Indian Journal of Chemistry Sect. B: Organic Chemistry including Medicinal Chemistry

VOL. 38B NUMBER I JANUARY 1999

CONTENTS

Rapid Communications

A facile synthesis of acid anhydrides

P K Dul>ey* & R Vinod Kumar

A facile synthesis of symmetric and unsymmetric acid anyydrides using phase-transfer catal ys is is described .

- + R-CO-O K + CI-CO-R' CHCl" lTEBAC R-CO-O-CO-R' + KCI ..

RT: 2hr 2 3

.. A novel diketosesquiterpenoid from the soft Structure of a novel d ik etosesq uiterpenoid, iso lated from

8

coral Sillularia illtacta of the Indian Ocean the so ft coral Sinularia illlacla, has been elucidated as 8,9-secoafricanane-8,9-dione 4.

A S R Anjaneyulu* & P Mangala Gowri

Facile annulation of six-membered ether rings on to carboh ydrate templat( based on ring closing metathesis. Synthes[s of enantiopurr l>icyclic ethers

Azizul Haque, Jagannath Panda & Subrata G hosh*

4

.A facile annulati on of six -membered cycli c ethers on to carbohydrate templates through ring closing metathes is to lead to enan tiopure bicyclic ethers is reported .

~ ~O o CI2Ru(l'CyJ):CHPh ~O'"

"'5>! 0 • l._A--.I'i -R- L-O b-\- 0 ~ ot ~H OH

(i) INDIAN J CHEM, 38B (I) 1999

10

CONTENTS

Papers

Chemo-enzymatic synthesis of chiral 3-hydr­oxy-azetidin-2-ones

S S Bari*, S Madan & M K Sethi

Azetidin-2, 3-diones'3 prepared by mild basic hydrolysis of 3-acetoxy-4, 4-bis(alkylthio)azetidin-2-ones I and followed by ox idation on subsequent bioreduction wi.th fermenting and immobilised Baker's Yeast in aqueous and organic media, respecti vely affords 3-hydroxy­azetidin-2-ones 4 with high enantioselectivity.

'.2 a , R,= RZ = SCH:!

b. R,=R2 = SC2HS

_. t , R,=R 2 =SC3H7

3-Sa.R,=R2=H

b , R,=H,R2=SC 2HS

18 Condensation of 3-methyl/ethyl-S-mercapto-s- Condensation of I with either 3-(2-bromoacetyl) couma-tril1Zolc with 3-acetylcoumarin and its deriva- rin or 3-acetylcoumarin yields the uncyclized product 2. tives This on cyclization with PPA furnishes 3-alkyl-5-

coumarinylthiazolo[3, 2-b ]-s-triazole 3 . Synthesis of 5 via cyclocondensation of 4 with either 3-(2-bromoacetyl) coumarin or 3-acetylcoumarin followed by cycloconden­sation gives isomeric product 6.

V Aditya Vardhan, V Ravi Kumar & V Rajeswar Rao*

(1)

R,r6!y ~~Jl ( 3) R

R~Y ~jLNHNHCOR

(5 )

H ii R-C-NHNH - C-NH2

( l.)

(ii) INDIAN J CHEM, 388 (I) 1999

24

CONTENTS

Catalytic cyclocondensation of acetone to phorone

Acetone

Cyclocondensation of acetone involves aldol condensa­tion leading initially to diacetone alcohol and mesityl oxide which agai n react with acetone to form phorone and other products.

[)acetone A lcohO!

(CH:V2 C=CH-C-CH3 II o

MesitylOxide

9H3

+ CH3-G=e ----__ (CH:V2 C=CH-C-CH=C(CH:V2 + Other products

II o

Phorone

K V Ramanamurty & G S Salvapati*

2'.1 S~' nthesis of some benzopyranoquinoline deri- Synthesis of benzopyranoquinoline diones 2 and chloro-vatives benzopyranoquinolinones 3 via I and their anilino de­

ri vatives 4 is described.

v V Mulwad* & 8 S Mahaddalkar

.n Applications of carbon-nitrogen bond cleav­age reaction: A synthesis/derivatisation of II H-indenoll, 21isoquinolines

Bansi Lal* & Ramesh M Gidwani

(ii i)

-O~ = I N 0 - 0 II" -~ ~ ------...

