LIEBIGS ANNALEN DER CHEMIE - uni-muenchen.de · LIEBIGS ANNALEN DER CHEMIE \ HERAUSGEGEBEN VON DER GESELLSCHAFT DEUTSCHER CHEMIKER \ ... Blount, J. F. Reactions of l,4-pentadien-3-ones,

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LIEBIGS ANNALEN DER C H E M I E \

H E R A U S G E G E B E N V O N D E R

G E S E L L S C H A F T D E U T S C H E R C H E M I K E R \

J A H R G A N G 1984 · H E F T 9 · S E I T E I - X L

© Verlag Chemie GmbH, D-6940 Weinheim, 1984 0170-2041/84/0909-1 $ 02.50/0

1984 2001

Autorenregister

Abase , A . Carbony l a n d th iocarbonyl compounds: r e a c tions of 4 - ch loroxanthione w i t h diazoalkanes and compounds conta in ing active hydrogen. 191

Abase , A . Reactions o f 4 - c h l o r o - 9 H - x a n t h e n e - 9 - t h i o n e w i t h te trachloro -o -benzoquinone . 196

A b d E l - B a r y , H . Reactions w i t h 2 - m e t h y l - and 2 - s t y = ry l -4 - th io chromones . 186

A c k e r m a n n , Κ. Chemis try of reactive cations derived f rom sul fur dioxide analogs. X . Reaction w i t h a r o m a t = ic carbodi imides - synthesis o f benzothiadiazines. 904

A e b i , J . D . Enant i omer i ca l l y pure synthons f r o m branched malates (correction). 407

A f z a , N . Stereospecific syntheses of D-ossamine and D - to lyposamine. 636

A l d a g , R . Crown ethers w i t h triose and pentose s t ruc= t u r a l un i t s . 1036

A l l g a i e r , H . I t u r i n A L : s t ructure and derivatives of a pept ido l ip id w i t h a h igh content of Ci6 - i tur in ic acids. 854

A n k e , Τ. Ant ib i o t i c s f r o m Basidiomycetes, X I X . N a e = mato l in and naematolone, two caryophyllane der iva= tives f r om cultures of H y p h o l o m a species (Agaricales) 1332

A n k e , Τ. Ant ib i o t i c s f r om basidiomycetes, X X . S y n t h e = sis o f s t r o b i l u r i n A and revision of the stereochemistry of n a t u r a l s t rob i lur ins . 1616

A n t u s , S . A n a t t e m p t e d synthesis of polystachin. 1068 Aoyagi , M . M u l t i s t e p reversible redox systems, X X X I X .

Isomeric biazulenyls: U V / V I S spectroscopy, v o l t a m = metry , and H M O energies. 1952

A r n d t , F . Syntheses o f t h i a z o l o - and [ l , 3 ] t h i a z i n o [ l , 2 , = 4)triazinones. 1302

A u m u e l l e r , A . M u l t i s t e p , reversible redox systems. X X X V I . l l , l l , 1 2 , 1 2 - T e t r a c y a n o - 9 , 1 0 - a n t h r a q u i n o d i = methan ( T C N A Q ) and its derivatives: synthesis and redox properties. 618

B a c h , T . C . Syntheses w i t h nucleic acid constituents , X . Mass spectrometry of nucleotides, V I I . Synthesis of deoxyoligonucleotide l inker fragments for genetic engineering using improved preparat ive and analyt ical techniques. 835

B a c k e n s , S . A n t i b i o t i c s f r om Basidiomycetes, X I X . Naemato l in and naematolone, two caryophyllane derivatives f r o m cultures of H y p h o l o m a species (Agar= icales). 1332

B a n e r j e e , S . K . Lactonic constituents of Angelica g lau= ca. 888

B a r l o s , Κ. App l i ca t i on of N - t r i t y l amino acid l - b e n z o = tr iazo ly l esters i n peptide synthesis. 1308

B a u e r , H . K inet i c s , catalysis, and mechanism of the secondary reaction i n the f i n a l phase of the formose reaction. 623

B a u r , R . Pteridines , L X X I V . Acylations of lumazines by radical nucleophil ic subst i tut i on . 1798

B e g t r u p , M. A n n u l a t e d 1,2,3-triazoles, I . Synthesis of 8 -azapurin-6-ones and 8 -azapur in -6 - imines f rom e t h y l 5 - (acety lamino) - l ,2 ,3 - tr iazo le -4 -carboxylates . 1848

B e l l i n g e r , O. Chemistry of d i m e t h y l (1α,2/3,5/3,6α,70,= 8j8) -3 ,4-dioxotricyclo[4 .2 .1 .0 2 . 5 ]nonane-7,8-dicarboxy= late. 1109

B e l l i n g e r , O. T h e behavior of ( l a , 2 a , 5 a , 6 a ) - 3 , 4 - b i s ( t r i = methyls i loxy)tr icyclo[4 .2 .1 .0 2 - 5 ]nona-3,7-diene on t reatment w i t h oxidative reagents. 1778

B e l l m a n n , P . Synthesis of 2 -acy l -3 -amino furans by Thorpe cycl ization. 1702

B e n z , G . A l b omycins, I . Enzymic cleavage o f the deferr i f orm of albomycins δι and hi. 1399

B e n z , G. Albomycins , I I . Absolute conf igurat ion of the deferr i f orm of the albomycins. 1408

B e n z , G. Albomycins , I I I . Synthesis o f N 5 - a c e t y l - N 5 - = h y d r o x y - L - o r n i t h i n e f r om L - g l u t a m i c acid. 1424

B e n z , G . Albomycins , I V . Isolation and t o t a l synthesis o f ( N 5 - a c e t y l - N 5 - h y d r o x y - L - o r n i t h y l ) ( N 5 - a c e t y l - N 5 - = h y d r o x y - L - o r n i t h y l ) - N 5 - a c e t y l - N 5 - h y d r o x y - L - o r n i t h = ine. 1434

B e r n e t h , H . M u l t i s t e p reversible redox systems. X X X V . V o l t a m m e t r y o f vinylogous polyenes w i t h cross-conjugated end groups and U V / V I S spectrosco= py of t h e i r radical anions and cations. 354

B e s t m a n n , Η. J . Retinoids and carotenoids, I I . Synthe= sis of (13Z)-ret inoic acids. 1740

B i e b e r , Μ . I od inat i on of monosaccharide derivatives w i t h iodotr imethyls i lane . 1052

B i g n a r d i , G . Constituents of Cupuli ferae, 8. A novel, h igh ly -acy lated astragalin f r o m Quercus ilex L . 1864

B i n h V u A simple method for the preparat ion of 2 - a r y l = benzofurans and the synthesis of moracin A and B . 734

B i r k o f e r , L . Organosilicon compounds. L X X X I V . /3-Lactams. I I I . 0 -Lactams via N-s i ly l carbodi imides 1193

B l o u n t , J . F . Reactions o f l ,4 -pentadien-3 -ones , 22. Synthesis and structure of the epimers of 3 , 5 - d i a r y l - = 4 - h y d r o x y - l , 4 - t h i a z i n a n e 1,1-dioxides. 1013

B o b e r g , F . N e f reaction. V I . 4 , 5 - D i h y d r o - 5 - ( m e t h y l e = neamino) -3- furancarboxylates . 223

B o b e r g , F . Heterocycles f r om α-nitroolefins, V I I . 4 ,5 -= D i h y d r o - 2 - m e t h y l - 5 - ( m e t h y l e n e a m i n o ) - 3 - f u r a n c a r b = oxylates f r om α-nitroolefins, acetoacetates, and com= pounds w i t h an active methylene group. 911

B o e c k e r , R. O r i g i n of 3,6-epoxyalkanedioic acids i n h u m a n ur ine . 1513

B o e h m , H . Synthesis of stereoisomers 3 , 4 - d i h y d r o b i l i = rub in i c acid derivatives as synthons for bile pigments 1441

B o h l m a n n , F . New sesquiterpene lactones and rosane derivatives f r o m Trichogonia species. 162

B o h l m a n n , F . New spirosequiterpene lactones, germa= cranolides, and eudesmanolides f r o m Wunder l i ch ia mirab i l i s . 228

B o h l m a n n , F . New germacranolides, heliangolides, and elemanolides f r om Cronquist ianthus chacnapoyensis. 240

B o h l m a n n , F . Epoxycannabinol ide and diterpenes w i t h a new carbon skeleton f r o m Vi l lanova titicaensis. 250

B o h l m a n n , F . Heliangolides and trachylobane and vil lanovane derivatives f r o m Viguiera species. 495

B o b l m a n n , F . Pseudoguaianolides and other sesquiterp= enes f r o m Monact is macbridei . 503

B o h l m a n n , F . Synthesis of rac -40 -hydroxyobovata= chromene. 1382

B o h l m a n n , F . Synthesis of fur ther eremophilane der iva= tives. 1785

B o i d o l , W . Syntheses w i t h nucleic acid constituents, X . Mass spectrometry o f nucleotides, V I I . Synthesis o f deoxyoligonucleotide l inker fragments for genetic engineering using improved preparative and analyt ical techniques. 835

B o r n , L . Albomycins , I I . Absolute conf igurat ion of the deferr i f o r m of the albomycins. 1408

Boroes , F . A n a t tempted synthesis o f polystachin. 1068 B o s c h , R . Conformat ion of B o c - L - A l a - A i b - L - A l a - O M e

i n the crystal and i n so lut ion . 1117 B o s c h , R . Conf igurat ion and conformation of the n u =

cleoeide residues of the n ikkomycins . 1216 B o t u l i n s k i , A . M e t a l complexes w i t h tetrapyrro le l i =

gands, X X X V . Synthesis of fur ther more or less sterically hindered 5 ,15 -d ia lky loc taethy lporphodimet= henes by reductive a l k y l a t i o n of o c tae thy lporphyr ina= tozinc. 1259

B r a e u n e r , H . J . Orthoamides. X I . Preparat ion o f 1,1,2,= 3 ,3 -penta-subst i tuted and 1,1,2,2,3,3-hexa-substituted g u a n i d i n i u m salts and 1,1,2,3,3-pentaalkylguanidines. 108

B r e w e r , C. F . Reactions of enolic sugar derivatives, X V I . Synthesis of a diastereotopic proton probe [ ( Z ) - 3 , 7 - a n h y d r o - l , 2 - d i d e o x y - D - g l u c o - o c t - 2 - e n i t o l ] for a- and (8-D-glucosidases. 1078

B r e w e r , C. F . Reactions of enolic sugar derivatives, X V I . Synthesis of a diastereotopic proton probe [ ( Z ) - 3 , 7 - a n h y d r o - l , 2 - d i d e o x y - D - g l u c o - o c t - 2 - e n i t o l ] for a- and /3-D glucosylases (correction). 1626

B r i e d e n , Μ . Albomycins , I I . Absolute conf iguration of the deferr i f o r m of the albomycins. 1408

Liebigs Ann. Chem. 1984

2002 Autorenregister 1984

B r o c k m a n n , R . Enehydrazines, 37. Synthesis of a pyrazole analog o f 7-aminomitosene. 1711

B u c h l e r , J . W . M e t a l complexes w i t h te trapyrro le Uganda, X X X V . Synthesis of f u r t h e r more or less sterically hindered 5 ,15 -d ia lky loc taethy lporphod imet= henes by reductive a lky la t i on o f o c tae thy lporphyr ina= tozinc. 1259

B u e n z e l , M . M e t a l l o p o r p h y r i n s i n po lymeric matrixes , micelles, and vesicles, V . 5 - ( l ' - M e t h y l - 4 , 4 ' - b i p y r i d i = n i u m - l - y l ) o c t a e t h y l p o r p h y r i n d ichlor ide , a meso -v io l= ogenporphyrinate . 426

B u r g e r , K . 4H- l ,3 ,5 -Oxad iaz ines a n d 4 H - l , 3 , 5 - t h i a = diazines f rom cyanamides and perhalo ketones and t h i o ketones. 982

B u r g e r , K . T r i f l u o r o m e t h y l - s u b s t i t u t e d pyr imid ines f r om enamines and t r i f luoroaceton i t r i l e . 991

B u s a m , L . Macrocycl ic trichothecenes f r o m Baccharis cor id i fo l ia , I . M i o t o x i n Β and C, t w o new macrocyclic trichothecenes f r om Baccharis cor id i fo l ia D C . 1746

B u s s m a n n , W . Anomers o f tuberc id in derivatives w i t h 2 - m e t h y l t h i o and N M A M s o p e n t e n y l ) residues. 1972

C a l d e r o n , O . Synthesis o f 4 -aminocinnol ines f r o m (arylhydrazono)(cyano)acetic acid derivatives. 1390

C a p l a r , V . Cycloarenes, a new class of aromatic c om= pounds. I I I . Studies towards the synthesis of cyclo= [d.e.d.e.e.d.e.d.e.e.]decakisbenzene (correction). 408

C a r l s e o n , G. Conf igurat ion and conformat ion of the nucleoside residues of the n ikkomyc ins . 1216

C a s t r o , V . Heliangolides and trachylobane and v i l l a n o ~ vane derivatives f r o m Viguiera species. 495

C h r i s t , J . l ,5 -Dimethylb icyc lo [3 .3 .0 ]octane-2 ,6 -d ione and 1,5-di methy lbicyclo[3.3.0] o c ta -3 ,7 -d i ene -2 ,6 -= dione. Basic synthons for subst i tuted semibul lva l= enes. 1180

C h y l i n s k a , B . Reactions of organic anions. 113. V i c a r i ous nucleophil ic subs t i t u t i on of hydrogen i n n i t r o p y r i = dines by α-chloroalkyl pheny l sulfone carbanions. 8

C i c h y , M . New constituents of Lev i s t i cum officinale Koch . 397

D a n n , Ο. Syntheses of ant imic rob ia l biscationic 2 - = (phenoxyphenyl) indoles and -1 -benzofurans . 409

D a u b , J . Selective reactions of hydroazulenes: ch i ra l norcarane derivatives by the reaction of a d ihydroaz= ulene w i t h singlet oxygen. 773

D e c k e r , K . Feodor L y n e n . 1911-1979. Issue 9. i Deger , S . Synthesis and structure o f cyano (d ihydrod i=

benzofb.i] [1,4,8,1 l ] tetraazacyclotetradecinato)cobalt= ( I I I ) . 1791

D i c k e r h o f , Κ. Occurrence of hydrogen transfer, 73. Reduct ion of proch i ra l a l k y l (aryl ) ketones t o c a r b i = nols and pinacols w i t h a lka l i meta l amalgams. 1240

D i e d e r i c h , F . Cycloarenes, a new class of aromatic compounds. I I I . Studies towards the synthesis of cyclo[d.e.d.e.e.d.e.d.e.e.]decakisbenzene (correction). 408

D i t t e l , W. Po lyhydroxyamino compounds via diene synthesis w i t h nitroso compounds. I X . t r a n s - 6 - A z i = do - l , 3 - cy c l ohexad ien -5 - o l as educt for the synthesis of condurodiamine and streptamine isomers. 203

D r i l l e r , H . 7 - ( 0 - D - A r a b i n o f u r a n o s y l ) - 2 , 4 - d i c h l o r o - 7 H - = p y r r o l o [ 2 , 3 - d ] p y r i m i d i n e - synthesis, selective d i s= placement o f halogen, and effect of glyconic protect ing groups on the react iv i ty of the aglycon. 722

D u d d e c k , H . Synthesis and carbon-13 N M R spectro= scopic studies of br idgehead-subst i tuted endo -b i cy= clo[3.3.1]nonan-3-ols and oxaadamantanes. 1981

E c k s t e i n , Z . Chemis try of hydroxamic acids. 10. A convenient rearrangement of 4 -qu ino l inecarbohydrox= amic acid. 395

E i d e n , F . Benzothiazoles by carbon-carbon cleavage of o - [ ( 2 - n i t r o p h e n y l ) t h i o ] ketones. 1100

E i d e n , F . Pyrans, 100. 5 , 6 - D i h y d r o - 2 H - p y r a n - 3 ( 4 H ) - = one as a synthon for p y r a n - a n n u l a t e d heterocyclic compounds. 1759

E l - M o g h a z y A l y , S . M . Studies o f the chemistry of natura l organic materials . 89. Halogenation reactions of l , 3 - d i h y d r o x y - 1 0 - m e t h y l - 9 ( 1 0 H ) - a c r i d i n o n e and its ethers - a s imple regiospecific synthesis of acronym cine. 31

E l - S a k k a , I . Carbonyl and thiocarbonyl compounds: reactions of 4 -chloroxanthione w i t h diazoalkanes and compounds conta in ing active hydrogen. 191

E l - S a k k a , I . Reactions of 4 - c h l o r o - 9 H - x a n t h e n e - 9 - = thione w i t h tetrachloro-o -benzoquinone. 196

E r m a n n , P . Ret inoids and carotenoids, I I . Synthesis of (13Z)-ret inoic acids. 1740

F a l s o n e , G. Const i tuents o f Boraginaceae, 7. Anchuso= side-8 and - 9 : two new t r i t e rpene saponins f rom Anchusa off icinalis L . 1869

F e r w a n a h , A . R . Syntheses w i t h a l iphat i c dialdehydes, X X X V I I I . Synthesis a n d properties o f cyc loa lky lmal= onaldehydes. 649

F e u s t e l , M . Polyynes. 3. Synthesis of ( l , 3 - a l k a d i y n y l ) = amines. 586

F i l i p o v i c - M a r i n i c , N . C o n t r i b u t i o n s to the chemistry of tetraketones. I I . Reaction of 3 ,4 -d ibenzoy l -2 ,5 -= hexanedione w i t h hydroxy lamine . 199

F l i t s c h , W . C o n t r i b u t i o n t o the synthesis o f 8-azapros= tanoids: reaction of succinimides w i t h (benzoylme= thylene) tr iphenylphosphorane . 1878

F o r m a c e k , V . Reactions w i t h isocyanides. Synthesis of d a r k - b l u e dyes f r om 1,4-quinones and a r y l isocyan = ides. 1003

F o r m a c e k , V . S t ruc ture o f the 1:1 adducts of a r y l iso= cyanides t o 4 -benzoy l -5 -pheny l furan -2 ,3 -d i one and the i r products w i t h nucleophiles. Nove l rearrange^ ments of 5 ,5 -d isubst i tuted 4 - m e t h y l e n e f u r a n - 2 , 3 - = diones. 1137

