Cinnamoyl

In the attempted thermolytic preparation of pyrroloisoxazole (32) from azidoisoxazole (31a), only cinnamoyl cyanide was isolated. The assumed intermediate nitrene (33) did not insert into the styryl bond, but rather ring rupture and loss of acetonitrile produced the product. Similar products were obtained from the homolog (31b) (Scheme 7) (79TL4685). The stabilized nitrene intermediate is similar to that postulated for diazofuryl- and diazoisoxazolyl-methanes (78JA7927, 79TL2961). 

Benzo[b]furan, 2-aryl-2,3-dihydro- H NMR, 4, 570 Benzo[b]furan, 2-bromo-nitration, 4, 604 Benzo[b]furan, 5-cinnamoyl-properties, 4, 708 Benzo[b]furan, 2-cyano-photochemical reactions, 4, 636 Benzo[b]furan, 2,3-dialkyl-synthesis, 4, 710 Benzo[b]furan, 2,3-dihydro-aromaticity... 

As with poly(vinyl alcohol), poly(vinyl cinnamate) is prepared by chemical modification of another polymer rather than from monomer . One process is to treat poly(vinyl alcohol) with cinnamoyl chloride and pyridine but this is rather slow. Use of the Schotten Baumann reaction will, however, allow esterification to proceed at a reasonable rate. In one example poly(vinyl alcohol) of degree of polymerisation 1400 and degree of saponification of 95% was dissolved in water. To this was added a concentrated potassium hydroxide solution and then cinnamoyl chloride in methyl ethyl ketone. The product was, in effect a vinyl alcohol-vinyl cinnamate copolymer Figure 14.8)... 

The isomeric -cinnamylcocaine (methylcinnamoyl-d- -ecgonine) prepared by Einhorn and Deckers by the action of cinnamoyl chloride at 150-60° on d-i/r-ecgonine methyl ester, crystallises in prisms, m.p. 68°, [ Id + 2° (EtOH). The hydrochloride, B. HCl, forms needles, m.p. 186° the platinichloride, needles, m.p. 208°, and the aurichloride orange needles, m.p. 164°. 

The initial anhydride concentration was about 3 x 10 M, and the amine concentration was much larger than this. The reaction was followed spectrophoto-metrically, and good first-order kinetics were observed hence, the reaction is first-order with respect to cinnamic anhydride. It was not convenient analytically to use the isolation technique to determine the order with respect to allylamine, because it is easier to observe the cinnamoyl group spectrophotometrically than to follow the loss of amine. Therefore, the preceding experiment was repeated at several amine concentrations, and from the first-order plots the pseudo-first-order rate constants were determined. These data are shown in Table 2-1. Letting A represent... 

We conclude that the rds transition state includes the elements of one cinnamoyl-imidazole and two butylamine molecules, but we do not know anything about their assembly. However, because a termolecular collision is very improbable, we are justified in supposing that this is a complex reaction, the three molecules having been brought together in stepwise fashion. 

These rate constants are for the cinnamoylation of hydroxy compounds by cinnamic anhydride catalyzed by A-methylimidazole. The reaction is first-order in each reactant. The kinetics were followed spectrophotometrically in acetonitrile solution. Analyze the data that is, attempt to account for the relationship between structure and reactivity. 

A/-o-(Benzoyloxymethyl)benzoyl, 562 A/-(2-Acetoxymethyl)benzoyl, 562 A/-2-[(t-Butyldiphenylsiloxy)methyl]benzoyl, 562 A/-3-(3, 6 -Dioxo-2, 4, 5 -trimethylcyclohexa-1, 4 -diene)-3,3-dimethylpropionyl, 562 AZ-o-Hydroxy-frans-cinnamoyl, 562... 

Sml2, THE or DMPU, it, 76-94% yield. Deprotection of the pyridinesul-fonamide in the presence of a cinnamoyl group was possible when done without a proton source. BOC, A-benzyl, A-allyl, and trifluoroacetamido groups were all stable to these conditions. ... 

Cyclization of 4-cinnamoyl-l,2,3,4-tetrahydroquinoxalin-2-one (416) by treatment with AICI3 yielded l,2,3,5-tetrahydropyrido[l,2,3-[Pg.319]

The reaction has wide scope in respect of the dienophUe / -substituent. The representative less reactive dienophiles, crotonoyl- and cinnamoyl-oxazolidinone, react with cyclopentadiene at -15 °C and 25 °C for 20 h and 24 h giving cycloadducts in 99% ee and 96% ee, respectively. The 3-chloropropenoyl derivative also affords the adduct in high optical purity (96% ee) this adduct is transformed to 2-(methoxycar-bonyl)norbornadiene, a useful chiral building block. Thus, the 3-chloropropenoyl derivative can be regarded as a synthetic equivalent of an acetylene dienophile. 

