[go: up one dir, main page]

IE50485B1 - Novel substituted 2-phenylamino-imidazolines-(2),the acid addition salts thereof,pharmaceuticals containing same and processes for the preparation thereof - Google Patents

Novel substituted 2-phenylamino-imidazolines-(2),the acid addition salts thereof,pharmaceuticals containing same and processes for the preparation thereof

Info

Publication number
IE50485B1
IE50485B1 IE2555/80A IE255580A IE50485B1 IE 50485 B1 IE50485 B1 IE 50485B1 IE 2555/80 A IE2555/80 A IE 2555/80A IE 255580 A IE255580 A IE 255580A IE 50485 B1 IE50485 B1 IE 50485B1
Authority
IE
Ireland
Prior art keywords
acid addition
addition salts
group
general formula
imidazolines
Prior art date
Application number
IE2555/80A
Other versions
IE802555L (en
Original Assignee
Boehringer Sohn Ingelheim
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Boehringer Sohn Ingelheim filed Critical Boehringer Sohn Ingelheim
Publication of IE802555L publication Critical patent/IE802555L/en
Publication of IE50485B1 publication Critical patent/IE50485B1/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D233/00Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/04Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D233/28Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
    • C07D233/44Nitrogen atoms not forming part of a nitro radical
    • C07D233/50Nitrogen atoms not forming part of a nitro radical with carbocyclic radicals directly attached to said nitrogen atoms
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61PSPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P9/00Drugs for disorders of the cardiovascular system

Landscapes

  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • Cardiology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)

Abstract

1. Claims for the Contracting state : BE, CH, DE, FR, GB, IT, LI, LU, NL, SE Substituted 2-phenylamino-imidazolines-(2) of general formula (I) see diagramm : EP0030616,P7,F1 wherein R represents an n-propyl, cyclopropylmethyl, cyclopentylmethyl, allyl or methallyl group, and the physiologically acceptable acid addition salts thereof. 1. Claims for the Contracting state : AT Process for preparing substituted 2-phenylamino-imidazolines-(2) of general formula (I) see diagramm : EP0030616,P8,F1 wherein R represents an n-propyl, cyclopropylmethyl, cyclopentylmethyl, allyl or methallyl group, and the physiologically acceptable acid addition salts thereof, characterised in that a) 2-(2,6-dibromo-4-methylphenyl-imino)-imidazolidine of formula II see diagramm : EP0030616,P8,F2 is reacted with a halide of general formula III Hal-R wherein Hal represents a chlorine, bromine or iodine atom and R is as hereinbefore defined, at 40 degrees C to 150 degrees C, or b) a compound of general formula IV see diagramm : EP0030616,P8,F3 wherein R is as hereinbefore defined and A represents a cyano group or the group see diagramm : EP0030616,P8,F4 wherein Y represents an alkoxy or alkylthio group with up to 4 carbon atoms or a mercapto group or an amino group, is reacted with ethylenediamine or the acid addition salts thereof at 60 to 180 degrees C, and the end product obtained according to one of these processes is optionally converted into a corresponding acid addition salt.

