GB2145714A - U V Absorbing unsaturated organic esters - Google Patents
U V Absorbing unsaturated organic esters Download PDFInfo
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- GB2145714A GB2145714A GB08420569A GB8420569A GB2145714A GB 2145714 A GB2145714 A GB 2145714A GB 08420569 A GB08420569 A GB 08420569A GB 8420569 A GB8420569 A GB 8420569A GB 2145714 A GB2145714 A GB 2145714A
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- 150000002895 organic esters Chemical class 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- 150000003961 organosilicon compounds Chemical class 0.000 claims abstract description 13
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 5
- 150000007524 organic acids Chemical class 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000005375 organosiloxane group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 6
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 abstract description 4
- 229960004889 salicylic acid Drugs 0.000 abstract description 4
- 239000002250 absorbent Substances 0.000 abstract description 3
- 230000002745 absorbent Effects 0.000 abstract description 3
- 239000000543 intermediate Substances 0.000 abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 33
- -1 alkali metal salts Chemical class 0.000 description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 11
- 239000011541 reaction mixture Substances 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229920002554 vinyl polymer Polymers 0.000 description 5
- 230000008033 biological extinction Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000006459 hydrosilylation reaction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001843 polymethylhydrosiloxane Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000003039 volatile agent Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- AFDXODALSZRGIH-QPJJXVBHSA-N (E)-3-(4-methoxyphenyl)prop-2-enoic acid Chemical compound COC1=CC=C(\C=C\C(O)=O)C=C1 AFDXODALSZRGIH-QPJJXVBHSA-N 0.000 description 1
- KILURZWTCGSYRE-LNTINUHCSA-K (z)-4-bis[[(z)-4-oxopent-2-en-2-yl]oxy]alumanyloxypent-3-en-2-one Chemical compound CC(=O)\C=C(\C)O[Al](O\C(C)=C/C(C)=O)O\C(C)=C/C(C)=O KILURZWTCGSYRE-LNTINUHCSA-K 0.000 description 1
- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical compound [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- CNXZMGRWEYQCOQ-UHFFFAOYSA-N 2-methoxy-3-phenylprop-2-enoic acid Chemical compound COC(C(O)=O)=CC1=CC=CC=C1 CNXZMGRWEYQCOQ-UHFFFAOYSA-N 0.000 description 1
- CGOJOQBYEAVATL-UHFFFAOYSA-N 3-(4-methoxyphenyl)prop-2-enoyl chloride Chemical compound COC1=CC=C(C=CC(Cl)=O)C=C1 CGOJOQBYEAVATL-UHFFFAOYSA-N 0.000 description 1
- YDIYEOMDOWUDTJ-UHFFFAOYSA-N 4-(dimethylamino)benzoic acid Chemical compound CN(C)C1=CC=C(C(O)=O)C=C1 YDIYEOMDOWUDTJ-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229960004050 aminobenzoic acid Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004181 carboxyalkyl group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011953 free-radical catalyst Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- AFDXODALSZRGIH-UHFFFAOYSA-N p-coumaric acid methyl ether Natural products COC1=CC=C(C=CC(O)=O)C=C1 AFDXODALSZRGIH-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 150000003284 rhodium compounds Chemical class 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical class [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
- C07C69/84—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
- C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/24—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran
- C07C67/26—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran with an oxirane ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
- C07C69/734—Ethers
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Silicon Polymers (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Novel compounds represented by the general formula <IMAGE> when a and b are each 0 or 1 and R represents OH or lower alkoxy when a is 1, or OH or -NR'2 when a is zero, can be prepared by the reaction of allyl glycidyl ether with the appropriate organic acid e.g. salicylic acid. The compounds are useful as ultra-violet absorbent substances and as intermediates for the preparation of other such substances, for example by polymerisation and copolymerisation and by reaction with organosilicon compounds having silicon-bonded hydrogen atoms.
Description
SPECIFICATION
Organic compounds
This invention relates to organic compounds and to the use of such compounds as ultra violet absorbing substances. The invention also relates to the use of said organic compounds as intermediates in the preparation of other ultra violet absorbing substances.
According to this invention there are provided compounds represented by the general formula
wherein a and b are each 0 or 1 and R when present represents a hydroxy group or an alkoxy group having from 1 to 4 carbon atoms when a is 1, and a hydroxy group or the group - NR'2, in which each R' represents
H or an alkyl group having from 1 to 4 inclusive carbon atoms, when a is zero.
