US3221006A - 5-amino-3-substituted-1,2,4-thiadiazole azo compounds - Google Patents

5-amino-3-substituted-1,2,4-thiadiazole azo compounds Download PDF

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US3221006A
US3221006A US237307A US23730762A US3221006A US 3221006 A US3221006 A US 3221006A US 237307 A US237307 A US 237307A US 23730762 A US23730762 A US 23730762A US 3221006 A US3221006 A US 3221006A
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William H Moore
Edmund B Towne
Joseph B Dickey
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Eastman Kodak Co
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D285/00Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
    • C07D285/01Five-membered rings
    • C07D285/02Thiadiazoles; Hydrogenated thiadiazoles
    • C07D285/04Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
    • C07D285/081,2,4-Thiadiazoles; Hydrogenated 1,2,4-thiadiazoles

Description

United States Patent 3,221,006 5-AMINO-3-SUBSTITUTED-1,2,4-THIADIAZOLE AZO COMPOUNDS William H. Moore, Edmund B. Towne, and Joseph B.

Dickey, Kingsport, Tenn., assignors to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey No Drawing. Filed Nov. 13, 1962, Ser. No. 237,307 7 Claims. (Cl. 260-158) This invention relate to new monoazo compounds and their application to the art of dyeing or coloring.

While numerous compounds have been proposed as dyes for cellulose alkyl carboxylic acid ester, having 2 to 4 carbon atoms in the acid groups thereof, textile materials, polyester textile materials, nylon textile materials and acrylonitrile polymer textile materials, much time and effort are being expended to find improved dyes for these materials.

It is an object of our invention to provide new monoazo compounds which are dyes for the aforesaid textile materials. Another object is to provide colored textile materials which have good fastness to light, gas and washing, good resistance to sublimation and which undergo little change in color under artificial light. A further object is to provide colored textile materials which discharge to a pure white. Another object is to provide satisfactory means for the preparation of the new monoazo compounds of our invention.

We have discovered that the new monoazo compounds having the formula:

wherein X represents a low carbon alkylthio group or a low carbon alkylsulfonyl group and R represents an aniline coupling component free of a water-solublizing group are dyes for the aforesaid textile materials. The term water-solubilizing group refers to groups such as a sulfonic acid group or a carboxylic acid group, for example. Representative of a low-carbon alkylthio group are methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec.-butylthio and tert.-butylthio.

Representative of a low-carbon alkylsulfonyl group are methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec.-butylsulfonyl and tert.-butylsulfonyl.

Our new monoazo compounds have good to excellent afiinity for cellulose alkyl carboxylic acid ester, having 2 to 4 carbon atoms in the acid groups thereof, textile materials, polyester textile materials, acrylonitrile, polymer textile materials and nylon textile materials and yield dyeings thereon which have good fastness to light, gas and washing, good resistance to sublimation, good dischargeability and which undergo little change in color under artificial light.

The new monoazo compounds of our invention are water-insoluble. They are applied to the aforesaid textile materials by known dyeing techniques. Being waterinsoluble they can be applied from aqueous dispersion in the manner of the so-called disperse dyes. However, coloration can also be effected, for example, by incorporating the azo compounds into the spinning dope and spinning the fiber as usual. The azo compounds of our invention have varying utility as dyes. The degree of utility varies, for example, depending upon the material being dyed and the formula of the azo compound. Thus, for example, all the azo compounds will not have the same degree of utility for the same material.

By cellulose alkyl carboxylic acid esters having 2 to 4 carbon atoms in the acid groups thereof, we mean to include, for example, both hydrolyzed andunhydrolyzed cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate-propionate and cellulose acetate-butyrate.

Insofar as polyester textile materials are concerned, our invention is primarily directed to the dyeing of linear aromatic polyester textile materials having a melting point of at least 200 C.

Linear aromatic polyester textile materials that can be dyed with the new azo compounds of our invention include polyethylene terephthalate textile materials obtained, for example, as described in US. Patent 2,465,319 patented March 22, 1949, or polyester textile materials formed from other fiber-forming linear polyesters, such as polyesters derived from p,p-diphenylsulfonedicarboxylic acid and various aliphatic acids and glycols as described in US. Patent 2,744,088 patented May 1, 1956, and polyesters derived from various acids, such as terephthalic acid and 1,4-cyclohexanedimethanol'(1,4-dimethylolcyclohexane) as described in Kibler, Bell and Smith US. Patent 2,901,466.

The polyester materials sold under the trademarks Kodel, Dacron and Teryle-ne, for example, in the form of filaments, yarn and fabric, for example, are illustrative of the linear polyester textile materials that can be dyed. Kodel polyester materials are more particularly described in U.S. Patent 2,901,466. Dacron and Terylene polyester materials are described, for example, in US. Patent 2,465,319. The polyester textile materials specifically referred to hereinbefore are linear aromatic polyesters having a melting point of at least 200 C. Linear aromatic polyesters having a lower melting point than 200 C. can also be dyed or colored with the new azo compounds of our invention. US. Patents 2,945,010, 2,957,745 and 2,989,363 also disclose polymeric linear polyester materials that can be dyed.

Unless otherwise indicated, the term acrylonitrile polymer as used herein includes polymers consisting essentially of polymerized acrylonitrile (i.e., acrylonitrile polymers containing at least by weight of acrylonitrile) as well as modified acylonitrile polymers known in the art as modacrylics. The modacrylics contain at least 40% but less than 85% acrylontrile by weight. US. Patents 2,811,409, 2,831,826 and 2,843,572 disclose modacrylic fibers that can be dyed with our new monoazo compounds. Our new monoazo compounds are particularly suited for the dyeing of modacrylic textile materials.

The acrylonitrile polymer materials sold under the trademarks Verel, Orlon and Acrilan, in the form of filaments, yarn and fabric, for example, are illustrative of the acrylonitrile polymer textile materials that can be dyed with our new monoazo compounds.

The new monazo compounds of our invention are prepared by diazotizing a 5-amino-3-substituted-1,2,4-thiadiazole compound having the formula:

S I 2 Q (III) 'ample.

wherein X has the meaning previously assigned to it, R and R each represents a hydrogen atom, an alkyl radical having 1 to 4 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, an alkoxyalkyl group having 3 m4 carbon atoms, a cyanoalkyl group having 3 to 5 carbon atoms, an acetoxyalkyl group having 4 to 6 carbon atoms, a carbomethoxymethyl group, a carboethoxymethyl group, a ,B-carbomethoxyethyl group, a B-carboethoxyethyl group, a 2-bromoethyl group, a 2-chloroethyl, a 2,2-difluoroethyl group, a 2,2-difluoro-n-propyl group, a 3,3-difluoropropyl group, a 3,3-difluoro-n-butyl, a 2,2,2-trifluoroethyl, a 3,3,3-trifluoropropyl group, a 4,4,4-trifluorobutyl group, an alkenyl group having 3 to 4 carbon atoms, a chloroalkenyl group having 3 to 4 carbon atoms, a .bromoalkenyl group having 3 to 4 carbon atoms, a 2,3-epoxypropyl group, an N-fl-(phenylcarbamyloxy)ethy1 group, an N-fl-(phenylthiocarbamyloxy)ethyl group, a low carbon alkylcar-bamyloxye-thyl group or a low carbon alkylthiocarbamyloxyethyl group, Q represents a hydrogen atom, a bromine atom, a chlorine atom, a methyl group, an ethyl group, a rnethoxy group, an ethoxy group, an acetamido group, an n-propionylainino group or an n-butyrylamino group, and Y represents a hydrogen atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a chlorine atom or a bromine atom.