Description

DE-A- 25 23 103, DE-A- 26 36 732, DE-A- 19 57 722 and DE-A- 22 59 160 disclose substituted 2-phenylamino-imidazolines-(2) which exhibit therapeutic properties. The compounds disclosed in tnese references especially possess analgesic, blood-pressure decreasing, sedative and secretion inhibiting properties.
According to the present invention novel substituted 2-phenylaminoimidazolines of the general formula (I) Br Br (I) and the physiologically acceptable acid addition salts thereof are 10 provided which also have valuable therapeutic properties, especially bradycardiac activity.
In formula I R represents a n-propyl, cyclopropyl-methyl, cyclopentyl rnothyl, the allyl or methallyl radical.
According to a further aspect of the present invention we provide a 15 process for the preparation of 2-pheny1amino-imidazolines-(2) of fonnula I (as defined above) and addition salts thereof which process 50488 comprises at least one of the following steps:(a) react ing 2-(2,6-dibromo-4-methylphenyl-imino)imidazolidine with a halideof formula III Hal-R (HI) (wherein Hal represents a chlorine, bromine or iodine atom and R is as defined above); (b) reacting a compound of formula IV (wherein R is as defined above and A represents a cyano group or a group of formula ;NH -c [wherein- Y represents an alkoxy or alkylthio group with up to 4 carbon atoms, a sulfhydril group or an amino group]) with ethylene diamine or an acid addition salt thereof; and (c) converting a 2-phenylamino-imidazoline-(2) of formula I (wherein R is as defined above) into an acid addition salt thereof.
The reaction according to process (a) may be effected by heating the reactants - preferably in the presence of a polar or apolar solvent - to temperatures from 40 to 150°C.
To a great extent the specific reaction conditions employed depend upon the reactivity of the reagents.
It is recommended that during alkylation the halide of general formula III is employed in excess and also that the reaction is carried out in the presence of an acid-binding agent.
With process (b) it is normally necessary to work at elevated temperature, appropriately between 60° and 180°C. Solvents are not necessary, but they may if desired be used.
The starting compounds of formulae II and IV are known from the literature (vide, for example, Belgian Patent No. 623 305, Chem. Ber. 107, 2644 (1974) and Liebigs Ann. Chem. 751, 159 (1971)).
Compounds of formula III may be produced by halogenation of the basic alcohols.
The acid addition salts of compounds of formula 50483 X are preferably physiologically acceptable acid addition salts. Other acid addition salts may however be useful in the preparation of the 2-phenylaminoimidazolines-(2) of formula I or of physiologically acceptable acid addition salts thereof and are therefore included within the scope of the invention. Compounds of formula I can be converted in the conventional way into their physiologically acceptable acid addition salts. Acids suitable for the preparation of physiologically acceptable acid addition salts include, for example, hydrochloric acid, hydrobromic acid, hydriodic acid, hydrofluoric acid, sulfuric acid, phosphoric acid, nitric acid, acetic acid, propionic acid, butyric acid, caproic acid, valeric acid, oxalic acid, malonic acid, .succinic acid, maleic acid, fumaric acid, lactic acid, tartaric acid, citric acid, malic acid, benzoic acid, p-hydroxybenzoic acid, p-aminobenzoic acid, phthalic acid, cinnamic acid, salicylic acid, ascorbic acid, methanesulfonic acid and 8-chlorotheophylline.
The novel compounds of general formula I and their physiologically acceptable acid addition salts possess a very strong bradycardiac action and are, therefore, suitable for treatment of coronary diseases and ailments. Their influence on the heart rate has been tested in rabbits and pithed rats as well as intact, narcotized rats.
According to a further aspect of the present invention we provide pharmaceutical compositions comprising at least one compound of formula I or physiologically acceptable acid addition salt thereof together with a carrier and/or excipient.
The pharmaceutical compositions of the invention are advantageously in forms suitable for oral, rectal or parenteral administration and preferably are in dosage unit form. Pharmaceutical compositions of the invention in dosage unit form conveniently contain 0.1 to 80 mg, preferably from 1 to 30 mg, of the compound of formula I or addition salt thereof.
The pharmaceutical compositions of the present invention optionally may contain active substances other than the compounds of the invention.
Suitable galenic dosage forms are, for example, tablets, capsules, suppositories, solutions or powders; for their production may be used the conventional galenic excipients, carriers, disintegrants or lubricants or substances for obtaining sustained release.' According to a yet further aspect of the present invention we provide a method of treatment of the human or animal body to control heart or coronary diseases or ailments thereof which method comprises administering to the said body an effective amount of a compound of formula I or a physiologically acceptable acid addition salt thereof.
The following Examples are provided to illustrate the present invention without restricting the scope of protection sought therefor:6 S048S Example 1 Preparation of 2[N-(cyclopropylmethyl)-N-(2,6-dibromo4-methyl-phenyl)amino]-2-imidazoline hydrochloride 4.2 g (0.013 mol) of 2-[(2,6-dibromo-4-methyl5 phenyl)-imino]-imidazolidine are refluxed together with 1.7 g (150%) of ehloromethylcyclopropane in 25 ml of acetonitrile for 42 hours while stirring. Thereafter, the reaction mixture is evaporated in vacuo and the remaining residue is dissolved in approx.
IN HCI. The hydrochloric acid solution is extracted twice with ether (these ether extracts being abandoned) and subsequently extracted with ether at increasing pH-values in fractions (alkalizing with 2 N NaOH) .
Out of the 12 ether fractions obtained, the uniform ones are united (control by thin-layer chromatogram), dried over magnesium sulfate and admixed with etheric hydrochloric acid up to the congo-acid reaction.
In doing so the novel imidazoline hydrochloride precipitates. It is sucked off, washed with ether and dr ied.
Yield: 1.9 g (corresponding to 36.5% of theory).
Melting point: 140°C.
Analogously to the preceding Example the foil owing 5 compounds of formula 1 were produced: Example No. R Yield Melting Process % of theory Point °C -CH. 57.7 152-153 (base) -^3^7 ΰ a 77.5 280 (hydrobromide) -CH. 9.3 92-93 (base) -CH2-CH = CH2 a 80.7 272-274 (hydrohromide) Example A: Sugar-coated Tablets Active ingredient according to the present invention 5 mg lactose 65 mg corn starch 130 mg sec. calcium phosphate 40 mg soluble starch 3 mg magnesium stearate 3 mg colloidal silicic acid 4 mq total 250 mg The active ingredient is admixed with part of the excipients, kneaded thoroughly with an aqueous solution of the soluble starch and granulated in the conventional way with the aid of a screen.
The granulate is admixed with the remaining excipients and pressed to tablet-cores of 250 ma weight; the cores being coated in the conventional way with sugar, talcum and gum arabic.
Example B: Ampoules Active ingredient according to the present invention 1.0 mg sodium chloride 18.0 mg distilled water ad 2.0 ml The active ingredient and sodium chloride are dissolved in water and filled under nitrogen into glass ampoules. . 50485 Ε χam ηle C: Drops \ctiv? ingredient according to the present invention 0.02 g methyl-p-hydroxy-benzoate 0.07 g prooy1-D-hydroxy-benzoate 0.03 g demineralized water ad 100.00 ml The active ingredient and the p-hydroxybenzoates are dissolved in the demineralized water.

