Undecyl esters and preparation thereof

The available invention concerns I 1-Amino-undecylester, which are substituted in the carbon chain of the molecule part coming from the 11-Amino-undeeanol 2fach at least, as well as the Herstellungsverîahren for these connections. These esters are again and as original substances for the production of high-quality Azofarbstoffsalzen geeignet.

In the carbon chain at least 2fach substituted 11-Amino-undecanole already are in the DE-OS 2,831,299 besehrieben.

If Farbstoffsahe, as for example in 1,296,857 described Azofarbstoffalkalisalze of the GB-PS, admitted it exhibits the disadvantage that their release borrowingness in organic solvents limits verhältnismãssig strongly ist.

The task of the invention exists in the creation of esters satisfied aliphatic Amin0alkohole, which fûr the production of salts of anioniseher coloring materials, in particular suitably by Azofarbstoffsulfonsäuresalzen, which are superior in their solubility in organic solvents to the well-known salts of anionischer coloring materials, sind.

The subject of the invention is a connection of the formula I R3 æ R6 R5 R6 Rì I I I I I I H N-C-CH - CilCH (CH,) “- CH-CH-CH - CCile-0CO-R7 I I Rt+ R2 (I), woñn RI and RA independently hydrogen or a geradkettigen or branched alkyl residue with 1-8 CAtomen, R2 a geradkettigen or branched alkyl residue with 1-8 C-atoms and R+ a geradkettigen or branched alkyl residue with I-18 C-atoms represent or R and R2 and/or RA and R+ as well as the Bindungs639 066 C-atom a cyclo-aliphatic ring with 4-8 C-atoms form, and R5 and R6 independently hydrogen or alkyl with 1-4 C-atoms and R7 a geradkettigen or branched alkyl residue with altogether l-17 C-atoms bedeuten.

A connection of the formula I is preferential, where R5 and R represent “for each hydrogen, g 1 and R3 independently hydrogen or alkyl with 1-5 C-atoms, RZ alkyl with 1-5 C-atoms and R4 alkyl with 1-7 C-atoms, or where R3, R-S and R6 for each hydrogen, g 1 and R2 as well as the connection C atom Cyclopentyl or cyclohexyl and R4 alkyl with 1-7 C-flavours bedeuten.

Further preferentially also a connection of the formula is I, where R3, R-S and R for each hydrogen, RI and R2 independently alkyl with 1-4 C-atoms or together with the connection C atom cyclohexyl and R4 alkyl with 1-7 CAtomen darstellen.

Preferentially also such connections of the formula I are, 1 R hydrogen and R4 the remainder - CK/-- leg of the R3 deuten.NR2 into the R7 the same definition as in formula I has, to the appropriate ester of the formula I umsetzt.

Suitable reaction partners ffir the respective 11-Aminodecanol are thus for example acetic acid, Propionsäure, butter acid, Valeñansäure, Capronsäure, stearic acid and ISO butter acid as well as Isovaleriansäure.

After mixing the reaction partners the Veresterung takes place generally under return flow, possibly in presence of a wässñgen inorganic acid, and she is terminated lo after approximately 3 to 10 hours. After Abdestillieren of the respective surplus acid the reaction mixture is taken up to water and shifted with an organic solvent, like toluol. After attitude of the pH value on 8 with alkali is out-vibrated and anschlies12 sends the organic phase separated, dried and if necessary destilliert.

During the production above in detail of the aforementioned advantages forms of the connections of the formula I the respective suitable output products of the formula II and III are used, whereby the remainders of RI to R7 in each case the same meaning as those the formula I of the special connections which can be manufactured haben.

