US3364228A - 3-hydroxymethyl-4-(indol-3-yl)-hexahydro-1h-azepines and method of preparation - Google Patents
3-hydroxymethyl-4-(indol-3-yl)-hexahydro-1h-azepines and method of preparation Download PDFInfo
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- US3364228A US3364228A US466101A US46610165A US3364228A US 3364228 A US3364228 A US 3364228A US 466101 A US466101 A US 466101A US 46610165 A US46610165 A US 46610165A US 3364228 A US3364228 A US 3364228A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
Definitions
- This invention relates to novel 3-hydroxymethyl-4-(indol-3-yl)-hexah,ydro-lH-azepines and to processes for making the same.
- novel 3-hydroxymethyl-4-(indol-3-yl)-hexahydrolH-azepines of the present invention can be represented by the following formula:
- R, R and R are hydrogen or alkyl of not more than 4 carbon atoms, and R is hydrogen, alkyl of not more than 4 carbon atoms, alkoxy of not more than 4 carbon atoms, or halogen.
- alkyl of not more than 4 carbon atoms are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, and tertiary butyl.
- alkoxy are methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, secondary butoxy, and tertiary butoxy.
- halogen are fluoro, chloro, and bromo.
- novel compounds of the invention are nitrogenous bases and, as such, can exist in the protonated and nonprotonated forms according to the pH of the environment.
- R alkyl
- the nonprotonated form can be oxidized, with hydrogen peroxide, for example, to form the N- oxide.
- the N-oxide can exist in both the protonated and nonprotonated forms according to the pH of the environment.
- the protonated forms can be isolated as acid addition salts which are useful in upgrading the free base and the free base N-oxide forms, that is, the nonprotonated forms.
- Suitable acids for this purpose include hydrochloric acid, sulfuric acid, phosphoric acid, thiocyanic acid, fluosilicic acid, picric acid, Reineckes acid, azobenzenesulfonic acid, palmitic acid, acetic acid, maleic acid, and cyclohexanesulfamic acid.
- the acid addition salt can be formed by neutralizing the free base or free base N-oxide with the appropriate acid or by metathesis of a simple acid addition salt such as the hydrochloride or sulfate with another salt of the desired acid.
- the novel compounds of the invention are useful intermediates, thus, the condensation products obtained from thiocyanic acid addition salts and formaldehyde, according to U.S. Patents 2,425,320 and 2,606,155, are useful as pickling inhibitors, and the fluosilicic acid addition salts are useful as mothproofing agents according to U.S. Patents 1,915,334 and 2,075,359.
- Novel compounds of the invention wherein R is alkyl can also exist in the form of quaternary ammonium salts such, for example, as those obtained by coordinating the free base form with a loweralkyl halide, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl chloride, bromide, or iodide, including the isomeric forms thereof.
- the quaternary ammonium salts are useful for forming the corresponding quaternary ammonium fluosilicic acid salts which are useful as mothproofing agents.
- fluosilicic acid salts can be formed by metathesis of a quaternary ammonium salt with an inorganic flu-osilicate or by liberating the free base, that is, the quaternary ammonium hydroxide (by treating the quaternary ammonium salt with an equivalent of base, for example, sodium hydroxide) and neutralizing with fluosilicic acid.
- alkyl halides up to 18 carbon atoms, for example, where the alkyl group is nonyl, decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, and the isomeric forms thereof, are surface-active compounds useful as wetting agents and as disinfectants.
- the compounds of the invention can be prepared by reducing with lithium aluminum hydride a compound of the following formula:
- R, R R and R are as given above, and R is alkyl, for example, methyl, ethyl, propyl, butyl, and the isomeric forms thereof.
- the lithium aluminum hydride reduction can be effected in the manner already known in the art using, for example, ether, dioxane, or tetrahydrofuran as an inert solvent.
- the starting compounds or intermediates of Formula II can be prepared by reacting with dialkyl malonate, for example, diethyl malonate, a compound of the following formula:
- reaction is carried out in the presence of a strong base, for example, sodium hydroxide, and in an inert solvent, for example, xylene.
