Patent Grant
9068080
The present invention relates to the use of merocyanine derivatives for protecting human and animal hair and skin from UV radiation and to cosmetic compositions comprising such compounds.
The compounds for use in accordance with the invention correspond to formula
Halogen is chloro, bromo, fluoro or iodo, preferably a fluoro, more preferably fluoro alkyl like trifluormethyl, α,α,α-trifluorethyl or perfluorinated alkyl groups like heptafluorpropyl.
Alkyl, cycloalkyl, alkenyl, alkylidene or cycloalkenyl residues can be straight-chain or branched, or also monocyclic or polycyclic.
Alkenyl is for example straight-chain C2-C12alkenyl or preferably branched C3-C12alkenyl.
C1-C22alkyl is for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, n-hexyl, n-octyl, 1,1,3,3-tetramethylbutyl, 2-ethylhexyl, nonyl, decyl, n-octadecyl, eicosyl, oder dodecyl.
C3-C12cycloalkyl is for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, trimethylcyclohexyl, menthyl, thujyl, bornyl, 1-adamantyl or 2-adamantyl.
C2-C12alkenyl or C3-C12cycloalkenyl refers to unsaturated hydrocarbon residues containing one or multiple double bonds such vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, 1,3-butadiene-2-yl, 2-cyclobutene-1-yl, 2-pentene-1-yl, 3-pentene-2-yl, 2-methyl-1-butene-3-yl, 2-methyl-3-butene-2-yl, 3-methyl-2-butene-1-yl, 1,4-pentadiene-3-yl, 2-cyclopentene-1-yl, 2-cyclohexene-1-yl, 3-cyclohexene-1-yl, 2,4-cyclohexadiene-1-yl, 1-p-menthene-8-yl, 4(10)-thujene-10-yl, 2-norbornene-1-yl, 2,5-norbornadiene-1-yl, 7,7-dimethyl-2,4-norcaradiene-3-yl or different isomers selected from hexenyl, octenyl, nonenyl, decenyl or dodecenyl.
C7-C18aralkyl is for example benzyl, 2-benzyl-2-propyl, β-phenyl-ethyl, 9-fluorenyl, α,α-dimethylbenzyl, ω-phenyl-butyl, ωphenyl-octyl, ω-phenyl-dodecyl or 3-methyl-5-(1′,1′,3′,3′-tetramethyl-butyl)-benzyl.
The C7-C18aralkyl moiety may be unsubstituted or substituted on the alkyl- as well at the aryl-moiety of the aralkyl-group, but preferably is substituted on the aryl-moiety.
(C1-C6)alkylidene is for example methylene, ethyl-1-ene or propyl-2-ene.
C6-C20aryl is for example phenyl, naphthyl, biphenylyl, 2-fluorenyl, phenanthryl, anthracenyl or terphenylyl.
C2-C12heteroaryl is for example an unsaturated or aromatic radical with 4n+2 conjugated π-electrons, such as 2-thienyl, 2-furyl, 2-pyridyl, 2-thiazolyl, 2-oxazolyl, 2-imidazolyl, isothiazolyl, triazolyl or any other ringsystem consisting of thiophene-, furan-, pyridine, thiazol, oxazol, imidazol, isothiazol, triazol, pyridine- and phenyl rings, which are unsubstituted or substituted by 1 to 6 ethyl, methyl, ethylene and/or methylene groups, such as benzotriazolyl.
C3-C18heteroaralkyl is for example a C1-C8 alkyl moiety which is substituted by a C2-C12heteroaryl group.
If Sil1, Sil2 Sil3 and Sil4 are an oligosiloxane radical, it is preferably selected from a group of formula
If Sil1, Sil2 Sil3 and Sil4 are an polysiloxane radical, it is preferably selected from a group of formula
Preferred silane groups are trimethylsilane, triethylsilane, tripropylsilane, triisopropylsilane, dimethyl tert-butylsilane, dimethyl thexylsilane, triphenylsilane, dimethylphenylsilane and the like.
