EP0494906A1 - KONTINUIERLICHES VERFAHREN ZUR HERSTELLUNG VON $g(D)1-ENOLETHERN - Google Patents
KONTINUIERLICHES VERFAHREN ZUR HERSTELLUNG VON $g(D)1-ENOLETHERNInfo
- Publication number
- EP0494906A1 EP0494906A1 EP90914531A EP90914531A EP0494906A1 EP 0494906 A1 EP0494906 A1 EP 0494906A1 EP 90914531 A EP90914531 A EP 90914531A EP 90914531 A EP90914531 A EP 90914531A EP 0494906 A1 EP0494906 A1 EP 0494906A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- formula
- alkyl
- reaction
- acid
- iii
- 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.)
- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000010924 continuous production Methods 0.000 title description 2
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 239000011541 reaction mixture Substances 0.000 claims abstract description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 3
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- 150000002367 halogens Chemical class 0.000 claims abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract 3
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims description 2
- -1 where R3 is H Chemical group 0.000 abstract description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 2
- 125000006526 (C1-C2) alkyl group Chemical group 0.000 abstract 2
- 125000005157 alkyl carboxy group Chemical group 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 238000004821 distillation Methods 0.000 description 14
- JEPJBZHWRGLINP-UHFFFAOYSA-N 2,2-dimethoxy-3-methylbutane Chemical compound COC(C)(OC)C(C)C JEPJBZHWRGLINP-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 6
- 150000002084 enol ethers Chemical class 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000011005 laboratory method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- XYHKNCXZYYTLRG-UHFFFAOYSA-N 1h-imidazole-2-carbaldehyde Chemical compound O=CC1=NC=CN1 XYHKNCXZYYTLRG-UHFFFAOYSA-N 0.000 description 1
- LTMRRSWNXVJMBA-UHFFFAOYSA-N 2,2-diethylpropanedioic acid Chemical compound CCC(CC)(C(O)=O)C(O)=O LTMRRSWNXVJMBA-UHFFFAOYSA-N 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-M 3-Methylbutanoic acid Natural products CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical class CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N beta-methyl-butyric acid Natural products CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000006567 deketalization reaction Methods 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
- 150000002170 ethers Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- IMFKDZCVWYKAAL-UHFFFAOYSA-N phosphoric acid pyridine Chemical compound P(=O)(O)(O)O.N1=CC=CC=C1.N1=CC=CC=C1 IMFKDZCVWYKAAL-UHFFFAOYSA-N 0.000 description 1
- 231100000208 phytotoxic Toxicity 0.000 description 1
- 230000000885 phytotoxic effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 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 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/28—Preparation of ethers by reactions not forming ether-oxygen bonds from acetals, e.g. by dealcoholysis
Definitions
- the present invention relates to a process for the preparation of compounds of the formula I.
- R 1 and R 2 have the meanings given above, at temperatures between 50 ° C and 200 ° C to the submitted
- R 3 H, (C-j ⁇ -CG) alkyl which may be halogenated, (Cg-CgJCycloalkyl, phenyl which is mono- or polysubstituted by (C ⁇ -C ⁇ ) - may be substituted alkyl or halogen, or carboxy - (C * ⁇ - C 6 ) alkyl means, metered and the formed reaction products of formula I and formula IV
- R 2 has the abovementioned meaning, continuously distilled off from the reaction mixture.
- Alkyl means both straight-chain and branched alkyl.
- R ⁇ - preferably means isopropyl.
- Halogenated alkyl represents alkyl substituted one or more times, in particular by F, Cl or Br.
- the radicals trifluoromethyl, trichloromethyl and
- Tribromomethyl Tribromomethyl.
- alkylene oil ethers of the formula I are valuable
- the compounds of the formula I can be prepared by acid-catalyzed elimination of alcohol from the corresponding ketals of the formula II at elevated temperatures and then distilled off from the reaction mixture by conventional laboratory methods.
- acidic catalysts e.g. p-Toluenesulfonic acid, phosphoric acid, sulfuric acid, alkali hydrogen sulfate, boric acid and phosphoric acid pyridine or quinoline (Houben-Weyl, Methods of Organic Chemistry, Volume 6/3 p. 97; Kunz, Lindig, Chem. Ber. 116, 220-229
- the desired ⁇ l-enether can be produced in yields of> 97% of theory using the process according to the invention, the proportions of ⁇ 2-enol ether and polymeric residue each being ⁇ 1%.
