GB1596897A - Process for the preparation of naphthalene-1,3,6-trisulphonic acid - Google Patents
Process for the preparation of naphthalene-1,3,6-trisulphonic acid Download PDFInfo
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- GB1596897A GB1596897A GB15194/78A GB1519478A GB1596897A GB 1596897 A GB1596897 A GB 1596897A GB 15194/78 A GB15194/78 A GB 15194/78A GB 1519478 A GB1519478 A GB 1519478A GB 1596897 A GB1596897 A GB 1596897A
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- naphthalene
- acid
- weight
- sulphuric acid
- trisulphonic
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- ZPBSAMLXSQCSOX-UHFFFAOYSA-N naphthalene-1,3,6-trisulfonic acid Chemical compound OS(=O)(=O)C1=CC(S(O)(=O)=O)=CC2=CC(S(=O)(=O)O)=CC=C21 ZPBSAMLXSQCSOX-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims description 56
- 238000002360 preparation method Methods 0.000 title claims description 13
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims abstract description 120
- 235000011149 sulphuric acid Nutrition 0.000 claims abstract description 51
- 239000001117 sulphuric acid Substances 0.000 claims abstract description 51
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000011541 reaction mixture Substances 0.000 claims abstract description 39
- UBDHSURDYAETAL-UHFFFAOYSA-N 8-aminonaphthalene-1,3,6-trisulfonic acid Chemical compound OS(=O)(=O)C1=CC(S(O)(=O)=O)=C2C(N)=CC(S(O)(=O)=O)=CC2=C1 UBDHSURDYAETAL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims description 23
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 150000007513 acids Chemical class 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 10
- GPUMPJNVOBTUFM-UHFFFAOYSA-N naphthalene-1,2,3-trisulfonic acid Chemical class C1=CC=C2C(S(O)(=O)=O)=C(S(O)(=O)=O)C(S(=O)(=O)O)=CC2=C1 GPUMPJNVOBTUFM-UHFFFAOYSA-N 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- ROZRLDJKXCKWCD-UHFFFAOYSA-N naphthalene-1,2,3,4-tetrasulfonic acid Chemical class C1=CC=CC2=C(S(O)(=O)=O)C(S(=O)(=O)O)=C(S(O)(=O)=O)C(S(O)(=O)=O)=C21 ROZRLDJKXCKWCD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- INMHJULHWVWVFN-UHFFFAOYSA-N naphthalene-1,3,5-trisulfonic acid Chemical compound C1=CC=C(S(O)(=O)=O)C2=CC(S(=O)(=O)O)=CC(S(O)(=O)=O)=C21 INMHJULHWVWVFN-UHFFFAOYSA-N 0.000 claims description 4
- FEWNRIKJXAQRJJ-UHFFFAOYSA-N naphthalene-1,3,7-trisulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=C(S(O)(=O)=O)C2=CC(S(=O)(=O)O)=CC=C21 FEWNRIKJXAQRJJ-UHFFFAOYSA-N 0.000 claims description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 claims description 4
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 3
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 claims description 2
- SITVNOOPPBSYNB-UHFFFAOYSA-N naphthalene-1,3,5,7-tetrasulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=C(S(O)(=O)=O)C2=CC(S(=O)(=O)O)=CC(S(O)(=O)=O)=C21 SITVNOOPPBSYNB-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 14
- APRRQJCCBSJQOQ-UHFFFAOYSA-N 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid Chemical compound OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S(O)(=O)=O)=CC2=C1 APRRQJCCBSJQOQ-UHFFFAOYSA-N 0.000 abstract description 3
- KVBGVZZKJNLNJU-UHFFFAOYSA-N naphthalene-2-sulfonic acid Chemical compound C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 KVBGVZZKJNLNJU-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- YZMHQCWXYHARLS-UHFFFAOYSA-N naphthalene-1,2-disulfonic acid Chemical class C1=CC=CC2=C(S(O)(=O)=O)C(S(=O)(=O)O)=CC=C21 YZMHQCWXYHARLS-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000000975 dye Substances 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000006396 nitration reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- AMIPJIZAILLNHP-UHFFFAOYSA-N naphthalene-1,2,5-trisulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC2=C(S(O)(=O)=O)C(S(=O)(=O)O)=CC=C21 AMIPJIZAILLNHP-UHFFFAOYSA-N 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
- C07C303/06—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with sulfuric acid or sulfur trioxide
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Naphthalene-1,3,6-trisulphonic acid is prepared by sulphating naphthalene at elevated temperature using 2 part-quantities of sulphuric acid and oleum. The naphthalene is initially introduced in liquid form at 80-120 DEG C and 1.0-3.0 mol of sulphuric acid are added per mol of naphthalene at 20-120 DEG C. The reaction mixture is maintained at 80-120 DEG C for 0.1 - 5 hours and is then heated to 130-170 DEG C and kept at this temperature for 0.2 - 5 hours. The mixture is then cooled to 20-120 DEG C and 1.0-1.5 mol of sulphuric acid are added per mol of naphthalene. 2.5-2.9 mol of SO3 per mol of naphthalene is then added in the form of oleum at 40-100 DEG C and the mixture is heated to 140-160 DEG C and kept at this temperature for 1 - 4 hours. 0.01-1.0 mol of SO3 per mol of naphthalene employed is then added in the form of oleum at 60-160 DEG C and the mixture is then stirred at 140-160 DEG C for 0.5 - 4 hours. The product which is obtained can be used for preparing T acid and H acid.
