Category: 30431-99-3

Stepannikova, Kateryna O. published the artcileSynthesis of Spirocyclic β- and γ-Sultams by One-Pot Reductive Cyclization of Cyanoalkylsulfonyl Fluorides, Related Products of nitriles-buliding-blocks, the publication is European Journal of Organic Chemistry (2021), 2021(47), 6530-6540, database is CAplus and MEDLINE.

One-pot intramol. cyclization of novel sp³-enriched cyanoalkylsulfonyl fluorides into spirocyclic β- or γ-sultams is disclosed. The method relies on nitrile group reduction followed by sulfonylation of amino group thus formed upon mild conditions (NaBH₄, NiCl₂·6H₂O in MeOH). Cyclization proceeds smoothly with considerable efficiency (48-84%, 10 examples) on up to 30 g scale. The cyanoalkylsulfonyl fluoride intermediates can be obtained via S-nucleophilic substitution in β-functionalized alkanenitriles or double alkylation of α-alkylthioacetonitrile, followed by oxidative chlorination with Cl₂ and further reaction with KHF₂. The title mono- and bifunctional sultams are advanced sp³-enriched building blocks for drug discovery and organic synthesis providing novel substitution patterns and frameworks mimicking saturated nitrogen heterocycles such as pyrrolidine/pyrrolidone.

European Journal of Organic Chemistry published new progress about 30431-99-3. 30431-99-3 belongs to nitriles-buliding-blocks, auxiliary class Tetrahydropyran,Nitrile,Ester, name is Ethyl 4-cyanotetrahydro-2H-pyran-4-carboxylate, and the molecular formula is C9H13NO3, Related Products of nitriles-buliding-blocks.

Referemce:
https://en.wikipedia.org/wiki/Nitrile,
Nitriles – Chemistry LibreTexts

Surzur, Jean M. published the artcileRadical addition to unsaturated alcohols. IV. Synthesis of 4-cyano-4-carbethoxytetrahydropyrans by intramolecular radical addition, SDS of cas: 30431-99-3, the publication is Bulletin de la Societe Chimique de France (1970), 3070-5, database is CAplus.

Esters (I) (Y = CN) were cyclized with Bz2O2 in refluxing cyclohexane. After decomposition of the excess peroxide, the products were distilled to sep. cyclohexane and the telomers. The distillate was analyzed by vapor-phase chromatog. I (m = 2, n = 0, R = H,Me) gave 71-88% tetrahydropyran derivative (II). I (m = 2; n = 1; R and R1 = H (or Me) gave 96-98% tetrahydropyran derivatives and no 7-membered heterocyclic O-containing compounds could be detected. I (m = n = 1, R = H and Me, and X = CO2Et, Y = CO2Et and CN) gave only polymerized products. This type of reaction gave substituted tetrahydropyran or tetrahydrofuran derivatives which are often not readily accessible by other methods. However, the presence of the O atom makes it necessary to operate at very high dilutions and to use longer reaction times if polymerization, is to be avoided.

Bulletin de la Societe Chimique de France published new progress about 30431-99-3. 30431-99-3 belongs to nitriles-buliding-blocks, auxiliary class Tetrahydropyran,Nitrile,Ester, name is Ethyl 4-cyanotetrahydro-2H-pyran-4-carboxylate, and the molecular formula is C8H7NO4, SDS of cas: 30431-99-3.

Referemce:
https://en.wikipedia.org/wiki/Nitrile,
Nitriles – Chemistry LibreTexts

Henze, Henry R. published the artcileHydantoins containing a tetrahydropyranyl substituent, Computed Properties of 30431-99-3, the publication is Journal of the American Chemical Society (1942), 1672-4, database is CAplus.

