US3345378A - N-(decachloro-3-hydroxypentacyclo (5, 3, 0, 02, 6. 04, 10. 05, 9) decyl-3) amides and carbamate esters - Google Patents

Description

United States Patent N (DECACHLORO, .3 IIYDROXYPENTACYCLO (5,3 0,0 -0% -0 )DECYL-3) AMIDES AND CAR- BAMATE' ESTERS i t Y Edward D. Weil, Lewiston, and Keith J.. Smith, Lockport, N.Y., assignors to Hooker Chemical Corpogitiogn, Niagara Falls, N.Y., a corporation or New or Y N0 Drawing. Filed Nov. 30, 1965, Ser. No; 510,680

I Claims. (Cl. 260-326) r This is a 'co'ntinuationdn-part of my copending application Ser. No. 97,771, filed March 23, 1961, now US. Patent 3,281,453. I I 1 v This invention concerns novel pentacyclic compositions of matter useful as toxicants and intermediates for organic synthesis. More particularly, this invention describes a new class of compounds, N-(decachloro-3-hydroxypentacyclo(5.3.0.0 .0 .0 decyl-3) amides, which because of their apparent toxicity or repulsion toward lower forms ,of marine life such as barnacles, function effectively as marine fouling retardants. The. scope of the present invention encompasses the compounds Withirithe generic formula below (numbering of the positions is shown) of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, R is a member selected from the group consisting of hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, amino, substituted amino, alkoxy, and aryloxy, X is an element selected from the group consisting of sulfur and oxygen, oxygen being preferred for reasons of cost and, generally, stability. i

The group R or R may be of high molecular weight and either or both may in fact represent macromolecular chains; and the compositions of the invention may, therefore, be macromolecular (polymeric) substances as wel as lower molecular weight substances.

For the sake of simplicity the below portion of the generic formula given previously will be referred to as 10 10( 3,345,378 Patented Oct. 3, 1967 CmClMOHi-NHC ONH,

CO-GH cmchowm-n C O 0 H2 011,011, mammoth-N cH,

' coorncn,

and related structures.

In the latter five structures at represents the degree of polymerization, greater than one and with no upper limit. These macromolecular products of the invention may be made by the same general process as the lower molecular weight products, and are characterized by the same type of anti-fouling activity, while at the same time retaining certain of the desirable physical properties of the parent macromolecular compound, such as the ability to form films. Being resins, these products may serve not only as anti-fouling components 'of'marine paints but also as filmforming or film-reinforcing ingredients.

The foregoing list oflcompounds is merely intended to be illustrative of the scope of this invention and is not in any sense intended to limit or define the invention.

While the causes of marine fouling are presently obscure, its effect on economic and military affairs is readily apparent. It is estimated that the cost of preventing, slowing down and treating marine fouling runs into millions of dollars annually, and no satisfactory solution is in sight. For example, the efficiency and the period of use of a pier, ship, boat, buoy or marine structure is greatly reduced unless some prophylactic treatment is followed. Ships which have become encrusted with marine organisms lose a substantial part of their normal speed and mechanical efliciency. Furthermore, many ships and marine structures such as bulkheads, buoys, off-shore radar towers and oil drilling rigs and platforms once fouled are much more prone to become corroded or rotted. For this reason, an extensive and costly program of prophylaxis and maintenance is followed in an effort to cut down the even more expensive deleterious effects of the marine fouling.

The most common method of reducing the amount of the shell-like encrustation built up by the lower forms of marine life such as barnacles or other lower marine creatures is to paint the material to be protected with a special copper oxide based paint. However, the amount of copper oxide required adversely effects the physical characteristics of the paint and its normal life is reduced. In addition, the presence of a large quantity of copper oxide on a metal boat or ship will eventually create an electrolytic cell which greatly accelerates the tendency toward corrosion. To prevent this electrolytic corrosion the surface must first be covered by an additional and expensive coat of paint to insulate the copper oxide from the hull. But even when so protected, the hull of any ship or boat must be routinely scraped to remove the fouled surface which forms though albeit more slowly. Obviously too, this is expensive, since in addition to requiring costly and time-consuming dry-docking, scraping and repainting, the ship is removed from profitable use. For the above reasons, it can readily be seen that the discovery of compounds possessing anti-marine fouling properties at low concentrations is of extreme commercial and naval importance. While the mechanism by which the compounds of this invention retard marine fouling is not understood, it has been found that these compounds function well at economically feasible concentrations, are non-corrosive in themselves and being readily compatible with the oils, bases and adjuvants commonly used in points can readily be formulated in marine paints and coatings in general.

