US2993909A - Quaternary ammonium compounds containing the 8-(6-chloro-1, 3-benzodioxanyl) methyl group - Google Patents
Quaternary ammonium compounds containing the 8-(6-chloro-1, 3-benzodioxanyl) methyl group Download PDFInfo
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- US2993909A US2993909A US836583A US83658359A US2993909A US 2993909 A US2993909 A US 2993909A US 836583 A US836583 A US 836583A US 83658359 A US83658359 A US 83658359A US 2993909 A US2993909 A US 2993909A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
- C07D319/08—1,3-Dioxanes; Hydrogenated 1,3-dioxanes condensed with carbocyclic rings or ring systems
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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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/24—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms
- A01N43/32—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms six-membered rings
Definitions
- This invention concerns quaternary ammonium compounds of the formula wherein X is an anion, R is a lipophilic group, includingalkylgroups of at least 10 carbon atoms, preferably 12 to 20 carbon atoms, alkenyl groups of 11 to 18 carbon atoms, and arylaliphatic groups having at least 12 carbon atoms, preferably 15 toi25 carbon atoms, and R and R when taken individually, represent alk'yl groups of one to two carbon atoms, the hydroxyethyl group, ora benzyl group, and when taken together, form a divalent aliphaticfchain of four to five atoms which with the nitrogen forms a heterocyele, such as -'CH CH OH CH -CH CH CH CH CH OH deceriyl, dodecenyl, or oleyl, aliphatichydrocarbon chains interrupted by ether groups as in octyloxypentenyl or nonyloxypentenyl or an N-aryla
- pentadecylbenzyl, octadecylbenz yl, octylmethylbenzyl, or octyldimethylbenzyl, trimethylphenylpentenyl (CH C I-I CH CH 'CH CHOH or diethylphenylpentenyl, octylrnethylphenoxyethoxyethyl ordodecylphenoxyethoxyet'hyl.
- the otherN-substituents" forming the quaternary group also have considerable latitude and may be ethyl, methyl,
- benzyl chlorobenzyl, dichlorobenzyl, methylbenzyl, phenoxyethyl, ethoxyethyl, hydroxyethyl', or hydroxypropyl, when taken individually.
- R may form a divalent chain, such as found in morpholine, 2-methyl or 2,6-dime thyl-morpholine, thiamorpholine, pyrrolidine, or piperidine.
- the anion X is most commonly chlorine but may equally well be bromine and such a halogen may be i replaced with sulfate, phosphate, methyl sulfate, nitrate, acetate, and so on, by conventional steps.
- quaternary ammonium compounds are characterized by possessing fungicidal properties together with low phytotoxicity for living plants.
- the object of the present invention is to provide quaternary ammonium compounds which possess fungicidal activity against common plant pathogens and which at the same time have low phytotoxicity. Another object is to furnish compounds which may be used to control apple scab, a use requiring both prote'ctant and eradicant actions. I e
- the above-defined quaternary ammonium salts are prepared by reacting 6-chloro-8 chloromethyl-1,3-benzodioxane with a tertiary amine having at least one lipophilic substituent. Approximately equivalent quantities of the two reactants are mixed, preferably in an organic solvent. The mixture may be heated between about 25 and about C. for a time suflicient to substantially complete the reaction. The solventis then distilled oif to leave a residue in the form of an oil or a paste which may be used without further purifica'tionif so desired. Alternatively, the residue may be purified by treatment with charcoal or extraction or in the case of solids,
- Suitable solvents for the reaction include acetone, methyl hexyl ketone, 'die'thyl keto'ne, acetonitrile, nitromethane, ethyl acetate, naphtha, benzene, toluene, or xylene.
