US2013181A - sulphonic acib and carboxyhc acid - Google Patents
sulphonic acib and carboxyhc acid Download PDFInfo
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- US2013181A US2013181A US2013181DA US2013181A US 2013181 A US2013181 A US 2013181A US 2013181D A US2013181D A US 2013181DA US 2013181 A US2013181 A US 2013181A
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- Prior art keywords
- bis
- pyrazolone
- acid
- phenylene
- sulphonic
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- 239000002253 acid Substances 0.000 title description 30
- 239000000843 powder Substances 0.000 description 52
- XEKOWRVHYACXOJ-UHFFFAOYSA-N acetic acid ethyl ester Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 40
- -1 aromatic hydrazines Chemical class 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 28
- 239000000243 solution Substances 0.000 description 28
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 22
- FORCWSNQDMPPOC-UHFFFAOYSA-N 5-methyl-4-(3-methyl-5-oxo-1-phenyl-4H-pyrazol-4-yl)-2-phenyl-4H-pyrazol-3-one Chemical group CC1=NN(C=2C=CC=CC=2)C(=O)C1C(C1=O)C(C)=NN1C1=CC=CC=C1 FORCWSNQDMPPOC-UHFFFAOYSA-N 0.000 description 20
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 20
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical class O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 14
- 238000005755 formation reaction Methods 0.000 description 14
- 235000019439 ethyl acetate Nutrition 0.000 description 12
- 150000002148 esters Chemical class 0.000 description 10
- LSNNMFCWUKXFEE-UHFFFAOYSA-N sulfonic acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 8
- 125000002252 acyl group Chemical group 0.000 description 8
- 239000003513 alkali Substances 0.000 description 8
- 229940051880 analgesics and antipyretics Pyrazolones Drugs 0.000 description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 150000007857 hydrazones Chemical class 0.000 description 8
- 238000006798 ring closing metathesis reaction Methods 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- SVSGKVLJUJOBNO-UHFFFAOYSA-N 3-chloro-4-hydrazinylbenzenesulfonic acid Chemical compound NNC1=CC=C(S(O)(=O)=O)C=C1Cl SVSGKVLJUJOBNO-UHFFFAOYSA-N 0.000 description 6
- 125000002843 carboxylic acid group Chemical group 0.000 description 6
- 230000000875 corresponding Effects 0.000 description 6
- 150000008049 diazo compounds Chemical class 0.000 description 6
- 230000005484 gravity Effects 0.000 description 6
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000001187 sodium carbonate Substances 0.000 description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 4
- FNORUNUDZNWQFF-UHFFFAOYSA-N 2,6-dimethyl-4-nitrophenol Chemical compound CC1=CC([N+]([O-])=O)=CC(C)=C1O FNORUNUDZNWQFF-UHFFFAOYSA-N 0.000 description 4
- QDUJVEOOSNUDDW-UHFFFAOYSA-N 2-chloropyrimidine-4,5-diamine Chemical compound NC1=CN=C(Cl)N=C1N QDUJVEOOSNUDDW-UHFFFAOYSA-N 0.000 description 4
- BMDSAXKBAODBMC-UHFFFAOYSA-N 2-hydrazinylbenzene-1,4-disulfonic acid Chemical compound NNC1=CC(S(O)(=O)=O)=CC=C1S(O)(=O)=O BMDSAXKBAODBMC-UHFFFAOYSA-N 0.000 description 4
- ZDGHHRPKFCVOJL-UHFFFAOYSA-N 3-hydrazinylbenzenesulfonic acid Chemical compound NNC1=CC=CC(S(O)(=O)=O)=C1 ZDGHHRPKFCVOJL-UHFFFAOYSA-N 0.000 description 4
- 229960000583 Acetic Acid Drugs 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 125000004957 naphthylene group Chemical group 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- YBQZXXMEJHZYMB-UHFFFAOYSA-N 1,2-diphenylhydrazine Chemical compound C=1C=CC=CC=1NNC1=CC=CC=C1 YBQZXXMEJHZYMB-UHFFFAOYSA-N 0.000 description 2
