GB1226981A - - Google Patents

Info

Publication number
GB1226981A
GB1226981A GB1226981DA GB1226981A GB 1226981 A GB1226981 A GB 1226981A GB 1226981D A GB1226981D A GB 1226981DA GB 1226981 A GB1226981 A GB 1226981A
Authority
GB
United Kingdom
Prior art keywords
compounds
alkyl
reacting
acid
oco
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
Application number
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 filed Critical
Publication of GB1226981A publication Critical patent/GB1226981A/en
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/42—Singly bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three 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
    • C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/24—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals

Abstract

1,226,981. Thiophene and furan derivatives. IMPERIAL CHEMICAL INDUSTRIES Ltd. 17 March, 1969 [16 April, 1968; 25 Oct., 1968; 10 Dec., 1968], Nos. 17895/68, 50788/68 and 58666/68 Heading C2C: [Also in Division A5] The invention comprises novel thiophene and furan derivatives of the Formula I wherein X is H, CH 3 , CH 3 CH 2 , Cl or Br, Y is a phenyl radical, optionally substituted by one or two F, Cl, or Br atom(s), and Z is a group of the formula -CR<SP>1</SP>R<SP>2</SP>R<SP>3</SP>, wherein R<SP>1</SP> is H, CH 3 or CH 3 CH 2 , R<SP>2</SP> is H, CH 3 or CH 3 CH 2 , C 2-6 alkoxycarbonyl, benzyloxycarbonyl or phenoxycarbonyl, and R<SP>3</SP> is -CO 2 R<SP>4</SP>, CONHR<SP>5</SP> or CONR<SP>6</SP>, wherein R<SP>4</SP> is H, C 1-5 alkyl, benzyl or phenyl, R<SP>5</SP> is H, OH, NH 2 or C 4-8 dialkylaminoalkyi, and NR<SP>6</SP> is N-piperidino, N-morpholino or N-pyrrolidino, and wherein when R<SP>2</SP> is C 2-6 alkoxycarbonyl, benzyloxycarbonyl or phenoxycarbonyl R<SP>3</SP> is the same radical, and B is O or S, and wherein Y and Z are linked to non- adjacent carbon atoms of the heterocyclic nucleus and when X is H and Y is linked to position 2 of the nucleus, Z is not CH 2 CO 2 R<SP>4</SP> linked to position 5 of the nucleus; and non- toxic pharmaceutically acceptable salts of said compounds, wherein R<SP>3</SP> is a carboxy radical, and non-toxic pharmaceutically acceptable acidaddition salts of said compounds which are sufficiently basic to form said acid-addition salts. The novel compounds are obtained by the following methods: (a) Compounds of the above general formula in which R<SP>2</SP> is H, CH 3 or C 2 H 5 and R<SP>3</SP> is CO 2 R<SP>4</SP>, wherein R<SP>4</SP> is C 1-5 alkyl by reacting the appropriate cyanide with an alkanol of the formula R<SP>4</SP>0H, in the presence of sulphuric or hydrochloric acid, provided that when B is O the acid is hydrochloric acid. (b) Compounds in which both R<SP>1</SP> and R<SP>2</SP> are H and R<SP>3</SP> is CO 2 R<SP>4</SP>, wherein R<SP>4</SP> is H or C 1-5 alkyl by carrying out the Arndt-Eistert reaction on the corresponding halocarbonylthiophene or halocarbonylfuran derivatives. (c) Compounds in which R<SP>2</SP> is H, CH 3 or C 2 H 5 and R<SP>3</SP> is CONH 2 by hydrolysing the appropriate nitriles. (d) Compounds in which R<SP>2</SP> is H, CH 3 or C 2 H 5 and R<SP>3</SP> is CO 2 H by hydrolysing the corresponding compounds in which R<SP>3</SP> is replaced by a radical Cy, where Cy stands for CN, CONH 2 , CSNH 2 , C 2-6 alkoxycarbonyl? C 6 H 5 CH 2 OCO, or C 6 H 5 OCO. (e) Compounds in which R<SP>2</SP> is H, CH 3 or C 2 H 5 and R<SP>3</SP> is CONHR<SP>5</SP> or CONR<SP>6</SP> by reacting the corresponding acid halide with a compound of the