US3925487A - Substituted diphenyl ethene - Google Patents

Substituted diphenyl ethene Download PDF

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Publication number
US3925487A
US3925487A US887335A US88733569A US3925487A US 3925487 A US3925487 A US 3925487A US 887335 A US887335 A US 887335A US 88733569 A US88733569 A US 88733569A US 3925487 A US3925487 A US 3925487A
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Prior art keywords
ethenes
bis
preparation
formula
diphenyl
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Expired - Lifetime
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US887335A
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Bernt Borretzen
Knut Gunnar Olsson
Bertil Sundbeck
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Pharmacia Animal Health Inc
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Ferrosan AB
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
    • C07F3/02—Magnesium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
    • C07C39/205—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic, containing only six-membered aromatic rings as cyclic parts with unsaturation outside the rings
    • C07C39/21—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic, containing only six-membered aromatic rings as cyclic parts with unsaturation outside the rings with at least one hydroxy group on a non-condensed ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/70—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form
    • C07C45/71—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form being hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/15—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction of organic compounds with carbon dioxide, e.g. Kolbe-Schmitt synthesis
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/367—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in singly bound form
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D309/08—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D309/10—Oxygen atoms
    • C07D309/12—Oxygen atoms only hydrogen atoms and one oxygen atom directly attached to ring carbon atoms, e.g. tetrahydropyranyl ethers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
    • C07F1/02—Lithium compounds

