L mesylate

Ethyl 1/7-azepine-l-carboxylate (1) yields the [2 + 4] enc/o-cycloadducts 16 with isobenzofuran (15, R = H) and with 1,3-diphenylisobenzofuran (15. R = Ph).251 l-Mesyl-lZ/-azepine behaves likewise. 

Surprisingly, 2,5-dimethyl-3,4-diphenylcyclopentadienone (17) with ethyl l//-azepine-l-carb-oxylate (1) behaves as both diene and dienophile to give a separable mixture of the [4 + 2] 18 and [2 + 4] 19 7t-ewfo-cycloadducts,251 259 the latter being incorrectly formulated in the original paper251 as the opposite regioisomer. l-Mesyl-1//-azepine under similar conditions yields only the [2 + 4] cycloadduct [42% mp 158°C (dec.)],157 251 whereas with tetraphenylcyclopen-tadienone low yields of the [4 + 2] (9.7%) and [6 + 4] (1.7%) rc-adducts are reported.157... 

A sirupy pentapropionate of L-sorbose was described by Hurd and Gordon.142 Crystalline esters of L-sorbose, such as the 1-benzoyl-,55 1-p-aminobenzoyl-148 and 1-tosyl-, 144,56 have also been synthesized. 1-p-Aminobenzoyl-L-sorbose was prepared as a possible substance for measuring the rate of glomerular filtration. It was synthesized by esterifying 2,3 4,6-diisopropylidene-L-sorbose with p-nitrobenzoyl chloride, with subsequent reduction of the nitrobenzoyl ester to 1-p-amino-benzoyl-2,3 4,6-diisopropylidene-L-sorbose. Removal of the isopropyli-dene groups by dilute acid hydrolysis furnished the desired product. 1-Tosyl-L-sorbose was independently prepared by two different methods. The first method,55 discussed on page 110, involves the oxidation of a properly substituted sorbitol derivative, while the latter method144 is similar to the one used for the preparation of the 1-p-aminobenzoyl derivative, namely esterification of 2,3 4,6-diisopropylidene-L-sorbose, followed by acid hydrolysis. This cyclic acetal has also been esterified to the crystalline l-mesyl-2,3 4,6-diisopropylidene-L-sorbofuranose by... 

A series of l-(alkynyl-X)-4-phenylpyridazino[4,5-<7]pyridazines 16 (X = O, NH, S) was prepared starting from l-mesyl-4-phenylphthalazine (15).36... 

Similar alkylations may be effected on oxygen. l-(2-Chloroethyl)imidazolidin-2-one (312) when treated with potassium hydroxide or sodium hydride underwent ring closure to the tetrahydroimidazo[2,l-6]oxazole (313) (57JA5276). This approach can be used for the preparation of bicyclic hydantoins and the corresponding dihydro derivatives of (313) using the mesylate of (312) and NaH (77JHC5U, 79JMC1030). 

H-3-Benzazepin-l-one, tetrahydro-nucleophilic reactions, 7, 515 3H-3-Benzazepin-l-one, 1,2,4,5-tetrahydro-JV-mesyl-formylation, 7, 514... 

Disulfonate esters of vicinal diols sometimes undergo reductive elimination on treatment with sodium iodide in acetone at elevated temperature and pressure (usually l(X)-200°). This reaction derived from sugar chemistry has been used occasionally with steroids, principally in the elimination of 2,3-dihy-droxysapogenin mesylates. The stereochemistry of the substituents and ring junction is important, as illustrated in the formation of the A -olefins (133) and (134). 

Reactions of ar>l or alkyl bis(siloxy)isopropyl ethers with tetrabutyl-ammoninm fluoride-mesyl fluoride reagent lead to replacement of one siloxy group by fluorine and dehydrosiloxylation, providing an efficient access to fluoroisopropenyl ethers, which are useful as specific building blocks in drug design The reactions proceed via the intermediate allyl methanesulfonates [30, 31] (equation 23)... 

Trifluoromethyl thiirane is formed by the action of tris(diethylamino)-phosphineon l-chloromethyl-2,2,2-trifluoroethyldisulfide [S2] (equation 73) Difluoromethyl phenyl selenide is prepared by treatment of lithium phenyl-selemde with chlorodifluoroniethane via a carbene mechanism [Si] (equation 44) Bis(2,2,2-trifluoroethyl)diselenide is formed in the reaction of 2,2,2-trifluoroethyl mesylate with lithium diselenide [84] (equation 74). 

