SOT.TE HALOGEIT DERIVATIVES OF ANILINE

AND

TEE DETE-FlJHNATION OF CHL'JRINE AND BROMINE IN SOME

ORGANI c C01.!POmrns BY THE USE OF LIQUID PJ!MOHIA.

by

T .. H. Vaughan.

A thesis submitted to the Department of Chemistry

and the. Fa.cul ty of the Graduate School

in partial fulfillment of the

requirements for the

Me.,ster' s degree~

Dept. of Chem ..

PART I. TABLE OF CONTENTS.

Preparation of 4-brom, 2--fodo aniline

Constitution of n " Reaction of HCl with No.I. -

Reaction· of acetic anhydride with No. I.

Reaction of benzoyl chloride with No. I.

Reaction of phenyl mustard oil w~th No.I.

Reaction of allyl mustard oil with No. Ie

Reaction of anisal aldehyde with No. I.

Reaction of cinnamic aldehyde with No. I.

Reaction of piperonal with No. I. -

Reaction of "on nitro benzaldehyde with No. t.

Reaction of Benzaldehyde with No. I. -

Reaction of potassium cyanate with No. I. -

Reaction of ortho tormic .ca,ster with.No. I. -

Preparation of 4-brom di-iodo aniline - -

~~Preparation of 4-chlor di-iodo aniline -

Reaction of HCl with No. III. -

Reaction of acetic anhydride with NO. III. -

Reaction of benzoyl chloride with No. III.

Preparation of 3-brom 6-iodo aniline -

Reaction of HCl with No •. IV. -

Reaction of acetic anhydride vii th No. IV. -

page.

3

5

7

7

9

10

11

12

14

15

16

17

17

18

19

21

23

23 ;'1./

23

25

25

26

Part II. page.

Determimation of chlorine

Analysis No. I. - 30

Analysis No. II. 31

Analysis No. III. - 32

Determination of bromine

Analysis No. IV. 32

Analysis No. v. - 33

Analysis No. VI. 34

Analysis No. VII. 34

Analysis No. VIII. - 35

AnalysiesNo. IX. 36

Analyrsis No. x. .j. 37

Analysis Nt5 • XI. 38

Analysis No. XII. 39

Analysis No~ XIII. 40

Analysi9 No. XIV. 40

Determination of chlorine by the use of calcium 41

Preparation of a hydroohlo ride a.alt 43

The purpose of .the first part of this work was to

'try out the substitution of iodine in the ring of some of

the anilines by heating together the iodine and the aniline

in the presence of calcium carbonate., finely divided and a

small amount of water and ether, and to try the reactions

of the ·resulting products with va~ious agents.

I. The 4~rom- 2-iodo aniline was prepared from

the 4-b:rom aniline. The following reactions were tried out:-(a) HCl-7the hydrochloride sa1;.

(b) Acetic anyh5fride ~the corres.ponding acetanilide.

(c) Benzoyl chloride ~the. benzanilide.

(d) Phenyl musta1·d oil~the diphenyl thiourea.

(e) Allyl mustard oil~~the allyl phenyl thiourea.

(f) RCHO -?ROH: NR

( Five aldehydes were tried; four reacted.)

(g) Potassium cyanate ~the phenyl urea.

(h) Constitution of the 4-brom 2-iodo aniline.

II. The 4-brom di-iodo aniline was prepared both

from the 4- brom 2-iodo aniline and directly from the 4-brom

aniline.

(a) HCl gas -7no reaction.

III. The 4-chlor di-iodo aniline waa prepared from

4-chlor aniline.

(a) HCl gas -7no reaction • • (b) Acetic anhydride--?no reaction

2

Acetic anhydride and sorJ.ium acetate plus heat

-7 no reaction ..

( o) Benzoyl chloride~ benzanilide.

IV. The 3-brom 6-iodo aniibine was prepared form

3-brom aniline.

(a) HCl gas -7the hydrochloride salt.

(b) Acetic anhydride --7 the acetanilide.

NH .... I G

c 11::::- C ~ "a -I

_J I II H-0 C-H

~c/

\ Br

I.

NH2 I

I-C~C'c-I I I!

H-C C-H· . ~c/ I Cl

III.

II.

NH2 J

~c, I-C~ C-H

r _ II H-0~ /C-Br ~c

I .H

IV.

3

EXPERIMENTAL.

P~eparation of 4-brom 2-iodo aniline.

Twcm·ty five grams of 4-brom aniline and 37. grams of

iodine, were heated in a flask with a reflux condenser with

18 grams of pure calcium carbonate,· 60 oc. of ether and 60 cg.

of water. Afmer several hours the reaction seemed to be

oomple te due to the disappearance of the deep iodine color1•

An oily product settled to the bottom of the flask and

hardened when cooled •. This black solid is soluble in ehher 1

alcohol 1 gasoline and benzene. With the alcohol, however,

is the color beat destroyed. The substance is dissolved in

warm dilute alcohol and cooled or precipitated by the addi-

tion <Jf water. A final product of fine white crystals was 0 0

obtained which melted at 71 • 4-brom aniline melts at 66.5 •

A mi.x:ture of the two melted at 48°. On analysis for nitrogen

this prooved to be 4-brom 2-iodo aniline.

Analysis as CefI5NBrI

Wt. of sample I - 0.2389 gms.

No. of cc. of Hen used - 25. co. (?;

:F'a.ctor for NaOH - .... 1.04

1 cc of HCl - 0.00226 gms N.

