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GB2025954A - Anthraquinone Sulphonamides - Google Patents

Anthraquinone Sulphonamides Download PDF

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Publication number
GB2025954A
GB2025954A GB7922526A GB7922526A GB2025954A GB 2025954 A GB2025954 A GB 2025954A GB 7922526 A GB7922526 A GB 7922526A GB 7922526 A GB7922526 A GB 7922526A GB 2025954 A GB2025954 A GB 2025954A
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compound
disulphonamide
formula
hydrogen
bissulpho
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Novartis AG
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Ciba Geigy AG
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Priority to GB7922526A priority Critical patent/GB2025954A/en
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1493Selection of liquid materials for use as absorbents

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Compounds having the general formula: <IMAGE> where A is a C1-C4 straight or branched chain alkylene radical, B is a -SC3M, -CO2M, -PO3HM or -PO3M2 grouping, M is hydrogen, or a cation giving a water-soluble derivative, R is hydrogen, a cation giving a water-soluble derivative, or a C1-C4 straight or branched alkyl, R, is hydrogen, methyl or -COOH, and m is 0 or 1 and processes of preparing them.

Description

SPECIFICATION Chemical Compounds The present invention relates to novel anthraquinone sulphonamides and to processes of preparing them.
According to the present invention there is provided a compound having the general formula:
where A is a C1-C4 straight or branched chain alkylene radical, B is a -SO3M, -C02M, -P03HM or ~PO3M2 grouping, M is hydrogen, or a cation giving a water-soluble derivative, R is hydrogen, a cation giving a water-soluble derivative or a C1-C4 straight or branched chain alkyl, R1 is hydrogen, methyl or -COOH. and m is 0 or 1.
Where M or R is a cation giving a water-soluble derivative this is preferably an alkali metal for example sodium or potassium or an unsubstituted or substituted ammonium cation, for example, ammonium or optionally substituted C,--C, alkylammonium, examples of alkyl substituents being methyl, ethyl, propyl, butyl or mono-, di- or tri-hydroxyethyl.
Preferably B is a -SO3M grouping, Rr is hydrogen and M and R are hydrogen, sodium, potassium or ammonium.
More preferably R1 is hydrogen, M and R are hydrogen, sodium, potassium or ammonium and A is a C1-C4 straight chain alkylene radical.
Especially preferred compounds of those where R, is hydrogen, M and R are hydrogen, sodium, potassium or ammonium and A is methylene or ethylene and m is 1.
Non-limiting Examples of the compounds covered by the general formula I are as follows: Where m=O and R=Rt=H N-Sulphomethylanthraquinone#2-sulphonamide N-Sulpho-2-ethylanthraquinone-2-sulphonamide N-Sulpho-3-propylanthraquinone-2-sulphonamide N-Sulpho-4-butylanthraquinone-2-sulphonamide N-Sulpho( 1 , 1 -dimethylethyl)anthraquinone-2-sulphonamide Where m=0, R=C1~C4 alkyl and R=H N-Methyl-sulpho-methylanthraquinone-2-sulphonamide N-methyl-N-sulpho-2-ethylanthraquinone-2-sulphonamide N-methyl-N-sulpho-3-propylanthraquinone-2-sulphonamide N-Methyl-N-sulpho-4-butylanthraquinone-2-sulphonamide Where m=1, R=R1=H N,N'-Bissu lphomethylanthraquinone-1 ,5-disulphonamide N,N'-Bissulphomethylanthraquinone-1 ,6-disulphonamide N,N'-Bissulphomethylanthraquinone#1 ,7-disulphonamide N,N'-Bissulphomethylanthraquinone-2,6-disulphonamide N,N'-Bissulphomethylanthraquinone-.2,7-disulphonamide N,N'-Bissulpho-2-ethylanthraquinone-1 ,5-disulphonamide N,N'-Bissulpho.