Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages
  • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages
  • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
  • C07F7/1804—Compounds having Si-O-C linkages
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages

Definitions

• the field of the invention is that of the synthesis of functionalized organosilicon compounds.
• the organosilicon compounds more particularly concerned by the invention are those comprising at least one activated azo group. This activation may result, for example, from the presence of neighboring carbonyl groups of the nitrogens.
• the organosilicon portion of these compounds may comprise, for example, hydrolysable or condensable groups of the type ⁇ SiOR or ⁇ SiOH.
• Such activated azo group (s) organosilicon compounds are very useful, especially in the synthesis of active organic molecules (for example nitrogenous heterocycles). useful in the fields of agrochemistry and pharmaceuticals, for example as dienophiles in reaction of hetero-Diels Aider.
• X and X 1 are identical or different and each represents an imino group, an oxygen atom or a substituted or unsubstituted methylene group; Y is a substituted or unsubstituted alkyl, aryl or aralkyl group, or is the same as Z *; Z * is an alkyl, aryl or aralkyl group which has as substituent at least one silane group of formula Si (OR) 3 or OSi (OR) 3 in which R is a straight or branched chain alkyl group, preferably with 1 to 6 carbon atoms.
• R 1 * -O-CO-N N-CO-NH- (C 6 H 6 ) - (CH 2 ) m -Si (OR 2 * ) 3
• R 1 * - O-CO-N N-CO-NH- (CH 2)
• n -Si (oR 2 *) 3 in which R 1 * and R 2 * are identical or different and each represents a straight-chain or branched alkyl group containing preferably between 1 and 6 carbon atoms, m is 0, 1, 2 or 3 and n is 1, 2 or 3, are mentioned.
• Example 3 of FR-A-2340323 provides for the implementation of an organic precursor solution Ethyl-O-CO-HN-NH-CO-NH- (CH 2 ) 3 -
• the NBS-pyridine oxidizing system is in excess (10 mol%) relative to the precursor.
• one of the essential objectives of the present invention is to propose an improved process for the preparation of organosilicic compounds containing azo group (s), by oxidation of the hydrazino group of a precursor in an azo group, this process providing a route of access to the compounds of interest, avoiding the implementation of rigorously anhydrous operating conditions and / or the filtration step for separating the salts generated by the reaction.
• Another essential objective of the invention is to provide a process for the preparation of organosilicic compounds with azo group (s), which are more stable, especially at high temperatures, for example between 80 and 180 ° C. (differential scanning calorimetry stability DSC ).
• Another essential objective of the invention is to provide a preparation method organosilic compounds with azo group (s), which are more efficient than those disclosed in the prior art especially in terms of productivity and azoalcoxysilane yield referred.
• Another essential objective of the present invention is to provide an economical process for the preparation of organosilicic compounds with azo group (s).
• Another essential objective of the invention is to provide a process for the preparation of organosilicon compounds containing azo group (s), which makes it possible to optimize the quality of the final product, in particular as regards the purity of these compounds, and especially in terms of reducing or even eliminating unwanted residues, particularly in terms of the desired performance in applications and industrial and environmental hygiene.
