US3095353A - Aqueous mixture of surface active agents - Google Patents
Aqueous mixture of surface active agents Download PDFInfo
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- US3095353A US3095353A US18507A US1850760A US3095353A US 3095353 A US3095353 A US 3095353A US 18507 A US18507 A US 18507A US 1850760 A US1850760 A US 1850760A US 3095353 A US3095353 A US 3095353A
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/017—Mixtures of compounds
Definitions
- This invention relates to an aqueous mixture of surface-active agents which exert a synergistic action, ne1ther surface-active agent alone being effective.
- alkali metal alkyl sulfate as employed herein and in the appended claims is meant water-soluble anionic surfactants of the structure RO.SO .OM wherein R is a long chain alkyl radical (either straight or branched) containing from 8 to 18 carbon atoms as exemplified by octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, pentadecyl, cetyl, octadecyl, and the various isomeric forms thereof, and wherein M is an alkali metal such as sodium, potassium or lithium. It is preferred that R be a straight chain alkyl radical.
- mono-higher fatty acid ester of hexitol anhydrides as employed herein and in the appended claims is meant mono-esters of hexitol anhydrides and a higher fatty acid such as lauric acid, palrnitic acid, oleic acid, ricinolcic acid, stearic acid and the like fatty acids containing from 12 to 20 carbon atoms.
- mono-esters of hexitol anhydrides and a higher fatty acid such as lauric acid, palrnitic acid, oleic acid, ricinolcic acid, stearic acid and the like fatty acids containing from 12 to 20 carbon atoms.
- esters are sorbitan mono-laurate, mannitan mono-laurate, sorbitan mono-palmitate, sorbitan mono-oleate, mannitan mono-oleate, sorbide mono-oleate.
- alkylene oxide as employed herein and in the appended claims is meant ethylene oxide and propylene 3,095,353 Patented June 25, 1963 oxide and mixtures thereof. These materials can be represented by the empirical formula C H O wherein n is a whole number from 2 to 3.
- the preferred alkylene oxide is ethylene oxide.
- Typical mixtures of the surface-active agents of this invention comprise (in parts by weight) I i B 0 Sodium lauryl sulfate 1 l 2 1 mole of sorbitan monooleate condensed with 20 moles of ethylene oxide 1 2 VVatcrt 0-... 3 2 6 These aqueous mixtures of surface-active agents, i.e.
- compositions A, B and C are clear liquids soluble in water.
- the mixture of surface-active agents of this invention is characterized by excellent stability. To demonstrate such the following respective compositions (in parts by 1 Commercial water-soluble anionic wetting agent.
- compositions B, C, D, E, F and G after 2 days showed oiling out of 6- ethoxy-2,2,4-trimethyl-1,Z-dihydroquinoline while composition A after standing 5 months showed no signs of oiling out of 6-ethoxy-2,2,4-trimethyl-l,Z-dihydroquinoline. Further Composition A after standing for 5 months was still self-emulsifiable with Water.
- 2,2,4-trimethyl-1,2-dihydroquinolines such as 6-ethoxy- 2,2,4-trimethyl-1,2-dihydroquinoline which is a waterinsoluble yellow oily liquid
- organic solvents usually high molecular Weight alcohols such as decyl alcohol and dodecyl alcohol
- aqueous surface-active mixture of this invention is soluble in 2,2,4-trimethyl-l,2-dihydroquinolines such as 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline and provides solventless concentrates which are self-emulsifiable in water.
- Concentrates containing 0.5 to 8.0 but preferably 1.5 to 2.5 by weight of 2,2,4-trimethyl-1,Z-dihydroquinoline per 1 part by weight of the aqueous surface-active agent mixture of this invention exhibit good stability in storage and excellent self-emulsifying properties when admixed with water at the point of use.
