Benzo-nitrile chloride

Optically active 3-arylisoxazoline-5-carboxylic acid derivatives 403 or 404 have been, prepared by the reaction of (S)- or (/ )-3-acryloyl-4-benzyl-5,5-dimethyloxazolidin-2-one (405 or 406) with nitrile oxides, obtained from benzo-hydroximoyl chloride and its substituted derivatives in the presence of a catalytic amount of metal salt, for example, Yb(OTf)3 (445). This procedure improves the diastereoselectivity of compounds 403 or 404, which are industrially useful as intermediates for various drugs and agrochemicals. It also enables the amount... 

The UV spectrum of the 3-oxide in ethanol exhibits maxima at 254 nm (e = 19300) and 320 nm (e = 3000), the latter appearing as a shoulder. On irradiation (A = 250 nm, in methylene chloride), benzo-nitrile and phenyl isothiocyanate are formed in 65% and 3% yields, respectively. A similar result is obtained on photolysis of 5-phenylthiatri-azole (Section III, C). The major part of the products was shown to be formed from the singlet excited state.23... 

Nitriles can condense cyclically with aldehydes, in the presence of acid, to yield hexahydro-.s-triazines e.g., propionitrile and formaldehyde give the hexahydro-l,3,5-tripropionyl-s-triazine (25b).62 When benzo-nitrile (1 mole) and benzoyl chloride (2 moles) were heated to 150° with zinc (or stannic) chloride, a high yield of 2,4,6-triphenyl-3,5-diaza-pyrylium salt (46) was formed,623 which was converted into 2,4,6-triphenyl-s-triazine by ammonia. 

Palladous chloride is soluble in hydrochloric acid, forming the ion [PdClJ2- and will also react with many ligands, L, such as amines, benzo-nitrile and phosphines to give complexes of the types L2PdCl2 and [LPdCl2]2 PtCl2 is similar. 

Later K. Hoesch [8, 18, 19] proposed the condensation of benzo-nitrile with resorcinol in ether solution, heating the mixture with ZnCl2 and with simultaneous saturation of the reaction mass by dry hydrogen chloride. After hydrolysis of the intermediate ketoimine compound, 2,4-dihydrojqrbenzophenone is formed ... 

A new reagent to effect the amide-to-nitrile dehydration is trimethylsilyl polyphosphate, and new reagents for the desulphydration of thioamides are dibutyltin oxide and formamide chlorides. A-(Phenylsulphonyl)-benzo-hydrazonyl azide decomposes in the presence of triethylamine to give benzo-nitrile. ... 

For UV and fluorescence measurements, the most commonly used liquid crystals are mixtures of the nematic 4 -alkylbicyclo-hexyl-4-carbonitrile s (CCH) (e.g., ZLI 1167 and 1695), which are transparent down to 200 nm and exhibit nematic ranges between =30 and 80 °C (see, for example, [315, 331, 333, 334]), and various cholesteric or compensated nematic phases of cholesteryl chloride/cholesteryl ester mixtures, which are transparent to =240 nm [310, 313, 326, 329]. Some use has also been made of 4 -(4-alkylcyclohexyl)benzo-nitriles (PCH-n), which are transparent to =290 nm [330, 335]. Several other meso-phases, including thermotropic smectics, discotics, and lyotropic phases, have low absorption in the UV region and have been used from time to time as well. The most commonly used liquid crystals in FTIR studies are the CCH-mixtures ZLI 1167 and 1695 [314, 321, 336, 337]. The orientation of the liquid crystalline solution is most commonly achieved either by cell surface treatment or the application of an electric or magnetic field. 

The most direct synthesis of 2-acylbenzo[6]thiophenes involves reaction of the readily available 2-lithio derivative with acylating agents, such as nitriles, acid anhydrides, etc. (equation 19). Benzo[f>]thiophene-2-carboxylic acids are available by a variety of cyclization reactions (Section 3.15.9.2.4) and the acid chlorides or esters can be used to synthesize 2-acyl derivatives by conventional means. 

Methods (a) Diethylethoxymagnesium malonate and an acid chloride (b) nitrile and a Grignard reagent (c) dimethylcadmium and an acid chloride and (d) lithium acetate or lithium benzoate and a 2-benzo[6]thienyllithium. 

Friedel-Crafts reactions have found application to form the 1,2-bond of pyrrolizines. Treatment of anhydride 78 with aluminum chloride gave 93% of acid 79, which on heating in the presence of copper gave a 91% yield of 2,3-benzo-1 H-pyrrolizin-1 -one (17).55 Benzopyrrolizinones (81) have been obtained from acid chlorides (80) by a similar route.56,57 Houben-Hoesch cyclization of nitrile 82 gave 2,3-benzo-lf/-pyrrolizin-l-one (17) in a reaction that resembles the formation of 17 from 16a.58... 

Treatment of the Reissert compound derived from 4-chloroisoquinoline with phosphorus pentachloride yielded 4-chloro-l-cyanoisoquinoline. Similar treatment of the benzo[/]quinoline Reissert compound gave a mixture of nitrile and amide." The Reissert compound from 2-bromo-benzo[/]quinoline with thionyl chloride gives 2-bromo-3-cyanobenzo-[/]quinoline." Oxidation of a Reissert compound in the presence of 50% sodium hydroxide and a phase transfer catalyst also gives the isoquinaldonitrile. ... 

Analogous cyclization of enamino nitrile 156 in PPA afforded benzo[c][2,7]nap-hthyridine 157, which was converted into perlolinium chloride 158 (herbaceous alkaloid perloline 159) (1985CZ139). 

A common intermediate in the synthesis of benzo[c]phenanthridines is the 2-aryl-l-tetralone, which provides rings A, B, and D of the alkaloid nucleus. In 1973, two independent research groups reported the synthesis of nitidine via the 3,4-dihydro-2-(3,4-dimethoxyphenyl)-6,7-methylenedioxy-(2/7)-naphthalone 29 (Scheme 2). The synthesis of this intermediate was arrived at by two different routes. Kametani ei al. (73JHC31) reduced 3-(3,4-methylenedioxyphenyl)proprionate 21 to the corresponding alcohol 22 with lithium aluminium hydride, which was then converted to the chloride 23 with thionyl chloride. After production of the nitrile 24 by reaction with sodium cyanide and subsequent hydrolysis to the carboxylic acid 25, Friedel-Crafts cyclization of the acid chloride 26 afforded the tetralone intermediate 27. Reaction with l-bromo-3,4-dimethoxybenzene 28 in the presence of sodium amide yielded the tetralone intermediate 29 in an overall yield of 4%. 

Contrary to benzo[b]thiophen, benzo[b]selenophen is acylated at position 2. 2-Bromobenzo[b]selenophen, prepared from the 2-lithium derivative and bromine, is acylated at position 3, and from this derivative the 3-isomers could be synthesized. A large number of 2- and 3-aroylbenzo[b]seleno-phens were synthesized, either by Friedel-Crafts reaction of benzo-[bjselenophencarboxylic acid chlorides and benzenes or from benzol bjselenophens and benzoic acid chlorides. Also the reaction between Grignard reagents and nitriles was used for the synthesis of aroylbenzo[b]selenophens. 4,S-Diaminobenzo[b]selenophen has been synthesized via nitration of 5-aminobenzo[b]selenophen or via the reaction of the diazonium salt derived from the S-amino-derivative with p-sulphanilic acid. From the diamino-derivative, several fused benzo[b]selenophens, e.g. (525), (526), and (527), were prepared. Reaction of the phenyl-... 

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