US3399242A - Chemical process and products produced thereby - Google Patents

Chemical process and products produced thereby Download PDF

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US3399242A
US3399242A US560023A US56002366A US3399242A US 3399242 A US3399242 A US 3399242A US 560023 A US560023 A US 560023A US 56002366 A US56002366 A US 56002366A US 3399242 A US3399242 A US 3399242A
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allyl
dibenzo
group
cycloheptene
carbon atoms
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US560023A
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Norman L Wendler
Taub David
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Merck and Co Inc
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C33/05—Alcohols containing rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
    • C07C1/325—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a metal atom
    • C07C1/326—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a metal atom the hetero-atom being a magnesium atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
    • C07C13/54—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings
    • C07C13/547—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings at least one ring not being six-membered, the other rings being at the most six-membered
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
    • C07C13/54—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings
    • C07C13/605—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings with a bridged ring system
    • C07C13/615—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings with a bridged ring system with an adamantane ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C35/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C35/22—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a condensed ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/30—Ortho- or ortho- and peri-condensed systems containing three rings containing seven-membered rings
    • C07C2603/32—Dibenzocycloheptenes; Hydrogenated dibenzocycloheptenes

Definitions

  • a perfiuoroalkoxyl group having up to 4 carbon atoms ABSTRACT OF THE DISCLOSURE cyano, carboxy, carbamyl, an alkylcarbamyl group having The method of the present application includes the steps up to 5 carbon atoms dlalkylcarbamyl group having up of condensing a 5-halo-5H-dibenzo[a,d]cycloheptene with to 9 carbon atoms a carbalkoxy group having up 9 6 carbon atoms, mercapto, an alkylmercapto group having up to 4' carbon atoms, a perfluoroalkylmercapto group having up to 4 carbon atoms, an alkylsulfonyl group having up to 4 carbon atoms, a perfluoroalkylsulfonyl group having up to 4 carbon atoms, sulfamyl, an alkylsulfamyl group having up to 4 carbon atoms, or a
  • the starting compound namely, the S-halo-SH-dibenzo- [a,d]-cycloheptene, which may be substituted by X, X and'Y as defined above, may be made using the process described by G. Berti in the Gazz. Chim. Ital. 87, 293-309 (1957); F. I Villani, C. A. Ellis, C. Teichman and C. Bigos, J. Med. Pharm. Chem. 5, 373 (1962); and M. Protiva et al., ibid, 4, 411 (1961), and the references cited therein.
  • ketone namely, 5H-dibenzo-[a,d] -cycloheptene-S-one, which may be prepared by using the process described by A. C. Cope et al., entitled Cyclic Polyolefins, XV, 1 methylene 2,3,6,7 dibenzocycloheptatriene, appearing in J.A.C.S. 73, 1673, 1678 (1951).
  • Starting compounds of ketones having substituents on the benzene rings may be made by the following teachings of T. W.
  • This invention relates to a process for making inter- 3O mediates for the synthesis of 5H-dibenzo[a,d] -cyc1oheptenes which are substituted at the S-carbon atom with an aminopropyl radical.
  • the invention also includes the synthesis of certain novel compounds produced by said process.
  • aminopropyl compounds which are formed from the intermediates of the present invention are useful in the treatment of mental health conditions as they are antidepressants and serve as mood elevators or psychic energizers. These compounds are preferably administered in the form of their acid salts and these salts are included in the scope of this invention.
  • the process of the present invention may be represented by the following flow sheet.
  • the first step in the similar and are selected from the group consisting of by method of the present invention involves the condensadrogen, an alkyl group having up to 6 carbon atoms, an tion of a S-halo-SH-dibenzo[a,d]-cycloheptene with an allyl or a 1', 2 and 3'-alkyl substituted allyl magnesium halide to form the corresponding -allyl-5H-di-benzo- [a,d]-cycloheptene.