- aqueous surface active mixture of this invention is useful in preparing emulsifiable concentrates of other 2,2,4-trimethyl-1,2-di'hydroquinolines as for example those disclosed in U.S. 2,562,970 (issued August 7, 1951) of the structure wherein R is hydrogen, a hydrocarbon radical or a hydrocarbonoxy radical (e.g. methyl, ethyl, isopropyl, nbutyl, isobutyl, hexyl, phenyl, benzyl, methoxy, ethoxy, propoxy, isoamyloxy, ph'enoxy, benzyloxy, etc.) contain ing not more than 7 carbon atoms.
- R is hydrogen, a hydrocarbon radical or a hydrocarbonoxy radical (e.g. methyl, ethyl, isopropyl, nbutyl, isobutyl, hexyl, phenyl, benzyl, methoxy, ethoxy
- a homogeneous mixture of surface-active agents for emulsifying and dispersing water-insoluble substances in water which mixture is water-soluble and contains from about 1 to 2 parts by weight of (a) an alkali metal alkyl sulfate water-soluble surfactant of the structure RO.SO .OM wherein R is a long chain alkyl radical containing 8 to 18 carbon atoms and wherein M is an alkali metal, about 1 to 3 parts by weight of (b) the watersoluble condensation product of a mono-higher fatty acid ester of hexitol anhydride with 10 to 30 moles of alkylene oxide of the empirical formula C H O wherein n is a whole number from 2 to 3 per mole of ester, and 2 to 6 parts by weight of (c) water.
- a an alkali metal alkyl sulfate water-soluble surfactant of the structure RO.SO .OM wherein R is a long chain alkyl radical containing 8 to 18 carbon atoms and wherein M
- composition of claim 1 wherein the weight ratio of (a) to (b) to (c) is 1:2:3.
- An emulsifiable concentrate containing 0.5 to 8.0 parts by weight of a 2,2,4-trim'ethyl-1,2-dihydroquinoline and 1 part by weight of the composition of claim 1.
- An emulsifiable concentrate containing 1.5 to 2.5 parts by weight of 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline and 1 part by weight of the composition of claim 2.
- An emulsifiable concentrate containing 1.5 to 2.5 parts by weight of 6-ethoxy-2,2,4-trimethyl-1,Z-dihydroquinoline and 1 part by weight of a mixture of (a) sodium lauryl sulfate, (b) water-soluble condensation product of 1 mole of sorbitan mono-oleate with 10 to 30 moles of ethylene oxide, and (c) water, the weight ratio of (a) to (b) to (0) being 1:2:3.
- a homogeneous mixture of surface-active agents for emulsifying and dispersing water-insoluble substances in water which mixture is water-soluble and contains from about 1 to 2 parts by weight of sodium lauryl sulfate, about 1 to 3 parts by weight of the water-soluble condensation product of one mole of sorbitan monooleate with 10 to 30 moles of ethylene oxide, and 2 to 6 parts by weight of water.
Description
3,095,353 AQUEOUS MIXTURE OF SURFACE ACTIVE AGENTS John M. Surgant, Richmond Heights, Mo., assignor to Monsanto Chemical Company, St. Louis, Mo., a corporation of Delaware No Drawing. Filed Mar. 30, 1960, Ser. No. 18,507
6 Claims. (Cl. 167-43) This invention relates to an aqueous mixture of surface-active agents which exert a synergistic action, ne1ther surface-active agent alone being effective.
'From a practical 'standpoint'the manufacturer of' a' water-insoluble pesticidal agent must supply the agriculturist with a low-cost concentrate thereof in such form that by merely mixing with Water at the point of use he will have an easily prepared pesticidal spray. It has been customary in the preparation of concentrates that such water-insoluble pesticidal agents be dissolved in an organic solvent therefor and to admix with the organic solution a water-soluble surface-active agent. As those skilled in the art are well aware, the specifications for an emulsifying and/or wetting agent in packaged goods which must withstand the effects of storage are exacting. The passage of time and changes of temperature encountered in normal storage often materially effect the emulsifying and/or wetting properties of the surfaceactive agent. Additionally the surface-active agent may react with the pesticidal agent or be otherwise affected by it over a period of time and thus cause the active ingredient to lose or materially lessen its pesticidal properties. Also in many instances while a particular waterinsoluble pesticidal agent may be highly useful in combatting certain pests its usage has been limited or negatived by virtue of the particular organic solvent employed to solubilize it, e.g. o-ily films and/r objectionable odor or solvent residues after application and for other reasons those skilled in the art are thoroughly familiar.