While the compounds of this invention are advantageous as anti-marine fouling agents, they possess in addition other important advantages. For example, the novel compositions of this invention are useful as fire retardants and mildew retardants when formulated in organic coatlIlgS.

In addition, these compositions may be used as intermediates in the preparation of other anti-fouling compositions. Thus, when is produced. This compound also has activity as a marine anti-fouling substance.

A related but ancillary advantage that the compounds of this invention possess generally is that they are valuable intermediates for organic synthesis, in that the reactive and free OH group may be further replaced by NRC(=X)R where R, R and X have the same meaning as previously defined.

A further attribute that these compounds possess as synthetic intermediates is that in many instances they form complex addition compounds with water, amines, and even with additional moles of amide beyond the stoichiometrically combined amount. This characteristic is believed to be due to the ability of the OH group to form a hydrogen bond with an electron-rich atom, particularly with a divalent oxygen atom or a trivalent nitrogen atom. For example, the product C Cl (OH) NHCHO when dissolved in an excess of formamide, and the solution then poured into water, forms a more or less hydrated solid complex approximating to A further characteristic of the .new compounds of the invention is that they have weak acidic properties, per.- haps due to the --OH group butalso in some cases perhaps due to the NHCO- group. Regardless of the theoretical reasons, it has empirically been found that strong bases such as sodium methoxide, hydroxide, and the like can form salts with the compounds of the invention. Since the above mentioned salts and complexes can revert to the parent compounds of the invention, they constitute usable formulations for the purposes of antifouling coatings, a fact which we have impiri-cally con- The novel compoupnds of thisinvention may be prepared by reacting hexachlorocyclopentadiene with chlorosulfonic acid, then heating the intermediate that forms in an appropriate solvent with atleast one molar equivalent of an amide or trioamide of the structure NHRC(=X)R'. The amide NHR(C=X)R' may be added at the beginning of the heating, graduallyduring the heating, or after the heating has commenced for several hours. The rate and order of addition has not been foundv to be a critical feature of our process. It has also been found possible to employ polymeric compounds having a free and reactive structure NHRC(=X)R' as reactants, for example, proteins, nylon, partially or fully hydrolyzed acrylonitrile polymers or coploymers and the polyurethanes. Starting with macromolecular amides, macromolecular products are obtained. -Itis not necessary to use a solvent for the reaction when the amide NHRC(=X)R' is a. liquid or low melting solid, but where the amide is,not easily fused, a solvent is convenient. Appropriate solvents include but are not limited to chlorinated hydrocarbons, such as chlorobenzene or acetylene tetra chloride, aliphatic and aromatic compounds such asv cyclohexane, xylene or toluene; ketones such as methyl ethyl and methyl propyl ketone, ethers such as diethyl, dipropyl, isobutyl, nitrohydrocar-bons such as the nitrobenzen'es, esters such as the lower alkyl acetates, N,N-diall sylamides such as dimethylformamide and acids such as formic acid. Where the NHRC(=X)R' is a liquid the solvent may be dispensed with using an excessof the amide or thioamide instead. The temperatures needed to initiate and continue this reaction are not critical and vary considerably according to the reactants used. However, the extremes have been found to be from about zero degrees centigrade to two hundred degrees centrigrade with a satisfactory range generally being between twenty degrees and one hundred and seventy-five degrees centrigrade. Similarly, the time for the reaction to become compelte, as measured by infra-red analysis, varies according to several factors such as temperature and reactants. Many reactions are completed in less than an hour, but others ocasionally take as long as a day. The reaction may also be followed by checking the rate of S which is evolved, the reaction being halted when theflow of S0 has substantially ceased. A variation of the above process'is to use a nitrile or imide capable of being hydrolyzed to the desired amide NHR(( =X)R plus at least the stoichiometric quantity of water required for said hydrolysis, the hydrolysis being run concurrently with the reaction of the invention. The structures of the products are proved by elemental analysis by infra-red spectra which shows the OH group absorption and the characteristic amide C=O or thioamide C=Sbands1 The presence of the pentacyclo (5.3.00 .0 .0 decane skeleton is proved byfu'si'o'n with several parts byw'eight of PCl in a sealed tube at elevated temperatures, which yields the known dodecachloropentacyclo-(5.3.0.0 .0 .0 decane, melting point four hundred and eighty-five degrees. Amore detailed discussion of the process and compositions produced is presented in the examples which follow. 4

