CA1185533A - Dialkyl malonates as organic sunscreen adjuvants - Google Patents
Dialkyl malonates as organic sunscreen adjuvantsInfo
- Publication number
- CA1185533A CA1185533A CA000412071A CA412071A CA1185533A CA 1185533 A CA1185533 A CA 1185533A CA 000412071 A CA000412071 A CA 000412071A CA 412071 A CA412071 A CA 412071A CA 1185533 A CA1185533 A CA 1185533A
- Authority
- CA
- Canada
- Prior art keywords
- malonate
- methoxy
- diethyl
- diethyl malonate
- benzal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Abstract
ABSTRACT OF THE DISCLOSURE
Compositions containing an organic sunscreen and particular substituted dialkyl malonates adjuvants therefor are very effective in providing broad spectrum sunscreen protection.
Compositions containing an organic sunscreen and particular substituted dialkyl malonates adjuvants therefor are very effective in providing broad spectrum sunscreen protection.
Description
I~is invention rel.ates -to the use of dialkyl malonates as or~anic sunscreen adjuvants (PM-l) Extensive s-tudies have been made of the ultra-violet radiation of sunlight and skylight reaching the sur-~ace of the earth and the ef~ects of such radiation on the human skin. It has been established that the radiation between 290 n~mometers and 315 nanometers produces sub-stantially all of the burning, or erythemal energy, and a substantial portion of the tanning energy, while the between 315 nanometers and 400 nanometers promotes incident tanning~
The cosmetic industry has divided these spectra into respec-tively W-B, and W-A. The dif~erent intensities and the erythemal and tanning effectiveness of the various wave lengths within these ranges have been established and meth ods have been determined for calculating accurately their effects on normal untanned skin.
Approximately 76% of the physiological tanning potential of sunlight is found in the ultraviolet range between ~90 nanometers and 315 nanometers, the so-called W-B or erythema area' the balance is ~ound in the range between 315 nanometers and 400 nanometers, the so-called W-A tanning area.
Typical organic sunscreenssuch as 2-ethylhexyl para methoxy cinnamate, homomenthyl salicylate, p-amino-benzoic acid and its esters, p-dimethyl amino benzoates, hydroxy and dihydroxy-4-methoxy benzophenones, and ben~al-phthalides provide protection in the ~rythemal W -B area, but lesser protection in the tanning areaO
It is becoming increasingly apparent that ultra-violet in the tanning UV-A area can also have detrimental ~ - :L -3~
effects on skin health, e.g. causing premature aging as well as skin cancer. Accordingly, the need has developed for more effective broad spectrum sunscreens to filter out ~he entire radiation. This need can mean disrupting established formulation prDcedures, with the usual cosmetic oil carriers.
Some malonates have been disclosed as UV
absorbers for industrial uses. Typically they are com-pletely unsuitable for cosmetic purpose in human applications, e.g~ German Patent No~ 1,087,902. A malonate, diethyl p-dimethyl-amino-benzalmalonate has been disclosed in U.S.
Patent No. 3,895,10~ as a conventional UV absorber in a polyamide resin film, but actually provides substantially no protection, even in the burning range.
It has now been found that particular sub-stituted dialkyl malonates provide surprising protection in the tanning area, particularly around 370 nanometers, and are compatible with and adjuvants for organic sunscreens.
This permits of utilizing established formulation procedures.
The adjuvants of this invention are substituted dialkyl malonates in which the R alkyl ~roup has from 1 to 5 carbon atoms as illustrated in the following moiety:
H ~ / COOR
-- C = C
COOR
The efficacy of the dialkyl malonates as adju-vants are determined in a empiric manner. Thus the parti-~~~cularly preferred compounds are p-methoxy benzal diethyl malonate, p-methoxy benzal diisobutyl malonate, cinnamal diethyl malonate, indolal diethyl malollate, fural dietl~
,~ _ ~5~3~
~alonate, and 3,4,5-trimethoxy benzal diethyl malonate. The cinnamal compound is especially effective~
The adjuvants of this invention are prepared by a typical knoevenagel reaction.
~ COOC2H5 R' - C - H + CH2 benzoic acid piperidine ~
H 0 + R' - C = C
R' = aromatic The solids are crystallized from e.g. isopropanol and the liquids are fractionately distilled off under vacuum.