- Typical tertiary amines include n-'- dodecyldimethylamine, cetyldimethylamine; decyld iethylamine, dodecylbenzylmethylamine, dodecyldibengy lamine, N do decylniorpholine, N octadecylmorpholine, N-myristylpy-rrolidine, l I'-cetylpiperidine, oleyldimethylar'nin'e, (5,5,7,7 tetramethyl 2 octenyl )'dimethylamine,
- EXAMPLE 1 A mixture of 8 parts of 6-chloro-8-chloromethyl-l,3- benzodioxane, 12.4 parts of t-octylphenoxyethoxyethylclirnethylamine, and 80 parts of acetone was refluxed with stirring for 3 hours. The mixture was concentrated under 1 reduced pressure to give 17.5 parts of a viscous oil which corresponded in composition to E j or H Analysis.-Calcd. for C H Cl NO N, 2.6. Found: .N, 2.5. a
- EXAMPLE 7 A mixture of 11 parts of 6-chloro-8-chloromethyl-1,3- benzodioxane, 10.1 parts of (5,5,7,7-tetramethyl-2-octenyl) dimethylamine, and 120 parts of acetone was refluxed with stirring for 3.5 hours. The solvent was removed, and there was a residual semi-solid which was triturated with warm ether. The solid thus separated was filtered E, washed, with ether, and dried. There was obtained 18.3 parts of a product which melted at 110-112 and has the structure Analysis.-Calcd. for C H C1 NO Cl, 16.5; N, 3.3. Found: CI, 16.0; N, 3.2.
- the quaternary ammonium compounds of this invention appear stable in light and in air. There is evidence that they have antlie'lmintic properties and can act as snailicides. For the latter purpose they may be used from aqueous solution or they may be mixed with a solid carrier, such as clay, diatomaceous earth, pyrophyllite, or talc, at concentrations of 5% to 50%. They may also serve against bacteria.
- a solid carrier such as clay, diatomaceous earth, pyrophyllite, or talc
- the chloride or bromide ion may be replaced in known ways with other anions.
- a concentrated solution of a quaternary ammonium chloride may be treated with a sodium phosphate solution to exchange anions with formation of quaternary ammonium phosphate.
- any anion can be introduced, including acetate or propionate, as typical anions of organic acids. It is thus possible to have present any desired anion.
- R is a lipophilic group selected from the class consisting of 'alkyl groups of 10 to 20 carbon atoms, alkenyl groups of 11 to 18 carbon atoms, alkylbenzyl groups of 15 to 25 carbon atoms, and alkylphenoxyethoxyethyl groups of 15 to 25 carbon atoms,
- R and R when taken individually, represent alkyl represent a saturated divalent aliphatic chain of --CH CH OCH CH groups which together with the nitrogen atom forms a heterocycle.
Description
United States Patent QUATERNA'RY AMMoNIiJM CQMPOUNDS CON- TAINING THE 8-(6-CHLORO L3-BENZODIOX- ANYDMETHYL GROUP Chren-Pen Lo, Philadelphia, Pa., assignor to Rohm & Haas Company, Philadelphia, Pa., a corporation of Delaware No Drawing. Filed Aug; 28, 19 59, Ser. No.- 836,583
This invention concerns quaternary ammonium compounds of the formula wherein X is an anion, R is a lipophilic group, includingalkylgroups of at least 10 carbon atoms, preferably 12 to 20 carbon atoms, alkenyl groups of 11 to 18 carbon atoms, and arylaliphatic groups having at least 12 carbon atoms, preferably 15 toi25 carbon atoms, and R and R when taken individually, represent alk'yl groups of one to two carbon atoms, the hydroxyethyl group, ora benzyl group, and when taken together, form a divalent aliphaticfchain of four to five atoms which with the nitrogen forms a heterocyele, such as -'CH CH OH CH -CH CH CH CH OH deceriyl, dodecenyl, or oleyl, aliphatichydrocarbon chains interrupted by ether groups as in octyloxypentenyl or nonyloxypentenyl or an N-arylaliphatic group such as 'diamylben'zyl, octylbenzyl, non-ylbenzyl, dodecylbenzyl,
pentadecylbenzyl, octadecylbenz yl, octylmethylbenzyl, or octyldimethylbenzyl, trimethylphenylpentenyl (CH C I-I CH CH 'CH=CHOH or diethylphenylpentenyl, octylrnethylphenoxyethoxyethyl ordodecylphenoxyethoxyet'hyl.
