4 hydroxybenzaldehyde

All commercially available chemicals were purchased as pure for synthesis or analytical grade reagents (Sigma-Aldrich, St. Louis, MO, USA; ARMAR, Muligasse, Switzerland; Fluka Hamburg, Germany; Loba Feinchemie AG, Fischamend Austria; POCh Gliwice, Poland) and solvents were primarily used without further purification. In particular, 4-hydroxybenzoic acid hydrazide (36), acetic acid hydrazide (37), benzaldehyde (41), 3-phenylpropionaldehyde (42), 4-methylbenzaldehyde (43), 4-iso-propylbenzaldehyde (44), benzaldehyde-2-sodiumsulfonate (45), salicylic aldehyde (46), 3-hydroxy-benzaldehyde (47), 4-hydroxybenzaldehyde (48), 2-methoxybenzaldehyde (49), 3-methoxy-benzaldehyde (50), anisaldehyde (51), gentisaldehyde (52), vanillic aldehyde (56) (LobaFeinchemie), 3-tert-butyl-salicylic aldehyde (57), 2,4-dihydroxy-benzaldehyde (59), 3,5-di-tert-butyl-salicylic aldehyde (64), nicotinic acid methyl ester (76), 4-methoxybenzoic acid (77), and benzoic acid (78), syringaldazine (SNG, 4-hydroxy-3,5-dimethoxybenzaldehyde azine), guaiacol (2-Methoxyphenol), dimethyl sulfoxide for plant cell culture, laccase from Trametes versicolor in lyophilized powder were bought from Sigma-Aldrich. vanillic aldehyde (56) was purchased from Loba Feinchemie. The 5-nitro-2-furfural diacetyl acetal (69) and phloroglucinol (73) were purchased from Fluka. Inorganics, citric acid monohydrate, and sodium phosphate dibasic dodecahydrate were purchased from POCh. The 99.8 atom % D solvents for NMR spectroscopy, chloroform-d₁ (CDCl₃), and dimethyl sulfoxide-d₆ (DMSO-d₆) and ethanol (95%) for biological tests were purchased from ARMAR (Muligasse, Switzerland) and were used without further purification.
Methanol was distilled prior to the condensation reaction from Mg element shavings in the presence of I₂. Analytical TLC was performed on PET foils precoated with silica gel (Merck silica gel, 60 F254) and was made visual under UV light (λ_max = 254 nm) or by staining with iodine vapor. Melting points were determined on an Electrothermal IA 91100 digital melting-point apparatus (Sigma-Aldrich, Saint Louis, MO, USA) using the standard open capillary method. FT-IR spectra (4000–400 cm⁻¹) were recorded on a 2000 FT-IR (Perkin–Elmer, Manchester, UK) or VERTEX 70V spectrometer (Bruker, Ettlingen, Germany) using a diamond ATR accessory. Absorption maxima are reported in wavenumbers (cm^–1). ¹H-NMR and ¹³C-NMR spectra were recorded on Jeol 400yh (Tokyo, Japan) (399.78 MHz for ¹H and 100.52 MHz for ¹³C) at 295 K. Chemical shifts (δ) are given in parts per million (ppm) downfield relative to TMS, and coupling constants (J) are in Hz. Residual solvent central signals were recorded as follows: DMSO-d₆, δ_H = 2.500 ppm, δ_C = 39.43 ppm; CDCl₃, δ_H = 7.263 ppm, δ_C = 77.00 ppm. When measured, DEPT and ATP experiments signals are referred to as (+) or (–). High-resolution mass spectra (HRMS) were recorded on a LCD Premier XE instrument (Waters, Manchester United, UK), and only the [M + H]⁺ or [M + Na]⁺ molecular species were reported.
The literature procedure was adapted for the preparation of hydrazide–hydrazones 1–3, 5–11, 14–25, 27–30 [48 (link)], 32 [71 ], 31, and 33–35 [47 (link)]; hydrazides 38–40 [47 (link)]; aldehydes 53–55, 58, 61, 62 [48 (link),89 (link)], 60 [66 (link)], 63 [67 (link)], 65 [48 (link),90 (link)], 66, 67 [48 (link)], and 68 [69 (link)]; and phenol 72 [68 (link)].
Purity and homogeneity of known compounds were confirmed by measuring their m.p. for 1–3, 5–11, 14–21, 24, 25, 27–30 [48 (link)], 12 [91 (link)], 31, 33–35 [47 (link)], 32 [71 ], 38 [48 (link)], 39 [92 (link),93 (link)], 40 [47 (link),93 (link)], 60 [94 (link)], 63 [67 (link)], and 68 [69 (link)]; boiling points for 65 [48 (link)] and 68 [67 (link)]; FT-IR spectra for 3 [48 (link)], 22 [95 (link)], 25 [48 (link)], 38, 39 [52 (link)], 40 [47 (link)], and 68 [69 (link)]; ¹H-NMR spectra for 3 [48 (link)], 4 [96 (link)], 12 [97 (link)], 13 [98 ], 22 [99 (link)], 23 [41 (link)], 25, 28 [48 (link)], 38, 39 [52 (link)], 40 [47 (link)], 60 [66 (link)], 65 [48 (link)], and 68 [69 (link)]; ¹³C-NMR spectra for 3 [48 (link)], 4 [96 (link)], 22 [95 (link)], 25, 28 [48 (link)], 38, 39 [52 (link)], 40 [47 (link)], 65 [48 (link)], and 68 [69 (link)]; and/or HRMS for 3 [48 (link)], 4 [96 (link)], 22 [95 (link)], 25, and 28 [48 (link)] and comparing them with literature data. Two new aroylhydrazide–hydrazones, 26 and 32, were fully characterized. The position of hydrogen and carbon atoms in the NMR data was determined by supporting the standard dept-135 experiment and by 2D map analysis of Heteronuclear Multiple Quantum Correlation (HMQC), Heteronuclear Single Quantum Coherence (HSQC), Heteronuclear Multiple Bond Correlation (HMBC), and Nuclear Overhauser Enhancement Spectroscopy (NOESY) experiments, if measured. The spectra images of FT-IR and NMR for the following compounds are placed in the Supplementary Materials.
The cultures of Botrytis cinerea strain FBc05 and Sclerotinia sclerotiorum strain FSc10 were obtained from the collection of the Division of Plant Pathology and Mycology at the Department of Plant Protection of Wroclaw University of Environmental and Life Sciences (Poland). Cerrena unicolor (Bull.ex.Fr.) Murr, strain no. 139, originated from the culture collection of the Department of Biochemistry, University of Lublin (Poland). The stock cultures were maintained on potato dextrose agar at +4 °C and periodically transferred to a fresh medium.

