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US2867658A - Halo substituted sulfanilides - Google Patents

Halo substituted sulfanilides Download PDF

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US2867658A
US2867658A US657016A US65701657A US2867658A US 2867658 A US2867658 A US 2867658A US 657016 A US657016 A US 657016A US 65701657 A US65701657 A US 65701657A US 2867658 A US2867658 A US 2867658A
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parts
compound
formula
sulphamide
wool
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US657016A
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Wilhelm E Frick
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Novartis AG
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JR Geigy AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C307/00—Amides of sulfuric acids, i.e. compounds having singly-bound oxygen atoms of sulfate groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C307/02—Monoamides of sulfuric acids or esters thereof, e.g. sulfamic acids

Definitions

  • the sulphamide derivatives usable according to the present invention are new. They can be produced by methods known per se from known starting materials. A simple process consists in condensing, possibly in steps, suitably substituted amines with sulphuryl chloride. The condensation is performed advantageously in the presence of hydrochloric acid binding agents. Sulphamide can also be used instead of sulphuryl chloride and in this case, the condensation can be performed both in indifferent solvents or diluents as well as, possibly, in the melt. By condensing two different amines with sulphuryl chloride advantageously in two steps, unsymmetrically substituted sulphamides are'obtained.
  • a further method of production consists in alkylating halogenated N.N-diphenyl sulphamides of the general Formula II A HNSO --NHA (II) wherein A and A have the meanings given above.
  • the alkylation is performed advantageously in aqueous/ alkaline solution at a moderately raised temperature with sulphuric acid alkyl esters; naturally it can also be performed with alkyl halides.
  • the new compounds can be produced by halogenating N.N-diphenyl sulphamides.
  • the methyl, ethyl, propyl and butyl radicals are meant by alkyl groups and, for technical and economical reasons, chiefly chlorine is meant by halogen.
  • the phenyl radicals can contain other, advantageously non-ionogenic, substituents such as, e. g. alkyl, alkoxy and aryl ether groups, nitro and cyano groups.
  • substituents such as, e. g. alkyl, alkoxy and aryl ether groups, nitro and cyano groups.
  • Those compounds are particularly active insecticides in which the phenyl radicals are t'richlorinated.
  • Very particularly valuable compounds are the symmetrically formed compounds, in particular ,the ,N.N'-di-(trichlorophenyl)- sulphamides and the N.N-dimethyl and 'N.N'-diethyl derivatives thereof.
  • the sulphamide compounds usable according to the present invention are colourless to weakly yellowish'coloured powders or viscous liquids. They dissolve in the usual organic solvents. Insofar as they can form salts, i. e. when R or R represents hydrogen, the alkali salts are easily formed and are soluble in water. They are applied to keratin material from organic solution or from aqueous solution or suspension.
  • sulphamide derivatives can be applied from dyebaths, chiefly together with the so-called neutral to weakly acid-drawing dye'- stuffs.
  • a particularly favourable property of the sulphamide derivativesaccording to the present 'invention is that they draw on to keratin fibres even from relatively low temperatures (30 to 60) and are fast to washing and rubbing. This is a very valuable property as it enables the application to be made under conditions which protect the fibres.
  • the application however, is not limited to the use of aqueous solutions or suspensions.
  • organic solutions of the active substances e. g. in aliphatic or aromatic, possibly chlorinated, hydrocarbons which are used for dry cleaning of clothes, can be used to fix the agents on the keratin material.
  • the active substances can also be used in the form of dispersions or powders, possibly blended with carriers.
  • Example 1 0.4 g. of the monosodium salt of a compound of the formula
  • mQNH-sor-NHQm C F3 1 F3 are dissolved in 500 com. of water. 10 g. of wool are treated in this solution for 30 minutes at about 40. After rinsing, the wool is dried in the usual way and tested as to moth-proofness according to SNV (Swiss Association for Standardisation) Normenblatt 901. It is found to be mothproof.
  • the active substance used in this example can be produced, for example, in the following way:
  • Example 2 0.1 g. of N.N'-bis-(2.4.5-trichlorophenyl)-sulpharnide (melting point 8-160") in the form of the monosodium salt is dissolved in 2 litres of water and 50 g. of wool are treated for 30 minutes in this solution at 90. After rinsing and drying, on testing according to the SNV (Swiss Association for Standardisation) Normenblatt 95 901, the wool proves to be resistant to attack by moth larvae.
  • SNV Tins Association for Standardisation
  • the compound used in this example can be produced in a manner analogous to that described in Example 1 from 2.4.5-trichloraniline and sulphuryl chloride.
  • N.N-bis-(2.3.4-trichlorophenyl)-sulphamide is dissolved in a 10% concentration in ethanol. 1 part of this solution is diluted with 10 parts of a dry cleaning agent (e. g. white spirit) and the wool which is to be impregnated is treated with this solution. The material is then squeezed out to 100% of its weight and dried in the usual way.
  • a dry cleaning agent e. g. white spirit
  • the active substance used in this example can be produced analogously to the N.N'-bis-(3-trifluoromethyl-4- chlorophenyl)-sulphamide used in Example 1.
  • the pure compound melts at 146-148".
  • CH5 CH3 is dissolved in parts of alcohol and the solution is poured into a solution of 2 parts of sulphonated formyl castor oil in 5000 parts of water. The resulting suspension can be used for moth-proofing 100 parts of wool. The wool is treated by circulating it well for 1 hour at boiling temperature. It is then rinsed and dried. On testing the wool with larvae of T ineola biselliella, it was found to be proof to attack by these insects. The test was made according to the SNV (Swiss Association for Standardisation) Normenblatt 95 901.
  • Example 6 c1 01 I I @t tQ CzHs 02116 01 C1 are dissolved in 20 parts of methyl Cellosolve and the solution is diluted while stirring with a solution of 2.5 parts of sulphite waste liquor in 5000 parts of water, 50 parts of woolare treated in this liquor for 30 minutes at The wool is rinsed and driedin the usual way.
  • the material is moth-proof tested by the method given in Example 4. It proves to be resistant to attack by pests which are injurious to keratin material.
  • the compound used in this example is obtained by the method given in Example 4, the alkylating of the hexachlorodiphenyl sulphamide being performed with diethyl sulphate instead of with dimethyl sulphate.
  • the pure compound melts at 78-79".
  • This compound melts at 155-156. Applied in an amount of 1.5 parts according to the above example, it has a good moth-proofing efiect.
  • R represents a member selected from the group consisting of hydrogen and lower alkyl radicals
  • X represents a member selected from the group consisting of Cl, Br and CF;
  • n is one of the numerals 0 and 1.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Description