• organosilicon compounds comprising one or more compounds, which are identical or different from each other, of formula (I) below :
• - a ' represents an integer selected from 0, 1 and 2;
• G 0 which may be identical or different, each represent one of the groups corresponding to G 2 or G 1 ;
• the symbols G 2 which may be identical or different, each represent: a hydroxyl group, a hydrolysable monovalent group or two G 2 together with the silicon to which they are bonded form a ring having 3 to 5 hydrocarbon-bearing members and which may comprise at least one heteroatom, at least one of these links may also be a link of at least one other hydrocarbon or aromatic ring;
• the symbols G 1 which may be identical or different, each represent: a saturated or unsaturated aliphatic hydrocarbon group; a carbocyclic group, saturated or unsaturated and / or aromatic, monocyclic or polycyclic; or a group representing a saturated or unsaturated aliphatic hydrocarbon portion and a carbocyclic moiety as defined above;
• the symbol Z represents a divalent radical chosen from: a saturated or unsaturated aliphatic hydrocarbon group; a carbocyclic group, saturated, unsaturated and / or aromatic, monocyclic or polycyclic; and a group having a saturated or unsaturated ali
• an aliphatic hydrocarbon group saturated or unsaturated; a carbocyclic group, saturated or unsaturated and / or aromatic, monocyclic or polycyclic; or a group representing a saturated or unsaturated aliphatic hydrocarbon portion and a carbocyclic moiety as defined above;
• X represents -O-, -S- or -NG 4 - with G 4 taking any of the meanings given above for G 1 ;
• G 3 identical to or different from G 4 , represents any one of the groups defined for G 1 ;
• G o 4-P iSi (G 2 ') p i
• G ° which may be identical or different, each represent: a saturated or unsaturated aliphatic hydrocarbon group; a carbocyclic group, saturated or unsaturated and / or aromatic, monocyclic or polycyclic; or a group representing a saturated or unsaturated aliphatic hydrocarbon portion and a carbocyclic moiety as defined above; or a polysiloxane residue;
• this method being characterized in that the oxidation is carried out in aqueous / organic biphasic medium and in that the pH of the aqueous phase is made between 3 and 11, preferably between 5 and 9.
• This process consists in operating in two-phase water / organic solvent medium.
• the transformation of the precursors (II) into activated azo group (s) (I) organosilicon compounds is carried out in the organic phase, while the aqueous phase solubilizes the various water-soluble compounds generated by the transformation.
• ionic compounds the acids in particular are known to be particularly well soluble in the aqueous phase. It is therefore preferable in accordance with the invention for the process which it concerns to provide for the use of an aqueous phase whose pH remains between 3 and 11 during the reaction and preferably between 5 and 9. for example, it could be advantageous to use an aqueous solution whose pH would remain close to neutral (pH ⁇ 7) during the reaction.
• the process according to the invention improves the prior art by making it possible to overcome the very heavy industrial constraints related to the implementation of anhydrous conditions and / or a filtration step and / or a solid reagent.
• these compounds (I) obtained by the process according to the invention are remarkably pure. In particular, these compounds have little or no (undetectable traces) of undesirable residues, such as pyridine residues.
• this purity is at the origin of the excellent stability found for these compounds (I) from the biphasic process according to the invention.
• stability is meant especially storage stability especially in wet conditions, but especially heat stability.
• One of the means recommended according to the invention for controlling, if necessary, the pH of the aqueous phase consists in the implementation of at least one buffer system and / or in the addition of at least one base and or at least one acid.
• the buffer system can be chosen from the group comprising phosphate, borate and carbonate buffers and mixtures thereof. According to the invention, it is appropriate to select the oxidant (Ox) among oxidants capable of oxidizing a hydrazine function azo function and may lead to acid production.
• halogenated e.g., chlorinated
• Oxidants of the type are the oxidants of choice according to the invention. These are both oxidants and bases capable of neutralizing, if necessary, the acidity that they are likely to generate by combining their halogen with an H +. These oxidants (OxI) do not therefore require the implementation of a complementary base.
• the base B ° is preferably cast substantially simultaneously with the oxidant (0x2), preferably progressively.
• (B 0 ) and (Ox) are added simultaneously, in small amounts (eg dropwise) and very slowly (a few minutes to several hours, eg 0.5-2 hours) to the reaction mixture.
• the oxidant (Ox) is (are) used in stoichiometric quantities relative to the precursor (II).
• the reaction is then carried out in the reaction medium, preferably kept under stirring and at room temperature, for several hours (eg 2-4h) after the end of the addition of the oxidant (Ox) .
• the organic phase is then separated, dried and filtered before being concentrated e.g. under reduced pressure.
• the base (B 0) or (B) is used in a stoichiometric amount relative to the amount of acid released by the reaction.
• the choice of the base (B °) or the base (B 1 ) is preferably carried out among the mineral bases, preferably in the group comprising: carbonates, phosphates (eg K 2 HPO 4 ), borates, soda and mixtures thereof.
• the reaction medium comprises at least the organic adjuvant (A), preferably selected from organic bases, more preferably still from nitrogenous bases and even more preferably, from those whose pK a is lower than the pH of the aqueous phase.