The compounds of this invention can be prepared by the reaction of allyl glycidyl ether with the appropriate organic acid. Included within the scope of this invention therefore is a process which comprises reacting together, (A) allyl glycidyl ether and (B) an organic acid represented by the general formula
wherein a, b and R are as hereinabove defined.
Reactant (A) is a well-known commercially available material. Reactants (B) are also well-known and readily available and include for example cinnamic acid, methoxy-cinnamic acid, salicylic acid and p-dimethylamino-benzoic acid.
The reaction between (A) and (B) is preferably carried out at elevated temperatures, generally from about 50"C to the reflux temperature of the reaction mixture. Catalysts may be employed to expedite the reaction.
Suitable catalysts are those effective in opening the oxirance ring, for example pyridine, triethylamine, inorganic basis, alkali metal salts and Lewis acids and bases e.g. aluminium acetyl acetonate. Also, if desired, solvents for example toluene, xylene, esters, alcohols and ethers may be employed to facilitate the reaction or assist in the recovery of the reaction product.
Preferably the reaction is performed employing (A) and (B) in stoichiometric proportions. It may however be carried out with either (A) or (B) in stoichiometric excess although excess (A) is generally more easily removed from the reaction mixture when recovering the product.
The compounds of this invention are absorbent to ultra violet radiation and may therefore be incorporated into products e.g. polishes, polymers and paints for reducing or slowing deterioration arising from exposure to such radiation. For absorbtion in the erythemic region (280 - 320 m) the preferred compounds are those wherein R represents an alkoxy group or the group -NR'2wherein each R' is preferably methyl.
Although they may be advantageously employed perse in formulating various products the compounds of this invention are of particular interest as intermediates. For example they may be reacted via the OH group with acid chlorides e.g. cinnamoyl cgloride or p-methoxycinnamoyl chloride to introdice an additional e.g. cinnamic acid residue. They may also be reacted with organosilicon compounds containing SiH groups to produce silanes and siloxanes having both U.V. absorbing properties and the properties associated with organosilicon compounds. For example organosiloxane fluids can be readily formulated into cosmetic preparations such as hand creams and lotions which provide a soft, protective, durable, water-repellent barrier on the skin.In another aspect, therefore, this invention comprises a process for the preparation of U.V. absorbing organosilicon compounds which comprises reacting together (i) a compound represented by the general formula
wherein a, b and R are as hereinbefore defined, and (ii) an organosilicon compound having in the molecule at least one silicon-bonded hydrogen atom.
TheSiH-containing compound (ii) may be a silane e.g. CH3HSiC12, HSiC13, (CH3)2SiHCI, C6H5HSiC12, C2H5SiH(OCH3)2 and (CH3)2SiHBr but is more preferably an organosiloxane. Examples of organosiloxanes are cyclic methyl hydrogen polysiloxanes, trimethylsiloxy end-stopped methyl hydrogen polysiloxanes, copolymers of dimethylsiloxane (CH3)2SiO, methylhydrogensiloxane (CH3)HSiO and trimethylsiloxane (CH3)3SiO units, copolymers of dimethylsiloxane and dimethylhydrogensiloxane (CH3)3HSiO,A2 units and
units, 1/2 copolymers of phenylmethylsiloxane, dimethylsiloxane, methylhydrogensiloxane and dimethylphenylsiloxane units.The organic substituents present in (ii) are preferably substantially all methyl groups but other organic substituents such as phenyl, higher alkyl and substituted alkyl groups e.g. halogenoalkyl and carboxyalkyl may also be present if desired, any substituents present in addition to methyl groups and hydrogen atoms preferably constituting no more than about 30% of the total number of substituents.
The reaction between (i) and (ii) may be carried out according to known procedures for the addition of silicon-bonded hydrogen atoms to groups containing olefinic unsaturation. Thus the reaction is normally catalysed by the presence of a platinum group metal or compound or complex of a platinum group metal.
