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Alkyl halides, alkylation with

Jouannetaud and co-workers229 have explored electrophilic trifluoromethylation under superacidic conditions of aniline derivatives229 and /V-heterocycles. Methyl-substituted anilines and substituted acetanilides [Eq. (5.85)] react with the CC13+ cation generated from CC14 in HF-SbF5 followed by fluorination to yield the corresponding trifluoromethyl derivatives. Under similar conditions, indolines are transformed to the 6-triluoromethyl derivatives, whereas substituted indoles yield 5-triluoromethyl derivatives.230 [Pg.566]

Boron tris(triflate) has also been tested in the adamantylation of benzene and toluene with 1-haloadamantanes [Eq. (5.87)] and2-haloadamantanes.232B(OTf)3 is a highly active catalyst to promote the transformation in very short time under mild conditions to yield isomeric aryladamantanes and adamantane byproduct (Table 5.15). Of the isomeric 1-tolyladamantanes, 1-meto-tolyladamantane predominates, whereas the para isomer is the main product of the 2-tolyladamantanes. The ortho isomers were [Pg.567]

Alkyl halide Time (min) Yield (%) Isomer Distribution (%)  [Pg.570]

Reaction conditions 10mol% catalyst, 25° C. aIn dichloromethane as solvent. [Pg.570]

Reaction conditions toluene/l-haloadamantane/B(OTf)3 molar ratio — 1 1 0.25, dichloromethane, room temperature. [Pg.570]

Protic acids are usually used as catalysts for alkylation with olefins rather than with alkyl halides. Anhydrous hydrogen chloride, in the absence of metal halides, is a catalyst for the alkylation of benzene with terf-butyl chloride only at elevated temperatures96 where an equilibrium with isobutylene may exist. Other alkyl halides and cyclohexene were also reacted with benzene and toluene using this catalyst. [Pg.232]

Acidic mixed oxides, including alumina and silica, as well as natural clays, and natural or synthetic aluminosilicates, are sufficiently (although mildly) hydrated to be effective as solid protic acids for the alkylation of aromatic hydrocarbons with olefins. The most studied of these catalysts are zeolites that are used in industrial [Pg.232]

Frequently substantially more than catalytic amounts of a Lewis acid metal halide are required to effect Friedel-Crafts alkylation. This is due partly to complex formation between the metal halide and the reagents or products, especially if they contain oxygen or other donor atoms. Another reason is the formation of red oils. Red oils consist of protonated (alkylated) aromatics (i.e., arenium ions) containing metal halides in the counterions or complexed with olefin oligomers. This considerable drawback, however, can be eliminated when using solid acids such as clays,97 98 zeolites (H-ZSM-5),99,100 acidic cation-exchange resins, and perfluoro-alkanesulfonic acid resins (Nafion-H).101-104 [Pg.232]

More details about Friedel-Crafts catalysts can be found in the review literature 79 82 86 105-107 [Pg.232]

Friedel and Crafts apparently assumed that the alkyl group in the alkylated product had the same structure as that of the alkyl halide. However, it is seldom [Pg.232]


The higher homologues of propyne, e.g. 1-decyne, can be obtained in a similar way. Starting from 1-butyne and its homologues, alkylation with alkyl halides leads to 1-alkynes with a branched substituent. [Pg.49]

Lithium dialkylamides are excellent bases for making ketone enolates as well Ketone enolates generated m this way can be alkylated with alkyl halides or as illus trated m the following equation treated with an aldehyde or a ketone... [Pg.904]

Many Jluonnaled aromatic compounds are alkylated with alkyl halides under Fnedel-Crafis conditions For example, the intramolecular alkylation of 3-fluoro-At-(chloroaee-tyl)amhne with alununum chlonde gives 6-fluorooxmdole [5] (equation 5) Similarly, 3 -chloro-4-fluoropropiophenone affords 5-fluoromdanone [6] (equation 6)... [Pg.408]

Alkylation takes an entirely unexceptional course. The nitrogen atom of the 7r-excessive five-membered ring of the indole nucleus resists alkylation, md-A-Alkylation with alkyl halides can be achieved only after forcing deprotonation with, for example, sodamide, potassium amide or ethoxide. In this manner... [Pg.148]

