GB2190080A - Anthraquinones - Google Patents
Anthraquinones Download PDFInfo
- Publication number
- GB2190080A GB2190080A GB08610765A GB8610765A GB2190080A GB 2190080 A GB2190080 A GB 2190080A GB 08610765 A GB08610765 A GB 08610765A GB 8610765 A GB8610765 A GB 8610765A GB 2190080 A GB2190080 A GB 2190080A
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- United Kingdom
- Prior art keywords
- process according
- catalyst
- reaction
- butadiene
- anthraquinone
- 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.)
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- 150000004056 anthraquinones Chemical class 0.000 title claims abstract description 20
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims abstract description 15
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 claims abstract description 13
- -1 mono-substituted anthraquinone Chemical class 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 5
- 125000002252 acyl group Chemical group 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 4
- 150000002367 halogens Chemical class 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 17
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract 1
- 238000005580 one pot reaction Methods 0.000 abstract 1
- 125000001424 substituent group Chemical group 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 150000002791 naphthoquinones Chemical class 0.000 description 3
- 150000003839 salts Chemical group 0.000 description 3
- ZVALGBPJYGUWIS-UHFFFAOYSA-N 1,4-dihydroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1CC=CC2 ZVALGBPJYGUWIS-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- LKNKAEWGISYACD-ONEGZZNKSA-N (1e)-1-bromobuta-1,3-diene Chemical compound Br\C=C\C=C LKNKAEWGISYACD-ONEGZZNKSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- SXAMGRAIZSSWIH-UHFFFAOYSA-N 2-[3-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,2,4-oxadiazol-5-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NOC(=N1)CC(=O)N1CC2=C(CC1)NN=N2 SXAMGRAIZSSWIH-UHFFFAOYSA-N 0.000 description 1
- WWJSRLYOPQYXMZ-UHFFFAOYSA-N 2-bromobuta-1,3-diene Chemical compound BrC(=C)C=C WWJSRLYOPQYXMZ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- NMQQBXHZBNUXGJ-SNAWJCMRSA-N [(1e)-buta-1,3-dienyl] acetate Chemical compound CC(=O)O\C=C\C=C NMQQBXHZBNUXGJ-SNAWJCMRSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- PMOLKBNSJNLKGB-UHFFFAOYSA-N buta-1,3-dien-2-yl acetate Chemical compound CC(=O)OC(=C)C=C PMOLKBNSJNLKGB-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- RBHJBMIOOPYDBQ-UHFFFAOYSA-N carbon dioxide;propan-2-one Chemical compound O=C=O.CC(C)=O RBHJBMIOOPYDBQ-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- AHAREKHAZNPPMI-UHFFFAOYSA-N hexa-1,3-diene Chemical compound CCC=CC=C AHAREKHAZNPPMI-UHFFFAOYSA-N 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000005487 naphthalate group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- LPNBBFKOUUSUDB-UHFFFAOYSA-M p-toluate Chemical compound CC1=CC=C(C([O-])=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-M 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N penta-1,3-diene Chemical compound CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 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
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C46/00—Preparation of quinones
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
Anthraquinone or a mono-substituted anthraquinone, wherein the substituent is selected from hydrogen, halogen, acyl, and alkyl, was prepared in a one step reaction which comprises reacting 1,4-naphthaquinone with a 1,3-butadiene compound which may be substituted as above, in the presence of a transition metal salt catalyst.
Description
SPECIFICATION
Anthraquinones
This invention relates to a process for preparing anthraquinones.
The anthraquinones probably comprise a greater number of dyes having outstanding fastness properties than anyothergroup of dyes, and anthraquinone is one of the mostvaluable intermediates in the manufacture of dyestuffs.
Conventionally, anthraquinone is manufactured from phthalic anhydride and dry benzene using a large amount of anhydrous aluminium chloride and an excess of benzenethat must be recovered. Other products ofthe process include hydrogen chloride and aluminium hydroxide.
German Offenlegungschrift No. 2,460,922 (Nippon Steel Chemical Co. Ltd.) describes a processor preparing pure anthraquinone by the reaction of 1 ,4-naphthaquinone with a small excess of 1 ,3-butadiene at 100-1 1 O"C in an autoclave followed by air oxidation of the resultanttetrahydroanthraquinone in the presence of a base. It is also known that anthraquinone can be prepared by the direct reaction of 1,3-butadiene with a mixture of naphthalene, phthalic anhydride and 1,4-naphthaquinone obtained by thevapoour phase oxidation of naphthalene (see U.S. Patent Specifications Nos. 2,652,408; 2,938,913; and 2,536,833).
