CA1087212A - Triphenylalkene derivatives and process for preparing same - Google Patents
Triphenylalkene derivatives and process for preparing sameInfo
- Publication number
- CA1087212A CA1087212A CA271,086A CA271086A CA1087212A CA 1087212 A CA1087212 A CA 1087212A CA 271086 A CA271086 A CA 271086A CA 1087212 A CA1087212 A CA 1087212A
- Authority
- CA
- Canada
- Prior art keywords
- diphenyl
- butene
- acid
- general formula
- butanol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/80—Ketones containing a keto group bound to a six-membered aromatic ring containing halogen
- C07C49/813—Ketones containing a keto group bound to a six-membered aromatic ring containing halogen polycyclic
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P35/00—Antineoplastic agents
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
- C07C25/24—Halogenated aromatic hydrocarbons with unsaturated side chains
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Medicinal Chemistry (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Pharmacology & Pharmacy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
Abstract
ABSTRACT
Novel triphenyl-alkene derivatives and process for preparing same The invention relates to novel triphenylalkene derivatives of the general formula I
(I) wherein R denotes a C1-4 alkyl group and X stands for a halogen atom, with the restriction that when R denotes a methyl group, then X may denote only a halogen atom other than chlorine, and their geometrical isomers. Furthermore, the invention relates to a process for the production of these compounds.
The compounds according to the invention can be used for the preparation of Tamoxifen, a known agent against ???illary ??ncer, and of related compounds. Furthermore, they possess a valuable biological activity.
Novel triphenyl-alkene derivatives and process for preparing same The invention relates to novel triphenylalkene derivatives of the general formula I
(I) wherein R denotes a C1-4 alkyl group and X stands for a halogen atom, with the restriction that when R denotes a methyl group, then X may denote only a halogen atom other than chlorine, and their geometrical isomers. Furthermore, the invention relates to a process for the production of these compounds.
The compounds according to the invention can be used for the preparation of Tamoxifen, a known agent against ???illary ??ncer, and of related compounds. Furthermore, they possess a valuable biological activity.
Description
1~872~2 The invention relates to novel triphenylalkene derivatives of the general formula I
X - ~ ~ - C = C - ~ (I) ~, wherein R denotes a Cl 4 alkyl group and X denotes a halogen atom, with the restriction that if R is a methyl group then X may denote only a halogen atom other than chlorine, and to their geometrical isomers. Furthermore the inven-tion relates to a process for the production of these compounds.
The compounds according to the invention possess a valuable bi-ological activity. Further they can be used for the preparation of Tamoxifen [/Z/-1,2-diphenyl-1~ p-[2-(dimethylamino)-ethoxy]-phenyl}-1-butene], a known agent against mammillary cancer, and of related compounds (see British Patent Specifications 1,013,907 and 1,064,629) as well.
The 1,2-diphenyl-1-(p-chlorophenyl)-1-propene has been described by G.E. Nousa et al. ~J. Appl. Chem. 1970, 256) but its biological activity has not been investigated. Besides, also some ethylene derivatives with a struc-ture related to that of the compounds of the general formula I had been de-I scribed already ~Ng. Ph. Buu-Hoi, J. Chem. Soc. 1948, 1080; W. Tadros, J.
,; Chem. Soc. 1949, 439; Ng. Ph. Buu-Hoi, J. Org. Chem. 22, 1057 /1957/ ; A.
g Boris et al., Arch. int. Pharmacodyn. 151, 475 /1964/ ; H.N. Fox et al., r 20 J. Med. Chem. 8, 250 /1965/ ). These known compounds mentioned above have been prepared by the method generally used for the synthesis of alkene derivatives, by elimination of water from the corresponding tertiary alkanol derivative.
., .
. ~
,: ~ :
The novel triphenylalkene derivatives of the general formula I
and their geometrical isomers can be prepared by dehydrating a novel tri-phenylalkanol derivative of the general formula II
X - ~ 1l 12 ~ II
wherein R and X have the same meaning as above, and Rl and R2 have different meanings, and stand for a hydrogen atom or a hydroxyl group. This means that when Rl stands for a hydrogen atom ~hen R2 denotes a hydroxyl group and vice versa. The dehydration, i.e. the elimination of water, is carried out in the presence of an inorganic acid, e.g. hydrochloric acid, hydrobromic acid, phos-phoric acid, or of an organic acid, such as trifluoroacetic acid or formic acid, in a diluting agent or in a solvent, e.g. in aqueous ethanol. The geometrical isomers can be separated by fractionated crystallization or by chromatography.
