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Author: Subject: Azo Dyes and Colored Smoke
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thumbup.gif posted on 28-8-2011 at 14:02
Azo Dyes and Colored Smoke


Today I synthesized 3,4'-dicarboxy, 4-hydroxyazobenzene.


By louf11 at 2011-08-28

It was made by coupling salicylic acid and para-aminobenzoic acid. No procedure in literature was followed. The synthesis was made on a 1/15 mol scale.

The purpose for synthesizing this azo dye was to make colored smoke with it. This did not turn out well.

Reagents:


By louf11 at 2011-08-28

Hydrochloric acid- technical, hardware store grade
PABA- relatively pure- extracted from a nutritional supplement
Salicylic acid- reagent grade, from Elemental Scientific
Sodium nitrite- Reagent grade, from Mallinckrodt
KI-Starch paper- Pure, from an old chemistry set

Procedure:

A basic solution of para-aminobenzoic acid (9.13 g) was made by adding granulated PABA to a solution of sodium hydroxide. All dissolved. Approximately 100 mL of 31.45% hydrochloric acid, a large excess, was then added. This gave a very fine acidic suspension of PABA, which would allow a quick reaction with nitrous acid.


By louf11 at 2011-08-28

The suspension was cooled in a NaCl salted ice bath. Ice cubes were added to the beaker. The temperature was -4C. An aqueous solution containing 5 grams sodium nitrite (4.6 grams required) was added slowly, keeping the temperature below 0C.

The NaNO2 solution was added until the solution turned potassium iodide-starch paper blue. Granular urea was added until the KI-starch paper was no longer blue. Urea reacts with excess nitrous acid generating gaseous products.

9.2 grams of salicylic acid was dropped in the beaker.


By louf11 at 2011-08-28

The salicylic acid seemed to dissolve to an extent. A saturated solution of sodium hydroxide, NaOH, was added.


By louf11 at 2011-08-28

By louf11 at 2011-08-28

The solution turned dark brown, and began boiling (due to adding the NaOH too quickly).

The goopy mixture was filtered, and the filtrate was clear.


By louf11 at 2011-08-28

The filter cake was dried in the oven for about half an hour.


By louf11 at 2011-08-28

The weight of the slightly moist powder was 19 grams, which would be a 100% yield (except for the moisture).

The powder will be recrystallized from ethanol tomorrow.


By louf11 at 2011-08-28

The dye is water and alcohol soluble, and depending on the concentration, gives solutions whose color can be anywhere between yellow, orange, or brown.


The dry powder was mixed with sodium chlorate, sodium bicarbonate, and sugar. The mix was ignited, but the smoke was pure white, not orange-brown as hoped.


By louf11 at 2011-08-28
This is a picture of the pyrotechnic mixture.

Does anybody know how to make colored smoke with azo dyes? I have searched the forum, but found nothing.

There is a youtube video by Chemx01 which shows smoke coloring of Para Red, so it definitely possible.

Is it possible that this dye simply doesn't color smoke? :( Could smoke coloring be somewhat of a physical property?

Thanks!


Oh, and one more thing... 250th post! AWWW YEAH! :D








[Edited on 28-8-2011 by redox]




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[*] posted on 28-8-2011 at 15:20


Quote: Originally posted by redox  
Today I synthesized 3,4'-dicarboxy, 4-hydroxyazobenzene.
Does anybody know how to make colored smoke with azo dyes? I have searched the forum, but found nothing.

There is a youtube video by Chemx01 which shows smoke coloring of Para Red, so it definitely possible.

Is it possible that this dye simply doesn't color smoke? :( Could smoke coloring be somewhat of a physical property?

Thanks!



