2- Phenylethyl iodide

Deuterium labeling experiments show that oxidation of 2-phenylethyl iodide proceeds through the bridged carbonium ion 11 [21]. Both iodocyclobutane and... 

The opposite of the stabilisation of an ester is its activation. If we include in the concept ester the alkyl halides, their Friedel-Crafts reactions provide familiar examples of this phenomenon. An unusual example especially relevant to our present considerations is provided by some results made available to me in advance of publication by Giusti and Andruzzi. Their results [38] on the polymerisation of styrene by iodine and hydrogen iodide can be interpreted in terms of an organic iodide derived from styrene, probably 1-phenylethyl iodide, being activated by the co-ordination of one or two molecules of iodine. This process appears to polarise the C—I bond to such an extent that the normally stable ester becomes activated to a chain-propagating species and induces a pseudocationic polymerisation ... 

Phenylethyl Iodide. Use 146 g. (142 ml.) of (J-phenylethyl alcohol (b.p. 216 5-217°), 16 54 g. of purified red phosphorus and 154 g. of iodine. Lag the arm C (Fig.///, 40, 1) with asbestos cloth. Heat the alcohol - phosphorus mixture to boiling until sufficient alcohol (usually one-third to one-half of the total volume) passes into the reservoir B to dissolve all the iodine. Remove the flame and add the iodine solution at such a rate that the mixture boils gently. A little hydrogen iodide is evolved towards the end of the reaction. Allow the mixture to cool, add water and filter off the excess of phosphorus. Decolourise the filtrate with a little sodium bisulphite and add ether to assist in the separation of the water layer. Wash the ethereal solution with water, dry with anhydrous potassium carbonate, and distil under diminished pressure. B.p. 114 116°/12 mm. Yield 215 g. 

P-Phenylethyl alcohol, 812,816 Phenylethylene, 1015,1024 a-Phenylethylamine, 560, 566 P-Phenylethy,amine, 560, 567,569 Phenylethylbarbituric acid, 1003,1005 P-Phenylethyl bromide, 283 P-Phenylethyl iodide, 288 Phenylglycine-o-carboxylic acid, 980 Phenylglyoxal, 866 Phenylhydrazine, 635, 636 hydrochloride, 636, 637 Phenylhydrazine acetate reagent, 343, 721 ... 

The use of the chiral alkyl iodides sec-butyl iodide and a-phenylethyl iodide on CpFe(COXCNR)CN (R =Me, Et) has produced configurationally nonlabile diastereoisomers (82). 

Phenylethylamine has been made by a number of reactions, many of which are unsuitable for preparative purposes. Only the most important methods, from a preparative point of view, are given here. The present method is adapted from that of Adkins,1 which in turn was based upon those of Mignonac,2 von Braun and coworkers,3 and Mailhe.4 Benzyl cyanide has been converted to the amine by catalytic reduction with palladium on charcoal,5 with palladium on barium sulfate,6 and with Adams catalyst 7 by chemical reduction with sodium and alcohol,8 and with zinc dust and mineral acids.9 Hydrocinnamic acid has been converted to the azide and thence by the Curtius rearrangement to /3-phenyl-ethylamine 10 also the Hofmann degradation of hydrocinnamide has been used successfully.11 /3-Nitrostyrene,12 phenylthioaceta-mide,13 and the benzoyl derivative of mandelonitrile 14 all yield /3-phenylethylamine upon reduction. The amine has also been prepared by cleavage of N- (/3-phenylethyl) -phthalimide 15 with hydrazine by the Delepine synthesis from /3-phenylethyl iodide and hexamethylenetetramine 16 by the hydrolysis of the corre-... 

The authors concluded that the polsmierisation must be pseudocationic, the active spedes being both 1-phenylethyl iodide and styrene diiodide polarises by the specific solvatirai of iodine molecules. 

Alkylation of the metallated enol derived from 52 with m-methoxy-phenylethyl-iodide to afford the tricyclic jj-keto ester 53, followed by cationic cydization of this to furnish the steroid derivative 54, warrants particular attention. Corey and colleagues have recently published another total synthesis of 40 [82], beginning with an enantioselective Diels-Alder reaction between Dane s diene 14 and dienophile 61. An oxazaborolidinium salt (see Section 1.3.2.3) was used as an efficient catalyst (Scheme 1-14). 