The otherN-substituents" forming the quaternary group also have considerable latitude and may be ethyl, methyl,
or other lower alkyl group, benzyl, chlorobenzyl, dichlorobenzyl, methylbenzyl, phenoxyethyl, ethoxyethyl, hydroxyethyl', or hydroxypropyl, when taken individually. Together-TR and R may form a divalent chain, such as found in morpholine, 2-methyl or 2,6-dime thyl-morpholine, thiamorpholine, pyrrolidine, or piperidine.
The anion X is most commonly chlorine but may equally well be bromine and such a halogen may be i replaced with sulfate, phosphate, methyl sulfate, nitrate, acetate, and so on, by conventional steps.
These quaternary ammonium compounds are characterized by possessing fungicidal properties together with low phytotoxicity for living plants.
ice
The bactericidal action of surface-active quaternary ammonium salts has long been recognized. Some offth e known quaternary ammonium compounds have also exhibited action against fungi. Attempts have been made to utilize various types of quaternary ammonium salts on plants but without the development of any practical applications in the field of plant protection. This lack' of practical application in this field has been due'in large part to the relatively severe phytotoxicity of previously known quaternary ammonium compounds, some of which have also been lacking in tenacity or persistence onplants.
As typical of the observations which have been made with previously known quaternary ammonium cornpounds, it may be mentioned that when young tomato plants in the greenhouse were sprayed with a 1% solution of various known salts, the plants were killed. Compounds giving this result included n-dodecyl(benz yl) dimethylammonium chloride, n hexadecyl(benz'-yl)dimethylammonium chloride, t-octylphenoxyethoxyethyl (benzyl)dimethylammonium' chloride, t-octylcresoxyethoxyethyl(benzy1)dimethylammonium chloride, tdcde'cenyltrimethylammo-nium chloride, (dodecylbenzyDtrimethylammonium chloride, and (dodecylmethylbenzyl trimethylamrnonium-chloride. Even at concentrations of 0.1% the phytotoxic efiects were objectionable.
The object of the present invention is to provide quaternary ammonium compounds which possess fungicidal activity against common plant pathogens and which at the same time have low phytotoxicity. Another object is to furnish compounds which may be used to control apple scab, a use requiring both prote'ctant and eradicant actions. I e
The above-defined quaternary ammonium salts are prepared by reacting 6-chloro-8 chloromethyl-1,3-benzodioxane with a tertiary amine having at least one lipophilic substituent. Approximately equivalent quantities of the two reactants are mixed, preferably in an organic solvent. The mixture may be heated between about 25 and about C. for a time suflicient to substantially complete the reaction. The solventis then distilled oif to leave a residue in the form of an oil or a paste which may be used without further purifica'tionif so desired. Alternatively, the residue may be purified by treatment with charcoal or extraction or in the case of solids,
crystallization. 1 p v I Suitable solvents for the reaction include acetone, methyl hexyl ketone, 'die'thyl keto'ne, acetonitrile, nitromethane, ethyl acetate, naphtha, benzene, toluene, or xylene.
The preparation of 6-chloro-8-chloromethyl-l,3-benzodioxane has been described by Buehler et al., J, Amer. Chem. .Soc. 62, 890 1940).
Tertiary amines which are reacted with the above compounds supply at least one li'pophilicgroup; =In-,ger 1- eral, such a igroup will'conta'in at least 10 carbon? atoms.
The upper limit of carbon atoms is dictatedby matters.
