Birch Reduction of Aromatic Compounds

BIRCH REDUCTION OF AROMATIC COMPOUNDS

BIRCH REDUCTION OFAROMATIC COMPOUNDS

A. A. Akhrem, I. G. Reshetova, and Yu. A. Titov Institute of Organic Chemistry Academy of Sciences of the USSR Moscow, USSR

Translated from Russian by B. J. Hazzard

IFI/PLENUM • NEW YORK-WASHINGTON-LONDON • 1972

Afanasii Andreevich Akhrem was born in 1914. In 1934 he completed his studies at the Minsk Polytechnic Institute. In 1949 he received the degree of Candidate of Chemical Sciences and in 1959 that of Doctor of Chemical Sciences. He began work in the Institute of Organic Chemistry of the Academy of Sciences of the USSR in 1946, and in 1962 he became head of the Laboratory of Corticoid Chemistry. Dr. Akhrem is a member of the Academy of Sciences of the Belorussian SSR.

Irina Grigor'evna Reshetova was born in 1934. She completed her studies at the Moscow Institute of Fine Chemical Technology, and since then has been working at the Institute of Organic Chemistry of the Academy of Sciences of the USSR in the field of modified steroids.

Yurii Andreevich Titov was born in 1932. In 1954 he completed his studies at the Moscow Institute of Fine Chemical Technology, and since then has been working at the Institute of Organic Chemistry of the Academy of Sciences of the USSR, first as an assistant and, since 1965. as senior scientific researcher of the Laboratory of Corticoid Chemistry.

The present work originally appeared as pages 7-128 in Reaktsii i Metody Issledovaniya Organicheskikh Soedinenii, Vyp. 20, published by Khimiya Press in Moscow in 1969. This translation, revised and corrected by the authors, is published by special agreement with Mezhdunarodnaya Kniga, the Soviet book export agency.

Library of Congress Catalog Card Number 70-183103

ISBN 978-1-4757-0431-0 ISBN 978-1-4757-0429-7 (eBook) DOI 10.1007/978-1-4757-0429-7

© 1972 IFI/Plenum Data Corporation Softcover reprint of the hardcover 1st edition 1972 A Subsidiary of Plenum Publishing Corporation

227 West 17th Street, New York, N.Y. 10011

United Kingdom edition published by Plenum Press, London

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All rights reserved

No part of this publication may be reproduced in any form without

written permission from the publisher

Contents

Introduction .......... .

Reaction Mechanism

Field of Application

Side Reactions ....

Methods and Examples of the Performance ot 'le Reaction. 2.5-Dihydroanisole ........ . 6-Alkylcyc1ohex-2-en-l-ones ..... . Piperitone .................. . 3-Methoxyestra-2.5(10)-dien-17 8-01 .

Review of Literature Information ....

Index of Reagents ..

Literature Cited ...

v

1

2

4

8

15 16 16 17 17

18

112

116

Introduction

Birch reduction (see reviews [1-5]) is the name given to the reaction of unsaturated organic compounds with alkali metals and alcohols in liquid ammonia. This method was first used for aromatic compounds in 1937 by Wooster [6J, who showed that benzene and its derivatives are reduced by sodium in liquid ammonia in the presence of an alcohol, while this reaction does not take place in the absence of an alcohol. However, the general recognition and broad application of this reaction was achieved only after a series of investigations by Birch published from 1944 onwards [7J.

Since the presence of an alcohol in the reaction medium is not indispensable for pOlycyclic aromatic systems, the present review includes only derivatives of the simplest aromatic compounds - benzene and naphthalene.

1

Reaction Mechanism

The most probable mechanism of Birch reduction, adopted by the majority of workers in this field [4, 8 -12] can be represented by the following stages:

3)

4)

5)

6)

7)

'v\ I NH -'" ,.+ -i T 1 3 +-- "'(NHa) , , ,e (NHa)

Q')', ",,\\+ / (NHa) . (NH:,)

H H H H

X~.H~ 0 >< lIT V H H

+ ROH ----+ () ll.. (NHa)

A H H

H H

+ RO" ~ Q + 110M,,,,,,

Ii Ij H H

H+ X/~H M,l<Utl 0 <~ ~J"H • ~

2

REACTION MECHANISM

8)

When an alkali metal (M) is dissolved in liquid ammonia (stage 1) the solvated cation and electron formed remain weakly attached to one another

3

in the form of an ion pair [13]. The reaction of the latter with the aromatic nucleus is accompanied by electron transfer and the formation of a radical anion which occupies the place of the electron on the ion pair (stage 2). The radical anion of monobenzenoid systems is an extremely unstable particle [14-16] because of the low electron affinity of the aryl nucleus. Consequently, a shift of the equilibrium of stage 2 to the right is possible only if the radical anion is constantly eliminated from the equilibrium mixture, which is achieved by its irreversible protonation by means of the alcohol ROH (stage 3). Ammonia cannot provide the electron necessary for this in view of its low acidity (pKa ~ 34), while the acidity of alcohols (pKa ~ 16 -18) is sufficient.

The intermediate radical obtained in stage 3 immediately adds a second electron, being converted into an anion (stage 4). Protonation by the alcohol again leads to a 1,4-dihydro derivative (stage 5).

If NHi ions are present in the reaction mixture, conditions are created for the ionization of the 1,4-dihydro derivative, in consequence of which the more thermodynamically stable 1,2-dihydro derivative accumulates in the reaction mixture. The latter, being a conjugated diene, is reduced further to the tetrahydro derivative <stage 6). However, in the majority of cases with an alcohol present in the reaction mixture a strongly acid buffer (as compared with the acidity of ammonia) is created, which prevents the accumulation of NH; ions.

The radical anion formed in stage 2 can react further with a second electron, forming a dianion (stage 7) the subsequent double protonation of which (stage 8) also leads to the 1,4-dihydro derivative. Because of the low electron affinity of the aryl nucleus mentioned above, this possibility is apparently not realized in the case of systems with a simple benzene nucleus. On the other hand, naphthalene and its derivatives react in just this way [8, 9,17,18], i.e., via stages I, 2, 7, and 8.

Hiickel et a!. [19, 20] have proposed an alternative mechanism for Birch reduction including in the first stage an attack of atomic hydrogen with the formation of a radical. On the successive addition of an electron and a proton, this radical is converted into the anion of a dihydro derivative, which then reacts in the manner of stage 5.

Field of Application

The Birch reaction is used for the reduction of very diverse aromatic compounds differing in their degree of substitution and in the nature of the substituents. In the first stage of the reaction, l,4-dihydro derivatives are always formed and through the further reactions of these are effected transformations to various compounds frequently difficult of access by other methods of synthesis.

In the reduction of benzene and its derivatives, the corresponding cyclohexadienes are obtained (yield up to 80-900/0). In this process the orientation of the reduction is of prime importance. In accordance with the mechanism illustra ted above. the structure of the products obtained is determined by the direction of the addition of the protons to the radical anion in stage 3 and to the anion in stage 5. It is obvious that in both cases the protons will a ttack the carbon atoms of the ring with the highest electron density. The electron densities of all the carbon atoms of mono- and disubstituted benzenes and also of the anion radicals formed from them ha ve been calculated by the molecular orbitals method [18, 21j. When electron-donating substituents (alkyl, alkoxyl, and amino groups) are present, the carbon atoms bearing the substituents or those in the para position to them have the greatest tendency to undergo protonation. Consequently. the Birch reduction of such compounds leads to l,4-dihydro derivatives (I) containing the maximum number of substituents on the remaining double bonds [8, 22]. This rule had previously been deduced empirically by Birch [2, 7, 23, 24]:

A different distribution of electron densities is found when electronaccepting substituents are present; in this case the addition of protons takes

4

FIELD OF APPLICATION

place in the 1,4- positions with respect to the carbon atom bearing the substituent, leading to compounds of type (II) [25-27J:

5

In the reduction of polycyclic derivatives of anisole (III), the addition of protons in the 1,4- positions may take place in two directions with the formation of compounds (IV) and (V). It is found, however, that the isomers of type (V) always predominate in the mixture of reaction products [28J:

Examples are also known in which the reduction product originally arising - the l,4-cyclohexadiene (VI) - then rearranges into the conjugated 1,3- derivative (VII) [8, 23, 29. 30J:

VI

_ ()/CHa

(CHa)2N/'V VII

When the reaction is carried out with alkoxy- and aminobenzenes, the reduction products formed are ethers of the enolic forms (VIII) or are enamines (IX) corresponding to the unsaturated ketones (X) into which they can be converted by acid hydrolysis [22J:

(Y0CH3 (yOCH:l I ~II

,,?

V/II

6 FIELD OF APPLICATION

The Birch reduction of anisole derivatives is used particularly widely in steroid chemistry to effect the passage from ethers of estrogens to 19-norandrostanes. These compounds possess a high and diverse physiological activity and are therefore of great value for medicine (see the reviews [31-33J. The acid hydrolysis of the reduction products (XI) under severe conditions (hydrochloric acid) leads to b,4 -3-oxosteroids (XII), while milder hydrolysis using oxalic or acetic acid permits the double bond in the b,5(lO)_position to be retained with the formation of (XIII):

The method of reduction under consideration has proved acceptable in the total synthesis of various steroids [34J, alkaloids [35, 36J, resin acids [37], and various terpenes [38-43J, including such complex ones as totarol (XIV) [44J and cx-onocerin (XV) [45j:

3 :?' I HCJ:XOH Q6 CH(CH,),

H,C CH3

XIV

Birch reduction has also found use for the synthesis of hydrogenated naphthalene derivatives. Depending on the reaction conditions, naphthalene itself forms the 1,4-dihydro derivative (XVI) or the 1,4,5, 8-tetrahydro derivative (XVII) [46,47]:

CO~(X) + (X) XVI XVII

FIELD OF APPLICATION 7

For substituted naphthalenes, the degree and direction of reduction depend on the number, nature, and positions of the substituents in the aromatic nucleus, as is shown by,the examples of the reactions of compounds (XVITI)-(XX) given below:

OH OH

~ ~ ~ 0) 1

~, ~-----(() XVIJI

COOH COOH I 06, ~

~ 8 XIX

-(X)

Thus, I-naphthol (XVIII) is reduced in the unsubstituted ring and 2-naphthol (XX) in the substituted ring [7, 48]. I-Naphthoic acid (XIX), containing an electron-accepting substitutent, is also reduced in the substituted ring [49J.

In the case of compounds with several substituents, a more complex reaction pattern is observed, as can be illustrated by the reduction of compound (XXI), forming the 3,4,6, 9-tetrahydro derivative and of compound (XXII), giving a hexahydro derivative under the conditions of the Birch reaction [50]:

OCHa ,

(X) --I

CHsO XXI

OCHa I

O/~ dy I

CH30

Side Reactions

Since the main reaction considered in the present review is the reduction of the aromatic nucleus, side reactions must be considered to include, in the first place, the reduction of other unsaturated functional groups and, in the second place, the hydrogenolysis of certain substituents under the conditions of the Birch reaction.

The compounds to be red uced most frequently contain, besides the aromatic ring, other unsaturated groupings which are also capable of reduction under the action of alkali metals and alcohols in liquid ammonia. The fate of such groupings in the reaction process is important for the successful application of the Birch red uction to the synthesis of organic compounds.

Double carbon-carbon bonds not conjugated with a keto group of an aromatic nucleus are not usually reduced in the Birch reaction. The numerous exceptions [51-53] include the reduction of the 17cx-allyl grouping of compound (XXII):

HaC OH

(I (')j--CH,cH

CH:lV ~X) '( XIII

A double bond conjugated with an aromatic ring (a "styryl" bond) is reduced more rapidly than the ring. and this effect has been made use of in the total and partial synthesis of steroids. The reactions of b,,6_, b"s(g)_, and b,,11_ steroids [(XXIV) [54], (XXV) [55,56], and (XXVI) [57]] may serve as

examples of this. As a rule, the reduction of the double bonds forms products with the trans - linkage of the corresponding rings. The few exceptions (5, 58-61] are due to special features of the structure of the initial compounds and the nature of the alkali metal used:

8

SIDE REACTIONS

CH" I

~--I-OH \

~X~"" / -~ (yy CH}V 10 ) CHHO/V",)

xxv

CH3

(,1-=0

ClI"vO(rV XXVI

Conjugated dienes of the type of (xxvII) are reduced to olefinic compounds under the conditions of the Birch reaction [62]. If the diene system is conjugated with an aromatic ring (XXVIII), on reduction only the double bond attached directly to the ring is affected [38, 39]:

C~ C~ I I

ty~ ri) (~H30AJI)1 -- CH 0))

- 3 II A A

HaC CHa HaC CHa

XXVIII

Triple carbon -carbon bonds conjugated with an aromatic ring [63] or with a carboxyl group (XXIX [64-66]) are completely or partially reduced by

9

10 SIDE REACTIONS

alkali metals and alcohols in liquid ammonia. The degree of reduction depends on the conditions of the reaction:

HaC OH

('-1-1---C==CCOOH

t'X)/"-./ CHaOA

XXIX

-+

As a rule, under the conditions of the Birch reaction, carbonyl groups are reduced to hydroxy groups, the thermodynamically more stable stereoisomers being formed predominantly. Keto groups conjugated with aromatic rings undergo complete hydrogenolysis, as was shown on the basis of acetophenone (XXX), which is reduced to ethylbenzene [67]. In this case, hydrogenolysis is not prevented even by using the corresponding ketal (xxxI) in the reaction [68]:

-I -I o 0 "-/

~I ()CCHa

~

XXXI

When it is necessary to retain a keto group not conjugated with an aromatic ring, either it may be previously protected by conversion into the ethylene ketal (XXXIII [69, 70]) or, after the reaction, the keto grol,lp can be regenerated by the Oppenauer oxidation of the carbinol (XXXIV) originally formed [71-75], as was done in the synthesis of 19-norprogesterone (XXXV)

SIDE REACTIONS

from an aromatic precursor (XXXII):

CH3

('i)CHOHCH' CHaOmA --+

XXXIV

In some cases [76), the reduction of a keto group is prevented by its conversion into an enol ether.

11

When a keto group conjugated with a double bond is present in the compound, the double bond is reduced first, and then the keto group, and last the aromatic rings present in the molecule. This difference in reactivities is widely used for the selective reduction of the functional groups mentioned (5).

Generally, carboxyl groups undergo no change under the conditions of the Birch reaction (47, 77). At the same time, ester groupings are completely or partially reduced to primary alcohols, this reaction taking place faster than the reduction of an aromatic ring. Compounds (xxxvI) [77, 78) and (XXXVII) (79) may serve as examples. In the case of substituted naphthalenes of type (XXXVIII), alkoxycarbonyl groups attached to the aromatic ring are retained on Birch reduction [80):

12 SIDE REACTIONS

XXXVII

'XXOH (I : COOCH a XXXVIII

Hyd roxyl and thiol groups remain unaffected in the Birch reaction if they are not present in the benzyl (0:-) position with respect to an aromatic ring. In this case, hyuroxyl groups undergo hydrogenolysis, but this can be prevented by the introduction of an electron-donating substituent in the para position of the aromatic ring. For example, the hydroxyl group of compound (XXXIX) undergoes complete hydrogenolysis in Birch reduction, while compound (xL)

forms the normal reaction product [81]:

i CHaO

XXXIX

-;?''" I !I-:=O CH:P'/~/"'''/

XL

/' .. --1 I . V"./

CH"O

Benzoylation or the conversion of alcohols with such a structure into benzyl ethers does not protect their hydroxyl gr oups from hydrogenolysis [82 • 83].

Sometimes a methoxyl group directly attached to an aromatic ring is also eliminated in the Birch reaction, particularly if it is present in the para position to a carboxyl group (XLI) [76, 84]:

COOH

~'" i II CH:;O/~(Y"OCl-la

OCH" XLI

COOH

For naphthalene derivatives, such elimination is observed when alcohols are added at the end of the reaction [85].

SIDE REACTIONS 13

Vinyl and eth ynyl carbinols, of which compounds (XLII) [86] and (XLIII) [51, 87] may serve as examples, also undergo hydrogenolysis on reduction with alkali metals and alcohols in liquid ammonia. The corresponding ethylidene derivatives are formed, and in the first case the ethylidene group is red uced further to an ethyl group, since the double bond is conjugated with the aromatic ring:

'.LIII

Hydrogenolysis of the hydroxyl group of ethynyl carbinols can be prevented by the addition of alkali-metal amides to the reaction mixture [51, 88].

The acetoxy groups of a:-acetoxy ketones of type (XLIV) undergo hydrogenolysis during the Birch reaction with a change in the configuration of the side chain, which is further reduced to the corresponding carbinol [64, 89, 90]:

xuv XLV

The migration of the acyl group observed in the Birch reduction of compound (XLVI), with the formation of compound (XLVII) [57], can be explained in the following way. The attack of the anion (XLVIII) (see the section "Reaction Mechanism," stage 4) on the carbonyl of the acetate grouping leads to the intermediate product (XLIX). The subsequent migration of the acetyl group from C(ll) to C(l) takes place in the manner of a Claisen reaction, and this is followed by the addition of a proton to the hydroxyl group and the re-

14 SIDE REACTIONS

duction of the carbonyl groupings:

0 OH

~

CH30 CH30

(XLVI) i t (XLVII)

I ?) 9~o I

I CH'w CHw --CH30 CHaO

H H H H

(XLVllI) (XLIX)

Methods and Examples of the Performance of the Reaction

In the performance of the Birch reduction, a number of experimental variants have been proposed which differ from one another by the ratio and order of addition of the reagents - the alkali metal, the ammonia, and the alcohol - and also by the presence or absence of supplementary solvents. Since the reaction is carried out in liquid ammonia, its temperature range is determined by the boiling and solidification points of ammonia (from -34°C to -80 °C).

Of the many variants described in the literature, we shall consider only the main ones: the Birch, the Nelson-Wilds, the Iohnson, and the Dryden methods.

According to the Birch method [38], the alkali. metal - sodium or potassium - is added to a well-stirred mixture of an alcohol (taken in stoichiometric amount with respect to the meta!), liquid ammonia, and the substance to be reduced. The method is applicable predominantly to simple aromatic compounds; for more complex compounds (methyl ethers of hexestrol and estradiol) the yields fall sharply, mainly because of the low solubility of the compounds to be reduced. The modification of the reaction proposed by Wilds and Nelson [10] differs from the Birch method by the use of an auxiliary solvent (ether, tetrahydrofuran. etc.) by the replacement of sodium by lithium, which is more soluble in liquid ammonia and has a higher reduction potential, and, finally, by the addition of the alcohol at the end of the process, which reduces the probability of an undesirable reaction of the alcohol with the alkali metal. This modification has found application mainly for the reduction of pOlycyclic derivatives of anisole, primarily steroid estrogens.

