US3657296A - Organogold compounds - Google Patents
Organogold compounds Download PDFInfo
- Publication number
- US3657296A US3657296A US59713A US3657296DA US3657296A US 3657296 A US3657296 A US 3657296A US 59713 A US59713 A US 59713A US 3657296D A US3657296D A US 3657296DA US 3657296 A US3657296 A US 3657296A
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- US
- United States
- Prior art keywords
- gold
- carbon atoms
- compounds
- group containing
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 150000001875 compounds Chemical class 0.000 title abstract description 44
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 4
- 239000010931 gold Substances 0.000 description 39
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 32
- 229910052737 gold Inorganic materials 0.000 description 31
- 125000004432 carbon atom Chemical group C* 0.000 description 26
- 125000000217 alkyl group Chemical group 0.000 description 24
- -1 2- ethylhexyl Chemical group 0.000 description 21
- 125000003118 aryl group Chemical group 0.000 description 14
- 125000001309 chloro group Chemical group Cl* 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 125000004122 cyclic group Chemical group 0.000 description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 8
- 239000010408 film Substances 0.000 description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 125000005037 alkyl phenyl group Chemical group 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- ZBKIUFWVEIBQRT-UHFFFAOYSA-N gold(1+) Chemical compound [Au+] ZBKIUFWVEIBQRT-UHFFFAOYSA-N 0.000 description 5
- 125000001624 naphthyl group Chemical group 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- 125000000623 heterocyclic group Chemical group 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- HQEMVCBNLSTVAX-UHFFFAOYSA-N 1,3-diethyl-2-isocyanobenzene Chemical compound CCC1=CC=CC(CC)=C1[N+]#[C-] HQEMVCBNLSTVAX-UHFFFAOYSA-N 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- 150000002344 gold compounds Chemical class 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- GQKWLGUUHHQIQJ-UHFFFAOYSA-N 1-fluoro-3-isocyanobenzene Chemical compound FC1=CC=CC([N+]#[C-])=C1 GQKWLGUUHHQIQJ-UHFFFAOYSA-N 0.000 description 2
- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 description 2
- 125000004180 3-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(F)=C1[H] 0.000 description 2
- ZZLCFHIKESPLTH-UHFFFAOYSA-N 4-Methylbiphenyl Chemical group C1=CC(C)=CC=C1C1=CC=CC=C1 ZZLCFHIKESPLTH-UHFFFAOYSA-N 0.000 description 2
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920002871 Dammar gum Polymers 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000007818 Grignard reagent Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 229940052303 ethers for general anesthesia Drugs 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 150000004795 grignard reagents Chemical class 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- BRKADVNLTRCLOW-UHFFFAOYSA-M magnesium;fluorobenzene;bromide Chemical compound [Mg+2].[Br-].FC1=CC=[C-]C=C1 BRKADVNLTRCLOW-UHFFFAOYSA-M 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 1
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 description 1
- RNQKOGLJJFVNRD-UHFFFAOYSA-N 1-isocyano-4-methylbenzene Chemical compound CC1=CC=C([N+]#[C-])C=C1 RNQKOGLJJFVNRD-UHFFFAOYSA-N 0.000 description 1
- RZELGCMBQAPXRI-UHFFFAOYSA-N 1-isocyanododecane Chemical compound CCCCCCCCCCCC[N+]#[C-] RZELGCMBQAPXRI-UHFFFAOYSA-N 0.000 description 1
- AWJCOFYWVBNFET-UHFFFAOYSA-N 1-isocyanohexane Chemical compound CCCCCC[N+]#[C-] AWJCOFYWVBNFET-UHFFFAOYSA-N 0.000 description 1
- ZZKQDMRCHFQQCQ-UHFFFAOYSA-N 2-Naphthyl isocyanide Chemical compound C1=CC=CC2=CC([N+]#[C-])=CC=C21 ZZKQDMRCHFQQCQ-UHFFFAOYSA-N 0.000 description 1
- AAPXKKZEPJFEEX-UHFFFAOYSA-N 2-isocyano-1,3-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC(C(C)C)=C1[N+]#[C-] AAPXKKZEPJFEEX-UHFFFAOYSA-N 0.000 description 1
- PLAZTCDQAHEYBI-UHFFFAOYSA-N 2-nitrotoluene Chemical compound CC1=CC=CC=C1[N+]([O-])=O PLAZTCDQAHEYBI-UHFFFAOYSA-N 0.000 description 1
