CA1038399A - 1-AMINOBENZENE-5-.beta.-SULFATOETHYLSULFONE-2,4-DISULFONIC ACID, THE 5-VINYLSULFONE COMPOUND AND THE ALKALL SALTS THEREOF AND PROCESS FOR PREPARING THEM - Google Patents
1-AMINOBENZENE-5-.beta.-SULFATOETHYLSULFONE-2,4-DISULFONIC ACID, THE 5-VINYLSULFONE COMPOUND AND THE ALKALL SALTS THEREOF AND PROCESS FOR PREPARING THEMInfo
- Publication number
- CA1038399A CA1038399A CA211,513A CA211513A CA1038399A CA 1038399 A CA1038399 A CA 1038399A CA 211513 A CA211513 A CA 211513A CA 1038399 A CA1038399 A CA 1038399A
- Authority
- CA
- Canada
- Prior art keywords
- aminobenzene
- beta
- sulfuric acid
- mixture
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Abstract of the Disclosure:
New compounds had been found which correspond to the formula as well as processes for preparing them by sulfonation of 3-.beta.-sulfato- or 3-.beta.-hydroxyethylsulfonyl - aminobenzene.
The novel compounds are valuable intermediary products for the preparation of azo fibre-reactive dyestuffs which have very good dyeing properties and a high fibre-reactivity yielding dyeings of excellent fastnesses, especially to light and wet processing.
New compounds had been found which correspond to the formula as well as processes for preparing them by sulfonation of 3-.beta.-sulfato- or 3-.beta.-hydroxyethylsulfonyl - aminobenzene.
The novel compounds are valuable intermediary products for the preparation of azo fibre-reactive dyestuffs which have very good dyeing properties and a high fibre-reactivity yielding dyeings of excellent fastnesses, especially to light and wet processing.
Description
The present in~rention relates to novel compounds of th~
general formula (1) N~2 ' ~' - 02S- ~ S03X (~) Wherein Y is one of the groups of the formulae X03S_ O - CH2~ CH2 (2) or CH2 = CH - . (3) and X is a hydrogen, alkyli metal or alkaline earth metal ion, especially a sodium, potassium or calcium atom, and a i process for preparing them with good yields, wherein 1-amino-benzene-3-B-sulfatoethyl-sulfone or 1-amino-benzene-3-B-hydroxy-ethyl-sulfone either (a) is dissolved or suspended in anhydrous sulfuric acid (monohydrate) between about -15C and +40C, pre-ferably between about 10C and 20C, to which subsequently sulfur trloxide, dissolved in anhydrous sulfuric acid, pre-ferably a sulfuric acid/sulfur trioxide mixture having a mixture ratio of 30 : 70 to 90 : 10 is added in the temperature range mentioned above, or tb) is introduced immediately into a mixture of sulfuric acid/sulfur trioxide having a content of up to ~0 percent by weight of sulfur trioxide, and subsequently heated to about 100~C to about 150C, preferably 125C - 135C, and wherein if desired, the 1-aminobenzene-5-B-sulfato-ethyl-sulfone-2,4-disulfonic acid formed or t~.e salt thereof is heated in an aqueous solution at 2.5 to 7~preferably at 4 to 6, 29 ~o about 30C to about 60C, the sulfur~c acid which has been ~L
general formula (1) N~2 ' ~' - 02S- ~ S03X (~) Wherein Y is one of the groups of the formulae X03S_ O - CH2~ CH2 (2) or CH2 = CH - . (3) and X is a hydrogen, alkyli metal or alkaline earth metal ion, especially a sodium, potassium or calcium atom, and a i process for preparing them with good yields, wherein 1-amino-benzene-3-B-sulfatoethyl-sulfone or 1-amino-benzene-3-B-hydroxy-ethyl-sulfone either (a) is dissolved or suspended in anhydrous sulfuric acid (monohydrate) between about -15C and +40C, pre-ferably between about 10C and 20C, to which subsequently sulfur trloxide, dissolved in anhydrous sulfuric acid, pre-ferably a sulfuric acid/sulfur trioxide mixture having a mixture ratio of 30 : 70 to 90 : 10 is added in the temperature range mentioned above, or tb) is introduced immediately into a mixture of sulfuric acid/sulfur trioxide having a content of up to ~0 percent by weight of sulfur trioxide, and subsequently heated to about 100~C to about 150C, preferably 125C - 135C, and wherein if desired, the 1-aminobenzene-5-B-sulfato-ethyl-sulfone-2,4-disulfonic acid formed or t~.e salt thereof is heated in an aqueous solution at 2.5 to 7~preferably at 4 to 6, 29 ~o about 30C to about 60C, the sulfur~c acid which has been ~L
- 2 -~ .