According to the present invention there is provided a process for preparing a compound which can be represented by the general formula:
wherein X is hydrogen, halogen, an acyl group oran alkyl group, which process comprises reacting 1 ,4-naphthaquinonewith a 1,3-butadiene compound which can be represented by the general formula:
wherein Xis as previously defined, in the presence of a catalytic amount of a transition metal salt catalyst.
It has now been discovered that anthraquinones of the general formula (I) above can be obtained in good yield in a one step process by reacting 1 Anaphthaciuinone with a 1 ,3-butadiene, which may be substituted, in the presence of a transition metal salt catalyst and, preferably, phthalic acid. The 1 ,3-butadiene may be substituted, for example, with halogens such as chloro and bromo, acyl groups containing from 2 to 4carbon
atoms, such as acetyl, propionyl and n-butyryl; alkyl groups containing from 1 to 3 carbon atoms, such as
methyl, ethyl and isopropyl. The substitution can be in the 1 or 2 position.Representative examples of
substituted 1 ,3-butadienes which can be used in the process of the invention include 1 -acetoxy-1 ,3-butadiene; 2-acetoxy-1 ,3-butadiene; 1 -ch loro-1 ,3-butadiene; 2-chloro-1 ,3-butadiene; 1 -methyl-1 ,3-butadiene; 2-methyl-1 ,3-butadiene; 1 -ethyl-1 ,3-butadiene; 2ethyl-l ,3-butadiene; 1-bromo-1,3-butadiene; and 2-bromo-1,3-butadiene.
Preferably,the catalyst is a salt of Cr, Mn, Fe, Co, Ni, Cu or Zn, although other transition metals may be used
but are less preferred because of higher cost and limited availability. The anion used to form the salt may be
selected from a number of inorganic and organic anions, including chloride, nitrate, carbonate, bicarbonate, sulphate, sulphide, oxide, phthalate, benzoate, naphthalate, toluate and phosphate. If desired, the salt may beformed in situ. Whilst it is preferred to use catalysts containing iron, the particular anion employed aswell as the cation employed (otherthan iron) is not particularly important.The amount of catalyst employed will
depend upon the reactants butgenerallyfrom about 1% to about 20% by weight of the naphthaquinonewill
be sufficient.
Depending upon the reactant employed, it may be necessary to use a solvent. Useful solvents are alcohols
containing from 1 to 4 carbon atoms, such as methanol, ethanol, propanol and butanol; tetrahydrofuran and
dioxane.
For best results, there should be used a slight excess of 1 ,3-butadiene compound to naphthaquinone.
Thus,whilesubstantially equimolaramounts may be used, it is preferred that the molar ratio of naphthaquinoneto butadiene should be in the range 1:1.1 to 1:1.4.
Preferably, the reaction is conducted at a temperature in the range of from about 80"C to about 130 C and at a pressure in the range of about3 to about 8 atmospheres over a period in the range of from about 4 hoursto about 10 hours. A preferred temperature range is from 90"C to 11 00C and a preferred pressure range is from 4 to 6 atmospheres.
Inthefollowing Examples, which will serveto illustratethe invention and preferred embodiments thereof, all parts and percentages (as elsewhere in the specification and claims) are by weight unless otherwise indicated.
Example 1
Chemically pure 1 ,4-naphthaquinone (2.0 g, 0.013 mole), 13-butadiene (1.0 g, 0.018 mole) and anhydrous
FeCI3 (0.20 g, 0.0013 mole) were dissolved into 12 ml absolute alcohol and placed in a thick reaction tube (O.D.
1/2 to 5/8 inch, wall thickness 3/32 inch).
Chemically pure naphthaquinone was used as commercial grade naphthaquinone contains phthalic anhydride which causes the formation of anthraquinone. The tube was cooled to -70 C (dry ice-acetone) and evacuated by a high vacuum pump. Thetube was sealed in vacuum and heated at 90"-1 20"C for 17 hours, The pressure built up to 4-6 atmospheres during the reaction. Upon cooling the solution, the solid precipitated and was isolated by filtration and washed with dilute aqueous HCI and water. The solid was crystallized from 95% alcohol asyellow needles (m.p. 285-287"C) and identified as anthraquinone by l.R. and by mixed melting point. The yield was 2.30g (88%).
