CA1192575A - Preparation of bis-(aminocyclohexyl)-dialkylmethanes - Google Patents
Preparation of bis-(aminocyclohexyl)-dialkylmethanesInfo
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- CA1192575A CA1192575A CA000432518A CA432518A CA1192575A CA 1192575 A CA1192575 A CA 1192575A CA 000432518 A CA000432518 A CA 000432518A CA 432518 A CA432518 A CA 432518A CA 1192575 A CA1192575 A CA 1192575A
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- aniline
- carbon atoms
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- bis
- acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
- C07C209/78—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton from carbonyl compounds, e.g. from formaldehyde, and amines having amino groups bound to carbon atoms of six-membered aromatic rings, with formation of methylene-diarylamines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
- C07C209/70—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by reduction of unsaturated amines
- C07C209/72—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by reduction of unsaturated amines by reduction of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Abstract of the Disclosure: Bis-(aminocyclohexyl)-dialkyl-methanes of the general formula I
Description
C~se 1379 7~
Preparation o~ b;~i(sm;nocyclotlexyl3~d;alkyl~
me~h~nes The present inven~ion reLa~es to a noveL process for th~ preparation o~ bis-(aminocyclohexyl)-dialkyl-methanes by reacting a para-unsubstituted aniline ~i~h an aliphatir ke~one to give a diphenylmethane deriva~ive an~
then hydrogenating the arDm~t;c nucLei in the product.
It has been disclosed that ~nil;ne or its deriY0-tiveS ~hich are unsubstitu~ed in the para-pDsi~ion can be reacted ~ith formaldehy~e in aqueous solution in the pre-sence of a mineral ac;d to give a bis-~aminophenyl)-methane sompound; in this con~extO cf~, inter aLia, German Patents 2~227,110f 2,343,65B~ 2r5~7~301 ~nd 2,528,694 and U.S. Pat~nts 2,638,730, 2,9sn,263, 3,260,751, 3,277,173, 3,297,759~ 3,476~S06 and 4~130~S88D
In r,ontras~ the condensa~ic,n of a para-unsub-st;tuted aniline ~ith an alipha~ic ke~one has been invest-iga~ed to a Lesser extent~
The react;on of aniline hydrochloride ~ith an aLiphatic ket~ne in aqueo~s solu~ion ;n the presence of hydror,hloric ac;d was first describecl in German Patent 3 9 9 ~ 9 r Ho~ev~rO it was possible to sho~ tJ. Amer. Chem.
Soc. 60 (193R~ 5Bj that9 in aqueous solu~ionO in ~he presence o~ a r~La~ively high hydrochloric acid concen-tratiDn and at ~rom 120 to 150~C~ a quinoline or dihydro-quinoline derivative is pr~erably ~Dr~ed. Under these conditions~ the bis-SaminopherlyL)-dialkylme~hanes are formed onLy as by-produtts~
.~
Resarding the formation and isoLation of ~he des~
;red prcdurts, the presence o~ d;phenylamine~ f~r~ed at the same time, has a particularly disadva~ageous ef~ect, since it reacts wi~h the bis-(aminophenyl)~dialkylme~hane in ~he presence of hydrochloric acid to give undesirabLe se~ondary products.
The second rPaction step~ ;eO hydro~ena~ion of the aromatic rings by means of a ruthenium cataLyst or of a cobalt, nickel, platinum Dr palladium satalyst is des-cribed in German Paten~ 1~282,D18 ~nd in the Liter~ure c;ted therein, respectively. However~ as ;s eviden~ ~romthe Examples ;n this publicat;s~n, this reaction gives deamination products and cslndensa~es which conta~inate the end product and reduce its yield~
The use of a ru~heniu~/nickel ca~aLyst, ~oo, gives substantial amounts o~ deconposition products and relat-ively high-boiling condensates ~U~S. Patent 2,~D6~925~.
Ue have found that bis-(aminocyclc,hexyl)-dialkyl~
methanes of the general f~rmula I
R3-~ ~ R ~-R3 (I) ~here R1 and R2 are iden~ical or different and are each lower alkyl of 1 to ~ ~arb~n atoms, R3 is hydrogen or Lower alkyl of 1 to 4 carbon atoms and the t~o ~yclo~exane rin~s ~ay each be unsubstituted or substituted by one or ~uo lDuer alkyl ~roups9 each of ~ to 4 carbon atoms, or by a carboxyalkyl group ~here al~yl i~ of 1 to ~ sarbon ato~s~
. ~..
\
can advanta~eously be obta;ned by condensing a para-unsubstituted an;line of the general ~ormuLa lI
~ R3 ~II) uhere R3 has ~he above meanin~s and the aniline may be ~nsubs~itu~ed or subst;tuted in the nucleus by one or t~c lo~er alkyl groups o~ 1 ~o 4 carbon atoms nr a carboxy-alkyl group ~here alkyl is of 1 to 4 rarbon a~oms~ ~ith a lo~er aliphatic ketone in which the alkyl radicals are each o~ 1 to 4 carbr,n atc,~s, in the presence o-f a strong monobasic or polybasic acid and hyclrogenating the product obtained, if the ~ondens3tion is carried out at from 100 to 16D~C and under ~ro~ 1 to 20 bar in ~he presence of from 10 to ~0 % by ~eight~ based on ~he reaction mixtureO
of ~ater, the molar ratio o~ aniline to ketone is from
Preparation o~ b;~i(sm;nocyclotlexyl3~d;alkyl~
me~h~nes The present inven~ion reLa~es to a noveL process for th~ preparation o~ bis-(aminocyclohexyl)-dialkyl-methanes by reacting a para-unsubstituted aniline ~i~h an aliphatir ke~one to give a diphenylmethane deriva~ive an~
then hydrogenating the arDm~t;c nucLei in the product.
It has been disclosed that ~nil;ne or its deriY0-tiveS ~hich are unsubstitu~ed in the para-pDsi~ion can be reacted ~ith formaldehy~e in aqueous solution in the pre-sence of a mineral ac;d to give a bis-~aminophenyl)-methane sompound; in this con~extO cf~, inter aLia, German Patents 2~227,110f 2,343,65B~ 2r5~7~301 ~nd 2,528,694 and U.S. Pat~nts 2,638,730, 2,9sn,263, 3,260,751, 3,277,173, 3,297,759~ 3,476~S06 and 4~130~S88D
In r,ontras~ the condensa~ic,n of a para-unsub-st;tuted aniline ~ith an alipha~ic ke~one has been invest-iga~ed to a Lesser extent~
The react;on of aniline hydrochloride ~ith an aLiphatic ket~ne in aqueo~s solu~ion ;n the presence of hydror,hloric ac;d was first describecl in German Patent 3 9 9 ~ 9 r Ho~ev~rO it was possible to sho~ tJ. Amer. Chem.
Soc. 60 (193R~ 5Bj that9 in aqueous solu~ionO in ~he presence o~ a r~La~ively high hydrochloric acid concen-tratiDn and at ~rom 120 to 150~C~ a quinoline or dihydro-quinoline derivative is pr~erably ~Dr~ed. Under these conditions~ the bis-SaminopherlyL)-dialkylme~hanes are formed onLy as by-produtts~
.~
Resarding the formation and isoLation of ~he des~
;red prcdurts, the presence o~ d;phenylamine~ f~r~ed at the same time, has a particularly disadva~ageous ef~ect, since it reacts wi~h the bis-(aminophenyl)~dialkylme~hane in ~he presence of hydrochloric acid to give undesirabLe se~ondary products.
The second rPaction step~ ;eO hydro~ena~ion of the aromatic rings by means of a ruthenium cataLyst or of a cobalt, nickel, platinum Dr palladium satalyst is des-cribed in German Paten~ 1~282,D18 ~nd in the Liter~ure c;ted therein, respectively. However~ as ;s eviden~ ~romthe Examples ;n this publicat;s~n, this reaction gives deamination products and cslndensa~es which conta~inate the end product and reduce its yield~
The use of a ru~heniu~/nickel ca~aLyst, ~oo, gives substantial amounts o~ deconposition products and relat-ively high-boiling condensates ~U~S. Patent 2,~D6~925~.