-"~ HOE 73/F ~16 )38399 ~ split off in the aqueous solution, is neutralized by the - addition of an acid-bindin~ agent, and the 1-amino- benzene-5-~inylsulfon~-2,4-disulfonic acid is iso~ted in the form of the alkali metal or alkaline earth metal sal~.
The molar ratio of the compound to be sulfonated, to the free sulfur trioxide of the reaction mixture is at about 1 : 2.5 to 1 : 6, preferably at 1 : 2.7 to 1 : 4. To con-~ert the B-hydroxy-ethyl group into the 3-sulfatoethyl group, ~ one mol of sulfur tri~ide is additionally requirad so th~t the ratio i8 1: ~.5 to 1.7, prefera~ly 1 : 3,7 to 1 : 5.
~uring the sulfonation of the benzene nucleus the mcno-sulfonation product 1-aminobenzene-5-B-sulfatoethyl-3ulfone-2-sulfonic acid is formed first as ~n intermediar-J ~ro~uct.
To isolate the 1-aminobenzene-5-B-sul~atoethylsulfone-2,4-disulfonic acid in the for~ of the free acid, o~tained after the disulfonation in a sulfuric acid/sulfur trioxide-mixture, the sulfonation mixture is introduced, while stirring, into a mixture of ice and pot&ssium chloride, whereby the di-sulfonic acid mentioned is precipitated in form of the free aci~
and may be fil+ered.
To isolate the 1-aminobenzene-5-B-sulfatoethyisulfone_ 2,4 disulfonic acid in form of a salt the sulfonation mixture is poured onto ice and the sulfuric acid in excess is n~utralized with an alkall metal hydroxide or carbonate or with an al-kaline earth metal hydroxide or carbonate. After filterin~ the precipitations of alkali metal or alkaline earth metal sulfate the disulfonic acid mentioned may be obtained in the form of the alkali meta~ salt or alkaline earth me~al s~lt, for example 29 of the sodium or potassiu~ salt, by s~ray drying.
_ 3 _ ~ .
\ HOE 731F 316 (~) ` 1038399 The yield of 1-aminobenzene-5-~-sulfatoethylsulfone-2,4-disulfonic acid is 70 to 90 % of the theory, calcu1ated on the free acid.
To isolate the 1-aminobenzene-5-vinylsulfone-2,4-disulfor.ic acid in form of a salt the procedure may be the followir.g one:
the sulfuric acid split off during the preceding heating of the 1-aminobenzene-5-B-sulfatoethylsulfone-2,4-disulfonic acid may be neutralized by the addition of an acid-binding agentj for example an alkali metal or alkaline earth metal hydroxide or carbcnate, preferably sodium hydroxide or sodium carbonate, and the alkali metal or alkaline earth metal salt, for example the sodium salt, may be obta~ned by spray-dryin~ t~e neutral solution. The alkali metal salts of the compounds mentior.ed may also be isolated by precipitating the 1-aminobenzene-5-vinyl-sulfone-2,4-disulfonic acid from tke solution obtained by means of alkali halides.
m e duration of disulfonation, i.e. the treatment of the 8tarting product8 in a mixture of sulfuric acid/Xulfur trioxide may be between or.e hour and about 20 hours.
The 1-aminobenzene-5-B-sulfatoethylsul~one-2,4-disulfonic acid, 1-amino-benzene-5-vinylsulfone-2,4-disulfonic acid and the alkali salts thereof are novel, valuable diazo components for the praparation of valuable azo dyestuffs.
In the preparation of azo dyestuffs from the amines of the 2~ invention as diazo components and from azo compou~ds usual for azo dyestuffs, ~ibre reactive azo dyestuffs are obtained which show, in many reSPects, valuable tinctorial properties. ~uc~
azo dyQstuffs are prepared in know~ manner by diazotation and 29 couplin~.
