IE892464L - Preparation of n-allylanilines and n-alkylanilines - Google Patents

Abstract

The present invention relates to a process for monoalkylation and monoallylation on the nitrogen of an aniline by bringing the latter and an alkylating or allylating agent into contact in an organic solvent in homogeneous liquid phase in the presence of an onium and of a stoichiometric quantity of a nonquaternisable base.

Description

61 5 21 2 Ths present invention relates to a process for the preparation of aBcylanilines and M-allylaniUnas. It more particularly relates to the preparation of N-allylanilines and more particularly to the preparation of M-naonoallylanilines.

The preparation of M-raonoallylanilines is particularly important in the case of trifluoromethylaniline, because the monoallyl derivative obtained is an important intermediate in the synthesis of a herbicide, such as is described in French Patent Mo. 2 305 '43^. According to the latter, for the preparation of the desired herbicide, ^-1-(3~ trifluoromethylphenyl) -3-chloro-«~chloromethyl-2-pyrrolidone, it is necessary to start with a trifluoromethylaniline one of whose hydrogen atoms is protected by an acetyl group prior to carrying out allylation, in order to prevent the formation of secondary diallvlation products, which are of no use.

The industry has for a considerable time attempted to obtain wtono£ 11 y 11rif 1 uorometh y 1 an i 1 in e directly in a single stage, in place of the three stages described in French Patent Mo. 2 305 434, with good yields calculated on the basis of the starting substance used, viz. 3-trifluoromethylaniline, which is a very onerous compound which the industry does not wish to lose.

A first solution to this problem was proposed in US Patent Mo. 4 701 5609 which describes a process for the allylation of 3-trifluoromethylaniline in a two-phase medium, namely water and an organic solvent in the presence of a mineral base, e.g. caustic soda or a carbonate, and in the presence of catalytic quantities of a quaternizable tertiary amine. In order to obtain a small quantity of diallyl by-products, it is necessary to limit the 3-trifluoromethylaniline conversion rate and therefore to work in the presence of an allyl halide deficiency. The test states that the ratio of 3-trifluoromethylaniline to allyl halide is preferably approximately 2:1. The M-monoallylaniline yields calculated on the 3-trifluoromethylaniline introduced do not exceed 40%, which is inadequate for the process to be economically viable.

The allylation reaction on anilines other than 3-trifluoromethylaniline are described in inter alia US Patent Mo. 2 286 678, which in particular describes the allylation of U- 3 hydroxvaniline in a medium constituted by an alcohol and in the presence of a carbonate as the neutralizing agent.

The indicated M-monoallylhvdroxyaniline yields do not exceed those of the aforementioned patent and there is also appreciable 5 formation of diallyl derivatives, which it is sought to avoid. Therefore this method cannot be used in the present case.

US Patent Mo. 3 668 25^ describes a process consisting of allvlating 4-aminodiphenylamine with 2,3-dichloropropene in the presence of triethylamine. As in the two previous cases, the indicated 10 yields do not exceed 40$. Moreover, the trie thy lainine is used in a higher than stoichiometric quantity compared with the allyl halide. From the economic standpoint this method is particularly uninteresting, because the yields are low and the cost of the starting materials used is high.

US Patent Mo. 3 819 708 describes the alkylation of paraphenvlenediamines in various solvents in the presence of a tertiary amine such as triethylamine or a mineral base as the neutralizing agent of the hydracid formed. The alkylating agents described are much less reactive than allyl halides and the dialkylating problem is much less 20 important. The selectivity, i.e. the monoalkvl product yield compared with the die.Iky 1 derivatives, is not described.

Despite the existence of a large amount of literature describing the alkylation or allylation of various anilines, no process has made it possible to provide a good transformation or conversion rate of the 25 starting aniline and obtain a good selectivity for the W-mono-substituted aniline compared with the disubstituted aniline.

The present invention provides a process for the n-iaonoalkylation or M-monoallvlation of an aniline, comprising putting into contact an aniline and an alkylating or allvlating agent in an organic solvent in 30 a homogeneous liquid phase in the presence of a catalytic quantity of an onium and of a stoichiometric quantity of a non-quaternizable base.

The alkylating or allylating agent may be an alkyl sulphate or halide, whose alkyl chain can have unsaturations, can be straight or branched, and can have halogen, aryl. aralkyl, haloaryl and/or 35 nitroarvl substituents. Among the halides, preference is given to the use of chlorides and bromides, in particular chlorides, because they are less expensive.

I Among the alkyl and allyl halides, the present invention is concerned more particularly with allyl halides, because they (and particularly the chloride) are not very reactive with respect to alkylation.