Try this ....>


Accession Number : ADA107286

Title : Evaluation of Replacement Red Smoke Dyes for 1-N methylaminoanthraquinone

Descriptive Note : Technical rept. Nov 1979-May 1980

Corporate Author : ARMY ARMAMENT RESEARCH AND
DEVELOPMENT COMMAND ABERDEEN PROVING GROUND MD
CHEMICAL SYSTEMS LAB

Personal Author(s) : Vigus, Ellen S. ; Deiner, Albert

Handle / proxy Url : http://handle.dtic.mil/100.2/ADA107286

Report Date : OCT 1981

Pagination or Media Count : 18

Abstract : A list of 114 dyes was compiled from a literature
search for replacement red smoke dyes for 1-N
methylaminoanthraquinone. Two of the dyes reviewed (9-
diethylaminorosindone and O-methoxyphenylazo-B-naphthol)
were found to meet the requirements for use in pyrotechnics.
There are insufficient toxicological data at this time to assess
the health effects of these dyes.


And abstract.

4. DISCUSSION OF RESULTS
Investigators 1 4,14 generally agree upon the following
properties of dyes suitable for the production of colored smokes:
a. The molecular weight must not exceed 450.
b. The dye should be a member of one of the following series:
anthraquinone, azine, azo, quinoline, or xanthene.
c. The following groups must be absent: sulfonic, hydrochloride,
nitro, nitroso, quaternary ammonium, and oxonium.
d. The following groups may be present: amino and substituted
amino, alkyl, aryl, chloro, bromo, hydroxy, and alkoxy.
e. The dye must not have a tendency to undergo auto
condensation. Of the dyes reviewed, the following have these properties:
(1) Rhodamine B
(2) Sudan IV
(3) 1 Xylylazo 2 naphthol
(4) Citrus Red #2 (2,5 dimethyoxyphenylazo 2 naphthol)
(5) 9 Diethylaminorosindone
(6) 0 Methoxyphenyazo B naphthol

In the interest of safety — potassium chlorate not sodium chlorate, which also dobe hygroscopic is used.
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[*] posted on 28-8-2011 at 15:32
What Ukl Sap currently uses for red smoke


Accession Number : ADA477977

Title : Demonstration of the Replacement of the Dyes and Sulfur in the M18 Red and Violet Smoke Grenades: Cost & Performance Report

Corporate Author : ARMY ENVIRONMENTAL CENTER ABERDEEN PROVING GROUND MD

Personal Author(s) : Rush, Tamera

Handle / proxy Url : http://handle.dtic.mil/100.2/ADA477977

Report Date : JAN 2007

Pagination or Media Count : 45

Abstract : The objective of this demonstration was to validate alternative materials and products so that they may be written into new military specifications (MILSPECS), including modified formulations of the smoke grenades to be used in manufacturing. The proposed effort provided production and testing of four potential material substitutions for two smoke munitions items that are considered essential to Army training operations. The potential material replacements included (1) replacing the dye in M18 red grenades, (2) replacing the dye in the M18 violet grenades, (3) an evaluation of the starter patches for use in the colored smoke grenades, and (4) replacing sulfur with a sugar-chlorate formulation. of this program will introduce safer smoke munitions for the soldiers in training and active service. This demonstration included the survey, testing and manufacturing of test, pilot and production runs of these munitions (red and violet smoke grenades) to ensure they met the specifications of their predecessors and the safety requirements for our soldiers to use them safely during training and also in active service.

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[*] posted on 28-8-2011 at 16:35


Thanks Wizard, I'll check out those links.

My compound satisfies that list you supplied:

a. The molecular weight must not exceed 450.
b. The dye should be a member of one of the following series:
anthraquinone, azine, azo, quinoline, or xanthene.
c. The following groups must be absent: sulfonic, hydrochloride,
nitro, nitroso, quaternary ammonium, and oxonium.
d. The following groups may be present: amino and substituted
amino, alkyl, aryl, chloro, bromo, hydroxy, and alkoxy.
e. The dye must not have a tendency to undergo auto
condensation.

Thus, I still don't know why it won't color smoke.