Another type of Grignard reaction is the alkylation with alkyl halides. Upon treatment of a Grignard reagent RMgX with an alkyl halide 5, a Wwrtz-like coupling reaction takes place. [Pg.147]

Alpha hydrogen atoms of carbonyl compounds are weakly acidic and can be removed by strong bases, such as lithium diisopropylamide (LDA), to yield nucleophilic enolate ions. The most important reaction of enolate ions is their Sn2 alkylation with alkyl halides. The malonic ester synthesis converts an alkyl halide into a carboxylic acid with the addition of two carbon atoms. Similarly, the acetoacetic ester synthesis converts an alkyl halide into a methyl ketone. In addition, many carbonyl compounds, including ketones, esters, and nitriles, can be directly alkylated by treatment with LDA and an alkyl halide. [Pg.866]

Alkylation with alkyl halides in organic solvents other than nitromethane The first reliable kinetic study of alkylation appears to have been that of... [Pg.139]

Alkylation With Alkyl Halides The Williamson Reaction... [Pg.477]

Ferrocene behaves in many respects like an aromatic electron-rich organic compound which is activated toward electrophilic reactions.In Friedel-Crafts type acylation of aromatic compounds with acyl halides, ferrocene is lO times more reactive than benzene and gives yields over 80%. However, ferrocene is different from benzene in respect to reactivity and yields in the Friedel-Crafts alkylation with alkyl halides or olefins. The yields of ferrocene alkylation are often very low. and the separations of the polysubstituted byproducts are tedious. [Pg.155]

The carbon-carbon bond forming reactions of nitro compounds by alkylation with alkyl halides or acylation with acyl halides have been encountered with difficulties of the competing O-alkylation or O-acylation, respectively. In this chapter, the recent developments of C-alkylations and C-acylations of nitro compounds are summarized. The O-alkylated compounds undergo cycloaddition reactions, which are discussed in the chapter of cycloaddition (Chapter 8). [Pg.126]

Dithio-l-nitroalkenes are prepared by the reaction of nitromethane with CS2 and KOH followed by alkylation with alkyl halides (Eq. 10.84).43 They are important reagents for synthesis... [Pg.356]

The anionic intermediates generated by the cathodic reduction of CHT and some of its derivatives such as 1-MeO- and 3-MeO-CHTs are regioselectively alkylated with alkyl halides to give 6-alkyl-l,3-cycloheptadiene and l-MeO-6-alkyl-l,3-cycloheptadiene as the main products, respectively21. [Pg.770]

The sodium salts of dialkyl malonates were reacted with isothiocyanates (346) in diethyl ether or in THF at -10°C-0°C. The products were then alkylated with alkyl halides to give mixtures of tautomeric (alkylthio)ami-... [Pg.96]

AK5-Hydroxy-6-methyl-2-pyridyl)aminomethylenemalonate (1492, R = H) was alkylated with alkyl halides in DMF in the presence of potassium carbonate at 90-110°C for 1 hr to give the 5-alkoxy derivatives (1492, R = Et, /Pr, CH2Ph, CH2OMe) [81JAP(K)131583]. [Pg.308]

Because of their lower hydrophilicity and higher stability to oxidation, O-protected hydroxylamines are more convenient substrates for alkylation than hydroxylamine itself. Commercially available 0-benzylhydroxylamine was successfully alkylated with alkyl halides and alkyl sulfonates ". ... [Pg.121]

Hydrazinothiatriazole (133) reacts rapidly with ketones and aldehydes to give thermally relatively stable hydrazones (134) in good yields ( 80%) <85ZC136, 87JPR409). Compounds (134) are alkylated with alkyl halides exclusively at the hydrazino functionality (rather than at N(4)) to give (135) (Scheme 27). [Pg.718]

In addition to alkylation with alkyl halides, electrophilic amination has been achieved with di-(/< /r-butyl) azodi-carboxylate <2004HCA1016>, and reactions with aldehydes have generated alcohol derivatives <1999JOC8668, 2003TL671>. Dialkylation at the 5-position has also been achieved <1998TA3881>. [Pg.180]