The organic sunscreens with which the adjuvants of this invention are employed are discussed above. A
benzalphthalide may also be used, U.S Patent No. 4,333,920, particularly 4-pentoxybenzalphthalide.
The overall composition adapted for application to the human skin thus comprises a cosmetic oil carrier known to the trade, e.g. mineral, vegetable and animal oils and isopropyl myristate, with an organic sunscreen, and an ad-juvant of this invention~ The sunscreen and the adjuvant are utilized in an amount sufficient to provide the desired pro-tection for the skin. Typical total amounts of sunscreens and adjuvants comprise up to about 10 wt. % of the composi-tion.
This invention, product workup and properties ~-of the composition will be bet-ter understood by re~erence to the following non-limiting examples~
Example 1 A mixture containing 35,' 2,~-dihydroxy~ ethoxy ~ s~
benzophenone and 65% cinnamal diethyl malonate produced a total block when used at a concentration of between 5% to 10% in the final composition.
Exa~le 2 Between 5% - 6% of a mixture containing 50%
The cosmetic industry has divided these spectra into respec-tively W-B, and W-A. The dif~erent intensities and the erythemal and tanning effectiveness of the various wave lengths within these ranges have been established and meth ods have been determined for calculating accurately their effects on normal untanned skin.
Approximately 76% of the physiological tanning potential of sunlight is found in the ultraviolet range between ~90 nanometers and 315 nanometers, the so-called W-B or erythema area' the balance is ~ound in the range between 315 nanometers and 400 nanometers, the so-called W-A tanning area.
Typical organic sunscreenssuch as 2-ethylhexyl para methoxy cinnamate, homomenthyl salicylate, p-amino-benzoic acid and its esters, p-dimethyl amino benzoates, hydroxy and dihydroxy-4-methoxy benzophenones, and ben~al-phthalides provide protection in the ~rythemal W -B area, but lesser protection in the tanning areaO
It is becoming increasingly apparent that ultra-violet in the tanning UV-A area can also have detrimental ~ - :L -3~
effects on skin health, e.g. causing premature aging as well as skin cancer. Accordingly, the need has developed for more effective broad spectrum sunscreens to filter out ~he entire radiation. This need can mean disrupting established formulation prDcedures, with the usual cosmetic oil carriers.
Some malonates have been disclosed as UV
absorbers for industrial uses. Typically they are com-pletely unsuitable for cosmetic purpose in human applications, e.g~ German Patent No~ 1,087,902. A malonate, diethyl p-dimethyl-amino-benzalmalonate has been disclosed in U.S.
Patent No. 3,895,10~ as a conventional UV absorber in a polyamide resin film, but actually provides substantially no protection, even in the burning range.
It has now been found that particular sub-stituted dialkyl malonates provide surprising protection in the tanning area, particularly around 370 nanometers, and are compatible with and adjuvants for organic sunscreens.
This permits of utilizing established formulation procedures.
The adjuvants of this invention are substituted dialkyl malonates in which the R alkyl ~roup has from 1 to 5 carbon atoms as illustrated in the following moiety:
H ~ / COOR
-- C = C
COOR
The efficacy of the dialkyl malonates as adju-vants are determined in a empiric manner. Thus the parti-~~~cularly preferred compounds are p-methoxy benzal diethyl malonate, p-methoxy benzal diisobutyl malonate, cinnamal diethyl malonate, indolal diethyl malollate, fural dietl~
,~ _ ~5~3~
~alonate, and 3,4,5-trimethoxy benzal diethyl malonate. The cinnamal compound is especially effective~
The adjuvants of this invention are prepared by a typical knoevenagel reaction.
~ COOC2H5 R' - C - H + CH2 benzoic acid piperidine ~
H 0 + R' - C = C
R' = aromatic The solids are crystallized from e.g. isopropanol and the liquids are fractionately distilled off under vacuum.
The organic sunscreens with which the adjuvants of this invention are employed are discussed above. A
benzalphthalide may also be used, U.S Patent No. 4,333,920, particularly 4-pentoxybenzalphthalide.
The overall composition adapted for application to the human skin thus comprises a cosmetic oil carrier known to the trade, e.g. mineral, vegetable and animal oils and isopropyl myristate, with an organic sunscreen, and an ad-juvant of this invention~ The sunscreen and the adjuvant are utilized in an amount sufficient to provide the desired pro-tection for the skin. Typical total amounts of sunscreens and adjuvants comprise up to about 10 wt. % of the composi-tion.