Refluxing a mixture of 155 g. NCCH₂CO₂Et and 97 g. (ClCH₂CH₂)₂O with 31.5 g. of Na in 450 cc. EtOH for 3 h. gives 31% of the Et ester, b₁₆ 135°, n_D²⁰ 1.4539, d₄²⁰ 1.1109, γ²⁰ 37.4, of 4-cyanotetrahydro-4-pyrancarboxylic acid; heating the acid at 180-200° gives 90% of tetrahydro-4-pyrancarbonitrile (I), b₁₀ 82-3°, n_D²⁰ 1.4521, d₄²⁰ 1.0343, γ²⁰ 40.7. 4-Acyltetrahydropyrans, RCOCH(CH₂.CH₂)₂O, were prepared by addition of a mol. proportion of I in absolute ether to 1.2-2 M proportions of the Grignard reagent (R is given): Me, b₁₄₄ 205-7°, n_D²⁰ 1.4530, d₄²⁰ 1.0243, γ²⁰ 35.8, MR 33.98, 53% yield (semicarbazone, m. 178° (all m. ps. corrected)); Et, b₂₀ 101°, n 1.4541, d. 1.0016, γ 37.2, MR, 38.60, 72% (semicarbazone, m. 151°); Pr, b₅ 85-8°, n 1.4545, d. 0.9828, 57% (semicarbazone, m. 145-6°); Bu, b₅ 100°, n 1.4551, d. 0.9700, 67% (semicarbazone, m. 180°; 2,4-dinitrophenylhydrazone, m. 99°); iso-Bu, b₆ 90-2°, n 1.4545, d. 0.9648, γ 33.2, MR 47.83, 69% (semicarbazone, m. 187-8°; 2,4-dinitrophenylhydrazone, m. 122°); Am, b₅ 106-7°, n 1.4573, d. 0.9589, γ 33.3, MR 52.45, 64% (semicarbazone, m. 117°; 2,4-dinitrophenylhydrazone, m. 89-90°); iso-Am, b₇ 116-17°, n 1.4567, d. 0.9562, γ 32.9, MR 52.45, 65% (semicarbazone, m. 158-9°; 2,4-dinitrophenylhydrazone, m. 134-5°); hexyl, b₆ 134-5°, n 1.4569, d. 0.9446, MR 57.07, 61% (semicarbazone, m. 161°); cyclohexyl, b₅ 142°, n 1.4839, d. 1.0262, MR 54.87, 46% (semicarbazone, m. 213-14°); Ph, m. 57-8°, 67%. The ketone with 1.8 molar equivalents of KCN and 3.6 molar equivalents of (NH₄)₂CO₃ in about 150 cc. 50% EtOH heated 12 h. at 58-60° gives 5-substituted 5-(tetrahydro-4-pyranyl)hydantoins, HN.CO.NH.CO.CRCH(CH₂.CH₂)₂O (R given): Me, m. 250°, 51%; Et, m. 246°, 70%; Pr, m. 223°, 66%; Bu, m. 195°, 49%; iso-Bu, m. 222°, 53%; Am, m. 171-2°, 79%; iso-Am, m. 195-6°, 68%; hexyl, m. 169°, 48%; cyclohexyl, m. 304-6°, 65%; Ph, m. 253°, 72%. The iso-Am and Ph derivatives exhibit mild anticonvulsant activity and are devoid of any hypnotic action.

Journal of the American Chemical Society published new progress about 30431-99-3. 30431-99-3 belongs to nitriles-buliding-blocks, auxiliary class Tetrahydropyran,Nitrile,Ester, name is Ethyl 4-cyanotetrahydro-2H-pyran-4-carboxylate, and the molecular formula is C9H13NO3, Computed Properties of 30431-99-3.

Referemce:
https://en.wikipedia.org/wiki/Nitrile,
Nitriles – Chemistry LibreTexts

Li, Feng published the artcileSynthesis of ethyl 4-cyanotetrahydropyran-4-carboxylate via solid-liquid phase transfer catalysis, Application of Ethyl 4-cyanotetrahydro-2H-pyran-4-carboxylate, the publication is Jingxi Huagong (2008), 25(6), 614-617, database is CAplus.

Eethyl 4-cyanotetrahydropyran-4-carboxylate was synthesized from di-(β-chloroethyl) ether, Et cyanoacetate and K₂CO₃ via solid-liquid phase transfer catalysis, using DMF as solvent and dodecyltrimethylammonium bromide (DTMAB) as catalyst [n(DTMAB):n(Et cyanoacetate) = 0.05:1]. The water produced was separated, sp. surface area of potassium carbonate was 6.72 × 10⁴ m^-1 and reaction temperature was 153°, the yield was 90.6%, the reaction time was 2 h. The mechanism and kinetics of the reaction were also studied. The reaction could be described by the pseudo-second-order kinetics. With DTMAB, CTMAB, TBAB and BETAC as catalysts, K_app were 0.01336, 0.01158, 0.00343. and 0.001738 L/(mol/min) respctively. The activation energy of di-(β-chloroethyl) ether and Et cyanoacetate was 58.94 kJ/mol.

Jingxi Huagong published new progress about 30431-99-3. 30431-99-3 belongs to nitriles-buliding-blocks, auxiliary class Tetrahydropyran,Nitrile,Ester, name is Ethyl 4-cyanotetrahydro-2H-pyran-4-carboxylate, and the molecular formula is C9H13NO3, Application of Ethyl 4-cyanotetrahydro-2H-pyran-4-carboxylate.

Referemce:
https://en.wikipedia.org/wiki/Nitrile,
Nitriles – Chemistry LibreTexts

Gibson, Charles S. published the artcileSyntheses with β,β’-dichlorodiethyl ether. I. Derivatives of tetrahydropyran, Computed Properties of 30431-99-3, the publication is Journal of the Chemical Society (1930), 2525-30, database is CAplus.