According to the method of Johnson et al. [28, 82, 91] a comparatively large excess of ethanol (up to 400/0) is used in the reaction. The alkali metal is added until a bronze-colored phase has been formed, showing the achievement of the maximum concentration of the metal in the ammonia. This procedure was developed for tetracyclic compounds difficult to reduce. Dryden et al. [11, 65] established that the presence of small amounts of iron in technical ammonia catalyzes the reaction of sodium and potassium and, to a far

15

16 METHODS AND EXAMPLES OF THE PERFORMANCE OF THE REACTION

smaller degree, lithium with ammonia and alcohols. This fact explains the inapplicability of the Birch method to sparingl y-soluble anisoles and the success achieved by Wilds and Nelson in the use of lithium. Consequently, Dryden et al. proposed to use redistilled ammonia freed from contamination with iron and a system of solvents consisting of liquid ammonia, tetrahydrofuran, and tert - butanol in a ratio of 2:1 :1. The improved solubility in this system has enabled the reduction of a large group of aromatic compounds to be carried out successfully.

The other modifications of the Birch reduction process consist in the use of two alkali metals in the reduction of polycyclic derivatives of styrene [28, 92], in the use of the monometh yl ether of 1 ,2- propylene gl ycol as proton donor [93], and the use of dimethoxyethane as auxiliary sol vent [91], and in a variation in the order of addition of the reagents and in the working up of the reaction products, etc.

2,5-Dihydroanisole [94]

With stirring. 200 ml of liquid ammonia is added to a solution of 15 g of anisole in 50 ml of anhydrous ether cooled with dry ice, after which 4.5 g of lithium in small pieces is added to the flask and the reaction mixture is stirred for 10 min. Then 35 g of absolute ethanol is added dropwise over 30 min. After the evaporation of the ammonia at room temperature. ether and water are added to the reaction products, the layers are separated, and the aqueous layer is extracted with ether. Distillation of the combined ethereal extracts gives 12.8 g (yield 84'1d of 2,5-dihydroanisole containing, according to its UV spectrum (A. C2H 50H 268 nm), about 20'10 of the 2,3-dihydro derivative.

max

6-Alkylcyclohex-2-en-l-ones [22]

An 0.05 g solution of a substituted aniline or anisole in 20 ml of tertbutanol is added over 5 min to a solution of 1.4 g (0.2 g -atom) of lithium in 100 ml of liquid ammonia, the mixture is stirred until its color disappears

Initial compound

Anisole Aniline N, N-Dimethylaniline 2-Methylanisole a-Toluidine N, N-Dimethyl-a-toluidine

TABLE 1

Reaction product

Cyclohex- 2-en-l-one

6-Methylcyclohex-2-en-l-one

49 42 37 52 50 43

-The yields are given only for the desired products; in addition to these, saturated alkylcyclohexanones are also formed in small amount.

METHODS AND EXAMPLES OF THE PERFORMANCE OF THE REACTION 17

TABLE 2

Metal Alcohol Yield of (XI), 0/0

Li CHsOH 84 Li tert -C"HgOH 79 Na iso -CSH70H 88 Na tert -C"HgOH 88 Na tert -C5HUOH 85 Ca tert -C"HgOH 86

(about 1 h), the ammonia is evaporated off, and 150 ml of water is carefully added to the residue. The aqueous solution is extracted with ether, the solvent is distilled off, the resid ue is treated with 100 ml of ice-cooled 50/0 hydrochloric acid, and the mixture is heated from 0 to 90°C over 20 min. After COOling, it is again extracted with ether, and the extract is dried over potassium carbonate and distilled. The results shown in Table 1 are obtained.

Piperitone [38]

A solution of 22 g of the B -hydroxyethyl ether of 2-isopropyl- 5-methylphenol is added to 350 ml of liquid ammonia. The mixture is reduced with 15 g of sodium and is worked up in the same way as described in the preceding method. This gives 14 g (yield 820/0) of piperitone (3-methyl-6 -isopropylcyclohex-2-en-1-one).

3-Methoxyestra-2,5(10)-dien-17B-ol (XI) [11]

A I-liter three-necked flask cooled with dry ice is charged with 300 ml of liquid ammonia. Then with stirring, a solution of 0.035 mole of the methyl ether of estradiol in a mixture of 150 ml of tetrahydrofuran and 150 ml of ethanol is added through a dropping funnel. Over 15 min, 0.6 g-atom of an alkali metal is added to the resulting solution. After the disappearance of the blue coloration of the solution, which generally requires 4-5 h, the reaction mixture is carefully treated with 40 ml of methanol. The ammonia is evaporated off in room temperature, and 250 ml of water is carefully added to the residue. The tetrahydrofuran is distilled off in the vacuum of a water pump, after which another 250 ml of water is added to the mixture. The precipitate of the reaction product (XI) is collected on a filter, carefully washed with cold water, and dried in the air. The results shown in Table 2 are obtained.

The authors express their deep gratitude to N. N. Pivnitskii for valuable advice and assistance in the work.

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16

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Al

tTl Z

'Tl ~ ::.>

>-:l o Z .... c:o

Sta

rtin

g m

ater

ial

No

Em

piri

cal

Str

uctu

ral

form

ula

form

ula

......

, .....

. I

c ~

I ..

....

....

" ,

.,

7 C

gHS01

("

'yC

OO

H

I I I

I

B I

~)l"CHa

I >i

C

OO

H

1 1 I

I ~',

I

~~CH

3 I

3 i

::rC

OO

I!

If"

I L

H,.

C/

:0..

1

D

CsH

aO:;

(X

OC

Ha

. I

'~

CO

OH

2 2 1

C8H

sO;;

CO

OH

"',,

/'· ..

.. ()C

II

. .

:~

Rea

ctio

n pr

oduc

t

Str

uctu

ral

form

ula

I

/'.

/CO

Ol!

l :r

Ii //

-"C

I1;;

CO

Ol!

I I

(. il

I I

)l"C

Ha

i , ,

/CO

OH

(/

''/

HaC

/')

A/

OC

H,.

~)"'COOH

CO

OH

, I

/">

""

~

[, .

)"'O

ClL

,

(Con

tinue

d)

~~

Met

al,

prot

on ~g L

iter

-do

nor,

au

xil

--<

ll "=

l ...

. .-

<0

atu

re

iary

sol

vent

s <l

l<ll

'~..

c :>-

< ...

Na,

NH

3,

73

100

C2H

.oH

Na,

N

1l3

, 87

84

C

H30

11

!\ia,

N

Ha,

--

27

C)-1

50B

;\ii!

, N

H3

, -

10/

CH

PH

Na,

NH

a, C

HaO

J-!

80

84

t>:l o ;>

::l tr:l <:

tTl ::s Sil r-' ;:J

tr:l

;>::l >

>-3 c:: ;>

::l tr:l ......

Z

'T1 ~ ~ >

>-3 o Z

22

I \:

iI,

\: I

['I'

io ~J

i'.

,,:

(')I

"UJI

;0

23

I C

sHgO

N

t':I

~,~/

COMi

2 ,V

<'D

NH

2 M

g,

NH

a,

97

< ......

C2H

uOH

, t':

I

II;r

/')

(Clf

,lP

<:

IT~C

/ ~/

0

24

1 C

,Hn0

2l\

."

",C

OC

H!

Na,

N

H3

, 25

76

t"

" ......

7X

C21

I[,O

II, (

HC

I) >-

l

~ I 'N

IIC

II"

t':I

()

s; >-l

25

I p

VC

ON

I12

.C

ON

H,

Na,

N

lla.

27

C

/:"

" C

2H;;O

H

S;

I~)

l)

z ."

I G

CH

I ¥

OC

Ha

I $::

26

C

sHlo

(yC

2Ho

/\./

C21

I,.

Li,

NH

:l'

I 8

:>

C2H

,;OH

1

>-l

~I

I~,,)

......

Nil.

NH

3,

CH

aOH

i98

il(}

2

0 Z

27

(X~113

(XC

Iia

CH;1

e

lLI

28 I

CH

a C

H3

Li,

NH

3,

I~i

8

I ,

i C

2H5O

H

p)

,f'.

I

~)\CH:

I l)

"'C

H: 1

29 I

Na,

N

Ha•

7

C2H

"OH

30 I

})

JyC

Ha

/\./

CH

a L

i, N

Ha•

R

Ha C

/l )

C

2HI>

0H

HP/~

~

I--'

Sta

rtin

g m

ater

ial

No.

E

mpi

rica

l S

truc

tura

l fo

rmul

a fo

rmul

a

CSHI

O I

NC

II,

;/,

HaC

~

3

, CSHI

OO

(yC

HO

HC

H3

»

(XC

Ha

: I

OC~-13

» »

" ('

''V

0CH

a

~)

I CH

a »

»

» ((

CH

3 ;/

, CH.,o/~/

I

Rea

ctio

n pr

oduc

t M

etal

, pr

oton

do

nor,

au

xil

-

Str

uctu

ral

form

ula

iary

sol

vent

s

A/C

Ha

HaC/

~)

/~</

C2H5

~)

(~/C

Ha

\"/~O

(XCH

3 I

lOC

H 3

A/O

CH

:, f\

U

,

I CB

a »

CH

,()/

3

I n

#

v !

21

(Con

tinue

d)

~~

~~ L

iter

-.(

])

"0 ..

.. -0

atu

re

(])(

])

'~..

c:

>-< ...

.

87

75

78

-

[-

t-.:l

t-.:l

::0

trl < t;:l <: ~ t'"

'" ;::J

trl ~ >-:l

C ~ Z

'Tl ~

, -

, '8

;;:;::

80 I

:>

>-:l (3

Z

38

I CS

H1OO

., CHPy~(OCH:j

CH

aO

yyO

CH

:;

Na,

N

H3

, -

108

C2H

5OH

'"

I ,I

~)

tTl <

,f"'

......

tTl

39 I

CS

HllO

N

(~yCH:l

/XCH

:; Li

, N

Hs,

99

<:

~ I

C2H

5OH

, 0

~

(C2H

5hO

'T

l

CH

30/'

''

NH

2 t-<

C

Hp

/ NH

~ .....

.

40 I

CsH

uN

(yN

(CH

3 h

Li,

NH

a,

>-l

/;.y

N(C

Ha )

2 22

tT

l

l)

tert

-Cll

90

H

~ >-l

,/

c:::

41 I

'''

'-.;f

"0

Na,

N

H3

, 23

fg

C

2HrP

H,

(HC

I) .....

.

l)

z 'Tl ~

42

I "'II

,\H

I. (,,)

112

Na,

N

H3

, -

104

$:

I ~ I

-C

2H5O

H

:>

~)""

) >-

l .....

. 0 Z

CD

43 I

CgH

gOaN

ry

/-:O

OH

(,

,/C

OO

H

Na,

N

H3

, I-I

27

C2H

5OH

["

I C

HaC

O:\

IIA

) C

H3C

Oi'-

HI/

"V

44

! C

9111

0 C

lio

CH

2 "

ILi,

NH

:;, C

HaO

HI -I 1

0~)

-" •

/CH

c i

/CH

2

(y/C

H

A/

CH

~)

L)

45 I

()

")

(~)

INa,

NH

s, C

HaO

HI

-I

lIJ6

t\? '"

Sta

rtin

g m

ater

ial

No •

Em

pir

ical

S

tru

ctu

ral

form

ula

form

ula

I f

) Ct

HtoO

~ _"

/C

OO

CzH

o

I I

f'{

~.~J

4, 7

C9Hl

(J0~

(X

CO

CH

U

~ O

ClI

a

4 4 3

» C

OO

!l

; ~

t. I

113C'~

CH

: J

4 ~

C9H

lU0

4 C

OO

H

,

f .

~(lCH"

~ I

OC

Ha

5 )

x· C

OO

H

I

ClI

:P" /~

1, AoC

H!J

Rea

ctio

n pr

oduc

t M

etal

, pr

oton

do

nor,

au

xil

-

Str

uct

ura

l fo

rmul

a ia

ry s

olve

nts

f'. J

-C0

0C2H

" M

g.

NB

s.

l)

C2B

5OB

.

I (C

2H5)

20

(,<

ClI

. N

a.

NB

s.

CH

sOH

. (C

2H.)2

0,

(HC

I)

\/~O

CO

Ol I

N

a, N

Hs•

CH

aOH

I (~

ilcA

C

H

s 3

CO

OH

N

a, N

Hs•

CH

aOH

I

fXO

CH

:l

. O

CH

a

CO

OH

N

a. N

Hs•

CH

aOH

CIl.O'

Q OCH~

(Con

tinue

d)

fo'-;G ~~ L

iter

--c

U

"0

'"

......

0 at

ure

cU

cU

'~.d

:>-< .

... -I (r

.

I

I

4t!

68

95

84

7fJ

84

85

84

t-:l "" ~ .... t%l ~ $il t"

" ::3 t%l s: ~ c::: Gl .... Z

'Tl ~ ~ > ~ o z

51 I

C!l

IIII

():I

\ (":

:nV

" "C

ONII

~ C1

1:IO

('

C()

\IL

\;

" \1

1",

l7

" (:)

'1:,0

11

;;0

I~ tT

l

~)

< ,J

1

-1

tTl

6CH3

I <:

OC

Ha

~

52 I

ell,

" ,(

:,;H

;II.

I()

/ ..

. <

:)1;

/(11

1 Li

, M

I;1'

H

t-<

( ~/

, "\/

C"H

aOB

1

-1

I I

>-:l

~/

tTl

~/

;;0

53 I

,\l

a,

NH

;J'

19

:>

>-:l

CH

aOH

C

;;

0

54 I

(J

I"

('II

:,

U,

NH

", 8

tTl

1-1

C"H

,;011

Z

;~"

'Tl 0

i I

~ J

~ II:

,C"

"'~

(' II

II

"e

;;/

'UI"

:>

55

I

>-:l

\a,

Nil;

!, 19

0

CII

,PH

Z

56

I C

~III

P (:1

1"

(II

UI,

;"'

;a,

NH

",

lil

.;""

,/ (

)(]

I"

()

CJI

:;O

I!

(""

;. J

'I

"'/

-"

ell"

',/

'UI"

"'-

) "

ell"

57 I

II:J

C,-

-ryO

CI

L, II

F

()

11/:

.

-f'..,

:-"

'a,

N11 3

• \-

1

ilL

~"

C)1

;;O

H

I

l)

.' I

) '~

'/

1 ell;1

CI

1"

ell;

j

58 I

CilH1P~

(yC

l!(O

II)C

II:I

/"

/C

)i;;

K

, N

H;!,

I-

I G8

r;

II te

rt-c

'iHU

OH

il

0 ~/

'·(JU

I.,

-()(

J I

r-:>

CI1

Sta

rtin

g m

ater

ial

NGl.

Em

piri

cal

Str

uctu

ral

form

ula

form

ula

9 C

9H12

02

I O

CHa

I I

#y

CH

s

I (I

I I ~

5

I I OCH~

6 0

C9H

12O

S O

CH

a i

CH

,»O

CH

, 1

C9H1

SN

()

NH

CH

s ~

I,)

6

2 »

(XN

(CH

ab

~ C

Hs

6

3 ,)

(J /N

(CH

a)2

I I I

i CH

a

I

Rea

ctio

n pr

oduc

t M

etal

, pr

oton

do

nor,

aux

il-

Str

uctu

ral

form

ula

iary

sol

vent

s

0 IN

a.

NH

a•

(yeH.

C

2H,O

H.

(HC

I)

: ",

I

° °

Na.

NH

s•

" C

2H,O

H.

(HC

I) "

("1

i ~)

~O

i

('11 N

HC

Ha

Na.

NH

s•

I A)

C2H

,OH

(XN

(CH

ah

Li

, N

Hs•

te

rt-C

,H9O

H

/ C

H a

(/'y

fO

Na.

NB

3•

C2H

50H

. (H

CI)

'f CH;j

(Con

tinue

d)

~'-;;j

~g

-Ill L

iter

-'0

....

.......

0 at

ure

III I

II '~,Q

:>-<

...

47

107

-76

72

108

-22

-28

t-:>

Cl)

:;>::l m

<:

til ::s o 'T

1 r ~

m

~ >-l c::: Ri Z

'T1 ~ ;::: > >-l (3

Z

64

I C9

H\3

N

~yCila

(yC

H3

Na,

NH

a,

84 2

3,

30

C2H

5OH

~

tTl

(CH

ahN

~)

(CHahN/~)

< -tTl I

~

"~~'~"""

""""''''

'I 0 'T

l

r -65

1 C

lOHS

(X

)

(X

)

Na,

NH

a.

I-I 46

""'l

tTl

CzH

oOH

, ~ >

(CZH

5120

""'

l c 66

I

(X

)

Na,

NH

a.

65 4

6,47

~

CZH

5OH

, tT

l -(C

ZH5h

O

z 'Tl

67

I C 1

oH80

O

H

OH

N

a, N

H3

, 7

0

00

I tert-

C.H

n OH

~

(X

)

>

""'l 0 Z

68 I

O

H

(X

)#

O

Na,

NH

3,

1-

7

(X

X

tert-C,

HnOH

69

1 C1

0HsN

N

H2

NH

z N

a. N

Ha,

I-I

48

I I

CZH

50H

(X

)

(X

)

70 1 C

loH

lO02

~)

J=0

j)T

H

Li,

NH

a,

I 67

1 81

C

2H5O

H,

CHaO

~

)-

CHaO

(C

2H5)2

0

711

Na,

NH

a,

1-1

10

9

C2H

5OH

I I

'" -.::J

Sta

rtin

g m

ater

ial

Rea

ctio

n pr

oduc

t

No,

E

mpi

rica

l S

truc

tura

l fo

rmul

a S

truc

tura

l fo

rmul

a fo

rmul

a

7 2

C10

H12

eX)

(X)

3 C

10H

12O

e),,)

A_

lj

,,)

I I

OC

Hs

OC

Ha

7

4 C

lOH

IPS

CH

s A

/C

2H5

I C--

S

l)

()6J

7 7 5

C

lOH

IPz

CH

a »

I c--o

()6J

6

» ~J1.