Description
(54) PROCESS FOR THE PREPARATION OF
NAPHTHALENE- 1 ,3,6-TRISULPHONIC ACID
(71) We, BAYER AKTIENGESELLSCHAFT, a body corporate organised under the laws of
Germany, of Leverkusen, Germany, do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:
The present invention relates to a process for the preparation of naphthalene- 1,3 ,6-trisul- phonic acid by the sulphonation of naphthalene.
It is known from Ullmanns Enzyklopadie der technischen Chemie (Ullmann's Encyclopaedia of Industrial Chemistry), 3rd edition, (1960), volume 12, page 593 that various isomers can be obtained in the sulphonation of naphthalene, naphthalene-1,3,6-trisulphonic acid being accessible via the intermediate stages naphthalene-1,3-, -1,6- and -2,7-disulphonic acid. These intermediate stages are accessible both via naphthalene-l-sulphonic and via naphthalene-2-sulphonic acid, but further naphthalenedisulphonic acids are obtained, such as naphthalene-1,5-, -1,7- and -2,6-disulphonic acid, which interfere with the preparation of naphthalene-1,3 ,6-trisulphonic acid.
Naphthalene-1,6- and -2,7-disulphonic acids can be almost quantitatively converted into naphthalene-1,3,6-trisulphonic acid (see
Fierz-David and Richter, Helv. Chim. Acta 28, page 257 (1945)). However, Naphthalene1,6- and -2,7- disulphonic acid are accessible in the pure form only with difficulty, so the processes for the preparation of naphthalene1,3,6-trisulphonic acid using these naphthalene disulphonic acids as starting materials are uneconomic and have hitherto not been used industrially.
Using pure naphthalene-2-sulphonic acid as the starting material, naphthalene-l ,3,6-tri sulphuric acid can be obtained in a yield of 80 to 85% (see Fierz-David and Richter loc.
cit.). However, the preparation of naphthalene2-sulphonic acid is associated with a high formation of naphthalene-disulphonic acids and dinaphthyl-sulphones and the isolation of the product is complicated (see DT-AS (German Published Specification) 1167 333 and French Patent Specification 1 326 174).
This process is therefore not more advantageous industrially than other known processes.
Naphthalene is therefore in general used for preparing naphthalene-1,3,6-trisulphonic acid on an industrial scale, and by maintaining a particular temperature programme and a step.
wise addition of sulphuric acid and oleum during the sulphonation, it is ensured that as advantageous as possible an isomer composition or isomer rearrangement is obtained in the intermediate stages. For example, according to
FIAT Final Report No. 1,016, page 37, it is possible to prepare naphthalene-1,3 ,6-trisul- phonic acid on an industrial scale as follows: naphthalene is introduced into an initial amount of sulphuric acid monohydrate (= 100% strength sulphuric acid), cooled to 20 C. The mixture is then warmed to 80 to 85"C and kept at this temperature for one hour. It is then heated up to 1450C. After it has been cooled to 850C, the reaction mixture is diluted with sulphuric acid monohydrate and then further sulphonated at 400C with 65% strength oleum. Most of the oleum is first added in the course of 8 hours and the mixture is then heated to 1450C and kept at this temperature for 2.5 hours. After the mixture has been cooled to 600 C, the remainder of the 65% strength oleum is added at this temperature and the reaction mixture is heated to 150 to 1550C for 2 to 3 hours. Yields of naphtha lene-l ,3,6-trisulphonic acid of more than 75% of theory cannot be achieved in this procedure (see Ullmann, loc. cit. page 596). The yield is usually significantly below 75% of theory.
