CA2072019A1 - Procede d'obtention de dialkyl 3-thienylmalonates - Google Patents

Procede d'obtention de dialkyl 3-thienylmalonates

Info

Publication number: CA2072019A1
Authority: CA; Canada
Prior art keywords: copper; mol; dialkyl; bromothiophene; reaction
Prior art date: 1989-12-23
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.): Abandoned

Application number

CA 2072019

Other languages

English (en)

Inventor

Knut Riedel

Heinz Litterer

Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

Hoechst AG

Original Assignee

Individual

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.)

1989-12-23

Filing date

1990-12-11

Publication date

1991-06-24

1989-12-23 Priority claimed from DE19893942952 external-priority patent/DE3942952A1/de

1990-02-20 Priority claimed from DE19904005258 external-priority patent/DE4005258A1/de

1990-12-11 Application filed by Individual filed Critical Individual

1991-06-24 Publication of CA2072019A1 publication Critical patent/CA2072019A1/fr

Status Abandoned legal-status Critical Current

Links

238000000034 method Methods 0.000 title claims abstract description 14
GCOOGCQWQFRJEK-UHFFFAOYSA-N 2-thiophen-3-ylpropanedioic acid Chemical class OC(=O)C(C(O)=O)C=1C=CSC=1 GCOOGCQWQFRJEK-UHFFFAOYSA-N 0.000 title claims abstract description 11
238000002360 preparation method Methods 0.000 title claims abstract description 10
XCMISAPCWHTVNG-UHFFFAOYSA-N 3-bromothiophene Chemical class BrC=1C=CSC=1 XCMISAPCWHTVNG-UHFFFAOYSA-N 0.000 claims abstract description 36
238000006243 chemical reaction Methods 0.000 claims abstract description 19
229910021589 Copper(I) bromide Inorganic materials 0.000 claims abstract description 13
JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical class [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 13
229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
239000001257 hydrogen Substances 0.000 claims abstract description 13
-1 aliphatic monocarboxylic acids Chemical class 0.000 claims abstract description 12
229910021595 Copper(I) iodide Inorganic materials 0.000 claims abstract description 7
UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims abstract description 6
125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 5
LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims abstract description 4
150000002690 malonic acid derivatives Chemical class 0.000 claims abstract description 4
125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 4
239000003880 polar aprotic solvent Substances 0.000 claims abstract description 4
239000005749 Copper compound Substances 0.000 claims abstract description 3
150000001880 copper compounds Chemical class 0.000 claims abstract description 3
150000002431 hydrogen Chemical group 0.000 claims abstract description 3
125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 3
125000004178 (C1-C4) alkyl group Chemical group 0.000 claims abstract 4
RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 8
OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical compound [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 description 7
239000010949 copper Substances 0.000 description 7
LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 6
WGKRMQIQXMJVFZ-UHFFFAOYSA-N 3-iodothiophene Chemical group IC=1C=CSC=1 WGKRMQIQXMJVFZ-UHFFFAOYSA-N 0.000 description 6
ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
AURROROYQPIDRG-UHFFFAOYSA-N diethyl 2-thiophen-3-ylpropanedioate Chemical compound CCOC(=O)C(C(=O)OCC)C=1C=CSC=1 AURROROYQPIDRG-UHFFFAOYSA-N 0.000 description 6
239000011541 reaction mixture Substances 0.000 description 6
239000000843 powder Substances 0.000 description 5
VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 4
VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
JBAKCAZIROEXGK-LNKPDPKZSA-N copper;(z)-4-hydroxypent-3-en-2-one Chemical compound [Cu].C\C(O)=C\C(C)=O JBAKCAZIROEXGK-LNKPDPKZSA-N 0.000 description 4
239000000725 suspension Substances 0.000 description 4
HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
NAWKBJDDFVZPNQ-UHFFFAOYSA-N dimethyl 2-thiophen-3-ylpropanedioate Chemical compound COC(=O)C(C(=O)OC)C=1C=CSC=1 NAWKBJDDFVZPNQ-UHFFFAOYSA-N 0.000 description 3
BEPAFCGSDWSTEL-UHFFFAOYSA-N dimethyl malonate Chemical compound COC(=O)CC(=O)OC BEPAFCGSDWSTEL-UHFFFAOYSA-N 0.000 description 3
239000000203 mixture Substances 0.000 description 3
238000010626 work up procedure Methods 0.000 description 3
OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 2
GWZCLMWEJWPFFA-UHFFFAOYSA-N 2-thiophen-3-ylacetonitrile Chemical compound N#CCC=1C=CSC=1 GWZCLMWEJWPFFA-UHFFFAOYSA-N 0.000 description 2
MBUSOPVRLCFJCS-UHFFFAOYSA-N 3-bromo-4-methylthiophene Chemical compound CC1=CSC=C1Br MBUSOPVRLCFJCS-UHFFFAOYSA-N 0.000 description 2
LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
239000005662 Paraffin oil Substances 0.000 description 2
239000002253 acid Substances 0.000 description 2
OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 2
125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
238000004821 distillation Methods 0.000 description 2
150000002170 ethers Chemical class 0.000 description 2
230000002349 favourable effect Effects 0.000 description 2
239000000706 filtrate Substances 0.000 description 2
150000004820 halides Chemical class 0.000 description 2
GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 2
229960000443 hydrochloric acid Drugs 0.000 description 2
235000011167 hydrochloric acid Nutrition 0.000 description 2
XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
150000002500 ions Chemical class 0.000 description 2
239000002798 polar solvent Substances 0.000 description 2
239000000047 product Substances 0.000 description 2
239000007858 starting material Substances 0.000 description 2
YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
BHMLFPOTZYRDKA-IRXDYDNUSA-N (2s)-2-[(s)-(2-iodophenoxy)-phenylmethyl]morpholine Chemical compound IC1=CC=CC=C1O[C@@H](C=1C=CC=CC=1)[C@H]1OCCNC1 BHMLFPOTZYRDKA-IRXDYDNUSA-N 0.000 description 1
HFDIJTIPFVXOED-OWOJBTEDSA-N (e)-1,4-dichlorobut-3-en-2-one Chemical compound ClCC(=O)\C=C\Cl HFDIJTIPFVXOED-OWOJBTEDSA-N 0.000 description 1
UODXWHPNUCOZEZ-UHFFFAOYSA-N 3-bromo-2,5-dimethylthiophene Chemical compound CC1=CC(Br)=C(C)S1 UODXWHPNUCOZEZ-UHFFFAOYSA-N 0.000 description 1
XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
229930186147 Cephalosporin Natural products 0.000 description 1
229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
QENGPZGAWFQWCZ-UHFFFAOYSA-N Methylthiophene Natural products CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 1
229930182555 Penicillin Natural products 0.000 description 1
YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
125000002015 acyclic group Chemical group 0.000 description 1
229910000102 alkali metal hydride Inorganic materials 0.000 description 1
150000008046 alkali metal hydrides Chemical class 0.000 description 1
239000000010 aprotic solvent Substances 0.000 description 1
GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 1
229940124587 cephalosporin Drugs 0.000 description 1
150000001780 cephalosporins Chemical class 0.000 description 1
229910052802 copper Inorganic materials 0.000 description 1
OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
LOUMXILPZINTNW-UHFFFAOYSA-N diethyl 2-(4-methylthiophen-3-yl)propanedioate Chemical compound CCOC(=O)C(C(=O)OCC)C1=CSC=C1C LOUMXILPZINTNW-UHFFFAOYSA-N 0.000 description 1
125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
QKFCPZYFJCPGFN-UHFFFAOYSA-N dimethyl 2-(2,5-dimethylthiophen-3-yl)propanedioate Chemical compound COC(=O)C(C(=O)OC)C=1C=C(C)SC=1C QKFCPZYFJCPGFN-UHFFFAOYSA-N 0.000 description 1
WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
239000008601 oleoresin Substances 0.000 description 1
150000002960 penicillins Chemical class 0.000 description 1
125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
238000010992 reflux Methods 0.000 description 1
150000003839 salts Chemical class 0.000 description 1
239000002904 solvent Substances 0.000 description 1
238000003756 stirring Methods 0.000 description 1