--'~~~'~~~-~ rl . , , ,, ,,,_~_,,,_,,,_,_,,_ ,_ _, _ ~
(~J .~
The following Examples illustrate the in~ention.
E X A M P L E
~ . . .. .
281 g (1 mol) o~ 1-aminobenzene-3-~-su fatoethylsul~one were introduced portionwise, while coolin~ and stirring ard with exclusion of humidit~J. into 843 g of sulfuric acid mono-hydrate at 15 to 20C. After stirring for 60 m~utes,350g of ~eum having a content of S03 of 65 percent by ~weight were slowly added dropwise, whereby the temperature was maintained at 15C
to 20C by cooling from the outside. Subse~uently the mixture wa~ heated for 12 hours to 130C. The cooled reaction mixture was then introduced, while stirring, into 2 mix~ure of ice and potassium cnloride, whereby the 1-aminobenzene-5-B~ulfato-ethyl~ulfone-Z,4-disulfonic acid of the for~ula ( t ) Ho~s ~3 t ) -C~ C}1~_0~;o3 ~0 H
was precipitated. It was filtered and dried. The yield was 75 ~ of the theory.
The analysis showed a ratio of carbon to s-llfur of 2 : 1 corresponding ~o the formula C8H11N012S4. The two protons being in a par~-position in the benzene nucleus could be de-termir.ed in the nuclear resona~ce spectrum of ~MR spectroscopy.
E X A M P L E 2:
.
2~1 g (1 mol) of 1-aminobenzene-3-~-sulfatoethyl-sulfone were introduced portionwise~ while cooling and stirring and with evclusion of humidity, into 1193 g of ol~um h~ing a con-29 tent of S03 of 19 percent by weight at 15 to 20C. After ~ o 5 _ f . ~
iO3B3g9 stirring for 60 minutes the mixture was heated for 12 hou.s to 130C. The reaction mixture obtained was tnen introduced, while stirring, into a mixture of ice and potassium chloride, whereby the 1-aminobenzcne-5-B-sulfatoethylsulfone-2,4-disulfonic acid of the formula (+) ~3 J~03S ~ ~-~~,L_ S03 c~-C~I2-so3 was p~ecipitated. It was filtered and dried. The yield of 1-aminobenzene-5-B-sulfatoethyl-sulfone-2,4-disulfonic acid was 70 % of the theory.
E X A M P L E 3:
201 g (1 mol) of 1-aminobenzene-3-B-hylroxyethylsu]fone were introduced portionwise, while cooiing and stirring and with exclusion of humidity, into 723 g of sulfuric acid mono-hydrate at 15 to 20C. Stirring was continued for 3 hours and then 473 g of oleum having a content of S03 of 65 percent by weight were slowly added dropwise, whereby the tempe-ature was maintained at 15 to 20C by cooling from the outside. Then the mixture was heated for 12 hours to 130C. The cooled reac~ion mixture was introduced, while stirring, into a mixture of ice and potass~um chloride, whereby the 1-aminobenzene-5-~-sulfato-ethylsulfone-2,4-d~sulfonic acid of the fornula (~) - ~H3 }ro3~
~52 --CH~-cH2-oso 29 ~0 ~ 3 HOE 7~/F ~16 (~ 1038399 precipitated. It was flltered and dried. The yield was 75 % of ~he theory.
E X A M P L E 4:
.
441 g (1 mol) of 1-aminobenzene-5-B-sulfatoe~hylsulfone-2,4-disulfonic acid were introduced into 1500 ml of water at pH 6 to 7. Then the mixture was adjusted to pH 6 to 7 with 80dium c~rbonate and heated to 50 - 60C. The sulfuric acid splitting off was neutralized by further addition of sodium carbonate. Afier 10 minutes the reaction was finished. The disodium salt of the 1-a~inobenzene-5-~inylsulfone-2,4-di-~ulfonic acid was obtained by spray drying the neutral solution.
The analvsis of the novel compound sho~red a ratio of caroon ~o sulfur of 8 : 3 correspor,ding to the molecular formula C8 ~ N08S3Na2. The signals of the vinyl protons in the NMR
~5 spectrum-were in the range of ~= 6.0 to 6.4.