- a strong base for example, sodium hydroxide
- inert solvent for example, xylene.
- suitable strong bases include sodium, sodium hydride, and potassium hydroxide.
- suitable inert solvents include toluene, chlorobenzene, and decahydronaphthalene.
- the reaction mixture can be worked up for the recovery of the product by neutralization of the base followed by solvent extraction and/or chromatography and like methods already known in the art. In some instances, two isomeric forms of the compounds of Formula II are obtained.
- the starting 3-(2-pyrrolidinyl)indoles of Formula III can be prepared by processes already known in the art, for example, Youngdale et al., J. Med. Chem, 7, 415 (1964).
- Typical 3-(2-pyrrolidinyl)indoles which can be thus prepared and which can be used as starting compounds for the process of the invention include 3-(2-pyrrolidinyl) indole, 1-methyl-3-(2-pyrrolidinyl)indole, 3-(1-methyl-2- pyrrolidinyl)indole, 3-(1-ethyl 2-pyrrolidiny1)indole, 1- methyl-3- l-methyl-2-pyrrolidinyl) indole, 5 -methyl-3-( 1- methyl-Z-pyrrolidinyl)indole, 7-methyl-3-( 1-methyl-2-pyrrolidinyl)indole, 5 methoxy-3-(l-methyl-2-pyrrolidinyl) indole, 4 chloro-3-(1-methyl-2-pyrrolidinyl)indole, 5-
- the 3-(l-methyl-Z-pyrrolidinyl) indole can be substituted by any of the 3-(2-pyrrolidinyl) indoles embraced in Formula III, e.g., those given above.
- the diethyl malonate can be substituted by other dialkyl malonates, for example, dimethyl, dipropyl, diisopropyl, dibutyl, diisobutyl, disec.butyl, and di-tert.butyl malonates.
- R, R and R are members of the group consisting of hydrogen and alkyl of not more than 4 carbon atoms, and R is a member of the group consisting of hydrogen, alkyl of not more than 4 carbon atoms, alkoxy of not more than 4 carbon atoms, and halogen, and the acid addition salts thereof, the N-oxides thereof where R is alkyl and the acid addition salts thereof, and the alkyl quaternary ammonium salts thereof where R is alkyl.
- R, R and R are hydrogen or alkyl of not more than 4 carbon atoms, and R is hydrogen, alkyl of not more than 4 carbon atoms, alkoxy of not more than 4 carbon atoms, or halogen.
- R, R and R are hydrogen or alkyl of not more than 4 carbon atoms, and R is hydrogen, alkyl of not more than 4 carbon atoms, alkoxy of not more than 4 carbon atoms, or halogen, which comprises reacting with 6 a dialkyl malonate in the presence or a strong base a compound having the following formula:
- R, R R and R are as given above, and R is alkyl, and reducing the resulting compound with lithium aluminum hydride.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
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- Nitrogen Condensed Heterocyclic Rings (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
Description
United States Patent ()fiice 3,364,228 Patented Jan. 16, 1968 3 HYDROXYMETHYL 4 (INDOL 3 YL) HEXA- HYDRO 1H AZEPINES AND METHOD OF PREPARATION Jackson B. Hester, In, Portage, Mich., assignor to The Upjohn Company, Kalamazoo, Mich., a corporation of Delaware No Drawing. Filed June 22, 1965, Ser. No. 466,101
5 ClaimsKCl. Mil-326.15)
This invention relates to novel 3-hydroxymethyl-4-(indol-3-yl)-hexah,ydro-lH-azepines and to processes for making the same.
The novel 3-hydroxymethyl-4-(indol-3-yl)-hexahydrolH-azepines of the present invention can be represented by the following formula:
l ds I wherein R, R and R are hydrogen or alkyl of not more than 4 carbon atoms, and R is hydrogen, alkyl of not more than 4 carbon atoms, alkoxy of not more than 4 carbon atoms, or halogen. Examples of alkyl of not more than 4 carbon atoms are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, and tertiary butyl. Examples of alkoxy are methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, secondary butoxy, and tertiary butoxy. Examples of halogen are fluoro, chloro, and bromo.