F r a n k e , W . Syntheses of t h i a z o l o - and [ l , 3 ] t h i a z i n o [ 1,2,4] = triazinones. 1302

F r i s c h k o r n , H . Naphthylenedi (heteroarenes) , I I I . S y n = thesis and spectroscopic behavior of 2 ,2 ' -naphthy lene= dibenzazoles. 1129

F u h r h o p , J . H . M e t a l l o p o r p h y r i n s i n polymeric m a t r i x = es, micelles, and vesicles, V . 5 - ( l ' - M e t h y l - 4 , 4 ' - b i p y = r i d i n i u m - l - y l ) o c t a e t h y l p o r p h y r i n d i ch lor ide , a meso~= vio logenporphyrinate . 426

F u h r h o p , J . H . M e t a l l o p o r p h y r i n s i n po lymeric m a t r i c = es, micelles, and vesicles. V I . Hydrophob i c and h y d r o = ph i l i c derivatives of 3 , 8 - d i f o r m y l d e u t e r o p o r p h y r i n d i m e t h y l ester and their in terac t i on w i t h vesicles. 1057

F u h r h o p , J . H . Synthesis and react iv i ty o f 13 l , 13 2 , 17 i ,= n ^ t e t r a d e h y d r o d e u t e r o p o r p h y r i n . 1386

F u h r h o p , J . H . Chelat ing vesicles made f r o m N , N - d i = hexadecyl-1,2-ethanediamine-N' ,Ν'-diacetic acid. 1634

F u k a z a w a , Y . M u l t i s t e p reversible redox systems, X X X I X . Isomeric biazulenyls: U V / V I S spectrosco= py, vo l tammetry , and H M O energies. 1952

G a r b u r g , Κ. H . Heterocycles f r om α -n i t roo le f ins , V I I . 4 , 5 - D i h y d r o - 2 - m e t h y l - 5 - ( m e t h y l e n e a m i n o ) - 3 - f u r a n = carboxylates f r o m α -n i t roo le f ins , acetoacetates, and compounds w i t h an active methylene group. 911

G a r m i n g , A . N e f reaction. V I . 4 , 5 - D i h y d r o - 5 - ( m e t h y = leneamino) -3- furancarboxylates . 223

G e f f k e n , D . l , 2 -Oxazet id in -3 -ones f r o m ( 2 - t h i e n y l ) g l y = colohydroxamic acids and Ι ,Γ-carbonyldiimidazole. 894

G e r k e , T . New sesquiterpene lactones and rosane der i = vatives f rom Trichogonia species. 162

G e w a l d , K . Synthesis of 4 -aminocinnol ines f r om ( a r y l = hydrazono)(cyano)acetic acid derivatives. 1390

G e w a l d , K . Synthesis of 2 -acy l -3 -amino furans by T h o r p e cycl ization. 1702

G n i c h t e l , H . Cyc loaddit ion w i t h unsaturated c a r b o h y d = rates, I I I . T h e stereochemistry of the D i e l s - A l d e r reaction w i t h hex-2-enopyranoside and hex -2~enopy= ranosid-4-uloses. 1531

G n i c h t e l , H . Chemistry of amino oximes, X V I I I . T h e cyclocondensation of (E ) -0 - ( ch lo roace ty lamino )pro= piophenone oxime derivatives. 1696

G o e r l i c h , K . J . Heterocycles f rom α -n i t roo le f ins , V I I . 4 , 5 - D i h y d r o - 2 - m e t h y l - 5 - ( m e t h y l e n e a m i n o ) - 3 - f u r a n = carboxylates f rom α -n i troo le f ins , acetoacetates, and compounds w i t h an active methylene group. 911

G o r a , J . Synthesis of new te t rahydro furan and t e t r a h y = dropyran derivatives f r om α -p inene and 3-carene. 1860

G o t t s c h a l l , Κ. Synthesis of stereoisomeric 3 , 4 - d i h y d r o = b i l i r u b i n i c acid derivatives as synthons for bile p i g = ments. 1441

G o t t s c h a l l , Κ. Synthesis of rac -stercobi l in I X a w i t h the conf igurat ion of the natura l product and of some urob i l ins , hal f -s tercobi l ins , and stercobi l ins w i t h unequivocal const i tut ion and conf igurat ion. 1454

G r a s e r , F . Crystal s tructure and color of perylene-3,4:9,= lO-bis (d icarboximide) pigments, 2. 483

G r a u m a n n , J . R ing - cha in isomerism of N - ( l - c a r b o x y a l = kyl )n i trones . I . C - A r y l - N - ( l - c a r b o x y l a l k y l ) n i t r o n e s . 1545



Grieeemeier , Η. Syntheses of a n t i m i c r o b i a l biscationic 2 - (phenoxyphenyl ) indoles and - l - b e n z o f u r a n s . 409

G r o s s e r , R . A lbomyc ins , I I . Absolute conf igurat ion of the de ferr i f o r m o f the albomycins. 1408

G r u n d l e r , G . Glycosyl imidates , 13. App l i ca t i on o f the t r i ch loroacet imidate procedure to 2-azidoglucose and 2-azidogalactose derivatives. 1826

G u e n d e l , W . H . Studies of quaternary p y r i d i n i u m salts. X V I . N o t e on cycl izat ion reactions w i t h salts of amides of n i co t inoy lamino acids. 612

G u e n t h e r , H . J . Synthesis of 4 -penten-4 -o l ides (γ-ηιβ= t h y l e n e - 7 - b u t y r o l a c t o n e s ) via 4-pentenoic acids. 15

G u m p r e c h t , C . Cyc loaddi t ion w i t h unsaturated carboh= ydrates, I I I . T h e stereochemistry of the D ie l s -A lder reaction w i t h hex-2-enopyranoside and h e x - 2 - e n o p y = ranosid-4-uloses . 1531

G u n t r u m , E . Synthesis o f 4 -penten-4 -o l ides ( 7 - m e t h y l = ene -7 -butyro lac tones ) via 4-pentenoic acids. 15

G u p t a , B . D . Lactonic const i tuents of Angelica glauca. 888

H a b e r m e h l , G . G . Macrocycl ic trichothecenes f r o m Baccharis cor id i fo l ia , I . M i o t o x i n Β and C, two new macrocyclic trichothecenes f r om Baccharis cor idi fo l ia D C . 1746

H a e d i c k e , E . Crysta l s t ructure and color of perylene-3 ,= 4 :9 , l0 -b is (d i carbox imide ) pigments, 2. 483

H a e f e l i n g e r , G . Syntheses of mes i ty l - subs t i tu ted azul= enes. 1605

Hägen, Η. Orthoamides . X I . Preparat ion of 1,1,2,3,3-= p e n t a - s u b s t i t u t e d and 1,1,2,2,3,3-hexa-substituted g u a n i d i n i u m salts and 1,1,2,3,3-pentaalkylguanidines. 108

H a g e n b r u c h , B . M u l t i s t e p reversible redox systems. X X X I V . Polyenes as f our - s tep redox systems: synthe= sis and spectroscopy. 340

H a g e n b r u c h , B . M u l t i s t e p reversible redox systems. X X X V . V o l t a m m e t r y o f vinylogous polyenes w i t h cross-conjugated end groups and U V / V I S spectrosco= py of t h e i r radical anions and cations. 354

H a g e n m a i e r , H . Conf igurat ion and conformat ion of the nucleoside residues of the n ikkomyc ins . 1216

H a i m o v a , M . Reactions o f glutaconic and homophthal i c anhydrides w i t h imidates , i m i d o y l chlorides, and 1-chloroisoquinoline. 389

H a i n , U . Synthesis of 4 -aminocinnol ines f r om ( a r y l h y = drazono)(cyano)acetic acid derivatives. 1390

H a i n , W . A c on t r ibut i on to the s t ruc tura l assignment of pos i t ional isomers of bis-galacto and b i s -manno crown ethers. 1046

H a m m a n n , Η. Synthesis of 1,2,4-triazines. X I . Synthe= sis and reactions of 6 - a m i n o - l , 2 , 4 - t r i a z i n - 5 - o n e s and 6 - a m i n o - l , 2 , 4 - t r i a z i n e - 5 - t h i o n e s . 283

H a n a c k , M . Synthesis and structure of cyano (d ihydrod i= benzo[b,i] (1,4,8,1 l ] tetraazacyc lotetradec inato)cobalt= ( I I I ) . 1791

H a n e f e l d , W . Studies of 1,3-thiazines, 24. α-Carbamoyl sulfoxides and sulfones, 1. 5 , 6 - D i h y d r o - 2 H - l , 3 - t h i a z = ine -2 ,4 (3H) -d ione 1-oxides and 1,1-dioxides, novel cyclic α-carbamoyl sulfoxides and sulfones. 1627

H a n k e , M . M u l t i s t e p reversible redox systems, X X X I X . Isomeric biazulenyls: U V / V I S spectroscopy, v o l t a m = metry , a n d H M O energies. 1952

H a r s c h , G . K inet i cs , catalysis, and mechanism of the secondary reaction in the f ina l phase of the formose reaction. 623

H a r t k e , K . Boron complexes of malonamides and m a l o = namidines. 370

H a r t k e , K . Preparation of sulfonioindenides. 552 H a t j i i s s a a k , A . Chemistry of reactive cations derived

f rom su l fur dioxide analogs. X . Reaction w i t h a r o m a t = ic carbodi imides - synthesis of benzothiadiazines. 904

H a u g , E . Orthoamides. X I . Preparat ion of l , l , 2 , 3 , 3 - p e n = t a - s u b s t i t u t e d and 1,1,2,2,3,3-hexa-substituted guani = d i n i u m salts and 1,1,2,3,3-pentaalkylguanidines. 108

H a u p t , Η. J . Enehydrazines, 37. Synthesis of a pyrazole analog o f 7-aminomitosene. 1711

H a y a u c h i , Y . Synthons of oligosaccharides, L I I . S y n = thesis o f disaccharides f r om 3 - d e o x y -D - m a n n o - 2 - o c = tulosonic acid ( K D O ) and D-glucosamine. 1270

H a y a u c h i , Y . Synthons of oligosaccharides, L I I I . S y n = thesis o f trisaccharides conta in ing 3 - d e o x y - D - m a n = no-2-octulosonic acid ( K D O ) . 1288

H e h r e , E . J . Reactions of enolic sugar derivatives, X V I . Synthesis of a diastereotopic proton probe [ ( Z ) - 3 , 7 - = a n h y d r o - l , 2 - d i d e o x y - D - g l u c o - o c t - 2 - e n i t o l ] for a -and /S-D-glucosidases. 1078


H e h r e , E . J . Reactions o f enolic sugar derivatives, X V I . Synthesis of a diastereotopic p r o t o n probe [ ( Z ) - 3 , 7 - = a n h y d r o - l , 2 - d i d e o x y - D - g l u c o - o c t - 2 - e n i t o l ] for a~ and β-Ό glucosylases (correction) . 1626

H e i n , F . T r i f l u o r o m e t h y l - s u b s t i t u t e d pyr imid ines f r o m enamines and t r i f luoroaceton i t r i l e . 991

Helbig , W . Stereoselective synthesis of alcohols, X V I I . Stereoselective synthesis o f opt i ca l ly active a - m u l t i s = t r i a t i n , an a t t rac tant of the smaller European e lm bark beetle, Scolytus m u l t i s t r i a t u s . 1165

Helbig , W . Stereoselective synthesis of alcohols, X V I I I . Synthesis of ( 3S ,4S ) -4 -methy l -3 -heptano l and of (5S,6S)-anhydroserr icornin. 1170

H e n n , L . Cycloaddit ions, I I I . Reactions of ynamines w i t h silyiketenes. 1358

Hett inger , P . Synthesis o f the first leaf movement factor f r om Mimosa pudica L . 1230

H i l l e r , W . Synthesis and structure of cyano (d ihydrod i= benzo[b, i ] [ 1,4,8,1 l ] tetraazacyc lotetradecinato)cobalt= ( I I I ) . 1791

H i m b e r t , G . A m i n o e t h y n y l metalations. 13. Synthesis and reactions of 3 -aminopropio lamidines . 85

H i m b e r t , G . Polyynes. 3. Synthesis o f ( l , 3 - a l k a d i y n y l ) = amines. 586

H i m b e r t , G . Cycloaddit ions, I I I . Reactions of ynamines w i t h silyiketenes. 1358

H i r t e , K . Chemistry of amino oximes, X V I I I . T h e cyclocondensation of (E)- )S- (chloroacetylamino)pro= piophenone oxime derivatives. 1696

H i s s m a n n , E . T h e (2* — 5 ' ) - and (3' — 5 ' ) - tuberc idy ly l tuberc id ins - synthesis via phosphite triester and studies of secondary s tructure . 692

Hoefle, G . Ant ib i o t i c s f r o m g l id ing bacteria. X V I I I . T h e absolute conf igurat ion of myxalamide A and B. 78

Hoefle, G . New constituents of Lev i s t i cum officinale K o c h . 397

Hoefle, G . Lactonic constituents of Angelica glauca, 888

Hoefle , G . Ant ib i o t i c s f r o m g l id ing bacteria, X X I I . Biosynthesis of m y x o p y r o n i n A , an ant ib io t i c f r om Myxococcus fulvus , s t ra in M x f50. 1088

Hoefle, G . Ant ib i o t i c s f r o m g l id ing bacteria, X X I I I . S t i gmate l l in A and Β - two novel ant ibiot ics f r om St igmate l la aurantiaca (Myxobacterales) . 1883

H o e l z e l , C . P iper ine - an example o f an i n d i v i d u a l l y d i f f e rent (po lymorphic ) metabol ism of an omnipresent n u t r i t i o n a l component. 1319

H o f f m a n n , Ε. H . Dehydrogenat ion reactions w i t h gallic acid esters. 929

H o f f m a n n , R. Boron complexes of malonamides and malonamidines . 370

H o f f m a n n , R . W . Stereoselective synthesis of alcohols, X V I I I . Synthesis of ( 3S ,4S ) -4 -methy l -3 -heptano l and of (5S,6S)-anhydroserr icornin. 1170

H o f m a n n , K . Sul fos i ly lat ion of carbonyl compounds and t r i m e t h y l s i l y l enol ethers w i t h t r i m e t h y l s i l y l chlorosulfonate. 39

H o l l m a n n , J . Synthesis and conformational analysis of some 5'-homoadenosine derivatives. 98

Hoppe, I . Synthesis and biological activit ies of the ant ib i o t i c Β 371 and its analogs. 600

Hoppe, I . Synthesis w i t h α-metalated isocyanides. L I I I . Synthesis of m e t h y l 2,3-epoxy-2-isocyanoalkanoates. 608

H o r n e r , L . Occurrence of hydrogen transfer, 73. Reduc= t i o n of proch i ra l a l k y l (aryl) ketones to carbinols and pinacols w i t h a lka l i meta l amalgams. 1240

Hosmane , R. S . A n ef f ic ient , one-step synthesis of 2 - imidazo l in -4 (5 ) - one . 831

H u b e r , W . Chemistry and stereochemistry of i r ido ids , I V . Synthesis and x - r a y s tructure analysis of 15 -me= t h y l - 1 2 - e p i - p r o s t a g l a n d i n F20. 761

H u b e r - P a t z , U . Chemis try and stereochemistry of i r ido ids , I V . Synthesis and x - r a y structure analysis of 1 5 - m e t h y l - 1 2 - e p i - p r o s t a g l a n d i n F20. 761

H u e n i g , S . M u l t i s t e p reversible redox systems. X X X I V . Polyenes as f our -s tep redox systems: synthesis and spectroscopy. 340

H u e n i g , S . M u l t i s t e p reversible redox systems. X X X V . V o l t a m m e t r y of vinylogous polyenes w i t h cross-conju= gated end groups and U V / V I S spectroscopy of the ir radical anions and cations. 354

H u e n i g , S . M u l t i s t e p , reversible redox systems. X X X V I . l l , l l , 1 2 , 1 2 - T e t r a c y a n o - 9 , 1 0 - a n t h r a q u i n o d i = methan ( T C N A Q ) and its derivatives: synthesis and redox properties. 618


H u e n i g , S . M u l t i s t e p reversible redox systems, X X X V I I . Biazulenyls and a>,ü)'-diazulenylpolyenes: syntheses and spectroscopic properties. 1905

H u e n i g , S . M u l t i s t e p reversible redox systems, X X X V I = I I . Biazulenyls and ω,ω'-diazulenylpolyenes: reactions w i t h prot i c acids, nucleophiles, a n d reducing and oxid iz ing agents. 1936

H u e n i g , S . M u l t i s t e p reversible redox systems, X X X I X . Isomeric biazulenyls: U V / V I S spectroscopy, v o l t a m = m e t r y , and H M O energies. 1952

H u e n i g , S . M u l t i s t e p reversible redox systems, X L . ω,ω'-Biazulenyl polyenes: v o l t a m m e t r y and H M O energies. 1959

H u n d s , A . Compounds w i t h U r o t r o p i n s tructure , L X . Orthooxal ic and orthocarbonic acid derivatives w i t h adamantane s tructure . 1577

H u n k l e r , D . Reactions o f l , 4 -pentad ien -3 -ones , 22. Synthesis and s tructure of the epimers of 3 , 5 - d i a r y l - = 4 - h y d r o x y - l , 4 - t h i a z i n a n e 1,1-dioxides. 1013

H u t h , A . 7 - A r o y l - l H , 7 H - s - t r i a z o l o [ l , 2 - a ] - s - t r i a z o l e - l , = 3 (2H)-d iones , a new class of compounds f r o m 5 - p h e = nyloxazoles and 4 - p h e n y l - 4 H - l , 2 , 4 - t r i a z o l e - 3 , 5 - = dione. 641

I b i s , C . T h i o - s u b s t i t u t e d butynes and butadienes f r om polychlorobutenes and th io ls . 1873

I p a k t s c h i , J . Reaction o f diphenylcyclopropenone w i t h al ly l idenetriphenylphosphoranes. 1989

