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Патент USA US3030285

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United States Patent O?ice
Patented Apr. 17, 1962
radiation by ultraviolet irradiation, and which do not
stain either the person or the clothing of the user, hav
ing the following structural formulae:
Saui hKreps, Cedar Grove, Ernst Ohisson, Summit, and
Daniel Epstein, Union, Ni, assiguors to Van Dyk &
Company, Inc, Believiiie, Ni, a corporation of New
wherein Z is a member of a group consisting of 0X
and NY2, and when Z is OX, X represents hydrogen,
alkali metal, alkaline earth metal, and NH,, and when
10 Z is NY2 Y represents hydrogen, alkyl groups having 1
The present invention is directed to compositions for
to 8 carbon atoms, and hydroxyl alkyl groups wherein
topical application, .and more particularly to those ap
the alkyl groups have 2 to 3 carbon atoms.
plicable as sun-screening agents against ultra-violet rays.
Among the esters which are eifective are those in which
The use of sun-screening compounds in sun protective
the 1,2 ~diphenylethylene- l -carboxylic acid has been
preparations is well understood. The function of the
esteri?ed by ethyl alcohol, isopropyl alcohol, isobutyl a1
sun screen is to absorb practically all of the erythemato
cohol, methyl alcohol, glycols' or glycerol. The amides
genie radiation found in sunlight before it strikes the
which are effective include the simple amide, and nitro
No Drawing. Filed Mar. '50, 1959, Ser. No. 302,663
2 Ciaims. (Cl. 167—%)
skin of the user. This erythematogenic radiation is a
gen-substituted amides. The free acid itself is also an
portion of the electromagnetic radiation of the sun, and
effective and stable sun-screen.
extends, in the ultraviolet range from wave lengths of 20
For example, the spectrophotometric measurement of
approximately 290 millimicrons to a wavelength of ap
the extinction coefficient of ethyl-1,2-diphenylethylene-1
proximately 320 millimicrons. Ultraviolet radiation of
carboxylate indicates that a 3 percent concentration of
Wavelenght shorter than 290 millimicrons is absorbed by
this material in a solution or a lotion would be ade
the earth’s atmosphere and does not reach the surface
quate to provide protection against painful erythema.
of the earth in sui‘?cient quantity to have an erythemato 25 This is substantiated by skin tests, for when a 3 percent
genie effect. Wavelengths above 320 millimicrons do
(by weight) solution of the ethyl-1,2-diphenylethylene
not have an appreciable erythematogenic effect, and
l-carboxylate is applied to normal human skin and the
hence need not be screened from the human skin in
skin is exposed to the ultraviolet radiation of mid-day,
order to prevent painful sunburn. On the contrary these
mid-summer sunlight for four hours, no painful sun
higher wavelengths result in melanin formation leading 30 burn, and no perceptible erythema results. The same
to a desirably tanned skin.
diphenylethylene) is a very effective sun-screening com
efficient protection is afforded by solutions of, for in
stance, the isobutyl ester, the methyl ester, the simple
amide, the ammonium salt, the sodium salt and the po
pound in the desired erythematogenic range. It has been
tassium salt, as Well as by a solution of the free acid
It has long been known that trans-stilbene (trans-1,2
found, however, that trans-stilbcne is readily and rapidly 35
converted by ultraviolet irradiation to the cis-stilbene
isomer, which is not a good absorber of the erythemato
genie radiation. This ready interconversion of the trans~
stilbene to the cis-stilbene renders the former material
It is to be understood that the concentrations of choice
of the sunscreens herein described are not limited to 3%
solutions or lotions. Depending upon the normal re
sponse range of human skin to sunlight, and depending
unsuitable for use in cosmetic sun screen preparations. 40 upon the amount of protection desired, the effective con
According to spectrophotometric measurement of the ex
centrations of the sunscreens may be varied over a rela
tinction coe?icient of trans-stilbene, 2 percent of this
tively wide range. Thus, where less protection and
more rapid tanning is desired, concentrations below 3%
concentration to afford protection to the average human
would be preferred, say .5% to 1.5%. ‘Conversely,
skin against the development of a painful erythema. 45 where tanning is not desired, or for use by humans
However, this observation is not substantiated by actual
extraordinarily sensitive to sunlight, concentrations above
material in a solution or lotion should be a sufficient
use tests.
