IE61521B1 - Process for the 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

Ths present invention relates alkylanilines and H-allylanilines. preparation of N-allylanilines and to a process for the preparation of N It more particularly relates to the more particularly to the preparation of N-monoallvlanilines.

The preparation of N-monoallylanilines 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 No. 2 305 '434. According to the latter, for the preparation of the desired herbicide, N-1-(3fcrifluoromethylphenyl)~3"ChIoro~«~chloromethyi-2-pvrrolidone, it is necessary to start with a trifluoromethylaniline one of whose hydrogen atoms is protected by an acetyl group prior to carrying out allvlation, 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 ffltonoallyltrifluoromethylaniline directly in a single stage, in place of the three stages described in French Patent No. 2 305 434, with good yields calculated on the basis of the starting substance used, viz. 3trifluoromethvlaniline, 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 No. 4 701 56O9 which describes a process for the allvlation of 3trifluoromethyianiline 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-trifluoromethvlaniline conversion rate and therefore to work in the presence of an allyl halide deficiency. The text states that the ratio of 3-trifluoromethylaniline to allyl halide is preferably approximately 2:1. The N-monoallylaniline yields calculated on the 3-trifluoromethylaniline introduced do not exceed 40$, which is inadequate for the process to be economically viable.

The allvlation reaction on anilines other than 3" trifluoromethylaniline are described in inter alia US Patent No. 2 28b b?8, which in particular describes the allvlation of 4<4 hydroxyaniline in a medium constituted by an alcohol and in the presence of a carbonate as the neutralizing agent.

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

US Patent Mo. 3 668 254 describes a process consisting of allylating 4-aminodiphenylamine with 2,3-dichloropropene in the presence of triethylamine. As in the two previous cases, the indicated vields do not exceed 40$. Moreover, the triethylamine 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 paraphenylenediamines 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 important. The selectivity, i.e. the monoalkvl product yield compared with the dialkyl derivatives, is not described.

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

The present invention provides a process for the n=monoalkylation or M-monoallylation of an aniline, comprising putting into contact an aniline and an alkylating or allylating 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.

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, arvl. aralkyl, haloaryl and/or nitroaryl substituents. Among the halides, preference is given to the use of chlorides and bromides, in particular chlorides, because they are less expensive. Ή 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 chloride, 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 aniliniusn ions having a pKa below «.5. In the case of reactive anilines, whose proton form has a pKa higher than A.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 1}.5, are represented by the following Formula (I): MH2 I c I (I) (R)n in which R represents a halogen atom, a nitro group, or a group of formula -ACn Xgn-I in wilich x 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, ehloroanilines, fluoroanilines, nitroanilines, trihalomethylanilines, fcrihalomethoxyanilines and trihalomethylthioanilines.

The oniums used in the process of the invention are more particularly those derived from nitrogen, phosphorus, arsenic, sulphur, selenium, oxygen, carbon or iodine. These oniums 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 alkyl, alkenyl, aryl, cycloalkvl or arylalkyl radicals, which are optionally substituted, whereby two coordinated hydrocarbon radicals can together form a single bivalent radical.

Among the oniums that can be used in the present invention, those in accordance with one particularly suitable; of the following general formulae are JS c (ail) - Κ! » S (Πϊ in which; Z represents M, P or As; ¥ represents S, 0, Se, S=0 or C; Ri, R^, R^ and Rh8 which can be the same or different represent: a straight or branched alkyl radical with 1 to 16 carbon atoms and optionally substituted by one or more phenyl, hydroxyls halogen. nitroj alkoxy or alkoxycarbonyl atoms or groups, the alkoxy groups having 1 to ί carbon atoms, a straight or branched alkenyl radical 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 « carbon , alkoxy or alkoxycarbonyl atoms, the alkoxy radical having to 4 carbon atomse or halogen, whereby two of said radicals R^ to R^ can together form a straight or branched alkylene, alkenylene or alkadienylene radical with 3 to 6 carbon atoms; 2q Rr, R, , R^, and Πθ, which can be the same or different represent: a straight or branched alkyl radical with 1 to J~ carbon atoms; the radicals R„ and Rn can together form an alkylene radical with I o to 6 carbon atoms; the radicals R, and R„ or R, and R„ can together form an alkylene. 0,00 alkenylene or alkadienylens radical containing H carbon atoms and constituting with the nitrogen atom a nitrogen-containing heterocycle.