An analogous embodiment for the preparation of naphthalene-1 ,3,6-trisulphonic acid, in which 60% strength oleum is used and the cooling of the reaction mixture before the addition of the remainder of the oleum is dispensed with, is described in Japanese Patent
Publication No. 96,552 (1975). In this pro cedure, no higher yields of naphthalene-1 ,3,6- trisulphonic acid are achieved than with the process described above.
A process for the preparation of 1,8,3,6naphthylamine-trisulphonic acid starting from naphthalene, in which the first stage, that is to say the sulphonation of naphthalene to give naphthalene-2-sulphonic acid, sulphuric acid monohydrate is allowed to run into liquid naphthalene at 1650C and then the reaction is continued in a manner analogous to that in the process described above from FIAT Final
Report, is described by H.E. Fierz, Grundlegende Operationen der Farbenchemie (Fundamental Operations of Dye Chemistry), Zurich 1920, page 15 to 30. In Fierz's process, as repetition has shown (see Example 9), a very high formation of dinaphthyl-sulphones and dinaphthylsulphone-tetrasulphonic acids takes place. The yield of naphthalene-1 ,3,6-tri- sulphonic acid relative to naphthalene is only 72%.
According to the present invention there is provided a process for the preparation of naphthalene-1,3,6-trisulphonic acid comprising carrying out the following process steps seriatim. a) Introducing naphthalene in liquid form into a reaction vessel at 80 to 1200C, b) adding from 1.D to 3.0 mols of sulphuric acid, per mol of naphthalene, at 80 to 1200C, c) maintaining the reaction mixture at 80 to 1200C for from 0.1 to 5 hours, d) heating the reaction mixture to from 130 to 1 700C and maintaining this temperature for from 0.2 to 5 hours, e) cooling the reaction mixture to from 20 to 1 200C and adding from 0 to 2.0 mols of sulphuric acid per mol of naphthalene, f) adding for the purpose of sulphuration from 2.5 to 2.9 mols of S03, in the form of oleum, per mol of naphthalene, at 40 to 100-C, g) heating the reaction mixture to from 140 to 1600C and maintaining this temperature for from 1 to 4 hours, h) adding from 0.01 to 1.0 mol of SO3, in the form of oleum, per mol of naphthalene, at 60 to 1600C and i) stirring the reaction mixture for from 0.5 to 4 hours at 140 to 1600C.
The process according to the invention mainly differs from known processes by process steps a) and b).
The temperatures in process steps a), b) and c) are preferably in the range from 80 to 900 C.
The concentration of the sulphuric acid which is used in process steps b) and e) can be, for example, 80 to 100% by weight. It is also possible to use oleum which has an SO3 content of up to 10% by weight. Sulphuric acid with a concentration between 95 and 100% by weight is preferably used. The use of so-called sulphuric acid monohydrate, that is to say 100% strength by weight sulphuric acid, is very particularly preferred.
In process step b), 1.5 to 2.0 mols of sulphuric acid are preferably added. In process step c), the reaction mixture is preferably kept at 80 to 900C, preferably for 0.5 to 2 hours.
In process step d), the reaction mixture is preferably heated to a temperature between
140 to 1500C and this temperature is maintained for 0.5 to 2 hours.
In process step e), the reaction mixture is preferably cooled to a temperature between 40 to 100-C and preferably 1.0 to 1.5 mols of sulphuric acid per mol of naphthalene employed are added.
The oleum which is employed in process steps f) and h) preferably contains 20 to 100% by weight of free S03. An oleum which contains 50 to 80% by weight of free SO3 is preferably used. The use of commercially available, approximately 65% strength oleum is particularly preferred.
In process step f), 2.6 to 2.8 mols of SO3, in the form of oleum, are preferably added and the addition is preferably carried out at tempeatures between 40 and 50"C.
In process step g), the reaction mixture is preferably heated to 145 to 1500C and kept at this temperature for 2 to 3 hours.
In process step h), 0.1 to 0.5 mol of SO3, in the form of oleum, is preferably added and the addition is preferably carried out at 145 to 1500C.