-2-ethylanthraquinone- 1 ,6-disulphonamide N,N'-Bissulpho-2-ethylanthraquinone-1 ,7-disulphonamide N,N'-Bissulpho#-ethylanthraquinone-2,6-disulphonamide N,N'-Bissulpho-2-ethylanthraquinone-2,7-disulphonamide N,N'-Bissulpho-3-propylanthraquinone- 1 ,5-disulphonamide N,N'-Bissulpho-3-propylanthraquinone- 1 ,6-disulphonamide N,N'-Bissulpho-3-propylanthraquinone-1 7-disulphonamide N,N'-Bissulpho-3-propylanthraquinone-2,6-disulphonamide N,N'-Bissulpho-3-propylanthraquinone-2,7-disulphonamide N,N'-Bissulpho-4-butylanthraquinone-1 ,5-disulphonamide N,N'-Bissulpho-4-butylanthraquinone-1 ,6-disulphonamide N,N'-Bissulpho-4-butylanthraquinone-1 ,7-disulphonamide N,N'-Bissulpho-4-butylanthraquinone-2,6-disulphonamide N,N'-Bissulpho-4-butylanthraquinone-2,7-disulphonamide N,N'-Bissulpho( 1,1 -dimethylethyl)anthraquinone-2,6-disulphonamide N,N'-Bissulpho( 1 , 1 -dimethylethyl)anthraquinone-2,7-disulphonamide where m=1, Fl=C1-C4 alkyl, R1=H N,N'-Dimethyl-N,N'-bissulphomethylanthraquinone-1 ,5-disulphonamide N,N'-Diethyl-N,N'-bissulphomethylanthraquinone-1 ,6-disulphonamide N,N'-Dipropyl-N,N'-bissulphomethylanthraquinone-1 ,7-disulphonamide N,N'-Dimethyl-N,N'-bissulphomethylanthraquinone-2,6-disulphonamide N,N'-Diethyl-N,N'-bissulphomethylanthraquinone-2,7-disulphonamide N,N'-Dimethyl-N,N'-bissulpho-2-ethylanthraquinone- 1,5-disulphonamide N,N'-Diethyl-N,N'-bissulpho-2-ethylanthraquinone-1 ,6-disulphonamide N.N'-Dimethyl-N,N'-bissulpho-2-ethylanthraquinone-2,6-disulphonamide N,N'-Diethyl-N,N'-bissulpho-2-ethylanthraquinone-2,7-disulphonamide N,N'-Diethyl-N,N'-bissulpho-3-propylanthraquinone-1 ,6-disulphonamide N,N'-Dipropyl-N,N'-bissulpho-3-propylanthraquinone-1,7-disulphonamide N,N'-Dimethyl-N,N'-bissulpho-3-propylanthraquinone-2,6-disulphonamide N,N'-Diethyl-N,N'-bissulpho-3-propylanthraquinone-2,7-disulphonamide N,N'-Diethyl-N,N'-bissulpho-4-butylanthraquinone-1,6-disulphonamide N,N'-Dipropyl-N,N'-bissulpho-4-butylanthraquinone-1,7-disulphonamide N,N'-Dimethyl-N,N'-bissulpho-4-butylanthraquinone-2,6-disulphonamide N,N'-Diethyl-N,N'-bissulpho-4-butylanthraquinone-2,7-disulphonamide or a compound corresponding to any of the above compounds, but where Bis--CO2H N,N'-Diethyl-N,N'-bissulpho-4-butylanthraquinone-2,7-disulphonamide or-PO3H2 instead of --SO,H or any mixture thereof.
Especially preferred compounds are: N,N'-Bissulphomethylanthraquinone-2,6-disulphonamide N,N'-Bissulphomethylanthraquinone-2,7-disulphonamide or a mixture of these compounds in any proportion N,N'-Bissulpho-2-ethylanthraquinone-2,6-disulphonamide N,N'-Bissulpho-2-ethylanthraquinone-2,7-disulphonamide or a mixture of these compounds in any proportion.
Further Examples of compounds of general formula I include the alkali metal or amine salts of any of the above compounds particularly the sodium, potassium or ammonium salts.
The compounds of formula I where R is H or C1-C4 straight or branched chain alkyl may be prepared by reacting the corresponding anthraquinone sulphonyl halide having the general formula
with a compound having the general formula
where X is halogen, especially chlorine, R2 is H or C1~C4 straight or branched chain alkyl and A, m, B and R1 have their previous significance.
The reaction may conveniently be carried out by adding the compound of formula Ill to a solution of the compound of formula II in a solvent system consisting of aqueous alkali and a water-soluble ether at less than 200C. The reaction time may vary depending on the circumstances but is conveniently from 1 to 12 hours. An example of a water-soluble ether is tetrahydrofuran.
The compound of formula 11 may be prepared by the method described by Kozlev et al., J. Gen.
Chem. Russ 1947, 17, 289.
The compounds of formula I where A is -CH2- may also be prepared by reacting the corresponding anthraquinone sulphonamide having the general formula
with a compound having the general formula HOCH2B V where m, B, R and R1 have their previous significance.