I r n g a r t i n g e r , H . Chemis try and stereochemistry of i r ido ids , I V . Synthesis and x - r a y s tructure analysis of 1 5 - m e t h y l - 1 2 - e p i - p r o s t a g l a n d i n F20. 761

I r s c h i k , H . Ant ib i o t i c s f r o m g l id ing bacteria, X X I I . Biosynthesis of m y x o p y r o n i n A , an ant ib io t i c f r om Myxococcus fulvus, s t ra in M x f50. 1088

I t o , S . M u l t i s t e p reversible redox systems, X X X I X . Isomeric biazulenyls: U V / V I S spectroscopy, v o l t a m = metry , and H M O energies. 1952

Jaeger , V . Synthesis of 4 -penten-4 -o l ides ( γ - m e t h y l -ene-7-butyrolactonee) v ia 4-pentenoic acids. 15

J a e n s c h , H . J . Synthesis o f 2 -acy l -3 -amino furans by Thorpe cycl ization. 1702

J a k u p o v i c , J . New sesquiterpene lactones and rosane derivatives f r om Tr ichogonia species. 162

J a k u p o v i c , J . New spirosequiterpene lactones, germa= cranolides, and eudesmanolides f r o m Wunder l i ch ia mirab i l i s . 228

J a k u p o v i c , J . Heliangolides and trachylobane and vil lanovane derivatives f r o m Viguiera species. 495

J a n s e n , R . Ant ib i o t i c s f r o m g l id ing bacteria. X V I I I . T h e absolute conf igurat ion of myxalamide A and B . 78

J e r m a n n , F . C o n t r i b u t i o n to the synthesis o f 8-azapros= tanoids: reaction of succinimides w i t h (benzoylme= thylene)tr iphenylphosphorane. 1878

J u n g , G. I t u r i n A L : s tructure and derivatives of a p e p t i = d o l i p i d w i t h a h igh content of C i 6 - i t u r i n i c acids. 854

J u n g , G. Conformat ion o f B o c - L - A l a - A i b - L - A l a - O M e i n the crystal and i n solut ion. 1117

J u t z , C . M u l t i s t e p reversible redox systems, X X X I X . Isomeric biazulenyls: U V / V I S spectroscopy, v o l t a m = m e t r y , and H M O energies. 1952

K a j t a r - P e r e d y , M . A n a t t e m p t e d synthesis o f po lysta= ch in . 1068

K a n t l e h n e r , W . Orthoamides. X I . Preparat ion of 1,1,2,= 3 ,3 -penta-subst i tuted and 1,1,2,2,3,3-hexa-substituted g u a n i d i n i u m salts and 1,1,2,3,3-pentaalkylguanidines. 108

K a p a s s a k a l i d i s , J . J . Orthoamides. X I . Preparat ion of 1,1,2,3,3-penta-substituted and l , l , 2 ,2 ,3 ,3 -hexa -sub= s t i t u t e d g u a n i d i n i u m salts and l , l , 2 , 3 , 3 - p e n t a a l k y l = guanidines. 108

K a p p e l , Μ. Pter idines , L X X V . Synthesis and p r o p e r = ties of b i op te r in and b i op ter in analogs. 1815

K a t s u r a d a , M . Pheromone synthesis. L X I V . Synthesis o f the enantiomers of 2 - m e t h y l - l , 7 - d i o x a s p i r o [ 5 . 6 ] d o = decane, a component of the vo lat i le secretion f rom the mandibu lar glands of Andrena haemorrhoa F. 157

K a w a s a k i , T . Biological ly active glycosides f r o m A s t e r = oidea. V I I . Steroid oligoglycosides f r o m the starf ish L u i d i a maculata Mue l l e r et Troschel . 2. T h e s t ruc= tures of t w o new oligoglycoside sulfates. 296

K e r n , W . T e t r a h y d r o f u r a n acids - a new class o f c om= pounds i n h u m a n metabol ism. 1504

K e t t l e r , R. Chemistry of nitrosamines, I V . Syntheses of α-C-functionalized N-n i t rosod ia lky lamines : esters and ethers of l - [ (a lky l ) (n i t roso )amino ]a l coho ls . 1468

K i n g , R. M . New sesquiterpene lactones and rosane derivatives f r o m Tr ichogonia species. 162

K i n g , R . Μ . N e w spirosequiterpene lactones, germacra= nolidee, and eudesmanolides f r o m W u n d e r l i c h i a m i r a = bi l i s . 228

K i n g , R . M . New germacranolides, heliangolides, and elemanolides f r o m Cronquis t ianthus chachapoyensis. 240

K i n g , R . M . Epoxycannabinol ide and diterpenes w i t h a new carbon skeleton f r om Vi l lanova titicaensis. 250

K i n g , R . M . Heliangolides a n d trachylobane and v i l l ano= vane derivatives f r om Viguiera species. 495

K i n g , R . M . Pseudoguaianolides and other sesquiterp= enes f r o m Monact is macbr ide i . 503

K l a u s e n e r , A . Reactions of p a r t i a l l y acylated aldohexo= pyranosides, I I . Regioselective ox idat i on of p a r t i a l l y acylated aldohexopyranosides w i t h p y r i d i n i u m ch lo= rochromate and a new photochemical method for the preparat ion of m e t h y l 3 , 6 - d i d e o x y - a - D - r i b o - h e x o p y = ranoside. 783

K l e f f e l , D . Reactions o f l , 4 -pentad ien -3 -ones , 22. Synthesis and s tructure of the epimers of 3 , 5 - d i a r y l - = 4 - h y d r o x y - l , 4 - t h i a z i n a n e 1,1-dioxides. 1013

K l e i n e r , E . Pter id ines , L X X I V . Acylat ions of lumazines by radical nucleophil ic subs t i tu t i on . 1798

K l e m e r , A . I o d i n a t i o n of monosaccharide derivatives w i t h iodotr imethyls i lane . 1052

K l e m e r , A . L i t h i u m enolates o f carbohydrates, 2. A x i a l α-C-methylation and - h y d r o x y m e t h y l a t i o n of carboh= ydrate uloses. 1094

K l e m e r , A . One-step stereoselective syntheses of C - = branched α-deoxycyclitols f r o m l , 6 - a n h y d r o h e x o p y r a = noses. 1662

K l i e g e l , W . R i n g - c h a i n isomerism of N - ( l - c a r b o x y a l = ky l )n i t rones . I . C - A r y l - N - ( l - c a r b o x y l a l k y l ) n i t r o n e s . 1545

K l o s e , W . Syntheses of t h i a z o l o - and [ l , 3 ] t h i a z i n o [ l , 2 , = 4]triazinones. 1302

K n o e c h e l , T . Selective reactions of hydroazulenes: ch i ra l norcarane derivatives by the reaction of a dihydroazulene w i t h singlet oxygen. 773

K o e k s a l , Y . Cyclopentenone derivatives. V I I . T h e stereoselective synthesis of bre fe ld in precursors. 450

K o e k s a l , Y . Cyclopentenone derivatives. V I I I . Reac= t ions w i t h acetoxycyclopentenones, b r e f e l d i n - A cyc l i= zations. 462

K o e l l , P . 1,6-Anhydrofuranoses, X I V . Selective m o n o = tosylat ion of l ,6 -anhydro- /3 -D -mannofuranose . 1591

K o e l l , P . 1,6-Anhydrofuranoses, X V . Compet i t ive preparat ion of 1,6:2,5- and l , 6 : 3 , 5 - d i a n h y d r o - a - L - g u = lofuranoses, r ing opening of l , 6 : 3 , 5 - d i a n h y d r o - a - L - = gulofuranose. 1597

K o e n i g , W . A . Conf igurat ion and conformation o f the nucleoside residues of the n ikkomyc ins . 1216

K o e n i g , W . A . T h e structure of s tenothr ic in - revis ion o f a previous s tructure assignment. 1672

K o e s l i n g , V . Chelat ing vesicles made f rom N , N - d i h e x a = d e c y l - l , 2 - e t h a n e d i a m i n e - N ' , N ' - d i a c e t i c acid. 1634

K o h l , W . Ant ib i o t i c s f r om g l id ing bacteria, X X I I . B i o s = ynthesis of m y x o p y r o n i n A , an ant ib io t i c f rom M y x o = coccus fulvus, s t ra in M x f50. 1088

K o h l a , M . One-step stereoselective syntheses of C - = branched α-deoxycyclitols f rom l , 6 - a n h y d r o h e x o p y r a = noses. 1662

K o l l e n z , G. S t ruc ture of the 1:1 adducts of a r y l isocyan= ides to 4 -benzoy l -5 -pheny l furan-2 ,3 -d ione and t h e i r = products w i t h nucleophiles. Novel rearrangements of 5 ,5 -d isubst i tuted 4 -methylenefuran-2 ,3 -d iones . 1137

K o m a n d e r , H . 1,6-Anhydrofuranoses, X I V . Selective monotosylat ion of l ,6 -anhydro - /3 -D -mannofuranose . 1591

K o m a n d e r , H . 1,6-Anhydrofuranoses, X V . Compet i t i ve preparat ion of 1,6:2,5- and l , 6 : 3 , 5 - d i a n h y d r o - a - L - g u = lofuranoses, r i n g opening of l , 6 : 3 , 5 - d i a n h y d r o - a - L - = gulofuranose. 1597

K o m o r i , T . Biological ly active glycosides f r o m A s t e r o i = dea. V I I . Steroid oligoglycosides f rom the star f ish L u i d i a maculata Mue l l e r et Troschel . 2. T h e s t r u c = tures of two new oligoglycoside sulfates. 296

K o v a c , S . Contr ibut ions to the chemistry of t e t r a k e = tones, I I I . Synthesis and some reactions of l , 6 - b i s = (p -hydroxyphenyl ) - l , 3 ,4 ,6 -hexanetetrone . 1755

K r e b s , Η. C. Biological ly active glycosides f r o m A s t e r o i = dea. V I I . Steroid oligoglycosides f rom the star f ish L u i d i a maculata Mue l l e r et Troschel . 2. T h e s t r u c = tures of two new oligoglycoside sulfates. 296



K r e s z e , G . Po lyhydroxyamino compounds via diene synthesis w i t h ni troso compounds. I X . t r a n s - 6 - A z i = d o - l , 3 - c y c l o h e x a d i e n - 5 - o l as educt for the synthesis of condurodiamine and streptamine isomers. 203

K r e s z e , G . Chemis try of reactive cations derived f r o m sul fur dioxide analogs. I X . Reactions w i t h a l iphat i c carbodi imides. 900

K r e s z e , G . Chemistry of reactive cations derived f rom sulfur d ioxide analogs. X . Reaction w i t h aromatic carbodi imides - synthesis of benzothiadiazines. 904

K r o h n , K . Intramolecu lar a d d i t i o n of carbanions to anthraquinones . 306

K r u g , Β. Boron complexes of malonamides and m a l o = namidines . 370

K u b i c a , Z . Synthesis of peptides w i t h a , 0 -dehydroamino acids, I . Synthesis of N- (benzyloxycarbonyl ) and N - ( t r i f l u o r o a c e t y l ) dipeptides of dehydroalanine and dehydrophenylalanine . 920

K u e m b e l , B . Synthesis of new carbox imidoy l chlorides and the i r reaction w i t h nucleophiles. 564

K u l a , J . Synthesis of new te t rahydro furan and t e t r a h y = dropyran derivatives f rom α-pinene and 3-carene. 1860

K u n k e l , Ε. Synthesis of 2 - s i l oxy - subs t i tu ted m e t h y l cyclopropanecarboxylates. 512

K u n k e l , Ε. R i n g opening reactions of m e t h y l 2 - = si lyloxycyclopropanecarboxylates to 4-oxoalkanoic acid derivatives. 802

K u n z , Η. Synthesis of the m e t h y l ether of cardeno l ide -= derived methy lreduct i c acid s tar t ing f r o m D-glucose. 66

K u n z e , Β. Ant ib i o t i c s f rom g l id ing bacteria, X X I I I . S t i gmate l l in A and Β - two novel ant ib iot ics f r om St igmatel la aurantiaca (Myxobacterales) . 1883

K u r z , J . A lbomycins , I I . Absolute conf igurat ion of the deferri f o r m of the albomycins. 1408

L a a t e c h , H . D imer ic naphthoquinones. I X . Isodiospyrin and e l l ipt inone . Synthesis o f 6 ,6 ' -dimeric bijuglones by phenol ox idat ion . 319

L a a t e c h , H . D imer ic naphthoquinones, X I . Ox idat i on products of subst i tuted b inaphthy ls . 1367

L a c a n , M . Contr ibut ions to the chemistry of t e t rake= tones, I I I . Synthesis and some reactions of l , 6 - b i s = (p -hydroxypheny l ) - l , 3 ,4 ,6 -hexanete trone . 1755

L a d n e r , W . Stereoselective synthesis of alcohols, X V I I I . Synthesis of ( 3S ,4S ) -4 -methy l -3 -heptano l and of (5S,6S)-anhydroserricornin. 1170

L a y , K . L . M e t a l complexes w i t h te trapyrro le ligands, X X X V . Synthesis of f u r t h e r more or less sterically hindered 5 ,15-dialkyloctaethylporphodimethenes by reductive a lky la t ion of octaethylporphyrinatoz inc . 1259

L e b u h n , R . Conformat ional analysis, X X I V . D e t e r m i = nat ion o f the conformations o f t r i - and tetrasacchar= ide sequences of N-glycoprote ins . Problem of the (1 - * 6)-glycosidic bond. 951

L e h m a n n , J . Reactions of enolic sugar derivatives, X V I . Synthesis of a diastereotopic p ro ton probe [ ( Z ) - 3 , 7 - = a n h y d r o - l , 2 - d i d e o x y - D - g l u c o - o c t - 2 - e n i t o l ] for a-and ß-D glucosylases (correction). 1626

L e h m a n n , J . Reactions of enolic sugar derivatives, X V I . Synthesis o f a diastereotopic p ro ton probe ( ( Z ) - 3 , 7 - a n h y d r o - l , 2 - d i d e o x y - D - g l u c o - o c t - 2 - e n i t o l ] for a- and 0-D-glucosidases. 1078

L e h m a n n , Τ. Meta l l oporphyr ins in polymeric matrices, micelles, and vesicles. V I . Hydrophob i c and h y d r o = phi l i c derivatives o f 3 ,8 -d i f o rmyldeuteroporphyr in d i m e t h y l ester and their interact ion w i t h vesicles. 1057

L e h m a n n , Τ. Synthesis and react iv i ty of 13ι,132,ΙΊι,=

172-tetradehydrodeuteroporphyrin . 1386 L e h m a n n , W . D . T h e structure of s tenothr i c in - revision

of a previous structure assignment. 1672 L e h n e r t , R. A contr ibut i on t o the s t ruc tura l assignment

of posit ional isomers of bis-galacto and b is -manno crown ethers. 1046

L e n d e r i n g , U . 1,6-Anhydrofuranoses, X I V . Selective monotosylation of l , 6 -anhydro - # -D -manno furanose . 1591

L e n d e r i n g , U . 1,6-Anhydrofuranoses, X V . Compet i t ive preparat ion of 1,6:2,5- and l , 6 : 3 , 5 - d i a n h y d r o - a - L - g u = lofuranoses, r ing opening of l , 6 : 3 , 5 - d i a n h y d r o - a - L - = gulofuranose. 1597

L e s z c z y n s k a , E . Chemistry of hydroxamic acids. 10. A convenient rearrangement o f 4 -qu ino l inecarbohydrox= amic acid. 395


L i m a n , U . ara-7-Deazaxanthosine - a xanthine nucleo= side w i t h a stabile N-glycosyl ic bond. 273

L i p c z y n e k a - K o c h a n y , E . Chemistry of hydroxamic acids. 10. A convenient rearrangement of 4 - q u i n o l i 0

necarbohydroxamic acid. 395 L o e s c h , N . Dehydrogenation reactions w i t h gallic acid

esters. 929 L o e w e , W. Note on the synthesis of 1,2-benzoxathiin

2,2-dioxide derivatives f r o m 3-chromonesulfonic acid. 1395

L o r e n z , J . Syntheses of t h i a z o l o - and [ l , 3 ] t h i a z i n o [ l , 2 , = 4]triazinones. 1302

L o r k e , M . 4 - Imidazol id inones f rom nitrones and iso= cyanides. Molecular s tructure of ö - t e r t - b u t y l - l ^ ^ - ^ t r i m e t h y l - 3 - ( 2 , 4 , 6 - t r i b r o m o p h e n y l ) - 4 - i m i d a z o l i d i = none. 1685

L u d w i g , G . W . New spirosequiterpene lactones, germa= cranolides, and eudesmanolides f r o m Wunder l i ch ia mirab i l i s . 228

L u e c k e n h a u e , W . Organosilicon compounds. L X X X I V . /3-Lactams. I I I . - L a c t a m s via N-s i ly l carbodi imides 1193

L u g e r , P . Cyc loaddit ion w i t h unsaturated carbohyd= rates, I N . T h e stereochemistry of the Die l s -A lder reaction w i t h hex-2-enopyranoside and hex -2 - enopy= ranosid-4-uloses. 1531

M a i e r , T . Orthoamides. X L Preparat ion of 1,1,2,3,3-= penta - subs t i tu ted and 1,1,2,2,3,3-hexa-substituted g u a n i d i n i u m salts and 1,1,2,3,3-pentaalkylguanidines. 108

M a k o e z a , M . Reactions o f organic anions. 113. V i c a r i = ous nucleophil ic subs t i tu t i on of hydrogen i n n i t r o p y r i = dines by α-chloroalkyl pheny l sulfone carbanions. 8

M a k o w e k i , M . Synthesis of peptides w i t h α,β-dehy-droamino acids, I . Synthesis of N- (benzyloxycarbo= ny l ) and N - ( t r i f l u o r o a c e t y l ) dipeptides of dehydroa la^ nine and dehydrophenylalanine. 920

M a l i k , A . Stereospecific syntheses of D-ossamine and D - to lyposamine. 636

M a r k o w s k a , A . Thiophosphat id i c acid esters containing a carbon-sul fur -phosphorus bond. 1

M a r t i n , R. Azolides, 7. Phosphonate and phosphate group transfer w i t h pyrazolides. 1641

M a r x , Κ. H . Cyclopentenone derivatives. I X . Enant ios= elective routes to b re f e ld in -A . 474