Titration.

NaOH HCl

19.36 cc 0.33 cc

Total acid requires ~ 25 .. 33 cc.

Percenaage of nitrogen -

Wt of sample II- - -

No. cc. of HCl used -

Titration

NaOH HCl

4.91

0.3577 gms

25.

.17 .zo cc 0.38 cc.

Total acid'used - - - -

Percentage of nitrogen --

Wt. of sample III

No. of cc. of ~Cl used

Titration

NaOH

11.()4 cc

Total acid used

Percentage of ni.trogen

Cale. as C6H5NBrI

4.712N2

HCl

0.10

25. 38 cc.

.... .... O. 6586 gms

25.

cc

25.10 cc.

- 4 .69

Sample Found

·I 4.91

II 4.7 6

III' 4 .69

4

5

CONSTITUTION OF No. I.

Some previous ·work has been done by Malleis 1

whereby the iodine substituted in the ring of an acetanilide

was replaced by ~bromine quantitatively. Some of No.I. was

treated with acetic anhydride and the dried product was dis-

solved in chloroform and treated with bromine. The two were

heated together on a water bath for a period of ten hours

and the resuJ.ting product was recrystallized from alcohol 0

and melted at 146 • The original acetanilide melted at 147°

and the mixture of the two melted at 146 to 147°. There was

evidently no iodine replaced by the bromine as in the case

of the para iodo aniline mentioned above.

Some of the No I. was diazotized in the presence

of cuprous bromide in order to replace the amino group Wlb.th

a bromine and obtain a substituted benzene. A heavy black

oil was either ~xtraced with ether or steam distilled and

an almost colorless (red) oil resulted. This w~s extratced i,.,.~·l.:

with ether and separated off 1 the ~ther boiled off and the

oil dried in a des~tcator. The 1-4 dibrom 2-iodo benzene

should melt at 38 to 39°• This oil has not yet cryaatllized

out even though it aas been oouf-d in an ice bath and· is quit e

pure.

To prepare the substituted benzene, 1-brom 3-iodo

benzene, from No.I. by diazotizing it and heating it up

with absolute alcohol:-

5 gms of No. I.

2 cc. cone. HzS04 •

17.5 cc of absolute alcohol.

2.5 cc of amyl nitrite.

The acid and absolute alcohol were mixed andi. the aniline

added. This precipitated the sulphate salt. The mixture

6

was cooled to 30 to 35° and the amyil nitrite slowly added.

The action was not vigorous but a slow effervescence took

place and. a gray product resulted. This was warmed with a

little alcohol and the mixture turned red. Water was added

and a dark brown oil separated to the bottom of the solution.

This was steam distilled and a colorless oil came over.

The 1-brom 3-iodo benzene is an oil so the product was nitrat-

ed with a mixture of supphuric and ni trio acids. This

required some heating and was quite slow. When cooled yellow

needle crystals formed which were separated and dried on a

porous plate. After recrystallization from alcohol, the

yellow substance.melted at 85°. The accepted melting point

of 4-brom 2-iodo 1-ni tro benzene is 83. 5°. This is probably

what the product is. Not enough was obtained for analysis.

PREPARATION OF THE HYDROCHLORIDE

OF NO. I.

The aniline was suspended in benzene and dry HCl

gas passed in until the precipitation of a white salt was

complete/. When dried on a plate the product melted at

205 to 266°.

Analysis as c6H5NBrI. HCl

Wt. of sample -

Normality of HCl

0.2432 gms.

- - - 0.1620

Factor for sodium.hydroxide -

1 cc. of HCl solution

Titration.

NaOH

4i194 cc

L.04 I

0.00590 gms HCl.

HCl

0.73 co.

Percentage of HCl - ..;.. 10. ?O

Calculated for c6H5~BrI. HCl 10.90

REACTION OF ACETIC ANHYDRIDE

AND NO.I.

7

The dry aniline was treated with acetic anhydride

and a product \w~s obtained which> when recrystallized from

alcohol gaie fine white crystalts ( with a slight purple

hue) which melted from 147 to 148°. This is the 4-brom

2-iodo acetanilide.

Analysis as CgH70NIBr

CH COOH. 3

WT. of sa~~le I - - - - - -

No cc. of HCl used - - - - -

- 0.3035 gms,

25 •. cc.

Factor for NaOH 1.04

l cc. of HCl o.00226 gms N2 •

Titration.

NaOH HCl

18.64 cc 0.25 cc

Total acid used - - - - - - 25~25 cc.

Percentage nitrogen - - - .4 .36 -=-

Wt. of sample II. - ~ - - M 0.3034 gms

No. of, cc. of HCl used - - - - - 25.

Titration.

NaOH HCl

19.05 cc 0.78 cc

Total acid used - - - - - - 25.78 cc~

Percentage of nitrogen - - - - 4 .. 44 -===--== Cale. for c8H70NIBr Found.

4 .11 7o n 7..- I. 4.36

II. 4.44

8

9

REACTION OF BENZOYL CHLORIDE WITH

NO. I.

The aniline and benzoyl chloride reacted easily

to give a solid product which was purified from recrystall-

ization from hot alcohol,, and was shown to be the substituted

benzanilide. It melted at 151 to 152°.

Wt. of sample

No.of cc. of HCl used -

Factor for NaOH - -

1 cc. of HCl - - - -

/H N-CO-C6H5

l r-l\-H I II + HCl

H~~C-H

J Br

- - 0.3053

- 25.

