1 -Phenyl-1 - cyclopropan

A solution of the above ester (207.8 grams) and 64.5 grams of sodium hydroxide in 80 cc of water and 600 cc of ethanol is refluxed for 9 hours. The carboxylic acid of 2-phenyl-cyclopropane is liberated with 200 cc of concentrated hydrochloric acid. The 2-phenyl-cyclopropanecarboxylic acid contains 3 to 4 parts of the trans isomer to 1 part of the cis isomer. The acid is recrystallized from hot water. The pure trans isomer comes out as crystalline material (solid) while the cis isomer stays in solution. 

Aluminiumhydrid reduziert Zimtsaure-ester nur zu den Zimtalkoholen4. In sieden-dem 1,2-Dimethoxy-athan werden mit Lithiumalanat Phenyl-cyclopropane gebildet (s.S. 219)5. 

Durch Pyrolyse der aus Zimtaldehyd oder den (2-Aryl-vinyl)-alkyl- bzw. -aryl-ketonen mit Lithiumalanat erhaltlichen Komplexe werden Phenyl-cyclopropane erhalten (vgl. S. 173 u. 219). Als Nebenprodukte bilden sich gesattigte und ungesattigte offenkettige Kohlenwasserstoffe. 

Chlor-2-phenyl-propen —> Phenyl-cyclopropan 55% d. Th. Kp4S 86°... 

Ahn et al. [20] reported the synthesis of homochiral bis(oxazolinyl)-biferrocene ligands (structure 11 in Scheme 7), which also have both planar and central chirality. With these complexes, 2-(phenyl)cyclopropane carboxy-lates were obtained in up to 99% ee and a trans/cis ratio of 88/12. 

The course of decomposition of confirmed or presumed metallocyclo-butane intermediates is important, but most results reported deal with stoichiometric rather than catalytic processes. Retention of the 3-carbon skeleton via pathways d or f in Eq. (26) occurs much more frequently than does cleavage to metathesis-related products. For example, thermolysis of phenyl-substituted platinocyclobutanes yields propenylben-zenes and phenyl-cyclopropane, but no styrene or ethylene (77). Similarly, the decomposition of tantalum carbene adducts (8) with olefins... 

Cyclopropanes. XIII. 1-Acetyl-2-nitro-3-phenyl-cyclopropane and its... 

It is however not ruled out that the reaction might have proceeded through the formation of a symmetrical intermediate such as phenyl-cyclopropane. 

X-ray crystal structures for spirooxazolones including 4-spirocyclopropane 353 (m = 1, R2 = 4-spiro-(phenyl)cyclopropane 353 (n = 1, R2 = Ph), 4-spiro-... 

Zur analogen Herstellung von l-Amino-l-carboxy-2-(4-hydroxy-phenyl)-cyclopropan [(Z)-Cyclopropyl-tyrosin s. Lit.4. 

C[ 1. KN3/(H3C)3SiN3/Benzol/ l8-Krone-6, Riickfl. 35 b dann eindampfen 2. Ruckstand + Ether/HCl/ H20, 100% 20 min Amin HC1 mit Aceton ausfallen 1-Amino-l-phenyl-cyclopropan 88 7... 

Phenyl-1,2-propadiene, b.p. 64°-65°C (11 mm), d4 1-5809, is obtained in a similar manner in 82% yield by the reaction of l,l-dibromo-2-phenyl-cyclopropane with methyllithium at —60°C. 

Thus the unsaturated ketones carvone, eucarvone and 1-acetyl-cyclohexane formed the cyclopropyl ketones (6), (7) and (8) while benzalaceto-phenone (9) affords l-benzyl-2-phenyl-cyclopropane as a mixture of cis and trans isomers (10) and (ll).233,234... 