Maty us, P . Reactions of uracils, 4. Some aspects of the chemistry of pyr ido [2 ,3 -d ]pyr imid ines . A novel s - = t r iazo lo [4 ' , 3 , : l , 6 ]pyr ido|2 ,3 -d ]pyr imid ine . 1653

M a y e r , W. Dehydrogenation reactions w i t h gallic acid esters. 929

Meier , L . Reactions of carboxonium ions of cyclic ace= tals, V I I I . Synthesis of (±) -4,5,6,7-tetrahydro-3,7-di= m e t h y l - 1-benzofuran. 1298

Meister , C . Diastereoselective synthesis of ( l R S ) ~ e n d o - = brevicomin. 147

Mengel , R. Pter idines , L X X V . Synthesis and properties of b iopter in and b iopter in analogs. 1815

M e n t l e i n , R. A new method for the degradation of anthocyanidins , flavones, chalcones, and coumarins. 401

M e n t l e i n , R . T h e red membrane pigments of the peat moss Sphagnum rube l lum. 1024

M e r g e n , W . W . Orthoamides. X I . Preparat ion of 1,1,2,3, 3 -penta - subs t i tu ted and 1,1,2,2,3,3-hexa-substituted g u a n i d i n i u m salts and 1,1,2,3,3-pentaalkylguanidines. 108

Mester , I . Studies of the chemistry of natural organic materials . 89. Halogenation reactions of i . S - a i h y d r ^ o x y - 1 0 - m e t h y l - 9 ( 1 0 H ) - a c r i d i n o n e and its ethers - a s imple regiospecific synthesis of acronycine. 31

Metzger , J . O. 1,6-Anhydrofuranoses, X V . Compet i t ive preparat ion of 1,6:2,5- and l , 6 : 3 , 5 - d i a n h y d r o - a - L - g u = lofuranoses, r ing opening of l . e ^ . ö - d i a n h y d r o - a - L - ^ gulofuranose. 1597

Meyer , B . Conformat iona l analysis, X X I V . D e t e r m i n a = t i o n o f the conformations of t r i - and tetrasaccharide sequences of N-glycoprote ins . Prob lem of the (1 - * 6)-glycosidic bond. 951

M e y e r , B . 1,6-Anhydrofuranoses, X I V . Selective mono tosylat ion of l ,6 -anhydro- /3 -D -mannofuranose . 1591

M e y e r , Η. H . Syntheses of (+ ) - oudemans in and (+) -ep= ioudemansin s tart ing f r om enantiomerical ly pure precursors; absolute conf igurat ion of the natura l l y occurring ( - ) - oudemansin . 791

M e y e r , Η. H . Syntheses and absolute configurations of (+ ) - (6R,2 'S) -cryptocaryalactone and (-)- (6S,2'S)-epi= cryptocaryalactone. 977


M e z e y - V e n d o r , G. Α simple method for the preparat ion o f 2-arylbenzofurans and the synthesis of moracin A a n d B . 734

M i c h e l , J . Glycosyl imidates , 12. D i re c t synthesis o f 0 - a - and O-0-glycosyl imidates. 1343

M i c h e l s , W . Syntheses o f 5'-capped ol igoribonucleo^ tides. 867

M i n a m i , T . Chemistry of reactive cations derived f rom sulfur dioxide analogs. X . Reaction w i t h aromatic carbodiimides - synthesis of benzothiadiazines. 904

M l o t k o w s k a , B . Thiophosphat id i c acid esters containing a carbon-sul fur -phosphorus bond. 1

M o d e r h a c k , D . 3 - P h e n y l - l , 2 , 4 - t r i a z o l e - 5 - c a r b a l d e h = ydes subst i tuted i n posit ion 1. 48

M o d e r h a c k , D . 4 - Imidazol id inones f r om nitrones and isocyanides. Molecular s tructure of 5 - t e r t - b u t y l - l , 2 , = 2 - t r imethy l -3 - (2 ,4 ,6 - t r ib romopheny l ) -4 - imidazo l id i== none. 1685

M o r i , K . Pheromone synthesis. L X I V . Synthesis of the enantiomers of 2 -methy l - l , 7 -d i oxasp i ro [5 .6 ]dode= cane, a component of the volati le secretion f rom the mandibu lar glands of Andrena haemorrhoa F. 157

M o r i t a , T . M u l t i s t e p reversible redox systems, X X X I X . Isomeric biazulenyls: U V / V I S spectroscopy, v o l t a m = metry , and H M O energies. 1952

M u d r y k , B . Reactions of organic anions. 113. Vicarious nucleophil ic subst i tut i on of hydrogen i n n i t ropyr id ines by α-chloroalkyl phenyl sulfone carbanions. 8

M u e l l e r , E . Chemistry of nitrosamines, I V . Syntheses of α-C-functionalized N-n i t rosod ia lky lamines : esters and ethers of l - [ (a lky l ) (n i t roso )amino]a lcoho ls . 1468

M u e l l e r , U . Intramolecular add i t i on of carbanions to anthraquinones. 306

M u e l l e r - M e n k e , C. Note on the synthesis of l , 2 - b e n = zoxathi in 2,2-dioxide derivatives f r om 3-chromonesul^ fonic acid. 1395

N a g y , Z. Synthesis of the pterocarpan constituents of Swartzia laevicarpa. 127

N a l i c , G. Contr ibut ions t o the chemistry o f t e t r a k e = tones. I I . Reaction of 3,4-dibenzoyl-2,5-hexanedione w i t h hydroxylamine . 199

N a u m a n n , A . Synthesis of the Lycopod ium alkalo id rac - luc idu l ine f rom hexahydro -7 -methy lqu ino l ine . 1519

N e u n h o e f f e r , H . Synthesis of 1,2,4-triazines. X I . S y n = thesis and reactions of 6 - a m i n o - l , 2 , 4 - t r i a z i n - 5 - o n e s and 6 - a m i n o - l , 2 , 4 - t r i a z i n e - 5 - t h i o n e s . 283

N i e l s e n , F . E . Annu la ted 1,2,3-triazoles, I . Synthesis of 8 -azapurin-6-ones and 8 -azapur in -6 - imines f r om e t h y l 5 - (acety lamino) - l ,2 ,3 - tr iazo le -4 -carboxylates . 1848

N i x d o r f , M . Chemistry and stereochemistry of i r ido ids , I V . Synthesis and x - r a y structure analysis of 15 -me= t h y l - 1 2 - e p i - p r o s t a g l a n d i n F2ß. 761

N o g r a d i , M . Synthesis of the pterocarpan constituents of Swartzia laevicarpa. 127

N o g r a d i , M . A simple method for the preparat ion of 2-arylbenzofurans and the synthesis of moracin A and B. 734

N o g r a d i , M . A n a t tempted synthesis of polystachin. 1068

O g n y a n o v , V . Reactions of glutaconic and homophthal i c anhydrides w i t h imidates, i m i d o y l chlorides, and 1 - chloroisoquinoline. 389

O r t , Β. M u l t i s t e p reversible redox systems. X X X V . V o l t a m m e t r y of vinylogous polyenes w i t h cross-conju= gated end groups and U V / V I S spectroscopy of the ir radical anions and cations. 354

O r t , Β. M u l t i s t e p reversible redox systems, X X X V I I . Biazulenyls and ω,ω ' -diazulenylpolyenes: syntheses and spectroscopic properties. 1905

O r t , Β. M u l t i s t e p reversible redox systems, X X X V I I I . Biazulenyls and ω,ω ' -diazulenylpolyenes: reactions w i t h prot ic acids, nucleophiles, and reducing and oxidizing agents. 1936

O r t , Β. M u l t i s t e p reversible redox systems, X X X I X . Isomeric biazulenyls: U V / V I S spectroscopy, v o l t a m = metry , and H M O energies. 1952

O r t , Β. M u l t i s t e p reversible redox systems, X L . ω,ω'-= Biazulenyl polyenes: vo l tammetry and H M O ener= gies. 1959

O t t , G. Syntheses of mes i ty l - subs t i tu ted azulenes. 1605 O t t , J . The (2' — 5 ' ) - and (3' — 5 ' ) - tuberc idy ly l t u b e r =

cidins - synthesis via phosphite triester and studies of secondary structure . 692

O t t , W . Reactions w i t h isocyanides. Synthesis of d a r k - = blue dyes f rom 1,4-quinones and ary l isocyanides. 1003

O t t , W . S t ruc ture o f the 1:1 adducts of a r y l isocyanides t o 4 - b e n z o y l - 5 - p h e n y l f u r a n - 2 , 3 - d i o n e and the i r products w i t h nucleophiles. Nove l rearrangements of 5 ,5 -d isubst i tuted 4 -methylenefuran-2 ,3 -d iones . 1137

O t t o , Η. H . Reactions o f l , 4 -pentad ien -3 -ones , 22. Synthesis and s t ruc ture of the epimers of 3 , 5 - d i a r y l - = 4 - h y d r o x y - l , 4 - t h i a z i n a n e 1,1-dioxides. 1013

P a p a i o a n n o u , D . A p p l i c a t i o n o f N - t r i t y l amino acid 1-benzotriazolyl esters i n pept ide synthesis. 1308

P a r o d i , B . Const i tuents of Cupul i ferae , 8. A novel, h igh ly -acy la ted astragalin f r o m Quercus ilex L . 1864

P a r o d i , B . Const i tuents of Cupul i ferae, 9. A n unusual diester of astragalin w i t h e i s - and t rans -p - coumar i c acid f r o m Quercus i lex L . 1867

P a r o d i , B . Const i tuents of Boraginaceae, 7. Anchuso= side-8 and - 9 : two new t r i terpene saponins f r om Anchusa off icinalis L . 1869

P a u l , Α . Η. K . Synthesis of rac -4# -hydroxyobovata= chromene. 1382

P a u l s e n , H . Cyc l i t o l reactions. X . Synthesis of enan= t iomer ica l ly pure pseudo-a -D -galactopyranose and pseudo-jS -D -mannopyranose. 433

P a u l s e n , H . Conformat iona l analysis, X X I V . D e t e r m i = nat i on of the conformations o f t r i - and tetrasacchar= ide sequences of N-g lycoprote ins . Prob lem of the (1 — 6)-glycosidic bond . 951

P a u l s e n , H . Synthons of oligosaccharides, L I I . S y n t h e ^ sis of disaccharides f r o m 3 - d e o x y - D - m a n n o - 2 - o c t u l o = sonic acid ( K D O ) and D -glucosamine. 1270

P a u l s e n , H . Synthons o f oligosaccharides, L I I I . S y n t h e = sis of trisaccharides conta in ing 3 - d e o x y - D - m a n n o - 2 - = octulosonic acid ( K D O ) . 1288

P a u l s e n , H . Albomycins , I I . Absolute conf igurat ion of the deferr i f o r m of the albomycins. 1408

P e d e r s e n , Ε. B . A n n u l a t e d 1,2,3-triazoles, I . Synthesis of 8 -azapur in-6 -ones and 8 - a z a p u r i n - 6 - i m i n e s f r om ethy l 5 - (acety lamino) - l ,2 ,3 - t r iazo le -4 - carboxy lates . 1848

P e t e r s , Ε. M . S t ruc ture of the 1:1 adducts o f ary l iso= cyanides t o 4 -benzoy l -5 -pheny l furan -2 ,3 -d i one and the i r products w i t h nucleophiles. Novel rearranges ments of 5 ,5 -d isubst i tuted 4 -methy lene furan -2 ,3 -= :

diones. 1137 P e t e r s , K . S t ruc ture of the 1:1 adducts of a r y l isocyan=

ides to 4 -benzoy l -5 -pheny l furan -2 ,3 -d i one and the i r products w i t h nucleophiles. Novel rearrangements of 5 ,5 -d isubst i tuted 4 -methylenefuran-2 ,3 -d iones . 1137

P e t e r s , T . Conformat iona l analysis, X X I V . D e t e r m i n a = t i o n of the conformations of t r i - and tetr»saccharide sequences of N-g lycoprote ins . Problem o f the (1 — 6)-glycosidic bond. 951

P f l e i d e r e r , W . Pter idines , L X X I V . Acylat ions of l u m a = zines by radical nucleophil ic subst i tut i on . 1798

P f l e i d e r e r , W . Pter id ines , L X X V . Synthesis and p r o = perties of b i opter in and b iopter in analogs. 1815

P i p e r e i t , E . Heterocycles f r o m α-nitroolefins, V I I . 4 , 5 - D i h y d r o - 2 - m e t h y l - 5 - ( m e t h y l e n e a m i n o ) - 3 - f u r a n = carboxylates f r om α-nitroolefins, acetoacetates, and compounds w i t h an active methylene group. 911

P l a t e n , M . Oxidat ive deblocking of the 4 - m e t h o x y b e n = zyl thioether protect ing group: appl icat ion to the directed synthesis of po lycyst iny l peptides. 1563

P l e s c h , W . Syntheses of α-C-functionalized N - n i t r o = d ia lkylamines : esters of [ ( a l k y l ) ( n i t r o ) a m i n o ] m e t h a = nol and l - [ ( a l k y l ) ( n i t r o ) a m i n o ] e t h a n o l . 1494

P l i e n i n g e r , Η. Synthesis of stereoisomeric 3 , 4 - d i h y d r o = b i l i r u b i n i c acid derivatives as synthons for bile p i g ments. 1441

P l i e n i n g e r , Η. Synthesis of rac-stercobi l in I X a w i t h the conf igurat ion of the natura l product and of some urob i l ins , ha l f - s tercob i l ins , and stercobilins w i t h unequivocal const i tut ion and configuration. 1454

P o n c i n i , L . A convenient synthesis of phenylpropargy = laldehyde d i e t h y l acetal. 1529

P r e s s l e r , W . Syntheses w i t h aliphatic dialdehydes, X X X V I I I . Synthesis and properties of cyc loa lky lmal= onaldehydes. 649

P r e u t , H . Enehydrazines, 37. Synthesis of a pyrazole analog of 7-aminomitosene. 1711

P r i y o n o , W . Intramolecu lar addi t ion of carbanions to anthraquinones. 306



Q u a s t , Η. Synthesis and reactions of some p y r i d o [ 3 , 2 - = g]quinol ines (1,8-diazaanthracenes). 133

Q u a s t , Η. 1 -Aza- and 1,9-diazatriptycenes. 381 Q u a s t , Η. 5 ,10-Bridged pyr ido[3 ,2 -g ]quinol ines via [4 +

2] cyc loaddit ion of dienophiles to p y r i d o [ 3 , 2 - g ] q u i n o = lines. 877

Q u a s t , H . S t ruc ture of the 1:1 adducts of ary l isocyan= ides t o 4 -benzoy l -5 -pheny l furan-2 ,3 -d ione and the i r products w i t h nucleophiles. Novel rearrangements of 5 ,5 -d isubst i tuted 4-methylenefuran-2 ,3-diones . 1137

Q u a s t , Η. l ,5 -Dimethylb icyc lo [3 .3 .0 ]octane-2 ,6 -d ione and 1 ,5 -dimethylbicyc lo [3 .3 .0]octa-3 ,7-diene-2 ,6-= dione. Basic synthons for subst i tuted semibul lva l= enes. 1180

R a d d a t z , P . Cyclopentenone derivatives. V I I . T h e stereoselective synthesis of brefe ldin precursors. 450

R a d d a t z , P . Cyclopentenone derivatives. V I I I . Reac= t ions w i t h acetoxycyclopentenones, b r e f e l d i n - A cyc l i= zations. 462

R a d d a t z , P . Cyclopentenone derivatives. I X . Enant ios= elective routes to bre fe ld in -A . 474

R a p i c , V . Contr ibut ions to the chemistry of t e t rake= tones, I I I . Synthesis and some reactions of l , 6 - b i s = (p -hydroxyphenyl ) - l , 3 ,4 ,6 -hexanetetrone . 1755

R a t h m a n n , R . Conf igurat ion and conformation of the nucleoside residues of the n ikkomyc ins . 1216

R a u , O . T e t r a h y d r o f u r a n acids - a new class of c o m = pounds i n human metabol ism. 1504

R a u , O. O r i g i n of 3,6-epoxyalkanedioic acids i n h u m a n ur ine . 1513

R e g i t z , Μ . Azolides, 7. Phosphonate and phosphate group transfer w i t h pyrazolides. 1641

R e i c h a r d t , C. Syntheses w i t h a l iphat ic dialdehydes, X X X V I I I . Synthesis and properties of cyc loa lky lmal= onaldehydes. 649

R e i c h e l t , I . Synthesis of 2 - s i l oxy -subst i tuted m e t h y l cyclopropanecarboxylates. 512

R e i c h e l t , I . Deprotonat ion and diastereoselective a l k y l a = t i o n of 2 - s i l oxy -subst i tuted m e t h y l cyclopropanecarb= oxylates. 531

R e i c h e l t , Τ. R ing opening reactions of methy l 2 - = silyloxycyclopropanecarboxylates to 4-oxoalkanoic acid derivatives. 802

R e i c h e l t , I . Flexible and efficient synthesis of m e t h y l 4-oxo-2-alkenoates. 820

R e i c h e l t , I . R ing opening of methy l 2 - ( t r i m e t h y l s i l y l m e = thyDcyclopropanecarboxylate. 828

R e i c h e η b a c h , Η. Ant ib io t i c s f rom g l id ing bacteria, X X I I . Biosynthesis of myxopyron in A , an ant ib io t i c f r om Myxococcus fulvus , s t ra in M x f50. 1088

R e i c h e n b a c h , Η. Ant ib io t i c s f r om g l id ing bacteria, X X I I I . St igmate l l in A and Β - two novel ant ibiot ics f rom Stigmatella aurantiaca (Myxobacterales) . 1883

R e i s c h , J . Studies o f the chemistry of na tura l organic materials . 89. Halogenation reactions of 1 ,3 -a ihydr^ o x y - l 0 - m e t h y l - 9 U 0 H ) - a c r i d i n o n e and its ethers - a simple regiospecifi«c synthesis of acronycine. 31

