3- Phenyl-2-propen

Phenyl-2-propenal [104-55-2], also referred to as cinnamaldehyde, is a pale yeUowHquid with a warm, sweet, spicy odor and pungent taste reminiscent of cinnamon. It is found naturally in the essential oils of Chinese cinnamon Cinnamomum cassia, Blume) (75—90%) and Ceylon cinnamon Cinnamomum lanicum, Nees) (60—75%) as the primary component in the steam distilled oils (27). It also occurs in many other essential oils at lower levels. 

Phenyl-2-propen-l-ol [104-54-1], commonly referred to as cinnamyl alcohol, is a colorless crystalline soHd with a sweet balsamic odor that is reminiscent of hyacinth. Its occurrence in nature is widespread as, for example, in Hyacinth absolute (Hyacinthus orientalis) (42), the leaf and bark oils of cinnamon Cinnamomum cassia, Cinnamomum lancium, etc), and Guava fmit [Psidiumguajava L.) (43). In many cases it is also encountered as the ester or in a bound form as the glucoside. 

Diastereoselective preparation of a-alkyl-a-amino acids is also possible using chiral Schiff base nickel(II) complexes of a-amino acids as Michael donors. The synthetic route to glutamic acid derivatives consists of the addition of the nickel(II) complex of the imine derived from (.S )-,V-[2-(phenylcarbonyl)phenyl]-l-benzyl-2-pyrrolidinecarboxamide and glycine to various activated olefins, i.e., 2-propenal, 3-phenyl-2-propenal and a,(f-unsaturated esters93- A... 

C14H17N3O4S 103628-49-5) see Sumatriptan dimethyl A -methylcarbonimidodithioate (C4H9NS2 18805-25-9) see Ranitidine (E)-A, Af-dimethyl-3-(4-methylphenyl)-3-phenyl-2-propen-1-amine... 

Phenyl-2-propenoic acid, e279 3-Phenyl-2-propen-l-ol, c282 3-Phenyl-2-propenoyl chloride, c280 3-Phenylpropyl alcohol, pi46 Phenyl propyl ketone, b619... 

It is convenient to investigate the selectivity provided by a given catalyst in the hydrogenation of / rans-cinnamaldehyde (3-phenyl-2-propenal, A) which can yield three products cinnamyl alcohol (3-phenyl-2-propenol, B), dihydrocinnamaldehyde (3-phenylpropanal, Q and 3-phenylpropanol (D) (Scheme 3.18). Data of a few catalytie systems are eollected into Table 3.8. 

Chem. Abstr. Name 3-Phenyl-2-propen-l-ol, 2-aminobenzoate lUPAC Systematic Name Anthranilic acid, cinnamyl ester Synonyms Cinnamyl alcohol anthranilate 3-phenyl-2-propenyl 2-aminobenzoate 3-phenyl-2-propenyl anthranilate... 

Tanaka and co-workers have investigated the dehydrogenative double silylation of carbonyl-containing compounds with o-bis(dimethylsilyl)ben-zene [Eqs. (66) and (67)].173 High-yield 1,2-double silylation occurs in reactions of heptanal, benzaldehyde, and diphenylketene catalyzed by Pt(CH2 = CH2)(PPh3)2 or Pt(dba)2. In contrast, the 1,4-double silylation product is formed for a,/3-unsaturated aldehyde or a,/3-Unsaturated ketone substrates, such as prop-2-enal and but-3-en-2-one. The system may also be affected by sterics reaction of ( )-3-phenyl-2-propenal gives 1,2-adduct as the major product and only minor amounts of 1,4-adduct. Hydrosilylation products were not formed in any of the carbonyl systems studied. 

CH3)2C=CHCH2CH2CHO + CeH5CH=CHCH2OH 5-methyl-4-hexenal 3-phenyl-2-propen-1-ol... 

A cationic Ir complex possessing phosphanodihydrooxazole 26 is usable for asymmetric hydrogenation of allylic alcohols. (E)-2-Methyl-3-phenyl-2-propen-l-ol can be converted in CH2C12 containing 1 mol % of the Ir complex to the saturated product in 95% yield and 96% ee (Scheme 1.26) [141]. The process is used in the enantioselective synthesis of the artificial fragrance filial. 

