THE PREPARATION OF 1 - METHYL - 2 - HYDROXY - 5 - DIAZOBENZENE - 5 - SULPHONIC ACID

• Document Type: CREST
• Collection: General CIA Records
• Document Number (FOIA) /ESDN (CREST): CIA-RDP83-00423R002000130004-1
• Release Decision: RIPPUB
• Original Classification: K
• Document Page Count: 6
• Document Creation Date: November 9, 2016
• Document Release Date: February 22, 1999
• Sequence Number: 4
• Publication Date: August 1, 1952
• Content Type: REPORT

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SEPARAAT
2055
LABORATORIA
N.V. PHILIPS' GLOEILAMPENFABRIEKEN
EINDHOVEN (HOLLAND)
THE PREPARATION OF 1- METHYL - 2 - HYDROXY -
3 - DIAZOBENZENE - 5 - SULPHONIC ACID
K. H. KLAASSENS and C. J. SCHOOT
GEPUBLICEERD IN: RECUEIL DES TRAVAUX CHIMIQUES DES PAYS BAS 71,
920-924, AUGUSTUS 1952
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RECUEIL DES TRAVAUX CHIMIQUES DES PAYS-BAS
publ. par la Soc. chim. need. ['s-Gravenhage (Hollande), Lange Voor1 out 51
T. 71, 8 (aout 1952).
Soc. anon. d'editions scientifiques D. B. CENTEN, Amsterdam.
547.564.8-541.113
THE PREPARATION OF 1-METHYL-2rHYDROXY-3-DIAZO-
BENZENE-5-SULPHONIC ACID.
BY
K. H. KLAASSENS and C. J. SCHOOT
(Philips Research Laboratories, N.V. Philips' Gloeilampenfabrieken,1
Eindhoven - Netherlands).
The preparation of 1-methyl-2-hydroxy-3-diazobenzene-5-sulphonic acid,
starting from o-cresol, is described. With a small quantity of a strong acid
a suspension of 1-methyl-2-hydroxy-3-aminobenzene-S-sulphonic acid in a
solution of sodium nitrite gives the sodium salt of the diazonium compound.
The preparaton of 1 methyl-2-hydroxyr3rdiazobenzene-5-sulphonic
acid, as needed for photochemical work in this laboratory, can be
divided into the preparation of the methyl-hydroxy-aminobenzene-
stilphonic acid and the preparation of the diazonium compound.
Starting with o-cresol the amino compound was prepared by sulpho-
nation; nitration'and reduction.
OH OH OH OH OH
H3C H3C H3C NO2 H3C \NH3+ H3C,/\N2+
0 J U
0
SO3H SO3H S03 S03
I II III IV V
A ' method was followed whereby the products II and III were not
separated and the compound IV was prepared in about twenty-four
hours.
Little is known about the preparation of the compounds II, III and
IV. Claus and Jackson 1) obtained II by heating a mixture of o-
cresol and concentrated sulphuric acid on a water bath for 8 to 10
hours. Gomberg and Anderson 2) heated the mixture for one hour.
None of these authors give details about the yield.
1) A. Claus and U. A. Jackson, J. prakt. Chem, [21,38, 330 (1888).
2) M. Gomberg and L. C. Anderson, J. Am. Chem. Soc. 47, 2027 (1925).
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921 K. H. Klaassens and C. J. School,
There are three compounds which may be formed from the reaction
of o-cresol with sulphuric acid, namely:
OH OH OH
Nj OjN H3C1 SO3H
H3Cf
0
SO3H
II VI
SO3H
VII
Having regard to the yield of IV, however, it is important to know,
how much of II is formed. In the experimental section a method is
described which proves that about 85 % of II is formed. It is found
that when mixing o-cresol with concentrated sulphuric acid the
temperature rises to 110 ?C and the reaction is complete after about
15 minutes.
Schultz;) prepared nitrocresol-sulphonic acid (III) by nitrating
cresol-sulphonic acid (II), but he does not give any details. We have
nitrated II with nitric acid as well as with potassium nitrate, In the
latter case the monopotassium salt of III precipitates. This salt is very
insoluble, reduction of the separated potassium salt of III giving the
same yield as reduction of the potassium salt together with the mother
liquid. Nitration with nitric acid gives somewhat higher yields.
The aminocresol-sulphonic acid (IV) was prepared by Schultz 3)
by reducing the nitro compound with stannous chloride and hydro-
chloric acid. He reports that the compound crystallizes with half a
molecule of water, but we found variable quantities of water. We
have also investigated reduction with sodium sulphide, with cast iron
and hydrochloric acid and electrolytic reduction. Reduction with
sodium sulphide is carried out in an alkaline medium and after
acidifying there is precipitation of some sulphur, which is difficult
to remove, moreover the yield is somewhat smaller. Reduction with
cast iron gives a smaller yield of a rather greyish product and the
method is more laborious. Electrolytic reduction was investigated with
a variation of voltage, density of current and cathode materials. The
yield was in all cases less than when reducing with stannous chloride.
