Heterocyclic analogs of pleiadiene

In most cases 2-R-2,3-dihydroperimidines are smoothly dehydrogenated by sulfur in refluxing xylene to give 2-substituted perimidines in high yields. 2-(5-Halo-2-furyl)-2,3-dihydroperimidines, which form IV and 2-(5-halo-2-furyl)perimidines when they are heated with sulfur, constitute an exception.See [1] for communication XXVIII.Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, p, 986–988, July, 1977.     

Heterocyclic analogs of pleiadiene

The corresponding phenalenones are formed immediately in the reaction of 1,3-dialkyl-substituted perimidones, thioperimidones, and 2,3-dihydroperimidines with propiolic acids and -keto acid esters in polyphosphoric acid (PPA) at 40–75°C. Acylation of the perimidone and 2,3-dihydroperimidine derivatives with cinnamic and acrylic acids in PPA occurs in the 6 position and is accompanied by recyclization with the formation of a dihydrophenalenone ring. Acylation of 1,3-dialkylperimidones with aliphatic acids in PPA leads to 6,7-diacyl derivatives, by crotonization of which the corresponding phenalenones were also synthesized. The properties of the compounds are discussed.See [1] for communication XXXIII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 833–842, June, 1978.     

Effect of geminal substituents on dehydrogenation of dihydro derivatives of nitrogen heterocycles. 2,3-dihydroperimidines and benzimidazolines

A study was carried out on the rate of hydride ion displacement from 1,3-dimethyl-2-R-2,3-dihydroperimidines and 1,3-dimethyl-2-R-benzimidazolines to 1,3,5-trinitrobenzene. In all cases, inhibition by the substituents at C(₂) is observed but this effect is much more pronounced in 2,3-dihydroperimidines than in benzimidazolines. An x-ray diffraction structural analysis of 1,3-dimethyl-2-phenyl-2,3-dihydroperimidine showed that the geometry of 2,3-dihydroperimidines causes steric blocking of the hydrogen atom at C(₂) by the geminal substituent and substituents at the nitrogen atom.Translated from Khimiya Geterotsiklicheskikh Saedinenii, No. 7, pp. 977–985, July, 1985.     

peri-Naphthylenediamines. 31. Study of interconversions of 2,3-dihydroperimidines and 1,8-bis(dialkylamino)naphthalenes. Convenient synthesis of 1,2,2,3-tetramethyl-2,3-dihydroperimidine and a monoisopropyl analog of the “proton sponge”

Efficient procedures were developed for the two-step synthesis of 1,2,2,3-tetramethyl-2,3-dihydroperimidines and for the one-step synthesis of 1,3-dimethyl-2,3-dihydroperimidines starting from 1,8-diaminonaphthalenes. New possibilities of the use of 2,3-dihydroperimidinium salts in the synthesis of 1,8-bis(dialkylamino)naphthalenes (proton sponges) containing the N-isopropyl group along with the N-methyl groups were demonstrated. The 1,1,2,2,3-pentamethyl-2,3-dihydroperimidinium cation exists in the acyclic iminium form responsible for its high reactivity.     

Heterocyclic analogs of pleiadiene. 67. Formylation of perimidones, 2,3-dihydroperimidines, and perimidines

Vilsmeier formylation of 1,3-dialkylperimidones, 1,3-dialkyl-2,3-dihydroperimidines, and 2-trifluoromethyl-perimidines is performed. The¹H NMR spectra of the resulting mono- and dialdehydes are discussed.For No. 66, see [1].Rostov State University, Rostov-on-Don 344006Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 365–374, March, 1999.     

Heterocyclic analogs of pleiadiene str]XXVI. Reaction of 1-methylperimidine and 1-methyl-2-chloroperimidine with alkali metals and their naphthalenides

1-Methylperimidine reacts with alkali metals or their naphthalenides to give, depending on the nature of the metal and the experimental conditions, an anion radical or a dianion. The latter are converted to a mixture of 1-methyl- and 1-methy1-2,3-dihydroperimidines. In the case of naphthyllithium, 1-methyl-2--naphthylperimidine was also isolated in 30% yield. 1-Methyl-2-chloroperimidine reacts with the same reagents to give primarily 1-methylperimidine. 1-Methyl-2,3-dihydroperimidine and 1,1-dimethyl-2,2-diperimidinyl are also formed in small amounts.See [1] for communication XXV.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 825–830, June, 1977.     