The reaction may conveniently be carried out by adding a compound of formula IV to a solution of a compound of formula V in water and heating at a temperature up to 10000. The reaction time may vary depending upon the circumstances but is conveniently from 1 to 12 hours. The temperature of the reaction is preferably from 6000 to 800C.
The compound of formula V where B is --SO,Na may conveniently be prepared from formaldehyde and sodium bisulphite in aqueous solution at 800 C. In this case the compound of formula I is normally prepared by adding the compound of formula IV to such a solution.
The compounds of formula IV may be prepared by the method described by Tr. Leningr. Khim Farmatseut. Inst., 1960, 11,48.
The compounds having the general formula I may be used as intermediates for dyestuff chemicals, agrochemicals or pharmaceuticals.
Also, the removal of hydrogen sulphide as sulphur from gases by the methods described in British Patent Specification 871,233 and 948,270 may be carried out but using the compounds of formula I in aqueous alkaline solution instead of the anthraquinone disulphonic acids there used, as described in our copending Application No. MA 1738 Div.
This invention also provides an aqueous alkaline solution of a compound of formula I which solution may contain a compound of a metal having at least two valency states for example a vanadium compound and if necessary a chelating or sequestering agent for retaining such metal compounds in solution. Such solutions are suitable for the absorption of hydrogen sulphide and converting it to sulphur. The vanadium compound may be an ortho-, meta-, or pyrovanadate of ammonia or of an alkali metal for example sodium ammonium vanadate or sodium orthovanadate.
Since the presence of chloride ions may lead to corrosion in the treatment plants for the removal of hydrogen sulphide as sulphur the method of preparing the compound of formula I by the reaction of compounds IV and V is advantageous in that it gives a product substantially free from chloride ions.
The following Examples further illustrate the present invention in which the anthraquinone sulphonyl chlorides and sulphonamides are prepared by the literature methods indicated above.
Example 1 76.9 Parts sodium formaldehyde bisulphite and 22.9 parts sodium hydroxide in 300 parts of water are charged into a 3-neck flask equipped with a stirrer, thermometer, condenser and the solution heated to 700. 105 parts of a 1:1 mixture of anthraquinone-2,6/2,7-disulphonamides are added portionwise and the resulting mixture heated at 700 during 3 hours. Evaporation of the resulting solution gives 171.4 parts of the dark brown tetrasodium N,N'-disulphonomethylanthraquinone2,6/2,7-disulphonamides having a melting point of > 3000 and the following analysis: 0,25.9; H, 2.2; N, 4.1; 5, 17.7; Na, 13.2; Cl-,0.1 S0,2-, 16.9% and a water content of 5.4%.
Example 2 4.4. Parts aminomethanesulphonic acid and 1.6 parts sodium hydroxide in 50 parts water and 150 parts tetrahydrofuran are charged into a 4-neck flask equipped with a stirrer, thermometer, condenser and pH electrode. 8 Parts anthraquinone-2,6-disulphonylchloride are added portionwise, the pH being maintained at 11.5 by the addition of 8N sodium hydroxide solution and the temperature at < 20 with ice cooling. Evaporation of the resulting solution gives 14.2 parts mustard coloured disodium N,N'-disulphonomethylanthraquinone-2,6-disulphonamide having melting point > 3000 and the following analysis: C, 24.1;H, 2.0; N, S,15.7; Na,15.8; Cl-,8.0 and S042#, 12.7%.
Example 3 10 Parts taurine and 3.2 parts sodium hydroxide in 100 parts water and 160 parts tetrahydrofuran are charged into a 4-neck flask as in Example 2. 1 6 Parts anthraquinone-2,6disulphonylchloride are added portionwise, the pH maintained at 12.5 with 8N sodium hydroxide solution and the temperature at < 200 with ice cooling. Evaporation of the resulting solution gives 34.5 parts of the brown disodiu m disodium N,N'-disulphonoethylanthraquinone-2,6-disulphonamide having a melting point > 3000 and the following analysis: C, 30.9; H, 2.6; N, 3.1; S, 16.7; Na, 7.4; Cl-,5.9 and So42-, 7.2%.