Illustrative of the S-amino-l,2,4-thiadiazole compounds used in preparing the new monoazo compounds of our invention are 5-amino-3-methylthio-l ,2,4-thiadiazole, S-amino-S-ethylthio- 1 ,2,4-thiadiazole, '5-amino-3-n-propylthio-1,2,4-thiadiazole, 5-arnino-3-isopropy1thio-l ,2,4-thiadiazo1'e,

15 -amino-3-n-butylthio- 1 ,2,4-thiadiazole, 5-amino-3-isobutylthio-1,2,4-thiadiazole, 5-amino-3-sec.-butylthio-1,2,4-thiadiaz0le,

5 -amino-3-tert.-butylthio- 1,2,4-thiadiazole, 5amino-3 -methylsulfonyl-l ,2,4-thiadiazole, 5-amino-3-ethylsulfonyl-1,2,4-thiadiazole, 5-amino-3-n-propy1sulfonyl-1,2,4-thiadiazo1e, 5-amino-3-isopropylsulfonyl-1,2,4-thiadiazole, S-amino-j-n-l' utylsulfonyl-l ,2,4-thiadiazole, 5-amino-3-isobutylsulfonyl-1,2,4-thiadiazole, 5-amino-3-sec. butylsulfony1-1,2,4-thiadiazole and S-amino-3-tert.-butylsulfonyl-1,2,4-thiadiazole.

Illustrative of the alkyl groups represented by R and R are methyl, ethyl, n-propyl, isopropyl and n-butyl. Similarly, B-hydroxyethyl, ,B-hydroxypropyl, 'y-hydroxypropyl, 8, y-dihydroxypropyl, fi-methyl-fl,' -dihydroxypropyl and fi-hydroxybutyl are illustrative of the hydroXyalkyl groups R and R represent.

Illustrative of the alkoxyalkyl groups represented by R and R are B-methoxyethyl and fl-ethoxyethyl. Similarly, fl-cyanoethyl, 'y-cyanopropyl and fi-cyanobutyl groups are illustrative of the cyanoalkyl groups R and R represent.

Allyl, propenyl, isopropenyl, l-butenyl, Z-butenyl and 3-butenyl are illustrative of the alkenyl groups represented by R Chloroallyl (CH CH=CHCl), bromoallyl (CH CH=CHBr), 4-chloro-3-butenyl (CH CH CH=CHCI) and 3-bromo-3-butenyl are illustrative of halogenated alkenyl groups. Illustrative of the low carbon alkyl carbamyloxyethyl and arylcarbamyloxyethyl groups are fi-methylcarbamyloxyethyl, B-ethylcarbamyloxyethyl, B-n-propylcarbamyloxyethyl, /8-n-butylcarbamyloxyethyl and fl-phenylcarbamyloxyethyl, for ex- Illustrative of the low carbon alkyl thiocarbamyloxyethyl and arylthiocarbamyloxyethyl groups are fi-methylthiocarbamyloxyethyl, fi-ethylthiocarbamyloxyethyl, fi-n propylthiocarbamyloxyethyl, B-n-butylthiocarbamyloxyethyl and fl-phenylthiocarbamyloxyethyl, for example.

Typical of the aniline coupling components used in the preparation of the azo compounds of our invention are aniline, m-toluidine, m-anisidine, m-chloroaniline, 2-methoxy-5-chloroaniline, 2,5-dimethoxyaniline, 2-methoxy-5-methylaniline, N-fl-hydroxyethylaniline, N-fl-hydroxypropylaniline, N-,8,'y-dihydroxypropylaniline, N-y-hydroxypropylaniline, N-fi-hydroxybutylaniline, N-[B-hydroxyethyl-o-chloroaniline, N-fl-hydroxyethyl-o-methoxyaniline, N-fi-cyanoethylaniline, N-fi-methoxyethylaniline, N-fi-ethoxyethylaniline, N-[i-carbomethoxyethyl-m-toluidine, N-B-carboe-thoXyethyl-m-chloroaniline, N,N-di-B-hydroxyethylaniline, N,N-di-,8-hydroxyethyl-m-chloroaniline, N,N-di-,8-hydroXyethyl-m-toluidine, N-ethyl-N-B,' -dihydroxypropyl-m-toluidine, N-ethyl-N- ,B-methyl-,B;y-dihydroxypropyl) aniline, N-methyl-N-tflwdihydroxypropyl-m-toluidine, N-B-rnethoxyethyl-N-fl -dihydroXypropyl-m-toluidine, N,N-di-/3-hydroxyethyl-m-bromoaniline, N-ethyl-N-a-hydroxybutylaniline, N-fl-hydroXyethyl-N-p,18,,8-trifluoroethylaniline, N-B-hydroxyethyl-N-w,'y,' -trifluoropropylaniline, N-B-hydroxyethyl-N-8,5,-trifiuorobutylaniline, N-fl-hydroXyethyl N-fi,B-difluoroethylaniline, N-fi-hydroxypropyl-N-'y,q-difluoropropylaniline, N-fi-hydroxyethyl-N-fiw-difiuoropropylaniline, N-,B,' -dihydroXypropyl-N- -difluorobutylaniline, N-,B,'y-dihydroXypropyl-N-5,a-difluoroamylaniline, N-methyl-N-fi-hydroxyethyl-m-bromoaniline, N,N-di-;3-hydroxyethyl-2,S-diethoxyaniline, N,N-di-[3-hydroXyethyl-2,S-dichloroaniline, N-n-propyl-N-B-hydroxyethylaniline, N-isopropyl-N-fi-hydroxyethy]aniline, -N-n-'butyl-N-B-hydroxyethylaniline, 1 N-[3-hydroxyethyl-N-cyanoethyl-m-chloroaniline, -N-fl-hydroxyethyl-N- -cyanopropylaniline, N-B-carbomethoxyethylaniline, N-{S-carboethoXyethyl-N-B-hydroxyethylaniline, N-B-carbomethoxyethyl-N-B-hydroxyethyl-m-chloroaniline, N-B-hydroxyethyl-N-fi-chloroallylaniline, N-B-hydroXyethyl-N-B-nitroethylaniline, N-methyl-N-fl-chloroethylaniline, N-ethyl-N-/8-chloroethylaniline, N-ethyl-N-,8-chloroethyl-m-chloroaniline, N-fi-hydroxyethyl-N-fl-chloroethylaniline, N-ethyI-N- S-bromoethylaniline, N-ethyl-N-[i-bromoethyl-m-anisidine, N-ethyl-N-fi-(phenylthiocarbamyloxy)ethyl-m-chloroaniline,

N-fi-hydroxyethyl-N-flmethylcarb amyloxy) ethylaniline, N-ethyl-N-flethylcarbamyloxy) ethyl-m-toluidine, N-ethyl-N-fi-(ethylthiocarbamyloxy)ethyl-aniline,

'N-ethyl-N-B-(methyl tlriocarbamyloxy)ethyl-2,5-

dimethoxyaniline, N-methyl-N- 2,3-epoxypropyl) aniline, N-ethyl-N (2,3-epoxypropyl) aniline, N,N-di- (2,3-epoxypropyl) aniline, N,N-di(fi-chloroethyl) aniline, N,N-difi-brornoethyl aniline, N-ethyl-N- ('y-chloro-fi-hydroxypropyl) aniline, N,N-di ('y-bromo-fl-hydroxypropyl) aniline and N-fl-IfilethOXYfithYl-N- -chloro-fi-hydroxypropyl) an me.