Ue have found that bis-(aminocyclc,hexyl)-dialkyl~
methanes of the general f~rmula I
R3-~ ~ R ~-R3 (I) ~here R1 and R2 are iden~ical or different and are each lower alkyl of 1 to ~ ~arb~n atoms, R3 is hydrogen or Lower alkyl of 1 to 4 carbon atoms and the t~o ~yclo~exane rin~s ~ay each be unsubstituted or substituted by one or ~uo lDuer alkyl ~roups9 each of ~ to 4 carbon atoms, or by a carboxyalkyl group ~here al~yl i~ of 1 to ~ sarbon ato~s~
. ~..
\
can advanta~eously be obta;ned by condensing a para-unsubstituted an;line of the general ~ormuLa lI
~ R3 ~II) uhere R3 has ~he above meanin~s and the aniline may be ~nsubs~itu~ed or subst;tuted in the nucleus by one or t~c lo~er alkyl groups o~ 1 ~o 4 carbon atoms nr a carboxy-alkyl group ~here alkyl is of 1 to 4 rarbon a~oms~ ~ith a lo~er aliphatic ketone in which the alkyl radicals are each o~ 1 to 4 carbr,n atc,~s, in the presence o-f a strong monobasic or polybasic acid and hyclrogenating the product obtained, if the ~ondens3tion is carried out at from 100 to 16D~C and under ~ro~ 1 to 20 bar in ~he presence of from 10 to ~0 % by ~eight~ based on ~he reaction mixtureO
of ~ater, the molar ratio o~ aniline to ketone is from
2:1 to 10.1 and that of aniline to acid equivalent is from 1:1 to 4~ nd the subsequen~ hydrosenation of ~he resulting product is rarried out at fro~ 30 ~o ~5~C under a pressure of above 50 bar in the presence of a suspenaed ruthenium~containing ~atalys~.
In this process, it was surprising that, by vary-ing the molar ra~ios o~ aniline to ketone or o~ aniline to acid, changing the ~ater cont~nt o~ the reaction mix ture or usin0 a h;gher pressure, the conrJensation o~ an an;line ~ith an aliphatic ketone and the conYersion of the initially obta;ned condens~te c~n be controlled so as to give the desired diphenylmethane der;va~ive ~i~h high selectivity D
i7S
Also unexpected ~as the fact that ~hese diph~nyl-~ethane derivat;ves can be con~er~ed ~o the corresponding alieycLic compounds ;n v;rtualLy quantit~tiYe y;eLd by hydrogenation ;n the presence of a special ru~heniu~
cataLyst.
~ he novel process is described in more detail belo~:
Apart from the paren~ sompoundO it i~ alsD pos-sibLe ~o use anllines which are ~ubstituted a~ the nucleus and/or at ~he amino ~roup in the process ~ccording ~o ~he invention. The nucleus may be substituted by one or t~o alkyl groups or an esterified carboxyl group in any pO5i-tion except the para-position~ whereas substi~u~i~n at ~he amino group is restriçted to alkyL, eg. o toluidine~ ~-tolu;dine, N-methylanil;ne, N-ethylaniline~ 2~6-di~ethyl aniline~ ~rS~diethylan;line~ 2v6-diisc,propylan;line, methyl-o-toluidine or ethyl an~hranilate.
Sui~able alipha~ic ketones~ ;n adcli~ion to acet-rne~ are those where the rourse of the condensation is not stericaLly hindered, e~. bu~an-2 one, pentan-2-one~ pentan-
In this process, it was surprising that, by vary-ing the molar ra~ios o~ aniline to ketone or o~ aniline to acid, changing the ~ater cont~nt o~ the reaction mix ture or usin0 a h;gher pressure, the conrJensation o~ an an;line ~ith an aliphatic ketone and the conYersion of the initially obta;ned condens~te c~n be controlled so as to give the desired diphenylmethane der;va~ive ~i~h high selectivity D
i7S
Also unexpected ~as the fact that ~hese diph~nyl-~ethane derivat;ves can be con~er~ed ~o the corresponding alieycLic compounds ;n v;rtualLy quantit~tiYe y;eLd by hydrogenation ;n the presence of a special ru~heniu~
cataLyst.
~ he novel process is described in more detail belo~:
Apart from the paren~ sompoundO it i~ alsD pos-sibLe ~o use anllines which are ~ubstituted a~ the nucleus and/or at ~he amino ~roup in the process ~ccording ~o ~he invention. The nucleus may be substituted by one or t~o alkyl groups or an esterified carboxyl group in any pO5i-tion except the para-position~ whereas substi~u~i~n at ~he amino group is restriçted to alkyL, eg. o toluidine~ ~-tolu;dine, N-methylanil;ne, N-ethylaniline~ 2~6-di~ethyl aniline~ ~rS~diethylan;line~ 2v6-diisc,propylan;line, methyl-o-toluidine or ethyl an~hranilate.
Sui~able alipha~ic ketones~ ;n adcli~ion to acet-rne~ are those where the rourse of the condensation is not stericaLly hindered, e~. bu~an-2 one, pentan-2-one~ pentan-
3-one, hexan-2-one, hexan 3-one or isobutyl methyl ketone.
The strong monobasit Pr polybasic ac;ds required ~or the conden~a~ion are, in particular, ~ater-soLuble acids having a pKA o~ less than 2.5, pre~erably less ~han 1~5, for exa~pLe hydrochloric acid, hydrobromic acid, sulfuric ac;dO trifluoroacetic acid, methanesul~onic acid, trifluoro~ethanesulfon;c ac;d, benzenesul~onic acid or phosphoric acid, tlrdrochloric acid is preferably used.
~he ac;ds can be e~ployed e;ther in pure form or ~4~
to~ether ~ith the;r neu~raL or acidic salts, eg. the alkali metal or a~mc,nium salts. ~n ~he noveL process, the ~cid is present in the a~ueous phase partially as the ammonium salt of ~he aniline required for ~he reaction.
Instead of ~a~er-soluble acids, it ;s also pos-sible to use strongly acidic ~ater-insoluble iorl ex-changers having a pKA in ~he abovementioned range~
Pre~erabLy, the ion exchanger resins used are based on copolymers of highly sulfona~ed s~yrene wi~h divinyl-benzene.
In the condensation step, the ~olar ratio o~
ani line to ketone shouLd be from 2;1 ~o 10 1s preferably from 3:1 to ~ e have found tha~ values less ~han 2:1 promote the formation of undesirable by-products.
~here unsubstituted an;line i~ condensed with acetone, the principal by-products are 2~2,~t-~r;methyl 1,2-dihydroqu;noline~ 2,3,4-trimethylquinDline~ 2~4-di-methylquinoline, W-isopropenyl-2,2~b;s-(4-aminophenyl)-propane and N,~ diphenyl-2~2-bis-S~-aminophenyl)-propane.
The upper Lîmi~, ie. 10:1, is no~ cri~ical ~ith regard to the formation of by-products~ but ~he further ;n~rease ;n the anil;ne concentration is of no fur~her advanta~e~
The nolar rati~ of aniline to acid equivalent can be varied fro~ 1:1 to 401~ preferably ~rom 1~1 ~o 2~1~
Increasing the ratio ~bove 4:1 res~l~s ;n the ~ormation of ;ncreasing amounts of by prod~cts.
In the above react;on of unswbstituted aniline vith acetone and hydro~hloric acid, these are~ ;n ~5--particular, d;phenylam;ne and ;ts secondary product ~rom the reac~ion ~ith 2,2-bis~4-aminophenyl~-propane~ On ~he other hand, ~here lthe moLar ra~io of ani line to acid equivalent is less than 1~ he ra~te of ~orma~ion of 2,2-b;s-(4-a~n;nophenyl)-pr~pane is reduced, thereby promoting side reacti3ns which in the above case lead principaLly ~o ~he formation o~ N-isopropenylaniline and 2,2,4-tri-methyl-192-d;hydroqu;nol;ne.