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000006306 4-iodophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1I 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 241000723346 Cinnamomum camphora Species 0.000 description 1
- WEEGYLXZBRQIMU-UHFFFAOYSA-N Eucalyptol Chemical compound C1CC2CCC1(C)OC2(C)C WEEGYLXZBRQIMU-UHFFFAOYSA-N 0.000 description 1
- VFPDAAQAKDGSHQ-UHFFFAOYSA-M [Br-].FC1=CC=CC([Mg+])=C1 Chemical compound [Br-].FC1=CC=CC([Mg+])=C1 VFPDAAQAKDGSHQ-UHFFFAOYSA-M 0.000 description 1
- 229960001040 ammonium chloride Drugs 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 229930008380 camphor Natural products 0.000 description 1
- 229960000846 camphor Drugs 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 229930007050 cineol Natural products 0.000 description 1
- 229960005233 cineole Drugs 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229960004132 diethyl ether Drugs 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- YQALRAGCVWJXGB-UHFFFAOYSA-M gold(1+);methylsulfanylmethane;chloride Chemical compound CS(C)=[Au]Cl YQALRAGCVWJXGB-UHFFFAOYSA-M 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- SGZHLLQPCVCEDC-UHFFFAOYSA-L magnesium;bromide;chloride Chemical compound Cl[Mg]Br SGZHLLQPCVCEDC-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 150000002900 organolithium compounds Chemical class 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229940087124 spike lavender oil Drugs 0.000 description 1
- FAGLEPBREOXSAC-UHFFFAOYSA-N tert-butyl isocyanide Chemical compound CC(C)(C)[N+]#[C-] FAGLEPBREOXSAC-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
- C23C16/18—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metallo-organic compounds
-
- 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
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/105—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by conversion of non-conductive material on or in the support into conductive material, e.g. by using an energy beam
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/11—Treatments characterised by their effect, e.g. heating, cooling, roughening
- H05K2203/1105—Heating or thermal processing not related to soldering, firing, curing or laminating, e.g. for shaping the substrate or during finish plating
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/12—Using specific substances
- H05K2203/121—Metallo-organic compounds
Definitions
- novel organogold compounds having the formula RNCAuR where R is an alkyl group containing up to 12 carbon atoms or an aryl group containing up to 12 carbon atoms in the ring system where R is an alkyl group containing up to 12 carbon atoms, an aryl group containing up to 12 carbon atoms in the ring system or a heterocyclic or 6-membered ring containing 0, S or N in the ring, and Au is gold in the +1 oxidation state. These compounds are useful in the production of gold films.
- a composition containingan organogold compound is applied, in the desired pattern or configuration, to the-substrate and heated to decompose the compound and volatilize the organic constituents leaving a metallic gold film adhering to the substrate.
- the gold compounds principally used for this purpose have been gold resinates which possess certain disadvantages, chiefly odor and lack of purity.
- novel compounds of the present invention have the Formula RNCAuR where R is an alkyl group containing up to 12 carbon atoms or an aryl group containing up to 12 carbon atoms in the ring system; where R is an alkyl group containingup to 12 carbon atoms, an aryl group containing up to 12 carbon atoms in the ring system or a heterocyclic 5- or 6-membered ring containing 0, S or N in the ring, and where Au is gold in the +1 oxidation state.
- the compounds of the invention may readily be prepared by reacting a chloro(organisocyanide)gold(l) complex, RNCAuCl, with a Grignard reagent, R MgBr, according to the equation RNCAuCl +R MgBr- RNCAuR MgBrCl
- R MgBr a Grignard reagent
- the reaction involves 1 mol of the chloro(organoisocyanide)gold(I) complex .per mol of Grignard compound.
