US2207071A - Process of converting compounds of the acetylene series into compounds of the ethylene series - Google Patents
Process of converting compounds of the acetylene series into compounds of the ethylene series Download PDFInfo
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- US2207071A US2207071A US202274A US20227438A US2207071A US 2207071 A US2207071 A US 2207071A US 202274 A US202274 A US 202274A US 20227438 A US20227438 A US 20227438A US 2207071 A US2207071 A US 2207071A
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- acetylene
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- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 title description 18
- 150000001875 compounds Chemical class 0.000 title description 17
- 238000000034 method Methods 0.000 title description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical class C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 27
- WFYPICNXBKQZGB-UHFFFAOYSA-N butenyne Chemical group C=CC#C WFYPICNXBKQZGB-UHFFFAOYSA-N 0.000 description 15
- 239000011701 zinc Substances 0.000 description 14
- 229910052725 zinc Inorganic materials 0.000 description 14
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000005984 hydrogenation reaction Methods 0.000 description 8
- 229910017464 nitrogen compound Inorganic materials 0.000 description 8
- 150000002830 nitrogen compounds Chemical class 0.000 description 7
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- HSFWRNGVRCDJHI-UHFFFAOYSA-N Acetylene Chemical class C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 5
- 239000012736 aqueous medium Substances 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- BMRVLXHIZWDOOK-UHFFFAOYSA-N 2-butylnaphthalene-1-sulfonic acid Chemical compound C1=CC=CC2=C(S(O)(=O)=O)C(CCCC)=CC=C21 BMRVLXHIZWDOOK-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 150000000475 acetylene derivatives Chemical class 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 150000003974 aralkylamines Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- LLCSWKVOHICRDD-UHFFFAOYSA-N buta-1,3-diyne Chemical group C#CC#C LLCSWKVOHICRDD-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000007859 condensation product Substances 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
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- -1 heterocyclic nitrogen compounds Chemical class 0.000 description 1
- AUBDSFLQOBEOPX-UHFFFAOYSA-N hexa-1,5-dien-3-yne Chemical group C=CC#CC=C AUBDSFLQOBEOPX-UHFFFAOYSA-N 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002443 hydroxylamines Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- XNERWVPQCYSMLC-UHFFFAOYSA-N phenylpropiolic acid Chemical compound OC(=O)C#CC1=CC=CC=C1 XNERWVPQCYSMLC-UHFFFAOYSA-N 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- UORVCLMRJXCDCP-UHFFFAOYSA-N propynoic acid Chemical compound OC(=O)C#C UORVCLMRJXCDCP-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical class [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 235000009529 zinc sulphate Nutrition 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
- C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
Definitions
- the present invention relates to a process of converting compounds of the acetylene series into compounds of the ethylene series.
- Basic nitrogen compounds of the said kind are for example ammonia, hydroxylamines and hydrazines and organic amines, especially those soluble or easily dispersible in water such as primary, secondary and tertiary aliphatic monoamines and polyamines, aralkylamines, such as benzylamine, cycloaliphatic amines, aromatic amines, heterocyclic nitrogen compounds such as pyridine or piperidine, and quaternary ammonium hydroxides derived from these compounds.
- activating metals which are capable of forming galvanic elements with zinc there may be mentioned for example copper, manganese, iron, cobalt and nickel.
- the addition necessary for .the activation is usually very small. It can be established without trouble by a simple preliminary experiment which combination is most suitable for the hydrogenation to be carried out. In most cases, the addition of an activating metal can entirely be dispensed with.
- the zinc is obtained in so finely divided a form that it is suitable for direct re-use without further treatment.
- the zinc employed is 15 mainly obtained in the form of a zinc hydroxide suspension.
- the basic reacting nitrogen compounds are especially suitable for the reduction of acetylene compounds which are immiscible or diflicultly miscible with water because they act as solvent agents for the acetylene compounds and considerably accelerate the reaction. They may be used in various concentrations, for example in 20 per cent or preferably in from 4 to 6 per cent solu- 25 tions or suspensions. If desired, organic solvents which have a good solvent power for the acetylene compounds and which are not attacked under the reaction conditions may be added to the aqueous solutions, as for example aliphatic 30 alcohols. The hydrogenation may also be carried out in thepresence of indifferent substances.
