US3051736A - Cuprous complexes - Google Patents
Cuprous complexes Download PDFInfo
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- US3051736A US3051736A US78250A US7825060A US3051736A US 3051736 A US3051736 A US 3051736A US 78250 A US78250 A US 78250A US 7825060 A US7825060 A US 7825060A US 3051736 A US3051736 A US 3051736A
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- cuprous
- cyclohexenecarbonitrile
- complex
- reaction
- complexes
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- 238000006243 chemical reaction Methods 0.000 claims description 14
- GTMWGXABXQTZRJ-UHFFFAOYSA-N cyclohexene-1-carbonitrile Chemical compound N#CC1=CCCCC1 GTMWGXABXQTZRJ-UHFFFAOYSA-N 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 13
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 13
- 229940045803 cuprous chloride Drugs 0.000 description 13
- GYBNBQFUPDFFQX-UHFFFAOYSA-N cyclohex-3-ene-1-carbonitrile Chemical compound N#CC1CCC=CC1 GYBNBQFUPDFFQX-UHFFFAOYSA-N 0.000 description 10
- 238000004043 dyeing Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- -1 copper sulfate Chemical class 0.000 description 9
- 229910002651 NO3 Inorganic materials 0.000 description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- WIVXEZIMDUGYRW-UHFFFAOYSA-L copper(i) sulfate Chemical compound [Cu+].[Cu+].[O-]S([O-])(=O)=O WIVXEZIMDUGYRW-UHFFFAOYSA-L 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 3
- SHQBSKNMMFNYGZ-UHFFFAOYSA-N cyclohex-2-ene-1-carbonitrile Chemical compound N#CC1CCCC=C1 SHQBSKNMMFNYGZ-UHFFFAOYSA-N 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- QNBUNDFJTSPPAD-UHFFFAOYSA-N 2-methylcyclohex-3-ene-1-carbonitrile Chemical compound CC1C=CCCC1C#N QNBUNDFJTSPPAD-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000000980 acid dye Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000012430 organic reaction media Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic Table without C-Metal linkages
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/70—Material containing nitrile groups
- D06P3/704—Material containing nitrile groups using metallisable or mordant dyes or dyeing by cupro-ionic method
Definitions
- This invention relates to novel cuprous complexes. More particularly, this invention relates to novel, stable, cyclohexenecarbonitrile cuprous complexes useful in aiding the dyeing of acrylonitnile fibers.
- a distinct advantage of the compounds of this invention pertains to the fact that not only are the cuprous complexes of cyclohexene-carbonitrile a dyeing aid in acid dyes but also in the dyeing process, the cyclohexenecarbonitrile molecules act as dye carriers. Thus very deep color shades of the dyed fabric can be obtained in the use of the compounds of this invention without the addition of conventional dye carriers.
- each R individually, represents a hydrogen atom or an alkyl radical, preferably containing from 1 to 6 carbon atoms.
- cyclohexenecarbonitriles which are used to prepare the novel cuprous complexes of this invention include, for example: 3-cyclohexenecarbonitrile, 2-cyclohexenecarbonitrile, l-cyclohexenecarbonitrile, 2-methyl-3-cyclohexenecarbonitrile, 3-ethyl-3-cyclohexenecarbon-itrile, 5- n-hexyl-3-cyclohexene-canbonitrile, 2-isopropopyl-2-cyclohexenecarbonitrile, 5-ethyl-2-cyclohexenecarbonitrile, 4-nhexyl-Z-cyclohexenecarbonitrile, 3-isopropyl-l-cyclohexenecarbonitrile, Sal-hexyl-l-cyclohexene-carbonitrile, and the like.
- cuprous salts which are preferably used in the production of the cuprous complexes of this invention include the cuprous salts such as, for example, cuprous chloride, cuprous bromide, cuprous iodide, cuprous nitrate, cuprous sulfate, cuprous phosphate, and the like.
- the novel cuprous complexes of cyclohexenecarbonitrile can be readily produced by reacting the cuprous salts such as, for example, cuprous chloride, with a cyclohexenecarbonitrile such as, for example, 3-cyclohexenecarbonitrile at a temperature of from about 20 C. to about 100 C. for a period of time suflicient for the cuprous complex to form and dissolve in the reactant solution.
- the reaction can be conducted in an inert organic reaction medium which has a function of a solvent in the event that the cyclohexenecar bonitrile star-ting material is a solid at room temperature.
- the time of reaction can range from a few minutes to as long as 24 hours depending on the reaction temperature and the specific reactants used.
- the resulting reaction is exothermic.
