Category: 15732-75-9

Xie, Jianing published the artcilePd-catalyzed stereoselective tandem ring-opening amination/cyclization of vinyl ¦Ã-lactones: access to caprolactam diversity, Formula: C11H10O3, the publication is Chemical Science (2020), 11(33), 8839-8845, database is CAplus and MEDLINE.

A stereoselective amination/cyclization cascade process was developed that allowed for the preparation of a series of unsaturated and substituted caprolactam derivatives I [R = Ph, 3,5-di-MeC₆H₃, 2-naphthyl, etc.; R¹ = Ph, Bn, CH(Ph)₂, etc.; R² = H, Me, R³ = CH₂, C=CH₂, CHPh] in good yields. This conceptually novel protocol took advantage of the easy access and modular character of vinyl ¦Ã-lactones that could be prepared from simple precursors. Activation of the lactone substrate in the presence of a suitable Pd precursor and newly developed phosphoramidite ligand offers a stereocontrolled ring-opening/allylic amination manifold under ambient conditions. The intermediate (E)-configured ¦Å-amino acid could be cyclized using a suitable dehydrating agent in an efficient one-pot, two-step sequence. This overall highly chemo-, stereo- and regio-selective transformation streamlined the production of a wide variety of modifiable and valuable caprolactam building blocks in an operationally attractive way.

Chemical Science published new progress about 15732-75-9. 15732-75-9 belongs to catalysis-chemistry, auxiliary class Alkenyl,Carboxylic acid,Benzene,Ketone, name is 2-Methylene-4-oxo-4-phenylbutanoic acid, and the molecular formula is C9H5ClO4S, Formula: C11H10O3.

Referemce:
https://courses.lumenlearning.com/boundless-chemistry/chapter/catalysis/,
Catalysis – Wikipedia

El-Ghandour, Nagui published the artcilePreferential manner of the cycloaddition of diazomethane to some methyl ¦Â-acylacrylates, Application of 2-Methylene-4-oxo-4-phenylbutanoic acid, the publication is Bulletin de la Societe Chimique de France (1972), 2817-29, database is CAplus.

The addition of CH2N2 to acrylate esters (I; R = EtO, Ph, Me) and (II; R = Ph, Me) is governed only by electronic effects. Mixtures of 4-carbomethoxy-2-pyrazolines III (major products) and 3-carbomethoxy compounds IV (minor products) are obtained from I. 1-Pyrazolines V and 2-pyrazolines VI are the major and minor products, resp., in the addition of CH2N2 to II.

Bulletin de la Societe Chimique de France published new progress about 15732-75-9. 15732-75-9 belongs to catalysis-chemistry, auxiliary class Alkenyl,Carboxylic acid,Benzene,Ketone, name is 2-Methylene-4-oxo-4-phenylbutanoic acid, and the molecular formula is C11H10O3, Application of 2-Methylene-4-oxo-4-phenylbutanoic acid.

Referemce:
https://courses.lumenlearning.com/boundless-chemistry/chapter/catalysis/,
Catalysis – Wikipedia

Bailey, Philip S. published the artcileFurther studies with cis- and trans-¦Â-benzoyl-¦Á- and ¦Â-methylacrylic acids and ¦Â-benzoyl-¦Á-methylenepropionic acid, Related Products of catalysis-chemistry, the publication is Journal of Organic Chemistry (1956), 624-7, database is CAplus.