R e i s s i g , Η. U . Synth <esis of 2 - s i l oxy -subst i tuted m e t h y l

cyclopropanecarbo.xyiates. 512 R e i s s i g , Η. U . Deprotonat ion and diastereoselective

a lky lat ion of S-s i lo^y-gubgt i tuted m e t h y l cyclopropa= necarboxylates. Styj

Re i ss ig , Η. U . Ring opening reactions of m e t h y l 2- - -s i l y l o x y c y c l o p r o p a i n e c a r D o x y l a t e s to 4-oxoalkanoic acid derivatives. 8>02

R e i s s i g , Η. U . Flexible and efficient synthesis of m e t h y l 4-oxo-2-alkenoate>s. 820

R e i s s i g , Η. U . Ring opening of methy l 2 - ( t r i m e t h y l s i l y l = methyl)cyclopropanecarboxylate. 828

R i e d , W. Synthesis o f new carboximidoyl chlorides and their reaction w i t h nucleophiles. 564

R i e d , W. Chemistry of d i m e t h y l (Ια,2β,5β,βα,Ίβ,8β)-3,~ 4~dioxotr icyclo[4 .2 .1 .0 2 5 )nonane-7,8-dicarboxylate . 1109

R i e d , W. T h e behavior of ( l« ,2«,5rt ,6a)-3,4-bis(trime= thyls i loxy)tr icyc lo [4 .2 .1 .0 2 - 5 ]nona-3 ,7-diene on t r e a t ment w i t h oxidative reagents. 1778

R i n k e n , Μ. T h e structure of s tenothr ic in - revision of a previous structure assignment. 1672

R o b i n s o n , H . New sesquiterpene lactones and rosane derivatives f rom Trichogonia species. 162

R o b i n s o n , H . New sp ; rosequiterpene lactones, germacra= nolides, and eudetmanolides f rom Wunder l i ch ia m i r a = bil is . 228

R o b i n s o n , H . N e w germacranolides, heliangolides, and elemanolides f rom Cronquis t ianthus chachapoyensis. 240

R o b i n s o n , H . Epoxycannabinol ide and diterpenes w i t h a new carbon skeleton f r o m Vi l lanova titicaensis. 250

R o b i n s o n , H . Heliangolides and trachylobane and v i l l a = novane derivatives f r o m Viguiera species. 495

R o b i n s o n , H . Pseudoguaianolides and other s e s q u i t e r p enes f r o m Monact i s macbr ide i . 503

R o d e w a l d , Η. Chemistry and stereochemistry of i r i = doids, I V . Synthesis and x - r a y s tructure analysis of 1 5 - m e t h y l - 1 2 - e p i - p r o s t a g l a n d i n F23. 761

Roe b e n , W . Cyc l i t o l reactions. X . Synthesis of enan= t iomer i ca l ly pure pseudo-a -D -galactopyranose and pseudo- j3 -D -mannopyranose. 433

R o m u s s i , G . Const i tuents o f Cupul i ferae , 8. A novel , h igh ly -acy la ted astragalin f r o m Quercus ilex L . 1864

R o m u s s i , G. Const i tuents of Cupul i ferae , 9. A n unusual diester o f astragalin w i t h e i s - and t rans -p - coumar i c acid f r o m Quercus ilex L . 1867

R o m u s s i , G . Const i tuents of Boraginaceae, 7. Anchuso= side-8 and - 9 : two new t r i terpene saponins f rom Anchusa of f ic inal is L . 1869

Roos, M . Glycosyl imidates, 12. D i r e c t synthesis of O - a - and O-0-g lycosy l imidates . 1343

R o s e n b e r g , D . 7 - A r o y l - l H , 7 H - s - t r i a z o l o [ l , 2 - a ] - s - t r i a = zo l e - l , 3 (2H) -d iones , a new class o f compounds f r o m 5-phenyloxazoles and 4 - p h e n y l - 4 H - l , 2 , 4 - t r i a z o l e - 3 , = 5-dione. 641

R o t t e g g e r , S. T r i f l u o r o m e t h y l - s u b s t i t u t e d pyr imid ines f r om enamines and t r i f luoroaceton i t r i l e . 991

R u b i o E n c i n a s , M . J . Synthesis of heterocyclic com= pounds. X X X V I I . Preparat i on o f 4 , 6 - d i a r y l - l , 2 - d i h y = d r o - 2 - t h i o x o - 3 , 5 - p y r i d i n e d i c a r b o n i t r i l e s and related compounds. 213

R u f f , J . Syntheses of a n t i m i c r o b i a l biscationic 2 - (phen= oxyphenyl ) indoles and -1 -benzofurans . 409

R u h r , M . N e f reaction. V I . 4 , 5 - D i h y d r o - 5 - ( m e t h y l e = neamino) -3 - furancarboxylates . 223

R u h r , M . Heterocycles f r o m α-nitroolefins, V I I . 4 ,5 -= D i h y d r o - 2 - m e t h y l - 5 - ( m e t h y l e n e a m i n o ) - 3 - f u r a n c a r b = oxylates f rom «-nitroolefins, acetoacetates, and com= pounds w i t h an active methylene group. 911

R u n s i n k , J . Reactions of p a r t i a l l y acylated aldohexopy= ranosides, I I . Regioselective ox idat ion of par t ia l l y acylated aldohexopyranosides w i t h p y r i d i n i u m chlo= rochromate and a new photochemical method for the preparat ion of m e t h y l 3 , 6 - d i d e o x y - a - D - r i b o - h e x o p y = ranoside. 783

R u n s i n k , J . Reactions of carboxonium ions of cyclic acetals, V I I I . Synthesis o f (±) -4,5,6,7-tetrahydro-3,= 7 - d i m e t h y l - l - b e n z o f u r a n . 1298

R z e s z o t a r s k a , B . Synthesis o f peptides w i t h a ,0 -dehy= droamino acids, I . Synthesis of N- (benzy loxycarbo= nyl ) and N - ( t r i f l u o r o a c e t y l ) dipeptides of dehydroala= nine and dehydrophenylalanine . 920

S a a d a t m a n d i , Ä . Reaction of diphenylcyclopropenone w i t h a l ly l idenetr iphenylphosphoranes . 1989

S a n c a e s a n , F . Const i tuents o f Cupul i ferae, 8. A novel, h igh ly -acy la ted astragalin f r om Quercus ilex L . 1864

S a n c a e s a n , F . Const i tuents of Cupuli ferae, 9. A n u n u = sual diester of astragalin w i t h e is - and t r a n s - p - c o u m = aric acid f r om Quercus ilex L . 1867

S a n i d a , C. App l i ca t i on of N - t r i t y l amino acid l - b e n z o = t r iazo ly l esters in pept ide synthesis. 1308

S a r s t e d t , Β. Intramolecu lar a d d i t i o n of carbanions to anthraquinones . 306

S a u e r , Μ . (2.2](2,7)Anthracenophane: synthesis and conformat ional studies. 615

S a u e r , Μ . Cycloarenes, a new class of aromatic com= pounds. I V . A t t e m p t s to synthesize cyclofd.e.e.d.e.e.-d.e.e.Jnonakisbenzene and cyclo[d.e.d.e.d.e.d.e.d.e)de= cakisbenzene. 742

S c h a e f e r , H . Synthesis of 4 -aminocinnol ines f rom {arylhydrazono)(cyano)acetic acid derivatives. 1390

S c h a n b a c h e r , U . Syntheses o f peptide alkaloids, I X . A m i n o acids and peptides, X L V I . T o t a l synthesis of m u c r o n i n B. 1205

S c h a r f , Η. D . Diastereoselective synthesis of ( l R S ) - = endo -brev i comin . 147

S c h a r f , Η. D . Reactions of par t ia l l y acylated aldohexo= pyranosides, I I . Regioselective ox idat ion of par t ia l l y acylated aldohexopyranosides w i t h p y r i d i n i u m chlo= rochromate a n d a new photochemical method for the preparat ion o f m e t h y l 3 , 6 - d i d e o x y - a -D - r i b o - h e x o p y = ranoside. 783



S c h a r f , Η. D . Reactions of carboxonium ions of cyclic acetals, V I I I . Synthesis o f (±) -4 ,5 ,6 ,7-tetrahydro-3,= 7 - d i m e t h y l - l - b e n z o f u r a n . 1298

S c h e u e r , R . Asymmetr i c synthesis v ia heterocyclic intermediates , X X I I I . Studies of the enantioselective synthesis o f a - a l k y l - a - ( 2 - f u r y l ) g l y c i n e s by a l k y l a t i o n o f 3 - ( 2 - f u r y l ) - 3 , 6 - d i h y d r o - 2 H - l , 4 - o x a z i n - 2 - o n e s ch ira l ly subst i tuted at C-6. 939

S c h i e b e l , Η. Μ. Syntheses w i t h nucleic acid const i= tuents , X . Mass spectrometry of nucleotides, V I I . Synthesis of deoxyoligonucleotide l inker fragments for genetic engineering using improved preparat ive and analyt ical techniques. 835

S c h i l d k n e c h t , Η. Synthesis of the f i r s t leaf movement factor f r o m Mimosa pudica L . 1230

S c h i l l i n g , G . Dehydrogenat ion reactions w i t h gallic acid esters. 929

S c h i l l i n g - P i n d u r , A . Preparat ion o f sulfonioindenides. 552

S c h i n z e l , E . Naphthylenedi (heteroarenes) , I I I . S y n t h e = sis and spectroscopic behavior o f 2 ,2 ' -naphthy lened i= benzazoles. 1129

S c h l i m m e , Ε. Synthesis and conformat ional analysis of some 5'-homoadenosine derivatives. 98

S c h l i m m e , Ε. Syntheses o f 5 ' -capped ol igoribonucleo= tides. 867

S c h m a l l e , H . Conf igurat ion and conformat ion of the nucleoside residues o f the n ikkomyc ins . 1216

S c h m e d a - H i r s c h m a n n , G . Heliangolides and t r a c h y l o = bane and vi l lanovane derivatives f r o m Viguiera spe= cies. 495

S c h m i d t , D . A lbomyc ins , I V . Iso lat ion and t o t a l s y n = thesis of ( N 5 - a c e t y l - N 5 - h y d r o x y - L - o r n i t h y l ) ( N 5 - a c e = t y l - N S - h y d r o x y - L - o r n i t h y D - N ^ - a c e t y l - N S - h y d r o x y - ^ L - o r n i t h i n e . 1434

S c h m i d t , J . Propert ies of an (ary l th iomethylene)cyc lo= hexanone. 576

S c h m i d t , R . R . Glycosyl imidates , 10. Glycosyl phosp= hates f rom glycosyl tr ichloroacet imidates . 680

S c h m i d t , R . R . Glycosyl imidates , 12. D i rec t synthesis of O-a- and O-0-g lycosy l imidates . 1343

S c h m i d t , R . R . Glycosyl imidates , 13. App l i ca t i on of the t r i ch loroacet imidate procedure to 2-azidoglucose and 2-azidogalactose derivatives. 1826

S c h m i d t , U . Syntheses o f pept ide alkaloids , I X . A m i n o acids and peptides, X L V I . T o t a l synthesis of m u c r o = n i n B . 1205

Schoel lkopf , U . Synthesis and biological act ivit ies of the ant ib io t i c Β 371 and its analogs. 600

Schoel lkopf , U . Synthesis w i t h or-metalated isocyan= ides. L I I I . Synthesis of m e t h y l 2 ,3-epoxy-2- isocya= noalkanoates. 608

Schoel lkopf , U . Asymmetr i c synthesis via heterocyclic intermediates , X X I I I . Studies of the enantioselective synthesis of a - a l k y l - a - ( 2 - f u r y l ) g l y c i n e s by a lky la t i on of 3 - ( 2 - f u r y l ) - 3 , 6 - d i h y d r o - 2 H - l , 4 - o x a z i n - 2 - o n e s chira l ly subst i tuted at C-6 . 939

S c h o e n , N . Synthesis and reactions of some p y r i d o [ 3 , 2 - = g jquinol ines (1,8-diazaanthracenes). 133

S c h o e n , N . 1 -Aza- and 1,9-diazatriptycenes. 381 S c h o e n , N . 5 ,10-Bridged pyr ido [3 ,2 -g ]quino l ines v ia [4 +

2] cyc loaddit ion of dienophiles t o p y r i d o f S ^ - g J q u i n o ^ lines. 877

Schoenberger , G . Chelat ing vesicles made f r o m N , N - d i = hexadecy l - l , 2 - e thaned iamine -N ' ,N ' -d ia ce t i c acid. 1634

S c h o l z , D . New synthet ic methods. 9. S - A l k y l 4 - m e = thylbenzenethiosulfonates, excellent reagents for α-thiolation o f cyclic ketones. 259

S c h o l z , D . New synthet ic methods. 10. ß-Keto sulfones as ethylene carbanion equivalents: the synthesis o f unsaturated carboxylic acids. 264

S c h o m b u r g , D . 4 - Imidazo l id inones f rom nitrones and isocyanides. Molecular s tructure of 5 - t e r t - b u t y l - l , 2 , = 2 - t r i m e t h y l - 3 - ( 2 , 4 , 6 - t r i b r o m o p h e n y l ) - 4 - i m i d a z o l i d i = none. 1685

S c h r a m m , G . Ant ib i o t i c s f r om basidiomycetes, X X . Synthesis of s t r o b i l u r i n A and revision o f the stereo= chemistry of n a t u r a l s t rob i lur ins . 1616

S c h r o e d e r , G . Crown ethers w i t h triose and pentose s t ruc tura l un i t s . 1036

S c h r o e d e r , G . A c o n t r i b u t i o n to the s t ruc tura l assign= m e n t o f posit ional isomers of bis-galacto and b i s - = manno crown ethers. 1046

S c h u l t e n , Η. R . Syntheses w i t h nucleic acid const i= tuents, X . Mass spectrometry of nucleotides, V I I .

Synthesis of deoxyoligonucleotide l inker fragments for genetic engineering using improved preparat ive and analyt i ca l techniques. 835

S c h u m a n n , D . Synthesis of the L y c o p o d i u m a l k a l o i d rac - luc idu l ine f r o m h e x a h y d r o - 7 - m e t h y l q u i n o l i n e . 1519

S c h u m a n n , I . 7 - A r o y l - l H , 7 H - s - t r i a z o l o [ l , 2 - a ] - s - t r i a = zo le - l , 3 (2H) -d iones , a new class of compounds f r o m 5-phenyloxazoles and 4 - p h e n y l - 4 H - l , 2 , 4 - t r i a z o l e - 3 , = 5-dione. 641

S c h w a i g e , Β. A n t i b i o t i c s f r o m basidiomycetes, X X . Synthesis of s t r o b i l u r i n A and revision o f the stereo= chemistry of n a t u r a l s t rob i lur ins . 1616

S c h w a r t i n g , W . 1,6-Anhydrofuranoses, X V . C o m p e t i = t ive preparat ion of 1,6:2,5- and l , 6 : 3 , 5 - d i a n h y d r o - a - = L-gulofuranoses, r i n g opening o f l , 6 : 3 , 5 - d i a n h y d r o - = a -L -gu lo furanose . 1597

S c h w a r z , Κ. Syntheses of t h i a z o l o - and [ l ^ J t h i a z i n o l l . ^ 2,4]triazinones. 1302

S c h w i c k e r a t h , W . A m i n o e t h y n y l metalat ions . 13. Synthesis and reactions of 3 -aminoprop io lamid ines . 85

S c h w o e b e l , A . Chemis t ry of reactive cations der ived f r o m sul fur d ioxide analogs. I X . Reactions w i t h a l i p = hat ic carbodi imides. 900

S c h w o e b e l , A . Chemis try of reactive cations der ived f r o m sul fur d ioxide analogs. X . Reaction w i t h a r o m a t = ic carbodi imides - synthesis of benzothiadiazines. 904

Seebach , D . Enant iomer i ca l ly pure synthons f r o m branched malates (correction) . 407

Seela , F . ara-7-Deazaxanthosine - a xanth ine nucleoside w i t h a stabile N-glycosyl i c bond. 273

Seela , F . T h e (2' — 5 ' ) - and (3' — 5 ' ) - t u b e r c i d y l y l tuberc id ins - synthesis v ia phosphite tr iester a n d studies of secondary s tructure . 692

Seela , F . Synthesis and furanoside /pyranoside i s o m e r i = zat ion of 7 -deaza-2 ' -deoxy-7 -methylguanos ine . 708

Seela , F . 7 - ( / 3 - D - A r a b i n o f u r a n o s y l ) - 2 , 4 - d i c h l o r o - 7 H - = p y r r o l o [ 2 , 3 - d ] p y r i m i d i n e - synthesis, selective d i s = placement of halogen, and effect of glyconic pro tec t ing groups on the reac t iv i ty of the aglycon. 722

Seela , F . Synthesis of 2 ' -deoxyribofuranosides of 7 H - = p y r r o l o [ 2 , 3 - d ] p y r i m i d i n e : effect of the C-2 s u b s t i = tuents on the fluorescence. 1719

Seela , F . Anomers o f tuberc id in derivatives w i t h 2 - m e = t h y l t h i o and N M A M s o p e n t e n y l ) residues. 1972

S e i d e n s p i n n e r , Η. Μ. Reactions w i t h isocyanides. Synthesis of d a r k - b l u e dyes f rom 1,4-quinones and a r y l isocyanides. 1003

S e l i g e r , Η. Syntheses w i t h nucleic acid const i tuents , X . Mass spectrometry of nucleotides, V I I . Synthesis of deoxyoligonucleotide l inker fragments for genetic engineering using improved preparative and ana ly t i ca l techniques. 835

Seoane, C. Synthesis of heterocyclic compounds. X X X V I I . Preparat ion of 4 , 6 - d i a r y l - l , 2 - d i h y d r o - 2 - = th ioxo -3 ,5 -pyr id ined i carbon i t r i l e s and related c o m = pounds. 213

S h e l d r i c k , W . S. Ant ib i o t i c s f rom g l id ing bacteria. X V I I I . T h e absolute conf iguration o f myxa lamide A a n d B . 78

S h e l d r i c k , W . S. Lactonic constituents of Angel ica glauca. 888

S h e n , Z . Diastereoselective synthesis of ( l R S ) - e n d o - = brevicomin. 147

S i e m a n o w s k i , W . Synthesis and properties o f 2 , 2 ' - b i p y = r i d i n - 3 - o l s and -3 ,3 ' -d io l s . 1731