, , . , ~ .
,, . ' .
~ .
fi F-~
-"~ HOE 73/F ~16 )38399 ~ split off in the aqueous solution, is neutralized by the - addition of an acid-bindin~ agent, and the 1-amino- benzene-5-~inylsulfon~-2,4-disulfonic acid is iso~ted in the form of the alkali metal or alkaline earth metal sal~.
The molar ratio of the compound to be sulfonated, to the free sulfur trioxide of the reaction mixture is at about 1 : 2.5 to 1 : 6, preferably at 1 : 2.7 to 1 : 4. To con-~ert the B-hydroxy-ethyl group into the 3-sulfatoethyl group, ~ one mol of sulfur tri~ide is additionally requirad so th~t the ratio i8 1: ~.5 to 1.7, prefera~ly 1 : 3,7 to 1 : 5.
~uring the sulfonation of the benzene nucleus the mcno-sulfonation product 1-aminobenzene-5-B-sulfatoethyl-3ulfone-2-sulfonic acid is formed first as ~n intermediar-J ~ro~uct.
To isolate the 1-aminobenzene-5-B-sul~atoethylsulfone-2,4-disulfonic acid in the for~ of the free acid, o~tained after the disulfonation in a sulfuric acid/sulfur trioxide-mixture, the sulfonation mixture is introduced, while stirring, into a mixture of ice and pot&ssium chloride, whereby the di-sulfonic acid mentioned is precipitated in form of the free aci~
and may be fil+ered.
To isolate the 1-aminobenzene-5-B-sulfatoethyisulfone_ 2,4 disulfonic acid in form of a salt the sulfonation mixture is poured onto ice and the sulfuric acid in excess is n~utralized with an alkall metal hydroxide or carbonate or with an al-kaline earth metal hydroxide or carbonate. After filterin~ the precipitations of alkali metal or alkaline earth metal sulfate the disulfonic acid mentioned may be obtained in the form of the alkali meta~ salt or alkaline earth me~al s~lt, for example 29 of the sodium or potassiu~ salt, by s~ray drying.
_ 3 _ ~ .
\ HOE 731F 316 (~) ` 1038399 The yield of 1-aminobenzene-5-~-sulfatoethylsulfone-2,4-disulfonic acid is 70 to 90 % of the theory, calcu1ated on the free acid.
To isolate the 1-aminobenzene-5-vinylsulfone-2,4-disulfor.ic acid in form of a salt the procedure may be the followir.g one:
the sulfuric acid split off during the preceding heating of the 1-aminobenzene-5-B-sulfatoethylsulfone-2,4-disulfonic acid may be neutralized by the addition of an acid-binding agentj for example an alkali metal or alkaline earth metal hydroxide or carbcnate, preferably sodium hydroxide or sodium carbonate, and the alkali metal or alkaline earth metal salt, for example the sodium salt, may be obta~ned by spray-dryin~ t~e neutral solution. The alkali metal salts of the compounds mentior.ed may also be isolated by precipitating the 1-aminobenzene-5-vinyl-sulfone-2,4-disulfonic acid from tke solution obtained by means of alkali halides.
m e duration of disulfonation, i.e. the treatment of the 8tarting product8 in a mixture of sulfuric acid/Xulfur trioxide may be between or.e hour and about 20 hours.
The 1-aminobenzene-5-B-sulfatoethylsul~one-2,4-disulfonic acid, 1-amino-benzene-5-vinylsulfone-2,4-disulfonic acid and the alkali salts thereof are novel, valuable diazo components for the praparation of valuable azo dyestuffs.
In the preparation of azo dyestuffs from the amines of the 2~ invention as diazo components and from azo compou~ds usual for azo dyestuffs, ~ibre reactive azo dyestuffs are obtained which show, in many reSPects, valuable tinctorial properties. ~uc~
azo dyQstuffs are prepared in know~ manner by diazotation and 29 couplin~.
--'~~~'~~~-~ rl . , , ,, ,,,_~_,,,_,,,_,_,,_ ,_ _, _ ~
(~J .~
The following Examples illustrate the in~ention.
E X A M P L E
~ . . .. .