J:(CO

OC,H

. H

C ~

HsC

/

3

7

I I

Met

al,

prot

on

dono

r, a

ux

il-

iary

sol

vent

s

Na,

N

Ha.

C

2H6O

H

Li,

NH

a,

C2H

5OH

, (C

~H6)

20

Na,

N

Ha•

C

HaO

H,

(C~H5)P

I N

a, N

H3

,

CH

3OH

, (C

2H5)

P

Mg,

N

Hs'

C

2H5O

H,

(CZH

,)20

(Con

tinue

d)

to~

~~

-Ill L

iter

-"0

....

......

0 at

ure

III I

II '~.d

>-< ..

.. 91

6.

7

75

81

1-

68

I I

-68

-97

I>:l

00

::0

tTl < -tTl ~ ~ t"

" ~ ~ '"'l c::: f;l ~ 2 ~ '"'l (3

Z

I I

77

1 C

lOH

1P;

I C

OO

H

CO

OH

IN

a. N

Ha•

CH

aOH

93

76,

84

,

I ::0

A

I i

tTl

()

i <

CH

aO

::::"'1 I

OC

H3

>--< >-l

C2H

5O

H

tTl

I S;

79 I

Clo

HlS

04N

C

ON

H2

CONH

z N

a.

NH

a,

27

I I

C2H

5O

H

>-l

I c:::

:

C~~fOCH.

/'" ~

1" cH

aoA I

OC

Ha

t-<

Z

'Tl ~

OC

H3

$::

80 I

Clo

Hu

(yC

4 Hu -

tert

A~4H9-tert

Li.

NH

3,

8 :>

C

2H5O

H

>-l

~)

0 Z

81 I

~yCH

3 I 'y

,CH

a

Na,

N

Ha•

7

C2H

5O

H

iso-.C

aH7 I:

iSO-

CaH

7,J(/

821

C1o

H14

O

(XO

CH

a (X

OC

Ha

Li.

NH

a•

I-I

22

tert

-C4H

9OH

~ CS

H7-

iso

I I

C 3H7-

iso

83 I

V

A/O

CH

a

Na.

N

Ha•

I-I

38

~)

C2H

.OH

~H,.-i

SO 1 CaH

,-iso

I I

t-:l co

Sta

rtin

g m

ater

ial

Rea

ctio

n pr

oduc

t

No.

E

mpi

rica

l S

truc

tura

l fo

rmul

a S

truc

tura

l fo

rmul

a fo

rmul

a

4 Cl

OH

lOO

N

OC

Ha

OC

Ha

I I

(~ N

HC

Ha

A

NH

CH

a

~ I

) l)

",)

8 5 C1

oH1S

N

C(: .. ,,,,

(XN

H2

I I

C,H

o-te

rt

......

......

......

......

..

Cll

....

....

....

..•.

....

..

:6

Cll

Hs0

2 C

OO

H

CO

OH

c()

I I

(X)

I 7

»

WCOO

H (()

,COO

H :8

C

llH10

~

( XyC

H3

~I

,9

I

Met

al,

prot

on

dono

r, a

uxil

-ia

ry s

olve

nts

Na,

N

Ha,

C

2HsO

H

Li,

NH

3•

tert

-C4H

"OH

Na,

N

Ha•

C

zHsO

H

Li.

NH

a•

Czl

"I,,o

H,

(C2H

s)P

Na.

NH

3•

CH

aOH

. (C

lfs)

P

(Con

tinue

d)

~~

~g L

iter

-b:!'

~ ..

....

0 at

ure

<U< ... 87

llO

-2:

!

-49

41

111

.-11

2

CJ.

) o G;

-< ~ ~ t""' q t"Z:I ~ >-l c::: G;

.....

Z

'"r1 ~ :>

>-l o Z

89

I C

IlH10

0

90

I C

UH

120

'2

91

92

93

94 1

Cll

H14

0

95

;f'1(~

cH

aO

M}

%

WCO

OH

o

~!\

CHaO~

OC

Ha

! (X)

~ ~''

', /'"

,

fl 'f

I~ Cl

f30A

~,)

(q-)

(X

yCOO

H

OH

[

OH

J 1

1/

/"/ ",

/'\.

/'\

. !I

II 1+

II

II I

CH

30

' '\.

/'\.

/ C

HaO

/"/"/

2

24:3

7

OH

I

CH,o)

J()

o il CX)

OC

I-la

I (X)

! ,

I ,

! i

Na,

N

HS

' I -I

47

,

CZI-

l 50

I-l

I I

i I

I

INa,

NH

3,

CH

30H

I! R

ol1J

3 i

I I I

I

Li,

NH

s'

C2H

50H

, (C

2li 5

hO

Li,

NH

3,

C2H

50B

, (C

2H5)

20

Na,

N

Ha,

C

ZHbO

H

341

111

, i I

I -I 86

I

771

86

, 10

9,

114

Li, NH

~, C

HaO

H,1

63

1 11

te

rt-C

4H90

H,

(C2H

5)P

, (H

CI)

Li,

NH

3,

C2B

50B

, (C

Zli 5

)P

-'1115'

11

6

J I

fg < .... tTl <: ~ t"' ~

tTl ~ >-l c::: fg Z

." ~ >

>-l o Z

C.:>

I-'

Sta

rtin

g m

ater

ial

Rea

ctio

n pr

oduc

t

No.

E

mpi

rica

l S

truc

tura

l fo

rmul

a S

truc

tura

l fo

rmul

a fo

rmul

a

961

Cll

H14

0 O

CH

a O

CH

a I

I

(X)

eX)

97

» \,

0 !i ex)

98

)\

CH

ON

:)

(X

)

CH

aOA

3

99

» ,)

\\

100

» >\

101

Cn

H1

402

OH

01

-1

I I I

I C

l-lo

/()()

CH

o/(X

)

3 3

I

(Con

tinue

d)

ro~

Met

al,

prot

on ~~

Lit

er-

dono

r, a

uxil

-o

(\)

"0 .

...

'-<

0 a

ture

ia

ry s

olve

nts

(\)(

\)

'~.J

::

>-< ..

..

Li,

NH

a,

87

C2H

DOH

, is

o-C

sH7O

H,

(CH

PC

Hab

Na,

NH

a,C

HaO

H,

-te

rt-C

4HgO

H,

(C2H

.)P

, (H

CI)

Li,

NH

a,

90

C2H

5OH

, (C

2H5)

P

Na,

N

Ha,

-

CH

aOH

, (C

2HD)

P

Na,

N

Ha,

-

I~

C2H

ijOH

, (C

2H5)

P

Na,

N

Ha,

-

C2H

5OH

7

t.) ~ fg <

>-<

tTl ~

0 'Tl r ::J tTl

::0

)- ..., c:::

::0

tTl

>-< Z

'Tl ~ ~ )- ..., >-< 0 Z

10

2'

Cll

HI4

0a

CH~

, 6~

()6

J I I OC

Hs

1031

CU

H16

0

XcOC

" (I

4 H

g'-te

rt

1041

Cll

H16

0Z

O

CH

s I ((Ji

. I OC

Hs

C12

........

........

~ .......

... 10

51 C

12H

s04

CO

OH

i

r/X

)

~

~ tO

OH

1061

C12

H1O

O8

OH

(XX

~

~

CO

OC

Ha

A/C

zH

D

~)

6CHa

(X

OC

H:<

C4H

9-te

rt

OC

Hs

I /~/CaH7

~)

I OC

H:; C

OO

H

(()

~OOH 0

(X

:(O

OC

H 3

I INa,

NH

s ' C

HaO

HI-

68

Li,

NH

s'

22

tert-

C4H

9OH

Na,

NH

3,

37

118

C2H

sOH

, (C

zHo)

P

Na,

NB

s,

16

01

11

9

C2H

5OH

INa,

NH

8,

CH

aOH

I-I

80

::0

tTl <:

.....

tTl ~ ~ r .....

t-'j

tTl S; t-'j c Gi ......

Z

'Tl 2 ~ t-'j .....

0 Z

C.:>

C.:>

Sta

rtin

g m

ater

ial

Rea

ctio

n pr

oduc

t

No.

E

mpi

rica

l S

truc

tura

l fo

rmul

a S

truc

tura

l fo

rmul

a fo

rmul

a

07

C12

H10

03

HO

OC

I

cocm

I

I (X

yO

CH

3 (X

yO

CH

3

I I

I, /

1

08

» C

H30

(xyeO

OIl

(X

yC

OO

H

09

» C

OO

H

(X

Xo

cH

,

(X

yC

OO

H

10

C12H

1202

OCH2CH~ml

OC

H2C

HP

H

I

O()

I (X

)

11

»

)(X'

~ I

M)

HO

CH

zCH

P 'J

,,~

HO

CH

2CH

2 /

i i I

!

(Con

tinue

d)

~

Met

al,

prot

on ~~

~~

dono

r, a

uxil

--<

ll

"""'

......

0

iary

sol

vent

s <l

l<ll

'~..

c:

>-....

Li,

N

H3

, 52

C

2H5O

H,

(C2H

5hO

Li,

NH

3,

41

C2H

r;OH

, (C

2H5)

20

Li,

NH

3,

-C 2

H5O

H,

(C2H

5)20

Na,

NH

3,

CH

30H

-

Na,

NH

a, C

HaO

H -

Lit

er-

atur

e

111

111

111 47

47

::0

tTl <

......

tTl ~ ~ r-< ~

tTl ~ >-3

C ~ Z

.." ~ ~ >

>-3 o Z

I I

I I

I ,

N

NH

16

,,1

50

112/

d;H,

O

CH

I

3 1

a,

:1'

'ell

C2H

fjOH

, TH

F :::0

I ~(

~I

I tT

l

I -

< tT

l

I ~

OC

Ha

OCH

a 0 '-r

l

1131

CH~:crH'

CH'm

+CH,

oW Li

, N

Ba,

CH

aOH

-85

t'"

' >-

<

f/ I ~

>-l

tTl

~

~

~ 11

41

CH,o'(

XyOCH

, I

Li,

N

Ha ,

96

12

0 >-

l c

I I

I C 2

H50

H, T

HF

:::0

tTl

>-<

"-./

IN

a,

NH

s'

Z

1151

'-r

l 96

85

, ~

I CzH

.OH

, TH

F 12

0 ~

116,1

W

OCH

, jx

jO

CH

a N

a,

NH

3,

, 74,5

50

:>

I~

>-

l C 2

HsO

H,

THF

: 0

CHaO

~

~

I z

CHaO

..-

1171

CH~~

CH~(

(~OH

IN

a,

NH

a,

I 721

67

C 2

Hr;O

H,

(HC!

)

I)

OH

o

f'

) C

HaO

~

1181

C12

H14

02

H,CW

-H

'lo

L

i,

NH

s'

I 851

113

C

HaO

H,

THF

'" I

0)

I I

0 ,

0:)

119\

C12

H14

Oa

(XXCOO

H /X

XCOOH

Na,

NH

a,

I-I 4

7 I

I I

C~HfjOH

I I

i "'

-.0

O

CHa

" 'O

CB

a 0

0

en

Sta

rtin

g m

ater

ial

No.

E

mpi

rica

l S

truc

tura

l fo

rmul

a fo

rmul

a

20

CI2

H14

Oa

CO

OH

CH

,0'd)

1 21

C

l2H

l6O

(y)"

CH

a O

C2H

5

1

l2

» H

aC

~)J C

Ha

CH

O ~

3

1

23

C 12H

1P2

O

CH

2CH

PH

!

I (X)

:

1

24

C 12H

1S0

2 :

HaC

(YOCH

.CH'OH

1

I C HH

7-is

o

Rea

ctio

n pr

oduc

t

Str

uctu

ral

form

ula

CO

OH

I

°

I ~CX)

())~

CHa

0

HaC

(1-:

CH3 O~ f/

V

OC

H2C

HP

H

I O~)

CHa

A/O

CH

2C

H2

0H

l)

I CaH

7-iso

Met

al,

prot

on

dono

r, a

uxil

-ia

ry s

olve

nts

Li,

NH

a•

C 2H

5OH

. (C

H2O

CH

ah,

(H2S

O4)

Na,

N

Ha,

~H50H.

(HC

l)

Na,

N

Ha,

C 2

H5O

H.

(H2S

O4)

Na.

N

Ha•

C

2H5O

H

Na.

N

Ha•

C 2

H5O

H

(Con

tinue

d)

~~

~~ L

iter

--<

ll ."

....

.......

0 at

ure

<ll<

ll '~.d

:>-<

....

-12

1

-76

-42

-'

47,

122

-88

C» m

~

< til ~ ~ r ~

tTl ~ >-'I c::: ~ Z

'n ~ :>

>-'I o Z

1251

C12

H19

ON

1

K

)J(

Na.

N

Ha•

(

92

123

::0

/1

I 1

CH

aOH

t"

l <:

~

til

CHuO

(C

H2h

N(C

Ha)2

CH

a (C

H2h

N(C

Ha)

2 ::E

: 12

61 C

12H

uN

(XN

(OJ,)

, «

N(o

!'),

Li

. N

Ha•

22

0

~I

tert-

C.H

gOH

'T

l

t'"""

~

::J 'C

4Hg-

tert

C

.Hg-

tert

t"

l s: >-l

CIa

c:::

fg 12

71 C

iaH

Io

I l-

I

OV

() (~O

Na.

N

Ha•

-1

00

12

4 Z

C

2H

60H

. T

HF

'Tl ~

1281

C1s

H1

4

CHa

CHa

Na.

N

Ha,

12

5 )-

1 I

~H60H.

>-l

l-I

(X~

(X)

( H

5)20

0 Z

~

~

~H3 ~

H3 ~Ha

~H.1

1291

~3H140

OH

~"~o

Na.

N

Ha•

I-

I 37

JXl

~H50H

iso-

CaH

7 ~

U

iso-C

aH7 ~ 1

) 13

0 I C

13H

1602

~C(Q

H,Cm.-

Li.

l'-J

Hs.

1 48

1 11

3

~I

0 lI,

C I

I 0)

C

HaO

H.

TH

F

HaC

' 0

:)

I I

~

..:J

Sta

rtin

g m

ater

ial

Rea

ctio

n pr

oduc

t

No.

E

mpi

rica

l S

truc

tura

l fo

rmul

a S

truc

tura

l fo

rmul

a fo

rmul

a

31

C1

31-1 1

602

CH

2=

CH

O

il

C2H

. V

I

CH,Om

C

HO

J:X

)

a

1 1

32

C1a

H18

O

CH

O/()-()

J:)-

()

CH

a .

'..

33\

3

» »

»

1 1 34 i

»

» ),

......

......

.....

.....

C14

..

....

....

....

....

....

.

1 35

C14

HI2

O

('

(X~O

(X~OH

Met

al,

prot

on

dono

r, a

uxil

-ia

ry s

olve

nts

Na,

NH

3, C

HaO

H

Li,

N

H: l

,

C2H

5OH

, (C

2H5)

P

Na,

N

Ha,

C

HaO

H,

tert

-C4H

90 H

, T

HF

Na,

N

Ha,

C

2H

5O

H,

(C2H

S)P

Na,

NH

~>

C2H

50H

, T

HF

(Con

tinue

d)

ro~

~g L

iter

--Q

) ", ...

......

0 at

ure

Q)Q

) '~..c::

:>< ..

.

39

86

88

29,

115

84

11

35

29,

115

I

34

126

to:>

00

::0 ~ til ~ ~

t"'" ::3 t>:I s: >-:l c:: ~ Z

'TJ ~ >

>-:l o Z

I I i

I I I

1361

C14

H12

02

CH~At"

CH

aO

,-()

/" ,,~(.OH

Li

(6 g

-eq

),

7311

27

::0

ll-(

~ N

H3,

Cll

50H

t"

l -

l t"

l

(xX

C2H

.OH

, T

HF

~ >-l

c:::: fg

1391

C14

H14

O

Na,

N

H3,

12

6 .....

.

(:O~OH

(ifO

H

61

Z

C2H~

OH,

TH

r I

"T1 ~ 3::

:>

>-l

140~

C

14H

16

......

HaC

C

H3

HaC

C

Ha

Na,

N

H3

, -

125

0 I

I

eX)

C2H

5OH

, z

(X)

(C2H

5)P

HJ

~H3

I I

HaC

C

Ha

1411

»

06)

(I

IN

a,

NH

3,

1-1

12

4

C2H

sOH

, T

HF

(X)

1421

C14

H16

02

My

OC

2H

5

jJ(yO

QI'

IN

a,

NH

a,

i 751

50

C 2H

.OH

, T

HF

C2H

sO ~

,9

C2H

r.

I I

1:.0

)

co

Sta

rtin

g m

ater

ial

Rea

ctio

n pr

oduc

t

No.

E

mpi

rica

l S

truc

tura

l fo

rmul

a S

truc

tura

l fo

rmul

a fo

rmul

a

1 43

CU

H1S

02

0 O

H

II

CH~,;w

c,.a

m ~aH,-i

SO 44

»

HOiA

_ ~I

v ~y

ly!

CHaO

/~)

CH

O

.6-a

1

45

» H

OiA

1_

("'I-

~yv

A/V

CH

ao

/V

CH

O

.6-3

1 1 46

C

14H

200

2 O

H

OH

d'

CH'~~

CH

aO'" ~

I)

CaH

,-iso

C

aH7-

iso

Met

al,

prot

on

dono

r, a

ux

il-

iary

sol

vent

s

Na.

N

Ha•

C

2H.O

H

Li.

NH

a•

C2H

oOH

. (C

2Hoh

O

Ll.

NH

a•

C2H

.OH

. (C

2H.)

P

Na.

N

Ha•

C

2HoO

H

(Con

tinue

d)

'0';\1

~g L

iter

--<

l.l "'

0 .

...

......

0 at

ure

<l.l<

l.l '-,

.c:

>-.... 70

12

9

-10

0

130.

13

1

-\0

0

130.

13

1

-12

9

oj:> o ~ til :E: ~ t"' ::3 tr.I S; i-l

c:: fg

......

Z

." ~ )- i-l @

CII

i fg

14

7'1 C

I.H

140

2

CH'°'C

'Arr'YO

CH,

<:

~'L:()'

Li.

NH

a•

83

127

til

~)_I~

~HoOH

:E:

1/1

-('

0 'Tl

1481

ClO

H20

O

CH

a C

H3

Na.

N

Ha•

85

38,

39

t"

' .....

