FR2619811A1 - New ethoxylated amides, processes for their synthesis and their applications - Google Patents
New ethoxylated amides, processes for their synthesis and their applications Download PDFInfo
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- FR2619811A1 FR2619811A1 FR8711930A FR8711930A FR2619811A1 FR 2619811 A1 FR2619811 A1 FR 2619811A1 FR 8711930 A FR8711930 A FR 8711930A FR 8711930 A FR8711930 A FR 8711930A FR 2619811 A1 FR2619811 A1 FR 2619811A1
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- c2h4o
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- 150000001408 amides Chemical class 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 title claims description 10
- 230000015572 biosynthetic process Effects 0.000 title description 7
- 238000003786 synthesis reaction Methods 0.000 title description 7
- 239000004094 surface-active agent Substances 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 125000003118 aryl group Chemical group 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims abstract description 3
- 239000002253 acid Substances 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 10
- 150000002148 esters Chemical class 0.000 claims description 10
- 150000003573 thiols Chemical class 0.000 claims description 10
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 3
- 125000000963 oxybis(methylene) group Chemical group [H]C([H])(*)OC([H])([H])* 0.000 claims 11
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000000047 product Substances 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- 238000004949 mass spectrometry Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Polymers OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 150000003869 acetamides Chemical class 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 208000027697 autoimmune lymphoproliferative syndrome due to CTLA4 haploinsuffiency Diseases 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 238000000451 chemical ionisation Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- VXIVSQZSERGHQP-UHFFFAOYSA-N chloroacetamide Chemical compound NC(=O)CCl VXIVSQZSERGHQP-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- VEUUMBGHMNQHGO-UHFFFAOYSA-N ethyl chloroacetate Chemical compound CCOC(=O)CCl VEUUMBGHMNQHGO-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000002123 sulfanediylbis(methylene) group Chemical group [H]C([H])(*)SC([H])([H])* 0.000 description 1
- -1 thioryl chloride Chemical compound 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
- C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/60—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton with the carbon atom of at least one of the carboxyl groups bound to nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/004—Surface-active compounds containing F
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
La présente invention concerne à titre de produits industriels nouveaux, des amides éthoxylés répondant à la formule
dans laquelle
RF est une chaine alkyle perfluorée comprenant de 2 à 12 atomes de carbone.The present invention relates, as new industrial products, to ethoxylated amides corresponding to the formula
in which
RF is a perfluorinated alkyl chain comprising from 2 to 12 carbon atoms.
R est de l'hydrbgène, un groupement hydroxy-alkyletel que C2H40H, un groupement alkyle ou aryle. R is hydrogen, a hydroxyalkyl group such as C2H40H, an alkyl or aryl group.
. n est un entier naturel compris entre 0 et 7. . n is a natural integer between 0 and 7.
. x est un entier naturel compris entre O et 2. . x is a natural integer between 0 and 2.
Les nouveaux composés de cette famille présentent d'intéressantes propriétés d'abaissement de la tension superficielle. The new compounds of this family have interesting properties of lowering the surface tension.
Les tensio-actifs fluorés trouvent actuellement de nombreuses applications notamment en tant qu'agents mouillants, qu'agents d'étalement sous forme d'additifs à des polymères, à des verres, à des encres, à des vernis, des émulsions photographiques, des liquides d'extraction... Fluorinated surfactants currently find many applications, particularly as wetting agents, as spreading agents in the form of additives for polymers, glasses, inks, varnishes, photographic emulsions, extraction liquids ...
Il s'est avéré par ailleurs, très intéressant de disposer de produits tensio-actifs parfaitement définis, notamment pour accéder à des Systèmes ternaires isotropes ou micro-émulsiorsconstitués de ces tensio-actifs, de fluorocarbures et d'eau. It has also been found that it is very advantageous to have surfactant products that are perfectly defined, in particular to access isotropic or microemulsified ternary systems consisting of these surfactants, fluorocarbons and water.
La reproductibilité de la préparation de telles micro-émulsions nécessite l'utilisation d'un tensio-actif non-ionique et mono-dispersé. De tels composés sont rarement disponibles industriellement du fait de problèmes liés à la mise en oeuvre de leur méthode de préparation et à la faiblesse des rendements généralement observés. On connait toutefois une famille de produits de la forme s C2H4 S R H où RF est une chaine perfluorée et R un enchainement de groupementsC2H40 et C2H4S décrite dans le brevet européen O 165853 qui peuvent être préparés industriellement avec de bons rendements dans une méthode itérative consistant à préparer un thiol et à le faire réagir sur un glycol monochloré.L'hydrophilie des produits de cette famille peut être modulée en jouant sur le nombre de groupements du type étheroxyde. The reproducibility of the preparation of such microemulsions requires the use of a nonionic and mono-dispersed surfactant. Such compounds are rarely available industrially because of problems related to the implementation of their method of preparation and the low yields generally observed. However, there is a family of products of the form C2H4 SRH where RF is a perfluorinated chain and R a sequence of groups C2H40 and C2H4S described in European Patent O 165853 which can be prepared industrially in good yields in an iterative method of preparing a thiol and to react it on a monochlorinated glycol.The hydrophilic products of this family can be modulated by varying the number of groups of the etheroxide type.
