WO2001079212A1 - Silicon derivatives of fragrant, flavouring and medicinal substances - Google Patents

Silicon derivatives of fragrant, flavouring and medicinal substances Download PDF

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Publication number
WO2001079212A1
WO2001079212A1 PCT/RU2000/000135 RU0000135W WO0179212A1 WO 2001079212 A1 WO2001079212 A1 WO 2001079212A1 RU 0000135 W RU0000135 W RU 0000135W WO 0179212 A1 WO0179212 A1 WO 0179212A1
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cas
compounds
mole
groups
product
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PCT/RU2000/000135
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French (fr)
Inventor
Vyacheslav Vasilievich Kireev
Valery Alexandrovich Dyatlov
Viktor Mikhailovich Kopylov
Valentin Antonovich Vinogradov
Hartmut Hoehne
Original Assignee
Vyacheslav Vasilievich Kireev
Dyatlov Valery A
Viktor Mikhailovich Kopylov
Valentin Antonovich Vinogradov
Hartmut Hoehne
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Application filed by Vyacheslav Vasilievich Kireev, Dyatlov Valery A, Viktor Mikhailovich Kopylov, Valentin Antonovich Vinogradov, Hartmut Hoehne filed Critical Vyacheslav Vasilievich Kireev
Priority to PCT/RU2000/000135 priority Critical patent/WO2001079212A1/en
Priority to AU66019/00A priority patent/AU6601900A/en
Publication of WO2001079212A1 publication Critical patent/WO2001079212A1/en

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    • 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 Table
    • C07F7/02—Silicon compounds
    • C07F7/04—Esters of silicic acids
    • C07F7/06—Esters of silicic acids with hydroxyaryl compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q15/00—Anti-perspirants or body deodorants
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89—Polysiloxanes
    • A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
    • A61K8/893—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by an alkoxy or aryloxy group, e.g. behenoxy dimethicone or stearoxy dimethicone
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q13/00—Formulations or additives for perfume preparations
    • 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 Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0838—Compounds with one or more Si-O-Si sequences
    • 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 Table
    • 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 Table
    • 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
    • C07F7/1896—Compounds having one or more Si-O-acyl linkages
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/57—Compounds covalently linked to a(n inert) carrier molecule, e.g. conjugates, pro-fragrances
    • 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 Table
    • C07F7/02—Silicon compounds
    • C07F7/04—Esters of silicic acids

Definitions

  • the invention relates to the method for preparing hydrolyzing silicon derivatives of actual aromatic and medicinal substances. Slow hydrolysis of silicon derivatives on contact with water results in gradual liberation of these substances into the environment. The ability to graft onto surfaces by the interaction with hydroxyl groups of various materials, and also slow liberation of aromatic and medicinal substances account for the prolonged action of these substances as medicinal preparations and fragrant substances.
  • UK Patent No. 2,042,890 describes synthesis of esters of silicic and polysilicic acids of the general formulas (RO) a Si(OR')b(R")4-a-b and (RO) m (R")SiO(4. m -n)2 5 where RO is an organic group of an aromatic substance ( ⁇ -phenylethanol, citronellol, geraniol); R' is an alkyl group, preferably lower alkyl; and R" is alkyl, aryl, or carbon functional group. Silicon derivatives of aromatic alcohols are responsible for persistent fragrance which lasts longer than in the starting alcohol. The disadvantage of the described method is that it fails to control the composition of the substance.
  • Silicate ester derivatives of menthol of the formula (C ⁇ oH 19 0) 2 Si(OC 2 H 5 ) 2 are described in US Patent No. 3,215,719.
  • the product is synthesized by the reaction between menthol and tetraethylsilicate (tetraethoxysilane) in the presence of silicon tetrachloride as catalyst. This method does not ensure controlled and complete substitution of the ethoxy groups either. Removal of chlorion from the reaction products is required.
  • RO is an organic oxy-group of a hydroxyl-containing organic compound described by the formula RON
  • R' is an organic group of aromatic substance ( ⁇ -phenylethanol, terpinol, ⁇ -/-menthol, eugenol, geraniol, cinnamic alcohol)
  • R' and R" are an alkyl group, preferably lower radical with the number of carbon atoms from 1 to 6.
  • the product is synthesized by the interesterification reaction at elevated temperatures in the presence of a catalyst, such as tetraisopropyl titanate or silicon tetrachloride.
  • a catalyst such as tetraisopropyl titanate or silicon tetrachloride.
  • the obtained derivatives of aromatic alcohols can be used to treat textile fabrics to give them fragrance, which persists after several launder cycles.
  • the disadvantage of the method is that it cannot give products of the desired composition.
  • R is an organic group of an aromatic substance ( ⁇ -phenylethanol, tr ⁇ w.s-2-hexanol, geraniol, cinnamic alcohol, cw-3-hexenol); R' is an alkyl group having from 1 to 6 carbons; R" is methyl, ethyl, or vinyl.
  • Silicate esters of aromatic substances are obtained by interesterification of lower alcohol ethers with aromatic substances at elevated temperatures.
  • An European Patent Dow Corning No. 273,266 describes a method for synthesizing organosilicon compounds containing a menthoxy-group characterized by the general formula R 4 .
  • x Si(OC 10 H ⁇ 9 ) x where the OC 10 H ⁇ 9 group is a menthoxy radical;
  • R stands for the radical having from 1 to 6 carbons selected from the group consisting of alkyl, phenyl, and phenoxy radicals; and JC is 2, 3, or 4.
  • the product is synthesized at elevated temperatures or in the presence of a suitable catalyst, such as potassium carbonate, sodium hydroxide, sodium borohydride, and organometal compounds, e.g., tetrabutyl titanate.
  • a suitable catalyst such as potassium carbonate, sodium hydroxide, sodium borohydride, and organometal compounds, e.g., tetrabutyl titanate.
  • the disadvantage of the method is that controlled and complete substitution is infeasible.
  • This invention relates to a method for preparing compounds characterized by the general formula [RC(0)0] a Si(OR') 4 . a . b R" b (I) a
  • RC(0)0 is an acid radical of one or several saturated or unsaturated carboxylic acids with the number of carbon atoms from 2 to 18, a is from 0 to 3, R'O - the same or different organoxy-groups derived from hydroxyl-contaning fragrant, flavouring or medicinal substances after removing H atoms
  • R" is an aliphatic group with the number of carbon atoms from 1 to 6, phenyl, or (possible) linear siloxane chains formula -0(R"') 2 SiO-[Si(R'") 2 ⁇ ] n -H or branched siloxanes fragments formula -0(R"')2SiO[Si(R'")O ⁇ )5 ]m- [Si(R'") 2 ⁇ ] n -
  • Compounds of formula I may be prepared by reaction silanes or siloxanes general formula [RC(0)0] c SiR" 4 .
  • siloxanes of formula I can be prepared as reacydolisis consequent siloxanes by R'OH, so hydrolitic polycondensation silanes of formula I or their mixtures with another organoacylsilanes.
  • Starting compound of formula II (or I in case of preparing compounds with different radicals R'O-) are derivatives of acetic acid (CAS 64-19-7), butyric acid (CAS 107-92-6), caprylic (octanoic) acid (CAS 124-07-2), oleic acid (CAS 112-80-1), and linolic acid (CAS 60-33-3).
  • the end products are obtained from the starting substances [R"'C(0)0] c SiR" 4 . c or [RC(0)0] a Si(OR') 4 . a . b R"b which may have one or two organic groups R" at the silicium atom; said groups include ethyl, cyclohexyl, octyl and phenyl groups.
