An anti-solar cosmetic composition contains as the anti-solar agent a compound of the formula ##STR1## wherein R represents a member selected from the group consisting of hydrogen, a halogen selected from the group consisting of chlorine and fluorine and alkyl containing 1-4 carbon atoms; R' and R" each independently represent a member selected from the group consisting of hydrogen and SO.sub.3 M wherein M represents a member selected from the group consisting of hydrogen, organic ammonium group and a metal, wherein at least one of R' and R" is other than hydrogen, and R" is a substituent at the para or meta position relative to the bornylidene ring. The anti-solar agent is present in amounts of 0.5-10 percent by weight of said composition.

The invention relates to new compounds capable not only of absorbing 
ultra-violet rays of a specific range but also of exhibiting a broad range 
of solubility in certain solvents or mixtures of solvents. Thus, the novel 
compounds of the present invention can be incorporated in cosmetic 
compositions either as an active component, especially when the 
composition is to be used to protect human skin from harmful effects of 
actinic rays, or as a preservative for cosmetic preparations susceptible 
to degradation or discloloration by exposure to light waves. 
It is known, for instance, that sunburn, or erythema, results from the 
excessive exposure to human skin to the rays of the sun and the wave 
lengths of light in the range of 280-315 millimicrons, often called the 
"erythematous zone", are those which produce such sunburn. Below this wave 
length range the sun rays do not present any particular danger, for they 
are filtered by the ozone in the atmosphere. However, the UV rays which 
are responsible for or which produce a desirable suntan are those in the 
zone ranging from 315 to 400 millimicrons. 
Consequently, if one desires to be exposed to solar radiation, it is 
important that the skin be protected with the aid of a composition 
containing a substance which absorbs the UV rays in the erythematous zone, 
thereby avoiding an undesirable sunburn, which composition however also 
transmits those wave lengths in the range of 315 to 400 millimicrons so as 
to obtain a desirable suntan. In particular, it is necessary to transmit 
those rays of wave lengths in the neighborhood of 340 millimicrons, which 
impart maximum browning of the skin without erythema. 
Thus, the protective agent must exhibit a high absorbency power between 
280-315 millimicrons, and a weak absorbency power above 315 millimicrons. 
In addition to this critical absorbing power, the protective agent must 
have other properties and in particular it should exhibit good resistance 
to the exterior elements, that is, exhibit good photochemical stability, 
good thermal stability, and have sufficient affinity for the skin and 
sufficient chemical stability so as not to be removed or degraded by 
perspiration or at least by washing. 
Further, it is also known that certain components and particularly certain 
dyes often contained in various cosmetic preparations do not always 
possess sufficient stability to light. These cosmetic compositions are 
often provided in the form of a solution, emulsion, gel, suspension, 
aerosol or dispersion, packaged in clear glass or transparent plastic 
containers and thus can be exposed to light rays not only during use but 
also during storage. To protect these dyes there is generally incorporated 
into the preparation containing the same a "protective filter", or a 
compound capable of filtering light rays, as disclosed, for instance, in 
French Pat. No. 2,004,142. However, such protective filters often exhibit 
insufficient solubility in those solvents or cosmetic bases most often 
employed and thus their use has been considerably limited. 
It has also been observed that some essentially colorless cosmetic 
compositions, for example, colorless nail enamels frequently experience 
some alteration and turn yellow after prolonged exposure to light. 
Thus it has been found that such cosmetic compositions, colored or 
colorless, can be preserved in storage only for a certain limited period 
of time, generally in the order only of a few weeks. To overcome these 
disadvantages, it has been proposed to incorporate in these compositions a 
compound capable of filtering light rays. Such a compound, however, must 
not only exhibit good filtering characteristics, but also good stability 
and a sufficient degree of solubility in the vehicles conventionally 
employed in these cosmetic compositions. The present invention now 
provides new compounds having these different criteria which effectively 
overcome the disadvantages noted above. 
Thus it is an object of the present invention to provide a compound of the 
formula 
##STR2## 
wherein R represents a member selected from the group consisting of 
hydrogen; halogen such as Cl or F; and alkyl containing 1-4 carbon atoms; 
R' and R" each independently represent a member selected from the group 
consisting of hydrogen and SO.sub.3 M wherein M represents a member 
selected from the group consisting of hydrogen, organic ammonium group and 
a metal, at least one of R' and R" being other than hydrogen, and R" is a 
substituent at the para or meta position relative to the bornylidene ring. 