In accordance with this invention it has been found that the combination of about 1 to 2 parts by weight of (a) alkali metal alkyl sulfate water-soluble anionic surfactant, about 1 to 3 parts by weight of (b) the condensation product of 1 mole of a mono-higher fatty acid ester of hexitol anhydrides, i.e. sorbitan (C H O mannitan, sorbide (C H O mannide etc. with 10 to 30 moles of alkylene oxide, and 2 to 6 parts by weight of (c) water provides a homogeneous water-soluble surfaceactive mixture which fulfills the rigorous requirement of emulsifying and/ or wetting agents which must Withstand storage as concentrates. Optimum results are obtained when the weight ratio of (a) to (b) to (c) is 1:213.
By alkali metal alkyl sulfate as employed herein and in the appended claims is meant water-soluble anionic surfactants of the structure RO.SO .OM wherein R is a long chain alkyl radical (either straight or branched) containing from 8 to 18 carbon atoms as exemplified by octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, pentadecyl, cetyl, octadecyl, and the various isomeric forms thereof, and wherein M is an alkali metal such as sodium, potassium or lithium. It is preferred that R be a straight chain alkyl radical.
By mono-higher fatty acid ester of hexitol anhydrides as employed herein and in the appended claims is meant mono-esters of hexitol anhydrides and a higher fatty acid such as lauric acid, palrnitic acid, oleic acid, ricinolcic acid, stearic acid and the like fatty acids containing from 12 to 20 carbon atoms. As exemplary of such esters are sorbitan mono-laurate, mannitan mono-laurate, sorbitan mono-palmitate, sorbitan mono-oleate, mannitan mono-oleate, sorbide mono-oleate.
By alkylene oxide as employed herein and in the appended claims is meant ethylene oxide and propylene 3,095,353 Patented June 25, 1963 oxide and mixtures thereof. These materials can be represented by the empirical formula C H O wherein n is a whole number from 2 to 3. The preferred alkylene oxide is ethylene oxide.
Typical mixtures of the surface-active agents of this invention comprise (in parts by weight) I i B 0 Sodium lauryl sulfate 1 l 2 1 mole of sorbitan monooleate condensed with 20 moles of ethylene oxide 1 2 VVatcrt 0-... 3 2 6 These aqueous mixtures of surface-active agents, i.e.
compositions A, B and C, are clear liquids soluble in water.
The mixture of surface-active agents of this invention is characterized by excellent stability. To demonstrate such the following respective compositions (in parts by 1 Commercial water-soluble anionic wetting agent.
2 Commercial water-soluble anionic emulsifying agent. were prepared by initially mixing the sorbitan monooleate-ethylene oxide condensation product with a solution of the recited anionic surfactant in the water and passing the mix and 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline through a colloid mill. The resulting concentrates were then permitted to stand in closed containers under normal storage conditions. Compositions B, C, D, E, F and G after 2 days showed oiling out of 6- ethoxy-2,2,4-trimethyl-1,Z-dihydroquinoline while composition A after standing 5 months showed no signs of oiling out of 6-ethoxy-2,2,4-trimethyl-l,Z-dihydroquinoline. Further Composition A after standing for 5 months was still self-emulsifiable with Water.