formula R<SP>5</SP>NH 2 or HNR<SP>6</SP>. (f) Compounds in which R<SP>2</SP> is H, CH 3 or C 2 H 5 and R<SP>3</SP> is C0 2 R<SP>4</SP>, wherein R<SP>4</SP> is C 1-5 alkyl, benzyl or phenyl, by esterifying the corresponding acids, acid halides or carboxylic acid anhydrides. (g) Compounds in which R<SP>3</SP> is C0 2 R<SP>4</SP> in which R<SP>4</SP> is C 1-5 alkyl, C 6 H 5 CH 2 - or C 6 H 5 - by reacting alkali metal derivatives of the corresponding compounds in which R<SP>1</SP> is H, with methyl or ethyl chloride, bromide or iodide. (h) Compounds in which R<SP>2</SP> and R<SP>3</SP> are both CO 2 R<SP>4</SP>, wherein R<SP>4</SP> is C 1-5 alkyl, C 6 H 5 CH 2 or C 6 H 5 -, by reacting sodium or potassium or a hydride, amide or C 1-4 alkoxide thereof, with carbonates of the formula CO.(OR<SP>4</SP>) 2 and compounds of the above general formula in which R<SP>2</SP> is H or R<SP>3</SP> is CO 2 R<SP>4</SP>. (i) Compounds in which R<SP>2</SP> is H or R<SP>3</SP> is CO 2 H by reacting compound of the above general formula in which both R<SP>2</SP> and R<SP>3</SP> are -CO 2 R4, wherein R<SP>4</SP> is <SP>C</SP>1-5 alkyl, C 6 H 5 CH 2 or C 6 H 5 -, which an inorganic base in the presence of water and under the influence of heat, or, in the case where B is S, with an inorganic acid in the presence of water and under the influence of heat. (j) Compounds in which X is Cl or Br, and R<SP>3</SP> is C0 2 R<SP>4</SP>, wherein R<SP>4</SP> is C 1-5 alkyl, C 6 H 5 CH 2 - or C 6 H 5 - by reacting the corresponding compounds in which X is hydrogen, in the presence of alkali metal acetates, with solutions of chlorine or bromine in organic solvents. (k) Compounds in which R<SP>2</SP> is H, CH 3 , C 2 H 5 , C 4-6 alkoxy carbonyl, C 6 H 5 CH 2 OCO or C 6 H 6 OCO and R<SP>3</SP> is C0 2 R<SP>4</SP>, wherein R<SP>4</SP> is C 3-5 alkyl, C 6 H 5 CH 2 or C 6 H 5 , by reacting corresponding compounds in which R<SP>2</SP> is H, CH 3 , C 2 H 5 , CH 3 OCO or CH 3 CH 2 OCO and R<SP>3</SP> is C0 2 R<SP>4</SP>, wherein R<SP>4</SP> is CH 3 or C 2 H 5 , with a C 3-5 alkanol C 6 H 5 CH 2 OH or C 6 H 5 OH in the presence of dibutyl tin dilaurate at a temperature in the range 25‹ to 200‹ C. (1) Compounds in which R<SP>1</SP> and R<SP>2</SP> are both H and R<SP>3</SP> is CO 2 H by first carrying out the Willgerodt reaction on the corresponding acetyl furan or thiophene derivatives and then hydrolysing the product by means of an inorganic base, and, if desired, converting the resulting salts into the corresponding acids. The following compounds and intermediates are described: Ethyl 5 - p - chlorophenylthien - 2 - ylacetate, 2 - cyanomethyl - 5 - p - chlorophenylthiophene, 2 - chloromethyl - 5 - p - chlorophenylthiophene, 2 - hydroxy - methyl - 5 - p - chlorophenylthiophene, 3 - chlorocarbonyl - 2 - methyl - 5 - phenylthiophene, 3 - carboxy - 2 - methyl - 5 - phenylthiophene, ethyl - 2 - methyl - 5 - phenylthien- 3-yl-carbozylate, 3 - ethoxy - carbonyl - 1 - phenylpentane - 1,4 - dione, 2 - (α - cyanoethyl)-5- p - chlorophenylthiophene, methyl - 5 - p - chlorophenylfur - 2 - ylacetate, sodium 5 - p - chlorophenylthien - 2 - ylacetate, 5 - p - chlorophenylthien - 2 - ylacetic acid hemihydrate, 5 - p - bromophenyl - 3 - chloromethylfuran, 5 - p - bromophenyl - 3 - hydroxymethylfuran, 5 - p - bromophenyl - 3 - ethoxycarbonyl - 2 - methylfuran, and 1 - p - bromophenyl - 3 - ethoxycarbonyl - pentane - 1,4 - dione.
GB1226981D 1968-04-16 1968-04-16 Expired GB1226981A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB1789568 1968-04-16

