2-Imino-4-phenyl

Thiazoline, 3-aryl-2-imino-4-phenyl-synthesis, 6, 316 4-Thiazoline, 2-imino-... 

Rearrangement reactions involving 1,3-thiazines are often very facile. For example, reaction of 2-imino-4-phenyl-2/7-1,3-thiazinium perchlorate 957 with NaOH at room temperature gave 4-phenylpyrimidine-2(l//)-thione 958 <2004CHE1595>, while treatment of 6-amino-2,3-dihydro-l,3-thiazin-4(l// )-ones 959 with KOH readily gave the potassium salt of the dihydropyrimidinone 960 <2005HAC426>. 

The condensation of arylamines with phenacyl thiocyanate (443) affords 3-aryl-2-imino-4-phenyl-A4-thiazolines (444 Scheme 253) (72IJC318). 

Amino-5-(2-imino-4-phenyl-2,5-dihydro-1.3-thiazol-2-ylidenmethyl)-4-phenyl- 331 2-Amino-4-(3-indolyl)- 50 2-Amino-5-(2-indolyl-azo)-4-phenyl- 64 2-Amino-5-iod- 305... 

Benzo[2,l ]thiazolo[2,3-c][l,2,4]triazines [CsNS-CsNs-C ].—Oxidative cyclization of 3-(o-amino-aryl)-2-imino-4-phenyl-AMhiazolines (117) with A -bromo-succinimide gives the corresponding 9/f-benzo[2,l-c]thiazolo[2,3-c][l,2,4]-triazine. ... 

Porphyrin complexes, which have been mentioned in the previous section as catalysts for the epoxidation of olefins, can also catalyze aziridination120 using [A-(p-toluenesulfonyl)imino]phenyl iodinane or other nitrene precursors. 

The synthesis of 2-substituted-l, 3-dithiane-l -sulfimides using T-( -tolylsulfonyl)imino(phenyl)iodinane (TsN=IPh) and a catalytic amount of Cu(OTf)2-box was reported to proceed with good yields (57-70%) and diastereoselectivity (trans xis 96 4-100 0). However, the ee was low (32 0%) (Equation 42) <1998J(P1)2373>. 

Other convenient reagents for the imidation of sulfides and selenides are imidoiodanes such as A-(/>-tolylsulfonyl)-imino(phenyl)iodane (PhI=NTs).304 Unfortunately, these reagents are sometimes difficult to prepare due to their thermal sensitivity and some have even been claimed to be explosive.305 Selenimides are tricoordinate tetravalent compounds and can be isolated in optically active forms. They can be prepared from optically active selenoxides, a reaction which was shown to occur with an overall retention of stereochemistry.306 They can also be obtained by optical resolution of a diastereomeric selenimide and stereochemical issues including kinetics of epimerization by pyramidal inversion were studied in detail.307 Also the enantioselective imidation of prochiral selenides of type 179 is possible by using a combination of A-(/>-tolylsulfonyl)imino(phenyl)iodane (PhI=NTs) and a catalytic amount of... 

Several reports describe the reaction of pyrazol-3-ones with amidines and iminium salts where the group displaced is an amine. Nucleophilic substitution of ammonia by 2,5-dimethylpyrazol-3-one 591 attack on benzamidine hydrochloride 592 requires 220 °C to give via addition intermediate 593 4-[imino(phenyl)methyl]pyrazol-3-one... 

The chiral phosphoric acid (218)-catalysed enantioselective transfer hydrogenation of unprotected disubstituted 2-(imino (phenyl) methyl) phenol using a Hantzsch ester (2, R = BuO as the hydrogen source gave the corresponding chiral Af,0-unprotected amines in high yields with excellent ee. The presence of the ortho-OW group enabled conversion to medicinally relevant compounds. ... 

Related Reagents. [fV-(/>-Toluenesulfonyl)imino]phenyl iodane [(V-(/)-Nitrobenzenesulfonyl)imino]phenyliodane. 