Among suitable alkylating and allylating agents are allyl chlorides allyl bromide, benzyl chloride, benzyl bromide, isopropyl bromide, crotyl chloride and l-chloro-2-butene.

The process according to the present invention is applicable to all anilines. However, it is of particular interest for slightly basic anilines, i.e. for anilinium ions having a pKa below «.5. In the case of reactive anilines, whose proton form has a pKa higher than 1.5, the use of onium makes it possible to considerably shorten the reaction time or reduce the reaction temperature, the two criteria being very frequently linked with one another.

The preferred anilines, i.e. having a pKa below '4,5, are represented by the following Formula (I): MH2 i ] (I) (R>„ in which R represents a halogen atom, a nitro group, or a group of formula -ACn J^n^l *n wil*ch * represents a halogen atom, A a covalent bond or a sulphur or oxygen atom, and n is 0, 1 or 2. Among suitable anilines of Formula (I) are aniline, chloroanilines, fluoroanilines, nitroani lines, trihalornethylanilines, trihalomethoxyanilines and trihalomethylthioanilines.

The oniurns used in the process of the invention are more particularly those derived from nitrogen, phosphorus, arsenic, sulphur, selenium, oxygen, carbon or iodine. These oniuias are coordinated to hydrocarbon radicals. The onium ions derived from nitrogen, phosphorus or arsenic are quadricoordinated and those derived from sulphur, selenium, oxygen, carbon or S=0 are tricoordinated.

The hydrocarbon radicals coordinated to these different elements are alkvl. alkenvl. aryl. cycloalkvl or arylalkvl radicals, which are (/ r 9 # v p V V w • optionally substituted, whereby two coordinated hydrocarbon radicals can together form a single bivalent radical.

Among the oniusns that can be used in the present invention, those in accordance with one of the following general formulae are particularly suitable: 6 i * I ■ s {lit bis) % l.

% Csfl /f *) 4* j! in which; Z represents Ms P or Is 5 Y represents S, Os Se8 S=0 or C; Ri, 3 and Hh3 which can be the same or different represents a straight or branched alkyl radical with 1 to 16 carbon atoms and optionally substituted by one or more phenyl, hydroxyl, halogen. nitro, alkoxy or alkoxycarbonyl atoms or groups s the alkoxy groups having 1 to % carbon atoms, a straight or branched alkenyl radieal with 2 to 12 carbon atoms; an aryl radical having 6 to 10 carbon atoms, optionally substituted by one or more alkyl atoms or groups having 1 to « 1 5 carbon s alkoxy or alkoxycarbonyl atoms, the alkoxy radieal having 1 to 4 carbon atoms, or halogen, whereby two of said radicals to R^ can together form a straight or branched alkylene, alkenylene or alkadienylene radieal with 3 to 6 carbon atoms 1 2o B,, H,,, and RgS which can be the same or different represent: a straight or branched alkyl radical with 1 to k carbon atoms1 the radicals and Eg can together form an alkylene radieal with 3 to 6 carbon atoms? 7 the radicals R, and R or R. and 3. can together form an alkylene. © 7 o » alkenylene or alkadienylene radical containing k carbon atoms and constituting with the nitrogen atom a nitrogen-containing heterocycle. r represents a divalent radieal forming with 2 nitrogen atoms a 9 * 5 cycle having 4 to 6 atoms, which can have one or more nitrogens, sulphur and/or oxygan atoms, thereby said cycle can be substituted by one or more radicals such as H1.

R and represent identical or different aryl radicals.

Examples of oniusas in accordance Mith formula (II) are: -] 0 tetrarasthyl ammonium, triethylmethyl ammonium, tributylmethyl ammonium9 trimethylpropyl ammonium, tetraethyl ammonium, -] 5 tetrabutyl ammonium, dodecyltrimethyl ammonium.