281 g (1 mol) o~ 1-aminobenzene-3-~-su fatoethylsul~one were introduced portionwise, while coolin~ and stirring ard with exclusion of humidit~J. into 843 g of sulfuric acid mono-hydrate at 15 to 20C. After stirring for 60 m~utes,350g of ~eum having a content of S03 of 65 percent by ~weight were slowly added dropwise, whereby the temperature was maintained at 15C
to 20C by cooling from the outside. Subse~uently the mixture wa~ heated for 12 hours to 130C. The cooled reaction mixture was then introduced, while stirring, into 2 mix~ure of ice and potassium cnloride, whereby the 1-aminobenzene-5-B~ulfato-ethyl~ulfone-Z,4-disulfonic acid of the for~ula ( t ) Ho~s ~3 t ) -C~ C}1~_0~;o3 ~0 H
was precipitated. It was filtered and dried. The yield was 75 ~ of the theory.
The analysis showed a ratio of carbon to s-llfur of 2 : 1 corresponding ~o the formula C8H11N012S4. The two protons being in a par~-position in the benzene nucleus could be de-termir.ed in the nuclear resona~ce spectrum of ~MR spectroscopy.
E X A M P L E 2:
.
2~1 g (1 mol) of 1-aminobenzene-3-~-sulfatoethyl-sulfone were introduced portionwise~ while cooling and stirring and with evclusion of humidity, into 1193 g of ol~um h~ing a con-29 tent of S03 of 19 percent by weight at 15 to 20C. After ~ o 5 _ f . ~
iO3B3g9 stirring for 60 minutes the mixture was heated for 12 hou.s to 130C. The reaction mixture obtained was tnen introduced, while stirring, into a mixture of ice and potassium chloride, whereby the 1-aminobenzcne-5-B-sulfatoethylsulfone-2,4-disulfonic acid of the formula (+) ~3 J~03S ~ ~-~~,L_ S03 c~-C~I2-so3 was p~ecipitated. It was filtered and dried. The yield of 1-aminobenzene-5-B-sulfatoethyl-sulfone-2,4-disulfonic acid was 70 % of the theory.
E X A M P L E 3:
201 g (1 mol) of 1-aminobenzene-3-B-hylroxyethylsu]fone were introduced portionwise, while cooiing and stirring and with exclusion of humidity, into 723 g of sulfuric acid mono-hydrate at 15 to 20C. Stirring was continued for 3 hours and then 473 g of oleum having a content of S03 of 65 percent by weight were slowly added dropwise, whereby the tempe-ature was maintained at 15 to 20C by cooling from the outside. Then the mixture was heated for 12 hours to 130C. The cooled reac~ion mixture was introduced, while stirring, into a mixture of ice and potass~um chloride, whereby the 1-aminobenzene-5-~-sulfato-ethylsulfone-2,4-d~sulfonic acid of the fornula (~) - ~H3 }ro3~
~52 --CH~-cH2-oso 29 ~0 ~ 3 HOE 7~/F ~16 (~ 1038399 precipitated. It was flltered and dried. The yield was 75 % of ~he theory.
E X A M P L E 4:
.
441 g (1 mol) of 1-aminobenzene-5-B-sulfatoe~hylsulfone-2,4-disulfonic acid were introduced into 1500 ml of water at pH 6 to 7. Then the mixture was adjusted to pH 6 to 7 with 80dium c~rbonate and heated to 50 - 60C. The sulfuric acid splitting off was neutralized by further addition of sodium carbonate. Afier 10 minutes the reaction was finished. The disodium salt of the 1-a~inobenzene-5-~inylsulfone-2,4-di-~ulfonic acid was obtained by spray drying the neutral solution.
The analvsis of the novel compound sho~red a ratio of caroon ~o sulfur of 8 : 3 correspor,ding to the molecular formula C8 ~ N08S3Na2. The signals of the vinyl protons in the NMR
~5 spectrum-were in the range of ~= 6.0 to 6.4.
, , . , ~ .
,, . ' .
~ .
fi F-~
Claims (3)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A compound of the general formula wherein Y is XO3S - O - CH2 - CH2 or CH2 = CH -and X is a hydrogen, an alkali metal or alkaline earth metal atom.
