benit^en, isoliert.viorin Ar u.ndHA. use the above mentioned interpretation, isolated.

Die erfind'ingsgein^.ßen Sulfone stellen wichtige Yerbindungen sur HerR+ellung.der Säure- und Esterderivate des Cyclopropane gemäß der Stamraanrneldung dar.The sulfones according to the invention constitute important compounds sur HerR + ellung.der acid and ester derivatives of cyclopropane according to the Stamra declaration.

s erfindungsgemäße Verfahren besitzt den Vorteil sehr allgemein KU pein.-Tatsächlich erhält man ein SuIfon V vom Aryl ally1-typ j wo die Arylgruppe sehr verschieden sein kann, nnncoyoli fioh so gut wie polycyclisch, u?id zahlreiche ver-The method according to the invention has the advantage of very general KU pein.-In fact, one obtains a sulfon V of the aryl ally 1 type j where the aryl group can be very different, nnncoyoli fioh as good as polycyclic, u? id numerous different

2 0 9 B U 3 / 1 1 3 22 0 9 B U 3/1 1 3 2

schiedene Substituenten tragen kann, wobei die p-Tolylgruppe besonders gute Ergebnisse liefert. Außerdem, und dies ist klarerweise viel wichtiger, kann die Allylgruppe H-A ^dIe Yer echiedeneten Strukturen aufweisen. Sie kann beispielsweise vom linearen Typ sein, wiecan carry different substituents, the p-tolyl group delivers particularly good results. In addition, and this is clearly much more important, the allyl group H-A ^ dIe Yer have different structures. For example, you can be of the linear type, like

R2 R 2

.C=CH - CH2-.C = CH - CH 2 -

worin Rp und R, beispielsweise Ithyl-, Isopropyl-, Phenyl- oder selbst Cycloalkylrest sind, wobei R2 und R-, gleichermaßen einen Ring mit 5 Kohlenstoffatomen oder einen heterocycli sehen Ring bilden können. Die Gruppe H-A kann auch vom cyclischen Typ sein, wiewherein Rp and R, for example ethyl, isopropyl, phenyl or even cycloalkyl radical, where R 2 and R-, can equally see a ring with 5 carbon atoms or a heterocyclic ring. The group HA can also be of the cyclic type, such as

worin R. einen Alkylrest bedeutet.where R. is an alkyl radical.

Die zur Herstellung der Sulfone Y durchgeführte Umsetzung-wird vorteilhafterweise in' Gegenwart eines Lösungsmittels, insbesondere in methanol!schein oder äthanolischem Milieu, und in Gegenwart eines basischen Mittels, wie eines Alkalimetallcarbonate oder -acetats, durchgeführt. Man arbeitet vorzugsweise in Methanol, wobei man als basisches Reagens Natrium- oder Kaliumcarbonat verwendet.The reaction carried out to produce the sulfones Y-is advantageously in the presence of a solvent, in particular in methanol! or ethanol, and in the presence a basic agent such as an alkali metal carbonate or acetate. It is preferable to work in methanol, with sodium or potassium carbonate as the basic reagent used.

Als Variation kann die Herstellung der Sulfone V bewirkt werden, indem man das Alkalimetallarylsulfinat III in Gegenwart von. Ameisensäure, rait dem Alkohol HA-OH umsetzt.As a variation, the production of the sulfones V can be effected, by the alkali metal aryl sulfinate III in the presence of. Formic acid, which converts the alcohol HA-OH.

Die Sulfone Υ können auch durch Anwendung des in der französischen Batentschrift· 1 483 715 beschriebenen Verfahrenr» erhalten werden^-.,_., ' BAD ORIGINALThe sulfones can also be obtained by using the process described in the French Batentschrift 1 483 715 ^ -., _., ' BAD ORIGINAL

209843/1132 AL 209843/1132 AL

Die folgenden Beispiele erläutern die Erfindung. (3-Äthyl~2-pentenyl)-phenylsulfonThe following examples illustrate the invention. (3-ethyl ~ 2-pentenyl) phenyl sulfone