I 1

C2H

liOH

>-

l tt

l

m

C~~;

s:

CH

O ~,

/

>-l c::

a II

fg H

acA

cH

a

cH

aA

cH

a

52 14

91

Ha

A)

HaC

(~

Na.

NH

a• C

HaO

H

80

132

'Tl ~

('I "

I ('

h/

$':

:>

HO

/ )0

>-

l H

O/ A

)

(3 z

1501

1

}fN

HaC

(~

Na.

NH

s• C

HaO

H

-13

2

J:+V

HO

)V

H

A

) 15

11 C

IIiH

200

2 C

Ha

CH

s N

a. N

Hs•

I

671

133

("I-O

H

('-1

-C

HaO

H.

tert

-C,H

9OH

.

))V

A

)""

(~Ho

)20

CH8o

/~)

CH

aO

d-

1521

L

i. N

Ha•

C

2HliO

H

1-1

13

4

I I

Il>-

......

Sta

rtin

g m

ater

ial

Rea

ctio

n pr

oduc

t

Str

uctu

ral

form

ula

Str

uctu

ral

form

ula

OH

n6

~,~

c!)/

: C

Ha

~

CH

aO

/V

1

OH

,

all

all

rnft

0 )~

/'"

CH

aO

/V

1

» O

CHa

\ 0 II

1

H(/e

x))

() H

O/(X

)

Li.

NH

a•

C2H

5OH

(C

2H5)

20

Li.

NH

a ~H

50H:

(C

2H5)

20

Na.

N

H

CH

aOH

. (lo

R:l)

(Con

tinue

d)

t

-13

5

-13

5

-13

6

~ ~ ~ t"" ~ ~ t-i

c:: ~ Z

'n ~ ) t-i

(5

Z

1561

O

CH

3

H~)

I i

0 1

_1

13

6

Ii L

i, N

Ha

H$

C 2H

r;OH

'

1571

C H

(CzH

5)zO

;0

tTl

15

22

<

Clia

tTl ~

I

0

C~m

CH3

'T]

i N

a,

NH

a,

r

J:)('"

C

2H

5OH

_

I

38

::3 tTl

II C

Ba

)

~

1581

C H

0

Hac

AcH

0-3

15

22

a a

II

C

-1

--

Hac

AcH

fg

o b

3

-""

'/

C'V/ (CH

2 )aC

OC

H

Z

MICH

,),-C-

CH

0,1

)~

a

Li,

NH

a,

'T]

CH

O ~ I

a

CzH

r;OH

, (H

Cl)

~ H

a

a C

H

:>

a

0-3 - 0 z

......

......

..... ~

C16

1591

'c~~H~~O~

,,,·,,·1

CHa

I Li

. N

H,.

I I

("IA

d~)

~M'"

I I

C2H

50H

, (H

Cl)

-13

8

I C

Hs

.-9

(')

'"

'O

H

, I I

0/7

'''./

i

I I

: I

I I I

~

c.:>

Sta

rtin

g m

ater

ial

Rea

ctio

n pr

oduc

t

No.

E

mpi

rica

l S

truc

tura

l fo

rmul

a S

truc

tura

l fo

rmul

a fo

rmul

a

60 I C:t

SH18

02

I ;]A

yH'

HC

A

/OC

Ha

3 ~

,(IN

O

f'

.&I ,

,)

HO

),,)

1 61

» »

HC

(V

O

/~I/

) H

O

),,)

1

52

C:t6H

1S0S

O:tH

0

(X)~

: 1,,

9 CO

OC&

Hll-

iso

~ "c

OO

C;H

ll-iS

O

1 1 13

»

OCH

a 0

I O

CH

3 Ii

CV(Y

/)

'I

,(f

~)V

HO

I'

) I

Met

al,

prot

on

dono

r, a

uxil

-ia

ry s

olve

nts

Li,

NH

s' ~H&OH

Na,

N

Ha,

C

HsO

H,

(HC

!)

Na,

NH

s' C

HaO

H

(HC

!)

Na,

NH

s,CH

a0H

(H

C!)

(Con

tinue

d)

t

~~

~~

-til

"0

'"

......

0 til

til

..... ,

d

>-< ..

.

- - 80

-

Lit

er-

atur

e

139

136 80

136

~ ~ ~

t'"" ::3 ~ >-l c:: f;l .... Z

'T1 ~ >

>-l @

::>:l

ttl <:

>-< ttl

164/

CuH

soO

s

H,C~

HaC

A/O

CH

a

~!JI

Li,

NH

s'

H~~

~I;O

H,

=E:

( H

&)zO

, ~

diox

ane

t""

>-< >-:l

ttl S c:

165

/ C

18H

200

8 I

CH

a

19~

(1 N

a N

H

C

' 8

' -

141

2H&O

H,

(HC

I) ::>

:l

CHs~b

ttl

>-<

J)"

Z

'T

I ~ >- >-:l

>-< 0 Z

166/

C

16H

200

4 I

;YCOO

H I

1 771

142

CH

~

I C

H3

0m

Li,

NH

a•

~H50H

3

1671

)

HjfCO

OH

$ rn

A Li

, N

Ha•

/

62/1

42

C2H

&OH

t

(Con

tinue

d)

~

Sta

rtil

lg m

ater

ial

Rea

ctio

ll pr

oduc

t ro-

;;s M

etal

, pr

otol

l ~~ L

iter

-N

o.

dOllo

r, au

xil-

oQ)

"0 ..

.. E

mpi

rica

l '-

<0

atu

re

Str

uctu

ral

form

ula

Str

uctu

ral

form

ula

iary

sol

vellt

s Q

)Q)

form

ula

.~;::

:>-< .

...

68

Ct6

H22

02

HsC

r

HsC

Li

, N

Hs,

143

I -

I O

H

I O

H

tert

-C4H

gOH

,

(' -1

---C

Hs

(~-I

-'CH

3 (C

2H6)

20

~V

A/V

CHaO

Q

CH

O/~)

I

~

1

......

... ~ .

.... ~.~

.....

I C

t7

~ r;;

....

... -

--

.. ~

69

Cl?

H20

02

CHaO

Q

CH'~y

Li,

NH

s, C

HaO

H,

-14

4 (C

2H6)

20

XX)

COCH

s I )

"'/

1 ~ t'"

.... 0-'3 S c:::

: 70

C

17H

220

2 C

Hs

CH3

Li,

NH

3•

-14

5

(,I

90 CHO

HC~

C2H

oOH

,

))O

CH

s

(C2H

6hO

JC) "

CH~

CH

//

3

1 ~ ~ ~ )

- 0-'3

(3

Z

II I

1711

~7

H2Pa

~)/CH'

11

0'(y"

, ::0

N

a,

NH

s'

24

107

M <

CHaO

C 2

H50

H,

(HC

l) .....

. M

~'I

I ~

oDJ

~

CHs ~)V

t"" ......

>-l

M

::0

:>

>-l c::

172

1 C1

7H24

02

CHa

CHs

Li,

NH

s,

80

146

::0

M

('I~HOHC

H'

(,,1-

C2H

6O

H,

'"" (C

2H5h

O

z 'Tl

f'i"

G5

J)~

~

:>

CHs

~

oA

>-

l '""

0 z

1731

C a

H7

C aH

7 N

a,

NH

a,

1-1

14

7

("I--O

H

("I-

---r

l)H

C 2

H5O

H,

(C2H

5)p

. (H

Cl)

())

ri")

CH

a<Y

I ~

oA

174

C 17H

2,Oa

HO

",()

/.C

HO

HC

Hs

1 Li

. N

Ha,

1

861

148

~(

C?H

I\OH

(X~r

CH

lV ~/

/ oj:

>. -.

1

Sta

rtin

g m

ater

ial

No,

E

mpi

rica

l S

truc

tura

l fo

rmul

a fo

rmul

a

75

CI7

H24

0a

H"'

eyA

:HO

HC

H,

()()

C

H C

Y' ~

3

1

.~ ...

~.-.. ~

.~.~ ...

.. ~ ...

CIS

......

......

......

.....

1 76

. C

lsI-fl

S02

Ocr

-I;,

rxl vi'

CH

iY ~

77

C1s

H2P

2 ,,/-0

NCY"

r C

HO

~

3

1

Rea

ctio

n pr

oduc

t M

etal

, pr

oton

do

nor,

au

xil

-

Str

uctu

ral

form

ula

iary

sol

vent

s

I Li

, N

Ha,

CH

o/(X

Y

C2H

.OH

3

OC

H' I

Na,

NH~,

I .

C2H

ijOH

, T

HF

oi/X

) (H

2SO

4)

(~I-OH

I L

i, N

H3

,

(VV

V

! C

2HDO

H,

(HC

l)

of )~

)

(Con

tinue

d)

1'Q';;j

~g L

iter

-b:

l'~

'-<

0 a

ture

(l

)(l)

'~..c::

>-< ..

.

76

148

42

149

-15

0

.... 00

::<l

t"l <

......

('Z

l :E: ~ t'"' ::; ~ :>

>-l c g; ~ ~ :>

>-l (3

Z

I

1781

C

H 0

18

22

3

rf 0

CHa

I

('ITH

I

Li.

NH

~/'0

C2H

sOH

. TH

F

CHa

~,,)

~)/j/i

::<:l

t'r.I

0

<:

.....

CHa

" /

t'r.I

0

~ ~

t'"'

1791

~ H

0

82

4.2

H

3C O

H

(I)

uOl

~I/"J

Li.

NH

a

.....

149.

t-l

C2H

!;OH

. THF

t'r.

I

CHaO

~

I I

/0

152

::<:l

1801

(H2S

O4)

>

»

t-l

0#

c

HaC

OH

::<:l

t'r.I

fl)

H3C

OH

.....

z 'Tl

~IVO

vC

1 )

Na.

N

H

68

149

~

I AJ

C

2H!;O

H. T

HF

(H2S

O4)

>

CHa

~

t-l

.....

Off

0 z

1811

H

aC I

COCH

H

aC

I'j.--C~a

I C

HO

HC

H

Li.

NH

a 1

-11

45

)(y:

~.-I---CH3 a

C~

H!;O

H'

CH

aO

~

I ~/:"v'

( 2H

S)20

CH

ao/0

18

21

lC7°CH

. ifH

. Li

. N

Ha

~!"~

I

481

45

~/

CH

aOH

'

1

(C2!

I o)20

HaC

r.

Hs

I !

0l:>-

eo

Sta

rtin

g m

ater

ial

Rea

ctio

n pr

oduc

t

No.

E

mpi

rica

l fo

rmul

a S

truc

tura

l fo

rmul

a S

truc

tura

l fo

rmul

a

C 1sH

2P2

CH

a

~I-OH

/ I

o~~XY

~/V

I H

O ~

»

I ~I-OH

/ I

~V,)

CH

aj()(Y

I CH

a ~

)

ClsH

240a

CH

a

I rlT

H

I /'

I

CH,)lY

Y ()A

/: CH

aO/~

,,)

0

I I

C1s

H2P

4

0

Hi O

H CH

a

~ j-

(CH

z)zC

OO

H

Cl /

~)/i

/"')

" CH

a ,&

CH

30/~

)

1 ~8

185

186

Met

al,

prot

on

dono

r, a

uxil

-ia

ry s

olve

nts

I

Li,

N

Ha,

~H50H,

(CZH

5)P

Li,

NH

a,

tert

-C4H

9OH

, (C

ZH5)

20

i I L

i,

NH

3,

C ZH

50H

Li,

NH

a.

tert-

C4H

9OH

(C~H5)P

, "0';;\

~~

-<ll

Lit

er-

"" ....

.....

0 at

ure

<ll<

ll '~.c

>-0 ..

. I -

153

-15

4

-I 155

I

-15

6

I

en

o ::<l

ttl <

1-1

tt

l ::E: $fl t-' :::J ~ d 1'g Z

'TI ~ >

>-l o Z

1871

C1

sH2.

ON

I

1881

Cls

H25

02N

1891

C1

sH2P

190

191

((TreH ,

CH

,O' ~ '0

C

Ha

/'I

-O

H

(yl,r

v CHaO/~/")

a~YO

CH'

~:,,)

HaC

CH

a

OCHa

I

.

a~)

Xl"

) Ha

CH

~

(I I

'1/

/"}('

~H30A, J~

/"

'Vi

( II )/

CH

aO

/"/"

)

HaC

("

yP

~I~f

HaC

A/O

CH

a

"I/~)

/iV °

II

HaC 9 (

"1/

/i"-

Li,

NH

a·

C2H

50H

, (C

2H5)

20

Li,

NH

a,

tert

-ClI

90

H,

TH

F

Li,

NH

a,

C2H

50H

, (H

CI)

i -115

7 I

I I

I I

I

44,

159

K,

NH

a,

I 98

1 41

C

2H50

H,

(C2H

5)20

Li,

NH

3,

I 48

1 16

0 C

2H50

H,

TH

F

(HC

I)

;0

t:r:I <

.....

t:r:I ~ ~ r q t:r

:I ~ >-l c::: f;:l Z

'Tl ¥ 3:: >

>-l o Z

C1I

......

Sta

rtin

g m

ater

ial

I

No

, Ii E

mpi

rica

l fo

rmul

a S

truc

tura

l fo

rmul

a

I 92

C

1sH

26O

2 O

CH!J

I

Ci6)

/""'-

H3C

C

HP

H

1 93

»

»

....

....

....

. _ ..

.. ' ..

'

C19

..

....

....

....

....

....

1 94

, C

19H

lS02

°

II

()()

C

HQ

/(X

)

3

Rea

ctio

n pr

oduc

t

Str

uctu

ral

form

ula

OC

Ha

H3C

I ,A

'''I/l)

/"

')

).

°

I'

O1)(x

90

(Con

tinue

d)

ro';;i

Met

al,

prot

on ~g L

iter

-do

nor,

au

xil

-0(

1)

"0

'"

......

0 at

ure

Q

)Q)

iary

sol

vent

s ...

.. ,.d

;.-.

...

Li,

NH

3,

97

161

tert

-C4H

gOH

, T

HF

Ca,

N

Ha,

te

rt-C

4H9O

H,

57

11

TH

F

K,

NH

a, C

HaO

H -

162

CII

1):)

~ til :E: ~ r ::J ~ >-l

C fg Z

'Tl ~ ~ '6 z

195/

~ H

O

N

9 20

2

i #

' A

,'- J II

~ \(

"-/

' h

l6 I C

HaO

19

61 C

IDH

200a

1

0 o

ii

~(~0

CHm

1971

C H

0

19

22

2 C

Ha

7 c*

rH

CH30~XY'

1981

C

Ha

('1-=

0 MV1~

CH

aO ~

)

I l\: "-

./ " ~A

~)

i C

HaO

OH

"-.,'

)

H~'~'

O#

cx (J(Y

C

Ha

O"'

'' ~

CH

a

("I)

'H

CH

aJ:X

)/i

"-.

Na,

N

Ha,

te

rt-C

,HpO

H

88

36

Na,

N

Ha,

C

2H&O

H,

(Hel

) -

163

Na,

NH

87

te

rt-C

,H9O

H

164

TH

F

'

1\,

Li,

NH

1

1 C

2HijO

H a

--

56

:;0 tTl <: ~

~

0 ."

r ;:J

tTl S! >-l c fg

.....

Z

." ~ >

>-l ..... @

CI1

Co)

Sta

rtin

g m

ater

ial

Rea

ctio

n pr

oduc

t

Np.

E

mpi

rica

l S

truc

tura

l fo

rmul

a S

truc

tura

l fo

rmul

a fo

rmul

a

I ~9~202

CHa

CHa

("'/

-=

0

("'/

-.-

oH

~'V

(lY'v

CH

aO ~

off

"

1

I »

. "I

()~fO

,/X

wO

H

CH

ao

M)

I I)

CHa

2

~9H2

'0

9J~

I

O/()

~ 0:

" CH

ao/~

I I

C1g

H2,0

2 CH

a C

Bs

2 2

("'/

-=

0

("'i-

OH

JJ:)

'V

,/XV

!V

+

CHaO

~

CHa

)

! I

. I

Met

al,

prot

on

dono

r, a

uxil

-ia

ry s

olve

nts

Li,

NH

a,

~H50H,

(~Ho

)20,

(H

Cl)

I I L

i, N

H3

,

I te

Tt-C

4HgO

H,

TH

F I I I

Li,

NH

a,

I te

Tt-C

4HgO

H,

TH

F (H

Cl)

I I L

i, N

Ha,

C

2H5O

H,

(CZH

o)20

(Con

tinue

d)

1'C

i';;

~g L

iter

--<

0 tsC

i atu

re

<0<0

.~~

>-.... -

57

62

154,

16

5,

166

24

165

I

-16

7

I I

en

of>. f;l <:

til ~ ~ t'""

::j

t:<:I S; >-l c:: f;l Z

'Tl ~ > >-l @

204

»

205

CHa

OH

+ I

(,,,1_

1 _ CH

"O/"C(

:(~-

CH

"I a

(x00 0

H

CIJ

ao

A I

) CH

a

o~9~ OH

CB

s

I d 0

0l1

CH

aO

/()(

) CH

a

-, _,2

I

U, ~H

3'

C2H

DO

H,

TH

F

Li,

NH

a, C

2HsO

H,

TH

F

I

I L

i. N

Bs.

I-I

iC

H30

CH

2CH

(OH

)CH

a I

I I

!

Na,

N

Ha,

C2H

[;OH

, di

oxan

e (H

CI)

/,,1

"'V

i ) -G

H

("/'

I "

i

0#"')

"')

I i

169 93

~

tTl < .... tTl

::E:

0 "Tl

r .... >-l

tTl ~ >-l

C ~ .... Z

"Tl f6 $::

:>

>-l .... 0 Z

en

en

(Con

tinue

d)

<:II en

Sta

rtin

g m

ater

ial

Rea

ctio

n pr

oduc

t

No.

1 M

etal

, pr

oton

Str

uctu

ral

form

ula

Str

uctu

ral

form

ula

2071

Clu

H24

02

osr'

CH~)(Y

)~-OH

Li,

NH

a•

CJl,<

v: I

I ~

C2H

5OH

1-1

171

.

208!

(C2H

6)20

17

2

CH

a

,,1-ToH

CH

.)XY

1<:,

Li,

NH

fg

(X~/l'"

C2H

sOH

a·

CHaO

/~ I

)

<

(C2H

6)2 0

, T

HF

......

t>l ~ $fl t"'

" -f-j t>l 5:

209i

C

H

0 19

24

3

C2H

f>

,,1

--0

CzH

o

/ "O

-oH

Li,

NH

(xy!