• A organic adjuvant
• These adjuvants (A) may have, in particular to further improve the quality of the final product, can be introduced into the reaction medium.
• These adjuvants (A) are advantageously organic compounds.
• this organic adjuvant (A) is selected from organic bases, more preferably still from nitrogenous bases and even more preferably from among those whose pK a is lower than the pH of the aqueous phase.
• the pyridine whose pK a is 5 can be advantageously chosen in the case of the implementation of an aqueous phase of pH ⁇ 7.
• the adjuvant (A) is more especially chosen from the group comprising: pyridine, quinoline, nicotinate or isonicotinate derivatives and mixtures thereof.
• the additive (A) is preferably present in a molar ratio (A) / (II) between 1.10 "4 and 2, preferably between 1.10" and 1.0 2.
• adjuvant (s) (A) in the reaction medium is possible irrespective of the oxidant: OxI, 0x2, 0x3 or 0x4.
• oxidant eg bleach
• auxiliary at a ratio (A) / auxiliary of between 0.1 and 2.0, preferably substantially equal to 1.
• the method according to the invention of preparation of azo (I) -organosilicic compounds may be part of a synthetic process comprising at least the following steps: (i): a precursor silane of formula (IV) is reacted with:
• step (ii) corresponds to the preparation process according to the present invention.
• organosilicon compounds with an azo (I) group in the structure of which the symbol Z then represents the divalent radical - (CH 2 ) S -NH-
• the synthetic scheme that is applied may be the following (i): a precursor silane of formula (IV) is reacted:
• Organosilicon compound recovery with activated azo group (I) Organosilicon compound recovery with activated azo group (I). It should be noted that prior to the extraction of the aqueous phase, the biphasic reaction medium of the process according to the invention may for example be in the form of an organic phase emulsion in the aqueous phase.
• the organosilicon compound with an activated azo group (I) obtained is advantageously essentially, or even exclusively, present in the organic phase.
• This purification post-treatment consists in recovering the organosilicon compounds of formula (I) obtained, this recovery comprising at least one separation of the organic phase, optionally at least one filtration and / or at least one concentration of the separated organic phase.
• the post-treatment consists essentially of: a) mixing an ion-affinity support, preferably carbon black, with an organic filler solution, in a proportion of 0.1 to 20% by weight, preferably 1 to 10% by weight of ionic carrier with respect to the filler, b) to be left in contact preferably with stirring for a few minutes to several hours, c) to separate the carrier loaded with impurities from the filler solution, preferably by filtration, d) removing the solvent preferably by evaporation, e) mixing a chemical-affinity support, preferably an acidic resin (preferably a slightly acidic resin of type IR50), with an organic solution of the filler, in a proportion of 0.01 to 10% by weight, preferably in a proportion of 0.1 to 5% by weight of support with a chemical affinity relative to the load agent, f) at the in contact, preferably with stirring for a few minutes to several hours, g) separating the carrier loaded with impurities from the filler solution, preferably by filtration
• steps a) to d) constitute a first treatment and steps e) to h) a second treatment, these two treatments can be implemented successively in any order or simultaneously.
• the post-processing implemented in the method according to the invention comprises only one of these two treatments a) to d), on the one hand, and e) to h), of somewhere else. Beyond the general operating conditions described above, it is necessary to dwell a little more on the compounds (I) organosilicic functional group (s) azo activated (I) 5 obtained or likely to be obtained by this process according to the invention.
• these compounds (I) are free or virtually free (undetectable traces) of impurities, especially pyridine residues.
• the invention thus aims as new products, compounds (I) organosilicic functional group (s) azo activated (s) (I), obtainable by the method according to the invention characterized in that they are free or virtually free (undetectable traces) of impurities, including pyridine residues.
• organosilicon compounds (I) with activated azo functional group (s) (I) are also characterized in that they are heat stable. eg at temperatures between 80-180 0 C.
• the invention also concerns, as new products, the organosilicon compounds (I) with activated azo functional group (s) (I) characterized by a degree of hydrolysis / condensation (% molar) of the functions. G 2 less than or equal to 40, preferably 10, and even more preferably 1.
• aliphatic hydrocarbon group is meant, in the sense of the invention, a linear or branched group, preferably comprising from 1 to 25 carbon atoms, optionally substituted.