The novel compounds of the invention are nitrogenous bases and, as such, can exist in the protonated and nonprotonated forms according to the pH of the environment. When R is alkyl the nonprotonated form can be oxidized, with hydrogen peroxide, for example, to form the N- oxide. The N-oxide can exist in both the protonated and nonprotonated forms according to the pH of the environment. The protonated forms can be isolated as acid addition salts which are useful in upgrading the free base and the free base N-oxide forms, that is, the nonprotonated forms. Suitable acids for this purpose include hydrochloric acid, sulfuric acid, phosphoric acid, thiocyanic acid, fluosilicic acid, picric acid, Reineckes acid, azobenzenesulfonic acid, palmitic acid, acetic acid, maleic acid, and cyclohexanesulfamic acid. The acid addition salt can be formed by neutralizing the free base or free base N-oxide with the appropriate acid or by metathesis of a simple acid addition salt such as the hydrochloride or sulfate with another salt of the desired acid. The novel compounds of the invention are useful intermediates, thus, the condensation products obtained from thiocyanic acid addition salts and formaldehyde, according to U.S. Patents 2,425,320 and 2,606,155, are useful as pickling inhibitors, and the fluosilicic acid addition salts are useful as mothproofing agents according to U.S. Patents 1,915,334 and 2,075,359.
Novel compounds of the invention wherein R is alkyl can also exist in the form of quaternary ammonium salts such, for example, as those obtained by coordinating the free base form with a loweralkyl halide, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl chloride, bromide, or iodide, including the isomeric forms thereof. The quaternary ammonium salts are useful for forming the corresponding quaternary ammonium fluosilicic acid salts which are useful as mothproofing agents. These fluosilicic acid salts can be formed by metathesis of a quaternary ammonium salt with an inorganic flu-osilicate or by liberating the free base, that is, the quaternary ammonium hydroxide (by treating the quaternary ammonium salt with an equivalent of base, for example, sodium hydroxide) and neutralizing with fluosilicic acid. Higher quaternary ammonium salts, as are obtained as described above by using alkyl halides up to 18 carbon atoms, for example, where the alkyl group is nonyl, decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, and the isomeric forms thereof, are surface-active compounds useful as wetting agents and as disinfectants.
The compounds of the invention can be prepared by reducing with lithium aluminum hydride a compound of the following formula:
0 I N R1000 4 R3 II wherein R, R R and R are as given above, and R is alkyl, for example, methyl, ethyl, propyl, butyl, and the isomeric forms thereof. The lithium aluminum hydride reduction can be effected in the manner already known in the art using, for example, ether, dioxane, or tetrahydrofuran as an inert solvent.
The starting compounds or intermediates of Formula II can be prepared by reacting with dialkyl malonate, for example, diethyl malonate, a compound of the following formula:
B. T R4 R3 III wherein R, R R and R are as given above. The reaction is carried out in the presence of a strong base, for example, sodium hydroxide, and in an inert solvent, for example, xylene. Other suitable strong bases include sodium, sodium hydride, and potassium hydroxide. Other suitable inert solvents include toluene, chlorobenzene, and decahydronaphthalene. The reaction mixture can be worked up for the recovery of the product by neutralization of the base followed by solvent extraction and/or chromatography and like methods already known in the art. In some instances, two isomeric forms of the compounds of Formula II are obtained. These isomers can be separated by chromatography and/or fractional crystallization, if desired, and both isomers on reduction with lithium aluminum hydride yield compounds of the invention. It is not necessary, however, to effect a separation because mixtures of the two isomers as crude reaction products can be reduced with lithium aluminum hydride to give the compounds of the invention.
The starting 3-(2-pyrrolidinyl)indoles of Formula III can be prepared by processes already known in the art, for example, Youngdale et al., J. Med. Chem, 7, 415 (1964).
