GB855115A - Improvements in or relating to ª‰-aminoalkylthianaphthene and ª‰-aminoalkylbenzofuran derivatives - Google Patents
Improvements in or relating to ª‰-aminoalkylthianaphthene and ª‰-aminoalkylbenzofuran derivativesInfo
- Publication number
- GB855115A GB855115A GB18397/59A GB1839759A GB855115A GB 855115 A GB855115 A GB 855115A GB 18397/59 A GB18397/59 A GB 18397/59A GB 1839759 A GB1839759 A GB 1839759A GB 855115 A GB855115 A GB 855115A
- Authority
- GB
- United Kingdom
- Prior art keywords
- thianaphthene
- substituted
- compounds
- alkyl
- followed
- 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
Links
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical class C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 abstract 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 abstract 2
- 125000003282 alkyl amino group Chemical group 0.000 abstract 2
- 125000000217 alkyl group Chemical group 0.000 abstract 2
- 238000006243 chemical reaction Methods 0.000 abstract 2
- 239000000460 chlorine Chemical group 0.000 abstract 2
- 150000001875 compounds Chemical class 0.000 abstract 2
- 238000009833 condensation Methods 0.000 abstract 2
- 230000005494 condensation Effects 0.000 abstract 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract 2
- 230000026030 halogenation Effects 0.000 abstract 2
- 238000005658 halogenation reaction Methods 0.000 abstract 2
- 239000000543 intermediate Substances 0.000 abstract 2
- OFFSPAZVIVZPHU-UHFFFAOYSA-N 1-benzofuran-2-carboxylic acid Chemical compound C1=CC=C2OC(C(=O)O)=CC2=C1 OFFSPAZVIVZPHU-UHFFFAOYSA-N 0.000 abstract 1
- HSOMHPHYGAQRTF-UHFFFAOYSA-N 1-benzofuran-2-ylmethanol Chemical class C1=CC=C2OC(CO)=CC2=C1 HSOMHPHYGAQRTF-UHFFFAOYSA-N 0.000 abstract 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 abstract 1
- WDBPZYOUMCCOEO-UHFFFAOYSA-N 2-bromo-3-(bromomethyl)-1-benzofuran Chemical group C1=CC=C2C(CBr)=C(Br)OC2=C1 WDBPZYOUMCCOEO-UHFFFAOYSA-N 0.000 abstract 1
- ZRXHLJNBNWVNIM-UHFFFAOYSA-N 3-methyl-1-benzofuran Chemical compound C1=CC=C2C(C)=COC2=C1 ZRXHLJNBNWVNIM-UHFFFAOYSA-N 0.000 abstract 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract 1
- 230000021736 acetylation Effects 0.000 abstract 1
- 238000006640 acetylation reaction Methods 0.000 abstract 1
- 239000002253 acid Substances 0.000 abstract 1
- 125000003545 alkoxy group Chemical group 0.000 abstract 1
- 150000001540 azides Chemical class 0.000 abstract 1
- RFRXIWQYSOIBDI-UHFFFAOYSA-N benzarone Chemical compound CCC=1OC2=CC=CC=C2C=1C(=O)C1=CC=C(O)C=C1 RFRXIWQYSOIBDI-UHFFFAOYSA-N 0.000 abstract 1
- IANQTJSKSUMEQM-UHFFFAOYSA-N benzofuran Natural products C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 abstract 1
- 125000004618 benzofuryl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 230000031709 bromination Effects 0.000 abstract 1
- 238000005893 bromination reaction Methods 0.000 abstract 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract 1
- 229910052794 bromium Inorganic materials 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 229910052801 chlorine Inorganic materials 0.000 abstract 1
- BULLHNJGPPOUOX-UHFFFAOYSA-N chloroacetone Chemical compound CC(=O)CCl BULLHNJGPPOUOX-UHFFFAOYSA-N 0.000 abstract 1
- 238000007796 conventional method Methods 0.000 abstract 1
- 150000001907 coumarones Chemical class 0.000 abstract 1
- -1 cyclopentylamino, cyclohexylamino Chemical group 0.000 abstract 1
- 238000007256 debromination reaction Methods 0.000 abstract 1
- 238000006114 decarboxylation reaction Methods 0.000 abstract 1
- 238000007429 general method Methods 0.000 abstract 1
- 230000002140 halogenating effect Effects 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract 1
- 230000007062 hydrolysis Effects 0.000 abstract 1
- 238000006460 hydrolysis reaction Methods 0.000 abstract 1
- AQYSYJUIMQTRMV-UHFFFAOYSA-N hypofluorous acid Chemical group FO AQYSYJUIMQTRMV-UHFFFAOYSA-N 0.000 abstract 1
- 239000012948 isocyanate Substances 0.000 abstract 1
- 150000002513 isocyanates Chemical class 0.000 abstract 1
- 239000012280 lithium aluminium hydride Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 abstract 1
- ZIYVHBGGAOATLY-UHFFFAOYSA-N methylmalonic acid Chemical compound OC(=O)C(C)C(O)=O ZIYVHBGGAOATLY-UHFFFAOYSA-N 0.000 abstract 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 abstract 1
- 231100000252 nontoxic Toxicity 0.000 abstract 1
- 230000003000 nontoxic effect Effects 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- 150000005599 propionic acid derivatives Chemical class 0.000 abstract 1
- 238000007363 ring formation reaction Methods 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 abstract 1
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