In 60 cm Methanol bringt man 1,85 g Natriumcarbonat und 18,5 g MatriOraphenylsulfinat ein und gibt su der erhaltenen Sus7)ension im Verlauf von etwa 50 Minuten bei Umgebungstemperatur 20 g 1-Brow~5-äthyl-2--penten. Man rührt noch eine Stunde und 50 Minuten bei 'Umgebungstemperatur, gießt die Reaktionsmischung in Eiswasser, trennt die organische Phase durch Dekantieren ab, extrahiert die wäßrige Phase mit Äthyläther,- vereinigt die Ätherextrakte mit der organischen Hauptlösung, trocknet die erhaltene Lösung über Magnesiumsulfat, entfernt das Lösungsmittel -bei vermindertem Druck und erhält 21,665 g (5-Atbyl-2-p entenj'l) -phenyl su 1 f on.1.85 g of sodium carbonate and 18.5 g of matrix phenyl sulfinate are introduced into 60 cm of methanol and 20 g of 1-Brow ~ 5-ethyl-2-pentene are added to the suspension obtained in the course of about 50 minutes at ambient temperature. The mixture is stirred for a further hour and 50 minutes at ambient temperature, the reaction mixture is poured into ice water, the organic phase is separated off by decantation, 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, removed the solvent - under reduced pressure and receives 21.665 g (5-Atbyl-2- pent enj'l ) -phenyl su 1 f on.

Eine Probe dieses Produkts wird bei vermindertem Druck rektifiziert: Kp = 1250O bei 0,02 mm Hg, n|5 = 1,550.A sample of this product is rectified under reduced pressure: Bp = 125 0 O at 0.02 mm Hg, n | 5 = 1.550.

O15H18SO2 (258,54)O 15 H 18 SO 2 (258.54)

Berechnet: C 65,55 H 7,61 S 15,46 $ Gefunden: 0 65,4 H7,6 S 15,2 ^ Dieses Produkt ist in der Literatur nicht beschrieben. .l§i5Ili§2i^2. (3-Isobutyl~5-rae thyl-2-hexen3r-l /-phenyl sul fönCalculated: C 65.55 H 7.61 S $ 15.46 Found: 0 65.4 H 7.6 S 15.2 ^ This product is not described in the literature. .l§i5Ili§2i ^ 2. (3-Isobutyl ~ 5-rae thyl-2-hexen3r-l / -phenyl sul fön

In 500 cm- Methanol löst man 55 g Ifatrlumphenylsulfinat, fügt 8 g Kaliumcarbonat, 1 g Natriumiodid und dann 71 g 1-"Brom-3-isobiityl-5-rnethyl~2-hexen zu und x'ührt 15 Stunden bei Umgebungstemperatur. Dann konzentriert man bei vermindertem Druck zur Trockne, fügt Wasser zu, extrahiert die wäßrige Phase mit Methylenohlorid, vereinigt die Methylenchloridextrakte, wäscht--die erhaltene organische Lösung mit Wasser, trocknet diese imcl konzentriert sie bei vermindertem Druck zur !Trockne.55 g of ifatrium phenyl sulfinate are dissolved in 500 cm methanol 8 g of potassium carbonate, 1 g of sodium iodide and then 71 g of 1- "bromo-3-isobiityl-5-methyl-2-hexene and stirs for 15 hours at ambient temperature. Then concentrate under reduced pressure to dryness, add water, extract the aqueous phase with methylene chloride, combine the methylene chloride extracts, washes - the obtained organic solution with water, dries this is concentrated to dryness under reduced pressure.

Der Rückstand'wird an einer Aluminiumoxydsäule chromatographiert, man erhält 62,32 g (3-Isobutyl-5-methyl-2-hexenyl)-The residue is chromatographed on an aluminum oxide column, one receives 62.32 g (3-isobutyl-5-methyl-2-hexenyl) -

llf On. ,.«nnnii ■#--«.» ßADllf On. ,. «Nnnii ■ # -«. » ß AD

Das Produkt ist in der Literatur nicht beschrieben. Bei spiel 3 3,3-Diphenyl-(2-prQpenyl)-phenyleulfonThe product is not described in the literature. In game 3 3,3-diphenyl (2-prQpenyl) -phenyleulfon