  • hydroxyl-containing aromatic substances 4-allyl-2-methoxyphenol (eugenol, CAS 97-53-0), 3,7-dimethoxy-6-ene-l-ol (citronellol, CAS 10622-9), 4-hydroxy-3-methoxybenzaldehyde (vanillin, CAS 121-35-5), 3,7-dimethylocta-2,6-diene-l-ol (geraniol, CAS 106-24-1), 3,7- dimethylocta-2,6-diene-3-ol (linalool, CAS 78-70-6), 7-hydroxy-3,7- dimethy loctanal (hydroxycitronellal), 2(4-methylcyclohex-3 -enyl)propan- 2-ol (terpineol, CAS 10482-56-1), 2- ⁇ henylethanol( ⁇ - ⁇ henylethyl alcohol, CAS 60-12-8), 3-phenylpropanol (hydr
  • the advantages of the proposed method are mild reaction conditions (temperatures from 20 to 130°C) and high conversion of the starting reagents (99.5 - 99.8%). Since the reaction occurs at moderate temperatures, substances, which are readily oxidized or decomposed at elevated temperatures, can be used. High reactivity of the acyl groups enables conduction of reactions with substances associated with steric hindrances. Characteristics ofthe products are given in Table 1.
  • the proposed compounds liberate fragrance or medicating factor, or both simultaneously, for long periods of time.
  • Products containing the acyl group at the silicium atom are readily grafted onto the surface of organic materials, such as textiles, paper, wood, acetyl cellulose, and also mineral substances, such as silica gel, metal hydroxides, or construction materials owing to the interaction of this group with the hydroxyl groups of the material, or they may form a polymer coat on the surface of the material owing to the interaction of acyl group with water.
  • organic materials such as textiles, paper, wood, acetyl cellulose, and also mineral substances, such as silica gel, metal hydroxides, or construction materials owing to the interaction of this group with the hydroxyl groups of the material, or they may form a polymer coat on the surface of the material owing to the interaction of acyl group with water.
  • organic materials such as textiles, paper, wood, acetyl cellulose, and also mineral substances, such as silica gel, metal hydroxides, or construction materials owing to the interaction of this group with the hydroxyl groups of the
  • the rate of hydrolysis of organoxy-groups of aromatic and medicinal substances can be varied by changing the number and size of the acyl groups, as well and the number and size of organic groups at the silicon atom in the molecule.
  • the rate of hydrolysis of organoxy-groups increases with the increasing number of the acyl groups from 1 to 3 and with decreasing size of the acyl group (in the transition from oleinol to butyrol and acetyl groups).
  • Hydrolysis rate of organoxy-groups increases with decreasing number and size of organic groups R ⁇ , at the silicon atom in the molecule.
  • Hydrolysis rate of organoxy-groups of fragrant and medicinal substances in compounds containing no acyl group can be controlled by introducing into I residues of various aromatic and medicinal substances and also by changing the number and size of organic groups R ⁇ at the silicon atom in the molecule. It has been shown that the rate of hydrolysis of menthoxy-groups and citronellol groups increases with introduction of vanillin and eugenol groups into the molecule, and also with their increasing number. These statements are confirmed by the data given in Table 2, which show the amount of aromatic and medicinal substances liberated during 200-hour hydrolysis of methyl ethyl ketone solutions of the obtained products (0.2 mole/1) in water (1 mole per each hydrolyzing group) at 20°C. The rate of hydrolysis of vanillin groups is so high that the results of their hydrolysis are given for 4 hours from the start of hydrolysis. Rate of release fragrant, flavoring and medicinal compounds from products of present invention illustrate tables 3-10.
  • Example 1 except that the reactants are 66 g (0.25 mole) of tetraacetoxysilane and 82 g (0.5 mole) of eugenol. Gas-liquid chromatography confirms 99.7% conversion by eugenol.
  • Example 1 except that the reactants are 52.8 g (0.2 mole) of tetraacetoxysilane and 98.4 g (0.6 mole) of eugenol. Gas-liquid chromatography confirms 99.6% conversion by eugenol.
  • Example 1 except that the reactants are 58.4 g (0.2 mole) of triacetoxy(butyryloxy)silane and 98.4 g (0.6 mole) of eugenol. Gas-liquid chromatography confirms 99.7% conversion by eugenol. The reaction yields 117.2 g (97%) of tri(4-allyl-2-methoxyphenoxy) (butyryloxy)silane,
  • the short name is Si[OC(0)C 3 H 7 ][OEug] 3 .
  • the product composition is confirmed by H NMR spectra.
  • the product is obtained by a procedure similar to that described in Example 1, except that the reactants are 42.2 g (0.16 mole) of tetraacetoxysilane and 105 g (0.64 mole) of eugenol. Titration of the acetoxy groups confirms their 99.7% conversion.
  • the product is obtained by a procedure similar to that described in Example 1, except that the reactants are 26.4 g (0.1 mole) of tetraacetoxysilane and 68.6 g (0.44 mole) of citronellol. Excessive citronellol is removed by treatment in vacuum at 130°C and a residual pressure of 5 mm Hg. Titration of the acetoxy groups confirms their 99.6% conversion.
  • the product composition is confirmed by 'H NMR spectra.
  • Example 6 except that the reactants are 38.6 g (0.105 mole) of triacetoxy(4-allyl-2-methoxyphenoxy) silane
  • the product composition is confirmed by ⁇ NMR spectra.
  • Example 6 except that the reactants are 47 g (0.1 mole) of diacetoxydi(4- allyl-2-methoxyphenoxy)silane
  • Example 6 except that the reactants are 50 g (0.087 mole) of acetoxy-tri(4- allyl-2-methoxyphenoxy)silane
  • Example 1 except that the reactants are 69.91 g (0.318 mole) of methyltriacetoxysilane and 49.60 g (0.318 mole) of menthol. Gas-liquid chromatography confirms 99.8% conversion by menthol.
  • Example 6 except that the reactants are 33.73 g (0.107 mole) of methyl(3- methyl-6-isopropylcyclohexanoxy)diacetoxysilane and 36.80 g (0.235 mole) of citronellol. Titration ofthe acetoxy groups confirms their 99.7%.
  • the product composition is confirmed by H NMR spectra.
  • the product composition is confirmed by ! H NMR spectra.
  • Example 1 except that the reactants are 45.89 g (0.209 mole) of methyltnacetoxysilane and 68.46 g (0.418 mole) of eugenol. Gas-liquid chromatography confirms 99.6% conversion by eugenol.
  • Example 6 except that the reactants are 34.3 g (0.13 mole) of tetraacetoxysilane and 40.56 g (0.26 mole) of citronellol. Titration of the acetoxy groups confirms their 99.6% conversion.
  • Example 1 except that the reactants are 11.56 g (0.04 mole) of cyclohexyltriacetoxysilane and 20.6 g (0.125 mole) of eugenol. Titration of the acetoxy groups confirms their 99.5%) conversion.
  • Example 6 except that the reactants are 12.02 g (0.0417 mole) of cyclohexyltriacetoxysilane and 20.5 g (0.131 mole) of menthol. Titration ofthe acetoxy groups confirms their 99.6% conversion.
  • Example 1 except that the reactants are 11.26 g (0.039 mole) of cyclohexyltriacetoxysilane and 20 g (0.131 mole) of vanillin. Titration of the acetoxy groups confirms their 99.5%) conversion.
  • the product composition is confirmed by l H NMR spectra.
  • Example 6 except that the reactants are 45.89 g (0.209 mole) of methylt acetoxysilane and 98.30 g (0.630 mole) of citronellol. Titration of the acetoxy groups confirms their 99.6% conversion. The reaction yields
  • Example 6 except that the reactants are 35.1 g (0.077 mole) of diacetoxydi(3,7-dimethyl-6-octenoxy)silane Si[OC(0)CH 3 ] 2 [OC ⁇ oH ⁇ 9 ] 2 and
  • the product composition is confirmed by ⁇ NMR spectra.