1.04

0.00226 gms N~

Titration

NaOH HCl

19.35 cc~ o.oo cc

Percentage of nitrogen - - a.e1 Cale. for c13HgONIBr - - 3.48

REACTION OF PHENYL MUSTARD OIL

WITH NO. I.

10

Phenyl mth.stard oil reacted with the aniline 'dis~

solved in a little alcohol to give at once a crystalline Ct

product which was soluble in alcohol and was rec.ystallized t

°i~-')

from it by cooling¢ adding a little water. Fine hair-like

crystals of 4-brom 2-iodo diphenyl thiourea, almost white,

resulted which melted at 167°.

Wt. of sample .±. -

No of cc. of acid used

Factor for NaOH -

l cc. of HCl

Titration

NaOH

15.37 cc

Total acid used - -

Percentage nitrogen

wt. of sample II •. -

No. of cc. of HCl usei

- 0.3083

- 25 •

1.04

0.00226 gms N.

HCl

0.10.cc

- 25.10 cc.

6.68 -

- 0.3057 gms

25. cc

Titration.

NaOH

15.59 cc

Total acid used - -

Percentage nitrogen -

Cale. for c13H10NaIBrS

6.4 6 7() yL "V

HCl

0.10 Co

2'5.lOco

Found

II, 6051

REACTION OF ALLYL MUSTARD 01D'L

A}ID NO. I. ;

The two reacted readily in alcohol solution to

11

give a solid product which was purified by recrystallizatio n

from hot alcohol. The product, flall:y silver white crystalls,

was allyl 4-brom 2-iodo phenyl thiourea, whivh melted at

177°.

2-I . ~Csfl3NH2 ~

4-Br

Wt of sample I. - - - - - 0.3017 gms

No. of ec. of HCl used - 25.

Factor for NaOH 1.04

l cc of HCl - 0.00226 gms N.

Titration.

NaOH HCl

14.71.cc O.o60cc

Percentage nitrogen -

Wt. of sample II.

No. cc .. of HCl used - -- - ....

Titration.

Na.OH

16.05 cc

' Total acid used

Percentage nitrogen

Cale. for c10H10N2IBrS

7 .05 Jo ll-v

HCl.

0.78 cc

Found

I. 7 .26

II. 6.66

7.26

o. 308€1 ~

25.

25~78 cc

6.66

REACTION OF ANISAL ALDEHYDE WITH

NO. I.

The two substances reacted slowly, being warmed

occassionally, to give a product of highly refractive

cr~stals, the anisal aniline from anisal aldehyde and 0

2-iodo 4-brom aniline. The me'l ting point is 117 to 118 • ·

12

, Analysis as c14 H11 NOIBr

wt. of sample I. - - -

Factor for ~aOH -

No of cc. of HCl used

lee. of HCl -

Titration.

NaOH HCL

- - 0.3200 gms.

1.04

25.

13.

0.00227 gms of N.

19.30 cc 0.35 cc~

Total·acia used -

Percent of nitrogen -

Wt. of sample II. -

No cc of HCl used -

Titration.

NaOH HCl

18.65 cc 0.25

Total acid used - - - -Percentage of nitrogen -

Cale. for C14H11NOIBr

3 .36 7o YI. 'l- I.

II.

25.35 cc

3.72 -

0.3660

25.

cc

- 25.25 cc

3.61

·Found

3.72

3.61

REACTION OF CINNAMIC ALDEHYDE

AND NO. I.

14

The aldehyde and aniline reacted slowly on being

warmed to give a solid product, aoluble ~n a1cohol, ether,,

gaso_line and benzene. It was recrystallized from alcohol 0 to give fine crystals •ith a green tint that melt at 96 •

2-I c~5~:~-oo:~c~~ + ~o

4-Br

Analysis as c15H11NIBr

Wt. of sample No. I. -

No. of cc. of HCl used -

Factor for NaOH -

1 cc of HCl - -

Titration,

NaOH

18.14 cc

Total acid used - -

Percentage nitrogen -

Wt of sample No.II -

No of cc of HCl used ·-Titration.

NaOH

15.05 C.,(!...

- - O .3495 gms

HCl

0.10 cc

HCl

- 25.

1.04

0.00226 gms N.

25.10 cc

3.38

0.3046 gms

2e.

--· Total acid us~ - - ~ - - - - 20.1 cc

Percentage o& nitrrugen

Cale. for c15H NIBr -

. 11 - - - -Found No. I No, II

3.38 3.30

REACTION' OF PIPEROUAL WITH

NO. I.

3.30

A The two reacted slowly at room temperature and

15

when warmed occassionally gave solid mass. This dissolved

.only in hot alcohol and when crystallized out by cooling, 0 melted at 120 • It is the piperonal 2-iodo 4-brom aniline.

W ... I.>. of sample - - - .... - - o. 5730 gms.

Factor for NaOH - - - - - - - 1.04

No. of cc. of HCl used - - - - 25.

1 cc. of HCl - - -

Titration.

Na OH HCl

15.55 cc. o.oo co

Percentage of Nitrogen - - - - - 3.48

Cale. as C H902NIBr 14

3 ,.2 5 Ja 'Y\,_

Fpd>und.

3.48

REACTION OF ORTHO~NITRO BENZALDEHYDE

WITH NO. I.

16".