Displacement of a phenylthio group by lithium using LiDBB at —78°C was found to be effective for the preparation of a /ra r-4-lithio-l,3-dioxane configurationally stable at that temperature. Reaction with alkyl halides with retention of the configuration afforded the /ra r-dioxanes with 99 1 selectivity. Equilibration of the trans-configurated 4-lithio-l,3-dioxane to the thermodynamically more stable r-derivative was achieved upon warming the solution to —20 °C. The transjcis-ratio was approximately 1 5. This ratio was also found after alkylation with alkyl halides (Scheme 60) <1999JOC6849>. [Pg.799]

The chemistry of chiral 1,3-dithiane 1-oxides, in particular their use as chiral auxiliaries, has been reviewed <19980PP145>. Some further developments in this field are the stereoselective a-alkylation with alkyl halides <1997T13149> or a-hydrazination with di-fert-butyl azodicarboxylate (DBAD) <2000T9683>. The carbonyl group of 2-acyl-l,3-dithiane 1-oxides was also used as an electrophile (Scheme 82). Interestingly, acyclic enolates react with these substrates to give a 95 5 mixture of anti- and ry -adduct, whereas cyclic enolates produce a mixture of anti- and ry -adduct in 8 92 ratio <2000JOC6027>. [Pg.813]

Alkylation with Alkyl Halides. Scope and Limitations... [Pg.39]

In view of the limited stability of the "carbenoid" LiCsCCP Cl, functionalization reactions have to be carried out a temperatures Lhat are as low as possible. Silylations of meiallated acetylenes are usually rather slow in Et20 at temperatures below -20 C. A small amount of HMPT appears to cause a considerable enhancement of the rates of silylatton with tri-methylchlorosilane. It is not known whether this effect is only due 10 the typical properties of HMPT as a dipolar aprotic solvent (also shown in alkylation with alkyl halides) or whether it is a result of active participation of this solvent in the reaction as depicted in the following equations ... [Pg.121]

S )-3-Hydroxy-4-butanolide (1), which is readily available from (—)-(S)-malic acid, can be converted into the dianion and the latter alkylated with alkyl halides or mesylates with moderate yields but with high diastereoselectivity (d.r. >98 2)39. [Pg.771]

Pd- or Ni-catalyzed alkylation with alkyl halides and related... [Pg.459]

Di- and polyalkylation can occur during alkylation with alkyl halides since the product alkylbenzenes are more reactive, although the reactivity difference with reactive alkylation systems is small. Toluene, for example, reacts only about 2-5 times faster in some benzylations than benzene.118,119 As alkylbenzenes, however, dissolve preferentially in the catalyst containing layer, heterogeneous systems can cause enhanced polysubstitution. The use of appropriate solvents and reaction conditions as well as of an excess of aromatics allow the preparation of monoalkyl-ated products in high yields. [Pg.233]


See other pages where Alkyl halides, alkylation with is mentioned: [Pg.69]    [Pg.104]    [Pg.126]    [Pg.708]    [Pg.263]    [Pg.587]    [Pg.21]    [Pg.270]    [Pg.516]    [Pg.1011]    [Pg.195]    [Pg.370]    [Pg.57]    [Pg.647]    [Pg.655]    [Pg.694]    [Pg.526]    [Pg.528]    [Pg.536]    [Pg.232]   
See also in sourсe #XX -- [ Pg.408 ]

See also in sourсe #XX -- [ Pg.210 ]

See also in sourсe #XX -- [ Pg.408 ]

See also in sourсe #XX -- [ Pg.408 ]

See also in sourсe #XX -- [ Pg.75 , Pg.78 , Pg.81 , Pg.212 ]

See also in sourсe #XX -- [ Pg.3 , Pg.299 ]

See also in sourсe #XX -- [ Pg.299 ]

See also in sourсe #XX -- [ Pg.3 , Pg.299 ]




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2.4- Diketones, alkylation at the 1position with alkyl halides