- R is derived from the R of the chloro(organoisocyanide)gold(I) compound, and hence R in the latter compound will be alkyl containing up to 12 carbon atoms or aryl containing up to 12 carbon atoms in the ring system.
- alkyl includes cycloalkyl, and examples of alkyl R in the chloro(alkylisocyanide)gold(I) compound, and hence in the products 3,657,296 Patented Apr. 18, 1972 of the invention, are: methyl, ethyl, t-butyl, n-hexyl, 2- ethylhexyl, dodecyl, cyclopentyl and cyclohexyl.
- R may be aryl, such as phenyl, biphenyl or naphthyl and the aryl nucleus may contain substituents such as up to five alkyl groups, each containing up to 6 carbon atoms, or up to 4 halogens.
- aryl R in the chloro(arylisocyanide)gold(I) compounds are: phenyl, m-fluorophenyl, p-fiuorophenyl, p-iodophenyl, p-tolyl, 2,6-diethylphenyl, 2,6-diisopropylphenyl, 2-methyl-6-ethyl phenyl, 2,6 di-n-hexyl phenyl, 2,3,4,5,6-pentamethyl phenyl, biphenyl, 4-methylbiphenyl, naphthyl and Z-methyl-l naphthyl.
- Particularly preferred Rgroups are dialkyl phenyl groups, each alkyl group containing up to 6 carbon atoms, especially where the alkyl groups are in the 2 and 6 positions.
- chloro(organoisocyanide)gold(I) compounds may be prepared by reacting the appropriate organoisocyanide with chloro(dimethylsulfide)gold(I) as disclosed and claimed in my copending application Ser. No. 59,712 filed July 30, 1970 [See also J. Am. Chem, Soc., 91, 6151 (1969)].
- R in the products of the invention is derived from the Grignard compound R MgBr.
- R in the Grignard compound may be alkyl containing up to 12 carbon atoms, aryl containing up to 12 carbon atoms, in the ring system or a heterocyclic 5- or 6-membered ring containing an O, S or N in the ring.
- alkyl includes cycloalkyl, and examples of alkyl R in the Grignard compound, and hence in the products of the invention are: methyl, ethyl, t-butyl, 2-ethylhexyl, dodecyl, cyclopentyl and cyclohexyl.
- -R may be aryl, such as phenyl, biphenyl or naphthyl and the aryl nucleus may contain substituents such as up to five alkyl groups, each containing up to 6 carbon atoms, or up to five halogens.
- aryl R in the Grignard compound examples are: phenyl, m-fiuorophenyl, p-fiuorophenyl, ptolyl, ethylphenyl, p-t-butylphenyl, p-n-hexylphenyl, 2,6- diethylphenyl, 2,6-diisopropylphenyl, Z-methyl -6-ethyl phenyl, 2,6-di-n-hexylphenyl, 2,3,4,5,6-pentamethyl phenyl, biphenyl, 4'-methylbis phenyl, naphthyl and Z-methyl-lnaphthyl.
- R as a 5-'or 6-membered ring containing an O, S or N in the ring are: Z-thienyl, 2-furyl, 3-isothiazolyl and 2-(6-methyl)pyridyl.
- Particularly preferred R groups are alkylphenyl groups in which the alkyl group contains up to 6 carbon atoms.
- the chloro (organoisocyanide)gold(I) compound and the Grignard compound are reacted in an organic solvent.
- the preferred solvents are ethers, like diethylether and tetrahydrofuran.
- the concentration of the reactants in the solvent is not critical and may range, in terms of the chloro (organoisocyanide)gold(I) compound, from about 0.05 to about 2 molar and, in most cases, from about 0.1 to about 1 molar, including any undissolved initially. In this connection, any of the reactant that does not dissolve initially will eventually become dissolved'and reacted as the reaction proceeds.
- the reaction temperature is not especially critical and may range from 0 to about 100 C. or to reflux depending upon the solvent. Generally, a slight heating is preferred and the preferred temperature range is from about 30 to about C.