In 80 cnr Methanol bringt man T5i5 g Natriuraphenylsulfinat und 1,5 g Natriumcarbonat ein, fügt bei Umgebungstemperatur unter einer Stickstoffatmosphäre 25*6 g 1-Brom-3,3-diphenyl-2~propen zu und ^rührt eine Stunde und 30 Minuten. Dann gießt man in kaitee Wasser, extrahiert nit Methylenchlorid, vereinigt die Methylenchlorid extrakte, wäscht die erhaltene organische Lösung mit Wasser, trocknet sie und konzentriert sie zur Trockne. Der Rückstand kristallisiert teilweise. Man isoliert den gebildeten Niederschlag durch Absaugen, trocknet und erhält 25,48 g 3,3-Diphenyl-(2-propenyl)-phenylsulfon mit einem 1? = 1040C.T5.5 g of sodium phenyl sulfinate and 1.5 g of sodium carbonate are placed in 80 cnr of methanol, 25.6 g of 1-bromo-3,3-diphenyl-2-propene are added at ambient 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 concentrated to dryness. The residue partially crystallizes. The precipitate formed is isolated by suction filtration, dried and 25.48 g of 3,3-diphenyl- (2-propenyl) -phenylsulfone with a 1? = 104 0 C.

Eine Probe wird in Isopropyläther kristallisiert: P = 1060C.A sample is crystallized in isopropyl ether: P = 106 0 C.

Analyse:Analysis: C21 C 21 H18 H 18 SO2 SO 2 (33(33 4,44.4 3)3) SS. Berechnet:Calculated: CC. 7575 ,41, 41 HH 5,5, 4242 SS. Gefunden:Found: CC. 7575 ,3, 3 HH 5,5, 44th

9,4 $ $ 9.4

Das Produkt iat in der Literatur nicht beschrieben. Beispiel 4 (2-Cyclopentylidenäthyl)-phenylsv.lfonThe product is not described in the literature. Example 4 (2-Cyclopentylidenäthyl) -phenylsv.lfon

In 50 cm^ Methanol bringt man 22,3 g Natriumphenylsulfinat, 2,2 g Kaliumcarbonat, 0,2 g Natriumiodid ein und fügt bei etwa +1O0C unter Rühren 23,6 g i-Brom-2-cyclopentxlidenäthan zu und rührt 2 Stunden bei 200C. Man gießt die Reaktionsraischung in Eiswasser, kühlt auf O0G, isoliert den gebildeten Niederschlag durch Absaugen und trocknet im Vakuum in Gegenwart von# Kaliumhydroxyd. In 50 cm ^ of methanol, 22.3 g of sodium phenylsulfinate, 2.2 g of potassium carbonate, 0.2 g of sodium iodide brings and inserts at about + 1O 0 C with stirring 23.6 g i-bromo-2-cyclopentxlidenäthan added and stirred for 2 hours at 20 0 C. It is poured into ice-water, the Reaktionsraischung, cooled to 0 G, the precipitate formed by filtration with suction and dried in vacuo in the presence of potassium hydroxide #.

Han erhäl.t 15 g (2-Cyclopentylidenäthyl)~phen3'lsulfon mit einemHan receives 15 g (2-Cyclopentylidenäthyl) ~ phen3'lsulfon with a

J) = DO K) ·J) = DO K)

Eine Probe dieses Produkts wird in Isopropyläther kristalliA sample of this product will crystallize in isopropyl ether

siert: P «. 680C.siert: P «. 68 0 C.

209843/1132209843/1132

M QfIM QfI
1311Io8"13 11 Io 8 " 22 (256(256 - 7 -- 7 - SS. 13,13, 5757 ** Analyse: C.Analysis: C. O 66O 66 ,06, 06 HH ,33).33) SS. 13,13, 22 ** BerechnetιCalculated O 65O 65 .a.a HH 6t826 t 82 Gefunden:Found: 6,86.8

Dae.-.Produkt* let in der Literatur nicht "beschrieben.Dae .-. Product * let not "described in the literature".