S i e w e r t , G . Syntheses w i t h nucleic acid const i tuents , X . Mass spectrometry of nucleotides, V I I . Synthesis of deoxyoligonucleotide l inker fragments for genetic engineering using improved preparative and ana ly t i ca l techniques. 835

S i m c h e n , G . Sul fos i ly lat ion of carbonyl compounds and t r i m e t h y l s i l y l enol ethers w i t h t r i m e t h y l s i l y l c h l o r o = sulfonate. 39

S i m m e r l , R. 4H- l , 3 ,5 -Oxad iaz ines and 4 H - l , 3 , 5 - t h i a = diazines f rom cyanamides and perhalo ketones a n d t h i o ketones. 982

S i n n w e l l , V . Conformat iona l analysis, X X I V . D e t e r m i = nat i on of the conformations of t r i - and tetrasacchar= ide sequences of N-g lycoprote ins . Prob l em of t h e (1 6)-glycosidic bond. 951

S i n n w e l l , V . Albomycins , I I . Absolute conf igurat ion of the deferr i f orm of the albomycins. 1408



S o n a r , P . Reactions of uracils , 4. Some aspects of the chemistry o f p y r i d o [ 2 , 3 - d ] p y r i m i d i n e s . A novel s - = t r i a z o l o [ 4 , , 3 ' : l , 6 ] p y r i d o [ 2 , 3 - d ] p y r i m i d i n e . 1653

Soto, J . L . Synthesis of heterocyclic compounds. X X X V I I . Preparat ion of 4 , 6 - d i a r y l - l , 2 ~ d i h y d r o - 2 - = th i oxo -3 ,5 -pyr id ined i carbon i t r i l e s and related c om= pounds. 213

S p e h , P . Orthoamides . X I . Preparat ion of l , l , 2 , 3 , 3 - p e n = t a - s u b s t i t u t e d and 1,1,2,2,3,3-hexa-substituted guan i= d i n i u m salts and 1,1,2,3,3-pentaalkylguanidines. 108

S p i t e l l e r , G . P iper ine - an example of an i n d i v i d u a l l y d i f f e rent (po lymorphic ) metabol ism of an omnipresent n u t r i t i o n a l component. 1319

S p i t e l l e r , G . T e t r a h y d r o f u r a n acids - a new class of compounds i n h u m a n metabol ism. 1504

S p i t e l l e r , G . O r i g i n of 3,6-epoxyalkanedioic acids i n h u m a n ur ine . 1513

S t a a b , H . A . Cycloarenes, a new class of aromatic c om= pounds. I I I . Studies towards the synthesis of cyclo= [d.e.d.e.e.d.e.d.e.e.Jdecakisbenzene (correction). 408

S t a a b , H . A . [2.2)(2,7)Anthracenophane: synthesis and conformat ional studies. 615

S t a a b , H . A . Cycloarenes, a new class of aromatic com= pounds. I V . A t t e m p t s t o synthesize cyclofd.e.e.d.e.e.: 2

d.e.e.Jnonakisbenzene and cyclo[d.e.d.e.d.e.d.e.d.e]de= cakisbenzene. 742

S t a n o e v a , E . Reactions of glutaconic a n d homophthal i c anhydrides w i t h imidates , i m i d o y l chlorides, and 1-chloroisoquinoline. 389

S t e c k h a n , Ε. Oxidat ive deblocking of the 4 - m e t h o x y = benzyl th ioether protect ing group: appl icat ion to the directed synthesis of po lycys t iny l peptides. 1563

S t e f f a n , B . Ant ib i o t i c s f r o m Basidiomycetes, X I X . Naemato l in and naematolone, two caryophyllane derivatives f r om cultures of H y p h o l o m a species (Agar= icales). 1332

Stef fan , B . Ant ib i o t i c s f r o m basidiomycetes, X X . S y n = thesis of s t r o b i l u r i n A and revision of the stereochem= istry of n a t u r a l s t rob i lur ins . 1616

S t e g l i c h , W . Ant ib io t i c s f r o m Basidiomycetes, X I X . Naemato l in and naematolone, two caryophyllane derivatives f r om cultures o f H y p h o l o m a species (Agar= icales). 1332

S t e g l i c h , W . Ant ib io t i cs f r om basidiomycetes, X X . Synthesis of s t r o b i l u r i n A and revision of the stereo^ chemistry o f n a t u r a l s t rob i lur ins . 1616

S t e k e r , H . Synthesis of 2 ' -deoxyribofuranosides o f 7 H - p y r r o l o [ 2 , 3 - d ] p y r i m i d i n e : effect of the C-2 sub= st i tuents on the fluorescence. 1719

Stetter , H . Compounds w i t h U r o t r o p i n s tructure , L X . Orthooxal ic and orthocarbonic acid derivatives w i t h adamantane structure . 1577

Stoffregen, A . Intramolecular a d d i t i o n of carbanions to anthraquinones. 306

Stoppa, H . M e t a l complexes w i t h te trapyrro le l igands, X X X V . Synthesis of fur ther more or less sterical ly hindered 5 ,15-dialkyloctaethylporphodimethenes by reductive a lky la t ion of octaethylporphyr inatoz inc . 1259

S t r a e h l e , J . Synthesis and structure o f cyano (d ihydrod i= benzo[b , i ] ( l ,4 ,8 , l l ] te traazacyc lotetradec inato )cobal t= ( I I I ) . 1791

S t u m p p , M . Glycosyl imidates , 10. Glycosyl phosphates f rom glycosyl tr ichloroacetimidates. 680

S u c r o w , W . Enehydrazines, 37. Synthesis of a pyrazole analog of 7-aminomitosene. 1711

S u r a n y i , M . Synthesis of the pterocarpan constituents of Swartzia laevicarpa. 127

S u t t e r , M . A . Enant iomer ica l ly pure synthons f rom branched malates (correction). 407

Szabo , B . Synthesis of the pterocarpan constituents of Swartzia laevicarpa. 127

T a k a s e , K . M u l t i s t e p reversible redox systems, X X X I X . Isomeric biazulenyls: U V / V I S spectroscopy, v o l t a m ^ metry , and H M O energies. 1952

T a u e r , M . L . Synthesis of new carboximidoyl chlorides and t h e i r reaction w i t h nucleophiles. 564

T h i e l e r t , K . 7 - A r o y l - l H , 7 H - s - t r i a z o l o [ l , 2 - a ] - s - t r i a = zo le - l ,3 (2H) -d iones , a new class of compounds f r om 5-phenyloxazoles and 4 ~ p h e n y l - 4 H - l , 2 , 4 - t r i a z o l e - 3 , = 5-dione. 641

T h i e m e y e r , H . L i t h i u m enolates of carbohydrates, 2. A x i a l o - C - m e t h y l a t i o n and - h y d r o x y m e t h y l a t i o n of carbohydrate uloses. 1094

Todaro , L . J . Reactions of l , 4 -pentad ien -3 -ones , 22. Synthesis and structure of the epimers of 3 , 5 - d i a r y l - = 4 - h y d r o x y - l , 4 - t h i a z i n a n e 1,1-dioxides. 1013


T o e p e r t , M . Syntheses w i t h nucleic acid constituents, X . Mass spectrometry of nucleotides, V I I . Synthesis of deoxyoligonucleotide l inker fragments for genetic engineering using improved preparat ive and analyt ica l techniques. 835

U n g e r , F . M . Synthons of oligosaccharides, L I I . Synthe sis of disaccharides f r o m 3 - d e o x y -D - m a n n o - 2 - o c t u l o = sonic acid ( K D O ) and D-glucosamine. 1270

U n g e r , F . M . Synthons of oligosaccharides, L I I I . S y n = thesis of t r i saccharides conta in ing 3 - d e o x y - D - m a n ^ no-2-octulosonic acid ( K D O ) . 1288

V o e l t e r , W . Kinet i cs , catalysis, and mechanism of the secondary reaction i n the f ina l phase of the formose reaction. 623

V o e l t e r , W . Stereospecific syntheses of D-ossamine and D - to lyposamine. 636

Voges , K . P . Conformat ion of B o c - L - A l a - A i b - L - A l a - = O M e i n the crystal and i n so lut ion. 1117

V o n D e y n , W . Cyc l i to l reactions. X . Synthesis of enantiomerical ly pure pseudo-or-D-galactopyranose and pseudo -ß-D -mannopyranose. 433

V o n S c h n e r i n g , H . G . S t ruc ture of the 1:1 adducts of a r y l isocyanides to 4 - b e n z o y l - 5 - p h e n y l f u r a n - 2 , 3 - = dione and the i r products w i t h nucleophiles. Nove l rearrangements of 5 ,5 -d isubst i tuted 4 -methylenefu= :

ran-2 ,3-diones . 1137 V o w i n k e l , Ε. A new method for the degradation of

anthocyanidins, flavones, chalcones, and coumarins. 401

V o w i n k e l , Ε. T h e red membrane pigments of the peat moss Sphagnum r u b e l l u m . 1024

W a g n e r , P . Synthesis and carbon-13 N M R spectroscopy ic studies of br idgehead-subst i tuted endo-bicyc lo [3 .= 3 .1]nonan-3-ols and oxaadamantanes. 1981

W a h n e r , J . U . Chemistry of amino oximes, X V I I I . T h e cyclocondensation of (E)-|9-(chloroacetylamino)pro= piophenone oxime derivatives. 1696

W a l l m e y e r , M . New sesquiterpene lactones and rosane derivatives f r om Trichogonia species. 162

W a l z , Β. A c o n t r i b u t i o n t o the s t ruc tura l assignment o f posit ional isomers of bis-galacto and b is -manno crown ethers. 1046

W a m h o f f , H . Reactions o f uracils , 4. Some aspects of the chemistry of pyr ido [2 ,3 -d ]pyr imid ines . A novel s - t r i a z o l o [ 4 ' , 3 , : l ! 6 ] p y r i d o [ 2 , 3 - d ] p y r i m i d i n e . 1653

W a n j a , U . Meta l l oporphyr ins i n polymeric matrixes , micelles, and vesicles, V . 5 - ( r - M e t h y l - 4 , 4 ' - b i p y r i d i : = :

n i u m - l - y l ) o c t a e t h y l p o r p h y r i n dichloride, a meso-vio l ogenporphyrinate . 426

W a n n e r , Κ. T . Benzothiazoles by carbon-carbon cleav^ age of o r - [ (2 -n i t ropheny l ) th io ] ketones. 1100

W a n n e r , Κ. T . Pyrans, 100. 5 , 6 - D i h y d r o - 2 H - p y r a n - 3 = (4H) -one as a synthon for p y r a n - a n n u l a t e d hetero= cyclic compounds. 1759

W a s m u t h , D . Enant iomer i ca l ly pure synthons f r om branched malates (correction). 407

W a s s m u t h , U . T r i f l u o r o m e t h y l - s u b s t i t u t e d pyr imid ines f r om enamines and tr i f luoroacetoni tr i le . 991

W e b e r , B . Albomycins , I I . Absolute conf iguration of the deferr i f o r m of the albomycins. 1408

W e g n e r , P . Synthesis of fur ther eremophilane der iva= tives. 1785

Weinges , K . Chemistry and stereochemistry of i r ido ids , I V . Synthesis and x - r a y s tructure analysis of 15 -me= t h y l - 1 2 - e p i - p r o s t a g l a n d i n F20. 761

W e i s e r , W . Reactions of enolic sugar derivatives, X V I . Synthesis of a diastereotopic proton probe ( (Z)~3,7-= a n h y d r o - l , 2 - d i d e o x y - D - g l u c o - o c t - 2 - e n i t o l ] for a-and /3-D-glucosidases. 1078

W e i s e r , W . Reactions of enolic sugar derivatives, X V I . Synthesis of a diastereotopic pro ton probe [ ( Z ) - 3 , 7 - = a n h y d r o - l , 2 - d i d e o x y - D - g l u c o - o c t - 2 - e n i t o l ] for a-and /3-D glucosylases (correction). 1626

Weiss , Μ . M . Po lyhydroxyamino compounds via diene synthesis w i t h nitroso compounds. I X . t r a n s - 6 - A z i = do - l , 3 - cy c l ohexad ien -5 - o l as educt for the synthesis of condurodiamine and streptamine isomers. 203

W e i s s m u e l l e r , J . Synthesis of the me thy l ether of cardenol ide-derived methylreduct i c acid s tar t ing f r o m D-glucose. 66

W e l z e l , P . Properties of an (arylthiomethylene)cyclohex anone. 576

W e n d i s c h , D . Const i tuents of Boraginaceae, 7. A n c h u = soside-8 and - 9 : two new tr i terpene saponins f rom Anchusa off icinalis L . 1869


W i e c z o r e k , P . Synthesis of peptides w i t h a,ß-dehy~ droamino acids, I . Synthesis of N- (benzy loxycarbo= nyl ) and N - ( t r i f l u o r o a c e t y l ) dipeptides of dehydroala= nine and dehydrophenylalanine. 920

W i e s s l e r , M . Chemistry o f nitrosamines, I V . Syntheses of α-C-functionalized N-n i t rosod ia lky lamines : esters and ethers of l - [ (a lky l ) (n i t roso )amino ]a l coho ls . 1468

W i e s s l e r , M . Syntheses o f α-C-functionalized N - n i t r o = d ia lkylamines : esters of ( ( a l k y l ) ( n i t r o ) a m i n o ] m e t h a = nol and l - [ ( a l k y l ) ( n i t r o ) a m i n o ] e t h a n o l . 1494

W i n k e l e r , Η. D . Synthesis and furanoside /pyranoside isomerization of 7 -deaza -2 , -deoxy -7 -methy lguano= :

sine. 708 W i n k e l m a n n , G . I t u r i n A L : s tructure and derivatives

of a p e p t i d o l i p i d w i t h a h igh content of C i e - i t u r i n i c acids. 854

W i n t e r , W . Conformat ion of B o c - L - A l a - A i b - L - A l a - O M e i n the crystal and i n so lut ion . 1117

W i n t e r , W . Conf igurat ion and conformat ion of the nucleoside residues of the n ikkomyc ins . 1216

Winter fe ldt , E . Cyclopentenone derivatives. V I I . T h e stereoselective synthesis of bre fe ld in precursors. 450

Winter fe ldt , E . Cyclopentenone derivatives. V I I I . Reactions w i t h acetoxycyclopentenones, b r e f e l d i n - A cyclizations. 462

Winter fe ldt , E . Cyclopentenone derivatives. I X . E n a n = tioselective routes to b r e f e l d i n - A . 474

W i t z e l , H . Synthesis and properties of 2 , 2 ' - b i p y r i d i n - = :

3 - ols and -3 ,3 ' -d io ls . 1731 Wobig, D . Thiazole derivatives, V I . Synthesis of

t h i a z o l o [ 4 , 5 - d ] - v - t r i a z i n - 7 ( 6 H ) - ones. 1994 Wolf, B . A new method for the degradation of a n t h o =

cyanidins, flavones, chalcones, and coumarins. 401 Wolf, H . Dehydrogenat ion reactions w i t h gallic acid

esters. 929 Wolff, H . P . Syntheses of ant imic rob ia l biscationic

2- (phenoxyphenyl ) indoles and -1 -benzofurans . 409 Wolter , Β. Dehydrogenat ion reactions w i t h gallic acid

esters. 929 W r a y , V . New constituents of Lev i s t i cum officinale

Koch . 397 Y a m a m u r a , H . Reactions of l , 4 -pentad ien-3 -ones , 22.

Synthesis and s tructure of the epimers of 3 , 5 - d i a r y l - = 4 - h y d r o x y - l , 4 - t h i a z i n a n e 1,1-dioxides. 1013

Y a s s i n , S . Reactions w i t h 2 - m e t h y l - and 2 - s t y r y l - 4 - = thiochromones. 186

Y a s s i n , S . Carbonyl and th iocarbonyl compounds: reac= t ions of 4 -chloroxanthione w i t h diazoalkanes and compounds conta in ing active hydrogen. 191

Y a s s i n , S . Reactions of 4 - c h l o r o - 9 H - x a n t h e n e - 9 - t h i o n e w i t h tetrachloro-o -benzoquinone. 196

Y u n , Κ. Y . Syntheses w i t h a l iphat ic dialdehydes, X X X V I I I . Synthesis and properties of cyc loa lky lmal= onaldehydes. 649

Z a h r a n , M . Reactions w i t h 2 - m e t h y l - and 2 - s t y r y l - 4 - = thiochromones. 186

Zdero, C . New sesquiterpene lactones and rosane der iva= tives f rom Tr ichogonia species. 162

Zdero, C . New germacranolides, heliangolides, and elemanolides f r om Cronquis t ianthus chachapoyensis. 240

Zdero , C . Epoxycannabinol ide and d i ter penes w i t h a new carbon skeleton f r o m Vi l lanova titicaensis. 250

Zdero, C . Heliangolides and trachylobane and v i l l a n o = vane derivatives f r om Viguiera species. 495

Zdero, C . Pseudoguaianolides and other sesquiterpenes f r om Monact is macbridei . 503

Z e c h l i n , L . Ant ib i o t i c s f rom Basidiomycetes, X I X . Naemato l in and naematolone, t w o caryophyllane derivatives f r o m cultures of H y p h o l o m a species (Agar= icales). 1332

Zeid , I . Reactions w i t h 2 - m e t h y l - and 2 - s t y r y l - 4 - t h i o = chromones. 186

Zeid , I . Carbonyl and th iocarbonyl compounds: reac= tions of 4 -chloroxanthione w i t h diazoalkanes and compounds conta in ing active hydrogen. 191

Zeid , I . Reactions of 4 - c h l o r o - 9 H - x a n t h e n e - 9 - t h i o n e w i t h tetrachloro-o -benzoquinone. 196

Ziegler , E . S tructure of the 1:1 adducts of ary l isocyan= ides to 4 -benzoy l -5 -pheny l furan -2 ,3 -d i one and t h e i r = products w i t h nucleophiles. N o v e l rearrangements of 5 ,5 -d isubst i tuted 4 -methylenefuran-2 ,3 -d iones . 1137

Z o r z i n , C . Ant ib i o t i c s f rom g l id ing bacteria, X X I I I . S t igmate l l in A and Β - two novel antibiot ics f r o m St igmatel la aurantiaca (Myxobacterales) . 1883


1100 ΑΓ. 77?. Wanner und F. Eiden

Liebigs Ann. Chem. 1984, 1100-1108

Benzothiazole durch C - C-Spaltung von a-[(2-Nitrophenyl)thio]ketonen

Klaus Th. Wanner u n d Fritz Eiden *

Institut für Pharmazie und Lebensmittelchemie der Universität München, Sophienstraße 10, D-8000 München 2

Eingegangen am 1. Dezember 1983

Einwirkung von Ammoniak bzw. Natronlauge auf die a-[(2-Nitrophenyl)thio]ketone 4, l l a - c und 16 führt unter C-C-Spal tung zu den Benzothiazol-N-oxid-Derivaten 8, 12a - c und 17; aus dem 3-[(2-Nitrophenyl)thio]-4-piperidon-Derivat 22 entsteht der 2-Benzothiazolcarbaldehyd 23.