• said aliphatic hydrocarbon group comprises from 1 to 18 carbon atoms, better still from 1 to 8 carbon atoms and better still from 1 to 6 carbon atoms.
• alkyl groups such as the methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, isopentyl, neopentyl, 2-methylbutyl and 1-ethylpropyl radicals.
• hexyl isohexyl, neohexyl, 1-methylpentyl, 3-methylpentyl, 1,1-dimethylbutyl, 1,3-dimethylbutyl, 2-ethylbutyl, 1-methyl-1-ethylpropyl, heptyl, 1-methylhexyl, 1-p-butyl, 4 , 4-dimethylpentyl, octyl, 1-methylheptyl, 2-ethylhexyl, 5,5-dimethylhexyl, nonyl, decyl, 1-methylnonyl, 3,7-dimethyloctyl and 7,7-dimethyloctyl, hexadecyl.
• the unsaturated aliphatic hydrocarbon groups comprise one or more unsaturations, preferably one, two or three unsaturations of the ethylenic (double bond) or / and acetylenic (triple bond) type.
• Examples are alkenyl or alkynyl groups derived from the alkyl groups defined above by removal of two or more hydrogen atoms. So Preferred, the unsaturated aliphatic hydrocarbon groups comprise a single unsaturation.
• the term "carbocyclic group” means a monocyclic or polycyclic radical, optionally substituted, preferably C 3 -C 5O .
• it is a C 3 -C 18 radical, preferably mono-, bi- or tricyclic.
• the carbocyclic group comprises more than one ring nucleus (case of polycyclic carbocycles)
• the cyclic rings are condensed in pairs. Two fused rings may be ortho-condensed or pericondensed.
• the carbocyclic group may comprise, unless otherwise indicated, a saturated portion and / or an aromatic moiety and / or an unsaturated moiety.
• saturated carbocyclic groups are cycloalkyl groups.
• the cycloalkyl groups are C 3 -C 18 , more preferably C 5 -C 10 . Mention may in particular be made of cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl or norbornyl radicals.
• the unsaturated carbocycle or any unsaturated carbocyclic moiety has one or more ethylenic unsaturations, preferably one, two or three. It advantageously has from 6 to 50 carbon atoms, more preferably from 6 to 20, for example from 6 to 18. Examples of unsaturated carbocycles are C 6 -C 10 cycloalkenyl groups.
• aromatic carbocyclic radicals are (C 6 -C 18 ) aryl groups, more preferably (C 6 -C 12 ) aryl and especially phenyl, naphthyl, anthryl and phenanthryl.
• a group having both a hydrocarbon aliphatic moiety as defined above and a carbocyclic moiety as defined above is, for example, an arylalkyl group such as benzyl, or an alkylaryl group such as tolyl.
• the substituents of the hydrocarbon aliphatic groups or moieties and carbocyclic groups or moieties are, for example, alkoxy groups in which the alkyl moiety is preferably as defined above.
• such a hydrolysable monovalent group is a radical: alkoxy, linear or branched, C 1 -C 8 optionally halogenated and / or optionally substituted with one or more (C 1 -C 8 ) alkoxy; C 2 -C 9 acyloxy optionally halogenated or optionally substituted by one or more (C 1 -C 8 ) COXy; C 5 -C 10 cycloalkyloxy; aryloxy or C 6 -C 1S.
• the hydrolysable group is methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, methoxymethoxy, ethoxyethoxy, methoxyethoxy, ⁇ -chloropropoxy or ⁇ -chloroethoxy or else acetoxy.