The reaction of Ab-acetyl-1 -hydroxytryptamine (39) with mesyl chloride (MsCl) in THF in the presence of EtsN provides 1-acetyl-1,2,3,8-tetrahydropyrrolo[2,3-(j] indole (49a, 35%) (70JA343), Ab-acetyl-6-mesyloxytryptamine (50a, 4%), Ab-acetyl-2,3-dihydro-2-oxotryptamine (51a, 5%), l-acetyl-3a-(4-chlorobutoxy)-l,2,3,3a,8,8a-hexahydropyrrolo[2,3-(j]indole (52a, 7%), and Ab-acetyltryptamine (53a, 2%) as shown in Scheme 6 (2000H483). In the same reaction with MsCl, l-hydroxy-Ab-methoxycarbonyltryptamine (34) produces 50b (7%), 51b (34%), and 52b (9%), while the formation of 49b is not observed at all. In the case of Ab-trifluoroacetyl-l-hydroxytryptamine (48), 49c (45%), 50c (8%), 51c (4%), and 52c (6%) are produced. These data suggest that the yield of 49 increases, whereas the yield of 51 decreases in the order of electron-withdrawing ability of Ab substituents (COOMe < COMe < COCF3). Stability of 49 seems to govern the quantity of 51, which is probably formed by hydrolysis of 49. 

This tricyclic ring system was prepared from the functionalized pyrazo[l,5-n]pyridines. Thus, pyrazo[l,5-n]pyridine-3-carboxylate 462 gave 465 upon mesylation and subsequent reaction with 2-ethoxy-2-lithioxyethy-lene, whose cyclization afforded 466 (94AP435). Intramolecular aldol... 

Intramolecular dipolar azide-olefin cycloaddition of 723 took place upon heating in benzene to afford 724 (83JA3273). An alternative rearrangement process can take place upon photolysis of 724 to give 725. Mesylation of 4-(3-hydroxypropyl)-2,4,6-trimethyl-2,5-cyclohexadiene-l-one (78JA4618) and subsequent treatment with sodium azide in DMF afforded the respective azide 726 which underwent intramolecular cycloaddition to afford the triazoline 727 (83JOC2432). Irradiation of 727 gave the triazole derivative 728 (Scheme 126). 

Diphenyl diazomethane Benztropine mesylate a/l -Diphenyl-7.dimethylamino valeronitrile Aminopentamide Diphenylmethane... 

O-isopropylidene derivative (57) must exist in pyridine solution in a conformation which favors anhydro-ring formation rather than elimination. Considerable degradation occurred when the 5-iodo derivative (63) was treated with silver fluoride in pyridine (36). The products, which were isolated in small yield, were identified as thymine and l-[2-(5-methylfuryl)]-thymine (65). This same compound (65) was formed in high yield when the 5 -mesylate 64 was treated with potassium tert-hx Xy -ate in dimethyl sulfoxide (16). The formation of 65 from 63 or 64 clearly involves the rearrangement of an intermediate 2, 4 -diene. In a different approach to the problem of introducing terminal unsaturation into pento-furanoid nucleosides, Robins and co-workers (32,37) have employed mild base catalyzed E2 elimination reactions. Thus, treatment of the 5 -tosylate (59) with potassium tert-butylate in tert-butyl alcohol afforded a high yield of the 4 -ene (60) (37). This reaction may proceed via the 2,5 ... 

Intermediate 10 must now be molded into a form suitable for coupling with the anion derived from dithiane 9. To this end, a che-moselective reduction of the benzyl ester grouping in 10 with excess sodium borohydride in methanol takes place smoothly and provides primary alcohol 14. Treatment of 14 with methanesulfonyl chloride and triethylamine affords a primary mesylate which is subsequently converted into iodide 15 with sodium iodide in acetone. Exposure of 15 to tert-butyldimethylsilyl chloride and triethylamine accomplishes protection of the /Mactam nitrogen and leads to the formation of 8. Starting from L-aspartic acid (12), the overall yield of 8 is approximately 50%, and it is noteworthy that this reaction sequence can be performed on a molar scale. 

Tricarbonyl[>74-l-(phenoxycarbonyl)-l//-azepine]iron(0) [48% mp 108-109=C (dec.)] and tricarbonyl(i/4-1-mesyl-lW-azepine)iron(O) (69% mp 94-96 C) were prepared similarly. 

Very few 1-unsubstituted 17/-azcpines have been isolated and, as a consequence, substitution at nitrogen is a rare event however, 1-mesyl-l//-azepine (8) and l-(trimethylsilyl)-l //-azepine (9) can be obtained by treating 1//-azepine (7) with mesyl chloride and with trimethylsilyl trifluoromethanesulfonate, respectively.9... 

Diazomethane and 1 -substituted 1 //-azepine-4,5-dicarboxylates 44 yield the C4 — C5 pyrazoline adducts, e. g. 45.234 In contrast, the 1-mesyl and the 1-tosyl derivatives yield only adducts of the benzene imine valence tautomers of the l//-azepines. 

UV spectra of a variety of 1 -alkyl-1 //-1-benzazepines,20,21 3//-l-benzazepines,20 l-acyl-l//-l-benzazepines,1 3,22,23 3-acyl-3//-3-benzazepines,22-23 3-alkyl-37/-3-benzazepines and their cations in concentrated sulfuric acid,24,25 and 3-mesyl-3//-3-bcnzazepine,2ft have been recorded. A comparison of the UV spectra of 3-alkyl-l, 5-dihydroxy-3//-3-benzazepinc-2,4-dicarboxylates and their bis-O-methyl ethers supports an enol rather than an amide structure for these derivatives.14... 