A chiral titanium complex with 3-cinnamoyl-l,3-oxazolidin-2-one was isolated by Jagensen et al. from a mixture of TiCl 2(0-i-Pr)2 with (2R,31 )-2,3-0-isopropyli-dene-l,l,4,4-tetraphenyl-l,2,3,4-butanetetrol, which is an isopropylidene acetal analog of Narasaka s TADDOL [48]. The structure of this complex was determined by X-ray structure analysis. It has the isopropylidene diol and the cinnamoyloxazolidi-none in the equatorial plane, with the two chloride ligands in apical (trans) position as depicted in the structure A, It seems from this structure that a pseudo-axial phenyl group of the chiral ligand seems to block one face of the coordinated cinnamoyloxazolidinone. On the other hand, after an NMR study of the complex in solution, Di Mare et al, and Seebach et al, reported that the above trans di-chloro complex A is a major component in the solution but went on to propose another minor complex B, with the two chlorides cis to each other, as the most reactive intermediate in this chiral titanium-catalyzed reaction [41b, 49], It has not yet been clearly confirmed whether or not the trans and/or the cis complex are real reactive intermediates (Scheme 1.60). 

An X-ray structure of the complex formed between 3-cinnamoyl-l,3-oxazohdin-2-one and a chiral TADDOL-Ti(IV) complex (see Chapters 1 and 6 by Hayashi and Gothelf, respectively) has been characterized [16]. The structure of this complex has the chiral TADDOLate and cinnamoyloxazohdinone ligands coordinated to titanium in the equatorial plane and the two chloride ligands in the axial plane and is similar to A in Fig. 8.8. The chiral discrimination was proposed to be due to... 

Acylation of the monosubstituted piperazine, 99 (obtainable by the protection-deprotection scheme outlined above), with cinnamoyl chloride gives the corresponding amide (100). Reduction of the carbonyl by means of lithium aluminum hydride affords cinnarizine (101). ... 

A solution of 1-piperazino ethyl acetate (Q2 mol) in benzene (300 ml) is treated with 3,4.5-trimethoxy cinnamoyl chloride (0,2 mol) in the presence of sodium bicarbonate (0.3 mol). After contacting for one hour at room temperature, the mixture is refluxed for a further hour. The benzene solution is then treated with an aqueous solution of sodium bicarbonate. After evaporation of the solvent, a solid product is obtained which is recrystallized from isopropyl ether. Melting point = 96°C. This base, when treated with hydrochloric acid, gives a hydrochloride having a melting point of 200°C with decomposition. By the action of malaic acid the acid maleate is obtained, having a melting point of 130°C. 

Cinnamoyl chloride Benzhydryl piperazine Lithium aluminum hydride... 

This compound can be prepared by the reaction of cinnamoyl chloride with benzhydryl-piperazine. The reaction is carried out in dry benzene under reflux. The benzene is then evaporated, the residue taken up in chloroform, washed with dilute HCI and then made alkaline. 

Cortisone acetate Demegestone Fluocortolone Medrogestone Norethindrone Chromic anhydride Fludiazepam HCI Nimetazepam Sulpro stone Cinchonidine Melphalan Cinnamoyl chloride Cinnarizine... 

Hydroxylamine, IV-benzoyl-lV-phenyl-in gravimetry, 1, 532 liquid-liquid extraction, 1, 544 Hydroxylamine, A -cinnamoyl-A -phenyl-liquid-liquid extraction, 1,544 Hydroxylamine, Ar,A -di-(-butyl-metal complexes, 2, 798 Hydroxylamine, Ay/V-diethyl-metal complexes, 2,798 Hydroxylamine, AAmethyl-metal complexes, 2,798 Hydroxylamine, A -2-naphthol-A -nitroso-ammonium salt — see Ncocupferron Hydroxylamine, A -nilrosophenyl-ammonium salt — see Cupferron Hydroxylamine ligands, 2, 101 Hydroxylamine oxido reductase, 6, 727 Hydroxylases molybdenum, 6,658,662 Hydroxylation arenes... 

C,H802 140-10-3) see Tolterodine cinnamoyl chloride (C9H7CIO 102-92-1) see Cinmetacin cinnamyl alcohol... 

The pure enzyme was tested for activity against several methylated phenolic and cinnamic acids (Table 2). The enzyme was active on methyl esters of cinnamic acids caffeio p-coumaric> ferulic, and is therefore termed a cinnamoyl esterase (CinnAE). 

Ralph, J. Kim, H. Lu, F. Grabber, J. H. Boerjan, W. Leple, J.-C. Berrio Sierra, J. Mir Derikvand, M. Jouanin, L. Lapierre, C. Identification of the structure and origin of a thioacidolysis marker compound for ferulic acid incorporation into angiosperm lignins (and an indicator for cinnamoyl-CoA reductase deficiency). Plant J. 2008, 53, 368-379. 

---