Where an at;dit ;on ex~hanger is used~ it is employed in an amount equ;valent to that of the water soluble acid.
The amount of wa~er used accord;ng to the ;nven tion is from 10 to 6D X by ~eigh~, based on the rea~ior, ~ixtur~. Amo~nts of wa~er beLow 10 Z by ~ei~ht favor the format;on of by-products (in ~he abDve case~ parti~wlarly the formation of qu;nolines~ the amount of ~ater is increased above 60 % by weightO the pro~ess becomes un-ecDnomical~
~he reactan~s are to~nbine~ in a pressure-ti~ht vessel, advantageDusly by stirrin~, and the sequenGe o~
add;t;on is not cr;tical. In a pre~erred embodiment, the amine is taken and ~he ke~one, ~a~er and the acid are then added.
The re~ctants are ~sually mixed a~ room ~empera--ture ~20 - 25C), and the s~irred mixture is then hea~ed ~ closed reactor ~ from 100 to ~60C, preferably ~rom 1 in to 140C. The ~emperature can be intreased stepwise or 20 cDn~;nuously, either rapidly or slowly.
The condensation is wsually carr;ed GU~t under a --6-~
7~
pres~ure of from 1 to 20 bar~ In general, the a~togenous pressure of the s~stem is su~ficient, th;s pressure being governerJ by the vapor pressure of ~he readily voLatile reactants as a function o~ their temperature and concen-trat;on. The pressure ~ay also be ;ncreased uith ~he aid of an inert gas~ eg. n;~rsgen~ bu~ increasing it above 20 bar does not result in an improvement in the yield or se lectivi ~y .
7he reaction t;me is in general from 2 to 2D hours.
The progress of the reaction can be ~onitored ~y removing aliquot parts of the reaction mixture from the pressure-~ight vessel, for exa~ple thrDugh a siphon tube, rendering this sa~ple slightly alkaline ~ith 25 X strength by weight sodium hydroxide solu~ion, separating ~he result-ing mixture into an ~queous and an organic phase and analyzing the organic phase by gas or liquid chromato-graphy.
~ he reac~ion tan be carried out ei ther ba~chwise or continuously. ~here a continuous procedure is employed, ~0 it is advantageous t~ carry out the reaction in a cascade comprising two or more appropriately equipped s~irred kettles.
Depending on the aç;dic catalys~ used, the reac t;on ~i~ture obtained according to the inven~;on is either hetero~eneou~ (solid-liqu;d) or homc~geneous Sli~uid), and ran be treated further or ~fter~treated in varisus wa~s. As a ruLe, the reacted mixture is brough~
to pH 8 to 1D uith 25 - ~,0 ~ strength by weigh~ sodium hydro~ide solution, and the mi~ture ;s s~;rred for so~e 7~
time at ~G~ and then separated into ~n aquPous and ~n organic phase~
Start;ng materi~ls which are part;ally d;ssolved in ~he aqueous phase~ e~. atetone and aniline, car, be su~-stantially recovered by extraction with a hydrophobic soLvent. 5~i~able hydrophob;c solven~s are ar,y o~ thcse wh;ch are water-immiscible and inert to ~he reactantsf eg chlorobenzene, benzene, toluene~ xylene~ dichloro-ethane, chloro~orm, rarbon ~etrachlor;de, etc. o-Xylene is a particularly preferred solvent.
Where a solid highly sul~ona~ed polystyrene ion exchanger resin crosslinked ~ith divinylbenzene is used~
the sol;d catalyst ;s separated off by filtr3tion a~er the addition of ~he sodium hydroxide solution~
The organic phase is ~ashed with water~ a~ter ~hich this phase and the combined ex~rac~s, separateLy or t~gether, are fractionally dis~illed, first under atmospheric pressure and then under reduced pressureO
The diphenylmethane derivatives obtained are employed in the hydrogenation process, ~h;le any startins materials recovered ran be recyrled to the condensation stage~
The hydrogena~ion is carried DUt under a pressure greater than 5D bar, in general from bO ~o 3ao bar, pre-~erably ~rom 150 to 3DO bar.
AdvantageouslyO ~he process is rarried ou~ at ~rom 30 ~o 250C~ particularly preferabLy ~rom ~20 ~o 180C.
~ he products to be hydro~enated can be employed in the pre~ence or absenre of a solven~O However~ ;t has -8~
proved advantageous ~o ~arry out the hydroyenation in solution~ suitable solvents bein~ e~hers~ e9. diethyl e~her, glycol dimethyl e~her, dioxane or tetr~hydro~uran.
S~;tabLe rutheniu~-containing ca~alys~s are those ~hich are obtained in situ J ie. in ~he reaction mixture, by reduring ru~henium(IV~ oxide hydra~e with hydrDgen.
This cataly~t intermed;ate can be obtained in suspended for~, as a dry powder or ;n a form ~here ;t is applied onto a conventional ~arrier, e~. siLica~ aluminum oxide lû or active carbon. The preparation o~ ru~henium~IY) oxide hydrate from rutheniu~ tri~hLoride trihydrate, RuCl3.3H20 is described in detail in German Pa~ent Z,132,547.
A pulverulent catalyst intermediate containing ~bou~ 60 - 70 X by ~e;ght of ruthen;~m and having a particLe size o~ from ~0 to 60 nm sives a particularly active hydrogenation catalyst.
The ca~alyst ;ntermediate ~ay either be ~mployed in moist form or be dried before use. This can b achieve~ by heating it at 8D - 10~C under rPduced pres-sure. Ho~ever, it is aLso possible to wash the moist centr;fuged catalyst ;n~r~ediate ~ater-free with an organic soLvent and to employ ;~ ;n the ~orm of a suspended concentrate~ most advantageously ;n the solvent intended ~or use in the hydro~ena~ion.
In ~eneral~ it is sufficien~ to use fr~m 10 tc, 1,000, pre~erably from ~0 to 1~0, ppmO based on the di~
phenylmethane derivative, uf ruthen;um(IV~ oxide hydrate.
The Examples whi h follow illustrate ~he noveL
process. Parts are by ~eight.
_9_ 7~i a) An enameled au~sclave ~quipped ~;th a heating jacket and ther~o oiL cycle, a stirrerO a thermometær, a ~eed device, ~ rupture disk (~0 bar~ and a siphon tube with a sampler ~as charged wi~h 521 parts of aniline, 116 parts o~ acetone, 200 parts of ~a~er and 568 parts of 36 X s~rength by ~eigh~ hydrochloric acid and ~25 ~hen cl~sed. The stirred autoclave ~as heated to ~30C in the course o~ abou~ 1 hour, the pressure reaching 3OZ bar.
Fro~ ~;me to t~me, a sampLe was taken via the siph~n ~ube and neutral;zed with sodium hydroxide solu-~ion and the organic phase was separated off ~rom the resulting mixture~ dist;LLed and analyzed by gas chromato graphy. Af~er 15 hours, the reaction mixture ~as trans-fe.red to a glass flask, 565 p~rts of 40 X strength sodium hydroxide solu~ion ~ere added ~nd the mixture ~as stirred for a short time at 30 - 40C and then s parated into an aqueous and an organic phase, usin~ a separating funneL.
The ~q~eDus phase, which, under ~he sta~ed con-ditions, was saturated ~ith anil;ne and acetone~ was ex-tracted with twice 10D parts of o-xylene, and the resul~-;ng extract phase was combined with the or~anic phase from the reacted ~ixture. The combined organic phase was ~ashed chloride-free ~i~h water, ~ashing beiny repeated several timesO and ~as ~hen ~orked up in ~ t~D-stage d;s-tillation apparatus.