Definitions

  • ABSTRACT relates to a new process for the preparation of unsymmetrical substituted dihydroxy diphenyl ethenes or esters thereof comprising both new and known compounds and having valuahlc pharmacological activity. According to the new process acetals oi the dihydroxy diphenyl ethenes are used instead of their esters for protecting the phenol groups.
  • the monoor diaeetals ol' the earhinols corresponding to the desired diphenyl ethenes are dehydrated in a manner known per se to form mono or diacetals. of the desired diphenyl ethenes and either cleaving said acetals in a way known per se to form the desired dihydroxy diphenyl ethenes and, if desired, esterifying said dihydroxy compounds in a way known per se. or converting said acetals directly in a way known per se to the desired esters of the dihydroxy di phenyl ethenes.
  • the dehydration step and the cleavage step or the conversion step resp. may be combined into a single step.
  • the invention also relates to certain new dihydroxy diphcnyl ethenes pre pared according to the invention.
  • the present invention relates to a new process for the preparation of unsymmetrical substituted diphenyl ethenes having the general formula or esters thereof with suitable acids such as saturated aliphatic carboxylic acids having from I to 18 carbon atoms such as e.g.
  • Dihydroxy diphenyl ethenes of formula I and their esters are previously known from the U.S. Pat. Nos. 3,237,200; 3,406,209 and 3,287,397. Said compounds have pharmacological activity comprising estrogenic and antiestrogenic activity and inhibition of the secretion of gonadotropins from the pituitary gland.
  • the process according to the invention for the preparation of the diphenyl ethenes of formula I is characterized in that mono or diacetals having the general formula wherein R, and R, have the above-mentioned meaning and R represents a group having the general formula R, c
  • the cleavage of the mono or diacetals of formula IV occurs very easily, preferably with an alcoholic acid, e.g. I ethanolic hydrochloric acid, said acetals of formula IV being converted to the diphenols of formula I.
  • the cleavage may also be carried out in such a way that the esters of the phenols of formula I are obtained directly from the acetals of formula IV, e.g. with the aid of lower acid anhydrides.
  • Acetic acid anhydride in pyridine gives e.g., the diacetate of a diphenol of formula I.
  • the cleavage may also, when R is not hydrogen, be carried out by vigorous heating, the acetal groups being removed as vinyl ethers with the formation of diphenols of formula I.
  • the dihydroxy diphenyl ethenes of formula I are, as already mentioned, previously known from the U.S. Pat. Nos. 3,237,200; 3,406,209 and 3,287,397 according to which they are prepared by another process with the fundamental difference that the protecting group used for the protection of the phenol groups instead of being an acetal group as in the process of the present invention is a lower alkyl group, generally a methyl group.
  • This difference is of decisive importance. While the acetal group easily can be removed e.g., as already mentioned above, by short boiling in diluted alcoholic acid the removal of the methyl group in the first place is carried out by treating with alkali (NaOI-I, KOI-I) in alcoholic solution at 200C.
  • carbinols of formula II which are used as starting materials in the process of the present invention can be prepared by reacting esters having the general formula wherein R and R have the above-mentioned meaning and R represents a lower alkyl group,
  • metal-organic compounds containing the group 5 eg compounds having the formula R0 Q-Lt VI VII ' wherein R represents an acetal group with the abovementioned meaning and Y represents halogen, preferably bromine.
  • R represents an acetal group of formula Ill, ammonium chloride solution, preferably a saturated with ketones having the general formula no- CH wherein R and R, have the above-mentioned meaning
  • R in formula VI represents an acetal group
  • 1 mole of metal-organic compound is used per mole of ketone
  • R in formula Vlll represents hydrogen
  • 2 moles of metal-organic compound per mole of ketone are used since I mole of the metalorganic compound will be consumed by the phenol group of the ketone.
  • the carbinols of formula [I are either extracted as such or as acetals of formula IV after the dehydration.
  • the extraction is in both cases carried out with a suit- VIII 5 able organic solvent, e.g. an ether, a ketone or a hydrocarbon.
  • the carbinols of formula [I can be isolated by evaporation of the solvent and are dehydrated either already at slightly above room temperature or through heating up to from to C. at water pump suction vacuum.
  • the acetals of formula [V are isolated in a conventional manner, such as by distillation at low pressure (0.000l to 0.02 mm Hg). They can also be purified by chromatography, reprecipitation or by recrystallization. The acetals are obtained as oils or as crystallized solids in good yields and in a pure state.
  • the dihydroxy diphenyl ethenes of formula I can also be prepared by treating the crude product from, e.g., a Grignard reaction directly with alcoholic hydrochloric acid whereupon the diphenol formed is isolated in a known manner.
  • the pharmacological activity of the dihydroxy diphenyl ethenes of formula I are disclosed in the US. Pat. No. 3,237,200 as well as different preparation forms of the compounds and different ways of administration.