To a 2 L, 3-neck Morton flask fitted with a thermometer, a mechanical stirrer, and an addition funnel was added the methyl 3-hydroxy-2-methylene-3-phenylpropionate (305.9 g, 1.585 mol) followed by addition of 48% HBr (505 ml, 4.46 mol) in one portion. The flask was immersed in an ice-water bath, at which time concentrated sulfuric acid (460 ml, 8.62 mol) was added dropwise over 90 min and the internal temperature of the reaction mixture was maintained at 23°-27°C throughout the addition process. After removal of the ice-water bath, the mixture was allowed to stir at room temperature overnight. The solution was then transferred to a separatory funnel and the organic layer was allowed to separate from the acid layer. The acids were drained and the organic layer was diluted with 2 L of a 1 1 ethyl acetate/hexane solution, washed with saturated aqueous sodium bicarbonate solution (1 L), dried over sodium sulfate, and concentrated to yield 400.0 g (99%) of the desired (Z)-l-bromo-2-carbomethoxy-3-phenyl-2-propene as a light yellow oil, which was used without any additional purification, boiling point 180°C (12 mm). 

To a 12 L, 3-neck round bottom flask fitted with a mechanical stirrer, thermometer and an addition funnel was added the (Z)-l-bromo-2-carbomethoxy-3-phenyl-2-propene (400.0 g, 1.57 mol) and methanol (4 L). The mixture was warmed to 50°C and a solution of sodium sulfite (199.0 g, 1.57 mol) dissolved in water (4 L) was added over 75 min while the internal temperature of the flask was maintained at 50°C. After the addition was complete, the clear solution was allowed to stir at 50°C for an additional 45 min. The reaction mixture in solution was taken to the next step without additional purification. The (Z)-2-carbomethoxy-3-phenyl-2-propene-l-sulfonic acid sodium salt may be isolated by concentration to an amorphous powder. 

To the 8 L of 1 1 methanol/water mixture containing the (Z)-2-carbomethoxy-3-phenyl-2-propene-l-sulfonic acid sodium salt was added 60.0 g of W-24 raney nickel. The resulting suspension was pressurized under 50 psi of hydrogen and was allowed to shake on a Parr shaker for 24 h, at which time an additional 20.0 g of raney nickel catalyst was added. After 6 h under 50 psi of hydrogen, the catalyst was removed by filtration and the solution was concentrated to dryness. To the dry white solid was added ethyl acetate (6 L) and heptane (4 L) and the solution was vigorously stirred with a mechanical stirrer overnight. The white suspension was removed by filtration yielding 530.0 g (88%) of the desired 2-carbomethoxy-3-phenylpropane-l-sulfonic acid sodium salt as an amorphous powder. 

Hydroxy-phenyl-methan- -diphenylester XII/1, 477 aus Phosphorigsaure-chlorid-diphenylester, Benzaldehyd und Eissessig XII/1, 496 Hydroxy-phenyl-methan- -dipropylester XII/1, 478 Hydroxy-phenyl-methan- -ester E2, 318 1-Hydroxy-3-phenyl-2-propen- -dimethvlester XII/I, 480... 

Phenyl-2-propen-l-ol has been investigated as part of an FIK study of 3-phenylpropanal [931] (Sect. 6.4.2). It was proposed that the... 

The acetyl-methyl group in 2-acctylphenyl methyl tellurium condenses with benzaldehyde to give methyl 2-(3 -phenyl-2 -propen-l -oyl)phenyl tellurium3. 

Methyl 2-(3 -Phenyl-2 -propen-r-oyl)phenyl Tellurium3 A stirred mixture of 12 g (46 mmol) of 2-acetylphenyl methyl tellurium, 17.6 m/(18.4 g, 170 mmol) of benzaldehyde, 88 mlof acetic acid, and 35 ml of piperidine is heated under reflux for 6 h. The mixture is then steam-distilled to remove unreacted benzaldehyde. The resultant red oil is separated by extraction with chloroform, the extract is evaporated, and the residue is fractionally distilled under vacuum. The fraction boiling above 200°/0.1 torr is collected and redistilled to give a condensate that should solidify. This solid is recrystallized several times from a mixture of petroleum ether and benzene yield 3.2 g (20%) m.p. 102-104° (from heptane/benzenc). 

Benzyl-2-propen- IX, 504 2-Methyl-3-phenyl-2-propen- IX, 504 Thiokohlensaure -S-benzylester-O-... 

Treatment of 2 with 3 equiv of 3-phenyl-2-propenal in refluxing toluene-cfe while the reaction progress was monitored by H NMR spectroscopy resulted in the disappearance of the aldehyde hydrogen peak (5 1.56). The IR spectrum of 4 shows a new absorption due to a vC-o stretch at 1448 cm 1. The mass spectrum of the product shows a molecular ion at m/z 538. To our surprise, an X-ray study of 4 showed it to be the insertion product of the two carbonyl ligands into the C-Si bond in 2. The reaction has the potential for developing a new method for double C-C bond formation between the carboranyl unit and carbonyl compounds. Such an insertion of the carbonyl functionality into the o-carborane has been observed in Yamamoto s work on the chemoselective addition of o-carborane to the aldehyde groups by a palladium-catalyzed9 or a fluoride-promoted reaction.10... 

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