Typical 3-(2-pyrrolidinyl)indoles which can be thus prepared and which can be used as starting compounds for the process of the invention include 3-(2-pyrrolidinyl) indole, 1-methyl-3-(2-pyrrolidinyl)indole, 3-(1-methyl-2- pyrrolidinyl)indole, 3-(1-ethyl 2-pyrrolidiny1)indole, 1- methyl-3- l-methyl-2-pyrrolidinyl) indole, 5 -methyl-3-( 1- methyl-Z-pyrrolidinyl)indole, 7-methyl-3-( 1-methyl-2-pyrrolidinyl)indole, 5 methoxy-3-(l-methyl-2-pyrrolidinyl) indole, 4 chloro-3-(1-methyl-2-pyrrolidinyl)indole, 5-
3 chloro-3-(1-methyl-2-pyrrolidinyl)indole, -bromo-3-(1- methyl-Z-pyrrolidinyl)indole, and 5-fluoro-3-(l-methyl-2- pyrrolidinyl)indole. By use of appropriate starting indoles in the processes of Youngdale et al., supra, other starting compounds of Formula III are readily obtained.
The following example is given by way of illustration, it being understood that the 3-(l-methyl-Z-pyrrolidinyl) indole can be substituted by any of the 3-(2-pyrrolidinyl) indoles embraced in Formula III, e.g., those given above. It is to be understood also that the diethyl malonate can be substituted by other dialkyl malonates, for example, dimethyl, dipropyl, diisopropyl, dibutyl, diisobutyl, disec.butyl, and di-tert.butyl malonates.
Example 1.-3-l1ydr0xymethyl-4-(ina'0le-3-yl)-1-methylhexahydro-IH-azepine (A) Ethyl 1-methyl-2-oxo-4-(indol-3-yl)-hexahydro- 1H-azepine-3-carboxylate LN EtOOC J I? CHa(COOEt)g NaOH T H on. l H H A mixture of 3-(l-methyl-Z-pyrrolidinyl)indole (50 g.; 0.25 mole), diethyl malonate (42 g.; 0.262 mole), powdered sodium hydroxide (1.0 g.) and xylene (300 ml.) was allowed to reflux under nitrogen for 31.25 hours. During this period ethanol, formed in the reaction, was removed by distillation. Additional 500-mg. portions of powdered sodium hydroxide were added to the reaction mixture after the reaction had proceeded for 7.5 hours and 25.5 hours. The cooled reaction mixture was poured into dilute acetic acid and the mixture was extracted with chloroform. The extract was washed successively with water, dilute ammonium hydroxide, and saturated aqueous sodium chloride, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The last traces of xylene were removed from the residue by azeotropic distillation, first with toluene and then benzene. A benzene solution of the resulting brown oil was adsorbed on 2 pounds of neutral alumina and chromatographed. With benzene 4.006 g. of indole, M.P. 5154 C., was eluted. Elution of the column with 50% ether-chloroform followed by ethyl acetate crystallization yielded 11.132 g. of ethyl 1 methyl-2-oxo-4-(indol-3-yl)hexahydro-1H- azepine-3-carboxylate (isomer A); M.P. 191-195" C. A sample of this material was recrystallized several times from methanol-ethyl acetate for analysis; M.P. 1965-- 198 C. The ultraviolet spectrum (ethanol) had A max. 220, 281.5, and 290 m (6 35,750, 5,950, and 5,150, respectively) with an inflection at 275 mu (6 5,550). The infrared spectrum (mineral oil) showed NH: 390 cm." and C 0: 1740 and 1627 CHIS-1.
Analysis.-Calcd. for C H N O C, 68.77; H, 7.05; N, 8.91. Found: C, 68.36; H, 7.13; N, 8.98.