Hie thy 11 r iocty 1 ammon iusa, heptyltributyl ammonium, tetrapropyl ammonium s 20 tetrapentyl ammonium, tetrahexyl ammonium, tetraheptyl ammonium. tetraoetyl ammonium. fcetradscyl ammonium. butyltripropyl ammonium, methyltributyl ammonium, pentyltributyl ammonium, saethyldiethylpropyl aaiaoniu®, ethyldimethylpropyl ammonium, 3Q tetradodecyl ammonium, tetraoctadecyl ammoniuia, hexadecyltrimethylammonium, benzyltrimethyl ammonium, benzyldimethylpropyl ammoniuss, on bensyldimethyloctyl ammonium. 8 bensyltributyl ammonium, bensyltriethyl asamoniuas. phenyltrimethyl aiamoniua, bensyId i me thy 1 te t rad ecy 1 ammonium, 5 be nsy 1 d ime thy 1 he xa.d scy 1 ammonium, dimethyldiphenyl afiasaonium, methyltriphenyl ammonium, butene-2-yltriethyl ammonium, M, N-dimethyl-tetramethylene ammonium, 10 N, M-diethyl-tetramethylane ammonium, tetramethyl phosphonium, tetrabutyl phosphonium, ethyltrimethyl phosphoniusa, fcr iae thyIpenty1 phosphoniusa, 15 octyltrimethyl phosphonium, dodeeyltrisaethyl phosphoniusa, triuethylphenyl phosphonium, die thyId ipheny1 phosphonium, dicyclohexyldimethyl phosphoniusa, 2 0 dimathyldiphenyl phosphonium, cyclohexy Itr imethy 1 phosphonium, triethyImethy1 phosphonium, methyltri(isopropyl) phosphonium, methyltri(n-propy1) phosphoniua, 25 methyltri(n~butyl) phosphonium. methyltri(methy 1-2 propyl) phosphoniusa, methyltrieyclohexyl phosphoniusa, methyltriphenyl phosphoniusa, methyltribenzyl phosphoniusa, 3 0 methyltri(methyl-™ phenyl) phosphonium, methyltrixylyl phosphoniusa, diethylmethylphenyl phosphonium, di benzy1msthy1phenyl phosphoniua, ethy ltr iphany 1 phosphoniusa, 3 5 tetraethyl phosphoniua, ethyltri(n-propyl) phosphonium, triethylpentyl phosphoniusa, utyltriphenyl phosphoniusa. bensyltriphenyl phosphoniusa. (0~phenyiethyl )dimethylphenyl phosphoniusa, tetraphenyl phosphoniua. triphenyl(methyl-4 phenyl) phosphoniusa. tetrakis (hydroxymethyl) phosphonium, tetraphenyl arsoniu®.

Among the oniums complying with formulas (III) and (III bis), reference can be made to; M-methyl pyridiniussj N-ethyl pyridinium, N-hexadecyl pyridinium, N-methyl pieeliniuias 1,2,fe-triphenyl-triasoliura.

Examples of organic oniums complying with formula (IV) are the cations trimethyl sulphonium. triethyl sulphonium, triphenyl sulphonium. trimethyl sulphoxonium, triphenyl earbeniusn, triethyl oxonlum.

As examples of oniums complying with formula (V), reference is mads to diphenyl iodoniua, 4,lP-dimethoxydiphenyl iodonium (or the compounds described in JACS 1958, 81, 3*2), 2-diphenyliodonium carboxylate.

J6 3005040.

Among the oniums, preference is given to tha use of oniums with a molecular weight between 150 and 400 and preferably between 200 and 300. Kmong thasa oniums ara more particularly suitable ammoniums, whose four alkyl groups are similar and have four to five carbon atoms.

The onium can be associated with various counterions, e.g. halides, hydroxyIs, hydrogen sulphates, trifluoromethanesulphonate and hexachloro-antimonates.

The onium can ba soluble in the reaction medium9 which would give a homogeneous medium reaction, or can be insoluble in the form of a solid and there would then be a reaction in a two-phase solid - liquid saadiua.

The onium can also be supported by a mineral or polymeric resin.

Among the "supported" oniums, reference is made to: tetrabutyl ammonium fluoride on silica gel9 tributvl ammonium chloride on the polymer e.g. marketed by FLUKA, methvltributyl phosphonium chloride linked with the polystyrene e«g. marketed by FLUKA, benzyltrimethyl ammonium bromide on polymer.

The reaction can then take place in a solid - liquid two-phase medium. The base used in the process of the invention is used for neutralising the hydraeid freed during the alkylation or allylation.

It can also be chosen from among mineral bases, such as sodium hydroxide or carbonates, or from among the organic bases such as sodium acetate, or the non-quaternisable tertiary amines.

Mon-quaternisable tertiary amines are all the tertiary amines having at least one branched alkyl chain and preferably at least two branched alkyl chains. Among these amines reference can be made in exemplified manner to diisopropylallyl amine, diisopropylethyl amine and triisopropyl amine. Preference is given from among these bases to the use of diisopropylethyl amine.

The onium can be supplied to the reaction medium in totally synthetized form, or can be prepared in situ. In the latter case use is made of a catalytic quantity of a quaternizable tertiary amine which, in the presence of alkyl or allyl halide, will give the desired ammonium. This amine is preferably triethyl amine.

