Tetrahydrofuran benzoyl chlorides

A total of 8.9 parts of 3-sulfamyl-4-chloro-benzoyl chloride In a solution of 50 parts of anhydrous tetrahydrofuran are added portionwise in the course of 60 minutes, while stirring, to a solution of 5.2 parts of N-amino-2-methyl indoline and 3.5 parts of triethylamine in 150 parts of anhydrous tetrahydrofuran. The reaction mixture is left to stand 3 hours at room temperature, then the precipitated chlorhydrate of triethylamine is filtered off. 

Typical procedure Phenyltellurotrimethylsilane (2.10 mL, 10.9 mmol) was added into astirred solution of benzoyl chloride (1.42 g, 10.1 mmol) in 30 mL of dry tetrahydrofuran under an argon atmosphere. The mixture was stirred for 3 h at room temperature and concentrated under a reduced pressure. The residual Te-phenyl tellurobenzoate was purified by recrystallization from pentane to give yellow needles. Yield 2.71 g (87%). 

Prepared in tetrahydrofuran by the action of sodium hydride, the sodium salt (203) formed the O-benzoate (204) when treated with benzoyl chloride at — 20°. A similar reaction at ambient temperature, followed by refluxing in toluene, gave (105). Clearly O-acylation is... 

Phenyl Tellurohenzoate1 A stirred solution of 1.42 g (10.1 mmol) benzoyl chloride in 30 m/ dry tetrahydrofuran and 2.1 ml (10.9 mmol) phenyl trimcthylsilyl tellurium are mixed under an atmosphere of argon. The mixture is stirred at 20° for 3 h and then concentrated under reduced pressure. The residue is rccryslallized from pentane to give yellow needles yield 87% m.p. 72°. 

The diazepinone (127) reacted with benzoyl chloride to give the A,Ar -dibenzoyl derivative137 and was brominated in acetic acid at 20°.138 Compounds 127 and 128 undergo the bis-semidine inversion when heated with 3% hydrochloric acid.117 The thione (128) is converted in high yield into the methylmercapto diazepine (126, R = SCH3) by reaction with methyl iodide in tetrahydrofuran.129 The thione does not react with amines, but the 6-methylmercapto compound on heating with amines or amine hydrochlorides gave rise to the 6-amino compounds (126, R = NR R")120 A number of these amino derivatives have exhibited some medicinal activity. With -butanol the 6-methylmercapto compound is quantitatively converted into 127.120... 

Complexation with zinc effectively separates the C3S5 dianion from the trithiocarbonate ion in high yield, and the material obtained is sufficiently pure for further reactions. The quaternary ammonium zincate salt is alkylated slowly but smoothly by many halides at room temperature in solvents such as acetone or tetrahydrofuran. Reaction of the zincate with benzoyl chloride followed by cleavage of the resulting benzoate by sodium ethoxide in ethanol provides the much more reactive species NajCaSs. The sodium salt is, however, very air sensitive,5 whereas the zinc salt is completely stable. 

Tetrahydrofuran is dried over sodium benzophenone and a fresh sample is distilled under nitrogen into the reaction vessel immediately before use. Pyridine is sequentially dried over powdered KOH and CaH2 for a total of 12 h. The CaH 2-dried sample is distilled under nitrogen into a flask containing activated 4 A molecular sieves (Aldrich). The flask is stoppered under a nitrogen blanket. Benzoyl chloride is distilled under nitrogen and is used immediately. 

Chlorobutyl benzoate has been prepared by the action of benzoyl chloride on tetrahydrofuran in the presence of titanium chloride, stannic chloride, or zinc chloride. ... 

Oxide fission. Benzoyl chloride reacts with tetrahydrofurane in the presence of a catalytic amount of zinc chloride to give 4-chlorobutyl benzoate. The reaction is... 

Rare examples of normal Michaelis-Becker reactions which involve co-chloroalkanal diethyl acetals are to be found, and although the formation of dialkyl acylphosphonates from sodium dialkyl phosphites and, for example, benzoyl chloride, is to be observed at -85 °C, the system is further complicated, even at -10 °C, by further addition steps followed by rearrangements which would seem to render the process of little value for the synthesis of oxoalkyl phosphonic esters On the other hand, in a more detailed and systematic study of reactions between sodium dialkyl phosphites, (RO)2PONa(R = Et or Bu), and the ketones R CO(CH2) Cl, Sturtz and others have observed the formation of epoxides when n = 1 and (1-hydroxy alk-2-enyl)phosphonic diesters when n = 2(R = Me or Pr ), according to the displacement in 532, and of derivatives of tetrahydrofuran or tetrahy-dropyran, according to 533 n = 3 or 4) when R = Et, the formation of the cyclic ethers was accompanied by low yields of the expected (oxoalkyl)phosphonic diester, but otherwise the latter were isolated as a single product only for R = Me, n = 5, and R = Et or Pr when n = 2. 

Caution. Tetrahydrofuran is extremely flammable and forms explosive peroxides only fresh peroxide-free material should be used. Pyridine, benzoyl chloride, and dichloromethane are harmful if inhaled. Benzoyl chloride causes severe skin and eye burns. All manipulations should be carried out in a well-ventilated fume hood protective gloves and goggles should be worn. 