In the ~irst s~age, acetone~ ~niL;ne~ o xyLene and N-isopropenylan;line ~ere distilled off under atmos-pher;c press~re9 thæ tondens3tes remain;ng at the bo~om of the distiliation apparatus. 23 par~s of acetone and Z33 parts of aniline ~ere recovered, corresponding to a convers;on of 77.5 % based on aniline, and 79.8 X based on acetone. The botto~ produc~ was fracti~nalLy dis-tilled at 0.5 mbar in a second stage, using 2 c~L~n con-taining ~;re gauze pack;ng and possessing not less than 15 trays. 292 parts of 97 % pure 2~2-bis-t4-aminophenyl~-pr~pane of boiling poin~ 183-18~C/0.5 mbar and ~elting point 132C ~ere obtained~ The selec~iv;ty was 82 X.
b) 170 parts of the 2,2-b;s-~4-aminophenyLj-propane obta;ned as descr;bed in Example 1a~ 25D parts of dioxane and D.~6 part of a ruthen;um~IV3 oxide hydrate dr;ed at 100C under a reduced pressure ~f 30 mbar ~ere intro-duced into a rolLing autoclave, the latter ~as tlushed with nitrogen and then ~iLled ~ith hydrogen, and the mix~
ture ~as heated at 150C, the hydrogen pressure being brought to 250 bar. Hydrogenation ~as c~ntinued until hydrogen ~as no longer absorbed. The catalyst ~as then separated of~ from the reat~ed mixture, the solven~ uas removed under redured pressure and the residue ~as ~rac~
~ionated under 4 mbar. 171 parts (95 X of ~heory) of 2~2-b;s-~4-aminocyclohexyl~-propane o~ b~ilin~ p~int ~68 170C
~ere obtained~
a) 372 parts of an;lineO 1~6 parts of acetone9 S00 parts o~ water and 800 par~s Df a sulfonated polystyrene resin ~hich was crosslinked with divinylbenzene and had a particle size o~ 0.3 - 1~5 mm, ~ ~ater content of 50 -55 % and a total H~ capacity of ~.9 milliequiv~len~s -11~
~ 7 ~
of ~39 ~ere employed in the pressure-ti~ht ~pparatus descr;bed in Example la). ~he ~pparatus ~as closed, and th2 s~irred mix~ure ~as heated for 20 hour~ ~t 13DC, the press~re re~rhing 3.~ barO The acidic ca~alyst ~as then removed ~y ~;ltrat;c,n, the liqu;d reacted mixture ~as sep-arated into an aqueous and an or~anic phase, ~nd these phases ~ere ~forked up as described in Exa~np~e 1a~.
25 par~s of açe~one and 86 parts of anili~e were rerovered, correspond;ng to a conversion of 77 % based on aniline and 78.5 X baced on ace~one. 350 parts of 95 X pure 2~2-b;s~ aminophenyl)-propane ~ere obta;ned. The selettiv~
- ity ~a~ 77 ~O
b) A shaking autQclave uas ch3rged ~;~h 30D parts r,f dioxane, 200 parts o~ the 2,2-bis-(4~aminophenyl)-prr,pane obta;ned as des~r;bed ;n Exa~ple 3a and 0.5 part of a ruthenium(IV) ox;de hydrate ~hich contained 19 X by ~e;ght of Ru, had been washed ~;th dioxane and was moist after having been centrifuged. Th~ reac~ion mixture uas hydrogenated under a pressure o~ 300 bar and a~ 150C, and ~as ~hen worked up as described in Example 1b). 190 par~s ~95 X of theory) of 2,2-bis-(b~a~inoryclohexyl)-propane ~re obtained.
a) ln the pressure-t;ght apparatus described in Example 1a~, 6~0 parts o7 o-toluidine, 116 parts of acet-one, 200 parts D~ ~ater and 568 parts of 36 Z 5 tr~ngth by ~e;ght hydrorhloric acid ~ere hea~ed a~ 130C for 20 hoursO the pressure rea~hing 3~1 b~r~ ~he reaction mixture ~a~ trans~erred to a ~lass ~lask~ 565 parts of ~12-5~
~0 X strength by ~eight sDdium hydroxide solution ~ere added, and the m;xture ~as stirred ~or a short time at 30C and th~n separated into an aqueous and an organic phase, usin~ a separating funnel~ The organic phase ~as ~ashed chlor7de-free ~ith 1Q % s~rength by weight sDd;um hydroxide solu~ion, ~ashing being r~peated several timesO and uas then worked up by distilla~ion.
In the f;rst sta~e, ace~one, o-toLuidine and N-isopropenyl-o-tol~;dine ~ere distilled o~f at 140 ~bar, and the condensates were obta;ned as the bo~tom produc~
3D1 parts of o-toluidine and 3~ parts of acetone ~ere recDvered, correspondin~ to a conversion o~ ~9.7 X based on o-toluidine and 70.7 X based on acetone. The bott~m product was fractionally distilLed as described in ~x-ampLe 1a). 336 parts of 2~2-bis-14-amino 3 me~hylphenyl)-propane C~electivi~y: 63 X, bp.: 197 - 20D~C a~ 0.5 mbar), 6 parts of 2,2~4O8-tetramethyl-1D2-dihydroquinoline and 8 parts of N-isoprGpenyl ~,2-bis-~4-am;no-3-me~hylphenyl)-propane uere ob~ained.
b) A shaking autor,lave ~as charged wi~h 200 parts of the 2,2-bis-~4-amino-3-methylphenyl~propane obtained as descr;bed ;n Exa~ple 3a), 3D0 parts of dioxane and 0.1 part of a ruthenium(IV~ oxide hydrate ~hich con~ained 67 X by veight of Ru and had been dried a~ 100C under a redur,ed pressure of 3D mbar. The react;on ~ixture ~as hydrogenated under ~ pressure of 200 bar ~nd at 20D~C, and then worked up as described in Example 1b). 197 parts (9~ % o~ theory~ of 2~7-bis~ amino~3 methylcytlohexyl)-propane of boilin~ point 190 - 193C/~ mbar were ob~ained.
~ c ~
EXAMPLE ~
a~ In ~he pressure~ti~h~ apparatus described ;n xample la), 521 parts of ani~ine, 14~, parts of ~ethyl ethyL ketone~ 2ûO parts of water and 56~ parts of 36 X
streng~h by ~ight hydrochloric acid ~ere heated at 130C
for 2~ h~ursO ~he pressure reaching 3~2 bar. The working up steps preceding the t~o-sta~e distillation ~ere as des-cr;bed in Fxample 3a).
In the f;rst s~age of the tis~illation, methyl ethyl ke~one, ani~;ne ~nd N-;sobutenylaniline ~ere dis-tilled off at 140 mbar, and the condensates were obtained ~s the bott~m produc~
29 parts o~ methyl ethyl ke~one and 225 parts of aniline were rec~vered, corresponding to a conYersion of ~9.5 X based on anil;ne and ~0 X based on methyl ethyl ketone. The bottom product was ~ract;onally dis~illed as described in Example 1aaO 3b2 parts of 2,2-bis ~4-aminopheny~)-butane o~ boiling point 186 - 18&C/
0.5 mbar ~ere obtainedO ~he selectivi~y ~as 7S.2 aZ, b) A shaking autoclave ~as charged with 200 parts of the 2,2~bis~ aminophenyl)-butane obtained as des-cr;bed ;n E~ample 4a)~ 300 parts of dioxane and 0~1 par~
of a ruthenium(IV) oxide hydratæ ~hich contain~d 67 X by weight of Ru and had been dried at 100~t ~nder a reduced pressure o~ 30 mbar. ~he reaction 0i~t~re ~as hydrogen~
ated under a pressure of 2~G bar and at 200C~ and ~hen ~orked up as described in Ex~mple 1b~ 196 par~s (93 % o~
$heory~ o~ 2~2-bis-~4-aminocyr,lohexy~-butane of ~oiling poin~ 173 175C/4 ~bar ~ere obta;ned~
~z~
COMPARATlVE EX~MPl.E 'I
Us;ng the pressure-ti~ht apparatus described in Example 1a~, 559 par~s of aniline~ 232 parts of a~etone, ~1D parts of ~a~er ~nd 2D3 par~s D~ 36 X s~rength by weigh~ hydrochloric ac;d ~ere heated at 130C ~or 2D hours, ~he pres~ure reaching bar. 202 parts of ~0 X streng~h by weight sodium hydro~ide solu~ion ~ere addedO the phases ~ere separated and the organir phase ~las subjected to a t~o-~tage distillation proc~dure~ after ~hich 28 parts of acetone a~d 271 par~s ~f aniline ~ere recovered, corres-prJnd;ng to a convers;on of 38n7 X b~sed on anilineO
70 parts o~ 2~2,4-~ri~ethyl 1,2-d;hydroquinoline (bp.:
130G/10 mbar~ mp.: 21t)~ 28 parts o~ N-isopropenyl-2,2-bis-~-amin~phenyl)~propane and 71 parts of 2,Z-bis-(4-amino-phenyl)-propane were ~btain~d as condensates~ The select-;v;ty ~a~ 20.3 X~ ~he d;stilla~;on residue conprised 150 parts.