This invention, product workup and properties ~-of the composition will be bet-ter understood by re~erence to the following non-limiting examples~
Example 1 A mixture containing 35,' 2,~-dihydroxy~ ethoxy ~ s~
benzophenone and 65% cinnamal diethyl malonate produced a total block when used at a concentration of between 5% to 10% in the final composition.
Exa~le 2 Between 5% - 6% of a mixture containing 50%
2-ethylhexyl-p-dimethylamino benzoate and 50% diethyl cinnamal malonate produced a total block.
Exa~ple 3 Between 5% - 5.5% of a mixture containing 50%
2-ethylhexyl-p-methoxy cinnamate and 50% diethyl cinnamal malonate produced a total block.
Example 4 Between 4.5% - 5% of a mixture containing 25%
4-pentoxy benzalphthalide and 75% diethyl p-methoxy benzal malonate produced a total block.
Example 5 Between 5% - 6% of a mixture containing 30%
diisobutyl p-methoxy benzal malonate and 70% 4-pentoxy benzal phthalide produced a total block.
Example 6 Between 3% - 4% of a mixture containing 50%
p-methoxy benzalphthalide and 50% diethyl fural malonate produced a total block.
Other formulations according to this invention provide similar results.
Substituted derivatives of the adjuvants of this invention can be employed, particularly o~ the cinnamal diethyl malonate.
~ hese examples demonstrate that the materials of this inven~ion in even small ~lantities are e~tremely .~ _ effective adjuvants for organic sunscreens and remedy the short-comings of the latter.
~ s can be seen, mixtures of the materials of this invention, and also the organic sunscreens, can be employed where desired.
The advantages of this invention will be ap-parent to the skilled in the art. Improved, highly effec-tive, novel broad spectrum sunscreen compositions are made available, utilizing a dialkyl malonate.
It will be understood that this invention is not limited to the specific examples which have been offered as particular embodiments, and that modifications can be made without departing from the spirit thereof.
_ , SUPPLEMENT~RY DISCLOSURE
As mentioned in the principal disclosure, partic-ular dialkyl malonates have been found useful as organic sunscreen adjuvants providing effective protection in the tanning area, especially around 370 nanometers~ These partic-ular dialkyl malonates are p~methoxy benzal diethyl malonate, p-methoxy benzal diisobutyl malonate, cinnamal diethyl malonate, indolal diethyl malonate, fural diethyl malonate and 3,4,5 trimethoxy benzal diethyl malonate.
It has now been further found that a substituted cinnamal diethyl malonate is especially useful in the present invention. This additional compound is diethyl-~ methyl cinnamal malonate having the following structural formula:
CH = C - CH = C \
CH3 COOC2~5 Accordingly, a feature of the invention with which this supplementary disclosure is concerned with resides in the provision o-f a composition adapted for application to the ~0 human skin, comprising a cosmetic oil carrier containing distributed therein an effective amount to provide substantial protection against erythemal and tanning radiation of an organic sunscreen selected from the group consisting of 2-ethylhexyl para methoxy cinnamate, homomenthyl salicylate, p-amino benzoic acid and its esters, p-dimethyl amino benzoates, hydroxy and dihydroxy-4-methoxy benzophenones, and benzalphthalides, and as an adjuvant therefor diethyl- ~ -methyl cinnamal malonate.
In another aspect, there is also provided a method of protecting the human skin from the effects of erythema and tanning radiation in sunlight, ~hich comprises ~ - 6 -applying to the skin an effective sunscreening amount of an organic sunscreen as defined above, and as an adjuvant there-for diethyl- ~ -methyl cinnamal malonate.
The following additional example further illustrates the invention.
Example 7 Between 5% - 6% of a mixture containing 50% 4-pentoxybenzalphthalide and 50% diethyl-,~ -methyl cinnamal malonate produced a total block.
Exa~ple 3 Between 5% - 5.5% of a mixture containing 50%
2-ethylhexyl-p-methoxy cinnamate and 50% diethyl cinnamal malonate produced a total block.
Example 4 Between 4.5% - 5% of a mixture containing 25%
4-pentoxy benzalphthalide and 75% diethyl p-methoxy benzal malonate produced a total block.
Example 5 Between 5% - 6% of a mixture containing 30%
diisobutyl p-methoxy benzal malonate and 70% 4-pentoxy benzal phthalide produced a total block.
