DE2010124C - Process for the preparation of 2 6 dimethyl 3 amino 6 (beta cyanoathyl) cyclo hexen (2) one - Google Patents
Process for the preparation of 2 6 dimethyl 3 amino 6 (beta cyanoathyl) cyclo hexen (2) oneInfo
- Publication number
- DE2010124C DE2010124C DE19702010124 DE2010124A DE2010124C DE 2010124 C DE2010124 C DE 2010124C DE 19702010124 DE19702010124 DE 19702010124 DE 2010124 A DE2010124 A DE 2010124A DE 2010124 C DE2010124 C DE 2010124C
- Authority
- DE
- Germany
- Prior art keywords
- amino
- dimethyl
- preparation
- cyanoathyl
- beta
- 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
- HGCIXCUEYOPUTN-UHFFFAOYSA-N Cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 title 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 title 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 title 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 8
- FDPIMTJIUBPUKL-UHFFFAOYSA-N 3-Pentanone Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 3
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N acetic acid ethyl ester Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000007363 ring formation reaction Methods 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- SDTMFDGELKWGFT-UHFFFAOYSA-N 2-methylpropan-2-olate Chemical compound CC(C)(C)[O-] SDTMFDGELKWGFT-UHFFFAOYSA-N 0.000 description 1
- 229920000180 Alkyd Polymers 0.000 description 1
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M Benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000002026 chloroform extract Substances 0.000 description 1
- LKYXEULZVGJVTG-UHFFFAOYSA-N chloromethane Chemical compound Cl[CH] LKYXEULZVGJVTG-UHFFFAOYSA-N 0.000 description 1
- -1 cyclic amino acids Chemical class 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000002349 favourable Effects 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 150000001261 hydroxy acids Chemical class 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L na2so4 Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- TWXTWZIUMCFMSG-UHFFFAOYSA-N nitride(3-) Chemical compound [N-3] TWXTWZIUMCFMSG-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N t-BuOH Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
Description
Die vorliegende Erfindung betrifTt ein Verfahren zur Herstellung von 2,6-Dimethyl-3-amino-6-(,;-cyanoäthyl) - cyclohexen - (2) - on, im folgenden kurz mit »DACO« bezeichnet.The present invention relates to a method for Production of 2,6-dimethyl-3-amino-6 - (,; - cyanoethyl) - cyclohexen - (2) - one, hereinafter referred to as "DACO" for short.
Es ist bekannt (Journal Am. Chem. Soc. Bd. 64. 2855, rechte Spalte [1942]), durch Umsetzung von 4 Mol Acrylsäurenitril mit 1 Mol Diäthylketon in etwa 90 g Lösungsmittel und in Gegenwart von etwa 10 g Trimethylbenzylammoniumhydroxid als Katalysator tricyanäthyliertes Diäthylketon in einer Ausbeute von unter 30% zu gewinnen.It is known (Journal Am. Chem. Soc. Vol. 64. 2855, right column [1942]), by reacting 4 mol of acrylonitrile with 1 mol of diethyl ketone in about 90 g of solvent and in the presence of about 10 g of trimethylbenzylammonium hydroxide as a catalyst To win tricyanethylated diethyl ketone in a yield of less than 30%.
überraschenderweise wurde nun gefunden, daß man 2,6-Dimethyl-S-amino-o-i^-
hexen-2-on der folgenden FormelSurprisingly, it has now been found that 2,6-dimethyl-S-amino-oi ^ -
hexen-2-one of the following formula
NC-CH2-CH2 NC-CH 2 -CH 2
' NH1 'NH 1
erhält, wenn man Diäthylketon mit Acrylsäurenitril im Molvcrhältnis von 3:1 bis 1 :2 in 300 bis 5000 g eines tertiären Alkanols pro Mol Acrylsäurenitril und in Gegenwart von wässerigem Alkalihydroxid oder wässerigem Alkalialkoholat als Katalysator bei 0 bis 150" C umsetzt.obtained when diethyl ketone with acrylonitrile in a molar ratio of 3: 1 to 1: 2 in 300 to 5000 g of a tertiary alkanol per mole of acrylonitrile and in the presence of aqueous alkali hydroxide or aqueous alkali metal alcoholate as a catalyst at 0 to 150 "C.