2,2,4-trimethyl-1,2-dihydroquinolines, such as 6-ethoxy- 2,2,4-trimethyl-1,2-dihydroquinoline which is a waterinsoluble yellow oily liquid, have been found to be useful in the control of common apple scald and Anjou pear scald and for preserving the nutritive value of feeds and forage plants, particularly alfalfa. However their usage has been curtailed by virtue of the organic solvents (usually high molecular Weight alcohols such as decyl alcohol and dodecyl alcohol) employed to make concentrated solutions thereof because of injury to the treated surface as well as objectionable odors and/or oily films characterizing the residues after application in the field. Further to date, no-water-soluble surface-active agent in admixture with such concentrated organic solutions has provided a concentrate capable of withstanding the effects of storage. The aqueous surface-active mixture of this invention is soluble in 2,2,4-trimethyl-l,2-dihydroquinolines such as 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline and provides solventless concentrates which are self-emulsifiable in water. Concentrates containing 0.5 to 8.0 but preferably 1.5 to 2.5 by weight of 2,2,4-trimethyl-1,Z-dihydroquinoline per 1 part by weight of the aqueous surface-active agent mixture of this invention exhibit good stability in storage and excellent self-emulsifying properties when admixed with water at the point of use.
The aqueous surface active mixture of this invention aforementioned is useful in preparing emulsifiable concentrates of other 2,2,4-trimethyl-1,2-di'hydroquinolines as for example those disclosed in U.S. 2,562,970 (issued August 7, 1951) of the structure wherein R is hydrogen, a hydrocarbon radical or a hydrocarbonoxy radical (e.g. methyl, ethyl, isopropyl, nbutyl, isobutyl, hexyl, phenyl, benzyl, methoxy, ethoxy, propoxy, isoamyloxy, ph'enoxy, benzyloxy, etc.) contain ing not more than 7 carbon atoms.
While this invention has been described with respect to certain embodiments it is to be understood that it is not so limited and that variations and modifications thereof obvious to those skilled in the art can be made without departing from the spirit or scope of this invention.
What is claimed is: g
1. A homogeneous mixture of surface-active agents for emulsifying and dispersing water-insoluble substances in water which mixture is water-soluble and contains from about 1 to 2 parts by weight of (a) an alkali metal alkyl sulfate water-soluble surfactant of the structure RO.SO .OM wherein R is a long chain alkyl radical containing 8 to 18 carbon atoms and wherein M is an alkali metal, about 1 to 3 parts by weight of (b) the watersoluble condensation product of a mono-higher fatty acid ester of hexitol anhydride with 10 to 30 moles of alkylene oxide of the empirical formula C H O wherein n is a whole number from 2 to 3 per mole of ester, and 2 to 6 parts by weight of (c) water.
2. The composition of claim 1 wherein the weight ratio of (a) to (b) to (c) is 1:2:3.
3. An emulsifiable concentrate containing 0.5 to 8.0 parts by weight of a 2,2,4-trim'ethyl-1,2-dihydroquinoline and 1 part by weight of the composition of claim 1.
4. An emulsifiable concentrate containing 1.5 to 2.5 parts by weight of 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline and 1 part by weight of the composition of claim 2.
5. An emulsifiable concentrate containing 1.5 to 2.5 parts by weight of 6-ethoxy-2,2,4-trimethyl-1,Z-dihydroquinoline and 1 part by weight of a mixture of (a) sodium lauryl sulfate, (b) water-soluble condensation product of 1 mole of sorbitan mono-oleate with 10 to 30 moles of ethylene oxide, and (c) water, the weight ratio of (a) to (b) to (0) being 1:2:3.
6. A homogeneous mixture of surface-active agents for emulsifying and dispersing water-insoluble substances in water which mixture is water-soluble and contains from about 1 to 2 parts by weight of sodium lauryl sulfate, about 1 to 3 parts by weight of the water-soluble condensation product of one mole of sorbitan monooleate with 10 to 30 moles of ethylene oxide, and 2 to 6 parts by weight of water.
References Cited in the file of this patent UNITED STATES PATENTS Re. 24,184 Sanders et a1. July 24, 1961 2,372,807 Brown Apr. 3, 1945 2,509,233 Kaberg et a1. May 30, 1950 2,562,970 Thompson Aug. 7, 1951 2,845,380 Mayhew et al. July 29, 1958 2,870,058 Loder Jan. 20, 19-59 2,872,368 Sanders et a1. Feb, 3, 1959 2,898,267 Lindner Aug. 4, 1959 2,946,721 Hyatt et al. July 26, 1960 OTHER REFERENCES Schwartz et al.: Surface Active Agents and Detergents, Interscience Publishers, Inc., NY. 1958, vol. II, pp. 205, 209, 231, 232-235, 238-241, 318-322, 380-381, 383, 607, 611, 652- 6. Esp. pertinent pages of Schwartz et al., disclosing enhanced effects arising from surfactant adjuvation of residual plant sprays, are on pages 652-656.