Example 6 Between 3% - 4% of a mixture containing 50%
p-methoxy benzalphthalide and 50% diethyl fural malonate produced a total block.
Other formulations according to this invention provide similar results.
Substituted derivatives of the adjuvants of this invention can be employed, particularly o~ the cinnamal diethyl malonate.
~ hese examples demonstrate that the materials of this inven~ion in even small ~lantities are e~tremely .~ _ effective adjuvants for organic sunscreens and remedy the short-comings of the latter.
~ s can be seen, mixtures of the materials of this invention, and also the organic sunscreens, can be employed where desired.
The advantages of this invention will be ap-parent to the skilled in the art. Improved, highly effec-tive, novel broad spectrum sunscreen compositions are made available, utilizing a dialkyl malonate.
It will be understood that this invention is not limited to the specific examples which have been offered as particular embodiments, and that modifications can be made without departing from the spirit thereof.
_ , SUPPLEMENT~RY DISCLOSURE
As mentioned in the principal disclosure, partic-ular dialkyl malonates have been found useful as organic sunscreen adjuvants providing effective protection in the tanning area, especially around 370 nanometers~ These partic-ular dialkyl malonates are p~methoxy benzal diethyl malonate, p-methoxy benzal diisobutyl malonate, cinnamal diethyl malonate, indolal diethyl malonate, fural diethyl malonate and 3,4,5 trimethoxy benzal diethyl malonate.
It has now been further found that a substituted cinnamal diethyl malonate is especially useful in the present invention. This additional compound is diethyl-~ methyl cinnamal malonate having the following structural formula:
CH = C - CH = C \
CH3 COOC2~5 Accordingly, a feature of the invention with which this supplementary disclosure is concerned with resides in the provision o-f a composition adapted for application to the ~0 human skin, comprising a cosmetic oil carrier containing distributed therein an effective amount to provide substantial protection against erythemal and tanning radiation of an organic sunscreen selected from the group consisting of 2-ethylhexyl para methoxy cinnamate, homomenthyl salicylate, p-amino benzoic acid and its esters, p-dimethyl amino benzoates, hydroxy and dihydroxy-4-methoxy benzophenones, and benzalphthalides, and as an adjuvant therefor diethyl- ~ -methyl cinnamal malonate.
In another aspect, there is also provided a method of protecting the human skin from the effects of erythema and tanning radiation in sunlight, ~hich comprises ~ - 6 -applying to the skin an effective sunscreening amount of an organic sunscreen as defined above, and as an adjuvant there-for diethyl- ~ -methyl cinnamal malonate.
The following additional example further illustrates the invention.
Example 7 Between 5% - 6% of a mixture containing 50% 4-pentoxybenzalphthalide and 50% diethyl-,~ -methyl cinnamal malonate produced a total block.
Claims (14)
1. - A composition adapted for application to the human skin comprising a cosmetic oil carrier containing distributed therein an effective amount to provide sub-stantial protection against erythemal and tanning radiation of an organic sunscreen selected from the group consisting of 2-ethylhexyl para methoxy cinnamate, homomentyl salicylate, p-amino-benzoic acid and its esters, p-dimethyl amino benzoates, hydroxy and dihydroxy-4-methoxy benzo-phenones, and benzalphthalides, and as an adjuvant there-for a dialkyl malonate selected from the group consisting of p-methoxy benzal diethyl malonate, p-methoxy benzal di-isobutyl malonate, cinnamal diethyl malonate, indolal diethyl malonate, fural diethyl malonate, and 3,4,5-trimethoxy benzal diethyl malonate.
2. - The composition of claim 1, in which the adjuvant is p-methoxy diisobutyl malonate.
3. - The composition of claim 1, in which the adjuvant is cinnamal diethyl malonate.
4. - The composition of claims 1, 2 or 3, in which the organic sunscreen is 4-pentoxybenzalphthalide.
5. - A method of protecting the human skin from the effects of erythema and tanning radiation in sunlight which comprises applying to said skin an effective sun-screening amount of an organic sunscreen selected from the group consisting of 2-ethylhexyl para methoxy cinnamate, homomenthyl salicylate, p-amino-benzoic acid and its esters, p-dimethylamino benzoates, hydroxy and dihydroxy-4-methoxy-benzophenones, and benzalphthalides, and as an adjuvant therefor a dialkyl malonate selected from the group consist-ing of p-methoxy benzal diethyl malonate, p-methoxy benzal diisobutyl malonate, cinnamal diethyl malonate, indolal di-ethyl malonate, fural diethyl malonate, and 3,4,5-trimethoxy benzal diethyl malonate.