')

CZH

60H

. y'

HF

f-j c::

I Ol

aO/~

,,)

~)i/

fg

0

-

I

CH

aO

" /

Z

'Ti

0

0 ~ :>

f-j - 0 Z

I I

2101

C

Ha

ff~O

I '

CH

a ~

2111

HO r

"'1

'-=

0

M,0

C

Ha

~

2121

2131

C1u

H24

04

HaC

OCOCH~

('~.""

OC",

j)/:

' I

' I

CH

a(

§

2141

BY

H3C

\

~

OC

Ra

(,0 ~

CH

a

HO

, 1

'1

" --O

H

Mi 0

C

Ha

CH

a

HO

1

"'(

"'-

OH

$;0

C

Ha

CH

a

('I)"O

HC

". ('1

/:"-

ey/'

J C

HaOn I i /

I O

CH

a

U,

NH

a,

C2H

sOH

Li,

NH

a,

-17

4 ~HsOH,

diox

ane

Li,

NH

a,

57,

C2H

sOH

. 17

3 (C

2Hsh

O

I L

i, N

Ha,

75

89

, C

HsO

H,

175

(C2H

s)20

, (H

CI)

Li,

NH

a,

.-,,1

001

176

C2H

sOH

, (C

2H5h

O,

diox

ane

::0

tTl <:

.....

tTl ~

0 'Tl

t""' .....

>-l

tTl s: >-l c:: ~

.....

Z

'Tl

0 ::0

3::

)- >-l .....

0 Z CI1

-J

CTI

00

Sta

rtin

g m

ater

ial

Rea

ctio

n pr

oduc

t

No·

1 I'

",n

;r;,

.."l I

Str

uctu

ral

f orm

ula

I S

truc

tura

l fo

rmul

a I i"

y ;o

lveo

"

CH&

~ {'~OH

I

ex)

I Li

, C

2H

NH

I

ex '/i~

~.I

,)

tert

. C H

6i;

801

177

5 11

I CB

3

I

I 21

61.

C

H

0

CH

a

19

26

2 C

Hs

OI,o

yx('I)

OH

CH

aO

I C

Li,

NH

a

~

~ I )/

:~

'DC)

39

17

8 <

zH,O

ff,

TH

F

I-<

179'

tT

l ~ ~ L

" I-

<

>-3 ~ >-3

2171

C

lis

('1 0oH

I

((J/

C

Hao

fX

)/

Li,

NH

a>

I 66

180

CHaO

/'~

!

CZH

50

H

c::::

(CZH

5)20

;;0

tT

l Z

'Tl ~ :>

>-3 '6 z

218

219

220,

221

222

223

2241

2251

CH

" ,

/ I

, /1

----

011

,.<""

'/""

"')

l

Il I'

i. I

. C

IJlY

' ... ~/ ")

CI I

}

i "

/',

/

"/

'v

" I

ii i

>/"

/,,

/)

Li,

NH

s,

CzH

.OH

, (C

2Hs)

20

Li,

NH

a.

CZH&

OH,

(C2H

.)20

U.

:\11:

1' C

) I;,

C)H.

IC

)1;;

)/).

TH

F

Li.

\H:!

. (:

IIP

CH

2C1f

(OH

)(:H

:1

Li(K

). :-J

H3

•

tert

-Cll~OH.

(C!I

"OH

, C

)I,o

H).

TH

F

\a.

NJ-l

;).

CI-I

30

f!.

(ClU

lU

Ii'l

C);

,I}II,

71

) 11

5.

153.

1I

iR.

lR2-

-18-

1

k:zl

IRS

181;

11

187.

fli

R

~il,

N

H;j.

I 8~

1 f(l

iso

-C:

11I 7

OH

. (C"H:»~O

"C!.

Nll

a.

I 11

te

rt-

Ci1

"OH

, T

HF

fg <

iTl ~ ~

r ::3 ~ o-j c: fg Z

'Tl o ~ >

o-j @

C11 ~

Sta

rtin

g m

ater

ial

Rea

ctio

ll p

rodu

ct

No.

E

mpi

rica

l S

truc

tura

l fo

rmul

a S

truc

tura

l fo

rmul

a fo

rmul

a

2 Cl

~H2'

P~

Cll

a C

Ha

kl -ol

l

CIl';::

CY''')

~'l--O

H /v

r)

CH

a(Y

JlJ

l

, C

Ha

I

/Vd~

) ~,

/''

) /

AX ./

C

HO

,.,j

~

I II

CH,p/~./' .. )

2

Cl.I

I~,;

()a

CHe;

I

("-I·

··CO

OII

{):"

l\

.j' ....

/:"I/i-C~llfo

CII

:p/ ,,/ "./

')

C:Hi

Y~ ,

,)

2

I

Met

al,

prot

on

dono

r, a

uxil

-ia

ry s

olve

nts

Li,

NH

a.

C2H

PH

, (C

2H5h

O. T

HF

I I 1

Li,

NIl

:..

tert

·C1H

!,(

)H

I

Li,

NH

3.

C2H

,,oH

(Con

tinu

ed)

I'o~

~g L

iter

-o

(\)

-0 .

...

-0

atu

re

(\)(

\)

.....

,.t:l

>-0 ..

.

I ~J111 f

i9

I

...

/911

".

191

I

I I

0)

o ~ til

:E: ~ t"

" ::J tTl ~ ,., c ~ Z

'Tt ~ :> ,., (3 z

2291

I

2 N°

Oj ,

H~C

(""j

OC

ll:l

I i ("J~)

Li,

NHa

/),,)

I

C2H

.OH

' --

77,

78

HaC

'" "t

OO

CH

a

\/l)

(C

2H.h

O

~

/""-

t:rl

IlsC

C

H20

H

-< I:a ~ ~ c-' -

2301

»

HO r

~(~')OH

1

CH3c

Y~X)

/ Li

, N

Hs

57,

( II

)/1"

~H60

H'

'"'l

(~H.

)20,

19

2 ~

2311

CH

30/ ~_A,

'"'l c:

CH

: 1

fg

In

I

-

d('

,0H

I

Z

Li,

NH

'Tl

~

C

3'

193,

~

CHl{V~

I Y

2H.O

H

(C2H

6)20

19

4 > " - ~

2321

»

CH

!i

(r,(b

-oH

I

I L

i, N

H

I

I /.

"'0

C

H3O

/O

CY

C2H

OH

T'

701

195

CH

!iO/ ~

,,)

H

6 ,H

F

» I

I I

» L

' I

I

I

ClI

1,

N

H3,

-

' aO

CH

2 CH

(OH

)CH

19

fJ

3,

diox

ane

I ,

0)

.....

Sta

rtin

g m

ater

ial

Str

uctu

ral

form

ula

OH

(""I

OH

~

/j--CH~

CH

pAX

) ,

235

OH

:

OH

(""j-

j-CH

a

~X)/:V

cHao

A

C2H

.

('i-r

lJH

A

/,

/;",

,)

I II

N

CHO

/V""

) a

Rea

ctio

n pr

oduc

t

Str

uctu

ral

form

ula

I

o~()~y

oJ(x

Y

I n

' !:I~/

:; !:

i CH

p/V

V

-----

Li,

NH

a,

tert

-C

4H90

H,

TH

F

(HC

I)

Li,

N

Ha,

te

rt-C

4HgO

H.

TH

F

(HC

I)

Li,

NH

3•

tert

-C4H

90H

. T

HF

(Con

tinue

d)

0>

tv

~

<

t:;:J

~ ~ r q ~ >-l c::: ~ Z

'Tl o ~ >-l o Z

23

7l

CHo

" I

., ()t

I

(y(

'rjcl

" {/

" /"

v

\ ,\'

ClI

P/V

")

C

-~luIl2~O:l

<

~11;jJl

,.:/

/'

"

GI:I

O,)~

XICJ

IzhO

I !

239

Ol-l

(' I

01

!

~'-.... h

.'

10

!"

r r ,

', /

CHl()/

~' .. )

v

OC

H

/)((XI

!~ .1

j I

' )

Ol:.o/~·

,)

/ I

~ y)/

CH

P/"-

/'-...

.)

" /"

'

II ,./

-"v,,

//

.!i)l!

: C

J!})

/ .../

(yl

cHsA

) OC

H:,

,

(1/)

_"

J!

()f(

)~ r/'

~f

Li.

NH

s•

tert:~C4H90H.

TH

F

Li.

'\H

:l'

C)-

I})I

I. T

HF

Li.

NH

",

tert-

ell nO

ll

IC}I

:,)p

. T

HF

Li,

NH

".

CzH

"OH

, T

HF

IH

CI,

}.)8

-~ ...

19

R

197

::0

r::I <

til ~ o 'T

l

t"" ::J r::I g; >-:l

C fg Z

'Tl ~ :>

>-:l (3

Z

0)

C.:>

Sta

rtin

g m

ater

ial

Rea

ctio

n pr

oduc

t

No.

E

mpi

rica

l S

truc

tura

l fo

rmul

a S

truc

tura

l fo

rmul

a fo

rmul

a

41.

C~OH

2202

I

()()/l

CII '

(XyO

CH,

~''j

//

/):/'1

) CH

aO)~

I,)

Ii

I /

CH3~' ,

)

2 2 !l2

>:~

(?

CH

'l 0

/ I

"

HaC

/ X)

H

aC (";/

"

0

("I/

~/I

~ I

I I

•

vO~l

')+

(Y)

o#~),,-)

H

' A

/"

I

!l3

» lie

NO

CfI

, lla

C ('

,(f "

v:)

0 3

I ""

(,I)~

1//

(,,

,-1/"-

1)"')

(J

#"')"

') H~/'''')

2

l4

I »

" 2

Met

al,

prot

on

dono

r, a

ux

il-

iary

sol

vent

s

K,

NH

3•

C2H

5O

H

Li.

NH

a.

C2H

.OH

, di

oxan

e (H

CI)

Li,

NH

a,

C2H

50H

. (H

CI)

Li,

NH

:J.

C2H

5OH

, (C

2Hfj}

zO,

diox

ane

(He

I)

(Con

tinue

d)

'O~

~g L

iter

-0<

1)

'0 .

...

.....

0 at

ure

<1)<

1)

'~..c::

>--.... 45

16

2

-91

, 20

1,

202

75

60,

20.1

~-

204

I !

0)

~

:::0 ~ til ~ ~ t'

" ::J ~ >-3

C fg Z

'Tl ~ 3:::

:>

>-3

(3

Z

245

246

CZU

H24

0"

247

»

248

2491

G

!oH

2.oz

"

r~y)(~k)COCH

8 Ct

I80/

~ H

aC I ? C

/~

(Y~/

:"')

CH30

/~,k

) ..

HaC

011

,,,I)

.iYV~)

CHp/~

HaC

I O

H

("-I

·--C

=C

I-I

A/, /'v

I

Ii N

II

)

CH

aO/

V"-

HaC

/', /~OCH

(,I)

):J/

'

IlcA

)'·,)

('I /(

"'/ J

CH

OH

CH

/

,("

,j

O,;

?V

V

HaC

OI

-I

(',,1)

1 ("

/)/.

"/

o,;;~),

HaC

O

H

(",1/

\ (

' I

I

. 'j

/!I~

"/

()//

)V I

A/"

-/

!i II

N/

:I I

'I 'I

) CH:JO/~)""

\a,

;\H

;!,

C2H

,oH

, c:,

;H5N

Hz

Li.

NH

a,

1 -

1 15

(1

C~H50H.

(HC

I)

l\,

Li.

NH

a,

1 -I 2

06

C2H

50H

. (H

el)

Li,

NH

~,

1 80

1 20

7 C

2H50

H,

TH

F

(HC

l)

Li,

NJj

;j' T

HF

1-

'-1 1

58

tert

-t4H~( lH

::0

t>l < tTl

::E: $il r ::J t>l ~ >-l c:::

fg Z

'T1 ~ 3:::

)- >-l ~ 0)

en

Sta

rtin

g m

ater

ial

Rea

ctio

n pr

oduc

t

No.

E

mpi

rica

l S

truc

tura

l fo

rmul

a S

truc

tura

l fo

rmul

a fo

rmul

a

50 C2

oH~o

02

CH

3 0-0

-,-C

2H

5 (hC

>-I-C 2H

"

CH

P-O

-_

CzH

o

O~ ~)-l-C2I!"

2 51

» C

If;,

I

(~I-~o

tyy

~XY)

CJJ

;pA

/ v/

CH

O ~

3

2 2 52

»

01:,

ell"

~H3 ('

,1-=

0 !

~IL, (

"I--O

H

MY"

) f)

/\/"

) C

HO

~

(]-I

:P~

'v '-./

3

2 53

» »

,.

(Con

tinue

d)

~';;

i M

etal

, pr

oton

~g L

iter

-do

nor,

au

xil

--(

1)

"0

'"

"-'0

atu

re

iary

sol

vent

s (1

)(1)

'-<

..1::

>-..

Na,

N

Bs,

-20

8 C

2H50

H,

(HC

I)

Li,

"-'

Ha,

-20

9 C

2H,;O

H

Li,

NH

3,

G~H[,oH

-21

f1

Li.

NH

a, -

. 4"

-

" C

H;P

r:Jl

zCH

(OH

)CH

s I

a>

a>

::0

tTl < ra :.::: ~ r ;:::j

tTl ~ >-'l e ~ Z

'n ~ :>

>-3 o Z

2541

C

"H5

(~I-=O

((

f')

CH

:p/ ~

2551

CH~

I

Clla

(""I

I

TIl

;:fX

V':'

2561

CH30/~

) Ha

C 1 O

H

/ ("

'-I-

--C

H3

(~X)

/""/

CH

aO/~

I I

' .

2571

("'

10 C

OC

H3

(("/

C

H3<

Y ~

1 )

2581

H

aC O

H

" I)

/ '"

",xl./

,,)

CJ

l~1

J -1 3

0'

":

v'

C)-I

;; Li

, N

H- j

I

(,I

C~H50If

---.

17

4

. -I-

-J-O

H

dio

xan

e

~"(,/:,,

C!-Ia

A

) Ha

C I I

Li,

NH

a,

f)('Y

C tH

5OH

, -

54

CJ-J3~ 1

,,/

( ~H)P

((' /

Li,

NH

3

I I

Y'

caH5O

H'

--1,

17

1

CH

:P/

)! (

H5)

20

("'/

TH

OH

CH

I

Li,

NH

s,

1--

1 :11

1

/X"'/

" "

CH

aOH

cH

pA

I )

' (C

'2Hu)

z6

I (l"

/ I

, •

.. /"

J/

/ 1

K,

Li,

NH

, -

(yf'

\'"'

~.

( )

)\ I

C,H

,OH

." I I

92. 0

:''''

'''''

""

(CZ H

5 )20

, TH

F 2

12

-' 9

(H

CI)

214

I,

: ill

::0

t"l <

Fil

:E:

0 'Tl

t"' ~

t"l S; t-"l

C ~ Z

'Tl ~ 2::: >

t-"l .....

0 Z

0>

-.J

Sta

rtin

g m

ater

ial

No.

E

mpi

rica

l fo

rmul

a S

truc

tura

l fo

rmul

a

59

40H

2S0

2

~!j~

OC~

HO

/ /1

"')

2 60

» O

CH

3 I

HaC /X

) (I

Alb

H

O/ )0

2 2 61

C2

oH2S

03

CH

s

Ho

",1

1H~

1-,=

0 ~)/!V

CH

~

3

2 62

~OH2

6()~

O

H

CH

3 0-O

-i -C

2H6

CH30-0~Ho

Rea

ctio

n pr

oduc

t M

etal

, pr

oton

do

nor,

aux

il-

Str

uctu

ral

form

ula

iary

sol

vent

s

)(y),f

O

Li,

NH

a,

~HIiOH,

(HC

I)

/ '/" 0

Li,

K.

NH

3•

" ~H50H,

Ii

JX)

(~H5

)20.

(H

CI)

CHa

Li,

NH

fi

HO

I

C2H

50H

. (

CI)

1H~"

'I-1

OH

C()

iV

0#

~

-

OH

L

i. N

Ha.

0=

C>

-i_

C2Ho

~H.OH,

[( O

OH

hl

o=C>

-1 -C

2 H.;

OH

(Con

tinue

d)

rca;

~g L

iter

-~.~

«i5 at

ure

..... ,a

><

... 37

215

-28

-21

6

-21

7

C»

00

::a

tTl < Fa ~ ~ r ~

tTl ~ >-l c: fg Z

'Tl ~ > >-l @

I

263

1

2641

CtO

H2P

2

265

"

267

CH3

CH3 ?

("'i-.-o

H W

'V

tH;o

CJI

-

AA('

~)')

OH

I )/

.""

CH

P ~

CH'I

CH

. ('I

' I O

H

YX

)/:V

CH

a OA

1 '

~y ('I a

) O

H

I "]/

"-,,

--'C

H.

CHa ~)

,I

OH

#~

I CH

aO-'\J

I-C

"H"

CH30

-<=>

-+C~

H5

OH

eXy

~H:I /X

!y ~I

CH

3<Y

v

.

CH

s"y/

.....

"

CH

:<o

AX

Y

(Vly

0

'; ,,-

}'~/

Na.

N

Ha.

C

2HijO

H.

diox

ane

218

Li.

NH

a•

1-

I 17

7 is

o-C

aH70

H,

digl

yme

.TH

F

Li.

NH

a•

I 90

1 21

9 C

2H50

H. T

HF

Li.

NH

a•

,,-,IO

UI

220

C 2H

sOH

. (C

2H5)

20

Li.

NH

a.

1 --

1 22

1 C

2H.O

H. T

HF

(HC

I)

1

R; <

til

::E: ~ r !:i

tTl S; >-l

C R; Z

'Tl ~ :>

>-l ~ 0)

co

Sta

t'

r m

g m

at

' ef

tal

No.

Str

uctu

ral

f or m

ula

2681

CQn

HQoO

Q C

Ha

( (l

)'H

:?'X

)/" -C

H~

2691

CHP/~

:

HaC

("'I O

H

:?'

/:,

/ ~

( -I

---C

H

CH~O/ ~X

)/ • v

2721

I

Rea

ctio

fl p

rodu

ct

Str

uctu

ral

f orm

ula

I

CH~~X)

lX')/

1

(j/.

Y/

\,//

" )

/ I

)1 Y

)/ .