- the temperature is controlled and prefer-ably maintained in the range of from about 40 C. to about C. After the initial exothermic reaction has run its course, additional heat can be applied to maintain the temperature and complete the reaction more rapidly.
- the cyclohexenecar-bonitrile is preferably employed in mole ratios greater than the equivalent amount of cuprous salt present.
- the preferred range is from about a 1:1 to 1:4 mole ratio of cuprous salts to cyclohexenecarbonitrile. Higher or lower ratios are operable; however a high excess of cyclohexenecarbonitrile is not economically feasible and lower ratios do not make full use of the cuprous salts charged.
- the novel cuprous complexes of this invention it is desirable, although not necessary, to conduct the reaction in an atmosphere of an inert gas free of elemental oxygen, such as an atmosphere of nitrogen, carbon dioxide, helium, and the like.
- an atmosphere of an inert gas free of elemental oxygen such as an atmosphere of nitrogen, carbon dioxide, helium, and the like.
- the inert atmosphere aids in decreasing the possible air oxidation of the cuprous salts to the undesirable cupric salts although the cuprous complexes of cyclohexenecarbonitrile can be produced in the presence of air.
- cuprous complexes of this invention which can be produced by the above described process are, for example: complex of cuprous chloride and 3-cyclohexenecarbonitrile, complex of cuprous chloride and Z-cyclohexene-carbonitrile, complex of cuprous chloride and 5- n-hexyl-3-cyclohexenecarbonitrile, complex of cuprous chloride and 2-isopropyl-3-cyclohexenecarbonitrile, complex of cuprous bromide and 3-cyclohexenecarbonitrile, complex of cuprous bromide and S-n-hexyl-l-cyclohexenecarbonitrile, complex of cuprous nitrate and 2-cyclohexenecanbonitrile, complex of cuprous nitrate and 1- cyclohexenecarbonitrile, and the like.
- cuprous complexes of the invention can be recovered from their reaction mixtures in high purity by cooling the reaction mixture to precipitate the cuprous complex and isolation by conventional filtration procedure. If the cuprous complex reaction product does not crystallize on cooling, the reaction product can be precipitated by the addition of an organic non-solvent such as acetone, ethyl ether, ethyl acetate, dioxane, and the like. If additional purification of the copper complexes is desired, Conventional recrystallization pro-- cedures can be used.
- Example 1 Cuprous chloride (10 grams) was added portionwise with agitation to 54 grams of 3-cyclohexenecarbonitrile in a nitrogen atmosphere. The reaction was exothermic, raising the temperature from about 20 C. to 35 C. during the addition. After completion of the addition of the cuprous chloride, the reaction mixture was kept at 75 C. for 4 hours. The reaction mixture was filtered warm and stored overnight in a refrigerator at a temperature of approximately 10 C. where the reaction mixture crystallized to a solid mass. The reaction mixture was warmed to room temperature and the solid was filtered, the filter cake was recrystallized from acetone, dried at room temperature and analyzed to be the desired cuprous chloride complex of 3-cyclohexenecarbonitrile. -It melted at 7 274 C.
- Example 2 A 5 gram sample of scoured and dried knitted tubing of continuous yarns composed of a terpolymer of acrylonitrile; vinyl chloride and vinylidene chloride [in a ratio, respectively, of 70:20:10] was added to a 200 milliliter total Volume aqueous dyebath containing 1 percent by Weight of the yarn of Pergegal OK (a cationic condensation product of ethylene oxide and an organic amine marketed by General Aniline and Film Corporation), 2 percent by weight of the yarn of concentrated sulfuric acid, 3 percent by weight of the yarn of Xylene Milling Blue G.L. (Acid Blue 1 02-50315) and 3.0 percent by weight of the yarn of the cuprous chloride complex of 3-cyclohexenecarbonitrile.
- Pergegal OK a cationic condensation product of ethylene oxide and an organic amine marketed by General Aniline and Film Corporation
- 2 percent by weight of the yarn of concentrated sulfuric acid 3 percent by weight of the yarn of Xylene Milling Blue G.
- cuprous chloride complex of 3-cyclohexenecarbonitrile was added as a mixture of 5 parts by weight of acetonitrile to 1 part by Weight of cuprous chloride complex of 3-cyclohexenecarbonitrile.
- the bath temperature was raised to boiling in about 20 minutes and held for 90 minutes at the boiling temperature.
- the dyed fabric was then raised, scoured, rinsed, hydroextracted and dried at 130 C. for 10 minutes. After drying, the dyed fabric had a final K/S* value of 12.9.
