2-methylthio-l-phenyl

Cyano-2-methyl-l -phenylthio- 132 2-Cyano-2-methylthio-l-phenyl- 97 Cyclopropenthione Dimethylamino-phenyl- 3002, 3052, 3109, 3110, 3198... 

Die ,/3-ungesattigten Sulfoxide derE- oderZ-Isomeren der 2-Methylthio-l-phenyl- bzw. 2-Phenyl-1-phenylthio-ethene reagieren u.a. mit Phosphor(V)-chlorid in Dichlor-methan bei 0—20° unter Umlagerung zu Methylthio- bzw. Phenylthio-acetaldehyd (10-23%) (uber schwefelsubstituierte Oxirane)35. 

Methoxy-a-(phenylthio) ketones, e.g., 3-methoxy-l-phenyl-2-phenylthiopropanone and 5-methoxy-l-phenyl-4-phenylthio-l-penten-3-onc (Table 6), can also be reduced with syn selectivity by zinc borohydride. calcium borohydride and lithium triethylborohydride82. For zinc and calcium borohydride, at least, it is reasonable to suppose that the transition state 4 (where R3 = MOM) is reinforced by /1-chclation. These reagents are actually more successful than L-Selectride in the reduction of 3-methoxy-1-phenyl-2-phenylthiopropanone, where the L-Se-lectridc result is anomalously poor. A /5-hydroxy substrate, 3-hydroxy-2-mcthylthio-l-phenyI-propanone, could be reduced to 2-methylthio-l-phenyl-l,2-propanediol with good syn selectivity using zinc borohydride (yield 65% d.r. 93 7)81. 

Reaction of 1,3-propanediamine and 3-cyano-4-methyl-6-methylthio-l-phenyl-2-0X0-],2-dihydropyridine-5-carboxylate 385 yielded 7-cyano-8-methyl-6-oxo-],2,3,4-tetrahydro-6/7-pyrido[],2-a]pyrimidine-9-carboxylate (386) (94JHC393). 

N-Diphenylmethylen- 374 N-Diphenylmethylen-O-aminocarbonyl- 612 N-[l,3-Diphenyl-propyl-(2) - 374 N-[l,3-Diphenyl-propyliden-(2)]- 374, 377, 380 N-(4-Halogen-phenyI)- 683 N-Heptyl- 375 N-Heptyl-N-acetyl- 376 N-Heptyliden- 375 N-Hcptyliden-O-acetyl- 376 0-(2-Hydroxy-athyl)-N-athoxycarbonyl- 133 N-(4-Hydroxy-phenyl)- 683 0-(2-Hydroxy-l-phenyl-athyI)-N-athoxycarbonyI-aus 0-(ci-AthoxycarbonyI-benzyl)-N-athoxycar-bonyl-hydroxylamin und Lithiumalanat 133 N-Isopropyl- 682 N-Isopropylidcn- 613 N-Methyl- 133, 682 O-Methyl-N-bcnzyliden- 377 O-Methyl-N-benzyliden- 375 0-Methyl-N-(4-chlor-benzyl)- 375 0-Methyl-N-(4-chlor-benzyliden)- 375 N-Methy -N,0-diacetyI- 682 N-(4-Methyl-phenyl)- 683 0-McthyI-N-( 1 -phenyl-athyliden)- 375 N-(4-Methylthio-phenyl)- 684 N-(4-Nitro-benzyl)- 374 N-[4-Nitro-benzyliden - 374, 377 N-(2-Nitro-phenyl)- 562 N-(4-Nitro-phenyl)- 682 N-Nitroso-N-cyclohexyl- 697 N-Octyl- 374 N-Octyl-(2)-N-acetyl- 376 N-Octyliden- 374 N-0ctyliden-(2)-0-acctyl- 376 N-(Pentafluor-phenyl)-0,N-diacetyl- 697 N-Phenyl- 474, 481, 682, 783 N-Phenylacetyl-O-benzoyl- 265 N-(l-Phenyl-athyl)- 374 N-(l-Phenyl-athyl)-N-acetyl- 376 N-(l-Phenyl-athyliden)-374, 613 N-( l-Phenyl-athyliden)-0-acetyl- 376 N-[ 1 -Phenyl-buten-( 1 )-yl-(3)-iden]- 582 N-f4-Phenyl-butyl-(2)-iden]- 581 N-Phcnyl-N,0-diacetyl- 682 N-(4-Phenylthio-phenyl)- 684 N-Propyl-N-cyclohexyl- 376 N-Propyl-N-isopropyl- 376 O-Sulfonyl- 481 N-(4-Sulfonyl-phenyI)- 683 N-(2-Vinyl-phenyl)- 698... 

Methylthio- 500 2-Nitro- 682 2-Nitro-2-methyl- 6< f2 2-Nitro-l-phenyl- 506... 

CN ( ()-l-[2-(Methylthio)-l-[2-(pentyloxy)phenyl]ethenyl]-l//-imidazole monohydrochloride... 