( 1

CH~O

//~'

Li,

NH

C

2HsO

H, T

HF

Li,

NH

a•

tert

-C4H

90H

, T

HF

~I

Li,

NH

a.

1 -I 1

81

C2H

.OH

. (C

2H5hO

Li,

NH

3•

1 -I l

fi.9

C2H

,PH

, T

HF

Li.

NH

: I•

C,l-

fsO

H.

(C2H

:,hO

--

224·

-22

fi

-.J

0 f;:i < tTi ~ o 'T

1 r-' ::J tTl ~ >-l c::: f;:i .....

Z

'T1 2 2::: ~

>-l @

27·1

274

I I I I 27

5j I i

2761

C2

oH~R

O"

H"C

OH

(,,1)

"1

(X)/

,j

CH

:P/ ~

'--

<;>CH

:1

HaC

(X

'I ~

rl/)

'-')

11

0/ ,)

'"

OC

H' j

HaC

(X

l .

H;j~) I

) H

aC ~,

~OCH

3

("I/(,

G )"

') .'

'-H

aC

(OO

ClI

:;

c"'O

'{lY

o

r~~)

I

o ()

D)m

,

I t

HaC

(v

'()

(,,1/,,

) )"

j /'

,

HaC

C

H/)

H

. L

i, N

H: j

•

1 C~

H:;O

H,

I (C

~H5)

"O,

TH

F

I L

i, N

H: j,

I C

2H;;O

H,

(HC

I)

I I I L

i, N

H: 1,

I C

2H

;;OI-J

, (H

CI)

Li,

NH

a,

C2H

aOH

, di

oxan

e (H

CI)

I ,

I I

1191

212,

227

I

28

22

8'

91 77

::0

t>l < ~ Sil t"'

" ::J t>l ~ o-,J c: ~ Z

'Tl ~ ~ :>

o-,J o z -.1 .....

(Con

tinue

d)

-'I

t-o

erIa

l S

tart

ing

mat

.

Rea

ctio

n pr

oduc

t hi

S

truc

tura

l f o

rmul

a S

truc

tura

l ~ o

rmul

a

2771

CoH

ooO

o CH

a

I AA

fb-O

H

oiX

) IN

a, N

H

1

I I ~ I

:

CH

aOH

, (ri

b)

-I 1

,4

I

0

2781

»

"'-C

H2C

H2O

H

I C

Ha

N(QL

J OH

1

;:0

('''(Y

L

i, N

H

t':l

r:HP)"~)

C.~H50~'

-22

9 <

CH

aO ~

I )

.

"..

. t':

l

i

~

2791

H6

'"

(tIs

~

CH

a

I:'"

"...

HaC

t-j

t':l

I

HO

",-

"'I O

H

S;

(-I--'C

Ha

I

t-j

Cf1ly

J:x)

Li,

NH

c

(XY"

/

~H.m

t 57

, f;l

CH

ive ~ I ~ '

v'

"..

.

diox

ane

174,

Z

230

."

0 ~ :>

t-j

"..

. 0 Z

280

281

282

1 I 28

31 I

284

285

CH

a

("',

I-O

H

/.X·,

, 1

,;/'

"/;,

V':

-,C

H

I '

v,

' 3

J, I ).

: CH

a O/ ,,~,

OH

CH

a

("I-

IOH

(X' )/V

'-O

H

CH

uA

C

H

a H

HaC

('

I C

H3

", --

I"~OH

fr)/V

<'O

H

CHaO~'

'

HaC

(~I

OH

~

,-I-

--C

Ha

(X)/,

,,/"-0

H

CHaO

/~

,

I

01

,»)

/ I

il X"~/

OI:J

~"

) f

cHpA

Jj/

I

CH

30))(

Y

Li,

NH

!I'

tert

· C4H

gOH

, T

HF

Li,

NH

3,

C2H

sOH

, (C

2Hs)

20

Li,

NH

a, te

rt·C

4H

90H

, (C

2Hs)

P

Li,

NH

a, C

zH.o

H,

TH

F

Li,

NH:c,

C~H30H,

TH

F

231,

28

2 ~ <

.....

m

::E: ~

t"' .....

i-l ~ i-l

C ~ Z

'T] o ~ :>

i-l (3

Z

-J

C.:l

Sta

rtin

g m

ater

ial

Str

uctu

ral

form

ula

OC

Ha

HOV""/~

HaC

I

II I

/(j/)/

V

HO

/ "

OC

H"

I ..

HO

" /'

)"

V

"'-

/ "-'

-

HaC

I

I! I

(',j

/"lI

V

Ho

NV

OH

O

CH'I

HO

VI

I,,'

Y

~

HaC

I

; i

(""I

/i"I/"

! H~.V

Rea

ctio

n pr

oduc

t

Str

uctu

ral

form

ula

o I

o il H

O'j

/))

AI

! ;::()

I

o

HOyX

!)~'

/"

'"

I

°

II H

O'lA

(,!

),"I/~)

I

Li,

NH

3,

C 2H;

OH,

(HC

I)

Li,

NH

3,

C2H

;OH

, (H

CI)

Li,

NH

;J'

CzH

sOH

, (H

tl)

(Con

tinue

d)

...J "'" ::0

t'l <:

.....

t'l ~ ~ r ::3 t'l ~ >-j

c::; ~ ~ o ~ :>

>-j o z

C~UH~90/-.J

CH~

?,-II

.. )--CH

OH

CH

1/ .

/ ",

/:'

:1

II N:

·· CH

P/~)

"')

C~I-1,

p(,

I-j-

OH

y

' ,,/

" /'

I II

N

V

CH~O

/'\'

/") H:1C

I O

il

('"

-I-

'C,C

CO

-I

i~';

(~/V

ill):

CHa(

)//~

/"'"

0/\ I

~ C

Hp

/ "')

AI

,I ("~V

'I il

CH

aO

/V''')

CH

: j

X(., ··.I--

"=cH

ClL

I

~ liN

C

H"O

/ ....

, I

/ +

1f

3C

/",1.

Of I

+

('(U<JCil~c!L

CH

PA

)l)

Li.

l\H

::.

tert

-C

lluO

H.

TH

F

Li,

NH

a.

tert

-C4H

"OH

, T

HF

Li.

~H::.

C,H;;<

)H.

(~,H:,)~O

235

10

~

<

1-4

t7

l ~ ~

r ::::j

t7l s: I-j c::: ~ ~ o ~ :>

I-j (3

Z

-.il

C11

Sta

rtin

g m

ater

ial

Rea

ctio

n pr

oduc

t

No.

E

mpi

rica

l S

truc

tura

l fo

rmul

a S

truc

tura

l fo

rmul

a fo

rmul

a

2 92

CZ

IHz4

02

CHa

CH;j

(~/~

I (~/)

M~/'"

CH

(V V

")\;H

I)

I 3

oi

~k.)

3

CH

O ~

OH

3

93

C21H

240a

H

aC O~

CHa

F8

')""

0

~

~.

~I

CH

O ~

0-7

'.)

3

2

94 C2

tH26

0~

CHa

CHa

0IT(

~H'

0~CHOHCH.

X'/·

M)/

'"

f I

:'" C

HO

)'

,).

CH

30

a

2

Met

al,

prot

on

dono

r. a

uxil

-ia

ry s

olve

nts

Li.

NH

s•

C2H

.OH

. TH

F (H

CI)

Li.

NH

a•

C2H

.OH

. (C

2H6~

0. T

HF

( C

l)

Li,

NH

a•

C2H

5OH

. di

oxan

e

(Con

tinue

d)

I'o~

~~ L

iter

--Q

) "0

'"

....

0 at

ure

Q)Q

) .~~

:>< ...

..

-23

7

-23

8

--23

9

-J

0')

~ til ~ ~ t"' ::3 ~ >-:l

C ~ ~ ~ )- t-

i (3

Z

295

CH

a

('

1 O

H

~ "

-/-.

-.C

=C

H

I/"'X"

/o CH

aOJ~

I )

: v

//XI -..

/ II

I Y

C

Hao

/'"

/)

296

HaC

("I_

OH

/yh

)

.I--

-CH

=C

H"

II II

" V

-.

CH3~A)

HaC

0

(""1)1

)

.:?J

U'; /V,,,

) C

HaO

~

I :

HaC

OH

/ ("

"I)')

(j )0,

,1/ i""

) C

HaO

/"'"

2981

C21

Hz6

0a

HSC

H3~

CH

30

Ct-

I{f

'v""

-'-.

. /'

:\a,

NH

3,

C2H

oOH

, IC

zH5)

P

Li,

NH

3,

CzH

oOH

, (C~H5)P

K,

Li,

NH

a,

CzH

.OH

,TH

F

Li,

NH

a,

C 2H

5.OH

I I 7J

88 I

821

51,

88,

240,

24

1 92

185,

23

8

::0

tTl < -tTl ~ ~ r ~

tTl ~ I-j c:: ::0

tTl Z

'TI ~ :>

I-j (3

Z

-J

-J

Sta

rtin

g m

ater

ial

Rea

ctio

n pr

oduc

t

No.

E

mpi

rica

l S

truc

tura

l fo

rmul

a S

truc

tura

l fo

rmul

a fo

rmul

a

2 I

C21H

2tlO

a C

Ha

CHa

I'I~H

(~I~

H I

.(X

Y:V

-O

H

~X

'V-O

H

I I

/;

. I

.'

CH

aO .)

CH,=CH

~ I

CH

(Y

~

):

C=

CH

a

I C

21H

26O

" C

Ha

CI-!:

l

CH3c

oo~(

~I_,

_ =

0

HO

" (

I .

'-'-

-O

f!

((('

) (V

"!/,,)

CH

ao

/ ~

O,f~)~)

:

3 3 »

» C

H3

}-1O

, A

, I

"'/

":-~OH

HO

CH

3TH

" I

I I

fX'1/~/

CH

i)/ ")

Met

al,

prot

on

dono

r, a

uxil

-ia

ry s

olve

nts

Li.

NH

a.

C2H

5OH

. (C

2H5)

P

Li.

NH

a.

C2H

.OH

. di

oxan

e (H

CI)

Li.

NH

a.

C2H

:,OH

. di

oxan

e

(Con

tinue

d)

ro«i

~g

oQ) L

iter

-"0

....

-0

Q

)Q) at

ure

'~..d

:>-<

....

-28

2

-57

. 24

2

-24

8

~

(1J ~

< ......

t"l ~ ~ t"

" ......

>-l ~ >-l

C ~ Z

'7l o ~ :>

t-"'J 5 z

C~lH270~l\:

3031

C21

H2S

02

»

30

5"

» »

CtH

o A

I

OH

( ,

-I-·C

:~=CH

/f'v

' /:

'" /

I Ii

N'"

,~

II )

CH:p/~A

CHa

l~x()J

) CO

CH

,

CH

oA

I

: 3

.

HaC

~Ol-l

. i'

I-·-C

H.

(J:)/

:V

.1 ),

:

\,

CHa O

/ ~

I :

CH

2

HaC

OH

("I),

CH:1

fYY

:V

CHl)~N :

A

OH

(I,l{

;; A

I'

.~-I--

-C==CH

ii

,,"N

/' "'

v'

I "

~

CH

P/")')

CHa

(yr:

I,)

CH

OH

CH

,

CH

:P)"

,J,,

) : »

!

(yfCX

Y I

o~(X

Y

Li.

NH

a.

tert

-C4H

~OH.

T

HF

Li,

NH

a.

C2H~

OH.

(C~H5hO

Na.

N

Ha•

C

Ji;;O

H.

(C2H

5hO

Li

. N

Ha•

C

2HijO

H.

TH

F

K.

Li.

N

Ha•

C

2H50

H.

(HC

I)

158

fg < -M ::E

; Q

r ::J M s: >-3

c:::

fg Z

'n ~ :>

>-3 6 z -

J

co

Sta

rtin

g m

ater

ial

Rea

ctio

n pr

oduc

t

No.

E

mpi

rica

l S

truc

tura

l fo

rmul

a S

truc

tura

l fo

rmul

a fo

rmul

a

3 07

~lH2

sDa

CHa

CH3

3

01-)

Coa

CH

, (~

I--C

HPH

I W

i (Y

)')

~Il

: I

CH

a()/

~

CHa

j""

)81

» li3

C 0

)

I

CH

P)(D

'

I

~

I

~I

I

CH

30

3 )9

i>

» "

3 10

» »

}i

I I

Met

al,

prot

on

dono

r, a

uxil

-ia

ry s

ol v

ents

Li,

NH

a,

C2H

6O

H.

(C2H

.hO

Li,

NH

a,

cls

OH

, (

2H5

)P

Li.

NH

a,

C2H

5OH

, (C

ZH5)

20,

TH

F

Li,

NH

3,

tert

-C4H

9OH

, T

HF

(Con

tinue

d)

I'o~

~~ L

iter

-1:

9'~

....

..0

atur

e (l

)(l)

'~..c::

:>-<

...

-79

. 24

5

.-24

6-24

9

-18

5

85

250

00

o Ri <

-ttl ~ ~ t"

" ~ ~ >-:l c::: Ri 52 'T1 o ~ :>

>-:l ~

3111

»

CH;l

CHaO

CH"

("'1--1

~O CH

: l

CH

,x

xl'i

T'H

CH

,OX

X}

:')

I I

Y:"'

, CH

aO

//',

,,)

3121

CH

;l

("'I

-O

H

X

1 I

((y

'vL

OH

C

Hao

A ,)

~ I

..

CH

aW' ~

,)

CH

=CH

2

3131

~ IH

2S0

4 CH

a

CH

nl'l

rO

CH

'

CHa

CH

,O

('I

T)H

{/

'1/'"

' H

O ~

I j.

' 11

:'(>/'"

",

) 31

41

CHa

ml),O

H

CHa

I (,I_

/O

yp

CHa

~ I

• CH

2 CO

Ol-I

(:

)'!v

-0

/ ,)

,

Li,

NH

a ---

88

Cj!H

"OH'

Li,

NH

a -

232

C 2H

5OH

' (C

2HohO

Na,

NH

a C 2

H5O

H'

-17

9

U,

NH

I

tert

-C H

3 0H

81

1 25

1 T

HF'

(HC

I) ,

~

t>:I < -t>:I ::E: ~

t"' ->-l ~ >-l c ~ - z 'T

J ~ 2:::

:>

>-l - 0 Z 00

1-

1

316

317

Sta

rtin

g m

ater

ial

Str

uctu

ral

form

ula

C aH

7

(" ('I

v O

H

CllaO/

~X): C:

JH7

("'1

-) OH

(Y

"/:'"

CHaQ/~)

: CaH

7-is

o

('1

-) OH

(X

:"(>

CHp/~

V

Rea

ctio

n pr

oduc

t

Str

uctu

ral

form

ula

/ I

CHP~X)

I

CHaC

Y~X)

/X)I

Ii \

~

CH~O

/ "

Li,

NH

a_

1 --

1 25

2 C

2H50

H

Li,

NH

a_

821

219

CjH

50H

I I

Li,

N

Ha,

66

1258

C~H50H, T

HF

ex>

t-:)

:;0 tTl <

&!

::E; ~

t""'

>-< >-l ~ >-l

C g:; ~ ~ ~ >-l (3

Z

CaH

i-iso

I ~b-OB

X

i I

'" Li

, N

H

CHaOA

I :

CH3(

~ .. ,/(

C~H.oH,

THF

·Hi

2/i,1

:;0 tTl -j

("I O

H

c:::

1

:;0

NYJ--C~'

tTl

CXy

Lj,

N

H

t-I

CHaO

~

I :

ClI

.OJ-

t

~

. /

( 2H5)~O

~ >

>-j

t-I @

I

CH

s):X

Y

Li,

NH

~H50lr

-51

(~H5

)~O

181'

22

5'

226:

25

5,

256

»

(Y

Li,

NH

f'",Y

s,

1-1

16

9

. 323

1

i Li

, (N

a K)

N

CH

.J-

I )'

tert

-'c4H~oN8' I

-I

11

(C2H

60H

'

CH

aOH

), T

liF

j

I 0

0

Co)

No.

Sta

rtin

g m

ater

ial

Str

uctu

ral

form

ula

CI2H

50H

('" -J.

-.CH a

(x)<

V

CH

ao/\

:' '

HaC

("'I O

H

CHa

x

-J---CH

;"

'j()

/V

a

CHaO

~/

~ : H

5C2

0H

r'(+~

)Xy,V

CH

lY~'

)'

Rea

ctio

n pr

oduc

t

Str

uctu

ral

form

ula

(yl

CH

scA

A)

CHa 6

I"

/ C

Hso

X/1

/ I

rrx"/

CH

P/"

,,

)

Li.

NH

a•

C2H

.OH

. di

oxan

e

Li.

NH

a.

I 49

CH

aCH

(OH

)CH

IPC

I-/a,

T

HF

Li.

NH

3,

C2H

r,oH

. (C

2H

.)20

Li.

NH;

J. C

2HIiO

H. T

HF

25

2.

258

00

"'" ~

<:

til

=E: ~ t""' :=i ~ 0-3 c: ~ ~ o ~ :>

0-3 5 z

CH

: 1

(~~I-'

-{)H

I

~'/"

)'

Cfl,

o~

CH

:P

~,I

) .S

CcH

:,

CH

' 1

((~i

)CHO

HCH"

o/cxl (

CH

0/ ~

I :

~

HaC

(~~OH

(X ;

",1--c

HOHC

", I

r:'j(

' /

CH~O/

~ ).

' A

I'!

C

HaO

/'

''/)

H~C

HO~

I O

H

, 0:

9)-0,

,,, (V

iV

n~ )

~)

CHlY'~ /'

Li,

NH

62

25

9 C

2H5mr

(C~Hr,)~d

261

Li.

NH

C

2HsO

H,

(ikl)

-21

6

Li,

NH

C

2H50

1l

(C~H

")~d

Li,

NH

a 1

CZH

50H

' -I

57

diox

ane

(HC

I)

::0

t>l <

~

~

0 "Tl

t'" ->-l t>l s: >-l

C fg -z "Tl ~ :>

>-l -0 Z

00

C1

1

Sta

rtin

g m

ater

ial

No.