Example 1.Preparati0n of C Cl (OH) (NHCOCH Hexachlorocyclopentadiene is reacted with chlorosulfonic acid as disclosed in US. Patent 2,516,404, an intermediate (described in said patent asC 'H O SCl isformed which has a melting point. of'oue hundred, and forty-six to one hundred and forty-eight degrees centigrade. This intermediate is a definite chemical'entity of. melting point one hundred and forty-six to one hundredandforty-seven degrees and having a chlorine content M67 .8 percent and sulfur content of 5.09. percent. Because of its high molecular weight (six hundred andeleventosix hundred and thirty-nine) and difiicult. combustibility, the number of hydrogenatoms in, the molecule is in doubt, and consequently its exact structure is uncertain. A solution of 62.8 parts by weight of this compound and 5.9 parts by weight of acetamide in one hundred and seventy-six parts by weight of xylene is refluxed for six hours until evolution of SO had substantially dwindled. The solution is concentrated and the resultant crystalline product removed by filtration and dried in air. An infrared spectrum showed the compound to have an OH group, an NH group, an amide C=O group, and a'methyl group.

Anzlysis.Calcd. for C10C110(OH) Cl, 64.5; N, 2.5. Found; Cl, 63.5; N, 2.5.

Upon heating the product for twenty four hours at three hundred degrees centigrade with an excess of phosphorus pentachloride in -a sealed tube, and evaporating the reaction mixture under vacuum at one hundred degrees centigrade, the volatile substances are removed leaving a crystalline substance which upon recrystallization, melts at four hundred and eighty-five degrees centigrade, which is the melting point of the expected and known derivative d-odecachloropentacyclo;(5;3.0.0. .0 .0 decane, and has the correct percentage of chlorine for C Cl Example 2. Pr-epar ation of C C1 (OH) (NHCHO) NH CHO hydrate One part by weight of the intermediate chlorosulfonation product of Example 1 melting at one hundred and forty-six to one hundred and forty-eight degrees centigrade is dissolved in ten parts by weight of formamide at one hundred degrees centigrade. After twenty-four hours at this temperature, the reaction mixture is cooled and poured into distilled waterpThecolorless crystalline product which precipitates out, is filtered ofi" and air dried. Infra-red analysis shows the presence of the desired OH, NH andv amide C=.O groups,- as well as an additional shoulder in the carbonyl region.

Analysis.Calcd. for

- CmCl (OH) (NHCHO) .NHCHQH O 01, 59.7; N, 4.7. Found: 01, 60.7; N, 4.5

Example 3.Prpdriztion of O1oClio(OH) (No 0 oij g'ncmomc om expect for the desired product.

Found: N, 3.6; 01,- 48.6.

Example 4.-Preparati0n a) C Cl (OH) (NHCOC H In two hundred and sixty-four parts of Xylene, 12.1 parts by weight of benzamide is reacted with 62.8 parts by weight of the crystalline C Cl /ClSO H product, melting at onehundred and forty-six to one hundred and forty-eight degrees. After four hours, the S0 evolution dwindles. On partial evaporation of the xylene and cool- 7 ing, a colorless crystalline product is obtained whose infra-red spectrum showed OH, -NH and amide C=O groups as well as C=C double bond vibrations characteristic of an aromatic ring.

Analysis.Calcd. for C Cl (OH) (NHCOC H Cl, 58.0; N, 2.3. Found: Cl, 57.9; N, 2.3.

It is found possible to titrate the product in acetone solution using tetrabutylamrnonium hydroxide (0.1N) as the base. The end point occurs at the point where one molar equivalent of the base is added, showing that the C Cl (OH)N-HCOC H is a monobasic acid.

Example 5.Preparation f C CI (OH)NHCOC H A mixture of 62.2 parts of octadecylamide (ten percent molar excess), one hundred and twenty-five parts of the crystalline product of hexachlorocyclopentadiene and chlorosulfonic acid, and two hundred and twenty parts of dry xylene are heated at reflux for one day, until S0 evolution dwindled. The xylene is evaporated under wateraspirator vacuum and the waxy residue recrystallized from heptane and a white waxy solid is obtained, melting point seventy to seventy-five degrees.