  • the next step in the method involves the addition of a molecule of water to the 5-allyl intermediate to form the corresponding S-(y-hydroxypropyl)-5H-dibenzo-[a,d]-cycloheptene.
  • the desired addition is accomplished by a process of hydroboration, which term denotes herein reaction with a suitable boron compound, subsequent oxidation and hydrolysis to form the desired hydroxy compound.
  • Suitable boranes contain preferably at least one B-H bond in the molecule as, for example, amine boranes, alkyl boranes, aryl boranes, alkylaryl boranes, boranealuminum oxides, and the like.
  • a basic solution of hydrogen peroxide is a preferred hydrolysis medium although others may be used as well.
  • the 'y-hydroxy compounds are obtained, they are converted to the useful aminopropyl compounds by a process of halogenation with a hydrogen halide to produce the corresponding halide derivative, and amination with an amine to form the desired end product or 5-aminopropyl derivative.
  • the 5-allyl intermediate is converted. to the S-y-bromopropyl intermediate by a peroxidecatalyzed addition of hydrogen bromide.
  • the bromo intermediate then is converted to the aminopropyl end compound by direct amination according to the aforementioned copending application.
  • reaction mixture is then cooled below the point of reflux, but not so low as to cause the Grignard reagent to precipitate, and 10 g. of S-chloro- 5H-dibenzo-[a,d]-eycloheptene in 20 ml. of dry ether is added with stirring in 15 minutes.
  • the reaction mixture is stirred and allowed to react at room temperature for /2 hour.
  • the reaction mixture then is chilled in an ice bath and treated with 45 ml. of saturated ammonium chloride solution.
  • the layers are separated and just enoughv water is added to dissolve the solid salts in the aqueous layer.
  • the latter is extracted with 2X25 ml. of ether.
  • the combined organic layers are washed with ml. of saturated salt solution, dried over magnesium sulfate and the solvent removed in vacuo to yield the desired product as an oil. This oil is further purified by chromatography on alumina.
  • EXAMPLE 2 S-(y-hydroxypropyl)-5H-dibenzo-[a,d]-cycloheptene
  • a solution of 0.5 g. of the 5-allyl intermediate produced in Example 1 in 15 cc. of dry ethyl ether is treated I Following the procedure described in detail above and 1 using starting compoundshaving'X, X and Y substituents as presented above, there are produced the corresponding 1 X, X and Y substituted 5-('y-hydroxypropyl)-5H-dibenzo- [a,d]-cycloheptenes.
  • a method of making 5-allyl-5H-dibenzo-[a,d]-cycloheptene intermediates which comprises reacting a 5- halo-5H-dibenzo-[a,d]-cycloheptene with an allyl magnesium halide to produce the desired intermediates.
  • Y is selected from the group consisting of a halogen and hydrogen and Z is selected from the group consisting of allyl and alkyl-substituted allyl, which comprises reacting a compound having the formula:
  • Hal is a halogen with an allyl magnesium halide, ZMg halide, where [is as defined above, to produce the corresponding 5-allyl intermediate.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