Les demandeurs ont découvert que l'introduction d'un groupement amide portant un substituant du type hydroxyle, permet d'accéder à des produits nouveaux d'hydrophilie accrue et qui présentent en outre, l'avantage de pouvoir être obtenus avec un bon degré de pureté et en particulier sans être souillés par des esters tels qu'ils se forment généralement, en équilibre, avec les amides à fonction alcool terminale. De tels équilibres sont notamment décrits dans "Non ionic surfactants - Chemical Analysis - John CROSS (1987) p. 15". Applicants have discovered that the introduction of an amide group bearing a substituent of the hydroxyl type makes it possible to access new products of increased hydrophilicity and which, moreover, have the advantage of being able to be obtained with a good degree of purity and in particular without being soiled by esters as they are generally formed in equilibrium with amides terminal alcohol function. Such equilibria are especially described in "Nonionic Surfactants - Chemical Analysis - John CROSS (1987)".
Ainsi donc l'invention vise des produits nouveaux qui peuvent trou ver des applications comme tensio-actifs, notamment dans les domaines où une forte hydrophilie est recherchée, cette hydrophilie pouvant être modulée à la fois en jouant sur le nombre de groupements étheroxydes et sur la nature des substituants de l'azote. Thus, the invention is aimed at novel products which can find applications as surfactants, especially in the fields where a strong hydrophilicity is desired, this hydrophilicity being able to be modulated both by varying the number of ethereal groups and on the nature of nitrogen substituents.
L'invention vise également des procédés pour l'obtention de ces composés à partir de produits de la forme
RF C2H4 DS (C2H40)n C2H42 SH, où RF, n et x ont la signification donnée précédemment, eux-mêmes synthétisés selon les procédés décrits dans le brevet européen 0 165853.The invention also relates to processes for obtaining these compounds from products of the form
RF C2H4 DS (C2H40) C2H42 SH, where RF, n and x have the meaning given above, themselves synthesized according to the methods described in European Patent 0 165853.
Une première voie de synthèse consiste à opérer selon le schéma A cidessous. A first synthetic route consists of operating according to scheme A below.
RF C2H4 Es (C2H4O)n C2E42 SH
Dans ce procédé, on condense sur le thiol de départ un ester o-halo- géné de l'acide acétique, par exemple Cl CH2 Et pour obtenir l'ester poly éthoxyléCI).Cet ester est ensuite hydrolysé pour obtenir l'acide correspondant qui est à son tour chloruré pour obtenir le chlorure d'acide(II). In this process, an o-halogenated ester of acetic acid, for example Cl CH 2 Et, is condensed on the starting thiol to give the polyethoxylated ester C. This ester is then hydrolysed to obtain the corresponding acid which is in turn chlorinated to obtain the acid chloride (II).
L'hydrolyse est de préférence réalisée en milieu alcalin, par exemple en présence de potasse alcoolique. La chloruration est avantageusement réalisée en Drésence de chlorure de thioryle. On fait ensuite réagir le cblo- rure d'acide(II)sur l'amine secondaire hydroxylée
Cette dernière réaction d'acylation conduit à des amides pratiquement purs qui peuvent etre purifiés par distillation ou par filtration sur colonne de silice avec des rendements compris entre 50 et 80 Z. This latter acylation reaction leads to substantially pure amides which can be purified by distillation or filtration on a silica column with yields of between 50 and 80%.
Un second procédé particulièrement avantageux, surtout avec des thiols de départ polyéthoxylés,permet d'obtenir directement l'amide recherché par réaction du thiol sur un halogéno-2 acétamide selon le schéma représenté cidessous (schéma B).
Les halogéno-acétamides, lorsqu'ils ne sont pas commerciaux, sont obtenus classiquement par réaction d'un a-halogéno chlorure d'acide, par exem ple le chlorure de chloroacétyle sur l'amide
La réaction du thiol polyéthoxylé sur l'halogéno-2 acétamide permet d'accéder aux amides purs avec des rendements compris entre 80 à 95 % en une seule étape. The reaction of the polyethoxylated thiol with 2-haloacetamide gives access to the pure amides with yields of between 80 and 95% in a single step.
La présente invention concerne également les applications des produits selon l'invention notamment en tant qu'agents tensio-actifs. The present invention also relates to the applications of the products according to the invention in particular as surface-active agents.
Les exemples ci-dessous sont donnés à titre d'illustration nullement limitative de la présente invention. The examples below are given by way of non-limiting illustration of the present invention.