The two reacted similarly to the other cases of the

aniline and aldehyde to give a solid, 2-nitro benzal 4-brom

2-iodo aniline. This was soluble in ether, alcohol, benzene

and gasoline. Recrystallized from alcohol the p+oduct of

greenish yellow crystal!, which turned brown in the presence 0

of light> melted at 159 •

Analysis as c13H802N2IBr

Wt. of sample ; - - - - - - - 0.4051 gms

Factor for NaOH - ·- - - 1.04

No. of cc. of HCl used - - - - 20.

1 cc. of HCl - - - 0.00227 gmse N2

•

Titration.

NaOH HCl

8.81 cc. 0.40 cc.

Percentage of nitrogen - -

Wt. of sampl'e II - - - - - 0.4020 u

17

No. of cc. of ttc1 used - - ~ - - ~ 20.00 ,.,.

1 co. of HCl - - - - - 0.00227 gms N.

Titration.

Na OH HCl

8.78 co. 0.20 cc •.

Total acid used - - - - - -. - - 20.20

Percenta.g·e of nitrogen - - - 6.25 ==------

Calo. for C13Ha02NaIBr Found

6.50 lb Y\-v I 6.30

II 6.25

REACTION OF BENZALpEHYDE WITH

NO.I.

The aniline was heated at 135 - 140° for several

hours on an oil bath with benzaldehyde but no :reaction took

place between the two.

REACTION' OF POTASSIUM CYANATE

WITH NO~ I.t

Molecular proportions of the aniline and potassium

cyanate were heated together in glacial acetic acid.~ They re-

acted at once to give a gas ,and a. white solid. The solid

mass was found to be very slightly soluble in water. It is

soluble in alcohol and is precipitated by the addition of

large amounts of water as a white crystalline mass, 4-brom

2-iodo phenyl urea., which melted at 167°.

KNCO

Analysis as c7H6oN2IBr

wt. of sample - - ~ - - - - - 0.3010 gms.

Factor for NaOH ~ - - - - - - 1.04

No. of cc. of HCl used - - - - -20.00-cc.

18

l cc. of HCl - - - - - - - - 0.00227 gms N. ·

Titration.

NaOH HCl

9.06 cc. 0.08 CCe

Total acid used - - - -

Percentage of nitrogen ~ - - -

Cale. for c7H60N2IBr

a.21 % 1'1-v

·Found

8.04

- 20.08 cc.

8 .04 =

REACTION OF omTHO FORMIC ESTER

WITH NO.I.

Two mols of the aniline were heated with one mol

of the e~ter in an oil bath at 120 - 130° for three hours,

to aee whether or not there was any reaction. The substances

were expected to react, if at all~ in the following manner.

The product after being purified was dried amd melted at 70°,

0 . The original aniline melted at 71 • A hydrochloride was

prepared which showed by .it's melting p~int, and that of

a mixture with the original, that there was no reaction.

This was proba~ly due to the presence of a negative group

19

in the orhho position of the ring which hindered the reaction ·

with the ester.

PREPAHATION OF 4-BROM DI~IODO ANILINE.

45 grams @f iodine and 20 grams of para-brom

aniline with 30cc. of ether, 30cc. ,of water, and 15 grams

of caloi1.un carbonate were heated together in a flask with

a reflux condenser for several hours. A black solid was obtain

obtained which was not apparently soluble in anything but

warm pyridine. It was reprecipitaed by the addition of water

to the pyridine solution in a finely divided form which was

less soluble in alcohol tham the mono-iodo derivative. Some

of the mono derivative was.found to be present with the di-

iodo product and was separated from it by fractional.

crystallization from alcohol. By repeated crystallization

tije 4-brom di-iodo aniline was obtained as a white solid

which melted at 148°. NH2 c I-C~ 'c-I

I · II H-<\yC-H Br

20

When the 4-brom 2-iodo aniline was heated with the

proper amount of iodine, with ether1 water and calcium carbon-

ate for several hours, the 4-brom di-iodo aniline was obtain-

ed alone. Any excess iodine was taken up by sodium thho·

sulphate.

Analysis as CeH4 NI2Br.

wt. of sample I - - - - 0.4080 gms.

No. of cc. of HCl used -

lee .-of HCl - - -Factor for NaOH - -

Titration.

MaOH HCl

2s.· O.Q0226 gms N.

1.04

18.23 cc. o.oo co.

Percentage of nitrogen

Wt. of sample II -

N'o. of cc. of HCl used -

Titration~

1'TaOH

. 17. 7 5 cc.

Total acid used -

Percentage of nitrog,en -

Cale. for c6H4NI2Br

3.30 7• Yl ._

- -- --

HCl

0.20 cc.

- 25.20 cc.

Found

I 3.34

II 3.52

21

When the 4-brom di-iodo aniline was suspended in benzene and dry HCl gas passed in, the solid that precipitat-

ed out pro~ved to be the original ~ubatanse and ga~e no

HCl when heated Wlhth standard NaOH.

PREPARATION OF 4-CHLOR DI-IODO ANILINE. Twenty grams of par~chlor aniline with 40 grams of

iodine and.20 grams of calcium carbonate in 60 cc. of water

with an equal amount of ether1 were heated in a flask with

reflux condenser, over a water bath, for several hours until the deep iodine color had disappeared. A solid was obtained which was crystaJlized from alcohol or separated by steam

distillation. The yield was 23 grams after the first recryst-altlza tion. If not all of the par2=-chlor aniline is U$ed it can be separated from the iodo-product by dissolving in alcohol and adding water, wher'eupon the iodo:-product separates out and leaves the po..r~chlor aniline as a milky emulsion which, on standing, separates as a fine white crystalline compound. The iodine derivative mefuted at 129 o c. When analyzed it was found to be a di-iodo compotmd instead of a mono-iodo deri va.ti ve.