R represents a divalent radical forming with 2 nitrogen atoms a 9 cycle having 4 to 6 atoms, which can have one or more nitrogen, sulphur and/or oxygen atoms, whereby said cycle can be substituted by one or aore radicals such as R,1. ΗΊθ and Rn represent identical or different aryl radicals.

Examples of oniums in accordance with formula (II) are: tetramethyl ammonium, triethylmethyl ammonium. tributylmethyl ammonium, triaethylpropyl ammonium. tetraethyl ammonium. tetrabutyl ammonium, dodecyltrimethyl ammonium. methyItr ioctyl ammonium, heptyltributyl ammonium, tetrapropyl ammonium, tetrapentyl ammonium, tetrahexyl ammonium, tetraheptyl ammonium, tetraoetyl ammonium. tetradeeyl ammonium, butyItripropyl ammonium, methyltributyl ammonium, pentyltributyl ammonium, methyldiethylpropyl ammonium, ethyldimethylpropyl ammonium, tetradodecyl ammonium, tetraoctadecyl ammonium, hexadecyltrimethylaramonium, benzyltrimethyl ammonium, benzyldimethyIpropyl ammonium, bensyldimethyloetyl ammonium, benayltributyl ammonium, benzyltriethyl ammonium, phenylfrimethyl ammonium, bensyldimefhyltetradecyl ammonium, benzyIdimefhylhexadecyl ammonium, dimethyIdiphenyl ammonium, methyItriphenyl ammonium, butene-2-yltriefhyl ammonium, N, H-dimethyl-tetramefchylene ammonium, N, M-diethyl-tetramethylsne ammonium, tetramethyl phosphonium, tetrabutyl phosphonium, ethyltrimethyl phosphonium, trimethyIpentyl phosphonium, octyltrimethyl phosphonium, dodeeyltrimethyl phosphonium, trimethylpheny1 phosphonium, diathyldiphenyl phosphonium, dieyclohexyldimethyl phosphonium, dimethyldiphenyl phosphonium, cyclohexyItrimethy1 phosphonium, triethylmethyl phosphonium, methyltri(isopropyl) phosphonium, methyltri(n-propyl) phosphonium, methyltri(n-butyl) phosphonium, methyltri(methyl-2 propyl) phosphonium, methyltricyclohexyl phosphonium, methyItriphenyl phosphonium, raethyltribenzyl phosphonium, methyltri(methyl-» phenyl) phosphonium, methyltrixylyl phosphonium, diethylmethylphenyl phosphonium, dibenzylmethylphenyl phosphonium, ethyItriphenyl phosphonium, tetraethyl phosphonium, ethyltri(n-propyl) phosphonium, triethylpenfyl phosphonium, hexadeeyltributyl phosphonium. ethyltriphenyl phosphorus, n-butyItri(n-propy1) phosphonium, butyltriphenyl phosphonium, benzyl triphenyl phosphonium, (6-phenylethyl )dimethylphenyl phosphonium, tetraphenyl phosphonium, triphenyl (methy 1-4 phenyl) phosphonium, tetrakis (hydroxymethyl) phosphonium, 0 tetraphenyl arsonium.

Among the oniums complying with formulas (III) and (III bis), reference can be made to; N-methy1 pyridinium, N-ethyl pyridinium, N-hexadeeyl pyridinium, N-methy1 pieelinius, 1,2,4-triphenyl-triasolius.

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

As examples of oniums complying with formula (V), reference is made to diphenyl iodonium, 4,4’-dimethoxydiphenyl iodonium (or the compounds described in JACS 1958, 81, 342), 2-diph@nyXiodonium carboxylate. 3θ J6 3005040.

Among the oniums, preference is given to the use of oniums with a molecular weight between 150 and 400 and preferably between 200 and 300.

Among these oniums are 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, hydroxyls, hydrogen sulphates, trifluoromethanesulphonate and hexachloroant imonates.

The onium can be soluble in fhe reaction medium, 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 medium.

