DE77354C - Process for the preparation of ethoxymethylene and oxymethylene derivatives - Google Patents
Process for the preparation of ethoxymethylene and oxymethylene derivativesInfo
- Publication number
- DE77354C DE77354C DENDAT77354D DE77354DA DE77354C DE 77354 C DE77354 C DE 77354C DE NDAT77354 D DENDAT77354 D DE NDAT77354D DE 77354D A DE77354D A DE 77354DA DE 77354 C DE77354 C DE 77354C
- Authority
- DE
- Germany
- Prior art keywords
- ether
- oxymethylene
- ethoxymethylene
- derivatives
- preparation
- 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 - Lifetime
Links
- -1 ethoxymethylene Chemical group 0.000 title claims description 7
- 125000005704 oxymethylene group Chemical group [H]C([H])([*:2])O[*:1] 0.000 title claims description 7
- 238000000034 method Methods 0.000 title claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 39
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 4
- 150000002170 ethers Chemical class 0.000 claims description 2
- OZWKMVRBQXNZKK-UHFFFAOYSA-N Ketorolac Chemical compound OC(=O)C1CCN2C1=CC=C2C(=O)C1=CC=CC=C1 OZWKMVRBQXNZKK-UHFFFAOYSA-N 0.000 claims 1
- RLAHWVDQYNDAGG-UHFFFAOYSA-N Orthoformic acid Chemical compound OC(O)O RLAHWVDQYNDAGG-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 125000005594 diketone group Chemical group 0.000 claims 1
- 238000009835 boiling Methods 0.000 description 6
- YRKCREAYFQTBPV-UHFFFAOYSA-N Acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PXBFSRVXEKCBFP-UHFFFAOYSA-N 2-(4-acetamidophenoxy)ethyl 2-acetyloxybenzoate Chemical compound C1=CC(NC(=O)C)=CC=C1OCCOC(=O)C1=CC=CC=C1OC(C)=O PXBFSRVXEKCBFP-UHFFFAOYSA-N 0.000 description 1
- YIFCWYUSYGFFMH-UHFFFAOYSA-N 2-(ethoxymethylidene)propanedioic acid Chemical compound CCOC=C(C(O)=O)C(O)=O YIFCWYUSYGFFMH-UHFFFAOYSA-N 0.000 description 1
- 241000530268 Lycaena heteronea Species 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N Sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L Zinc chloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- RFKZUAOAYVHBOY-UHFFFAOYSA-M copper(1+);acetate Chemical compound [Cu+].CC([O-])=O RFKZUAOAYVHBOY-UHFFFAOYSA-M 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/80—Acids; Esters in position 3
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/673—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/34—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D309/36—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with oxygen atoms directly attached to ring carbon atoms
- C07D309/38—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with oxygen atoms directly attached to ring carbon atoms one oxygen atom in position 2 or 4, e.g. pyrones
Description
KAISERLICHESIMPERIAL
PATENTAMT.PATENT OFFICE.
Verbindungen, welche die Gruppirung:
— CO—CH2- CO — Connections which the grouping:
- CO — CH 2 - CO -
enthalten, können nach dein gewöhnlichen Verfahren (durch Behandlung mit Ameisenäther und Natriumäthylat bezw. Natrium) nicht in Oxymethylen-Derivate:can contain, according to your usual procedure (by treatment with ant ether and sodium ethylate respectively. Sodium) not in oxymethylene derivatives:
—CO—C—CO— CHOH—CO — C — CO— CHOH
verwandelt werden. Leicht gelingt dies aber, wenn man auf Körper der erwähnten Art (wie Acetessigäther, Acetylaceton, Malonsäureäther u. s. w.) Orthoameisenäther bei Anwesenheit eines geeigneten alkoholentziehenden Condensationsmittels — am besten Essigsäureanhydrid — einwirken läfst. Es werden dabei, wie das folgende Schema darstellt:be transformed. But this is easy to do if you look at bodies of the type mentioned (such as acetoacetic ether, acetylacetone, malonic acid ether, etc.) Ortho ant ether if present a suitable alcohol-removing condensation agent - preferably acetic anhydride - works. It will be as shown in the following scheme:
-CO-CO
C H, +(C2H5O)2: CH-O C2H5 =CH, + (C 2 H 5 O) 2 : CH-O C 2 H 5 =
-1CO -CO- 1 CO -CO
C=CH- OC2H5 + 2'C2H5OH,C = CH- OC 2 H 5 + 2'C 2 H 5 OH,
-CO-CO
zunächst die Aethyläther der betreffenden Oxymethylen-Derivate erzeugt; diese, im Folgenden als Aethoxymethylen-Verbindungen bezeichnet, können durch Austausch der Aethylgruppe gegen Wasserstoff leicht in die eigentlichen Oxymethylen-Verbindungen verwandelt werden.first produced the ethyl ethers of the oxymethylene derivatives concerned; these, in the following referred to as ethoxymethylene compounds, by exchanging the ethyl group can easily be converted into the actual oxymethylene compounds against hydrogen.