The 5-arnino-3-alkylthio-l,2,4-thiadiazole compounds used in the preparation of the monoazo compounds of our invention can be prepared by reacting a 2-alkyl-2-thiopseudourea salt with NaSCN in the presence of bromine and sodium methoxide in methanol as described in Ber., 89, 2742 (1956). The 3-alkylsulfonyl derivatives can be obtained by oxidizing the 3-alkylthio compounds as described in Ber., 89, 2747 (1956). We prefer however to use H as the oxidizing agent instead of the phthalic monoperacid of the reference.

The following examples illustrate our invention. Example 1.Preparation of 5-amin0-3-methylthi0-1,2,4- thiadiazole A. In a 3-l.,3-necked flask, equipped with a mechanical stirrer, thiourea (76 grams), methyl iodide (142 grams), and anhydrous methanol (330 ml.) were stirred together. As soon as complete solution occurred, the reaction mixture began to warm up, after which it was heated on a steam bath. After stirring at reflux for one hour, the condenser was set for distillation, and approximately 70 ml. of the volatile materials were distilled to remove any excess methyl iodide. The solution containing 2-methyl- 2-thiopseudourea was cooled to room temperature and a solution of sodium thiocyanate (100 grams) in anhydrous methanol (600 ml.) was added. The resulting solution was cooled to C. by means of a Dry Ice-acetone bath. The flask was equipped with two dropping funnels. In one was placed a cold sodium methoxide solution prepared by dissolving sodium (46 grams) in anhydrous methanol (600 ml.); in the other funnel was placed a cold solution of bromine (160 grams) in anhydrous methanol (425 ml.). With vigorous stirring, approximately of the methoxide solution was run into the flask, then both solutions were added at the same rate during 1 /2 hours, keeping the temperature below 5 C. When the addition was completed, the cooling bath was removed and the reaction mixture stirred for two hours at room temperature. The faintly alkaline solution was neutralized with concentrated HCl and the reaction mixture evaporated to dryness under reduced pressure. The residue was extracted with water to remove inorganic salts, then recrystallized from water with addition of charcoal. The weight of product was 104 grams (71% melting at 13942 C.

Calculated for 5-amino-3methylthio-1,2,4-thiadiazole: C=24.49%, H=3.40%, S=43.54%. Found: C: 24.70%, H=3.49%, S=43.34%.

B. 2-methyl-2-thiopseudourea sulfate, prepared as in Org. Syn. Coll., vol. II, p. 411, was substituted for the above in situ preparation of 2methyl-2-thiopseudourea hydrogen iodide to give a 71% yield of the 5-amino-3- methylthio-1,2,4-thiadiazole.

Example 2.-Preparati0n of 5-amino-3-ethylthio-1,2,4- thiadiazole 30 grams of sodium thiocyanate were dissolved in 250 ml. of methanol with good stirring. To this were added with stirring 54.5 grams of 2-ethyl-2-thiopseudourea hydrobromide (Org. Syn. Coll., vol. III, p. 440). After chilling to 14" C., this solution of sodium thiocyanate and 2-ethyl-2-thiopseudourea hydrobromide was treated simultaneously from two separate dropping funnels containing solutions of 1) bromine (48 grams) in 140 ml. of methanol and (2) sodium methylate in methanol, prepared from sodium (13.8 grams) in 150 ml. of methanol. The reaction mixture was stirred and cooled, and the additions where at such a rate as to keep the temperature at 5 C. and took 1 hour. About of the sodium methylate solution was added first, after which the two solutions were added simultaneously. The reaction was stirred 1 hour more without cooling after the addition was complete. The reaction mixture was slightly alkaline and was carefully neutralized with concentrated HCl. It was then filtered from a small amount of precipitated NaBr.

The methanol was removed in vacuo, and the resulting solid residue was triturated and washed twice with water and then air dried. The crude product weighed 39.5 grams (81.7%) and melted at 7492 C. Crystallization from 100 ml. of water yielded 30 grams of product, M.P. 5 C., softening point 60 C. Recrystallization from benzene-hexane yielded 26.2 grams of 5-amino-3-ethylthio-l,2,4-thiadiazole in the form of white needles melting at 926 C.

Example 3.-Preparati0n of 5-amin0-3-n-propylthio-1,2,4- thiadiazole A solution of 76 grams of thiourea and 123 grams of n propylbromide in 330 ml. of methanol was heated with stirring on a steam bath under reflux for 2 hours. The reaction mixture was then distilled until 50 cc. of solvent had been removed, thus assuring complete removal of any excess n-propylbromide (B.P. 70 C.). If it is desired to isolate 2n-propyl-Z-thiopseudourea hydrobromide at this stage, the solution is further concentrated and then cooled. A white crystalline product is obtained which melts at 59-61 C. when crystallized from alcohol-ether. (See Bellock and Witt, J. Agric. & Food Chem, 1176 (1954); CA 49, 3463 (1955).

In order to prepare 5-amino-3-n-propylthio-1,2,4-thiadiazole, the above methanol solution of 2-n-propyl-2- thiopseudourea hydrobromide was treated in a 3-liter flask with a solution of grams of sodium thiocyanate in 600 ml. of anhydrous methanol at room temperature. The solution was then cooled to 15 C. and stirred vigorously as the addition of the sodium methoxide solution (46 grams metallic sodium in 600 ml. anhydrous methanol) and of the cold solution of bromine (160 grams bromine in 425 ml. of cold anhydrous methanol) was carried out exactly as described in Example 1 at 5 C. After the addition was complete, the reaction mixture was stirred two hours at room temperature after which it was neutralized with concentrated hydrochloric acid and then evaporated to dryness under reduced pressure.

The residue was extracted with cold water to remove inorganic salts and then was crystallized from water, using charcoal. The dried, tan product weighed grams (77.2%) and melted at 74 C. when crystallized from aqueous ethanol.

