CA1067508A - Process for producing alkoxymethylene malonic acid esters - Google Patents
Process for producing alkoxymethylene malonic acid estersInfo
- Publication number
- CA1067508A CA1067508A CA229,137A CA229137A CA1067508A CA 1067508 A CA1067508 A CA 1067508A CA 229137 A CA229137 A CA 229137A CA 1067508 A CA1067508 A CA 1067508A
- Authority
- CA
- Canada
- Prior art keywords
- acid
- ester
- process according
- reaction
- malonic acid
- 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
- 238000000034 method Methods 0.000 title claims abstract description 30
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical class OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 title claims abstract description 26
- -1 alkoxy methylene malonic acid ester Chemical class 0.000 claims abstract description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 150000002148 esters Chemical class 0.000 claims abstract description 19
- RLAHWVDQYNDAGG-UHFFFAOYSA-N Methanetriol Chemical compound OC(O)O RLAHWVDQYNDAGG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002841 Lewis acid Substances 0.000 claims abstract description 6
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 239000011541 reaction mixture Substances 0.000 claims abstract description 6
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 5
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract 8
- 238000006243 chemical reaction Methods 0.000 claims description 49
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims 1
- 239000011261 inert gas Substances 0.000 claims 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical group C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 claims 1
- 239000001384 succinic acid Substances 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 30
- IYXGSMUGOJNHAZ-UHFFFAOYSA-N Ethyl malonate Chemical compound CCOC(=O)CC(=O)OCC IYXGSMUGOJNHAZ-UHFFFAOYSA-N 0.000 description 16
- GKASDNZWUGIAMG-UHFFFAOYSA-N triethyl orthoformate Chemical compound CCOC(OCC)OCC GKASDNZWUGIAMG-UHFFFAOYSA-N 0.000 description 14
- 238000009835 boiling Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 11
- LTMHNWPUDSTBKD-UHFFFAOYSA-N diethyl 2-(ethoxymethylidene)propanedioate Chemical compound CCOC=C(C(=O)OCC)C(=O)OCC LTMHNWPUDSTBKD-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 238000004821 distillation Methods 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- BEPAFCGSDWSTEL-UHFFFAOYSA-N dimethyl malonate Chemical compound COC(=O)CC(=O)OC BEPAFCGSDWSTEL-UHFFFAOYSA-N 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 150000002905 orthoesters Chemical class 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- VGUWZCUCNQXGBU-UHFFFAOYSA-N 3-[(4-methylpiperazin-1-yl)methyl]-5-nitro-1h-indole Chemical compound C1CN(C)CCN1CC1=CNC2=CC=C([N+]([O-])=O)C=C12 VGUWZCUCNQXGBU-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- PSZAEHPBBUYICS-UHFFFAOYSA-N 2-methylidenepropanedioic acid Chemical compound OC(=O)C(=C)C(O)=O PSZAEHPBBUYICS-UHFFFAOYSA-N 0.000 description 1
- ZPSJGADGUYYRKE-UHFFFAOYSA-N 2H-pyran-2-one Chemical class O=C1C=CC=CO1 ZPSJGADGUYYRKE-UHFFFAOYSA-N 0.000 description 1
- PBVZQAXFSQKDKK-UHFFFAOYSA-N 3-Methoxy-3-oxopropanoic acid Chemical class COC(=O)CC(O)=O PBVZQAXFSQKDKK-UHFFFAOYSA-N 0.000 description 1
- 229910015400 FeC13 Inorganic materials 0.000 description 1
- 241000286819 Malo Species 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000002844 continuous effect Effects 0.000 description 1
