USRE32154E - Production of 2-(o-alkylthiophenyl)-1,3-diazocycloalkene hydrohalides - Google Patents

Production of 2-(o-alkylthiophenyl)-1,3-diazocycloalkene hydrohalides Download PDF

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Publication number
USRE32154E
USRE32154E US06/237,961 US23796181A USRE32154E US RE32154 E USRE32154 E US RE32154E US 23796181 A US23796181 A US 23796181A US RE32154 E USRE32154 E US RE32154E
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US
United States
Prior art keywords
parts
carbon atoms
spiro
methanol
oxadiazolyl
Prior art date
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Expired - Lifetime
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US06/237,961
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English (en)
Inventor
Helmut Hagen
August Amann
Hubert Giertz
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/06—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/04—Heterocyclic 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
    • C07D233/20—Heterocyclic 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 substituted hydrocarbon radicals, directly attached to ring carbon atoms

Definitions

  • the invention relates to a process for the production of new 2-(o-alkylthiophenyl)-1,3-diazacycloalkene hydrohalides by reaction of a benzothietane-2-spiro-2'-(1',3'-diazacycloalkane) with an alkyl halide.
  • Another object of this invention is the new 2-(o-alkylthiophenyl)-1,3-diazacycloalkene hydrohalides themselves.
  • Y is the radical ##STR2## in which the individual radicals R 2 may be identical or different and each is hydrogen or an aliphatic radical,
  • R 3 is hydrogen or an aliphatic, cycloaliphatic, araliphatic, aromatic, or heterocyclic radical
  • X is halogen is obtained advantageously by reacting a benzothietane-2-spiro-2'-(1',3'-diazacycloalkane) of the general formula (II): ##STR3## in which R 1 and Y have the meanings given above with an alkyl halide of the general formula (III):
  • reaction of the invention may be represented by the following equation: ##STR4##
  • the process of the invention gives the new 2-(o-alkylthiophenyl)-1,3-diazacycloalkene halides in a good yield and high purity.
  • the starting material (II) is conveniently reacted with the starting material (III) in stoichiometric proportions.
  • Starting material (III) may however be used in excess, for example an excess of up to 1.2 times the stoichiometric amount based on starting material (II).
  • the starting material (II) may be prepared for example by the method described in German published Application No. 2,034,987 laid open Jan. 20, 1972 (see also U.S. Pat. No. 3,776,870) by reaction of a halobenzaldehyde compound with a diaminoalkane and sulfur.
  • Preferred starting materials (II) and (III) and consequently preferred end products (I) are those in whose formulae R 1 is hydrogen, bromo, iodo, chloro or alkyl of one to seven carbon atoms, Y is the radical ##STR5## the individual radicals R 2 may be identical or different and each is hydrogen or alkyl of one to four carbon atoms, R 3 is hydrogen, alkyl of one to seven carbon atoms, alkenyl or alkynyl of two to seven carbon atoms, cyclohexyl, aralkyl of seven to twelve carbon atoms, phenyl or a heterocyclic five-membered or six-membered ring containing one or two nitrogen atoms and/or an oxygen atom and bearing as a substituent alkyl of one to four carbon atoms, aralkyl of seven to 12 carbon atoms or phenyl and X is bromo, iodo or chloro.
  • the heterocyclic ring may bear, as a substituent, another five-membered or six-membered heterocyclic ring containing one or two nitrogen atoms and/or an oxygen atom. They are preferably 1,2,3-oxadiazoles, 1,2,5-oxadiazoles, 1,2,4-oxadiazoles and 1,3,4-oxadiazoles.
  • the said radicals and rings may also bear groups which are inert under the reaction conditions, for example alkyl groups, alkoxy groups in each case of one to four carbon atoms, chloro or bromo as substituents on the phenyl radical.
  • alkyl halides suitable as starting materials (III) are as follows: ethyl chloride, propyl chloride, hexyl chloride, benzyl chloride, o-chlorobenzyl chloride, m-chlorobenzyl chloride, p-chlorobenzyl chloride, isopropenyl chloride, methyl chloride, allylchloride, propargyl chloride, methallyl chloride, phenylethyl chloride, o,p-dichlorobenzyl chloride, o,o'-dichlorobenzyl chloride, o,m-dichlorobenzyl chloride, p-methoxybenzyl chloride, m-butoxybenzyl chloride, cyclohexyl chloride, pyrryl-(2)-methyl chloride, imidazolyl-(2) methyl chloride, pyridinyl-(2) methyl chloride, morpholinyl-(2)-methyl chloride,
  • the reaction is carried out as a rule at a temperature of from 10° to 150° C., preferably from 50° C. to 100° C., at atmospheric or superatmospheric pressure, continuously or batchwise.
  • an organic solvent which is inert under the reaction conditions, for example an aromatic hydrocarbon such as benzene or toluene; an alkanol such as methanol, ethanol, propanol or a butanol; a glycol ether such as glycol monomethyl ether or glycol monoethyl ether; or appropriate mixtures.
  • a ratio of from 5 to 20 moles of solvent per mole of starting material (II) is preferred.
  • the reaction may be carried out as follows: the starting materials (II) and (III), with or without a solvent, are heated to the reaction temperature. The mixture is then allowed to react at the reaction temperature for fron one to five hours. The end product is then separated by a conventional method, for example by crystallization or filtration of the mixture. If necessary the end product may be purified by recrystallization.
  • the new compounds which can be prepared by the process of the invention are pharmaceuticals, auxiliaries for the textile and rubber industries, plant protection agents and also valuable starting materials for the productions of pharmaceuticals, plant protection agents and dyes.
  • they are administed perorally or intravenously they cause prolonged increase in blood pressure and affect the central nervous system. They are capable of neutralizing eyelid paralysis in mice caused by reserpin and they increase excretion of urine in rats.
  • the blood pressure-raising action is detected in the conventional manner on rats narcotized with urethane. Blood pressure is measured from the carotid artery by means of Statham elements. Intravenous injection of the end product (I) is effected through a cannula inserted into the jugular vein. The increase in blood pressure after administration of the test substances is measured in mm of Hg and the duration of action in minutes. The tests are discontinued thirty minutes after administration of the test substance.
  • IV approximately toxicity in mg/kg administered intravenously
  • V maximum increase in blood pressure in mm of Hg after intravenous injection of 1 mg/kg

