Progress in organic microsynthesis: 1959, 1960

MICROCHEMICAL

Progress

JOURNAL

VOL.

in Organic

V, PAGES

439-508

(1961)

Microsynthesis:

1959,196O tjDoN

K. J. KOVhCS, Institute of Organic Chemistry, University Szeged, Sxeged, Hungary

of

A review of the literature of the past two years increasingly reveals the tendency to reduce the quantity of material used in the experimental work. This fact is a necessary consequence of the type of research carried out in different fields of chemistry; for illustration, it is sufficient to remind the reader of the laborious and difficult isolation of natural products and the minute quantities of the materials obtained, or of the poor overall yields of syntheses consisting of many steps; the nature of biological research and experiments with radioactive labelled compounds present similar problems. Another factor is that the time requirement of modern essential fractionation procedures and isolation techniques does not increase proportionally but at an accelerated rate with the amount of the material involved. Apart from the important aspect of economy of effort, micropreparative methods also result in a considerable saving of t’ime when employed in connection with classical methods. Another important factor is that when preparative work is done on microscale, many more experiments can be carried out with the same available amount of material, which will result in a more thorough study of the problems. As a consequence of the above reasons, the gleaning of the information on micropreparative work within the limits of a review is at best a difficult task. Difficulties encountered in the gathering of data have been excellently stated by Ronzio:’ “However, the greatest obstacle in the dissemination of even the small amount of information published on microsyntheses is the fact that there is nothing in the 439

Gtle of the article t,o indicate the range of quant,ity of material employed in the experimentation.” The main abstracting journals cannot list problems of theoretical or prsrtical microchemical interest, under separat,e entries, and useful information can be gained from the original papers only when not only t,he title but also t)he exprrimrntal part is st,udied by t,he reader. In t’his respect, an essential help has been offered since 1057 to microchemist’s through t.he abstracts published in some issues of the illicrochemical Journal, which call t,he attention of those concerned to publications on microchemistry and of microt,echniques by references of a few sentences, grouped under different, headings. 2 The yearly expansion of the column, i.e., increase of t,he number of papers abst’ract,ed, clearly indicates progress in this field, and theL growing inWest for such nil nhst,rart.ing servic*f>.

No. of :tbstracts Inorganic microsyntheses ( kganic microsyntheses Tot al

1957

1958

1959

1960

2 37 39

6 33 30

17 63 80

23 209 X32

The tabulated values may be further increased by the inclusion of papers dealing with experiments involving the use of radioactive It is most desirable that, this elements or biochemical materials. excellent work of the abstracters of t’he Microchemical Journal should continue in t,he future, embracing further, mainly foreign journals in addition to the ones abstracted so far. The present survey, in addition to reviewing a few important handbooks, is partly based on the material published in the abstract’s of the Microchemical Journal, complet’ed with references of apparent interest selected from ot,her periodicals. The large amount of information collectred in this way necessitates selected illustrative treatment, which may not, exempt the reader from consulting the original literature. Perusal of t,he original papers represents interesting features not only in the ideas and of accompanying techniques, but also by the elegance which enables the researchers to solve their problems wit,h usually quite small quantities of starting materials. MICROCHEMlClL

.JOURN.4L,

VOL.

V. ISSUE

:J

ORGAPr’IC

MICROSYNTIII!XS

441

General Aspects It is repeat’edly demonstrated in the latest literature that, though rules for general experimental methods of organic micropreparative technique can be given and are even very necessary, especially for beginners, the solution of a particular problem under special conditions depends nevertheless upon t,he ingenuity and skill of the experimenter. Thus, e.g., the scale of the experiment is determined by the nature of the reaction; while a few milligrams of material are sufficient for microhydrogenation or 10 t’o 50 mg. for chromic acid oxidation, carrying out a more difficult, reaction of poor yield may require as much material as 100400 mg. Auot,her decisive factor is the extent, of dilution: in tdm micropreparativc t.echnique, in general, usually the molar quantities of the employed reactants are not so important; it is the total volume of the reaction mixture that is critical. The purpose of more convenient running of a reaction and further processing of the products is served by employing the reactants in molar quantities, and by such combination of various steps which results in the use of the minimum number of reaction vessels and minimized surfaces in contact with the material. The practice of micropreparative manipulation-just on account of the scale employed-should not be treated separat’ely from modern fractionation procedures, and especially from differential migration methods. These techniques render possible a further reduction in the dimensions of the experimentation resulting in a necessary revision of experimental methods: e.g., chromatography is used instead of distillation, sublimation inst’cad of cryst,allization, rather two methods are combined instead of t,he reputation of one, etc. Potentialities in chromatographic methods, such as differences in the forces affecting separation, and the great number of variable chemical and physical parameters involved in one and the same method, make it possible to effect the most critical steps of microsyntheses, i.e., isolations and purifications, with small losses of material; thus the prospect of success is cnhanccd for t’he whole experiment. Another inevitable attribute of chemistry on the microscale is an increased use of physicochemical and analytical methods. Possession of only small quantities of material sets a limit to the number of experiments to be carried out and it will demand greater soundness

442

in the single steps. smaller quantities methods, it follows investigation it is analytical data as success.

0. KOVACS

Since analytical procedures require considerably of material than micropreparative experimental that in the course of an organic microchemical of fundamental importance to obtain as many possible, and increase thereby the outlook of

Teaching Views mentioned in the introduction as well as aspects of economy direct also higher education to adopt more and more the practice of the laboratory experimentation of the students done partly or completely on the semimicro scale. Of the books which have in view this goal, mention must be made at first of Semimicro Experimental Organic Chemistry by Cheronis;3 the subject matter and the system of the book makes it recommendable not only for undergraduate but also for graduate work. Micropreparative work can be done in many ways and with many kinds of apparatus: still, it is a practical and pedagogical experience that the beginner is in all cases deterred from availing himself of these procedures because of the multiplicity and complexity of the procedures available. A method is sound only if it can accomplish the purpose and if it can be made simple and routine without losing the requirements of precision. Consideration of this extremely practical aspect is apparent in the text by Cheronis, because he gives techniques to be carried out with such simple tools and methods that its adoption and its financial means are within the possibilities of every laboratory. The treatment has in view the founding of modern attitude to methodology. Another merit is the subject matter of the book; selection of the preparations indicates many years of personal exAnother text by the author in collaboration with Stein4 perience. is a guide for individual laboratory practice in general and qualitative inorganic analysis on a semimicroscale. Most known laboratory manuals devote in their recent editions a separate chapter to methods of experimentation on the microscale, Good trade in the welland examples are given for the practice. known handbook&l4 dealing with organic microtechniques, and an increasing number of copies published as the new editions, is also a sign of the great interest shown by chemists all over the world in MlCROCHEMICAL

JOURNAL,

VOL. V, ISSUE

3

ORGANIC

MICROSYNTHESIS

443

teaching and adopting the laboratory technique of work with small quantities of material. Valuable papers15-18 are to be found in the Microchemical Journal on the problems of teaching small-scale experimentation; similar questions were discussed at the international Symposium on Microchemistry. l9 Among the aspects of teaching, mention should be made also of the educative value of micropreparative work: only the size of human hand cannot be reduced among its tools, thus the chemist, in order to achieve the results of macro experimentation also on the microscale, is compelled to proceed much more prudently and carefully with his work. Consequently, practice in micropreparative techniques results in a qualitatively better working method which is made manifest in a more careful execution of the experiments, in better attention, development of improved ability for observation, and in easier overcoming of possible difficulties.