COMPARAT~VE EXAMPLE 2 In ~he pressure-tight apparatus descr;bed in Example 1a), 521 parts of aniline~ 116 parts of acetone and 142 par~s of 3b % s~ren~th by ~e;ght hydrochloric ac;d ~ere heated at 130C for 2D h~urs, the pressure reachin~
3~5 b3r. The product was transferred ~o a glass flaskO
145 parts of ~0 X strength by wei~ht sodium hydroxide sGlution ~ere added~ and the mixture was st;rred for a short time at 4DC and then separated into an organic and an aqueous phase. After a t~o-st~ge distillation pro-cedureO 21 parts of acetone and 309 par~s of aniline were r~cov~red~ corr~spc,nd;ng to a rrinver~ion of 56a8 X based ~n ani~;ne. 31 parts o~ 2,2,4~trimethyl~1~2-dihydro-~uinoline, ~0 parts of N-;sopropenyl-2~2~bis-(~-amino-phenyl) propane~ 12 parts of N~N' diphenyl-Z,2~bis~(4-a~inophenyl)-propane and 52 parts of ~,2-bis~5~aminn-phenyL~-propane were ob~ained as condensates. The select-iv;ty ~as 20D2 Z. The dis~illati~n residue comprised 127 parts.
~16~
The strong monobasit Pr polybasic ac;ds required ~or the conden~a~ion are, in particular, ~ater-soLuble acids having a pKA o~ less than 2.5, pre~erably less ~han 1~5, for exa~pLe hydrochloric acid, hydrobromic acid, sulfuric ac;dO trifluoroacetic acid, methanesul~onic acid, trifluoro~ethanesulfon;c ac;d, benzenesul~onic acid or phosphoric acid, tlrdrochloric acid is preferably used.
~he ac;ds can be e~ployed e;ther in pure form or ~4~
to~ether ~ith the;r neu~raL or acidic salts, eg. the alkali metal or a~mc,nium salts. ~n ~he noveL process, the ~cid is present in the a~ueous phase partially as the ammonium salt of ~he aniline required for ~he reaction.
Instead of ~a~er-soluble acids, it ;s also pos-sible to use strongly acidic ~ater-insoluble iorl ex-changers having a pKA in ~he abovementioned range~
Pre~erabLy, the ion exchanger resins used are based on copolymers of highly sulfona~ed s~yrene wi~h divinyl-benzene.
In the condensation step, the ~olar ratio o~
ani line to ketone shouLd be from 2;1 ~o 10 1s preferably from 3:1 to ~ e have found tha~ values less ~han 2:1 promote the formation of undesirable by-products.
~here unsubstituted an;line i~ condensed with acetone, the principal by-products are 2~2,~t-~r;methyl 1,2-dihydroqu;noline~ 2,3,4-trimethylquinDline~ 2~4-di-methylquinoline, W-isopropenyl-2,2~b;s-(4-aminophenyl)-propane and N,~ diphenyl-2~2-bis-S~-aminophenyl)-propane.
The upper Lîmi~, ie. 10:1, is no~ cri~ical ~ith regard to the formation of by-products~ but ~he further ;n~rease ;n the anil;ne concentration is of no fur~her advanta~e~
The nolar rati~ of aniline to acid equivalent can be varied fro~ 1:1 to 401~ preferably ~rom 1~1 ~o 2~1~
Increasing the ratio ~bove 4:1 res~l~s ;n the ~ormation of ;ncreasing amounts of by prod~cts.
In the above react;on of unswbstituted aniline vith acetone and hydro~hloric acid, these are~ ;n ~5--particular, d;phenylam;ne and ;ts secondary product ~rom the reac~ion ~ith 2,2-bis~4-aminophenyl~-propane~ On ~he other hand, ~here lthe moLar ra~io of ani line to acid equivalent is less than 1~ he ra~te of ~orma~ion of 2,2-b;s-(4-a~n;nophenyl)-pr~pane is reduced, thereby promoting side reacti3ns which in the above case lead principaLly ~o ~he formation o~ N-isopropenylaniline and 2,2,4-tri-methyl-192-d;hydroqu;nol;ne.
Where an at;dit ;on ex~hanger is used~ it is employed in an amount equ;valent to that of the water soluble acid.
The amount of wa~er used accord;ng to the ;nven tion is from 10 to 6D X by ~eigh~, based on the rea~ior, ~ixtur~. Amo~nts of wa~er beLow 10 Z by ~ei~ht favor the format;on of by-products (in ~he abDve case~ parti~wlarly the formation of qu;nolines~ the amount of ~ater is increased above 60 % by weightO the pro~ess becomes un-ecDnomical~
~he reactan~s are to~nbine~ in a pressure-ti~ht vessel, advantageDusly by stirrin~, and the sequenGe o~
add;t;on is not cr;tical. In a pre~erred embodiment, the amine is taken and ~he ke~one, ~a~er and the acid are then added.
The re~ctants are ~sually mixed a~ room ~empera--ture ~20 - 25C), and the s~irred mixture is then hea~ed ~ closed reactor ~ from 100 to ~60C, preferably ~rom 1 in to 140C. The ~emperature can be intreased stepwise or 20 cDn~;nuously, either rapidly or slowly.
The condensation is wsually carr;ed GU~t under a --6-~
7~
pres~ure of from 1 to 20 bar~ In general, the a~togenous pressure of the s~stem is su~ficient, th;s pressure being governerJ by the vapor pressure of ~he readily voLatile reactants as a function o~ their temperature and concen-trat;on. The pressure ~ay also be ;ncreased uith ~he aid of an inert gas~ eg. n;~rsgen~ bu~ increasing it above 20 bar does not result in an improvement in the yield or se lectivi ~y .
7he reaction t;me is in general from 2 to 2D hours.
The progress of the reaction can be ~onitored ~y removing aliquot parts of the reaction mixture from the pressure-~ight vessel, for exa~ple thrDugh a siphon tube, rendering this sa~ple slightly alkaline ~ith 25 X strength by weight sodium hydroxide solu~ion, separating ~he result-ing mixture into an ~queous and an organic phase and analyzing the organic phase by gas or liquid chromato-graphy.
~ he reac~ion tan be carried out ei ther ba~chwise or continuously. ~here a continuous procedure is employed, ~0 it is advantageous t~ carry out the reaction in a cascade comprising two or more appropriately equipped s~irred kettles.
Depending on the aç;dic catalys~ used, the reac t;on ~i~ture obtained according to the inven~;on is either hetero~eneou~ (solid-liqu;d) or homc~geneous Sli~uid), and ran be treated further or ~fter~treated in varisus wa~s. As a ruLe, the reacted mixture is brough~
to pH 8 to 1D uith 25 - ~,0 ~ strength by weigh~ sodium hydro~ide solution, and the mi~ture ;s s~;rred for so~e 7~
time at ~G~ and then separated into ~n aquPous and ~n organic phase~
Start;ng materi~ls which are part;ally d;ssolved in ~he aqueous phase~ e~. atetone and aniline, car, be su~-stantially recovered by extraction with a hydrophobic soLvent. 5~i~able hydrophob;c solven~s are ar,y o~ thcse wh;ch are water-immiscible and inert to ~he reactantsf eg chlorobenzene, benzene, toluene~ xylene~ dichloro-ethane, chloro~orm, rarbon ~etrachlor;de, etc. o-Xylene is a particularly preferred solvent.