Examples of catalysts which may be employed for the reaction of (i) and (ii) are platimum on carbon, chloroplatinic acid, platinum acetyl acetonate, complexes of platimum compounds with unsaturated compounds e.g. olefins and vinyl siloxanes, complexes of rhodium or palladium compounds and complexes of platinum and rhodium compounds supported on inorganic substrates (see British Patent 1 527 598). The addition (or hydrosilylation) reaction may be performed at sub-atmospheric, atmospheric or superatmospheric pressures and in the presence of absebce of solvents. It is generally preferred to employ a solvent e.g. toluene or xylene in the reaction between (i) and (ii). It is also preferred to employ elevated temperatures e.g. from about 60 C up to the reflec temperature of the reaction mixture.When the organosilicon compound (ii) is a halosilane it may be desirable in some cases to protect the OH group in (i), e.g. by protective silylation, during the reaction between (i) and (ii).
The compounds of this invention may also take part in vinyl polmerisation reactions to form
homopolymers and copolymers having ultra violet absorbing properties. Such a reaction, may be performed
according to known addition polymerisation techniques, for example in the presence of a free radical catalyst, e.g. benzoyl peroxide or azo-bis-isobutyronitrile. Copolymers may be formed by including in the
reaction mixture comonomers which are susceptible to vinyl copolymerisation, for example vinyl chloride,
methyl methacrylate, vinyl silanes, styrene and vinyl acetate.
Organosilicon compounds formed by the hydrosilylation of the compounds of this invention and polymers obtained byvinyl polymerisation and copolymerisation may be employedperse as U.V. absorbents or may be formulated into U.V. absorbing compositions as hereinabove described for the compounds themselves.
Where the chemical and physical nature of the products permits, for example as in the vinyl addition copolymers, the products may be fabricated into articles and coating compositions. Thus for example they may be compounded with fillers, curing agents, antioxidants, flame retardants and any other conventional ingredients of such articles and compositions.
The following example, in which Me represents the methyl group, illustrate the invention.
Example 1
Allyl glycidyl ether (389,0.33 mole), p-methoxy cinnamic acid (59.3g, 0.33 mole) and toluene (939) were charged to a 3 neck, 500ml flask fitted with a thermometer and reflux condenser. An atmosphere of nitrogen was maintained in the flask.
The contents of the flask were heated to reflux and N,N,-dimethylethanolamine (0.49) dissolved in toluene (4g) added to the reaction mixture. After one hour a second addition of N,N-dimethylethanolamine (0.49) was made and the reaction mixture maintained at 110 - 120"C for a further 4.5 hours. Gas liquid chromatographic analysis then indicated that the allyl glycidyl ether had been almost totally consumed.
When volatiles had been removed by heating to 180 C under 10mb a viscous, brown liquid was obtained having the structure
This substance had a A max of 308nm and a molar extinction coefficient at this wavelength of 19,000. The extinction coefficient of a 1% by weight solution in methylene chloride was 638.
Example 2
Allylglycidyl ether (38g, 0.33mole), salicylic acid (469, 0.33mole) and toluene (93g) were charged to a flask as described in Example 1 and heated to 110 C. Triethylamine (0.8g) in toluene (79) was added to the reactants and the reaction mixture then maintained at 105 - 115 C for 6 hours. After this time g.l.c. analysis showed that all of the allylglycidyl ether had been consumed.
The reaction mixture was heated to 145DC/10mb to remove volatiles and yielded a viscous dark red liquid having the structure
This liquid exhibited a A max of 306 nm (A max for salicylic acid = 307 nm) and a molar extinction coefficient at this wavelength of 4420.
Example 3
Employing the method described in Example 1 p-amino-benzoic acid (46g) was reacted with allyl glycidyl ether (389) in the presence of toluene (1 00g) and triethylamine (0.8g). After 4 hours the reaction mixture was filtered while hot. The filtrate separated into two clear layers. The lower layer crystallised on cooling and was separated from the upper layer which was shown to be toluene.
Example 4
Toluene (5g) and a complex (0.349) of chloroplatinic acid and a vinyl siloxane were placed in a flask and heated to 1 00'C. To this mixture were then added over a period of 67 minutes (1) the reaction product (29.49) of allyl glycidyl ether and p-methoxycinnamic prepared as Example 1, (2) toluene (70g) and (3) (Me3SiO)2SiMeH (24.4g). The reaction mixture was maintained at 100"C for 22 hours and a second portion of the platinum complex (0.34g) then added. After a further 5 hours the toluene was removed by distillation to leave the organosilicon addition product having the following absorption characteristics: A max 310 nm molar extinction coefficient 19050
Claims (8)
1. Compounds represented by the general formula
wherein a and b are each 0 or 1 and R when present represents a hydroxy group or an alkoxy group having from 1 to 4 carbon atoms when a is 1, and a hydroxy group or the group -NR'2, in which each R' represents
H or an alkyl group having from 1 to 4 inclusive carbon atoms, when a is zero.