Examples of Microsynthesis Selected from the Literature Published in 1959 and 1960 The arbitrarily selected material summarized in Tables I-XII does not aim to give a complete coverage because of reasons discussed above. The examples contained in the tables strive primarily t’o illustrate the results which can be obtained when various processes are carried out on the microscale. Choice of the scale of the experiments was, of course, determined by given conditions in the majority of cases; however, a study of the literature reveals that research teams well acquainted with the technique of microsynthesis decided to work on the microscale even in those cases when they had ample quantities of starting material at their disposal. This is a proof to show the advantages of microexperimentation over macroscale work, as it was pointed out in the introduction of the present review. Naturally, the practicability of microsyntheses cannot be decided without considering the nature of the group of compounds in question. There are easily crystallizable compounds which can be handled without difficulty, such as the classes of steroids, polycyclic terpenes, the mainly organic polycyclic compounds, numerous classes of heterocyclics, and fortunately also several other groups of natural products; experimentation on the milligram scale is more convenient and usual with these materials. However, today publications can

5

2 A15-Androsten-3fl-ol-17-one -p .+ r-Phthalimidocrotonic acid 6 methyl ester 3 -~ Anthracene-2-carboxylic acid methyl ester E g Ai ist,olactone R Azulenecarboxylic acid j;

E ?: 6 sL3 g 3-Ethyl-Zvinylpyridine g trans-4,5-Dehydronormuscarin

:: $

n-Ergthro-2-amino-1,3,4trihydeoxy-butane-1,4-dibeneyl ether I-Fluoro-2(or -4- or 7-) -nitrofluorene Zierone semicarbazone (Evodia Me ,yana) 7-Methyl-4,6-pregnadiene-l7w 21-diol-3,11,20-trione-%l-acetate 2-Bromohexahydrosantonin

Gt,arting material(s)

Pd/BaS& Li;ZlH, Li.41Hd Li nlanxtc

200

120 48

PW,

100

6.01

214

181

200

Pd/SrCOr in benzene; chromstography on Florisil Pd/C ; chromatography on alumina RO? Ilane>- Ni

Osoaristoiil A-H?-clros?-llirth?~lazrllene

2,3-Diethylpy~~idine picrate Xormusca-in + allo Kormuscarin (105;) dndrostan-3@-ol-17-one r-PhthalimidobutyIic acid methyl ester S-Hydroxymethylanthracene

Hexahydrosantonin

F-Y02

818

620

1-Fluoro-2-(or -4- or -7-)-aminofluorene Khydroeierone semicarbazone alcoholate i&?vlethylcortisone acetate

PtOr

220

material(s)

wErythro-2-amino-1,3,4-trihydroxybutane

Isolated

Pd/C

Agent(s) and condition(s) used

___~

75

Amt. starting material, mg.

TABLE I Reduction

10

Good yield 100

-

165

410

lit?

3io

147

23.1

Amt. product, mg.

30 31

29

27 28

25 26

21

20

Refer. ence

4-Benzyloxybenzoic acid (carbony1 IlC) through acid chloride (SOClz) 5@-B-Norandrostan-3wacetoxy-17-one 3-Dehydrodigitoxigenin

HoY-

6a-Methylcholestane-6&ol-3one 4Aeachole&4-en perchlorate a-Nor-5@-cholestan-3-one (20 S)-3@Acetoxy-20-hydroxy5wpregnan-18-acid lactone (- 20)

161

70

428

146

30 a5 35

240

in THF

Li.41 [OC( CHa)a] SH

1. LiAlH, 2. Ac,O/P, 3. Pyrolize at 100” C. Isolation on paper chromatogram

LiAlH4 LiAlH, LiAIHa

2 I -rllotlo-O-:lcetate

3-Epidigitoxigenin From mother-liquid Chromatography on alumina: toxigenin

digi-

4-%cnz~lo~~l)r~laaldrh!-de (carbonyl 14C) as ,rz-~lit,ropherl~l~~~dra~o~~e

&Aldosteron

4-Aza-501-cholestane a-Nor-5@-cholestan-X$-o1 (20 S)-3g, 18,20-Trih~tIror?--j,-prc~gnanc

37 38

123 36 13

33 34 66

32

50

211

27

21 69 -

IGO

$ w

r 4 t;

“s

2

9

2

I2 z i; $

i;

z

Et

Quinolizinium perchlorate trans-9-Methyl-l~ethynil-laoxy-6-decalone 2.Nitroestrone 4-Nitroestrone 2,4Nitroestrone

cm-

Bisdehyd: o-cassaidin Protoemetine perchlorate

NaBH, NaBH, NaBH4

500

perchlorate

Quinolizine perchlorate trans-9 .Methyl-lp-ethynil-lol,6p-dioxydecalin 2-Nitro-17p-estradiol 4-Nitro-17p-estradiol 2,4Nitro-17p-est .adiol

Cassain Dihydroprotoemetine

23 300

110 56

16.0

46

44 45

42 43

41

40

120

1,3,5,6-Tetraacetyl-2,4-ethyliden-D sorbitol IX-0-acetpl-cannogenol

Rcference 39

material(s)

Amt. product, mg.

