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Publication numberUS2314846 A
Publication typeGrant
Publication dateMar 23, 1943
Filing dateDec 24, 1940
Priority dateDec 24, 1940
Publication numberUS 2314846 A, US 2314846A, US-A-2314846, US2314846 A, US2314846A
InventorsJack C Bacon, Paul P Mcclellan
Original AssigneeAmerican Cyanamid Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Sulpho esters of cis-endomethylene-3, 6-delta 4-tetrahydrophthalic acid
US 2314846 A
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Description  (OCR text may contain errors)

Patented Mar. 23, 1943 SULPHO ESTERS F CIS-ENDOMETHYLENE- 35-.A9-TETRAHYDROPHTHALIC ACID Paul P. McClellan, Old Greenwich, and Jack c.

Bacon, Stamford, Conn., assignors to American Cyanamid Company, New York, N. Y., a corporation of Maine No Drawing. Application December 24, 1940, Serial No. 371,594

14 Claims.

This invention relates to a new class of esters of cis endomethylene 3,6 sulpho hexahydrophthalic acid which have been found to possess wetting, emulsifying and detergent properties and to methods of making the same.

We have found that it is possible to sulphonate the mono-, diand mixed esters of cis-endomethylene-3,6-A -tetrahydrophtha1ic acid and its anhydride at the double bond position in the ring, although there are no adjacent activating groups, by means of sulphites and bisulphites under appropriate conditions which will be described hereinafter.

The sulphonated esters of cis-endomethylene- 3,6-A -tetrahydrophthalic acid are particularly valuable principally on account of their wetting and detergent properties. As stated above the mono-, dior mixed esters may be sulphonated. Those esters prepared from alcohols of 3 to 8 carbon atoms when sulphonated posses marked wetting properties, the wetting power generally increasing with the length of the alcohol chain. The sulphonated esters prepared from longer chain alcohols, such as lauryl, have more pronounced detergent and foaming qualities. The monobutyl, mono-octyl, monolauryl. monocetyl, dibutyl, diamyl, dioctyl and dilauryl esters may be sulphonated according to the procedure described below and are representative of the entire class of wetting and detergent compoundsvof the invention.

Ourinvention enables us to prepare all alkyl,

aryl or alkyl-aryl diesters of sulphonated cis-em domethylene-3,6-A -tetrahydrophthalic acid and its metallic, ammonium or organic salts; the diesters of partially esterified polyhydric alcohols of the sulphonated acid and its salts; alkyl or aryl monoesters of the sulphonated acid and its salts; and half-esters of partially esterified (alkyl or aryl) polyhydn'c alcohols of the sulphonated acid and its salts. In addition to the preparation of esters, this invention also permits us to prepare the alkyl, aryl or mixed (alkyl-aryl) diamides of the sulphonated acid and their metallic, ammonium or organic base salts; alkyl or aryl monoamides of the sulphonated acid and metallic, ammonium or organic base salts; alkyl or aryl substitut'ed imides and the metallic, ammonium or organic base salts thereof; mixed amides (alkyl,

'arylor alkyl-aryl) and esters (alkyl or aryl) of the sulphonated acid. These various compounds are illustrated by the following general structural in-which R. represents an alkyl or aryl radical, R

H, NH4 or ametal or organic base radical.

The compounds prepared in this manner have wetting and detergent properties which make them'useful in wetting, detergent, dispersing, vemulsifying and foaming processes; in processing I and in improving textiles; in the preparation of sizing compositions; in dye assistants; in the filling assistants; in waxes and polishes; shampoos; dentifrices; in the paper industry as penetrants for cooking pulp and the like; in latex star FlCE bili'zatiom' for prevention or pelting inelectro- Pl ting} in pigment dispersion for grinding; in/

- cosmetic creams: insecticide and tun'sicide sprays:

and to the; oifpetroleum emulsio f han v I v y julphonating' the: esters, cis-endon ethylene-3,6-A4- potassium" (in-ammonium salts. A mixture of the j ester, amide I or imide to. be sulphonated, a

n solvent such as ethyl alcohol and water or water. alone,and the desired sulphite;or bisulphite, are -fheated in a vesselfltted'with a reflux condenser t l the x iflphq ii i omp e- "cases-it maybe morepractical tojchargethe ve's- InIJsonie sel with the'ester; amideor'imide and anaqueous or'alcoholicsolution of an alkali and addSOz tothe mixture as the reaction proceeds. a

' The sulphonation of the diester' of .cisendomethylenee3,6- -tetrahydrophthalic acid "may,

,. be illustrated with the following reaction equa- The sulphonation of the monoesters with sodium sulphite is believed to be as follows:

It is not definitely known whether the NaSOagroup takes the 4 or 5 position in-the ring or whether a'mixture, is obtained. It is' probable that in most cases a mixture of.4-sulpho and 5sulpho acids is obtained but'we wish it understood, however, that we intend to cover both possibilities in the appended claims. v

The sulphonates prepared according to the above equations may if desired be hydrolyzed with dilute acids to yield the corresponding sulphonic acids. a I I An alternative method of preparing our new class .of compounds is to react cls-endomethylene-3,6-A tetrahydrophthalic acid or its "an hydride with a solutionof caustic soda to obi-"in the disodium salt. This may besulphonatsd by reacting with sodium bisulphite to yield a come our new class of 'sulpho j out the bisulphites.

' pound having the following structural formula which may be hydrolyzed with dilute acids and x then esterifled with a desired alcohol to yield the sulphonic acid ester of cis-endomethylene- 3,6-A tetrahydrophthalic acid.

Specific examples will now be given to illustrai'e' in greater detaii the preparation of esters and half-esters of cis-endomethylene-3,6-A-

tetrahydrophthalic acid and the subsequent sulphonation procedures using both sulphites and It should be understood that the invention is not limited to these particular examples which are given by way of illustration and not of limitation.

Ermmple 1 d 16.4 parts of cis-endomethylene-3,6-A -tetrahydrophthalic anhydride and 81 parts of n-butyl alcohol were heated under a reflux condenser for 4 hours and the unreacted butanol then distilled off. The solid half-ester from this process when washed with n-hexane was found to have an acid numbervery nearly that of the calculated value. 1

5.7 parts of the'halI-ester prepared above was sulp'nonated by refluxing for 20 hours in 30 parts of water and 4''! parts of ethyl alcohol containing 3.1 parts of sodium sulphite. The excess sodium;

sulphite was filtered off and the solution evaporated to dryness. A white, water-soluble powder wasobtained which was believed to be disodium n-butyl cis-endomethylene-3,6-sulpho-4-hexahydrophthalate with the probable structural Example 2 33 parts of cis-endomethylene-3,6-A-tetrahydrophthalic anhydride, 162 parts of n-butyl alcohol and 1 part of toluene sulphonic acid as catalyst were heated in a vessel equipped with' a reflux condenser and water collector. When the acid number of the reaction mixture had dropped to a very low value the unreacted butanol was removed by distillation under reduced pressure.

47 parts ethyl alcohol. A clear solution was obtained. This solution upon drying gave a yellow resinous material which was ground to a white, hygroscopic powder analyzing 48.35% carbon,

6.93% hydrogen, and 7.91% sulphur which corresponds closely to the expected values calculated from di-n-butyl-sodium sulpho-4-cls-endometh The ester was then distilled oil. A- yield of a pale yellow liquid boiling at ylens-3,6-hexahydrophthalate of the probable structural formulat H 3. Naois-c H o-d-c.n.

Example 3 17.2 parts cis-endomethylene-3,6-A -tetrahydrophthalic anhydride, 106 parts active amyl alcohol and 0.25 part H2804 were heated at about 130135 C. for 4 hours, under a reflux con denser fitted with a water collector. At the end of this time the reaction was practically complete as indicated by the acid number of the reaction mixture and the amount of water collected in the water collector. The crude ester-alcohol mixture was washed with dilute NazCOs followed by water until no longer alkaline and then the water and alcohol were removed by distilling under reduced pressure. An 82% yield of the diamyl ester of cis-endomethylene-3,6-A -tetrahydrophthalic anhydride was obtained.

11.0 parts of the diamyl ester thus prepared were sulphonated by adding to it 3.3 parts sodium bisulphite in 47 parts ethyl alcohol and 30 parts water and refluxing for 48 hours. A sticky yellowish product of good wetting properties was obtained. On analysis it was found to contain 51.07% carbon, 7.33% hydrogen and 7.14% sulphur which corresponds closely to the expected value calculated from diamyl cis-endomethylene- 3,6-sodium sulpho-4-hexahydrophthalate.

Example. 4

16.4 parts cis-endomethylene-3,S-A -tetrahy drophthalic anhydride and 13 parts Z-ethyl hexyl alcohol were heated together at 130 C. for 2 hours. The reaction mixture was allowed to cool and unreacted anhydride was filtered oil. The 2- ethyl hexyl half-ester of cis-endomethylene-3,6-

n -tetrahydrophthalic anhydride was obtained as -a yellow oily liquid.

