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8 protocols using phenyl isocyanate

1

Synthesis of N-phenyl carbamates

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Methyl N-phenyl carbamate (CAS: 2603-10-3) was purchased from TCI chemicals. Phenyl isocyanate (≥98%), aniline (≥99%), 1,3-Diphenylurea (98%), 1-(2-Pyridyl) piperazine (≥99%), Dimethyl sulfoxide (anhydrous ≥ 99.9%) and diphenyl ether (≥99%) were purchased from Sigma-Aldrich.
Acetonitrile (HPLC grade), water (HPLC grade), ammonium acetate (≥98%), and formic acid (For LC-MS 98–100%) were all purchased from Sigma-Aldrich for use in analytical equipment (LC).
Catalysts include montmorillonite K10 (H2Al2(SiO3)4−nH2O, surface area 220–270 m2/g), zinc oxide (nanopowder, ≤100 nm, 10–25 m2/g), and aluminium oxide (50–300 mesh, acid, 155 m2/g) purchased from Sigma-Aldrich and Bismuth(III) oxide (nanopowder 99.9%, 3.8–5.5 m2/g) was purchased from Fischer scientific. The catalysts were stored in an oven (110 °C) prior to experiments.
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2

Synthesis of Functionalized Adamantanes

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Triethylamine (BioUltra ≥ 99.5%, CAS 121-44-8), 3-chloroaniline (99%, CAS 108-42-9), cyclohexyl isocyanate (98%, CAS 3173-53-3), phenyl isocyanate (98%, CAS 103-71-9) manufactured by Sigma-Aldrich (St. Louis, MO, USA) were used without purifying.
4-(Trifluoromethoxy) isocyanate (97%, CAS 35037-73-1), aniline (99+%, CAS 62-53-3), 2-fluoroaniline (99%, CAS 348-54-9), 3-fluoroaniline (98%, CAS 372-19-0), 4-fluoroaniline (99%, CAS 371-40-4) produced by the AlfaAesar (Ward Hill, MA, USA) were used without additional purification.
Diethyl ether was purified by well-known methods. trans-4-Amino-(cyclohexyloxy)benzoic acid 7a [2 (link)], 1,3-dehydroadamantane 2a [12 (link)], 1,3-dehydro-5,7-dimethyladamantane 2b [12 (link)], 2-(adamantane-1-yl)-2-phenylacetic acid ethyl ester 3a [15 (link)], 2-(adamantane-1-yl)-2-phenylacetic acid 4a, 1-(isocyanato(phenyl) methyl)adamantane 5a [10 (link)] were obtained by well-known methods.
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3

Organic Synthesis Reagent Procurement

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Aniline (≥99%), 1,2-dichlorobenzene (99%), dimethyl sulfoxide (>99%), 1,3-diphenyl urea (98%), diphenyl ether (99%), γ -valerolactone (98%), phenyl isocyanate (>98%), and 1-(2-pyridyl)piperazine (>99%) were purchased from Sigma-Aldrich. For the analytical equipment, acetonitrile (HPLC grade), ammonium acetate (>98%), formic acid (for LC-MS 98–100%), and water (HPLC grade) were purchased from Sigma-Aldrich.
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4

Synthesis and Characterization of Organic Compounds

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The composition of the C-steel used throughout all experiments was (wt%) 0.20 C, 0.045 P, 0.30 Si, 0.53 Mn, 0.055 S, Fe balance. The corrosive solution (1.0 M HCl) was prepared by direct dilution with double-distilled water.
Malonic diethyl ester, salicylaldehyde, phenyl isocyanate, and hydrazine hydrate (80%) were purchased commercially from Sigma Aldrich, St. Louis MO, USA, and used without any further purification. Absolute ethanol, DMSO, diethyl ether, and all used solvents were purchased from Merck, Mumbai, India. The melting points were reported on a heated stage Gallen Kamp melting point equipment (Gemini Lab, Apeldoom, Netherlands). Elemental C, H, N, and S analyses were carried out on a Fison EA 1108 analyser (Shimadzu, Kyoto, Japan). The infrared (FTIR) spectra were recorded by employing a FTIR.8300 Shimadzu Spectrophotometer (Shimadzu, Kyoto, Japan) by using KBr disc in the frequency range of 4000–400 cm−1. The 1H NMR spectra were recorded on an Ultra-Shield™ 500 MHz NMR Spectrometer (Shimadzu, Kyoto, Japan) using deuterated DMSO-d6s the solvent and tetramethylsilane (TMS) as the internal standard.
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5