- the process according to the invention is particularly easy to handle due to its continuous implementation.
- the process according to the invention is advantageously carried out in such a way that the ketals of the formula II are metered continuously into the heated carboxylic acid of the formula III and the resulting ⁇ l-enol ether of the formula I with the alcohol of the formula IV formed is distilled off continuously from the reaction mixture.
- the separation of the end products I from the alcohols IV is unproblematic and is carried out by distillation or extraction.
- reaction temperatures are between 50 ° C. and 200 ° C., preferably between 60 ° C. and 150 ° C.
- the ketal of formula II is either on the
- the process according to the invention is to be assessed as all the more surprising since the carboxylic acid of the formula III present in high excess at the time of the actual reaction does not undergo any reactions with the ⁇ 1-enol ethers formed.
- the polymerization products occurring in the known processes are not obtained here.
- Fe ner is known to have vinyl ether (enol ether)
- Carboxylic acids e.g. Acetic acid
- Carboxylic acids easily react to vinyl acetates or semi-acylals and thus yield reductions in products I can occur (. Reppe A, 601 (1956) 81-138; DF Schorstakowski and NA Ger ⁇ tein, J. allg. Chem. 21, 1452 (1951); Chem Zbl. 1952, 5395).
- distillate After a further 25 hours of distillation, a total of 569 g of distillate are obtained, which consists of 375 g of ⁇ l-enol ether, 55 g of ⁇ 2-enol ether and 139 g of methanol, which gives a yield of 75% of theory corresponds.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3933247 | 1989-10-05 | ||
| DE3933247A DE3933247C1 (enrdf_load_stackoverflow) | 1989-10-05 | 1989-10-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0494906A1 true EP0494906A1 (de) | 1992-07-22 |
Family
ID=6390869
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP90914531A Withdrawn EP0494906A1 (de) | 1989-10-05 | 1990-10-01 | KONTINUIERLICHES VERFAHREN ZUR HERSTELLUNG VON $g(D)1-ENOLETHERN |
Country Status (9)
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4433949A1 (de) * | 1994-09-23 | 1996-03-28 | Huels Chemische Werke Ag | Verfahren zur Herstellung von ungesättigten Ethern |
| CN116444352B (zh) * | 2022-01-06 | 2024-06-25 | 万华化学集团股份有限公司 | 一种2-甲氧基丙烯液相合成的新方法 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE596888A (fr) * | 1959-11-19 | 1961-05-09 | Hoffmann La Roche | Procédé pour la préparation d'éthers énoliques |
| DE3804162A1 (de) * | 1988-02-11 | 1989-08-24 | Basf Ag | Verfahren zur herstellung von vinylethern |
-
1989
- 1989-10-05 DE DE3933247A patent/DE3933247C1/de not_active Expired - Fee Related
-
1990
- 1990-10-01 JP JP2513602A patent/JPH05500667A/ja active Pending
- 1990-10-01 AU AU64429/90A patent/AU6442990A/en not_active Abandoned
- 1990-10-01 KR KR1019920700773A patent/KR950006801B1/ko not_active Expired - Lifetime
- 1990-10-01 WO PCT/EP1990/001646 patent/WO1991004956A1/de not_active Application Discontinuation
- 1990-10-01 EP EP90914531A patent/EP0494906A1/de not_active Withdrawn
- 1990-10-03 IL IL95896A patent/IL95896A0/xx unknown
- 1990-10-04 ZA ZA907922A patent/ZA907922B/xx unknown
-
1992
- 1992-04-03 HU HU9201136A patent/HUT61259A/hu unknown
Non-Patent Citations (1)
| Title |
|---|
| See references of WO9104956A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| KR927003496A (ko) | 1992-12-18 |
| DE3933247C1 (enrdf_load_stackoverflow) | 1991-01-17 |
| HU9201136D0 (en) | 1992-07-28 |
| WO1991004956A1 (de) | 1991-04-18 |
| AU6442990A (en) | 1991-04-28 |
| JPH05500667A (ja) | 1993-02-12 |
| ZA907922B (en) | 1991-07-31 |
| IL95896A0 (en) | 1991-07-18 |
| KR950006801B1 (ko) | 1995-06-22 |
| HUT61259A (en) | 1992-12-28 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| 17P | Request for examination filed |
Effective date: 19920304 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH DE FR GB IT LI NL SE |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN |
|
| 18W | Application withdrawn |
Withdrawal date: 19921210 |