Claims (1)
1. A HMOMGENEOUS MIXTURE OF SURFACE-ACTIVE AGENTS FOR EMULSIFYING AND DISPERSING WATER-INSOLUBLE SUBSTANCES IN WATER WHICH MIXTURE IS WATER-SOLUBLE AND CONTAINS FROM ABOUT 1 TO 2 PARTS BY WEIGHT OF (A) AN ALKALI METAL ALKYL SULFATE WATER-SOLUBLE SURFACTANT OF THE STRUCTURE RO.SO2OM WHEREIN R IS A LONG CHAIN ALKYL RADICAL CONTAINING 8 TO 18 CARBON ATOMS AND WHEREIN M IS AN ALKALI METAL, ABOUT 1 TO 3 PARTS BY WEIGHT OF (B) THE WATERSOLUBLE CONDENSATION PRODUCT OF A MONO-HIGHER FATTY ACID ESTER OF HEXITOL ANHYDRIDE WITH 10 TO 30 MOLES OF ALKYLENE OXIDE OF THE EMPIRICAL FORMUAL CNH2NO WHEREIN N IS A WHOLE NUMBER FROM 2 TO 3 PER MOLE OF ESTER, AND 2 TO 6 PARTS BY WEIGHT OF (C) WATER.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US18507A US3095353A (en) | 1960-03-30 | 1960-03-30 | Aqueous mixture of surface active agents |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US18507A US3095353A (en) | 1960-03-30 | 1960-03-30 | Aqueous mixture of surface active agents |
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| Publication Number | Publication Date |
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| US3095353A true US3095353A (en) | 1963-06-25 |
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| US18507A Expired - Lifetime US3095353A (en) | 1960-03-30 | 1960-03-30 | Aqueous mixture of surface active agents |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3265568A (en) * | 1962-03-12 | 1966-08-09 | Exxon Research Engineering Co | Wax-water emulsions containing pyrethrum in the phase |
| US3330768A (en) * | 1964-06-29 | 1967-07-11 | Monsanto Chemicals | Mycobacteriostatic compositions |
| US3462437A (en) * | 1963-02-11 | 1969-08-19 | Soc D Etudes Prod Chimique | N-dodecyl sulfate of 5-methyl-8-hydroxy quinoline |
| US4681900A (en) * | 1984-01-13 | 1987-07-21 | Kao Corporation | Biocide activator |
| EP0498785A1 (en) * | 1991-02-08 | 1992-08-12 | Monsanto Europe S.A./N.V. | Glyphosate compositions and their use |
| US5696133A (en) * | 1994-12-22 | 1997-12-09 | Ligand Pharmaceuticals Incorporated | Steroid receptor modulator compounds and methods |
| US6696459B1 (en) | 1994-12-22 | 2004-02-24 | Ligand Pharmaceuticals Inc. | Steroid receptor modulator compounds and methods |
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| US2372807A (en) * | 1941-07-05 | 1945-04-03 | Atlas Powder Co | Absorption bases |
| US2509233A (en) * | 1946-09-11 | 1950-05-30 | Monsanto Chemicals | Emulsifiable oil concentrates of biological toxicants |
| US2562970A (en) * | 1950-04-14 | 1951-08-07 | Thompson Chester Ray | Preservation of forage crops |
| USRE24184E (en) * | 1956-07-24 | Emulsifiers and toxrcants containing | ||
| US2845380A (en) * | 1953-11-16 | 1958-07-29 | Gen Aniline & Film Corp | Emulsifier mixture, method of preparing same, and biocidal compositions therewith |
| US2870058A (en) * | 1955-12-02 | 1959-01-20 | Du Pont | Fungicide-oil formulations |
| US2872368A (en) * | 1954-05-03 | 1959-02-03 | Herbert L Sanders | Emulsifiers and toxicants containing the same |
