Condensation of Aldehydes with Fluorene and Nitrofluorenes

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P U R D U E U N IV E R S IT Y

THIS IS TO CERTIFY THAT THE TH ESIS PREPARED U N D ER MY SUPERV ISIO N

by

Seymour Polansky

ENTITLED

Condensation of Aldehydes with Fluorene and Nitrofluor enes

COMPLIES WITH THE UNIVERSITY REGULATIONS ON GRADUATION TH ESES

AND IS APPROVED BY ME A S FULFILLING THIS PART O F THE REQUIREMENTS

FO R THE D EGREE OF

Doctor of Philosophy

P ro fesso r

H ea d

/

of

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in

Charge

chool or

of

Th e s is

D epartm ent

19

TO THE LIBRARIAN:-----

-*eTHIS TH ESIS IS NOT TO B E REGARDED A S CONFIDENTIAL.

PROFES a OH I S

GHA1». SCH O O L FORM 9 —3 - 4 9 —1M

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CONDENSATION OF ALDEHYDES WITH FLUORENE AND NITROFLUORENES

A Thesis Submitted to the Faculty of Purdue University

I#" Seymour Polansky In Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy

June, 1950

ProQuest Number: 27714144

All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is d e p e n d e n t upon the quality of the copy subm itted. In the unlikely e v e n t that the a u thor did not send a c o m p le te m anuscript and there are missing pages, these will be noted. Also, if m aterial had to be rem oved, a n o te will ind ica te the deletion.

uest ProQuest 27714144 Published by ProQuest LLC (2019). C opyright of the Dissertation is held by the Author. All rights reserved. This work is protected against unauthorized copying under Title 17, United States C o d e M icroform Edition © ProQuest LLC. ProQuest LLC. 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 48106 - 1346

ACKNOWIEDGMENT The author mshes to acknowledge gratefully the helpful suggestions and advice of Professor G* B* Bachman, whose inspiration and constant in terest in the progress of the work insured i t s successful completion.

The author also wishes to

acknowledge gratefully the help and inspiration given by Dr. S, Boyk and Dr* H* B* Hass on previous problems*

Acknowledgment

is also made to F* E* Anderson and C* A* Sluhan and to the Purdue Research Foundation for financial support*

TABLE OF CONTENTS

Page ABSTRACT ..............................................................................................................................

i

INTRODUCTION....................................................................................................................

1

DISCUSSION................................................................

2

EXPERIMENTAL

....................................................................................................

Preparation of 9-Alkyüdenefluor enes

. . . . . . . . . .

22 22

Preparation of 9-Alkylfluorenes.........................

2U

Sulfonation of 9-Alkylfluor enes . . . . . . . . . . . . .

25

Nitration of 9-Alkylfluo r enes Surface Tension Measurements

..........................................29 . . . . . . . . . . . . . .

29

Condensation of Aliphatic Aldehydes with Dinitrofluorenes

31

Condensation of Aromatic Aldehydes with Dinitrofluorenes.

37

Condensation of n- Heptaldehyd e with 2-Nitr oflucre ne . . .

U2

SUMMARY...................................................................................................................................U6 BIBLIOGRAPHr.......................................................................................................... VITA........................................................................................................................................

LISTS (F TABLES AND FIGURES l i s t of Tables I. II. III. IV. V. VI.

Page

9-AlkyHdenefluorenes..........................................................................

7

9-Alkylfluor ene

7

..........................................................................................

9-Alkyl- 2-xluorenesulf o n a te s ............................................................10 Substituted 9-Alkyl- and9 -A rylfluorene...............................

11

Condensation Products of Nitrofluorenes with Aromatic A ldehydes.........................

lU

. . .

Condensation Products of Nitr ofluor enes with ........................................................................20 Aliphatic Aldehydes

l i s t of Figures I.

Preparative Method for 9-Alkylfluor enesulfonates . . .

5

(Contribution from the Purdue Research Foundation and the Department of Chemistry, Purdue University)

CONDENSATION OF ALDEHYDES TRUTHFLUORENE AND NITROFLUORENES1

By G* Bryant Bachman and Seymour Polansky

AN ABSTRACT In a study of wetting agents of special structures derived from fluor ene i t became necessary to investigate the condensation of this hydrocarbon and some of i t s nitro derivatives with aldehydes. The reaction has been shown to lead to 9-alkyIidene or 9-arylidenefluorenes in certain cases.

Schultz and Smullin condensed propio­

naldéhyde, butyraldéhyde, and isobutyraldéhyde with fluor ene success­ fully using potassium ethylate as catalyst.