Where a solid highly sul~ona~ed polystyrene ion exchanger resin crosslinked ~ith divinylbenzene is used~
the sol;d catalyst ;s separated off by filtr3tion a~er the addition of ~he sodium hydroxide solution~
The organic phase is ~ashed with water~ a~ter ~hich this phase and the combined ex~rac~s, separateLy or t~gether, are fractionally dis~illed, first under atmospheric pressure and then under reduced pressureO
The diphenylmethane derivatives obtained are employed in the hydrogenation process, ~h;le any startins materials recovered ran be recyrled to the condensation stage~
The hydrogena~ion is carried DUt under a pressure greater than 5D bar, in general from bO ~o 3ao bar, pre-~erably ~rom 150 to 3DO bar.
AdvantageouslyO ~he process is rarried ou~ at ~rom 30 ~o 250C~ particularly preferabLy ~rom ~20 ~o 180C.
~ he products to be hydro~enated can be employed in the pre~ence or absenre of a solven~O However~ ;t has -8~
proved advantageous ~o ~arry out the hydroyenation in solution~ suitable solvents bein~ e~hers~ e9. diethyl e~her, glycol dimethyl e~her, dioxane or tetr~hydro~uran.
S~;tabLe rutheniu~-containing ca~alys~s are those ~hich are obtained in situ J ie. in ~he reaction mixture, by reduring ru~henium(IV~ oxide hydra~e with hydrDgen.
This cataly~t intermed;ate can be obtained in suspended for~, as a dry powder or ;n a form ~here ;t is applied onto a conventional ~arrier, e~. siLica~ aluminum oxide lû or active carbon. The preparation o~ ru~henium~IY) oxide hydrate from rutheniu~ tri~hLoride trihydrate, RuCl3.3H20 is described in detail in German Pa~ent Z,132,547.
A pulverulent catalyst intermediate containing ~bou~ 60 - 70 X by ~e;ght of ruthen;~m and having a particLe size o~ from ~0 to 60 nm sives a particularly active hydrogenation catalyst.
The ca~alyst ;ntermediate ~ay either be ~mployed in moist form or be dried before use. This can b achieve~ by heating it at 8D - 10~C under rPduced pres-sure. Ho~ever, it is aLso possible to wash the moist centr;fuged catalyst ;n~r~ediate ~ater-free with an organic soLvent and to employ ;~ ;n the ~orm of a suspended concentrate~ most advantageously ;n the solvent intended ~or use in the hydro~ena~ion.
In ~eneral~ it is sufficien~ to use fr~m 10 tc, 1,000, pre~erably from ~0 to 1~0, ppmO based on the di~
phenylmethane derivative, uf ruthen;um(IV~ oxide hydrate.
The Examples whi h follow illustrate ~he noveL
process. Parts are by ~eight.
_9_ 7~i a) An enameled au~sclave ~quipped ~;th a heating jacket and ther~o oiL cycle, a stirrerO a thermometær, a ~eed device, ~ rupture disk (~0 bar~ and a siphon tube with a sampler ~as charged wi~h 521 parts of aniline, 116 parts o~ acetone, 200 parts of ~a~er and 568 parts of 36 X s~rength by ~eigh~ hydrochloric acid and ~25 ~hen cl~sed. The stirred autoclave ~as heated to ~30C in the course o~ abou~ 1 hour, the pressure reaching 3OZ bar.
Fro~ ~;me to t~me, a sampLe was taken via the siph~n ~ube and neutral;zed with sodium hydroxide solu-~ion and the organic phase was separated off ~rom the resulting mixture~ dist;LLed and analyzed by gas chromato graphy. Af~er 15 hours, the reaction mixture ~as trans-fe.red to a glass flask, 565 p~rts of 40 X strength sodium hydroxide solu~ion ~ere added ~nd the mixture ~as stirred for a short time at 30 - 40C and then s parated into an aqueous and an organic phase, usin~ a separating funneL.
The ~q~eDus phase, which, under ~he sta~ed con-ditions, was saturated ~ith anil;ne and acetone~ was ex-tracted with twice 10D parts of o-xylene, and the resul~-;ng extract phase was combined with the or~anic phase from the reacted ~ixture. The combined organic phase was ~ashed chloride-free ~i~h water, ~ashing beiny repeated several timesO and ~as ~hen ~orked up in ~ t~D-stage d;s-tillation apparatus.
In the ~irst s~age, acetone~ ~niL;ne~ o xyLene and N-isopropenylan;line ~ere distilled off under atmos-pher;c press~re9 thæ tondens3tes remain;ng at the bo~om of the distiliation apparatus. 23 par~s of acetone and Z33 parts of aniline ~ere recovered, corresponding to a convers;on of 77.5 % based on aniline, and 79.8 X based on acetone. The botto~ produc~ was fracti~nalLy dis-tilled at 0.5 mbar in a second stage, using 2 c~L~n con-taining ~;re gauze pack;ng and possessing not less than 15 trays. 292 parts of 97 % pure 2~2-bis-t4-aminophenyl~-pr~pane of boiling poin~ 183-18~C/0.5 mbar and ~elting point 132C ~ere obtained~ The selec~iv;ty was 82 X.
b) 170 parts of the 2,2-b;s-~4-aminophenyLj-propane obta;ned as descr;bed in Example 1a~ 25D parts of dioxane and D.~6 part of a ruthen;um~IV3 oxide hydrate dr;ed at 100C under a reduced pressure ~f 30 mbar ~ere intro-duced into a rolLing autoclave, the latter ~as tlushed with nitrogen and then ~iLled ~ith hydrogen, and the mix~
ture ~as heated at 150C, the hydrogen pressure being brought to 250 bar. Hydrogenation ~as c~ntinued until hydrogen ~as no longer absorbed. The catalyst ~as then separated of~ from the reat~ed mixture, the solven~ uas removed under redured pressure and the residue ~as ~rac~
~ionated under 4 mbar. 171 parts (95 X of ~heory) of 2~2-b;s-~4-aminocyclohexyl~-propane o~ b~ilin~ p~int ~68 170C
~ere obtained~
a) 372 parts of an;lineO 1~6 parts of acetone9 S00 parts o~ water and 800 par~s Df a sulfonated polystyrene resin ~hich was crosslinked with divinylbenzene and had a particle size o~ 0.3 - 1~5 mm, ~ ~ater content of 50 -55 % and a total H~ capacity of ~.9 milliequiv~len~s -11~
~ 7 ~
of ~39 ~ere employed in the pressure-ti~ht ~pparatus descr;bed in Example la). ~he ~pparatus ~as closed, and th2 s~irred mix~ure ~as heated for 20 hour~ ~t 13DC, the press~re re~rhing 3.~ barO The acidic ca~alyst ~as then removed ~y ~;ltrat;c,n, the liqu;d reacted mixture ~as sep-arated into an aqueous and an or~anic phase, ~nd these phases ~ere ~forked up as described in Exa~np~e 1a~.
25 par~s of açe~one and 86 parts of anili~e were rerovered, correspond;ng to a conversion of 77 % based on aniline and 78.5 X baced on ace~one. 350 parts of 95 X pure 2~2-b;s~ aminophenyl)-propane ~ere obta;ned. The selettiv~
- ity ~a~ 77 ~O
b) A shaking autQclave uas ch3rged ~;~h 30D parts r,f dioxane, 200 parts o~ the 2,2-bis-(4~aminophenyl)-prr,pane obta;ned as des~r;bed ;n Exa~ple 3a and 0.5 part of a ruthenium(IV) ox;de hydrate ~hich contained 19 X by ~e;ght of Ru, had been washed ~;th dioxane and was moist after having been centrifuged. Th~ reac~ion mixture uas hydrogenated under a pressure o~ 300 bar and a~ 150C, and ~as ~hen worked up as described in Example 1b). 190 par~s ~95 X of theory) of 2,2-bis-(b~a~inoryclohexyl)-propane ~re obtained.
a) ln the pressure-t;ght apparatus described in Example 1a~, 6~0 parts o7 o-toluidine, 116 parts of acet-one, 200 parts D~ ~ater and 568 parts of 36 Z 5 tr~ngth by ~e;ght hydrorhloric acid ~ere hea~ed a~ 130C for 20 hoursO the pressure rea~hing 3~1 b~r~ ~he reaction mixture ~a~ trans~erred to a ~lass ~lask~ 565 parts of ~12-5~
~0 X strength by ~eight sDdium hydroxide solution ~ere added, and the m;xture ~as stirred ~or a short time at 30C and th~n separated into an aqueous and an organic phase, usin~ a separating funnel~ The organic phase ~as ~ashed chlor7de-free ~ith 1Q % s~rength by weight sDd;um hydroxide solu~ion, ~ashing being r~peated several timesO and uas then worked up by distilla~ion.