  • Example 6 except that the reactants are 22.44 g (0.085 mole) of tetraacetoxysilane and 59.4 g (0.38 mole) of menthol. Titration ofthe acetoxy groups confirms their 99.7% conversion.
  • reaction yields 51 g (93%) of tetra(5-methyl-2(l- methylethyl)cyclohexanoxy)silane, Si[OC 6 H 9 (CH 3 )(C 3 H 7 )] 4 .
  • the short name is Si[OMent] 4 .
  • Example 6 except that the reactants are 37 g (0.14 mole) of tetraacetoxysilane and 43.75 g (0.28 mole) of menthol. Titration ofthe acetoxy groups confirms their 99.7% conversion.
  • the short name is Si[OAc] 2 [OMent] 2 . Density ofthe product cf° 4 1.0159; refractive index n O 1.4495.
  • Example 24 The product composition is confirmed by H NMR spectra. Example 24.
  • the product is obtained by a procedure similar to that described in Example 6, except that the reactants are 6.86 g (0.026 mole) of tetraacetoxysilane, 15.98 g (0.105 mole) of vanillin, and 15 ml of toluene. Titration ofthe acetoxy groups confirms their 99.8% conversion.
  • the reaction yields 16 g (97%) of tetra(4-formyl-2-methoxyphenoxy)silane, Si[OC 6 H 3 (CHO)(OCH 3 )] 4 .
  • the short name is Si[OVanil] 4 .
  • the product composition is confirmed by *H NMR spectra.
  • reaction yields 50 g (97%) of (4-formyl-2-methoxyphenoxy)tri(3,7- dimethyl-6-octenoxy)silane Si[OC 6 H9(CHO)(OCH 3 )][OC2H4CH(CH3)C 2 C4CH C(CH3) 2 ]3.
  • the short name is Si[OCitr] 3 [OVanil].
  • the product composition is confirmed by H NMR spectra.
  • Example 1 except that the reactants are 45.89 g (0.209 mole) of methylt acetoxysilane and 102.8 g (0.627 mole) of eugenol. Titration of the acetoxy groups confirms their 99.8% conversion.
  • Table 2 Release of fragrant, flavouring and medicinal substances during hydrolysis of methyl ethyl ketone solutions of products obtained according to the invention at 20°C during 200 hours. In this table and tables 3-9 were used 0.2 mole/1 solutions examed substances and 1.0 mole of water per each h drolizin rou .
  • OEug is 4-allyl-2-methoxyphenoxy-; OCitr is 3,7-dimethyl-6-octenoxy-;
  • OMent is 5-methyl-2(l-methylethyl)cyclohexanoxy- radicals Table 3.

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Abstract

Proposed is a method for preparing compounds of the general formula [RC(O)O]aSi(OR')4-a-bR''b, where RC(O)O is an acid radical of one or several saturated or unsaturated carboxylic acids with the number of carbon atoms from 2 to 18, a is from 0 to 3, R'' is an aliphatic group with the number of carbon atoms from 1 to 6, b is from 0 to 3, R'O are organoxy groups of one, two, three, or four hydroxyl-containing aromatic or medicinal substances. Owing to gradual and long hydrolysis of the alkoxy groups, the proposed compounds liberate fragrance or medicating factor, or both simultaneously, for long periods of time.

Description

SILICON DERIVATIVES OF FRAGRANT, FLAVOURING AND MEDICINAL SUBSTANCES
Inventors: Diatlov Valeri Alexandrovich, Kireev Viatcheslav Vasilievich,
Kopylov Viktor Mikhailovich, Vinogradov Valentin Antonovich, Hoehne
Hartmut
Assignee: Kireev Viatcheslav Vasilievich '
Filed of Search: 556/482, 556/483, 88/27, 524/858, 524/868, 525/17,
525/27, 525/43, 525/44, 525/48,
References Cited:
US PATENT DOCUMENTS
No. Patented Class US Class Intern.
3,215,719 10/1965 260-448.8
3,271,305 09/1966 252-8.6
4,500,725 02/1985 556/482 C07F 7/04
4,351,919 09/1982 524/858 C08L 83/00
5,858,543 01/1999 428/447 B32B 27/28
5,919,752 07/1999 512/1 A6 IK 007/46
EUROPEAN PATENT DOCUMENTS 0273,266 06/1988 A61K 31/695
UK PATENT DOCUMENTS 2,042,890 9/1980 A61K 7/46 7/32 FIELD OF THE INVENTION
The invention relates to the method for preparing hydrolyzing silicon derivatives of actual aromatic and medicinal substances. Slow hydrolysis of silicon derivatives on contact with water results in gradual liberation of these substances into the environment. The ability to graft onto surfaces by the interaction with hydroxyl groups of various materials, and also slow liberation of aromatic and medicinal substances account for the prolonged action of these substances as medicinal preparations and fragrant substances.
BACKGROUND OF THE INVENTION
UK Patent No. 2,042,890 describes synthesis of esters of silicic and polysilicic acids of the general formulas (RO)aSi(OR')b(R")4-a-b and (RO)m(R")SiO(4.m-n)25 where RO is an organic group of an aromatic substance (β-phenylethanol, citronellol, geraniol); R' is an alkyl group, preferably lower alkyl; and R" is alkyl, aryl, or carbon functional group. Silicon derivatives of aromatic alcohols are responsible for persistent fragrance which lasts longer than in the starting alcohol. The disadvantage of the described method is that it fails to control the composition of the substance.
Silicate ester derivatives of menthol of the formula (CιoH190)2Si(OC2H5)2 are described in US Patent No. 3,215,719. The product is synthesized by the reaction between menthol and tetraethylsilicate (tetraethoxysilane) in the presence of silicon tetrachloride as catalyst. This method does not ensure controlled and complete substitution of the ethoxy groups either. Removal of chlorion from the reaction products is required.
US Patent No. 3,271,305 describes synthesis of esters of silicic and polysilicic acids of the general formulas (RO)3Si(OR')b(R")4-m-n)/2. where RO is an organic oxy-group of a hydroxyl-containing organic compound described by the formula RON, where R' is an organic group of aromatic substance (β-phenylethanol, terpinol, ^-/-menthol, eugenol, geraniol, cinnamic alcohol); R' and R" are an alkyl group, preferably lower radical with the number of carbon atoms from 1 to 6. The product is synthesized by the interesterification reaction at elevated temperatures in the presence of a catalyst, such as tetraisopropyl titanate or silicon tetrachloride. The obtained derivatives of aromatic alcohols can be used to treat textile fabrics to give them fragrance, which persists after several launder cycles. The disadvantage of the method is that it cannot give products of the desired composition.
US Patent No. 4,500,725 describes the method, in which silicon derivatives of aromatic alcohols are used to give stable fragrance to liquid and solid materials. Silicate esters of the general formula
(RO)aSi(OR')b(R")4-a-b, where R is an organic group of an aromatic substance (β-phenylethanol, trøw.s-2-hexanol, geraniol, cinnamic alcohol, cw-3-hexenol); R' is an alkyl group having from 1 to 6 carbons; R" is methyl, ethyl, or vinyl. Silicate esters of aromatic substances are obtained by interesterification of lower alcohol ethers with aromatic substances at elevated temperatures.
An European Patent Dow Corning No. 273,266 describes a method for synthesizing organosilicon compounds containing a menthoxy-group characterized by the general formula R4.xSi(OC10Hι9)x, where the OC10Hι9 group is a menthoxy radical; R stands for the radical having from 1 to 6 carbons selected from the group consisting of alkyl, phenyl, and phenoxy radicals; and JC is 2, 3, or 4. The product is synthesized at elevated temperatures or in the presence of a suitable catalyst, such as potassium carbonate, sodium hydroxide, sodium borohydride, and organometal compounds, e.g., tetrabutyl titanate. The disadvantage of the method is that controlled and complete substitution is infeasible.