The linkers X1, X2, X3 and X4 are preferably a divalent radical of formula
Preferably compounds of formula (1) are used, wherein
L1 and L3 together form a bivalent radical selected from
R1 and R2 together form a bivalent radical selected from
Preferred is also the use of compounds of formula (1), wherein
R1 and L3 form a bivalent radical selected from
Preferably merocyanine derivatives are used in the present invention, wherein in formula (1)
Furthermore, merocyanine derivatives are used, wherein in formula (1)
R1 is a tetravalent radical of formula
Most preferred merocyanine derivatives are those compounds, wherein in formula (1)
R2 is hydrogen; or C1-C3alkyl; and
R1, R3, R4, L1, L2, L3 and n are defined as in formula (1).
Further preferred merocyanine derivatives are those compounds, wherein in formula (1)
R3 is X2—Sil2, wherein Sil2 is a radical of formula
X2 is C1-C18alkylene; or a bivalent radical of the formula
wherein the asterix * is linked to Sil1 or Sil2 and the asterix ** is linked to R3 or R4; and
w is a number from 0 to 30.
Most preferred are also merocyanine derivatives, wherein in formula (1)
R4 is —COOR5; or C≡N;
R5 is hydrogen; or C1-C22alkyl; and
R1, R2, R3, L1, L2, L3 and n are defined as in formula (1).
Very most preferred merocyanine derivatives correspond to formula
R1 and R2 independently from each other are hydrogen; or C1-C5alkyl;
L1, L2 and L3 are hydrogen; or L1 and L3 form a bivalent radical selected from
R4 is —COR5;
R5 is C1-C5alkyl;
Sil2 is a radical of formula
X2 is C1-C18alkylene; or a bivalent radical of the formula (5a), (5b) or (5c).
Very most merocyanine derivatives correspond to formula
R2 is hydrogen; or C1-C3alkyl;
L1 and L3 together form a bivalent radical selected from
R3 and R4 independently from each other are CN; —COR5; —COOR5; or —CONR5R6; and
R5 and R6 independently of each other are hydrogen; or C1-C22alkyl; and
L2 is defined as in formula (1).
Very most merocyanine derivatives correspond to formula
R2 is hydrogen; or C1-C3alkyl;
R3 and R4 independently from each other are CN; —COR5; —COOR5; or —CONR5R6;
R5 and R6 independently of each other are hydrogen; or C1-C22alkyl;
L1, L2 and L3 are hydrogen; or L1 and L3 form a bivalent radical selected from
Examples of merocyanine derivatives which are useful for the present invention are listed in Table 1 below:
The compounds according to this invention can be prepared as follows:
In a first step compounds of the general formula (1) are synthesized in which one of the groups R1, R2, R3 or R4 are defined as above and containing an unsaturated C—C bond which can be subsequently hydrosilylated. In the next step the reaction between the unsaturated compound and a SiH containing silane, oligosiloxane and polysiloxane is performed in the presence of a hydrosilylation catalyst. The following reaction scheme exemplifies the hydrosilylation reactions.
An example for a transesterification reaction is given below for the reaction between a carboxylic acid ester and an alcohol containing an organo siloxane group. In the following scheme the groups R1, R2, R3, R4, L1, L2 or L3 are defined as described above.
The merocyanine precursors which are described in the two reaction schemes above can be prepared according to known procedures as described in several patent applications like for example U.S. Pat. No. 4,045,229, U.S. Pat. No. 4,195,999, WO 0020388, U.S. Pat. No. 4,455,368, U.S. Pat. No. 4,309,500 or WO 04/006878.
The compounds of the formula (1) according to the present invention are particularly suitable as UV filters, i.e. for protecting ultraviolet-sensitive organic materials, in particular the skin and hair of humans and animals, from the harmful effects of UV radiation. These compounds are therefore suitable as sunscreens in cosmetic, pharmaceutical and veterinary medical preparations. These compounds can be used both in dissolved form and in the micronized state.
