FR2616145A1 - Process for synthesising an alpha -fluoro- beta -sulphide organic compound - Google Patents

Process for synthesising an alpha -fluoro- beta -sulphide organic compound Download PDF

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FR2616145A1
FR2616145A1 FR8708102A FR8708102A FR2616145A1 FR 2616145 A1 FR2616145 A1 FR 2616145A1 FR 8708102 A FR8708102 A FR 8708102A FR 8708102 A FR8708102 A FR 8708102A FR 2616145 A1 FR2616145 A1 FR 2616145A1
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group
compound
sep
alkene
fluoride
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FR2616145B1 (en
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Andre Laurent
Gunter Haufe
Gerard Alvernhe
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Centre National de la Recherche Scientifique CNRS
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    • 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
    • C07J—STEROIDS
    • C07J31/00—Normal steroids containing one or more sulfur atoms not belonging to a hetero ring
    • C07J31/003—Normal steroids containing one or more sulfur atoms not belonging to a hetero ring the S atom directly linked to a ring carbon atom of the cyclopenta(a)hydrophenanthrene skeleton
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered
    • C07C2601/20—Systems containing only non-condensed rings with a ring being at least seven-membered the ring being twelve-membered
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
    • C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms

Abstract

Process for synthesising an alpha -fluoro- beta -sulphide organic compound, characterised in that it consists in reacting in a single reaction an alkene with a compound R-S-Y chosen from the group comprising thiosulphonium salt and sulphenyl halides, in the presence of a fluorinating agent (F<->) according to the general formula:

Description

PROCEDE DE SYNTHESE D'UN COMPOSE ORGANIQUE d - FLUORO B-SULFURE. PROCESS FOR SYNTHESIS OF AN ORGANIC COMPOUND d - FLUORO B-SULFIDE.

L'invention concerne un nouveau procédé de synthèse d'un composé organique U -fluoro t -sulfure. The invention relates to a new process for the synthesis of an organic compound U -fluoro t -sulfide.

Comme on le sait, les composés organiques -fluoro t-sulfure répondent à la formule générale

Figure img00010001
As is known, the organic compounds -fluoro t-sulfide correspond to the general formula
Figure img00010001

Ces composés ont été essentiellement proposés comme intermédiaires de synthèse. These compounds have essentially been proposed as synthetic intermediates.

On connait déjà plusieurs types de synthèse de ces composés à partir d'alcènes (voir par exemple : Tetrahe- dron 1985, 41, pp. 2419-2433 ou J. Chem. Research (S), 1985, p. 6-7). Dans tous les procédés décrits jusqu'alors, il est nécessaire d'opérer en phases successives, ce qui est l-ong, coûteux et conduit à un rendement jugé encore trop insuffisant. Several types of synthesis of these compounds are already known from alkenes (see for example: Tetrahedron 1985, 41, pp. 2419-2433 or J. Chem. Research (S), 1985, p. 6-7) . In all the processes described up to now, it is necessary to operate in successive phases, which is l-ong, expensive and leads to a yield which is still considered too insufficient.

L'invention pallie ces inconvénients. Elle vise un procédé pour la préparation des composés en question à partir d'alcènes qui s'effectue en une seule étape (one pot reaction) et qui soit plus économique, moins coûteuse et donne des rendements nettement améliorés. The invention overcomes these drawbacks. It relates to a process for the preparation of the compounds in question from alkenes which is carried out in a single step (one pot reaction) and which is more economical, less expensive and gives markedly improved yields.

Ce procédé de synthèse d'un composé organique - fluoro t -sulfure, se caractérise en ce qu'il consiste à faire réagir en une seule réaction un alcene avec un composé R-S-Y choisi dans le groupe comprenant les sels de thiosulfonium et les halogénures de sulfényle, en présence d'un agent de fluoration (F-) selon la formule générale

Figure img00020001
This process for the synthesis of an organic compound - fluoro t -sulfide, is characterized in that it consists in reacting in a single reaction an alkene with an RSY compound chosen from the group comprising thiosulfonium salts and sulfenyl halides. , in the presence of a fluorinating agent (F-) according to the general formula
Figure img00020001

En d'autres termes, l'invention consiste à faire réagir simultanément les composés en question sur la double liaison du composé alcène par une réaction de transaddition qui peut conduire à un seul composé dia stéréoisomére. In other words, the invention consists in causing the compounds in question to react simultaneously on the double bond of the alkene compound by a transaddition reaction which can lead to a single dia-stereoisomeric compound.