Example 2 (Comparative)
The reaction was carried out under the same conditions as described in Example 1 except that a catalyst was not employed. The white solid produced was filtered and identified as 1,4-dihydro-9,10-anthraquinone (m.p. 105 -108 C). The yield was 2.29 g, (86%).
Example 3
The reaction was carried out under the same conditions as described in Example 1 except that equal molar amounts of FeCI3 and phthalic acid were used. Anthraquinone (m.p. 284 -286 C) was obtained. The yield was 2.33 g, (90%).
Example 4
The reaction was carried out under the same conditions as described in Example 1 except that equal molar amounts of NiCI2 and phthalic acid were used, Anthraquinone (m.p. 284 -286"C) was obtained. The yield was 1.49, (54%). In addition to anthraquinone, many side products were obtained and the structures were not identified.
Example 5
The reaction was carried out under the same conditions as described in Example 1 except that equal molar amounts of Ni(NO3)2 and phthalic acid were used. Anthraquinone (m.p. 284 -286 C) was obtained. The yield was 1.5 g, (56%). Other side products were also obtained.
Example 6
The reaction was carried out under the same conditions as described in Example 1 except that equal molar amounts ofCo(NO3)2 and phthalic acid were used. Anthraquinone (m.p. 284 -286"C) was isolated. The yield was 1 9, (54%). Other side products were also obtained.
Example 7 1 ,4-Naphthaquinone (7.9 g, 0.05 mole), 1,3-butadiene (3.5 g, 0.07 mole), Fe(NO3)3 (1.0 g, 0.0025 mole) and phthalic acid (0.4 g, 0.0025 mole) were dissolved into 60 ml absolute alcohol. The mixture was placed in an autoclave. This was then cooled in dry ice/acetone and degassed.
The autoclavewasthen heated at 1 1O"Cfor 6 hours. The pressure built upto 6 atmospheres duringthe reaction. Afterthe reaction, the container was cooled to room temperature. The volatile gases were analyzed by mass spectrum and found to be hydrogen and unreacted butadiene.
The solid produced was isolated and recrystallized from 95% alcohol (m.p. 285 -287 C). The solid was identified as anthraquinone by l.R. measurement and by mixed melting point measurement. The yield was 9.3 g, (89.5%).
Example 8
The reaction was carried out using the same conditions as described in Example 7 except that Co(NO3)2 (0.073 g, 0.0025 mole) instead of FeCI3 was used as the catalyst. Hydrogen and unreacted butadiene were detected and anthraquinone (m.p. 285 -287 C) was obtained. The yield was 8.5 g, (87.7%).
Claims (17)
1. A process for preparing a compound which can be represented by the general formula:
wherein Xis hydrogen, halogen, an acyl group or an alkyl group which process comprises reacting 1,4-naphthaquinone with a 1 ,3-butadiene compound which can be represented by the general formula:
wherein Xis as previously defined, in the presence of a catalytic amount of a transition metal salt catalyst.
2. A process according to claim 1, wherein the catalyst is an iron salt.
3. A process according to claim 2, wherein the catalyst is FeCI3.
4. A process according to claim 2, wherein the catalyst is Fe(NO3)3.
5. A process according to claim 1 wherein the catalyst is a cobalt salt.
6. A process according to claim 5 wherein the catalyst is Co(NO3)2.
7. A process according to claim 1 wherein the catalyst is a nickel salt.
8. A process according to claim 7 wherein the catalyst is Ni(NO3).
9. A process according to claim 7 wherein the catalyst is Nick2.
10. A process according to any one of claims 1 to 9 wherein the reaction is conducted in the presence of phthalic acid.
11. A process according to any one of claims 1 to 10 wherein 1,4-naphthaquinone is reacted with 1,3-butadieneto produce anthraquinone.
12. A process according to any one of claims 1 to 11 wherein the reaction is carried out in a solvent.
13. A process according to claim 12 wherein an alcohol is employed as the solvent.
14. A process according to any one of claims 1 to 13 wherein the molar ratio of 1 ,4-naphthaquinoneto 1,3-butadiene compound is in the range offrom 1:1.1 to 1:1.4.
15. A process according to any one of claims 1 to 14, wherein the reaction is carried out at a temperature in the range of from 80"C to 130 C,
16. A process according to any one of claims 1 to 15, wherein the reaction is carried out at a pressure in the range offrom about 3 to about 8 atmospheres.