Acetoacetates reacting with alkyl halides

Acetylide anions reactions with alkyl halides

Active methylene compounds with alkyl halides

Alcohol conversion to alkyl halides with

Alcohols reaction with alkyl halides

Alkenes reaction with alkyl halides

Alkenes reductive coupling with alkyl halides

Alkoxide ions with alkyl halides

Alkyl and Acyl Halides with the Sodio-derivatives of Ethyl Cyanoacetate

Alkyl groups alcohol reactions with hydrogen halides

Alkyl halide malonic ester synthesis with

Alkyl halide reaction with Gilman reagents

Alkyl halide reaction with carboxylate ions

Alkyl halide reaction with phthalimide ion

Alkyl halide reaction with thiourea

Alkyl halide reaction with tributyltin hydride

Alkyl halide with pyrimidines

Alkyl halide, reduction with organotin

Alkyl halide, reduction with organotin hydride

Alkyl halides Compounds with halogen

Alkyl halides Compounds with halogen Table

Alkyl halides Compounds with halogen ammonia

Alkyl halides Compounds with halogen elimination reaction

Alkyl halides Compounds with halogen from alcohols

Alkyl halides Compounds with halogen nucleophilic

Alkyl halides alcohol reactions with hydrogen

Alkyl halides elimination with bases

Alkyl halides formation with phosphorus reagents

Alkyl halides reacting with

Alkyl halides reaction with acetylides

Alkyl halides reaction with water

Alkyl halides reactions with ambident

Alkyl halides reactions with organocopper reagents

Alkyl halides reactions with sulfur

Alkyl halides superacidic alkylation with

Alkyl halides synthetic reactions with

Alkyl halides treatment with alkoxide

Alkyl halides with (3-diketones

Alkyl halides with acetylide anions

Alkyl halides with alkali metals

Alkyl halides with alkynide ions

Alkyl halides with amines

Alkyl halides with ammonia

Alkyl halides with carbonyls

Alkyl halides with chlorine, reaction

Alkyl halides with coenzyme

Alkyl halides with cyanide

Alkyl halides with enamines

Alkyl halides with lithium

Alkyl halides with lithium dialkylcuprates

Alkyl halides with magnesium

Alkyl halides with metal cations

Alkyl halides with metal hydrides

Alkyl halides with nitrogen, reaction

Alkyl halides with organocopper reagents

Alkyl halides with organometallics

Alkyl halides with sodium azide

Alkyl halides with thiourea

Alkyl halides with transition metal reagents

Alkyl halides with triphenylphosphine

Alkyl halides with typical nucleophiles

Alkyl halides, from alcohols nitrile alkylation with

Alkyl halides, reaction with aluminum

Alkyl halides, reaction with indole Grignard

Alkyl halides, reaction with indole Grignard reagents

Alkyl halides, reactions with arene

Alkyl halides, reactions with arene Table

Alkyl halides, reactions with trimethylsilyl

Alkylation of Alkenes with Organic Halides

Alkylation of Pyrroles with Allyl Halides

Alkylation of Pyrroles with Propargyl Halides

Alkylation reactions phenols with alkyl halides

Alkylation with Alkyl Halides. Scope and Limitations

Alkylation with alkyl halides in organic solvents other than nitromethane

Alkylation with allylic halide

Alkylation with organic halides

Alkylation, mechanism with alkyl halides

Alkyne anions reaction with alkyl halides

Allylsilanes with alkyl halides

Ammonia reaction with alkyl halides

Antimony, reaction with alkyl halides

Aromatic hydrocarbons with alkyl halides

Azide ion reaction with alkyl halides

Benzene with alkyl halides

Benzylic reaction with alkyl halides

Butyrolactones, reactions with alkyl halide

By Reaction with Alkyl Halides

Carbocation alkyl halide reaction with Lewis

Catalytic asymmetric cross-coupling reactions with secondary alkyl halides

Conversion of Alcohols to Alkyl Halides with HX

Conversion of Alcohols to Alkyl Halides with SOCI2 and PBr

Copper reactions with alkyl halides

Copper with alkyl halides

Coupling of alkyl halides with organometallic compounds

Coupling with alkyl halides

Cross-coupling reactions alkyl halides with Grignard reagents

Cross-coupling reactions with alkyl halides

Cyanamide reaction with alkyl halides

Cyanides, metal, reaction with alkyl halides

Cyanocuprates, reactions with alkyl halides

Diastereoselective Alkylation of Glycine Schiff Base with Optically Enriched Alkyl Halides