Claims (9)

1. Substituted 2-phenylamino-imidazolines-(2) of general formula (I) wherein R represents an n-propyl, cyclopropylmethyl, 5 cyclopentylmethyl, allyl or methallyl group, and the physiologically acceptable acid addition salts thereof.
2. Process for preparing substituted 2-phenylamino-imidazolines as claimed in claim 1, wherein a) 2-(2,6-dibromo-4-methylphenyl-imino)-imidazoline of 10 formula (II) is reacted with a halide of general formula III Hal - R (III) wherein Hal represents a chlorine, bromine or iodine atom and 15 R is as hereinbefore defined, at 40°C to 150°C, or b) a compound of general formula IV wherein R is as hereinbefore defined and A represents a cyano group or the group wherein Y represents an alkoxy or alkylthio group with up to 4 carbon atoms or a mercapto group or an amino group, is reacted with ethylenediamine or the acid addition salts thereof at 60 to 180°C, and the end product obtained according to one of these methods is optionally 10 converted into a corresponding acid addition salt.
3. Pharmaceutical preparations, which contain, as active substance, one or more compounds as claimed in claim 1.
4. Process for preparing pharmaceutical compositions as claimed in claim 3, wherein one or more compounds as claimed in claim 1 are 15 combined with conventional galenic excipients, carriers, disintegrants or lubricants or substances for obtaining delayed release, to form tablets, capsules, suppositories, solutions or powders.
5. Compounds of general formula I or the physiologically acceptable acid addition salts thereof as claimed in claim 1 for use in combatting cardiac and coronary diseases.
6. Substituted 2-phenylamino-imidazolines -(2) of formula I 5 as claimed in claim 1 or physiologically acceptable acid addition salts thereof substantially as described herein with reference to Examples 1 to 5.
7. Pharmaceutical preparations containing as active compound a compound of formula I as claimed in claim 1 or physiologically 10 acceptable acid addition salts thereof substantially as described herein with reference to Examples A to C.
8. A process for the preparation of a compound of formula I as claimed in claim 1, or physiologically acceptable acid addition salts thereof, substantially as described herein with reference to 15 Examples 1 to 5.
9. Substituted 2-phenylamino-imidazolines -(2) of general formula I as claimed in claim 1 or physiologically acceptable acid addition salts thereof whenever prepared by a process as claimed in claim 2 or claim 8.
IE2555/80A 1979-12-07 1980-12-05 Novel substituted 2-phenylamino-imidazolines-(2),the acid addition salts thereof,pharmaceuticals containing same and processes for the preparation thereof IE50485B1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19792949287 DE2949287A1 (en) 1979-12-07 1979-12-07 NEW SUBSTITUTED 2-PHENYLAMINO-IMIDAZOLINE (2), THE ACID ADDITION SALTS THEREOF, THE MEDICINAL PRODUCTS CONTAINING THE SAME AND METHOD FOR THE PRODUCTION THEREOF