2. A process for preparing a compound of the formula wherein Y is XO3S - O - CH2 - CH2 or CH2 = CH -and X is hydrogen, an alkali metal or alkaline earth metal atom, which comprises either (a) dissolving or suspending 1-aminobenzene-3-.beta.-sulfato ethylsulfone or 1-aminobenzene-3-.beta.-hydroxyethylsulfone in an anhydrous sulfuric acid (monohydrate) between about -15°C and about +40°C, subsequently adding sulfur trioxide, dissolved in anhydrous sulfuric acid, in the temperature range indicated above, or (b) introducing 1-aminobenzene-3-.beta.-sulfatoethylsulfone or 1-aminobenzene-3-.beta.-hydroxyethylsulfone into a mixture of sulfuric acid/sulfur trioxide having a content of up to 30 percent by weight of sulfur trioxide, and subsequently heating to about 100°C - about 150°C, and optionally heating the 1-amino-benzene-5-3-sulfato-ethylsulfone-2,4-disulfonic acid formed during this process, or the salt thereof in an aqueous solution at pH 2.5 to 7, to about 30°C to about 60°C, neutralizing the sulfuric acid split off by addition of an acid-binding agent and isolating the 1-amino-benzene-5-vinylsulfone-2,4-disulfonic acid formed in form of the alkali metal or alkaline earth metal salt.
3. A process as claimed in claim 2 a), wherein the 1-amino-benzene-3-.beta.-sulfatoethylsulfone or 1-aminobenzene-3-.beta.-hydroxyethylsulfone is dissolved or suspended at temperatures between 10° and 20°C in an anhydrous sulfuric acid (monohydrate), and subsequently a mixture of sulfuric acid/
sulfur trioxide having a mixture ratio of 30 : 70 to 90 : 10 is added, and the mixture is subsequently heated to temperatures of from 125° to 135°C.
sulfur trioxide having a mixture ratio of 30 : 70 to 90 : 10 is added, and the mixture is subsequently heated to temperatures of from 125° to 135°C.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19732352059 DE2352059C3 (en) | 1973-10-17 | i-aminobenzene-5-beta-sulfatoethylsulfone-2,4-disulfonic acid, its 5-vinylsulfone compound and its alkali metal or alkaline earth metal salts and processes for the preparation of these compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1038399A true CA1038399A (en) | 1978-09-12 |
Family
ID=5895664
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA211,513A Expired CA1038399A (en) | 1973-10-17 | 1974-10-16 | 1-AMINOBENZENE-5-.beta.-SULFATOETHYLSULFONE-2,4-DISULFONIC ACID, THE 5-VINYLSULFONE COMPOUND AND THE ALKALL SALTS THEREOF AND PROCESS FOR PREPARING THEM |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS5644067B2 (en) |
| BE (1) | BE821194A (en) |
| CA (1) | CA1038399A (en) |
| CH (1) | CH605719A5 (en) |
| FR (1) | FR2248269B1 (en) |
| GB (1) | GB1438878A (en) |
| IN (1) | IN143126B (en) |
| IT (1) | IT1022898B (en) |
-
1974
- 1974-10-14 CH CH1376574A patent/CH605719A5/xx not_active IP Right Cessation
- 1974-10-15 IT IT2845474A patent/IT1022898B/en active
- 1974-10-16 CA CA211,513A patent/CA1038399A/en not_active Expired
- 1974-10-16 JP JP11832574A patent/JPS5644067B2/ja not_active Expired
- 1974-10-17 GB GB4501274A patent/GB1438878A/en not_active Expired
- 1974-10-17 FR FR7434950A patent/FR2248269B1/fr not_active Expired
- 1974-10-17 IN IN2306/CAL/74A patent/IN143126B/en unknown
- 1974-10-17 BE BE149637A patent/BE821194A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| DE2352059B2 (en) | 1975-08-21 |
| FR2248269B1 (en) | 1978-11-24 |
| DE2352059A1 (en) | 1975-04-24 |
| CH605719A5 (en) | 1978-10-13 |
| GB1438878A (en) | 1976-06-09 |
| JPS5644067B2 (en) | 1981-10-16 |
| BE821194A (en) | 1975-04-17 |
| IN143126B (en) | 1977-10-08 |
| IT1022898B (en) | 1978-04-20 |
| FR2248269A1 (en) | 1975-05-16 |
| JPS5064243A (en) | 1975-05-31 |
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