of availability and also of solubility of the final quaternary' ammonium salt. Typical tertiary aminesinclude n-'- dodecyldimethylamine, cetyldimethylamine; decyld iethylamine, dodecylbenzylmethylamine, dodecyldibengy lamine, N do decylniorpholine, N octadecylmorpholine, N-myristylpy-rrolidine, l I'-cetylpiperidine, oleyldimethylar'nin'e, (5,5,7,7 tetramethyl 2 octenyl )'dimethylamine,
' octyloxypentenyldimetliylamine, (octylbenzyl) dimethylainine', dodecylbenzyldimethylamine, 'octylphenoxyethoxydimethylamine', nonylphenoxyethoxyethylbenzylmethylarnine, nonylphenoxyethyldi (hyd-roxyethyl) amine octylphenoxyethoxyethylmorpholine, nonylphenoxyetlioxyethyIpiperi'dine, amine. Additional details of the preparation of the compounds of this invention are presented in the following ili'ilstrative (dietliylphenyl 2' penterryl) dimetlry l- Patented July 25", 196
dimethylammonium same test organisms at 3 examples, wherein parts are by weight unless otherwise specified. EXAMPLE 1 A mixture of 8 parts of 6-chloro-8-chloromethyl-l,3- benzodioxane, 12.4 parts of t-octylphenoxyethoxyethylclirnethylamine, and 80 parts of acetone was refluxed with stirring for 3 hours. The mixture was concentrated under 1 reduced pressure to give 17.5 parts of a viscous oil which corresponded in composition to E j or H Analysis.-Calcd. for C H Cl NO N, 2.6. Found: .N, 2.5. a
In the fungitoxicity test (slide-germination method), ,[8 (6-chloro-l,S-benzodioxyanyDmethyl]-(t-octylphen- -oxyethoxyethyl)-dimethylammonium chloride gave ED values of 5-10 p.p.m. against Monolinia fructicola and of less than 5 p.p.m. against Stemphylium sarcinaeforme.
On tomato plants, it showed slight injury at 1%, but me injury at 0.1%.
In the greenhouse test against apple scab (Venturia inequalis) on apple seedlings (McIntosh), this com- .pound gave 92% protection at 0.75 lb. per 100 gallons and 80% protection at 0.25 lb. per 100 gallons, and 51% eradication at 0.75 lb. per 100 gallons.
In the greenhouse test against late blight (Phytophthorea .infestans) on tomatoes, this compound showed excellent performance, having an ED value of 53 p.p.m. against 480 p.p.m. for zineb as a standard. There was no injury shown at 1 lb. per 100 gallons.
The corresponding compounds in which the two. N- :methyl groups are replaced by ethyl groups or hydroxy- -ethyl have almost the same properties as the above quaternary ammonium salt. Likewise, there may be used the benzyl group as an N-substitutent to give again closely related compounds.
EXAMPLE 2 A mixture of 17.5 parts of 6-chloro-8-chloromethyl- 1,3-benzodioxane, 20.9 parts of (nonylbenzyl)dimethyl- .amine, and 120 parts of acetone was refluxed with stirring for 3.5 hours. The solid was cooled, whereupon it separated. It was filtered 01f, washed with acetone, and dried in air. There was obtained 30 parts of a product which melted at 126-128 C. and has the structure *(C O:CHaCeHACnHu-C."
C1 the Analysis.Calcd. for CgqHggClgNOgI Cl, 14.8; N, 2.9. Found: Cl, 14.9; N, 2.8. In the fungitoxicity test (slide-germination method), [8 (6 chloro-l,3-benzodioxanyl)methyl](nonylbenzyl) chloride gave the following E1350 values: 1-10 p.p.m. against both Alternaria solani and Monalim'a fructicola and less than 1 p.p.m. against Stemphylium sarcinae'forme.
Replacement of (nonylbenzyl)dimethylamine with an equivalent weight of N-nonylbenzylmorpholine gives (8- (6-chloro 1,3 benzodioxanyl)methyl) nonylbenzylmorpholinium chloride, which has ED values against the least as favorable as the above quaternary ammonium chloride. In the same way, there may be used nonylbenzylpiperidine or nonylbenzylpyrrolidine to give corresponding piperidinium and pyrrolidinium chlorides of similar activity and low phytotoxicity.
, EXAMPLE 3 i A mixture of 10 parts of 6-ch1oro8-chloromethyl-L3- benzodioxane, 13.9 parts of dodecylbenzyldimethylamine, and parts of acetone was refluxed with stirring for 3.5 hours. After the solvent was removed under reduced pressure, there was obtained 24 parts of a viscous oil which corresponded in composition to CHzNKCHs)zCHzCsHaCnHu-Q1 o CH2 K 01 E10 Analysis.-Calcd. for C H Cl NO N, 2.7. Found:
In the fungitoxicity test (slide-germination method), [8 (chloro 1,3-benzodioxanyl) methyl] (dodecylbenzyl) dimethylammonium chloride gave ED values of less than 5 p.p.m. against both Monolinia jructicola and Stemphylium sarcina e'forme.
