US3270067A - Chemical process and products produced thereby - Google Patents

Chemical process and products produced thereby Download PDF

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US3270067A
US3270067A US209311A US20931162A US3270067A US 3270067 A US3270067 A US 3270067A US 209311 A US209311 A US 209311A US 20931162 A US20931162 A US 20931162A US 3270067 A US3270067 A US 3270067A
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carbon atoms
dibenzo
allyl
cycloheptene
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US209311A
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Norman L Wendler
Taub David
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Merck and Co Inc
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Merck and Co Inc
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Priority to US209311A priority Critical patent/US3270067A/en
Priority to GB22384/63A priority patent/GB1042472A/en
Priority to GB3183365A priority patent/GB1042474A/en
Priority to DE19631468264 priority patent/DE1468264A1/en
Priority to AT485063A priority patent/AT260202B/en
Priority to CH760463A priority patent/CH446311A/en
Priority to CH1417267A priority patent/CH446314A/en
Priority to CH1417367A priority patent/CH447153A/en
Priority to ES289439A priority patent/ES289439A1/en
Priority to US560023A priority patent/US3399242A/en
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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

  • This invention relates to a process for making intermediates for the synthesis of SH-dibenzo-[a,d]-cycloheptenes which are substituted at the S-carbon atom with Ian aminopropy-l 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 repre sented by the following flow sheet.
  • 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. J. 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.
  • the first step in the method of the present invention involves the condensation of a 5-halo-5H-dibenzo-[a,d]-cycloheptene with an allyl or a 1, 2' and 3'-alkyl substituted allyl magnesium halide to form the corresponding S-allyl-SH-dibenzo- [a,d]-cycloheptene.
  • S-chloro-SH-dibenzo-[a,d]-cycloheptene is reacted with allyl magnesium bromide in dry diethyl ether under reflux to form S-aHyl-SH-dibenzo-[a,d]-cycloheptene.
  • the next step in the method involves the addition of a molecule of water to the S-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, borane-aluminum 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 S-aminopropyl derivative. These steps are described in the copending application, Serial Number 188,873, filed April 19, 1962.
  • the 5-allyl intermediate is converted to the 5-' -bromopropyl intermediate by a peroxidecatalyzed addition of hydrogen bromine.
  • the bromo intermediate then is converted to the aminopropyl end compound by direct amination according to the aforementioned copending application.
  • a stirrer, addition funnel, and ether-type condenser are charged 4.8 g. of clean magnesium turnings and 15 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 sufficient to maintain a gentle reflux. Stirring and refluxing is continued until all the metal is gone.
  • 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-SH-dibenzo-[a,d]-cycloheptene 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 enough 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 25 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.