| US2898267A (en) * | 1955-09-07 | 1959-08-04 | Witco Chemical Corp | Emulsifiable toxicant compositions and emulsifying agents therefor |
| US2946721A (en) * | 1954-12-17 | 1960-07-26 | Gen Aniline & Film Corp | Emulsification of water-insoluble organic solvents |
-
1960
- 1960-03-30 US US18507A patent/US3095353A/en not_active Expired - Lifetime
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| USRE24184E (en) * | 1956-07-24 | Emulsifiers and toxrcants containing | ||
| US2372807A (en) * | 1941-07-05 | 1945-04-03 | Atlas Powder Co | Absorption bases |
| US2509233A (en) * | 1946-09-11 | 1950-05-30 | Monsanto Chemicals | Emulsifiable oil concentrates of biological toxicants |
| US2562970A (en) * | 1950-04-14 | 1951-08-07 | Thompson Chester Ray | Preservation of forage crops |
| US2845380A (en) * | 1953-11-16 | 1958-07-29 | Gen Aniline & Film Corp | Emulsifier mixture, method of preparing same, and biocidal compositions therewith |
| US2872368A (en) * | 1954-05-03 | 1959-02-03 | Herbert L Sanders | Emulsifiers and toxicants containing the same |
| US2946721A (en) * | 1954-12-17 | 1960-07-26 | Gen Aniline & Film Corp | Emulsification of water-insoluble organic solvents |
| US2898267A (en) * | 1955-09-07 | 1959-08-04 | Witco Chemical Corp | Emulsifiable toxicant compositions and emulsifying agents therefor |
| US2870058A (en) * | 1955-12-02 | 1959-01-20 | Du Pont | Fungicide-oil formulations |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3265568A (en) * | 1962-03-12 | 1966-08-09 | Exxon Research Engineering Co | Wax-water emulsions containing pyrethrum in the phase |
| US3462437A (en) * | 1963-02-11 | 1969-08-19 | Soc D Etudes Prod Chimique | N-dodecyl sulfate of 5-methyl-8-hydroxy quinoline |
| US3330768A (en) * | 1964-06-29 | 1967-07-11 | Monsanto Chemicals | Mycobacteriostatic compositions |
| US4681900A (en) * | 1984-01-13 | 1987-07-21 | Kao Corporation | Biocide activator |
| EP0498785A1 (en) * | 1991-02-08 | 1992-08-12 | Monsanto Europe S.A./N.V. | Glyphosate compositions and their use |
| AU650091B2 (en) * | 1991-02-08 | 1994-06-09 | Monsanto Europe S.A. | Glyphosate compositions and their use |
| US5696133A (en) * | 1994-12-22 | 1997-12-09 | Ligand Pharmaceuticals Incorporated | Steroid receptor modulator compounds and methods |
| US5994544A (en) * | 1994-12-22 | 1999-11-30 | Ligand Pharmaceuticals Incorporated | Steroid receptor modulator compounds and methods |
| US6093821A (en) * | 1994-12-22 | 2000-07-25 | Ligand Pharmaceuticals Incorporated | Process for preparing steroid receptor modulator compounds |
| US6121450A (en) * | 1994-12-22 | 2000-09-19 | Ligand Pharmaceuticals Incorporated | Intermediates for preparation of steroid receptor modulator compounds |
| US6448405B1 (en) | 1994-12-22 | 2002-09-10 | Ligand Pharmaceuticals Incorporated | Steroid receptor modulator compounds and methods |
| US6696459B1 (en) | 1994-12-22 | 2004-02-24 | Ligand Pharmaceuticals Inc. | Steroid receptor modulator compounds and methods |
| US20040186132A1 (en) * | 1994-12-22 | 2004-09-23 | Jones Todd K. | Steroid receptor modulator compounds and methods |
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