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 gel, tributvl ammonium chloride on the polymer e.g. marketed by FLUKA, methvltributyl phosphonium chloride linked with the polystyrene e.g. marketed by FLUKA, bensyltrimethyl 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 hydracid 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 diisopropylailyl amine, diisopropylethyl amine and triisopropyl amine. Preference is given from among these bases to the use of diisopropyl ethyl amine.

The onium can be supplied to the reaction medium in totally synthetised form, or can be prepared in situ. In the latter case use is made of a catalytic quantity of a quaternisable 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 solubilise 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 hexane cyclohexane heptane octane aromatic hydrocarbons sueh as toluene xylene halogenated hydrocarbons such as chloroform o methylene chloride chlorobenzene carbontetrachloride dichloroethane alcohols such as ' ethanol isopropanol butanol octanol aprotic polar solvents such as .. ^sN-dimethylformamide acetonitrile ^-methylpvrrolidone 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 formation of the onium. the alkyl or allyl halide quantity will exceed the stoichiometry 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 and 80°C. It will vary as a function of the reagents used, particularly 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 will vary between 1 and a few hours.

The present invention will 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 * TT = ----------------------------------- % number of aniline moles introduced 0 RT - numbec_of„mglgg„sC„ScS0USi_£S^Sfi % number of converted aniline moles quantity of M-allyl or N-alkyl formed Selectivity * --------------quantity of M-allyl or i-alkyl formed e· quantity of diallyl or dialkyl formed EXAMPLES 1 TO 12 AND COMPARATIVE EXAMPLES 1 TO 12 Into a 30 ml reactor are introduced 0.64 g of m-trifluoromethylaniline (4 mM), 0.3 g of allyl chloride (4 mM), 2 ml of solvent and 0.51 g of diisopropylethylamine (4 mM), as well as optionally allyltriethylammonium bromide (0.4 mM). The reaction mixture is heated for 210 minutes at 80°C. At the end of the reaction and after cooling, 5 ml of N soda are added. The organic products are extracted by 3 x 10 ml of isopropylether.

The collected organic phase is diluted to 50 ml In a graduated flask for gas chromatography dosing.

Solvent STest IS a tn e sOnium: o Yes No Yes No Yes Cl : No ¢1 ο o oe L Η-allyl^ Diallvl ML-’ ω g β e x : S.5 x : SS ϊ: e o o ο ο e θ β Q D · 109 : iiibm jisopropyl Sether 67,5 X $a % US :97,2 12.5 X : IM X ?«« :160 2! 3.5 rv 5 9 A SS Ϊ :160 £ Test sOnium® Solvent : Yes , (wifCS «, CS : Mo Yes Mo Yes Yes C9 «I : Mo ί 10 : Mo ,: essays • 1-octanol Etfeiid §3 ies if’ ?19 F 'SJ .m-TFMA, HI N-allyl)Diallyl ,BAL-° RT RT »ANCS; c c io pi ία mo SI in 0 SI Q| U) lit X 0 0 0 0 O <4 :i0 0 (.1 33.S ® butanol I® 0 O O Β»ϋ»ϋ«ααίή i»^i*aw«.~> ; «ΙΕ^Ίμιμ IS» : iS« a ; ex :mox: O ol 0 0 O COMPARATIVE EXAMPLES 13 AND 14 Allylation by onium salts The procedure of example 1 is repeated with the filling of 0.64 g of trifluoromethylaniline (4 mM)s 2 ml of heptane and 4 mM of oniurn chloride. The reaction mixtures are heated for 5 hours at 75°G.

Tests Con- ditions ο a b *. m-TFMA* M-allyl Diallyl *lum ; tt : rt : rt C 13 75®C - 5 b 0 0 a /VI £LCI ; © s © : o 0 0 0 β . _ „ 0 C 75*C - 5 & • π Β β SO Cl XV e φ ; e - —.....?------------».......— 0 The onium halides do not have an allylating action under the operating conditions.

