DEP0012019DA - Process for the preparation of w-cyanoacetyl derivatives of heterocyclic methylene bases - Google Patents
Process for the preparation of w-cyanoacetyl derivatives of heterocyclic methylene basesInfo
- Publication number
- DEP0012019DA DEP0012019DA DEP0012019DA DE P0012019D A DEP0012019D A DE P0012019DA DE P0012019D A DEP0012019D A DE P0012019DA
- Authority
- DE
- Germany
- Prior art keywords
- weight
- parts
- preparation
- methylene
- heterocyclic methylene
- 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 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N Hydrogen cyanide Chemical class N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000000732 arylene group Chemical group 0.000 claims description 2
- -1 ethylene, vinylene Chemical group 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- SIKJAQJRHWYJAI-UHFFFAOYSA-N indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- NNFCIKHAZHQZJG-UHFFFAOYSA-N Potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- IRFSXVIRXMYULF-UHFFFAOYSA-N 1,2-dihydroquinoline Chemical compound C1=CC=C2C=CCNC2=C1 IRFSXVIRXMYULF-UHFFFAOYSA-N 0.000 description 1
- CPBZARXQRZTYGI-UHFFFAOYSA-N 3-cyclopentylpropylcyclohexane Chemical compound C1CCCCC1CCCC1CCCC1 CPBZARXQRZTYGI-UHFFFAOYSA-N 0.000 description 1
- UZFMOKQJFYMBGY-UHFFFAOYSA-N 4-Hydroxy-TEMPO Chemical compound CC1(C)CC(O)CC(C)(C)N1[O] UZFMOKQJFYMBGY-UHFFFAOYSA-N 0.000 description 1
- DBDLTJRCKGCKSK-UHFFFAOYSA-N 5-methoxynaphthalene-1,4-dione Chemical compound O=C1C=CC(=O)C2=C1C=CC=C2OC DBDLTJRCKGCKSK-UHFFFAOYSA-N 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M CHEMBL593252 Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- LFAGQMCIGQNPJG-UHFFFAOYSA-N Silver cyanide Chemical compound [Ag+].N#[C-] LFAGQMCIGQNPJG-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000008079 hexane Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229940098221 silver cyanide Drugs 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Description
Dr.Earl KamannjErexeid-Uerdingen
Br οJakob WillemsjKrefeld-Uerdingen
Farbenfabriken BayerDr Earl Kamann j Erexeid-Uerdingen
Br οJakob Willems j Krefeld-Uerdingen
Paint factories Bayer
Kref eId-TUerdingen, den 24 ,Sept. 1948 Kref eId -T Uerdingen, Sept. 24 1948
,■-, ■ -
Es wurde gefunden, dass sich -tCyanaoe tyl^derivate heterocyclisch Methylenbasen der allgemeinen FormellIt has been found that -tCyanaoe tyl ^ derivatives heterocyclic methylene bases of the general formula
1X 1 X
S2 S 2
Iii der k, - Ati^itin, Vinylen Qder Arylen wie ζ .B» Phenylen und x 7 Naphthylenl III the k, - ati ^ itin, vinylene Qder arylene such as ζ .B »phenylene and x 7 naphthylene l
I ss. Stickstoff, Schwefel, Sauerstoff, Yinylen oder MethyJse bedeuten,) in technisch einfacher Weise herstellen lassen, wenn man die durch· Umsatz der Methylenbasen oder ihrer SatIze mit ChJLor·- acetylchlorid in bekannter Weise erhältlichen »-Chloraeetylderivaft der allgemeinen Formel:I ss. Mean nitrogen, sulfur, oxygen, or Yinylen MethyJse leave) in a simple manner can be prepared when the Ize by · Sales of methyl bases or their Sa t with ChJLor · - acetyl chloride available in a known manner »-Chloraeetylderivaft the general formula:
IiIi
C = CS--« S Cflg- Tl, C = CS-- « S Cflg- Tl,