- indifferent gases as for example indifferent gases. It is often advantageous to work in the presence of dispersing or wetting substances, for example of alkyl 35 naphthalene sulphonic alkali salts or the addition products of 20 molecular proportions of ethylene oxide to fatty alcohols of high molecular weight, in order to produce the most intimate possible contact between all the reactants.
- dispersing or wetting substances for example of alkyl 35 naphthalene sulphonic alkali salts or the addition products of 20 molecular proportions of ethylene oxide to fatty alcohols of high molecular weight
- the process according to this invention may be used for practically all compounds having triple carbon linkages, as for example for acetylene, phenylacetylene, vinylacetylene, diacetylene, divinylacetylene, methylbutinol, propiolic acid, phenylpropiolic acid and many other acetylene derivatives.
- Example 1 3 liters of vinylacetylene are shaken with a suspension of grams of about 7''! per cent electrolytic zinc dust, 1 gram of the condensation product of 1 molecular proportion of oleyl alcohol and 20 molecular proportions of ethylene oxide as a wetting agent and 23 grams of ethylamine in 200 cubic centimeters of water for several hours. Pure butadiene, containing only traces of unchanged vinylacetylene and butylene in addition to a little hydrogen, is obtained in almost the quantitative yield.
- butadiene is obtained in practically the quantitative yield from vinylacetylene when using the following mixtures:
- Example 3 2 liters of acetylene are shaken for several hours with a suspension of about 100 grams of 80 per cent electrolytic zinc dust and 1 gram of the sodium salt of butylnaphthalene sulphonic acid in a 5 per cent ammoniacal solution.
- the resulting gas consists of ethylene, unchanged acetylene, a little hydrogen and traces of ethane.
- Example 4 15 grams of phenylacetylene are shaken with a suspension of grams of about 80 per cent electrolytic zinc dust in 5 per cent ammonia solution containing dissolved therein a small amount of the sodium salt of butylnaphthalene sulphonic acid until a sample withdrawn is free from phenylacetylene, which is the case after some hours. Styrene is mainly obtained,
- a process for the conversion of compounds of the acetylene series into those of the ethylene series which consists in treating compounds of the acetylene series in an aqueous medium in the presence of basic reacting nitrogen compounds with metallic zinc.
- a process for the conversion of compounds of the acetylene series into those of the ethylene series which consists in treating compounds of the acetylene series in an aqueous medium in the presence of basic reacting nitrogen compounds with zinc dust.
- a process for the conversion of compounds of the acetylene series into those of the ethylene series which consists in treating compounds'of the acetylene series in an aqueous medium in the presence of basic reacting nitrogen compounds with zinc dust in the presence of a dispersing agent.
- a process for the conversion of vinylacetylene into butadiene which consists in treating vinylacetylene in an aqueous medium in the presence of basic reacting nitrogen compounds with zinc dust.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Patented July 9, 1940 UNITED STATES PATENT OFFICE,
PROCESS OF CONVERTING COMPOUNDS OF THE ACETYLENE SERIES INTO COM- POUNDS OF THE ETHYLENE SERIES No Drawing.
Application April 15, 1938, Serial No. 202,274. In Germany May 14, 1937 4 Claims.
The present invention relates to a process of converting compounds of the acetylene series into compounds of the ethylene series.
It has already been proposed to convert acety- 5 lene derivatives into ethylene derivatives by treating them with aqueous suspensions of zinc dust to which copper sulphate solution has been added. The zinc activated by precipitated copper thus reacts with water with the formation of hydrogen. This process has the objection that the hydrogenation proper requires a multiple of the calculated amount of zinc because on the one hand the reaction proceeds incompletely and on the other hand a considerable part of the zinc 5 is used up by the activation, passing into solution as zinc sulphate, and is thus consumed without being used for the hydrogenation. In order to obtain a satisfactory utilization of zinc, about one third of the zinc must be replaced by copper. We have now found that compounds of the acetylene series can be converted into compounds of the ethylene series in a considerably simpler and more advantageous manner by treating com pounds of the acetylene series in aqueous medium in the presence of basic reacting nitrogen compounds with metallic zinc, preferably in fine dispersion. as it is obtained, for example, in the electrolytic production of zinc. There may also be added as activators metals capable of forming galvanic elements with the zinc.