EXAMPLES 13 TO 17 Influence of the onium quantity The general operating procedure is adopted with the introduction of 0.64 g of m-trifluoromethylaniline (4 mM)., 2 ml of heptane, 0.3 g of allyl chloride (4 mM) and 0.5 g of diisopropylethylamine (4 mM), together with allyltriethylammonium bromide quantities ranging between 0 and 4 mM, reaction being allowed to take place for 4 hours. bl a Jm-TFMA; S-allyl": Diallyl ^BAL- SELECT; tt : rt : rt :ance : ivity " e j.-f'.2mi~ir.:C * on· ιΐ ι_ι _ ~ ϋιιιυιιιαι*111 _____ _ g _ ρ .-·ιιτ···ιγ.ι.τ— mr — *’* g β is u a a @X (.1 a a · a a s as e a u a M X ; 100 S : 95.2 S s u a a ο π ® Θ x ; WZ ϊ : 82 s «05 s i 2S 1.6 «W : : 100 X ; lira X ; ο·τ««β«·^ββ«ι®ιϊ»»ί O 0 0 EXAMPLES 18 TO 30 Influence of the ammonium structure The procedure of example 1 is repeated with the filling of 0.64 g of m-trifluoromethylaniline (4 mM), 2 ml of heptane, 0,3 g of allyl chloride (4 mM), 0.5 g of diisopropylethylamine (4 mM) and 0.4 mM of an ammonium. The reaction is carried out for 4 hours at 80eC.

I : Test : Oniua ° P.B : 28 : KSkCI* .: 53.3 Hi] Bills :10S„8 U/y«^cis ELBC1 jn-TFMA H-allyl Diallyf BAL-'. SELECl RT IOS S R" ANCE. IVITY :1654 :47.5 5: 94.7 S I »ιβΛββ®ββΟ (s><3e64«a»*4U 0 :4445: 86.75 Tranees : 160 S : 0 o e 0 2Ϊ : 98 2 : 87 5 e o PI C hecii : 160 5 : 106 5 • 0 3.3 5 : 106 5 : 96.7 5 : 22 : fcCI :1714 0 Ammoniums not soluble in the reaction medium EXAMPLES 31 TO 36 Influence of the ammonium chain length The procedure of example 1 is repeated with the filling of 0.64 g of sa-trif luoromethylanil ine (4 mM), 2 sal of heptane, 0.3 g of allyl chloride (4 mM), 0.5 g of diisopropylethvlamine (4 mm) and 0.4 nM of an ammonium chloride. The reaction is performed for 4 hours at 80’C. ; 31 3’ β 1 1 0 . 8 Si jn-TFKX β N~ 0} σ o Diallyl Bal- ^Select- Onium 1 • I all 0 • TT a α λ e 0 0 allyl ° 0 RT • ance °i 9 Q vitv ί ( : BH Cl •j : 53.5 • <3fl W a 0 liSJ <4 Q • a wo £ ·, TtfICM ; 109 £ : ICO 3 ; > ► duxbh) e u^iyjooaia * a DO · a ο o o » nmnmnnn ηπηηηιηπιπππΜ χ i ; Kite xi :109.1 • fl«J «ρ · o SI «0 β SB s : *5 » : 98 x : 97 s : 1 0 • 9 9 0 0 ’ g»jpajjoc»a»»«»aco > o e β a o e o n 1 : El XI 4 :115.5 : «.7 £: O 0 95.7 ϊ : 71 * ft? t3o aa 44) : IOS s : Cl Π 35.7 3 :1 ββ®βι<·«Λ*·«Λ®«ΐ! 1 e 0 • 0 0 · a φ β a ; ί-Βιι,ϋ :277 : 70s : 93 S : 5 J £ :98.3 £ ; 91.5 3 ; : 3*3 β · 0 * «·»· .· 33 : u · ί H«CSH13J4C1 :389.3 : 52.5 $: ΗΟ,,ΕΠ :333.5 : SO ί : j lii 83.3 £ :92.5 £ : 95.3 3 a 4.7 3 : 92 3 .· 84.5 £ EXAMPLES 3? TO 49 Influence of the onium counterion The operating procedure of example 1 is repeated with the filling of 0.64 g of m-trifluoromethylaniline (4 mM), 2 ml of heptane, 0.3 g of allyl chloride (4 mM), 0.5 g of diisopropylethylamine (4 mM) and 0.4 ®M of an onium salt. The reaction Is performed for 4 hours at 80°C.