Synthetic Routes for Nitrogen-Containing Heterocycles

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Thiophene-2-carbonitrile
(Alfa Aeser, 98%), thiophene-2-carbaldehyde (Merck, 93%), N-chlorosuccinimide (Alfa Aeser, 98%), p-anisidine (Alfa Aeser, 99%), aluminum chloride anhydrous (Fluka,
98%), p-toluidine (Adwic, Egypt), hydroxylamine hydrochloride
(Oxford, 98%), aniline (Adwic, Egypt), O-phenylenediamine
(Sigma-Aldrich, 98%), α-naphthylamine (Adwic, Egypt), tetralin
(Alfa Aser, 97%), 2-amino-5-chlorophenol (Sigma-Aldrich, 97%), acetonitrile
(Sigma-Aldrich, HPLC grade), 2-amino-5-methylphenol (Sigma-Aldrich,
98%), phenyl isocyanate (Sigma-Aldrich, 98%), 4-methoxyphenyl isocyanate
(Sigma-Aldrich, 98%), 4-methylphenyl isocyanate (Sigma-Aldrich, 98%),
and 1,1,2,2-tetrachloroethane (Fluka, 95%) were used. Other reagents
and solvents were purchased and used as received unless otherwise
listed.
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6

Fatty Acid Methyl Ester Characterization

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Fatty Acid Methyl Ester of Very High Oleic Sunflower Oil (FAMEVHOSO) with 3.32 mmol double bond/g was kindly supplied by the ITERG group (Canéjan, France). The FAMEVHOSO is composed of 83% of oleic acid. Table S1 presents the distribution of fatty methyl esters of unsaturated FAMEVHOSO. Glacial acetic acid (AA), toluene (99%), H2O2 30%, ethyl acetate (99%), and ethanol (99.9%) were obtained from Fisher Scientific (Illkirch-Graffenstaden, France). Amberlyst® 15H (strongly acidic cation exchanger dry), Amberlite® IR120H (strongly acidic hydrogen form), CDCl3, phenylisocyanate (98%), dibutylamine (DBA) (99.5%), HBr (48% in water), HCl (37% in water), and diethylamine (99%) (DEA) were provided by Sigma-Aldrich (Saint-Quentin-Fallavier, France). ethanol absolute (EtOH) was purchased from VWR (Briare, France). All of the chemicals were used without any purification.
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7

Polyurethane Synthesis Protocol

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Phenyl isocyanate (98%) (PI), p-tolyl isocyanate (PTI), dimethyl sulfoxide (DMSO, anhydrous, 99.9%), D-sorbitol (98%), and glycerol (99%), tin(II) 2-ethylhexanoate (TEH) and toluene were purchased from Sigma-Aldrich (Darmstadt, Germany) and all were used as received except the toluene, which was purified and dried according to the well-known procedure [23 (link)]. The D(+)-sucrose (puriss, Ph. Eur. 6.) was obtained from Reanal (Budapest, Hungary) and dried in a vacuum oven at 40 °C for overnight before use. Methanol (HPLC grade) from Merck (Darmstadt, Germany) was used without any purification.
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8

Cellulose Characterization via Derivatization

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Pyridine (≥ 99.9%, Sigma, USA), phenyl-isocyanate (≥ 99.9%, Sigma, USA), methanol (Stanlab, Poland) and tetrahydrofuran (Chempur, Poland) were used for cellulose derivatisation and SEC analyses. Four different cellulose samples were purchased from Sigma, USA: Sigmacell type 20 (labelled "S20", from cotton linters, product n° 310697), Sigmacell type 50 (labelled "S50", from cotton linters, product n° S5504), Microcrystalline cellulose (labelled "SMC", from cotton linters, product n° 435263), and acid-washed cellulose (labelled "SAW", from fir, product n° 22182). All cellulose samples were milled for 30, 60 and 120 min using a Pulverisette 23 ball-mill (Fritsch, Germany).
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