The solvent constituting the reaction medium must solubilisa the aniline and the alkyl or allyl halide, whereby as the onium or base can be solid, they are not always solubilised by the reaction medium. However, it is preferable for them both to be soluble in the reaction medium. The solvents are chosen from among: aliphatic hydrocarbons such as 11 hexane cyclohexane heptane octane aromatic hydrocarbons such as toluene xylene halogenated hydrocarbons such as chloroform 1 o methylene chloride chlorobenzene carbontetrachloride dichloroethane alcohols such as 1 5 ' ethanol isopropanol butanol octanol aprotic polar solvents such as 2 0 .. MsM-dimethylformamide aeetonitrile M-methylpyrrolidone non-quaternisable tertiary amines such as diisopropylethylamine.

Among these solvents preference is given to the use of heptane or diisopropylethylamine.

For a better performance of the invention, preference is given to the use of an approximately stoichiometric quantity of alkyl or allyl halide with respect to the aniline. When the base is used for the in situ 30 formation of the onium, the alkyl or allyl halide quantity will exceed the stoichioraetry with respect to the aniline.

The onium is used in a catalytic quantity, i.e. in accordance with a molar ratio between 0.025 and 0.2 based on the aniline. The reaction temperature is advantageously between 0 and 150°C and preferably between 35 25 and 80°C. It will vary as a function of the reagents used, particularly 12 as a function of the pKa of the anilinium and the nature of the halide.

The reaction pressure is preferably atmospheric pressure. The duration of the reaction Kill vary between 1 and a few hours.

The present invention uill be described in greater detail hereinafter relative to examples, which in no way limit the scope of the invention. In the following examples, conversion rate (TT) is understood to mean: _ number of converted aniline moles ^ number of aniline moles introduced 1 0 aU9&SC.&£~B8l£S_Q£_BC6dU&£-fflEB£d % number of converted aniline moles Selectivity quantity of N-allyl or N-alkyl formed quantity of M-allvl or N-alkyl formed 4- quantity of diallyl or dialkyl formed 1 5 EXAMPLES 1 TO 12 AMD COMPARATIVE EXAMPLES 1 TO 12 Into a 30 ml reactor are introduced 0.5- g of m-trifluoroaiethyl-aniline (« mH), 0.3 g of allyl chloride (4 mM), 2 ml of solvent and 0.51 g of diisopropylethylamine (M mM), as well as optionally allyltriethyl-ammonium bromide (0.4 mM). The reaction mixture is heated for 210 minutes 20 at 80°C. At the end of the reaction and after cooling, 5 sal of N soda are added. The organie products are extracted by 3 * 10 ®1 of isopropyl-ether.

The collected organic phase is diluted to 50 ml in a graduated flask for gas chromatography dosing. 13 „ . " . ! _ . „ I .c : n-TFMA I N-allyl [ Diallyl SAL-! Cest -Oniusa. Solvent ■*•»_„» s_ • \«rv' U, u <9 0 © 0 n i 0 e»X oAi^CSo 'es " ° • ^ ' 2 82 S J 6.5 X ; 55 J : Heptifi .r 1.8 £ i : No : ' ° ?J.S I: £00 s Yas ° • ! 25 S ; 3M S ; Ff®e®$ 0 ffj 0 i • few I A " O P |^Q o o o ^ % ! (n u) • j ' U*t(>HVWW :K»«: 14 Test sOnium- Solvent ! Yes t% : No Yes £ £ 2 Mo OKI.

C!CH,CH,C3 ;m-TFMA I N-allyl.Diallyl 1 < : I8.J 18 % *W1 ® <&3 m 1 <5 v o u) f3 f*l O loo i e% 9* s 75 * RT •BAL- o oAMCs ■ Kffuts ?,3f J S! x: 8 X :W0 I: • an 5 » 0 <3w 'V 0 Yes £ I : Ho' sl-oetanol 41 X : 66.4 ISJ % : 100 X 33,8 X :!04 I ; g f „ . „ Con-Tests ■ Onium a e m-TFMA.M-allyl » Diallyl 8AL- » . ditions TT ; RT J RT AMCE ; C 13 : <§®C - 5 h ✓VIILCI J 0 s e i Q : § O 0 « . 0 (3 100 ; 0 D t 14 : 7S*C - 5 h e • ✓VPB^Cl D B 0 0 9 : Q : I s 0 « (!) 100 :: 0 IP 1 0 The onium halides do not have an ally1sting action under the operating conditions.