R2 R 2
in der R^, Rg und X die gleiche Bedeutung wie oben haben, Alt Salzen der Cyanwasserstoffsäure umsetzt*in which R ^, Rg and X have the same meaning as above, Alt converts hydrocyanic acid salts *
Als heterocyclisohe Methylenbasen der genannten Art'können z.B» Ver .vendung finden: 1,3f3-Trime+hyl-2-methylen*indolin> 5-Methoxy-l,3f3 -irimethyl-2--methylen^rindolin, 5-Chlor-l,3»3^trimethyl~2-methylen«t-ii] dolin, I-Me thy 1-2-me thy len~l,2~dihydro^enzthiazol, 1-Me thy 1-2-methylen-l,2-dihydro«rchliiolint For as heterocyclisohe methyl bases of the said Art'können eg "Ver .vendung: 1.3 f 3 + Trime hyl-methylene-2 * indoline> 5-methoxy-l, 3 f 3 -irimethyl-2 - methylene ^ rindolin, 5-chloro-1,3 "3 ^ trimethyl ~ 2-methylene" t-ii] dolin, I-methy 1-2-methylene ~ 1,2-dihydro-enzthiazole, 1-methy 1-2- methylene-1,2-dihydro-rchliiolin t
Als Salze der Cyanwasserstoffsäure eignen sich ζ.Β· Natriumoyanid, Iialiumcyanid oder Silbercyanid.Suitable salts of hydrocyanic acid are ζ.Β Sodium yanide, Iialium cyanide or silver cyanide.
In de,r Regel erweist es sieh als zweckmässig, den Umsatz bei jrhöl. -ter Temperatur in Gegenwart eines inerten Lösungsmittels durchs u~As a rule it proves to be expedient to increase the turnover at jrhöl. -ter temperature in the presence of an inert solvent through u ~
führen. Als geeignete Lösungemittel/können Z jJB. verwendet fa^A/ werden: Methanol, Äthanol, η-fund 4--Ä^panol, n-^Aind^T^^tanol, Tetrahydrofuran, Dloxan oder Mischungen dieser Lösungsmittel,to lead. Z j JB. used fa ^ A / are: methanol, ethanol, η-fund 4 - Ä ^ panol, n - ^ Aind ^ T ^^ tanol, tetrahydrofuran, Dloxan or mixtures of these solvents,
Die nach dem vorliegenden Verfahren erhältlichen Kondensationsprodukte können z.B. zur Herstellung von Cyaninfarhstoffen Verwendung finden.The condensation products obtainable by the present process can be used, for example, for the production of Cyaninfarhstof fen .
Beispiel I^J 25 Gewichtsteile 1,3,3 -Tr i me thy 1-2 -me t hy len-iM -chlor -acetyl*indolin werden zusammen mit 7 Gewichtsteilen Kaliumcyanid In 250 Gewichtsteilen Äthylalkohol 4 Styijfdflfn,zum Sieden erhitzt. Das sich allmählich gelbbraun färbende Reaktionsgemisch wird nach dem Erkalten mit 500 Gewichtsteilen Wassel? versetzt und das ausgeschiedene Reaktionsprodukt zusammen mit nicht umgesetztem Ausgangsmaterial in Benzol aufgenommen. Mach Abdampfen des Benzole wird das Rohprodukt duroh mehrfaches Umkristallisieren aus Cyolo· hexan unter Zugabe von aktiver Kohle vom anhaftenden gelbbraunen Nebenprodukt getrennt. Man erhält so etwa 20 Gewichtsteile 1,3 ,v3-Trimethyl-2-methylen-^~cyanacetyl**indolin als gelbliche Example I ^ J 25 parts by weight of 1,3,3 -Tr i me thy 1-2 -me t hy len-iM -chlor -acetyl * indoline are heated to the boil together with 7 parts by weight of potassium cyanide in 250 parts by weight of ethyl alcohol 4 Styijfdflfn. The reaction mixture, which gradually turns yellow-brown, is after cooling with 500 parts by weight of Wassel? added and the precipitated reaction product taken up together with unreacted starting material in benzene. Mach evaporation of benzene, the crude product duroh repeated recrystallization from hexane Cyolo · with addition of active carbon is separated from the adhering yellow brown by-product. This gives about 20 parts by weight of 1,3, v3- trimethyl -2- methylene- ^ ~ cyanoacetyl ** indoline as yellowish