SUMMARY OF THE INVENTION
This invention relates to a method for preparing compounds characterized by the general formula [RC(0)0]aSi(OR')4.a.bR"b (I)a where RC(0)0 is an acid radical of one or several saturated or unsaturated carboxylic acids with the number of carbon atoms from 2 to 18, a is from 0 to 3, R'O - the same or different organoxy-groups derived from hydroxyl-contaning fragrant, flavouring or medicinal substances after removing H atoms; R" is an aliphatic group with the number of carbon atoms from 1 to 6, phenyl, or (possible) linear siloxane chains formula -0(R"')2SiO-[Si(R'")2θ]n-H or branched siloxanes fragments formula -0(R"')2SiO[Si(R'")Oι)5]m- [Si(R'")2θ]n-m-H, in wich R'" - organic radicals (preferably Me, Et, Ph), n - integer from 1 to 1000, m = 0 - 500; b is from 0 to 3.
Compounds of formula I may be prepared by reaction silanes or siloxanes general formula [RC(0)0]cSiR"4.c (II) with hydroxy-containing fragrant, flavouring or medicinal compounds R'OH, c=l - 4, but c>a in formula I; radicals R,R" in II are all the same as in I.
In case of preparing mixed silanes and siloxanes of formula I (R'O are different radicals) starting compounds II must be undergo reaction at first with one R'OH, and then - with other R'OH and ets. Siloxanes of formula I can be prepared as reacydolisis consequent siloxanes by R'OH, so hydrolitic polycondensation silanes of formula I or their mixtures with another organoacylsilanes.
Starting compound of formula II (or I in case of preparing compounds with different radicals R'O-) are derivatives of acetic acid (CAS 64-19-7), butyric acid (CAS 107-92-6), caprylic (octanoic) acid (CAS 124-07-2), oleic acid (CAS 112-80-1), and linolic acid (CAS 60-33-3).
The end products are obtained from the starting substances [R"'C(0)0]cSiR"4.c or [RC(0)0]aSi(OR')4.a.bR"b which may have one or two organic groups R" at the silicium atom; said groups include ethyl, cyclohexyl, octyl and phenyl groups. The following compounds are used as hydroxyl-containing aromatic substances: 4-allyl-2-methoxyphenol (eugenol, CAS 97-53-0), 3,7-dimethoxy-6-ene-l-ol (citronellol, CAS 10622-9), 4-hydroxy-3-methoxybenzaldehyde (vanillin, CAS 121-35-5), 3,7-dimethylocta-2,6-diene-l-ol (geraniol, CAS 106-24-1), 3,7- dimethylocta-2,6-diene-3-ol (linalool, CAS 78-70-6), 7-hydroxy-3,7- dimethy loctanal (hydroxycitronellal), 2(4-methylcyclohex-3 -enyl)propan- 2-ol (terpineol, CAS 10482-56-1), 2-ρhenylethanol(β-ρhenylethyl alcohol, CAS 60-12-8), 3-phenylpropanol (hydrocinnamic alcohol, CAS 122-97-4), 3-phenylprop-2-en-l-ol (cinnamic alcohol, CAS 104-54-1), 4(4- hydroxyphenyl)-2-butanone (raspberry ketone, CAS 5471-51-2), [2(2- hydroxyethyl)-6,6-dimethylbicyclo[3.1.1]-hept-2-ene] (Nopol, CAS 33836- 73-8), 1,5-dimethyloxime bicyclo-3.2.1-octan-8-one (buccoxime); the following compounds are used in the capacity of hydroxyl-containing medicinal substance: 3-methyl-6-isopropylcyclohexanol (menthol, CAS 89-78-1), 2-hydroxybenzoic acid (salicylic acid, CAS 69-72-7), methyl salicylate (CAS 119-36-8), 2,3-bis(hydroxymethyl)quinoline-N.N-dioxide (dioxidine, CAS 97-53-0), N(hydroxymethyl)nicotinic amide (nicodin, CAS 3569-99-1), 5-nitro-8-oxyquinoline (nitroxoline, CAS 4008-48-4), 2- hydroxyacetanilide (paraacetamol, CAS 614-80-2), 2-hydroxybenzamide (salicylamide, CAS 65-45-2), 2-isopropyl-5-methylphenol (thymol, CAS 89-83-8).
The advantages of the proposed method are mild reaction conditions (temperatures from 20 to 130°C) and high conversion of the starting reagents (99.5 - 99.8%). Since the reaction occurs at moderate temperatures, substances, which are readily oxidized or decomposed at elevated temperatures, can be used. High reactivity of the acyl groups enables conduction of reactions with substances associated with steric hindrances. Characteristics ofthe products are given in Table 1.
Owing to gradual and long hydrolysis of the organoxy-groups, the proposed compounds liberate fragrance or medicating factor, or both simultaneously, for long periods of time.
Products containing the acyl group at the silicium atom are readily grafted onto the surface of organic materials, such as textiles, paper, wood, acetyl cellulose, and also mineral substances, such as silica gel, metal hydroxides, or construction materials owing to the interaction of this group with the hydroxyl groups of the material, or they may form a polymer coat on the surface of the material owing to the interaction of acyl group with water. For example, if a compound containing the acetyl group is applied to a material in amount of 25 g/m , the odor of acetic acid disappears in 1-2 hours, which indicates completion of the grafting reaction and hydrolysis with involvement of the acyl group. Remaining organoxy-groups of aromatic and medicinal substances continue hydrolyzing for a long period of time, lasting from several hours to a few months.
The rate of hydrolysis of organoxy-groups of aromatic and medicinal substances can be varied by changing the number and size of the acyl groups, as well and the number and size of organic groups at the silicon atom in the molecule. The rate of hydrolysis of organoxy-groups increases with the increasing number of the acyl groups from 1 to 3 and with decreasing size of the acyl group (in the transition from oleinol to butyrol and acetyl groups). Hydrolysis rate of organoxy-groups increases with decreasing number and size of organic groups Rλ ,at the silicon atom in the molecule.
Hydrolysis rate of organoxy-groups of fragrant and medicinal substances in compounds containing no acyl group can be controlled by introducing into I residues of various aromatic and medicinal substances and also by changing the number and size of organic groups R^at the silicon atom in the molecule. It has been shown that the rate of hydrolysis of menthoxy-groups and citronellol groups increases with introduction of vanillin and eugenol groups into the molecule, and also with their increasing number. These statements are confirmed by the data given in Table 2, which show the amount of aromatic and medicinal substances liberated during 200-hour hydrolysis of methyl ethyl ketone solutions of the obtained products (0.2 mole/1) in water (1 mole per each hydrolyzing group) at 20°C. The rate of hydrolysis of vanillin groups is so high that the results of their hydrolysis are given for 4 hours from the start of hydrolysis. Rate of release fragrant, flavoring and medicinal compounds from products of present invention illustrate tables 3-10.
In order to make the invention clear, the following examples of its practical embodiment are given by way of illustration.
Example 1.
Place, in a nitrogen flow, 79.2 g (0.3 mole) of tetraacetoxysilane into a reaction flask equipped with a stirrer, a reflux condenser, and a calcium chloride tube and add, with intensively stirring, 49.2 g (0.3 mole) of eugenol. Continue stirring the mixture at room temperature for 5 hours and then for an hour at a temperature of 50°C. Now distil the formed acetic acid from the reaction mixture in a rotary evaporator at a temperature of 60-70°C with gradually lowering pressure to 6 mm Hg. Treat the viscous remainder in vacuum for an hour at 80°C and residual pressure of 5 mm Hg. The reaction product crystallizes on cooling. Gas-liquid partition chromatography shows 99.8% conversion by 4-allyl-2-methoxyphenol. The reaction yields 107.1 g (97%) of triacetoxy(4-allyl-2- methoxyphenoxy)silane Si[OC(0)CH3]3[OC6H3(CH30)CH2CH=CH2]. The short name is Si[OAc] [OEug]. The product composition is confirmed by !H NMR spectra.