~

200

Isolated

~~~__

2-l)esoxy-n-ribitol

I (conlinued)

NaBHp; chromatography on IRA 410 Zeo-Karb ion exchanger 1. LiBHd 2. AcnO/Py 1. NaBH,; chromatography on alumina 2. AczO NaBH, NaBH4

Agent(s) and condition(s) used

31 340

120 85

19.5

400

2,4-Ethyliden-n-glucoron

Cannogenin

268

material(s)

2-Desoxy-n-ribose

Starting

Amt. starting material, mg.

TABLE -~

ORGANIC

MICROSYNTHESIS

447

material(s)

Cl-

Pyrolin

in chloride

HCl

bOOH peptide derivative

Bluoro~uma!

Pyridosine .\‘-oxide Sor-C-tosiferin-I

(‘IH

1,2-Dichloro-1,1,2,2-tetrakis(3,5-dichloro-4-methoxy phenyl)ethane Tetraacetyl- e-pyrromycinone

Starting

50-100

20

120 10

33

320

Amt. starting material, a.

e-

1. Zn/H,SO1 (55°C.) 2. pH 5 (iO”C.)

2. Zn

Zn/EtOH 1. HBr/AcOH

Isolated

material(s)

-..

c

ir

N I --

R-YH-CH2 r;TH, OH

+ \

/

Cl-

LX--OH

HS’

I>ihydrot,osiferinchl(~litlr

Pyridosinc HCl Nordihvdrotosifrl,ill

C-H,, *

HO

(‘ll,-OH

I ’

&WH

CH -CH?

CH,-CH,

2,3-Tetramethylen-9,1 O-diawtosyanthracene derivative

Tetrakis-(3,5-dichloro--L-met,hos.vphenyl-ethylene

I (continued)

1. Zn/XaOAc 2. Ac,O; chromatography on alumina

Zn/AoOH

Agent(s) and conditions(s) used

TABLE

-

37

57

323

71

5G

55 7

45

54

Reference

160

Amt. product., mg.

-

g

x 2

c

f m

100

18-I>imcthylamino-5,~pregnan-

Thioketal

CH~-SH

100

182 180

4

CH,-SH Thioketal Tet,rahydroambrosin

t

250 140

I

Thioketal fl!ffiTsH a-Vetivanone

BF:<

truns-Z-ilcetoxy-wtetrahydrosantonine CH,-SH

810

101

L)ihydrcdemethanol-aconinone

Y-OIlP

60

i

Raney Xi in dioxane

Raney Ni in dioxane

Raney Ni in dioxane

Wolff-Kishner reduct,ion Wolff-Kishner reduction Wolff-Kishner reduction

Wolff-Kishrier reduction

300

320

Fr( II)SO,

64.5

n-home-ketone

croa

I)ihydro-15,1&dihydroxyphllocladene I

Cyanidinc chloride

67

l8-IXmetl~yl:tmino-5~-prrgnanr

Guaian-O,lL’-elide

Vetivane

-

-

140

5-1

Uihydrodemethnnoldel~~drox~aconinc

3-~eos~-a-trtrah!-dro~:~frltoI~iue

45

170

15.8

o-Homo-phlloclndcne

Ci)OH

IIydroso-di(rynnitlino)-iron(IIT)

(continued)

65

64

62

61

59 60

58

Ketone

0

Thioketal

ArO

8

k

Starting

-

H

H

-

CHs

&Hz

SH

SH

material(

8)

160

Amt. starting material, mg.

AcO

Isolated

H

materials(s)

~_~_____

db3p,l7@Diacetoxy-l%nor-n-homoandrostane

I (conlinued)

Raney Ni in dioxane

Agent(s) and condition(s) used

TABLE

115

Amt. product, mg.

67

Reference

ORGANIC

MICROSYNTHESIS

451

material(s)

from above

80

HIOh ( +5”C. NaBH, HI04

157

(60%)

HClO,

50

38-Acetoxy-14&15fl-oxidoetiansav methyl ester a-Methyl-n-glucofuranoside Aldehyde from above Khellactone

HCIO,

)

1540 30

O2 (NaOH)

59 500 100

Ag,O ( NaZS04) MgOz in chloroform CH,N,; subsequent chramatography on alnmina MnOn MnOt K3[Fe(CN)6] pH 7.5

20 30

Agent(s) and condition(s) used

Maculosine

l,nns-Dee-%ene-4,6,8-triyn-l-01 l-i-Hydroxycodeine 4-Oxp+methyl-3,4-dihydroquinazoline 2-Thiohydant,oin

Acidic product

2-/2,5-Dihydroxyphenyl/indole Methyl cinnabarin

Starting

Amt.

starting material, w. Isolated

material(s)

Octahydro-4,4’-dioxo-2,2’-dit.hio-1,5’diglyoxalinylidene 3-Ethyl-4-hydroxy-6.i-meth~lwedioxy-2-quinolone X@-Acetoxy-15-keto-14wetirtnsuv methyl ester Aldehyde derivative ru-Methyl-n-xylofuranoside Dialdehyde

truns-Dec-2-e~~e-4,6,8-tri~-~~-l-:~l 1CHydroxycodeinone 3-Methylquinazolone (4)

2’-Indolyl-l,~bcnzoq~~i~~o~~e Methyl cinnabarin ( rwovrred) + acidic product 1,9-dimethox~wr~~on~~l-2-aminol~h~~roxazin-3-onr

TABLE II Oxidation

78 7!)

35.2

Si

76

324

73 74 75

24 7”

Reference

87

30

7

350

23 350 29

2

18.5 25

Amt. product, w.

2 c1 iii

g

.P

5,6-Dehydrokavaine 3-te&Butylcyciohexanol 2-Hydroxy-3-phenylcyclohexanone

?W,

500

3,4-Diphenylcyclopentanonel,&dione 5-(8-Carboxyoct-1-yl)-2-(8carboxyoct-1-en-1-yl) furan Oxidation product (from above) 3-Chloro-5a-androsta-2-ene

123 240 350

100

94

240

4.2

3,5-Dimethylaniline

Cyclohemiketal

2,3-&co-5+androstane-2,3-dioic

raphy IiRlnOl

CrOa [also with HIO, and Pb(OAc),J

suberic

Paper chromatog-

+ CBenzoyibutanoic

acid

Benzoic acid Nert-Butylcyclohexanone Starting material

acid + sebacic acid

3 -diphenylbutyric

( )sidation product

+1x0-@,

acid

d,f-3,11-Dioxo-1%hydroxy-hJ-etien acid (20 + 18) lactonc 2,6-Dimethylbeneoquinone (1,4)

Potassium nitrosodisulfonatel NaHzPO, I
HIO,

acid

-

25

208 60

(continued)

85 86 87

84

83

84

20

52

81

80

-

200

2 1

2 r c 2 s w

-&

2

z

FJ

8 3 z Fi

$ f

CH2OC(CcjH,)s

material(

84 500 500

Dihydrocaloptropagenin 7,7-Dimethylcholesterol 7,7-Dimethylcholesterol

240

51

300

123 100

8)

Methyl-9-oxo-lo-oxa-ll-hydroxy-S-nitrohydroabiate ( - )-Dihydrosedinine Xysmalogenin

3-Trityl-oxymethyl-cyclopentan01 fi-(p-Methoxybenzoyl)-propanol-1

h

OH

Starting

Amt.

starting material, mg.

II

CrOa Cr03/H2S04 (“Kiliani-Losung”) CrOa (AcOH) CrOa with Al( 0-i-CaH, )S

CrOs in AcOH

CrOt

CrOdPy

Agent(s) and condition(s) used

TABLE

Isolated

CHpOC(C,jH&

material(s)

derivative

Stable keto acid (C&H2,07) 7,7-Dimethylcholestenone 7,7-Dimethylcholestenone

Diketo-dihydrosedinine Xysmalogenon

Octahydrophenanthrene

@(p-Methoxybenzoyl)-propionic

3-Trityl-oxymethyl-cyclopentanone

(continued)

acid

Amt.

199 132

-

110 7 92

33

280

product, w.

93 93

29

234 90 91

89

88

Reference

ORGANIC

MICROSYNTHESIS

455

material(s)

adduct

// YOH---0-W-CH2-C&l5 F

; Dihydroceroptene m IX-Gacetyldihydro derivative g of a plant quinone (CeiH&) CL