The cosmetic formulations or pharmaceutical compositions according to the present invention may additionally contain one or more than one further UV filter as listed in Table 3.
The cosmetic or pharmaceutical preparations can be prepared by physically mixing the UV absorber(s) with the adjuvant using customary methods, for example by simply stirring together the individual components, especially by making use of the dissolution properties of already known cosmetic UV absorbers, like octyl methoxy cinnamate, salicylic acid isooctyl ester, etc. The UV absorber can be used, for example, without further treatment, or in the micronised state, or in the form of a powder.
Cosmetic or pharmaceutical preparations contain from 0.05-40% by weight, based on the total weight of the composition, of one UV absorber or UV absorber mixtures.
Preference is given to the use of mixing ratios of the UV absorber of formula (1) according to the present invention and optionally further light-protective agents (as described in Table 2) from 1:99 to 99:1, preferably from 1:95 to 95:1 and most preferably from 10:90 to 90:10, based on weight. Of special interest are mixing ratios of from 20:80 to 80:20, preferably from 40:60 to 60:40 and most preferably approximately 50:50. Such mixtures can be used, inter alia, to improve the solubility or to increase UV absorption.
The UV absorbers of formula (1) according to the present invention or combinations of UV filters are useful to protect skin, hair and/or natural or artificial hair color.
The cosmetic or pharmaceutical preparations may be, for example, creams, gels, lotions, alcoholic and aqueous/alcoholic solutions, emulsions, wax/fat compositions, stick preparations, powders or ointments. In addition to the above mentioned UV filters, the cosmetic or pharmaceutical preparations may contain further adjuvants as described below.
As water- and oil-containing emulsions (e.g. W/O, O/W, O/W/O and W/O/W emulsions or microemulsions) the preparations contain, for example, from 0.1 to 30% by weight, preferably from 0.1 to 15% by weight and especially from 0.5 to 10% by weight, based on the total weight of the composition, of one or more UV absorbers, from 1 to 60% by weight, especially from 5 to 50% by weight and preferably from 10 to 35% by weight, based on the total weight of the composition, of at least one oil component, from 0 to 30% by weight, especially from 1 to 30% by weight und preferably from 4 to 20% by weight, based on the total weight of the composition, of at least one emulsifier, from 10 to 90% by weight, especially from 30 to 90% by weight, based on the total weight of the composition, of water, and from 0 to 88.9% by weight, especially from 1 to 50% by weight, of further cosmetically acceptable adjuvants.
The cosmetic or pharmaceutical compositions/preparations according to the invention may also contain one or one more additional compounds like fatty alcohols, esters of fatty acids, natural or synthetic triglycerides including glyceryl esters and derivatives, pearlescent waxes, hydrocarbon oils, silicones or siloxanes (organosubstituted polysiloxanes), fluorinated or perfluorinated oils, emulsifiers, super-fatting agents, surfactants, consistency regulators/thickeners and rheology modifiers, polymers, biogenic active ingredients, deodorising active ingredients, anti-dandruff agents, antioxidants, hydrotropic agents, preservatives and bacteria-inhibiting agents, perfume oils, colourants, polymeric beads or hollow spheres as SPF enhancers.
Cosmetic or Pharmaceutical Preparations
Cosmetic or pharmaceutical formulations are contained in a wide variety of cosmetic preparations. There come into consideration, for example, especially the following preparations:
The final formulations listed may exist in a wide variety of presentation forms, for example:
Of special importance as cosmetic preparations for the skin are light-protective preparations, such as sun milks, lotions, creams, oils, sunblocks or tropicals, pretanning preparations or after-sun preparations, also skin-tanning preparations, for example self-tanning creams. Of particular interest are sun protection creams, sun protection lotions, sun protection milk and sun protection preparations in the form of a spray.