Basic nitrogen compounds of the said kind are for example ammonia, hydroxylamines and hydrazines and organic amines, especially those soluble or easily dispersible in water such as primary, secondary and tertiary aliphatic monoamines and polyamines, aralkylamines, such as benzylamine, cycloaliphatic amines, aromatic amines, heterocyclic nitrogen compounds such as pyridine or piperidine, and quaternary ammonium hydroxides derived from these compounds.
Contrary to expectation, only relatively small amounts of free hydrogen are formed in the hydrogenation by the present process, so that-the utilization of the zinc is very favorable. Moreover, the hydrogenation of the acetylene linkage proceeds only to the formation of the ethylene linkage without any appreciable formation of the corresponding saturated compounds. Even when acetylene compounds which contain olefinic double linkages in addition to the triple linkages are hydrogenated, the hydrogenation is limited to the triple linkages. The present invention, therefore, can most advantageously be used for the conversion of vinylacetylene into butadiene.
Among suitable activating metals which are capable of forming galvanic elements with zinc there may be mentioned for example copper, manganese, iron, cobalt and nickel. The addition necessary for .the activation is usually very small. It can be established without trouble by a simple preliminary experiment which combination is most suitable for the hydrogenation to be carried out. In most cases, the addition of an activating metal can entirely be dispensed with.
It is preferable toeifect the regeneration of 10 the zinc by electrolysis of the zinc compounds formed because in this way the zinc is obtained in so finely divided a form that it is suitable for direct re-use without further treatment. At the end of the hydrogenation the zinc employed is 15 mainly obtained in the form of a zinc hydroxide suspension. i
The basic reacting nitrogen compounds are especially suitable for the reduction of acetylene compounds which are immiscible or diflicultly miscible with water because they act as solvent agents for the acetylene compounds and considerably accelerate the reaction. They may be used in various concentrations, for example in 20 per cent or preferably in from 4 to 6 per cent solu- 25 tions or suspensions. If desired, organic solvents which have a good solvent power for the acetylene compounds and which are not attacked under the reaction conditions may be added to the aqueous solutions, as for example aliphatic 30 alcohols. The hydrogenation may also be carried out in thepresence of indifferent substances.
as for example indifferent gases. It is often advantageous to work in the presence of dispersing or wetting substances, for example of alkyl 35 naphthalene sulphonic alkali salts or the addition products of 20 molecular proportions of ethylene oxide to fatty alcohols of high molecular weight, in order to produce the most intimate possible contact between all the reactants.
Generally speaking it is suflicient to work at atmospheric pressure and at ordinary or slightly elevated temperature, but any other pressures may be used within a wide range of temperatures. The process maybe carried out continuously, discontinuously or in a cycle.
The process according to this invention may be used for practically all compounds having triple carbon linkages, as for example for acetylene, phenylacetylene, vinylacetylene, diacetylene, divinylacetylene, methylbutinol, propiolic acid, phenylpropiolic acid and many other acetylene derivatives.
The following examples will further illustrate how the said invention may be carried out in 66 practice but the invention is not restricted to these examples.
Example 1 3 liters of vinylacetylene are shaken with a suspension of grams of about 7''! per cent electrolytic zinc dust, 1 gram of the condensation product of 1 molecular proportion of oleyl alcohol and 20 molecular proportions of ethylene oxide as a wetting agent and 23 grams of ethylamine in 200 cubic centimeters of water for several hours. Pure butadiene, containing only traces of unchanged vinylacetylene and butylene in addition to a little hydrogen, is obtained in almost the quantitative yield.
In an otherwise identical manner, butadiene is obtained in practically the quantitative yield from vinylacetylene when using the following mixtures:
(1) 3 liters of vinylacetylene, 50 grams of '77 per cent electrolytic zinc dust and 36 grams of diethylamine.
( 2) 2 liters of vinylacetylene, 50 grams of 77 per cent electrolytic zinc dust and 36 grams of butylamine or grams of dibutylamine,
(3) 2 liters of vinylacetylene, 20 grams of about per cent electrolytic zinc dust and 43 grams of piperidine,
(4) 3 liters of vinylacetylene, 20 grams of 70 per cent electrolytic zinc dust, 23 grams or ethanolamine or 53 grains of diethanolamine or '75 grams of triethanolamine.