The triphenylalkene derivatives according to the invention inhibit to a significant extent the growth of hormone-dependent experimental tumors induced in animals by DMBA.
The compounds according to the invention can be used for the produc-tion of pharmaceutical preparations by converting at least one compound of ; the general formula I into a pharmaceutical preparation together with non-toxic, therapeutically suitable diluents and/or carriers. The preparation can be given orally or parenterally.
The compounds and the process according to the invention are further illustrated by the aid of the following Examples, without, however, restrict-ing in any way the scope claimed.
,,' ~ ' ~L~8721Z
Example 1 The solution of 135.0 g. (0.355 moles) of 1,2-diphenyl-1-~p-bromo-phenyl)-l-butanol in 1400 ml. of ethanol is boiled for 5 hours with 300 ml of 36 % hydrochloric acid. Ethanol is distilled off in vacuo, and the aque-ous residue is extracted in several portions with a total of 1500 ml. of methylene dichloride. The org~nic phase is washed with water until neutral, then dried. On evaporating the solvent, the crude crystalline product is re-crystallized from ethanol, affording 120.0 g (93%) of 1,2-diphenyl-1-(p-bromophenyl)-l-butene; m.p. 64 - 82C; the ratio of the ~Z/ isomer to the /E/
isomer is 1:1. On recrystallizing the product thrice from isopropanol, the /Z/ isomer having a m.p. of 112 - 115C is obtained. The mother liquor is evaporated to dryness, and the residue is recrystallized twice from methanol, affording the /E/ isomer of m.p. 89 - 92C.
1,2-Diphenyl-l-(p-bromophenyl)-l-butanol serving as starting sub-stance is obtained as follows:
A solution of 20.6 g. (0.90 moles) of sodium in 600 ml. of an-hydrous ethanol is combined with 165.0 g. (0.60 moles) of 4-bromodeoxybenzoin ~I.L. Kotlyarevskii and N.I. Popova, Izv. Aked. Nauk SSSR, Ser. Khim. 1967, 208). The cooled solution is combined with 140.0 g. (0.90 moles) of ethyl iodide and boiled for 5 hours. On pouring the reaction mixture into ice-water, the oily product which solidifies within a few hours is filtered and dried. The obtained 4-bromo-a-ethyl-deoxybenzoin is purified by distillation.
Yield: 155.5 g. (85.5 %); m.p. 50 - 53C; b.p.: 173 - 180C at 0.7 torr.
14.6 g. (0.60 moles) of magnesium in 600 ml. of anhydrous ether are :
allowed to react, under stirring, with the solution of 94.2 g. (0.60 moles) of bromobenzene in 100 ml. of anhydrous ether. To the cooled solution of the formed Grignard reagent a solution of 151.5 g. (0.50 moles) of 4-bromo-a-,, ethyl-deoxybenzoin in 300 ml. of anhydrous ether is added, and the mixture is boiled for an hour. Then 600 ml. of 1.0 _ hydrochloric acid are added to the -cooled reaction mixture, and the organic phase is separated. The aqueous ..
,. ,:, . . - - -. ~ .
phase is extracted several times with ether, then the combined ethereal phases are shaken with a 10% solution of ammonium chloride and with water.
After drying the solvent is removed by distillation, and the crude cTystal-line product is recrystallized from 90% ethanol, affording 152.0 g. t79.6%) of 1,2-diphenyl-1-(p-bromophenyl)-1-butanol; m.p.: 138 - 140C.
Example 2 To a solution of 320.0 g. (1.0 mole) of 1,2-diphenyl-1-(p-fluoro-phenyl)-l-butanol in 3800 ml. of ethanol, 850 ml. of 36% hydrochloric acid are added and the mixture is boiled for an hour. The crystals precipitated from the cooled solution are filtered and washed with several portions of water until neutral. On evaporating the mother liquor to the half of its initial volume, further amounts of the product are obtained. On recrystal-lizing the crude product (290 g.) from 90% ethanol an isomer mixture of 1,2-diphenyl-l-(p-fluorophenyl)-l-butene is obtained, with a yield of 257.0 g.
