Aliphatic diazo compounds. X. The reaction of α-diazoacetophenone with methanolic sodium methoxide

1977 ◽  
Vol 55 (1) ◽  
pp. 145-152 ◽  
Author(s):  
Peter Yates ◽  
R. J. Mayfield
Keyword(s):  
Acrylic Acid ◽  
Benzoic Acid ◽  
Sodium Methoxide ◽  
Methyl Benzoate ◽  
Diazo Compounds ◽  
Dilute Solution ◽  
Cis And Trans

The reaction of α-diazoacetophenone (1) with methanolic sodium methoxide in dilute solution gives 3-benzoyl-5-hydroxy-4-phenylpyrazole (4), 3-benzoyl-4-hydroxy-5-phenyl-pyrazole (5), 3-benzoyl-5-methoxy-4-phenylpyrazole (9), 3-benzoyl-4-phenylpyrazole (6), 5-benzoyltetrazole (7), 3,6-dibenzoyldihydro-s-tetrazine (10), cis- and trans- β-benzoyl- α-phenyl-acrylic acid, acetophenone, methyl benzoate, and benzoic acid. The pyrazoles 4, 5, and 9 are considered to arise via reaction of 1 to give α-methoxyacetophenone followed by further reaction of the anion of the latter with 1. Evidence in accord with this view was obtained by a study of the products formed when 1 was treated with methanolic sodium methoxide in the presence of 2-methoxy-4′-methylacetophenone. Acetophenone is considered to arise by reduction of 1 via phenylglyoxal 2-monohydrazone (37); condensation of 1 with the enolate ion derived from acetophenone then can give the pyrazole 6, while condensation of 1 with 37 could give the tetrazole 7.

Rotational Study of cis- and trans-Acrylic Acid–Trifluoroacetic Acid

2013 ◽  
Vol 117 (50) ◽  
pp. 13500-13503 ◽  
Author(s):  
Qian Gou ◽  
Gang Feng ◽  
Luca Evangelisti ◽  
Walther Caminati
Keyword(s):  
Acrylic Acid ◽  
Trifluoroacetic Acid ◽  
Cis And Trans

Diels–Alder and Dehydration Reactions of Biomass-Derived Furan and Acrylic Acid for the Synthesis of Benzoic Acid

ACS Catalysis ◽  
2015 ◽  
Vol 5 (11) ◽  
pp. 6946-6955 ◽  
Author(s):  
Eyas Mahmoud ◽  
Jingye Yu ◽  
Raymond J. Gorte ◽  
Raul F. Lobo
Keyword(s):  
Acrylic Acid ◽  
Benzoic Acid ◽  
Diels Alder ◽  
Dehydration Reactions

scholarly journals Aliphatic diazo compounds. IX. The base-induced dimerization of α-diazo ketones

1969 ◽  
Vol 47 (21) ◽  
pp. 3997-4004 ◽  
Author(s):  
Peter Yates ◽  
R. G. F. Giles ◽  
D. G. Farnum
Keyword(s):  
Benzoic Acid ◽  
Dimethyl Sulfoxide ◽  
Potassium Hydroxide ◽  
Ammonium Acetate ◽  
Butyl Alcohol ◽  
Diazo Compounds ◽  
Prolonged Treatment ◽  
Independent Synthesis

Treatment of 2-diazoacetophenone (1) with potassium t-butoxide in t-butyl alcohol gives a colorless dimer, which is shown to be 5-benzoyl-2-phenacyltetrazole (4) by its independent synthesis by phenacylation of 5-benzoyltetrazole. The latter reaction also gives 5-benzoyl-1-phenacyltetrazole (3), which is distinguished from 4 by its reduction to di(2-hydroxy-2-phenylethyl)amine and by its cyclization on treatment with ammonium acetate. The assignment of the structure of the colorless dimer of 1 permits the postulation of related pathways for its formation and that of the red-brown dimer obtained on treatment of 1 with potassium hydroxide in dimethyl sulfoxide. 2-Phenacyltetrazole (22) and benzoic acid are formed in addition to 4 on treatment of 1 with potassium t-butoxide in t-butyl alcohol; these are considered to arise via cleavage of 4, since prolonged treatment of 4 and 3 with potassium t-butoxide in t-butyl alcohol gives 22 and 1-phenacyltetrazole (24), respectively. Compounds 22 and 24 have been prepared independently by phenacylation of tetrazole.

scholarly journals Coordinated and High-Level Expression of Biosynthetic Pathway Genes Is Responsible for the Production of a Major Floral Scent Compound Methyl Benzoate in Hedychium coronarium

2021 ◽  
Vol 12 ◽  
Author(s):  
Yuechong Yue ◽  
Lan Wang ◽  
Rangcai Yu ◽  
Feng Chen ◽  
Jieling He ◽  
...  
Keyword(s):  
Gene Expression ◽  
Benzoic Acid ◽  
Methyl Salicylate ◽  
Biosynthetic Pathway ◽  
Floral Scent ◽  
Methyl Benzoate ◽  
High Level Expression ◽  
Developmentally Regulated ◽  
Hedychium Coronarium ◽  
High Level

Methyl benzoate is a constituent of floral scent profile of many flowering plants. However, its biosynthesis, particularly in monocots, is scarcely reported. The monocot Hedychium coronarium is a popular ornamental plant in tropical and subtropical regions partly for its intense and inviting fragrance, which is mainly determined by methyl benzoate and monoterpenes. Interestingly, several related Hedychium species lack floral scent. Here, we studied the molecular mechanism of methyl benzoate biosynthesis in H. coronarium. The emission of methyl benzoate in H. coronarium was found to be flower-specific and developmentally regulated. As such, seven candidate genes associated with methyl benzoate biosynthesis were identified from flower transcriptome of H. coronarium and isolated. Among them, HcBSMT1 and HcBSMT2 were demonstrated to catalyze the methylation of benzoic acid and salicylic acid to form methyl benzoate and methyl salicylate, respectively. Methyl salicylate is a minor constituent of H. coronarium floral scent. Kinetic analysis revealed that HcBSMT2 exhibits a 16.6-fold lower Km value for benzoic acid than HcBSMT1, indicating its dominant role for floral methyl benzoate formation. The seven genes associated with methyl benzoate biosynthesis exhibited flower-specific or flower-preferential expression that was developmentally regulated. The gene expression and correlation analysis suggests that HcCNL and HcBSMT2 play critical roles in the regulation of methyl benzoate biosynthesis. Comparison of emission and gene expression among four Hedychium species suggested that coordinated and high-level expression of biosynthetic pathway genes is responsible for the massive emission of floral methyl benzoate in H. coronarium. Our results provide new insights into the molecular mechanism for methyl benzoate biosynthesis in monocots and identify useful molecular targets for genetic modification of scent-related traits in Hedychium.

Cu-Catalyzed C–H Alkenylation of Benzoic Acid and Acrylic Acid Derivatives with Vinyl Boronates

2020 ◽  
Vol 22 (12) ◽  
pp. 4692-4696
Author(s):  
Jian-Jun Li ◽  
Cheng-Gang Wang ◽  
Jin-Feng Yu ◽  
Peng Wang ◽  
Jin-Quan Yu
Keyword(s):  
Acrylic Acid ◽  
Benzoic Acid ◽  
Vinyl Boronates
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