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 2
- NNUQEZBWGDSLCX-UHFFFAOYSA-N 2-hydrazinylbenzenesulfonic acid Chemical compound NNC1=CC=CC=C1S(O)(=O)=O NNUQEZBWGDSLCX-UHFFFAOYSA-N 0.000 description 2
- KFGVDCBVGNMCJC-UHFFFAOYSA-N 2-hydrazinylbenzoic acid Chemical compound NNC1=CC=CC=C1C(O)=O KFGVDCBVGNMCJC-UHFFFAOYSA-N 0.000 description 2
- APRAPPIPQFRWOZ-UHFFFAOYSA-N 2-hydrazinylnaphthalene-1-sulfonic acid Chemical compound C1=CC=CC2=C(S(O)(=O)=O)C(NN)=CC=C21 APRAPPIPQFRWOZ-UHFFFAOYSA-N 0.000 description 2
- IOMZCWUHFGMSEJ-UHFFFAOYSA-N 4-(azaniumylamino)benzenesulfonate Chemical compound NNC1=CC=C(S(O)(=O)=O)C=C1 IOMZCWUHFGMSEJ-UHFFFAOYSA-N 0.000 description 2
- DZRLKMNAQIOEOG-UHFFFAOYSA-N 4-hydrazinyl-3-nitrobenzenesulfonic acid Chemical compound NNC1=CC=C(S(O)(=O)=O)C=C1[N+]([O-])=O DZRLKMNAQIOEOG-UHFFFAOYSA-N 0.000 description 2
- ZQDXDMDCKWXGDY-UHFFFAOYSA-N 4-hydrazinyl-5-methylbenzene-1,2-disulfonic acid Chemical compound CC1=CC(S(O)(=O)=O)=C(S(O)(=O)=O)C=C1NN ZQDXDMDCKWXGDY-UHFFFAOYSA-N 0.000 description 2
- PCNFLKVWBDNNOW-UHFFFAOYSA-N 4-hydrazinylbenzoic acid Chemical compound NNC1=CC=C(C(O)=O)C=C1 PCNFLKVWBDNNOW-UHFFFAOYSA-N 0.000 description 2
- HKOOXMFOFWEVGF-UHFFFAOYSA-N Phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 2
- ZKPUPHSBFMNFHO-UHFFFAOYSA-N [ClH]1C=CC=C1 Chemical compound [ClH]1C=CC=C1 ZKPUPHSBFMNFHO-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000001809 detectable Effects 0.000 description 2
- RDJCIKZLXHKBPH-SEPHDYHBSA-L disodium;5-[2-(4-oxocyclohexa-2,5-dien-1-ylidene)hydrazinyl]-2-[(E)-2-[4-[2-(4-oxocyclohexa-2,5-dien-1-ylidene)hydrazinyl]-2-sulfonatophenyl]ethenyl]benzenesulfonate Chemical compound [Na+].[Na+].C=1C=C(\C=C\C=2C(=CC(NN=C3C=CC(=O)C=C3)=CC=2)S([O-])(=O)=O)C(S(=O)(=O)[O-])=CC=1NN=C1C=CC(=O)C=C1 RDJCIKZLXHKBPH-SEPHDYHBSA-L 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229940083761 high-ceiling diuretics Pyrazolone derivatives Drugs 0.000 description 2
- 150000002429 hydrazines Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000005648 named reaction Methods 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 230000001264 neutralization Effects 0.000 description 2
- 229940067157 phenylhydrazine Drugs 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/04—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
Definitions
- the present invention relates to sulphonic acid and carboxylic acid derivatives of 1,1-diaryl-3,3- arylene-5,5-bis-pyraz01ones.
- an aqueous medium has the advantage over the reaction of acyl acetic esters containing heavy acyl radicals with hydrazine derivatives containing sulphonic or carboxylic acid groups, known according to literature, that the desired pyrazolone derivatives are obtained with very good yields.
- the formation of the bis-hydrazones occurs with especial advantage in acid solution, the ring-closure to the bis-pyrazolone is advantageously conducted in a neutral or alkaline medium.
- the condensation to the bis-hydrazone and the subsequent ring-closure are preferably effected in the same aqueous medium, without elimination of the bis-hydrazone.
- terephthaloyl-bis-acetic ester instead of the terephthaloyl-bis-acetic ester there may also be used its substitution products. There may be obtained, for instance, from chloroterephthaloyl-bis-acetic ester and m-sulphophenylhydrazine 1,1-di-(3"-sulphophenyl) -3,3 (chloro-p-phenylene)-5,5-bis-pyrazolone (yellow powder); 2-chloro-4-sulphophenyl-hydrazine l,1-di- (2 chloro 4" sulphophenyl) 3,3- (chloro p phenylene) -5,5 bis pyrazolone (yellow powder).