The production of the advantages form of the invention further as output products for the associations being connections of the formula I represent used I l-Aminoundecanole dungen to the formula I, where R7 a geradkettigen or a 2a of the formula II effected in the procedures described in the DE-OS 2,831,299 beverzweigten alkyl residue with altogether 1-7 C-atoms in the way that one a l-Azadeutet. 1,5,9-cyclododecatrien of the formula IV the production of the connections according to invention of the formula I takes place in the way that one a 11-Amino-11311 4 undecanol the formula II so B R5. RH R5 R6 RI I I I I I I - C ìH, - OE-C - (Cri) ““,”, C - OE-OE - C-OE OH/I “I Æ R4 R2 (II), in which the remainders of g 1 to Ró have the same meaning as in formula I, with a carbonic acid of the formula III í.” BLANK-CO-OH (III), (Iv) in aqueous or aqueous-organic medium in presence of an inorganic acid to a connection of the formula V R R R R R R 131 5161 516 II H2N - C -, not-oxidizing under the Reaktionsbedìngungen, CH2 - C = C - (CH2) 2 - C = C - CH2 - C - I! R4 R2 CHO IL (v) converts, whereby in the formulas IV and V is valid for g 1 to Ró in formula the I indicated, X the anion of an inorganic, under which reaction conditions represent not-oxidizing acid and n one the priority of X corresponding whole number, and which connection of the formula V afterwards catalytically to the respective connection of the formula II hydriert.

The conversion of the connection of the formula IV to the connection of the formula V preferably takes place in wässdgem medium in presence of sulfuric acid. The hydrogenation takes place generally also in aqueous medium in presence of usual hydrogenation catalysts, as for example platinum/coal or palladium/Kohle.

The erfindungsgemãssen l output products for the production of particularly salts of anionischer coloring materials, preferably anionischer Azofarbstoffe well soluble in organic solvents are I-Amino-more undecylester. Using the esters according to invention leaves itself in particular the very favorable Azofarbstoffsulfonsäuresalze of the formula VI 639,066 4 X ®oe (s°3 " s) m (sign.) or a formula tautomeren in addition manufacture where A a carbocyclischen or heterocydischen aromatic remainder, B the respective 11-Amino-und more ylester the formula I, X an H-atom or an alkyl group substituted if necessary, a Cycloalkyl, Aralkyloder group of aryls, Y a Hoder halogen atom or an electron-attractive group, like e.g. a Nitro, a cyanogen, an ecyl, a sulfone acid, an aryl sulphonyl, Alkoxycarhonyloder an alkyl, a Sulfamoyloder Carbamoylgruppe, Z an alkyl group substituted if necessary or an aryl residue, an m and a n the number of 1 or 2 substituted if necessary bedeuten.

If n stands for the number of 1, A means a univalent, preferably carbocyclischen aromatic remainder, for example a Naphthalinrest, in particular however a Phenylrest substituted if necessary. If n stands fûr the number of 2, A means thus a bivalent remainder, then this is preferably a Diphenyl, Diphenylätheroder Diphenylsulfonrest. If the substituent X stands for an alkyl group, then it preferably concerns a CI-C1 s-alkyl group, which can be replaced for example with hydroxy groups, alkoxy groups with 1-8 C-atoms or if necessary by chlorine, methyl, oder-SO3 H substituted Phenylgruppen. If n = 1 means, then the alkyl group knows also a remainder of the formula preferably delt itself it around a Phenylrest, that by chlorine, methyl or Alkoxy with 1-6 C-atoms substitutes 5 its kann.

At the Farbsalzen one arrives, if one the appropriate Azofarbstoffmonooder - disulfonsäure with 1 and/or 2 mol of the Aminoesters B umsetzt.

The Azofarbstoffsulfonsäuren represents well-known connections, which are descriptive for example in the following publications: DE-it 1,924,570, 2,004,487, 2,050,901, 2,134,453, 2,150,817, 2,237,006, 2,533,723, 1,930,491, 2004 488, 2,115,449, 2,141,449, 2,162,612, 2,238,795, 2545 828, 1,956,142, 2033 281, 2,123,061, 2s 2,141,453, 2216206, 2,349,709, 2,701,290, GB-PS 1,296,857, 1,331,261, 1,345 864.