Test ’ _ :m □ Counter-. -TFMA N-allyl » Diallyl : Bal- Select- • . o • « ion ; TT . RT J ’ RT · ance 0 . .. 0 ivifcy • e 0 • · ; 0 o ; 37 : £! : 0 . . ... β . SBj'X 9U X ... . . . ; 8.9 X : 109 35 0 * · SU X G a6 * 0 O ti 0 0 ; 33 : Sf : ο n 0 _ u ?e s 78.6 X ; XS x :87.5 X an 0 • * Cation : /V J Test ·’ ’m-TFMA .Counter-.· ± · . ion · Λ Si-allyl • RT " Diallyl - Bal' RT anee a o Selectivity · 0 a 0 O " S i » n 0 0 : 39 : 0 : β . β S3 1! a s Ξ Ζ X ; 109 x ® o O 0 38 X • β ; 4Q θ w 0 ; Sr ; 75 X J 93.3 S 1!» M : U ϊ s IM x 9X3 X 0 e < 9 Φ ... ( _, 9 9 ...... u 0 ............ a • ,: T®sfc : Counter- . ion σ u :nKTFMA - : XT ; N-allyl RT Diallyl RT A o • Bal-: Vance: Select- ivity 0 0 β » 41 0 (Ml : Cl O 0 0 B : 44 i : 96,7 S 3JX a e In ft : IOS S : 65*6 5 0 0 ο 0 η II n e 0 } ο ω β . ..0 n 0 M α o o a 0 s> O fl 0 n a : 42 : Sr : 77,5 5 : 33,.5 5 S«4 5 : 200 5 : 93 J 5 :0 o e 0 a 1,1 » . . 0 fl 0 ui D Cation : Bu^S Test' Counter- Lm-TFMA N-allyl ion TT '. RT OH ‘.iii Diallyl RT Traces 3al-°. Select-", ance’. ivity : ICO 5 : IM % <3 0 o no X Tracts ’ : ICO x : 4ti : 54 5 : 95,,2 X ; 4J S :200^ K SU X : EXAMPLES 50 TO 5¾ 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 0-64 g of m-trifXuoromethylaniline (4 mM), 0.3 g of allylchloride (4 mM), 2 al of heptane, 0,,51 g of diisopropy lethy lamine (4 mM) and 0.4 mM of an onium The reaction is performed for 4 hours at 80°C. 0 Onium ° m-TFMA· M-allyl «Μ',Μ-d ially 1 0 σ ο 0 0 TT RT . RT 0 0 υ 0 SO : • (@J3CSfcCI5 : as £ : 854 x 0 ί 9,3 X .. ·........ 1 0 0 β 0 • lE| Wil B 0 (Bi/Cl j ______] ,-., c- -, -J-JJ 0 50 5 : 95,8 x fl 0 : M x n * 4 0 0 0 52 : 0 ‘hyo ; as s 0 BO X σ 0 34 x β _ 0 β 0 0 0 0 55 : 0 61,4 % 0 : 9SL.6 X 0 0 2 5,4 X ϋ g 0 . 0 • 0 9 0 0 54 : 0 (MJJ! SbClg : S3 J £ 0 : 784 x 0 β J ® W • ro 1 aj • EXAMPLES 55 TO 58 Influence of supported oniums The procedure of example 1 Is repeated with the filling of 0.64 g of m-trifluoromefhylaniline (4 mM), 0.3 g of allyl chloride (4 mM), 2 ml of heptane and 0.51 g of diisopropylethylamine (4 mi-1) and a quantify of supported onium. The reaction is performed for 4 hours at 80°C.

Test ; Onium m-TFMA * M-allyl^ Diallvl ’Bal- ’ Select £ % JS ®>-ω -MS«XHs : :®,« «Η Of CB: 5U X : SU x ΟΚοΑϊ: US : 92.4ί SS SSS s S B-CJ.03J : : :OJ ir: 1,8 X X : 58 :S«JFon.sii: . : : : i-ica gel : Π X : 89b5 X : ϊ®® X s :0,83 «3 ?: : is a polymer.