Dae 1->Broe-2-oyolopentylidejiathan kann nach des in Bull. Soc. Chim., 19641. 2618, beschriebenen Verfahren hergestellt werdemDae 1-> Broe-2-oyolopentylidejiathan can according to the in Bull. Soc. Chim., 19641, 2618

Balgplel 5 (2*Oyclohexylidenäthyl)~phenylsulfon Balgplel 5 (2 * Oyclohexylidenäthyl) ~ phenylsulfon

In 116 cm' Methanol bringt man 3Q»5 g Natriunphenylsulfinat und dann 5,85 g Natriumcarbonat ein und fügt tropfenweise unter Rühren im Verlauf von etwa 30 Minuten bei Umgebungstemperatur 44 g frisch hergestelltes I^Brom^-cyclohexylidenäthan zu. Man rührt noch eine Stunde und 30 Minuten bei Umgebungstemperatur und gießt dann die Reaktionsmischung in 400 wir Eiewasser. 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 56,4 g (2~Cyclohexylidenäthyl)-phenylsuifon mit einem P = 70°C.Three quarters of 5 g of sodium phenyl sulfinate and then 5.85 g of sodium carbonate are introduced into 116 cm of methanol, and 44 g of freshly prepared bromine-cyclohexylidene ethane are added dropwise with stirring over a period of about 30 minutes at ambient temperature. The mixture is stirred for a further hour and 30 minutes at ambient temperature and then the reaction mixture is poured into 400 liters of egg water. The precipitate formed is filtered off with suction, washed with water and dried. The crude product thus obtained is dissolved in a hot mixture of methylene chloride and methanol. The resulting solution 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 56.4 g of (2 ~ cyclohexylidene ethyl) phenyl sulfone with a P = 70 ° C. are obtained.

Eine Probe dieses Produkts wird in Isopropyläther für die Ana-A sample of this product is dissolved in isopropyl ether for analysis

Iyse gereinigt: F » 700C.Iyse cleaned: F »70 0 C.

Analyse: C14H10SO2 (250,35) Berechnet: C 67,16 H 7,24 S 12,01 £ Gefunden: C 67 K 7,1 S 12,5 $ Analysis: C 14 H 10 SO 2 (250.35) Calculated: C 67.16 H 7.24 S 12.01 £ Found: C 67 K 7.1 S 12.5 $

Das Produkt ist in der Literatur nicht beschrieben.The product is not described in the literature.

Das 1-Brom-2-Cyclohexylidenäthan kann nach dem in Helvetica gj? (1942) 29 beschriebenen Verfahren hergestellt werden.The 1-bromo-2-cyclohexylidenethane can after that in Helvetica gj? (1942) 29 processes described.

BAD 209 84 3/1132BATH 209 84 3/1132

Geht raan gleichermaßen von verschiedenen halogenierten Allyl derivaten ans, so erhält man in analoger Weiße." wie in den vorstehenden Beispielen, verschiedene AGoes equally well from different halogenated allyl derivaten ans, one receives in analogous white. "as in the above examples, various A

209843/1132 BA°209843/1132 BA °

Beispielexample ββ 7 .7th 88th Ausgangs-
produktStarting
product l-Brom-3-propy1-2-hexen1-bromo-3-propy1-2-hexene 1-Brom-3-(isopropyl)-4-methyl—
2-penten1-bromo-3- (isopropyl) -4-methyl-
2-pentene l-Brom-2-(2T,6'-dimethyl-
eyclöhexyliden)-äthanl-bromo-2- ( 2T , 6'-dimethyl-
eyclöhexyliden) ethane (3-Propyl-2-hexeny1)-
phenylsulfon(3-propyl-2-hexeny1) -
phenyl sulfone (3-1 soioropy 1-4-methyl-2-OeDt e-
nyl)-phenylsulfon,; F = 500C(3-1 soioropy 1-4-methyl-2-OeDt e-
nyl) -phenylsulfon; F = 50 ° C [2-(2!,ö'-Dimethylcyclo-
hexy lid en)-äthy 1]-pheny 1-
s.ulfon, P = 96 C j[2- (2 !, Ö'-dimethylcyclo-
hexy lid en) -äthy 1] -pheny 1-
s.ulfon, P = 96 C j