EXAMPLES 13 TO 17 Influence of the onium quantity The general operating procedure is adopted with the introduction of 0.6M g of sa-trifluoromethylanilina (4 mM)., 2 sal of heptane, 0.3 g of allyl chloride (U mM) and 0.5 g of diisopropylethylamine (4 mM), together with allyltriethylanraonius bromide quantities ranging between 0 and 4 mM, reaction being allowed to take place for M hours. 16 Test H KljBr m-TFHA TT N-allyl RT » Diallyl HT "BALANCE SELECT- j IVITY I £ IS » C 91 a '« 9 9 100 % 3 9 is loo i IP % : 0 0.1 ■A 39 i 90.2 I 3 J 1 100 x 90.2 % : 14 > 0.4 Wl 595 ,2 i 44 % 100 t 95.21 : IS 6.8 ill AS «->e»«e #<>)<■) 32 t 1I 101 X S2 x : 11 1.6 «M 70.4 % 63.11 61 103 1 94 s : w 4 rf 86.1 £ (■ll'fnaiO«»^«»»l <=>«>« »ob iao aa O % | ijl 100 % uuuonju' 0 • im i : 0 EXAMPLES 18 TO 30 Influence of the ammonium structure Tli® procedure of example 1 is repeated with the filling of 0.64 g of sn«trifluoromethylaniline (4 saH). 2 ml of heptane, 0.3 g of allyl chloride (4 mM), 0.5 g of diisopropylethylaraine (J! mM) and 0.4 mM of an ammonium. The reaction is carried out for 4 hours at 80°C. 17 1 0 1 5 test . . * » ja-TFMii N-allyJ. Diallyl BAL-! SELEC1 un iuin i" • oii o nm a «u o . TT „ HT . RT . AMCE, IVITY RT M.CIs : 53.3 : 10 s : 100 x * . o » Id O 0 19 : Kile .CI* :109.S : 17 a : 6G * I e 0 o o saaaaaw1 0 wwe^AASi «iea>a("»<>u eusiMaeeaii 0 QUO 0 0UO B :lfil :47.5x: 94.7 X 0 ^ ' 0 o • 2! ; EiJCl :1B 5.5 : 44-7 a: 96.7 a : —: • O Id G a 22 s Offle-GI :17U : 75 s : 83,3 X 23 i^V NELCI im,5 sis: 91.1 M B ■ #<*>(■» ELCI :227.B : 62 x : 92: 24 : Ma,CI :235.5 : 72.5 X : 8! $ IffflSfS ° IN % I 2 X S7 X luces : 100 X : 100 % • 0 • 0 3.3 % : 106 X : 96.7 X 4 X : 92 x : 36.4 x 8.9 I : 96 X : SLi % I % % : IS : Bi^NCI :277 : 70 a : S3 .8 X :90.5 X : S3.? X 9 _ ° -e o o 9 .3 x :98.3 X : ®ii '*) Tt : BOi^Cl :3!,2J : 72 a : 93 a 28 ^iTVc,,H,,Cl: 338 \ / IS J4 . 7 X S3 a 23 :»eH(gil.J.CI :4 I II j :0CHJH*,C,JL. :414 * CP 19 0 S7 s : 30 a ill : 94 0.8 a : 60 a : f? s • • o 0 • 0 ! .7 % : 30 X : 97 s luces : loo x : Ammoniums not soluble in the reaction medium. 18 EXAMPLES 31 TO 36 Influence of the amiaonlum chain length The procedure of example 1 is repeated aith the filling of 0.64 g of m-trifluoromethylaniline (4 mM), 2 sal of heptane, 0.3 g of allyl chloride (4 mM), 0.5 g of diisopropylethylaraine (4 mm) and 0.4 mM of an ammonium chloride. The reaction is performed for 4 hours at 80*C. 1 0 8 0 • 0 0 0 I iji in-TFH^ N- I,Diallyl° Bal-ISelect Test ! Onium ; "" ! TT I allyl ;* R? " Ianceoivity" IMII : S3.S : ios : WO s j Traces ..4 Wmp : 109.6 : 17 s : SS % : 1% ; 1 s : 9" % ..4 tEt XI 4 :155.5 : 44.7 s: %.1% i QS S : 96 J % Hh,ci iTfi 93 I J X :9B.3 I I 943 % : 33 : H([CeHl,)JCI :333.5 : SO i : 83.3 s : 3 U 4 . 44 s :92.S "8 1 • 1% : 'j.CI :389.S :52.5 s: s iJ * 4.7 1 :92* : 94.5 s ': 19 EXAMPLES 37 TO 49 Influence of the onium eounterion The operating procedure of example 1 is repeated with the filling of 0.6U g of m-trifluoromethylaniline (M mM),, 2 ml of heptane, 0.3 g of allyl chloride (H mM), 0.5 g of diisopropylethylamine (H mM) and 0.M mM of an onium salt. The reaction is performed for 4 hours at 80°C» «*> Cation : ^\/ 0 Test Counter-; ion :m~TFMA • TT °° J 0 N-allyl: • RT in® Diallyl RT Balance Select- ' ivity a i - 0 31 £1 : 50.3'5 » O 0 ® T-I..LJ ; 9 SU s : 6,5 * IMS SLi * : 1? e ym, e 39 : Bit 0 0 0 : 18 s : 7B.fi x : 3.S s B7.5 % %r% i 0 • Cation : /V P03 0 • Test = Counter- o .... ion m-TFMA : TT • : 0 i i ii > e S-allyl • R-T ■ Diallyl RT ° Bal-■ ance e Select- ■ ivity • : a 11 : a 0 r T S3 * : 1 S IS c : ioo i 0 0 0 SO X ! 0 40 : Br 0 0 75 S : 0 93.3 X SJ S n : 1001 93.3 t : Gatloa : St^Si * Test ; |il 0 0 n Counter- »m-ion ; -.tfma ! TT : ii-allyl RT Diallyl RT B&l->nee Select" ivitv |o 0 : 41 : O 0 Q CI : D S 44 % : #JX MX -U.JI l-l-.l _ 106 X .. _ -t T _ ^ SS»£ 1 0 f ' 4' : 0 "Jl*. 0 M 0 O Br : 0 e 0 «> 77,5 X : 0 fl % 5 % 6*4 X 100 X .. „ 33*5 % » Cation : Bu 4 Counter-^m-TFMA [ N-allyl ion I TT RT 44 ; C10„ 46 43 49 CI Br 44 <* 43; S4 X 76 I 67.3 % S3 *2 1 SB J % 31 X 33 I fix Diallyl Bal-°. Seleet-HT I ance] ivity Tuces loo x: too x Tiraccs '' ; 100 ». : 100 t a o _ j-L- _i _u-| — r;..-|0 :u j — t J,- ^ - ♦ j_ iLiiTn~..ij.n::r_ii_ii • » 0 0 0 0 4 J X : 100.5 x: 5*2 x 3»J % % J % 100 Six •3 x : 100 x : 94 J x I % 100 I : 93 X 21 EXAMPLES 50 TO 54 AMD COMPARATIVE EXAMPLE 50 Influence of the nature of the onium or the cation radicals The procedure of example 1 is repeated with the filling of 0.6M g of m-trifluorosethylanilina (& mM), 0.3 g of allylchloride (M mM), 2 ml of heptane9 0„51 g of diisopropylethylamina (4 mM) and O.1? mM of an onium. The reaction is performed for M hours at 80°C« s a est SO Si S4 Onium (aj3cstcis (1)^0 (lt'8)J SbClg m-TFMA• TT 43.6 X 50 m s Si* 4 % E3,7 £ M-allyl RT ISJ x 95,8 X 10 X 31,6 X J % N,N-diallyl RT .4 % w x 22 EXAMPLES 55 TO 58 Influerxe of supported oniums The procedure of example 1 Is repeated with the filling of 0. of m-trifluoromethylaniline (* mM), 0.3 g of allyl chloride (4 mM) 2 ml of heptane and 0.51 g of diisopropylethylasine (» snM) and a quantity of supported onium. The reaction is performed for « hour at 80°C. vac*- I rw,-;.,-, >-TFMA I N-allyll Diallyl .Bal- . Select iesw « unium «. ^ ..