R -....

R R

R

R = H / R = OCH.I

INDIAN J C1-IEM, 388 (1) 1999

40

CONTENTS

4-B eteryl- fl -lactams: A facile synthesis of I­II ry l-4-1 isopropy liden eamin o/meth yl-4(3 11)-ox 0<) II i nazolin-2-yll azetidin-2-ones

P S N Rcddy*, T Vasantha & C h Nagll Rajll

A facile and efficient synthesis of 4-quinazolinonyl-p­lactams starting from 2-chlorometh y lquinazolin-4(3H)­ones is described .

45 Studies in the sy nthesis of s-triazoloI4,3-al- The title compounds have been synthes ised from

52

56

quinoxalines 2-chloro-3-(aryl idene/alkyl idene hydrazino) quinoxalines by reaction with alkoxid es/phenoxide followed by dehy­drogenative cyclisation with ch lorani\.

v S H Krishnan*, K S Chowdary &

P K Dubey*

Lowering of Bohlmann intcnsities in confor-1lI1itionally homogenous 2, 6-diarylpiperidines due to ring distortion

R Jeyaraman*, T Ravindran, M Sujatha & M Venkatraj

Studies on (non) energetic compounds: . Part 10-Ring-substituted arylammonium chlo­rides

C~NyORI (~IOranil_ ~N~NH-N=(H-R

T he orientatio n· of th e lone pair of electrons on the ni tro­gen in 2, 6-diarylpiperdines has been stud ied employing the Bohlmann bands in the IR spectra.

X

J»A' U H

Simultaneous sublimation/decomposition processes are involved during the thermol ys is of RSACI.

Rn;m,cT ~ [Rn~:··H .... Ci ~ ~~ RnNH,+ IICI

J Cond.n.t d ph ...

"SACI (Solid ph ... )

Gurdip Singh*, Inder Pal Singh Kapoor & Jaspreet Kaur

(iv)

Rn~H,6 ~ Gaseous products

Arrosol

INDIAN J CHEM, 38B (I) ]999

.,

67

76

CONTENTS

Crown humus: Part I-The chemistry of the canopy organic matter of rain forests in Costa Rica

S Ghosal* , A V Muruganandam, S C hauhan , '" Kawanishi, K Saiki & N M Nadkarni

S~' nthes i s and biological activities of new 3, 5-disubstitutcd-2-(eth yl-S'-thioxo-I ', 3 ', 4 '-oxa­diazo l-4 ' -eth~' l aceta te-2 ' -yl)indoles, -2-(5 ' -thi­oxo-I ', .1', 4 '-oxadi azol-4 '-methyl carboxyhy­drazide-2'-y l)indoles and 2-(S'thioxo-I', 3', 4 ' -oxadiazol-4 ' -a lkyl-2 ' -yl)indoles

Rcnllka Devi Patil & J S Biradar*

The low and high Mw (mol. wt) core organic compounds of Crown humus of two rain forests, in Costa Rica, are represented by oxygenated dibenzo-a-pyrones (I and 3) and their di- and oligomeric metallo-humate complexes (9b, II , dotted line substd). The synthesis and metabo­li sm of Crown humus have thus close si milarties to other humic substances of terrestri al and aquati c origin .

R'W R1

o .!.: R' :OH, R':H

1..: R'. Rl = OH

-0

o .!l

( - ) FM

L : PHE NOL IC / AQUO - L IGANO. FA.: FULVIC ACIDS

3,S-Disubsti tu ted indole-2-carboxy lates 1 a-g are reacted wi th hyd razine hydrate to furni sh the correspond ing in­dole-2 -carboxyhydrazides 2a-g. These on reaction with alka line carbon-disulphide under thermal react ion condi­tions produce respective 2-[S'-th ioxo- I ', 3', 4'-oxadi­azol-2 ' -yl)indoles 3a-g. Reaction of 3a-g with ethylehlo­roacetate and alk yl halides in dry acetone and anhydrous potass ium carbonate yield 4a-g and 6a-r, respectivel y. 4a-g on further reaction with hydrazine hyd rate in etha­nol afford the compounds Sa-g. Compounds synthesi sed are s(; reened for the ir biological ac tivities.