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

Description

United States Patent 3,270,067 CHEMICAL PROCESS AND PRODUCTS PRODUCED THEREBY Norman L. Wendler, Summit, and David Taub, Metuchen, N.J., assignors to Merck & Co.,' Inc., Railway, N.J., a corporation of New Jersey No Drawing. Filed July 12, 1962, Ser. No. 209,311 2 Claims. (Cl. 260-649) This invention relates to a process for making intermediates for the synthesis of SH-dibenzo-[a,d]-cycloheptenes which are substituted at the S-carbon atom with Ian aminopropy-l 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 repre sented by the following flow sheet.
3,Z7@-,%7 Patented August 30, 1966 carbon atoms, cyano, carboXy, carbamyl, an alkylcarbamyl group having up to 5 carbon atoms, a dialkylcarbamyl group having up to 9 carbon atoms, a carbalkoxy group having up to 6 carbon atoms, mercapto, an .alkylmercapto group having up to 4 carbon atoms, a perfluoroalkylmercapto group having up to 4 carbon atoms, an alkylsulfony-l group having up to 4 carbon atoms, a perfiuoroalkylsulfonyl group having up to 4 carbon atoms, sulfamyl, an alkylsulfiamyl group having up to 4 carbon atoms, or a dialkylsulfamyl group having up to 8 carbon atoms; more than one of these substitu ents 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. J. 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, SH-dibenzo-[a,d]-cycloheptene-5-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-
X I X ZMgHal H Hal H Z HBr(peroxide hydroboratioy catalyzed) f UTILITY X X S.N. 188,873 Fi led 4/19/62 y n Z H ZBr dibenzocycloheptenes substituted at the 5-carbon atom with an aminopropyl rad cal in which Hal is a halogen, preferably chlorine or bromine; Y is a halogen or hydrogen; Z is allyl and a 1', 2 and 3'-alkyl-substituted allyl, Z is propyl and alkyl substituted propyl, and X and X are similar or dissimilar and are selected from the group consisting of hydrogen, an alkyl group having up to 6 carbon atoms, an alkenyl group having up to 6 carbon atoms, a perfluoroalkyl group having up to 4 carbon atoms, a phenyl or a substituted phenyl radical, an acyl group having up to 4 carbon atoms, a perflu-oroacyl group having up to 4 carbon atoms, amino, an alkylamino group having up to 4 carbon atoms, a dialkylamino group having up to 8 carbon atoms, an acylamino group having up to 4 carbon atoms, a per-fluoroacylamino group having up to 4 carbon atoms, an alkylsulfonylamino group having up to 4 carbon atoms, halogen (fluorine, chlorine, bromine or iodine), hydroxyl, an alkoxyl group having up to 4 carbon atoms, a perfluoroalkoxyl group having up to 4 UTILITY S.N. 188. 873 Filed: 4/ 19/62 dibenzocycloheptatriene," appearing in J.A.C.S., 73, 1673, 1678 (1951). Starting compounds for 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-dimethylfiuorene, lappearing in Helv. Chem. Acta, 36, 1489 to 1499 (1953). Starting compounds where the Y substituent is a halogen may be made following the teachings of Villani in the above-cited reference.
As shown in the flow sheet above, the first step in the method of the present invention involves the condensation of a 5-halo-5H-dibenzo-[a,d]-cycloheptene with an allyl or a 1, 2' and 3'-alkyl substituted allyl magnesium halide to form the corresponding S-allyl-SH-dibenzo- [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 S-aHyl-SH-dibenzo-[a,d]-cycloheptene.
The next step in the method involves the addition of a molecule of water to the S-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 hydrolysis, there is produced the corresponding S-(y-hydroxypropyl)-5H-dibenzo-[a,d]-cy- 'cloheptene.
Suitable boranes contain preferably at least one B-H bond in the molecule as, for example, amine boranes, alkyl boranes, aryl boranes, alkylaryl boranes, borane-aluminum 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 S-aminopropyl derivative. These steps are described in the copending application, Serial Number 188,873, filed April 19, 1962.
In an alternative route, the 5-allyl intermediate is converted to the 5-' -bromopropyl intermediate by a peroxidecatalyzed addition of hydrogen bromine. 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] -cyclheptene 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 15 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 sufficient 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-SH-dibenzo-[a,d]-cycloheptene 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 enough 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 25 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.
A solution of 0.5 g. of the 5-allyl intermediate produced in Example 1 in 15 cc. of dry ethyl ether is treated with 1 mol equivalent of bis-3-methyl-2-butyl borane at 05 C. for a period of 3 hours. At the conclusion of this period, 3 cc. of water is added, followed by 8 cc. of 2.5 N sodium hydroxide and the dropwise addition of 6-7 cc. of 30% hydrogen peroxide. The aqueous phase is then salted with potassium carbonate and the ether layer is separated, dried over magnesium sulfate, and the solvent is evacuated in vacuo. The residue is crystallized from pet. ether to give the desired 'y-hydroxy compound. 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-( -hydroxypropyl)- 5H-dibenzo-[a,d]-cycloheptenes.
EXAMPLE 3 5 'y-bromopropyl -5 H -di benzo- [a,d -cycl0hep tene Hydrogen bromide gas is bubbled into a solution of 1.0 g. of S-aIIyl-SH-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, ,6 and methyl and ethyl groups.
What is claimed is:
1. A compound having the structural formula wherein Z is selected from the group consisting of propyl and lower alkyl substituted propyl.
2. 5 bromopropyl) 5H dibenzo [a,d] cycloheptene.
References Cited by the Examiner UNITED STATES PATENTS 2,058,466 10/1936 Kharasch 260-663 2,082,946 6/1937 Fluchaire et a1. 260-651 2,540,157 10/1946 Zeiss 260-618 2,625,571 6/1951 Pines et a1. 260-618 2,744,149 5/1956 Enos 260-668 2,768,985 10/1956 Schmerling 260-668 2,901,517 8/1959 Warner 260-649 2,917,553 12/1959 McKeever 260-649 3,108,141 10/1963 Gasson et al. 260-663 3,189,657 6/1965 Mills 260-649 OTHER REFERENCES Protiva et al.: Jour. Medicinal and Pharm. Chemistry, vol. 4, No. 2 (1961), pp. 411-5.
LEON ZITVER, Primary Examiner.
O M. B. ROBERTO, K. H. JOHNSON, K. V. ROCKEY,
Assistant Examiners.

Claims (1)

1. A COMPOUND HAVING THE STRUCTURAL FORMULA
US209311A 1962-06-19 1962-07-12 Chemical process and products produced thereby Expired - Lifetime US3270067A (en)

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US209311A US3270067A (en) 1962-07-12 1962-07-12 Chemical process and products produced thereby
GB22384/63A GB1042472A (en) 1962-07-12 1963-06-05 Dibenzocycloheptenes
GB3183365A GB1042474A (en) 1962-07-12 1963-06-05 Dibenzocycloheptenes
DE19631468264 DE1468264A1 (en) 1962-06-19 1963-06-14 Dibenzocycloheptene and heptane derivatives and processes for their preparation
AT485063A AT260202B (en) 1962-07-12 1963-06-17 Process for the preparation of new dibenzocycloheptaene compounds
CH760463A CH446311A (en) 1962-06-19 1963-06-19 Process for the preparation of dibenzocycloheptenes
CH1417267A CH446314A (en) 1962-06-19 1963-06-19 Process for the preparation of dibenzocycloheptenes
CH1417367A CH447153A (en) 1962-06-19 1963-06-19 Process for the preparation of dibenzocycloheptenes
ES289439A ES289439A1 (en) 1962-06-19 1963-06-19 Procedure for preparing dibenzocicloheptenes (Machine-translation by Google Translate, not legally binding)
US560023A US3399242A (en) 1962-07-12 1966-04-28 Chemical process and products produced thereby