» Ti , HT . Hi „ance . ivity OS .r^^fsa -p.! fa? : : : : M^o/ci: SI.7* : 015 X : 6* : 56* : 9WI SS ®H3L,-fSaj:i: rt.39 iSofO: ■9 % 32*4 I is | 99 % : 331 ! SI ©O .j1J,W » A&fftr! 82 2 79 % 7*6 t SS 9! : 311 58 Ton-sil >ica gel I 77 S I &9U5 S S3 rf r i : I :S9»7 *: 9L31 ^ is e polymer. 23 EXAMPLES 59 TO 65 Influence of the base The operating procedure of example 1 is repeated with the filling of O.o1? g of m-trifluoromethylaraina (» ®M), 0.6 g of allyl chloride 5 (8 mM), 2 ml of heptanes « mM of a base and optionally 0.« or 4 mM of allyl triethylasnraonium bromide. The reaction is performed for 3 hours at 75°C.

Test Onium Base Sm-TFMA . TT N-allyl HT M,M-diallyl RT C53 Mo A H-El n I 44 X IM X 59 Yes' (4 a£f) ""V'si —* i ; 91 % <3 0 54 % 40 C 60 Mo fi c 0 H « : 48 0 1 SO Yes (M «•;) ft eOM* : (fi.9 u 15J u U i s Yes-(4 iK) H c 0 H * 0 1 *.7 e 49.9 5A.2 A second series of tests was carried out for 150 minutes at 75°C with the filling of 0.6« g of ra-1rifluoromethy 1 ani 1 ines 0.3 g of allyl chloride mM). 2 ml of heptane, 5 mM of base end 0.^ mM of allyltriethylamsaonium bromide.