- FDKLLWKMYAMLIF-UHFFFAOYSA-N cyclopropane-1,1-dicarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CC1 FDKLLWKMYAMLIF-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- KTLZQSZGORXBED-UHFFFAOYSA-N dimethyl 2-methylidenepropanedioate Chemical compound COC(=O)C(=C)C(=O)OC KTLZQSZGORXBED-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical compound O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
- C07C69/708—Ethers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2426964A DE2426964C3 (de) | 1974-06-04 | 1974-06-04 | Verfahren zur Herstellung von Alkoxymethylenmalonsäuredialkylestern |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1067508A true CA1067508A (en) | 1979-12-04 |
Family
ID=5917297
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA229,137A Expired CA1067508A (en) | 1974-06-04 | 1975-06-02 | Process for producing alkoxymethylene malonic acid esters |
Country Status (12)
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2635841C2 (de) | 1976-08-10 | 1983-02-24 | Dynamit Nobel Ag, 5210 Troisdorf | Verfahren zur Herstellung von Alkoxymethylenmalonsäurenitrilen |
| FR2559147B1 (fr) * | 1984-02-07 | 1986-06-13 | Rhone Poulenc Spec Chim | Procede d'obtention de composes organiques a groupe alkoxyalkylidene |
| FR2566395B1 (fr) * | 1984-06-25 | 1986-11-21 | Rhone Poulenc Spec Chim | Procede d'obtention de composes organiques a groupe alkoxyalkylidene |
| FR2589466B1 (fr) * | 1985-11-04 | 1988-10-14 | Rhone Poulenc Spec Chim | Procede de preparation de composes porteurs de motifs alkoxyalkylidenes |
| DE3927761C2 (de) * | 1989-08-23 | 1997-11-27 | Huels Chemische Werke Ag | Verfahren zur Herstellung von Alkoxyalkylidenmalonsäureestern |
| CN104860818A (zh) * | 2015-04-20 | 2015-08-26 | 浙江新和成股份有限公司 | 一种乙氧基甲叉丙二酸二乙酯的合成方法 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3637812A (en) * | 1967-10-02 | 1972-01-25 | Merck & Co Inc | Acylation of reactive organic acid esters |
-
1974
- 1974-06-04 DE DE2426964A patent/DE2426964C3/de not_active Expired
-
1975
- 1975-05-21 GB GB2199575A patent/GB1447351A/en not_active Expired
- 1975-05-29 BE BE156840A patent/BE829650A/xx not_active IP Right Cessation
- 1975-05-30 CH CH703375A patent/CH605583A5/xx not_active IP Right Cessation
- 1975-05-30 US US05/582,474 patent/US4058553A/en not_active Expired - Lifetime
- 1975-06-02 FR FR7517177A patent/FR2273793A1/fr active Granted
- 1975-06-02 CA CA229,137A patent/CA1067508A/en not_active Expired
- 1975-06-03 JP JP50066985A patent/JPS514123A/ja active Granted
- 1975-06-03 IT IT49869/75A patent/IT1035921B/it active
- 1975-06-03 ES ES438158A patent/ES438158A1/es not_active Expired
- 1975-06-04 FI FI751652A patent/FI63214C/fi not_active IP Right Cessation
- 1975-06-04 NL NLAANVRAGE7506605,A patent/NL187159C/xx not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| DE2426964A1 (de) | 1975-12-11 |
| GB1447351A (en) | 1976-08-25 |
| FI63214C (fi) | 1983-05-10 |
| FR2273793A1 (fr) | 1976-01-02 |
| JPS514123A (en) | 1976-01-14 |
| JPS5735822B2 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) | 1982-07-31 |
| US4058553A (en) | 1977-11-15 |
| DE2426964B2 (de) | 1978-10-12 |
| FI63214B (fi) | 1983-01-31 |
| IT1035921B (it) | 1979-10-20 |
| CH605583A5 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) | 1978-09-29 |
| NL7506605A (nl) | 1975-12-08 |
| BE829650A (fr) | 1975-09-15 |
| ES438158A1 (es) | 1977-02-01 |
| FI751652A7 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) | 1975-12-05 |
| FR2273793B1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) | 1980-05-30 |
| NL187159C (nl) | 1991-06-17 |
| DE2426964C3 (de) | 1979-06-07 |
| NL187159B (nl) | 1991-01-16 |
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