The diazonium compound (V) is very soluble in water (about
30 %). Diazotization with sodium nitrite and acid is therefore not
suitable, since then the product is contaminated' with the sodium salt
of the acid used. We have diazotized IV with gaseous nitrous
anhydride, the method which Griess used in 1858 for diazonium
compounds rather insoluble towards V. The solubility of V requires
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The preparation, etc. 71 (1952) RECUEIL 922
that the amount of water in which IV is suspended must be not too
large 4). The diazonium compound crystallizes with amounts of water
varying up to two molecules.
When suspending IV in a solution of "sodium nitrite and adding a
few drops of a strong acid, for instance concentrated fluoboric acid,
a violent reaction takes place and after a few minutes all the amino
compound is converted into the sodium salt of V. In the experimental
section a more moderate method is described. The sodium salt crystal-
lizes with 5 molecules of water.
Experimental Section.
I_.
Reaction of o-cresol and sulphuric acid.
10.9 g of o-cresol are mixed with 10 ml of concentrated sulphuric acid (sp.gr. 1.84).
The temperature rises. to 110-155?C. After 15 minutes the mixture is diluted with
300 ml of distilled water and the boiling solution is treated with an excess of barium
carbonate. Assuming the barium salt of VI to be entirely insoluble and the barium
salts of If and VII very good soluble, the precipitate consists of a mixture of barium
sulphate, the barium salt of VI and the excess of barium carbonate; the filtrate
contains only the barium salts of II and VII. The precipitate is filtered off and
washed, distilled water then being added to the filtrate to make it up to 1000 ml.
Analysis of 5 mi of the filtrate yielded 0.0660 and 0.0661 g of barium sulphate. It
has been calculated that 87 % of II and 13 % of VII is formed, assuming that VI
is not formed at, all.
The precipitate, consisting of barium sulphate,, the barium salt of VI and barium
carbonate, is first washed with dilute hydrochloric acid to remove barium carbonate
and afterwards washed with distilled, water. After drying the weight of the
precipitate was 14.7072 g. After heating with concentrated sulphuric acid a pare
of this mixture weighing 1.3733 g there was found to be a loss of weight of
0.0369 g. A calculation shows that less than 2 % of VI is formed. At least 85 %
of the desired, sulphonic acid (II) is therefore formed,
y I.
Preparation of 1-methyl-2-hydroxy-3-aminobenzene-5-sulphoric acid.
Five hundred grams of molten o-cresol (about 30? C) and 500 ml of concentrated
sulphuric acid (sp. gr. 1.84) are mixed in a two-litre round-bottomed flask. The
flask is warmed on a water bath for one hour and the liquid is stirred with a
mechanical stirrer. The-cooled mixture is poured into an enamelled vessel containing
2 litres of. distilled water. The stirred solution is cooled to about 30? C and 330 ml
of concentrated nitric acid (sp.gr. 1.37) are allowed to flow dropwise into the solution,
during one and a half hours; the temperature should not rise above 40? C.
Stirring is continued for another hour after the addition is complete, the mixture
then being quickly heated to the boiling temperature. A mixture of 3300 ml stannous
chloride solution containing 67 g SnC12 per 100 ml and 1-3 % hydrochloric acid,
and two litres of concentrated hydrochloric acid (sp. gr. 1.19) is added during a
period of 15 minutes, taking care that the contents of the flask do not foam over
the rim. the solution is allowed to boil for another 5 minutes and thereafter slowly
cooled during the night. The crystallized amino compound is collected on a Buchner
H. Alink and R. Dijkstra, Neth. Patent 69013.
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923 K. H. Klaassens and C. T. School.
funnel, fitted with a cotton filter. The precipitate is suspended in one litre of
hydrochloric acid (2 N), again filtered and washed with about one litre of distilled
water and 400 ml of alcohol. The product is dried for 6 hours at 100? C. The yield
is 540-560 g (57.5-59.5 % of white needles. The product decomposes at about
315? C before it melts. The compound is titrated with barium hydroxide and
bromocresol purple as an indicator.
Found: Eq. wt. 203.
Calculated for C7HeO4NS: Eq. wt. 203,
Nitration of 1-methyl-2-hydroxy-benzene-5-sulphonic acid with potassium nitrate,
Five hundred grams of o-cresol are sulfonated with 500 ml of concentrated
sulphuric acid (sp. gr. 1.84). and the mixture poured Into two litres of distilled
water. The stirred solution is heated at 70? C and a warm solution of 465 g of
potassium nitrate in two litres of distilled water is added. The temperature Is kept
at 70-75? C for 30 minutes. After slowly cooling, the potassium salt of III
crystallizes, this then being filtered off and dried in air for 24 hours. The yield
varies from 1000 to 2100 g but when dried at 100? C all the portions amount to
about 750 g (60%). Analysis of the product after recrystallization and drying at
100? C shows K = 13.97 %. calculated for C7H,,O5NSK: K = 14.41 %.
The reduction of 1-methyl-2-hydroxy-3-nitrobenz-ne-5-sulphonic acid with podium
sulphide.