O CD CXJ -ρω O CD CXJ -ρω

CO to CO to

Beispiel.Example. 99 ίοίο 1111 Ausgangspro
duktOutput pro
duct 1-Βγοιπ-2-(4! ^'-dimethyl-
cyclöhexyliden)-äthan1-Βγοιπ-2- (4 ! ^ '- dimethyl-
cyclöhexylidene) ethane tramethy1-cyclohexyli
den) -äthantramethy1-cyclohexyli
den) -ethane 1 -Brom-2-.(2' .-3: ,5' ,6'-te- |
trahydro-4'-pyranyliden)-
äthan. '. 3: 5' - 1-bromo-2 (2, 6'-te- |
trahydro-4'-pyranylidene) -
ethane [2-(4' -,^'-Dlmethyl-cyclo-
hexyliden)-äthyI]phenyl-
sulfon. .
P = 1100C '[2- (4 '-, ^' - Dlmethyl-cyclo-
hexylidene) ethyI] phenyl-
sulfone. .
P = 110 0 C ' [2-(3',3' ^'..S'-Tetrame-
thyl-cyclohexyliden) -
äthy 1 ]— -chen-v lsulf on,
F = 550C '[2- (3 ', 3' ^ '.. S'-tetram-
ethyl cyclohexylidene) -
ethy 1] - -chen-v lsulf on,
F = 55 0 C ' [2-(2j3',5f,ö'-Tetrahydro-
4' -py rany liden) -äthy ij- |
r>henv lsulf on.
F ='S8°C,[2- (2j3 ', 5 f , ö'-tetrahydro-
4 '-py rany liden) -äthy ij- |
r> henv lsulf on.
F = 'S8 ° C,

Beispielexample IP.IP. An s ^aP-SS-P-C o-
dulct An s ^ aP-SS - P - C o-
dulct 1-B??OTn~2~c;rclol)utyliden-
athan1-B ?? OTn ~ 2 ~ c; r clol) utylid
athan (2-Gycl oTdu tyl 1 rt en) -plienyl-
svulfon
Έ - 76 iDis 78°0(2-Gycl oTdu tyl 1 rt en) -plienyl-
svulfon
Έ - 76 iDis 78 ° 0

CD COCD CO

Di« erhaltenen Sulfone sind in der Literatur nicht beschrieben. Beispiel 13 (3-Methyl-2-cyclohe3cenyl)-phenylsulfonThe sulfones obtained are not described in the literature. Example 13 (3-Methyl-2-cyclohe3cenyl) -phenylsulfone

In 400 enr Ameisensäure bringt man 34,2 g rohes 3-Methyl-2·* cyclohexen-1-ol ein, fügt 6ö g ITatriumphenylsulfinaf zu und rührt-etwa 15 Minuten bei Umgebungstemperatur. Man gient in, eine Mischung von Wasser und Eis, extrahiert mit Methylenchlorid, vereinigt die Methylenchloridextrakte, wascht die erhaltene lösung mit Wasser, dann mit einer wäßrigen liatriumbicnrbonatlösung und schließlich mit Wasser, trocknet und konzentriert zur trockne.34.2 g of crude 3-methyl-2 * * cyclohexen-1-ol, adds 606 g of sodium phenylsulfinaf and stir - about 15 minutes at ambient temperature. One serves in a mixture of water and ice, extracted with methylene chloride, combined the methylene chloride extracts, washed the obtained solution with water, then with an aqueous lithium bicarbonate solution and finally with water, dry and concentrate to dry.

Der Rückstand wird zu einer Mischung von Isopropyläther und Petroläther gegeben. Man isoliert den gebildeten liieöerschlag durch Filtrieren, wäscht, trocknet und erhält 47 g (3-M^thyl-2-cyclohexenyl)-phenylsulfon. The residue becomes a mixture of isopropyl ether and petroleum ether given. The line strike formed is isolated by filtering, washing, drying and obtaining 47 g of (3-M ^ thyl-2-cyclohexenyl) -phenylsulfone.