U StfltCS r HALO SUBSTITUTED SULFANILIDES Wilhelm E. Frick, Birsfelden, Switzerland, assignorto J. R. Geigy A.-G., Basel, Switzerland, a Swiss firm No Drawing. Application May 6, 1957 Serial No. 657,016
Claims priority, application Switzerland May 18, 1956 6 Claims. (Cl. 260-551) of the general Forwherein R and R represent hydrogen or low alkyl radicals and A and A -represent benzene radicals, possibly nonionogenically further substituted, which contain in all at least four halogen atoms,
have very good insecticidal activity. This is chiefly e'fiece tive against insects which injure keratin fibres such 'as moths, fur and carpet beetles, so that these compounds are valuable auxiliary agents, in particular in the textile industry.
The sulphamide derivatives usable according to the present invention are new. They can be produced by methods known per se from known starting materials. A simple process consists in condensing, possibly in steps, suitably substituted amines with sulphuryl chloride. The condensation is performed advantageously in the presence of hydrochloric acid binding agents. Sulphamide can also be used instead of sulphuryl chloride and in this case, the condensation can be performed both in indifferent solvents or diluents as well as, possibly, in the melt. By condensing two different amines with sulphuryl chloride advantageously in two steps, unsymmetrically substituted sulphamides are'obtained. A further method of production consists in alkylating halogenated N.N-diphenyl sulphamides of the general Formula II A HNSO --NHA (II) wherein A and A have the meanings given above. The alkylation is performed advantageously in aqueous/ alkaline solution at a moderately raised temperature with sulphuric acid alkyl esters; naturally it can also be performed with alkyl halides. Finally, the new compounds can be produced by halogenating N.N-diphenyl sulphamides.
In the compounds usable according to the present in: vention, in particular the methyl, ethyl, propyl and butyl radicals are meant by alkyl groups and, for technical and economical reasons, chiefly chlorine is meant by halogen. Apart from halogen atoms and trifluoromethyl groups, the phenyl radicals can contain other, advantageously non-ionogenic, substituents such as, e. g. alkyl, alkoxy and aryl ether groups, nitro and cyano groups. Those compounds are particularly active insecticides in which the phenyl radicals are t'richlorinated. Very particularly valuable compounds are the symmetrically formed compounds, in particular ,the ,N.N'-di-(trichlorophenyl)- sulphamides and the N.N-dimethyl and 'N.N'-diethyl derivatives thereof.
2,867,658 Patented J an, 6, 1959 ice The following are examples of amines of the benzene series corresponding to the formula ANH which are used as starting materials: 2.4-, 3.5- or 3.4-dichloroor dibromo l aminobenzene,.2.4.5- or 3.4.5 trichloro- 1- aminobenzene, 3-chloro-4-bromo-l-aminobenzene, 3-t1ifluoromethyl-l-aminobenzene, 3-trifiuoromethyl-4-chloro- 1 aminobenzene, 3,4 dichloro 6 methyl l amino: benzene and 4 trifluoromethyl 2.5 dichloro l aminobenzene.
The sulphamide compounds usable according to the present invention are colourless to weakly yellowish'coloured powders or viscous liquids. They dissolve in the usual organic solvents. Insofar as they can form salts, i. e. when R or R represents hydrogen, the alkali salts are easily formed and are soluble in water. They are applied to keratin material from organic solution or from aqueous solution or suspension.
They can be applied from dyebaths, chiefly together with the so-called neutral to weakly acid-drawing dye'- stuffs. A particularly favourable property of the sulphamide derivativesaccording to the present 'invention is that they draw on to keratin fibres even from relatively low temperatures (30 to 60) and are fast to washing and rubbing. This is a very valuable property as it enables the application to be made under conditions which protect the fibres. The application however, is not limited to the use of aqueous solutions or suspensions. Also organic solutions of the active substances, e. g. in aliphatic or aromatic, possibly chlorinated, hydrocarbons which are used for dry cleaning of clothes, can be used to fix the agents on the keratin material. Finally, the active substances can also be used in the form of dispersions or powders, possibly blended with carriers.
The following examples serve to illustrate the invention without limiting it in any way. In these examples parts are given as parts by weight and the temperatures are in degrees centigrade. The relationship of parts by weight to parts by volume is as that of kilogrammes to. litres.
Example 1 0.4 g. of the monosodium salt of a compound of the formula;
mQNH-sor-NHQm C F3 1 F3 are dissolved in 500 com. of water. 10 g. of wool are treated in this solution for 30 minutes at about 40. After rinsing, the wool is dried in the usual way and tested as to moth-proofness according to SNV (Swiss Association for Standardisation) Normenblatt 901. It is found to be mothproof. The active substance used in this example can be produced, for example, in the following way:
391 parts of 3-trifluoromethyl-4-chloraniline are dissolved in 500 parts of abs. pyridine and the solution is cooled to 5'. 134 parts of sulfuryl chloride are slowly added dropwise while stirring well so that the temperature does not exceed 0. After the dropwise addition of sulphuryl chloride, the reaction mixture is heated to room temperature and then allowed to stand for about 20 hours at this temperature. It is then diluted with chloroform and the pyridine is removed in the usual way by shaking out with diluted hydrochloric acid. The residue is washed with water and the chloroform is evap N.N'-bis-(3 trifiuoromethyl-4-chlorophenyl)-sulphamide melts at ll7-1l8.5. v The compound dissolves easily in diluted caustic soda lye and in mostorganic solvents except petroleum ether.