Exemples
1 - Exemples de synthèse selon le schéma A
1-1 - Synthèse des esters fluorés polyéthoxylés
RFC2H4S-(C2H4O)n-C2H4S-CH2-CO2Et
Dans un ballon rodé équipé d'un réfrigérant, d'une ampoule a brome et refroidi par un bain de glace, on place 0,011 mole de sodium. On ajoute lentement 10 ml d'alcool éthylique absolu.Examples
1 - Synthesis Examples According to Scheme A
1-1 - Synthesis of polyethoxylated fluorinated esters
RFC2H4S- (C2H4O) n-C2H4S-CH2-CO2Et
In a ground flask equipped with a condenser, a dropping funnel and cooled by an ice bath, 0.011 mole of sodium is placed. Ten ml of absolute ethyl alcohol is slowly added.
Lorsque la totalité du sodium est dissoute, on purge le montage avec de l'azote puis on ajoute goutte à goutte 0,01 mole de thiol. When all of the sodium is dissolved, the assembly is purged with nitrogen and then 0.01 mole of thiol is added dropwise.
L'addition terminée, on ajoute goutte à goutte par l'ampoule à brome 0,01 mole de chloroacétate d'éthyle. When the addition is complete, 0.01 moles of ethyl chloroacetate are added dropwise to the dropping funnel.
On maintient la température à O C pendant 2 h puis on agite à température ambiante et toujours sous atmosphère inerte pendant 2 h. The temperature is maintained at 0 ° C. for 2 h and then the mixture is stirred at room temperature and still under an inert atmosphere for 2 hours.
Après avoir évaporé l'éthanol, on extrait le produit de la réaction dans l'éther éthylique et on lave plusieurs fois à l'eau. After evaporating the ethanol, the reaction product is extracted into ethyl ether and washed several times with water.
La phase éthérée est séchée sur sulfate de sodium et le solvant évaporé. The ether phase is dried over sodium sulfate and the solvent evaporated.
Le résidu est ensuite distillé sous pression réduite. The residue is then distilled under reduced pressure.
Les produits obtenus ont été identifiés par RMN du fluor et du proton, spectrométrie de masse et la pureté des produits contrôlée par analyse élémentaire. The products obtained were identified by fluorine and proton NMR, mass spectrometry and the purity of the products controlled by elemental analysis.
Le tableau 1 ci-après donne pour différents esters, les rendements obtenus (Rt) et les points d'ébullition (Eb) sous pression réduite. Table 1 below gives, for different esters, the yields obtained (Rt) and the boiling points (Eb) under reduced pressure.
Tableau 1
<tb> <SEP> Eb <SEP> OC/I
<tb> <SEP> mmHg <SEP> Rt%
<tb> C4F9C2H4S-CH2- <SEP> CO2Et <SEP> sa-sol <SEP> e.
<tb><tb><SEP> Eb <SEP> OC / I
<tb><SEP> mmHg <SEP> Rt%
<tb> C4F9C2H4S-CH2- <SEP> CO2Et <SEP> sa-soil <SEP> e.
<Tb>
<SEP> 20
<tb> C4F9C2H4S-C2H4O-C2H4S-CH2-CO2Et <SEP> Ol <SEP> /0.1 <SEP> 7J
<tb> C4F9C2H4S-(C2H4o)iC2H4s <SEP> CH2C 2Et <SEP> 123 <SEP> AI <SEP> 70
<tb> C6Fl3C2H4S-CH2-CO2Et <SEP> 10/20 <SEP> 90
<tb> C6F13C2H4S-C2H40- <SEP> C2H4S-C <SEP> H2- <SEP> CO2Et <SEP> 117/z1 <SEP> as
<tb> C613C2H45 <SEP> (C2H4o)2C2H4s-CH2Co2Et <SEP> 139/o.l <SEP> 00.
<tb> <SEP> 20
<tb> C4F9C2H4S-C2H4O-C2H4S-CH2-CO2Et <SEP> Ol <SEP> /0.1 <SEP> 7J
<tb> C4F9C2H4S- (C2H4o) iC2H4s <SEP> CH2C2Et <SEP> 123 <SEP> AI <SEP> 70
<tb> C6Fl3C2H4S-CH2-CO2Et <SEP> 10/20 <SEP> 90
<tb> C6F13C2H4S-C2H40- <SEP> C2H4S-C <SEP> H2- <SEP> CO2Et <SEP> 117 / z1 <SEP> as
<tb> C613C2H45 <SEP> (C2H4o) 2C2H4s-CH2Co2Et <SEP> 139 / ol <SEP> 00.
<Tb>
1-2 - Synthèse des acides fluorés polyethoxylés
RFC2H4S-(C2H4O)n-C2H4S-CH2-CO2H
Dans un ballon rodé surmonté d'une ampoule à brome et d'un réfrigérant, on place 0,125 mole d'ester.1-2 - Synthesis of polyethoxylated fluorinated acids
RFC2H4S- (C2H4O) n-C2H4S-CH2-CO2H
In a ground flask surmounted by a dropping funnel and a condenser, 0.125 moles of ester are placed.