Direct hydroxylation of imidazoles

It is shown that the N-substituted derivatives of 4,5-diphenylimidazole, benzimidazole, naphth[1,2]imidazole, perimidine, and aceperimidine are hydroxylated by alkali metal hydroxides to give the corresponding 2-imidazolones and perimidones in high yields.The material in this paper regarding the synthesis of perimidones and aceperimidones should be considered as communication V of our series entitled Heterocyclic Analogs of Pleiadiene. See [16] for communication IV.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 124–128, January, 1971.     

Synthesis of acylhydrazones from lupane and 19β,28-epoxy-18α-oleanane 2,3-<Emphasis Type="Italic">seco</Emphasis>-aldehydonitriles

2,3-seco-Triterpene acylhydrazones, which are interesting as new biologically active compounds, were prepared by reaction of lupane and 19β,28-epoxy-18α-oleanane 2,3-seco-aldehydonitriles with acylated hydrazines.     

Die umsetzung von azlactonen mit CH-aciden verbindungen. 2. Mitteil

Alkyl cyanoacetate, malonate, acetoacetate and methylsulfonyl acetic acid ethyl ester are acylated by alkylidenazlactones. The acyl compounds easily form alkylideneteramic acids by condensations. The acylcyanoacetates 2 isomerize into aminopyrrolinones 3 via acid catalysis.     

在H3PO4存在下2,3-二甲基-2-丁烯与乙酐的酰化反应

在H3PO4存在下进行了2，3－二甲基－2－丁烯与乙酐的酰化反应，结果表明，H3PO4是室温下催化2，3－二甲基－2－丁烯与乙酐酰化反应的有效催化剂，在H3PO4存在下，酰化产物的收率主要取决于：（a)H3PO4的用量，（b)乙酐的用量；（c)反应温度和（d)反应时间，在适宜反应条件下，所得3，3，4－三甲基－4－戊烯－2－酮（TMP）约为99％，另外还发现，反应体系中加入少量乙酸，不会明显减少酰化产物的收率，乙酐的纯度，反应物的加入顺序对该反应几乎没有任何影响，在有和没有溶剂CH2Cl2的条件下所得酰化产物的收率是可比的。     

Synthesis and properties of 2-substituted 1-aryl-4-oxo-1,4-dihydropyrido[2,3-d]pyrimidines

Cyclization of 2-(N-acetyl-N-arylamino)nicotinonitriles in the presence of dry HCl gave 1-aryl-2-methyl-4-oxo-1,4-dihydropyrido[2,3-d]pyrimidines. It was shown that they are acylated by acetic anhydride, aroyl chlorides, and phenyl isocyanate at the methyl group and that with benzaldehyde they give styryl derivatives. It was determined by UV, IR, and NMR spectra that 2-acetonyl, 2-phenacyl, and 2-(N-phenylcarbamoylmethyl) derivatives of 1-aryl-4-oxo-1,4-dihydropyrido[2,3-d]pyrimidines exist in enaminocarbonyl and imino enol forms with strong chelate-type intramolecular hydrogen bonding.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1397–1401, October, 1991.     

Heterocyclic analogs of pleiadiene. 58. Thiocyanogenation of permidones. Synthesis of perimidone-6,7-disulfides

The thiocyanogenation of 1, 3-disubstituted perimidones gives good yields of their 6 (7)-monothiocyano and 6, 7-dithiocyano derivatives. Alkaline hydrolysis of these derivatives leads to the formation of the corresponding disulfides. The reduction of 1, 3-dimethylperimidone-6,7-disulfide is accompanied by the destruction of the disulfide bridge and may be used for the synthesis of 6,7-dialkylmercaptoperimidones.Communication 57, see ref. [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1493–1496, November, 1985.     

Electrophilic substitution in N-aryl-2-pyrazolines. 3. Introduction of nitro-, sulfo-, and acyl groups. Reaction with Michler's ketone

1-Phenyl-3,5-diaryl-2-pyrazolines are nitrated, sulfurated, and acylated in the para-position of the 1-phenyl ring. In the presence of POCl₃, pyrazolines form triphenyl-methane dyes with a Michler's ketone.For Communication 2, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 965–968, July, 1984.     

Synthesis of some 2,3-Dihydro-11bH-thiazolo[3,2-d][1,4]benzoxazepin-5-(6H)one derivatives. A new heterocyclic ring system

Condensation of (S)-penicillamine methyl or ethyl ester hydrochloride with salicylaldehyde and its C-5 derivatives, provided the diastereomeric thiazolidine derivatives 1 and 2 . The resulting amino function was acylated to afford the amides 3 and 4. Cyclization of the latter led to the 2,3-dihydro-11bH-thiazolo[3,2-d]-[1,4]benzoxazepin-5-(6H)ones 5 and 6. Conformational data for these heterocyclic compounds are discussed.     