EXAMPLES 59 TO 65 Influence of the base The operating procedure of example 1 is repeated with of 0.64 g of m-trifluoromethylamina (4 mM), 0.6 g of allyl (8 mM), 2 sl of heptane, 4 mli of a base and optionally 0.4 allyl triethylawmonium bromide. The reaction is performed at 75°C. the filling chloride or 4 mM of for 3 hours Q Ο Ο ύ # Test 9 11 On ium .. .. Base m-TEMA : .....TT.--J. N-allyi:N _ bt . .:..... N-diallvl. RT j 0) β Λ a a a 0 a a : css No . Kt, Ms : IM s : a 0 Ύ a « a a n 0 Λ 0 0 a a a ; 59 Yes ΚΙ 9j S : 54 S : 4,0 a a a a l· "ϊ 0 : a P σ a c® □ a No fi « 0 8 « u 4,8 : a 0 0 : Q 0 a a a 0 Φ : SO Ies ft eOH« 66,9 : a 75*4 : u a 0 (0fl4 *ii) 0 a a e Yes- fl e 0 S3 « 9 : 49,9 : 50,2 a (4 1«) oh.

A second series of tests was carried out for 150 minutes at 75°C with the filling of 0.64 g of ra-trifluoromethylaniline, 0.3 g of allyl chloride (4 aM). 2 al of heptane, 5 mM of base and 0.4 mM of allyltriethylammonium bromide.

Test • Sol' vent Time/ ’ «Base temp. ’ ’ SB" • TFMA N- allyl N,N- diallyl « a u . . * TT RT RT 52 0 ; Hexane 0 75»-2b30: MW 0 : ns 7U, W 10 S3 : SkpbM 75·-2630: K,CO, : ,419,6 81,6 M S4] ’ Heptane1 73* - 2139 : : 50.5 76,6 6,2 65 •4 TS'-O.ySKs 88,3 MS 6,2 EXAMPLE 66 Test for the recycling of the supported ammonium First operation Into a reactor are introduced 4 mM of m-TFMA, 4 mM of allyl chloride, 2 ml of diisopropylethylamine and a quantity of <^--ch2- N Me3 Br corresponding to 0.4 mM of Br.

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 ' ρψ Α ώ = 87.5 £^ M-allyl RT = 48.5 & diallyl RT „ It fcf «► ¢9 onium = 58.7 cf selecti' vitv s 92 % 1o Second operation The previously filtered resin is filled with 4 mM of m-TFMA, ma of allylchloride and 2 ml of diisopropylethvlamine. The reaction is performed at 8O°C for 4 hours and is treated as hereinbefore.

Results m-TFMA TT s 80 &/ & M-allyl RT a 73.1 & & diallyl RT = 6.2 balance s 87.5 ef /9 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), ml of heptane, 0.51 g of diisopropylethvlamine (4 mM) and 0.4 mM of tetraethylammonium bromide. The reaction is carried out at 80°C for variable times. 2ό Test Time in min. m-TFMA TT allyl RT Diallyl RT Bal- ance Select- ivity 67 24® 17 X 04J X 91 9M S «0,3 X SB M® 65 X 8SX Mi 96 „6 X 93.0 0 6® a IB es s 3.SS 95.7 X SB J X 0 ...... 0 EXAMPLES 70 TO 77 Influence of the alkylating agent a) Allyl halide The procedure of example 1 is repeated with the filling of 0.64 g of m-trifluoromethylaniline (4 mM), 4 mM of an allyl halide, 2 ml of heptane, 0.51 g of diisopropylethylamine (4 mM) and optionally 0.4 mM of allyltriethylammonium bromide. The reaction is continued for 4 hours at 80°C,, Test sa- TFMA TT M- allyl RT Diallyl ' RT * Select- ivity 7® .. . Yes 1U X @2 X h 93.2 X ll Yes 83 X 83.,3 X 10,8 X 85.2 X .

In the absence of onium, the conversion rate is 7.5% for allyl chloride and 81.2% for allyl bromide.

