4-Phenyl-3-buten

Figure 14. Isomerization of 1-phenyl-3-buten-l-ol to 4-phenyl-3-buten-2-ol using 1 immobilized in cage-like FDU-12 [75].

Aryl migration in preference to vinyl or methyl migration is evident with 1,2-epcxy-2-methyl-1 -phenyl-3-butene, which givcB the corresponding aldehyde exclusively,4 as shown in Eq. (452)... 

Zinc-mediated pe/n-difluoroallylation of a carbonyl compound preparation of 2,2-difluoro-1-phenyl-3-buten-1-ol29... 

Bei der Hydroaluminierung von Alkinen tritt die Oligomerisierung oft bereits bei nied-rigeren Temperaturen in den Vordergrund. So erhalt man z.B. aus 3,3-Dimethyl-l-phe-nyl-butin (I) und Bis-[2-methyl-propyl]-aluminiumhydrid (1 1) bei 50° 94% d.Th. cis-3,3-Dimethyl-l-phenyl-buten-(l) (II)5 neben 6% d.Th. trans,trans-2,2,7,7-Tetramethyl-4,5-diphenyl-octadien-(3,5) (III) ... 

Aus 2-Methoxy-4-oxo-4-phenyl-buten-(2) erhalt man auf analoge Weise 92% d.Th. 3-Oxo-l-phenyl-buten3. Sind weitere mit Lithiumalanat reduzierbare Gruppen vorhan-den, so wird vor allem Natriumboranat eingesetzt z.B.4 ... 

Cyclohexanon Mesityloxid I - Acetyl-cyclohexen 3-Oxo- l-phenyl-buten-( 1)... 

Benzaldehyd + l-Brom-buten-(2) 4-Hydroxy-3-methyl-4-phenyl-buten-( I) ... 

Oxo-4-phenyl-buten-(2)-saure-nitril dimerisiert hingegen ausschlieBIich zu 2,3-Bis- 2-oxo-2-phenyl-athyl]-bernsteinsdure-dinitril (5% d. Th.)4. 

N-Diphenylmethylen- 374 N-Diphenylmethylen-O-aminocarbonyl- 612 N-[l,3-Diphenyl-propyl-(2) - 374 N-[l,3-Diphenyl-propyliden-(2)]- 374, 377, 380 N-(4-Halogen-phenyI)- 683 N-Heptyl- 375 N-Heptyl-N-acetyl- 376 N-Heptyliden- 375 N-Hcptyliden-O-acetyl- 376 0-(2-Hydroxy-athyl)-N-athoxycarbonyl- 133 N-(4-Hydroxy-phenyl)- 683 0-(2-Hydroxy-l-phenyl-athyI)-N-athoxycarbonyI-aus 0-(ci-AthoxycarbonyI-benzyl)-N-athoxycar-bonyl-hydroxylamin und Lithiumalanat 133 N-Isopropyl- 682 N-Isopropylidcn- 613 N-Methyl- 133, 682 O-Methyl-N-bcnzyliden- 377 O-Methyl-N-benzyliden- 375 0-Methyl-N-(4-chlor-benzyl)- 375 0-Methyl-N-(4-chlor-benzyliden)- 375 N-Methy -N,0-diacetyI- 682 N-(4-Methyl-phenyl)- 683 0-McthyI-N-( 1 -phenyl-athyliden)- 375 N-(4-Methylthio-phenyl)- 684 N-(4-Nitro-benzyl)- 374 N-[4-Nitro-benzyliden - 374, 377 N-(2-Nitro-phenyl)- 562 N-(4-Nitro-phenyl)- 682 N-Nitroso-N-cyclohexyl- 697 N-Octyl- 374 N-Octyl-(2)-N-acetyl- 376 N-Octyliden- 374 N-0ctyliden-(2)-0-acctyl- 376 N-(Pentafluor-phenyl)-0,N-diacetyl- 697 N-Phenyl- 474, 481, 682, 783 N-Phenylacetyl-O-benzoyl- 265 N-(l-Phenyl-athyl)- 374 N-(l-Phenyl-athyl)-N-acetyl- 376 N-(l-Phenyl-athyliden)-374, 613 N-( l-Phenyl-athyliden)-0-acetyl- 376 N-[ 1 -Phenyl-buten-( 1 )-yl-(3)-iden]- 582 N-f4-Phenyl-butyl-(2)-iden]- 581 N-Phcnyl-N,0-diacetyl- 682 N-(4-Phenylthio-phenyl)- 684 N-Propyl-N-cyclohexyl- 376 N-Propyl-N-isopropyl- 376 O-Sulfonyl- 481 N-(4-Sulfonyl-phenyI)- 683 N-(2-Vinyl-phenyl)- 698... 

Scheme 8. Three different routes from l-phenyl-buten-3-yne to biphenyl.

This review will illustrate examples of computer projected models of inclusion complexes of structural isomers (ortho, meta, para nitrophenol), enantiomers (d- and 1- propranolol) and diastereomers [cis and trans. l(p-B-dimethylaminoethoxy-phenyl-butene), tamoxifen] in either a- or B-cyclodextrin. The use of these computer projections of the crystal structures of these complexes allows for the demonstration and prediction of the chromatographic behavior of these agents on immobilized cyclodextrin. 