In process step i), the subsequent stirring time is preferably 1 to 2 hours and the temperature is preferably 145 to 1500C.
If relatively large amounts of water are introduced in process steps b) and/or e), for example by using sulphuric acid with a concentration in the range from 80 to 95% by weight, it can be advantageous to add more SO3 (in the form of oleum) in process step f) than has been indicated above. The additional amount of SO3 (in the form of oleum) should then be large enough to bind, in the form of sulphuric acid, the water introduced, rather than for taking part in the sulphonation.
By the process according to the invention, it is possible to obtain naphthalene-1,3,6trisulphonic acid in higher yields than hitherto, and the dinaphthyl-sulphone-sulphonic acids formed as a by-product are obtained in lower amounts. It is surprising that these advantages can be essentially achieved by using mean temperatures of 80 to 1200C at the start of the sulphonation of naphthalene and by adding sulphuric acid to naphthalene which has been initially introduced. If the sulphonation is started at lower temperatures, for example at 20"C (compare FIAT Final Report loc. cit.) using sulphuric acid as the initial material, or at higher temperatures, for example at 1650C (compare H.E. Fierz loc. cit. and Example 9) using naphthalene as the initial material, poorer yields and, particularly at higher starting temperatures, also an increased formation of dinaphthyl-sulphone-sulphonic acids are obtained.
The product which is present after carrying out the process according to the invention can be further used in any desired manner without isolating the naphthalene-1,3,6-trisulphonic acid. For example, it is suitable for the preparation of the important dyestuff intermediate products T-acid and H-acid, it being possible to carry out the steps of nitration, removing the sulphuric acid with chalk, reduction, separating out of T-acid and conversion of T-acid into
H-acid according to FIAT Fianl Report No.
1,016, page 32 to 39 or in another manner.
EXAMPLES
EXAMPLE 1 1 28g (1.0 mol) of molten naphthalene are initially introduced into a 2 1 five-necked flask, or sulphonating beaker, fitted with a sabreshaped stirrer, a reflux condenser, an internal thermometer, a dropping funnel and a gas inlet tube for nitrogen, after flushing the apparatus with nitrogen. 167 g of sulphuric acid monohydrate (= 100% strength sulphuric acid) are allowed to run in at 80 to 850C in the course of 30 minutes, whilst cooling. The reaction mixture is kept at 80 to 850C for 1 hour and then heated to 145 C and kept at this temperature for 1 hour. Whint cooling to 400C, a second portion of 123 g of sulphuric acid monohydrate is allowed to run in when the temperature falls below 800C and 330 g of 65% strength oleum are subsequently added to 40 to 45 C in the course of 45 minutes. The reaction mixture is then heated to 1450C and kept at this temperature for 3 hours, 25 g of 65% strength oleum are subsequently added and the mixture is stirred for a further 1 hour at 1450C. The resulting naphthalenetrisulphonic acid isomer mixture is further processed, without intermediate isolation of the naphthalene-1,3,6-trisulphonic acid, by nitration, adding chalk and reduction to give a naphthylamine-trisulphonic acid isomer mixture (T-acid isomer mixture).
The yield of naphthalene-1,3,6-trisulphonic acid is 77.5% relative to naphthalene, or 78.5%, relative to the sum of naphthalene-trisulphonic acids. The yield of 1-naphthylamine-3,6,8- trisulphonic acid (T-acid) was determined to be 69%, relative to naphthalene, by means of high pressure liquid chromatography.
The following contents of compounds were determined, by high pressure lqiuid chromatography, in the reaction mixture present after the sulphonation reaction: naphthalene- 1,3 ,5-trisul- phonic acid: 4.2% by weight naphthalene-1,3,6-trisul
phonic acid: 36.7% by weight naphthalene-1,3 ,7-trisul- phonic acid: 6.0% by weight naphthalene-l ,3,5,7-tetra
sulphonic acid: 0.05% by weight dinaphthyl-sulphone
tetrasulphonic acids: about 1.5% by weight sulphuric acid: about 52% by weight
EXAMPLE 2
A sulphonation carried out as in Example 1, but in which the major proportion of 65% strength oleum is allowed to run in at 80 to 85 C, gives a yield of naphthalene-1,3,6trisulphonic acid of 75.5%, relative to naphthalene, or 77%, relative to the sum of naphthalene-trisulphonic acids. The following contents of compounds were determined, by high pressure liquid chromatography, in the reaction mixture present after the sulphonation reaction: naphthalene. 1,3 ,5-tri- sulphonic acid: 3.5% by weight naphthalene- 1,3 ,6-tri- sulphuric acid: 35.5% by weight naphthalene-1,3 ,7-trisul- phonic acid 7.1% by weight naphthalene-1 ,3,5,7-tetra- sulphuric acid: 0.1% by weight dinaphthyl-sulphone
tetrasulphonic acids: about 1.6% by weight sulphuric acid: about 52% by weight
EXAMPLE 3
A sulphonation carried out as in Example 1, in which, instead of sulphuric acid monohydrate, the corresponding amount of 96% strength by weight sulphuric acid was employed, gave a yield of naphthalene-1,3,6-trisulphonic acids of 76%, relative to naphthalene. In this case, the major proportion of 65% strength oleum was increased to 410 g, in order to compensate for the water additionally introduced.