Displacement with cyanide ion on an alkyl halide

Dithiane anions reaction with alkyl halides

Enolate anions reaction with alkyl halides

Enolate anions, dianions reaction with alkyl halides

Enolate anions, esters, reaction with alkyl halides

Enolates reaction with alkyl halide

Enolates with alkyl halides

Ethers reaction with alkyl halides

Ethers, vinyl with alkyl halides

Friedel Crafts alkylation with alkyl halides

Friedel-Crafts reaction with alkyl halides

Gilman cuprates, reactions with alkyl halides

Grignard reaction: alkylation with mercury halides

Grignard reagents coupling reactions with alkyl halides

Grignard reagents with alkyl halides

Grignard reagents, bonding coupling with alkyl halides

Grignard reagents, reaction with alkyl halides

Halide ions reaction with alkyl halides

Halides alkyl transfer with

Halides coupling reactions with primary alkyl Grignard

Halides palladium-catalyzed coupling with alkyl

Halides, alkyl coupling with Grignard reagents

Halides, alkyl coupling with organocuprates

Halides, alkyl diastereoselectivity with enolate

Halides, alkyl intramolecular reactions with

Halides, alkyl oxidation with DMSO

Halides, alkyl reaction with NaSH

Halides, alkyl reaction with acetoacetic ester anions

Halides, alkyl reaction with acid salts

Halides, alkyl reaction with alkoxides

Halides, alkyl reaction with alkynes

Halides, alkyl reaction with aluminum hydride reagents

Halides, alkyl reaction with amide anions

Halides, alkyl reaction with amines

Halides, alkyl reaction with aromatic compounds

Halides, alkyl reaction with carbanions

Halides, alkyl reaction with carboxylic acid salts

Halides, alkyl reaction with cyanohydrins

Halides, alkyl reaction with enamines

Halides, alkyl reaction with hexamethylenetetramine

Halides, alkyl reaction with hydrazone anions

Halides, alkyl reaction with hydrogen sulfide

Halides, alkyl reaction with hydroxide

Halides, alkyl reaction with ketone enolate anions

Halides, alkyl reaction with ketones

Halides, alkyl reaction with lithium

Halides, alkyl reaction with magnesium

Halides, alkyl reaction with malonate anions

Halides, alkyl reaction with metals

Halides, alkyl, reaction with Bu3SnH

Halides, alkyl, reaction with Lewis acids

Halides, alkyl, reaction with Subject

Halides, alkyl, reaction with acid dianions

Halides, alkyl, reaction with amino ester enolates

Halides, alkyl, reaction with amino-alcohols

Halides, alkyl, reaction with azide

Halides, alkyl, reaction with cuprates

Halides, alkyl, reaction with cyanide

Halides, alkyl, reaction with cyanoborohydride

Halides, alkyl, reaction with dimethyl sulfide

Halides, alkyl, reaction with ester dianions

Halides, alkyl, reaction with ester enolates

Halides, alkyl, reaction with ferrate

Halides, alkyl, reaction with imides

Halides, alkyl, reaction with lactone enolates

Halides, alkyl, reaction with malonate enolates

Halides, alkyl, reaction with nitrile enolates

Halides, alkyl, reaction with nitro compounds

Halides, alkyl, reaction with organocuprates

Halides, alkyl, reaction with organolithium reagents

Halides, alkyl, reaction with phthalimide

Halides, alkyl, reaction with succinimide

Halides, alkyl, reaction with sulfides

Heck alkyl halides with styrenes

Heck-type Reaction of Alkyl Halides with Styrenes

Hydroxide, potassium reaction with alkyl halides

Hydroxy halides, alkylation reaction, with alkali

Indole Grignard reagents with alkyl halides

Internal alkynes with alkyl halides

Iodide, potassium reaction rates with alkyl halides

Iodide, sodium reaction with alkyl halides

Iron, reaction with alkyl halides

Lactams, alkylation with alkyl halides

LiAlH4, reaction with alkyl halides

Lithium dialkylcopper with alkyl halides

Lithium, vinylalkylation reaction with alkyl halides

Magnesium reaction of with alkyl and aryl halide

Magnesium reaction with alkyl halides, mechanism

Magnesium, reaction with alkyl halides form Grignard reagents

Mechanism, radical with alkyl halides

Mechanisms alkyl halides with alkoxides

Metal phosphites reaction with alkyl halides

Metals, activated reactivity with alkyl halides