Analysis as c6H4NI2Cl

Wt. of sample I.-

Factor for NaOH -

No. of cc. of acid used -

0 :4068 grams

- 1.04

-20 ..

l cc. of HCl - 0.00227 gms. N2

Titration

NaOH

12.97 cc.

HCl

o.oo cc.

Percentage of nitrogen -

Wt. of sample II. -

Factor for NaOH -

No. cc. acid used - -

1 cc. acid -

Titration

Na OH

15.05 cc.

Total acid used -

Percentage of Nitrogen -

Wt. of sample III .. -No. of cc .. of acid used

Titration

Na OH

14 .57 cc.

Total acid used -

Percentage of nitrogen -

HCl

- 0.3023 gms.

1.04

- - -20.00 cc.

O. 00227 gms • ·N2

0.20 cc.

- ·- 20.20 cc.

- - - 3 .48 -0.3033 gms.

- 20.00 cc.

HCl

0.23 cc.

- 20.23 cc.

3.210

22

Cale. for Csl4NI2Cl

3. 69 /o i'\-v

Found

I •. 3 .• 63

II. 3.48

III. 3.80

REACTION OF DRY HYDROGEN CHLORIDE GAS

WITH NO. III.

23

When some of the 4-chlor di-i'odo aniline was sus-

spended in.benzene and firy HCl gas added, a solid came down,

'which, however, by comparison with~the melting point of the

original, proved to be tha·t substance; no reaction having

taken place.

REACTION OF ACETIC ANHYDRIDE

WI"'I'H NO. III.

Some of the 4-chlor di-iodo aniline was treated

with acetic anhydride but with no interaction.

Later some of the aniline'was heated with acetic

anhydride in the presence of sodium acetate but this also

failed to produce any phange.

7_ REACTION OF BENOYL CHLORIDE " .

' WI TH NO • I I I •

The 4-chmor di-iodo aniline, which would not react

with acetic anhydride, was treated with benzoyl chloride and

the mixture warmed for some time. A white solid was obtained '

which, after recrys~allization from alcohol, melted at 205° C.

24

It is the substituted benzanilide.

2-I ~

Cl-COC6H5 --t4-C/C6H2NH-COC6H5 + HCl , ,

6-I

Wt. of aample I. -

Factor for NaOH - -

- - - - - 0.3004·

No. of cc. of HCl used- - - 20. cc.

1 cc •. HCl - - - - - o .00227 gms. Nz. · Titration.

HCl NaeH 15.05 cc. 0.10 cc.

Total acid used - - - - 20.10 cc.

Percentage of nitrogen - -3.27

Wt. of sample II. - - 0.3000 gms.

Mo. of cc. of acid used - - 20. cc.

Titration

Na OH HCl

15.80 cc. 0.50 cc.

Total acid used - - - 20.eo cc.

Percentage of n1 trogen - - - 3.09

Calo. for c13H901U2 Cl Found

2 .97 °1 'Y\-z.-.. I. 3.27 . /o II. 3.09

25

J jJ . PREPARATION OE3-BROM ~ODO ANILINE.

f

Thirty .... four grams of meta-brom aniline, 50 grams

of iodine and 24 grams of calcium carbonate, with 60 cc. of

water and 60 cc. of ether were heated. together for several

hours on a water bath with a reflux condenser. An oil

separated out, which could be either extracted and purified

f~om alcohol or steam distilled, as a red oil. This was

dried e .. nd allowed to stand for two months. When it crysta.LL-

lized out it melted at 55° e. to 56° c. Analysis proved this compound to be the 3-brom

6-iodo aniline. Its '1~onsti tutio~, whoweY.ei'i~c:wa~~··provehyby "'\

analy$.is of the hydrochloride and the acetyl deri va ti ve.

REACTION OF DRY HYDROGEN. CHLORIDE

WITH MO. IV.

The 3-brom 6-iodo aniJ:ine was suspended in benzene

and dry HCl gas passed in until until the reaction was com-

plete. A white solid was precipitated which melted at

191-192°c. when dried on a porous plate.

For analysis a weighed quantity of the hydrochloride

was titrated with standard sodium hydroxide solution.

Cale. for C6H51HBrCl)+

10.90 percent HCl

Found

I. 10.77

II. 10.64

Wt. of sample I. - -.0.5000 gms.

Factor for NaOH - - - - 1.04

26

1 cc. of HCl - - - - - - 0.005833 gms. HCl

Tditration

Na OH

10.00 co

HCl

1,17 cc

No. o;f cc. of N'aOH neutralj.zed by s·ample - - 9 .23cc.

Percent of HCl - - - - - - - - - - 10.77

·Wt. of sample iI - - - - - - 0.5000 gms.

Titration.

NaOH HCl

10.32 cc. 1.61 cc.

NaOH neutralized by sample - - - 9,12 cc.

Percent of HCl - l~

REACTION OF ACETIC .ANHYDRIDE

WITH NO. IV.

.:::::::

The aniline reacted readily with acetic anhydride,

giving shiny white crysta~s of 3-brom 6-iodo acetan~lide 0 which, when dried o~ a porous plate melted at 199 c.

Analysis as_CgH70NIBr

Wt. of sample I.

Factor for NaOH - -

0.3059 gms.

l.04

No. of cc. of HCl used - - - - 20.