(84.9%); m.p. 65 - 70C; ratio of the /Z/ isomer to the /E/ isomer: 1:1.
The mixture of isomers is separated on a column of silica gel having a grain size of 0.063 - 0.20 mm. impregnated with silver nitrate, by elution with an apolar solvent tsuch as petroleum ether or cyclohexane). From 5 g. of the mixture 2.46 g. t49.3%) of /Z/-isomer having a m.p. of 77 - 80C and 1.21 g.
~24.2%) of /E/-isomer having a m.p. of 78 - 81C are obtained.
1,2-Diphenyl-l-tp-fluorophenyl)-l-butanol used as starting sub-; stance is prepared as follows:
29.2 g. tl.20 moles) of magnesium in 150 ml. of anhydrous ether are allowed to react under stirring with the solution of 210.0 g. tl.20 moles) of l-bromo-4-fluorobenzene in 420 ml. of anhydrous ether, then the solution is cooled and treated with a solution of 224.3 g. tl.O mole) of ~-ethyl-deoxybenzoin tT.E. Zalleskaya and O.A. Netsetskaya, Zh. Org. Khim.
5, 1076 /1969/) in 1~00 ml. of ether. The reaction mixture is boiled for 4 hours, then cooled and decomposed by 1000 ml. of a 10% solution of ammonium chloride, the ethereal part is separated, then the aqueous phase is extracted :~.
~; _ 5 ., .
with further portions of ether, and the combined ethereal solutions are evaporated to dryness. The 1,2-diphenyl-1-(p-fluorophenyl)-1-butanol ob-tained in this way ~314.0 g. /98%/; m.p.: 80 - 88C) in crystalline form can be converted into the appropriate butene derivative without any further puri-fication. After recrystallization from 90% ethanol the m.p. of the product is 94 - 96C.
Example 3 The solution of 33.7 g. (0.10 moles) of 1,2-diphenyl-1-~p-chloro-phenyl)-l-butanol in 400 ml. of ethanol is boiled for 2 hours with 85 ml. of 36% hydrochloric acid, The solution is cooled, and the precipitated crystals are filtered, washed with water and then recrystallized from 90% ethanol, affording 28.3 g. (88.8%) of a mixture of 1,2-diphenyl-1-(p-chlorophenyl-1-butene isomers; m.p. 67 - 87C; ratio of /Z/ isomer to the /E/ isomer: 1:1.
The 1,2-diphenyl-l-(p-chlorophenyl)-1-butanol serving here as starting substance can be prepared as follows:
4.38 g. (0.18 moles) of magnesium in 25 ml. of anhydrous ether are allowed to react with a solution of 34.4 g. (0.18 moles) of 1-bromo-4-chloro-benzene in 70 ml. of anhydrous ether under stirring, then a solution of 33.6 g. (0.15 moles) of ~-ethyl-deoxybenzoin in 140 ml. of anhydrous ether is added to the cooled solution, and the mixture is boiled for 4 hours. On decomposing the cooled mixture with a solution of ammonium chloride, the aqueous phase is shaken with further amounts of ether. The crude crystalline -~
product obtained after the removal of the solvent by distillation is re-crystallized from ethanol, affording 44.0 g. (87.1%) of 1,2-diphenyl-1-(p-chlorophenyl)-l-butanol; m.p.: IOg - III~C.
.~
.
,~ .
. .-
X - ~ ~ - C = C - ~ (I) ~, wherein R denotes a Cl 4 alkyl group and X denotes a halogen atom, with the restriction that if R is a methyl group then X may denote only a halogen atom other than chlorine, and to their geometrical isomers. Furthermore the inven-tion relates to a process for the production of these compounds.
The compounds according to the invention possess a valuable bi-ological activity. Further they can be used for the preparation of Tamoxifen [/Z/-1,2-diphenyl-1~ p-[2-(dimethylamino)-ethoxy]-phenyl}-1-butene], a known agent against mammillary cancer, and of related compounds (see British Patent Specifications 1,013,907 and 1,064,629) as well.