An dem folgenden Beispiel mag die Ausführung dieser Operation erläutert werden:The following example explains how to perform this operation:
Acetessigäther (1 Mol.) wird mit Orthoameisenäther (1 Mol.) unter Zusatz von Essigsäureanhydrid Y2 bis ι Stunde am Rückflufskühler gekocht. Hierauf wird alles unter 200° Siedende (Essigäther, sowie etwas unzersetzter Acetessigäther und Orthoameisenäther) bei gewöhnlichem Druck abdestillirt und der Rückstand im Vacuum fractionirt. Der gleich bei der ersten Destillation sehr constant (unter 15 mm Druck bei 14g bis 1500) siedende Aethoxymethylen-Acetessi gather:Acetoacetic ether (1 mol.) Is boiled with ortho ant ether (1 mol.) With the addition of acetic anhydride Y for 2 to ι hour on the reflux condenser. Then everything boiling below 200 ° (vinegar ether, as well as some undecomposed acetoacetic ether and ortho-ant ether) is distilled off at ordinary pressure, and the residue is fractionated in a vacuum. The Aethoxymethylene Acetessi gather boiling very constantly right from the first distillation (under 15 mm pressure at 14g to 150 0):
CHCH
CO-CCO-C
COO C2H5 COO C 2 H 5
CH-OC2H5 CH-OC 2 H 5
ist ein farbloses OeI vom spec. Gewicht 1,0737; Siedepunkt unter gewöhnlichem Druck 266 °. In Berührung mit Wasser zerfällt er schon bei gewöhnlicher Temperatur in Alkohol und Oxymethylen-Acetessigäther:is a colorless OeI from the spec. Weight 1.0737; Boiling point under normal pressure 266 °. In contact with water it disintegrates at Ordinary temperature in alcohol and oxymethylene acetoacetic ether:
CHCH
CO-C-CO-C-
COOC2H5 COOC 2 H 5
CH-OH,CH-OH,
letzterer eine farblose Flüssigkeit, bei 199 bis 200° siedend und vom spec. Gewicht 1,141; der Aether ist, wie alle Oxymethylen-Verbindungen, eine ziemlich starke Säure, leicht löslich in Alkalicarbonaten und mit Kupferacetat ein schön krystallinisches blaues Kupfersalz bildend von der Zusammensetzung (C7 H9 OJ Cu. the latter a colorless liquid, boiling at 199 to 200 ° and of the spec. Weight 1.141; The ether, like all oxymethylene compounds, is a fairly strong acid, easily soluble in alkali carbonates and, with copper acetate, forms a beautifully crystalline blue copper salt of the composition (C 7 H 9 OJ Cu.