-5

2.F

Isonorlobaridone z c g Retroionon-2,3-dinitrophenylhydrazone 8 trl

4 crystalline

Ethusin (200 mg.) + maleic anhydride

Starting

160 900

317

03 03

1. 2. 1. 2.

106

cleavage)

Isolated

material(s)

Iknethylmalonic acid + p-phenylpropionic acid 2,5-Uiacetoxy-3,4dimethylphenylacetic acid

Acetaldehyde (as 2,4dinitrophenylhydrazone) n-Butyraldehyde-2,4-dinitrophenylhydrazone / Formaldimedone + ethylidendimedone

II (continued)

OS in AcOH Zn O3 in chloroform Dimedone

(reductive

0,

Agent(s) and condition(s) used

50

Amt. starting material, mg.

TABLE

30 21

28

73

105

104

103

102

24 3

101

Reference

-

Amt. product, mg.

2 $

2

e

0 Lcc

Starting

material(s)

g trans-Stilbene-2-carboxylic acid 3 4,5-Tetramethylen-3-methylz thiasolone hydrazone HCl Ir 2 16p-Methyl-A4-19-norandrosten ol-/l’ib/-one-(a) .F 3 \ PH

8 r

~-

500

1000 362

Amt. starting material, mg.

HCOOH/H&& IXmethylaniline (NH4)&Os NaC104 Jones reagent +

Agent(s) and condition(s) used

TABLE

+

material(s)

b,;H,

y-Lactone 2- { [ I-Dimethylaminophenyl-( 4)] -azo} 3-1neth.vl-4,5-tetramethylenothiazolium perchlorate 16p-Methyl-A4-19-norandrostendione(3,17)

HO%

derivative +

Isolated

Isocoumarin

II (continued)

350

300 385

453

,4mt. product, mg.

1 I-1

112 113

Reference

ORGANIC

MICROSYNTHESIS

459

materia.l(s)

3 co

E

g z m 5 9 r 2 Farnesiferol 2 6-Methoxycarbonyl-2-methyl-1,4z naphthoquinone :& 3@-Acetoxy-5fl-etien-( 14)-acid 2 methyl ester .r C 3@-Acetoxy-A’6-pregnene-29-one

5-en-l8-oic acid (18 -f 20) lactone ad-l&29-Cycle-3&20E-dihydroxypregnene Vitamin D3

% z (2OR)-3@,29-Dihydroxy-pregn-

Gitoxigenin

Starting

C&H&. COOH Chromatography alumina HZ02

358

591

72 620

1000

-41 tert-butoxide/ acetone -41 tert-butoxide acetone C,Hs. COOOH Hi-02

Al(O-i-&Hi),/ cyrlohexanone; rhromatography on alumina Al(O-i-C&H,)3 ryclohexanone

ilgent(s) and condition(s) used

190

90

554

Amt. starting material, mg.

TABLE

+

on

II

Isolated

1601,liwEpoxide

derivative

537

283

14ol,l&-Epoxide

derivative

68 400

Monoepoxide derivative Epoxide derivative

46

310

30

derivat.ive

material(s)

Amt. product, mg.

A’-18,20-Cycle-3%keto-20E-hydroxypregnen Iso-keto-vitamin D3

30x0

:GDehydrogit,oxigenin

(continued)

127

126

124 125

123

122

121

120

Reference

50

1000

derivative

1,2,3,4l>icyclohexanofluorene Se, 340-350°C.

PM*

Pd/asbestos Pd/C, 265°C. Pd/C (loo/,), 260 270°C. Pd/C (5y0), 250260°C.

750 115 113

Dihydropteridin

Pd, 190-195’C.

Agent(s) and condition(s) used

20

400

material(s)

Dihydropyrid-[3,4b]-indolel(2)-one 1,7-Dimethyloctahydroindol Dysoxylonene monoepoxide 1,2,3,4Tetrahpdro-lO-ethglphcnanthrene Pleurospcrmine

Starting

Amt. starting material, mg. Isolated

N

N

,~~s;~+\SH2

s)

L)-An~ino-6-h,vdroxypteridin-8-~:wl)oxamide 1,2,3,4-l )ibenzoflriorcrw

H:N’

OH

1,7-Dimethylindol Cadalene g-gth~lphrnanthretle

9

materisl(

Pyrid-[3,4b]-indole-l(2)-one

TABLE III Dehydrogenation

400

20

500

Amt. product, mg.

(continued)

135

134

130 131 132

129

Ileference

(‘H)

material(s)

L I)odecahyd:,o-12-methyl-Y-oso2 phenantht ene z 4 NaBH( ;c e I)-Hydroxy compeuud $ Crataegolsav methyl ester diacetate

Starting Isolated

material(s)

ester di-

136

18

325 137

Reference

Amt. nroduct. mg.

70 464 methyl

____~~

205 500

1-Methylphenanthrene Dehydrocrataegolsav acetate

I 2-Methyl-4,5-diethylpyridine

(con&ued)

20

Se, 220-230°C. SeOs ( AcOH); chromatography on alumina

Se

III

Agent(s) and condition(s)

TABLE ~__

218

400

Amt. starting material, mg.

-~

P

5.4

alkaloid-H

Calebassen

17.4

300 300

1000

300

125

ace-

Rhodoxanthin

Indole base A

0-Dimethylsophorol

6ol-Fluorohydrocortisone tate Sarcostene

MnOt; chromatography on ZnCOI/ Celite 535 AcOH/Py, 125°C.; paper chromatography

Se& I’d/C + cinnamic acid Zn dust, 300°C. ( N2)

SeO?; chromatography on alumina SeOz

(picrate) + (picrate) i 3-ethyL2methylindol [Zeaxanthin + 1 rhodoxanthin Calebassen alkaloid-F

3-Ethylpyridine

f Jacob’s compourld + 1 fluor ene derivative Dehydro-O-dimethy-lsophorol tt

F-Fluoroprednisoloneacetate

8.5 2.3

1.4 35

4.6

5 40 40

8

150

I

I , , / I

’

270 30 253

Dihydrorobinetin dZ-Reticulin perchlorate 1,3-Diphenyl-3-aminopropanol(1) 3-Iodo-4aminopyridine

(selertirc

,-

255

167

Chromat,ogmphy alumina

195 + 25.4

161

750

163

162

157 158 159

160 10 118

140

155 156

13

15-1

153

123 37

152

40

OHMorphine-S-n~ethyl-L’C. (crude product) + Pawformaldehyde :xddurt

f-Y

Tetramethyldih>-drorobinetin dl-Laudanosin 1,3-Diphenyl-3-dimrthylaminopropanol-( 1) I-Methyl-3-iodo-l-nminop!-ridinim~l iodide

O-:rlkpln-

:Icid hcxamethyl

520 on

20 120

( - )-Farrerol Crinamine

p-Phenyl+( cu-piperidino) ethyl chloride Kormorphine + paraformaldehyde-1%.

CHJ/NnH in dioxane; chromatography on alumina CH2N2 1. CH,SO&l/Py 2. CH30Na; chromatography on alumina (C&)3()4 CHzN2 1. CHzO/IGCOa 2. LiAlH, CHJ

45.4

500

O-Methyl-drl~orirle tion)

(CaH&CCl/Py

150

Methylmatteucinol O-~~ethyl-ol-isocrixl:~i[lillr

Dihydrothelrphorir ether 6-Trityl derivative

(CHs).JiO,/(IWO, + PY)

50

Thelephoric acid tetramethyl ether fl-Benzyl-2,3,2’,3’-tetraacetyl4’,6’-benzal maltoside Delcosine

g Aminopterin + paraformaldehyde 2 .r Mtilbenyldibenzylarsine

2

from di-

+ CHzO

material(s)

$ Compound obtained c) hydrocaranine $

Norisocorydin

Starting Ni

PH 2 CzHbBr

100