The compounds of formula (I) wherein R" is SO.sub.3 M are prepared by 
reacting a compound of the formula 
##STR3## 
wherein R and R' have the meanings given above with concentrated sulfuric 
acid, or oleum or chlorosulfonic acid. 
The compounds of formula (II) in turn can be prepared according to the 
Haller method which consists in condensing an aromatic aldehyde on the 
sodium salt of camphor, the latter being prepared by reacting camphor with 
sodium or a strong base such as sodium amide, sodium hydride or a sodium 
alcoholate. The reaction to produce compounds of formula (II) is 
preferably performed in an inert solvent such as benzene, toluene or 
ether, and there are selected as the initial reactants an aldehyde and a 
camphor derivative suitable for obtaining the desired compound. 
It is also an object of the invention to provide compounds of formula (II) 
in which R' represents SO.sub.3 M or when R' represents hydrogen R 
represents a member selected from the group of fluorine and alkyl 
containing 2-4 carbon atoms. 
The metallic and ammonium salts of formula (I), i.e., the compounds for 
which R' and/or R" have the value SO.sub.3 M, wherein M is other than 
hydrogen can be isolated directly from the reaction medium by treatment 
with an inorganic base or with a metallic salt such as a sulfate or 
chloride. These metallic salts can also be obtained easily according to 
the usual processes by neutralization of the corresponding sulfonic acid 
with an inorganic base such as a hydroxide, a carbonate or a metallic 
alcoholate, or alternatively with an organic base such as a primary, 
secondary or tertiary amine, a quaternary ammonium hydroxide, or an amino 
acid with a basic character. 
Finally, the ammonium salts of formula (I) can also be prepared by cation 
exchange between a quaternary ammonium halide and the corresponding 
sulfonic acid of formula (I) which can, if desired, be employed in the 
form of its sodium salt. 
Representative metallic salts of sulfonic acids of formula (I) include, for 
instance, the sodium, potassium, lithium, calcium, magnesium and zinc 
salts. Representative organic bases that can be used to prepare an organic 
ammonium salt of formula (I) include, for instance, monoethanolamine, 
diethanolamine, triethanolamine, 2-amino-2-methyl propanol, 
2-amino-2-methyl-1,3-propanediol, triisopropanolamine, lysine and 
arginine. 
Representative compounds of the present invention include, for instance: 
(1) 4-(2-oxo-3-bornylidene methyl) benzene sulfonic acid, 
(2) sodium 4-(2-oxo-3-bornylidene methyl) benzene sulfonate, 
(3) magnesium 4-(2-oxo-3-bornylidene methyl) benzene sulfonate, 
(4) calcium (4-(2-oxo-3-bornylidene methyl) benzene sulfonate, 
(5) 4-(2-oxo-3-bornylidene methyl) benzene sulfonate of bis(2-hydroxy 
ethyl) ammonium, 
(6) 4-(2-oxo-3-bornylidene methyl) benzene sulfonate of 
(1,3-dihydroxy-2-methyl-2-propyl) ammonium, 
(7) 2-methyl-5-(2-oxo-3-bornylidene methyl) benzene sulfonic acid, 
(8) potassium salt of 2-methyl-5-(2-oxo-3-bornylidene methyl) benzene 
sulfonic acid, 
(9) sodium 2-methyl-5-(2-oxo-3-bornylidene methyl) benzene sulfonic acid, 
(10) 4-(2-oxo-3-bornylidene methyl) benzene sulfonate of 5-amino-5-carboxy 
pentylammonium, 
(11) 2-chloro-5-(2-oxo-3-bornylidene methyl) benzene sulfonic acid, 
(12) sodium 2-chloro-5-(2-oxo-3-bornylidene methyl) benzene sulfonic acid, 
(13) 2-chloro-5-(2-oxo-3-bornylidene methyl) benzene sulfonate of 
tris-(2-hydroxy ethyl) ammonium, 
(14) 3-benzylidene-2-oxo-10-bornane sulfonic acid, 
(15) sodium 3-benzylidene-2-oxo-10-bornane sulfonic acid, 
(16) 2-chloro-5-(2-oxo-3-bornylidene methyl) benzene sulfonate of 
tetradecyl trimethylammonium, 
(17) 4-(2-oxo-3-bornylidene methyl) benzene sulfonate of benzyl dimethyl 
hexadecylammonium, 
(18) 2-methyl-5-(2-oxo-3-bornylidene methyl) benzene sulfonate of dodecyl 
pyridinium, 
(19) 4-(2-oxo-3-bornylidene methyl) benzene sulfonate of 4-amino-4-carboxy 
butyl guanidinium and 
(20) 2-methyl-5-(2-oxo-3-bornylidene methyl) benzene sulfonate of 
(1-hydroxy-2-methyl-2-propyl) ammonium. 