Of special importance as cosmetic preparations for the hair are the above-mentioned preparations for hair treatment, especially hair-washing preparations in the form of shampoos, hair conditioners, hair-care preparations, e.g. pretreatment preparations, hair tonics, styling creams, styling gels, pomades, hair rinses, treatment packs, intensive hair treatments, hair-straightening preparations, liquid hair-setting preparations, hair foams and hairsprays. Of special interest are hair-washing preparations in the form of shampoos.
A shampoo has, for example, the following composition: from 0.01 to 5% by weight of a UV absorber according to the invention, 12.0% by weight of sodium laureth-2-sulfate, 4.0% by weight of cocamidopropyl betaine, 3.0% by weight of sodium chloride, and water ad 100%.
The cosmetic preparation according to the invention is distinguished by excellent protection of human skin against the damaging effect of sunlight.
The following examples illustrate the invention in more detail, but do not limit its scope in any manner.
1.87 g (0.008 mol, 95%) of 1,1,1,3,5,5,5-heptamethyltrisiloxane are added to a mixture of 1.82 g (0.008 mol) of 2-(3-allylamino-5,5-dimethyl-cyclohex-2-enylidene)-malononitrile and 10 μl of platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (soln. in poly(dimethylsiloxane, vinyl terminated, purchased from the company Aldrich) dissolved in 6 ml of xylene at 65° C. Heating is continued at 140° C. for 18 h. Then another 1.87 g (0.008 mol, 95%) of 1,1,1,3,5,5,5-heptamethyltrisiloxane and 5 drops of the catalytic solution are added. Heating is continued at 110° C. for 30 h. After concentrating the residue is taken up in a hot 1/1 ethanol/toluene mixture. After adding charcoal the mixture is stirred at 80° C. for 1 h. The solid is filtered off and washed with a little amount of a 1/1 ethanol/toluene mixture. The filtrate is concentrated under vacuo and dried at 70-80° C.
2.99 g (83% yield) of a pasty residue are obtained which solidifies to an orangebrown resin. UV (CH3CN/H2O): λmax=382 nm; UV(EtOH): λmax=381 nm; ε=52829.
1.87 g (0.008 mol, 95%) of 1,1,1,3,5,5,5-heptamethyltrisiloxane are added to a mixture of 2.19 g (0.008 mol) of [3-allylamino-5,5-dimethyl-cyclohex-2-en-(Z)-ylidene]-cyano-acetic acid ethyl ester and 10 μl of platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (soln. in poly(dimethylsiloxane, vinyl terminated, from Aldrich) dissolved in 6 ml of toluene at 65° C. Heating is continued at 95° C. for 18 h. After concentrating the residue is taken up in a hot 1/1 ethanol/toluene mixture. After adding charcoal the mixture is stirred at 80° C. for 1 h. The solid is filtered off and washed with a little amount of a 1/1 ethanol/toluene mixture. The filtrate is concentrated under vacuo and dried at 70-80° C.
3.34 g (84% yield) of an orange resin are obtained. UV (EtOH): λmax=388 nm, ε=50383.
0.88 g (0.004 mol) of (2Z,4E)-5-(allyl-methyl-amino)-2-cyano-penta-2,4-dienoic acid ethyl ester and 5 drops of platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (soln. in poly-(dimethylsiloxane, vinyl terminated, from Aldrich) are mixed in 3 ml xylene and heated up to 65° C. After addition of 1.87 g (0.008 mol, 95%) of 1,1,1,3,5,5,5-heptamethyltrisiloxane heating is continued at 115° C. for 18 h. Then 3 ml of ethanol and charcoal are added and the resulting mixture is stirred at 80° C. for 1 h. The hot mixture is filtered over a silica gel pad which is subsequently washed with xylene and ethyl acetate. The collected eluent is concentrated. The residue is dried at 90° C. at 1×10−3 bar for 4 h rendering 0.69 g (39% yield) of the product as an orangebrown resin. UV (CH3CN/H2O): λmax=381 nm.
UV EtOH): λmax=380 nm; ε=69116.