1 cc. of HCl - - 0.00227 gms N2 •

27

Titration.

NaOH HCl

13.65 cc. e.oo cc.

Percentage of nitrogen - - - 4 .30. -· Wt. of sample II - - - - - 0.3014 gms

No • .;9f-. cc. of HCl used - - - - - 20.

Titration.

NaOH HCl

14.10 cc. o.oo cc

~ercentage of nitrogen - - - 4 .02 -Cale. for c8~0NIBr Found

4.11 7u 7l-v I 4.30

II 4.02

PART TWO.

TEE DETERMINATION OF HALOGENS IN SOME

ORGANIC cm~oUNDS BY THE USE OF LIQUID AMMOIUA.

28

Much recent work has been done with liquid ammonia

as a solvent, both in this country and abroad. The first work

to be done in this country was in the laboratory of this

University when, some years ago, H. P. Gady discoverai that

that liquid ammonia was an ionizing medium. Since that time

a great amount of work has been carried on in studyi~g both

the properties of liquid ammonia and reactions of substances

dissolved in this solvent.

It is connection with this last that this work was

undertaken. The idea of halogen determination in this medium

was originated by Prof, Cady and has· been further studied in

the' laboratory under the direction of Dr. F. B. Dains. A

method. similar to the one here used is described, with results

therefrom., in a book by the French chemist Chablay) "6n the

use of the Metal-Ammonium Compounds in Organic Chemistry".

THE METHOD.

The general methed &s to dissolve a weighed amount

of an organic halogen compound in about 30 cc. of liquid

ammonia drawn in a Dewar test tube~ To this ·solution small

pieces of clean) metallic soctium are:_·added until the blue

coloration that results is permanent. This is allowed to

stand for an hour, then pure ammonium nitrate is s1ov1ly

added to take up the excess sodium, forming sodium nitrate

and ammonia.. As a rule part o<ii complete destruction of the

organic c1.::m1pound seems to result, especially in the case of

aromatic compounds .. The reaction between sodium and the

halogen compound may be expressed thus:

R-Hal f Na ____, Na-Hal -1- X

29

where X represents the products resulting from the destruction·

of the organic compound1 whatever they may be.

After the excess sodium has been taken up by the

an:uuonium nitrate, the solution is allowed to evaporate to

dry~ess, and the dry product di!aolved in a small amount of

water~ The· water solution is then acidified with dilute ni trio

, acid and titrated with silver nitrate and ammonium thio cyan-

ate, using a nitrio acid solution of ferric aiurn·as an indi-

cator. The ferric alum solution is saturated and made acid

with ni trio acid until the red colo.r disappears. Five cubic

centimeters of the indicator were used for each titration-

Chlo rine and bromine compounds are quite easily

determined by this method but iodine compounds aan not be

determined by this method directly& In some instances the

organic material left :f·rom the liquid ammonia solution,

30

.after being evaporatei to dryness, redissolved and acidified

caused a dark red or brown precipitated to be formed which

made titration impossible without first:' filtering off the

dark precipitate.

In thms work no compounds containing more than one

of the halogens were successfully analyzed by.this method.

Several vrnre tried. The compounds analyzed are given below

with the data and calculations for each result"

EXPERHIBNTAL.

I. Determination of chlorine in Ol'tho chlor -phenyl

allyl thiourea.

wt. of sample ~

Fac·tor for NR4NCS

l cc. of AgN03 -

- - -..... - -

Titration

AgNe3 NH4NCS

0.4360 gms

o.9901

0.001113 gms 012 •

65 .98 oc e I 3.30 cc.

Correction factor for AgN03 0.996

( 65.98 - ( .99_Q.l x _3 .q_Q_)_)_t_OOlll3 x 100 x .996 °7 0.4360 = 15.94 1001.

wt. of sample II. - - - - - - o.4592 gms

Titration

AgN03

68. ?2 cc.

NH4NCS

3.75 cc.

31

( 69.7_? - l0.9901 x 3-.75)j_Q_.001113 x 100 x0.996= 15 .oo"f0

e_; 0 .4592 /o

Cale. for c10H1iNzClS. Found.

15.65 percent Cl. I. 15.94

II. 15. 69

II. Determination of chlorine in "m" chlor-phenyl

a.rlyl thio urea.

Wt. of sample - - -

Factor for UH4NCS

1 cc. of AgN03 ~ -

....... ...- ..... 0.4045 gms.

0.9901

- 0.001113 gms c12 •

Correction factor for AgN03 - - - 0.996

Titration.

AgN03 NH4NCS

59 .85 cc. . 8 .62 cc.

( 59 .85 - ( Q .9901 X 2 • ffi)) Q.001113 X 100 X e996 UJ - . Q.4045 =::l~ /D <!_Ql.·

. Ca.le. for c10H11 NzClS.

15.657212.

Found.

15.69

32

III. Determination of chlorine in °p" chlor~phenyl

allyl thiourea.

Wt. of sainple -

Factor for A.g_~o3 · l cc. of AgN03-

- -- -- --·

Titration.

AgN'03 32.20 CCe1

Cale, for c10H11NzClS.

is. e5zc12•

3.10 0011

0.2117 gms.

·o.-8347

0.00141 gms.

Found.

15.78

IV. Determination of bromine in 2-brom acetanilide.

Wt. of sample I - - - - - - - -0.2453 gms

Factor for MH4NCS -

l cc. of AgN63 -

Titration.

48 040 cc.

NH4NCS.