Example 4.-Preparati0n 0f 5amin0-3-is0pr0pylthi0-I,2,- 4-thiadiazole A methanolic solution of 28.2 grams of thiourea and 46 grams of isopropyl bromide were heated on the steam bath as described in Example 3 and yielded a practically quantitative yield of 2-isopropythiopseudourea, MP. 76 8 C. Treatment of a solution of this product with sodium thiocyanate, bromine and sodium methoxide in accordance with the procedure described in Example 1 gave a good yield of S-amino-Z-isopopylthio-l,2,4-thiadiazole.

Example 5.Preparati0n of 5-aminc-3terL-butylthio-L- 2,4-thiadiaz0le Example 4 was repeated using 70 grams of tert.-butyl bromide in place of isopropyl bromide. Crystalline 5- amino-3-tert.-butylthio-1,2,4-thiadiazole melting at 203 C. was obtained. (See Ber., 89, 2742 (1946).)

In a similar manner there were prepared:

5-amino-3-n-butylthio-1,2,4-thiadiazole 5-amino-3isobutylthio-1,2,4-thiadiazole 5-amino-3-sec.-butylthio-1,2,4-thiadiazole Example 6.Preparation of 5-amino-3-methylsufonyl- 1,2,4-thiadiaz0le 5-amino-3-methylthio-1,2,4-thiadiazole (7.35 grams) was dissolved in acetic acid (100 ml.) by warming gently on the steam bath. The solution was cooled to 30 C., and 30% hydrogen peroxide (20.5 grams, a 20% excess) was added all at once, causing precipitation of a white solid. The mixture was stirred and warmed gently to effect solution. Solution occurred at about 50 C., and the temperature then rose spontaneously to 70 C. The solution was stirred until the temperature dropped to 25 C., and was then concentrated to about At its volume under reduced pressure. On standing, 5-amino-3-methylsulfonyl-l,2,4-thiadiazole precipitated as a white solid and was recovered by filtration, washed With water and air dried. It weighed 5.4 grams (65.2%) and had a melting point of 196.8 C.

Calculated for 5-amino-3-methylsulfonyl-1,2,4-thiadiazole: C=20.11%, H=2.80%, S=35.75%. Found: C=20.18%, H=3.00%, S=35.67%.

Example 7.Preparati-n of -amin0-3-ethylsulf0nyl- 1,2,4-th'iadiaz0le 8.05 grams of 5-amino-3-ethylthio-1,2,44hiadiazole prepared in Example 2 and melting at 926 C. were oxidized to the sulfonyl compound using monoperphthalic acid as described in Ber., 89, 2747 (1956). 1.2 grams of crystallized 5-amino-3-ethylsulfonyl-1,2,4-thiadiazole were obtained, melting at 1369 C.

Example 8.Preparation of 5-amz'n0-3-n-pr0pylsulfonyl- 1,2,4-thiadiazole 8.7 grams of 5-amino-3-n-propylthio-1,2,4-thiadiazole prepared in Example 3 were dissolved in 100 ml. of acetic acid. To this solution at room temperature were added all at once 20.5 grams of 30% hydrogen peroxide, which is a 20% excess over theoretical. The mixture was then stirred'and warmed gently on a steam bath to effect solution of the precipitate. Solution was eifected at 50 C., and the temperature then rose spontaneously to 70 C. Stirring was then continued for one hour while allowing the temperature to fall to 25 C. The reaction mixture was then concentrated to about its volume under reduced pressure. On standing, a white solid separated which, after filtering, washing and drying, yielded 6.5 grams of 5-amino-3-n-propylsulfonyl-1,2,4-thiadiazole.

Example 9.Preparati0n of S-wmino-3-tert.- butylsulfonyl-l ,2,4-thiadiaz0le Example 8 was repeated using 9.4 grams of 5-amino-3- tert.-butyl-1,2,4-thiadiazole in place of 5-amino-3-npropylsulfonyl-l,2,4-thiadiazole. 6.9 grams of 5-amino- 3-tert.-butylsulfonyl-1,2,4-thiadiazole were obtained.

In a similar manner there were prepared:

5-amino-3 -n-butylsulfony1-1,2,4-thiadiazole 5-amino-3-isobutylsulfonyl-1,2,4-thiadiazole 5 -amino-3-sec.-butylsulfonyl- 1,2,4-thiadiazole.

Example 10 A. Diazotization.-Nitrosyl sulfuric acid was prepared by adding 1.52 grams (0.022 mole) of sodium nitrite portionwise and with vigorous stirring to 10 ml. of concentrated sulfuric acid. The temperature of the reaction mixture was not allowed to rise above 65 C. The resulting solution was then cooled to 5 C., and 20 ml. of a mixture of 3 ml. of n-propionic acid and 17 ml. of acetic acid were added dropwise, with stirring, while a1- lowing the temperature to rise to C. and maintaining the solution at this temperature during the remainder of the addition.

The nitrosylsulfuric acid mixture was cooled to 0-5 C., and 2.94 grams (0.02 mole) of 5-amino-3-methylthio- 1,2,4-thiadiazole were added thereto portionwise, with stirring, after which 20 ml. more of the propionic-acetic acid mixture was added, keeping the temperature at 05 C. The reaction mixture was then stirred at 05 C. for 2 hours, and the excess sodium nitrite was destroyed by adding 1 gram of urea. A clear diazonium solution was thus obtained.

B. Coupling-10 ml. of the S-amino-B-methylthio- 1,2,4-thiadiazole diazonium solution prepared as described in 10A were added, with stirring, at 05 C. to a solution of 0.82 gram of N-fi-cyanoethyl-N-B-hydroxyethyl-m-toluidine in 10 mlrof' the propionic-acetic acid mixture, cooled to 0 C. When the addition was completed, the reaction mixture was made neutral to Congo red paper by the addition of solid, anhydrous sodium acetate. The neutralized coupling mixture was allowed to stand in an ice bath for one hour, with occasional stirring, and then was diluted with 250 parts of cold water, with good stirring. The dye compound which precipiated was recovered by filtration, washed with Water until neutral and air dried. It has the formula:

CHaSC N CHzCHzCN CHzCHzOH The dye obtained weighed 1.02 grams (70.3%). It dyed cellulose acetate fabric bright red shades having excellent fastness to light, linear aromatic polyester fabric orange-red shades having good fastness to light, and acrylonitrile polymer fabric and nylon fabric red-violet shades having good light fastness.

Example 11 A solution of 057 gram N-ethyl-N-B-(phenylcarbarnyloxy)-ethylaniline in 5 ml. of a 61 1 propionic-acetic acid mixture was coupled according to the procedure of Example 10B with 5 ml. of a S-amino-S-methylthio-1,2,4- thi-adiazole diazonium solution prepared as in Example 10A. The dye obtained weighed 0.69 gram (78.5%) and dyed cellulose acetate fabric reddish-pink, linear aromatic polyester fabric orange-red, Verel modacrylic fabric winered, and nylon fabric red. Light fastness Was excellent on all these fabrics.