- the yield of precipitated pyrazolone amounts to about 90% of the theoretical.
- R and R stand for radicals of the benzene, naphthalene or diphenyl series and wherein the radical R contains at least one substituent of the group consisting of sulphonic acid and carboxylic acid groups, representing well crystallized bodies, easily soluble in aqueous alkalies, capable of combining with diazo compounds.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Patented Sept. 3, 1 935 rsr OFFICE STULPHONIC AGED AND CARBOXYLIC ACID DERIVATIVE S 0F 1,1 -DHARYL-3,3' -ARYL ENE-5,5-B]IS-PYRAZLONES Herbert Kracker and Richard Schmid, Frankfort-on-the-Main,
Germany, assignors to General Aniline Works, Inc., New York, N. Y., a corporation of Delaware No Drawing. Application March 9, 1934, Serial No. 714,888. In Germany March 11, 1933' 4 Glaims.
The present invention relates to sulphonic acid and carboxylic acid derivatives of 1,1-diaryl-3,3- arylene-5,5-bis-pyraz01ones.
We have found that sulphonic acid and carboxylic acid derivatives of 1,1'-cliaryl-3,3' arylene-5,5'-bis-pyrazolones of the formula:
1'2 R N It 00 N N oo R"OOC-CH2-CO-RCOCH2-COOR" with aromatic hydrazines of the formula? RP-NI-L-NHZ wherein R and R have the above indicated meaning and R stands for an alkyl radical to form the bis-hydrazones and then closing the bis-pyrazolone ring, likewise in water, the corresponding alcohol being split off. The formation of the bishydrazone and especially the ring-closure to the bis-pyrazolone occur without difiiculty and with Very good yields.
As is known from the literature, pyrazolones without sulphonic and carboxylic acid groups are easily obtainable by causing molecular proportions of an arylhydrazine to react upon acyl acetic esters. The reaction velocity in these cases is so high that it is not possible to eliminate the hydrazone formed as intermediate product; there is directly formed the respective pyrazolone (of. H. Wieland, Die Hydrazine (1913), page 126).
If acyl acetic esters are caused to react with sulphonated or carboxylated arylhydrazines the reaction velocity is much less. Thus it is possible, for instance, according to Berichte der deutschen chemischen Gesellschaft, vol. 25, (1892), page 1948, to condense para-phenylhydrazine-sulphonic acid with aoetoacetic ester only with an excess of the ester and even in this case only at temperatures of C.- C. The yield is extremely low, as the author himself states. Experiments have shown that, when working in a solution of acetic acid of 50% strength, the yield is better but attains even then only 50% of the theoretical. Furthermore, according to the statements in Chemisches Zentralblatt, 1911, I, page 83, it is not at all possible to condense free phenylhydrazine-para-sulphonic acid with furoyl acetic ester and ing pyrazoione from the sodium salt of phenylhydrazine-para-sulphonic acid and the same ester takes place only at a temperature of C. and with lowest yield. It, therefore, was to be expected that the formation of pyrazolones from arylhydrazine-sulphonic acids would be prevented by stearic or like hindrance, especially also in View of the observations which Rowe (cf. Chemisches Zentralblatt, 1921, III, page 331) made during his experiments to use arylhydrazine-ortho-sulphonic acids for condensing reactions.
In View of the fact that the last named reac-- tions occur much more slowly it is possible to eliminate the hydrazones from acyl acetic esters and sulphonated or carboxylated arylhydrazines, as will be seen from the examples of the present invention of the formation of bis-hydrazones from aroylene-bis-aoetic esters and arylhydrazines containing sulphonicor carboXylic-acid groups. Only by further treatment of these hydrazones, for instance, with alkalies at higher temperatures, the corresponding pyrazolones are formed.
A characteristic feature of the present process lies in the fact that thenew Chemisches Zentralblatt 1911, 1, page 83. It-
had rather to be supposed that the reaction of sulphonated or carboxylated arylhydrazines with aroylene-bis-acetic esters in an aqueous medium would not take place at all or only with bad yields, since according to Berend and Herms in Journal fiir praktische Chemie (2)74, page 125 et seq. the condensation of the water-insolthe formation of the correspondbis-pyrazolone derivatives are easily formed in an aqueous medium uble terephthaloyl-bis-acetic ester with phenylhydrazine to the corresponding 1,l-diphenyl- 3,3-(para-phenylene) 5,5-bis-pyrazolone occurs only by heating the components in glacial acetic acid. Moreover, the use of an aqueous medium has the advantage over the reaction of acyl acetic esters containing heavy acyl radicals with hydrazine derivatives containing sulphonic or carboxylic acid groups, known according to literature, that the desired pyrazolone derivatives are obtained with very good yields.