EXAMPLE 4 (comparison example)
167 g of sulphuric acid monohydrate are initially introduced, at a temperature of 40"C, into a sulphonating apparatus corresponding to that described in Example 1. After flushing the apparatus with nitrogen, 128 g (1.0 mol) of liquid naphthalene are allowed to run in in the course of 30 minutes. A temperature of 800C is not exceeded during this addition. The reaction mixture is then heated to 1500 C, kept at this temperature for 1.5 hours, then cooled to 1000C and diluted with 123 g of sulphuric acid monohydrate in the course of 10 minutes.
307 g of 65% strength oleum are then allowed to run into the reaction mixture at 80 to 850C in the course of 2 hours. The mixture is then warmed to 155no and kept at this temperature for one hour, 62 g of 65% strength oleum are then added and the mixture is allowed to react completely for one hour at 155 to 1600C.
The yield of naphthalene- 1,3 ,6-trisulphonic acid is 72.5%, relative to naphthalene, or 74.5%, relative to the sum of the naphthalenetrisulphonic acids and tetrasulphonic acids.
After further processing to give a naphthylamine-sulphonic acid isomer mixture, high pressure liquid chromatography shows a yield of T-acid of 64%, relative to naphthalene.
The following contents of compounds were determined, by high pressure liquid chromatography, in the reaction mixture present after the sulphonation reaction: naphthalene- 1,3 ,5-tri- sulphonic acid: 4.9% by weight naphthalene-1,5,6-tri- sulphonic acid: 34.3% by weight naphthalene-1,3,7-tri- sulphonic acid: 6.4% by weight naphthalene-l ,3,5,7-tetra sulphuric acid: 0.4% by weight dinaphthyl-sulphone-tetra
sulphonic acids: about 1.9% by weight sulphuric acid: about 52% by weight
EXAMPLE 5 (comparison example)
A sulphonation carried out as in Example 4, but in which the major proportion of 65% strength oleum is allowed to run in at 40 to 45"C, gives a yield of naphthalene-1,3,64ri- sulphuric acid of 74.5%, relative to naphthalene, or 75.5%, relative to the sum of naphthalene-trisulphonic acids and naphthalene-tetrasulphonic acids.
The following contents of compounds were determined, by high pressure liquid chromatography, in the reaction mixture present after the sulphonation reaction: naphthalene- 1,3 ,5-tri- sulphonic acid: 4.6% by weight naphthalene-l ,3,6-tri- sulphonic acid: 35.0% by weight naphthalene-1,3,7-tri sulphuric acid: 6.4% by weight naphthalene-1,3,5,7-tetra- sulphuric acid: 0.2% by weight dinaphthyl-sulphone-tetra
sulphonic acids: about 1.8% by weight sulphuric acid: about 52% by weight
EXAMPLE 6 (comparison example)
A sulphonation carried out as in Eample 4, but in which the second portion of 65% strength oleum is alloed to run in at 800 C, gives a yield of naphthalene-1,3,6-trisulphonic acid of 74%, relative to naphthalene, or 75%, relative to the sum of naphthalene-trisulphonic acids and naphthalene-tetrasulphonic acids.
EXAMPLE 7 (comparison example)
A sulphonation carried out as in Example 4, in a kettle of 6 m3 capacity and using 1,000 kg of naphthalene, a total of 2,270 kg of sulphuric acid monohydrate and a total of 2,900 kg of 65% strength oleum, gives a yield of naphtha lene-l,3,6-trisulphonic acid of 71 to 72%, relative to naphthalene, and a yield of T-acid of 63to64%.