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
- C07D307/79—Benzo [b] furans; Hydrogenated benzo [b] furans with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
-
- 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
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
- C07D307/79—Benzo [b] furans; Hydrogenated benzo [b] furans with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
- C07D307/81—Radicals substituted by nitrogen atoms not forming part of a nitro radical
-
- 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
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
- C07D307/82—Benzo [b] furans; Hydrogenated benzo [b] furans 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 carbon atoms of the hetero ring
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Furan Compounds (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention comprises compounds of the general formula: <FORM:0855115/IV(b)/1> (wherein Y is S, O, or SO2, R1 is hydrogen, hydroxy, fluorine, chlorine, bromine, nitro, trifluoromethyl, lower alkyl or lower alkoxy, in position 5 or 6, R2 is lower alkyl and Z is amino, mono lower alkylamino, di-lower alkylamino, cyclopentylamino, cyclohexylamino, N-piperidino or N-pyrrolidino) and their non-toxic acid addition salts and methods for their preparation. The general method involves condensation of a 2- or 3-halomethyl-R1-substituted benzofuran or thianaphthene with a diethyl a -alkyl malonate, hydrolysis of the resulting diethyl a -alkyl-a -thianaphthyl (or benzofuryl) methyl malonate, decarboxylation to the corresponding propionic acid derivative, conversion via the acid chloride and azide to the corresponding isocyanate followed (a) by heating with concentrated H Cl to yield the b -aminoalkyl thianaphthene or benzofuran, or (b) by reduction with lithium aluminium hydride to yield the analogous b -methylaminoalkyl compounds. The amino compounds are alkylated if desired by conventional methods. The S-dioxides are obtained by treatment with excess hydrogen peroxide, protecting primary amino groups by acetylation prior to oxidation. Detailed examples are given. The 3-halomethylthianaphthene intermediates are prepared from R1 substituted thiophenols by condensation with chloroacetone, cyclization and halogenation of the resulting 3-methyl-R1-substituted thianaphthene. The corresponding 2-halomethyl compounds are formed from the R1-substituted thianaphthene by treatment with butyl lithium and then formaldehyde followed by reaction of the 2-hydroxymethylthianaphthene with a halogenating agent. The 3-halomethylbenzofuran intermediates are prepared by bromination of 3-methylbenzofuran followed by debromination of the 2-bromo-3-bromomethylbenzofuran at position 2 preferably at a later stage of the synthesis. The analogous 2-halomethylbenzofurans are formed by reduction of a coumarilic acid and then halogenation of the 2-hydroxymethylbenzofurans so obtained.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US855115XA | 1958-07-11 | 1958-07-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB855115A true GB855115A (en) | 1960-11-30 |
Family
ID=22192095
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB18397/59A Expired GB855115A (en) | 1958-07-11 | 1959-05-29 | Improvements in or relating to ª‰-aminoalkylthianaphthene and ª‰-aminoalkylbenzofuran derivatives |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB855115A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1181715B (en) * | 1961-11-03 | 1964-11-19 | Byk Gulden Lomberg Chem Fab | Process for the preparation of 3- (ª ‰ -amino-ethyl) -5-methoxy-coumarone hydrochloride |
| DE1203276B (en) * | 1961-11-03 | 1965-10-21 | Byk Gulden Lomberg Chem Fab | Process for the preparation of N-substituted 3- (beta-aminoaethyl) -coumarones |
| FR2092731A1 (en) * | 1970-06-12 | 1972-01-28 | Innothera Lab Sa | |
| WO1999007667A1 (en) * | 1997-08-07 | 1999-02-18 | Fujimoto Brothers Co., Ltd. | Novel ethylamine derivatives |
-
1959
- 1959-05-29 GB GB18397/59A patent/GB855115A/en not_active Expired
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1181715B (en) * | 1961-11-03 | 1964-11-19 | Byk Gulden Lomberg Chem Fab | Process for the preparation of 3- (ª ‰ -amino-ethyl) -5-methoxy-coumarone hydrochloride |
| DE1203276B (en) * | 1961-11-03 | 1965-10-21 | Byk Gulden Lomberg Chem Fab | Process for the preparation of N-substituted 3- (beta-aminoaethyl) -coumarones |
| FR2092731A1 (en) * | 1970-06-12 | 1972-01-28 | Innothera Lab Sa | |
| WO1999007667A1 (en) * | 1997-08-07 | 1999-02-18 | Fujimoto Brothers Co., Ltd. | Novel ethylamine derivatives |
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