Concentration of the mother liquors from the above crystallizations yielded a brown oil (9.09 g.) which had practically the same infrared spectrum as the above crystalline product. An ice-cold solution of this material in 150 ml. of absolute methanol was treated with 30 m1. of 0.976 N aqueous sodium hydroxide. The resulting solution was allowed to warm to about 25 C. After a few hours a crystalline precipitate formed. After 24 hours standing, water was added to the mixture which was then concentrated to remove the methanol. The solid which remained was collected by filtration, washed with water, and dissolved in methylene chloride. The methylene chloride solution was washed with Water, dried over anhydrous sodium sulfate, and concentrated in vacuo. Crystallization of the residue from methanol-ethyl acetate yielded three crops: 2.888 g., M.P. 2095-2125 C.; 0.623
g., M.P. 202.5205 C.; and 0.132 g., M.P. 194198 C. An analytical sample of ethyl 1-methyl2-oxo-4-(indol-3- yl) hexahydro-1H-azepine-3-carboxylate (isomer B), M.P. 212.5214.5 C., was prepared by recrystallizing the first crop from methylene chloride-methanol. The ultraviolet spectrum (methanol) had A max. 221, 281, and 290 my. (5 37,100, 6,150, and 5,350, respectively) with an inflection at 274 m (6 5,700). The infrared spectrum (chloroform and mineral oil) was almost identical to that of isomer A. A mixed melting point with isomer A was taken; M.P. 20l212.5 C.
Analysis.--Calcd. for C H N O C, 68.77; H, 7.05; N, 8.91. Found: C, 68.75; H, 7.18; N, 8.92.
(B) 3 hydroxymethyl 4-(indol-3-yl)-1-methylhexahydro-lH-azepine OCH:
To a stirred, ice-cold suspension of 5.15 g. of lithium aluminum hydride in 500 ml. of dry tetrahydrofuran was added, under nitrogen, 5.0 g. (15.9 mmoles) of the lactamester of Part A (isomer A, M.P. 197-198 C.). This mixture was allowed to reflux gently for 4.75 hours and stand for 18 hours at about 25 C. It was then cooled in an ice bath and treated successively with 5 ml. of water, 5 ml. of 15% aqueous sodium hydroxide, and 15 ml. of water. The inorganic precipitate was collected by filtration and washed with ether. Concentration of the combined filtrate and washing yielded a solid which was dissolved in ethyl acetate, decolorized with activated carbon, and crystallized to yield 3-hydroXymethyl-4-(indol-3- yl)l-methylhexahydro-lH-azepine in two crops: 3.047 g., M.P. 143.5145.5 C., and 0.272 g., M.P. 143.5- 145.5 C. (80.7% yield). The analytical sample, M.P. 143145 C., was prepared by recrystallizing some of this material three times from methanol-ethyl acetate. The ultraviolet spectrum (ethanol) had max. 223, 282, and 290.5 my. (6 34,950, 5,700, and 5,000, respectively) with an inflection at 276 my. (6 5,300).
Analysis.-Calcd. for C H N O: C, 74.38; H, 8.58; N, 10.84. Found: C, 74.18; H, 8.37; N, 10.53.
I claim:
1. A member of the group consisting of compounds of the following formula:
HOCH: ,l,
wherein R, R and R are members of the group consisting of hydrogen and alkyl of not more than 4 carbon atoms, and R is a member of the group consisting of hydrogen, alkyl of not more than 4 carbon atoms, alkoxy of not more than 4 carbon atoms, and halogen, and the acid addition salts thereof, the N-oxides thereof where R is alkyl and the acid addition salts thereof, and the alkyl quaternary ammonium salts thereof where R is alkyl.
2. A compound of the following formula:
wherein R, R and R are hydrogen or alkyl of not more than 4 carbon atoms, and R is hydrogen, alkyl of not more than 4 carbon atoms, alkoxy of not more than 4 carbon atoms, or halogen.
3. 3-hydroxymethy1-4-(indol-3-yl)-1-methylhexahydrolH-azepine.
4. Process for making compounds of the following formula:
5 HOCH N wherein R, R and R are hydrogen or alkyl of not more than 4 carbon atoms, and R is hydrogen, alkyl of not more than 4 carbon atoms, alkoxy of not more than 4 carbon atoms, or halogen, which comprises reacting with 6 a dialkyl malonate in the presence or a strong base a compound having the following formula:
wherein R, R R and R are as given above, and R is alkyl, and reducing the resulting compound with lithium aluminum hydride.