Avantageusement en pratique
- l'alcène répond à la formule générale

Figure img00020002

dans laquelle R1 , R2 , R3 , R4 désignent un atome d'hydrogène, un atome d'halogène, un groupement aryle, un groupement alkyle, éventuellement substitués par des hétéroatomes, tels que par exemple des groupes fonctionnels esters ou amides
- l'alcène est linéaire ou cyclique
- dans le composé R-S-Y, le radical R désigne un groupement alkyle ou aryle, et Y désigne un halogène ou un groupement-S+R5R6 ,R5 et R6 identiques ou différents, désignent un groupement alkyle ou aryle
- avantageusement, le composé R-S-Y est choisi dans le groupe comprenant le dialkylthiométhylsulfonium, tel que par exemple le diméthyl (thiométhylsulfonium), le diarylthiomethylsulfonium, le chlorure de méthanesulfényle
- l'agent de fluoration F est choisi dans le groupe comprenant l'acide fluorhydrique, les fluorures alcalins, les fluorhydrates d'amines, et les fluorures d'ammonium quaternaire de formule générale
R'R R R N+ F, n HF] dans laquelle
7 8 9 10
R7 , R8 t Rg , R10 désignentunatome d'hydro
gène, des groupements, identiques ou non,
alkyles1 aryles ou alkenylènes, n n désigne un nombre entier compris entre
zéro et dix,
- l'agent de fluoration est compris dans le groupe comprenant la triethylamine/3HF, le fluorure de tétraéthylammonium/3HF, le fluorure d'ammonium/2,2.HF, la py ridine/l0 HF (réactif d'Olah), les méthylpyridines/l0HF, le fluorure de potassium, le fluorure de sodium, le fluorure de césium
- la réaction s'effectue dans un solvant aprotique non nucléophile
- ce solvant aprotique est choisi dans le groupe constitué par le chlorure de méthylène et le tétrachlorure de carbone
- la réaction s'effectue à une température comprise entre 00C et la température ambiante. Une fois la réaction terminée, on évapore le solvant sous vide puis on purifie par distillation ou chromatographie sur silice. Advantageously in practice
- the alkene corresponds to the general formula
Figure img00020002

in which R1, R2, R3, R4 denote a hydrogen atom, a halogen atom, an aryl group, an alkyl group, optionally substituted by heteroatoms, such as, for example, ester or amide functional groups
- the alkene is linear or cyclic
- in the compound RSY, the radical R denotes an alkyl or aryl group, and Y denotes a halogen or a group -S + R5R6, R5 and R6 which are identical or different, denote an alkyl or aryl group
- Advantageously, the compound RSY is chosen from the group comprising dialkylthiomethylsulfonium, such as for example dimethyl (thiomethylsulfonium), diarylthiomethylsulfonium, methanesulfenyl chloride
the fluorinating agent F is chosen from the group comprising hydrofluoric acid, alkali metal fluorides, amine hydrofluorides, and quaternary ammonium fluorides of general formula
R'R RR N + F, n HF] in which
7 8 9 10
R7, R8 t Rg, R10 denote a hydro atom
gene, groups, identical or not,
alkyls1 aryls or alkenylenes, nn denotes an integer between
zero and ten,
- the fluorinating agent is included in the group comprising triethylamine / 3HF, tetraethylammonium fluoride / 3HF, ammonium fluoride / 2,2.HF, py ridine / 10 HF (Olah reagent), methylpyridines / l0HF, potassium fluoride, sodium fluoride, cesium fluoride
- the reaction is carried out in a non-nucleophilic aprotic solvent
- this aprotic solvent is chosen from the group consisting of methylene chloride and carbon tetrachloride
- the reaction is carried out at a temperature between 00C and room temperature. Once the reaction is complete, the solvent is evaporated off in vacuo and then purified by distillation or chromatography on silica.