Benzothiazoles by C - C Cleavage of ct-[(2-Nitrophenyl)thio] Ketones

Reaction of a-[(2-nitrophenyl)thio] ketones 4, l l a - c , and 16 with ammonia and sodium hydroxide solution, resp., leads to C - C cleavage and formation of the benzothiazole A/-oxide derivatives 8, 1 2 a - c, and 17. The 3-[(2-nitrophenyl)thio]-4-piperidone derivative 22 yields 2-benzothia-zolecarbaldehyde 23.

Phenothiazine und Azaphenothiazine mit (Dialkylamino)alkyl-Seitenketten (ζ. B . l a und c) spielen als Arzneistoffe mit starker antipsychotischer Aktivität eine gewichtige R o l l e 1 } . Die neuroleptische Wirkung kann durch Substitution in 2-Stellung des Pheno-thiazinmoleküls gesteigert werden (ζ. B . l b ) .

Schema I

et [ C H 2 ] 3

N ( C H 3 ) 2

1 X R Namen

a CH Η ® P r o m a z i n , P r o t a c t y l

b CH O C H 3 M e t h o p r o m a z i n , Tentone® c Ν Η ®

P r o t h i p e n d y l , D o m i n a l

Wir versuchten, das Dihydro-l/ /-2-oxaphenothiazin 5 herzustellen, um es nach ^-Substitution auf zentrale Wirksamkeit zu untersuchen.

Zur Synthese haben wir 5,6-Dihydro-2//-pyran-3(4//)on (6) durch Erhitzen in Tetra-hydrofuran mit Trimethylsilylchlorid/Triethylamin zum Silylenolether umgesetzt, wobei in guter Ausbeute ausschließlich das A 3 - Isomer (3) entstand 2 ) . Dieser durch ^ - N M R - S p e k t r o s k o p i e gut identifizierbare Enolether reagierte mit (2-Nitrophenyl)-sulfenylchlorid (2) zum 5,6-Dihydro-4-[(2-nitrophenyl)thio]-2//-pyran-3(4i7)-on (4), das nun durch Reduktion mit Natriumdithionit in ammoniakalischer Lösung in das Oxaphenothiazin 5 übergeführt werden sollte. Wir erhielten eine farblose, kristalline Substanz, deren ^ H - N M R - S p e k t r u m zur Formel 5 paßte [5(ppm) = 3.40 (t) und 3.97 (t), je 2 H , / = 6 H z ( - O C H 2 C H 2 - ) , 4.10 (s), 2 H ( - O C H 2 C O - ) , 7 . 2 8 - 7 . 6 7

© Verlag Chemie GmbH, D-6940 Weinheim, 1984 0170-2041/84/0606-1100 $ 02.50/0

Benzothiazole durch C - C-Spaltung von a-[(2-Nitrophenyl)thio]ketonen 1101

(m) und 7 . 8 0 - 8 . 1 8 (m), je 2 H (Benzolring), 12.5 (breit) 1 H , H / D - A u s t a u s c h ] . Die Elementaranalysen dagegen, das Massenspektrum [m/e = 237 ( M + ) ] und das IR-Spek-trum (Banden bei 2 2 0 0 - 3 2 0 0 und 1730 c m " 1 ) sprechen für eine Aufspaltung des Pyranrings und Bildung eines Benzothiazoi-Derivates.

Schema I I

ι

Dieser Reaktionsablauf läßt sich durch Addition der CH-aciden Gruppe in 3-Stel-lung des Pyranrings (oder des entsprechenden Anions) an die Nitrogruppe unter Bil dung von 7 und Pyranringaufspaltung durch O H - I o n e n erklären. Das Benzothiazol-ZV-oxid 8 wird dann mit Natriumdithionit zum Benzothiazol-Derivat 9 reduziert. Tatsächlich entstand bei der Wiederholung der Reaktion in Abwesenheit des Reduktionsmittels das TV-Oxid 8 in guter Ausbeute.

Das Verfahren ließ sich auch mit carbocyclischen Ketonen bzw. ihren Silylenolethern 10a - c durchführen. Mit 2 entstanden die [(2-Nitrophenyl)thio]cyclanone I I a - c; E i n wirkung von Natronlauge führte dann zu den N-Oxiden der (2-Benzothiazolyl)alkan-säuren 1 2 a - c . Diese ließen sich mit Natriumdithionit zu den Benzothiazoi-Derivaten 1 4 a - c reduzieren. 12a und b setzten sich mit Diazomethan zu den Estern 13a und b u m . Die (2-Benzothiazolyl)alkancarbonsäuren lassen sich auch durch Kondensation von 2-Aminothiophenol mit entsprechenden Dicarbonsäureanhydriden darstellen 3 ) .

Auch der aus 3-Pentanon gewonnene Silylenolether 1 5 4 , 5 ) setzte sich mit 2 zu einem Nitrophenylthio-Derivat (16) u m , das dann mit Natronlauge erwartungsgemäß unter


1102 Κ. Th. Wanner und F. Eiden

Abspaltung von (nicht nachgewiesener) Propansäure 18 das 2-Methylbenzothiazol-N-oxid 17 bildete 6 ) ; durch Reduktion entstand daraus das entsprechende - auch anders herstellbare 7 ) - Benzothiazol-Derivat 19.

Schema I I I

OSi (CH 3 ) 3

+ 2 S Ο

[ C H 2 ] n

10 u o '

10, 11 ,12 ,14a : η = 3 b: η = 4 c : η = 5

12: R = Η 13: R = C H 3 , a: η = 3

b: η = 4

ι | ^ ^ V [ C H 2 ] n - C 0 2 H

14

Schema I V

S

H 3 C X C H 3 > CJ /"™3 ( + C H 3 C H 2 C 0 2 H )

16 ^ 6l 18

15 17

ι 19

Nicht ohne weiteres zu erwarten war das Ergebnis der Umsetzung von N-Methyl-4-piperidon (20). Das aus 20 über 21 hergestellte l-Methyl-3-[(2-nitrophenyl)thio]-4-piperidon (22) reagierte zwar mit Natronlauge, isoliert wurde jedoch nicht die Carbonsäure 26, sondern der 2-Benzothiazolcarbaldehyd (23), der bereits auf anderem Wege dargestellt worden i s t 8 ) . Dabei ist anzunehmen, daß auch hier - in Analogie zur B i l dung von 8 , 1 2 und 17 - zuerst das N - O x i d 26 entstanden ist, da sich durch Behandeln von 22 mit 0.01 Ν B a ( O H ) 2 eine instabile Verbindung isolieren ließ, deren ' H - N M R -Spektrum zur Struktur 26 paßt; das Spektrum veränderte sich jedoch nach kurzer Zeit . W i r schlagen als Weg zur Bildung von 23 die Folge 22 26 -> 27 23 vor, wenn es uns bisher auch nicht gelungen ist, 26 rein zu isolieren. Gut paßt zu dieser Vorstellung, daß wir nach dem Zufügen von Natriumdithionit zur neutralisierten Lösung von 26 ein Produkt isolieren konnten, bei dem es sich nach Analysendaten und Spektren u m die 7V-(2-Benzothiazolylmethyl)aminopropansäure 25 handelt.



Schema Y

OSi (CH 3 ) 3 Ο

I I l C 0 2 H C H 3 C H 3 C H 3

20 21 22 23 24

i ί

25 Ο θ 26 OH 27

R = C 0 2 H C H 3

Wir danken dem Fonds der Chemischen Industrie für die finanzielle Unterstützung unserer Arbeit, Frau A. Kärtner für ihre engagierte Mitarbeit beim Experimentieren.

Experimenteller Teil Schmelz- und Siedepunkte sind nicht korrigiert. - IR-Spektren: Accu Lab 6 (Beckman). -

^-NMR-Spektren: A 60 bzw. Τ 60 (Varian). - Massenspektren: CH7 (Varian). Darstellung von 3 wie in L i t . 2 ) beschrieben, von 10a - c und 15 nach dem von Housed angege

benen Verfahren (Erhitzen des Ketons mit Chlortrimethylsilan und Triethylamin in Dimethyl-formamid). 10a und b sind in L i t . 4 ) beschrieben, 10c und 15 in L i t . 5 ) .

l^Jyo-Tetrahydro-J-methyl-^ftrimethylsiloxyjpyridin (21): Eine Mischung aus 43.13 g (396 mmol) Chlortrimethylsilan, 80.10 g (792 mmol) Triethylamin und 33.90 g (300 mmol) 20 wurde in 120 ml absol. Dioxan unter Stickstoff 72 h rückfließend erhitzt. Nach Abdestillieren des Lösungsmittels i. Vak. wurde mit Pentan versetzt, filtriert und das Filtrat destilliert. Sdp. 8 0 - 8 5 ° C / 12 -15 Torr, Ausb. 25.2 g (45%). - IR (Film): 1675, 1460, 1365 c m " 1 . - l H - N M R (CDC1 3): δ = 0.18 (s; 9H) , 1.97-2.33 (m; 2H), 2.37 (s; 3 H), 2.47 - 2.75 (m; 2H), 2.85-3.04 (m; 2H), 4.71-4.92 (m; 1H).

C 9 H 1 9 N O S i (185.3) Ber. C 58.32 Η 10.33 Ν 7.56 Gef. C 58.20 Η 10.07 Ν 7.58 Molmasse 185 (MS)

A) Allgemeine Vorschrift zur Darstellung der a-[(2-Nitrophenyl)thio]ketone 4,11 a - c, 16 und 22 Der (Trimethylsilyl)enolether wurde unter Stickstoff in absol. Dichlormethan gelöst, auf die

angegebene Temp, abgekühlt und unter Rühren tropfenweise mit einer Lösung von 2 in absol. Dichlormethan versetzt. Nach der angegebenen Reaktionszeit und -temp, wurde i. Vak. vom Lösungsmittel befreit und das Rohprodukt wie angegeben gereinigt.

5,6-Dihydro-4-[(2-nitrophenyl)thio]-2H-pyran-3(4H)-on (4): 2.58 g (15.0 mmol) 3 in 15 ml absol. Dichlormethan und 2.84 g (15.0 mmol) 2 in 15 ml absol. Dichlormethan wurden bei - 50 bis - 4 0 ° C nach Vorschrift Α umgesetzt und anschließend bei Raumtemp. 12 h gerührt. Aus Toluol gelbe Kristalle, Schmp. 118-118.5°C, Ausb. 1.1 g (29%). - IR (KBr): 2910, 1723,


72

1104 Κ. Th. Wonner und F. Eiden

1510 c m " 1 . - *H-NMR (CDC1 3 ): δ = 1.97-2.90 (m; 2H), 3.78-4.53 (m; 5H), 6.97 - 7.70 (m; 3H), 7.88-8.13 (m; 1H).

C 1 i H 1 1 N 0 4 S (253.3) Ber. C 52.17 Η 4.38 Ν 5.53 S 12.66 Gef. C 52.03 Η 4.41 Ν 5.60 S 12.65 Molmasse 253 (MS)

2-[(2-Nitrophenyl)thio]-l-cyclopentanon ( I I a ) : 1.56 g (10.0 mmol) 10a in 15 ml absol. Dichlor-methan wurden mit 1.70 g (9.00 mmol) 2 in 15 ml absol. Dichlormethan bei - 7 0 ° C nach Vorschrift Α umgesetzt. Dann wurde 1 h bei Raumtemp. gerührt und nach dem Abdestillieren des Dichlormethans zweimal aus Essigester umkristallisiert. Zitronengelbe Kristalle, Schmp. 7 0 - 7 2 ° C , Ausb. 1.2 g (56%). - IR (KBr): 1735,1515,1335 c m - 1 . - *H-NMR (CDC1 3): δ = 1.8-2.8 (; 6H), 3.9 (t, J = 6.5 Hz; 1H), 7.20-8.05 (m; 3H), 8.23 (dd, J = 8/1.5 Hz; 1H).

C j j H ^ N C ^ S (237.3) Ber. C55.68 Η4.67 Ν5.90 S 13.51 Gef. C55.51 Η4.60 Ν5.99 S 13.57 Molmasse237(MS)

2-[(2-Nitrophenyl)thio]-l-cyclohexanon ( I I b ) : Nach Vorschrift Α wurden 11.07 g (65.0 mmol) 10b in 65 ml absol. Dichlormethan mit 12.35 g (65.0 mmol) 2 in 65 ml absol. Dichlormethan bei - 70°C versetzt. Man ließ dann 1 h bei - 70°C und 3 h bei Raumtemp. reagieren. Aus Essigester gelbe Kristalle, Schmp. 108-109°C (Lit. 9> Schmp. 113-114°C), Ausb. 8.59 g (53%). - IR (KBr): 2920, 1705, 1590 c m - 1 . - *H-NMR (CDC1 3): δ = 1.52-2.63 (m; 7H), 2.63-3.23 (m; 1H), 4.02 (t, / = 5 Hz; 1H), 7 .0-7.6 (m; 3H), 8.08 (dd, J = 8/1 Hz; 1H).

C 1 2 H 1 3 N 0 3 S (251.3) Ber. C 57.35 Η 5.21 Ν 5.57 S 12.76 Gef. C 57.12 Η 5.22 Ν 5.58 S 12.70 Molmasse 251 (MS)

2-[(2-Nitrophenyl)thio]-l-cycloheptanon (11c): Nach Vorschrift Α wurden 9.22 g (50 mmol) 10c in 50 ml absol. Dichlormethan mit 8.53 g (45 mmol) 2 in 45 ml absol. Dichlormethan bei - 7 0 ° C umgesetzt. Dann wurde auf Raumtemp. erwärmt. Nach wiederholtem Umkristallisieren aus Methanol und Essigester gelbe Kristalle, Schmp. 87 - 91 °C, Ausb. 4.02 g (34%). - IR (KBr): 2940, 1710, 1510 c m - 1 . - *H-NMR (CDC1 3): δ = 1.15-3.05 (m; 10H), 4.07 (dd, J = 9.5/5.5 Hz; 1H), 7.15-7.95 (m; 3H), 8.2 (dd, J = 8/1.5 Hz; 1H).


2-[(2-Nitrophenyl)thio]-3-pentanon (16): Nach Vorschrift Α wurden 1.58 g (10.0 mmol) 15 in 15 ml absol. Dichlormethan bei - 7 0 ° C mit 1.7 g (9.0 mmol) 2 in 15 ml absol. Dichlormethan umgesetzt. Man erwärmte anschließend auf Raumtemp. Der Rückstand wurde mit Methanol versetzt, Unlösliches abfiltriert und das Filtrat i. Vak. eingeengt. Die bei 5°C sich abscheidenden Kristalle wurden aus Methanol umkristallisiert, Schmp. 34 .5 -36°C, Ausb. 1.18 g (55%). - IR (KBr): 1710, 1520 c m - 1 . - ] H-NMR (CDC1 3 ): δ = 1.05 (t, J = 7.5 Hz; 3H), 1.58 (d, J = 7.5 Hz; 3H), 2.68 (q, J = 7.5 Hz; 2H), 4.07 (q, J = 7.5 Hz; 1H), 7.22-7.72 (m; 3H), 8.25 (d, J = 8 Hz; 1 H).

C n H 1 3 N 0 3 S (239.3) Ber. C 55.21 Η 5.48 Ν 5.85 S 13.40 Gef. C 55.12 Η 5.38 Ν 5.53 S 13.41 Molmasse 239 (MS)

l-Methyl-3-[(2-nitrophenyl)thio]-4-piperidon (22): Nach Vorschrift Α wurden 7.41 g (40.0 mmol) 21 in 50 ml absol. Dichlormethan bei - 4 5 bis - 3 0 ° C mit 6.82 g (36.0 mmol) 2 in 50 ml absol. Dichlormethan umgesetzt. Nach 30 min bei - 40°C wurde mit 10 ml Wasser und nach E r wärmen auf Raumtemp. mit Natriumhydrogencarbonat-Lösung versetzt. Die organische Phase wurde i. Vak. eingeengt und auf eine Kieselgelsäule gebracht (Korngröße 0.063-0.200 mm, Merck, 0 2.7 cm, Η = 27 cm). Nach Spülen mit 250 ml Essigester/Dichlormethan (2:8) wurde 22 mit Essigester eluiert. Aus Essigester gelbe Kristalle, Schmp. 107-109°C, Ausb. 3.58 g



(37%). - I R ( K B r ) : 1710, 1510 c m - 1 . - *H-NMR (CDC1 3): δ = 2.20-3.45 (m; 6H), 2.45 (s; 3H), 3.86-4.13 (m; 1 H), 7.20-7.93 (m; 3H), 8.11-8.33 (m; 1H).