(5) 3 liters of vinylacetylene, 12 grams of about 70 per cent electrolytic zinc dust and 40 grams of pyridine,
" (6) 2 liters of vinylacetylene, 20 grams of about Emample 2 3 liters of vinylacetylene are shaken for some hours with a suspension of 50 grams of 77 per cent electrolytic zinc dust and 1 gram of the sodium salt of butylnaphthalene sulphonic acid in 200 cubic centimeters 01. about 5 per cent ammonia in a shaking flask. The gas obtained consists almost exclusively of butadiene with which a few per cent of hydrogen and vinylacetylene and only traces of butylene are mixed.
Example 3 2 liters of acetylene are shaken for several hours with a suspension of about 100 grams of 80 per cent electrolytic zinc dust and 1 gram of the sodium salt of butylnaphthalene sulphonic acid in a 5 per cent ammoniacal solution. The resulting gas consists of ethylene, unchanged acetylene, a little hydrogen and traces of ethane.
Example 4 15 grams of phenylacetylene are shaken with a suspension of grams of about 80 per cent electrolytic zinc dust in 5 per cent ammonia solution containing dissolved therein a small amount of the sodium salt of butylnaphthalene sulphonic acid until a sample withdrawn is free from phenylacetylene, which is the case after some hours. Styrene is mainly obtained,
What we claim is:
1. A process for the conversion of compounds of the acetylene series into those of the ethylene series which consists in treating compounds of the acetylene series in an aqueous medium in the presence of basic reacting nitrogen compounds with metallic zinc.
2. A process for the conversion of compounds of the acetylene series into those of the ethylene series which consists in treating compounds of the acetylene series in an aqueous medium in the presence of basic reacting nitrogen compounds with zinc dust.
3. A process for the conversion of compounds of the acetylene series into those of the ethylene series which consists in treating compounds'of the acetylene series in an aqueous medium in the presence of basic reacting nitrogen compounds with zinc dust in the presence of a dispersing agent.
4. A process for the conversion of vinylacetylene into butadiene which consists in treating vinylacetylene in an aqueous medium in the presence of basic reacting nitrogen compounds with zinc dust.
WALTER REPPE. ALEXANDER ROTHHAAS.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2207071X | 1937-05-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2207071A true US2207071A (en) | 1940-07-09 |
Family
ID=7990076
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US202274A Expired - Lifetime US2207071A (en) | 1937-05-14 | 1938-04-15 | Process of converting compounds of the acetylene series into compounds of the ethylene series |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2207071A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2519631A (en) * | 1945-06-11 | 1950-08-22 | Ici Ltd | Catalytic hydrogenation of alkenyl furans |
| DE972502C (en) * | 1954-10-23 | 1959-07-30 | Bayer Ag | Process for the preparation of N-trichloromethyl-thioimides |
| US2950334A (en) * | 1957-11-04 | 1960-08-23 | Du Pont | Process of preparing o-divinylbenzene |
| US3009969A (en) * | 1958-12-17 | 1961-11-21 | Ici Ltd | Selective hydrogenation of conjugated diolefines to monoolefines |
| US4115466A (en) * | 1975-10-16 | 1978-09-19 | Scm Corporation | Synthesis of acetylenic compounds useful in preparing dehydrophytols and Vitamin E |
-
1938
- 1938-04-15 US US202274A patent/US2207071A/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2519631A (en) * | 1945-06-11 | 1950-08-22 | Ici Ltd | Catalytic hydrogenation of alkenyl furans |
| DE972502C (en) * | 1954-10-23 | 1959-07-30 | Bayer Ag | Process for the preparation of N-trichloromethyl-thioimides |
| US2950334A (en) * | 1957-11-04 | 1960-08-23 | Du Pont | Process of preparing o-divinylbenzene |
| US3009969A (en) * | 1958-12-17 | 1961-11-21 | Ici Ltd | Selective hydrogenation of conjugated diolefines to monoolefines |
| US4115466A (en) * | 1975-10-16 | 1978-09-19 | Scm Corporation | Synthesis of acetylenic compounds useful in preparing dehydrophytols and Vitamin E |
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