- the reaction product may be recovered from the reaction medium by the addition of water to precipitate the magnesium salts, separating the organic layer and removing the organic solvent by heating or under reduced pressure, or both.
- the product may be purified using conventional techniques, such as by recrystallization.
- Organo lithium compounds R Li where R is as defined above are generally equivalent to the Grignard compounds and may be used in place thereof in producing products of the invention.
- the compounds of the present invention may be dissolved in a suitable organic solvent.
- Solvents may be selected from chlorinated hydrocarbons, like chloroform; ketones, like acetone; ethers, like tetrahydrofuran, and the like depending upon the particular compound and its solubility and the concentration desired.
- concentration of the compound in the composition may range from as low as 0.1 to as high as about 50%, by weight, of gold.
- compositions there may also be included an agent to adjust the viscosity of the composition and/or to aid in film formation.
- Sulfurized damar gum serves both of these purposes.
- a flux to promote adhesion of the metallic gold to the substrate may be included in the composition. Resinates of metals like chromium, rhodium and bismuth, and combinations thereof, are suitable for this purpose.
- organo gold compounds of the invention illustrated by the following compounds: methyl (n-hexylisocyanide) gold(I); t-butyl(p-tolylisocyanide)gold(I); o-ethylphenyL (n-dodecylisocyanide)gold(I); 2 thienyl(t butylisocyanide)gold(I), and 2 furyl(2,6-diisopropylphenylisocyanide)gold(I), and 4-biphenyl(2-naphthylisocyanide) gold (I).
- EXAMPLE 6 One gram of the 4-t-butylphenyl(2,6-diethylphenylisocyanide) gold(I) of Example 1, 0.3 g. of sulfurized damar gum and 0.35 g. of a 4.5% solution of a mixed chromium-, rhodium-, bismuth resinate(0.4 chromium resinate, 0.9 rhodium resinate and 3.1 bismuth resinate) in a vehicle composed of 30% o-nitrotoluene, 25% cineol, 20% chlorobenzene, 15% camphor and 10% spike lavender oil, were mixed with 3 g. of chlorobenzene.
- the mixture was brushed onto a china plate and fired to 750 C.
- the resulting bright gold film had excellent abra- SlOll resistance.
- compositions may be prepared and used employing the compounds of Examples 2-5 and tetrahydrofuran, acetone or chloroform as principal solvent in place of the chlorobenzene used above.
- Gold compounds of the formula RNCAuR where R is selected from the group consisting of alkyl groups containing up to 12 carbon atoms, and aryl groups containing up to 12 carbon atoms in the ring system; R is selected from the group consisting of alkyl groups containing up to 12 carbon atoms, aryl groups containing up to 12 carbon atoms in the ring system and heterocyclic 5- or 6-membered rings containing 0, S or N in the ring, and Au is gold in the +1 oxidation state.
- R is a dialkyl phenyl group, each alkyl group containing from 1 to 6 carbon atoms.
- R is an alkylphenyl group, the alkyl group containing from 1 to 6 carbon atoms.
- R is an alkyl phenyl group, the alkyl group containing from 1 to 6 carbon atoms.
- R is an a1kylphenyl group, the alkyl group containing from 1 to 6 carbon atoms.
- R is an alkylphenyl group, the alkyl group containing from 1 to 6 carbon atoms.
- R is an alkylphenyl group, the alkyl group containing from 1 to 6 carbon atoms.
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Abstract
THERE IS PROVIDED NOVEL ORGANOLGOLD COMPOUNDS HAVING THE FOURMULA RNCAUR1 WHERE R IS AN ALKYL GROUP CONTAINING UP TO 12 CARBON ATOMS OR AN ARYL GROUP CONTAINING UP TO 12 CARBON ATOMS IN THE RING SYSTEM WHERE R1 IS AN ALKYL GROUP CONTAINING UP TO 12 CARBON ATOMS, AN ARYL GROUP CONTAINING UP TO 12 CARBON ATOMS IN THE RING SYSTEM OR A HETEROCYCLIC 5-OR 6-MEMBERED RING CONTAINING O, S OR N IN THE RING, AND AU IS GOLD IN THE + 1 OXIDATION STATE. THESE COMPOUNDS ARE USEFUL IN THE PRODUCTION OF GOLD FILMS.