The compounds of formula (I) exhibit like 3-benzylidene camphor and 
3-(4-methyl benzylidene) camphor designated respectively as compounds III 
and IV, the property of providing remarkable protection to the human skin 
in the erythematous zone, i.e., in the range of wave lengths of 280 to 315 
millimicrons, while at the same time allowing the passage of light rays of 
wave lengths greater than 315-320 millimicrons, thus providing selective 
protection as it appears in the attached figure. The compounds of the 
present invention offer the considerable advantage of having solubility 
properties that are clearly improved relative to compounds III and IV 
mentioned above, particularly in aqueous solutions in which these latter 
are insoluble, in hydroalcoholic solutions and in ethanol. 
The attached FIGURE, in which the abscissa indicates the wave lengths in 
millimicrons and the ordinate indicates the transmission, in percentage of 
radiations considered, represents the transmission curves 2, 9, 15, III 
and IV of the following compounds dissolved at a rate of 0.08 millimoles 
of active product in ethanol: 
Compound 2: sodium 4-(2-oxo-3-bornylidene methyl) benzene sulfonate, 
Compound 9: sodium salt of 2-methyl-5-(2-oxo bornylidene methyl) benzene 
sulfonic acid, 
Compound 15: sodium salt of 3-benzylidene-2-oxo-10-bornane sulfonic acid, 
Compound III: 3-benzylidene camphor and 
Compound IV: 3-(4-methyl benzylidene) camphor. 
It can be clearly seen that the curves relative to compounds 2, 9 and 15 
broadly cover the zone of 280 to 315 millimicrons. 
Solubilities were determined in grams of product in 100 ml of solvent 
represented by water, ethanol and a 50:50 water-ethanol solution for 
compounds 1 to 7, 9, 14 and 20, and for 3-benzylidene camphor and 
3-(4-methyl benzylidene) camphor, designated respectively as III and IV. 
The following table indicates the results obtained. 
______________________________________ 
Water-Ethanol 
Compound Water Ethanol (50:50) 
______________________________________ 
III Insol. 14% .ltoreq.0.5% 
IV Insol. 20% &lt;0.1% 
1 100% &gt;100% 100% 
2 5% 0.5% 14% 
3 0.1% 20% 20% 
4 0.2% 14% 10% 
5 25% 25% 50% 
6 17% 1% 33% 
7 4% 50% 100% 
9 10% 3% 25% 
14 50% 100% 100% 
20 50% 33% 50% 
______________________________________ 
The association of the properties demonstrated by the transmission curve, 
on the one hand, and by the table of solubilities, on the other, makes it 
possible to appreciate in a particularly advantageous way the problems and 
especially the limits of formulation imposed by the use of compounds III 
and IV, because of their insolubility in an aqueous and hydroalcoholic 
medium. 
The present invention also has for an object a cosmetic composition, stable 
in regard to light radiations, thus assuring a protection in the range of 
wave lengths of 280 to 315 millimicrons, but selectively permitting the 
passage of rays above 315 millimicrons to obtain, under the best 
conditions, a tanning free of erythema. This composition contains as the 
agent for protection from light radiations at least one compound of the 
formula: 
##STR4## 
wherein R, R' and R" have the meanings given above. 
This composition can be a solution in the form of a lotion, an emulsion in 
the form of a cream, gel, foam or milk, and generally in all the forms of 
the usual cosmetic compositions. The composition can also contain cosmetic 
adjuvants such as thickeners, softeners, superlubricants, emollients, 
wetting agents, surfactants, preservatives, antifoam agents, perfumes or 
any other compatible component usually employed in cosmetics. Finally, the 
composition of this invention can also contain one or more propellants and 
be packaged under pressure in an aerosol bomb or container. 
The composition of the present invention contains 0.5 to 10% by weight of 
the compound of formula (I). Representative solvents that can be used 
include water, lower mono- and polyalcohols and their mixtures or hydro- 
and oleo-alcoholic solutions. The alcohols employed are, preferably, 
ethanol, isopropyl alcohol, propyleneglycol, glycerol and sorbitol. 
Hydroalcoholic mixtures that can be used preferably are mixtures of water 
and ethyl alcohol wherein ethyl alcohol is present in amounts of about 
10-70 percent by weight of said mixture. 