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[*] posted on 28-8-2011 at 18:51


Quote: Originally posted by redox  
Thanks Wizard, I'll check out those links.
Thus, I still don't know why it won't color smoke.


If the ratio of — oxidizer - sugar - smoke dye is off it may
burn too hot - too cold for good effect.

I have removed these en bloc from my DB for your inspection.


Smoke red submarine Sig MK 51 MOD 0
OP2793
Potassium/chlorate 35.0%
Sugar 24.0
Methylamino (AQ) 48.0
Sodium/bicarbonate 6.0
Sil-o-cel 10.0
NC camphor 2.5


SMOKE RED III
MC 304
POTASSIUM/CHLORATE 26%
DYE RED 40
SODIUM/BICARBONATE 25
SULPHUR 9


SMOKE RED
MC 305
POTASSIUM/CHLORATE 29.5%
DYE RED 47.5
LACTOSE 18
MAGNESIUM/CARBONATE 5

SMOKE RED
MC 306
POTASSIUM/CHLORATE 31.3%
DYE RED 40.2
SODIUM/BICARBONATE 14.3
SULPHUR 12.3
DEXTRIN 1.9


Smoke red
MC 307
Potassium/chlorate 31%
Dye red 47
VAAR 2
Sugar 20

SMOKE RED
MC 308
POTASSIUM/CHLORATE 35%
DYE RED 36
SODIUM/BICARBONATE 1
SUGAR 26.5
ASBESTOS POWDER 1.5

SMOKE RED
MC 309
POTASSIUM/CHLORATE 27.4%
DYE RED 40.0
SULPHUR 10.6
SODIUM/BICARBONATE 22.0

SMOKE RED
MC 310
POTASSIUM/CHLORATE 23%
9 DIETHYLAMINOROSINDONE 54
SUGAR 23

SMOKE RED
MC 311
POTASSIUM/CHLORATE 24%
RED DYE MIL-D-3718 40
SODIUM/BICARBONATE 17
SULPHUR 5
POLYESTER RESIN 14

SMOKE RED
MC 312
POTASSIUM/CHLORATE 35%
SUGAR 17
1,METHYLAMINO (AQ) 45
1,4,di,p,TOLUIDINO (AQ) 3
POLYESTER RESIN 14

SMOKE RED
MC 313
POTASSIUM/CHLORATE 30.2%
SULPHUR 11.8
RED DYE 36
SODIUM/BICARBONATE 18
DEXTRIN 4

SMOKE RED
MC 314
POTASSIUM/CHLORATE 25.1%
SULPHUR 9.4
RED DYE 41.2
SODIUM/BICARBONATE 21.8
BINDER N|C ACETONE 8|92 2.5

SMOKE RED
MC 315
POTASSIUM/CHLORATE 32.1%
SULPHUR 12.4
RED DYE 37.9
SODIUM/BICARBONATE 16.6
BINDER N|C ACETONE 8|92 2.5



Smoke red
MC 317
Potassium/chlorate 27%
Red dye 50
Magnesium/carbonate 5
Lactose 18

Smoke red MK 2 MOD 0
OP2793
Cyclo red (A-32) 61.6
Potassium/chlorate 23.0
Lactose 15.4

Smoke red MK 7
OP2793
Flaming red A 66.0%
Potassium/chlorate 23.0
Lactose 11.0

Smoke red MK 3 MOD 1
OP2793
Paranitroaniline red 60.0
Potassium/chlorate 20.0
Lactose 20.0

Smoke pot red
Allen [Hitt]
Potassium/nitrate 21 pts
Sulphur 15
Lead/oxide red 6
Antimony/sulphide 18


SMOKE RED PISTOL ROCKET SIGNAL M2M1
OP2793
SMOKE RED D 50.0%
LACTOSE 14.0
POTASSIUM/CHLORATE 19.0
ASBESTOS SHORTS 17.0

SMOKE RED
FINKELSTEIN & MAGRAM USP 2,543,066
1-METHYLAMINO AQ 40%
POTASSIUM/CHLORATE SULPHUR 41
SODIUM/BICARBONATE 19
* KClO3 72% SULPHUR 28%