Description
United States Patent O 3,657,296 ORGANOGOLD COMPOUNDS Lawrence G. Vaughan, Wilmington, Del., assiguor to 11% du Pont de Nemours and Company, Wilmington,
No Drawing. Filed July 30, 1970, Ser. No. 59,713
' Int. Cl. .C07f 1/12 US. Cl. 260-430 1 11 Claims ABSTRACT OF THE DISCLOSURE There is provided novel organogold compounds having the formula RNCAuR where R is an alkyl group containing up to 12 carbon atoms or an aryl group containing up to 12 carbon atoms in the ring system where R is an alkyl group containing up to 12 carbon atoms, an aryl group containing up to 12 carbon atoms in the ring system or a heterocyclic or 6-membered ring containing 0, S or N in the ring, and Au is gold in the +1 oxidation state. These compounds are useful in the production of gold films.
BACKGROUND OF THE INVENTION In producing metallic gold films on substrates, for decorative purposes or for printed electrical circuitry, a composition containingan organogold compound is applied, in the desired pattern or configuration, to the-substrate and heated to decompose the compound and volatilize the organic constituents leaving a metallic gold film adhering to the substrate. The gold compounds principally used for this purpose have been gold resinates which possess certain disadvantages, chiefly odor and lack of purity.
It is the principal object of the present invention to provide novel organogold compounds which lack odor and can be obtained in a high state ofi purity and which are also highly soluble in organic solvents and decompose at relatively low temperature thereby being particularly useful in the productionof metallicagold films.
SUMMARY OF THE INVENTION The novel compounds of the present invention have the Formula RNCAuR where R is an alkyl group containing up to 12 carbon atoms or an aryl group containing up to 12 carbon atoms in the ring system; where R is an alkyl group containingup to 12 carbon atoms, an aryl group containing up to 12 carbon atoms in the ring system or a heterocyclic 5- or 6-membered ring containing 0, S or N in the ring, and where Au is gold in the +1 oxidation state.
DETAILED DESCRIPTION OF THE INVENTION The compounds of the invention may readily be prepared by reacting a chloro(organisocyanide)gold(l) complex, RNCAuCl, with a Grignard reagent, R MgBr, according to the equation RNCAuCl +R MgBr- RNCAuR MgBrCl As will be seen from the foregoing, the reaction involves 1 mol of the chloro(organoisocyanide)gold(I) complex .per mol of Grignard compound. However, in practice it is preferred to use some excess of the less expensive Grignard compound, generally not over 25% excess, to force the reaction to completion.
In the products of the invention R is derived from the R of the chloro(organoisocyanide)gold(I) compound, and hence R in the latter compound will be alkyl containing up to 12 carbon atoms or aryl containing up to 12 carbon atoms in the ring system. The term alkyl includes cycloalkyl, and examples of alkyl R in the chloro(alkylisocyanide)gold(I) compound, and hence in the products 3,657,296 Patented Apr. 18, 1972 of the invention, are: methyl, ethyl, t-butyl, n-hexyl, 2- ethylhexyl, dodecyl, cyclopentyl and cyclohexyl. R may be aryl, such as phenyl, biphenyl or naphthyl and the aryl nucleus may contain substituents such as up to five alkyl groups, each containing up to 6 carbon atoms, or up to 4 halogens. Examples of aryl R in the chloro(arylisocyanide)gold(I) compounds, and hence in the products of the invention, are: phenyl, m-fluorophenyl, p-fiuorophenyl, p-iodophenyl, p-tolyl, 2,6-diethylphenyl, 2,6-diisopropylphenyl, 2-methyl-6-ethyl phenyl, 2,6 di-n-hexyl phenyl, 2,3,4,5,6-pentamethyl phenyl, biphenyl, 4-methylbiphenyl, naphthyl and Z-methyl-l naphthyl. Particularly preferred Rgroups are dialkyl phenyl groups, each alkyl group containing up to 6 carbon atoms, especially where the alkyl groups are in the 2 and 6 positions.