The formation of the bis-hydrazones occurs with especial advantage in acid solution, the ring-closure to the bis-pyrazolone is advantageously conducted in a neutral or alkaline medium. The condensation to the bis-hydrazone and the subsequent ring-closure are preferably effected in the same aqueous medium, without elimination of the bis-hydrazone.
The pyrazolones thus obtainable are valuable intermediate products for the manufacture of dyestuffs.
The following examples serve to illustrate the invention, but they are not intended to limit it thereto:
(1) 388 grams of 4hydroxy-3'-carboXy-4- sulpho 1,1diphenyl-sulphone-2 hydrazine are suspended in 2500 cc. of water of 60 C. to 65 C. and the whole is rendered weakly acid to Congo paper by means of sodium carbonate solution. Thereupon, 155 grams of terephthaloyl-bis-acetic ethylester are quickly added and the whole is stirred for about a quarter of an hour at 60 C. to 65 C. The reaction hereby becomes strongly acid to Congo paper. In the course of half an hour a solution of grams of anhydrous sodium carbonate in water is slowly run in until the acid reaction to Congo has just disappeared. Now the reaction is still very acid to litmus paper; the whole is entirely dissolved to a brown-yellow solution. After stirring for 2 hours at 65 C. to 70 (3., free hydrazine can no longer be detected by means of Fehlings solution, that is to say, the formation of the bis-hydrazone is finished. 50 grams of prepared chalk are then added and the mass is heated to from 83 C. to 85 C. to effect the ring-closure. The temperature is maintained for 2 to 3 hours, the whole is filtered by suction, while hot, and the hot solution is run into a mixture'of 500 cc. of hydrochloric acid (specific gravity 1.163) and 300 grams of sodium chloride. The bis-pyrazolone formed of the formula m-sulphophenylhydrazine 1,1 -di (3-sulphophenyl) -3,3- (para-phenylene) 5,5-bis-pyrazolone (grey-yellow powder) p-sulphophenylhydrazine l,1'di- (4"sulph0phenyl) 3,3 (para-phenylene) -5,5bis-pyrazolone (yellow powder) o-carboxyphenylhydrazine 1,1 di- (2" -carboxyphenyl) -3,3 (para-phenylene) -5,5-bis-pyrazo1one (yellow powder) 2-chloro-4-sulphophenylhydrazine 1,1'di-(2" chloro l" sulphophenyl) 3,3- (para-phenylene) 5,5-bis-pyrazolone (yellowishgrey powder) 2-chloro-5su1phophenyl-hydrazine 1,l-di- (2 -chloro 5 sulphophenyl) 3,3 (pphenylene) 5,5 bis pyrazolone (yellowishbrown powder) 1-sulpho-2naphthyl-hydrazine l,l-di-(2-naphthyl- 1"su1ph0) 3,3- (p-phenylene) 5,5bis-pyrazolone (reddish-brown powder) 3-carboXy-2hydroxy-5-sulph0phenyl-hydrazine 1,1-di- (3-carboxy-2" hydroxy 5" -sulphophenyl) -3,3 (p-phenylene) -5,5 -bis -pyrazolone (reddish-brown powder) i-sulpho-4=diphenyl-hydrazine 1,l-di-( ="-diphenyl 4 sulpho) 3,3 (pphenylene)5,5-bis-pyrazolone (brownish powder).
Instead of the terephthaloyl-bis-acetic ester there may also be used its substitution products. There may be obtained, for instance, from chloroterephthaloyl-bis-acetic ester and m-sulphophenylhydrazine 1,1-di-(3"-sulphophenyl) -3,3 (chloro-p-phenylene)-5,5-bis-pyrazolone (yellow powder); 2-chloro-4-sulphophenyl-hydrazine l,1-di- (2 chloro 4" sulphophenyl) 3,3- (chloro p phenylene) -5,5 bis pyrazolone (yellow powder).