To a solution of 0.31 g (0.0018 mol) of 2-[(E)-3-(allyl-methyl-amino)-allylidene]-malononitrile and 3 drops of platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (soln. in poly-(dimethyl-siloxane, vinyl terminated, from Aldrich) dissolved in 2 ml of xylene are added 0.84 g (0.0036 mol, 95%) of 1,1,1,3,5,5,5-heptamethyltrisiloxane at 60° C. Heating is continued at 115° C. for 18 h. The reaction mixture is diluted with 2 ml ethanol and stirred with charcoal at 80° C. for 1 h. After filtration over a hot silica gel pad and washing the pad with toluene and ethyl acetate the eluent is concentrated in vacuo.
The residue is dried at 90° C. at 1×10−3 bar for 4 hours rendering 0.53 g (yield: 74%) of the expected derivative as an orangebrown resin.
UV(CH3CN, H2O): λmax=383 nm.
1.82 g (0.008 mol) of 2-(3-allylamino-5,5-dimethyl-cyclohex-2-enylidene)-malononitrile and 10 μl platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (soln. in poly(dimethylsiloxane, vinyl terminated, from Aldrich) are dissolved in 6 ml toluene at 65° C. 0.49 g (0.002 mol, 99%) 2,4,6,8-tetramethylcyclotetrasiloxane is added and heating is continued at 95° C. for 18 h. After concentrating the residue is dissolved in a hot 1/1 ethanol/toluene mixture. Charcoal is added and the mixture is stirred for 1 h at 80° C. The solid is filtered off. The filtrate is concentrated to dryness. After drying at 70-80° C. in vacuum 2.05 g (89% yield) of the desired product are obtained in form of a dark yellow solid having a melting point of ˜100° C.
UV (EtOH): λmax=381 nm, ε=177914;
To a hot solution of 2.19 g (0.008 mol) of [3-allylamino-5,5-dimethyl-cyclohex-2-en-(Z)-yli-dene]-cyano-acetic acid ethyl ester and 10 μl platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (soln. in poly(dimethylsiloxane, vinyl terminated, from Aldrich) dissolved in 6 ml toluene is added 0.49 g (0.002 mol, 99%) 2,4,6,8-tetramethylcyclotetrasiloxane. Heating is continued at 95° C. for 18 h. After addition of another 10 μl-quantity of the catalytic system the mixture is heated at 110° C. for 18 h. The mixture is then concentrated to dryness and dissolved in 10 ml of a hot 1/1 ethanol/toluene mixture. The resulting mixture is stirred together with charcoal at 80° C. for 1 h. After filtration the mixture is concentrated and the orange solid residue dried at 70-80° C. in vacuum yielding 2.69 g (100%) of the desired product.
UV (EtOH): λmax=388 nm, ε=181817.
0.88 g (0.004 mol) of (2Z,4E)-5-(allyl-methyl-amino)-2-cyano-penta-2,4-dienoic acid ethyl ester and 5 drops of platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (soln. in poly-(dimethylsiloxane, vinyl terminated, from Aldrich) are mixed in hot 3 ml toluene. After addition of 0.24 g (0.001 mol, 99%) of 2,4,6,8-tetramethylcyclotetrasiloxane at 65° C. the reaction mixture is stirred at 115° C. for 18 h. After diluting with 3 ml ethanol and adding charcoal stirring is continued for 1 h at 80° C. The resulting mixture is filtered over a hot silica gel pad, which is washed with small amounts of toluene and ethyl acetate. The eluents are concentrated in vacuum rendering 0.68 g (61% yield) of the product in form of a redbrown resin.
UV (CH3CN, H2O): λmax=381 nm.
A solution of 0.35 g (0.002 mol) 2-[-3-(allyl-methyl-amino)-allylidene]-malononitrile and 3 drops platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (soln. in poly(dimethylsiloxane, vinyl terminated, from Aldrich) dissolved in 2 ml of xylene is heated to 60° C. After addition of 0.12 g (0.0005 mol, 99%) of 2,4,6,8-tetramethylcyclotetrasiloxane heating is continued at 115° C. for 18 h. Another 3 drops of the catalyst solution are added and stirring is continued at 115° C. for 18 h. The reaction mixture is diluted with 2 ml ethanol and stirred with charcoal at 80° C. for 1 h. The hot mixture is then filtered over a hot silica gel pad which is subsequently washed with xylene and ethyl acetate. The eluents are concentrated and residue dried at 90° C. in vacuum for 4 h yielding 0.24 g (51%) of the desired product as an orange resin.