1 E

mpi

rica

l I

Str

uctu

ral

form

ula

form

ula

I I 33

21 C~

lH30

04

CH

a

(~'-OH

'J

:)";

I

I ·

CHP/~

, I I CH

OH

CH

PH

33

3

334

3351

C21

HsI

02N

/-"

"C,2

H5

A)

. I

CH

OH

CH

s

I II

"/,

V

'I N

, I

j ,

CHp/~) "'

J'

Rea

ctio

n pr

oduc

t

Str

uctu

ral

form

ula

I ~/xy

CH

2°"-'

'-/ ,)

, I CH

OH

CH

PH

I

o~(XY

("V

Y

o~~f

l)

I I

N/

/X"

CH

pJ,,

,,

)

Met

al,

prot

on

dono

r, a

ux

il-

iary

sol

vent

s

Li,

NH

s.

C2H

5OH

, (C

ZH5)

P

Na,

N

tla,

C

'lH50

H,

(A12

0a)

(Con

tinue

d)

..-<

0«

1

0,

~~ILiter-

"' ....

Q) 2

atur

e . ..

.-I.,d

: >-0

....

,18

K,

NH

a,

1 --

I 26

3 C

)-150

H,

(HC

I)

Li,

NH

a,

I-I

235

tert

-C

,H90

H,

TH

F

00

en

:;0

t'

l < .... t'l ~ ~ t"' .... >-l

t'l 5: >-l c:: fg Z

'"T1 ~ :>

>-l o Z

336

C,l-

L

/"-1-"

OH

//

'.)

.-I-

-C2 H

o

, ....

. ',

/V

i

\;

CHP/

~)""

) C2

~

3371

C2

2Hz4

0a

ell;

!

(,I

/ )

__

_

) -O

CO

C,)

I:,

II ~,

CHP/~';

3381

C22

H24

04N

2 .A

.,

UIi-/.,

'·· Ii

I ,

:\

"-/',/'

f',

I '.

I ~

I H

·(/

"1

Hoov

j~A

i O

CH

" O

CH:!

3391

C22

H2P

a -I -,

(]I}~3

I

liY

\/

CHP/~YvJ A/

( '>

.r

C1Lp

A)

~ '(

'I

l"r/,

IIO

OC

/'f"

'OC

lI;1

II:IC

I ('Y

",,,,m

'

Li,

NH

3,

-f5

R

tert

-C

,HuO

H,

TH

F

Li,

NH

a.

C2H

:,OH

-, 2

6,]

:\(a.

;"

\ir!:l

' I-

! 2M

j iso

-C

aH70

H

Li,

:.Jll;

J' C

2il.

OH

. (C

2H

o)l)

, d

ioxa

ne

741

'107

, 'l(

jl)

:;>;l

tTl <

'"""

tTl ::e: ~ r '"""

>-3

tTl S! >-3 c:: ~ Z

'Tl ~ ;s:: ) >-3

(3

Z

00

-3

Sta

rtin

g m

ater

ial

Rea

ctio

n pr

oduc

t

No.

E

mpi

rica

l S

truc

tura

l fo

rmul

a S

truc

tura

l fo

rmul

a fo

rmul

a

~o

C22

H?60

.3 O

CH

3 (X

':H.,

('"A

' H,C

Or)

),,)

~)

m/

::-"

'. /0

~

~o

3

U

C22I-12~04

I-I:,C

()

I O

H

HaC

('.

-I-

-'C

=0 C

CO

OH

I

0--

1

,cfX

'l/V

("

I-k)

J Ii·

(",/

'''.,

.": "

./

C11

:P/ ."

'.

/

<l J.

I .

o ',,

/ ',

/

3 3 42

" "

"

Met

al,

prot

on

dono

r, a

uxil

-ia

ry s

olve

nts

I Li

. i\I

-I:J.

C

,I-I

PH

I I

Li.

\Il;

j.

C ,H

"OI!

. (H

Ci)

Li.

NH

a•

tert

-C4H

gOH

. (H

CI)

(Con

tinue

d)

1'0-;0

~~

t9.~ L

iter

-.-

<0

atu

re

(l)(

l)

'~..

c >-<~ -12il

7

I -. 64

-.

1i5

CI)

C

I)

fg < -r.<l :E; ~ t"" ::l ~ t-l

c:::

fg Z

"T1 ~ :>

t-l o Z

41 C

22H

2s0 2

51 I 61 C

22H

zs03

HaC

HOC

H

A

:1

1 -,

h"-

.,

I ,

\CH

" (-?

~/,,,/:'

-

CH:p

A)~)

:

H~CI

0-«(

('_

-I

N' /

1,,/

II 1'

''''/

CHa

~/'/

HC

()

3 II

(xd,

~U

0';:

: /1

) H~C

(".,\_C~OHCHa

("J

/ -l

cH

a

I ).

~)

o.f(

'~""

•

CH: 1

(""'\

:-),

CH

OH

CH

a

('v

''1

/'

'·CH

a I

I I:

00 :

'.. '~""/ H

aC l

OB

(' -J

.(CH

~)aO

H ('''/

'']/ 'v

) J

) 0

/"-.

'-;:

" '/

Li,

:.JH

a, te

rt-

C4H

oOH

, (C

HaC

OO

H)

Li,

NH

s.

CH

aOH

, (C

2H5h

O,

(HC

I)

Li,

NH

a,

C2H

50H

, (H

CI)

Li,

NH

a.

CH

30H

, te

rt-C

4HoO

H,

TH

F

(HC

!)

(i6

66

270:

27

1

~

<

til

::E: ~ t'" ::J ~ ~ c::: ~ Z

'TI ~ :>

~

(5

Z

00

(0

No

. E

mpi

rica

l fo

rmul

a

347

1 C2

2H2s

Oa

1 I

348

'349/

Sta

rtin

g m

ater

ial

Str

uctu

ral

form

ula

H~C

°

I,i-O,

,-J;

j,yX" /.

, 1 v/

I

Y· "/

Cflp

/~

)

-1-:

H

:1C

OO

1

'/

("/~

(;X~/,,/

)~ I

•

/ CH

:P/~

,)

Rea

ctio

n pr

oduc

t

Str

uctu

ral

form

ula

HaC

I O

H

('" -1

--(C

HJh

OH

II I

'j/.

, /X'

/:. C

H:p

/""v

)

("X/'y

ni;{y~

/I )/

o Ii o

f))+

fX)

I I

(Con

tinue

d)

I ... .

--<

o CIS

",

0

Met

al,

prot

on ~,:iILiter-

-ill

dono

r, a

uxil

-;:g

0 at

ure

ill i

ll,

iary

sol

vent

s ~-

5'

Na,

N

Ha,

te

rt-C

4H

nOH

, T

HF

Li,

NH

3,

C2H

oOH

, TH

F

Li,

NH

3,

C2H

50

H,

diox

ane

272

I),,

",'

)

~/"

266,

27

4 58

to

o fg <

tTl ~ o 'Tl

t""' .....

>-l

t:<l s: >-l

C fg Z

'Tl ~ >

>-l (3

Z

3501

»

CHa

((r'b

-ocOCH

' cn

,coo

/ "I

Y'

C22

Hao

02

I H

5C2

("'I O

H

NC~

-1--

·C2 H

5

V:V

C

HO

~

I )

: _

3

» CH

a

CHa ("'I ~ /

v COC

H, C

HaO

~ I

)

: »

CHa

NC~,

CrH'

CHaO

~ I

);

--CHa

0 II

J:X)

I

/X CH'

COO~ I

Y

I

CH

aO

J:X

Y

CHa

CHa (~

I (V

/,j

CHOH

CH,

wI )~

) : CH

a

uC'h-

CHOH

CH'

I I )/~

'. C

HaO

' .

CH;j

Li,

NH

C

2H50

H,

T'H

F [(

CO

OH

hl

Li,

NH

C

zHsO

tl'

-15

3

(C2H

s)l)

C

Li,

NH

a H

aOCH

2CH

(OH

)CH

a-25

7

CH

aO(C

H r

OH

I

Li,

NH

(H

CI)

a '

Li,

NH

cH

a od'

(C

2H5lz

O

:;0 t'rl < .....

t'rl :E: ~ t'"' ::i ~ t-3

c::: ~ .....

Z

." ~ :>

t-3

..... ~ co

.....

»

357

»

Sta

rtin

g m

ater

ial

Str

uctu

ral

form

ula

HsC I

OH

1'-

1--

-CH

2

rYY

:V I

cH

sM

):

CH

=C

H2

H C

C2H

S

3

11

/O

H

1'//)

rf

X'\/

T"

CHa(

)/~

): O

H

H3C

I I ./C2H

s

("" //

ryv:

")

CH3cY~

:

»

Rea

ctio

n pr

oduc

t

Str

uctu

ral

form

ula

HaC

(""I

OH

/X

,-I--

-CaH

7

fl I )/V

C

Hp

A.

'

(vl/

0#

)"

")

('V'~(

n.l

)"

") I

(vy

0.

1 )"')

Met

al,

prot

on

dono

r, a

ux

il

iary

sol

vent

s

Li,

NH

S'

C2H

PH

, (C

2HSh

O

K,

Li,

NH

., C

2H50

H,

(HC

l)

K,

Li,

NH

a,

C2H

60H

, (H

Cl)

51

co

t<:l ::0

r::I <:

til

=E: ~ t"" ::j ~ >-l c::: Rl Z

'T1 ~ :>

>-l '6 z

3591

C~2

H300

3

360

»

363

I C

ZZ

H3

20

2

H3C

CHa

("'I C

OC

Ha

I -I

-,O

H

((

,\/V

C

HP

/ ~

I )

• -'

-I

HaC

00

("'I)~

! ;fy

/'. /.:"

. / i

I )'

: "..

/ C

HoO

/' ~/'"

.,

HO

CH

?CI1

20 .. ,r

···~

. ---

-C,~

!c

"=./

I

.. ,

H

--",

O

CH

.CH

.Q-.

#'

'>:"

. .

,\~---CJi"

CH

a C

I13 C

OO

1

Oll

1/'", -I

.. ·ctf a

::-X

"'/V

C

lll)

A ),

CH

a 1

OH

("'

I-I-·,

Ca H

7

r~/"'/V

CH:p/~)"')

H~C

CH

a ("'I

CH

OH

CH

a I

-I·

OH

(V

)/V

0'

;:)'"

• ,-/"

/

)1 Y

C

HaQ

/' ,,

,)'"

()

/--'

) --

,---

\,-/

I

C2 H

.

0.

/)

-~f -

---C

,Hc

HO

CH

zCH

, .,

i-I

CH,~XY

,

cH,eM

Y

Li,

NH

C

HP

(CH

)'O

H

2 3

Li,

N

H

C

3'

--21

2 2H

50H

' 20

8 I C2H

~6H~~H

cI) I-I

38.

I Li,

NH

1

-12

43

C2H

bm-t

diox

ane

Li,

NH

a 51

, C

ZH5O

H'

(C2H

5hO

22

5

:xl

trl < 'fil

:E:

0 "T1

r-' ,.... ..., trl s: ..., c:: ~ ,....

Z

"T1 ~ ~ )- ..., ,....

0 z ~

w

(Con

tinue

d)

to ""

Sta

rtin

g m

ater

ial

Rea

ctio

n pr

oduc

t I

I M

etal

, pr

oton

No.

1 -

I do

nor,

au

xil

-

Str

uctu

ral

f or m

ula

S

truc

tura

l f o

rmu

la

iary

sol

vent

s

C2H

5

(~I

OH

I

((

:)-C,

H,

J:Y)

/ L

i, N

H

I

CH

a O/ ~ I

)<

CH

a A

C2H

50H

T

HF

9°

1219

, ,

254.

27

8

»

3661

»

H7C

a

CH

L

i, N

Ha

257

a OC

H2 C

H(O

H)C

--

:;0

(~I

OH

/ I,

(C2H

5hO

, T

HF

' 3

tTl <

AX /j-

-CH

, cH

ao

AX

Y

I-<

Li,

NH

tTl

80

219

::E:

CH

aO ~ I

)

:

~,

pyrr

ole

0 'TI

t'"'

I-<

>-3

tTl ~ >-l c:::

fg

3671

»

HaC

CH

I

OH

)

a ~ -1-

--C2 H

5

ell

I 3

I Li

, N

H

m/~v

CH

aJ:X

Y

C2H

5 0rf

' -

279

......

CH

aO ~

I :

z

(C2H

5hO

'T

I ~ ~ :>

>-l

......

0 Z

» Ha

C ("'I O

H

m:-

I"-C

2H

5

)XI)

L

i, N

Ha

I ,V

"rn

CH

I

I ""

-C,H

,OH

CH

, '"

.,'

THF

' ~ t"t

l <

~ A

I OH

I

C

M)("

'/'vl

-<C

H,)

,oH

iY

) L

i NH

~

I :

(H

p/,

A

C H

' OH3 '

~ .

.'

.. ,

~ CH

,O

'"

. '"

'-C

,H,O

H,:

:;

TH

F

~ c:::

~ =

1

all

~ C

HP

CH

2 ('" -I-

-",H

CH

'XX

I L

~ Y

X)/

V'

CH a

I

I Y

~;Hr;gi'

1 83

~

3711

C

H,c

yA

,'

,/

,.

• j o

CH

Z

MI'

~OH

~Xl)

Li,

NH

I

)/:V,-D

H CH

I

I '"'-

C,H,

1'>H,

I-I 2

31,

CH,o ",'

' TH

F m

C3H

7

to

en

Sta

rtin

g m

ater

ial

No.

E

mpi

rica

l S

truc

tura

l fo

rmul

a fo

rmul

a

3 I

72

Cz2H

3a02

N

CaI-I

,

AI

1 I)

CH

OH

CH

3

A/"

/~'"

I II

N:

CH o

/v

",)

3

3 73'

»

C 3B

, OIl

AI

_I

1 I

---C

Z H5

A/,

/:'V

I II

N:

CH30/V~)

......

......

_--...

... _--

..

C23

3 74

CZ3H

3003

CH

3

(~I-=o

I I

A

o::y

v I I

1 I~

~

, !

,,/

/ o

0

I

Rea

ctio

n pr

oduc

t

Str

uctu

ral

form

ula

I /"/~/

II II

N

CH

aO

/V"')

[ }

v

I 11

N

C1

-laO

/',

) CH3

("'I

-O

H

A

((yv

1 I,

/ "

./

" /

" ""/

o 0

(Con

tinue

d)

1'Q';;i

M

etal

, pr

oton

~g L

iter

-do

nor,

au

xil

--Q

)

"""

.-<

0 a

ture

ia

ry s

olve

nts

Q)Q

) '-,

.c:

>-< ...

.

Li,

NH

3,

--23

5 te

rt-C

4H9O

H,

TH

F

Li,

:\H

".

1-15

8 te

rt-C

)-lp

H. I

TH

F

i

Na,

NH

3,

-28

1 C

H3O

H,

tert

-C4H

9OH

, T

HF

<D

0>

::0

ttl -< t=;:J ::s ~ t"" ::::j ~ >-l

C fg Z

'T1 ~ 3'::: ::. >-l @

3761

C23

H30

04

377

I C

23H

300i

j

378

I C

2aH

320

2

()

tI:jC

II

("'I-~

/)'

fY)/:

J"

CH

a OM

:

HaC

("'I

OCO

CH3

~X

,-I-

--C

OC

Ha

'/ "'

-/:V

CH

aO''' ~

I )

: o

H3C

\'T)

1_--

0

Hd~~

CHpA~) :

I

o#CXY

CHa

("'I

~) HOH

CH

a

CII,J

:(Y" I

CIi'»

Y i "".

/'.,

/

Ii 1('

T

" II

f /"

'-/'

" "

CH

aO'

,,/v

Li,

NH

a,

tert

-C

4HgO

H,

TH

F (H

CI)

Li,

NH

3,

CH

pH

, di

oxan

e

Li,

NH

a,

CzH

.OH

, di

oxan

e

Li,

NH

a, C

2H50

H,

TH

F

66

Ri <

>-<

tTl <: o ."

t"" ::J tTl s: >-l c:::

;:cl

tTl Z

." o ;:c

l ::;:: :.. >-l ~ co

-J

Sta

rtin

g m

ater

ial

No.

Str

uctu

ral

form

ula

3791

C23

H32

0a

CH

a

O

("1

-) OH

(X)/:

" o V~I

: 38

0 »

CH

3 :J

381

» CH

a

("I-o

H A

A)/

:V!-

OH

I

.'

CH

aO ~

: tH

zC=

CH

2

tH~

Rea

ctio

n pr

oduc

t

Str

uctu

ral

form

ula

I

(j"J:

XY

o 0

I

CH

aJ:X

Y

'I "'-

./ 'Xi

CHao

/~ I

)

(Con

tinue

d)

I ..........

. 0

«1

t)

Met

al,

prot

on ~QILiter-

-<l.l

dono

r, a

ux

il-

:8 0

atu

re

<l.l<

l.l ia

ry s

olve

nts

~.s'

Na,

NH

a,

CH

sOH

, te

rt-C

4H90

H,

TH

F

Li,

NI;I

~,

C2H

60H

, (C

2H5h

O

I

II 69

, 19

4

Li,

NH

a,

II -II

232

C2H

.OH

, (C

2H.)z

O

cD

00

~

<:

tTl

~ o 'T

I t'"

' ::3 ~ >-l

C ~ Z

'TI o ~ :>

>-l @

3821

C2s

H °

~2

4

Hi DH

m;J~~~(CHJ'COOH

I

Cll,oiX

Y CH

aO ~I

:

3831

»

~ ..

I

CH.<Y

W -~-OH

SH

30" ~"'-/

3841

C23

H °

32

6

rOH

~

CH,m

b

~~--DH

~I

: C

HaO

· ~

I

Li,

NH

t

a, er

t-C

H O

H

4 9

, T

HF

Li,

NH

C

2H50

tt'

(C2H

5)20

Li,

NH

~

3'

H5O

H,

diox

ane

65

28

3-

285

-23

9

::0

t'Il <:

......

t'Il

::E: 0 'Tl

r-<

......

>-l

t'Il S; >-l

c:::: ~

'""' ~ ~ >

>-l '""'

0 Z co

co

3861

C

23H

;IP

2

387

»

Sta

rtin

g m

ater

ial

Str

uct

ura

l fo

rmul

a

01::1

H3C

~~J

---O

H

HaC

(""1_° 1 ~

C H

fY)/

V

49

CHpA~

: CI2

H50

H

tx)~

J-C,

H'

CHl)

/~

.

Rea

ctio

n pr

oduc

t

Str

uct

ura

l fo

rmul

a

I

CII,)X

Y r i //', /.