Publications (2)

Publication Number Publication Date
IE802555L IE802555L (en) 1981-06-07
IE50485B1 true IE50485B1 (en) 1986-04-30

Family

ID=6087857

Family Applications (1)

Application Number Title Priority Date Filing Date
IE2555/80A IE50485B1 (en) 1979-12-07 1980-12-05 Novel substituted 2-phenylamino-imidazolines-(2),the acid addition salts thereof,pharmaceuticals containing same and processes for the preparation thereof

Country Status (12)

Country Link
EP (1) EP0030616B1 (en)
JP (1) JPS5692274A (en)
AT (1) ATE5818T1 (en)
AU (1) AU533756B2 (en)
DE (2) DE2949287A1 (en)
DK (1) DK521680A (en)
ES (1) ES497480A0 (en)
FI (1) FI69068C (en)
IE (1) IE50485B1 (en)
IL (1) IL61637A (en)
NO (1) NO151412C (en)
ZA (1) ZA807611B (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4644007A (en) * 1981-11-20 1987-02-17 Alcon Laboratories, Inc. 3-chloro-4-(4,5-dihydro-1H-imidazo-2-yl)-amino-5-alkylbenzoic acids, esters, salts, compositions and methods
US4515800A (en) * 1981-11-20 1985-05-07 Icilio Cavero Method of lowering intraocular pressure using phenylimino-imidazoles
US4461904A (en) * 1981-11-20 1984-07-24 Alcon Laboratories, Inc. 2-(Trisubstituted phenylimino)-imidazolines
US4517199A (en) * 1981-11-20 1985-05-14 Alcon Laboratories, Inc. Method for lowering intraocular pressure using phenylimino-imidazoles
HU192986B (en) * 1984-05-23 1987-08-28 Egyt Gyogyszervegyeszeti Gyar Process for production of imidasodiline derivatives
DE19514579A1 (en) 1995-04-20 1996-10-24 Boehringer Ingelheim Kg Use of alpha-1-olone agonists for the treatment of urinary incontinence

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT285599B (en) * 1968-06-21 1970-11-10 Boehringer Sohn Ingelheim Process for the preparation of new trisubstituted 2-arylaminoimidazolines and their salts
BE759048A (en) * 1969-11-17 1971-05-17 Boehringer Sohn Ingelheim NEW N-AMINOALCOYL-ARYLAMINO-IMIDAZOLINES- (2) SUBSTITUTES AND METHODS FOR MAKING THEM
DE2259160A1 (en) * 1972-12-02 1974-06-06 Boehringer Sohn Ingelheim NEW SUBSTITUTED 2-PHENYLAMINOIMIDAZOLINE, THEIR ACID-ADDITIONAL SALTS AND METHOD FOR MANUFACTURING THE SAME AND THEIR USE AS A MEDICINAL PRODUCT
DE2523103C3 (en) * 1975-05-24 1979-11-29 C.H. Boehringer Sohn, 6507 Ingelheim Substituted 2- [N-Progargyl-N- (2-chlorophenyl) amino] -imidazoline- ^), their acid addition salts, processes for their preparation and their use
DE2636732A1 (en) * 1976-08-14 1978-02-16 Boehringer Sohn Ingelheim NEW SUBSTITUTED 2-PHENYLAMINO IMIDAZOLINE (2), THE ACID ADDITION SALTS THEREOF, THE MEDICINAL PRODUCTS CONTAINING THE SAME AND METHOD FOR THE PRODUCTION THEREOF