Par l'ampoule à brome on additionne lentement 60 ml d'une solution basique préparée à partir de
, 35 g d'hydroxyde de potassium,
, 25 ml d'eau, le tout dilué jusqu'à 100 ml avec du méthanol.The dropping funnel is slowly added with 60 ml of a basic solution prepared from
35 g of potassium hydroxide,
25 ml of water, all diluted to 100 ml with methanol.
On chauffe le mélange réactionnel à 1000C pendant 1 h 30 mn puis on refroidit par un bain de glace. The reaction mixture is heated at 1000C for 1 h 30 min and then cooled with an ice bath.
On dilue la solution avec 80 ml d'eau froide puis on acidifie avec 32 ml d'HCl (d = 1,18) dilués dans 40 ml d'eau. The solution is diluted with 80 ml of cold water and then acidified with 32 ml of HCl (d = 1.18) diluted in 40 ml of water.
L'acide est extrait à l'éther éthylique, la phase éthérée est abondamment lavée à l'eau, séchée sur sulfate de sodium, filtrée et le solvant est évaporé. The acid is extracted with ethyl ether, the ether phase is thoroughly washed with water, dried over sodium sulfate, filtered and the solvent is evaporated.
Les acides sont purifiés par distillation sous pression réduite ou par chromatographie sur colonne. The acids are purified by distillation under reduced pressure or by column chromatography.
Les produits ont été identifiés par RMN du proton et du fluor, spectroscopie infra-rouge, spectroscopie de masse. L'analyse élémentaire a confirmé le pourcentage pondéral des éléments. The products were identified by proton and fluorine NMR, infra-red spectroscopy, mass spectroscopy. The elemental analysis confirmed the weight percentage of the elements.
Le tableau 2 ci-dessous donne les rendements observés (Rt) et les points d'ébullition (b) sous pression réduite. Table 2 below gives the observed yields (Rt) and the boiling points (b) under reduced pressure.
Tableau 2
<tb> <SEP> b0C/ <SEP> Ru
<tb> mm <SEP> Hg
<tb> <SEP> IWi
<tb> <SEP> C4F2H4S- <SEP> C <SEP> H2-CO2H <SEP> 0,15 <SEP> 91
<tb> <SEP> C4F9c2H4s-C2H40-C2H4S-CH2-CO2H <SEP> 135t
<tb> <SEP> 0,15
<tb> <SEP> C <SEP> F,C2H,S-(C?YO) <SEP> . <SEP> 88
<tb> <SEP> C6F13C2H4S-CH2-CO2H <SEP> 0,2
<tb> <SEP> 0,2
<tb> <SEP> 148,
<tb> <SEP> CF <SEP> CHS-CHO-CHS-CH-COH <SEP> 89
<tb> <SEP> 6 <SEP> 2 <SEP> 4 <SEP> 4 <SEP> - <SEP> r <SEP> 0,13
<tb> <SEP> C6F13C2H4s-(C2H4o)2-C2H4s.C <SEP> HiC <SEP> 02H <SEP> S5
<tb>
(+) Composes non distillables : Purification par colonne de
chromatographie (eluant CHC13). <tb><SEP> b0C / <SEP> Ru
<tb> mm <SEP> Hg
<tb><SEP> IWi
<tb><SEP> C4F2H4S- <SEP> C <SEP> H2-CO2H <SEP> 0.15 <SEP> 91
<tb><SEP> C4F9c2H4s-C2H4O-C2H4S-CH2-CO2H <SEP> 135t
<tb><SEP> 0.15
<tb><SEP> C <SEP> F, C2H, S- (C YO) <SEP>. <SEP> 88
<tb><SEP> C6F13C2H4S-CH2-CO2H <SEP> 0.2
<tb><SEP> 0.2
<tb><SEP> 148,
<tb><SEP> CF <SEP> CHS-CHO-CHS-CH-COH <SEP> 89
<tb><SEP> 6 <SEP> 2 <SEP> 4 <SEP> 4 <SEP> - <SEP> r <SEP> 0.13
<tb><SEP> C6F13C2H4s- (C2H4o) 2-C2H4s.C <SEP> HiC <SEP> 02H <SEP> S5
<Tb>
(+) Undistillable compounds: Purification by column of
chromatography (CHC13 eluent).
1-3 - Synthèse des chlorures d'acides fluorés polyéthoxylés
RFC2H4S-(C2H4O)n-C2H4S-CH2-COCl
Dans un ballon rodé, équipé d'une ampoule à brome et d'un réfrigérant, on place 1,1 mole de chlorure de thionyle distillé préalablement sur quinoléine et sur huile de lin.1-3 - Synthesis of polyethoxylated fluorinated acid chlorides
RFC2H4S- (C2H4O) n-C2H4S-CH2-COCl
In a ground flask equipped with a dropping funnel and a condenser, 1.1 mole of thionyl chloride previously distilled on quinoline and on linseed oil are placed.