Analysis.Calcd. for C H O NCl N, 1.8. Found: N, 1.9.

Example 6.--Prepalration of As above, using 61.8 parts of oleamide (ten percent molar excess). The residue on evaporation of the xylene is a liquid andcannot be induced to crystallize. v

The infra-red spectrum confirmed that the product has the structure.

Example 7.Preparati0n of A mixture of 62.8 {parts of the crystalline reaction prodnet of C Cl and ClSOgH is heated with 13.5 parts of acetanilide in one hundred and eighty parts of xylene at reflux for six hours, until S0 evolution dwindles. Cooling to room temperature gives a crystalline precipitate, 30.5 parts by weight. Its infra-red spectrum shows the characteristic amide carbonyl band at six microns.

Analysis.-Calcd. for C Cl (OH)N(COCH )C H Cl, 56.7. Found: Cl, 57.9.

Example 8.'Preparation 0f C Cl (OH)NI-ICHO A mixture of 31.3 parts of the crystalline reaction product of C Cl and C1SO H in one hundred and seventysix parts of xylene, mother liquor from a previous preparation of C Cl (OH)NHCHO, is refluxed for several hours, then while maintaining reflux, 9.0 parts of formamide is added and reflux continued for thirty hours. The mixture is then cooled to twenty to thirty degrees, and the resulting "crystalline precipitate filtered off. The mother liquor is employed for a repeat run. The crystalline precipitate melts at three hundred and thirty-six degrees.

Analysis.-Calcd. for C Cl (OH)NI-ICHO: N, 2.6. Found: N, 2.6.

Example 9.--Preparation 0 f CmCl1n(OH)NHCOC=CHCH=CHO A mixture of 62.8 parts of the crystalline product of C Cl and ClSO H and 26.8 parts of furamide in one hundred and seventy-six parts of xylene are refluxed for one day at the end of which time S0 evolution is negligible. On cooling, a dark amorphous precipitate is formed which is filtered and dried. The infra-red spectrum supports the structure, although some complexed or entrained furamide appeared to be present. The product is used in the crude form.

Analysis.-Calcd. for

N, 3.7. Found: N, 4.2.

Example 10.--Preparati0n of (3 ,01 onn u ration-x3 11 A mixture of 62.8 parts of the crystalline product of C Cl and ClSO I-I in one hundred and seventy-six parts of xylene is refluxed for one day with 13.5 parts of aphenylacetarnide. On cooling, a precipitate is obtained which, by infra-red, is established to have the desired C Cl (OH)NHCOCH C H structure.

Ana lySis.Calcd. for C Cl (OH)NHCOCH C H N, 2.2. Found: N, 2.5.

Exdmpie I 1 '.Preparation of C Cl (OH)-s'ubstituted polyamide Thirty-one parts of the crystalline product of C Cl and chlorosulfonic acid is pulverized with thirty parts of a commercial polyamide derived from ethylenediamine and a fatty dibasic acid C H (COOH) and the mixture is heated at one hundred and forty to one hundred and fifty degrees for eighteen hours, at which time no further $0 was evolved. The product is cooled and the resulting resin is pulverized. The infra-redspectrum establishes the presence of the C Cl (OH)N-RCOR' structure.

Example 12.--Prep*arati0'nof other representative compounds of this invention The chlorosulfonic acid intermediate of he'xachlorocyclopentadi'ene melting at one hundred and forty-six to one hundred and forty-eight degrees Centigrade is reacted with the appropriate amide as disclosed in the preceding examples. The following compounds are prepared (left hand column), in crude form. The right hand column gives the amides used.

I HO

1 1 Example 13.Formulatian of marine paint having antifowling properties The following ingredients are blended and ground together in a ball mill.

Pounds per 100 gallons Ingredient:

Gum rosin, grade WW 277 Blown fish oil 118 Zinc stearate 18 Versamide polyamide adduct of Example 11 197 1 Volume adjusted to 100 gal. by addition of naphtha.

Example 14.Formulation of marine paint having antifouling properties The following ingredients are blended andground together in a ball mill.