The anti-solar composition can be either colorless or colored with dyes 
and/or pigments usually employed in such compositions, particularly, iron 
oxides in amounts of about 0.001% to 0.05% by weight of the total weight 
of the composition. 
The present invention also relates to a cosmetic composition whose 
components are protected from light radiations by the presence of a 
compound of formula (I) present in an amount of 0.05 to 5% by weight, 
especially when the said composition contains one or more compounds 
particularly sensitive to ultraviolet rays. Representative of such 
sensitive compounds are photosensitive dyes used in amounts of about 
0.001% to 0.05% of the total weight of the composition, and 
triphenylmethane derivatives such as crystal violet, methyl violet, methyl 
green or Victoria blue BSA. 
In addition to the photosensitive dye or dyes and the compound of formula 
(I), such a composition can also contain a cosmetic film-forming resin, a 
foaming agent, perfume and other such cosmetic adjuvants. 
Representative cosmetic film-forming resins are those having generally a 
molecular weight ranging from 10,000-700,000 or even higher. 
Representative cosmetic film-forming agents that can be employed, 
generally in amounts of 0.5-5 weight percent include polyvinylpyrrolidone 
having a molecular weight of about 10,000 to 700,000, copolymer of 
vinylpyrrolidine/vinyl acetate, 70%/30% to 30%/70% having a molecular 
weight of 40,000-400,000, copolymer of vinyl acetate and an unsaturated 
carboxylic acid such as a copolymer containing 90% vinyl acetate and 10% 
crotonic acid having a molecular weight of 45,000 to 70,000; terpolymer of 
methyl methacrylate (15-25%)/stearyl methacrylate (18-28%) and dimethyl 
methacrylate (52-62%), and particularly in the proportions of 20%/23%/57%, 
respectively, and vinyl acetate (75-85%)/allyl stearate 
(10-20%)/allyloxyacetic acid (3-10%) terpolymer, particularly in 
proportions of 80%/15%/5%, respectively, copolymer of maleic anhydride and 
methylvinylether in a molar ratio of preferably 1:1 and having a specific 
viscosity between 0.1-3.5 when measured at 25.degree. C. and at a 
concentration of 1 g in 100 cc of methylethyl ketone, and the 
monoethylester, monoisopropylester of monobutylester of said maleic 
anhydride, methyl vinyl ether copolymer and copolymer of maleic anhydride 
and butyl vinyl ether. 
Representative examples of cosmetic compositions containing a compound of 
formula (I) either to protect the photosensitive dye contained in the 
composition or to avoid their yellowing, include capillary compositions 
such as hair lacquers, plastifying hair setting lotions, hair treating or 
disentangling setting lotions, shampoos, dye shampoos, hair dye 
compositions, fingernail polishes, skin treating creams and base makeups. 
These compositions can thus be packaged and stored without any risk of 
alteration, in transparent glass or plastic containers. 
Further, the compositions of the present invention can also be provided in 
the form of an aerosol and be packaged under pressure in an aerosol 
container together with one or more conventional aerosol propellants such 
as those known as "Freon" and particularly dichlorodifluoromethane, 
trichloromonofluoromethane and mixtures thereof. 
The present invention also has for an object a process for protecting 
cosmetic compositions capable of being altered or degraded by light rays 
which comprises incorporating into these compositions at least one 
compound of formula (I) in an amount of 0.05 to 5% by weight of said 
composition.

The following non-limiting examples in which the percentages unless 
otherwise indicated are by weight will give a better understanding of the 
present invention. 
EXAMPLES OF PREATION 
Example 1 
Preparation of 4-(2-oxo-3-bornylidene methyl) benzene sulfonic acid. 
120 g of benzylidene camphor (0.5 mole) are added with stirring to 320 ml 
of oleum containing 20% SO.sub.3, the rate of addition being regulated so 
that the temperature does not exceed 50.degree. C. The stirring is 
continued for an hour at ambient temperature. The reaction mixture is then 
slowly poured into 200 ml of ice water and the above sulfonic acid 
precipitates on cooling. After allowing to stand for several hours at 
0.degree. C., the precipitate is filtered, then dissolved in 50 ml of 
water and reprecipitated by addition of 25 ml of concentrated hydrochloric 
acid. After filtering and drying in a dessicator in the presence of 
potash, 104 g of a white powder melting at 100.degree. C. are obtained. 
This product contains 1.5 moles of crystallization water. 