Genau in derselben Weise erhält man aus Acetylaceton das Aethoxymethylen-Acetylaceton: Aethoxymethylene acetylacetone is obtained from acetylacetone in exactly the same way:
C H— C O — C — C O — C HC H - C O - C - C O - C H
Il
CH-OC2H5 Il
CH-OC 2 H 5
(Flüssigkeit, unter 15 mm Druck bei 140 bis 1420, unter gewöhnlichem Druck bei 256 bis 258° siedend). Zerfällt mit Wasser in Berührung sofort in Alkohol und in Oxyni'ethylen -Acetylaceton:(Liquid, under 15 mm pressure at 140 to 142 0, under ordinary pressure at 256 to 258 ° boiling). In contact with water it breaks down immediately into alcohol and into oxynethylene-acetylacetone:
CH- COCH- CO
CO— CHCO-CH
CHOH,CHOH,
einen krystallinischen Körper vom Schmelzpunkt 470, welcher sich beim Aufbewahren zu einem eigenthümlich riechenden OeI zersetzt.a crystalline body of melting point 47 0, which decomposes upon storage at a peculiar-smelling oil.
Malonsäureäther liefert, wenn man ihn mit Orthoameisenäther, Essigsäureanhydrid und etwas Chlorzink 10 bis 20 Stunden kocht, den bei 279 bis 281° siedenden, ebenfalls flüssigen Aethoxymethylen-Malonsäureäther:Malonic acid ether delivers when combined with ortho ant ether, and acetic anhydride some zinc chloride boils for 10 to 20 hours, while the one that boils at 279 to 281 ° is also liquid Ethoxymethylene malonic acid ether:
COO C2H5-C—C00C2Hs COO C 2 H 5 -C -COOC 2 H s
CH-O C2H5.CH-O C 2 H 5 .
Ist der Malonsäureäther im Ueberschufs vorhanden, so wird zugleich der von D res sei und Guthzeit (Ber. d. d. ehem. Ges. XXII, 1416) schon auf anderem Wege erhaltene Aethoxyla-pyrondicarbonsäureä'ther: If the malonic acid ether is in excess, so at the same time that of D res is and Guthzeit (Ber. d. d. former Ges. XXII, 1416) Aethoxyla-pyrondicarboxylic acid ethers already obtained by other means:
COO C2H6-C — COCOO C 2 H 6 -C - CO
Il IIl I
HC OHC O
COOC2H5-C=C-OC2H5 COOC 2 H 5 -C = C-OC 2 H 5
gebildet. Aus den Aethoxymethylen - bezw. Oxymethylen-Verbindungen können direct Pyridin-Verbindungen erhalten werden; zur Erzeugung des Lutidindicarbonsäureäthers z. B. genügt es, Aethoxymethylen-Acetessigäther mit Paramidoacetessigäther oder mit Acetessigäther (in letzterem Falle bei Gegenwart von Ammoniak oder Ammoniak liefernden Substanzen) längere Zeit zu erhitzen:educated. From the ethoxymethylene - respectively. Oxymethylene compounds pyridine compounds can be obtained directly; to produce the lutidinedicarboxylic acid ether z. B. it is sufficient Ethoxymethylene acetoacetic ether with paramidoacetoacetic ether or with acetoacetic ether (in the latter Trap in the presence of ammonia or ammonia-producing substances) for a longer period of time to heat:
COOC2H5 COOC 2 H 5
HCHC
CO-CH3 COO C2H5- C— C-CH6 CO-CH 3 COO C 2 H 5 -C-C-CH 6
Il IlIl Il
HC NHC N
I NH2 = IlI NH 2 = II
OC2H5 ι C O O C2 H5- C = C — C H3 OC 2 H 5 - COOC 2 H 5 - C =C - CH 3
+ C2H-OH-^-H2O.+ C 2 H-OH - ^ - H 2 O.
COOC2H5-CH=C-CH3 COOC 2 H 5 -CH = C-CH 3
Claims (1)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE77354C true DE77354C (en) |
Family
ID=350168
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT77354D Expired - Lifetime DE77354C (en) | Process for the preparation of ethoxymethylene and oxymethylene derivatives |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE77354C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2565822A (en) * | 1949-11-21 | 1951-08-28 | James F Mcclelland | Watch guard and band |
-
0
- DE DENDAT77354D patent/DE77354C/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2565822A (en) * | 1949-11-21 | 1951-08-28 | James F Mcclelland | Watch guard and band |
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