[1] Benzofuro[2,3-d] pyridazines. VI. Etude des reactions de scission des acyltetrahydrobenzofuropyridazones

The cleavage of the pyridazine ring of the acyltetrahydro [1] benzofuro [2,3-d] pyridazones was carried out by hydrolysis, alcoholysis or aminolysis reactions and they affect the lactam 3,4-bond. They lead chiefly to benzofuran derivatives with acid, ester, amide or hydrazide groups in the 2-position and eventually an acylated methylhydrazine group in the 3-position. The cyclization reactions of 3-hydrazinomethylbenzofuran-2-carboxylic acid and its derivatives or ethyl 3-bromome thylbenzofuran-2-carboxylate affords tetrahydrobenzofuropyridazones. The nmr spectra were studied.     

1,2,3,9a-Tetrahydro-9H-imidazo[1,2-a]indoles

When derivatives of 1,2,3,9a-tetrahydro-9H-imidazo[1,2-a]indol-2-one or 1-carbamoylmethyl-2-methylene-2,3-dihydroindole are reacted with lithium aluminum hydride, derivatives of 1,2,3,9a-tetrahydro-9H-imidazo[1,2-a]indole are formed. Under the same conditions 1-(N-phenylcarbamoylmethyl)-2-methylene-2,3-dihydroindole is not cyclized to an imidazo[1,2-a]indole. WHen treated with proton acids imidazo[1,2-a]indoles are converted to 3H-indolium salts. Opening of the imidazolidine ring is also found when imidazo[1,2-a]indole is acylated with benzoyl chloride.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 227–230, February, 1987.     

Syntheses of arsinolipids: non‐isosteric analogues of phospholipids

Reaction of alkaline benzenearsonous and 2,3‐dihydroxypropylarsonous acids with rac‐glycidol affords the corresponding arsinic acids, which after reduction with thiophenol are acylated with either fatty‐acid chlorides/pyridine or fatty acids/dicyclohexylcarbodiimide/4‐dimethylaminopyridine and oxidized with hydrogen peroxide to give the arsinolipids (rac‐2,3‐diacyloxypropyl)phenylarsinic and bis‐(rac‐2,3‐diacyloxypropyl)arsinic acids. The latter is a non‐isosteric analogue of bisphosphatidic acid. Copyright © 2000 John Wiley & Sons, Ltd.     

Synthesis of 2,3‐Diaryl‐3H‐pyrrolo[2,3‐c]pyridin‐3‐ol Derivatives by the Reaction of Aryl(3‐isocyanopyridin‐4‐yl)methanones with Aryl Grignard Reagents

The reaction of aryl(3‐isocyanopyridin‐4‐yl)methanones 1 , easily prepared from commercially available pyridin‐3‐amine, with aryl Grignard reagents gave, after aqueous workup, 2,3‐diaryl‐3H‐pyrrolo[2,3‐c]pyridin‐3‐ols 2 . These rather unstable alcohols were O‐acylated with Ac₂O in pyridine in the presence of a catalytic amount of 4‐(dimethylamino)pyridine (DMAP) to afford the corresponding 2,3‐diaryl‐3H‐pyrrolo[2,3‐c]pyridin‐3‐yl acetates 3 in relatively good yields.     

Heterocyclic analogs of pleiadiene. 52. Intramolecular C-acylation of perimidines and perimidones. synthesis of a new heterocyclic system — 3,4,5,6-tetrahydropyrido [3,2,1-k,l]perimidine

Intramolecular C-acylation in the 9 position of -(1-perimidinyl)- and -(1-perimidonyl)propionic acids and cyanoethylation of perimidines and perimidones were studied. Derivatives of a new bridged system, viz., 3,4,5,6-tetrahydropyrido [3,2,1-k,l]perimidine, were synthesized for the first time.See [1] for communication 51.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 973–979, July, 1981.     

Diazo carbonyl derivatives of heterocycles. 5. Intramolecular cyclization of 2-hetarylmercaptoalkyl-diazo ketones. Synthesis of condensed 1,3-thiazin-5-ones

The intramolecular heterocyclization of 2-benzazolylmercaptoalkyl diazomethyl ketones under the influence of acidic agents leads to 1,3-thiazino[2,3-b]benzim-idazole, 1,3-thiazino[2,3-b]benzothiazolium, and 1,3-thiazino[2,3-b]benzoxazolium systems. Under similar conditions 2-quinolylmercaptoalkyl diazomethyl ketones form 1,3-thiazino[2,3-a]quinolinium systems.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 635–639, May, 1984.