On tomato plants, it showed no injury even at 1%.
In the greenhouse test against apple scab (Venturia inequalis) on apple seedings (McIntosh), this compound gave complete protection at 0.75 lb. per 100 gallons and 91% protection at 0.25 lb. per .100 gallons, and 92% eradication at 0.75 lb. per 100 gallons.
In the greenhouse test against late blight (Phytophthora infestans) on tomatoes, this compound showed. excellent performance, having an ED' value of 33 p.p.m. against an ED value of 480 p.p.m. for zineb as a standard underthe same conditions. There was not injury shown at 1 lb. per 100 gallons.
The comparable compound having two ethyl groups in place of themethyl groups is likewise free of 'phytotoxic efiects at normal use concentrations and of almost the same activity against Venturia in'equalis and phytophthora infestans. H
EXAMPLE 4 A mixture of 10 parts of 6-chloro-8-chloromethyl-l,3- benzodioxane, 13.6 parts of n-octadecyldimethylarnine,
and 80 parts of acetone was heated under reflux with stirring for 2 hours. The mixture was cooled, and a solid separated. This was filtered ofi, washed with acetone, and dried in air. There was obtained 18 parts of a product which melted'at about C. and has the structure of OH:N (CHa)rCn tt-Cl' O 1 EH:
Cl the 11 m. against Sthi-phylium sarcinafofme and ofless that 5 p.p.m. against Mdrioliriia' fr'uc'tico'lal On tomato plants, it showed moderate injury at 1% but no injury at 011%.
Replacement of the above N-methyl groups with ethyl or hydroxyethyl groups gives quaternary salts of the same characteristics, but of even greater safety on tender plants.
EXAMPLE 6 The alkyldimethylamine used in this experiment had the following composition:
40% n-dodecyldimethylamine 50% n-tetradecyldimethylamine 10% n-hexadecyldimethylamine A mixture of 24.2. parts of the alkyldimethylamine, 21.9 parts of 6-chloro-8-chloromethyl-1,3-benzodioxane, and 120 parts of acetone was stirred and heated under reflux for 4 hours. The mixture was concentrated under reduced pressure to give 45 parts of a viscous oil which corresponded in composition to wherein R represents alkyl groups from C to C Analysis.--Calcd. for
C1, 14.8; N, 2.9. Found: CI, 15.4; N, 3.0.
In the fungitoxicity test (slide-germination method), the above [8-(6-chloro-1,3-benzodioxanyl)methyl] -alkyldimethylammonium chloride gave ED values of 1-10 p.p.m. against Alternaria solani, Monolinia fructicola, and Stemphylium sarcinaeforme.
EXAMPLE 7 A mixture of 11 parts of 6-chloro-8-chloromethyl-1,3- benzodioxane, 10.1 parts of (5,5,7,7-tetramethyl-2-octenyl) dimethylamine, and 120 parts of acetone was refluxed with stirring for 3.5 hours. The solvent was removed, and there was a residual semi-solid which was triturated with warm ether. The solid thus separated was filtered E, washed, with ether, and dried. There was obtained 18.3 parts of a product which melted at 110-112 and has the structure Analysis.-Calcd. for C H C1 NO Cl, 16.5; N, 3.3. Found: CI, 16.0; N, 3.2.
In the fungitoxicity test (slide germination method), [8-(6-chloro 1,3 benzodioxany)methy1]-(5,5,7,7-tetramethyl-2-octenyl)dimethylammonium chloride gave ED values of 10-50 p.p.m. against Monolinia fructicola and 510 p.p.m. against Stemphylium sarcinaeforme.
Replacement of the above 5,5,7,7-tetramethyl 2-octenyl group with other long-chained alkenyl groups or anal];-
undecenyl' group or the oleyl group with entirely satisfactory results.
The quaternary ammonium compounds of this invention appear stable in light and in air. There is evidence that they have antlie'lmintic properties and can act as snailicides. For the latter purpose they may be used from aqueous solution or they may be mixed with a solid carrier, such as clay, diatomaceous earth, pyrophyllite, or talc, at concentrations of 5% to 50%. They may also serve against bacteria.