-A-similar -result is obtained if, in the above example, instead of 0.4 g. of N.N'-b is-(3-trifluoromethyl-4-chlorophenyl)-sulphamide, 1.0 g. of a compound of the formula:
is used.
Example 2 0.1 g. of N.N'-bis-(2.4.5-trichlorophenyl)-sulpharnide (melting point 8-160") in the form of the monosodium salt is dissolved in 2 litres of water and 50 g. of wool are treated for 30 minutes in this solution at 90. After rinsing and drying, on testing according to the SNV (Swiss Association for Standardisation) Normenblatt 95 901, the wool proves to be resistant to attack by moth larvae.
The compound used in this example can be produced in a manner analogous to that described in Example 1 from 2.4.5-trichloraniline and sulphuryl chloride.
An analogous result is obtained if, in this example, instead of N.N-bis-(2.4.5-trichlorophenyl)-sulphamide, 0.4 g. of N.N-bis-(2.4-dichloro-S-bromophenyl)-sulphamide of the formula:
01 n ClQNH-SOz-NHO-Cl I Br Br is used.
Example 3 The compound of the formula:
01 01 c1 01 I I C.ONH SO. NH C.
N.N-bis-(2.3.4-trichlorophenyl)-sulphamide, is dissolved in a 10% concentration in ethanol. 1 part of this solution is diluted with 10 parts of a dry cleaning agent (e. g. white spirit) and the wool which is to be impregnated is treated with this solution. The material is then squeezed out to 100% of its weight and dried in the usual way.
After testing according to the SNV (Swiss Association for Standardisation) Normenblatt 95 901 the wool is found to be moth proof.
The active substance used in this example can be produced analogously to the N.N'-bis-(3-trifluoromethyl-4- chlorophenyl)-sulphamide used in Example 1.
The pure compound melts at 146-148".
.A similar result is attained if in this example, instead Of a 10% solution of N.N-bis-(2.3.4-trichlorophenyl)- sulphamide in alcohol, a 30% solution of N.N-bis-(3.4 dichlorophenyl)-sulphamide in methyl Cellosolve is used.
Example 4 0.75 part of a compound of the formula:
" CH5 CH3 is dissolved in parts of alcohol and the solution is poured into a solution of 2 parts of sulphonated formyl castor oil in 5000 parts of water. The resulting suspension can be used for moth-proofing 100 parts of wool. The wool is treated by circulating it well for 1 hour at boiling temperature. It is then rinsed and dried. On testing the wool with larvae of T ineola biselliella, it was found to be proof to attack by these insects. The test Was made according to the SNV (Swiss Association for Standardisation) Normenblatt 95 901.
01 (I'll na-smmnQor can be produced are dissolved at about in 1200 parts of 2 N-caustic soda lye. 25 parts of dimethyl sulphate are added dropwise at this temperature. The solutionis kept continually alkaline by the gr-adual addition of caustic soda lye.
After cooling, the precipitate which is to some extent oily, is taken up in ether, theethereal solutioniswashed with caustic soda lye and Water, dried with sodium sulphate and concentrated. The residue is recrystallised from ligroin when it then has a melting point of 153- 154.
If in the above example, instead of the N.N'-dimethyl- N.N-di-(2.4.5-trichlorophenyl)-sulphamide, 1.2 parts of a compound of the formula:
. CH3 CH: 01 01 are used, then moth-proofed wool is also obtained. This compound can be produced in a completely analogous manner. It melts at 123-125 1 Example 5 10 parts of wool flannel are soaked in a solution of 20 parts of a compound of the formula:
C lQT-S 0 FT OIQN-SOq-NQQ 01 l l Cl can be used with the same result instead of that'used in the above example. It can be produced in an analogous manner.
1.2 parts of thecompound of the formula:
Example 6 c1 01 I I @t tQ CzHs 02116 01 C1 are dissolved in 20 parts of methyl Cellosolve and the solution is diluted while stirring with a solution of 2.5 parts of sulphite waste liquor in 5000 parts of water, 50 parts of woolare treated in this liquor for 30 minutes at The wool is rinsed and driedin the usual way.
The material is moth-proof tested by the method given in Example 4. It proves to be resistant to attack by pests which are injurious to keratin material.
The compound used in this example is obtained by the method given in Example 4, the alkylating of the hexachlorodiphenyl sulphamide being performed with diethyl sulphate instead of with dimethyl sulphate. The pure compound melts at 78-79".
A compound of the formula:
CIQN-SOz-NQ-Cl 1 01 p l l 1 CH: C H:
can be applied to wool in an analogous manner. This compound melts at 155-156. Applied in an amount of 1.5 parts according to the above example, it has a good moth-proofing efiect.
A compound of the formula:
t- FQ CH3 CH:
wherein R represents a member selected from the group consisting of hydrogen and lower alkyl radicals, X represents a member selected from the group consisting of Cl, Br and CF;,, and n is one of the numerals 0 and 1.
2. The insecticidal compound of the formula:
3. The insecticidal compound of the formula:
4. The insecticidal compound of the formula:
5. The insecticidal compound of the formula:
| t rc} 6. The insecticidal compound of the formula:
(31 C1 QQHMOCI 3H: (5
References Cited in the file of this patent Wohl et al.: Berichte, vol. 43, pp. 3295-3307 (1910). Audrieth et al.: Chem. Reviews, vol. 26, pp. -81 (1940).,