CHzO/HCOOH; chromatography on alumina

Raney

Agent(s) and condition(s) used

200

95

470

Amt. starting material, mg.

TABLE

derivative

CHz-“,l

Isolated

material(s)

4Stilbenyl bromide

ethyldibenzylarsonium

Nr,,-Hydroxymethylaminopterin

N-methyl

Isocorydin

IV (continued)

72

120

79

322

Amt. product, mg.

167

166

164

Reference

P

201

(CH&NB&

N-Trimethyll)oraeane

HI (Nz scrubbing gas; liquid N) coolant) BF3 ethereate; chromatography on alumina L/G&NH,

106

439

HCl 1. HBr 2. AczO HBr in AcOH

40 150

Copaene 3p-Acetoxy-15p-bromo-16& 17p-oxido-5a-androstane I 7a-Chloro-21-acetoxy-A4pregnene3,11,20-trione 14CHz0H

1. Brp 2. Li#Oa + LiBr Bb Brp in Ccl,

Isolated

N-Trimethyl-p-monoiodoborazane

(CH&NBHJ

6@-Fluoropregnan-5wol-3,20-dione

(91%)

444

220

(100%)

470

334

35 168

47 26

51

4-Bromo-5.hydroxy-3-nitrothionaphthene 4-Bromo-17wpregnanol-3,11,2-trione 5-Bromo-deoxyuridine-5’-phosphate calcium salt ( - )-Cadinene dihydrochloride 3p,16@-Diacetoxy-15p, 17~dibromo-5olandrostane 4@-Bromo-17wchloro-21-acetoxypregnane-3,11,20-trione ‘%H,I

50 80 48

material(s)

Amt. product, mg.

Tetrabromide derivative Dibromide derivative

A4-Androstenone-(3)

Halogenation

NBS(Cr,H,COOOH) NBS

43

110 54

342

Agent(s) and condition(s) used

V.

41.3 29

17-p-Acetoxy-lcu,2wmethyleneandrostanone-(3) 29-Isofucosteryl acetate 2a-Acetoxy-8a,l3-oxidolabd14ene 5-Hydroxy-3-nitrothionaphthene 3~,17~Pregnandiol-11,20-dione Deoxyuridine-5’-phosphate

Sta, ting material(s)

Amt. starting material, mg.

TABLE

327

178

172

177

175 176

173 174

171

169 170

168

Reference

material(s)

Ac.&/SaOAc 1. HBr/AcOH 2. Ac&/NaOAc Stearoyl chloride/ PY

146 500

400

Go-Phytosphingosine base

N-Stearoyl-C~~-phyto6l’hilyoait~e hydra base

L-+.4, Monoacetnte derivative 1,5-Anhydro-3-0-benzoyl-4.6-O-lwnzylidene-2-0-tosyl-D-glwitol [Hexaacetyl-neoinoeil, + Hexaacetyl-alloinosit + I Hexaacetyl-dZ-inosit 5,7,8,4’-Tetraacetoxyisoflavour 5,7,4’-Triacetoxyisoflavone

CH,=C=O C~H&OC~/PJ

derivative

nn-

diphenyl-

material(s)

Monoacetate

5,7,8,4’-Tetrahydroxyisoflavone Trimethylgenistein

anhydro

Isolated 2-Hydrox~cvclohesatlollr acetate

Acylation

Ae&/Py; chromntography on alumina

Ac& /Py

120

100 50

400

IXphenylacetyl chloride/Py

120

diol

OH

80

Agent(s) and condition(s) used

VI.

o-Quinoline derivative 1,5-Anhydro-4,6-O-benzylidene2-0-tosy1-D-glucitol Kondurit-E-epoxid J. Ba(OH)z IXol derivative

Tricyclic

OH

w

2-Hydroxycyclohexanone

Starting

Amt. starting material, wt.

TABLE

50

10

50

300

20 220

-

230

140

Amt. product, mg.

186

184 185

183

181 182

180

Reference

43

6-Hydroxypiperonal

CHO

50

OCH3

COOH

160

1305

1141

65

125

25

380

G-Methoxycumaran-5-carboxylic acid +

(2)

I-Hydroxy-3-aminopyrrolidone-

Carbobenzoxyglyoine + N-Carboxybenzoxyserine

Carhobenzyloxy-glycocol + 38-&Tetraacetylglucopyranosylcitosin + ,Y,.Y’-dicyclohexyicarbodiimide

Benzyl-glycyl-alanylphenylalanine OC?Hj -

in ( CHa)J

SCXl?

1. IXimidazolglcarbony1 + t.riethylamine in THF 2. Hydrogenation on m/c CH,=C=O

CL, \

Cl

HCl

Cumaran

phenyl

ester derivative

qpl-yp

l-=icc,tos?--:3-:rlninopyrrolidone-(2)

0-glyq-lserine

SF.-Carbobenzyloxyglycyl-3~-d-tetraarrtyl-glllcopyranosylcitosin

Benzyl-carbcthoxyglycyl-alanylphenylalanine

328

180

I 20

188

xc;/

5.5

187

w

acid

Ac,O/Py

99

(87%)

Isolated

material(s)

diacetat’e

(picrate)

17a-Bromo-11-dehydrocorticosterone acetate

Methyl( f )-7-oxopodocarp-8-en-16oate 3&Formyloxy derivative

Albigenic-lactone

Viridiflorylsupinidine

Pentaphthalylglycyl-9@glucopyranosylguanine

VI (continued)

1. HBr 2. AczO; chromatography on alumina CHzN

SOClz

HCOOH

1

Agent(s) and condition(s) used

500

92

7-Oxopodocarp-8-en-16-ok

3@-Hydroxy -16&bromoandrost5-en-17-one 17a-Bromo-1 l-dehydrocorticosterone

300

Albigenic

2 0 2 -r 8 r -5 E 3

330

acid

Viridifloric

g

300

iacid

Supinidine

8)

100I PY 500 1

material(

9@-&Glucopyranosylguanine + Phthalyl-glycyl chloride

Starting

Amt.

starting material, mg.

TABLE

60

475

52

220

50

-

Amt. product, mg.

196

195

194

193

192

191

Reference

2 iz

8

P

z 0

’ OH

Telocinobufagin Antiarigenin o,o’-Aminobenzamidobenzamide Anthraquinonedioxime Ethyl isocyanate 5-Methoxy-4-ethoxyphthalic acid

d,C18-Nor-n-homo-A9(1~)-androstene-3,17a-diol 5&6&Oxidopregnane-3&20@diol 3&Tosyloxy-19-acetoxy-5aetianic acid methyl ester

HO cfi@

OH

derivative

238 710 100

Anthraquinonedioxime diacetate iV-Ethyldiacetamide N-Methyl-5-methoxy-4-ethoxyphthalimide

Mono-0-acetyl derivative Di-0-benzoyl-anti-arigenin o-Nitrobenzoyl derivative

301,19-Diacetoxy-5ol-etianic ester

1. KOAc in dimethylformamide 2. AczO/Py; chromatography on alumina AczO/Py ceHPcocl/Py o-Nitrobenzoyl chloride/Py AczO AczO 1. CHaNHz 2. 180”

75

7 50 250

5&6p-Oxidopregnane-3&2O&diacetate

Ac,O/Py

40

acid methyl

Diacetate

AcnO/Py

OH

d@

150

AcO

OAc

252 750 -

3 60 160

25

40

70

202 203 319

200 201 329

199

198

197

E

8

3

z

5 E

g 0

material(s)

OH

g 2-Methyl-Znitrosodihydroresorcine 3 2-0-Tosylkhellinone E 3-Vinylkinuclidine-8-carboxylic acid ethyl ester 9 w

l-Ethylcyclohexane-l,Pdiol-lz carbamate i;8 Palosin (from Aspidosperma polyneuron) i2 g ,%Oxy+(Cchlorophenyl)6 $ ,%Oxy+(Pchlorophenyl)propionitrile 5 propionitrile

OCONH?

0 C&IS

Starting

KOH/HtOz

500

Khellinone 3-Vinylkinuclidine-&carboxylic

KOH Hz0 (20”)

50 310

derivative

