Thiazole 2-methoxy-4-methyl

Thiazole, 2-methoxy-4-methyl-kinetic data, 6, 255 (75JCS(P2)1614)... 

Thiazole, 4-isopropyl-2,5-dimethyl-quatemization, 6, 254 Thiazole, 2-lithio-reactions, 5, 106 6, 292 4-substituted synthesis, 6, 305 Thiazole, 2-mercapto-4-phenyl-synthesis, 6, 300 Thiazole, 4-mercapto-2-phenyl-tautomerism, 6, 291 Thiazole, 5-mercapto-2-phenyl-tautomerism, 6, 289 Thiazole, 2-methoxy-reactions, 5, 102 rearrangement, 6, 289 Thiazole, 2-methyl-anions... 

Inder Reaktion von Isothiocyanat-allen mit Lithiumazid in Methanol erfolgt einezusatzliche Modifizierung der entstehenden 5-Methyl-Gruppe, so daO 2-Amino-5-(methoxy-methyl)-1,3-thiazol (76% Schmp. 96-97°) gebildet wird1 90. 

Me ether 2- 2-Methoxy-4-methyIphenylazo)thiazole. 5-Methyl-2 I-thiazolylazo)anisole CiiHjiNjOS M 233.293... 

On the other hand, phenanthroid-fused thiazoles possessing thiophene, furan, and methoxypyridine rings are readily available by the treatment of 2-methyl-4-(3, 4-dimethoxyphenyl)-5-heteroarylthiazoles with BF3-activated BTIB (02EJO2126). This is illustrated in Scheme 35 with oxidations of the 2-and 3-furyl and -thienyl analogs 118 and 119 to the regioisomeric thiazolo tetracycles 120 and 121. The 6-methoxy-2- and -3-pyridyl analogs of 118 provide similar access to thiazolobenzoquinoline derivatives. 

Thiazol 2-Amino-4-(methoxy-carbonyl-methyl)- E8b, 48 (ROOC-CH2-CO-CH2-Cl + Thioharnstoff)... 

Thiazol 5-Methoxy-2-methyl-4-(2-methyl-propyl)- E8b, 111 (HjC —CO—NH —CHR — COOR + P4S10)... 

The cycloaddition of l-methoxy-3-trimethylsilyoxy-1,3-butadiene with 3-methyl-1,2-benziso-thiazole 1,1-dioxide (107) (R = Me) affords the pyridone (108) <84H(22)67l>. An improved synthesis of 1,2-benzisothiazole 1,1-dioxide has led to the preparation of the benzothiazepine (109) (R = H) by cycloaddition of the ynamine followed by ring expansion <83CC520>. Addition of yV,7V-diaikylprop-l-ynamines to 3-substituted 1,2-benzisothiazole 1,1-dioxide (107) (R = SMe, SPh, SePh) gives mainly the imine-vinylamine (110) with only small amounts of the benzothiazepine (109) <85CC845>. 

Die Addition von Methanolat an 3-Methyl-2-phenyl-l,3-thiazolium-iodid verlauft in gleicher Weise zu 2-Methoxy-3-methyl-2-phenyl-2,3-dihydro-l,3-thiazol, das nicht isoliert wurde1693 ... 

Methoxy-benzyliden)-hydrazino]-4-(4-methyl-2-phenyl-l, 3-thiazol-5-yl)- 75 -Mcthoxycarbonyl- 188, 189 -Methoxycarbonyl- 219 -Mcthoxycarbonyl-5-(6-methoxycarbonyl-hexyl)- 111... 

Mercapto-cthyl)-2-thiono-2,3-dihydro- 1025 2-Mercapto-5-methoxy- 882 2-Mercapto-6-inethoxy- 977 2-Mercapto-6-methyl- 977 2-Mercapto-6-methyl-4-nitro- 977 2-Mercapto-5-nitro- 873 2-Mercapto-4-nitro-6-trifluormethyl- 914 2-Mercapto-4,5,6,7-tetrachlor- 960 2-Mercapto-4,5,6,7-tetrahydro- 87 2-(2-Mercapto-1,3-thiazol-4-yl)- 77, 987 2-Methansulfonyl- 979 2-(Methoximino-methyl)- 938... 

SNSj 6-Methyl-2-nitroimino2//-thiazolo[3,2-Z)][l,2,4]thiadiazole (11) <84CPB3483> NNSj 2-phenyl-5-[(4-ethoxycarbonyl)thiazol-2-yl]thiazolo[3,2-Z)][l,2,4]triazole (12) <85AX(C)1238> and AiV7V/5,6-dihydroxy-2-methoxy-4-[(l/ )-phenylethyl]-4//-imidazo[l,2-Z)][l,2,4]triazole-(55)-car-boxylic acid (13) <92TA5i>. 

Potassium carbonate and triethylamine converts 2-methoxycarbonylmethyl-3-methylthiazolo[3,2-c][l,2,3]triazolium bromide (160) into the yellow azomethine ylide (161) which reacts with methyl propiolate to give a mixture of (2E,4Z) and 2E,AE) isomers of methyl 4-methoxycarbonyl-5-(thiazol-2-yl)-2,4-hexadienoate (162) and (163) beside traces of 6-methoxycarbonyl-5-methoxy-carbonylmethyl-7-methylpyrrolo[2,l-i]thiazole (164) (Scheme 12) <94H2017>. 

Methyl 2-amino-4-(2-methoxy-2-oxoethyl)thiazole-5-carboxylate (80), prepared from dimethyl acetone-l,3-dicarboxylate (1), sulphuryl chloride and thiourea (46JA266), was transformed with DMFDMA into methyl 4-[l-(dimethylamino)-3-ethoxy-3-oxoprop-l-en-2-yl]-2-[(dimethylamino) methyleneamino]thiazole-5-carboxylate (81) in 96% peld (Scheme 27). Thiazole 64 was treated with 2-aminopyridine in hot ethanol to )deld... 

Nitrogen-containing volatiles such as methyl anthranilate (30), methyl N-methyl anthranilate (31), indole (32), 3-methyl indole (= skatole) (33), 2-methoxy-3-iso-butylpyrazine (34), alkyl pyrazines (35), quinoline (36), methyl quinoline (37), pyridines (38), and so on sulfur-containing volatiles such as sulfides and thiophenes (e.g., dimethyl sulfide (39), dimethyl disulfide (40), diallyl disulfide (42), 3,2-dimethylthiophene (43), 4-mercapto-4-methyl pentanone (44), 8-mercapto-/ -men-than-3-one (45), l-/ -menthene-8-thiol (46), 3-mercaptohexanol (47), 5-prenylth-ioesters, thiazols, sulfides of mono- and sesquiterpenes, mint sulfide (48), isomint sulfide (49), etc.) (1, 2, 13, 14). 

Dolastatins share many common features with bryosta-tins (see Chapter 22) both series of compounds were discovered by Professor Pettit and in both cases extreme cytotoxicity (IC50 about 1 pM) is associated with a very low content, averaging 4 x 10 to 3 x 10 % of the weight of fresh animals " (Pettit, 1997). Detailed structural analysis of these compotmds has shown that these peptides and depsipeptides often contain a-amino adds and atypical adds or amines, for which a particular nomendature has been created. Most of them have methyl or methoxy substituents, or thiazole rings, and several examples are shown in Figure 23.12. Figures 23.13 and 23.14 present the structures of a few dolastatins. 

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