Example 2.
The product is obtained by a procedure similar to that described in
Example 1, except that the reactants are 66 g (0.25 mole) of tetraacetoxysilane and 82 g (0.5 mole) of eugenol. Gas-liquid chromatography confirms 99.7% conversion by eugenol.
The reaction yield is 114 g (96%) of diacetoxydi(4-allyl-2- methoxyphenoxy)silane, Si[OC(0)CH3]2[OC6H3(CH3θ)CH2CH=CH2]2.
The short name is Si[OAc]2[OEug]2; d4 20 = 1.1712, nD 20 = 1.5205.
The product composition is confirmed by !H NMR spectra.
Example 3.
The product is obtained by a procedure similar to that described in
Example 1, except that the reactants are 52.8 g (0.2 mole) of tetraacetoxysilane and 98.4 g (0.6 mole) of eugenol. Gas-liquid chromatography confirms 99.6% conversion by eugenol.
The reaction yields 112.9 g (98%) of acetoxytri(4-allyl-2-methoxy- phenoxy)silane, Si[OC(0)CH3][OC6H3(CH30)CH2CH=CH2]3. The short name is Si[OAc][OEug]3; d4 20 = 1.1541, nD 20 = 1.5475. The product composition is confirmed by !H NMR spectra.
Example 4.
The product is obtained by a procedure similar to that described in
Example 1, except that the reactants are 58.4 g (0.2 mole) of triacetoxy(butyryloxy)silane and 98.4 g (0.6 mole) of eugenol. Gas-liquid chromatography confirms 99.7% conversion by eugenol. The reaction yields 117.2 g (97%) of tri(4-allyl-2-methoxyphenoxy) (butyryloxy)silane,
Si[OC(0)C3H7][OC6H3(CH3θ)CH2CH=CH2]3.
The short name is Si[OC(0)C3H7][OEug]3.
The product composition is confirmed by H NMR spectra.
Example 5.
The product is obtained by a procedure similar to that described in Example 1, except that the reactants are 42.2 g (0.16 mole) of tetraacetoxysilane and 105 g (0.64 mole) of eugenol. Titration of the acetoxy groups confirms their 99.7% conversion.
The reaction yields 103.6 g (95%) of tetra(4-allyl-2- methoxyphenoxy)silane, Si[OC6H3(CH30)CH2CH=CH2]4. The short name is Si[OEug]4; d4 20 = 1.1297, nD 20 = 1.5550. The product composition is confirmed by Η NMR spectra.
Example 6.
The product is obtained by a procedure similar to that described in Example 1, except that the reactants are 26.4 g (0.1 mole) of tetraacetoxysilane and 68.6 g (0.44 mole) of citronellol. Excessive citronellol is removed by treatment in vacuum at 130°C and a residual pressure of 5 mm Hg. Titration of the acetoxy groups confirms their 99.6% conversion.
The reaction yield is 62.8 g (97%) of tetra(3,7-dimethyloct-6-ene-l-oxy) silane, Si[OCH2CH2CH(CH3)CH2CH2CH=C(CH3)2]4.
The short name is Si[OCitr]4; d4 20 = 0.9117, nD 20 = 1.4605.
The product composition is confirmed by 'H NMR spectra.
Example 7.
The product is obtained by a procedure similar to that described in
Example 6, except that the reactants are 38.6 g (0.105 mole) of triacetoxy(4-allyl-2-methoxyphenoxy) silane
Si[OC(0)CH3]3[OC6H3(CH30)CH2CH=CH2] and 56.2 g (0.36 mole) of citronellol. Titration ofthe acetoxy groups confirms their 99.7% conversion.
The reaction yields 67.5 g (98%) of (4-allyl-2-methoxyphenoxy)tri(3,7- dimethyloct-6-ene- 1 -oxy)silane,
Si[OC6H3(CH3θ)CH2CH=CH2][OC2H4CH(CH3)C2H4CH=C(CH3)2]3.
The short name is Si[OEug][OCitr]3; d4 20 = 0.9497, nD 20 = 1.4790.
The product composition is confirmed by Η NMR spectra.
Example 8.
The product is obtained by a procedure similar to that described in
Example 6, except that the reactants are 47 g (0.1 mole) of diacetoxydi(4- allyl-2-methoxyphenoxy)silane
Si[OC(0)CH3]2[OC6H3(CH30)CH2CH=CH2]2 and 35.7 g (0.23 mole) of citronellol. Titration of the acetoxy groups confirms their 99.7% conversion. The reaction yield is 65.6 g (98%) of di(4-allyl-2-methoxyphenoxy)di(3,7- dimethyloct-6-ene- 1 -oxy)silane,
Si[OC6H3(CH3θ)CH2CH=CH2]2[OC2H4CH(CH3)C2H4CH=C(CH3)2]2. The short name is Si[OEug]2[OCitr]2; d4 20 = 0.9915, nD 20 = 1.4995. The product composition is confirmed by !H NMR spectra.
Example 9.
The product is obtained by a procedure similar to that described in
Example 6, except that the reactants are 50 g (0.087 mole) of acetoxy-tri(4- allyl-2-methoxyphenoxy)silane
Si[OC(0)CH3][OC6H3(CH3θ)CH2CH=CH2]3 and 15.6 g (0.1 mole) of citronellol. Titration of the acetoxy groups confirms their 99.7% conversion.
The reaction yields 65.3 g (99%) of tri(4-allyl-2-methoxyphenoxy)(3,7- dimethyloct-6-ene- 1 -oxy)silane,
Si[OC6H3(CH3θ)CH2CH=CH2]3[OC2H4CH(CH3)C2H4CH=C(CH3)2]. The short name is [EugO]3Si[OCitr]; d4 20 = 1.0605, nD 20 = 1.5275. The product composition is confirmed by *H NMR spectra.
Example 10.
The product is obtained by a procedure similar to that described in
Example 1, except that the reactants are 69.91 g (0.318 mole) of methyltriacetoxysilane and 49.60 g (0.318 mole) of menthol. Gas-liquid chromatography confirms 99.8% conversion by menthol.
The reaction yields 138.1 g (97.5%) of methyldiacetoxy((5-methyl-2(l- methylethyl)cyclohexanoxy)silane,
MeSi[0(0)CCH3]2[OC6H9(CH3)C3H7)].
The short name is MeSi[OAc]2[OMent]; d4 20 = 1.0066, nD 20 = 1.4405. The product composition is confirmed by *H NMR spectra.
Example 11.
The product is obtained by a procedure similar to that described in
Example 6, except that the reactants are 33.73 g (0.107 mole) of methyl(3- methyl-6-isopropylcyclohexanoxy)diacetoxysilane and 36.80 g (0.235 mole) of citronellol. Titration ofthe acetoxy groups confirms their 99.7%.
The reaction yields 138.1 g (97.5%) of methyl(3-methyl-6- isopropylcyclohexanoxy)di(3 ,7-dimethyloct-6-ene- 1 -oxy)silane,
MeSi[OC2H4CH(CH3)C2H4CH=C(CH3)2]2[OC6H9(CH3)(C3H7)].
The short name is MeSi[OCitr]2[OMent]; d4 20 = 0.9092, nD 20 = 1.4585.
The product composition is confirmed by H NMR spectra.
Example 12.