The 1,2-diphenyl-1-(p-chlorophenyl)-1-propene has been described by G.E. Nousa et al. ~J. Appl. Chem. 1970, 256) but its biological activity has not been investigated. Besides, also some ethylene derivatives with a struc-ture related to that of the compounds of the general formula I had been de-I scribed already ~Ng. Ph. Buu-Hoi, J. Chem. Soc. 1948, 1080; W. Tadros, J.
,; Chem. Soc. 1949, 439; Ng. Ph. Buu-Hoi, J. Org. Chem. 22, 1057 /1957/ ; A.
g Boris et al., Arch. int. Pharmacodyn. 151, 475 /1964/ ; H.N. Fox et al., r 20 J. Med. Chem. 8, 250 /1965/ ). These known compounds mentioned above have been prepared by the method generally used for the synthesis of alkene derivatives, by elimination of water from the corresponding tertiary alkanol derivative.
., .
. ~
,: ~ :
The novel triphenylalkene derivatives of the general formula I
and their geometrical isomers can be prepared by dehydrating a novel tri-phenylalkanol derivative of the general formula II
X - ~ 1l 12 ~ II
wherein R and X have the same meaning as above, and Rl and R2 have different meanings, and stand for a hydrogen atom or a hydroxyl group. This means that when Rl stands for a hydrogen atom ~hen R2 denotes a hydroxyl group and vice versa. The dehydration, i.e. the elimination of water, is carried out in the presence of an inorganic acid, e.g. hydrochloric acid, hydrobromic acid, phos-phoric acid, or of an organic acid, such as trifluoroacetic acid or formic acid, in a diluting agent or in a solvent, e.g. in aqueous ethanol. The geometrical isomers can be separated by fractionated crystallization or by chromatography.
The triphenylalkene derivatives according to the invention inhibit to a significant extent the growth of hormone-dependent experimental tumors induced in animals by DMBA.
The compounds according to the invention can be used for the produc-tion of pharmaceutical preparations by converting at least one compound of ; the general formula I into a pharmaceutical preparation together with non-toxic, therapeutically suitable diluents and/or carriers. The preparation can be given orally or parenterally.
The compounds and the process according to the invention are further illustrated by the aid of the following Examples, without, however, restrict-ing in any way the scope claimed.
,,' ~ ' ~L~8721Z
Example 1 The solution of 135.0 g. (0.355 moles) of 1,2-diphenyl-1-~p-bromo-phenyl)-l-butanol in 1400 ml. of ethanol is boiled for 5 hours with 300 ml of 36 % hydrochloric acid. Ethanol is distilled off in vacuo, and the aque-ous residue is extracted in several portions with a total of 1500 ml. of methylene dichloride. The org~nic phase is washed with water until neutral, then dried. On evaporating the solvent, the crude crystalline product is re-crystallized from ethanol, affording 120.0 g (93%) of 1,2-diphenyl-1-(p-bromophenyl)-l-butene; m.p. 64 - 82C; the ratio of the ~Z/ isomer to the /E/
isomer is 1:1. On recrystallizing the product thrice from isopropanol, the /Z/ isomer having a m.p. of 112 - 115C is obtained. The mother liquor is evaporated to dryness, and the residue is recrystallized twice from methanol, affording the /E/ isomer of m.p. 89 - 92C.
1,2-Diphenyl-l-(p-bromophenyl)-l-butanol serving as starting sub-stance is obtained as follows:
A solution of 20.6 g. (0.90 moles) of sodium in 600 ml. of an-hydrous ethanol is combined with 165.0 g. (0.60 moles) of 4-bromodeoxybenzoin ~I.L. Kotlyarevskii and N.I. Popova, Izv. Aked. Nauk SSSR, Ser. Khim. 1967, 208). The cooled solution is combined with 140.0 g. (0.90 moles) of ethyl iodide and boiled for 5 hours. On pouring the reaction mixture into ice-water, the oily product which solidifies within a few hours is filtered and dried. The obtained 4-bromo-a-ethyl-deoxybenzoin is purified by distillation.
Yield: 155.5 g. (85.5 %); m.p. 50 - 53C; b.p.: 173 - 180C at 0.7 torr.
14.6 g. (0.60 moles) of magnesium in 600 ml. of anhydrous ether are :
allowed to react, under stirring, with the solution of 94.2 g. (0.60 moles) of bromobenzene in 100 ml. of anhydrous ether. To the cooled solution of the formed Grignard reagent a solution of 151.5 g. (0.50 moles) of 4-bromo-a-,, ethyl-deoxybenzoin in 300 ml. of anhydrous ether is added, and the mixture is boiled for an hour. Then 600 ml. of 1.0 _ hydrochloric acid are added to the -cooled reaction mixture, and the organic phase is separated. The aqueous ..