cf. C.A. 49, 235g. In the preparation of ¦Â-benzoyl-¦Á-methylenepropionic acid (I) by the Friedel-Crafts reaction between C₆H₆ and itaconic anhydride (II), an acid (III), isomeric with I and cis- (IV) and trans-¦Â-benzoyl-¦Á- (V) and ¦Â-methylacrylic acid (VI), is obtained. The structure of III has been elucidated. Condensation of 50 g. II and 80 cc. C₆H₆ in 250 cc. CS₂ in the presence of 170 g. AlCl₃ as described earlier, treatment of the reaction product 2 h. with boiling Ba(OH)₂ to hydrolyze I, and steam distillation and acidification of the mixture give 1-oxo-2-indanacetic acid (VII), m. 147-8¡ã (semicarbazone, m. 240-1¡ã; morpholinium salt, m. 124-5¡ã). Refluxing 0.2 g. VII 0.5 h. with 0.8 g. KMnO₄ and 0.2 cc. 10% NaOH in 16 cc. H₂O, acidifying the mixture with H₂SO₄, refluxing it another 0.5 h., dissolving the MnO₂ with NaHSO₃, and extracting with Et₂O give o-C₆H₄(CO₂H)₂. Adding (4 min.) 2 g. VI to 7.5 g. CrO₃ and 6.2 cc. concentrated H₂SO₄ in 75 cc. boiling H₂O, refluxing the mixture 2 min., extracting with Et₂O, extracting the washed Et₂O solution with dilute NaOH, and acidifying the alk. solution give 47% homophthalic acid, m. 174-6¡ã. Treating 5 g. I 24 h. in 30 cc. morpholine (VIII) and evaporating the solution to 15 cc. give 8.2 g. crystals, m. 100-4¡ã, from which, on extraction with 30 cc. warm Et₂O-EtOH (1:1), 2.2 g. ¦Â-benzoyl-¦Á-morpholino-isobutyric acid (IX), m. 118-19¡ã, is obtained (HCl salt, 87%, m. 210-12¡ã); from the insoluble residue 5.5 g. morpholine salt (X) of IX, m. 105-6¡ã, is isolated. Similar results are obtained with IV and V. Treating IX or X with dilute aqueous HCl gives 91% V, m. 109-10¡ã, which is also obtained when IX.HCl is refluxed 1-3 h. in H₂O. I is recovered unchanged after treatment with EtOH-HCl. Treating 5 g. I in 50 cc. Et₂O 10 min. with 10 cc. VIII gives 66% VIII salt (XI) of I, m. 77-8¡ã, which, on acidification with dilute HCl, gives 60% I, m. 150-4¡ã. Treating XI with an excess of VIII gives 80% IX. On standing, XI is slowly converted into 30% IX. Treating 1 g. VI in 10 cc. Et₂O 24 h. with 10 cc. VIII and cooling the mixture with ice gives 83% VIII salt (XII) of ¦Â-benzoyl-¦Á-morpholino-butyric acid (XIII), m. 138-9¡ã, which (6 g.) in 80 cc. H₂O adjusted with 5% HCl to pH 5 gives 94% XIII, m. 115-16¡ã. Treating XIII with an excess of VIII gives XII again. XIII of XII in dilute HCl remains stable for several hrs. but when the solution is heated 10-15 min. on a water bath 80-90% VI is formed. An attempt to convert XIII to a dibenzoylmorpholinopropane by a Friedel-Crafts reaction failed.

Journal of Organic Chemistry published new progress about 15732-75-9. 15732-75-9 belongs to catalysis-chemistry, auxiliary class Alkenyl,Carboxylic acid,Benzene,Ketone, name is 2-Methylene-4-oxo-4-phenylbutanoic acid, and the molecular formula is C11H10O3, Related Products of catalysis-chemistry.

Referemce:
https://courses.lumenlearning.com/boundless-chemistry/chapter/catalysis/,
Catalysis – Wikipedia

Lutz, Robert E. published the artcileThe cis- and trans-3-aroyl-2- and 3-methylacrylic acids and 3-aroyl-2-methylenepropionic acids, Formula: C11H10O3, the publication is Journal of the American Chemical Society (1953), 5039-44, database is CAplus.