When l-methyl-4-phenylpyrimidiniun iodide reacts with 5-methylisourea, it is converted in the corresponding 2-amino-4-phenylpyrimidine (yield 70%). A similar conversion has been reported for l-methyl-5-phenylpyrim-idinium iodide, 2-amino-5-phenylpyrimidine being obtained in 40% yield (Scheme III.47) (76RTC209). In both reactions, no detectable amounts of 2-methylthio-4-phenyl- or 2-methylthio-5-phenylpyrimidines are ob-... 

There are many heterocyclic molecules in which 1,3,4-thiadiazoles are fused to other ring systems. For example, Molina et al. developed a procedure for building a thiadiazole ring on to a properly substituted imidazole moiety (Scheme 29). Reaction of l-amino-2-methylthio-4-phenylimidazole (161) with triphenylphosphine dibromide in dry benzene furnished the 2-methylthio-4-phenyl-l-triphenylphosphoranylidenamino imidazole (162) in a 95% yield. With aroyl chlorides at elevated temperature, this gave the 2-aryl-6-phenylimidazo[2,l-Z ][l,3,4]thiadiazoles (164) in yields between 50% and 70% via the imidoyl chloride intermediate (163) which could be isolated and shown to cyclize to the thiadiazole. The method developed for the imidazole ring was also applicable to the thiadiazolotriazine ring system <88H(27)1935). 

In a similar manner, aldazines afford pyridazinones 317 (Scheme 7.104). 1,3-Diazadienes such as l-aryl-4-(dimethylamino)-2-phenyl-l,3-diaza-l,3-butadienes or l-aryl-4-(dimethylamino)-2-methylthio-l,3-diaza-l,3-butadienes react with oxazolones and give rise to pyrimidin-6-ones 319 and 320 as single diastereo-... 

C6Hs ch3 H CH, c6h5 cooc2h5 5-Benzoyl-4-methyl-thio-l-phenyl-... 5-Benzoyl-2-methyl-4-methylthio-l-phenyl-... 5-Benzoyl-12-di-phenyl-4-methyl-thio-... 75 80 85 120 130 151 5-Benzoyl-4-methyl-thio-... 5-Benzoyl-2-methyl-4-methy/thio-... 5-Benzoyl-4-methyl-thio-2-phenyl-... 5-Benzoyl-2-e thoxy-carbonyl-4-me-thylihio-... 55 60 78 55 (Ol) 170 215 (Ol)... 

In like fashion, methyl ethoxycarbonyldithioacetate gives 3-ethoxycarbonyl - 2 - methylthio - 5 - phenyl -1,6,6a IV - trithiapentalene (43)46,61 and cyanothioacetamide gives 2-amino-3-cyano-5-phenyl-l,6,6a IV-trithiapentalene (44).30,64... 

The reaction of 2 moles of 2-methylthio-4-phenyl-l,3-dithiolylium perchlorate (192 R = Ph) with piperazine forms the double salt (194) (80AHC(27)15l). 

Ethan l-(4-Brom-phenyl)-2-hydroxy-2-methylthio-l-oxo-El4a/1, 787 [R-CO-CH2-S(0) —R/DMSO]... 

Azetidin 3-(Chlor-acetoxy)-4-methylthio-2-oxo-l-phenyl-E16b, 436 (RO C —CO —Cl + S-ester-imid)... 

Quaternization of thiones or thiols proceeds successively through alkylation to methylthio compounds to attack on annular N centres (S9JCS3799. 6ila(641)94, 67JOC224s) to triazolium salts or mesoionic compounds. However, 3,5-bis(methylthio)-l-phenyl-l,2,4-triazole could not be quaternized (54CI(L)1458). 

Secondary amines and 2-methylthio-l,3-dithiolium cations give, in good yield, mesomeric 2-amino-l,3-dithiolium cations (Eq. 41). Two moles of 2-methylthio-4-phenyl-l,3-dithiolium perchlorate with piperazine form 165. ... 

Zu einem photochemisch induzierten Austausch der Substituenten in 2- und 4-Position kommt cs am 3-Methyl-2-methylthio-5-phenyl-l, 3-thiazolium-4-olat 529. 

Thiazole konnen durch Reaktionen an den Substituenten ihren aromatischen Charakter verlieren. So tritt beispielsweise am 3-Methyl-2-methylthio-5-phenyl-l,3-thiazolium-perchlorat beim Erhitzen in Pyridin eine Abspaltung der S-standigen Methyl-Gruppe auf567. Dadurch entsteht 3-Methyl-5-phenyl-2-thiono-2,3-dihydro-1,3-thiazol (95%)567 ... 

Methylthio-l,3-benzothiazol ergibt photochemisch mit (/ . )-1,2-Diphenyl-ethen trans-2,3-Di-phenyl-4-methylthio-2,3-dihydro-1,5-benzothiazepin42S ... 

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