The mass spectra of l-acyl-l//-l-benzazepines have been recorded.23 The mass spectrum of 3-mesyl-3/7-3-benzazepine shows an intense base peak at m/e = 142duetothebcnzazepinylium ion and a peak (51 %) at m/e — 115 (-HCN) which is attributed to the indenium cation.26 Fragmentation patterns for 1H- and 5/7-2-benzazepines40 and for 5//-dibenz[c,e]azepine5 are available. The electron-impact induced fragmentation pattern of 5//-dibenz[6,/]azepine displays an intense molecular ion as the base peak, and a moderately intense (M + 1) peak.5 ... 

The methyl ether 10a is also formed in moderate yields (21-50%) by treating 8-chloro-l-(2-chlorophenyl)-5-mesyloxy-5//-2-benzazepine, prepared in situ from the 5-hydroxy derivative with mesyl chloride in triethylamine, with base.78... 

A mixture of 6-mesyl-6,7-dihydro-5/f-dibenz[ ,c]azepine (29, R = Ms 13.67 g, 50 mmol) in anhyd DMSO (160 mL) and t-BuOK (18.7 g, 165 mmol) was stirred for 45 min at 20 C under N2. Another portion of /-BuOK (2.65 g, 25 mmol) was added and stirring was continued for a further 45 min. The mixture was transferred to a separating funnel with ice-cold H20 (1.1 L) and extracted with Et20 (700 mL). The aqueous phase was extracted again with Et,0 (200 mL) and the combined ethereal extracts were then dried for 2 h (CaCl2) and evaporated to give the crude product as a pale-yellow oil (9.61 g, 99 %). which was purified bv distillation (bp 125 126/0.01 Torr) to give the product as colorless crystals yield 8.25 g (85 %) mp 84-85 C. 

The present route to (terminal alkynes reported by a group from the Chemical Process Department at the DuPont Pharmaceutical Company.2 This alcohol serves as a convenient starting material for the preparation of 1-acyloxy 4-mesylates 10 (eq 1). 

CN 4-methylbenzoic acid 4-[2-[(l, l-dimethylethyl)amino] l-hydroxycthyl]-l,2-phenylene ester mesylate... 

C9H19NO5 188923-21-9) see Nelfinavir mesylate (Z)-2-amino-a-[[2-(l,l-dimethylethoxy)-2-oxoethoxy]imi-no]-4-thiazoleacetic acid (CiiHijNjOjS 74440-02-1) see Carumonam... 

C 3H,5N04 1148-11-4) see Angiotensinamide Captopril 7V-benzyloxycarbonyl-L-proline tert-butyl ester (C17H23NO4 16881-39-3) see Captopril 7V-benzyloxycarbonyl-L-serine (CiiHijNOj 7745-80-8) see Nelfinavir mesylate iV-benzyloxycarbonyl-L-serine-P-lactone (C Hi,N04 26054-60-4) see Nelfinavir mesylate 7V-benzyloxycarbonylsuccinimide... 

C7Hf,N202 5444-02-0) see Nevirapine (35,4a5,8JL5)-2-[(2/f)-2-[(4S)-4,5-dihydro-2-(3-hydroxy-2-methylphenyl)-4-oxazolyl)-2-hydroxyethyl]- -(l,l-di-methylethyl)decahydro-3-i oquinolinecarboxamidc (C2f,H3yN304 188936-07-4) see Nelfinavir mesylate 3-[(4S)-4,5-dihydro-4-[(li )-2-hydroxy-l-[(methylsulfo-nyl)oxy]ethyl]-2-oxazolyl]-2-methylphenol (CpHpNOf S) see Nelfinavir mesylate... 

C21H21N3O9 4199-35-3) see Minocycline (/ )-[2-(dimethylamino)-2-oxo-l-[(phenylthio)methyl] ethyl]carbamic acid phenylmethyl ester (C,9H22N20iS 197302-34-4) see Nelfinavir mesylate lV-[3-[3-(dimethylamino)-l-oxo-2-propenylJphenyl]acet-amide... 

C32H45N3O4S 159878-04-3) see Nelfinavir mesylate (5)-2-[[(l,l-dimethylethyl)amino]carbonyl]-l,4-piperazi-nedicarboxylic acid 4-(l,l-dimethylethyl) l-(phenyl-methyl) ester... 

C 5H2gN03 188923-19-5) see Nelfinavir mesylate (l,l-dimethyl-2-phenylethyl)methylamine (C HnN /00-92-5) see Oxetacaine l-[(3,4-dimethylphenyl)iminol-l-deoxy-D-rihitol (C11H19NO4) see Riboflavin N-(2,6-dimethylphenyl)-2-iodobutanamide (C,2H 16INO 60119-84-8) see Etidocaine... 

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