Example 12 V 5 ml. of the diazonium solution prepared as in Example 10A were coupled with 0.51 gram of N-ethyl-N-(fimethanesulfonamido) ethyl m toluidine in accordance with the procedure of Example 1013. There was obtained 0.56 gram (67.5%) of dye which colored cellulose acetate fabric red-violet, linear aromatic polyester fabric red-pink, Verel modacrylic fabric violet, and nylon fabric violet, all with excellent light fastness.

Example 13 Example 14 1.79 grams (0.01 mole) of 5-amino-3-methylsulfonyl- 1,2,4-tlu'adiazole were diazotized in accordance with the general procedure described in Example 10A using the molar proportions of reactants indicated in Example 10A. 25 ml. of diazonium'solution were obtained.

5 ml. of the diazonium solution thus obtained were coupled with 0.38 gram of N-ethyl-N-fi-cya-noethyl-mtoluidine. Coupling and recovery of the azo dye compound formed were carried out in accordance with the general procedure described in Example 10B. The yield of dye was 0.28 gram (37.2%). It dyed cellulose acetate fabrics a bright red-violet shade with excellent light fastness, linear aromatic polyester fabric a bright pinkishred with very good light fastness, and Verel modacrylic fabric a deep red-violet with excellent light fastness.

Example 15 0.43 gram of N-fl-cyanoethyl-N-benzylaniline was coupled with 5 ml. of a 5-amino-3-methylsulfonyl-1,2,4-thiadiazole diazonium solution prepared as in Example 14. Coupling and recovery of the azo dye compound formed were carried out in accordance with the general procedure described in Example 108. The yield of dye was 0.56 gram (67%). -It dyed cellulose acetate fabrics deep winered shades having excellent fastness to light. The dyeing obtained on modacrylic fabric had good to excellent fastness to light.

Example 16 10 ml. of a -amino-3-methylsulfonyl-l,2,4-thiadiazole diazonium solution obtained as described in Example 14 were coupled with 0.912 gram (0.004 mole) of N-B-cyanm ethyl-N-B-hydroxyethyl-m-toluidine. Coupling and recovery of the azo compound formed were carried out in accordance with the general procedure described in Example 108. The azo dye compound obtained colored cellulose acetate fabrics deep wine-red shades having excellent fastness to light. The dyeing obtained on modacrylic fabrics also had excellent fastness to light.

Example 17 Example '18 0.01 gram mole of 5-amino-3-ethylthio-1,2,4-thiadia zole was diazotized in accordance with the general procedure described in Example A and the diazonium com. pound obtained was coupled with 0.01 gram mole of N-B- hydroxyethyl N 3,5 difluoroethyl-m-toluidine. Coupling and recovery of the red azo dye compound formed were carried out in accordance with the general procedure described in Example 10B. The dye compound thus obtained has good affinity for cellulose acetate and linear aromatic polyester fabrics and yielded dyeings thereon having good fastness to light.

Example 19 0.01 gram mole of 5-amino-3-ethylsulfonyl-1,2,4-thiadiazole was diazotized in accordance with the general procedure described in Example 10A and the diazonium compound obtained was coupled with 0.01 gram mole of -N,N- di-,8-hydroxyethyl-m-chloroaniline. Coupling and recovery of the azo dye compound formed were carrried out in accordance withthe general procedure described in Example 1OB. The dye compound thus obtained dyes cellulose acetate, linear aromatic polyester, nylon and modacrylic fabrics red-violet shades having good fastness to light.

Example 20 0.5 gram of the dye prepared in Example 10 by coupling diazotized 5 amino-3-methy-lthio-l,2,4 thiadiazole with N-B-cyanoethyl N-fi-hydroxyethyl-m-toluidine was dissolved in 20 ml. of acetic acid and treated with 1.0 gram of acetic anhydride and heated on the steam bath for 1 hour. Upon drowning in water, an acetylated dye precipitated and was recovered by filtration, washed with water and dried. It dyed the various fabrics essentially the same shades as did the unacetylated dye of Example 10, but the dyeings were somewhat faster to light, especially on polyester fabrics, and also had a higher degree of wash and sublimation fastness. This dye is the acetoxy derivative of the dye of Example 10 in which the N-B-hydroxyethyl group of the coupler has been acetylated.

10 Example 21 The dye of Example 20 was also obtained by coupling diazotized 5-amino-3-methylthio-1,2,4-thiadiazole with the pre-acetylated coupler, N-B-cyanoethyl-N-jS-acetoxyethylm-toluidine. This dye had the same excellent affinity, and gave dyeings on cellulose acetate, linear aromatic polyester, nylon and modacrylic fabrics having the same shades and good fastness to light as those obtained with the dye of Example 20.

Example 22 0.5 gram of the dye prepared in Example 19 was acetylated with acetic anhydride in accordance with the procedure described in Example 20. The resulting acetylated dye gave red-violet shades on linear aromatic polyester, cellulose acetate, nylon and modacrylic fabrics which have good fastness to light.

Example 23 0.5 gram of the dye compound prepared in Example 10 was heated in 20 ml. of dry benzene solution with 1.0 gram of phenylisothiocyanate for 1 hour on a steam bath The resulting new dye contained a phenylthiocarbamate group in the coupler and had excellent affinity and good light fastness on cellulose acetate, linear aromatic polyester, nylon and modacrylic fabrics. The dye compound obtained has the formula:

HaCS-CN The dye compound of this example can also be prepared by coupling diazoted 5-amino-3-methylthio-1,2,4-thiadiazole with the preformed coupling component.

Example 24 3.5 grams of 5-amino-3-n-propylthio-1,2,4-thiadiazole were diazotized using the procedure of Example 10A. 10 ml. of the diazonium solution obtained were coupled with 1.05 grams of N-(B,'y-dihydroxypropyl)-2-eth-oxy-5-acetamidoaniline. Coupling and recovery of the azo dye compound formed were carried out in accordance with the general procedure described in Example 10B. 1.23 grams of an azo dye compound which dyed cellulose acetate, linear aromatic polyester, nylon and modacrylic fabrics deep violet shades having good fastness to light and gas, for example, were obtained.

Example 25 3.78 grams of 5-amino-3-tert.-butylsulfonyl-1,2,4-thiadiazole were diazotized using the procedure ofExample 1 0A. 10 ml. of the diazonium solution obtained were coupledwith 0.82 gram of N-B-cyanoethyl N-fi-hydroxyethylm-toluidine. Coupling and recovery of the azo dye compound formed were carried out in accordance with the general procedure described in Example 10B. The dye compound thus obtained dyed cellulose acetate fabrics deep wine-red shades having excellent fastnessto light.

The dyeing obtained on Verel modacrylic fabric also had excellent fastness to light.