Diketo

0

NOH

CHa

KOH

C./f monooxime

COOH

p-Oxi+(CChlorophenyl)propionic acid amide

trans-4-Chlorocinnamic

acid

acid

25 180

70

400

350

209 210

208

206

206

205

-

Propionic

acid

204

Reference

-

OH

OH

GH, Gf

material(s)

Amt. product, mg.

l-Ethylcyclohexane-1,4diol

Isolated

300

60

H2SOI/H20; paper chromatography (R, = 0.31) KOH

LiOH

Agent(s) and condition(s) used

1038

10

Amt. starting material, mg.

TABLE VII Hydrolysis

( - )-Lunacrine methiodide Psilocybin 2,7-Dimethoxynaphthalic anhydride

l-p-Nitrobenzoylazaridine 6-Isobutyl-5,8dihydrourwil

50 31.6 40

384 1.50

30 400

Periplanetin Tct,rahydrocumarin

derivative

800

NaOH H,O (15”) HCl/Py (Ether sion)

fis-

H4W4 in MeOH HCl; chromatography on Ambrrlite 1114-B

Emulsin enzyme NaOH (2s)

HCl in acetone; chromatography on SiOp H$Oa (1X); paper rhromatography

200

in acetone

TosOH

AcOH (loo=‘)

120

21

Penta- and hexnsaccharides from Lychnis dioica

&I-Aldosteron-3-monoketal21-O-acetate Desoxycorticosterone dirycloethylene ketal Lukundjoside

30 83 i 70 HIOa oxidation

20-monocyclo-

( + )-Lunacridine I-Hydroxy-w-A-,.V-dimethyltryptamine %,T-IXhydroxy derivative

Subsequent Benzoic acid Methylglyoxal-w-( &nitrophwylhydrazone) LV-2-methoxyethyl-p-nitrobrllxamide I.-p-Homoleucine

Five fractions

/98 193

I>esoxycorticosterone ethylene ketal Bipindogenin

dl-Aldosterone-21-O-acetate

30 11 37

150

94

81

14

219 207 220

215 216

214

&

AcO-‘3%

h

HO

acid derivative

If1

r Marinobufangin c ;; 1-Methyl-4-nitro-2-pyrrolecarboxylic acid amide s w

v

2 5a-Etianic r

g

i2

g

5 s

material(s)

38Methyl-3or-hydroxy-178acetoxyandrostane &,7,7-Trimethyl-3p,6@-cholestanediol 3-monoacetate COOCH3

Starting

300

30

(97%)

AcOH; chromatography on alumina POCb/Py

SOC12/Py

SOCI,/Py

20

12

HCOOH

Agent(s) and condition(s) used

250

Amt. starting material, mg. Isolated

material(s)

derivative l-Methyl-4-nitro-2-pyrrolecarbonitrile

A4-3-Keto

0& ’

19-Acetoxy-5a-etien-(9,10)-acid methyl ester

k

COOCHJ

6q7,7-Trimethyl-3~acetoxycholesterin

3-Methyl-17@-acetoxy-2-androstene

TABLE VIII Elimination

5 180

7.7

13

160

Amt. product, mg.

223 224

222

93

221

Reference

144

Gal-Fluoro-l’i;wbromoprogesterone

240

Zn/AcOH LiCO3 + LiBr in dimethylformamide, chromatography on alumina LiCl in dimethylformamide; chromatography on alumina

164

Methyl-3-chloro-3-dcoxy-a-Dgulopyranoside &,6a-Dichloro-3@acetoxypregnane-20-one

980 350

Zn dust/AcOH

1950

3p-Benzoyloxycholestcne

2-Bromohexahydrosantonin 2qt$-Dibromo-4-methyltestosterone acetat.e

CHrCHMgBr; chromatography on alumina Alumina (activitate 1) NaOH

500

34.60-Diacetoxy-Sa-hydroxyandrostanc

200”

800

cis-m-Acetoxyranhydride

OAc

1,3)

Ga-Fluoro-16-dehydroprogesterone

AZ-Olefin derivative A’,4*6-4-Methylandrostatrien-17p-ol-3one acetate

Methyl-3,4-anhydro-u-n-galactopyranoside Pregnenolon acetate

Chblestadien-(

l-Methyl-A2~4-cyclohexadien-l,2-dicarboxylic anhydride 4or-~~~etoj;y-:u,Gu-oxidoaiidI-us:ialle n

70

465 130

190

101

63

79

380

(continued)

232

230 231

229

228

227

226

225

0

0

i-s:-

250 , Xl

CH20AC

materials

-g 2 6-Methoxytriptamin glycolaldehyde ” 1 M’ I-Hydroxymethyl-,%carboline & derivative 2g Stipitatonic acid W

c: !s

g 4@-Bromo-l7a-chloro-2l-acetc oxy-3,11,2O+ioxopregnane E 8 E 2 4a-Bromc+cholestane-3-one

Fz

s F5

Starting

VIII

HJ’O4 (90%) Heating in H& ( -co21

71

I. Semicarbazide 2. Pyruvic acid 3. NaI in dimethylformamide Collidine; 175-18OW. (Nz); chromatography on alumina

Agent(s) and condition(s) used

50

33

loo

322

Amt. starting material, w

TABLE

’

c=o

~OAC

material(s)

l-Methyl-7-methoxy-3,4-dihydro-ficarbolin (Harmalin) Stipitatic acid

Cholest-4-en-3-one

11,20-tdoxopregna-

\

LIiP

0

Isolated

A4nr6-21-Acetoxy-3, dien

0

(continued)

30

274

Amt. product, w.

233

17i

Reference

2

material(s)

i

*

rc’s.syrL,cis-n-homo-~u(“)-lOmethyl-3,14,17a-triketosteran

0

j,7,&TrihydroxyHavatllone H-Methoxyisoflavoue derivntive Sinostroside (II&H, l&k&o) 1)ihydrosandaracopimaric arid

trarts, Iruns, cis-3,+IXmethoxyryclohexane-l,%dirarbosylic acid anhydride Nrpetalic acid isomer [a]

Starting

Isomerization

(Nz)

Al203 HCl (-5°C.)

1. CHsNz 2. NaOCH, 3. CH2Nz NaOH (EtOH) NaOEt,

(S%)

Agent(s) and condition(s) used

IX.

240-250°C.

200 AcOH

10 73

3 200

5

200

w.

Amt. starting material,

TABLE

acid isomer

&s-Isomer

[b]

material(s)

Caudostroside (ll-keto,lZwOH) A’3-Dihydroisopimaric acid 0

cis, anti,

ris

ris, onfi, truns

5,6,7-Trihydroxyflavanone 6-Methoxyisoflavone derivative

Nepetalic

cis, trnns,

Isolated

and Rearrangement, -

4

40

5 58

(cooltinued)

242

240 241

238 239

-loo

237

236

Reference

5

100

Amt. nroduct, mg.

478

0. KOVACS

MICROCHEMICAL

JOURNAL,

VOL.

V, ISSUE

3

CH,

Spiro compound

NHd:=NH

C-NH

:? NaOCH8

H~SOI (6 drops)

100

400

AcOH

NaOTs/NaOAc, 110-120°C.; chromatography on alumina 1. IJPy (PhilipsAgar-Photolamp) 2. 3,5-Dinitro-4methylbenzoyl chloride/Py 210°C.; chromatography on alumina Ac20/HClOa AcOH

OH-

500

200 500

750

lGol,l7~,Kpoxy-17@-chloro5wandrostane 2-Phenyl-o-quinol acetate cis-9, IO-Dihydro-9, lo-phenanthrendiol trans-9,10-Dihydro-9, lo-phenanthrendiol Pristimerin

30

10

600

ketone

CHZ

Precalciferol-3,5-dinitrobenzoate

Corotoxigenin

Exomethylene

ti

C=O

YH3

248 249

460 41

9-Phenanthrol Rearrangement

2-Amino-4-hydroxybenzo[g]pteridine