One receives the Azofarbstoffsulfonsäuren by domes of a diazotierten or tetrazotierten carbocyclischen or heterocyeiischen of aromatic amine with a Pyñdon of the formula Z z i (x A-N-N (SO3 “RB) ME or a formula, where Q an H-atom or an easily split offable remainder, tautomeren in addition, for example the Carb! t0/amoylgruppe meant, X, Y and Z the indicated meaning have, whereby the components are to select in such a way s that the finished Azofarbstoffmindestens a sulfone containing. If X stands for Cycloalkyl, then it concerns primarily cyclohexyl; if X stands for Aralkyl, then concerns it see primarily a Phenylalkylgruppe with 1-4 C-flavours in the alkyl residue and mean X aryl, then • preferably if necessary by chlorine, methyl or - SO3 H substituted Phenyl. If Y stands for an alkyl group, then it preferably concerns a c1 --C6 - Alkyl group, which can exhibit a group of sulfone acids or a Alkanoylaminogruppe with 2-7 C-atoms as substituents for example; if Y stands for an acyl group, then it preferably concerns a Alkanoylgruppe with 2-7 C-atoms or a Benzoylgruppe. If Y stands for CarbamoyI or Sulfamoyl, then the same can unsubstituiert or by or two A1kylgruppen a Phenylrest containing with I-6 C-atoms or one chlorine atoms or groups of methyls if necessary to be substituted. If Y stands for a Alkoxycarbonylgruppe, then it preferably concerns such with 2-7 C-atoms, is preferably Y a group of aryl sulphonyls, then a Phenylsulfonylgruppe. If Z stands for an alkyl group, then it preferably concerns such with 1-6 C-atoms, which can exhibit a group of sulfone acids or a Phenylrest if necessary. If Z means an aryl residue, so group of striking acids enthält.

One accomplishes the Salzbildung appropriately in the way that one converts a solution or a suspension of an alkali salt of the coloring material sulfone acid with the wãssñgen solution of cines wasserlõsliehen salt of the respective 11-Amino-undecylesters, preferably such with a low fatty acid, in particular the Ameisensãure or Essigsãure. One works with advantage at temperatures between 40-80 °C and a pH value below 7.

Since the Farbsalze are insoluble in the wãssñgen reaction medium, they can be isolated by filtering off • one can the conversion in addition, in organic solvents alone or in mixtures with water durchführen.

As available Farbsalze exhibit an excellent Alkohollõsliehkeit, in particular in low Alkanolen, as methanol, ethanol, n-Propanol or isopropanol, in Alkylenglykolmonoatkyläthern, e.g. in Äthylenglykol more monomethyloder - ethyl ethers, in alkyl glycols, as in propylene glycols, or in araliphatic alcohols, as in benzyle alcohol, or e.g. in mixtures of such alcohols, furthermore in low aliphatic Ketonen. Aeeton, methylethylketone, Methylisobutylketon or also in Cyclohe639 066 xanon, furthermore in Carbonsäureestem, e.g. methyl acetate, ethyl acetate, butyl acetate or glycol mono acetate, as well as in halogenierten hydrocarbons, preferably low aliphatic hydrocarbons, like chloroform, dichloromethane, ethylen chloride or Kohlenstofftetrachlorid.

Because of their good solubility the descriptive Farbsalze are suitable for coloring Cellulose-2 1/2-acetate in the spin mass and for the Spinnf'årbung of Cellulosetñacetat. The spinngefårbte synthetic material draws by purity and strength of the colour, by perfect distribution of the color body and by very good genuinenesses as for example high wash, water, bleaching, Überfårbe, drying wash, friction, handle, Trockenhitzeund light fastness aus.

Due to their good Löslichkéit in alcohols, esters as well as their mixtures, the new Farbsalze are particularly suitable for coloring film-forming Polymeren.

As alcoholic and/or esterhaltige solutions of film-forming polymere ones is here in particular such liquid lacquer opal; or cellulose derivatives, for example cellulose ethers, like ethyl cellulose or cellulose ester, like Nitrocellulose, furthermore Maleinatharze or phenol formaldehyde resins, PP resins, Formaldehyd-Harnstoffund of FormaldehydMelamin condensates, Keton formaldehyde condensates, Polyvinylacetate or Polyacrylsäureharze, e.g. Polybutylacrylharz or their mixtures; furthermore polycondensation products of multi-valued alcohols, like Glycerin or Pentaerythrit, with more-basic acids, like maleic acid or lo Phthalsäure alone odex in combination with insatiated fatty acids like those Leinund Ricinusöls.

These solutions of film-forming polymere ones with a content of these Farbsalzen are suitable for example for printing different materials on, like of metal, e.g.

Aluminum foils, of paper, glass, synthetic resin foils and - film and dergleichen.