Classifications

- 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

Landscapes

Chemical & Material Sciences (AREA)
Organic Chemistry (AREA)
Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Plural Heterocyclic Compounds (AREA)
Mixers Of The Rotary Stirring Type (AREA)
Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Catalysts (AREA)

CA 2072019 1989-12-23 1990-12-11 Procede d'obtention de dialkyl 3-thienylmalonates Abandoned CA2072019A1 (fr)

Applications Claiming Priority (4)

Application Number	Priority Date	Filing Date	Title
DE19893942952 DE3942952A1 (de)	1989-12-23	1989-12-23	Verfahren zur herstellung von 3-thienylmalonsaeure-dialkylestern
DEP3942952.0		1989-12-23
DEP4005258.3		1990-02-20
DE19904005258 DE4005258A1 (de)	1990-02-20	1990-02-20	Verfahren zur herstellung von 3-thienylmalonsaeuredialkylestern

Publications (1)

Publication Number	Publication Date
CA2072019A1 true CA2072019A1 (fr)	1991-06-24

Family

ID=25888510

Family Applications (1)

Application Number	Title	Priority Date	Filing Date
CA 2072019 Abandoned CA2072019A1 (fr)	1989-12-23	1990-12-11	Procede d'obtention de dialkyl 3-thienylmalonates

Country Status (4)

Country	Link
EP (1)	EP0506687A1 (fr)
JP (1)	JPH05501414A (fr)
CA (1)	CA2072019A1 (fr)
WO (1)	WO1991009854A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US10201789B2 (en)	2013-12-27	2019-02-12	Sintokogio, Ltd.	Dispersing device, a dispersing system, and a process for dispersing
FR3042985A1 (fr) *	2015-11-04	2017-05-05	Commissariat Energie Atomique	Dispositif de melange de poudres par fluide cryogenique
FR3042986B1 (fr) *	2015-11-04	2017-12-15	Commissariat Energie Atomique	Dispositif de melange de poudres par fluide cryogenique et generation de vibrations

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
GB1359991A (en) *	1970-11-25	1974-07-17	Beecham Group Ltd	3-thienylacetic acid and derivatives thereof
GB2009158B (en) *	1977-12-06	1982-05-06	Oce Andeno Bv	Thienylmalonic acid and diesters thereof

1990
- 1990-12-11 CA CA 2072019 patent/CA2072019A1/fr not_active Abandoned
- 1990-12-11 JP JP3500661A patent/JPH05501414A/ja active Pending
- 1990-12-11 EP EP19910900019 patent/EP0506687A1/fr not_active Withdrawn
- 1990-12-11 WO PCT/EP1990/002152 patent/WO1991009854A1/fr not_active Ceased

Also Published As

Publication number	Publication date
WO1991009854A1 (fr)	1991-07-11
EP0506687A1 (fr)	1992-10-07
JPH05501414A (ja)	1993-03-18

Legal Events

Date	Code	Title	Description
1992-06-22	EEER	Examination request
1994-06-12	FZDE	Dead

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