  • the pharmacological activity is probably due to the free phenols in all cases, but the esters of the diphenols of formula I may modify the essential pharmacological activity while not influencing its general nature, i.e., estrogenicity, antiestrogenicity, pituitary gland inhibition etc. This modification may be due to a variable hydrolysis rate, excretion rate, etc., and increases the pharmacological and pharmaceutical applicability of the compounds.
  • the modification can also change the solubility, the emulsifying properties, the storability etc.
  • esters of lower alkane carboxylic acids are used, e.g., acetic acid and propionic acid. Even phosphates can be used.
  • the esters are prepared from the free diphenols by treating these with reactive acid derivatives, e.g., acetic acid anhydride, and catalytic amounts of acid, acid chlorides in pyridine etc.
  • the acyl compounds can also be prepared directly from the acetals of formula IV or from crude products from the metal-organic reaction which also may contain carbinols of formula II, by treating with reactive acid derivatives, e.g., acetic acid anhydride in pyridine.
  • dihydroxy diphenyl ethenes of the invention have come into clinical used in the humane as well as in the veterinary medicine.
  • Bis(p-acetoxyphenyl)-cyclohexylidene methane is used under the name CYKLOFENIL as an ovulation stimulating agent [Sv. farm. tidskr. 73 (I969) 233].
  • This compound was prepared from methyl t-butyiacetate as described in Example 2 a). The product was obtained in a yield of 80% and with a boiling point of l85187C. at 0.01 mm Hg.
  • the corresponding phenol was prepared from the methoxymethoxy compound as described in Example 2 b). 58 g of the crude phenol (m.p. l80l82C.) was dissolved in 230 ml of acetic anhydride, and a trace of cone. sulphuric acid was added. The reaction mixture, which immediately became warm, was heated for 30 minutes on a steam bath. After cooling, the mixture was poured into water and the acetylated compound, which had separated as an oil, was taken up in ether and washed with a saturated solution of sodium bicarbonate and twice with a sodium chloride solution. The solvent was evaporated and the product was distilled at 177-180C./0.02 mm Hg. Yield: 75 g. After recrystallization from ethanol, the product was obtained with a melting point of 86.5-87.5C.
  • the total amount of crude ethoxyethoxy compound was dissolved in 1000 ml of ethanol and 6 ml of cone. hydrochloric acid, whereupon the mixture was refluxed for 2 minutes.
  • the reaction mixture was poured into 3 liters of water and the crude phenol crystallized immediately. This was filtered, washed with water, dried and further washed with 2 X 200 ml of a boiling mixture of methylene chloride and carbontetrachloride (1:9) and dried.
  • the product was obtained in a yield of 250 g with a melting point of 216220C. After recrystallization from methanol-water (1:1), the product was obtained with a melting point of 221-222C.
  • This compound was prepared from the phenol (m.p. 216-220C.) from Example 4 b) as described in Example 3 b). The product was obtained in a yield of 90 and with a melting point after recrystallization from ethanol of 101103C.
  • This compound was prepared from ethyl Z-methylcylcopentylcarboxylate as described in Example 4 a). The crude product was obtained in a yield of 90 and this substance was used directly for acetylation.
  • This compound was prepared from the crude ethoxyethoxy compound described in Example 5 a) by acetylation according to Example 3 b) using about 0.1 ml of cone. H 80, to 100 ml of acetic anhydride. The product was obtained in a yield of 60% (calculated on the basis of the ethyl ester of Example 5 a)). The melting point of the product after recrystallization from 90% ethanol was 74-75C.
  • EXAMPLE 6 a Preparation of l,l-bis(pyranyloxyphenyl)-2-ethyll-pentene.
  • EXAMPLE 8 a Preparation of bis(p-methoxyethoxyphenyl)-2-ipropylcyclohexylidene methane.
  • This compound was prepared from p-bromobutoxyethoxy benzene and ethyl cyclohexane carboxylate as described in Example 2 a).
  • the crude oil was dried at 8090C. and 0.0002 mm Hg. Thereupon it was dissolved in a mixture of ether and petroleum ether (l:l) and chromatographed on neutral aluminum oxide (Wohler). The first fraction was discarded and the second, after evaporation of the solvent, dried at 80-90C./0.0002 mm Hg and then distilled at 95-97C./0.0001 mm Hg.
  • This compound was prepared according to Example 4 b) and c
  • the product was obtained in a yield of 60% and with a melting point after recrystallization from ethanol of l35l36C. (Lit. l37l38C. Mixed m.p. 135-l37C.).
  • This compound was prepared from pbromoisobutoxyethoxy benzene and ethyl cyclobutane carboxylate as described in Example 2 a).
  • This compound was prepared according to Example 5 b) in a yield of and with a melting point of l39-l40C. (Lit. l39-l41C.).
  • This compound was prepared under the conditions described in Examples 4 b) and 3 b). The product was obtained with a melting point of l36-l37c.
  • This compound was prepared from the methoxymethoxy compound of Example 13 a) as described in Example 2 b). After recrystallization from ethanol the product was obtained with a melting point of l78l80C.
  • This compound was prepared from ethyl 2-methylcyclohex-4-ene carboxylate as described in Example 2 a). The product was obtained with a boiling point of 2l0-215C. at 0.07 mm Hg. n 1.5700.
  • This compound was prepared as described in Example 2 a) from bis(p-methoxymethoxyphenyl)-2-methylcyclohex-4-enylidene methane, prepared according to Example 14 a). After recrystallization from methanol the product was obtained with a melting point of 229-23 lC.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US887335A 1968-12-24 1969-12-22 Substituted diphenyl ethene Expired - Lifetime US3925487A (en)