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
US06/237,961 1972-04-22 1981-02-25 Production of 2-(o-alkylthiophenyl)-1,3-diazocycloalkene hydrohalides Expired - Lifetime USRE32154E (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2219841A DE2219841A1 (de) 1972-04-22 1972-04-22 Verfahren zur herstellung von 2-(oalkylthiophenyl)-1,3-diazacycloalkenhydrohalogeniden
DE2219841 1972-04-22

Related Parent Applications (2)

Application Number Title Priority Date Filing Date
US34991573A Continuation-In-Part 1973-04-11 1973-04-11
US05/807,673 Reissue US4122263A (en) 1973-04-11 1977-06-17 Production of 2-(o-alkylthiophenyl)-1,3-diazocycloalkene hydrohalides

Publications (1)

Publication Number Publication Date
USRE32154E true USRE32154E (en) 1986-05-20

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Family Applications (1)

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US06/237,961 Expired - Lifetime USRE32154E (en) 1972-04-22 1981-02-25 Production of 2-(o-alkylthiophenyl)-1,3-diazocycloalkene hydrohalides

Country Status (6)

Country Link
US (1) USRE32154E (is")
JP (1) JPS4920171A (is")
CH (1) CH579054A5 (is")
DE (1) DE2219841A1 (is")
FR (1) FR2182994B1 (is")
GB (1) GB1418053A (is")

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5114482B1 (is") * 1970-12-29 1976-05-10
DE2965905D1 (en) * 1978-07-13 1983-08-25 Wellcome Found Antiprotozoal oxadiazole derivatives, processes for their preparation and pharmaceutical formulations containing them
DE2965906D1 (en) 1978-07-13 1983-08-25 Wellcome Found Oxadiazole derivatives, process for their preparation and their pharmaceutical compositions
DOP1981004033A (es) * 1980-12-23 1990-12-29 Ciba Geigy Ag Procedimiento para proteger plantas de cultivo de la accion fitotoxica de herbicidas.
DE3379544D1 (en) * 1982-06-08 1989-05-11 Ciba Geigy Ag 2-phenyl-2-naphthyl and 2-heterocyclic pyrimidines as antidotes for protecting cultured plants before phytotoxic damages caused by herbicides
US4648896A (en) * 1982-11-15 1987-03-10 Ciba-Geigy Corporation 2-aryl-4,6-dihalopyrimidines as antidote for protecting cultivated plants from phytotoxic damage caused by herbicides
GB2351081A (en) * 1999-06-18 2000-12-20 Lilly Forschung Gmbh Pharmaceutically active imidazoline compounds and analogues thereof
EP1204645A2 (en) * 1999-08-04 2002-05-15 Millennium Pharmaceuticals, Inc. Melanocortin-4 receptor binding compounds and methods of use thereof
US7375125B2 (en) * 1999-08-04 2008-05-20 Ore Pharmaceuticals, Inc. Melanocortin-4 receptor binding compounds and methods of use thereof
US6699873B1 (en) 1999-08-04 2004-03-02 Millennium Pharmaceuticals, Inc. Melanocortin-4 receptor binding compounds and methods of use thereof
AU2004202804B2 (en) * 1999-08-04 2009-01-29 Ore Pharmaceuticals Inc. Melanocortin-4 Receptor Binding Compounds and Methods of use thereof
EP1363890A4 (en) * 2001-02-07 2009-06-10 Ore Pharmaceuticals Inc MELANOCORTIN-4-RECEPTOR BINDING COMPOUNDS AND METHOD FOR THEIR APPLICATION
JPWO2016056606A1 (ja) * 2014-10-07 2017-07-20 国立大学法人京都大学 ベンゾイソチアゾロピリミジン誘導体またはその塩、およびウイルス感染阻害剤ならびに医薬品

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4122263A (en) * 1973-04-11 1978-10-24 Basf Aktiengesellschaft Production of 2-(o-alkylthiophenyl)-1,3-diazocycloalkene hydrohalides

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1770208A1 (de) * 1968-04-13 1971-10-07 Hoechst Ag Tetrahydropyrimidine und Verfahren zu ihrer Herstellung

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4122263A (en) * 1973-04-11 1978-10-24 Basf Aktiengesellschaft Production of 2-(o-alkylthiophenyl)-1,3-diazocycloalkene hydrohalides

Also Published As

Publication number Publication date
GB1418053A (en) 1975-12-17
CH579054A5 (is") 1976-08-31
FR2182994A1 (is") 1973-12-14
JPS4920171A (is") 1974-02-22
FR2182994B1 (is") 1977-07-15
DE2219841A1 (de) 1973-10-25

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