- the common Fade-O-Meter test indicated a light fastness rating of the dyed fabric of 40 hours.
- cuprous complex produced by'the reaction of a cuprous salt of an inorganic mineral acid with a cyclohexene-canbonitrile of the formula:
- each R individually is selected from the group consisting of hydrogen and the alkyl radicals of from 1 to 6 carbon atoms, at a temperature of from about 20 C. to about C.
- cuprous complex produced by the reaction of cuprous chloride with 3-cyclohexenecarbonitrile at a temperature of from about 20 C. to about 100 C.
- cuprous complex produced by the reaction of cuprous nitrate with 5-n-hexyl-3-cyclohexenecanbonitrile at a temperature of from about 20 C. to about 100 C.
- cuprous complex produced by the reaction of cuprous sulfate with 2-cyclohexenecarbonitrile at a temperature of from about 20 C. to about 100 C.
- the amount of dye on fiber or the depth of color are approximately pro ortional to the K/ S value which is a. measure of the light re eeted from the dyed sample.
- the determination of the K/S values is set forth in an article by D. B. Judd, Color in Business, Science and Industry, 1952, pp. 314-342. V
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
Description
United rates 3,051,736 CUPROUS COMPLEXES Christian F. Horn, South Charleston, W. Va., assignor to Union Carbide Corporation, a corporation of New York No Drawing. Filed Dec. 27, 1960, Ser. No. 78,250 4 Claims. (Cl. 260438) This invention relates to novel cuprous complexes. More particularly, this invention relates to novel, stable, cyclohexenecarbonitrile cuprous complexes useful in aiding the dyeing of acrylonitnile fibers.
It is known in the textile field that synthetic fibers composed of acrylonitrile interpolymers are extremely difficult to dye. To overcome this difiiculty, a copper dyeing method was proposed wherein dyeing occurred in the presence of cuprous ions. Satisfactory dyeing results are obtained using the above described process; however, there are some characteristics of this process which make it less desirable when used in large scale dyeing. When the cuprous ion is produced in the dye bath by the reaction of copper compounds, such as copper sulfate, and reducing agents, several deficiencies arise. These deficiencies center around the reduction of the cupric ion to to the active cuprous ion. If the rate of reduction is not carefully controlled, two undesirable occurrences may result. Initially, if the cupric ion is not fully reduced, the chemicals in the bath will be unsatisfactory for use in the dyeing process. On the other hand, if the cupric ion is over-reduced, metallic copper may be present in the bath which will impair both light stability and the color shade of the fiber. In addition, the above-described problems make the dyeing formulations extremely difiicult to reproduce. It is the combination of these problems which have discouraged the use of the cuprous-ion technique. There has therefore been a long felt need in the art for a stable cuprous-ion complex which could be added directly to the dyebath without going through the reduction process.
I have discovered a class of novel, inorganic acid salts of cuprous complexes of cyclohexenecarbonitnile which are stable and which can be used to provide outstanding results in the cuprous-ion dyeing technique. A distinct advantage of the compounds of this invention pertains to the fact that not only are the cuprous complexes of cyclohexene-carbonitrile a dyeing aid in acid dyes but also in the dyeing process, the cyclohexenecarbonitrile molecules act as dye carriers. Thus very deep color shades of the dyed fabric can be obtained in the use of the compounds of this invention without the addition of conventional dye carriers.
The cyclohexenecarbonitrile portion of these complexes can be representedby the general formula:
wherein each R, individually, represents a hydrogen atom or an alkyl radical, preferably containing from 1 to 6 carbon atoms.
The cyclohexenecarbonitriles which are used to prepare the novel cuprous complexes of this invention include, for example: 3-cyclohexenecarbonitrile, 2-cyclohexenecarbonitrile, l-cyclohexenecarbonitrile, 2-methyl-3-cyclohexenecarbonitrile, 3-ethyl-3-cyclohexenecarbon-itrile, 5- n-hexyl-3-cyclohexene-canbonitrile, 2-isopropopyl-2-cyclohexenecarbonitrile, 5-ethyl-2-cyclohexenecarbonitrile, 4-nhexyl-Z-cyclohexenecarbonitrile, 3-isopropyl-l-cyclohexenecarbonitrile, Sal-hexyl-l-cyclohexene-carbonitrile, and the like.
The cuprous salts which are preferably used in the production of the cuprous complexes of this invention include the cuprous salts such as, for example, cuprous chloride, cuprous bromide, cuprous iodide, cuprous nitrate, cuprous sulfate, cuprous phosphate, and the like.