6. - The method of claim 5, in which the adjuvant is p-methoxy benzal diisobutyl malonate.
7. - The method of claim 5, in which the adjuvant is cinnamal diethyl malonate.
8. - The method of claims 5, 6 or 7, in which the organic sunscreen is 4-pentoxybenzalphthalide.
CLAIMS SUPPORTED BY
THE SUPPLEMENTARY DISCLOSURE
CLAIMS SUPPORTED BY
THE SUPPLEMENTARY DISCLOSURE
9. - A composition adapted for application to the human skin comprising a cosmetic oil carrier containing distributed therein an effective amount to provide sub-stantial protection against erythemal and tanning radiation of an organlc sunscreen selected from the group consisting of 2-ethylhexyl para methoxy cinnamate, homomenthyl salicylate, p-amino-benzoic acid and its esters, p-dimethyl amino benzoates, hydroxy and dihydroxy-4-methoxy benzo-phenones, and benzalphthalides, and as an adjuvant there-for a dialkyl malonate selected from the group consisting of p-methoxy benzal diethyl malonate, p-methoxy benzal di-isobutyl malonate, cinnamal diethyl malonate, diethy-? -methyl cinnamal malonate, indolal diethyl malonate, fural diethyl malonate, and 3,4,5-trimethoxy benzal diethyl malonate.
10. - The composition of claim 9, in which the adjuvant is diethyl-?-methyl cinnamal malonate.
11. - The composition of claims 9 or 10, in which the organic sunscreen is 4-pentoxybenzalphthalide.
12. - A method of protecting the human skin from the effects of erythema and tanning radiation in sunlight which comprises applying to said skin an effective sun-screening amount of an organic sunscreen selected from the group consisting of 2-ethylhexyl para methoxy cinnamate, homomenthyl salicylate, p-amino-benzoic acid and its esters, p-dimethylamino benzoates, hydroxy and dihydroxy-4-methoxy-benzophenones, and benzalphthalides, and as an adjuvant therefor a dialkyl malonate selected from the group consist-ing of p-methoxy benzal diethyl malonate, p-methoxy benzal diisobutyl malonate, cinnamal diethyl malonate, diethyl-? -methyl cinnamal malonate, indolal diethyl malonate, fural diethyl malonate, and 3,4,5-trimethoxy benzal diethyl malonate.
13. - The method of claim 12, in which the adjuvant is diethyl-? -methyl cinnamal malonate.
14. - The method of claims 12 or 13, in which the organic sunscreen is 4-pentoxybenzalphthalide.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US404,964 | 1982-08-03 | ||
| US06/404,964 US4457911A (en) | 1981-01-28 | 1982-08-03 | Dialkyl malonates as organic sunscreen adjuvants |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1185533A true CA1185533A (en) | 1985-04-16 |
Family
ID=23601746
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000412071A Expired CA1185533A (en) | 1982-08-03 | 1982-09-23 | Dialkyl malonates as organic sunscreen adjuvants |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPS5938273A (en) |
| AU (1) | AU8873482A (en) |
| CA (1) | CA1185533A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4515774A (en) * | 1984-06-18 | 1985-05-07 | Van Dyk & Company Inc. | Liquid, cinnamal dialkyl malonates as sole organic sunscreens |
| JP4463549B2 (en) * | 2001-07-16 | 2010-05-19 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング | Photostable organic sunscreen compounds having antioxidant properties and compositions obtained therefrom |
| JP5311607B2 (en) | 2007-02-23 | 2013-10-09 | 株式会社 資生堂 | Skin or hair composition |
-
1982
- 1982-09-23 CA CA000412071A patent/CA1185533A/en not_active Expired
- 1982-09-27 AU AU88734/82A patent/AU8873482A/en not_active Abandoned
-
1983
- 1983-01-19 JP JP798583A patent/JPS5938273A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| AU8873482A (en) | 1984-02-09 |
| JPS5938273A (en) | 1984-03-02 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEC | Expiry (correction) | ||
| MKEX | Expiry |