Die Bildung von »DACO« ist besonders überraschend, da eine derartige Cyclisierung bisher noch nicht beobachtet wurde. Wesentlich Tür die Cyclisierung sind unter anderem d:r Zusatz von 300 bis 5000 s eines tertiären Alkanols pro Mol Acrylsuurenitriirwobei sich tertiärer Butylalkohol am besien bewährt hat. die Verwendung von Alkalihydroxid und oder Alkalialkoholat. vorzugsweise Kaliumhydroxid. als Katalysator, das Einhalten eines Molverhältnisses vonDiäthylkecon zu Acrylsäurenitril von 3:1 bis 1:2 sowie die Anwendung einer Reak-The formation of "DACO" is particularly surprising, since such a cyclization has so far been carried out was not observed. Essential for the cyclization are, among other things, the addition of 300 to 5000 s of a tertiary alkanol per mole of acrylic acid nitride where tertiary butyl alcohol has proven itself best. the use of alkali hydroxide and or alkali alcoholate. preferably potassium hydroxide. as a catalyst, maintaining a molar ratio of diethyl kecone to acrylonitrile from 3: 1 to 1: 2 as well as the use of a reaction
tionstemperatur von 0 bis 15O=C. Der Katalysator kann in einer Menge von 0.005 bis 0,5 Mol pro Mol Acrylsäurenitril zugegebc ^ werden. Die günstigsten Ergebnisse werden^ mit 0.01 bis 0,2 Mol Kaliumhydroxid oder Alkali-tert.-butylat erreicht.tion temperature from 0 to 15O = C. The catalyst can be added in an amount of 0.005 to 0.5 mol per mol of acrylonitrile. The cheapest Results are achieved ^ with 0.01 to 0.2 mol of potassium hydroxide or alkali tert-butoxide.
Die Zusammensetzung und Struktur der erPndungseemäß hergestellten Verbindung wurde durch CEN-Bestimmumien. Nachweis der fiinktionellen Gruppe durch chemische Anahsen. UV-. IR-. NMR- und Massenspeklrophotometrie sowie Molekulargewieliis-The composition and structure of the invention The connection established was determined by CEN regulations. Proof of the fictional group by chemical approaches. UV. IR-. NMR and mass spectrophotometry as well as molecular weight
bestimmungen sichergestellt.regulations ensured.
Die ertindungsgemäß hergestellte Verbindung kann als Zwischenprodukt fur organische Synthesen. /. B. für die Herstellung v«.n cyclischen Aminosäuren. Estern. Hvdroxysäuren und Epoxidverbindungen, alsThe connection established according to the invention can as an intermediate for organic syntheses. /. B. for the production of cyclic amino acids. Esters. Hydroxy acids and epoxy compounds, as
KunststoffrohstoflTur die Herstellung von Polyamiden. Alkyd- und Ketonharzen sowie als Modifizierungsmittel und Härter für Phenol- und Epoxidharze \ erwendet werden. Außerdem eignet sie sich als Schmieröladditiv und Waschmitielroh?toff.KunststoffrohstoflTur the production of polyamides. Alkyd and ketone resins as well as modifiers and hardeners for phenolic and epoxy resins will. It is also suitable as a lubricating oil additive and detergent raw material.
Die folgenden Beispiele sollen die Erfindung näher erläutern.The following examples are intended to explain the invention in more detail.
323 g Diäthylketon (3.75 Mol), 199 g Acrylsäurc-323 g diethyl ketone (3.75 mol), 199 g acrylic acid
nitril f3,75 Mol) und 5320 g tert.-ButanoI werden unter kräftigem Rühren am Rückflußkühler gekocht und mit 63ml einer 10",.igen, wässerigen Kalilauge versetzt. Nach 3 Stunden ist die Reaktion beendet. Das Reaktionsgemisch wird von den ausfallendennitrile f 3.75 mol) and 5320 g of tert-butanoI Boiled with vigorous stirring on the reflux condenser and mixed with 63 ml of a 10 ″, aqueous potassium hydroxide solution offset. The reaction has ended after 3 hours. The reaction mixture is of the precipitating
Kristallen des 2.2.4-Tri-(/>'-cyanoäthyl)-diäthylketons abgesaugt. Die Mutterlauge versetzt man mit destilliertem Wasser, stellt den pH-Wert mit konzentrierter Salzsäure auf etwa 5 ein und extrahiert anschließend mit Chloroform. Die wässerige Schicht wird noch zweimal mit CHCl3 behandelt. Die gesammelten Chloroform-Extrakte werden über Natriumsulfat getrocknet, abfiltriert und eingeengt. Der Rückstand wird in Äthylacetat aufgenommen. Die in der Kälte ausfallenden Kristalle werden nochmals aus Äthylacetat umkristallisiert. Man erhält 206 g 2,6-Dimethyl-3-amino-6-(p'-cyanoäthyl)-cyclohexen-(2)-on. Sucked off crystals of 2.2.4-tri- ( / >'- cyanoethyl) diethyl ketone. Distilled water is added to the mother liquor, the pH is adjusted to about 5 with concentrated hydrochloric acid and then extracted with chloroform. The aqueous layer is treated twice more with CHCl 3. The collected chloroform extracts are dried over sodium sulfate, filtered off and concentrated. The residue is taken up in ethyl acetate. The crystals which precipitate in the cold are recrystallized again from ethyl acetate. 206 g of 2,6-dimethyl-3-amino-6- (p'-cyanoethyl) -cyclohexen- (2) -one are obtained.