When left in air, the product fixes an additional 1.5 moles of water, the 
resulting compound thus obtained having the formula C.sub.17 H.sub.20 
SO.sub.4.3H.sub.2 O and the following characteristics: 
Mol. weight=374 
Acid value=2.68 meq/g 
Theory 2.67 meq (Milliequivalent/g) 
Elementary analysis: Calculated % C: 54.54, H: 6.95, S: 8.55; Found %: C: 
54.79, H: 6.84, S: 8.65. 
Example 2 
Preparation of sodium4-(2-oxo-3-bornylidene methyl) benzene sulfonate 
To a solution of 50 g of acid prepared according to example 1, in 100 ml of 
water, there are added 7.1 g of anhydrous sodium carbonate. The 
precipitate obtained is filtered and recrystallized in an 80:20 
water-acetone mixture. There are obtained 43 g of white flakes having a 
melting point of 240.degree. C. 
After prolonged drying on phosphoric anhydride, a determination of water 
indicates the presence of 2 moles of crystallization water. When left in 
the air, the salt fixes one additional mole of crystallization water. 
Example 3 
Preparation of magnesium 4-(2-oxo-3-bornylidene methyl) benzene sulfonate 
of the formula 
##STR5## 
The reaction mixture obtained by reacting 12 g of benzylidene camphor and 
32 ml of oleum with 20% SO.sub.3 in accordance with the procedures 
outlined in example 1 is poured into a saturated magnesium chloride 
solution. After crystallization in a mixture of water and acetone, 7.3 g 
of white-beige flakes, melting at a temperature above 360.degree. C., are 
collected. 
A determination of water indicates the presence of 8 moles of 
crystallization water. 
Of course, in the case of a metal with "n" valence in place of magnesium, 
the developed formula would comprise "n" radicals of [4-(2-oxo 
3-bornylidene methyl) benzene sulfonate]. 
Example 4 
Preparation of calcium 4-(2-oxo-3-bornylidene methyl) benzene sulfonate 
Calcium hydroxide is added, until a basic pH is reached, to a solution 
containing 7.48 g of acid prepared according to example 1 in 15 ml of 
water. The precipitate is filtered and recrystallized in 80 ml of water. 
Thus, 5.8 g of a whitish crystalline powder, retaining 5 moles of water 
per mole of sulfonate, and having a melting point above 360.degree. C., 
are obtained. 
Example 5 
Preparation of 4-(2-oxo-3-bornylidene methyl) benzene sulfonate of 
bis-(2-hydroxy ethyl) ammonium 
While stirring, 1.05 g of diethanolamine are added to an aqueous solution 
(10 ml) of 3.74 g of the acid prepared according to Example 1. After 
evaporation to dryness, a light yellow powder, melting at 85.degree. C., 
is obtained. The salt obtained retains a mole of water and has the 
empirical formula 
EQU C.sub.21 H.sub.31 NO.sub.6 S.H.sub.2 O 
Elementary analysis: Calculated %: C: 56.86, H: 7.50, N: 3.16, S: 7.23; 
Found %: C: 56.48, H: 7.38, N: 3.08, S: 7.51. 
Example 6 
Preparation of sodium 2-methyl-5-(2-oxo-3-bornylidene methyl) benzene 
sulfonate 
25.4 g of 3-p-tolylidene camphor are added to 64 ml of oleum containing 10% 
SO.sub.3, with cooling so as to keep the temperature of the reaction 
mixture around 35.degree. C. The resulting mixture is then poured into 150 
ml of a saturated sodium chloride solution, the mixture being cooled to 
below 25.degree. C. A precipitate is obtained which is filtered and then 
washed with a saturated sodium chloride solution. The wet product is made 
into paste in 70 ml of water. It is then filtered and recrystallized in an 
80:20 water-acetone mixture. Thus, 29.3 g of a white powder, melting at 
240.degree. C. are obtained. 
After drying in a dessicator on phosphoric anhydride, a determination of 
water indicates the presence of 2 moles of crystallization water. 
Example 7 
Preparation of 2-methyl 5(-2-oxo-3-bornylidene methyl) benzene sulfonic 
acid 
To 8.65 g of sodium salt, prepared according to Example 6 and dissolved in 
125 ml of water, there are added 62.5 ml of concentrated hydrochloric 
acid. The precipitate obtained is filtered and dried on potash to obtain 8 
g of a white powder. 
This product, crystallized with two moles of water, melts at 130.degree. C. 
It has the formula C.sub.18 H.sub.22 SO.sub.4.2 H.sub.2 O and a molecular 
weight of 370. 
Acid value: 2.63 meq/g (theory: 2.64 meq/g) 
Elementary analysis: Calculated %: C: 58.38, H: 7.03, S: 8.65; Found %: C: 
58.38, H: 6.84, S: 8.62. 