13 parts of the octyl half-ester thus prepared were sulphonated with 7.6 parts'sodiurn bisulphite dissolved in 47 parts ethyl alcohol and 30 parts water by refluxing for 30 hours. Upon removal'of the solvent by evaporation disodium mono-octyl cisendomethylene 3,6 sulpho-- hexahydrophthalate was obtained. 7

What we claim is;

1. An ester of sulphonated cis-endomethylenemethylene 3,6 M-tetrahydrophthalic acid in which the e'sterifying alkyl groups contain at least 3 carbon atoms.

4. A monoalkyl ester of sulphonated cis-endomethylene 3,6 M-tetrahydrophthalic acid in which the esterifying alkyl group contains at least 3 carbon atoms.

5. Disodium vmono-octyl cis-endomethylene- 3,( 5 sulpho-1-hexahydrophthalate.

6. Disodium mono-n-butyl ci's-endomethylene- 3,6-sulpho-4-hexahydrophthalate.

7. Diamyl cis-endomethylene-3,6-sodium sulpho'-4-hexahydrophthalate.

8. A process for the production of sulphonated esters of cis-endomethylene-3,6-A -tetrahydrophthalic acid which comprises heating esters of cis-endomethylene 3,6 A tetrahydrophthalic acid with a member of the group consisting of water-soluble sulphite and bisulphite salts.

9. A process for the production of sulphonated alkyl esters of cis-endomethylene-3,6-A-tetrahydrophthalic acid which comprises heating alkyl esters of cis-endomethylene-3,6-A -tetrahydrophthalic acid with a member of the group consisting of water-soluble sulphite and bisulphite salts.

10. A process for the production of sulphonated dialkyl esters of cis-endomethylene-3,-6-A -tetrahydrophthalic acid which comprises heating dialkyl esters of cis-endomethylene-3,6-A -tetrahydrophthalic acid with a water-soluble bisulphite.

11. A process for the production of sulphonated monoalkyl esters of cis-endomethylene-3,6-A tetrahydrophthalic acid which comprises heating monoalkyl esters of cis-endomethylene-3,6-A tetrahydrophthalic acid with a water-soluble sulphite.

12. A process for the production of disodium mono-octyl cis-endomethylene 3,6 sulpho 4- hexahydrophthalate which comprises heating the mono-octyl ester of cis-endomethylene-3,6-A tetrahydrophthaiic acid with a water-soluble sodium sulphite.

13. A process for the production of disodiummono-n-butyl-cis-endomethylene-3,6 p-sulpho 4- hexahydrophthalate which comprises heating the mono-n-butyl ester of cis-endomethylene-3,6-A tetrahydrophthalic acid with a water-soluble sodium sulphite.

14. A process for the production of diamyl-cis endomethylene-3,6-sodium-sulpho- 4-hexahydrophthaiate which comprises heating the diamyl ester of cis-endomethylene-3,6-A -tetrahydrcphthalic acid with a water-soluble sodium bisulphite.

\ PAUL P. MCCLELLAN.

JACK C. BACON.

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US2471790 *Apr 26, 1945May 31, 1949SowaInsect-affecting compositions
US2514564 *Nov 14, 1947Jul 11, 1950Hercules Powder Co LtdChlorinated terpene sulfone and insecticidal composition containing same
US2545283 *Oct 10, 1945Mar 13, 1951Du PontTertiary diacyl amine insecticides
US2551575 *Oct 12, 1946May 8, 1951Publicker Ind IncEsters of sulfo-4-cyclohexene-1, 2-dicarboxylic acid and process for producing same
US3000864 *Apr 4, 1958Sep 19, 1961Eastman Kodak CoHydroxynorcamphanecarboxylic acids and esters, and polyesters thereof
US3062898 *May 8, 1959Nov 6, 1962Hooker Chemical CorpPreparation of 1, 2, 3, 4, 5, 6, 7, 7-octachloro-2-methylbicyclo-(2.2.1)-heptene-5
US3221066 *May 8, 1959Nov 30, 1965Hooker Chemical CorpDehydrochlorination of polychloro chloromethylbicycloheptenes
US3299094 *Aug 2, 1965Jan 17, 1967Hooker Chemical CorpEsters, amides, and imides of octachloro-3, 6-methano-1, 2, 3, 6-tetrahydrophthalic anhydride
US3870533 *Nov 26, 1973Mar 11, 1975Nippon Zeon CoHydraulic composition
US4144244 *Dec 27, 1977Mar 13, 1979Ciba-Geigy CorporationIntermediates for surfactants
Classifications
U.S. Classification560/14, 548/435, 562/100
International ClassificationD21C3/22, C07D209/76, C10G33/04
Cooperative ClassificationC07C309/00, C07D209/76, C10G33/04, D21C3/222
European ClassificationC07C309/00, C10G33/04, C07D209/76, D21C3/22B