an allyl magnesium halide to form the corresponding r 3,399,242 Patented Aug. 27, 1968 1 I v I v 2 3 399 242 alkenyl group having up to 6 carbon atoms, a prefiuoro- CHEMICAL PROCESS AND PRODUCTS alkyl group having up to 4 carbon atoms, a phenyl or a PRODUCED THEREBY substituted phenyl radical, an acyl group having up to 4 Norman L. Wendler, Summit, and David Taub, Metuchen, carbon atoms, a perfiuoroacyl group having up to 4 car- N.J., assignors to Merck & Co., Inc., Rahway, N.J., a 5 bon atoms, amino, an alkylamino group having up to 4 corporation of New Jersey carbon atoms, a dialkylamino group having up to 8 car- No Drawing. Original application July 12, 1962, Ser. No. hon atoms an acylamino group having up to 4 carbon 209,311, now Patent No. 3,270,067, dated Aug..-30, atoms a rfluoroac lam-n on h Vin u to 4 arbon 1966. Divided and this application Apr. 28, 1966, Ser. P Y 1 P a g P c 560 023 atoms, an alkylsulfonylammo group having up to 4 car- 5 Claims (Cl. 260463) 10 bon atoms, halogen (fluorine, chlorine, bromine or iodine), hydroxyl, an alkoxyl group having up to 4 carbon atoms,
a perfiuoroalkoxyl group having up to 4 carbon atoms, ABSTRACT OF THE DISCLOSURE cyano, carboxy, carbamyl, an alkylcarbamyl group having The method of the present application includes the steps up to 5 carbon atoms dlalkylcarbamyl group having up of condensing a 5-halo-5H-dibenzo[a,d]cycloheptene with to 9 carbon atoms a carbalkoxy group having up 9 6 carbon atoms, mercapto, an alkylmercapto group having up to 4' carbon atoms, a perfluoroalkylmercapto group having up to 4 carbon atoms, an alkylsulfonyl group having up to 4 carbon atoms, a perfluoroalkylsulfonyl group having up to 4 carbon atoms, sulfamyl, an alkylsulfamyl group having up to 4 carbon atoms, or a dialkylsulfamyl group having up to 8 carbon atoms; more than one of these substituents may be on each benzenoid ring.
The starting compound, namely, the S-halo-SH-dibenzo- [a,d]-cycloheptene, which may be substituted by X, X and'Y as defined above, may be made using the process described by G. Berti in the Gazz. Chim. Ital. 87, 293-309 (1957); F. I Villani, C. A. Ellis, C. Teichman and C. Bigos, J. Med. Pharm. Chem. 5, 373 (1962); and M. Protiva et al., ibid, 4, 411 (1961), and the references cited therein. These compounds are, in turn, prepared from the known ketone, namely, 5H-dibenzo-[a,d] -cycloheptene-S-one, which may be prepared by using the process described by A. C. Cope et al., entitled Cyclic Polyolefins, XV, 1 methylene 2,3,6,7 dibenzocycloheptatriene, appearing in J.A.C.S. 73, 1673, 1678 (1951). Starting compounds of ketones having substituents on the benzene rings may be made by the following teachings of T. W. Campbell et al., in an article entitled Synthesis of 2-acetamido- 2,3:6,7-dibenzotropilidene and 2-acetamido-9,9-dimethyl fluorene, appearing in Helv. Chem. Acta 36, 1489 to 1499 (1953). Starting compounds where the Y substituent is allyl-5H-dibenzo[a,d] cycloheptene which is hydroborated, oxidized and hydrolyzed to form the corresponding 5-('yhydroxypropyl)-5H-dibenzo[a,d]cycloheptene, which is converted to a dibenzocycloheptene substituted at the 5- carbon atom with an aminopropyl radical in accordance with the procedure described in United States application Ser. No. 188,873 filed Apr. 19, 1962, now United States Patent 3,272,864.
This is a division of application Ser. No. 209,311, filed July 12, 1962.
This invention relates to a process for making inter- 3O mediates for the synthesis of 5H-dibenzo[a,d] -cyc1oheptenes which are substituted at the S-carbon atom with an aminopropyl radical. The invention also includes the synthesis of certain novel compounds produced by said process.
The aminopropyl compounds which are formed from the intermediates of the present invention are useful in the treatment of mental health conditions as they are antidepressants and serve as mood elevators or psychic energizers. These compounds are preferably administered in the form of their acid salts and these salts are included in the scope of this invention.
The process of the present invention may be represented by the following flow sheet.