Ultraviolet absorption studies on the cis-3-aroyl-2- and 3-methylacrylic acids and related compounds showed that the cis compounds in solution are cyclic but are open-chain in the form of anions. The cis-3-benzoyl-2- and 3-methyl compounds and both 3-aroyl-2-methylenepropionic acids have been made, resp., from citraconic (I) and itaconic anhydride (II) by Friedel-Crafts reactions. The trans isomers are the stable forms; the cis isomers are labile; and the 3-aroyl-2-methylenepropionic acids also are labile and the least stable of the 3 types. Interconversions of the various isomers are described. II (50 g.) added during 1 hr. with stirring to 140 g. AlCl₃, 80 cc. dry C₆H₆, and 150 cc. dry CS₂ at 45°, the mixture stirred 1 hr. at 50-5° and 10 hrs. at room temperature, hydrolyzed with ice and concentrated HCl, filtered, and the colorless crystalline material (59 g.), m. 138-40°, triturated with 500 cc. boiling C₆H₆ left 40 g. BzCH₂C(:CH₂)CO₂H (III), m. 148-52°. The EtOH filtrate from the III gave on cooling 12.5 g. material, m. 125-8°, which recrystallized from C₆H₆ (m. 130-1°) and fractionally recrystallized from 60% EtOH, yielded 7 g. III and 4 g. (5%) of a new isomer, m. 146-7°, which appeared to be a nuclear cyclization product and was oxidized by KMnO₄ to o-C₆H₄(CO₂H)₂. The alc. filtrate and the C₆H₆-CS₂ filtrate from the crude III gave an addnl. 6.7 g. III (total yield 63%). III is readily soluble in aqueous Na₂CO₃, very slowly soluble in aqueous NaHCO₃, and decolorizes KMnO₄ in Me₂CO. PhBr and II gave similarly 91% p-BrC₆H₄COCH₂C(:CH₂)CO₂H (IV). I (50 g.) added with stirring to 130 g. AlCl₃, 100 cc. C₆H₆, and 150 cc. CS₂ during 1 hr. at 50°, the mixture heated 0.5 hr., stirred overnight, and hydrolyzed with ice and HCl, the organic layer evaporated in an air stream, the residue extracted with 400 cc. 10% aqueous Na₂CO₃, the extract washed with C₆H₆, acidified with HCl, extracted with C₆H₆, and the extract concentrated to 100 cc., and cooled gave 39 g. (46%) cis-BzCMe: CHCO₂H (V), m. 65-75° (recrystallized, it m. 79-80°). The filtrate from the crude V diluted with petr. ether and cooled gave 12 g. (14%) cis-BzCH:CMeCO₂H (VI), m. 70-80° (recrystallized from CCl₄, it m. 92-3°). V and VI are soluble in hot H₂O and cold aqueous NaHCO₃, and decolorize acidic KMnO₄. III (1 g.) and 5 cc. Et₃N in 15 cc. Et₂O let stand 24 hrs., the mixture evaporated, extracted with dilute HCl, and the resulting product recrystallized from EtOH gave 0.85 g. trans-isomer (VII) of VI, m. 109-10°. The isomerization of III also occurred slowly in NaOH solution, and in 10 min. by heating at 175°. The oily Me ester of trans-BzCMe: CHCO₂H (VIII) was prepared by a previously described method (C.A. 27, 2426), immediately hydrolyzed during 2 hrs. at room temperature, the mixture washed with Et₂O, acidified, extracted with Et₂O, the extract evaporated, and the residue crystallized from C₆H₆CCl₄ to give 41% VIII, m. 90-4° (recrystallized from aqueous EtOH, it m. 102-3°). III hydrogenated over PtO₂ yielded 81% BzCH₂CHMeCO₂H (IX), m. 138-40°; semicarbazone, m. 220-3°. The hydrogenation of IV over Raney Ni at atm. pressure yielded 88% p-BrC₆H₄COCH₂CHMeCO₂H (X), m. 120-2°. The reduction with Zn and AcOH gave high-melting and presumably dimeric substances, m. 204-12°, from III, and m. above 350° from IV, which were not investigated further. VI and VII heated 10 min. with Zn and AcOH on the steam bath gave IX, m. 138-40°, in 79 and 81% yield, resp. The similar reduction of VII and VIII during 20 min. gave MeCHBzCH₂CO₂H, m. 59-60°, in 63 and 71% yield, resp.; semicarbazone, m. 177-8°. III, VI, and VII (1 g. each) refluxed 4 hrs. with 6-8 g. Ba(OH)₂, and the mixture steam-distilled gave in each case a high yield of PhAc, identified as the semicarbazone, m. 197-8°. V and VIII hydrolyzed similarly yielded 71 and 50% PhCOEt, resp.; semicarbazone, m. 172-3°. IV and cis-4-BrC₆H₄COCH:CMeCO₂H (XI) gave similarly 69 and 51% p-BrC₆H₄Ac, m. 51-2°, resp.; oxime, m. 127-9°. The trans isomer (XII) of XI gave similarly 57% p-BrC₆H₄COEt, m. 46-8°; oxime, m.88-9°. The following isomerizations were carried out by the method described for the isomerization of III to VII: IV to 90% trans-p-BrC₆H₄COCH:CMeCO₂H (XIII), m. 182-4°; XI to 70% XIII; and VI to 88% VII, m. 104-6°. VI dissolved in NaOH or aqueous NaHCO₃, or heated 10 min. at 175° was also isomerized to VII. Et₃N or heat failed to isomerize V. V in Et₂O treated with morpholine gave an addition compound, m. 138-40°, which, when decomposed with warm 10% HCl, yielded 40% VIII, m. 100-2°. Et₃N did not isomerize cis-p-BrC₆H₄COCMe:CHCO₂H (XIV) to the trans isomer. VII (1 g.) in 50 cc. dry Et₂O exposed 2 days to sunlight, the mixture evaporated, and the residue recrystallized from hot C₆H₆ gave 0.9 g. VI, m. 80-5° (recrystallized from C₆H₆, it m. 89-92°). VII in Et₂O exposed to sunlight 1 week, or VI 4 days, gave 40-50% III, m. 152-4° (from aqueous EtOH). Similarly were isomerized: XI to 30% IV, m. 160-2° (from C₆H₆); XIII to IV; VIII to 80% V, m. 68-76° (recrystallized from CCl₄, it m. 78-80°); and XII to 64% XIV, m. 130-5° (recrystallized from CCl₄, it m. 138-41°). The ultraviolet absorption spectra of XIV, the cyclic Me ester of XIV, the salt of XIV, the straight-chain cis-Me ester of XIV, XII, the salt and the Me ester of XII, p-BrC₆H₄COCHMeCH₂CO₂H, XI, the salt of XI, XIII, Me ester of XIII, X, and IV are recorded.

Journal of the American Chemical Society published new progress about 15732-75-9. 15732-75-9 belongs to catalysis-chemistry, auxiliary class Alkenyl,Carboxylic acid,Benzene,Ketone, name is 2-Methylene-4-oxo-4-phenylbutanoic acid, and the molecular formula is C11H10O3, Formula: C11H10O3.

Referemce:
https://courses.lumenlearning.com/boundless-chemistry/chapter/catalysis/,
Catalysis – Wikipedia