,. ,:, . . - - -. ~ .
phase is extracted several times with ether, then the combined ethereal phases are shaken with a 10% solution of ammonium chloride and with water.
After drying the solvent is removed by distillation, and the crude cTystal-line product is recrystallized from 90% ethanol, affording 152.0 g. t79.6%) of 1,2-diphenyl-1-(p-bromophenyl)-1-butanol; m.p.: 138 - 140C.
Example 2 To a solution of 320.0 g. (1.0 mole) of 1,2-diphenyl-1-(p-fluoro-phenyl)-l-butanol in 3800 ml. of ethanol, 850 ml. of 36% hydrochloric acid are added and the mixture is boiled for an hour. The crystals precipitated from the cooled solution are filtered and washed with several portions of water until neutral. On evaporating the mother liquor to the half of its initial volume, further amounts of the product are obtained. On recrystal-lizing the crude product (290 g.) from 90% ethanol an isomer mixture of 1,2-diphenyl-l-(p-fluorophenyl)-l-butene is obtained, with a yield of 257.0 g.
(84.9%); m.p. 65 - 70C; ratio of the /Z/ isomer to the /E/ isomer: 1:1.
The mixture of isomers is separated on a column of silica gel having a grain size of 0.063 - 0.20 mm. impregnated with silver nitrate, by elution with an apolar solvent tsuch as petroleum ether or cyclohexane). From 5 g. of the mixture 2.46 g. t49.3%) of /Z/-isomer having a m.p. of 77 - 80C and 1.21 g.
~24.2%) of /E/-isomer having a m.p. of 78 - 81C are obtained.
1,2-Diphenyl-l-tp-fluorophenyl)-l-butanol used as starting sub-; stance is prepared as follows:
29.2 g. tl.20 moles) of magnesium in 150 ml. of anhydrous ether are allowed to react under stirring with the solution of 210.0 g. tl.20 moles) of l-bromo-4-fluorobenzene in 420 ml. of anhydrous ether, then the solution is cooled and treated with a solution of 224.3 g. tl.O mole) of ~-ethyl-deoxybenzoin tT.E. Zalleskaya and O.A. Netsetskaya, Zh. Org. Khim.
5, 1076 /1969/) in 1~00 ml. of ether. The reaction mixture is boiled for 4 hours, then cooled and decomposed by 1000 ml. of a 10% solution of ammonium chloride, the ethereal part is separated, then the aqueous phase is extracted :~.
~; _ 5 ., .
with further portions of ether, and the combined ethereal solutions are evaporated to dryness. The 1,2-diphenyl-1-(p-fluorophenyl)-1-butanol ob-tained in this way ~314.0 g. /98%/; m.p.: 80 - 88C) in crystalline form can be converted into the appropriate butene derivative without any further puri-fication. After recrystallization from 90% ethanol the m.p. of the product is 94 - 96C.
Example 3 The solution of 33.7 g. (0.10 moles) of 1,2-diphenyl-1-~p-chloro-phenyl)-l-butanol in 400 ml. of ethanol is boiled for 2 hours with 85 ml. of 36% hydrochloric acid, The solution is cooled, and the precipitated crystals are filtered, washed with water and then recrystallized from 90% ethanol, affording 28.3 g. (88.8%) of a mixture of 1,2-diphenyl-1-(p-chlorophenyl-1-butene isomers; m.p. 67 - 87C; ratio of /Z/ isomer to the /E/ isomer: 1:1.
The 1,2-diphenyl-l-(p-chlorophenyl)-1-butanol serving here as starting substance can be prepared as follows:
4.38 g. (0.18 moles) of magnesium in 25 ml. of anhydrous ether are allowed to react with a solution of 34.4 g. (0.18 moles) of 1-bromo-4-chloro-benzene in 70 ml. of anhydrous ether under stirring, then a solution of 33.6 g. (0.15 moles) of ~-ethyl-deoxybenzoin in 140 ml. of anhydrous ether is added to the cooled solution, and the mixture is boiled for 4 hours. On decomposing the cooled mixture with a solution of ammonium chloride, the aqueous phase is shaken with further amounts of ether. The crude crystalline -~
product obtained after the removal of the solvent by distillation is re-crystallized from ethanol, affording 44.0 g. (87.1%) of 1,2-diphenyl-1-(p-chlorophenyl)-l-butanol; m.p.: IOg - III~C.