~ !.I

~. y

I! II

I r"/'

~

, '1

1}

l 'v

/ './'

'''xl

II I

CH

aO/" Y

(Con

tinue

d)

I I

I

Met

al,

prot

on

dono

r, a

ux

il-

iary

sol

vent

s

Li,

NH

'l' 70

1 28

2 C

2H

5OH

, di

oxan

e

Li,

NH

3,

I-I

51

C2H

50H

, (C

2HS}

zO

Li,

NH

a,

I 77

1 21

9 C

2H50

H,

TH

F

.....

0 0 ~ t=ri :E: ~ r ::J t'Il ~ >-cl c:::

::0

t'Il Z

'Tl 2 $:

:>

>-cl o Z

iso-C

H

3 "'/

I 01

1

§J.~II"

CHa

~ I )

,

» H

aC

CHa

"I O

H

I (-I·-

-C

H

NY

"

,V

CHaO

~

I ~ CH

a

~clJ"OH

CH3J

~ I ):

SC4 H

9

HaC

("I O

C2 Ho

oAA

.-i-OC

2H5

I )/!V~

CHa

~ ;

HaC

I O

H

~(,-I __ 'C

HC

H

f' y;

v I

' CH

~I

: C

H2

3 ~H20H

[

CH,,M

Y H

aC I

I

CHa~XY

eH'O~X

Y I

~D/

CHaO

I

I

eHAY

I L

i. ;\J

Ha.

c'll

sOH

, T

HF

Li,

NH

C

2HoO

rf'

(C2H

6)20

Li,

NH

a C

2H5O

H'

(C2H

o)20

1 L

i, N

H

CH

aOC

H2C

H(t

H)C

J 89

1 28

6,

3 28

7

Li,

NH

te

rt-c

,H:6

H

I -I

66

TH

F

'

::0

t>l <

.....

t>l ~

0 "T1 r .....

>-l ~ '"' c:: ~

..... ~ ~ ~ »- >-

l ..... ~ i-'

o i-'

395

Sta

rtin

g m

ater

ial

Str

uctu

ral

form

ula

CH3

(~I-

I OCH

a

~X)/V:-OH

I ::

CH30

~

: C 3B

7

() Ni

'~

Cll

aO

M)<

Rea

ctio

n pr

oduc

t

Str

uctu

ral

form

ula

1

CH

a)X

Y

i

O#()

:~Y

Met

al,

prot

on

dono

r, a

uxil

ia

ry s

olve

nts

(Con

tinue

d)

Li,

NH

a,

1 -I

232

C2H~OH,

(C2H

s)P

Li,

NH

a,

tert

-C.H

gOH

, (C

2HslP

Na,

N

Ha,

I

931

288

tert

-C,H

gOH

, T

HF

, (H

C!)

I-'

o N

::0

t%l <

t;:i

::E: ~ t"'" ::J t%l ~ >-l c:::

::0

t%l ~ ~ :>

>-l o Z

397

398 i C

Z!H

280

a

399

I C24

Hao

Os

() rf

Y~b-

oH

CH

30

M)

:

('I~oc

CH

,o,oN

oc,H

,

[pca

CH

~OJ

3

*,[

I '

I '

CH~O ~

/'1 Y

;:~)H

I

(~

~)

~ ('

1-)

OH

ijX"

"'~

CHau

A

) el

l,

("\-(l

/'~'

0

'7''''/

~~UH

(~I_I=O

(V

)/V

o#)~

~

N,.

~H". 17

41 28

8 te

rt-C

4HoO

H,

TH

F.

(HC

I)

Na,

N

Ha.

I -

I 28

8 te

rt-·C

4HoO

H,

TH

F,

(HC

l)

Na.

N

Ha.

I .

-I

289

C~H50H.

(HC

I)

Li,

NH

a•

I-I 1

50

C2H

sOH

, (H

CI)

~

<

,.....

tTl ~ ~

r ~ ~ >-:

l c:::

::0

tTl

,.....

Z

." o ~ » >-:

l o Z

I-'

o C.:l

(Con

tinue

d)

I-'

0

I *'"

Sta

rtin

g m

ater

ial

Rea

ctio

n pr

oduc

t '0"

;;1

Met

al,

prot

on

()

-S:B

ILite

r-N

o.1

dono

r, a

ux

il-

" ....

Em

piri

cal

Str

uct

ura

l fo

rmul

a S

tru

ctu

ral

form

ula

iary

sol

vent

s c:;

2 atu

re

form

ula

'~..c::

I :>-0

....

400 I C

24H

aP6

°t

--O

H

Li,

NH

a,

1-1

29

0

<0 °

HC

C

2H;O

H,

3

HaC;

: )

HO

I

=0

(C

2H5h

O,

---0

C

H V

'" -

---O

H

(HC

OO

H)

I :1 I

I ~

(VJ/

'V

CH

aO'

'"

o,f

,,)

:

1-'" tTl

4011

C24

HaP

:J <

C

II

I U

, N

H3

, 29

1 .....

. '.

3

tTl

~:J

CH

OJ:X

)/

CH

aOC

H2C

H(O

H)C

F:1

~

HaC

I 0 'T

I 3

r 1-0

>-l

tTl ~

CH

aO;

'0/'

'v

"

t-l

C ~

4021

C24

Ha4

04

CH

a C

Ha

Li,

NH

a,

-29

2 .....

. I

Z

PJ

HO

'vA

"i_

C

2H

;OH

'T

I

b ~

HaC

I

! s :>

/,,1 Y

'" t-

l

cH

oA

)",

•

0 C

H30

; 'V

""-/

Z

3

403

»

H3C 0-

0 "'/ f

1iO"

CH

0f::x

YiV" "-

3

404

4051

C2!I

-i a60

S

CHa

((/)~Iv SC

,H"o

;ro

CH

O

.~ I

: 3

/ ,

406

I C2,H

a60

2 H

aC

CH

a (""I

OH

)

.-\ ..

. C,H

9

CH,Q

/(J():

V

I

rn,J

):)

HaC

I I

CII,

)):)

I

CH

aO

)(X

)

HaC

: I

CH

,)):)

Na,

NH

3•

tert

·C,H

gOH

, T

HF

Li,

NH

a,

C2H

.oH

, (C

2H5)

20

Li,

NH

3•

CH

aOH

, (C

~H5)

~O

Li,

NH

3,

C2H

50H

, (C

2Hlih

O

231.

23

2

-·2

79

:;0

~ til ~ ~ r ;:J ~ o-'

l c: Gl Z

'Tl ~ :>

o-'l (3

Z .... o C11

Sta

rtil

1g m

ater

ial

No.

Str

uctu

ral

form

ula

407

ClaH

70H

aNC(' -

1--

-CaH

-

~I )

/tv'

. CH

a ~

.

408

C4H

"

("'I O

H

fX /v

l ---Cz

H"

cHa o

A I

) :

40

9'

C24H

as04

Ha

C,

OH

('"

-1

---C

H2C

H2

M)/

V

~H

I:

I C

HaO

~

(OC

Hah

C25

Rea

ctio

l1 p

rodu

ct

Str

uctu

ral

form

ula

I

CH

aO

/(X

Y

I

CH

aO

/(X

Y

(')

y

CH3aA~)

(Con

tinue

d)

Li,

NH

a•

I-I 25

7 C

H3O

CH

2CH

(OH

)CH

a

Li.

NH

a•

I -I

257

CH

sOC

H2C

H(O

H)C

Ha

Li.

NH

a•

I-I

295

tert

-C4H

90H

, T

HF

~

o en

:;0

tTl <

>-<

tTl :E: o '"Tl

r ::J tTl s: >-l

C ~ Z

'"Tl ~ ::::: ::. >-l (3

Z

410

I C2r>Ha~07

4111

C25

Ha6

0a

C26

4121

C26

Hao

O;1

4131

C26

Ha4

0a

HaC

~OH PJ '0 ~

--OH

I O

H

I" -\

.. -CZH

5

A

fX)/

V

l),,/~I

: o

0

CH3

~X~b-O

COC'H'

CH

30~~

/'

A

HaC

/1

1

I 0

,,/

~ (,,-\.-.C~H

-7')(

)/V

CH

aO ~

I :

11

0"

CH,J:(

9~ I

(),,/(

Xy

o 0

CHa

, ("1

-) Oil

(jX1 ,+:

" C

Hp

A,.

. /:

CB

3

CHml~~CHCH"

Li.

NI-l

3•

I-I

296

C2H

,.OH

Li,

NH

s'

I 88

1 87

tert~C4H90H,

TH

F

Li.

NH

a•

CZH

50H

. (C

2H5h

O

Li,

NH

a•

tert-

C,H

oOH

, T

HF

521

87

~ til ~ o '1

1 r ::J t'l s;: >-:l

C ~ Z

'Tl ~ :>

>-:l o Z

~

o ...:J

Sta

rtin

g m

ater

ial

Str

uctu

ral

form

ula A

H

aC

/'

,

I 0

'0/

MI'

-j---C

H=

CH

I )<

v 2

CH

aO ~

:

HaC

("'I O

H

HYij--

{CH,

J,CI

CH

aO

A)v

:

H3C

I O

H

(Yl'jJ-~-(?H2)

a cH

pM):

N(~H5)

2

Rea

ctio

n pr

oduc

t

Str

uctu

ral

form

ula

ella

fx(t

rCH~

' C

HaO

I)

: I

oJ:X

)

~$

Li,

NH

3,

tert

-C4H

90H

, T

HF

Li.

NH

3•

1-

CH

aOC

H2C

H(O

H)C

Ha

......

o 00

~ trl

:E: ~ r ::J ~ >-

l c:::

fg Z

'Tl 2 ;?:: > >-l @

4191

C27

H3S

03

eHa

~I-oc

(X"'

/"')

O

C6H

s

CH

3C

oo

A I

)

: iC'l

»C

H

10

_ 3

CH

;;C

OO

H

aC ~J

~OH

CH

aO/ W

I CH

a

("1-

1 OH

iX)'/:

," '..

OH

J~

I'

: ,./

C11

a O/

'~

'C=C

C(\H

J~

Cll:

l

("1

-) C8 1

f17

(X/)/

" CH

a O/ ~

.'

/yi,

CH,W

)UJ/

~OH

H3C

C7

0

HO

"'('i-

--OH

(V

)/V

' 0

,/ )"

I

CH:JO~U)

I -,

/',

/'

O?~)

~')/

Li.

NH

a•

C2HsOH

. (C

2Hs)

20

Li.

N

Ha•

C

zHsO

H.

(C2H

s)20

Li.

NH

3•

C2H

sOH.

I (C~

H5)P

· (H

el)

~.

153

G2i

'298

. 29

9

~ ..., tTl ~ o 'TI

t'"' :::J

tTl S; t-'l

C s:; Z

'TI ~ ~ >

t-'l (3

Z

I-'

o CD

Sta

rtin

g m

ater

ial

Str

uctu

ral

form

ula

4211

C2

7H42

02

HaC

I O

H

fYC~

J·-·

CSH1

7-n

cHaOA~)

;

4221

C2

7H42

0a

CHa ("

,I-rm

JX)

/~",<-OH

~ I

;;

CHa

CsH

17

42

3

» »

Rea

ctio

n pr

oduc

t

Str

uctu

ral

form

ula

1

CH):X

Y 1

CHaJ:

XY

»

Met

al,

prot

on

dono

r, a

uxil

ia

ry s

olve

nts

Li,

NH

a•

CjH

sOH

, (C

2H5)

20

Li,

NH

a•

C2H

sOH

, (C

ZH5)

zO

51

-, 2

32

Li,

NH

a•

1 -

1 23

1 te

rt-C

4HDO

H,

(~H5bO

l-'

l-'

o :::0

t"Il <:

I-<

t"

Il :E: o 'TI r :=j

t"Il s: t-:l C f;l Z

'TI ~ :>

t-:l ~

4241

C2sH

,oO

,

° rfx)

~I~

",/~I

: o

0

C29

........

........

........

.......

4251

CZO

H36

03

C 6B

S

N~!b-~

C

Hso

M)

: 42

6 1 C

2DH4

50aN

Ha

C ("'I O

H

oMY,-I-

--(CH 2

)a-N

'-'b

C

I !V

"j

,Ho

~

.

C 32

......

......

......

......

..

427 I C

32H

320

, CH

a

N~~T

~oc,

H,

C6

H5

CO

oM

) :

1

O",/(

XY

° 0

I

CH

,JC

(Y

I

O~(XY 1

CSB 5C

OJC

(Y

Li,

NH

3,

tert

-C,H

gOH

, T

HF

901

87

Na,

NH

s•

I 841

288

te

rt-C,

HgOH

, T

HF

Li,

NH

s'

I-I

297

CH

aOC

H2C

H(O

H)C

Ha.

[(C

OOH)

2J

Li,

NH

a,

C2H

50H

, (C

2H5)

P

-, 1

53

fg

<:

tTi

:E: o 'Tl

r'"

::j

t>l g; ""l

C fg Z

'Tl ~ :>

""l (3

Z ......

......

......

112

Index of Reagents Metal Proton donor Auxiliary solvent Serial numbers

Li CHaOH 44,113 Li CHaOH (C2H5)20 169, 182, 213, 344, 354,

405 Li CHaOH, tert-C4H9OH (C2Hs)20 94, 151 Li CHaOH THF 118, 130, 222, 323 Li CHaOH Dioxane 376 Li CHaOH, tert-C 4H9OH THF 346 Li C2HsOH I, 9, 26, 28, 30, 52, 54,

80, 136, 137, 147, 152, 158, 159, 160, 166, 167, 174, 175, 177, 185, 189, 210, 228, 243, 246, 251, 252, 259, 261, 262, 274, 275, 278, 286, 287, 288, 298, 311, 315, 316, 329, 337, 340, 341, 345, 357, 360, 370, 399, 402, 410, 418

Li C2HsOH (C2Hs)20 12, 16, 33, 37, 39, 70, 73, 87, 91, 92, 95, 98, 107, 108, 109, 132, 144, 145, 153, 154, 169, 171, 181, 183, 187, 199, 202, 207,212,217,218,219, 229, 230, 231, 255, 256, 257, 266,270, 272, 282, 291, 296, 299, 303, 307, 308, 312, 319, 320, 321, 326, 328, 330, 332, 332, 351, 355, 363, 367, 380, 381, 383, 386, 389, 390, 393, 400, 404, 406, 412, 417, 419, 420, 421, 422, 427

Li C2HsOH (C2Hs~0 260 Li C2HsOH (C2Hs )20, THF 220, 226, 273, 293, 309 Li C 2HsOH (C2Hs)20, dioxane 164, 214, 244, 239

INDEX OF REAGENTS 113

(Continued)

Metal Proton donor Auxiliary solvent Serial numbers

Li C2HsOH Dioxane 211, 242, 254, 276, 279, 300, 301, 324, 331, 349, 362, 377, 384, 385

Li C2HsOH THF 114, 178, 179, 191, 203, 204, 209, 216, 232, 238, 240, 248,265,267,268, 271, 281, 284, 285, 292, 305, 317, 318, 322, 323, 327, 348, 350, 364, 378, 387, 388

Li C2HsOH (C~OCHS}2 120 Li C2HsOH, iso-CsH70H (C~OCHs~ 96 Li C2HsOH, tert-C 4HgOH THF 369 Li iso-CsH70H Diglyme, 1HF 264 Li tert-C 4HgOH 3, 13, 15, 34, 40, 62,

82, 85, 103, 126, 227, 342, 343

Li tert -C 4HgOH (C2Hs}20 167, 184, 283, 394, 423 Li tert -C 4HgOH (C2Hs~O, THF 239 Li tert -C4 HgOH THF 186, 188, 192, 200, 201,

222, 234, 235, 236, 237, 249, 269, 282, 290, 302, 310, 314, 323, 335, 336, 368, 371, 372, 373, 375, 392, 409, 411, 413, 414, 424

Li Pyrrole 366 Li CHsOCH(OH}CHs 415 Li CHsOC ~CH(OH)C Hs 205, 221, 253, 352, 391,

401,407,408,416,426 Li CHsOCH2CH(OH}CHs (C2Hs~O, lHF 365 Li CHsOCH2CH(OH}CHs THF 325 Li CHsOC~CH(OH}CH3 Dioxane 233 Li CHsO(CH2}sOH 353,359 Li tert -CsHuOH 215 Na CHsOH 5, 10, 18, 20, 21, 27,

35, 45, 48, 49, 50, 53, 55, 77, 90, 102, 106,

114 INDEX OF REAGENTS

(Continued)


110, 111, 131, 149, 150, 155, 161, 163, 277

Na CHsOH (C2Hs)20 47, 74, 75, 88, 99, 223

Na CHsOH THF 323

Na CHsOH, tert-C 4 HgOH (C2H5)20 97 Na CHsOH, tert -C 4HgOH THF 133, 374, 379 Na C2H5OH 2,4,6,7, II, 14, 17,

19, 22, 24, 25, 29, 31, 36, 38, 41, 42, 43, 51, 56,57, 59, 60, 61, 63, 64,69,71,72,78,79, 81, 83, 84, 86, 89, 93, 101, 105, 117, 119, 121, 122, 123, 124, 125, 129, 143, 146, 148, 157, 165, 170, 196, 250, 313, 333, 361, 398

Na C2HsOH (C2H5)20 65, 66, 100, 104, 128, 134, 140, 172, 173, 295, 304

Na C2H5OH THF 112, 115, 116, 127, 135, 138, 139, 141, 142, 176, 180, 323

Na C2HsOH Dioxane 206, 263

Na C2H5OH C6H5NH2 245

Na iso-CsH7OH 338

Na iso -CSH70H (C2Hs)20 224

Na tert -C 4HgOH 195

Na tert -C 4HgOH THF 197, 225, 323, 347, 395, 396, 397, 403, 425

Na tert -C5Hll0H 67, 68

K CHsOH 194

K CHsOH THF 222, 323

K C2H5OH 241, 334

K,Li C2H5OH 198, 247, 306, 356, 358

K C2HsOH (C2H5~O 190

K,Li C2H5OH (C2H5)20, THF 208, 258

K,Li C2H50H THF 297

INDEX OF REAGENTS 115

(Continued)


K C2H5OH THF 222, 323 K tert -C 4H90 H 32, 58 K tert -C4~OH THF 222, 323 Mg C2 H5OH (C2H5)20 8, 23, 46, 76 Ca tert -C4~OH THF 193

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116

LITERATURE CITED 117

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Birch Reduction of Aromatic Compounds

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