Example 8 
Preparation of sodium 3-benzylidene-2-oxo-10bornane sulfonate 
A mixture of 37 g of anhydrous camphosulfonic acid and 173 g of sodium 
methylate in 600 ml of toluene is heated for 1 hour at reflux with 
stirring. After cooling to ambient temperature, 16.95 g of benzaldehyde 
are added with stirring. The resulting mixture is heated for 3 hours at 
reflux and then cooled to ambient temperature at which time there are 
added thereto 150 ml of water with good stirring. The resulting 
precipitated is filtered, dried, and then recrystallized in 200 ml of 
water to obtain, after drying in a dessicator, white flakes (40.55 g) 
melting at 230.degree. C. 
The sodium salt thus obtained contains 0.5 mole of water per mole. When 
left in the air, it stabilizes after having fixed about 3 moles of 
crystallization water. 
Example 9 
Preparation of 3-benzylidene-2-oxo-10-bornane sulfonic acid 
20 g of the sodium salt of Example 8 are dissolved with heating in 200 ml 
of water. 100 ml of concentrated hydrochloric acid are then added with 
stirring. The precipitate obtained is filtered and dried in a dessicator 
in the presence of potash and phosphoric anhydride. Thus, 15.3 g of a 
white powder, melting at 124.degree. C., are obtained. This product 
contains a mole of crystallization water. 
Acid value: (theory: 2.96 meq/g); found 2.95 meq/g 
When left in air, this compound fixes another mole of water to give the 
empirical formula: C.sub.17 H.sub.20 O.sub.4 S.2 H.sub.2 O; (molecular 
weight: 356). 
Acid value: 2.82 meq/g; theory: 2.81 meq/g 
Elementary analysis: Calculated %: C: 57.30, H: 6.74, S: 9.07; Found %: C: 
57.02, H: 6.62, S: 8.99. 
Example 10 
Preparation of sodium 2-chloro-5-(2-oxo-3-bornylidene methyl) benzene 
sulfonate 
There are added, by portions, 274.5 g of 3-p-chlorobenzylidene camphor to 
1000 ml of oleum containing 20% by weight of SO.sub.3, while maintaining 
the well stirred mixture at a temperature below 50.degree. C. When the 
addition has been completed, the resulting reaction mixture is poured into 
3 liters of a saturated solution of sodium chloride, while cooling the 
same. The precipitate formed is filtered and washed with a saturated 
solution of sodium chloride, then with a little cold water. There are thus 
obtained 215 g of a whitish powder melting at 260.degree. C. 
Determination of water, by the Fischer method, indicates the presence of 3 
moles of crystallization water. 
Example 11 
Preparation of 2-chloro-5-(2-oxo-3-bornylidene methyl) benzene sulfonic 
acid 
The salt produced in Example 10 is treated in accordance with the 
procedures described in Example 7. An oil, which crystallizes slowly, is 
obtained. 
The product thus produced (yield=90%) melts at 140.degree. C. The acid 
value and determination of water by the Fischer method indicate the 
presence of 4 moles of crystallization water. 
Acid value: Calculated 2.35 meq/g; Found 2.36 
Water: Calculated % 16.9; Found % 16.9 
Example 12 
Preparation of 4-(2-oxo-3-bornylidene methyl) benzene sulfonate of 
1,1-bis(hydroxymethyl) ethylammonium 
The procedures outlined in Example 5 are followed except that the 
diethanolamine is replaced by 2-amino-2-methyl propane-1,3-diol. There is 
thus obtained a white powder, melting at 145.degree. C., the solubility of 
which is 17% by weight in water and 33% by weight in ethanol at 50.degree. 
C. 
Elementary analysis: C.sub.21 H.sub.31 NO.sub.6 S-- Calculated %: C: 59.29, 
H: 7.29, N: 3.29, S: 7.53; Found %: C: 59.33, H: 7.04, N: 3.38, S: 7.62. 
Example 13 
Preparation of sodium 3-p-tolylidene-2-oxo-10-bornane sulfonate 
The procedures outlined in Example 8 are repeated except that the 
benzaldehyde is replaced by p-tolualdehyde. 
The above product is obtained in the form of light yellow crystals (yield 
74%), melting at 190.degree. C. Analysis indicates the presence of 3.5 
moles of crystallization water. 