Claims (1)

1. AN INSECTICIDAL COMPOUND OF THE FORMULA:
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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3034955A (en) * 1957-09-10 1962-05-15 Geigy Ag J R Aryl sulphonamide insecticides
US3143558A (en) * 1960-01-06 1964-08-04 Schering Ag Aryl sulfonylthionylamides and derivatives thereof and methods of producing the same
US3143549A (en) * 1962-09-14 1964-08-04 Smith Kline French Lab Phenylalkylsulfamides
US3147305A (en) * 1962-09-14 1964-09-01 Smith Kline French Lab 2-phenylcyclopropylsulfamides
US3183257A (en) * 1962-04-20 1965-05-11 American Cyanamid Co Preparation of n-substituted phosphoramidothioates
US3230141A (en) * 1959-08-14 1966-01-18 Geigy Ag J R Method for protecting fibers against attack by insects and bacteria with diphenyl urea compositions
US3236842A (en) * 1961-07-26 1966-02-22 Bayer Ag N-trifluoromethylated sulphenamides and process for the production thereof
US3269898A (en) * 1961-08-25 1966-08-30 Bayer Ag Agents for protecting materials against textile pests
US4243418A (en) * 1976-06-25 1981-01-06 Ciba-Geigy Corporation Compositions for fireproofing polyester fiber materials with substituted sulphurylamides
WO2017036405A1 (en) * 2015-09-02 2017-03-09 陈昆锋 Compound having protein tyrosine phosphatase shp-1 agonist activity