• Sol-Test . " vent Time/ °° ' m- »Base • temp. 8 * TFMA : : TT 0 0 N- allyl HT N,N- ° diallyl RT S2 : Mitflaoi® a o 75*-2U0: m : W.S 0 II TUB m 61 : Hcpbut - m : I/O.: 4S.6 9US 6,4 &l : Heptane 19 - m : : 50.5 6*2 SS 2 Heptane '-ZW:0HI : 8L3 34 S &2 ,« EXAMPLE 66 Test for the recycling of the supported ammonium First operation Into a reactor are introduced mH of m-TFMA, H mM of allyl chloride, 2 sal of diisopropylethylamina and a quantity of ® <@ CH2 " N Ma3 Br corresponding to O." ml8! of Bp"_ The reaction is performed at 80°C for 4 hours. At the end of the reaction the resin is eliminated by filtration. The filtrate is treated as in example 1.

Results m-TFMA TT : S 87 .5 cV 10 M-allyl RT = : 48 .5 a diallyl RT = = 4 fcf onium : s 58 .7 «! >9 selectivity ; s 92 «sf f Second operation The previously filtered resin is filled with 4 mM of m-TFMA, 4 jam of allylchloride and 2 ml of diisopropylethylamina. The reaction is performed at 80°C for 4 hours and is treated as hereinbefore.

Results m-TFMA TT * 80 C* & M-allyl RT s 73-1 % diallyl RT = 6.2 % balance = 87-5 % selectivity = 92 % EXAMPLES 67 TO 69 Influence of the reaction time The procedure of example 1 is repeated with the filling of 0.64 g of m-trifluororaethylaniline (4 mM), 0,3 g of allyl chloride (4 mM), 2 ml of heptanes 0.51 g of diisopropylethylajsine (4 ®M) and 0.4 mH ^of tetraethylammonium bromide. The reaction is carried out at 80°C for variable times. 26 0 0 Test Time in min. m-TFMA TT M- allyl HT Diallyl RT Balance Selectivity g 240 I 84 S S 9X 94.fi % S8.3X B 140 S3 X 89 X 6sJ % 9S„6 % SM1 S3 69 40 % iBii jipijcaiir c if.' S X M X < 95,1 X ■»««) JiWIPO 5S*S I 9 (*)Q CXO OHII■■■'■)<■> 0 EXAMPLES 70 TO 77 1 0 Influence of the alkylating agent a) Allyl halide The procedure of example 1 is repeated with the filling of 0«SM g of m-trifluoromsthylanilzne (4 uM), k mM of an allyl halide9 2 ml of heptane, 0>51 g of diisopropylethylamine (4 mM) and optionally 0.4 aM of allyltristhylamsaonium bromide. The reaction is continued for « hours at 80°C. 1 5 Test n 1 (es h/VP'° Yes a- N~ TFMA allyl Diallyl Select™ * TT HT IjajTi —' ■* 11 MMJi ' HT c ivity 7L 4 1 821 8 X 93.2 % : 83 X 83,,3 X *8 X 85.2 % T~-._ M-- -mi 1 -1 L„L„L.| I, m - m it i» m ti n -imiij8 In the absence of oniuas the conversion rate is 7„5% for allyl chloride and 81.2% for allyl bromide. 21 For 150 minutes at 25°C I Test » X ^ «9 a- " N_ * Di- "Select 0 13 Q TFMA'allyl I allyl 'ivity TT ' RT ' RT 12 : Ii/n^ i Yes :BS,1 x .a IS J x : U.6 x : SK.81 In the absence of onium, the conversion rate is 80%.