EXAMPLE 8
A sulphonation carried out as in Example 1, in a kettle of 6 m3 capacity and using 1,000 kg of naphthalene, a total of 2,260 kg of sulphuric acid monohydrate and a total of 2,880 kg of 65% strength oleum, gives a yield of naphtha lene-1,3,6-trisulphonic acid of 75.5 to 76.5%, relative to naphthalene, and a yield of T-acid of 67 to 69%.
EXAMPLE 9 (comparison example)
128 g (1.0 mol) of liquid naphthalene are initially introduced, at a temperature of 165"C, into a sulphonating apparatus, flushed with nitrogen, as indicated in Example 1. 140 g of sulphuric acid monohydrate are allowed to run in in the course of 30 minutes at 1650C, whilst cooling. The reaction mixture is kept at 1650C for 1 hour. Whilst cooling to 400C, a second portion of 150 g of sulphuric acid monohydrate is allowed to run in at from 750C and the further procedure followed is then as described in
Example 1.
The yield of napthalene-1 ,3,6-trisulphonic acid is 72%, relative to naphthalene, or 77%, relative to the sum of naphthalene-trisulphonic acids and naphthalene-tetrasulphonic acids.
After further reacting the reaction mixture to give l-naphthylamine-3,6,8-trisulphonic acid (T-acid), the yield of T-acid was determined as 63%, relative to naphthalene, by means of high pressure liquid chromatography.
The following contents of compounds were determined, by high pressure liquid chromatography, in the reaction mixture present after the sulphonation reaction: naplithalene- 1,3 ,5-tri- sulphuric acid: 4.3% by weight naphthalene-l ,3 ,6-tri- sulphuric acid: 34.3% by weight naphthalene-1,3,7-tri sulphuric acid: 5.6% by weight naphthalene-1,3,5,7-tetra
sulphonic acid: 0.4% by weight dinaphthyl-sulphone-tetra
sulphonic acid: about 3.5% by weight sulphuric acid: about 52% by weight
WHAT WE CLAIM IS:
1. A process for the preparation of naphthalene-1,3,6-trisulphonic acid comprising carrying out the following process steps seriatim. a) Introducing naphthalene in liquid form into a reaction vessel at 80 to 120 C, b) adding from 1.0 to 3.0 mols of sulphuric acid, per mol of naphthalene, at 80 to 1 200C, c) maintaining the reaction mixture at 80 to 1 200C for from 0.1 to 5 hours, d) heating the reaction mixture to from 130 to 170 C and maintaining this temperature for from 0.2 to 5 hours, e) cooling the reaction mixture to from 20 to 1200C and adding from 0 to 2.0 mols of sulphuric acid per mol of naphthalene, f) adding for the purpose of sulphonation from 2.5 to 2.9 mols of S03, in the form of oleum, per mol of naphthalene, at 40 to 100 C, g) heating the reaction mixture to from 140 to 1 600C and maintaining this temperature for from 1 to 4 hours, h) adding from 0.01 to 1.0 mol of SO3, in the form of oleum, per mol of naphthalene, at 60 to 1600C and i) stirring the reaction mixture for from 0.5 to 4 hours at
140 to 1600C.
2. A process according to Claim 1 wherein the temperature in process steps a), b) and c) is 80 to 900C.
3) A process according to Claim 1 or 2 wherein sulphuric acid with a concentration of from 80 to 100% by weight is used in process steps b) and e).