Par l'ampoule à brome on ajoute goutte à goutte 1 mole d'acide distillé exempt de traces d'humidité. The dropping funnel is added dropwise 1 mole of distilled acid free of traces of moisture.
Le mélange est chauffé à 700C pendant 1 h 30 mn en maintenant une très légère aspiration pour éliminer les gaz dégagés. The mixture is heated at 700C for 1 h 30 min while maintaining a very slight suction to remove the gases released.
Lorsque le dégagement gazeux cesse, on distille le chlorure d'acide sous pression réduite. When the evolution of gas ceases, the acid chloride is distilled under reduced pressure.
Le tableau 3 ci-dessous donne les rendements obtenus (Rt) et les points d'abullition (Eb) des produits sous pression réduite. Table 3 below gives the yields obtained (Rt) and the boiling points (Eb) of the products under reduced pressure.
Tableau 3
<tb> <SEP> Eb <SEP> OC/1 <SEP> X
<tb> <SEP> mm <SEP> Hg
<tb> 61 <SEP> co <SEP> ci <SEP> 61, <SEP> 90
<tb> 0.1
<tb> C4F9C2H4S-C2H40-C2H4S-CH2-COCI <SEP> 113, <SEP> 68
<tb> <SEP> 0.15
<tb> C6F13C2H4S-CH2-COCI <SEP> 75
<tb> <SEP> 1
<tb> <SEP> 67
<tb> C6F13C2H4S-C2H40-C2H4S-CH2-COCI <SEP> 135
<tb> <SEP> 0.18
<tb>
Les produits ont été contrôlés par RMN du proton et du fluor, par spectroscopie infra-rouge, par spectrométrie de masse et analyse élémentaire.<tb><SEP> Eb <SEP> OC / 1 <SEP> X
<tb><SEP> mm <SEP> Hg
<tb> 61 <SEP> co <SEP> ci <SEP> 61, <SEP> 90
<tb> 0.1
<tb> C4F9C2H4S-C2H4O-C2H4S-CH2-COCI <SEP> 113, <SEP> 68
<tb><SEP> 0.15
<tb> C6F13C2H4S-CH2-COCI <SEP> 75
<tb><SEP> 1
<tb><SEP> 67
<tb> C6F13C2H4S-C2H40-C2H4S-CH2-COCI <SEP> 135
<tb><SEP> 0.18
<Tb>
The products were monitored by proton and fluorine NMR, infra-red spectroscopy, mass spectrometry and elemental analysis.
1-4 - Synthèse des acétamides fluorés polyéthoxylés
a Sartir des chlorures d'acides fluorés 2olyethoxyles
Dans un ballon rodé surmonté d'une ampoule à brome, équipé d'un réfrigérant et redroidi par un bain de glace, on place 0,002 mole d'amine en solution dans 10 ml d'éther éthylique.1-4 - Synthesis of polyethoxylated fluorinated acetamides
to remove fluorinated acid chlorides 2olyethoxyls
In a ground flask surmounted by a dropping funnel, equipped with a condenser and cooled by an ice bath, 0.002 mol of amine in solution in 10 ml of ethyl ether are placed.
Par l'ampoule à brome on ajoute goutte à goutte 0,001 mole de chlorure d'acide en solution dans 10 ml d'éther éthylique. 0.001 mol of acid chloride dissolved in 10 ml of ethyl ether are added dropwise to the dropping funnel.
On maintient la température à 0 C pendant 2 h puis on agite 3 h à température ambiante. Le mélange est ensuite extrait à l'éther éthylique. The temperature is maintained at 0 C for 2 h and then stirred for 3 h at room temperature. The mixture is then extracted with ethyl ether.
La phase organique est lavée à l'eau, séchée sur sulfate de sodium et filtrée.The organic phase is washed with water, dried over sodium sulphate and filtered.
Après avoir évaporé le solvant, les amides sont si possible distillés soustpression réduite ou encore filtrés sur colonne de silice avec le mélange AcOEt /MeOB dans les proportions 9/1. After having evaporated the solvent, the amides are, if possible, distilled under reduced pressure or else filtered on a silica column with the AcOEt / MeOB mixture in the proportions 9/1.
Les résultats obtenus figurent dans le tableau 4 ci-après.