Examples 26-35 In the same manner as in Examples 24 and 25 the 5- amino-1,2,4-thiadiazole compounds containing the (26) isopropylthio, (27) isopropylsulfonyl, (28) sec.-butylthio, (29) sec.-butylsulfonyl, (30) isobutylthio,

(31) isobutylsulfonyl, (32) tert.-butylthio, (33) n-propylsulfonyl, (34) n-butylthio and the (35) n-butylsulfonyl 1 l 1 2 groups, respectively, in the 3-position were diazotized and of our invention on four different types of fabrics or texthe diazonium compounds obtained were coupled, respectile materials. This dye has the formula: tively, with the following aniline coupling compounds. (26) N-ethyl-N-B-(phenylcarbamyloxy)ethyl-aniline H3OS (31W 02115 27 N-ethyl-N-fi-(methanesulfonamido)ethyl-m- CN=N- -N/ I wluidine 1 s ourol-nooriO (28) N-cyclohexyl-N-B-hydr0xyethylaniline, u (29) N-ethyl-N-B-cyanoethyl-m-toluidine, (30) N- -cyanoethylN-benzylaniline,

(31) N-B-cyanoethyl-N-B-hydroxyethyl-m-toluidine, e (32) N-B-cyanoethyl-N-fl-acetoxyethyl-m-toluidine, Fabric Color f y Light (3 3 N,N- (di-B-hydroxyethyl) -2-methoxy-5-acetamidod llglotllacrylic lgecp wile-red Excellent.

(35) N,N-di-B-hydroxyethyl-m-chloroanrllne. y on eep m Diazotization, coupling and recovery of the monoazo dye compounds formed were carried out in accordance with In h pfecjedlng table, the 60111111? headed Llght the procedure set forth in Example 10. The dye comrefers to the llght fastness 0f the y pounds obtained dyed cellulose acetate, acrylonitrile poly- Another representative dye having equally good afiinmer, linear aromatic polyester and nylon textile materials ity and light fastness as the dye just noted is that predark red to violet shades which had good fastness to light. pared by coupling diazotized 5-amino-3-methylthio-1,2,4- Following the procedure described hereinbefore, the thiadiazole with N-ethyl-N-B-(methylsulfonamido)ethylmonoazo dye compounds indicated hereinafter were pre- -t 1uidi Thi d h th for ula;

pared. The color stated is that which is obtained on linear aromatic polyester textile materials. Nylon, cellu- 11 0 SO N I CH5 lose alkyl carboxylic acid ester, having 2 to 4 carbon l atoms in the acid groups thereof, and acrylonitrile poly- H mer textile materials are dyed shades that are shifted S CH3 GHZCENSONHS somewhat more toward blue.

Diazonium compound Coupling component Color N-ethyl-N-2,3-dihydroxy-propyl-m-toluidine Violet-red. N ,N-di-B-hydroxyethyl-m-chloroaniline Orange-red. N,N-di-fl-hydroxyethyl-3-methoxy-5-acetam Red-violet. N-B,B-difluoroethyl-N-fl-hydroxyethylaniline Orange-red. N-fi-cyanoethyl-N-B-hydroxyethylaniline. Orange. N-ethy1-N-B-hydroxyethy anilin Red- N-ethyl-N-fl-hydroxyethyl-In-tnlnidino D0. N,N-di-B-hydroxyethylsmilinP Red-pink. N-fl-hydloxyethyl-o-chlornanilinn Orange. N-fl-hydr0xyethyl-m-chloroan Do. N-fl-0yanoethyl-2,5-dichlorna'niline D0. N-be11zyl-N-B-cyanoethylanilinp D N-fi-hydroxyethyl-N-(fl-methoxycarbonyl-ethyl)-m-chloroaniline Pink. N-2,3-dihydroxypropyl-N-(fi-methoxycarbonyl-ethyl)-m-chloroaniline Do. N-B-cyanoethyl-m-toluidiue- Orange-red. N-B-cyanoethyl-N-B-acetoxyethylaniline Orang N-fi-hydroxyethyl-N-fi-(methylsulfonyl)ethyl-aniline Pink. N-fl-cyanoethyl-N-fi-hydroxyethyl-o-anisidine Red-pink. N-fl-cyanoethylanfline Orange-red, N-ethyl-N-fl-cyanoethyl-m- Red. N,N-di-B-cyanoethyl-m-tnlnirlinn Orange. N,N-di-(n-butyD-midinP Red-pink. N-fl-cyanoethyl-N-fi(methanesulfonamido)ethyl-aniline Orange. N -B-cyano ethy1-N-cyclohexyl-aniline Red-orange. N-fl-0yanoethyl-3-methoxydiphenylamine Red. N -ethyl-N-cyclohexylani1ine Do. N-benzyl-N-cyclohexylanilino Red-Pink. N-fl-hydroxyethyl-N-cyanornethylaniline Orange. N-B-(methanesulfonamido)ethyl-aniline D N-B-hydroxyethyl-N-fi-(methanesulfonamido)ethyl-aniline Pink. N,N-d1-18-hydroxyethyl-Z-methoxy-5-chloroaniline Red-violet. N-methyl-N-B-(phenylcarbamyloxy)ethyl-rn-toluidine Scarlet; N-B-cyanoethyl-N-fl-(phenylcarbamyloxy)ethyl-m-toluidine. Orange. N-fi-hydroxyothyl-N-B-cyanoethyl-m-toluidine Pink. N-B-hydroxyethyl-N-fl-cyanoethylaniline Do. N-benzyl-N-fi-cyanoethylaniline D N-ethyl-N-fl-(methanesulfonarnido)ethyl-m-toluidine Red-violet. N-ethyl-N-B-(mothanesulfonamido)ethyl-m-toluidine Pink. N,N-di-B-hydroxyethyl-m-chloroaniline D0. N-methyl-NB-(phenylcarbamyloxy)ethyl-m-toluidine Orange-red. N-Gl3hyl-N-B-acetOxyethyl-m-tolnidine Orange. Do N-B-cyanoethyl-N-fl-benzoxyethyl-mluidine Scarlet. 5-Amino3-ethylthi0-1,2,4-thiadiaz01e N-ethyl-N-B, -dihydroxypropyI-m-toluidine Red.

D N,N-di-B-hydroxyethyl-2-methoxy-fi-acetamidoanilino Red-violet. o N,N-dl-fi-hydroxyethyl-m-chloroaniline Orange-red. 5-Amino-3-ethylsulfonyl-l,2,4-thiadiazole N-ethyl-N-Bq-dihydroxy-propyltoluidine- Red-pink. Do N,N-di-B-hydroxyethyl-m-chloroanilino Pink. D N,N-di-fl-hydroxyethyl-?rmethoxy-5-acetamidoauih Violet.

The following table 1l1ustrates the colors imparted by These and the other azo dye compounds of our 1n- 3-methylth1o-1,2,4-th1ad1azo1yl-5-azo-4[N.- ethyl -N 13 ventron show good wash fastness and do not crock, es-

( henylcarbamyloxy)ethy1]-aniline, a representative dye pecially in the case of linear aromatic polester fabrics.

While numerous examples of the monoazo compounds of our invention have been given, these examples are illustrative and not limitative. Any of the -amino-1,2,4- thiadiazole compounds can be diazotized and coupled with an aniline coupling component free of a watersolubilizing group to obtain compounds of our invention.