Metals, activated with alkyl halides

Nickel with alkyl halides

Nitrite, sodium reaction with alkyl halides

Organocopper compounds, reactions with alkyl halides

Organocuprates, addition with alkyl halides

Organolithium reagents coupling with alkyl halides

Organolithium with alkyl halides

Organometallic compound, coupling with alkyl halide

Organometallic compounds reaction with alkyl halides

Organometallic compounds with alkyl halides

Organozinc reagents cross-coupling reactions with alkyl halides

Oxazine anions, reaction with alkyl halides

Oxazine anions, reaction with alkyl halides alkylation

Palladium, phenylbis catalysis arylmagnesium halide reaction with alkyl halides

Phosphines reaction with alkyl halides

Phosphines reaction with alkyl halides, kinetics

Phosphines with alkyl halides

Phosphines, alkylation with alkyl halides

Phosphoramidic acid, N- diethyl ester reaction with alkyl halides

Phosphorane, iminovinylidenetriphenylphosphonium ylide synthesis reactions with alkyl halides

Phosphorane, oxovinylidenetriphenylreactions with alkyl halides

Phosphorane, oxovinylidenetriphenylreactions with alkyl halides cycloaddition

Phosphorane, oxovinylidenetriphenylreactions with alkyl halides synthesis

Phosphorus, reaction with alkyl halides

Primary alkyl coupling reactions with alkenyl halides

Primary alkyl coupling reactions with aromatic halides

Primary alkyl reactions with alkenyl halides

Primary conversion to alkyl halides with

REDUCTION OF ALKYL HALIDES AND TOSYLATES WITH SODIUM CYANOBOROHYDRIDE

Radical mechanism, addition with alkyl halides

Radicals, coupling reactions with alkyl halides

Reaction of Alkyl, Alkenyl, and Aryl Halides with Metals

Reaction of Amines with Alkyl Halides

Reaction of Lithiated Bis(methylthio)methane with Alkyl Halides

Reaction of alkyl halides with sulfites and sulfinic acids

Reaction of stabilized carbanions (enolates) with alkyl halides (enolate alkylation)

Reaction with Alkyl and Aryl Halides

Reaction with alkyl halides

Reaction with alkyl halides to form

Reactions with Simple Alkyl Halides

Reactions with activated alkyl halides

Reactivity, alkyl halides with

Reactivity, alkyl halides with aromatic compounds

Reactivity, alkyl halides with dioxide

Reactivity, alkyl halides with ethanol

Reactivity, alkyl halides with reactions

Reactivity, alkyl halides with solvent polarity

Reactivity, alkyl halides with variation

Secondary alcohols conversion to alkyl halides with

Secondary alkyl halides acetylide anion reactions with

Secondary conversion to alkyl halides with

Silane, a-phenylthiomethyltrimethylreaction with alkyl halides

Silane, a-phenylthiomethyltrimethylreaction with alkyl halides synthesis of aldehydes

Silver cyanide, reaction with alkyl halides in synthesis of isocyanides

Silver nitrate, reaction with alkyl halides

Silver nitrite, with alkyl halides

Silver reaction with alkyl halides

Sodium acetylide reaction with, alkyl halides

Sodium cyanate with alkyl halides

Sodium nitrite, with alkyl halides

Sodium reaction with alkyl halides

Sodium sulfide, reaction with alkyl halides

Solvolysis rates with alkyl halides

Stabilized carbanions with alkyl halides

Sulfones anions, reaction with alkyl halides

Sulfonic acid salts, alkylation with aryl halides

Superoxide, potassium, with alkyl halides

Terminal alkynes with alkyl halides

Tertiary alkyl coupling reactions with alkenyl halides

Tertiary halides, alkylation with

Tetracarbonylferrate reaction with alkyl halides

The Reaction with Alkyl Halides

Thiocyanates reaction with alkyl halides

Thioethers reaction with alkyl halides

Thioethers with alkyl halides

Thiol reaction with alkyl halides

Thiolate ions reaction with alkyl halides

Thiols reaction with alkyl halides

Thioureas reaction with alkyl halides

Triphenylphosphine reaction with alkyl halides

Tris silane with alkyl halide

With Simple Alkyl Halides

With alkyl halides

With alkyl halides

Zinc reagents cross-coupling with alkyl halides

Zinc, reaction with alkyl halides

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