The chloro(organoisocyanide)gold(I) compounds may be prepared by reacting the appropriate organoisocyanide with chloro(dimethylsulfide)gold(I) as disclosed and claimed in my copending application Ser. No. 59,712 filed July 30, 1970 [See also J. Am. Chem, Soc., 91, 6151 (1969)].
R in the products of the invention, is derived from the Grignard compound R MgBr. Hence, R in the Grignard compound may be alkyl containing up to 12 carbon atoms, aryl containing up to 12 carbon atoms, in the ring system or a heterocyclic 5- or 6-membered ring containing an O, S or N in the ring. The term alkyl includes cycloalkyl, and examples of alkyl R in the Grignard compound, and hence in the products of the invention are: methyl, ethyl, t-butyl, 2-ethylhexyl, dodecyl, cyclopentyl and cyclohexyl. -R may be aryl, such as phenyl, biphenyl or naphthyl and the aryl nucleus may contain substituents such as up to five alkyl groups, each containing up to 6 carbon atoms, or up to five halogens. Examples of aryl R in the Grignard compound, and hence in the products of the invention, are: phenyl, m-fiuorophenyl, p-fiuorophenyl, ptolyl, ethylphenyl, p-t-butylphenyl, p-n-hexylphenyl, 2,6- diethylphenyl, 2,6-diisopropylphenyl, Z-methyl -6-ethyl phenyl, 2,6-di-n-hexylphenyl, 2,3,4,5,6-pentamethyl phenyl, biphenyl, 4'-methylbis phenyl, naphthyl and Z-methyl-lnaphthyl. Examples of R as a 5-'or 6-membered ring containing an O, S or N in the ring are: Z-thienyl, 2-furyl, 3-isothiazolyl and 2-(6-methyl)pyridyl. Particularly preferred R groups are alkylphenyl groups in which the alkyl group contains up to 6 carbon atoms.
In preparing the products of the invention, the chloro (organoisocyanide)gold(I) compound and the Grignard compound are reacted in an organic solvent. The preferred solvents are ethers, like diethylether and tetrahydrofuran. The concentration of the reactants in the solvent is not critical and may range, in terms of the chloro (organoisocyanide)gold(I) compound, from about 0.05 to about 2 molar and, in most cases, from about 0.1 to about 1 molar, including any undissolved initially. In this connection, any of the reactant that does not dissolve initially will eventually become dissolved'and reacted as the reaction proceeds.
The reaction temperature is not especially critical and may range from 0 to about 100 C. or to reflux depending upon the solvent. Generally, a slight heating is preferred and the preferred temperature range is from about 30 to about C.
Because of the sensitivity of the Grignard compound to air and moisture it is advisable to protect it, as by carry,- ing out the reaction under an atmosphere of inert gas like nitrogen or argon.
The reaction product may be recovered from the reaction medium by the addition of water to precipitate the magnesium salts, separating the organic layer and removing the organic solvent by heating or under reduced pressure, or both. The product may be purified using conventional techniques, such as by recrystallization.
Organo lithium compounds R Li where R is as defined above, are generally equivalent to the Grignard compounds and may be used in place thereof in producing products of the invention.
-In utilizing the compounds of the present invention to produce gold films, they may be dissolved in a suitable organic solvent. Solvents may be selected from chlorinated hydrocarbons, like chloroform; ketones, like acetone; ethers, like tetrahydrofuran, and the like depending upon the particular compound and its solubility and the concentration desired. Although it is often preferred to have a relatively high concentration of the gold compound in the compositions, particularly where a heavy or thick gold film is desired, much lower concentrations may be dictated when light or thin films are desired. Thus, the concentration of the compound in the composition (in terms of gold present) may range from as low as 0.1 to as high as about 50%, by weight, of gold. In such compositions there may also be included an agent to adjust the viscosity of the composition and/or to aid in film formation. Sulfurized damar gum serves both of these purposes. Also included in the composition may be a flux to promote adhesion of the metallic gold to the substrate. Resinates of metals like chromium, rhodium and bismuth, and combinations thereof, are suitable for this purpose.