Example 4 4 4. Parts aminomethanesulphonic acid and 1.6 parts sodium hydroxide in 250 parts water are charged into a 4 neck flask as in Example 2. 8 Parts of a 1:1 mixture of anthraquinone-2,6/2,7disulphonylchloride are added portionwise. The pH is maintained at 11.8 with 8N sodium hydroxide solution during 1 5 hours or until a complete solution is obtained. Evaporation of this solution gives the brown tetrasodium N,N'-disulphonomethylanthraquinone-2,6/2,7-disulphonamides having a melting point > 3000 and the following analysis C,21.8; H, 1.7; N, 2.4; S,13.9; Na,19.8; CI-, 10.2 and S042#,21 21.2%.
Example 5 6.2 Parts taurine and 2 parts sodium hydroxide in 50 parts water and 34 parts tetrahydrofuran are charged into a 4-neck flask in Example 2. 10 Parts of a 1:1 mixture of anthraquinone-2,6/2,7disulphonylchlorides are added portionwise, the pH maintained at 13.1 with 8N sodium hydroxide solution and the temperature at < 200 with ice cooling. Evaporation of the resulting solution gives 21.3 parts of the brown-black tetrasodium N,N'-disulphonoethylanthraquinone-2,6/2,7-disulphonamides having a melting point > 3000 and the following analysis: C, 23.3; H, 2.6; N, 3.1; S, 14.4; Na, 14.7; CI-, 7.9 and S042-, 4.5%.
Example 6 6 Parts glycine and 3.2 parts sodium hydroxide in 100 parts water and 100 parts tetrahydrofuran are charged into a four-neck flask equipped with a stirrer, thermometer, condenser and pH electrode.
16 Parts of a 1:1 mixture of anthraquinone-2,6/2,7-disulphonylchlorides are added portionwise, the pH being maintained at 12.3 by the addition of 8N sodium hydroxide solution and the temperature at < 200 with ice cooling. Evaporation of the resulting solution gives 28.7 parts of the black tetra-sodium N,N'-dicarboxymethylanthraquinone-2,6/2,7-disulphonamides having a melting point of 2500 dec.
Example 7 4 Parts sodium formaldehyde bisulphite and 1.2 parts sodium hydroxide in 20 parts water are treated with 5.6 parts anthraquinone-2,7-disulphonamide as described in Example 1. Evaporation of the resulting solution gives 6.5 parts of the dark brown sodium salts of N,N'disulphonomethylanthraquinone-2,7-disulphonamide having a melting point > 2500 and the following analysis: C, 16.3; H, 2.3; N, 3.6; S,19.5; Na, 14.4; CI- < 0.1 and S042#, 14.0%.
Example 8 3.7 Parts sodium formaldehyde bisulphite and 1.1 parts sodium hydroxide in 20 parts water are treated with 5 parts anthraquinone-1 ,5-disulphonamide as described in Example 1. Evaporation of the resulting solution gives 6.5 parts of the black sodium salts of N,N'-disulphonomethylanthraquinone1 5-disulphonamide having a melting point > 3000 and the following analysis: C, 20.2; H, 2.1 ; N, 3.7; S, 18.2; Na, 15.5; CI-, 0.9; S042-, 16.9% and a water content of 8.2%.
Example 9 6.1 Parts sodium formaldehyde bisulphite and 1.8 parts sodium hydroxide in 40 parts water are treated with 8.4 parts of a mixture of anthraquinone-1 ,6/1 ,7-disulphonamides as described in Example 1. Evaporation of the resulting solution gives 1 5.1 parts of the black sodium salts of N,N'disulphonomethylanthraquinone-1 ,6/1 ,7-disulphonamides having a melting point > 3000 and the following analysis: C, 26.1; H, 2.1; N, 3.6; S, 1 7.99; Na, 13.3; Cl-, 0.4; S042-, 15.9% and a water content of 6.7%.
The use of potassium formaldehyde bisulphite in Examples 1 and 7 ta 9 and potassium hydroxide in Examples 2-6 would provide the corresponding tetrapotassium salts. Similarly, ammonium formaldehyde bisulphite and ammonium hydroxide would provide the tetra-ammonium salts.
We are aware of British Patent No. 465343 but we make no claim to any of the acid amides of the anthraquinone series per se disclosed therein.