.~
.
,~ .
. .-
Claims (12)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for producing a triphenylalkene derivative of the general formula:
(I) wherein R denotes a C1-4 alkyl group and X stands for a halogen atom, with the proviso that when R denotes a methyl group, then X may denote only a halogen atom other than chlorine, and their geometrical isomers, which process comprises dehydrating a triphenylalkanol derivative of the general formula II
(II) wherein R and X have the meanings defined above, and R1 and R2 are different from each other and represent a hydrogen atom or a hydroxyl group, and, if necessary, separating the /Z/ and /E/ isomers of the triphenylalkene derivative of the general formula I, by chromatography or by subjecting the mixture of these isomers in an organic solvent or solvent mixture to fractionated crystallization.
(I) wherein R denotes a C1-4 alkyl group and X stands for a halogen atom, with the proviso that when R denotes a methyl group, then X may denote only a halogen atom other than chlorine, and their geometrical isomers, which process comprises dehydrating a triphenylalkanol derivative of the general formula II
(II) wherein R and X have the meanings defined above, and R1 and R2 are different from each other and represent a hydrogen atom or a hydroxyl group, and, if necessary, separating the /Z/ and /E/ isomers of the triphenylalkene derivative of the general formula I, by chromatography or by subjecting the mixture of these isomers in an organic solvent or solvent mixture to fractionated crystallization.
2. A process as claimed in claim 1, wherein the dehydration is carried out in the presence of an acid.
3. A process as claimed in claim 2, wherein the acid is hydrochloric acid, hydrogen bromide, phosphoric acid, tri-fluoroacetic acid or formic acid.
4. A process as claimed in claim 1, wherein the reaction is carried out in an inert diluent or solvent.
5. A process as claimed in claim 4, wherein the solvent is an alkanol or aqueous alkanol.
6. A triphenylalkene derivative of the general formula I as defined in claim 1 or a geometrical isomer thereof, when-ever produced by the process defined in claim 1, 2 or 4, or by an obvious chemical equivalent thereof.
7. A process for producing 1,2-diphenyl-1-(p-bromophenyl)-1-butene, which comprises dehydrating 1,2-diphenyl-1-(p-bromo-phenyl)-1-butanol.
8. 1,2-Diphenyl-1-(p-bromophenyl)-1-butene, whenever produced by the process claimed in claim 7, or by an obvious chemical equivalent thereof.
9. A process for producing 1,2-diphenyl-1-(p-fluoro-phenyl)-1-butene, which comprises dehydrating 1,2-diphenyl-1-(p-fluorophenyl)-1-butanol.
10. 1,2-Diphenyl-1-(p-fluorophenyl)-1-butene, whenever produced by the process claimed in claim 9, or by an obvious chemical equivalent thereof.
11. A process for producing 1,2-diphenyl-1-(p-chloro-phenyl)-1-butene, which comprises dehydrating 1,2-diphenyl-1-(p-chlorophenyl)-1-butanol.