Thus, when a lotion containing 2 percent
3% would be preferred, even up ‘to 6%—8%.
by weight of trans-stilbcne is placed on the skin, and
The 1,2-diphenylethylene-l-carboxylic acid may be
the skin is exposed to the ultraviolet radiation of mid
made in a variety of ways known to the art. For ex
day, midsummer sunlight for four hours, a painful sun 50 ample, in a 200 cc. round bottomed ?ask, 17.4 g. (0.10
burn results.
mole) of dry potassium phenylacetate, 5 g. of dry p04
The present invention is intended and adapted to over
tassium carbonate (0.035 mole), 0.5 cc. pyridine, 10.6
come the de?ciencies of prior preparations of the type
g. (0.10 mole) freshly distilled benzaldehyde, and 15.3
described, it being among the objects thereof to pro
g. (0.15 mole) freshly distilled acetic anhydride are
duce a series of eitective sun-screening compounds which 55 mixed thoroughly under nitrogen. An air-cooled re?ux
are derivatives of trans-stilhene.
condenser is attached and the ?ask is carefully inserted
It is also among the objects of the invention to so
in an oil bath at 180° C. A vigorous bubbling takes
design the structure of the compounds that the effective
place for a few minutes, after which the reaction pro
trans-isomers of the stilbene derivatives shall be stable
ceeds quietly. Heating is continued at 180-190° C. for
to ultraviolet irradiation and shall not be converted to 60 two hours. The mixture is allowed to cool, and 300~400
the ineffective cis con?gurations.
cc. water is added with gentle heating to break up lumps.
it is a further object of the invention to prepare such
Potassium hydroxide solution (6 N) is added until the
' derivatives which will not, on exposure to light and air,
discolor or form other products which will discolor the
person or the clothing of-the users.
In practicing the present invention it has been found
that salts, esters and amides of 1,2-diphenylethylene-1
carboxylic acid are ef?cient absorbers'ot erythematogenic
ultraviolet radiation, which are themselves stable to it'
solution is basic (about 30 cc. is required), but care
should be taken not to add a large excess of base as the
65 potassium salt of the acid is easily salted out of solution.
The mixture is heated until all soluble material has dis
solved; sorne oily material Will remain undissolved. The
?ask is cooled under the water tap and the solution ex
tracted with 300-400 cc. of ether to remove unchanged
benzaldehyde and a little stilbene (ca. 1 g.). The water
Hydro-Alcoholic Suntan Lotion
Parts by weight
solution is acidi?ed with 6 N hydrochloric acid (15-20
cc. is required), the precipitated acid ?ltered off, and the
?ltrate tested with more acid for completeness of precip
Ethyl alcohol SDA No. 40 ____________________ __ 47
itation. The precipitate is conveniently dried on a porous
plate in a vacuum desiccator. The crude acid melts at
Propylene glycol _____________________________ __
1,2-diphenylethylene carboxylic acid ____________ __
about 160° C. It is recrystallized by dissolving in 50%
Color and perfume (sufficient to suit).
ethanol at boiling temperature and adding Water until the
solution is just cloudy. The solution is cooled very 10
___ 47
slowly, ‘and long needles form gradually. The puri?ed
acid melts at 168—l70° C. (uncor.). The acid obtained
A composition according to Example 2 in which the
sun~screcning agent is partly in the form of its sodium or
potassium salt, or partly in the form of its glyceryl ester.
in this way is the trans-form.
The simple esters of the acid are prepared by direct
esteri?cation of the free acid by the appropriate alcohol 15 Any one or any combination thereof may be substituted,
in the presence of an acid catalyst, such as a minor
amount of sulfuric or p-toluene sulfonic acid. These es
in whole or in part for the free trans-stilbene carboxylic
ters may then be puri?ed by distillation under high
vacuum. The salts are made simply by dissolving the
Emulsi?ed Suntan Lotion
acid in a stoichiometric quantity of the desired basic 20
hydroxide or carbonate dissolved in a suitable quantity
compositions are provided:
of water or other solvent. Upon evaporation of the sol
vent and concentration of the solution, the salt may be
obtained in essentially pure form by crystallization. The
Parts by weight
amides may be prepared by heating the salt of the acid 25 Mineral oil, light ___________________________ -_ 5.3
and the appropriate amine until one molecular equiv
Stearic acid _______________________________ __
alent amount of water is removed from the compound.