SMOKE RED Smoke emitting game ball
Fumio Hosoya USP 4,614,340
POTASSIUM/CHLORATE 23-33%
RICE GRANULES 3-7
STARCH 9-15
PIGMENT RED 1 25-35
BEIGE VIOLET 10 20-30


Smoke red
Lancaster 3 pg377
Potassium/chlorate 25%
Rhodamine B 24
Para red 36
Wheat flour 15

Smoke Red
JA Domanico PGII 111
Sucrose 17.5%
Potassium/chlorate 17.5
Magnesium/carbonate 10
Terepthalic/acid 14
Disperse/red 11 6.8
Solvent/red 1 34.2

Smoke white "improved" M8 Smoke Gen
Smtih & Stewart 8th IPS
Red phosphorus 51.0
Magnesium 10.5
Manganese/dioxide 32.0
Magnesium/oxide 1.5
Microcrystalline wax 5.0

Smoke violet
Lancaster 3 pg377
Potassium/chlorate 26%
Indigo pure 22
Rhodamine B 21
Para red 21
Wheat flour 15

Smoke star red
Lancaster 3 pg403
Potassium/chlorate 28%
Lactose 20
Rhodamine B conc 30
Oil orange 22
Dextrin 3+
Water for 500gms 270 ml

Smoke red
Chemical Formulary 1-171
Paranitroaniline red 65%
Potassium/chlorate 15
Lactose 20



[Edited on 29-8-2011 by The WiZard is In]
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[*] posted on 29-8-2011 at 13:30


Quote: Originally posted by The WiZard is In  


If the ratio of — oxidizer - sugar - smoke dye is off it may
burn too hot - too cold for good effect.


Yeah, it looks like I'll have to experiment with the right ratio of components.

An update:

The dye was recrystalized from ethanol, yeilding 4.02 grams of a brown powder.

Cotton samples and pieces of paper towels were immersed in the supernatant liquid, which contained about 5 grams of contaminants and dye. The samples were dried, giving a very pleasant orange-brown stain.

Since I have found no common name for the dye, 3,4'-dicarboxy, 4-hydroxyazobenzene, I have named it "Carboxy Brown."


By louf11 at 2011-08-29

The dyeing solution, which is distinctly orange


By louf11 at 2011-08-29

A picture showing two dyed samples and the dry powder


By louf11 at 2011-08-29

A glass vial with a dyed sample, which will be a gift to a friend


I still cannot make the colored smoke. :(

[Edited on 29-8-2011 by redox]




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[*] posted on 29-8-2011 at 15:18


Quote: Originally posted by redox  

A glass vial with a dyed sample, which will be a gift to a friend

I still cannot make the colored smoke. :(



I would like to see smoke made from Turkey red dye!
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[*] posted on 29-8-2011 at 23:42


The putative product is a known compound. SciFinder gives 32 references (output attached bellow), lists a number of commercial sources and gives the mp of 223 °C. It is referred by a trivial or by partially rational names such as benzalazine, salicylazobenzoic acid, [(carboxyphenyl)azo]salicylic acid. It was investigated and claimed to be useful for the treatment of gastrointestinal illnesses. I would tend to believe that it is only a prodrug for 5-aminosalicylic acid.

Attachment: salicylazobenzoic acid.pdf (104kB)
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[*] posted on 30-8-2011 at 06:01


Thanks Nicodem! I must have been searching under the wrong name when I was trying to find information about the product.



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[*] posted on 1-9-2011 at 07:04


Quote:
Since I have found no common name for the dye, 3,4'-dicarboxy, 4-hydroxyazobenzene, I have named it "Carboxy Brown."

Do you watch Aqua Teen Hunger Force? I immediately thought of this guy:


If not, sorry to ruin your name for it :P
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