12. 1,2-Diphenyl-1-(p-chlorophenyl)-1-butene, whenever produced by the process claimed in claim 11, or by an obvious chemical equivalent thereof.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| HU76GO00001328A HU171269B (en) | 1976-02-05 | 1976-02-05 | Process for preparing new triphenyl-alkene derivatives |
| HUGO-1328 | 1976-02-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1087212A true CA1087212A (en) | 1980-10-07 |
Family
ID=10996802
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA271,086A Expired CA1087212A (en) | 1976-02-05 | 1977-02-04 | Triphenylalkene derivatives and process for preparing same |
Country Status (11)
| Country | Link |
|---|---|
| JP (1) | JPS52122352A (en) |
| AT (1) | AT345804B (en) |
| CA (1) | CA1087212A (en) |
| CH (1) | CH624655A5 (en) |
| DE (1) | DE2704690C2 (en) |
| HU (1) | HU171269B (en) |
| NL (1) | NL7701025A (en) |
| PL (1) | PL105534B1 (en) |
| SE (1) | SE431324B (en) |
| SU (1) | SU856376A3 (en) |
| YU (1) | YU39669B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4870219A (en) * | 1986-05-23 | 1989-09-26 | Hoffmann-La Roche Inc. | Novel tetrahydronaphthalene and indane derivatives |
| US4990703A (en) * | 1987-03-17 | 1991-02-05 | Hoffmann-La Roche Inc. | Novel tetrahydronaphthalene and indane derivatives |
| US5030764A (en) * | 1986-05-23 | 1991-07-09 | Hoffmann-La Roche Inc. | Novel tetrahydronaphthalene and indane derivatives |
| US5030765A (en) * | 1986-05-23 | 1991-07-09 | Hoffmann-La Roche Inc. | Novel tetrahydronaphthalene and indane derivatives |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2964736D1 (en) * | 1978-11-07 | 1983-03-17 | Ici Plc | 1-acyloxyphenyl-1,2-diphenylalkene derivatives, processes for their manufacture and a pharmaceutical composition containing these derivatives |
| GB9714310D0 (en) * | 1997-07-07 | 1997-09-10 | Smithkline Beecham Plc | Process |
-
1976
- 1976-02-05 HU HU76GO00001328A patent/HU171269B/en unknown
-
1977
- 1977-01-28 SU SU772446005A patent/SU856376A3/en active
- 1977-02-01 AT AT59577A patent/AT345804B/en not_active IP Right Cessation
- 1977-02-01 NL NL7701025A patent/NL7701025A/en not_active Application Discontinuation
- 1977-02-03 SE SE7701213A patent/SE431324B/en not_active IP Right Cessation
- 1977-02-04 CA CA271,086A patent/CA1087212A/en not_active Expired
- 1977-02-04 DE DE2704690A patent/DE2704690C2/en not_active Expired
- 1977-02-04 CH CH136077A patent/CH624655A5/en not_active IP Right Cessation
- 1977-02-04 PL PL1977195823A patent/PL105534B1/en unknown
- 1977-02-04 JP JP1084777A patent/JPS52122352A/en active Granted
- 1977-02-04 YU YU309/77A patent/YU39669B/en unknown
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4870219A (en) * | 1986-05-23 | 1989-09-26 | Hoffmann-La Roche Inc. | Novel tetrahydronaphthalene and indane derivatives |
| US4935560A (en) * | 1986-05-23 | 1990-06-19 | Hoffmann-La Roche Inc. | Novel tetrahydronaphthalene & indane derivatives |
| US5001276A (en) * | 1986-05-23 | 1991-03-19 | Hoffmann-La Roche Inc. | Novel tetrahydronaphthalene and indane derivatives |
| US5030764A (en) * | 1986-05-23 | 1991-07-09 | Hoffmann-La Roche Inc. | Novel tetrahydronaphthalene and indane derivatives |
| US5030765A (en) * | 1986-05-23 | 1991-07-09 | Hoffmann-La Roche Inc. | Novel tetrahydronaphthalene and indane derivatives |
| US5055622A (en) * | 1986-05-23 | 1991-10-08 | Hoffmann-La Roche Inc. | Novel tetrahydronaphthalene and indane derivatives |
| US4990703A (en) * | 1987-03-17 | 1991-02-05 | Hoffmann-La Roche Inc. | Novel tetrahydronaphthalene and indane derivatives |
Also Published As
| Publication number | Publication date |
|---|---|
| SE431324B (en) | 1984-01-30 |
| SE7701213L (en) | 1977-08-06 |
| DE2704690A1 (en) | 1977-08-11 |
| PL105534B1 (en) | 1979-10-31 |
| AT345804B (en) | 1978-10-10 |
| NL7701025A (en) | 1977-08-09 |
| YU30977A (en) | 1982-06-30 |
| CH624655A5 (en) | 1981-08-14 |
| ATA59577A (en) | 1978-02-15 |
| JPS6149294B2 (en) | 1986-10-29 |
| JPS52122352A (en) | 1977-10-14 |
| DE2704690C2 (en) | 1987-01-29 |
| HU171269B (en) | 1977-12-28 |
| SU856376A3 (en) | 1981-08-15 |
| YU39669B (en) | 1985-03-20 |
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