The product is obtained by a procedure similar to that described in Example 1, except that the reactants are 63.85 g (0.29 mole) of methyltriacetoxysilane and 47.62 g (0.29 mole) of 4-allyl-2- methoxyphenol, HOC6H3(CH3θ)CH2CH=CH2 eugenol. Gas-liquid chromatography confirms 99.8% conversion by eugenol. The reaction yields 92.15 g (98%) of methyldiacetoxy(4-allyl-2- methoxyphenoxy)silaneJ MeSi[OC(0)CH3]2[OC6H3(CH3θ)CH2CH=CH2]. The short name is MeSi[OAc]2[OEug]; d4 20 = 0.9475, nD 20 = 1.4350. The product composition is confirmed by !H NMR spectra.
Example 13.
The product is obtained by a procedure similar to that described in
Example 1, except that the reactants are 45.89 g (0.209 mole) of methyltnacetoxysilane and 68.46 g (0.418 mole) of eugenol. Gas-liquid chromatography confirms 99.6% conversion by eugenol.
The reaction yields 87.04 g (97.5%) of methylacetoxydi(4-allyl-2- methoxyphenoxy)silane, MeSi[OC(0)CH3][OC6H3(CH3θ)CH2CH=CH2]2.
The short name is MeSi[OAc][OEug]2; d4 20 = 1.0338, nD 20 = 1.4351.
The product composition is confirmed by !H NMR spectra.
Example 14.
The product is obtained by a procedure similar to that described in
Example 6, except that the reactants are 34.3 g (0.13 mole) of tetraacetoxysilane and 40.56 g (0.26 mole) of citronellol. Titration of the acetoxy groups confirms their 99.6% conversion.
The reaction yields 57 g (96%) of diacetoxy-di(3,7-dimethyl-6- octenoxy)silane,
Si[OC6H3(CH3θ)CH2CH=CH2]2[OC2H4CH(CH3)C2H4CH=C(CH3)2]2.
The short name is Si[OAc]2[OCitr]2; density d4 20 = 0.9778; refractive index, «D 2° = 1.4470.
The product composition is confirmed by *H NMR spectra.
Example 15.
The product is obtained by a procedure similar to that described in
Example 1, except that the reactants are 11.56 g (0.04 mole) of cyclohexyltriacetoxysilane and 20.6 g (0.125 mole) of eugenol. Titration of the acetoxy groups confirms their 99.5%) conversion.
The reaction yields 23.2 g (96%) of cyclohexyltri(4-allyl-2- methoxyphenoxy)silane, ChexSi[OC6H3(CH30)CH2CH=CH2]3..
The short name is ChexSi[OEug]3; d4 20 = 0.9184, nD 20 = 1.47521.
The product composition is confirmed by Η NMR spectra. Example 16.
The product is obtained by a procedure similar to that described in
Example 6, except that the reactants are 12.02 g (0.0417 mole) of cyclohexyltriacetoxysilane and 20.5 g (0.131 mole) of menthol. Titration ofthe acetoxy groups confirms their 99.6% conversion.
The reaction yields 22.8 g (95%) of cyclohexyltri(5-methyl-2-(l- methylethyl)cyclohexanoxy)silane, ChexSi[OC6H9(CH3)(C3H7)]3. The short name is ChexSi[OMent]3.
The product composition is confirmed by ]H NMR spectra.
Example 17.
The product is obtained by a procedure similar to that described in
Example 1, except that the reactants are 11.26 g (0.039 mole) of cyclohexyltriacetoxysilane and 20 g (0.131 mole) of vanillin. Titration of the acetoxy groups confirms their 99.5%) conversion.
The reaction yields 21 g (95%) of cyclohexyltri(4-formyl-2- methoxyphenoxy)silane, ChexSi[OC6H3(CH(0))(OCH3)]3. The short name is ChexSi[OVanil]3.
The product composition is confirmed by lH NMR spectra.
Example 18.
The product is obtained by a procedure similar to that described in
Example 6, except that the reactants are 45.89 g (0.209 mole) of methylt acetoxysilane and 98.30 g (0.630 mole) of citronellol. Titration of the acetoxy groups confirms their 99.6% conversion. The reaction yields
110,5 g (95%) of cyclohexyltri(3,7-dimethyl-6-octenoxy)silane,
ChexSi[OC2H4CH(CH3)C2H4CH=C(CH3)2]3. The short name is ChexSi[OCitr]3. d4 20 = 0.9318, nD 20 = 1.4666. The product composition is confirmed by *H NMR spectra.
Example 19.
The product is obtained by a procedure similar to that described in
Example 6, except that the reactants are 35.1 g (0.077 mole) of diacetoxydi(3,7-dimethyl-6-octenoxy)silane Si[OC(0)CH3]2[OCιoHι9]2 and
26.6 g (0.17 mole) of menthol. Titration ofthe acetoxy groups confirms their 99.7%) conversion.
The reaction yields 48 g (96%) of di((5-methyl-2(l- methylethyl)cyclohexanoxy))di(3,7-dimethyl-6-octenoxy)silane,
Si[OC6H9(CH3)(C3H7)]2[OC2H4CH(CH3)C2H4CH=C(CH3)2]2.
The short name is Si[OCitr]2[OMent]2. Density, d4 20 = 0.9241; refractive index, nD 20 = 1.4410.
Example 20.
Place, in a nitrogen flow, 20.5 g (0.077 mole) of tetraacetoxysilane into a reaction flask equipped with a stirrer, a reflux condenser, and a calcium chloride tube and add, with intensively stirring, 12.13 g (0.077 mole) of citronellol. Continue stirring the reaction mixture at room temperature for 5 hours and then for an hour at a temperature of 50°C. Now distil the formed acetic acid from the reaction mixture in a rotary evaporator at a temperature of 60-70°C with gradually lowering pressure to 6 mm Hg. Allow the reaction mixture to cool to room temperature, add 42.2 g (0.27 mole) of menthol, and stir the reaction mixture at room temperature for another 5 hours and then at 50°C for an hour. Now distil the formed acetic acid from the reaction mixture in a rotary evaporator at a temperature of 60-70°C with gradually lowering pressure to 6 mm Hg. Treat the mixture in vacuum for an hour at 110°C and residual pressure of 5 mm Hg. The resultant product is a white pasty mass. Gas-liquid chromatography shows 99.8% conversion by the acetoxy groups.
The reaction yields 49 g (98%) of tri(5-methyl-2(l- methylethyl)cyclohexanoxy)(3,7-dimethyl-6-octenoxy)silane
Si[OC6H9(CH)3(C3H7)]3[OC2H4CH(CH3)C2H4CH=C(CH3)2].
The short name is Si[OMent]3[OCitr].
The product composition is confirmed by !H NMR spectra.
Example 21.
Place, in a nitrogen flow, 27.2 g (0.103 mole) of tetraacetoxysilane into a reaction flask equipped with a stirrer, a reflux condenser, and a calcium chloride tube and add, with intensively stirring, 48.28 g (0.309 mole) of citronellol. Continue stirring the reaction mixture at room temperature for 5 hours and then for an hour at a temperature of 50°C. Now distil the formed acetic acid from the reaction mixture in a rotary evaporator at a temperature of 60-70°C with gradually lowering pressure to 6 mm Hg. Allow the reaction mixture to cool to room temperature, add 16.09 g (0.103 mole) of menthol, and stir the reaction mixture at room temperature for another 5 hours and then at 50°C for an hour. Now distil the formed acetic acid from the reaction mixture in a rotary evaporator at a temperature of 60-70°C with gradually lowering pressure to 6 mm Hg. Treat the mixture in vacuum for an hour at 110°C and residual pressure of 5 mm Hg. The resultant product is a white pasty mass. Gas-liquid chromatography shows 99.8% conversion by the acetoxy groups. The reaction yields 65 g (97%) of (5-methyl-2(l- methylethyl)cyclohexanoxy)tri(3,7-dimethyl-6-octenoxy)silane
Si[OC2H4CH(CH)3C2H4CH=C(CH3)2]3[OC6H9(CH3)(C3H7)].