The invention will be more readily understood from a consideration of the following specific examples which are given for purposes of illustration only and are not intended to limit the scope of the invention in any way.
EXAMPLE 1 Preparation of 4-t-butylphenyl(2,6-diethylphenylisocyanide) gold (I) CzH5 To a solution of the Grignard reagent (32.5 mmoles) in tetrahydrofuran at 0 C. was added dropwise a solution of 10.0 g. (25.6 mmoles) of the gold complex in 30 ml. tetrahydrofuran. The mixture was stirred at room temperature for one hour, then heated at 60 C. for thirty minutes. After hydrolysis with saturated aqueous ammonium chlo ride solution, the organic layer was filtered and dried over sodium sulfate. The solvent was then removed under reduced pressure and the solid residue recrystallized from cyclohexane. The yield of product, M.P. l67-170 C. dec., was 8.42 g. (67% Analysis.-Calcd. for C H AuN (percent): C, 51.53; H, 5.36; Au, 40.25; N, 2.86. Found (percent): C, 50.88; H, 5.21; Au, 40.01; N, 2.83.
EXAMPLE 2 Preparation of m-fiuorophenyl(m-fiuorophenylisocyanide) gold(I) Q-Mgllr @nozmor l I F F A solution of the m-fiuorophenylmagnesium bromide (14.3 mmoles) was prepared in 50 ml. of ether. The solution was cooled to 0 C. and 4.5 g. (12.8 mmoles) of chloro(m fluorophenylisocyanide)gold(I) was added in one batch. The mixture was allowed to warm, stirred at room temperature for 1 hour and then refluxed for 1 hour. After hydrolysis with excess water, the ether layer was separated, dried over sodium sulfate, treated with decolorizing charcoal and filtered. The ether was removed under reduced pressure. The product was recrystallized first from a mixture of 200 ml. of cyclohexane and 10 ml. of benzene (held at 65 C.) then recrystallized a second time from methanol (maximum temperature 60 C.), giving an analytical product of M.P. -l1l C., dec. The yield was 4.95 g. (94%).
Analysis.Calcd. for C H AuF N (percent): C, 37.78; H, 1.95; Au, 47.68; F, 9.20; -N, 3.39. Found (percent): C, 37.73; H, 1.80; Au, 47.51; F, 9.10; N, 3.24.
EXAMPLES 3-5 Following the procedure of Example 2 but using p-fluorophenylmagnesium bromide and chloro(p-fiuorophenylisocyanide)gold(I); p-fluorophenylmagnesium bromide and chloro(m-fluorophenylisocyanide)gold(I), and m-fluorophenylmagnesium bromide and chloro(p-fiuorophenylisocyanide)gold(l), respectively, the following respective compounds were prepared.
Ex.: Compounds 3 p-fluorophenyl(p-fiuorophenylisocyanide)gold(I). 4 p-fluorophenyl(m-fluorophenylisocyanide)gold (I). 5 m-fluorophenyl (p-fluorophenylisocyanide gold ('I) In preparing compounds of Examples 3 and 4, they were recrystallized first from a mixture (3:1 and 5: 1, respectively) of cyclohexane and benzene, then from methanol. The compound of Example 5 was recrystallized first from cyclohexane, then from ethanol.
Analysis.Calculated for C H AuF N (percent): C, 37.78; H, 1.95; Au, 47.68; F, 9.20; N, 3.39.
row-co zouq By following procedures analogous to those set forth in the foregoing examples there may be prepared other organo gold compounds of the invention illustrated by the following compounds: methyl (n-hexylisocyanide) gold(I); t-butyl(p-tolylisocyanide)gold(I); o-ethylphenyL (n-dodecylisocyanide)gold(I); 2 thienyl(t butylisocyanide)gold(I), and 2 furyl(2,6-diisopropylphenylisocyanide)gold(I), and 4-biphenyl(2-naphthylisocyanide) gold (I).