Example 14 
Preparation of 3-p-tolylidene-2-oxo-10-bornane sulfonic acid 
The sodium 3-p-tolylidene-2-oxo-10-bornane sulfonate produced in Example 13 
is treated in accordance with the procedures outlined in Example 9. The 
product obtained contains 1 mole of crystallization water and melts at 
220.degree. C. 
Acid value: Calculated 2.82 meq/g; Found 2.82 meq/g 
Elementary analysis=C.sub.18 H.sub.24 O.sub.4 S.H.sub.2 O-- Calculated %: 
C: 61.36, H: 6.82, S: 9.09; Found %: C: 61.76, H: 6.83, S: 9.11. 
Example 15 
Preparation of 4-methyl-5-(2-oxo-3-bornylidene methyl) benzene sulfonic 
acid having the formula 
##STR6## 
25.4 g of 3-o-methylbenzylidene camphor are dissolved with stirring in 84 
ml of oleum containing 20% by weight SO.sub.3 with cooling so as to 
maintain the temperature below 25.degree. C. Stirring of the resulting 
reaction mixture is continued for an additional 30 minutes at ambient 
temperature at which time it is poured into 200 ml of crushed ice. The 
precipitate which forms is filtered and crystallized in 100 ml of acetone 
to produce white crystals melting at 130.degree. C. and corresponding to 
the dihydrate. 
Acid index: Calculated 2.70 meq/g; Found 2.74 meq/g 
Elementary analysis: C.sub.18 H.sub.22 O.sub.4 S.2H.sub.2 O-- Calculated, 
%: C: 58.38, H: 7.03, S: 8.65; Found, %: C: 58.36, H: 6.97, S: 8.46. 
Example 16 
Preparation of zinc 4-(2-oxo-3-bornylidene methyl) benzene sulfonate of the 
formula 
##STR7## 
37.4 g of 4-(2-oxo-3-bornylidene methyl) benzene sulfonic acid trihydrate 
and 6.3 g of zinc carbonate are heated in 250 ml of water until 
dissolution occurs. The resulting solution is then filtered. The above 
zinc salt which precipitates on cooling is filtered and then crystallized 
in 400 ml of water. 64.5 g of white crystals are recovered, melting at 
250.degree. C. 
Determination of water by the Fischer method reveals the presence of 9.5% 
water, i.e. 4 moles of crystallization water. 
Acid index: Calculated 2.57 meq/g; Found 2.54 meq/g 
Example 17 
Preparation of 4-(2-oxo-3-bornylidene methyl) benzene sulfonate of 
4-amino-4-carboxy butyl guanidinium 
18.7 g of 4-(2-oxo-3-bornylidene methyl) benzene sulfonic acid and 8.7 g of 
arginine are dissolved in water (75 ml). The resulting solution is 
evaporated to dryness under a vacuum. The residue is ground in a little 
sulfuric ether and then filtered, yielding thus 25.6 g of a whitish powder 
melting at 265.degree. C. 
Amine Index: Calculated 2.03 meq/g; Found 2.05 meq/g 
Elementary Analysis: C.sub.23 H.sub.34 N.sub.4 O.sub.6 S-- Calculated, %: 
N: 11.33, S: 6.48; Found, %: N: 11.10, S: 6.55. 
EXAMPLES OF COMPOSITIONS 
The compounds of formula (I) can be incorporated directly either in a 
composition for protecting human skin against solar radiations or in a 
composition containing components sensitive to light. When the compounds 
of formula (I) are in the form of sulfonic acids, i.e. with R and/or R' 
being equal to SO.sub.3 H, they can easily be neutralized to the desired 
pH with an organic or inorganic base, selected as a function of its 
particular cosmetic properties and the desired solubility of the resulting 
compound. 
ANTISOLAR COMPOSITIONS 
Example A 
An antisolar lotion is prepared by admixing the following components: 
______________________________________ 
Lanolin 2.5 g 
Butylhydroxyanisole 0.025 g 
Butylhydroxytoluene 0.025 g 
Octyl gallate 0.0125 g 
Triglycerides of fatty acids having 
8-12 carbon atoms 40 g 
Perfume 1.25 g 
3-benzylidene-2-oxo-10-bornane 
sulfonic acid 4 g 
Ethyl alcohol, 96.degree. titer, q.s.p. 