Claims (23)

Claims:
1. A compound having the general formula:
wherein A is a C1-C4 straight or branched chain alkylene radical, B is a -S03M, -C02M, -P03HM or -P03M2 grouping, M is hydrogen or a cation giving a water-soluble derivative, R is hydrogen, a cation giving a water-soluble derivative or a C1-C4 straight or branched chain alkyl R, is hydrogen, methyl or-CO0H, and m is O or 1.
2. A compound as claimed in claim 1 in which B is a --SO,M grouping, R, is hydrogen and M and Rare hydrogen, an alkali metal or an unsubstituted or substituted ammonium cation.
3. A compound as claimed in Claim 1 or Claim 2 in which A is a C1-C4 straight chain alkylene radical.
4. A compound as claimed in any of the preceding claims in which A is methylene or ethylene and mist.
5. A compound as claimed in any of the preceding claims in which M and/or R is an alkali metal or amine salt.
6. A compound as claimed in any of the preceding claims in which M and/or R is sodium, potassium or ammonium.
7. N,N'-Bissulphomethylanthraquinone-2,6-disulphonamide.
8. N,N'-Bissulphomethylanthraquinone-2,7-disulphonamide.
9. A mixture of the compounds claimed in claim 7 and claim 8 in any proportion.
10. N,N'-Bissulpho-2-ethylanthraquinone-2,6-disulphonamide.
11. N,N'-Bissulpho-2-ethylanthraquinone-2,7-disulphonamide.
12. A mixture of the compounds claimed in claim 10 and claim 11 in any proportion.
13. A compound as claimed in Claim 1 substantially as described in any of Examples 1 to 9.
14. A process of preparing a compound of formula I defined in claim 1 which comprises reacting an anthraquinone sulphonyl halide having the general formula:
with a compound having the general formula:
where X is halogen, R2 is H or C1-C4 straight or branched chain alkyl, and A, m, B, and R1 are as defined in Claim 1.
15. A process as claimed in claim 14 in which X is chlorine.
1 6. A process of preparing a compound of formula I defined in Claim 1 where A is --CH,,- which comprises reacting an anthraquinone sulphonamide having the general formula
with a compound having the general formula HOCH2B V wherein m, B, R and R1 are as defined in Claim 1.
17. A process as claimed in Claim 1 6 in which and the compound of formula V is prepared from formaldehyde and sodium bisulphite in aqueous solution at 700 C, the compound of formula IV being added to this solution.
18.A process as claimed in claim 14 substantially as described in any of Examples 2 to 6.
19. A process as claimed in Claim 1 6, substantially as described in any of Examples 1 and 7 to 9.
20. A compound of formula I whenever prepared by a process as claimed in any of Claims 14 to 19.
21. An aqueous alkaline solution of a compound claimed in any of Claims 1 to 13 and 20.
22. An aqueous alkaline solution as claimed in claim 21 containing a compound of a metal having at least two valency states and, if necessary, a chelating or sequestering agent for retaining such metal compounds in solution.
23. An aqueous alkaline solution as claimed in claim 22 in which the compound of a metal having at least two valency states is ortho-, meta-, or pyrovanadate of ammonia or an alkali metal.
GB7922526A 1978-07-21 1979-06-28 Anthraquinone Sulphonamides Withdrawn GB2025954A (en)

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GB7922526A GB2025954A (en) 1978-07-21 1979-06-28 Anthraquinone Sulphonamides

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997000675A1 (en) * 1995-06-23 1997-01-09 Boonville Limited Mono- and disulfo-substituted anthraquinones and their use for the treatment of bone matrix disorders
WO2002064680A1 (en) * 2001-02-10 2002-08-22 Clariant Gmbh Acid pigment dispersants and pigment preparations
EA030302B1 (en) * 2008-11-21 2018-07-31 Форест Лэборетериз Холдингз Лимитед Anthraquinone dioximes and use thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997000675A1 (en) * 1995-06-23 1997-01-09 Boonville Limited Mono- and disulfo-substituted anthraquinones and their use for the treatment of bone matrix disorders
US5856358A (en) * 1995-06-23 1999-01-05 Boonville Limited Mono- and disulfo-substituted anthraquinones and their use for the treatment of bone matrix disorders
RU2202534C2 (en) * 1995-06-23 2003-04-20 Эйч-Ген Би.В. Mono- and disulfosabstituted anthraquinones and their application for treatment of osseous matrix lesion
WO2002064680A1 (en) * 2001-02-10 2002-08-22 Clariant Gmbh Acid pigment dispersants and pigment preparations
US6918958B2 (en) 2001-02-10 2005-07-19 Clariant Gmbh Acid pigment dispersants and pigment preparations
EA030302B1 (en) * 2008-11-21 2018-07-31 Форест Лэборетериз Холдингз Лимитед Anthraquinone dioximes and use thereof

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