OH

250

247 248 90 450

2,6-Diacetoxybiphenyl

43

84 37

16-Keto-17@chloro-(5a)-androstane

product

246

245

24.3

425

244

-

Tachyst,erin:-3,5-dinitro-4-methylbenzoate

3~-Hydroxy-16-methyl-A16-pregnene11,20-dione 17~Corotoxigenin

ti

CH3 c=o , CHs

480

0. KOVACS

MICROCHEMICAL

JOURNAL,

VOL.

V. ISSI!E

3

material(s)

.Y(a)-methylnorgelsemine bony1 methohydroxide

.I-,.V,.V’,,V’-Tetramethylholarrhimine

X-Methylneosamanonol methylate I k-N-methylrhoeadin

car-

iodo-

2-(2-Methoxy-3,4methylenedioxyphenyl)-3-nitrofuran SCarboxy-&[3 .3 0) -ortarw tj,ass-2-Aminocycloheptanol %Phenylp.yridine+carbosylic arid S-~Iethyl-Cuza,dp-~llolrst:tlle methiodide

Starting

48

200

300

260

245

129 500

16

Amt. starting material, mg.

1. AgtO 2. 190-250°C. 1. CHJ 2. Ag,C 3. 150°C. 1. CHJ 2. AgzO 3. Ba(OH), 4. 195-200°C. 150-190°C.

KOH (2 drops H,(I) (230”) cc. H&&/HN3 NaNOJAcOH 1. SOCI, 2. NaN3 150-200°C.; chromatography on alumina

Agent(s) and condition(s) used acid

Isolated

material(s)

octane

,~~(a)-methylnorgclsrmine

12,20-Oxidopregnn-3,5-dime

l)es-des-rhoeadin

carbinol

material + 3-Dimethylamino-:i,5-seco-A-norcholest,-5-enr ties-Base

Start,ing

3-Amino-cis-bicycle-[3.3.0] Hexahydrobenzaldehyde 3-Amino-2-phenylpyridine

Salicylic

TABLE S Degradation

5

i8

261

263

260

259 400

2T 132

257 258

256

Iteference

106-

4.8

Amt. product, w.

B g 4

Fz

7-Y g z z

_

z

material(s)

3-Hydroxy-4sulfolene 1,3-Dimethylbarbituric acid + Aniline + Ethyl orthoformate Crude 4(2-Tetrahydrothienyl)butanol Isatin + Phenyl phenacyl thioether Hydroquinone monomethyl ether + Malonic acid derivative Syringaaldehyd-(carbonyl I%) + Malonic acid cis and tram+Tetramethylbutadien + Malcic anhydride

Starting NaOCH3

196

600 217

2406 351

457 650

294

Aniline

300°C.

KOH

(2 drops)

-

Isolated

material(s)

3,4,5,6-Tetramethyl-1,2,3,4-tetrahydrophatic anhydride

Sinapinsav-(3-‘4C)

3-Benzyl-4-hydroxy-6-methoxycumarin

2-Phenyl-3-phenylmercaptocinchonine acid

Bicycle- [4.3.O]nonane-1-thianium (picrate)

5-Anilinomethylene-1,3-dimethylbarbituric acid

3-Hydroxy-4-methoxysulfolane

TABLE XI and Condensation

Agent(s) and condition(s) used

1 ml. t 100 HCl(120”)

460

400 780

Amt. starting material, mg.

Addition

(96%)

400

402

850

236

150

1200 (94%)

130

Amt. product, mg.

271

270

269

268

267

266

265

Reference

2 63

8

?

ORGANIC

MICROSYNTHESIS

OAc

-,,H

CL

W,j,,,CHO

H

2 l,&Bis( 4methoxyphenyl).F butandione-(2,3) 2 .r .5 Z %-Oxy-3-ehloro-tetrahydro2 fllran s w +

> r i 9 3

3 C* isomeric mixture of hydrinz daneaeetaldehyde dwivat,ive 8

E

g

s s

material(s)

5’-Benzoyl-2’-oxgchalcone

Starting

984

144

509

300

Amt. starting material, mg.

1. Triphenylphosphine isoamylidene 2. Ac&/K&03; chromatography on alumina CcHsNH-NH, in AcOH -

HeSO4 (10%)

Agent(s) and condition(s) used

TABLE

XI

Isolated

/ CH = N--CBH~

CH-Cl

(C&)2

I

OH

Osazone

Olefin derivative

bAC

H

6-Bcnxoylflavnnone

(continued)

material(s)

144

2%

200

Amt. product, mg.

281

280

&79

Reference -

g 2 8

0

$ +

P

Tosyl-a-Lglutamylglycine

Ket,onitrile

C

0

CN

Aniline 2,6-Diethoxy-3,5dichlorobenzoquinone-1,4 -IEthyleneimine 5-lNit,ro-2-hydroxyacetophenone -t Cinnamic aldehyde l-Methylflavilium perchlorate + 4-Methoxybenaopyrilium onitrobenzenesulfonate 2--Methyl-&triAuoromethylsulfonylbenathiazol f p-1)imethylaminobenzaldehyde Pyridoxal ph0sphat.e azine + Hydrazine hydrate 4Styrylbensil + Benzaldehyde.

770

100

250

750

130 237

200

132 640

200 181

746 500

-

-

Phenol/HBr AcOH

NaOEt

AC&

AC& (1OO’C.)

in

hydrazone

~5,1a,(17)-3,3-Ethylenedioxy-18-noretidiene carbonitrile Tosyl-L-pyroglutnmylglycinr

2,4Diphenyl-5-[(stilbenyl-(4)limidazole

PyridoxaM-phosphate

2-p-DimethylaminostryM-triAuoromethylsulfonylbenathiazol

4-[( r-benzopyraniliden)-methyl]-2phenylbenzopyrihum perchlorate

derivative

500

56

5Oyc

159

130

300

150

400

2,6-Diet,hylenimino-3,&dichlorquinone

w-Cinnamylidenc

902

Schiff base

290

289

288

287

286

285

284

283

282

de-

ii

o-Benzoylbenzoic(carboxyl‘%)acid ?r+ 1-p-Phenylbenzoylnaphthalene -4 8 5 ;; Kogagenin diacetate

2$

Hexahydrophenanthrene rivative

4

2

2-Amino-4,6-dichlorophenol + 2-Hydroxynaphthoyuinone-1,4 9

Starting material(s)

AlCL/NaCl (120130°C.); chromatography on alumina COClJPy in chloroform ( -15’C.); chromatography on allrmina

500

850

Trimethylbenzylammonium hydroxide in o-xylol (142’C.) HzSOa (SO’C.)

A&H; chromatography on alumina

Agent(s) and condition(s) used Iso!ated material(s)

(25d)-Spirostane-16, 20, 301,Sp-tetrol 1,5carbonate-2,3-diacetate

60

lo-Phenylmesobenzanthrone

300

130

derivative

210

Amt. product, w.

Labeled anthraquinone

2,3-Benzphenanthrene

CH30

3,4-Benz-6,8-dichlorophenoxaxone-2

XI (continued)

640

708) i 348)

Amt. starting material, mg.

TABLE

160

294

293

292

291

Reference

Kotarnon + Aniline Picene-13,lCquinone + o-Phenylenediamine o-Nitrophenoximalonic acid diethyl ester 2-Methyl-3-carbethoxo-4,5dioxinaphthofuran + o-Phenylenediamine 3,4-Dimethylthiazolon(2)hydrazone HCl + p-Nitrobenxaldehyde Threo-4-p-Nitrobenzamido-2pentyl methanesulfonate 1,2-Bis(2-anthraquinonecarbonyl)hydrazine Furyl-2P-chlorovinyl ketone + p-Nitrophenyl hydrazone p-Acetaminophenyl hydrazone

Pyrene-4,5-quinone + o-Phenylenediamine 4-Methoxy-2-hydroxy-3(2’hydroxyethyl)quinoline

200 400

200

500

605 800

250 720

500

50 297