Ingredient: Pounds per 100 gallons Rosin 311 Hydrogenated methyl abietate 115.5 Coal tar naphtha 92.4

Mineral spirits (paint thinner) approx. 103.7

Di-atomaceous silica 103.7 C1OC11G(OH)NHCOCGH5 311 Lampblack l .0

The following ingredients are blended together in the indicated proportions, in a ball mill.

Ingredient: Pounds per 100 gallons Rosin 265 Coal tar 80 Talc 80 Pine oil 42 C Cl (OH) (NHCOCH from Example 1. 200 High flash naphtha 135 Mineral spirits, make up to volume.

1 2 Example 17.Another formulation of marine paint having anti fouling properties The followin g ingredients are blended together in the denoted proportions, in a roller mill.

Ingredient: Percent by weight Chlorinated rubber (Parlon S-125) 2.5 Rosin 20.00 Dibutyl phthalate 0.30 Titanium dioxide pigment 21.65 Zinc oxide 8.55 Cobalt naphthenate 0.05 Lead naphthenate 0.19 Phenoxypropylene oxide 0.13 C C1 (OH)NCOC H -from Example 5 5.00 Xylene Remainder Example 18.Testing of paint formulations of the preceding examples for antifouling properties The formulations disclosed in the preceding examples are painted on steel test panels, allowed to dry and im- Inersed in sea Water at a sub-tropical location. At the same time other identical panels are painted with control test formulations identical with these paint preparations except that the N-decachlorohydroxypentacyclodecylamide derivatives are omitted from the formulationThese test panels are immersed in the same sub-tropical sea water. After one month both the control test panels and the panels containing the active component are examined and compared. It is found that the control panels are heavily crusted with a mixed population of barnacles and other marine organisms, while the panels containing the active anti-marine fouling component were not adversely affected.

Example 19.Testing of anti-marine fouling properties of different products of this invention To eliminate variables due to the other ingredients in the paint formulations a simplified comparison test is carried out by treating porous test panels with a number of the products of this invention applied as a three percent solution of methyl isobutyl ketone. The panels are allowed to dry and are then immersed in sea Water at a subtropical location where untreated test panels became heavily fouled during the test interval. After a one month period the degree of fouling control was observed according to the amounts of fouling organisms found on the treated panel surface compared to identical untreated panels. The results are recorded on Table I below.

TABLE LPEROENT CONTROL OF FOULING BY INDICATED ORGANISMS Compound Algae Amphl- Annelida Barnacles Bryozoa Hydroids Mollusks Tunicates Micropods fouling C1oCI1o(OH) (NHCHO) 100 100 100 100 100 100 100 100 100 C1oOlm(OH)(NHC 00113) 100 100 100 95 100 100 100 100 100 C1nC11o(OH)(NHCOCsH5) 100 100 100 100 100 100 100 100 100 CmClm(OH) (NHC OCHzCoHs) 100 100 100 100 100 100 100 CmCho(0H) (NHCONHz) 0 0 20 0 0 50 100 50 0 C Ol (OH)- N 100 100 100 100 100 100 100 C O CmC11n(OH) NHC 0% O 13 14 What is claimed is: 6. A compound according to claim 2 of the formula C Cl (OH)NHCOCH C H E1 7. A compound according to claim 2 of the formula Cl R Q OlMOID-NH-COQ i ii o1 I -R' $11 0 1 r 01 o C V 9. A compound according to claim 2 of thejormula wherein R is selected from the group consisting of hydrogen, lower alkyl, and phenyl; and R is selected from OwCIMOH) NHGOO the group consisting of phenyl, hydroxyphenyl, benzyl and phenoxy, and, when R is phenyl, R is lower alkyl; and X 20 is selected from the group consisting of oxygen and sulfur.

2. A compound according to claim 1 wherein X is CmClro(OH)-N oxygen.

3. A compound according to claim 2 wherein R is hydrogen and R is selected from the group consisting of 25 phenyl, phenoxy, hydroxyphenyl and benzyl. References (med 4. A compound according to claim 2 of the formula Ungnade et al.: Chem. Rev., vol. 58 (1958), pages C C1 (OH) (NHCOC H 5. A compound according to claim 2 of the formula 30 LORRAINE A. WEINBERGER, Primary Examiner.

C Cl (OH)N(COCH )C H RICHARD K. JACKSON, Examiner 10. A compound according to claim 2 of the formula