From nitroterephthaloyl-bis-acetic ester and p-carboxyphenylhydrazine 1,1di-(4-carboxypheny1) -3,3'-(nitro-p-phenylene)-5,5-bis-pyrazolone (yellow powder); 1su1pho-2-naphthylhydrazine 1,1-di-(2-naphthyl-1 -sulpho) 3,3 (nitrop-phenylene) -5,5bis-pyrazolone (reddish-yellow powder) The yields of precipitated pyrazolone amount to about (2) 188 grams of para-sulphophenylhydrazine are suspended in 1500 cc. of water of 55 C.-60 C.
- soOsogn HOaS-OSOQOH coon /N\ /N\ coon precipitates with a grey color and forms, after filtering with suction, washing and drying, a grey powder.
The yield of precipitated pyrazolone amounts to about 90% of the theoretical.
By using in the above example instead of terephthaloyl-bis-acetic ethyl-ester 143 grams of terephthaloyl-bis-acetic methyl-ester, the same pyrazolone is obtained.
In a similar manner there are obtained from: terephthaloyl-bis-acetic ester and o-sulphophenylhydrazine 1,ldi- (2-sulphopheny1) -3,3' (para-phenylene) -5,5bispyrazolone (yellow powder) and rendered feebly acid to Congo paper by means of sodium carbonate solution. grams of isophthaloyl-bis-acetic ester are quickly added, whereupon the mass is stirred for half an hour. The reaction becomes again very acid to Congo paper. In the course of half an hour a solution of 50 grams of anhydrous sodium carbonate in water is then run in, whereby the whole is entirely dissolved. The solution still shows a strongly acid reaction to litmus paper. After stirring for 2 hours at 55 C.60 C. the formation of hydrazone is finished and free hydrazine is no longer detectable. Thereupon, an aqueous solution of 50 grams of anhydrous sodium carbonate is added,
the whole is stirred for half an hour at 65 C.- 70 C. and heated to C.87 C. This temperature is maintained for half an hour, the whole is filtered and worked up as described in Example 1. The 1,1-di-(4-sulphophenyl)-3,3'-(mphenylene)-5,5'-bis-pyrazolone of the following formula:
is obtained in the form of a brownish-yellow crystalline powder with a yield of about 85% of the theoretical.
In a similar manner there are obtained from:
Isophthaloyl-bis-acetic ester and para-oarboxyphenylhydrazine 1,1-di- 1 -carboXy-pheny1) 3,3 -i (m-phenylene) 5,5'-bispyrazolone (yellowish powder);
Isophthaloyl-bis-acetic ester and Z-nethyllsulphophenylhydrazine 1,1-di-(2"-methyl-4 sulpho phenyl) -3,3- (in-phenylene) -5,5' bis pyrazolone (brownish powder);
Naphthoylene-1,4-bis-acetic ester and l-sulpho-2-naphthylhydrazine 1,1 di (2" naphthyl 1" sulpho) 3,3 (1", i" naphthylene) 5,5 bis pyrazolone (brown-yellow powder) Naphthoylene-1,5-bis-acetic ester and 3-carboxy-Z-hydroxy-fisulpho-phenylhydrazine l,1-di-(3-carboxy 2 hydroXy-5-sulphophenyl) -3,3-(1,5" -naphthylene) -5,5-bis-pyrazolone (brown-yellow powder) Diphenyloyli/i-bis-acetic ester and 2-chloro- 4-sulphophenylhydrazine 1,1 di (2 chloro 4 sulphophenyl) 3,3-(4,4-diphenylene) -5,5 -bis -pyrazolone (yellow powder) (3) 233 grams of 4-nitro-2-su1phonphenylhydrazine are suspended in 3000 cc. of water of 55 C.-60 C. and rendered feebly acid to Congo paper by means of sodium carbonate solution. grams of terephthaloyl-bis-acetic ethyl-ester are quickly added and the mass is then stirred for half an hour. The reaction becomes again very acid to Congo paper. In the course of half an hour a solution of 60 grams of anhydrous sodium carbonate in water is run in, until the reaction is no longer acid to Congo paper; the reaction is still very acid to litmus paper, the bis-hydrazone formed has precipitated with a pure yellow color. The whole is stirred for 2 hours at 60 C.-65 C. and again 50 grams of anhydrous sodium carbonate dissolved in water are added, whereby the reaction becomes distinctly alkaline to brilliant yellow and dissolution begins. The whole is stirred for a further 1-2 hours at 60 C.65 C. and 168 cc. of caustic soda solution (specific gravity 1.383) are added, whereby a clear solution is obtained. The temperature is raised to 65 C.-70 C., but not higher, since otherwise decomposition accompanied by frothing takes place. The whole is stirred for a quarter of an hour at the said temperature, cooled to 50 (3., filtered and the filtrate is run into 600 cc. of hydrochloric acid (specific gravity 1.163)
and 600 grams of sodium chloride. Thereby, 1,1 di (4 nitro 2" sulphophenyl) 3,3 (para-phenylene)-5,5'-bis-pyrazolone of the following formula:
02 OSOaH H033 precipitates with a brown-yellow color.
The yield of pyrazolone amounts to about 80% of thetheoretical. In a similar manner there are obtained from Terephthaloyl-bis-acetic ester and. 2,5-disulphophenylhydrazine 1,1 di (2",5 disulphophenyl) 3,3 (p phenylene) -5,5-bis-pyrazolone (yellow powder) Isophthaloyl-bis-acetic ester and 2-nitro-4- sulphophenylhydrazine 1,1 (11 (2" nitro 4 sulphophenyl) 3,3-(m-phenylene) -5,5' -bis pyrazolone (brown powder) Chloroterephthaloyl bis acetic ester and 2- methyl-4,5disulphophenyl-hydrazine 1,1 di 2" methyl 4",5 disulphophenyl) 3,3 (chloro p phenylene) 5,5 bis pyrazolone (yellow powder) Nitroterephthaloyl-bis-acetic ester and 4-mtro-2-sulpho-phenyl-hydrazine 1,1 di (4 nitro 2" sulphophenyl) 3,3 (nitro-p-phenylene) 5,5 bis pyrazolone (brown-yellow powder) Naphthoylene-1,5-bis-acetic ester and 2-mitro-4-sulphophenylhydrazine 1,1 di 2" nitro 4 sulphophenyl) 3,3- (1"',5" naphthylene) -5,5bis -pyrazolone (brown powder) Diphenyloyl-4A-bis-acetic ester and 2,5-disulphophenylhydrazine 1,1 di (2,5" di sulphophenyl) 3,3 (4=",4""-diphenylene)-5,5-bis-pyrazolone (yel- 10w powder) In these cases too the yields are very good. We claim: 1. The compounds of the following general formula:
N N 00 \N N oo Hz( l -R( f l( lHa wherein R and R stand for radicals of the benzene, naphthalene or diphenyl series and wherein the radical R contains at least one substituent of the group consisting of sulphonic acid and carboxylic acid groups, representing well crystallized bodies, easily soluble in aqueous alkalies, capable of combining with diazo compounds.
2. The compound of the following formula:
representing a yellow crystallized body, easily soluble in aqueous alkalies, capable of combining with diazo compounds.
3. The compound of the following formula:
NO: I @SOaH H033 00 O representing a brown-yellow crystallized body, easily soluble in aqueous alkalies, capable of combining with diazo compounds.
4. The compound of the following formula:
Ho3s ooon 11000 $0311 OH HO 1% N
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2013181A true US2013181A (en) | 1935-09-03 |
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ID=3427323
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US2013181D Expired - Lifetime US2013181A (en) | sulphonic acib and carboxyhc acid |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2013181A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2620339A (en) * | 1941-05-22 | 1952-12-02 | Gevaert Photo Prod Nv | Preparation of polymethine dyestuffs |
| US2903461A (en) * | 1957-12-23 | 1959-09-08 | Gen Aniline & Film Corp | Bis pyrazolones |
| US3929827A (en) * | 1972-09-26 | 1975-12-30 | Montedison Spa | 1N, 1N{40 -Phenylenbis(5-methyl-4-pyrazolin-3-ones) and process for preparing same |
-
0
- US US2013181D patent/US2013181A/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2620339A (en) * | 1941-05-22 | 1952-12-02 | Gevaert Photo Prod Nv | Preparation of polymethine dyestuffs |
| US2903461A (en) * | 1957-12-23 | 1959-09-08 | Gen Aniline & Film Corp | Bis pyrazolones |
| US3929827A (en) * | 1972-09-26 | 1975-12-30 | Montedison Spa | 1N, 1N{40 -Phenylenbis(5-methyl-4-pyrazolin-3-ones) and process for preparing same |
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