UV (CH3CN, H2O): λmax=378 nm.
1.82 g (0.008 mol) of 2-(3-allylamino-5,5-dimethyl-cyclohex-2-enylidene)-malononitrile are dissolved together with 10 μl of platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (soln. in poly(dimethylsiloxane, vinyl terminated, from Aldrich) in 6 ml xylene. The mixture is heated up to 65° C. and 1.99 g poly(dimethylsiloxane-co-methylhydrosilane) (trimethylsilyl terminated, Mw=950 Dalton, 50 mol % MeHSiO, from Aldrich) are added. Heating is continued at 95° C. for 18 h and then worked up according to the procedure of example 8 yielding 5 g (99%) of the desired derivative as a yellow, pasty resin.
UV (EtOH): λmax=381 nm; ε=165712.
2.01 g poly(dimethylsiloxane-co-methylhydrosilane) (trimethylsilyl terminated, Mw=950 Dalton, 50 mol % MeHSiO, from Aldrich) are added to a hot solution of 2.19 g (0.008 mol) [3-allylamino-5,5-dimethyl-cyclohex-2-en-(Z)-ylidene]-cyano-acetic acid ethyl ester and 10 μl platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (soln. in poly(dimethylsiloxane, vinyl terminated, from Aldrich) dissolved in 6 ml xylene. The mixture is stirred at 95° C. for 18 h. After addition of another 10 ml of catalyst solution heating is continued at 110° C. for 18 h. The reaction mixture is then concentrated and worked up according to the procedure described in example 8 rendering 4.7 g (yield: 82%) of the desired product in form of an orange pasty resin.
UV (EtOH): λmax=388 nm; ε=189103.
0.88 g (0.004 mol) of (2Z,4E)-5-(allyl-methyl-amino)-2-cyano-penta-2,4-dienoic acid ethyl ester and 5 drops of platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (soln. in poly-(dimethylsiloxane, vinyl terminated, from Aldrich) are mixed in 6 ml xylene at 65° C. After addition of 0.99 g of poly(dimethylsiloxane-co-methylhydrosilane) (trimethylsilyl terminated, Mw=950 Dalton, 50 mol % MeHSiO, from Aldrich) at 65° C. the reaction mixture is stirred at 115° C. for 18 h. After dilution with 6 ml ethanol the reaction mixture is worked up as described in example 7. 0.98 g (yield: 39%) of the expected product are obtained in form of a brownish pasty resin. UV (CH3CN, H2O): λmax=382 nm.
A solution of 0.35 g (0.002 mol) 2-[-3-(allyl-methyl-amino)-allylidene]-malononitrile and 3 drops of platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (soln. in poly(dimethylsiloxane, vinyl terminated, from Aldrich) dissolved in 2 ml xylene is heated to 60° C. After addition of 0.50 g poly(dimethylsiloxane-co-methylhydrosilane) (trimethylsilyl terminated, Mw=950 Dalton, 50 mol % MeHSiO, from Aldrich) at 65° C. the reaction mixture is stirred at 115° C. for 18 h. The mixture is then diluted with 2 ml ethanol and worked up according to the procedure as described in example 8.
The product (0.47 g) is yielded in 43% in form of a brownish resin.
UV (CH3CN, H2O): λmax=377 nm.
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|---|---|---|---|
| 06122222 | Oct 2006 | EP | regional |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP2007/060578 | 10/5/2007 | WO | 00 | 4/1/2009 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2008/080645 | 7/10/2008 | WO | A |
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| 20100035839 A1 | Feb 2010 | US |