C24H18Cl2NaNi04S2, Chloro(bis(2-((2-pyridylmethyl)imino)phenyl)-disulfide)nickel(II) perchlorate, 40B, 1015 C24H18C0N4S4, Bis(benzothiazole-2-thiolato)bis(pyridine)cobalt(II), 43B, 1401... 

Related Reagents. [A -(p-Toluenesulfonyl)imino]phenyl iodane [Af-(p-nitrobenzenesulfonyl)imino]phenyliodane. 

Nageh I, Baud C, BemardineUi G, Jacquier Y, Moran M, MiiUer P. Rhodium(II)-catalyzed CH insertions with [(4-nitrophenyl)sulfonyl]imino phenyl-X -iodane. Helv ChimActa. 1997 80 1087-1105. 

Hydroxypheny[)imino]phenyl -4 methylphenol, 9CI. 2-Hydroxy-5-methylbenzaldehyde 2-hydroxyanil [1761-40-6]... 

Acetylation of 2-phenyl-4-amino-5-benzoylthiazole takes place on the exocyclic nitrogen (49). This exocyclic nitrogen remains the reactive center even with 2-imino-3-aryl-4-amino-5-carboxamido-4-thiazoline (111). Its acetylation with acetic anhydride gives the 4-acetamido derivative (112), which reacts further on heating to yield 2-(acetylimino)-(3H)-3-aryl-5-methylthiazolo[4,5-d]pvrimidin-7-(6H)-one (113) (Scheme 76) (276). 

The amino group of 2-imino-3-phenyl-4-amino-5-carbethoxy-A4-thiazoline is very reactive and displaces the chlorine atom of various 2-chlorothiazoles (1577). 

Condensation of 2-phenyl-4-amino-5-benzoylthiazole with cyanamide yields the pyrimidothiazole (Scheme 88) (133) (49) 2-imino-3-aryl-4-amino-5-carbethoxy-4-thiazolines condense similarly with alkyl isothiocyanates (276). 

The high reactivity of the exocyclic 4-NH- group is again illustrated by the reaction of 2-imino-3-phenyl-4-amino-5-(ethoxycarbonyl)-4-thiazoline with EtOjCCH SCN, which yields 134 (296), and by the intramolecular preparation of the dihydrothiazolo[4,5-h]pyridine derivative 136 (297) (Scheme 89). 

Treatment of 2-imino-3-phenyl-4-amino-(5-amido)-4-thiazoline with isocyanates or isothiocyanates yields the expected product (139) resulting from attack of the exocyclic nitrogen on the electrophilic center (276). Since 139 may be acetylated to thiazolo[4,5-d]pyrimidine-7-ones or 7-thiones (140). this reaction provides a route to condensed he erocycles (Scheme 92). 

The synthesis of 9H-benzo[2,l-e]thiazolo-[2,3-c]-as-triazine (401) was achieved by oxydative cyclization of 2-imino-3-(o-aminophenyl)-4-phenyl-4-thiazoline (718, 719). This latter reacts also with paraformaldehyde in hot toluene yielding 3-phenyl-9H.10H-benzo[l,2-/]thiazolo-[2,3-d][l,3,5]triazepine (402) (720). This heterocyclic sytem is also formed when carboxylic acids replace paraformaldehyde (Scheme 230) (721). 

An interesting class of 2-imino-3-amino-4-thiazolines (408) has been described (578, 701, 726). These 3-amino derivatives of 4-thiazoiine may also be prepared from 2,3-diaminothiazolium salts (406) in basic medium (101) or through the acid-catalyzed rearrangement of 2-acylaminoimino-3-phenyl-4-phenyl-4-thiazolines (407) (Scheme 233) (99, 724). 

Aminophenyl)(4-imino-2,5-cyclohexadien-l-ylidene)methyl]-N-phenyl aniline, monohydrochloride [68966-31-4]... 

C3NS S — N — — Thiamine hydrochloride monohydrate rhodanine 2-imino-5-phenyl-4-thiazolidinone ... 

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