Schuppen, Tm* ^ Scales, Tm * ^
Beispiel 2KJ 30 Gewiohtsteile 5-Methoxy-lt3f3-trimethyl-2-methy"» Ien-«-chloracetyl^indolin werden zusammen mit 7 Gewichtsteilen Kaliumcyanid in 200 Gewichtsteilen Äthylalkohol, der 15 Gewichts?» teile Wasser, enthält, unter RiickfIuss zum Sieden erhitzt. Die Aufarbeitung des Reaktionsgemische!! erfolgt In der in?Beispiel 1 angegebenen Weisef, Man erhält so etwa 22 Gewichtsteile 5-Methoxy 1»3,3~trimethyl*-2MiiethyIen- UJ -oyanaoetyl»»indolln als gelbliche Blättchen,Example 2 K J 30 Gewiohtsteile 5-methoxy-l t 3 f 3-trime thyl -2-methylpropionic "" Ien - «- chloroacetyl ^ indoline together with 7 parts by weight of potassium cyanide in 200 parts by weight of ethyl alcohol of 15 weight"? contains parts of water, heated under RiickfIuss to boiling. If the processing of the reaction mixtures !! The quoted in? Example 1 f, is obtained as about 22 parts by weight of 5-methoxy 1 »~ 3.3 * trimethyl -2Miiethy IEn- UJ -oyanaoetyl »» indolln as yellowish leaflets,
Beispiel 3, / 23 Gewichtsteile I-Methyl-2-methyIen-Ul-chloracety1 l,2~dihydrochinolin werden zusammen mit 7 Gewichtsteilen Kaliumayanid in 200 Gewichtsteilen Methanol 6 Staden, unter lebhaftem Rühren und RflckfIuss zum Sieden erhitzt. Das Reaktionegemisch färbt sich durch Nebenprodukte dunkelbraun. Nach dem Erkalten giesst man es unter heftigem Rühren in eine Misohung -von 150 Gewichtsteilen Benzol und 300 Gewichtsteilen Wasser, trennt die benzolische Schicht ab und dampft sie zur Trockne ein. Es hinterbleibt ein dunkelbrauner harziger Rückstand,aus dem das Reak*· tionsprodukt mit Cyclohexan extrahiert wird. Das aus Cyolohexan gewonnene rohe I-Me thyl~2~me thy Ien-u# -cyanacetyl-l,2-dihydrp«-Example 3/23 parts by weight of I-methyl -2 -methyIen -Ul -chloracety 1 l, 2 ~ dihydroquinoline are heated together with 7 parts by weight in 200 parts by weight of methanol Kaliumayanid 6 Staden, with vigorous stirring and Rflckf IUSS to boiling. The reaction mixture turns dark brown due to by-products. After cooling, it is poured into a mixture of 150 parts by weight of benzene and 300 parts by weight of water with vigorous stirring, the benzene layer is separated off and evaporated to dryness. A dark brown resinous residue remains, from which the reaction product is extracted with cyclohexane. The derived Cyolohexan crude I-Me thyl ~ 2 ~ me thy IEn- u # -cyanacetyl-l, 2 -dihydrp "-
ohinoiiii kann durch Umkristallisieren aus Ligroin gereinigt werden, i)och gelingt es nur schwer, die braunen Nebenprodukte völlig zu entfernen. Man erhält 10 Gewiohtsteile des Kondensationsproduktes, das zur weiteren Verarbeitung zu Cyaninfarbstoffen hinreichend sauber ist, ^m^^^y^^^^y^/^p fohinoiiii can be purified by recrystallization from ligroin , i) och it is difficult to completely remove the brown by-products. 10 parts by weight of the condensation product are obtained, which is sufficiently clean for further processing into cyanine dyes , ^ m ^^^ y ^^^^ y ^ / ^ p f
Claims (1)
Family
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