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3034955A (en) * 1957-09-10 1962-05-15 Geigy Ag J R Aryl sulphonamide insecticides
US3230141A (en) * 1959-08-14 1966-01-18 Geigy Ag J R Method for protecting fibers against attack by insects and bacteria with diphenyl urea compositions
US3143558A (en) * 1960-01-06 1964-08-04 Schering Ag Aryl sulfonylthionylamides and derivatives thereof and methods of producing the same
US3236842A (en) * 1961-07-26 1966-02-22 Bayer Ag N-trifluoromethylated sulphenamides and process for the production thereof
US3269898A (en) * 1961-08-25 1966-08-30 Bayer Ag Agents for protecting materials against textile pests
US3183257A (en) * 1962-04-20 1965-05-11 American Cyanamid Co Preparation of n-substituted phosphoramidothioates
US3143549A (en) * 1962-09-14 1964-08-04 Smith Kline French Lab Phenylalkylsulfamides
US3147305A (en) * 1962-09-14 1964-09-01 Smith Kline French Lab 2-phenylcyclopropylsulfamides
US4243418A (en) * 1976-06-25 1981-01-06 Ciba-Geigy Corporation Compositions for fireproofing polyester fiber materials with substituted sulphurylamides
WO2017036405A1 (en) * 2015-09-02 2017-03-09 陈昆锋 Compound having protein tyrosine phosphatase shp-1 agonist activity
CN108026035A (en) * 2015-09-02 2018-05-11 陈昆锋 Compounds having protein tyrosine phosphatase SHP-1 agonist activity
US10745346B2 (en) 2015-09-02 2020-08-18 Kuen-Feng Chen Agonists of protein tyrosine phosphatase SHP-1

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