Fifty grams of o-cresol are sulfonated and nitrated as before and then 210 ml of
a sodium hydroxide solution (40 %) is added. A solution of 176 g Na2S. 9 HO in
66 ml of water is poured slowly into the hot alkaline solution of the nitro
compound. The mixture is heated under reflux for two hours and after cooling
poured Into a two litre beaker, then being neutralized with 325 ml concentrated
hydrochloric acid.
Some sulphur precipitates immediately and after twenty-four hours the amino
compound together with the sulphur is collected on a Buchner funnel. The mixture
is treated with 275 ml water and 50 ml of a 40% sodium-hydroxide solution. The
sulphur is filtered off, the filtrate neutralized with 100 ml concentrated hydrochloric
acid and the precipitated amino compound is collected on a filter, washed with
water and alcohol and dried at 100? C.
The yield is 50 g (53 %).
The reduction of 1-methyl-2-hydroxy-3-nitrobenzene-5-sulphonic acid with cast iron.
Fifty grams of o-cresol are sulfonated and nitrated In the known manner. This
solution is diluted with 800 ml water and 275 ml concentrated hydrochloric acid
(sp. gr. 1.19) and heated at 90? C while stirring. One hundred grams of degreased
iron filings are added in small portions. After all the filings have been added 25 ml
concentrated hydrochloric acid are poured in. After the gas evolution has ended the
hot solution is very quickly filtered through a glass filter. Very soon the amino
compound precipitates; it is filtered off, washed and dried at 100? C. The yield is
52 g (55%) of greyish white needles.
The electrolytical reduction of 1-methyl-2-hydroxy-3-nftrobenzene-5-sulphonic acid.
A rolled sheet is placed in a 500 ml porous jar and the jar filled up with 15%
sulphuric acid. The jar is placed in a two litre beaker containing a graphite plate
with a surface of 30 square cm. In the beaker arc placed a nitrated mixture obtained
from 18 g o-cresol, 20 ml SnCI, solution (67 g per 100 ml) and 80 ml concentrated
hydrochloric acid, the beaker then being filled up to 400 ml with distilled water.
The lead sheet serves as anode and the graphite plate as cathode. With a tension
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The preparation, etc. 71 (1952) RECUEIL - 924
of 16 volts and a density of 6.5 A per dm2 while stirring the liquid in the cathode
room, the reduction is-complete in 45 minutes at a temperature of 95? C. It is found
that 5 g of tin have been precipitated on the cathode. The amino compound is filtered
off, washed and dried at 100? C. The yield is 14.3 g (42%).
Preparation of 1-methyl-2-hydroxy-3-diazobenzene~5-sulphonic acid.
250 g arsenic trioxide or 250 g starch and'800 ml nitric acid (sp. gr. 1.37) are
put into a one litre round-bottomed flask, fitted with a reflux condenser attached
to' a drop-counter. The flask is slowly heated in a water bath and the gaseous
nitrous anhydride formed is decanted into an 800 ml beaker containing 190 ml
distilled water and 10 ml concentrated nitric acid (sp, gr. 1.37). The beaker is cooled
with a mixture of ice and salt and its contents are kept at a temperature of -5
to 0? C. A few minutes after the gas has been admitted, 150 g of amino compound
is added in small portions. The amino compound dissolves during diazotization and
after some time the diazonium compound crystallizes. The rate of the gas flow is
so regulated that the temperature does not rise above 5? C. When a sample entirely
dissolves in water, the reaction has been completed (2%-6 hours). The beaker is
then chilled in an ice-salt bath to -10? C and left at that temperature for one and
a half hours. The solid diazonium compound is separated by filtration through a
glass filter, then suspended in ice-cold alcohol, again filtered and dried in air, The
yield is 120-130 g (65-70%), The diazonium compound is titrated with barium
hydroxide and bromocresol purple as an indicator in yellow light. The compound
crystallizes into fine yellow needles mostly with 2 molecules.of water but also with
one molecule of water or none. In the air the crystal water gradually evaporates.
Found: Eq. wt. = 250.
Calculated for C7H5O4N2S . 2 H2O: Eq. wt.= 250.
Preparation of the sodium salt of 1-methyl-2-hydroxy-3-diazobenzene-5-sulphonic
acid.
400 ml water, 500 ml acetone, 600 g amino compound and 10 ml concentrated
f)uoboric acid are put into a 'three litre beaker. The suspension is mechanically
stirred and kept at 20? C by cooling in a mixture of ice and salt after which a
solution of 240 g sodium nitrite in 450 ml water is slowly added in the course of
one hour. The temperature may not rise above 30? C. After all the nitrite solution
has been added the mixture is cooled to 0? C. The compound is filtered off on a
glass filter, transferred to a beaker, stirred with ice-cold alcohol and again collected
on a glass filter. The sodium salt is dried in air and amounts to 750-775 g
(78=80%) of deep yellow plates.
Found: Na 6.92, 6.79; H2O 28.19, 28.23.
Calc. for C7H,O4N2SNa . 5 H2O: Na 7.05; H2O 27.60.
Eindhoven, October 1951.
(Received, November 29th 19
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