4. A process according to Claim 3 wherein sulphuric acid monohydrate is used in steps b) and e).
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (10)
- **WARNING** start of CLMS field may overlap end of DESC **.sulphonic acid: 34.3% by weight naphthalene-1,3,7-tri- sulphonic acid: 6.4% by weight naphthalene-l ,3,5,7-tetra sulphuric acid: 0.4% by weight dinaphthyl-sulphone-tetra sulphonic acids: about 1.9% by weight sulphuric acid: about 52% by weight EXAMPLE 5 (comparison example) A sulphonation carried out as in Example 4, but in which the major proportion of 65% strength oleum is allowed to run in at 40 to 45"C, gives a yield of naphthalene-1,3,64ri- sulphuric acid of 74.5%, relative to naphthalene, or 75.5%, relative to the sum of naphthalene-trisulphonic acids and naphthalene-tetrasulphonic acids.The following contents of compounds were determined, by high pressure liquid chromatography, in the reaction mixture present after the sulphonation reaction: naphthalene- 1,3 ,5-tri- sulphonic acid: 4.6% by weight naphthalene-l ,3,6-tri- sulphonic acid: 35.0% by weight naphthalene-1,3,7-tri sulphuric acid: 6.4% by weight naphthalene-1,3,5,7-tetra- sulphuric acid: 0.2% by weight dinaphthyl-sulphone-tetra sulphonic acids: about 1.8% by weight sulphuric acid: about 52% by weight EXAMPLE 6 (comparison example) A sulphonation carried out as in Eample 4, but in which the second portion of 65% strength oleum is alloed to run in at 800 C, gives a yield of naphthalene-1,3,6-trisulphonic acid of 74%, relative to naphthalene, or 75%, relative to the sum of naphthalene-trisulphonic acids and naphthalene-tetrasulphonic acids.EXAMPLE 7 (comparison example) A sulphonation carried out as in Example 4, in a kettle of 6 m3 capacity and using 1,000 kg of naphthalene, a total of 2,270 kg of sulphuric acid monohydrate and a total of 2,900 kg of 65% strength oleum, gives a yield of naphtha lene-l,3,6-trisulphonic acid of 71 to 72%, relative to naphthalene, and a yield of T-acid of 63to64%.EXAMPLE 8 A sulphonation carried out as in Example 1, in a kettle of 6 m3 capacity and using 1,000 kg of naphthalene, a total of 2,260 kg of sulphuric acid monohydrate and a total of 2,880 kg of 65% strength oleum, gives a yield of naphtha lene-1,3,6-trisulphonic acid of 75.5 to 76.5%, relative to naphthalene, and a yield of T-acid of 67 to 69%.EXAMPLE 9 (comparison example)128 g (1.0 mol) of liquid naphthalene are initially introduced, at a temperature of 165"C, into a sulphonating apparatus, flushed with nitrogen, as indicated in Example 1. 140 g of sulphuric acid monohydrate are allowed to run in in the course of 30 minutes at 1650C, whilst cooling. The reaction mixture is kept at 1650C for 1 hour. Whilst cooling to 400C, a second portion of 150 g of sulphuric acid monohydrate is allowed to run in at from 750C and the further procedure followed is then as described in Example 1.The yield of napthalene-1 ,3,6-trisulphonic acid is 72%, relative to naphthalene, or 77%, relative to the sum of naphthalene-trisulphonic acids and naphthalene-tetrasulphonic acids.After further reacting the reaction mixture to give l-naphthylamine-3,6,8-trisulphonic acid (T-acid), the yield of T-acid was determined as 63%, relative to naphthalene, by means of high pressure liquid chromatography.The following contents of compounds were determined, by high pressure liquid chromatography, in the reaction mixture present after the sulphonation reaction: naplithalene- 1,3 ,5-tri- sulphuric acid: 4.3% by weight naphthalene-l ,3 ,6-tri- sulphuric acid: 34.3% by weight naphthalene-1,3,7-tri sulphuric acid: 5.6% by weight naphthalene-1,3,5,7-tetra sulphonic acid: 0.4% by weight dinaphthyl-sulphone-tetra sulphonic acid: about 3.5% by weight sulphuric acid: about 52% by weight WHAT WE CLAIM IS: 1. A process for the preparation of naphthalene-1,3,6-trisulphonic acid comprising carrying out the following process steps seriatim. a) Introducing naphthalene in liquid form into a reaction vessel at 80 to 120 C, b) adding from 1.0 to 3.0 mols of sulphuric acid, per mol of naphthalene, at 80 to 1 200C, c) maintaining the reaction mixture at 80 to 1 200C for from 0.1 to 5 hours, d) heating the reaction mixture to from 130 to 170 C and maintaining this temperature for from 0.2 to 5 hours, e) cooling the reaction mixture to from 20 to 1200C and adding from 0 to 2.0 mols of sulphuric acid per mol of naphthalene, f) adding for the purpose of sulphonation from 2.5 to 2.9 mols of S03, in the form of oleum, per mol of naphthalene, at 40 to 100 C, g) heating the reaction mixture to from 140 to 1 600C and maintaining this temperature for from 1 to 4 hours, h) adding from 0.01 to 1.0 mol of SO3, in the form of oleum, per mol of naphthalene, at 60 to 1600C and i) stirring the reaction mixture for from 0.5 to 4 hours at140 to 1600C.