Jodzahl: berechnet 264,8, gefunden 266.Iodine number: calculated 264.8, found 266.
Ausbeute: 57.2% der Theorie; Schmp.: 156 bis 158'C.Yield: 57.2% of theory; M.p .: 156 to 158 ° C.
CRN-Bestimmung:CRN determination:
Berechnet ... C 68,7, H 8,4, N 14,6%:
gefunden ... C 68.7, 118,6, N 14,8%.Calculated ... C 68.7, H 8.4, N 14.6%:
found ... C 68.7, 118.6, N 14.8%.
Molekulargewicht: berechnet 1.92,85; gefunden 194.Molecular weight: calculated 1.92.85; found 194.
Das Ergebnis des Beispiels I ist in der folgenden Tabelle mit den Resultaten aus sechs weiteren Beispielen, die mit Ausnahme der aufgerührten Bedingungen wie im Beispiel 1 durchgeführt wurden, zusammengestellt. Daraus gehen die günstigsten Cyclisierungsbedingungcn klar hervor.The result of example I is shown in the following table with the results from six further examples, which were carried out as in Example 1 with the exception of the conditions listed. This clearly shows the most favorable cyclization conditions.
010 124010 124
6-(/i-cyanoäthyl)-2,6-dimethyl-3-amino-
6 - (/ i-cyanoethyl) -
DiälhylketonMolar ratio
Diethyl ketone
Claims (1)
Priority Applications (11)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19702010124 DE2010124C (en) | 1970-03-04 | Process for the preparation of 2 6 dimethyl 3 amino 6 (beta cyanoathyl) cyclo hexen (2) one | |
| NL7102836A NL7102836A (en) | 1970-03-04 | 1971-03-03 | |
| CA106,821A CA965102A (en) | 1970-03-04 | 1971-03-03 | Manufacture of 2,6-dialkyl-3-substituted-6-(beta-cyanoethyl)-cyclohexene-(2)-one and products |
| BE763712A BE763712A (en) | 1970-03-04 | 1971-03-03 | PROCESS FOR THE PREPARATION OF 2.6-DIALKYL-3-AMINO-6 (BETA-CYANETHYL) -CYCLOHEXENE- (2) -ONES AND THEIR DERIVATIVES |
| FR7107373A FR2084159A5 (en) | 1970-03-04 | 1971-03-03 | |
| US00120728A US3759973A (en) | 1970-03-04 | 1971-03-03 | Manufacture of 2,6-dialkyl-3-substituted-6-(beta-cyanoethyl-cyclohexene-(2)-one and products |
| JP46011577A JPS5133111B1 (en) | 1970-03-04 | 1971-03-04 | |
| GB3912672A GB1328706A (en) | 1970-03-04 | 1971-04-19 | 2,6-dialkyl-3-hydroxy-6-beta-carboxyethyl-caclohex-2-en-1-ones |
| GB2214871A GB1328705A (en) | 1970-03-04 | 1971-04-19 | 2,4-dialkyl-3-amino-6-beta-cyano-ethyl-cyclohex-2-en-1-ones |
| CA176,572,A CA950473A (en) | 1970-03-04 | 1973-07-17 | 2,6-dialkyl-3-hydroxy-6-(beta-carboxyethyl)-cyclohex-2-ene-1-one and manufacture |
| JP51011181A JPS51101954A (en) | 1970-03-04 | 1976-02-04 | 2 * 66jiarukiruu33hidorokishii66 * beetaa karubokishechiru ** shikurohekisenn * 2 ** onnoseiho |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19702010124 DE2010124C (en) | 1970-03-04 | Process for the preparation of 2 6 dimethyl 3 amino 6 (beta cyanoathyl) cyclo hexen (2) one |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| DE2010124A1 DE2010124A1 (en) | 1971-10-28 |
| DE2010124C true DE2010124C (en) | 1973-02-15 |
Family
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