As previously indicated, the new monoazo compounds of our invention are dyes for cellulose alkyl carboxylic acid ester, having 2 to 4 carbon atoms in the acid groups thereof, nylon, polyester and acrylonitrile polymer textile materials. In addition to these textile materials graft polymers such as those described in US. Patents 2,620, 324, 2,649,434, 2,657,191 and 2,827,450 can be dyed with out new monoazo dye compounds. The textile materials referred to herein can be dyed using known dyeing methods and can be in any desired form such as fiber, filament, yarn or cloth form, for example. Our new monoazo dyestuffs can be directly applied to said textile materials in the form of an aqueous suspension which can be prepared by finely grinding them to a paste in the presence of a solfonated oil, sodium lignin sulfonate, or other suitable dispersing agent and dispersing the resulting paste in water.

The following example illustrates one satisfactory way in which our new monoazo dye compounds can be used to dye graft polymer and acrylonitrile polymer textile materials. .1 gram of dye is dissolved by warming in 5 ml. of ethylene glycol monomethyl ether. A 2% aqueous solution of a nonionic surfactant, such as Igepal CA (a polymerized ethylene oxide-alkylphenol condensation product), is added slowly until a fine emulsion is obtained and then the dye mixture is brought to a volume of 200 ml. with Warm water. 5 ml. of a 5% aqueous solution of formic acid or acetic acid are added and then grams of fabric made from an acrylic fiber are entered. In the case of fabrics made of Orlon 42 fiber the dyeing is carried out at the boil for one hour. In the case of fabrics made of Verel acrylic fiber the dyebath temperature should not exceed 90 C. in order to avoid damage to the fiber. The dyed material is then washed well with hot water and dried.

The foregoing dyeing example is merely illustrative of the manner in which the new monoazo dye compounds of our invention can be applied to graft polymer and acrylonitrile polymer textile materials. Larger or smaller amounts of dye can be employed, for example. Similarly, dyeing assistants other than Igepal CA can be employed.

The same procedure can be used in the case of linear aromatic polyester textile materials with the exception that a dyeing assistant ordinarly referred to as a carrier is used in the dyeing operation and the dyeing is carried out at the boil. Butyl benzoate, o-phenylphenol, p-phenylphenol, salicyclic acid, methyl salicylate and benzoic acid are illustrative of the carriers that can be employed. Polyester textile materials can also be dyed by the method-s described in US. Patents 2,757,064 and 2,880,050, for example.

Nylon and said cellulose alkyl carboxylic acid ester textile materials can be dyed, for example, by the procedure described in US. Patent 2,785,157. Direct dyeing operations can, with advantage, be conducted at temperatures of about 70 C.90 C. but any suitable temperature can be used. Thus, the textile material such as cellulose acetate, for example, to be dyed or colored is ordinarily added to the dye bath at a temperaure lower than that at which the main portion of the dyeing is to be effected. A temperature approximating 45 C.55 C., for example, can be used, following which the temperature is raised to that selected for carrying out the dyeing operation. The temperature at which the dyeing is conducted may, of course, be varied somewhat depending upon the particular material undergoing coloration. As is understood by those skilled in the dyeing art,

1-4 the intensity of dyeing can be varied byvarying the proportion of dye to material undergoing coloration. The amount of dye used can be, for example, to 3% (by weight) of that of the textile material, although lesser or greater amounts of dye can be used.

Illustrative of such dyeing operations for cellulose ester and nylon textile materials with reference to the dyeing of cloth is the following procedure.

16 milligrams of dye are ground with an aqueous solution of sodium lignin sulfonate until well dispersed or alternately the dye can be dissolved in 5 cc. of hot ethylene glycol monoethyl ether. The dispersion or solution as the case may be, is then poured into cc. of water to which a small amount of a surface-active agent such as Igepon T (C H .CO.N(CH ).C H SO Na) Nekal BX (sodium alkylnaphthalenesulfonate) or Orvus (sodium lauryl sulfate-type) has been added. The dye bath is then brought to the desired temperature and 5 grams of well wet-out cloth are added thereto. Dyeing is continued until the proper shade is reacted. From time to time throughout the dyeing operation, the cloth is worked to promote even dyeing.

Although the invention has been described in considerable detail with reference to certain preferred embodiments thereof, it will be understood that variations and modifications can be effected without departing from the spirit and scope of the invention as described hereinbefore and as defined in the appended claims.

We claim:

1. The azo compounds having the formula:

XCN

IQI gN=N-R wherein X represents a low carbon alkylsulfonyl radical and R represents the residue of an aniline coupling component free of water-solubilizing groups.

2. The azo compound having the formula:

3. The compound 0 Has 0 2C N 4. The compound 0H3so.c-N

5. The compound CHzCHzCN CHzCnHs CHZCH2OH 6. The compound t-C .ms 0 O-N 7. The compound CHciSO C--N (References on following page) OHzCH OH References Cited by the Examiner UNITED STATES PATENTS FOREIGN PATENTS 2/1961 France.

OTHER REFERENCES Straley et a1. 260-158 Taube 2604458 5 (lgggrd ler et aL, Chem. Ber., v01. 89, pp. 2742-2747 Straley et a1. 260158 Marian 260-158 CHARLES B. PARKER, Primary Examiner.

Claims (1)

1. THE AZO COMPOUNDS HAVING THE FORMULA:
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Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3441554A (en) * 1965-12-03 1969-04-29 Basf Ag Thiadiazole monoazo dyes
US3673169A (en) * 1969-06-16 1972-06-27 Eastman Kodak Co 1,3,4-thiadiazolylazo-3-(cyclohexylamino)acylanilide dyes
FR2318205A1 (en) * 1975-07-18 1977-02-11 Ciba Geigy Ag Azo compounds, their method of preparing and their use for dyeing and printing textile materials
US4018756A (en) * 1970-06-12 1977-04-19 Sumitomo Chemical Company, Limited Thiazole and benzothiazole cationic dyes
US4282144A (en) * 1979-06-01 1981-08-04 Eastman Kodak Company Azo dyes derived from 5-membered heterocyclic amines and aromatic amine couplers containing sulfo groups, or salts thereof
US4407749A (en) * 1980-07-31 1983-10-04 Eastman Kodak Company AZO Dyes from 2-sulfonated, sulfated or thiosulfated organothiothiadiazole and aniline, tetrahydroquinoline, or benzomorpholine couplers
US4681699A (en) * 1984-09-15 1987-07-21 Basf Aktiengesellschaft Bisazo dyes and their use in liquid crystalline materials
US20070162107A1 (en) 2003-12-23 2007-07-12 Sadra Medical, Inc. Methods and apparatus for endovascularly replacing a patient's heart valve
US8182528B2 (en) 2003-12-23 2012-05-22 Sadra Medical, Inc. Locking heart valve anchor
US8231670B2 (en) 2003-12-23 2012-07-31 Sadra Medical, Inc. Repositionable heart valve and method
US8328868B2 (en) 2004-11-05 2012-12-11 Sadra Medical, Inc. Medical devices and delivery systems for delivering medical devices
US8343213B2 (en) 2003-12-23 2013-01-01 Sadra Medical, Inc. Leaflet engagement elements and methods for use thereof
US8828078B2 (en) 2003-12-23 2014-09-09 Sadra Medical, Inc. Methods and apparatus for endovascular heart valve replacement comprising tissue grasping elements
US8840663B2 (en) 2003-12-23 2014-09-23 Sadra Medical, Inc. Repositionable heart valve method
US9585750B2 (en) 2003-12-23 2017-03-07 Boston Scientific Scimed, Inc. Methods and apparatus for endovascularly replacing a patient's heart valve
US10201417B2 (en) 2015-02-03 2019-02-12 Boston Scientific Scimed Inc. Prosthetic heart valve having tubular seal
US10201416B2 (en) 2016-05-16 2019-02-12 Boston Scientific Scimed, Inc. Replacement heart valve implant with invertible leaflets
US10201418B2 (en) 2010-09-10 2019-02-12 Symetis, SA Valve replacement devices, delivery device for a valve replacement device and method of production of a valve replacement device
US10206774B2 (en) 2003-12-23 2019-02-19 Boston Scientific Scimed Inc. Low profile heart valve and delivery system
US10258465B2 (en) 2003-12-23 2019-04-16 Boston Scientific Scimed Inc. Methods and apparatus for endovascular heart valve replacement comprising tissue grasping elements
US10278805B2 (en) 2000-08-18 2019-05-07 Atritech, Inc. Expandable implant devices for filtering blood flow from atrial appendages
US10299922B2 (en) 2005-12-22 2019-05-28 Symetis Sa Stent-valves for valve replacement and associated methods and systems for surgery
US10335273B2 (en) 2018-01-08 2019-07-02 Boston Scientific Scimed Inc. Leaflet engagement elements and methods for use thereof