The novel cuprous complexes of cyclohexenecarbonitrile can be readily produced by reacting the cuprous salts such as, for example, cuprous chloride, with a cyclohexenecarbonitrile such as, for example, 3-cyclohexenecarbonitrile at a temperature of from about 20 C. to about 100 C. for a period of time suflicient for the cuprous complex to form and dissolve in the reactant solution. The reaction can be conducted in an inert organic reaction medium which has a function of a solvent in the event that the cyclohexenecar bonitrile star-ting material is a solid at room temperature. The time of reaction can range from a few minutes to as long as 24 hours depending on the reaction temperature and the specific reactants used. In general, when the cuprous salts are added to the cyclohexene-canbonitrile to produce the products of this invention, the resulting reaction is exothermic. The temperature is controlled and prefer-ably maintained in the range of from about 40 C. to about C. After the initial exothermic reaction has run its course, additional heat can be applied to maintain the temperature and complete the reaction more rapidly.
In producing the novel cuprous complexes of cyclohexenecarbonitrile the cyclohexenecar-bonitrile is preferably employed in mole ratios greater than the equivalent amount of cuprous salt present. The preferred range is from about a 1:1 to 1:4 mole ratio of cuprous salts to cyclohexenecarbonitrile. Higher or lower ratios are operable; however a high excess of cyclohexenecarbonitrile is not economically feasible and lower ratios do not make full use of the cuprous salts charged.
In producing the novel cuprous complexes of this invention, it is desirable, although not necessary, to conduct the reaction in an atmosphere of an inert gas free of elemental oxygen, such as an atmosphere of nitrogen, carbon dioxide, helium, and the like. The inert atmosphere aids in decreasing the possible air oxidation of the cuprous salts to the undesirable cupric salts although the cuprous complexes of cyclohexenecarbonitrile can be produced in the presence of air.
Among the cuprous complexes of this invention which can be produced by the above described process are, for example: complex of cuprous chloride and 3-cyclohexenecarbonitrile, complex of cuprous chloride and Z-cyclohexene-carbonitrile, complex of cuprous chloride and 5- n-hexyl-3-cyclohexenecarbonitrile, complex of cuprous chloride and 2-isopropyl-3-cyclohexenecarbonitrile, complex of cuprous bromide and 3-cyclohexenecarbonitrile, complex of cuprous bromide and S-n-hexyl-l-cyclohexenecarbonitrile, complex of cuprous nitrate and 2-cyclohexenecanbonitrile, complex of cuprous nitrate and 1- cyclohexenecarbonitrile, and the like.
The cuprous complexes of the invention can be recovered from their reaction mixtures in high purity by cooling the reaction mixture to precipitate the cuprous complex and isolation by conventional filtration procedure. If the cuprous complex reaction product does not crystallize on cooling, the reaction product can be precipitated by the addition of an organic non-solvent such as acetone, ethyl ether, ethyl acetate, dioxane, and the like. If additional purification of the copper complexes is desired, Conventional recrystallization pro-- cedures can be used.
The following examples are illustrative:
Example 1 Cuprous chloride (10 grams) was added portionwise with agitation to 54 grams of 3-cyclohexenecarbonitrile in a nitrogen atmosphere. The reaction was exothermic, raising the temperature from about 20 C. to 35 C. during the addition. After completion of the addition of the cuprous chloride, the reaction mixture was kept at 75 C. for 4 hours. The reaction mixture was filtered warm and stored overnight in a refrigerator at a temperature of approximately 10 C. where the reaction mixture crystallized to a solid mass. The reaction mixture was warmed to room temperature and the solid was filtered, the filter cake was recrystallized from acetone, dried at room temperature and analyzed to be the desired cuprous chloride complex of 3-cyclohexenecarbonitrile. -It melted at 7 274 C.
The'infrared spectrum and analytical data confirmed the structure as 2C H CN+C11CL In an analogous manner, -n-hexyl-3-cyclohexene-carbonitrile is reacted with cuprous nitrate to obtain the corresponding cuprous nitrate complex of 5-n-hexyl-3- cyclohexenecarobnitrile. Additionally, 2-cyclohexenecarbonitrile is reacted with cuprous sulfate to obtain the corresponding cuprous sulfate complex of 2-cyclohexenecanbonitrile.