For 150 minutes at 25°C " /4 a/k. ® N- Di~ Select. . . 0 TFMA „,allyl .allyl .ivity TT " RT ’ RT S : ir/^: Yes :85,7 ϊ : Ο ϊ : Ο x : 66,8 x : no pen ρ u WiOOgiPW®0 ΟΜΟίβ'ΒΒίιι,ιι.ίΜΙβΓΗώ W ίβοη«»<»«*® 0 wciVi»~lt~ini)r In the absence of onium» the conversion rate is 80%.

For 1 h at 25°C 1C Test : SZ^^BELBr : : W" : Di~ ".Select. . 3 .TFMA.allyl .allyl .ivity a p go a * α * - . . TT . RT „ RT : Yes In the absence of onium, the conversion rate is 20%. b) Benzyl halide The procedure of example 1 is repeated with the filling of 0.64 g of m'-trifluoromethylaniline (4 mM), 4mM of a benzyl halide, 2 ml of heptane, 0.51 g of diisopropylethylamine (4mM) and optionally 0.4 mM of a allyltriethylammonium bromide. The reaction is carried at 80°C for 4 hours. m- Benzyl Di- ‘ SelectRT · benzyl, ivity * * 0 . RT . rest £ 15 ? „ «< .TFMA Yes : 35 X : 85 x : ul |B 0 » 0 ..-η-'----.- 0 -·-·.--- β » 0 « « β In the absence of onium, the conversion rate is 85% for benzyl chloride and 90% for benzyl bromide.

At 25°C for 4 hours ’ TFMA "bensyl ‘benzyl TT RT ’ RT σ w m o . Select- . •ivity · In the absence of onium, the conversion rate is 1%. e) Isopropyl bromide The procedure of example 1 is repeated with the filling of 0.64 g of m-trifluoromefchylaniline (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.

Test aTFMA.

TT ‘ : s.n Di· Iso ;Pr^yl -proiyl RT RT LSO: Select· s ivity In the absence of onium, there is no reaction.

EXAMPLES 78 TO 84 Influence of the sains The procedure of example 1 is repeated with the filling of 4 mM of an amine, 4 mM of an allyl chloride, 2 ml of heptane. 4 oM of diisopropylethylamine and 0.4 mM of allyltriethylaamoniua bromide. The reaction is performed for 4 hours at 80°C.

Test » 0 X- · aniline py 0 0 .... ♦ - ^/HEyr X- aniline ..TT................ N- allyl HI : Di- : allyl LK ε 78 D HO, 0 0 : 1 Mo 0 £ 0 78 »2 0 0 Yes 3 43,J ϊ SOO X 0 : 0 x C 79 © : 28 Mo 7.5 £ ......... . . . wo χ : 0 X 79 e Yes 77' £ 82 X : 6.5 X 0 ε go Cl 0 0 ; Λ IS Mo 61.5 X 35 X : 5x ss «j 0 0 0 e Yes ... .ss 8i x 0 : ΙΠ • € 81 π o 0 : 4.63 Mo 50.3 S 81-2 X : as X : 0 0 «... ..0 @1 0 0 0 Yes 92,4 X 75 J X : 24.7 X : C 82 Ofo : 5 34 No 87 X 3 70 X σ θ : 30 s O Q 82 V KM, 0 s Yes SO X 60 X 0 0 : 40 χ : The reaction was also carried out for shorter times.

Test ’ Aniline: Temp.·

Claims (21)

1. A process for the n-monoalkvlation or N-monoallylation of an aniline, comprising putting into contact an aniline and an alkylating 5 or allylating 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 allylating 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 4.5.

5. A process according to Claim 4, in which the aniline is a haloaniline, a perhaloalkylaniline, a perhaloalkoxyaniline, a 20 perhaloalkyl thioanil ine or a nitroaniline of Formula (1) mh 2 (R)„ in which R represents a halogen atom, a nitro group, or a group of 30 formula -AC n in which X represents a halogen atom. A a covalent bond or a sulphur or oxygen atom, and n is 0, 1 or 2.

6. A process according to any preceding claim,, in which the onium is an ammonium, phosphonium, sulphoxonium, sulphonium, carbonium, arsenium 35 or oxonium. rf

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 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. A process according to any preceding claim, in which the nonquaternizable 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 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.

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 tri isopropylamine.

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.

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

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. I ·

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. 5

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.