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US2791579A (en) * 1953-04-13 1957-05-07 Bayer Ag Water insoluble thiodiazole monoazo dyestuffs
US2857371A (en) * 1954-09-10 1958-10-21 Eastman Kodak Co Benzothiazole azo diphenylamine compounds
FR1256899A (en) * 1960-05-13 1961-03-24 Basf Ag diazapolyméthiniques dyes
US3007915A (en) * 1958-05-26 1961-11-07 Sandoz Ltd Sparingly water-soluble azo dyestuffs

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Publication number Priority date Publication date Assignee Title
US2785157A (en) * 1952-11-05 1957-03-12 Eastman Kodak Co Benzothiazoleazoaniline compounds
US2791579A (en) * 1953-04-13 1957-05-07 Bayer Ag Water insoluble thiodiazole monoazo dyestuffs
US2857371A (en) * 1954-09-10 1958-10-21 Eastman Kodak Co Benzothiazole azo diphenylamine compounds
US3007915A (en) * 1958-05-26 1961-11-07 Sandoz Ltd Sparingly water-soluble azo dyestuffs
FR1256899A (en) * 1960-05-13 1961-03-24 Basf Ag diazapolyméthiniques dyes

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3441554A (en) * 1965-12-03 1969-04-29 Basf Ag Thiadiazole monoazo dyes
US3673169A (en) * 1969-06-16 1972-06-27 Eastman Kodak Co 1,3,4-thiadiazolylazo-3-(cyclohexylamino)acylanilide dyes
US4018756A (en) * 1970-06-12 1977-04-19 Sumitomo Chemical Company, Limited Thiazole and benzothiazole cationic dyes
FR2318205A1 (en) * 1975-07-18 1977-02-11 Ciba Geigy Ag Azo compounds, their method of preparing and their use for dyeing and printing textile materials
US4282144A (en) * 1979-06-01 1981-08-04 Eastman Kodak Company Azo dyes derived from 5-membered heterocyclic amines and aromatic amine couplers containing sulfo groups, or salts thereof
US4407749A (en) * 1980-07-31 1983-10-04 Eastman Kodak Company AZO Dyes from 2-sulfonated, sulfated or thiosulfated organothiothiadiazole and aniline, tetrahydroquinoline, or benzomorpholine couplers
US4681699A (en) * 1984-09-15 1987-07-21 Basf Aktiengesellschaft Bisazo dyes and their use in liquid crystalline materials
US10278805B2 (en) 2000-08-18 2019-05-07 Atritech, Inc. Expandable implant devices for filtering blood flow from atrial appendages
US10206774B2 (en) 2003-12-23 2019-02-19 Boston Scientific Scimed Inc. Low profile heart valve and delivery system
US8231670B2 (en) 2003-12-23 2012-07-31 Sadra Medical, Inc. Repositionable heart valve and method
US8246678B2 (en) 2003-12-23 2012-08-21 Sadra Medicl, Inc. Methods and apparatus for endovascularly replacing a patient's heart valve
US10314695B2 (en) 2003-12-23 2019-06-11 Boston Scientific Scimed Inc. Methods and apparatus for endovascular heart valve replacement comprising tissue grasping elements
US8343213B2 (en) 2003-12-23 2013-01-01 Sadra Medical, Inc. Leaflet engagement elements and methods for use thereof
US8182528B2 (en) 2003-12-23 2012-05-22 Sadra Medical, Inc. Locking heart valve anchor
US8840663B2 (en) 2003-12-23 2014-09-23 Sadra Medical, Inc. Repositionable heart valve method
US9585750B2 (en) 2003-12-23 2017-03-07 Boston Scientific Scimed, Inc. Methods and apparatus for endovascularly replacing a patient's heart valve
US9585749B2 (en) 2003-12-23 2017-03-07 Boston Scientific Scimed, Inc. Replacement heart valve assembly
US20070162107A1 (en) 2003-12-23 2007-07-12 Sadra Medical, Inc. Methods and apparatus for endovascularly replacing a patient's heart valve
US10258465B2 (en) 2003-12-23 2019-04-16 Boston Scientific Scimed Inc. Methods and apparatus for endovascular heart valve replacement comprising tissue grasping elements
US8828078B2 (en) 2003-12-23 2014-09-09 Sadra Medical, Inc. Methods and apparatus for endovascular heart valve replacement comprising tissue grasping elements
US8328868B2 (en) 2004-11-05 2012-12-11 Sadra Medical, Inc. Medical devices and delivery systems for delivering medical devices
US10299922B2 (en) 2005-12-22 2019-05-28 Symetis Sa Stent-valves for valve replacement and associated methods and systems for surgery
US10314701B2 (en) 2005-12-22 2019-06-11 Symetis Sa Stent-valves for valve replacement and associated methods and systems for surgery
US10201418B2 (en) 2010-09-10 2019-02-12 Symetis, SA Valve replacement devices, delivery device for a valve replacement device and method of production of a valve replacement device
US10201417B2 (en) 2015-02-03 2019-02-12 Boston Scientific Scimed Inc. Prosthetic heart valve having tubular seal
US10201416B2 (en) 2016-05-16 2019-02-12 Boston Scientific Scimed, Inc. Replacement heart valve implant with invertible leaflets
US10335273B2 (en) 2018-01-08 2019-07-02 Boston Scientific Scimed Inc. Leaflet engagement elements and methods for use thereof

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