Pyrrole (97%) was distilled before use, graphite powder (99%), and Acid Orange 7 dye (dye content ≥ 85%) was purchased from (Merck Darmstadt, Germany). 4-hydroxybenzaldehyde (98%) and propionic acid (99.5%), Chitosan medium Mwt with high purity (Mwt 150,000 g/mol, degree of deacetylation 81%), N,N-dimethylformamide (DMF) (99.8%), and cobalt (II) chloride hexahydrate (≥ 97%) were obtained from (Sigma-Aldrich). Hydrazine hydrate (80%), chloroacetyl chloride (> 99%), phthalic anhydride (98%), and triethylamine (99%) were obtained from (Alpha-Chemika, India). (El-Nasr Pharmaceutical Chemicals, Egypt) supplied chloroform (99.4%), methylene chloride (99.9%), methanol (99.9%), concentrated sulfuric acid (99%), phosphoric acid (99%), sodium carbonate, potassium permanganate, and hydrogen peroxide (30%, as an oxidant), and its initial concentration was determined using potassium permanganate⁴³ . Silica gel (60–120 mesh) was purchased from (Fisher Co., New Jersey, USA).

Corncob was composed of 34.5% cellulose, 30.9% hemicellulose, and 22.7% lignin. After pretreatment with dilute sulfuric acid at 160 °C for 60 min, the remaining solid residue was composed of 54.6% cellulose, 3.1% hemicellulose, and 32.3% lignin. The hydrolysate pretreatment was kindly provided by a biomass factory in China. Syringaldehyde and ferulic acid were purchased from TCI (Shiga, Japan). 4-hydroxybenzoic acid, vanillic acid, syringic acid, 4-hydroxybenzaldehyde, vanillin, and p-coumaric acid were purchased from Sigma-Aldrich (Saint Louis, MO, USA).

Malonic acid, tetrahydrofuran (THF), pyridine, piperidine, the deuterated solvent (DMSO-d₆) for NMR analysis, polyvinyl alcohol (PVA), hydrochloric acid, 4-hydroxybenzaldehyde, ethanol, sodium, chloroform, potassium hydroxide, and silver nitrate were products of Sigma Aldrich (Saint Louis, MO, USA). Collagen types I and II were purchased from Proteintech Group Inc. (Chicago, IL, USA). Microbial strains were purchased from BioVitrum (Saint Petersburg, Russia). The antibiotic Nitox was purchased from NITA-FARM (Saratov, Russia).