X x' X ZMgHal H Hal 11 Z hydroboratloi/ g igz Y I Y UTILITY X X! S.N. 188,873 Filed 4/19/62 H Z-OH H ZHBr UTILITY S.N. 188,873 Filed 4/19/62 dibenzocycloheptenes substituted at the 5-carbon atom with an aminopropyl radical in which Hal is a halogen, preferably chlorine or bromine; a halogen may be made following the teachings of Villani Y is a halogen or hydrogen; Z is allyl and a 1', 2' and 3'- in the above-cited reference. alkyl-substituted allyl, and X and X are similar or dis- As shown in the flow sheet above, the first step in the similar and are selected from the group consisting of by method of the present invention involves the condensadrogen, an alkyl group having up to 6 carbon atoms, an tion of a S-halo-SH-dibenzo[a,d]-cycloheptene with an allyl or a 1', 2 and 3'-alkyl substituted allyl magnesium halide to form the corresponding -allyl-5H-di-benzo- [a,d]-cycloheptene. In a typical run, S-chloro-SH-dibenzo- [a,d]-cycloheptene is reacted with allyl magnesium bromide in dry diethyl ether under reflux to form 5-allyl-5H- dibenzo-[a,d]-cycloheptene. I
The next step in the method involves the addition of a molecule of water to the 5-allyl intermediate to form the corresponding S-(y-hydroxypropyl)-5H-dibenzo-[a,d]-cycloheptene. In accordance with the invention, the desired addition is accomplished by a process of hydroboration, which term denotes herein reaction with a suitable boron compound, subsequent oxidation and hydrolysis to form the desired hydroxy compound. For example, upon treatment of 5-allyl-5H dibenzo-[a,d]-cycloheptene in ether solution with one mol equivalent of a borane, followed by oxidative hydroysis, there is produced the corresponding 5- -hyclroxypropyl -5I-I-dibenzoa,d] -cycloheptene.
Suitable boranes contain preferably at least one B-H bond in the molecule as, for example, amine boranes, alkyl boranes, aryl boranes, alkylaryl boranes, boranealuminum oxides, and the like. A basic solution of hydrogen peroxide is a preferred hydrolysis medium although others may be used as well.
Once the 'y-hydroxy compounds are obtained, they are converted to the useful aminopropyl compounds by a process of halogenation with a hydrogen halide to produce the corresponding halide derivative, and amination with an amine to form the desired end product or 5-aminopropyl derivative. These steps are described in the copending application, Ser. No. 188,873, filed Apr. 19, 1962.
In an alternative route, the 5-allyl intermediate is converted. to the S-y-bromopropyl intermediate by a peroxidecatalyzed addition of hydrogen bromide. The bromo intermediate then is converted to the aminopropyl end compound by direct amination according to the aforementioned copending application.
The examples which follow will more specifically illustrate the process of the present invention.
EXAMPLE 1 5-allyl-5H-dibenzo-[a,d] -cycloheptene To a 125 ml., 3-neck flask (flamed out and cooled under dry nitrogen) equipped with a stirrer, addition funnel, and ether-type condenser are charged 4.8 g. of clean magnesium turnings and ml. of dry ethyl ether. 17 g. of allyl bromide in 10 ml. of dry ethyl ether is added dropwise with stirring at a rate suflicient to maintain a gentle reflux. Stirring and refluxing is continued until all the metal is gone. The reaction mixture is then cooled below the point of reflux, but not so low as to cause the Grignard reagent to precipitate, and 10 g. of S-chloro- 5H-dibenzo-[a,d]-eycloheptene in 20 ml. of dry ether is added with stirring in 15 minutes. The reaction mixture is stirred and allowed to react at room temperature for /2 hour. The reaction mixture then is chilled in an ice bath and treated with 45 ml. of saturated ammonium chloride solution. The layers are separated and just enoughv water is added to dissolve the solid salts in the aqueous layer. The latter is extracted with 2X25 ml. of ether. The combined organic layers are washed with ml. of saturated salt solution, dried over magnesium sulfate and the solvent removed in vacuo to yield the desired product as an oil. This oil is further purified by chromatography on alumina.