- 2. A process according to Claim 1 wherein the temperature in process steps a), b) and c) is 80 to 900C.
- 3) A process according to Claim 1 or 2 wherein sulphuric acid with a concentration of from 80 to 100% by weight is used in process steps b) and e).
- 4. A process according to Claim 3 wherein sulphuric acid monohydrate is used in steps b) and e).
- 5. A process according to any one ofClaims 1 to 4 wherein, in step b) from 1.5 to 2.0 mols of sulphuric acid are employed, the raction temperature in step d) is from 140 to 150"C and is maintained for from 0.5 to 2 hours, and the reaction temperature in step e) is from 40 to 1000C.
- 6. A process according to any one of Claims 1 to 5 wherein oleum with a content of free S03 of 20 to 100% by wieght is used in process steps f) andh).
- 7. A process according to Claim 6 wherein approximately 65% strength oleum is employed.
- 8. A process according to any one of Claims 1 to 7 wherein, in step f) from 2.6 to 2.8 mols of SO3 in the form of oleum are added at a temperature of from 40 to 500C, in step g) the reaction mixture is heated to from 145 to 150"C and maintained at this temperature for from 2 to 3 hours, in step h) from 0.1 to 0.5 mol of SO3 in the form of oleum are added and the addition is carried out at from 145 to 150"C, and in step i) the stirring time is from 1 to 2 hours at from 145 to 1500C
- 9. A process for the preparation of naphthalene-1,3,6-trisulphonic acid substantially as hereinbefore described in any of Examples 1 to 3 or 8.
- 10. Naphthalene-1,3,6-trisulphonic acid whenever prepared by a process according to any one of claims 1 to 9.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2718207A DE2718207C3 (en) | 1977-04-23 | 1977-04-23 | Process for the preparation of naphthalene-1,3,6-trisulfonic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1596897A true GB1596897A (en) | 1981-09-03 |
Family
ID=6007133
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB15194/78A Expired GB1596897A (en) | 1977-04-23 | 1978-04-18 | Process for the preparation of naphthalene-1,3,6-trisulphonic acid |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS53132548A (en) |
| BE (1) | BE866223A (en) |
| BR (1) | BR7802456A (en) |
| CH (1) | CH634044A5 (en) |
| DE (1) | DE2718207C3 (en) |
| FR (1) | FR2387947A1 (en) |
| GB (1) | GB1596897A (en) |
| IT (1) | IT1104816B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2853337A1 (en) * | 1978-12-09 | 1980-06-26 | Bayer Ag | NEW NAPHTHALINE SULFURATION PRODUCTS, METHOD FOR THE PRODUCTION AND USE THEREOF |
| DE2901178A1 (en) * | 1979-01-13 | 1980-07-24 | Bayer Ag | METHOD FOR PRODUCING NAPHTHALINE-1,3,5-TRISULPHONIC ACID |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5649908B2 (en) * | 1973-12-28 | 1981-11-25 |
-
1977
- 1977-04-23 DE DE2718207A patent/DE2718207C3/en not_active Expired
-
1978
- 1978-04-18 GB GB15194/78A patent/GB1596897A/en not_active Expired
- 1978-04-20 BR BR7802456A patent/BR7802456A/en unknown
- 1978-04-20 CH CH425978A patent/CH634044A5/en not_active IP Right Cessation
- 1978-04-21 FR FR7811944A patent/FR2387947A1/en not_active Withdrawn
- 1978-04-21 JP JP4674078A patent/JPS53132548A/en active Granted
- 1978-04-21 BE BE2056897A patent/BE866223A/en not_active IP Right Cessation
- 1978-04-21 IT IT49013/78A patent/IT1104816B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| CH634044A5 (en) | 1983-01-14 |
| DE2718207C3 (en) | 1981-11-05 |
| IT1104816B (en) | 1985-10-28 |
| JPS5645909B2 (en) | 1981-10-29 |
| DE2718207B2 (en) | 1980-09-11 |
| DE2718207A1 (en) | 1978-11-02 |
| BE866223A (en) | 1978-10-23 |
| IT7849013A0 (en) | 1978-04-21 |
| JPS53132548A (en) | 1978-11-18 |
| FR2387947A1 (en) | 1978-11-17 |
| BR7802456A (en) | 1979-04-03 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PS | Patent sealed [section 19, patents act 1949] | ||
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19930418 |