For 1 h at 250C 1 C lest : j®" s : 0i~ ".Select TFMA.allyl .allyl .ivity TT ° RT RT : : Yes U X : 84 X : 71 : 92 x : In the absence of onium, the conversion rate is 20%. b) Benzyl halide The procedure of example 1 is repeated with the filling 15 of 0.64 g of m-trifluoromethylaniline (M mM), MtaM of a benzyl halide, 2 ml of heptane, 0.51 g of diisopropylethylamine ('•mM) and optionally 0.4 mM of a allyltriethylammonium bromide. The reaction is carried at 80°C for 4 hours. lest : C,HJ I lr I m~ '.Benzyl! Di- I Select-, '3 JFMA ] HT ..benzyl, ivity . I TT - 1 HT I ; 15 Yes 85 X : 15 x : El In the absence of onium, the conversion rate is 85% for benzyl chloride and 90% for benzyl bromide. 28 At 25°C for 4 hours CI _ SI Ue« 0 ©* • ® * ® m- 13 N- ° Di« " « «» ^eSl' : ' TFHA "benzyl 'benzyl * e""c • TT ' W! '■ RT =iVlty 0 (<) 0 0 n ffl ® ; Yes : is-3 % ; PS : $ % In the absence of onium, the conversion rate is 1%. c) Isopropyl bromide The procedure of example 1 is repeated with the filling of 0-64 g of m-trifluoromethylaniline (4 mM), 4 mM of isopropyl bromide , 2 ml of heptane and 0.51 g of diisopropylethylamine (4 mM) together with optionally 0.4 mM of allyltriethylammonium bromide. The reaction is performed for 4 hours at 80°C. ; : * " * m » T 1 Di~ : « Test :/V{EM' " " , : iso~ »* Select . . , .L*m. .propyl . propyl : lvity _ ig 1 ii is K A i>i ©T ® ID m a 0 S u) sg.Ii ^ Sis i si : Mix In the absence of onium, there is no reaction. 29 EXAMPLES 78 TO 8M Influence of the aalne The procedure of example 1 is repeated with the filling of « mM of an amine, « mil of an allyl chloride, 2 sal of heptane. 4 mM of diisopropylethylasaine and 0.4 mM of allyltriethylaamonium bromide. The reaction is performed for 4 hours at 80°C„ The reaction was also carried out for shorter times. q B ri 0 l» 0 0 (fi a ® « IP w o o vi : m :4b: Yes ° !2.41 : 75.31 : 24.71 31

Claims (21)

1. A process for the n-inonoalkvlation or N-monoallylation of an aniline, comprising putting into contact an aniline and an alkylating 5 or allvlating agent in an organic solvent in a homogeneous liquid phase in the presence of a catalytic quantity of an onium and of a stoichiometric quantity of a non-quaternizable base.

2. A process according to Claim 1, in which the alkylating or 10 allvlating agent is an allyl halide.

3. A process according to Claim 2, in which the allylating agent is allyl chloride. 15

4. A process according to any one of Claims 1 to 3, in which the aniline has a pKa below «.5.

5. A process according to Claim 4, in which the aniline is a haloaniline, a perhaloalkylaniline, a perhaloalkoxyaniline, a 20 perhaloalkylthioaniline or a nitroaniline of Formula (1) 25 NH, (I) (R), in which R represents a halogen atom, a nitro group, or a group of 30 formula -ACn in which X represents a halogen atom. A a covalent bond or a sulphur or oxygen atom, and n is 0, 1 or 2. 35

6. A process according to any preceding claim? in which the onium is an ammonium, phosphonium, sulphoxoniurn, sulphonium, carbonium, arsenium or oxonium. 32

7. A process according to Claim 6, in which the onium has a molecular weight between 150 and 400.

8. A process according to Claim 7, in which the molecular weight is 5 between 200 and 300.

9. A process according to any one of Claims 6 to 8, in which the onium is a supported onium.

10.10. A process according to any preceding claim, in which the non-quaternizable base is a mineral or organic base.

11. A process according to Claim 10, in which the non-quaternizable base is sodium acetate or a tertiary amine carrying at least one 15 branched alkyl group.

12. A process according to Claim 11, in which the non-quaternizable base is a tertiary amine carrying at least two branched alkyl groups. 20

13. A process according to Claim 11, in which the base is diisopropylethylamine.

14. A process according to Claim 11, in which the base is diisopropylallylamine or triisopropylamine. 25

15. A process according to any preceding claim, in which the onium is formed within the reaction medium by the quaternization of a tertiary amine. 30

16. A process according to any preceding claim, in which the molar ratio of the alkylating or allvlating agent to the aniline is approximately 1:1. 35

17. A process according to any preceding claim, in which the molar ratio of the onium to the aniline is between 0.025:1 and 0.20:1. 33

18. A process according to any preceding claim, in which the solvent is an aromatic or aliphatic hydrocarbon solvent, an alcohol, an aprotic polar solvent or a non-quaternizable tertiary amine.

19.- A process according to Claim 18, in which the solvent is heptane or diisopropylethylamine.

20. A process according to Claim 1, substantially as hereinbefore described in any one of the Examples.

21. An N-alkylaniline or W-allylaniline when prepared by a process according to any one of Claims 1 to 20. F. R. KELLY & CO., AGENTS FOR THE APPLICANTS.