Tableau 4
Table 4
<SEP> |
<tb> <SEP> AMINE <SEP> Rt%
<tb> <SEP> Me
<tb> <SEP> . <SEP> , <SEP> N- <SEP> C2H4OH <SEP> 80
<tb> <SEP> C4F9C2H4S-CH2-COCI <SEP> H
<tb> <SEP> HN <SEP> (c2H4oH)2 <SEP> 68
<tb> CF9C2H4s-C2H4o-C2H4s-CH2CoCI <SEP> HN <SEP> (C2HOH)2 <SEP> 52
<tb> <SEP> Me
<tb> <SEP> N-C,H <SEP> OH <SEP> 80
<tb> <SEP> C,FJC,H <SEP> S-CH-COCI <SEP> 4
<tb> <SEP> 4 <SEP> 2
<tb> <SEP> IHN <SEP> (C,H,O)Z <SEP> O
<tb> 613 <SEP> 2H4S-C2H40-C2H4S-CH2-COCI <SEP> HN <SEP> (C2H4OH)2 <SEP> - <SEP> 55
<tb>
L'identification des produits a été faite par RMN du proton, RMN du fluor, spectrométrie de masse et infra-rouge. La pureté des produits a été contrôlée par analyse élémentaire.<SEP>|
<tb><SEP> AMINE <SEP> Rt%
<tb><SEP> Me
<tb><SEP>.<SEP>,<SEP> N- <SEP> C2H4OH <SEP> 80
<tb><SEP> C4F9C2H4S-CH2-COCI <SEP> H
<tb><SEP> HN <SEP> (c2H4oH) 2 <SEP> 68
<tb> CF9C2H4s-C2H4o-C2H4s-CH2CoCl <SEP> HN <SEP> (C2HOH) 2 <SEP> 52
<tb><SEP> Me
<tb><SEP> NC, H <SEP> OH <SEP> 80
<tb><SEP> C, FJC, H <SEP> S-CH-COCI <SEP> 4
<tb><SEP> 4 <SEP> 2
<tb><SEP> IHN <SEP> (C, H, O) Z <SEP> O
<tb> 613 <SEP> 2H4S-C2H4O-C2H4S-CH2-COCI <SEP> HN <SEP> (C2H4OH) 2 <SEP> - <SEP> 55
<Tb>
The identification of the products was made by proton NMR, fluorine NMR, mass spectrometry and infra-red. The purity of the products was checked by elemental analysis.
2 - Exemple de synthèse selon le schéma B
Dans un ballon rodé, surmonté d'un réfrigérant et d'une ampoule à brome, on place 0,011 mole de sodium.2 - Example of synthesis according to scheme B
In a ground flask surmounted by a condenser and a dropping funnel, 0.011 mole of sodium is placed.
Le montage étant refroidi par un bain de glace, on ajoute goutte à goutte 10 ml d'éthanol absolu. The assembly being cooled by an ice bath, 10 ml of absolute ethanol are added dropwise.
Lorsque la totalité du sodium est dissoute, on place 0,01 mole de thiol dans l'ampoule à brome et on purge le montage à l'azote. On additionne goutte à goutte le thiol à la solution d'éthanolate de sodium puis on retransvase le tout dans l'ampoule à brome toujours sous atmosphère inerte. When all of the sodium is dissolved, 0.01 mole of thiol is placed in the dropping funnel and the assembly is purged with nitrogen. The thiol is added dropwise to the sodium ethanolate solution and the whole is then transferred back to the dropping funnel under an inert atmosphere.
Cette ampoule à brome est ensuite placée sur un autre ballon rodé, contenant 0,01 mole de chloro-2 acétamide en solution dans 10 ml d'éthanol absolu. This addition funnel is then placed on another ground flask containing 0.01 mol of 2-chloroacetamide dissolved in 10 ml of absolute ethanol.
Après avoir à nouveau purgé le système à l'azote, on le refroidit par bain de glace et on additionne lentement le contenu de l'ampoule à brome au chloro-2 acétamide. After purging the system again with nitrogen, it is cooled by an ice bath and the content of the dropping funnel is slowly added to chloro-2-acetamide.
L'agitation est maintenue à basse température pendant 2 h puis à température ambiante pendant 12 h. Stirring is maintained at low temperature for 2 h and then at room temperature for 12 h.
On évapore ltéthanol et on extrait à l'éther éthylique. The ethanol is evaporated and extracted with ethyl ether.
On lave la solution éthérée à l'eau, on la sèche sur sulfate de sodium, on la filtre puis on chasse le solvant. The ethereal solution is washed with water, dried over sodium sulfate, filtered and the solvent removed.
On distille si possible l'amide sous pression réduite ou on filtre sur colonne de silice avec le mélange Ac0Et /MeOH dans le rapport 9/1 puis avec MeOH comme éluants. If possible, the amide is distilled off under reduced pressure or filtered on a silica column with the mixture AcOEt / MeOH in the ratio 9/1 and then with MeOH as eluents.
L'absence de produits de la forme éther en équilibre avec l'amide a été mise en évidence par une étude en spectroscopie de masse en effectuant une ionisation chimique. The absence of products of the ether form in equilibrium with the amide was demonstrated by a study in mass spectroscopy by performing a chemical ionization.
Ces produits ont été caractérisés comme en 1-5. These products have been characterized as 1-5.
Les rendements (Rt) obtenus sont indiqués dans le tableau 5 cidessous. The yields (Rt) obtained are shown in Table 5 below.