0.9ml. 50

1030

200

8

17

I

i

1 1

1

7

I

-

(absolute)

C.)

H,P,O,a (114-120”

EtOH

KOAc in EtOAc closed vessel) H,POd

AcOH

Zn/NH,Cl (20°C.)

in

(in

in EtOH

1. NaH 2. Tosyl chloride tetrahydrofuran

AcOH

7 ) KOH

J

derivative

3-Furyl-(2’)-l-(p-nitrophcnyl)-pyrazole 2-Carbethoxy-3-diethylaminoethyl-5acetaminoindole

cis-2-p-Nitrophenyl-3,5-dimethyl-5,6dihydro-1,3,4-oxazine 2,5-Bis(2-anthraquinone)-1,3-oxadiazole

3,4-Dimethylthiazolon(2)-(p-nitrobenzene)-azine

2-Methyl-3-carbethoxyquinoxalino (2,3e)naphthofuran

4-Hydroxy-2-carbethoxy-1,4-benzoxazin-a-one

Phenazine

Kotarnonanil

Dihydrodictamine

Pyrene-4’,5’,2,3-quinoxaline

260

200

490

530

240

l~vx

120

50

710

100

19

305

304

303

302

301

300

299

298

297

296

295

5 Mercury compound 3-Nitro-5-carbethoxyphenyl5 boric acid

41.5

280 100

185

157

3 .4

kz 2 a-Tripiperidine

35

128

material(s)

301,7& 12a-Trihydroxycholanic acid l$Hydroxy-l-dehydrotestosEC terone diacetste g 1,2-Trimethyleneindol 0 + 2 p-Nitrobenaene diazonium chloride L i; Azulene

Starting

Amt. starting material, mg.

KtHgIJKOH. Hg(OAc)z/HC104/ KC1 in AcOH

POCl, in dimethylformamide AuBra/HBr

NaOAc

3Hz gas (200 mm. Htd K,COa

Agent(s) and condition(s) used

TABLE Miscellaneous

Isolated 3~,701,12~~-trihyacid of estradiol-138

material(s)

dialdehyde-(

derivative

1,:~)

Bicycle-[2,2,1]-hept-5-en-2-acetylene 3-Nitro-5-phenylmercury rhloride

Tetrabromoaurate

Azulene

3-(p-Nitrobenzeneazo)-1,2-trimethyleneindol

Tritium-labeled droxycholanic l7-Monoacetate

XII Reactions

240 97%

196

43%

307

3.0

312 313

310

308

306

Reference 19

Amt. product,, mg.

2

x

.-

294

L-&Methionine-(

f )-sulfoxide

250) 500

500

1. ClSOJ)H 2. Hz0 Crystallization 80% EtOH

NaOH

1. NBS 2. Aniline

1. Isopropylnitrite 2. Chloroaminc solution 1. NaNO2/HCl 2. NH,OH 1. NH&H 2. 300%

850

300

HNO, in A&H NaCN/p-nitrosodimethylaniline

250 150

+ 2,5-Dichloro-1,4-naphthoquinone S-Methoxypsoralene

Toluene-p-thiol

I-o-Aminophenyl-1-(5-bromo-2methoxyphenyl)-ethylene 1,2,3,4-Tetrahydro-1,4-naphthalenrdicarboxylic anhydride @-Garotene

2’-Nitro-2-hydroxybiphenyl Chloromethyl-@-[2,3,4,4’-tetramethoxy-5-bromo-diphcnylyl-(6)lethyl ketone 4,5,6,7-IXbenxoindnnone-1

from

I(+) Isomer + \ ( - ) Isomer (from

acid

the mother

9-Methoxypsoralene-4-sulfonyl

5-Chloro-2-p-tolylthio-l,Bnaphthoquinone

4,4’-Dianilido-b-carotene

liquor)

55 143

480

58%

60

460

322

3’21

320

33

318

31’7

-

4-(5-Bromo-%methoxyphcnyl)-cinnoline Dicarboximide derivative

31G 299

2-Diazo-4,5,6,i-dibenzoindanone

814 315

170 160

3,5;2’-Trinitro-2-hydroxybiphenyl &Ketovaleric nitrilr derivative

490

0. KOVACS

be found describing successful manipulations also with materials which are more difficult to handle. The examples given here are mostly selected from such researches where the majority of the experiments was carried out with less than 1 g. of material. Other reactions are mentioned on account of the marked interest of their chemistry or the technique involved. The yield of the product isolated from the reaction is of informative value concerning the nature of the react,ion or the processing of the reaction mixture, but of course these dat)a reflect the skill of the experimenter, too. There are also some typical reactions included to serve t,he purpose of generalization on basis of existing knowledge. Reduction procedures (Table I) are, in general, easily carried out, on the microscale, and give very little trouble. Difficulties are encountered mostly when more than one product is formed in the reaction, or if the reagent or any of the products suffer some deterioration under the conditions of the reaction as a consequence of their chemical nature. Several reactions of good yield can be found also among the less unequivocal processes of oxidation (Table II) ; this statement applies primarily to procedures carried out by means of selective oxidizing agents. A number of successful experiments are presented for aromatization reactions at higher temperatures, and dehydrogenations under milder conditions (Table III). Alkylation is highly influenced not only by the nature of the alkylating agent, but also by that of the atom to be alkylated (Table IV), by its electronic structure, and its state in the moment of the reaction which results from interactions with other components of the molecule. Not much novelty can be said in connection with halogenation (Table V) ; in the field of acylation (Table VI) and hydrolysis (Table VII), secondary processes are of interest in addition to the aspects of selectivity. Among elimination reactions (Table VIII) most examples are found for the creation of a double bond. Isomerizations and rearrangements (Table IX) are described in the literature primarily in connection with steroids; among degradations (Table X), successful Hoffman reactions are worth mentioning. Table XI, listing addition and condensation reactions, includes ringclosure reactions, too, without special regard t’o their mechanism. The last group (Table XII) consists of miscellaneous reactions which could not be classified with those contained in Tables I-XI, and also a number of comparatively rare conversions. MICROCHEMICAL

JOURNBL,

VOL.

V, ISSUE

3

ORGANIC

MICROSYNTHESIS

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4Y%

(). KOVA<‘q 1,

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