60 - r

(v) INDIAN J C I-IEM, 38B (I) 1999

83

CONTENTS

Isolation of monoterpenic ester, chromenone and steroidal lactone from Pillchea lanceolata root

Ramidi Ramachandram & Mohd AIi*

Three new phytoconstituents isolated from the roots of Pluchea lanceolala have been identified as 4-isopro­pylcyclohex-l-en~7-(2 ' -oxy-2 ' -methyl bUlyl)-oate; 2, 2-dimethyl-7-acetyl-8-hydroxychromenone and ergost-5, 22-diene-3p-ol-20, 28-olide on the basis of spectral. data analyses and chemical reactions.

2 R

Notes

S7 A facile synthesis of 7:8- and 6:7-fused py- A facile synthesis of 7:8- and 6 :7-fused pyrano pyrido r:lno pyrido coumarins coumarins 2a-e from 8/6-formyl-7- hydroxy-4-methyl­

coumarins I a-e by modified Hantzsch synthesis is descri­bed.

N G:lng:ldhar, Ch Harish Kumar &

<.; L David Krupadanam*

CHO "OWO R ~ h R

t

CH3

lo-d

0 H3C CH)

H:('OEt °l 0

H2N CH3 .. AcOH,rt ,96 h

Rt

CH3

2 o-d

1)0 ;\ sillll) le method for the removal of 4-meth- Removal of 4-methoxybenzyl group from a series of ox~' lJenzo:v1 group compounds having various protecting groups has been

achieved by treatment with 80% acetic acid ' in ' water at 80DC for 4 hr.

0

R

BnO oen

MBno~~oSE , BnO

AcOH ~

20"C

BnO OBn

HO~OSE BnO

Anup Kumar Misra, Indrani Mukherjee,

l3alaram Mukhopadhyay &

Nirmolendu Roy*

(vi) INDIAN J CHEM, 38B (I) 1999

l}l}

A new synthesis and I, 3-dipolar cycloaddi­tion of C-~ryl-N-(2, 4-dibromophenyl)-nitril­imines with arylmaleimides leading to the synthesis of 1-(2', 4' -dibromophenyl)-3, S-di­aryl-3a, 4, 6, 6a-tetrahydro-IH, SH-pyrrolo-13, 4-clpyrazole-4, 6-dione derivatives

"ewal "rishan Singal*, Baldev Singh &

Balkar Singh

S~' nthesis of 2-(N-methyl-N-(4-iotlollhenyl) aminomethyl)-I, 3, 4-oxadiazole and its use as a protective synthoil for indirect iodinlltion of ketosteroid's

Barakat M Shabsoug* & Mohamad A lIassan

Imidazolium tluorochromate (IFC): A new, mild, stable and selective chromium(VI) oxi­dant

A Pandurangan, G Abraham Rajkumar,

Banumathi Arabindoo & V Murugesan*

A new and convenient method for the synthesis of aryl­nitrilimines and their I, 3-dipolar cycloadditions to aryl­maleimides giving the cycloadducts in excellent yield has been carried out.

v

Iodination of 2-(N-mcthyl-N-phcnylaminomethyl)-I, 3, 4-oxaadazole 2 with iodine monochloride leading to the formation of 2-(N-methyl-N-(4-iodophenyl)amino­methyl)-I , 3, 4-oxadiazole .3 in described ,

HO

Preparation of imidazolium fluorochromatc (IFC), char­acterisation and its synthetic utility in the oxidation of primary and secondary alcohols, and in the oxidative deoximation of ketoximes to the corresponding carbonyl compounds at room temperature are reported,

(vii) INDIAN J CHEM, 38B (I) 1999

101

106

109

CONTENTS

Ring closure reaction of 4-tert-butyl-4-penten-1-01 with electrophilic reagents

c:f 3

M Lj MihailoviC, S GojkoviC, S MilosavljeviC & S KonstantinoviC*

Crysta l and molecular structure of Biatrac­tylolide from the Chinese herb plant Armcty­lodes macrocepha!a