In the f;rst sta~e, ace~one, o-toLuidine and N-isopropenyl-o-tol~;dine ~ere distilled o~f at 140 ~bar, and the condensates were obta;ned as the bo~tom produc~
3D1 parts of o-toluidine and 3~ parts of acetone ~ere recDvered, correspondin~ to a conversion o~ ~9.7 X based on o-toluidine and 70.7 X based on acetone. The bott~m product was fractionally distilLed as described in ~x-ampLe 1a). 336 parts of 2~2-bis-14-amino 3 me~hylphenyl)-propane C~electivi~y: 63 X, bp.: 197 - 20D~C a~ 0.5 mbar), 6 parts of 2,2~4O8-tetramethyl-1D2-dihydroquinoline and 8 parts of N-isoprGpenyl ~,2-bis-~4-am;no-3-me~hylphenyl)-propane uere ob~ained.
b) A shaking autor,lave ~as charged wi~h 200 parts of the 2,2-bis-~4-amino-3-methylphenyl~propane obtained as descr;bed ;n Exa~ple 3a), 3D0 parts of dioxane and 0.1 part of a ruthenium(IV~ oxide hydrate ~hich con~ained 67 X by veight of Ru and had been dried a~ 100C under a redur,ed pressure of 3D mbar. The react;on ~ixture ~as hydrogenated under ~ pressure of 200 bar ~nd at 20D~C, and then worked up as described in Example 1b). 197 parts (9~ % o~ theory~ of 2~7-bis~ amino~3 methylcytlohexyl)-propane of boilin~ point 190 - 193C/~ mbar were ob~ained.
~ c ~
EXAMPLE ~
a~ In ~he pressure~ti~h~ apparatus described ;n xample la), 521 parts of ani~ine, 14~, parts of ~ethyl ethyL ketone~ 2ûO parts of water and 56~ parts of 36 X
streng~h by ~ight hydrochloric acid ~ere heated at 130C
for 2~ h~ursO ~he pressure reaching 3~2 bar. The working up steps preceding the t~o-sta~e distillation ~ere as des-cr;bed in Fxample 3a).
In the f;rst s~age of the tis~illation, methyl ethyl ke~one, ani~;ne ~nd N-;sobutenylaniline ~ere dis-tilled off at 140 mbar, and the condensates were obtained ~s the bott~m produc~
29 parts o~ methyl ethyl ke~one and 225 parts of aniline were rec~vered, corresponding to a conYersion of ~9.5 X based on anil;ne and ~0 X based on methyl ethyl ketone. The bottom product was ~ract;onally dis~illed as described in Example 1aaO 3b2 parts of 2,2-bis ~4-aminopheny~)-butane o~ boiling point 186 - 18&C/
0.5 mbar ~ere obtainedO ~he selectivi~y ~as 7S.2 aZ, b) A shaking autoclave ~as charged with 200 parts of the 2,2~bis~ aminophenyl)-butane obtained as des-cr;bed ;n E~ample 4a)~ 300 parts of dioxane and 0~1 par~
of a ruthenium(IV) oxide hydratæ ~hich contain~d 67 X by weight of Ru and had been dried at 100~t ~nder a reduced pressure o~ 30 mbar. ~he reaction 0i~t~re ~as hydrogen~
ated under a pressure of 2~G bar and at 200C~ and ~hen ~orked up as described in Ex~mple 1b~ 196 par~s (93 % o~
$heory~ o~ 2~2-bis-~4-aminocyr,lohexy~-butane of ~oiling poin~ 173 175C/4 ~bar ~ere obta;ned~
~z~
COMPARATlVE EX~MPl.E 'I
Us;ng the pressure-ti~ht apparatus described in Example 1a~, 559 par~s of aniline~ 232 parts of a~etone, ~1D parts of ~a~er ~nd 2D3 par~s D~ 36 X s~rength by weigh~ hydrochloric ac;d ~ere heated at 130C ~or 2D hours, ~he pres~ure reaching bar. 202 parts of ~0 X streng~h by weight sodium hydro~ide solu~ion ~ere addedO the phases ~ere separated and the organir phase ~las subjected to a t~o-~tage distillation proc~dure~ after ~hich 28 parts of acetone a~d 271 par~s ~f aniline ~ere recovered, corres-prJnd;ng to a convers;on of 38n7 X b~sed on anilineO
70 parts o~ 2~2,4-~ri~ethyl 1,2-d;hydroquinoline (bp.:
130G/10 mbar~ mp.: 21t)~ 28 parts o~ N-isopropenyl-2,2-bis-~-amin~phenyl)~propane and 71 parts of 2,Z-bis-(4-amino-phenyl)-propane were ~btain~d as condensates~ The select-;v;ty ~a~ 20.3 X~ ~he d;stilla~;on residue conprised 150 parts.
COMPARAT~VE EXAMPLE 2 In ~he pressure-tight apparatus descr;bed in Example 1a), 521 parts of aniline~ 116 parts of acetone and 142 par~s of 3b % s~ren~th by ~e;ght hydrochloric ac;d ~ere heated at 130C for 2D h~urs, the pressure reachin~
3~5 b3r. The product was transferred ~o a glass flaskO
145 parts of ~0 X strength by wei~ht sodium hydroxide sGlution ~ere added~ and the mixture was st;rred for a short time at 4DC and then separated into an organic and an aqueous phase. After a t~o-st~ge distillation pro-cedureO 21 parts of acetone and 309 par~s of aniline were r~cov~red~ corr~spc,nd;ng to a rrinver~ion of 56a8 X based ~n ani~;ne. 31 parts o~ 2,2,4~trimethyl~1~2-dihydro-~uinoline, ~0 parts of N-;sopropenyl-2~2~bis-(~-amino-phenyl) propane~ 12 parts of N~N' diphenyl-Z,2~bis~(4-a~inophenyl)-propane and 52 parts of ~,2-bis~5~aminn-phenyL~-propane were ob~ained as condensates. The select-iv;ty ~as 20D2 Z. The dis~illati~n residue comprised 127 parts.
~16~
Claims (8)
1. A process for the preparation of a bis-(amino-cyclohexyl)-dialkylmethane of the formula I
(I) where R1 and R2 are identical or different and are each lower alkyl of 1 to 4 carbon atoms, R3 is hydrogen or lower alkyl of 1 to 4 carbon atoms and the two cyclohexane rings may each be unsubstituted or substituted by one or two lower alkyl groups, each of 1 to 4 carbon atoms, or by a carboxyalkyl group where alkyl is of 1 of 4 carbon atoms, by condensing a para-unsubstituted aniline of the formula II
(II) where R3 has the above meanings and the aniline may be unsubstituted or substituted in the nucleus by one or two lower alkyl groups of 1 to 4 carbon atoms or a carboxy-alkyl group where alkyl is of 1 to 4 carbon atoms, with a lower aliphatic ketone in which the alkyl radicals are each of 1 to 4 carbon atoms, in the presence of a strong monobasic or polybasic acid and hydrogenating the product obtained, wherein the condensation is carried out at from 100 to 160°C and under from 1 to 20 bar in the presence of from 10 to 60 % by weight, based on the reaction mix-ture, of water the molar ratio of aniline to ketone is from 2:1 to 10:1 and that of aniline to acid equivalent is from 1:1 to 4:1, and the subsequent hydrogenation of the resulting product is carried out at from 30 to 250°C under a pressure of above 50 bar in the presence of a suspended ruthenium-containing catalyst.