Benzoyl chloride added to an equimolar soln. of N-benzoylalanine azlactone and triethylamine in tetrahydrofuran 5-benzoyloxy-4-methyl-2-phenyloxazole 63-70%) warmed in pyridine and the resulting azlactone allowed to stand at room temp, in methanol -> methyl N,2-dibenzoylalaninate (Y 70-78%). S. H. Pines and M. Sletzinger, Tetrah. Let. 1969,121 prepn. of a-acylaminoketones cf. W. Steglidi and G. Hofle, B. 102, 883, 899 (1969). 

In 1956, Hattori and co-workers estabUshed that aluminum azide adds to alkyl isocyanates or acid chlorides in tetrahydrofuran to afford l-aUcyl-A -tetrazoline-5-ones in excellent yields [ 101 ]. Three years later, Horwitz and coworkers reported on the synthesis of l-aryl-A -tetrazoline-5-ones by reaction of aryl isocyanates with a mixture of sodium azide and aluminum chloride in tetrahydrofiuan at reflux temperature [102]. The in situ produced aluminum azide adds to the N=C-bond of the corresponding isocyanate 122 and yields the 1-substituted A -tetrazoHne-5-one 124. According to this method, different 1-substituted A -tetrazoUne-5-ones 124 were synthesized by reaction of phenyl isocyanate and further 1-p-substituted phenyl isocyanates with aluminum azide. In addition, acyl halides 123, like acetyl chloride and benzoyl chloride, were converted to 1-methyl and 1-phenyl-A -tetrazoline-5-one with aluminum azide under the same conditions (Scheme 28A). It is assumed that in the initial step of the reaction, aluminum azide is able to coordinate to the aryl isocyanate by foiu pathways, forming an aluminum salt 129. The first two possibilities (Scheme 28B 125 and 126) require the separation of an azide ion from the complex, recombination at the electrophihc carbon atom followed... 

A solution of CjHjYb, prepared by the reaction of ytterbium metal and C Hjl in tetrahydrofuran reacts with ketones, aldehydes, and nitriles just as Grignard reagents would. However, with esters the complex reacts to produce ketones as the main product (Fukagawa et al., 1981). With benzoyl chloride the ketone is obtained selectively in modest yields which is in contrast to the Grignard reaction (Fukagawa et al., 1982). 

It should be noted that in none of these decompositions in acetic anhydride and benzoyl chloride was a 1,2-nitrogen movement found, as is the case for analogous nucleophilic attack. Further support for an azirine intermediate and the first observation of a 1,2 movement of nitrogen comes from Senda s work. Photolysis of a 6-azidouracil (63) in acetyl chloride-tetrahydrofuran gives a 5-amino-6-chlorouracil (64). The formation of this product may be... 

SM was prepared in two steps first, formation of N-[3-[(tert-butyldimethylsilyl) oxy]-4-methoxybenzoyl]morpholine (SMI) by action of 3-[(tert-butyldimethyl-silyl)oxy]-4-methoxy-benzoyl chloride with morphohne in toluene for 4 h at r.t. under argon. Then, the amide SMI was allowed to react with the hthium derivative prepared from 3,4,5-trimethoxybromobenzene [1178] and tert-butyllithium in tetrahydrofuran at -78° to give SM [1177]. 

Acylmalonic acid esters. Diethyl malonate added to NaH covered with tetra-hydrofuran, after ca. 1 hr. when H2-evolution has ceased and a soln. is formed, benzoyl chloride added all at once, stirring continued 5-10 min., then poured into water -> diethyl benzoylmalonate. Y 72%.—Tetrahydrofuran is an excellent medium for condensation reactions. In it, sodio compounds are soluble, and active halogen compounds, e.g. acyl chlorides, react instantly. F. e. s. S.-O. Lawesson and T. Busch, Acta Ghem. Scand. 13, 1717 (1959). 

Treat compound 2 (55 g, 81.9 mmol) in dry tetrahydrofuran (250 mL) with dry ammonia (100 g) in a Teflon -lined, stainless-steel bomb at 70°C for 72 h. Silica gel TLC in ethanol/chloroform (1 9 by vol) should show complete reaction with a new spot at Rf 0.32. Open the cooled bomb carefully in a well-ventilated fume cupboard. Remove solvent in vacuo, and dry the residue by evaporation of pyridine (2 x 250 mL). Dissolve the residue in dry pyridine (500 mL), and cool the solution in an ice bath. Add benzoyl chloride (38 mL, 328 mmol) during 5 min with stirring and exclusion of moisture. Continue stirring for 1.5 h at room temperature at which time TLC should show complete reaction (spot Rf 0.71 in 10% ethanol/chloroform). Cool the mixture in ice, and quench the reaction by addition of water (20 mL) followed after 5 min by 25% ammonia solution (80 mL). Stir for an additional 20 min at room temperature, and then remove solvent in vacuo. Dissolve the residual gum in ethyl acetate (1 L), and wash the... 

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