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BE (1) BE743631A (xx)
BR (1) BR6915395D0 (xx)
CA (1) CA949071A (xx)
CH (2) CH544731A (xx)
DE (2) DE1963271A1 (xx)
FR (2) FR2030939A5 (xx)
GB (1) GB1289966A (xx)
LU (1) LU60027A1 (xx)
NL (1) NL6919273A (xx)
SE (2) SE360662B (xx)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5393741A (en) * 1990-11-30 1995-02-28 Norsk Hydro A.S. Acetal derivatives of aromatic aldehydes

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2425936C3 (de) * 1974-05-30 1981-05-27 Helmut 7060 Schondorf Seitzinger Abschleppstange
DE3060722D1 (en) * 1979-05-15 1982-09-30 Ici Plc 1-hydrocarbyloxyphenyl-1,2-diphenylalkene derivatives, their manufacture and a pharmaceutical composition containing them
GB2108486B (en) * 1981-10-26 1986-01-29 Farmos Group Ltd Alkane and alkene derivatives and their preparation and use

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1789352A (en) * 1931-01-20 louis
US1792716A (en) * 1927-05-12 1931-02-17 Frits E Stockelbach Process of making safrol derivatives such as protocatechuic aldehyde and isoeugenol
US2873297A (en) * 1955-11-28 1959-02-10 Metal & Thermit Corp Process of reacting olefin oxides with specified organomagnesium chlorides
US3237200A (en) * 1959-02-25 1966-02-22 Barany Ernst Herbert Carboxylic acid esters
US3287397A (en) * 1960-11-22 1966-11-22 Olsson Knut Gunnar P, p' substituted benzhydrylidine cycloalkanes
US3406209A (en) * 1966-02-08 1968-10-15 Ernst H. Barany 1, 1-bis(p-oh-phenyl)-2, 2-disubstituted ethylenes
US3506653A (en) * 1966-09-12 1970-04-14 Syntex Corp Non-steroid hormonal agents

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1789352A (en) * 1931-01-20 louis
US1792716A (en) * 1927-05-12 1931-02-17 Frits E Stockelbach Process of making safrol derivatives such as protocatechuic aldehyde and isoeugenol
US2873297A (en) * 1955-11-28 1959-02-10 Metal & Thermit Corp Process of reacting olefin oxides with specified organomagnesium chlorides
US3237200A (en) * 1959-02-25 1966-02-22 Barany Ernst Herbert Carboxylic acid esters
US3287397A (en) * 1960-11-22 1966-11-22 Olsson Knut Gunnar P, p' substituted benzhydrylidine cycloalkanes
US3406209A (en) * 1966-02-08 1968-10-15 Ernst H. Barany 1, 1-bis(p-oh-phenyl)-2, 2-disubstituted ethylenes
US3506653A (en) * 1966-09-12 1970-04-14 Syntex Corp Non-steroid hormonal agents

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5393741A (en) * 1990-11-30 1995-02-28 Norsk Hydro A.S. Acetal derivatives of aromatic aldehydes

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Publication number Publication date
BR6915395D0 (pt) 1973-01-16
FR2074815B1 (xx) 1974-08-30
DE1963997B2 (de) 1973-06-07
DE1963997C3 (xx) 1974-01-10
FR2074815A1 (xx) 1971-10-08
DE1963271A1 (de) 1970-07-16
SE360662B (xx) 1973-10-01
LU60027A1 (xx) 1970-02-16
BE743631A (xx) 1970-05-28
CH544731A (de) 1973-11-30
CH555861A (de) 1974-11-15
GB1289966A (xx) 1972-09-20
US3660501A (en) 1972-05-02
NL6919273A (xx) 1970-06-26
FR2030939A5 (xx) 1970-11-13
CA949071A (en) 1974-06-11
SE384363B (sv) 1976-05-03
DE1963997A1 (de) 1970-06-25

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