Hydro peroxy-2,3-bis- [4- methoxy-phenyl ]-buten - (1), ein Oxidationspro-dukt des entsprechenden Stilben-Derivats5, wird in Oyclohexan durch UV-Licht (125 W Quecksilbcr-Mitteldruck-Lampc, Osram wassergekiihlter Tauchschacht) aufgcspalten 4-Methoxy-acetophenon entsteht mit 21%iger Ausbeute ... 

Benzoylamino-4-(3,4-dimethoxy-phenyl)-buten-(3)-saure 5-Oxo-l, 5-diphenyl-pentadien-( 1,3) 4,4 -Dimethoxy-chalkon... 

D,L threo-l-Acetamino-l-phenyl-2-(4-methoxy-phenyI)-butan4 7 g /ram-1-Acetamine-1-phenyl-2-(4-methoxy-phenyl)-buten-(l) werden in 50 ml Methanol mit Palladium-Schwarz bei 20° und Normaldruck hydriert. Nach Aufnahmc der ber. Menge Wasserstoff wird vom Katalysator abgetrennt und das Losungsmittel bis auf wenige ml abdestilliert. Die beim Abkuhlen erhaltenen Kristalle werden aus Essigsaure-athylester/Hexan umkristallisiert Ausbeute 6,3 g (90% d.Th.) F 149-150° (farblose Nadeln). 

P tCH3 o2n Pt02/Pb c2h5oh 1 - 3-Oxo-J -(3-amino-phenyl) -buten-(l) >90 5... 

Phenyl-buten.(2)-carboDS uie (l)-kthyb ester 9 II414. 

Benzoyloxy.benzyIidenaoaton 9,152. 4-BanzoyIoxy.benzyIidenaoeton 9 II135. 2-Benzoyloxy.l.phenyl.buten-(l)-on.(8)... 

CjiHbi 6>Auiyl-d-phenyl -buten-y-in oder y-Methyl>e-pnenyl>/9.penten-6 in 5, 568. 

Indene derivatives 264a and 264b are formed by the intramolecular reaction of 3-methyl-3-phenyl-l-butene (263a) and 3,3,3-triphenylpropylene (263b) [237]. Two phenyl groups are introduced into the /3-substituted -methylstyrene 265 to form the /3-substituted /3-diphenylmethylstyrene 267 via 266 in one step[238]. Allyl acetate reacts with benzene to give 3-phenylcinnamaldehyde (269) by acyl—O bond fission. The primary product 268 was obtained in a trace amount[239]. 

The reaction of a halide with 2-butene-1,4-diol (104) affords the aldehyde 105, which is converted into the 4-substituted 2-hydroxytetrahydrofuran 106, and oxidized to the 3-aryl-7-butyrolactone 107[94], Asymmetric arylation of the cyclic acetal 108 with phenyl triflate[95] using Pd-BINAP afforded 109, which was converted into the 3-phenyllactone 110 in 72% ee[96]. Addition of a molecular sieve (MS3A) shows a favorable effect on this arylation. The reaction of the 3-siloxycyclopentene 111 with an alkenyl iodide affords the. silyl... 

Convincing evidence for oxidative addition by inversion has been presented by the reaction of chiral (5)-( )-3-acetoxy-l-phenyl-1-butene (4) with Pd(0)(dppe), followed by the treatment with NaBF4 to give optically active the TT-allylpalladium complex (l/ ,25,35) 5 with 81% stereoselectivity[19]. 

Furthermore, the catalytic allylation of malonate with optically active (S)-( )-3-acetoxy-l-phenyl-1-butene (4) yields the (S)-( )-malonates 7 and 8 in a ratio of 92 8. Thus overall retention is observed in the catalytic reaction[23]. The intermediate complex 6 is formed by inversion. Then in the catalytic reaction of (5 )-(Z)-3-acetoxy-l-phenyl-l-butene (9) with malonate, the oxidative addition generates the complex 10, which has the sterically disfavored anti form. Then the n-a ir rearrangement (rotation) of the complex 10 moves the Pd from front to the rear side to give the favored syn complex 6, which has the same configuration as that from the (5 )-( )-acetate 4. Finally the (S)-( )-mal-onates 7 and 8 are obtained in a ratio of 90 10. Thus the reaction of (Z)-acetate 9 proceeds by inversion, n-a-ir rearrangement and inversion of configuration accompanied by Z to isomerization[24]. 

It is known that tr-allylpalladium acetate is converted into allyl acetate by reductive elimination when it is treated with CO[242,243]. For this reason, the carbonylation of allylic acetates themselves is difficult. The allylic acetate 386 is carbonylated in the presence of NaBr (20-50 mol%) under severe conditions, probably via allylic bromides[244]. However, the carbonylation of 5-phenyl-2,4-pentadienyl acetate (387) was carried out in the presence of EtiN without using NaBr at 100 °C to yield methyl 6-phenyl-3,5-hexadienoate (388)[245J. The dicarbonylation of l,4-diacetoxy-2-butene to form the 3-hexenedioate also proceeds by using tetrabutylphosphonium chloride as a ligand in 49% yield[246]. 

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