The short name is Si[OCitr]3[OMent]. Density ofthe product d20 4 0.9146; refractive index «D 1.4422.
The product composition is confirmed by Η NMR spectra.
Example 22.
The product is obtained by a procedure similar to that described in
Example 6, except that the reactants are 22.44 g (0.085 mole) of tetraacetoxysilane and 59.4 g (0.38 mole) of menthol. Titration ofthe acetoxy groups confirms their 99.7% conversion.
The reaction yields 51 g (93%) of tetra(5-methyl-2(l- methylethyl)cyclohexanoxy)silane, Si[OC6H9(CH3)(C3H7)]4. The short name is Si[OMent]4.
The product composition is confirmed by *H NMR spectra.
Example 23.
The product is obtained by a procedure similar to that described in
Example 6, except that the reactants are 37 g (0.14 mole) of tetraacetoxysilane and 43.75 g (0.28 mole) of menthol. Titration ofthe acetoxy groups confirms their 99.7% conversion.
The reaction yields 62.3 g (97%) of diacetoxydi(5 -methy 1-2(1- methylethyl)cyclohexanoxy)silane, Si[OC6H9(CH3)(C3H7)]2[OAc]2.
The short name is Si[OAc]2[OMent]2. Density ofthe product cf°4 1.0159; refractive index nO 1.4495.
The product composition is confirmed by H NMR spectra. Example 24.
The product is obtained by a procedure similar to that described in Example 6, except that the reactants are 6.86 g (0.026 mole) of tetraacetoxysilane, 15.98 g (0.105 mole) of vanillin, and 15 ml of toluene. Titration ofthe acetoxy groups confirms their 99.8% conversion. The reaction yields 16 g (97%) of tetra(4-formyl-2-methoxyphenoxy)silane, Si[OC6H3(CHO)(OCH3)]4. The short name is Si[OVanil]4. The product composition is confirmed by *H NMR spectra.
Example 25.
Place, in a nitrogen flow, 21.12 g (0.08 mole) of tetraacetoxysilane into a reaction flask equipped with a stirrer, a reflux condenser, and a calcium chloride tube and add, with intensively stirring, 37.5 g (0.24 mole) of citronellol. Continue stirring the reaction mixture at room temperature for 5 hours and then for an hour at a temperature of 50°C. Now distil the formed acetic acid from the reaction mixture in a rotary evaporator at a temperature of 60-70°C with gradually lowering pressure to 6 mm Hg. Allow the reaction mixture to cool to room temperature, add 12.17 g (0.08 mole) of vanillin, and stir the reaction mixture at room temperature for another 5 hours and then at 50°C for an hour. Now distil the formed acetic acid from the reaction mixture in a rotary evaporator at a temperature of 60-70°C with gradually lowering pressure to 6 mm Hg. Treat the mixture in vacuum for an hour at 110°C and residual pressure of 5 mm Hg. The resultant product is a white pasty mass. Gas-liquid chromatography shows 99.8% conversion by the acetoxy groups.
The reaction yields 50 g (97%) of (4-formyl-2-methoxyphenoxy)tri(3,7- dimethyl-6-octenoxy)silane Si[OC6H9(CHO)(OCH3)][OC2H4CH(CH3)C2C4CH=C(CH3)2]3. The short name is Si[OCitr]3[OVanil].
The product composition is confirmed by H NMR spectra.
Example 26.
Place, in a nitrogen flow, 18.48 g (0.07 mole) of tetraacetoxysilane into a reaction flask equipped with a stirrer, a reflux condenser, and a calcium chloride tube and add, with intensively stirring, 21.88 g (0.14 mole) of citronellol. Continue stirring the reaction mixture at room temperature for 5 hours and then for an hour at a temperature of 50°C. Now distil the formed acetic acid from the reaction mixture in a rotary evaporator at a temperature of 60-70°C with gradually lowering pressure to 6 mm Hg. Allow the reaction mixture to cool to room temperature, add 21.3 g (0.14 mole) of vanillin, and stir the reaction mixture at room temperature for another 5 hours and then at 50°C for an hour. Now distil the formed acetic acid f >m the reaction mixture in a rotary evaporator at a temperature of 60-70°C with gradually lowering pressure to 6 mm Hg. Treat the mixture in vacuum for an hour at 110°C and residual pressure of 5 mm Hg. The resultant product is a white pasty mass. Gas-liquid chromatography shows 99.8% conversion by the acetoxy groups. The reaction yields 43.15 g (97%) of di(4-formyl-2- methoxyphenoxy)di(3,7-dimethyl-6-octenoxy)silane
Si[OC6H9(CH3)(C3H7)]2[OC2H4CH(CH3)C2H4CH=C(CH3)2]2. The short name is Si[OCitr]2[OVanil]2. The product composition is confirmed by Η NMR spectra.
Example 27.
The product is obtained by a procedure similar to that described in
Example 1, except that the reactants are 45.89 g (0.209 mole) of methylt acetoxysilane and 102.8 g (0.627 mole) of eugenol. Titration of the acetoxy groups confirms their 99.8% conversion.
The reaction yields 107.9 g (97%) of tri(4-allyl-2- methoxyphenoxy)methylsilane, MeSi[OC6H3(C3H7)(OCH3)]3. The short name is MeSi[OEug]3. Density d 20 = 1.1317.
The product composition is confirmed by !H NMR spectra.
Example 28.
To 32,2 g methyldiacetoxy-(4-allyl-2-methoxyphenyloxy) silane, (0,1 mole) add 0,18 g water, dissolved to 10 ml g methylethylketone, stir reaction mixture 2 h at 20°C and 6 h at 70°C. Than content of reaction vessel treat in vacuum at 140°C 4 h, cool and filter.
Resulting product - viscous white-yellow liquid with ordor of eugenol; yield 21,3 g (97%). Product have general formula [Me(CH2=CHCH2C6H3(OCH3)0)SiO]2o; Mn=4400. The product composition is confirmed by 1HNMR spectra.
Example 29.
To mixture of 32,2 g methyldiacetoxy-(4-allyl-2-methoxyphenyloxy) silane (0,1 mole), 37,2 g oligoethoxysiloxane [(C2H50)2;4 SiOo,s]5 (0,05 mole) add 2,52 g water. Mixture stir 2 h at 20°C and 6 h at 70°C. Than content of vessel treat in vacuum at 140°C and after cooling filter. Yield of transparent white-yellow viscous liquid with light ordor of eugenol is 52,9 g (96%). Product have Mn= 17000. 1HNMR spectra confirm next formula [Me(EugO)SiO]32[(EtO)2SiO]80 Example 30.
Mixture of 3,22 g methyldiacetoxy-(4-allyl-2-methoxyphenyloxy) silane (0,1 mole), and 32 g powder Si02 with specific surface 100 m /g stir and expose at air 20 h at 20°C, 10 h at 100°C and than treat 4 h in vacuum at 140°C. Resulting product is white powder with light ordor of eugenol; yield 33,8 g (99%) Si02, modificate of poly(4-allyl-2-methoxyphenyloxy)- siloxane. 20 g of this powder extract 10 h of boiling CH2C12 and dry in vacuum 4 h at 100°C. Weight of residue is 19,9 g (99%); it means, that degree of grafting eugenol derivative of silane at surface of Si02 is more 92%.
Example 31.
Mixture of 3,28 g 4-allyl-2-methoxyphenol (0,02 mole) and 32 g Si02 with specific surface 100 m2/g stir and treat 20 h at 20°C and 10 h at 100°C. Content of vessel undergo vacuum treatment 4 h at 100°C. Resulting product-pure Si02 (31,6 g) without ordor of eugenol.
Example 32.