Tableau 5
<tb> <SEP> Rt%
<tb> C4F9C2H45-CH2- <SEP> CON(C2H4OH)2 <SEP> 95
<tb> C4F9C2H4S-C2H40-C2H4S-CH2-CON <SEP> (C2H4oH)2 <SEP> 89
<tb> C4E9C2H4S <SEP> (C <SEP> 2H4 )2 <SEP> H <SEP> Chai <SEP> CON(C2H4OH)2 <SEP> 82
<tb> CF <SEP> t,C,H <SEP> S-CHCON(cz, <SEP> 92
<tb> C6Fl3C2H4s-C2H4o-C2H4s-C82CON <SEP> (c,H,o
<tb> <SEP> 9 <SEP> IJ <SEP> 2 <SEP> 4 <SEP> c
<tb> C6F13C2H4S- <SEP> (C2H4O)2 <SEP> C2 <SEP> H4S <SEP> -C <SEP> H2- <SEP> CON <SEP> (C2H40 <SEP> 1t)2 <SEP> 83
<tb>
3 - Propriétés tensio-actives
On a mesuré la tension superficielle de différentes solutions aqueuses de C6F13C2H4S(C2H4O)2-C2H4S-CH2-CON(C2H4OH)2 jusqu'à la limite de solubilité de ce produit.<tb><SEP> Rt%
<tb> C4F9Cl2H45-CH2- <SEP> CON (C2H4OH) 2 <SEP> 95
<tb> C4F9C2H4S-C2H4O-C2H4S-CH2-CON <SEP> (C2H4oH) 2 <SEP> 89
<tb> C4E9C2H4S <SEP> (C <SEP> 2H4) 2 <SEP> H <SEP> Chai <SEP> CON (C2H4OH) 2 <SEP> 82
<tb> CF <SEP> t, C, H <SEP> S-CHCON (cz, <SEP> 92
<tb> C6F13C2H4s-C2H4o-C2H4s-C82CON <SEP> (c, H, o)
<tb><SEP> 9 <SEP> IJ <SEP> 2 <SEP> 4 <SEP> c
<tb> C6F13C2H4S- <SEP> (C2H4O) 2 <SEP> C2 <SEP> H4S <SEP> -C <SEP> H2- <SEP> CON <SEP> (C2H40 <SEP> 1t) 2 <SEP> 83
<Tb>
3 - Surfactant properties
The surface tension of various aqueous solutions of C6F13C2H4S (C2H4O) 2-C2H4S-CH2-CON (C2H4OH) 2 was measured to the solubility limit of this product.
Le tableau 6 ci-dessous donne les valeurs des tensions superficielles en fonction de la concentration. Table 6 below gives the values of the surface tensions as a function of the concentration.
Tableau 6
<tb> CONCENTRATION <SEP> TENSION <SEP> SUPERFICIELLE
<tb> <SEP> (z) <SEP> (mN.m <SEP> ) <SEP>
<tb> <SEP> 0,0055 <SEP> 16,2
<tb> <SEP> 0,0028 <SEP> 16,9
<tb> <SEP> 0,0014 <SEP> 17,2
<tb> <SEP> 0,0007 <SEP> 19,1
<tb> <SEP> 0,00034 <SEP> 25,5
<tb> <tb> CONCENTRATION <SEP> VOLTAGE <SEP> SURFACE
<tb><SEP> (z) <SEP> (mN.m <SEP>) <SEP>
<tb><SEP> 0.0055 <SEP> 16.2
<tb><SEP> 0.0028 <SEP> 16.9
<tb><SEP> 0.0014 <SEP> 17.2
<tb><SEP> 0.0007 <SEP> 19.1
<tb><SEP> 0.00034 <SEP> 25.5
<Tb>
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8711930A FR2619811B1 (en) | 1987-08-26 | 1987-08-26 | NOVEL ETHOXYL AMIDES, THEIR SYNTHESIS METHODS AND THEIR APPLICATIONS |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8711930A FR2619811B1 (en) | 1987-08-26 | 1987-08-26 | NOVEL ETHOXYL AMIDES, THEIR SYNTHESIS METHODS AND THEIR APPLICATIONS |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| FR2619811A1 true FR2619811A1 (en) | 1989-03-03 |
| FR2619811B1 FR2619811B1 (en) | 1989-12-08 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| FR8711930A Expired FR2619811B1 (en) | 1987-08-26 | 1987-08-26 | NOVEL ETHOXYL AMIDES, THEIR SYNTHESIS METHODS AND THEIR APPLICATIONS |
Country Status (1)
| Country | Link |
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| FR (1) | FR2619811B1 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0414396A1 (en) * | 1989-08-11 | 1991-02-27 | Rohm And Haas Company | N-Hydroxyalkyl-mercaptoalkanamides |
| FR2669331A1 (en) * | 1990-11-19 | 1992-05-22 | Tranphyto Sa | New nonionic compounds possessing surface-active properties and process for their preparation |
| EP0652210A1 (en) * | 1993-11-10 | 1995-05-10 | L'oreal | Solar filters containing a fluorohydrocarbon group, process for their preparation, and their use in cosmetic compositions |
| US8017656B2 (en) | 2005-11-22 | 2011-09-13 | Sumitomo Chemical Company, Limited | Organic sulfur compounds and use thereof |
| US8158829B2 (en) | 2007-05-18 | 2012-04-17 | Sumitomo Chemical Company, Limited | Organic sulfur compound and its use for controlling harmful arthropod |
| US8247612B2 (en) | 2007-05-18 | 2012-08-21 | Sumitomo Chemical Company, Limited | Organic sulfur compound and its use for controlling harmful arthropod |