5. The process of making compounds of Formula I wherein R, R and R are hydrogen or alkyl of not more than 4 carbon atoms, and R is hydrogen, alkyl of not more than 4 carbon atoms, alkoxy of not more than 4 carbon atoms, or halogen, which comprises reducing with lithium aluminum hydride a compound of the Formula II wherein R, R R and R are as given above, and R is alkyl.
References Cited UNITED STATES PATENTS 3,214,438 10/1965 Youngdale 26-0326.15
ALEX MAZEL, Primary Examiner.
I. A. NARCAVAGE, Assistant Examiner.
Claims (2)
1. A MEMBER OF THE GROUP CONSISTING OF COMPOUNDS OF THE FOLLOWING FORMULA:
4. PROCESS FOR MAKING COMPOUNDS OF THE FOLLOWING FORMULA:
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US466101A US3364228A (en) | 1965-06-22 | 1965-06-22 | 3-hydroxymethyl-4-(indol-3-yl)-hexahydro-1h-azepines and method of preparation |
| IL25766A IL25766A (en) | 1965-06-22 | 1966-05-13 | 3-hydroxymethyl-4-(indol-3-yl)-hexahydro-1h-azepines and process for their preparation |
| NL6608201A NL6608201A (en) | 1965-06-22 | 1966-06-14 | |
| GB26525/66A GB1150932A (en) | 1965-06-22 | 1966-06-14 | Improvements in or relating to Heterocyclic Compounds and the Manufacture thereof |
| DE19661620635 DE1620635A1 (en) | 1965-06-22 | 1966-06-21 | Process for the preparation of 3-hydroxymethyl-4- (indol-3-yl) -hexahydro-1H-azepine |
| FR66283A FR1484225A (en) | 1965-06-22 | 1966-06-21 | New azepines and their preparation process |
| CH901166A CH469016A (en) | 1965-06-22 | 1966-06-22 | Process for the preparation of 3-hydroxymethyl-4- (indol-3-yl) -hexahydro-1H-azepines |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US466101A US3364228A (en) | 1965-06-22 | 1965-06-22 | 3-hydroxymethyl-4-(indol-3-yl)-hexahydro-1h-azepines and method of preparation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3364228A true US3364228A (en) | 1968-01-16 |
Family
ID=23850471
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US466101A Expired - Lifetime US3364228A (en) | 1965-06-22 | 1965-06-22 | 3-hydroxymethyl-4-(indol-3-yl)-hexahydro-1h-azepines and method of preparation |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US3364228A (en) |
| CH (1) | CH469016A (en) |
| DE (1) | DE1620635A1 (en) |
| GB (1) | GB1150932A (en) |
| IL (1) | IL25766A (en) |
| NL (1) | NL6608201A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3214438A (en) * | 1963-10-14 | 1965-10-26 | Upjohn Co | 3-substituted indoles |
-
1965
- 1965-06-22 US US466101A patent/US3364228A/en not_active Expired - Lifetime
-
1966
- 1966-05-13 IL IL25766A patent/IL25766A/en unknown
- 1966-06-14 GB GB26525/66A patent/GB1150932A/en not_active Expired
- 1966-06-14 NL NL6608201A patent/NL6608201A/xx unknown
- 1966-06-21 DE DE19661620635 patent/DE1620635A1/en active Pending
- 1966-06-22 CH CH901166A patent/CH469016A/en unknown
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3214438A (en) * | 1963-10-14 | 1965-10-26 | Upjohn Co | 3-substituted indoles |
Also Published As
| Publication number | Publication date |
|---|---|
| IL25766A (en) | 1970-02-19 |
| GB1150932A (en) | 1969-05-07 |
| NL6608201A (en) | 1966-12-23 |
| DE1620635A1 (en) | 1970-08-20 |
| CH469016A (en) | 1969-02-28 |
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