Mixture of 3,22 g methyldiacetoxy(4-allyl-2-methoxyphenoxy) silane and
32 g fibrous cellulose stir and treat in atmosphere of air 20 h at 20°C and 10 h at 100°C. Reaction product undergo vacuum treatment 4 h at 100°C and receive 33,5 g cellulose, containing grafting poly(4-allyl-
2-methoxyphenyloxy)siloxane.
20 g of this product treat of boiling CH2C12 10 h and dry in vacuum 10 h at 100°C. Weight of residue is 19,8 g. This means, that degree of grafting starting silane to surface of Siθ2 is 92%. Example 33.
Repeat procedure of example 32, using instead engenolsilane pure engenol- 4-allyl-2-methoxyphenol (0,02 mole). Resulting product is pure cellulose without ordor and any traces of eugenol.
Table 1. Characteristics of products
Figure imgf000024_0001
OEug is 4-allyl-2-methoxyphenoxy-; OCitr is 3,7-dimethyl-6-octenoxy-; OVanil is 4-formyl-2-methoxyphenoxy; OAc is acetoxy-; Chex is cyclohexyl- OMent is 5-methyl-2(l-methylethyl)cyclohexanoxy- radicals. Table 2. Release of fragrant, flavouring and medicinal substances during hydrolysis of methyl ethyl ketone solutions of products obtained according to the invention at 20°C during 200 hours. In this table and tables 3-9 were used 0.2 mole/1 solutions examed substances and 1.0 mole of water per each h drolizin rou .
Figure imgf000025_0001
* In 30 minutes
OEug is 4-allyl-2-methoxyphenoxy-; OCitr is 3,7-dimethyl-6-octenoxy-;
OVanil is 4-formyl-2-methoxyphenoxy; OAc is acetoxy-; Chex is cyclohexyl-;
OMent is 5-methyl-2(l-methylethyl)cyclohexanoxy- radicals Table 3.
Release of citronellol during hydrolysis of methyl ethyl ketone solutions of products according to the invention containing citronellol groups at 20°C.
Figure imgf000026_0001
Table 4. Release of eugenol during hydrolysis of methyl ethyl ketone solutions of products according to the invention containing eugenol groups at 20°C.
Figure imgf000027_0001
Table 5. Release of vanillin during hydrolysis of methyl ethyl ketone solutions of products according to the invention containing vanillin groups at 20°C.
Figure imgf000028_0001
Table 6. Release of menthol during-hydrolysis of methyl ethyl ketone solutions of products according to the invention containing menthol groups at 20°C.
Figure imgf000029_0001
Table 7. Release of menthol during hydrolysis of methyl ethyl ketone solutions of products according to the invention containing menthol groups at 20°C.
Figure imgf000030_0001
Table 8. Release of eugenol during hydrolysis of methyl ethyl ketone solutions of products according to the invention containing eugenol groups at 20°C.
Table 9. Release fragrant and medicinal substances during hydrolisis of methyl ethyl ketone solutions of products to the invention.
Figure imgf000032_0001
• Time of hydrolisis 0,5 hour
Content of released compounds were found by gas-liquid chromatografy.

Claims

WHAT IS CLAIMED IS:
1. A method for preparing compounds of the general formula [RC(0)0]aSi(OR')4.a.bR"b, where RC(0)0 is an acidic radical of one or several saturated or unsaturated carboxylic acids with the number of carbon atoms from 2 to 18, a is from 0 to 3, R" is an alkyl group having from 1 to 6 carbon atoms, phenyl, linear or branched siloxane chains of formula -0(R, , ,)2SiO[Si(R,")2θ]nΗ or branched siloxanes 0(R, , ,)2SiO[Si(R^ ,)Oι,5]m-[Si(R, , ,)20]n.m-H (R'" -organic radicals, preferable methyl, ethyl, phenyl , n - integer from 1 to 1000, m= 0-500);, b is from 0 to 3, and R'O are organoxy groups of one, two, three, or four hydroxyl-containing fragrant, flavouring or medicinal substances, by the interaction between silicon compounds of the general formula [RC(0)0]cSiR"4.c where RC(0)0 is an acidic radical of one or several saturated or unsaturated carboxylic acids with the number of carbon atoms from 2 to 18, c is from 1 to 4, R" is as above mentioned and b is from 0 to 3, with hydroxyl-containing fragrant, flavouring or medicinal substance, or by the interaction of silicon compounds ofthe general formula [RC(0)0]aSi(OR')4_a_bR"b, where RC(0)0 is an acidic radical of one or several saturated or unsaturated carboxylic acids with the number of carbon atoms from 2 to 18, a is from 1 to 3, R" is as above; b is from 0 to 3, and R'O are organoxy groups of one, two, or three aromatic or medicinal substances, with another hydroxyl-containing fragrant, flavouring or medicinal substance.
2. Compounds as claimed in Claim 1, characterized by that derivatives of acetic acid (CAS 64-19-7), butyric acid (CAS 107-92-6), caprylic (octanoic) acid (CAS 124-07-2), oleic acid (CAS 112-80-1), and linolic acid (CAS 60-33-3) are used as the starting materials [R"'C(0)0]cSiR"4.c or [RC(0)0]aSi(OR')4.a.bR" for the synthesis of said compounds.
3. Compounds as claimed in Claim 1, characterized by that said compounds are synthesized from the starting compounds [R"'C(0)0]cSiR"4.c or [RC(0)0]aSi(OR')4-a-bR", which may contain one or two aliphatic groups, including methyl, ethyl, cyclohexyl and octyl groups at the silicon atom.
4. Compounds as claimed in Claim 1, characterized by that 4-allyl-2- methoxyphenol (eugenol, CAS 97-53-0), 3,7-dimethyloct-6-en-l-ol (citronellol, CAS 106-22-9), 4-hydroxy-3-methoxybenzaldehyde (vanillin, CAS 121-35-5), 3,7-dimethylocta-2,6-dien-l-ol (geraniol, CAS 106-24-1), 3,7-dimethylocta-2,6-dien-3-ol (linalool, CAS 78-70- 6), 7-hydroxy-3,7-dimethyloctanal (hydroxycitronellal), 2(4- methylcyclohex-3-enyl)propan-2-ol (terpineol, CAS 10482-56-1), 2- phenylethanol(β-phenylethyl alcohol, CAS 60-12-8), 3-phenylpropanol (hydrocinnamic alcohol, CAS 122-97-4), 3-phenyl- prop-2-en-l-ol (cinnamic alcohol, CAS 104-54-1), 1,5-dimethyloxime bicyclo -3,2,1- octan -8-one (buccoxime), 4(4-hydroxyphenyl)-2- butanone (raspberry ketone, CAS 5471-51-2), [2(2-hydroxyethyl)-6,6- dimethylbicyclo[3.1.1]-hept-2-ene] (Nopol, CAS 35836-73-8) are used as the hydroxyl-containing fragrant and flavouring substances.
5. Compounds as claimed in Claim 1, characterized by that 3-methyl- 6(l-methylethyl)cyclohexanol (menthol, CAS 89-78-1), 2- hydroxybenzoic acid (salicylic acid, CAS 69-72-7), methyl salicylate (CAS 119-36-8), 2,3-bis(hydroxymethyl)quinoline-N,N-dioxide (dioxidine, CAS 97-53-0), N-(hydroxymethyl)nicotinic amide (nicodin) (CAS 3569-99-1), 5-nitro-8-oxyquinoline (nitroxolin, CAS 4008-48-4), 2-hydroxyacetanilide (paraacetamol, CAS 614-80-2), 2- hydroxybenzamide (salicylamide, CAS 65-45-2), and 2-isopropyl-5- methylphenol (thymol, CAS 89-83-8) are used as the hydroxyl- containing medicinal substances.
PCT/RU2000/000135 2000-04-17 2000-04-17 Silicon derivatives of fragrant, flavouring and medicinal substances WO2001079212A1 (en)

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