C 1 2 H 1 4 N 2 0 3 S (266.3) Ber. C 54.12 Η 5.30 Ν 10.52 S 12.04 Gef. C 53.98 H5*.27 Ν 10.51 S 11.93 Molmasse 266 (MS)

5-(2-Benzothiazolyl)-3-oxapentansäure-3'-oxid (8): 0.18 g (0.70 mmol) 4 wurden bei Raum-temp. in 15 ml Ethanol suspendiert und mit 1.5 ml konz. Ammoniak versetzt (die sofort eintretende Rotfärbung verblaßte nach 10 min). Nach 2 h wurde das Lösungsmittel i. Vak. entfernt, der Rückstand in Wasser gelöst, die Lösung mit 6 Ν H C l auf pH 2 - 3 eingestellt und mit Chloroform extrahiert. Die mit N a 2 S 0 4 getrocknete Chloroformphase wurde i. Vak. eingeengt und der Rückstand aus Methanol umkristallisiert. Farblose Kristalle, Schmp. 126-128°C (Zers.), Ausb. 0.12 g(68%). - I R ( K B r ) : 1735, 1 2 1 0 c m - 1 . - *H-NMR ([D 6]DMSO): δ = 3.43 (t, 7 = 5.5 Hz; 2H), 3.93 (t, J = 5.5 Hz; 2H), 4.13 (s; 2H), 7.45-7.83 (m; 2H), 7.83-8.27 (m; 2H), 11.6-13.3 (1H, D 20-Austausch). - MS: m/e = 237 ( M + - O).

C n H n N 0 4 S (253.3) Ber. C 52.17 Η 4.38 Ν 5.53 S 12.66 Gef. C 51.80 Η 4.42 Ν 5.37 S 12.45

Β) Allgemeine Vorschrift zur Darstellung der Benzothiazol-N-oxide 12a - c , 17 und des 2-Benzothiazolcarbaldehyds 23

Eine Mischung aus 10 ml 1 Ν NaOH, 90 ml Tetrahydrofuran und 45 ml Wasser wurde unter Rühren tropfenweise mit einer Lösung des [(Nitrophenyl)thio]ketons (5.0 mmol) in 15 -30 ml Tetrahydrofuran (je nach Löslichkeit) versetzt, wobei sich die Reaktionslösung anfangs violett und dann allmählich braun färbte. Anschließend wurde mit 16 ml 1 Ν H C l versetzt bzw. bei 17 und 23 auf pH = 7 eingestellt und i. Vak. weitgehend eingeengt. Wenn sich dabei ein Niederschlag bildete, wurde dieser isoliert und mit Wasser gewaschen. Sonst wurde mehrfach mit Dichlormethan extrahiert, der Dichlormethan-Extrakt mit Wasser gewaschen, mit N a 2 S 0 4 getrocknet und i. Vak. eingeengt. Der Rückstand wurde wie angegeben umkristaliisiert.

4- (2-Benzothiazolyl)butansäure-3'-oxid (12a): Nach Vorschrift Β schwach gelbe Kristalle; Schmp. 172-174°C (Methanol), Ausb. 0.53 g (44%). - IR (KBr): 3100-1750, 1680 c m " 1

(br). - ^ - N M R ([D 6 ]DMSO): δ = 1.7-2.53 (m; 4H), 3.18 (t, J = 7.5 Hz; 2H), 7.57-7.92(m; 2H), 7.97-8.43 (m; 2H), 11.7-12.7 (1H, D 20-Austausch).


5- (2-Benzothiazolyl)pentansäure-3'-oxid (12b): Nach Vorschrift Β farblose Kristalle; Schmp. 145-147°C (Methanol), Ausb. 0.85 g (68%). - I R ( K B r ) : 3200-2300, 1 7 1 0 c m - 1 . - *H-NMR ([D 6]DMSO): δ = 1.43-2.10 (m; 4H), 2.37 (t, J = 6 Hz; 2H), 3.20 (t, J = 6 Hz; 2H), 7.50-7.93 (m; 2H) , 7.93-8.45 (m; 2H), 11.6-12.5 (1H, D 20-Austausch).

C 1 2 H 1 3 N 0 3 S (251.3) Ber. C 57.35 Η 5.21 Ν 5.57 S 12.76 Gef. C57.25 H5.15 N5.46 S12.94 Molmasse251 (MS)

6- (2-Benzothiazolyl)hexansäure-3'-oxid (12c): Nach Vorschrift Β schwach gelbe Kristalle; Schmp. 137- 138°C (Methanol), Ausb. 0.9 g (68%). - LR (KBr): 3100-1750, 1690 c m " 1

(br). - ^ - N M R ([D 6 )DMSO): δ = 1.1-1.9 (m; 6H), 2.08-2.43 (m; 2H), 3.13 (t, J = 7 Hz; 2H), 7 .6-7.9 (m; 2H), 7.97-8.37 (m; 2H), 12.0(br.; 1 H , D 20-Austausch).


2-Methylbenzothiazol-3-oxid (17): Nach Vorschrift Β hellgelbe Kristalle (Dihydrat); Schmp. 45 -47 °C (wasserhaltiges Acetonitril) (Lit. 6> Schmp. 46 -48°C) , Ausb. 0.49 g (49%, ber. auf Dihydrat). - IR (KBr): 1660, 1495 c m " 1 . - MS: m/e = 165 ( C 8 H 7 N O S ) . - ! H - N M R


72«


([D 6]DMSO): δ = 2.67 (s; 3H), 3.37 (s; 4 H , D 20-Austausch), 7.52-7.88 (m; 2H) , 7.93-8.33

(m; 2H). C 8 H 7 N O S - 2 H 2 0 (201.2) Ber. C47.75 H5.51 N6.96 S 15.93 Gef. C 48.16 Η 5.23 Ν 6.97 S 16.03

2-Benzothiazolcarbaldehyd (23): Nach Vorschrift Β farblose Kristalle; Schmp. 70 -73°C (Petrolether) (Lit. 8> Schmp. 72 -74°C) , Ausb. 0.38 g (47%). - IR (KBr): 1695, 1485 c m " 1 . -^ - N M R (CDC1 3 ) : δ = 7.57-7.90 (m; 2H), 7.97-8.5 (m; 2H), 10.33 (s; 1 H) .

C 8 H 5 N O S (163.2) Ber. C 58.88 Η 3.09 Ν 8.58 S 19.65 Gef. C 58.76 Η 3.22 Ν 8.46 S 19.38 Molmasse 163 (MS)

C) Allgemeine Vorschrift zur Darstellung der Benzothiazole 9 und 14a - c Das TV-Oxid wurde in Wasser suspendiert, bei 7 0 - 8 0 ° C (Badtemp.) tropfenweise mit einer

wäßrigen Natriumdithionit-Lösung versetzt und die Mischung bei dieser Temp, die angegebene Zeit gerührt. Wenn nach dem Abkühlen ein Niederschlag auftrat, wurde dieser isoliert, mit Wasser gewaschen und mit dem Rückstand vereinigt, der anschließend durch mehrfache Dichlor-methan-Extraktion gewonnen wurde. Dann wurde wie angegeben gereinigt.

5-(2-Benzothiazolyl)-3-oxapentansäure (9) a) Nach Vorschrift C: 0.05 g (0.2 mmol) 8 in 2 ml Wasser; 0.29 g (1.6 mmol) Natriumdithionit

in 5 ml Wasser; Reaktionszeit 30 min; Schmp. 136-138°C; Ausb. 0.04 g (84% nicht umkristallisiert).

b) 1.27 g (5.00 mmol) 4 in 100 ml Ethanol wurden in der Siedehitze unter Rühren mit 10 ml konz. Ammoniak und anschließend mit 2.61 g (15.0 mmol) Natriumdithionit in 15 ml Wasser versetzt. Es wurde 1 h rückfließend erhitzt, nach dem Abkühlen filtriert und das Filtrat i. Vak. eingeengt. Der Rückstand wurde mit Diethylether gewaschen und in Wasser gelöst. Die Lösung wurde mit 2 Ν H C l auf pH = 2 - 3 eingestellt und mehrfach mit Chloroform extrahiert. Nach dem Einengen der Chloroform-Extrakte wurde aus Ethanol umkristallisiert. Farblose Kristalle, Schmp. 135-137°C, Ausb. 0.25 g (21%). - IR (KBr): 3200-2200, 1730, 1440 c m " 1 . - ^H-NMR ([D 6]DMSO): δ = 3.40 (t, J = 6.0 Hz; 2H), 3.97 (t, J = 6 Hz; 2H) , 4.10 (s; 2H) , 7.28 - 7.67 (m; 2H), 7.80-8.18 (m; 2H), 12.5 (br.; 1 H , D 20-Austausch).

C u H n N 0 3 S (237.3) Ber. C55.68 Η4.67 Ν5.90 S 13.51 Gef. C 55.62 Η 4.75 Ν 5.98 S 13.43 Molmasse 237 (MS)

4- (2-Benzothiazolyl)butansäure (14a): Nach Vorschrift C: 0.84 g (3.5 mmol) 12a in 40 ml Wasser; 3.15 g (17.5 mmol) Natriumdithionit in 30 ml Wasser; Reaktionszeit 14 h. Farblose Kristalle, Schmp. 145-147°C (Methanol) (Lit. 3> Schmp. 145-146°C), Ausb. 0.49 g (64%) . - IR (KBr): 3200-2200, 1705 c m " 1 . - l H - N M R ([DJDMSO): δ = 1.8-2.67 (m; 4H) , 3.2 (t, J = 7 Hz; 2H), 7.33-7.77 (m; 2H), 7.9-8.3 (m; 2H), 12.0 (br.; 1 H , D 20-Austausch).

C n H u N 0 2 S (221.3) Ber. C 59.71 Η 5.01 Ν 6.33 S 14.49 Gef. C 59.54 Η 5.09 Ν 6.26 S 14.37 Molmasse 221 (MS)

5- (2-Benzothiazolyl)pentansäure (14b): Nach Vorschrift C: 0.50 g (2.0 mmol) 12b in 10 ml Wasser; 1.39 g (8.00 mmol) Natriumdithionit in 25 ml Wasser; Reaktionszeit 30 min. Farblose Kristalle, Schmp. 130-132°C (Essigester) (Lit. 3> Schmp. 134°C), Ausb. 0.28 g (59%). - IR (KBr): 3200-2300, 1710 c m " 1 . - Ή-NMR (CDC1 3): δ = 1.43-2.07 (m; 4H) , 2.32 (t, J = 6.5 Hz; 2H), 3.15 (t, J = 6.5 Hz; 2H), 7.21-7.77 (m; 2H), 7.77-8.18 (m; 2H), 12.1 (br.; 1 H, D 20-Austausch).

C 1 2 H 1 3 N 0 2 S (235.3) Ber. C61.25 Η 5.57 Ν 5.95 S 13.63 Gef. C 60.77 Η 5.58 Ν 5.99 S 13.71 Molmasse 235 (MS)

6- (2-Benzothiazolyl)hexansäure (14c): Nach Vorschrift C: 0.81 g (3.0 mmol) 12c in 15 ml Wasser; 4.27 g (24.0 mmol) Natriumdithionit in 20 ml Wasser; Reaktionszeit 1.5 h. Farblose Kristalle,


Benzothiazole durch C - C-Spaltung von a-[(2-NitrophenyI)thio]ketonen 1107

Schmp. 7 2 - 7 3 °C (Benzol/Cyclohexan) (Lit. 3> Schmp. 70 -72°C) , Ausb. 0.37 g (50%). - IR (KBr): 3300-2300, 1710 c m " 1 . - 1 H-NMR (CDC1 3): δ = 1.25-2.23 (m; 6H), 2.23-2.62 (m; 2H) , 3.17 (t, J = 7.5 Hz; 2H), 7.22-7.72 (m; 2H), 7.72-8.20 (m; 2H), 10.03 (1H, D 2 0 -Austausch).

C 1 3 H 1 5 N 0 2 S (249.3) Ber. C 62.62 Η 6.06 Ν 5.62 S 12.86 Gef. C62.60 Η 6.11 Ν 5.68 S 13.01 Molmasse249(MS)

2-Methylbenzothiazol (19): 1.4 g (7.0 mmol) 17 in 20 ml Ethanol wurden unter Rühren bei 7 0 - 8 0 ° C tropfenweise mit 9.97 g (56.0 mmol) Natriumdithionit in 50 ml Wasser versetzt. Nach 1.5 h ließ man abkühlen und versetzte mit Cyclohexan. Die organische Phase wurde abgetrennt und die wäßrige Lösung mehrfach mit Cyclohexan extrahiert. Die vereinigten Extrakte wurden mit N a 2 S 0 4 getrocknet und destilliert. Farblose Flüssigkeit, Sdp. 72°C/1.8 Torr (Lit. 7> Sdp. 238°C/760 Torr), Ausb. 0.71 g (68%).

5-(2-Benzothiazolyl)-4-methyl-4-azapentansäure-3 '-oxid (26) und 5-(2-Benzothiazolyl)-4-methyl-4-azapentansäure (25): 650 ml 0.01 Ν Ba(OH) 2 wurden unter Stickstoff und starkem Rühren tropfenweise mit 1.35 g (5.00 mmol) 22 in 50 ml Tetrahydrofuran versetzt. Nach Zugabe von 65 ml 0.1 Ν H 2 S 0 4 wurde gekühlt und das entstandene Bariumsulfat abfiltriert. Das Filtrat wurde mit Dichlormethan geschüttelt (= Ausgangslösung zur Darstellung von 25). Zur Messung des Spektrums wurde 1/5 dieser Lösung möglichst rasch bei Raumtemp. i. Vak. eingeengt und der Rückstand mit wenig Aceton versetzt. Aus der bei - 5 °C aufbewahrten Lösung schied sich 26 in farblosen Kristallen (als Hydrat) ab. - j H-NMR (CD 3 OD) : δ = 2.27-2.73 (m; 5H), 2.73-3.17 (m; 2H), 4.13 (s, br.; 2H), 7.43-7.77 (m; 2H), 7.77-8.12 (m; 2H).

4/5 der Ausgangslösung (4.0 mmol) von 26 wurden mit 4.27 g (24.0 mmol) Natriumdithionit in 40 ml Wasser versetzt und 2.5 h bei 70°C gehalten. Nach dem Abkühlen wurde filtriert, das Fil trat mit Diethylether und dann mehrfach mit Dichlormethan geschüttelt. Die vereinigten Dichlor-methan-Extrakte wurden getrocknet und eingeengt. Dann wurde mit Diisopropylether versetzt und gekühlt. Farblose Kristalle, Schmp. 2 5 - 3 0 ° C , Ausb. 0.1 g (10%). - MS: m/e = 250 ( C 1 2 H 1 4 N 2 0 2 S ) . - ^ - N M R (CDCl 3 ) : δ = 2.53 (s; 3H), 2.57-2.80 (m; 2H), 2.88-3.17 (m; 2H) , 4.17 (s; 2H) , 7.30-7.77 (m; 2H), 7.87-8.23 (m; 2H). Dem ^-NMR-Spektrum in [DdDMSO zufolge liegt 25 als Oligohydrat vor.

C t 2 H 1 4 N 2 0 2 S - 4 . 5 H 2 0 (331.4) Ber. C43.49 Η 6.99 Ν 8.45 S9.67 Gef. C 43.85 Η 6.59 Ν 8.55 S9.81

4- (2-Benzothiazolyl)buiansäure-methylester-3'-oxid (13a): 0.31 g (1.3 mmol) 12a wurden bei Raumtemp. unter Stickstoff in 12 ml absol. Methanol suspendiert. Diese Suspension wurde bis zur vollständigen Auflösung tropfenweise mit etherischer Diazomethanlösung versetzt (Kontrolle der quantitativen Umsetzung durch DC) . Dann wurde i. Vak. eingeengt, Dichlormethan zugegeben, mit Wasser geschüttelt, mit N a 2 S 0 4 getrocknet und erneut vom Lösungsmittel befreit. Der Rückstand wurde auf eine Kieselgelsäule (Merck, Korngröße 0.063-0.200 mm; 0 2.7 cm, Η = 8 cm) aufgetragen und mit 150 ml Essigester gespült. 13a wurde dann mit Essigester/ Ethanol (1:1) eluiert und aus Diisopropylether umkristallisiert. Gelbliche Kristalle, Schmp. 65 -68 .5 °C , Ausb. 0.1 g (31%). - IR (KBr): 1730cm" 1 . - ! H - N M R (CDC1 3): δ = 1.92-2.67 (m; 4H) , 3.23 (t, J = 7 Hz; 2H), 3.67 (s; 3H), 7.27-7.87 (m; 3H), 7.97-8.23 (m; 1H).


5- (2-Benzothiazolyl)pentansäure-methylester-3'-oxid (13b): Wie bei 13a wurden 0.75 g (3.0 mmol) 12b in 25 ml Methanol mit etherischer Diazomethanlösung umgesetzt. Nach dem Abdampfen des Lösungsmittels wurde zweimal aus Essigester umkristallisiert. Farblose Kristalle, Schmp. 8 3 - 8 5 ° C , Ausb. 0.34 g (43%). - IR (KBr): 1735 c m " 1 . - 'H-NMR (CDC1 3 ): δ =



1.63-2.1 (m; 4H), 2.23-2.6 (m; 2H), 3.03-3.43 (m; 2H), 3.67 (s; 3H), 7.42-7.93 (m; 3H), 8.07-8.37 (m; 1H).


! ) M. Gordon in Psychopharmacological Agents (Edit. Μ. Gordon), Bd. I I , S. 2 und 305, Academic Press, New York und London 1967; / . Hoff mann und H. Ruschig in Arzneimittel (Edit. G. Erhart und H. Ruschig), Bd. 1, 2. Aufl., S. 222, Verlag Chemie, Weinheim 1972; E. Schröder, C. Rufer und R. Schmiechen, Pharmazeutische Chemie, 2. Aufl., S. 278, Thieme, Stuttgart und New York 1982.

2) F. Eiden und K. Th. Wanner, Arch. Pharm. (Weinheim, Ger.), im Druck. 3> F. S. Babichev und Ν. Y. Berkach, Ukr. Khim. Zh. 22, 208 (1953) [Chem. Abstr. 51, 373 c und d

(1957)]. 4> Η O. House, L . J. Czuba, M. Gall und H. D. Olmstead, J . Org. Chem. 34, 2324 (1969). 5> L . Birkofer und H. Diekopp, Chem. Ber. 102, 14 (1969). 6> S. Takahashi und H. Kano, Chem. Pharm. Bull. 17, 1598 (1969). 7> A. W. Hofmann, Ber. Dtsch. Chem. Ges. 13, 21 (1880). 8> 5. Linke, J. Kurz, D. Lipinski und W. Gau, Liebigs Ann. Chem. 1980, 542. 9 ) Μ Ε. Kuehne, J . Org. Chem. 28, 2124 (1963).

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