Following the procedure described in detail above and using starting compounds having X, X, and Y substituents as presented above, there are produced the corresponding X, X, and Y substituted 5-allyl-5H-dibenzo- [a,d]-cycloheptenes.
EXAMPLE 2 S-(y-hydroxypropyl)-5H-dibenzo-[a,d]-cycloheptene A solution of 0.5 g. of the 5-allyl intermediate produced in Example 1 in 15 cc. of dry ethyl ether is treated I Following the procedure described in detail above and 1 using starting compoundshaving'X, X and Y substituents as presented above, there are produced the corresponding 1 X, X and Y substituted 5-('y-hydroxypropyl)-5H-dibenzo- [a,d]-cycloheptenes.
EXAMPLE 3 5- ('y-bromopropyl)-5H-dibenzo-[a,d]-cycloheptene' Hydrogen bromide gas is bubbled into a solution of 1.0 g. of 5-allyl-5H-dibenzo-[a,d]-cycloheptene and 50 mg. of benzoyl peroxide in 50 cc. of benzene at 25 for 2 hours. The solvent is removed under vacuum and the residue is crystallized from ether hexane to give the desired 'y-bromopropyl compound.
EXAMPLE/4 Following the procedure described in detail in the above examples and using equivalent quantities of 1', 2' and 3'-methyl and ethyl substituted allyl bromides in place of allyl bromide in the above process, there are produced the corresponding propyl compounds substituted with 'a, 5- and 'y-methyl and ethyl groups.
What is claimed is:
1. A method of making 5-allyl-5H-dibenzo-[a,d]-cycloheptene intermediates which comprises reacting a 5- halo-5H-dibenzo-[a,d]-cycloheptene with an allyl magnesium halide to produce the desired intermediates.
2.'A method of making 5-allyl-5H-dibenzo[a,d]-cycloheptene which comprises reacting5-chloro-5H-dibenzo- [a,d]-cycloheptene with allyl magnesium bromide to produce the desired product;
3. S-alIyl-SH-dibenzoa,d] -cycloheptene.
4. A method of making 5-allyl-5H-dibenzo-[a,d]-cycloheptenes having the formula:
wherein Y is selected from the group consisting of a halogen and hydrogen and Z is selected from the group consisting of allyl and alkyl-substituted allyl, which comprises reacting a compound having the formula:
Hal
wherein Y is as previously defined and Hal is a halogen with an allyl magnesium halide, ZMg halide, where [is as defined above, to produce the corresponding 5-allyl intermediate.
5. 5 ally'l-5H-dibenzo[a,d]-cyc1oheptene intermediate gen and hydrogen, and Z is selected from the group concompounds having the formula: sisting of allyl and alkyl-substituted allyl.
Y References Cited UNITED STATES PATENTS 3,272,864 9/1966 Hoffsommer et a1. 260-649 3,321,535 5/1967 Peters et a1. 260-649 H Z DELBERT E. GANTZ, Primary Examiner. where Y is selected from the group consisting of a halo- 10 C. R. DAVIS, Assistant Examiner.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3272864A (en) * 1962-04-19 1966-09-13 Merck & Co Inc Process for preparing 5-(3-aminopropylidene)-5h-dibenzo [a, d] cycloheptene and 5h-dibenzo [a, d]-10, 11-dihydro-cycloheptene derivatives
US3321535A (en) * 1962-08-10 1967-05-23 Lilly Co Eli Process for dibenzo[a, d]cyclohepta[1.4]diene intermediates

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3272864A (en) * 1962-04-19 1966-09-13 Merck & Co Inc Process for preparing 5-(3-aminopropylidene)-5h-dibenzo [a, d] cycloheptene and 5h-dibenzo [a, d]-10, 11-dihydro-cycloheptene derivatives
US3321535A (en) * 1962-08-10 1967-05-23 Lilly Co Eli Process for dibenzo[a, d]cyclohepta[1.4]diene intermediates

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