Example 2 A 5 gram sample of scoured and dried knitted tubing of continuous yarns composed of a terpolymer of acrylonitrile; vinyl chloride and vinylidene chloride [in a ratio, respectively, of 70:20:10] was added to a 200 milliliter total Volume aqueous dyebath containing 1 percent by Weight of the yarn of Pergegal OK (a cationic condensation product of ethylene oxide and an organic amine marketed by General Aniline and Film Corporation), 2 percent by weight of the yarn of concentrated sulfuric acid, 3 percent by weight of the yarn of Xylene Milling Blue G.L. (Acid Blue 1 02-50315) and 3.0 percent by weight of the yarn of the cuprous chloride complex of 3-cyclohexenecarbonitrile. The cuprous chloride complex of 3-cyclohexenecarbonitrile was added as a mixture of 5 parts by weight of acetonitrile to 1 part by Weight of cuprous chloride complex of 3-cyclohexenecarbonitrile. The bath temperature was raised to boiling in about 20 minutes and held for 90 minutes at the boiling temperature. The dyed fabric was then raised, scoured, rinsed, hydroextracted and dried at 130 C. for 10 minutes. After drying, the dyed fabric had a final K/S* value of 12.9. The common Fade-O-Meter test indicated a light fastness rating of the dyed fabric of 40 hours.
What is claimed is:
1. The cuprous complex produced by'the reaction of a cuprous salt of an inorganic mineral acid with a cyclohexene-canbonitrile of the formula:
wherein each R, individually is selected from the group consisting of hydrogen and the alkyl radicals of from 1 to 6 carbon atoms, at a temperature of from about 20 C. to about C.
2. The cuprous complex produced by the reaction of cuprous chloride with 3-cyclohexenecarbonitrile at a temperature of from about 20 C. to about 100 C.
3. The cuprous complex produced by the reaction of cuprous nitrate with 5-n-hexyl-3-cyclohexenecanbonitrile at a temperature of from about 20 C. to about 100 C.
4. The cuprous complex produced by the reaction of cuprous sulfate with 2-cyclohexenecarbonitrile at a temperature of from about 20 C. to about 100 C.
No references cited.
The amount of dye on fiber or the depth of color are approximately pro ortional to the K/ S value which is a. measure of the light re eeted from the dyed sample. The larger the K/S value, the deeper the shade; and a K/S value of 20 is approximately twlce as deep as a. K/S value of 10. The determination of the K/S values is set forth in an article by D. B. Judd, Color in Business, Science and Industry, 1952, pp. 314-342. V
Claims (1)
1. THE CUPROUS COMPLEX PRODUCED BY THE REACTION OF A CUPROUS SALT OF AN INORGANIC MINERAL ACID WITH A CYCLOHEXENE-CARBONITRILE OF THE FORMULA:
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US78250A US3051736A (en) | 1960-12-27 | 1960-12-27 | Cuprous complexes |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US78250A US3051736A (en) | 1960-12-27 | 1960-12-27 | Cuprous complexes |
Publications (1)
Publication Number | Publication Date |
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US3051736A true US3051736A (en) | 1962-08-28 |
Family
ID=22142864
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US78250A Expired - Lifetime US3051736A (en) | 1960-12-27 | 1960-12-27 | Cuprous complexes |
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Country | Link |
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US (1) | US3051736A (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3156708A (en) * | 1960-12-27 | 1964-11-10 | Union Carbide Corp | Cuprous complexes |
US3247234A (en) * | 1961-10-03 | 1966-04-19 | Dow Chemical Co | Cupric catalyst |
US3883302A (en) * | 1970-11-16 | 1975-05-13 | Hacoba Textilmaschinen | High-bulk polyacrylonitrile yarn |
US3995992A (en) * | 1973-10-18 | 1976-12-07 | Ciba-Geigy Ag | Transfer printing process for dyeing and printing organic material which can be dyed with cationic dyes |
US4885368A (en) * | 1985-06-21 | 1989-12-05 | Basf Aktiengesellschaft | Radical ion salts |
-
1960
- 1960-12-27 US US78250A patent/US3051736A/en not_active Expired - Lifetime
Non-Patent Citations (1)
Title |
---|
None * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3156708A (en) * | 1960-12-27 | 1964-11-10 | Union Carbide Corp | Cuprous complexes |
US3247234A (en) * | 1961-10-03 | 1966-04-19 | Dow Chemical Co | Cupric catalyst |
US3883302A (en) * | 1970-11-16 | 1975-05-13 | Hacoba Textilmaschinen | High-bulk polyacrylonitrile yarn |
US3995992A (en) * | 1973-10-18 | 1976-12-07 | Ciba-Geigy Ag | Transfer printing process for dyeing and printing organic material which can be dyed with cationic dyes |
US4885368A (en) * | 1985-06-21 | 1989-12-05 | Basf Aktiengesellschaft | Radical ion salts |
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