We have followed their

directions in obtaining the corresponding products from n-hexaldehyde and n-heptaldehyde.

These alkylidene fluorenes were yellow, crystalline

solids which decomposed slowly in a ir, forming an o il and generating an aldehyde odor.

They were easily reduced a t room temperatures with

hydrogen in the presence of platinum oxide, but not with aluminum amalgam in moist ether (12), to the corresponding 9-alkyl fluorenes (Table I ) .

1

Based upon a Doctoral Thesis, Purdue University, June 1950.

Sulfonation of the 9-alkyl fluorenes with concentrated sulfuric acid gave the 9-alkyl-2-fluormesulfonic adds which were obtained as s a lts by neutralization of the acids with the appropriate alkali metal carbonates or ammonia.

The so lu b ilities and surface

tension lowering effects of these sa lts in water were determined. The S-benzylisothiuronium sa lts were prepared for characterization and analysis (Table I I ) .

The position of the sulfonic acid group

was established by oxidation to potassium 9-fluorenone-2-suifonate (11) and conversion of th is to i t s 9-oxime, a known compound (1). The nitration of fluor ene to 2-nitr of luor ene is successfully accomplished in glacial acetic acid using concentrated n itr ic add (7).

Dinitrofluorene may be prepared from fluor ene in the cold

using a glacial acetic acid—fuming n itric acid nitrating mixture (5). The n itratio n of 9-alkyI f luorene s , however, was found to require more vigorous conditions.

Nitration was accomplished a t 50° using

a mixture of concentrated sulfuric acid and concentrated n itric acid as the nitrating agent.

Low yields of the 2, 7-dinit ro-9-alkylf luor ene

were obtained (Table IV). The condensation of 2,7-d in itr ofluor ene with aromatic aldehydes in the presence of piperidine at 160° is reported by Candea and Hobrescu (2), although the purity of th eir starting material is questionable. benzaldehyde,

We have found that similar condensations with chlorobenzaldéhyde, and p-proponybenzaldéhyde

occur readily with 2,7- and 2,5-dinitrofluorene at less elevated temperatures.

Benzaldehyde reacts even at room temperatures, the

others in refluxing xylene.

Piperidine is a suitable catalyst.

ill

The reaction of dinitrofluorenes with aliphatic aldehydes has not been reported*

Our attempts to effect the condensation

with heptaldehyde using either alkali ethoxides, pyridine, or barium hydroxide as catalysts were unsuccessful. that piperidine gave the desired re s u lt,

I t was found, however, H-O-R

Heptaldehyde was condensed by adding a dilute solution of the aldehyde dropwise to a refluxing mixture of 2,7-din±trofluorene, piperidine and alcohol,

Hexaldehyde was condensed by refluxing a

mixture of i t with 2,7-dinitrofluorene, piperidine and xylene for several hours (Table I I I ) ,

The sane procedure with butyraldéhyde

gave only 1,1-bis- ( 21, 71-dinitrofluorenyl )-butane rather than 2, 7-dinitr o-9-butylidenef luorene ,

The yield of th is product was increased by adding a dilute solution of the aldehyde dropwise to a rapidly refluxing mixture of 2,7-dini tro f luorene *

This increase in yield may be explained in

terms of the difference in the ratio of reactants available in the two experiments.

In the second procedure the reaction occurs in

the alcohol phase between a large excess of 2,7-dlnitr of luorene and a limited amount of aldehyde.

This favors the reaction of

two molecules of 2,7-dinitr of luor ene with one of the aldehyde.

In

the f i r s t procedure the reaction takes place in the alcohol phase containing a high concentration of aldehyde and a concentration of 2,7-dinitr ofluorene limited by i t s solubility in xylene at the temperature used.

The conditions are therefore not as favorable

for the formation of the bis product, and hence the yield of th is material is lowered.

We were not successful in obtaining 2,7-

dinitro-9-butylidenefluorene, The formation of bis products also occurs in the hitherto unstudied condensation of aldehydes with 2-nitr ofluor ene .

The

sodium s a lt (1+) of the la tte r reacts with heptaldehyde to give poor yields of 1,1-bis-(2T-nitrofluorenyl)-heptane. (3) as catalyst or no

The use of piperidine

catalyst at all gave the same product from

2-nitr ofluor ene and heptaldehyde,

These products are shown in

Table I I I , Catalytic

reduction of the various alkylidene nitrofluorenes

gave the corresponding alkylf luorene amines in good yields (Table 17),

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