• G 1 which may be identical or different, each represent: a linear or branched C 1 -C 8 alkyl radical, a C 5 -C 10 cycloalkyl radical or a C 6 -C 18 aryl radical;
• G 2 which are identical or different, each represents: an alkoxy radical, linear or branched C 1 C6 alkyl optionally substituted by one or more (C 1 - C 8) alkoxy;
• Z represents the divalent radical Z'-Z "- where: Z 'represents: a C 1 -C 8 alkylene chain, a saturated C 5 -C 10 cycloalkylene group, a C 6 -C 18 arylene group; or a divalent group consisting of a combination of at least two of these radicals;
• A denotes a group -OG 3 or -NG 4 G 3 where G 3 and G 4 , which are identical to or different from each other, each represent: a linear or branched C 1 -C 8 alkyl radical or a C 5 cycloalkyl radical; 5 -C 1O aryl radical or a C 6 -C 1S in most preferred forms F2 of the formula (I).:
• the symbols G 0 which are identical or different, correspond to the same definition as that given below for the radicals G or G;
• the symbols G 1 which are identical or different, are chosen from the group formed by the methyl and ethyl radicals; propyl, isopropyl, cyclohexyl and phenyl;
• the symbols G 2 which are identical or different, are chosen from the group formed by the methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, methoxymethoxy, ethoxyethoxy and methoxyethoxy radicals;
• Z represents the divalent Z'-Z radical; - or :
• Z ' represents: a C 1 -C 8 alkylene chain
• A denotes a group -OG 3 or -NG 4 G 3 where G 3 and G 4 , which are identical or different from each other, are chosen from the group formed by the methyl, ethyl, propyl, isopropyl, cyclohexyl and phenyl radicals.
• Z ' is selected from the group consisting of divalent methylene, ethylene and propylene radicals
• - Z "represents: -O- or -NR 4 - with R 4 being a hydrogen atom;
• A denotes a group -OG 3 where G 3 is selected from the group consisting of methyl, ethyl, propyl, isopropyl, cyclohexyl and phenyl.
• the functionalized organosilicon compounds of general formula (I) are chosen from the group of the following species:
• the quantity of additional reagent (III) used is not critical, but it is preferable, in accordance with the invention, for this quantity, relative to the precursor (II), to be at least 0.1 M, preferably from at least 1M up to 100M or more, and even more preferably between 1 and 1OM.
• additional reagent (III) is trimethylethoxysilane.
• organosilicon compounds according to the invention comprise at least one mixture (3i) including compounds (i) and / or (2i.l) and / or (2i.2) of formula (I) in which :
• Z ' is selected from the group consisting of divalent methylene, ethylene and propylene radicals; - R 4 is a hydrogen atom.
• the invention also relates to organosilicon compounds of general formula (I), obtainable by the method according to the invention, taken in themselves and selected from the group of the following species:
• the compounds produced are silanes of the species (i) or, in other words, those corresponding to the following formula (I 1 ):
• a represents an integer selected from 1, 2 and 3;
• a ' represents an integer selected from O, 1 and 2;
• the organic phase is separated, dried over MgSO 4 and filtered before being concentrated under reduced pressure.
• the organic phase is separated, dried over MgSO 4 and filtered before being concentrated under reduced pressure.
• Example 2 is repeated but using only 113 mg (1.42 mmol) of pyridine instead of 2.25 g.
• the organic phase is separated, dried over MgSO 4 and filtered before being concentrated under reduced pressure.
• NMR H shows that the conversion of the compound (II) is substantially complete and that the azo function has been formed selectively without loss of SiOEt function.
• the final mixture contains 100 mol% of the compound (I 1 ). There are no detectable pyridine residues.
• the yield of compound (T) isolated is equal to 73%.
• Example 6 In a 1 L reactor, 100 g (284.5 mmol) of the compound (II) (hydrazo derivative of formula II) are dissolved in 185 mL of toluene (organic phase). 80 g of a buffer solution of pH 5, 1.13 g (14.2 mmol) of pyridine (adjuvant A) and 1.46 g of sodium bromide (14.2 mmol) (adjuvant A) are added to the solution. reactor which is stirred. 193 g of a solution of bleach (OxI) 12.1% by weight of active chlorine is added dropwise over 2 hours. The reaction mixture is stirred at room temperature for 10 minutes after the end of the addition of bleach (OxI).
• the organic phase is separated.
• the aqueous phase is extracted with twice 60 ml of toluene.
• the organic phases are combined, dried over MgSO 4 and then filtered before being concentrated under reduced pressure. 89.5 g of an orange liquid with no odor are recovered.
• the organic phase is separated.
• the aqueous phase is extracted twice with 20 ml of toluene.
• the organic phases are combined, dried over MgSO 4 and then filtered before being concentrated under reduced pressure.

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