La manière dont l'invention peut être réalisée et les avantages qui en découlent ressortiront mieux des exemples de réalisation qui suivent donnés à titre indicatif et non limitatif. The manner in which the invention can be implemented and the advantages which result therefrom will emerge more clearly from the exemplary embodiments which follow, given by way of indication and not by way of limitation.

MODE OPERATOIRE
Dans tous les exemples qui suivent, on utilise le mode opératoire suivant.PROCEDURE
In all the examples which follow, the following procedure is used.

A une solution de 10 millimoles de composé éthylénique dans 20 ml de CH2C12maintenue à OOC, on ajoute sous agitation 11 millimoles (2,16 g) de tétrafluoroborate de diméthyl-(thiométhyl) sùlfonium C(CH3) S±S-CH31 BF4 (préparé selon la. méthode décrite par TROST (J.AMER. To a solution of 10 millimoles of ethylenic compound in 20 ml of CH2Cl2 maintained at OOC, are added with stirring 11 millimoles (2.16 g) of dimethyl- (thiomethyl) sulfonium tetrafluoroborate C (CH3) S ± S-CH31 BF4 (prepared according to the method described by TROST (J. AMER.

Chem. Soc. 1982, 104, 3225). On agite à 00C durant 20 mn, puis on ajoute goutte-à-goutte 50 millimoles (8g) de Et3N, 3HF en solution dans 10 ml de CH2C12 en maintenant la température à 0 C. On laisse revenir le milieu réactionnel à température ambiante sous agitation. La disparition du composé éthylénique est suivie par chromatographie sur couche mince ou par chromatographie en phase vapeur. Après disparition complète de ce dernier, le milieu réactionnel est versé sur 100 ml d'eau glacée, basifié par addition goutte-à-goutte d'une solution d'ammoniaque 28 % jusqu'à pH basique (pH = 10), puis extrait au CH2CI2 .Après séchage sur MgS04 et évaporation du solvant sous vide, le brut réactionnel est purifié soit par distillation sous vide, soit par chromatographie sur colonne de Si02
Les exemples de réalisation sont schématisés dans les feuillets suivants, où pour chaque réaction, on a indiqué le pourcentage d'isomère(s) formé(s).

Figure img00050001
Chem. Soc. 1982, 104, 3225). Stirred at 00C for 20 min, then 50 millimoles (8g) of Et3N, 3HF in solution in 10 ml of CH2C12 are added dropwise while maintaining the temperature at 0 C. The reaction medium is allowed to return to room temperature under restlessness. The disappearance of the ethylenic compound is followed by thin layer chromatography or by vapor phase chromatography. After complete disappearance of the latter, the reaction medium is poured into 100 ml of ice-cold water, basified by dropwise addition of a 28% ammonia solution until basic pH (pH = 10), then extracted. with CH2Cl2. After drying over MgSO4 and evaporation of the solvent in vacuo, the reaction crude is purified either by vacuum distillation or by chromatography on a SiO2 column.
The embodiments are shown schematically in the following sheets, where for each reaction, the percentage of isomer (s) formed has been indicated.
Figure img00050001

Cyclohèxène 90%

Figure img00050002
Cyclohexene 90%
Figure img00050002

Cyclooctadiène 1,5 76%

Figure img00050003
Cyclooctadiene 1.5 76%
Figure img00050003

Cyclododecène

Figure img00050004
Cyclododecene
Figure img00050004

Figure img00060001
Figure img00060001

<tb> <SEP> (CH3)2 <SEP> S±SCH3 <SEP> BF4 <SEP> < <SEP> SCH3
<tb> <SEP> Et,N, <SEP> 77%SCH3
<tb> Norbornadiène <SEP> / <
<tb> <SEP> F <SEP> 23%
<tb> <SEP> F <SEP> 23%
<tb>