The following examples illustrate the utility of the compounds of the present invention.
EXAMPLE 6 One gram of the 4-t-butylphenyl(2,6-diethylphenylisocyanide) gold(I) of Example 1, 0.3 g. of sulfurized damar gum and 0.35 g. of a 4.5% solution of a mixed chromium-, rhodium-, bismuth resinate(0.4 chromium resinate, 0.9 rhodium resinate and 3.1 bismuth resinate) in a vehicle composed of 30% o-nitrotoluene, 25% cineol, 20% chlorobenzene, 15% camphor and 10% spike lavender oil, were mixed with 3 g. of chlorobenzene.
The mixture was brushed onto a china plate and fired to 750 C. The resulting bright gold film had excellent abra- SlOll resistance.
In a similar manner compositions may be prepared and used employing the compounds of Examples 2-5 and tetrahydrofuran, acetone or chloroform as principal solvent in place of the chlorobenzene used above.
What is claimed is:
1. Gold compounds of the formula RNCAuR where R is selected from the group consisting of alkyl groups containing up to 12 carbon atoms, and aryl groups containing up to 12 carbon atoms in the ring system; R is selected from the group consisting of alkyl groups containing up to 12 carbon atoms, aryl groups containing up to 12 carbon atoms in the ring system and heterocyclic 5- or 6-membered rings containing 0, S or N in the ring, and Au is gold in the +1 oxidation state.
2. The compounds of claim 1 where R is a phenyl group.
3. The compounds of claim 2 wherein R is a dialkyl phenyl group, each alkyl group containing from 1 to 6 carbon atoms.
4. The compound of claim 3 wherein the alkyl groups are in the 2- and 6-positions.
5. The compounds of claim 4 wherein R is 2,6-diethylphenyl.
6. The compounds of claim 1 wherein R is an alkylphenyl group, the alkyl group containing from 1 to 6 carbon atoms.
7. The compounds of claim 2 wherein R is an alkyl phenyl group, the alkyl group containing from 1 to 6 carbon atoms.
8. The compounds of claim 3 wherein R is an a1kylphenyl group, the alkyl group containing from 1 to 6 carbon atoms.
9. The compounds of claim 4 wherein R is an alkylphenyl group, the alkyl group containing from 1 to 6 carbon atoms.
10. The compounds of claim 5 wherein R is an alkylphenyl group, the alkyl group containing from 1 to 6 carbon atoms.
11. 4 t butylphenyl(2,6 diethylphenylisocyanide) gold(I).
References Cited Vaughan et al., J. Amer. Chem. Soc., vol. 91, pp. 6151-6 (October 1969).
TOBIAS E. LEVOW, Primary Examiner H. M. S. SNEED, Assistant Examiner US. Cl. X.R.
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US5971370A | 1970-07-30 | 1970-07-30 |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3755329A (en) * | 1970-12-22 | 1973-08-28 | Du Pont | Nitrogen-heterocyclylgold(i) compounds |
US4714627A (en) * | 1984-11-29 | 1987-12-22 | Ontario Development Corp. | Method of gold deposition using volatile organogold complexes |
US4757863A (en) * | 1987-04-24 | 1988-07-19 | Challacombe Robert D | Well cleaning method and apparatus |
-
1970
- 1970-07-30 US US59713A patent/US3657296A/en not_active Expired - Lifetime
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3755329A (en) * | 1970-12-22 | 1973-08-28 | Du Pont | Nitrogen-heterocyclylgold(i) compounds |
US4714627A (en) * | 1984-11-29 | 1987-12-22 | Ontario Development Corp. | Method of gold deposition using volatile organogold complexes |
US4757863A (en) * | 1987-04-24 | 1988-07-19 | Challacombe Robert D | Well cleaning method and apparatus |
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