The solutions of film-forming polymere ones own itself far surfaces, e.g. metal parts, most diverse for painting, shaped parts from plastics or wooden plates. They ke to understand, for use in printing inks for 2o are shelf stable and devoted on deh Mateñaden mentioned Flexodrnck are suitable. As polymers this Lösunlieh contains egale, colorstrong and water resistant Überzüge.

towards for example Naturharze, like Schnellaek or Manila manufacture examples example 1 C H CH 0 12 5 I 3 II H2N - CH - (eH2) 8 - C - CH2 - 0 C - (2II3 1 79 g (0.325 mol) 2,2-Dimethyl-11-äthyl-11-amino-undecanol (manufactured after example 2b of the DE-OS 2,831,299) are dripped under agitating to 100 valley glacial acetic acid. The developing solution is then cooked 6 hours at return flow temperature. The surplus glacial acetic acid is taken up abdestilliert, the arrears with 200 valley water, over-laminated with I00 valley toluol and set with aqueous caustic soda solution to pri 8. The organic phase is separated, dried and distilled. One receives 2,2Dimethyl1 l-äthyl11-amino-undecyl-acetat to 74.5 g (0.262 mol), according to a yield from 80,5% D. Th; nD2o = 1,4613.

It HR spectrum of z (ppm): 6.22 (s), 7.35 (m), 7.93 (s), 8.16 (s), 8.4-8.8 (m), 9.04 (I) m, 9.06 (s) in the relationship 2:1: 3: 2: 18: C71.53% H12.36% N4.91% O11.21% Ca3 35gefunden C71.65% H 12.24% N4.95% O 11.30% ms spectrum compute 9 analysis for CI H3 sNO2 (molar weight 285.47): Molecule peak 285, fragment masses 256, 212, 196.

JR-spectrum (liquid): v (C = O) - 1750-1 example 2 it similar to example 1 worked with the difference that in place of 79 g 50 g 2,2-Dimethyl-11 - ãthyl-11amino-undecanol and in place of 100 mi glacial acetic acid 100 mi butter acid to be used, and D tss under HC1-Gas (Uberschuss) worked wird.

In the long run the 2,2-Dimethyl-11-äthyl-11-amino-undecanol-n-butyrat is received, which a boiling point of 115 °C/0,01 torr and a density no2o of 1,4523 aufweist.

Analysis for C19 H39 NO2 (molecular weight 313.53) 50berechnet C72.79% H12.54% N4.47% O10.21% found C 72.86% H 12.58% N 4.47% O of 9.91% sample applications example I q S1 CH3 I • ° CN. /\. _N=N_,//l IL IL I “% o kl0 I _ C2 H5 _ CH (913 H, N-CH (CH) - C - Chi-O-C0 (approx. ù) - CH ù A l” l z z A C2H5 CE3 639,066 19.2 g (0.05 mol) of the Monoazofarbstoffs 2-AminobenzoI-sulfonsäure 1-Äthyl-2-hydroxy-4-methyl-5-cyan-pyñdon-6 (Natfiumsalz) in 500 valley water are angeschlämmt and drop by drop with the mixture of 15,7 g (0.05 mol) 2,2-Dimethyl-11-äthyl11 -, 4 mi 85%iger formic acid and 80 mi amino undecanyl nbutyrat water-transferred. One agitates the weakly sour suspension some Stuñden with 50-55 °C and filters her afterwards. One washes the filter property first with diluted formic acid, then with water and dries it with 80 °C in the vacuum. In such a way isolated solvent coloring material of above-mentioned formula weighs 33.8 G. it points in ethanol, acetone and ethylen glycol mono ethyl ether good solubility auf.

Example II g of the Farbsalzes received after example I in 95 g of a Nitrocelluloselackes, made of 15 g alcohol-soluble niedñgviskoser Nitrocellulose with approx. 18% Dibutylphthalat, l 0 g Athylenglykolmonoäthyläther, and 50 g 94%igem ethanol are registered to 20 g ÄthyIacetat. The mixture is agitated up to the even distribution of the color body. The lacquer with a Filmlo extracting equipment (Handcoater of the company RK Chemisai CO becomes subsequently. Ltd., Royston, GB) in a wet film thickness of approx. 12 Ima on Opalinpapier or on an aluminum concealment foil aufgetragen.

After drying a detention-firm, even, strongly yellow Laekierung is present, which exhibits high stabilities opposite exposure as well as Bel5 action with water and butter.