Figure img00060002

méthyl-styrène trans
Figure img00060003
<tb><SEP> (CH3) 2 <SEP> S ± SCH3 <SEP> BF4 <SEP><<SEP> SCH3
<tb><SEP> Et, N, <SEP> 77% SCH3
<tb> Norbornadiene <SEP> / <
<tb><SEP> F <SEP> 23%
<tb><SEP> F <SEP> 23%
<tb>
Figure img00060002

trans methyl styrene
Figure img00060003

<tb> <SEP> C8517
<tb> <SEP> F
<tb> C8H1l7 <SEP> 1 <SEP> 1 <SEP> } <SEP> 80%
<tb> <SEP> CH3 <SEP> S
<tb> <SEP> idern <SEP> idem
<tb> <SEP> CH3S
<tb> Cholestène <SEP> 2 <SEP> |
<tb> <SEP> t <SEP> < <SEP> < <SEP> 20%
<tb>
Les composés d -fluorot-sulfure ainsi obtenus présentent toutes les propriétés de ces composés. On peut donc les utiliser avec succès
. comme agents intermédiaires de synthèse, notam
ment pour la préparation de fluorure vinylique,
de fluorure allylique, et de fluorosulfoxyde
comme composés de synthèse susceptibles d'activi
té biologique, notamment en agrochimie comme
agents insecticides, voire en pharmacie. <tb><SEP> C8517
<tb><SEP> F
<tb> C8H1l7 <SEP> 1 <SEP> 1 <SEP>} <SEP> 80%
<tb><SEP> CH3 <SEP> S
<tb><SEP> idern <SEP> same
<tb><SEP> CH3S
<tb> Cholestene <SEP> 2 <SEP> |
<tb><SEP> t <SEP><<SEP><<SEP> 20%
<tb>
The fluorot-sulfide compounds thus obtained exhibit all the properties of these compounds. We can therefore use them successfully
. as synthetic intermediates, in particular
ment for the preparation of vinyl fluoride,
of allylic fluoride, and of fluorosulfoxide
as synthetic compounds capable of activi
organic, especially in agrochemicals such as
insecticidal agents, even in pharmacies.

Claims (10)