Eine Probe dieses Produkts wird durch Auflösen in Methylenchlorid, Koneentrieren und Zugabe von Isopropyläther gereinigt:A sample of this product is prepared by dissolving it in methylene chloride, Concentration and addition of isopropyl ether cleaned:

F = 700C.F = 70 0 C. O13HO 13 H. 16°216 ° 2 •• ** ,33).33) SS. 1313th ,57, 57 Analyse:Analysis: CC. 66,66 SS. (236(236 ,82, 82 SS. 1313th ,3, 3 Berechnet:Calculated: CC. 66,66 0606 H 6H 6 »8"8th Gefunden:Found: 33 H 6H 6

Das Produkt ist in der Literatur nicht beschrieben.The product is not described in the literature.

BAD ORiGiNAL 209843/1132 BAD ORiGiNAL 209843/1132

Claims (2)

allryl-, Oycloalkenylrest oder einen heterocyclischen Rest,allryl, Oycloalkenylrest or a heterocyclic radical, R1^5 einen Allorlrest mit mindestens 2 Kohlenstoffatomen, einen Aralkyl-, Aryl-, Alkenyl-, Alkinyl-. Cycloalkyl-, Cyoloalkenylrest oder einen heterocyclischen Rest bedeuten, oderR 1 ^ 5 an allorl radical with at least 2 carbon atoms, an aralkyl, aryl, alkenyl, alkynyl. Mean cycloalkyl, cycloalkenyl or a heterocyclic radical, or R'p, und R1^ Rueammen einen Kohl.enstoffhomocyclus, insbesondere mit 5 oder 6 KohlenstoffatoFien, einen ungesättigten Kohlenstoff homocyclus, v/ie Cyclohexen, oder Cyclopentadien, oder einen HeteroC3>*clus bilden, wobei diese Ringe einen öder mehrere Substituenten tragen können, ausgewählt insbesondere unter den Fiedrigalkyl- und Hiedrigalkoxygruppen, oder R'rt und R*^ zusammen einen polycyclisehen aromatischen Rest, wie den Fluorenrest,R'p, and R 1 ^ Rueammen form a carbon homocycle, in particular with 5 or 6 carbon atoms, an unsaturated carbon homocycle, v / ie cyclohexene, or cyclopentadiene, or a HeteroC3> * clus, these rings having one or more substituents can, selected in particular from the lower alkyl and lower alkoxy groups, or R'rt and R * ^ together a polycyclic aromatic radical, such as the fluorene radical, bilden,form, 2098437! 1322098437! 132 die Allylgr'uppethe allyl group R'5-CIIR ' 5 -CII worin R1^, einen iiiedrifralkyi^est, inPbfiRon^ere Methyl, und R'cj ein V/aspr->rß-i;o.ffatora oder einen Hied/r/where R 1 ^, a iiiedrifralkyi ^ est, inPbfiRon ^ ere methyl, and R'cj a V / aspr->rß-i; o.ffatora or a Hied / r / deuten,
oder R1^ und R1^. zn.rammen einen j^eR^^tigten orierto interpret
or R 1 ^ and R 1 ^. zn.rammen a j ^ eR ^^ tierter orier ' KnlilenetoffhoTnocycltiF! oöev einen Hete??ocyon.i,i8 bilden, und T" eine li^txr/len^u^-pe oder e?ne gfipättiirte, ode^ u.nge- ' sättigte Kohlenstoffkette bedeuten, oder'KnlilenetoffhoTnocycltiF! oöev form a Hete ?? ocyon.i, i8, and T "signify a li ^ txr / len ^ u ^ -pe or a gfipättiirte, ode ^ and n-saturated carbon chain, or HAcHAc R'c-0R'c-0 OHOH OH-OH- yii ιyii ι bedeuten, worinmean in which R', und R'j- die oben angegebene Bedeutung beeitsen und I"1 eine Hethingruprie oder eine gepättigte oder ungesättigte Kohlenstoffkette darstellt.R ', and R'j- leave the meaning given above and I " 1 represents a methine group or a saturated or unsaturated carbon chain. 2. Verfahren zur Herstellung von Verbindungen der Formel V des Anspruchs 1, dadurch gekennzeichnet, daß man ein Alkalimetallarylsulfinat der Formel 2. Process for the preparation of compounds of the formula V of claim 1, characterized in that an alkali metal aryl sulfinate of the formula ArSO2MArSO 2 M IIIIII worin M ein Alkalimetall, wie Natrium oder Kalium, bedeutet, und Ar einen Arylrest darstellt, der aus einem oder swei aromatischen Kernen besteht, der einen oder mehrere Substituenten tragen kann, ausgewählt unter Hiedrig-wherein M is an alkali metal, such as sodium or potassium, and Ar is an aryl radical consisting of one or two aromatic nuclei, which can carry one or more substituents, selected from low- 209843/1132209843/1132 alkyl-, Alkoxy-, Halo-o-eninetfry-l—, Halogen- imd Mi tr ο-0Ti1 η mit Pinen halogenierten Allylderivat der Porraelalkyl-, alkoxy-, halo-o-eninetfry-1—, halogen and Mi tr ο- 0 Ti 1 η allyl derivative halogenated with pinene from Porrael H-A-X IYH-A-X IY ι set Kt, worin" X. ein Jod-, B^om--, Oliloratora, dip. Me sy!- oder •rujipe "bedeutet und "HA die in Anspruch 1 an^e^ehen^. Beflen IA" "besitpit und da"? erhaltene Aryl al Iy lsn If on der al If·; Formelι set Kt, in which " X. a iodine, B ^ om--, Oliloratora, dip. Me sy! - or • rujipe" means and "HA which in claim 1 an ^ e ^ ehen ^. Beflen IA""besitpit and since"? obtained aryl al Iy lsn If on der al If ·; formula H - A - F, - Ar YH - A - F, - Ar Y worin Ar und HA d.i e olien erv^hnte Boc^utimg "henit.^en, isoliert.where Ar and HA d.i e olien mentioned Boc ^ utimg "henit. ^ en, isolated. BADORiQlMAL I O 9 H- h 3 / 11 3 2 BADORiQlMAL I O 9 H- h 3/11 3 2
DE19671793721 1966-08-26 1967-08-25 Phenylallylsulfones and process for their preparation Expired DE1793721C3 (en)