(I) where R1 and R2 are identical or different and are each lower alkyl of 1 to 4 carbon atoms, R3 is hydrogen or lower alkyl of 1 to 4 carbon atoms and the two cyclohexane rings may each be unsubstituted or substituted by one or two lower alkyl groups, each of 1 to 4 carbon atoms, or by a carboxyalkyl group where alkyl is of 1 of 4 carbon atoms, by condensing a para-unsubstituted aniline of the formula II
(II) where R3 has the above meanings and the aniline may be unsubstituted or substituted in the nucleus by one or two lower alkyl groups of 1 to 4 carbon atoms or a carboxy-alkyl group where alkyl is of 1 to 4 carbon atoms, with a lower aliphatic ketone in which the alkyl radicals are each of 1 to 4 carbon atoms, in the presence of a strong monobasic or polybasic acid and hydrogenating the product obtained, wherein the condensation is carried out at from 100 to 160°C and under from 1 to 20 bar in the presence of from 10 to 60 % by weight, based on the reaction mix-ture, of water the molar ratio of aniline to ketone is from 2:1 to 10:1 and that of aniline to acid equivalent is from 1:1 to 4:1, and the subsequent hydrogenation of the resulting product is carried out at from 30 to 250°C under a pressure of above 50 bar in the presence of a suspended ruthenium-containing catalyst.
2. A process as claimed in claim 1, wherein the acid used is hydrochloric acid.
3. A process as claimed in claim 1, wherein the acid used is a water-insoluble, strongly acidic ion exchanger from the group comprising highly sulfonated polystyrene resins crosslinked with divinylbenzene.
4. A process as claimed in claim 1, wherein the con-densation is carried out at from 120 to 140°C.
5. A process as claimed in claim 1, wherein the molar ratio of aniline to ketone is from 3:1 to 6:10
6. A process as claimed in claim 1, wherein the molar ratio of aniline to acid equivalent is from 1:1 to 2:1.
7. A process as claimed in claim 1, wherein the hydrogenation is carried out at from 120 to 180°C.
8. A process as claimed in claim 1, wherein the hydrogenation is carried out under from 150 to 300 bar.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3226889.0 | 1982-07-17 | ||
| DE19823226889 DE3226889A1 (en) | 1982-07-17 | 1982-07-17 | METHOD FOR PRODUCING BIS (AMINOCYCLOHEXYL) DIALKYLMETHANES |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1192575A true CA1192575A (en) | 1985-08-27 |
Family
ID=6168727
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000432518A Expired CA1192575A (en) | 1982-07-17 | 1983-07-15 | Preparation of bis-(aminocyclohexyl)-dialkylmethanes |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0099516A1 (en) |
| JP (1) | JPS5927855A (en) |
| CA (1) | CA1192575A (en) |
| DE (1) | DE3226889A1 (en) |
Families Citing this family (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH660879A5 (en) * | 1984-10-30 | 1987-05-29 | Ciba Geigy Ag | ONE-STEP PROCESS FOR THE PRODUCTION OF BIS-(AMINO-NITROPHENYL)-METHANE. |
| JPS63208555A (en) * | 1987-02-21 | 1988-08-30 | New Japan Chem Co Ltd | Production of bis(4-aminocyclohexyl)methane |
| ES2625119T3 (en) | 2006-07-28 | 2017-07-18 | Archroma Ip Gmbh | Basic hinge compounds |
| EP2078737A1 (en) | 2008-01-11 | 2009-07-15 | Clariant International Ltd. | Basic monoazo compounds |
| EP2098573A3 (en) | 2008-01-17 | 2009-10-07 | Clariant International Ltd. | Basic monoazo compounds |
| EP2085428A1 (en) | 2008-01-24 | 2009-08-05 | Clariant International Ltd. | Basic bisazo compounds |
| EP2103656A3 (en) | 2008-01-24 | 2009-10-28 | Clariant International Ltd. | Basic monoazo compounds |
| EP2085429A1 (en) | 2008-01-25 | 2009-08-05 | Clariant International Ltd. | Basic bisazo compounds |
| EP2251384A1 (en) | 2009-05-14 | 2010-11-17 | Clariant International Ltd. | Pyrazolone monoazo dyes |
| EP2258683A1 (en) | 2009-05-14 | 2010-12-08 | Clariant International Ltd. | Bisazo compounds |
| EP2251382A1 (en) | 2009-05-14 | 2010-11-17 | Clariant International Ltd. | Monoazo compounds |
| EP2251322A1 (en) | 2009-05-14 | 2010-11-17 | Clariant International Ltd. | Bisazo compounds |
| EP2258686A1 (en) | 2009-05-14 | 2010-12-08 | Clariant International Ltd | Monoazo compounds |
| EP2258685B1 (en) | 2009-05-14 | 2013-10-23 | Clariant Finance (BV) Limited | Bisazo compounds |
| EP2251388A1 (en) | 2009-05-14 | 2010-11-17 | Clariant International Ltd. | Organic compounds |
| EP2258684A1 (en) | 2009-05-14 | 2010-12-08 | Clariant International Ltd | Monoazo compounds |
| EP2251385A1 (en) | 2009-05-14 | 2010-11-17 | Clariant International Ltd. | Pyrazolone bisazo dyes |
| EP2251381A1 (en) | 2009-05-14 | 2010-11-17 | Clariant International Ltd. | Monoazo compounds |
| EP2251321A1 (en) | 2009-05-14 | 2010-11-17 | Clariant International Ltd. | Monoazo compounds |
| EP2251386A1 (en) | 2009-05-14 | 2010-11-17 | Clariant International Ltd. | Pyrazolone bisazo dyes |
| EP2251383A1 (en) | 2009-05-14 | 2010-11-17 | Clariant International Ltd. | Organic compounds |
| EP2251325A1 (en) | 2009-05-14 | 2010-11-17 | Clariant International Ltd. | Bisazo compounds |
| JP5707935B2 (en) * | 2010-12-28 | 2015-04-30 | 東ソー株式会社 | High purity 2,2-bis (4-aminophenyl) propane and process for producing the same |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2606925A (en) * | 1949-12-15 | 1952-08-12 | Du Pont | Ruthenium catalyzed hydrogenation process for obtaining aminocyclohexyl compounds |
| FR1555580A (en) * | 1967-07-24 | 1969-01-31 | ||
| FR1551119A (en) * | 1967-11-09 | 1968-12-27 | ||
| BE754023A (en) * | 1969-07-31 | 1971-01-28 | Kaiser Aluminium Chem Corp | PROCESS FOR THE MANUFACTURE OF POLYAMINES |
| DE2502893C2 (en) * | 1975-01-24 | 1982-10-14 | Bayer Ag, 5090 Leverkusen | Cycloaliphatic amines |
| JPS51125363A (en) * | 1975-04-22 | 1976-11-01 | Ube Ind Ltd | Process for freparation of alkylidenebiscyclohexylamines |
| DE2945614A1 (en) * | 1979-11-12 | 1981-05-21 | Bayer Ag, 5090 Leverkusen | 4,4'-Di:amino-3,3',5,5'-tetra:alkyl-di:cyclohexyl-methane prepn. - by reacting 2,6-di:alkyl-aniline with formaldehyde and reducing prod. over ruthenium catalyst |
-
1982
- 1982-07-17 DE DE19823226889 patent/DE3226889A1/en not_active Withdrawn
-
1983
- 1983-07-06 EP EP83106607A patent/EP0099516A1/en not_active Withdrawn
- 1983-07-15 CA CA000432518A patent/CA1192575A/en not_active Expired
- 1983-07-18 JP JP58129600A patent/JPS5927855A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5927855A (en) | 1984-02-14 |
| EP0099516A1 (en) | 1984-02-01 |
| DE3226889A1 (en) | 1984-01-19 |
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