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3686335A (en) * 1970-12-21 1972-08-22 Smith Kline French Lab 5-vinyl-5h-di benzo(a,d)cycloheptenes
US3832405A (en) * 1970-05-18 1974-08-27 American Home Prod 5-cycloalkylidene dibenzocycloheptene derivatives
US3965181A (en) * 1973-07-06 1976-06-22 Syntex (U.S.A.) Inc. Tricyclic pharmacological agents, intermediates and methods of making
US3979430A (en) * 1975-09-08 1976-09-07 Syntex (U.S.A.) Inc. Solvolytic process for the preparation of 2-(5H-dibenzo[a,d]cyclohepten-5-on-2-yl)acetic, propionic and butyric acids
US4912233A (en) * 1986-04-30 1990-03-27 Hitachi Chemical Company, Ltd. Para- or meta-terphenyltetracarboxylic acid, dianhydride thereof and process for preparing the same

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2058466A (en) * 1933-12-16 1936-10-27 Du Pont A process of adding a hydrogen halide to a compound containing an olefinic linkage
US2082946A (en) * 1934-09-25 1937-06-08 Usines Chimiques Rhone Soc D Process of preparing beta-bromethyl benzene
US2540157A (en) * 1946-10-26 1951-02-06 Pierce Lab Inc Tertiary rosin alcohols and method for making the same
US2625571A (en) * 1951-06-21 1953-01-13 Universal Oil Prod Co Di-(alkylphenyl)-alkenes
US2744149A (en) * 1953-06-29 1956-05-01 Hercules Powder Co Ltd Preparation of m- and p-cymene mixture by isomerization of cymene
US2768985A (en) * 1951-06-23 1956-10-30 California Research Corp Preparation of meta-dialkylbenzenes
US2901517A (en) * 1955-05-10 1959-08-25 Universal Oil Prod Co Preparation of substituted ortho-polymethylene aromatic hydrocarbons
US2917553A (en) * 1958-06-26 1959-12-15 Rohm & Haas Process for preparing 1,1-dichloro-2,2-diarylethanes
US3108141A (en) * 1958-04-09 1963-10-22 Distillers Co Yeast Ltd Production of aliphatic bromides
US3189657A (en) * 1960-11-03 1965-06-15 Lilly Co Eli 5-(3-bromopropylidene) dibenzo-[a, d] cyclohepta (1.4)diene

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2058466A (en) * 1933-12-16 1936-10-27 Du Pont A process of adding a hydrogen halide to a compound containing an olefinic linkage
US2082946A (en) * 1934-09-25 1937-06-08 Usines Chimiques Rhone Soc D Process of preparing beta-bromethyl benzene
US2540157A (en) * 1946-10-26 1951-02-06 Pierce Lab Inc Tertiary rosin alcohols and method for making the same
US2625571A (en) * 1951-06-21 1953-01-13 Universal Oil Prod Co Di-(alkylphenyl)-alkenes
US2768985A (en) * 1951-06-23 1956-10-30 California Research Corp Preparation of meta-dialkylbenzenes
US2744149A (en) * 1953-06-29 1956-05-01 Hercules Powder Co Ltd Preparation of m- and p-cymene mixture by isomerization of cymene
US2901517A (en) * 1955-05-10 1959-08-25 Universal Oil Prod Co Preparation of substituted ortho-polymethylene aromatic hydrocarbons
US3108141A (en) * 1958-04-09 1963-10-22 Distillers Co Yeast Ltd Production of aliphatic bromides
US2917553A (en) * 1958-06-26 1959-12-15 Rohm & Haas Process for preparing 1,1-dichloro-2,2-diarylethanes
US3189657A (en) * 1960-11-03 1965-06-15 Lilly Co Eli 5-(3-bromopropylidene) dibenzo-[a, d] cyclohepta (1.4)diene

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3832405A (en) * 1970-05-18 1974-08-27 American Home Prod 5-cycloalkylidene dibenzocycloheptene derivatives
US3686335A (en) * 1970-12-21 1972-08-22 Smith Kline French Lab 5-vinyl-5h-di benzo(a,d)cycloheptenes
US3965181A (en) * 1973-07-06 1976-06-22 Syntex (U.S.A.) Inc. Tricyclic pharmacological agents, intermediates and methods of making
US3979430A (en) * 1975-09-08 1976-09-07 Syntex (U.S.A.) Inc. Solvolytic process for the preparation of 2-(5H-dibenzo[a,d]cyclohepten-5-on-2-yl)acetic, propionic and butyric acids
US4912233A (en) * 1986-04-30 1990-03-27 Hitachi Chemical Company, Ltd. Para- or meta-terphenyltetracarboxylic acid, dianhydride thereof and process for preparing the same

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AT260202B (en) 1968-02-12

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