Publications (1)

Publication Number Publication Date
GB1226981A true GB1226981A (en) 1971-03-31

Family

ID=10103129

Family Applications (1)

Application Number Title Priority Date Filing Date
GB1226981D Expired GB1226981A (en) 1968-04-16 1968-04-16

Country Status (6)

Country Link
JP (1) JPS516144B1 (en)
AT (1) AT285594B (en)
CH (1) CH553177A (en)
CS (1) CS160101B2 (en)
GB (1) GB1226981A (en)
PL (1) PL80177B1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009030450A2 (en) 2007-09-03 2009-03-12 Syngenta Limited Novel herbicides
EP2527333A1 (en) 2007-06-28 2012-11-28 Syngenta Limited Pyrandione, thiopyrandione and cyclohexanetrione compounds having herbicidal properties
US20200255417A1 (en) * 2017-08-31 2020-08-13 Ahammune Biosciences Private Limited Novel thiophene compounds, process for synthesis and use thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2527333A1 (en) 2007-06-28 2012-11-28 Syngenta Limited Pyrandione, thiopyrandione and cyclohexanetrione compounds having herbicidal properties
WO2009030450A2 (en) 2007-09-03 2009-03-12 Syngenta Limited Novel herbicides
US20200255417A1 (en) * 2017-08-31 2020-08-13 Ahammune Biosciences Private Limited Novel thiophene compounds, process for synthesis and use thereof
US11739082B2 (en) * 2017-08-31 2023-08-29 Ahammune Biosciences Private Limited Thiophene compounds, process for synthesis and use thereof

Also Published As

Publication number Publication date
CH553177A (en) 1974-08-30
CS160101B2 (en) 1975-02-28
JPS516144B1 (en) 1976-02-25
AT285594B (en) 1970-11-10
PL80177B1 (en) 1975-08-30

Similar Documents

Publication Publication Date Title
SU784776A3 (en) Method of preparing quinazolone derivatives
GB1121922A (en) Pyrimidine derivatives
GB1254907A (en) Indenyloxy and indenylthio alkanoic acids
GB1140748A (en) New carboxylic acid derivatives
GB1442707A (en) Substituted phenylalkanoic acids and their derivatives and pharma ceutical compositions thereof
GB1226981A (en)
GB1164234A (en) Process for the production of Phthalocyanines and Phthalocyanine Derivatives
GB1413068A (en) Bromoergolines
SU513624A3 (en) Method for preparing 2-piperazinyl thiazole derivatives
GB1503119A (en) 7-aminobenzocycloheptenes
GB1446632A (en) 5-endo-benzoyloxy-n-amino-c2-4 alkyl- bicyclo-2,2,1-heptane - 2,3-d-endo-carboxylic acid imides
GB1432649A (en)
Izumi et al. Synthesis of indoles via amidoselenation
ES479273A1 (en) Syn isomers of 7-[2-(2-amino-4-thiazolyl)-2-(carboxymethyloxyimino)-acetamido]-ceph-3-eme-4-carboxylic acid compounds
GB1173312A (en) Heterocyclic Compounds
GB1331839A (en) Aryloxy-and arylthioalkanoic acids derivatives thereof processes for their production and compositions containing same
ES487175A1 (en) Process for preparation of piperidyl-indoles
US4018817A (en) 6-Halo-5-cyclohexylindan-1-carbohydroxamic acid
GB1391007A (en) Imidazolidinone derivatives and processes for the production thereof
US2759942A (en) Substituted piperidinecarboxylates and methods of preparing same
GB1088295A (en) Derivatives of alkanoic acids and methods for their preparation
IE46102B1 (en) 5-methylisoxazole-4-carboxylic acid anilides having pharmaceutical activity
US3821248A (en) Bis-(p-chlorphenoxy)acetic acid esters
GB1512537A (en) 2-(2&#39;-aryl-6&#39;-chromonyl) propionic acids and analgesic and anti-inflammatory derivatives thereof
JPWO2006123648A1 (en) Preparation of 3-substituted thiophene

Legal Events

Date Code Title Description
PS Patent sealed
PLNP Patent lapsed through nonpayment of renewal fees