Also Published As

Publication number Publication date
DE2949287A1 (en) 1981-06-11
FI803799L (en) 1981-06-08
NO803682L (en) 1981-06-09
EP0030616B1 (en) 1984-01-11
JPS5692274A (en) 1981-07-25
AU533756B2 (en) 1983-12-08
NO151412B (en) 1984-12-27
FI69068B (en) 1985-08-30
IE802555L (en) 1981-06-07
ZA807611B (en) 1982-08-25
ATE5818T1 (en) 1984-01-15
DE3066104D1 (en) 1984-02-16
FI69068C (en) 1985-12-10
EP0030616A1 (en) 1981-06-24
DK521680A (en) 1981-06-08
IL61637A (en) 1984-11-30
ES8201978A1 (en) 1982-01-01
ES497480A0 (en) 1982-01-01
NO151412C (en) 1985-04-10
AU6513680A (en) 1981-06-18
IL61637A0 (en) 1981-01-30

Similar Documents

Publication Publication Date Title
US3708485A (en) 2-(n-allyl-phenylamino)-imidazolines-(2)and salts thereof
IE51946B1 (en) Imidazolylphenyl amidines
US4166859A (en) 2-Bromo-6-fluoro-N-(2-imidazolidinylidene)-benzamine and salts thereof and the use to treat hypertension
IE50485B1 (en) Novel substituted 2-phenylamino-imidazolines-(2),the acid addition salts thereof,pharmaceuticals containing same and processes for the preparation thereof
CA1085861A (en) Substituted 2-phenylamino-imidazolines-(2), their acid addition salts, pharmaceuticals comprising same and processes for their production
US4213995A (en) 2-Phenylimino-imidazolidines and salts thereof
US4025607A (en) Propargyl-substituted 2-phenylamino-2-imidazolines and salts thereof
HU180430B (en) Process for preparing substituted 2-phenyl-imino-imidazolidines and acid addition salts thereof infulencing the cardiovascular system
IE50570B1 (en) 2-phenylamino-imidazolines-(2),compositions and processes for the preparation thereof
US4277487A (en) Substituted 2-phenylamino-2-imidazolines as bradycardiacs
US4438118A (en) Substituted imidazo[1,2-a]pyrimidines and pharmaceutical compositions containing them
US4263300A (en) Substituted 2-phenylamino-1,3-tetrahydro-2-pyrimidines and salts thereof
IL44266A (en) Substituted 2-pheylamino-imidazolines-(2) and their salts their preparation and pharmaceutical compositions containing them
US4103018A (en) 2-[4-(Polyhalo-2-hydroxy-2-propyl)anilino]-2-oxazolin-4-ones and thiazolin-4-ones corresponding thereto
US4215133A (en) 2-[N-(2'-Chloro-4'-methyl-thienyl-3')-N-(cyclopropyl-methyl)-amino]-2-imidazoline and salts thereof
US4036972A (en) 2-(N-thienylmethyl-phenylamino)-imidazolines-(2) and salts thereof
EP0274434A1 (en) Dopamine-beta-hydroxylase inhibitors
US4454149A (en) Imidazo[1,2-a]imidazoles in the treatment of pain, hypertonia and coronary diseases
US4478844A (en) Bradycardiac or analgesic 2-(N-(thienyl-2-methyl)-N-(2-fluoro-6-methyl-phenyl)-amino)-2-imidazoline and salts thereof
US4409235A (en) Substituted 7-(2,6-dibromo-4-methyl-phenyl)-2,3-dihydro-imidazo[1,2-a]imidazoles, compositions and use
IE48355B1 (en) Imidazo(1,2-a)imidazole derivatives
US4341788A (en) 2-(2-Chloro-4-cyclopropyl-phenyl-imino)-imidazolidine, and acid addition salts thereof as bradycardiacs
US4239764A (en) Substituted 2-phenylamino-2-imidazolines and salts thereof
KR830001441B1 (en) Process for preparing substituted 2-phenylamino-imidazolines (2)
US4112111A (en) Indolinylguanidines