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 true DE1793721A1 (en) 1972-10-19
DE1793721B2 DE1793721B2 (en) 1976-12-23
DE1793721C3 DE1793721C3 (en) 1977-08-25

Family

ID=

Also Published As

Publication number Publication date
IL38182A (en) 1975-11-25
GB1207371A (en) 1970-09-30
CS180598B2 (en) 1978-01-31
NL162060C (en) 1980-04-15
CH491071A (en) 1970-05-31
ES350839A1 (en) 1969-05-16
FR1507192A (en) 1967-12-29
NL172853C (en) 1983-11-01
NL7906529A (en) 1980-01-31
DE1668603A1 (en) 1971-07-01
BE702662A (en) 1968-02-14
CH509961A (en) 1971-07-15
CS180599B2 (en) 1978-01-31
ES344435A1 (en) 1968-10-16
YU33942B (en) 1978-09-08
YU290379A (en) 1983-10-31
DK140720B (en) 1979-11-05
YU35568B (en) 1981-04-30
DE1793721B2 (en) 1976-12-23
YU168467A (en) 1978-02-28
AT287671B (en) 1971-02-10
CH491851A (en) 1970-06-15
DK131538C (en) 1976-01-05
YU42168A (en) 1978-02-28
GB1207372A (en) 1970-09-30
FR1527844A (en) 1968-06-07
AT289754B (en) 1971-03-15
DE1668603B2 (en) 1974-01-17
CS180551B2 (en) 1978-01-31
DK140720C (en) 1980-04-21
ES344436A1 (en) 1968-10-16
IL28541A (en) 1975-11-25
SE369517B (en) 1974-09-02
YU33952B (en) 1978-09-08
SU691076A3 (en) 1979-10-05
YU168567A (en) 1980-10-31
SE391330B (en) 1977-02-14
NL162060B (en) 1979-11-15
FR93112E (en) 1969-02-14
NL172853B (en) 1983-06-01
DE1668603C3 (en) 1974-08-22
NL6711770A (en) 1968-02-27
FR94309E (en) 1969-08-01
FR1505423A (en) 1967-12-15
DK131538B (en) 1975-08-04
DK133579C (en) 1976-11-01
DK133579B (en) 1976-06-14

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Date Code Title Description
C3 Grant after two publication steps (3rd publication)
E77 Valid patent as to the heymanns-index 1977