Styrene (99%, Nacalai Tesque, Japan), MMA (99%, Nacalai), and azobis(isobutyronitrile) (AIBN) (99%, Nacalai) were purified by distillation or recrystallization. 1-Phenylethyl iodide (PE-1) and 2-cyanopropyl iodide (CP-1) were prepared according to Matyjaszewski (9) and Balczewski (10), respectively. 2,2 -Azobis(2,4,4-trimethylpentane) (VRllO) (99.9%, Wako Pure Chemical, Japan), f-butyl peibenzoate (BPB) (98%, Aldrich), di(4-f-butylcyclohexyl) peroxydicarbonate (PERKADOX16) (95%, Akzo), thymol iodide (TI) (95%, Wako), 2,4,6-trimethyl phenol (2,4,6-Me) (97%, Wako), 2,6-di-f-butyl-4-methyl phenol (3,5-di-f-butyl-4-hydroxy toluene (BUT)) (98%, Wako), 2,6-di-i-butyl-4-methoxy phenol (3,5-di-i-butyl-4-hydroxy anisole (BHA)) (97%, Aldrich), phenol (99%, Wako), vitamin E (VE) (99.5%, Wako), vitamin C (VC) (99%, Tokyo Kasei, Japan), and 2,2,6,6-tetramethylpiperidinyl-l-oxy (TEMPO) (99%, Aldrich) were used as received. 

We examined the polymerization of St at 80 °C, using 1-phenylethyl iodide (PE-I) as a low-mass alkyl halide initiator, GeLi as a deactivator, and benzoyl peroxide (BPO) as a conventional radical initiator. In this polymerization, P, which is originally supplied by BPO, is supposed to react with Gel4, in situ producing the activator Gelj (and P-I). If Gel effectively abstracts I from PE-I (or P-I) to produce PE (or P ), a useful sequence of activation and deactivation will be completed. 

The DT of acrylates (butyl acrylate and methyl acrylate) with alkyl iodides was reported by Gaynor et al. and Matyjaszewski et al in 1995. For instance, solution polymerization of butyl acrylate in benzene initiated by AIBN at 50 °C in the presence of 1-phenylethyl iodide provided poly(butyl acrylate) with 97% monomer conversion in 7.5 h and Mn = 19 SOOgmol" (close to Mn,theoredcai = 18000gmor ) (Scheme 15a). The PDI = 2.0 is large, indicating a rather low Cex value. Later on, 2-ethylhexyl acrylate and tert-butyl acrylate were also polymerized by DT in the presence of bis(iodomethyl)benzene or PS-I, respectively. ... 

Gaynor et al. and Matyjaszewski et al have shown that the polymerization of styrene can be controlled by alkyl iodides such as 1-phenylethyl iodide, iodoform (also investigated by... 

The present procedure was developed from those of Wallach and Freylon, based upon the general method discovered by Leuckart. a-Phenylethylamine also can be prepared satisfactorily by the reduction of acetophenone oxime with sodium and absolute alcohol or sodium amalgam, but the reagents are more expensive and the processes less convenient. The amine has been obtained by reducing acetophenone oxime electro-lytically, by reducing acetophenone phenylhydrazone with sodium amalgam and acetic acid, from a-phenylethyl bromide and hexamethylenetetramine, and by the action of methyl-magnesium iodide upon hydrobenzamide, as well as by other methods of no preparative value. 

To the stirred solution of 5 parts of N-(4-piperidyl)propionanilide, 6.85 parts sodium carbonate, 0.05 part potassium iodide in 120 parts hexone is added portionwise a solution of 3.8 parts /3-phenylethyl chloride in 24 parts 4-methyl-2-penlanone. The mixture is stirred and refluxed for 27 hours. The reaction mixture is filtered while hot, and the filtrate is evaporated. The oily residue is dissolved in 160 parts diisopropyl ether and the solution is filtered several times until clear, then concentrated to a volume of about 70 parts. The residue is then cooled for about 2 hours at temperatures near 0°C to yield N-[1-((3-phenyl-ethyl)-4-piperidyl] propionanilide, melting at about 83° to 84°C as described in U.S. Patent 3,141,823. 

The method described is successfully used for the alkylation and aralkylation of ethyl and /-butyl phenylacetate.3 The alkylation of ethyl phenylacetate with methyl iodide, M-butyl bromide, benzyl chloride, and a-phenylethyl chloride affords the corresponding pure monoalkylation products in 69%, 91%, 85%, and 70% (erythro isomer) yields, respectively. The alkylation of /-butyl phenylacetate with methyl iodide, M-butyl bromide, a-phenylethyl chloride, and /3-phenylethyl bromide gives the corresponding pure monoalkylated products in 83%, 86%, 72-73%, and 76% yields, respectively. 

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