REVENDICATIONS
Figure img00080001
Figure img00080001
 1/ Procédé de synthèse d'un composé organique cx - fluoro t-sulfure, caractérisé en ce qu'il consiste à faire réagir en une seule réaction un alcène avec un composé R-S-Y choisi dans le groupe comprenant les sels de thiosulfonium et les halogénures de sulfényle, en présence d'un agent de fluoration (F ) selon la formule générale 1 / Process for the synthesis of an organic compound cx - fluoro t-sulfide, characterized in that it consists in reacting in a single reaction an alkene with an RSY compound chosen from the group comprising thiosulfonium salts and halides of sulfenyl, in the presence of a fluorinating agent (F) according to the general formula 2/ Procédé selon la revendication 1, caractérisé en ce que l'alcène répond à la formule générale 2 / A method according to claim 1, characterized in that the alkene corresponds to the general formula
Figure img00080002
Figure img00080002
 dans laquelle R1 , R2, R3 , R4 désignent un atome d'hydrogène, un halogène, un groupement aryle, un groupement alkyle. in which R1, R2, R3, R4 denote a hydrogen atom, a halogen, an aryl group, an alkyl group. 3/ Procédé selon la-revendication 2, caractérisé en ce que les groupements aryles ou alkyles sont substitués par des hétéroatomes, notamment des groupes fonctionnels esters ou amides. 3 / A method according to claim 2, characterized in that the aryl or alkyl groups are substituted by heteroatoms, in particular ester or amide functional groups. 4/ Procédé selon l'une des revendications 2 et 3, caractérisé en ce que l'alcène est linéaire ou cyclique. 4 / A method according to one of claims 2 and 3, characterized in that the alkene is linear or cyclic. 5/ -Procédé selon l'une des revendications 1 à 4, caractérisé en ce que dans le composé R-S-Y,R désigne un groupement aryle ou alkyle, et Y désigne un halogèneou un groupement-S+R5R6, R5 et R6 étant identiques ou différents, désignent un groupement alkyle ou aryle 5 / -Procédé according to one of claims 1 to 4, characterized in that in the compound RSY, R denotes an aryl or alkyl group, and Y denotes a halogen or an -S + R5R6 group, R5 and R6 being identical or different , denote an alkyl or aryl group 6/ Procédé selon la revendication 5, caractérisé en ce que le composé R-S-Y est choisi dans le groupe comprenant le dialkylthiométhylsulfonium, tel que par exemple le diméthyl ( thiométhylsulfonium ), le diarylthiométhylsulfonium, le chlorure de methanesulfényle, tétrafluoroborate de diméthyl (thiométhylsulfonium). 6 / A method according to claim 5, characterized in that the R-S-Y compound is selected from the group comprising dialkylthiomethylsulfonium, such as for example dimethyl (thiomethylsulfonium), diarylthiomethylsulfonium, methanesulfenyl chloride, dimethyl tetrafluoroborate (thiomethylsulfonium). 7/ Procédé selon l'une des revendications 1 à 6, caractérisé en ce que l'agent de fluoration F est choisi dans le groupe comprenant l'acide fluorhydrique, les fluorures alcalins, les fluorhydrates d'amines, et les fluorures d'ammonium quaternaire de formule générale R7R8R9R10 N+[F, n HF]- dans laquelle : 7 / A method according to one of claims 1 to 6, characterized in that the fluorinating agent F is selected from the group comprising hydrofluoric acid, alkali fluorides, amine hydrofluorides, and ammonium fluorides quaternary of general formula R7R8R9R10 N + [F, n HF] - in which: . R7 , R8 , R9 , R10 désignent un atome d'hydrogène . R7, R8, R9, R10 denote a hydrogen atom ou des groupements, identiques ou non, alkyles, or groups, identical or not, alkyls, aryles, alkenylènes, aryls, alkenylenes, . n désigne un nombre entier compris entre zéro et . n denotes an integer between zero and dix. ten. 8/ Procédé selon la revendication 7, caractérisé en ce que l'agent de fluoration est compris dans le groupe comprenant la triéthylamine/3HF, le fluorure de tétraethylammonium/3HF, le fluorure d'ammonium/2,2 HF la pyridine/10 HF (réactif d'Olah), les méthylpyridines/ 1OHF, le fluorure de potassium, le fluorure de césium. 8 / A method according to claim 7, characterized in that the fluorinating agent is included in the group comprising triethylamine / 3HF, tetraethylammonium fluoride / 3HF, ammonium fluoride / 2.2 HF pyridine / 10 HF (Olah's reagent), methylpyridines / 1OHF, potassium fluoride, cesium fluoride. 9/ Procédé selon l'une des revendications 1 à 7, caractérisé en ce que la réaction s'effectue dans un solvant aprotique non nucléophile. 9 / A method according to one of claims 1 to 7, characterized in that the reaction is carried out in a non-nucleophilic aprotic solvent. 10/ Procédé selon la revendication 9, caractérisé en ce que le solvant aprotique est choisi dans le groupe constitué par le chlorure de méthylène et le tétrachlorure de carbone. 10 / A method according to claim 9, characterized in that the aprotic solvent is chosen from the group consisting of methylene chloride and carbon tetrachloride.
FR8708102A 1987-06-05 1987-06-05 PROCESS FOR THE SYNTHESIS OF AN ORGANIC COMPOUND A - FLUORO B - SULPHIDE Expired FR2616145B1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2823205A1 (en) * 2001-04-09 2002-10-11 Centre Nat Rech Scient COMPOSITION BASED ON AN AMINO COMPOUND AND AMMONIUM BIFLUORIDE AND USE THEREOF

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4941406A (en) * 1972-04-17 1974-04-18

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4941406A (en) * 1972-04-17 1974-04-18

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 83, 1975, page 453, résumé no. 27557n, Columbus, Ohio, US; & JP-A-74 41 406 (MITSUI PETROCHEMICAL INDUSTRIES LTD) 08-11-1974 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2823205A1 (en) * 2001-04-09 2002-10-11 Centre Nat Rech Scient COMPOSITION BASED ON AN AMINO COMPOUND AND AMMONIUM BIFLUORIDE AND USE THEREOF
WO2002081081A1 (en) * 2001-04-09 2002-10-17 Centre National De La Recherche Scientifique (C.N.R.S.) Composition based on an amine compound and ammonium bifluoride and use thereof

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