17. A process according to claim 1, substantially as described in the foregoing Examples.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8610765A GB2190080B (en) | 1986-05-02 | 1986-05-02 | Anthraquinones |
| JP11043986A JPS62267362A (en) | 1986-05-02 | 1986-05-14 | Production of anthraquinoes |
| DE19863616364 DE3616364A1 (en) | 1986-05-02 | 1986-05-15 | METHOD FOR PRODUCING ANTHRACHINONS |
| FR8607429A FR2599030B1 (en) | 1986-05-02 | 1986-05-23 | PROCESS FOR PRODUCING ANTHRAQUINONES. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8610765A GB2190080B (en) | 1986-05-02 | 1986-05-02 | Anthraquinones |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8610765D0 GB8610765D0 (en) | 1986-06-11 |
| GB2190080A true GB2190080A (en) | 1987-11-11 |
| GB2190080B GB2190080B (en) | 1990-03-21 |
Family
ID=10597239
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8610765A Expired - Lifetime GB2190080B (en) | 1986-05-02 | 1986-05-02 | Anthraquinones |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPS62267362A (en) |
| DE (1) | DE3616364A1 (en) |
| FR (1) | FR2599030B1 (en) |
| GB (1) | GB2190080B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0597287A1 (en) * | 1992-11-11 | 1994-05-18 | BASF Aktiengesellschaft | Process for the preparation of anthraquinones |
| WO1998033757A1 (en) * | 1997-02-03 | 1998-08-06 | Girex | Method for preparing substituted anthraquinone and application to the preparation of rheins |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB320375A (en) * | 1928-07-06 | 1929-10-07 | Ig Farbenindustrie Ag | Improvements in the manufacture and production of anthraquinone and its derivatives |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR39333E (en) * | 1930-06-19 | 1931-10-12 | Ig Farbenindustrie Ag | Process for the production of anthraquinone and its derivatives |
| US2652408A (en) * | 1951-07-14 | 1953-09-15 | American Cyanamid Co | Preparation of anthraquinone compounds |
| BE573902A (en) * | 1957-12-16 | |||
| DE2437220C3 (en) * | 1974-08-02 | 1979-06-13 | Bayer Ag, 5090 Leverkusen | Process for the production of anthraquinone |
| US4308211A (en) * | 1980-12-29 | 1981-12-29 | The Goodyear Tire & Rubber Company | Process for the preparation of anthraquinone |
| JPS57203027A (en) * | 1981-06-09 | 1982-12-13 | Kawasaki Kasei Chem Ltd | Purification of anthraquinone |
| JPS57206633A (en) * | 1981-06-12 | 1982-12-18 | Kawasaki Kasei Chem Ltd | Purifying method of anthraquinone |
-
1986
- 1986-05-02 GB GB8610765A patent/GB2190080B/en not_active Expired - Lifetime
- 1986-05-14 JP JP11043986A patent/JPS62267362A/en active Pending
- 1986-05-15 DE DE19863616364 patent/DE3616364A1/en not_active Ceased
- 1986-05-23 FR FR8607429A patent/FR2599030B1/en not_active Expired
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB320375A (en) * | 1928-07-06 | 1929-10-07 | Ig Farbenindustrie Ag | Improvements in the manufacture and production of anthraquinone and its derivatives |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0597287A1 (en) * | 1992-11-11 | 1994-05-18 | BASF Aktiengesellschaft | Process for the preparation of anthraquinones |
| US5387704A (en) * | 1992-11-11 | 1995-02-07 | Basf Aktiengesellschaft | Preparation of anthraquinones |
| WO1998033757A1 (en) * | 1997-02-03 | 1998-08-06 | Girex | Method for preparing substituted anthraquinone and application to the preparation of rheins |
| FR2759079A1 (en) * | 1997-02-03 | 1998-08-07 | Girex | PROCESS FOR THE PREPARATION OF SUBSTITUTED ANTHRAQUINONES AND APPLICATION TO THE PREPARATION OF RHEINES |
| US6057461A (en) * | 1997-02-03 | 2000-05-02 | Girex | Method for preparing substituted anthraquinone and application to the preparation of rheins |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3616364A1 (en) | 1987-11-19 |
| GB2190080B (en) | 1990-03-21 |
| FR2599030B1 (en) | 1988-12-02 |
| GB8610765D0 (en) | 1986-06-11 |
| JPS62267362A (en) | 1987-11-20 |
| FR2599030A1 (en) | 1987-11-27 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 732 | Registration of transactions, instruments or events in the register (sect. 32/1977) | ||
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19930502 |