| US8247595B2 (en) | 2007-05-18 | 2012-08-21 | Sumitomo Chemical Company, Limited | Organic sulfur compound and its use for controlling harmful arthropod |
| CN113105377A (en) * | 2021-03-01 | 2021-07-13 | 程伟 | Preparation method of plasticizer and application of plasticizer in plastic product |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1349559A (en) * | 1963-01-29 | 1964-01-17 | Geigy Ag J R | New amides of carboxylic acids and their preparation |
| FR2200259A1 (en) * | 1972-09-15 | 1974-04-19 | Ciba Geigy Ag | |
| FR2516920A1 (en) * | 1981-11-25 | 1983-05-27 | Inst Nat Rech Chimique | Fluorinated sulphide, sulphoxide and sulphone cpds. - useful as gas vehicles and blood substitutes |
| EP0165853A1 (en) * | 1984-05-29 | 1985-12-27 | Institut National De Recherche Chimique Appliquee | Non-ionic fluorine compounds, process for their preparation and their use as tensio-active agents |
| JPS62184087A (en) * | 1986-02-07 | 1987-08-12 | Nippon Mektron Ltd | Stainproof water and oil repellent |
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1987
- 1987-08-26 FR FR8711930A patent/FR2619811B1/en not_active Expired
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1349559A (en) * | 1963-01-29 | 1964-01-17 | Geigy Ag J R | New amides of carboxylic acids and their preparation |
| FR2200259A1 (en) * | 1972-09-15 | 1974-04-19 | Ciba Geigy Ag | |
| FR2516920A1 (en) * | 1981-11-25 | 1983-05-27 | Inst Nat Rech Chimique | Fluorinated sulphide, sulphoxide and sulphone cpds. - useful as gas vehicles and blood substitutes |
| EP0165853A1 (en) * | 1984-05-29 | 1985-12-27 | Institut National De Recherche Chimique Appliquee | Non-ionic fluorine compounds, process for their preparation and their use as tensio-active agents |
| JPS62184087A (en) * | 1986-02-07 | 1987-08-12 | Nippon Mektron Ltd | Stainproof water and oil repellent |
Non-Patent Citations (1)
| Title |
|---|
| CHEMICAL ABSTRACTS, vol. 108, no. 13, 28 mars 1988, no. 114168q, Columbus, Ohio, US; & JP-A-62 184 087 (NIPPON MECTRON CO., LTD.) 12-08-1987 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0414396A1 (en) * | 1989-08-11 | 1991-02-27 | Rohm And Haas Company | N-Hydroxyalkyl-mercaptoalkanamides |
| AU645983B2 (en) * | 1989-08-11 | 1994-02-03 | Rohm And Haas Company | Thiol-terminated hydroxyamides |
| FR2669331A1 (en) * | 1990-11-19 | 1992-05-22 | Tranphyto Sa | New nonionic compounds possessing surface-active properties and process for their preparation |
| EP0652210A1 (en) * | 1993-11-10 | 1995-05-10 | L'oreal | Solar filters containing a fluorohydrocarbon group, process for their preparation, and their use in cosmetic compositions |
| FR2712287A1 (en) * | 1993-11-10 | 1995-05-19 | Oreal | Novel hydrocarbon fluorinated sunscreens, process for their preparation and their use in cosmetic compositions |
| US8017656B2 (en) | 2005-11-22 | 2011-09-13 | Sumitomo Chemical Company, Limited | Organic sulfur compounds and use thereof |
| US8158829B2 (en) | 2007-05-18 | 2012-04-17 | Sumitomo Chemical Company, Limited | Organic sulfur compound and its use for controlling harmful arthropod |
| US8247612B2 (en) | 2007-05-18 | 2012-08-21 | Sumitomo Chemical Company, Limited | Organic sulfur compound and its use for controlling harmful arthropod |
| US8247595B2 (en) | 2007-05-18 | 2012-08-21 | Sumitomo Chemical Company, Limited | Organic sulfur compound and its use for controlling harmful arthropod |
| CN113105377A (en) * | 2021-03-01 | 2021-07-13 | 程伟 | Preparation method of plasticizer and application of plasticizer in plastic product |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2619811B1 (en) | 1989-12-08 |
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