(ClCH₂CH₂)₂O (I), m. -24.5°, b₁₂ 66°, b₁₅ 70°, b₇₄₄ 176°, with a large excess of NaI in Me₂CO, gives the β,β’-diiododiethyl ether (II), b₁₀ 123.5-4°. I, CH₂(CO₂Et)₂ and Na in EtOH, boiled 5 hrs., give Et tetrahydropyran-4,4-dicarboxylate, b₁₂ 134-5°; hydrolysis with EtOH-KOH gives 81% of the acid, which loses CO₂ at 175-85°, giving 94.5% of tetrahydropyran-4-carboxylic acid (III), b₁₅ 146-7°; acid chloride, b₁₆ 85-6°; Me ester, b₁₆ 80.5-1°; Et ester, b₁₂ 82.5°; amide, m. 179°; anilide, m. 163°. I and NCCHNaCO₂Et in EtOH, heated 3 hrs. and kept 12 hrs., give 33% of Et 4-cyanotetrahydropyran-4-carboxylate, b₁₆ 125°; free acid, m. 160-2°; amide, in. 158°; heating at 180-200° for 1 hr. gives 66% of 4-cyanotetrahydropyran, b₁₀ 82-3°; this could not be reduced to the amine by Na in AmOH. I and AcCHNaCO₂Et gave only a small amount of high-boiling material. II gives a product b₉ 122.5-3.5°, which, on hydrolysis, gives III, AcOH and a trace of a ketone. No results were obtained in the Friedel-Crafts reaction with I and C₆H₆ or between I and KCN. I, As₂O₃ and NaOH gave no condensation product.

Journal of the Chemical Society published new progress about 30431-99-3. 30431-99-3 belongs to nitriles-buliding-blocks, auxiliary class Tetrahydropyran,Nitrile,Ester, name is Ethyl 4-cyanotetrahydro-2H-pyran-4-carboxylate, and the molecular formula is C9H13NO3, Computed Properties of 30431-99-3.

Referemce:
https://en.wikipedia.org/wiki/Nitrile,
Nitriles – Chemistry LibreTexts

Schoellkopf, Ulrich published the artcileSyntheses with α-metalated isocyanides. XXIX. Higher amino acids by alkylation of α-metalated ethyl α-isocyanopropionate and alkyl isocyanoacetates, Synthetic Route of 30431-99-3, the publication is Chemische Berichte (1975), 108(5), 1580-92, database is CAplus.

Treatment of α-metalated CNCHR1CO2R2 [R1 = Me, R2 = Et (I); R1 = H, R2 = Et (II); R1 = H, R2 = CMe3 (III)] with alkylating agents (R3X, e.g., R3 = Bu, PhCH2, X = Br, Iodo) gave monoalkylation of I and III but dialkylation of II. Hydrolysis of the alkylated products with HCl/EtOH at 25° or KOH/EtOH at 80° gave R1R3C(NH2)CO2R2 or R1R3C(NHCHO)CO2R2, resp. II and III reacted with 1,2-dibromoethane, bis(2-chloroethyl) ether, and 1,4-dibromobutane to give IV, V, and VI, resp.

Chemische Berichte published new progress about 30431-99-3. 30431-99-3 belongs to nitriles-buliding-blocks, auxiliary class Tetrahydropyran,Nitrile,Ester, name is Ethyl 4-cyanotetrahydro-2H-pyran-4-carboxylate, and the molecular formula is C9H13NO3, Synthetic Route of 30431-99-3.

Referemce:
https://en.wikipedia.org/wiki/Nitrile,
Nitriles – Chemistry LibreTexts

Khomenko, Dmytro M. published the artcileSynthesis of α-substituted 2-(1H-1,2,4-triazol-3-yl)acetates and 5-amino-2,4-dihydro-3H-pyrazol-3-ones via the Pinner strategy, Application In Synthesis of 30431-99-3, the publication is Tetrahedron Letters (2021), 152956, database is CAplus and MEDLINE.

A series of 2-(1H-1,2,4-triazol-3-yl)acetates, as well as 4-mono- and 4,4-disubstituted 5-amino-2,4-dihydro-3H-pyrazol-3-ones (including spirocyclic derivatives) I [R¹ = H, i-Pr, Me; R² = H, Me; R¹R² = -(CH₂)₂-, -(CH₂)₃-, -(CH₂)₂O(CH₂)₂-] have been synthesized using the Pinner reaction strategy. α-Mono- and α,α-disubstituted Et cyanoacetates NCC(R¹)(R²)C(O)OEt were converted into the corresponding carboxyimidate salts EtOC(=NH)C(R¹)(R²)C(O)OEt.HCl that served as the key intermediates. Their further reaction with formylhydrazide or hydrazine hydrate provided triazolylacetates I or aminopyrazolones (including spirocyclic derivatives) II, depending on the structure of the starting Pinner salt and the nature of the nucleophile. The scope and limitations of the developed synthetic method have been established.

Tetrahedron Letters published new progress about 30431-99-3. 30431-99-3 belongs to nitriles-buliding-blocks, auxiliary class Tetrahydropyran,Nitrile,Ester, name is Ethyl 4-cyanotetrahydro-2H-pyran-4-carboxylate, and the molecular formula is C9H13NO3, Application In Synthesis of 30431-99-3.

Referemce:
https://en.wikipedia.org/wiki/Nitrile,
Nitriles – Chemistry LibreTexts