These compounds were examined for their bacteriostatic and bactericidal effects by the standard broth titer test, also known as the tube dilution test, (see page 71 of Surface-Active Quaternary Ammonium Germicides, Carl A. Lorentz, Academic Press, New York, 1950). In this test, the agent under test is successively diluted in broth in a series of tubes. The solutions are sterilized and inoculated with a test organism. The inoculated tubes are incubated for 24 hours at 37 C. The last dilution is noted at which no growth occurs. This is the bacteriostatic titer.
From the last dilutions which fail to show growth, transfers are made to sterile broth containing an inactivator for quaternary ammonium salts, here lecithin. These tubes are incubated and examined for growth. The last dilution to show no growth gives the bactericidal titer.
Summary of results is given in Table I.
Table I SUMMARY OF TITER TESTS S. typhosa S. aureus Compound of Example No. Bacterio- Bactericidal Bacterio- Bactericidal static Titer Titer static Titer Titer While in the examples there has been used the ch1oromethyl group, there may be used in the identical Way the bromomethyl group. The resulting quaternary ammonium bromides are at least as effective as the corresponding chlorides and in some instances are more active.
As is known in the art, the chloride or bromide ion may be replaced in known ways with other anions. Thus, a concentrated solution of a quaternary ammonium chloride may be treated with a sodium phosphate solution to exchange anions with formation of quaternary ammonium phosphate. Through conversion of halide to hydroxide and subsequent neutralization any anion can be introduced, including acetate or propionate, as typical anions of organic acids. It is thus possible to have present any desired anion.
I claim: 1. Compounds of the formula x R1 0111-1 1 12 \Ra 0H, 0 CH OH: CH
wherein X is an inert anion, R is a lipophilic group selected from the class consisting of 'alkyl groups of 10 to 20 carbon atoms, alkenyl groups of 11 to 18 carbon atoms, alkylbenzyl groups of 15 to 25 carbon atoms, and alkylphenoxyethoxyethyl groups of 15 to 25 carbon atoms,
R and R when taken individually, represent alkyl represent a saturated divalent aliphatic chain of --CH CH OCH CH groups which together with the nitrogen atom forms a heterocycle.
2. 8 (6 chloro 1,3 benzodioxanyDmethyl] (tert- 'octylphenoxyethoxyethyl)dimethylammonium chloride.
3. [8 (chloro 1,3 benzodioxanyDmethyl] (nonyltbenzyDdimethylammonium chloride. 7
4. [8 (6 ehloro 1,3 benzodioxanynmethyl] (doldecylbenzyndimethylammonium chloride. 1 5. [8 (6 chloro 1,3 benzodioxanyDmethyl] (5,5, 7,7:tetramethyl-2-octenyl)dimethylammonium chloride. 6. [8 (6 chloro 1,3 benzodioxanyhmethyl] n octadecyldimethylammonium chloride.
No references cited.
Claims (1)
1. COMPOUNDS OF THE FORMULA
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| Application Number | Priority Date | Filing Date | Title |
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| US836583A US2993909A (en) | 1959-08-28 | 1959-08-28 | Quaternary ammonium compounds containing the 8-(6-chloro-1, 3-benzodioxanyl) methyl group |
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| US836583A US2993909A (en) | 1959-08-28 | 1959-08-28 | Quaternary ammonium compounds containing the 8-(6-chloro-1, 3-benzodioxanyl) methyl group |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4056540A (en) * | 1974-01-01 | 1977-11-01 | Bristol-Myers Company | 4-Phenyl-1,3-benzodioxans |
| US5128362A (en) * | 1988-01-15 | 1992-07-07 | Abbott Laboratories | 1-aminomethyl-1,2,3,4-tetrahydronaphthalenes |
-
1959
- 1959-08-28 US US836583A patent/US2993909A/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| None * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4056540A (en) * | 1974-01-01 | 1977-11-01 | Bristol-Myers Company | 4-Phenyl-1,3-benzodioxans |
| US5128362A (en) * | 1988-01-15 | 1992-07-07 | Abbott Laboratories | 1-aminomethyl-1,2,3,4-tetrahydronaphthalenes |
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