Lanolin, anhydrous
The amide which is so formed may be puri?ed by crys
tallization from an appropriate solvent. Another method
is the treatment of the acid chloride with the desired 30
Ethyl ester of 1,2-diphenylethylene-l-carhoxylic acid 3.0
amine to form the amide.
Carbitol __________________________________ _ _
Those esters of mono-, di-, and tri-hydroxy alcohols
having 1 to 4 carbon atoms are particularly satisfactory
as Well as hydroxy alcohols, such as hydroxy ethyl and
dihydroxy propyl obtained from ethylene glycol, glycerol 35
and propylene glycol. For the amines used in making
amides, the aliphatic amines, primary and secondary are
preferable, the alkyl groups being preferably methyl,
ethyl and normal and isopropyl ‘and butyl. For alkanol
amines, the mono- and di-ethanol amines and mono-iso
propanol amines are preferred.
Glycerine _________________________________ _ _
2. 8
___________________________ _ ..
Water ____________________________________ __ 73.2
Sodium alginate ____________________________ __
The lotion is compounded according to the following
Suitable formulations of ‘carriers and sunscreen agents
for the application of these sun-screens to the human
skin can be prepared in a variety of Ways, depending upon
Heat the water and the sodium alginate to 70° C.
Add the glycerine and the triethanolamine. Heat parts
(A) and (C) separately to 70° C. While stirring (A),
the solubility characteristics of the particular derivative of 45 slowly add (C) and continue stirring until cooled to 50°
the 1,2-diphenyl-1-carhoxylic acid which is employed.
C. Heat part (B) to 60° C. and add it slowly to the mix
Thus, the ethyl and isobutyl esters may be dissolved in
ture of (A) and (C). Continue stirring until the lotion
mineral oil and be applied to the skin in this clear, oily
is cooled to 40° (3., add perfume and/or color as de
vehicle. The esters are also soluble in vegetable oils.
sired, and package.
The amides and the glycerol esters are not oil soluble, but 50
The invention is not limited to those derivatives of the
are soluble in alcohol and hydro-alcoholic solution. The
acid that are described herein, nor to the manner in
alcohols which may be used include the ethyl and iso
which the acid or its derivatives are made, or to the man
propyl alcohols which are suitable for application to the
ner in which the derivatives are formulated or dispensed.
skin. The salts of the acids are water soluble, alcohol
The‘ essence thereof is the use of such substances in sun
soluble and hydro-alcohol soluble, and may be incorpo 55 tan lotions to provide long lasting protection afforded
by the stability of said substances as set forth in the ap
tives, and the free acid may be dissolved in appropriate
pended claims.
rated in clear lotions of these media. All of these deriva
solvents and these solutions may be emulsi?ed to form
What is claimed is:
opaque emulsi?ed lotions of the water-in-oil, or the oil
1. A method of protecting the human skin from the
in-water type. The emulsi?ed lotions may either be of 60 effects of exposure to ultraviolet radiation which com
liquid consistency, or of the consistency of heavy pastes
prises providing a cosmetic carrier, incorporating in said
0r creams. The lotions may be designed to be dispensed
carrier a sunscreen agent having the formula
from glass bottles, plastic squeeze bottles, or from aerosol
packages, using any convenient propellant. Similarly, the
clear lotions may also be packaged in a variety of ways. 65
The following are speci?c examples of sun-screening
compositions containing the present compounds:
wherein Z is a member of a group consisting of OX and
Oily Suntan Lotion
NY2, and when Z is OX, X represents hydrogen, alkali
70 metal, alkaline earth metal, and NH4, and when Z is
Parts by weight
NY2, Y represents hydrogen, alkyl groups having 1 to 8
carbon atoms, and hydroxy alkyl groups wherein the
alkyl groups have 2 to v3 carbon atoms, and applying the
Medicinal mineral oil _________________________ __ 97
Ethylcor isobutyl esters of 1,2-diphenylethylene car
boxylic acid _______________________________ __
Color and perfume (sufficient to suit).
above composition to the skin.
2. A method according to claim 1 characterized in that
the amount of said agent in said composition is about
.5 % to 8%.
References Cited in the ?le of this patent
Merkel ______________ __ Jan. 4, 1938
Great Britain _________ __ Sept. 30, 1935
Codington: J. Org. Chem, vol. 17, 1952, pp. 1027
Chem. Abs., vol. 48, 1954, page 11307.
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