2. 69 cc"

0.906

i 48.40 - 2'!...!.~_x. 0.9\)_6)). ~- 9 .• 002 X 100 = 37 .48 /0

Bra. 0 .2453 /o

33

Wt. of sample II. - - - - - - - - 0.2652 gms.

Titration.

AgN03 63.22 cc.

NH NCS 4

14 .92 cc ..

{ 63 ._?~ - ( 14~92 x p~906)) ?t0.p02 ~ 100 37 35fB 0.2 652 -- .~ • /o' rz.

Cale. for c8H80NBr.

37 .34 Jo Br2

Found.

I. 37.48

II. 37 .35

V. Determination of bromine in "o" brom-phenyl

allyl thiourea. 2-Br-C6H4 NH .

- "c-s /-C3H51'IH

Wt. of sample - · - - - - -

Factor for AgN63 - -

0.19 69 gms.

0.834!7

1 cc. of AgN03 - - - 0.003188 gms Br2 •

Titration.

AgN03

22. 65 cc.

I

Cale. for c10H11N2BrS.

. 29 .48JJ3ra.

NH NCS 4

0.82 cc.

Found •

29.26

VI. Determination of bromine in nm" bromphenyl

allyl thiourea.

Wt. of sample I. -

Factor for NI4NCS

0.3016 gms •.

o.9901

34

l cc. of AgNO - -3 .

Correction for AgN03 - -o.002soe gms. Br2 •

0.996

Titration.

AgN03

36. 63 cc.

NH4 NCS

Q.95 cc.

( 36.63 - {0.95 x 0.9_90~)J x _!_90?508 x 100 x .996 =B9 , 467,0

Br. Q.3016 /0 1

Wt. of sample II.- - - - - - 0.3007 gms.

Titration.

AgNO,., 6

37.55 co.

Cale. for c10H1f2SBr

29 .48%Br2

~4NCS 1.70 cc.

I.

Found.

29 .4 6

II. 29.73.

VII. Determination of bromine in "p" brom-phenyl

allyl thiourea.

35

- O .3821 gms.

- 0.9901

Wt. of sample I. -

Factor for NH4NCS

1 cc. of AgN03 - 0.002508 gma. Br2 •

Correction for AgN03 - - - - 0.996

Titration.

AgN03 ·

46c05 CC.

~4NCS 0. 60 cc.

( 46.05 - ( 0.60 :ic 0.9901)) x 0.002508 x 100 x .996 -.29.71'70

Br. 0 .3821 /o

Wt. of sample II. - - - - - - 0.1969 gms.

Titration,

AgN63 18.08 cc.

NH4NCS

o.oo cc.

( 18 .oa) x o .002508 x100 x o.996 =- 29 .26 :sr2 • . • 1969 /o

Cale. for c10H11NzSBr.

29 .48/j;r·

Found.

I 29.71

II. 29.26

VIII. Determil).ation of bromine in "o" brom-0 p" tolyl,

"o" tolyl thiourea.

Factor for NH4NCS - - - 0.9901

36

1 cc.- AgN03 - · O .002508 gms. Br2 .•

Titration.

AgNO 3

26.16 cc.

MH4MCS

3.10 cc.

'( 26.16 - (_3.10 x 0.9901)) x 0.002508 x L60 23.6:3~Br. o.2558 '"

Wt. of sample II. - - - - - 0.2611 gms.

Titration.

AgN03 26.30 cc •

.L.§_6.30 - ( 1.60 x 0.990'.l-)) x Q.002508 x 100 ~ . 0 0 611 - -23.75

0Br: • i:;:,

Cale. for c15H15N2SBr

23. 83J.Br2 •

Foun~.

I. 23. 63.

II. 23. 75

IX. Determ1nation· of bromine in Z!m" brom-phenyl

thiazole .. N c:H2 II ·· I . .

m-Br-C H N.:;__C -S- C-H 6 4. . ... H· · 'cH3

The solution for t~tration had a red coloration

which made the end-point very indistinct.

Wt. of sample I - - - - - - - O .247·5 gms.

Factor for 1TH4NCS

1 cc. of Ag N03

- - o.~901

- 0.002508 gms Br.

37

Correction for AgN03 - - 0.996

· Tit rat ion •

AgNO NH4NCS 3

31.16 cc. 1.99 cc.

( 31.16 - ( 1.99 x 0.9901 )) x 0.002508 x 100 x .996:=29.45':,Br 0 .24 7 5 'lo

Wt •. of sample II. - - - - - - - 0.3405 gms

Titration.

AgN03 4 6.18 cc.

-29.78 Br. ( 4 6 .18 -_ ___,(._5_. 6_3_x_.;._. 9_9 __ 0_1_._) .._) _._...0~0_2 5_0 ___ 8_x_l_O_O_x_._.~...._9_6_ z Q.3405 ~ 0

Cale. for c10H11N2SBr

29 .48 7.Br2

Found.

I. 29.45

II. 29.78

X. Determination of bromine in

Wt. of sample - - - 0.2055 gms.

Factor for NH4NCS ~ - - - - 0.9901

1 cc. of AgN03 -

Cprreotion for AgN03

Titration.

- 0.002508 gms· Br.

0.996

AgN03

20.21 cc. 4.20 cc.

38

( 20.21 - J 4.20 x .9901)) o.ooasos x 100 x.996 ·~ 0.2055 19.44;

0Br.

Cale. for c22H1 60N3Br

1s.11°1Br • lo 2

Found.