100 g 
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Example B 
An antisolar lotion is prepared by admixing the following components: 
______________________________________ 
Glycerin 5 g 
Polyethylene glycol (MW = 400) 
0.5 g 
Ethoxylated lanolin 1 g 
Soluble perfume 2 g 
Sodium 2-methyl-5-(2-oxo-3-bornylidene 
methyl) sulfonic acid 2 g 
Ethyl alcohol, 96.degree. titer 
50 g 
Water, q.s.p. 100 g 
______________________________________ 
Example C 
An antisolar aerosol spray is prepared by admixing the following components 
and packaging the same under pressure in an aerosol container: 
______________________________________ 
Absolute ethyl alcohol 30 g 
Isopropyl myristate 20 g 
Castor oil 2 g 
Lanolin 5 g 
Perfume 1 g 
Magnesium-4-(2-oxo-3-bornylidene 
methyl) benzene sulfonate 
2 g 
Dichlorodifluoromethane 40 g 
______________________________________ 
Example D 
An antisolar aerosol foam is prepared by admixing the following components 
and packaging the same under pressure in an aerosol container: 
______________________________________ 
Sipol wax 3.5 g 
Vaseline oil 6 g 
Isopropyl myristate 3 g 
Preservative - "Nipa ester 82521" (mixture of 
methyl, ethyl, butyl and benzyl esters 
of hydroxy benzoic acid) 0.3 g 
Glycerin 10 g 
Perfume 0.3 g 
4-(2-oxo-3-bornylidene methyl) benzene 
sulfonate of (1,3-dihydroxy-2-methyl- 
2-propyl) ammonium 2.5 g 
Water, q.s.p. 100 g 
______________________________________ 
To make the aerosol, 87 g of the solution prepared above are admixed with 
13 g of dichlorodifluoromethane. 
Example E 
An antisolar cream is prepared by admixing the following components: 
______________________________________ 
Cetylstearyl alcohol 2 g 
Glycerol monostearate 4 g 
Cetyl alcohol 4 g 
Vaseline oil 5 g 
Butyl stearate 5 g 
Propylene glycol (MW = 400) 
7 g 
Silicone oil 0.125 g 
Ethylene oxide polymer having a 
molecular weight of 100,000- 
1,000,000 - sold under the 
tradename "Polyox" (0.5%) 3.5 g 
Preservative - "Nipa ester 82521" as 
in Example D 0.3 g 
Perfume 0.4 g 
4-(2-oxo-3-bornylidene methyl) benzene 
sulfonate of bis(2-hydroxy ethyl) 
ammonium 4 g 
Water, q.s.p. 100 g 
______________________________________ 
Example F 
An antisolar milk is prepared by admixing the following components: 
______________________________________ 
Sipol wax 5 g 
Vaseline oil 6 g 
Isopropyl myristate 3 g 
Silicone oil 1 g 
Cetyl alcohol 1 g 
Glycerin 20 g 
Preservative - "Nipa ester 82521" 
as in Example D 0.3 g 
Perfume 0.3 g 
2-methyl-5-(2-oxo-3-bornylidene methyl) 
benzene sulfonate of (1,3-dihydroxy- 
2-methyl-2-propyl) ammonium 
3 g 
Water, q.s.p. 100 g 
______________________________________ 
PRESERVATION OF COLORED PRODUCTS 
Example G 
A colored hair setting lotion for live human hair is prepared by admixing 
the following components: 
______________________________________ 
4-(2-oxo-3-bornylidene methyl) 
benzene sulfonic acid 0.2 g 
Vinylpyrrolidone-vinyl acetate copolymer, 
70%/30% MW = 40,000 2 g 
Victoria blue BSA dye, C.I. 44045 
0.001 g 
Ethyl alcohol 50 g 
Triethanolamine, q.s.p. pH 7 
Water, q.s.p. 100 ml 
Example H - A colored setting lotion is prepared by admixing 
the following components: 
2-methyl-5-(2-oxo-3-bornylidene methyl) 
benzene sulfonic acid 0.2 g 
Crotonic acid-vinyl acetate copolymer 
10%/90%, MW = 50,000 having a 
viscosity of 7-9 cps at 35.degree. C. in 
a 5% solution of tetrachloroethane 
2 g 
C.I. Basic Violet No. 3, C.I. 42555 
0.01 g 
Ethyl alcohol 50 g 
Triisopropanolamine, q.s.p. pH 7 
Water, q.s.p. 100 ml 
______________________________________ 
Example I 
A colored setting lotion is prepared by admixing the following components: 
______________________________________ 
2-methyl 5(-2-oxo-3-bornylidene methyl) benzene 
sulfonic acid 1.5 g 
Polyvinyl pyrrolidone K 30 3 g 
methyl violet C.I. 42535 0.005 g 
Ethyl alcohol 20.0 g 
Triethanolamine q.s.p. pH 8 
Water q.s.p. 100 cc 
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