2. Compounds as claimed in Claim 1 wherein a is 1, b is 1 and R is an alkoxy group having from 1 to 4 carbon atoms.
3. Compounds as claimed in Claim 1 wherein a isO, b is 1 and R represents the -NR'2 group.
4. A process for the preparation of compounds as claimed in Claim 1 which comprises reacting together (A) allyl glycidyl ether and (B) an organic acid represented by the general formula
wherein a, b and R are as defined in Claim 1.
5. A process for the preparation of compounds as claimed in Claim 4 substantially as described with reference to Examples 1 to 3 herein.
6. A process for the preparation of organosilicon compounds which comprises reacting together (i) a compound represented by the general formula
wherein a, band Rare as defined in Claim 1, and (ii) an organosilicon compound having in the molecule at least one silicon-bonded hydrogen atom.
7. A process as claimed in Claim 6 wherein the organosilicon compound (ii) is an organosiloxane.
8. A process as claimed in Claim 6 substantially as described with reference to Example 4.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB838322318A GB8322318D0 (en) | 1983-08-18 | 1983-08-18 | Organic compounds |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8420569D0 GB8420569D0 (en) | 1984-09-19 |
| GB2145714A true GB2145714A (en) | 1985-04-03 |
| GB2145714B GB2145714B (en) | 1986-12-03 |
Family
ID=10547529
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB838322318A Pending GB8322318D0 (en) | 1983-08-18 | 1983-08-18 | Organic compounds |
| GB08420569A Expired GB2145714B (en) | 1983-08-18 | 1984-08-13 | U v absorbing unsaturated organic esters |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB838322318A Pending GB8322318D0 (en) | 1983-08-18 | 1983-08-18 | Organic compounds |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS6058939A (en) |
| CA (1) | CA1245229A (en) |
| DE (1) | DE3430372A1 (en) |
| FR (1) | FR2550787B1 (en) |
| GB (2) | GB8322318D0 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2307240A (en) * | 1995-11-20 | 1997-05-21 | Lg Electronics Inc | Siloxanes containing cinnamate groups for liquid crystal devices |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1527598A (en) * | 1974-11-12 | 1978-10-04 | Dow Corning Ltd | Catalysts and carriers therefor |
| JPS5496595A (en) * | 1978-01-17 | 1979-07-31 | Toray Ind Inc | Production of impact-resistant resin |
-
1983
- 1983-08-18 GB GB838322318A patent/GB8322318D0/en active Pending
-
1984
- 1984-08-13 GB GB08420569A patent/GB2145714B/en not_active Expired
- 1984-08-15 CA CA000461043A patent/CA1245229A/en not_active Expired
- 1984-08-17 DE DE19843430372 patent/DE3430372A1/en not_active Withdrawn
- 1984-08-17 JP JP59170535A patent/JPS6058939A/en active Granted
- 1984-08-17 FR FR8412907A patent/FR2550787B1/en not_active Expired
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2307240A (en) * | 1995-11-20 | 1997-05-21 | Lg Electronics Inc | Siloxanes containing cinnamate groups for liquid crystal devices |
| US5824377A (en) * | 1995-11-20 | 1998-10-20 | Lg Electronics Inc. | Photosensitive material for orientation of liquid crystal device and liquid crystal device thereof |
| US5998563A (en) * | 1995-11-20 | 1999-12-07 | Lg Electronics Inc. | Photosensitive material for orientation of liquid crystal device and liquid crystal device thereof |
| GB2307240B (en) * | 1995-11-20 | 2000-02-16 | Lg Electronics Inc | Photosensitive material for orientation of liquid crystal device and liquid crystal device thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CA1245229A (en) | 1988-11-22 |
| GB8322318D0 (en) | 1983-09-21 |
| FR2550787B1 (en) | 1986-12-12 |
| JPS6058939A (en) | 1985-04-05 |
| GB8420569D0 (en) | 1984-09-19 |
| GB2145714B (en) | 1986-12-03 |
| DE3430372A1 (en) | 1985-03-07 |
| JPH0316938B2 (en) | 1991-03-06 |
| FR2550787A1 (en) | 1985-02-22 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19930813 |