Zhongqi I-I!--,ang, Yongcheng Lin*,

Sh ixiong Liu & W inglai Chan

An efficient and sim ple procedure for acetyla­tion of alcohols and phenols with acetic anhy­dride catalysed by expansive graphite

Tong-Shou Jin, Van-Ran Ma, Tong-Shuang LI*, Z han-/-Iui Zhang & Guang-Bo Duan

The reaction of 4-tert-butyl-4-penten-l-ol 3 with some electrophilic reagents (such as mineral acids, mercuric acetate, peracids) has been investigated. In the acid (H 2S04) catalysed reaction of 3, the products of I , 2-methyl rearrangement are produced (8 and 9).

~ d I

J;k H" ar --:

b (1.2·Me)

- -- - -- = r"; - H " @ H +

OH I

III IV H

a ! -H" I cY- ~ OJ:'~

7 8 9

Biatractylolid (Ill) , A nove l compound with a uni que bisesquiterpenoid skeleton has been obtained from Atractylodes macrocephala . The single crysta l belongs to space group P2,2,2, . The unit of cell con tains four mole­cules. The structure has been sol ved by direct methods and refined by least-squares method .

An easy acety lation of alcohols and pheno ls with acetic anhydride has been carried out in excellent yield under catalysis of expansive graphite.

Expansive graphitl! C H,Ci 2 or C II CI;

r.t. or rellll x. D.S -Ii h ROH + AclO -------•• ROAc + 110Ac

2 92-<)<)% -'

(viii) INDIAN J CI-IEM, 38B (1 ) 1999

II I

CONTENTS

Rapid synthesis of nitro substituted diaryl ethers under mild conditions

Various nitro substituted diaryl ethers have been synthe­sized rapidly by using polymer supported phenoxide anions and halides under mild conditions. The isolation of pure products by simple filtration and evaporation is an important feature of this method.

R = H. N~. Ar = Substituted aryl

n = 2...1 : Ar = 2.4.6- trin itrophen'·I: X = Br

8 P 8andgar*, V 0 Dhakane & J N Nigal

114 Fluorination of 2-chloro-3-formylquinolines Fluorination on 2-chloro-3-formylquinolines using mt-

116

using microwaves crowaves has been carried out in solfolane, acetonitrile and acetamide using potassium fluoride and tet­ramethylammonil.lm clllpJlide under microwave irradia­tion as well as conventional heating.

Mazaahir Kidwai*, Pooja Sapra &

Kumar Ranjan 8hushan

Synthesis and biological activity of some N­substituted' pyridine dicarboximide deriva­tins

l\1ohamad S I Makki, Seham Y Hassan &

lIassan M Faidallah*

R~CHO_ R~CHO ~N;:J-CI ~~F

1 (.~) 1(...,)

Various N-substituted pyridine dicarboximides have been prepared starting from pyridine dicarboxylic anhydride.

O co -0-~I >~!JR N CO

(ix) INDIAN J CHEM, 388 (I) 1999

CONTENTS

119 Two novel pentacyclic triterpenes from Cal­liuIIJru eriophylla (8enth) (Leguminosae)

C.<:riophvlla Roots Iso lation & ----I~~ Ex trac t . . ~ Extraction Charac t<:n zatJo n

I RJ

= 01-1 . R, = ~k . R, ~ Cli O

, RJ

= 0 1-1 . R, ~ CII ,OII . R, - CliO

Edet M Anam

122 (Z)-I '-Propylbutyl 3-octadecenoate from Fa- A new ester has been isolated from the medic inal plant J.:ara hudrullKa fruits Fagara budrullga. Its structure is elucidated as (2 )- 1'­

propyl butyl 3-octadecenoate ( I ) by chemi ca l transfor­mations and spectra l analysis.

la 16

17 15

o G Naik*, Sujata Katke, Padmini Banhatti & A 0 Natu

11. 12 10 8

13 II 9

(1)

Authors for correspondence are ind icated by (*)

(x)

7

6 I. 3

5 2 o ok.I.'

2'

INDIAN J CHEM, 388 (I ) 1999