While the reaction of 73 is stereoselective, it has been shown that the photodecarboxylation of simple y-butyrolactones gives product selectivities that depend on the nature of the substrate. From the phenyl-substituted lactones 77-80, only 79 gives rise to phenyl cyclopropane in low yields (Scheme 2.18) [49]. Diphenyl-substituted lactones cis-80 and trans-80 give identical mixtures of cis- and trans- 1,2-diphenylcy-clopropane in 50-60% yield. Cyano-lactone 81 was the most efficient of the set, giving cis- and trans-l-cyano-2-phenylcyclopropanes in 44% and 48% yields. The simple trend that surfaces from this small number of examples (i.e., 73 and 77-81) is that radical-stabilizing substituents alpha to the lactone carbonyl may be important for the reaction to take place. 

C9Hio)- 3-Phenyl-propanol, 3-phenyl-propene, phenyl cyclopropane, 2-phenylpropene, 1-phenylpropene 219-256 g, n, p 857... 

The cyclopropane hydrocarbons which nawe three substituent groups are all reactive substances. The 1,1,2 arid 1,2,3 trimethyl coiapounils have been discussed. Besides these,two 1,1,2 coiripounds are xnown which have been prepared by tne same laethod as was used for /uaicing phenyl cyclopropane, tnat is, from on... 

Dioxolan 5-Ethenyl-3-phenyl-E19a, 402 (aus 2-Ethenyl-l-phenyl-cyclopropan)... 

Cyclopropanol is significantly (a factor of 10 ) more reactive toward mercuric acetate than is phenyl cyclopropane. A cyclopropyl methyl ether is less reactive than the corresponding cyclopropanol by a factor of 10—20, and the cyclopropyl acetate is decreased in reactivity by a factor of nearly 10. These results are fully consistent with the large q value for the mercuration reaction reported by Oullette (vide supra). 

With the above theoretical procedure whole ORD curves can be easily calculated, for instance, that of cis-methyl 2-pheny Icyclopropane-1-car boxy late (25) . For that phenyl-cyclopropane the fit becomes inferior for A < 400 nm, i.e. for rotations coming closer to the light absorption region of the compound. 

Steric and electronic factors in the reductive cleavage of methyl-substituted phenyl cyclopropanes (145) and in spiro[2.4]hepta-4,6-dienes like 146 have been investigated by Staley and Rocchio. ... 

A reaction closely related to olefin oxidation in aqueous solution is the oxidation of cyclopropanes by NaaPdCl in 2 1 glyme-water solvents 210). The direct oxidation product of phenyl cyclopropane is pro-piophenone. If the reaction is carried out in glyme-DgO, no deuterium... 

Jorgensen et al. found that reduction of an allylic alcohol by lithium aluminum hydride can be carried beyond the stage of the saturated alcohol to give a cyclopropane. Thus a cinnamyl acid, ester, aldehyde, or ketone on reduction with 100% excess LiAlHj in refluxing tetrahydrofurane or dimethoxyethane affords a phenyl-cyclopropane in yield of 45-80%. The reaction complements the Simmons-Smith synthesis. 

By Sulfur-Metal Exchange from 1-Silyl-l-thio-phenyl-cyclopropanes... 

The addition of phenyllithium to cyclopropene occurred with 99% stereoselectivity to give cw-l-lithio-2-phenylcyclopropane, albeit in 3 /o yield. With 3-methylcyclopropene, the reaction was more efficient and, after protonation of the lithiocyclopropane, 2-methyl-1-phenyl-cyclopropane was obtained in 44.5% yield. The product is about 94% in the trans form thus attack of the organolithium occurs on the opposite face to that bearing the larger substituent at C3. When the cyclopropene is 3,3-disubstituted, e.g. 17, both faces are sufficiently hindered to slow the addition process and metalation of a vinylic hydrogen predominates. ... 

Arylcyclopropanes can be prepared from a variety of alkenes enamines react sluggishly, electron-rich alkenes are, in general, the most reactive. Thus, phenylcarbene, generated by dirhodium tetraacetate catalyzed decomposition of phenyldiazomethane, gave 2-butyl-1-phenyl-cyclopropane (2) in 6% yield from hex-l-ene, but l-butoxy-2-phenylcyclopropane (3) was obtained in 92% yield from butyl vinyl ether. ... 

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