19.44

XI. Determination of bromine in

CH -c c~cH-NH-C H 3/1 ,.. 65

N C:O · 'N/ -t-- Br2 C5H5

This compound was prepared by Henry R. O'Brien - 1915.

Wt. of sample I. -

Factor for NH4NCS

1 cc. of AgN03 Titration.

AgN~3

ioo.i:o cc.

- 0.4167 gms.

- 1.028

- o. 001954 gms. Br2 •

2.90 cc •

.LJ:Qo.?o - ( 2.so x i.oasL} x 0.001954 x loo 0 0.4167 ~o,0Br.

Wt. of sample II. - - - .;.. 0.3151 gms.

Titration.

AgN03

80.20 cc. 5.00 cc.

UQ_.20 ... ( 5.oo x i.oas ))@d.0019·54 x 100 _. 46~ 5o~.Br. 0. 3151 '"

Cale. for c17H130N3Br3

46.37j:Br9 Found.

I. 45.80

II. 4 6. 50

39

XII. Determination of bromine in i·-"p" brom-phenyl

3-phenyl, 4-benzal, 5-pyrazolon.

W~. of sample I - · - - - O .2024 gms.

Factor for NH4NCS - - - 0.9901

1 cc. of AgN03 - 0.002508 gms. B~.

Correction for AgN03 - - 0.99 6

Titration.

AgN03

17.49 cc •

NH4NCS

1.38 cc.

.l1_7.~9 - ( 1.38 x .9901 )) 0.002508 x 100 x .996 ~19.84~0Br. 0 .2024 /,

Wt.-of sample II. - - - - - 0.2155 gms.

Titration.

AgN03 20.50 cc.

NH4 NCS

f$.46 cc.

( 20.50 - (__3.46 x .9901))x0.002508x100 x .~~6.=19.7310Br. 0.2155

Cale. for c22H15oN2Br

19 .a5'j0Br2

Found.

l&. 19 084.

II. 19.73

XIII. Determination of bromine in

Vlt. of sample -

Factor for NH4NCS

1 cc. of AgN03 Correction for AgN03

- - - 0.2600 gms.

- - o.9901

- o.002508 gma. Br2 •

- 0.996

Titration.

AgN03 28.17 cc.

NH NCS 4

1.41 cc~

40.

0$~~17 - ( 1.41xo.990l))_xo.ooasoax100 x .996. 24_.s?:Br Q.2680 . k

Calo. for c31H20o2N4Br2 •

25.ooJ~r2 ~ Found.

24.87

XIV. Determination of BROMINE in

CH3-C C=CH-NH-CsH4Bf II f · N"-~fl:O .

c6H4 cH3

Wt. of sample I - - - - 0.2040 gms.

Factor for NH4NCS - - - 0.9901

1 cc. of AgN03 - - - - - - 0.002508 gms. Br2 •

Correction for AgN03 - - - - 0.996

Titration.

AgN03

17 .53 cc.

17~53 x Q.002508 x 100 x0.996 o.204e

Cale. for c18H16oN3Br

21.63 /o Br2 •

NH4

NCS

o.oo cc.

- 21.39 Br2 •

Found.

21.39

41

XV-. DETEfilUNATION OE CHLORINE IN 4-CHLOR-ANILINE

BY THE USE OF METALLIC CALCIUM INSTEAD OF SODIUM.

Since calcium is soluble in liquid ammonia, it

was thought that it might react with the halogens in liquid

ammonia solution in the same manne<t-as metallic sodium~

This was found to be true in the caes of the analysis of

4-chlor-aniline. The calcium, of course, must be absolutely

free from halogens. If it is not the exact amount ueed may w

be accurately eighed out and a check on the calcium run to

determine the exact amount of halogen present in it.

Wt. of sample -

Factor for NH4NCS

1 cc. of AgN03

Analysis.

- - o.1355 gms:.

- o.9901

- - 0.001113 gms. Clz.

Titration.

NH4NCS

39.06 cc. 6.90 cc.

( 39 .06 - ( 6.90 x .9901)) 0.001113 x 100 =- 26.48,0012. 0.1355 /o

Cale. for c6H6NC1

2 6. 551.012

Found.

26.48

42

PREPARATION OF THE HYDROCHIORIDE SALT OF:

/CH3 CH3-c C==CH-J':IB-CsH3

II I - "cH3 (m) N /c:o

~N........-

C€f5

43

The yellow compound was suspended in benz·e:rae and

dry hydrogen chloride gas was passed in until the formation

·Of a yellow precipitate \vas complete. The precipitate was 0

dried and melted at 189 - 190 • The original substance

melted at 1-?4 °. The weighed hydrochloride was boiled fo'r I

a time with standard alkali and titrated with standard acid

to determine the amount of HCl liberated.

Analysis.

Wt. of sample - - 0.5000 ~

Factor for NaOH - - 1.04

1 cc. of HCl solution - 0.00583 gms. HCl.

Titration •.

HCl MaOH

35.60 cc. 27.80 cc.

(( 35.eo :z 1.0·4) - 2WZ~~ao) 0.00583 x ioo = io.1siHc1. 0.50000 - lo

Cale. for c19H19oN3 °HCl

10. 6? {a HCl

Found.

l0e75

# The original base was prepared by Henry R. O'Brien.

44

In conclusion I am glad to ~ak~ this opportunity

to express my appreciation to Dr. F. B. Dains for the

many helpful suggestions in carrying out this work.

University of Kansas

May 22 1 1916.