CA1113479A - Process for the manufacture of furan compounds - Google Patents
Process for the manufacture of furan compoundsInfo
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- CA1113479A CA1113479A CA318,274A CA318274A CA1113479A CA 1113479 A CA1113479 A CA 1113479A CA 318274 A CA318274 A CA 318274A CA 1113479 A CA1113479 A CA 1113479A
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Abstract
PROCESS FOR THE MANUFACTURE OF FURAN COMPOUNDS
ABSTRACT OF DISCLOSURE
The present invention relates to a process for the manufacture of furan compounds by the direct oxidation of conjugated diolefins with air or oxygen in the liquid phase in the presence of a transition metal catalyst system.
ABSTRACT OF DISCLOSURE
The present invention relates to a process for the manufacture of furan compounds by the direct oxidation of conjugated diolefins with air or oxygen in the liquid phase in the presence of a transition metal catalyst system.
Description
BACKGROUND OF THE I~J~NTION
Present processes for the direct oxidation of dioiefins to furan compounds are ~rimarily vapor phase processes which are ~enerally characterized by low ccnversions and poor selectivities. These disadvantages are brought about by the lnstability of furan compounds at high tempe-atures in the presence of oxygen which leads to the formation of resinous compounds, charring and uncontrolled polymerization.
The iiquid phase process of the present invention eliminates these disadvantages by operating at moderate tempera~u~es.
Althou~h several liquid phase processes are known for the production of furan compounds, they involve ~he use of oxy~enated compounds as starting materials. For exam~le, .S. 3,932,468, issued January 13, 1976, and U.S. 3,996,2~C, issued December 7, 1976, pertain to the rearrangemen~ o butadiQne monoxide, and U.S. 3,933,861, issued Janua~y 2~, 1976, involves the reaction of an alkene and an aikene oxide to yield substituted furans. Both of these processes recuire oxygenated starting materials, whereas in the preser.~ ~r.ven~ion, furan compounds are obtained by the direct oxidation cf t~e
Present processes for the direct oxidation of dioiefins to furan compounds are ~rimarily vapor phase processes which are ~enerally characterized by low ccnversions and poor selectivities. These disadvantages are brought about by the lnstability of furan compounds at high tempe-atures in the presence of oxygen which leads to the formation of resinous compounds, charring and uncontrolled polymerization.
The iiquid phase process of the present invention eliminates these disadvantages by operating at moderate tempera~u~es.
Althou~h several liquid phase processes are known for the production of furan compounds, they involve ~he use of oxy~enated compounds as starting materials. For exam~le, .S. 3,932,468, issued January 13, 1976, and U.S. 3,996,2~C, issued December 7, 1976, pertain to the rearrangemen~ o butadiQne monoxide, and U.S. 3,933,861, issued Janua~y 2~, 1976, involves the reaction of an alkene and an aikene oxide to yield substituted furans. Both of these processes recuire oxygenated starting materials, whereas in the preser.~ ~r.ven~ion, furan compounds are obtained by the direct oxidation cf t~e
2~ con~ugated diolefin.
Whiie Japanese ~atent No. 77 77,049 discloses a process fo. the oxidation of butadiene 'o furan _n an acueous acidic medium, the process of the presen~ invention is 1- ...
~3 (5063~
dlstlnguished from this process in that the present process is conducted in an organ~c solvent medium in which the catalyst and furan products are more stable.
SUMMARY OF THE INVENTION
In accordance wlth the process of the present inventlon, acyclic conJugated dloleflns containlng from 4 to 10 carbon atoms are converted to furan and alkyl-substltuted furan compounds by the direct oxldatlon of the diolefln wlth molecular oxygen ln a liquld phase reactlon. The reactlon is carried out ln a non-aqueous reactlon medlum ln the presence of a transltlon metal organo-metalllc catalyst complex.
The liquld phase oxidatlon reactlon of this invention ls a free radlcal reaction, and these reactions appear to be lnltlated by means of the formatlon of an lnitial free radical. Thls inltlal free radlcal may generate the desired product (furan) dlrectly, or proceed to form other radlcal intermediates whlch can yleld elther furan, other oxygenated products, such as a dlolefin monoxide, 2,5-dihydrofuran, crotonaldehyde, or ollgomers and/or polymers.
The role of the catalyst of this invention is to react with the lnltial key radical intermediates, convertlng them directly to furan products before deleterious by-products can be produced. It ls thls selective catalytic behavior, coupled wlth speciflc reaction conditions herein defined that result in the enhanced selectivity of the oxidation of the diolefins to the desired furan compounds.
Suitable feeds in this inventlon for converslon to furan compounds comprise acyclic alkadienes having from 4 to
Whiie Japanese ~atent No. 77 77,049 discloses a process fo. the oxidation of butadiene 'o furan _n an acueous acidic medium, the process of the presen~ invention is 1- ...
~3 (5063~
dlstlnguished from this process in that the present process is conducted in an organ~c solvent medium in which the catalyst and furan products are more stable.
SUMMARY OF THE INVENTION
In accordance wlth the process of the present inventlon, acyclic conJugated dloleflns containlng from 4 to 10 carbon atoms are converted to furan and alkyl-substltuted furan compounds by the direct oxldatlon of the diolefln wlth molecular oxygen ln a liquld phase reactlon. The reactlon is carried out ln a non-aqueous reactlon medlum ln the presence of a transltlon metal organo-metalllc catalyst complex.
The liquld phase oxidatlon reactlon of this invention ls a free radlcal reaction, and these reactions appear to be lnltlated by means of the formatlon of an lnitial free radical. Thls inltlal free radlcal may generate the desired product (furan) dlrectly, or proceed to form other radlcal intermediates whlch can yleld elther furan, other oxygenated products, such as a dlolefin monoxide, 2,5-dihydrofuran, crotonaldehyde, or ollgomers and/or polymers.
The role of the catalyst of this invention is to react with the lnltial key radical intermediates, convertlng them directly to furan products before deleterious by-products can be produced. It ls thls selective catalytic behavior, coupled wlth speciflc reaction conditions herein defined that result in the enhanced selectivity of the oxidation of the diolefins to the desired furan compounds.
Suitable feeds in this inventlon for converslon to furan compounds comprise acyclic alkadienes having from 4 to
3 10 carbon atoms. ~xamples include butadiene-1,3, pentadiene-133, isoprene, hexadiene-1~3, decadiene-1,3, and the like, ~3~' (5063) and mixtures thereof. The acycllc alkadienes having from 4 to 5 carbon atoms are preferred in this process. The furan compounds produced by the process of the present in~ention have the ~ormula:
R-C-C-R
R-C C-R
o wherein each R ls indl~dually selected from the group consisting of hydrogen and an alkyl radlcal havlng from 1 to 6 carbon atoms, the total carbon atoms in the R
radicals being in the range of 0 to 6. Representative products include furan, 2-methylfuran, 3-methylfuran, 2,5-dlethyl~uran, 2-n-hexylfuran, 2-isopropyl-3-methylfuran, 3,4-n-dipropylfuran, 3-methyl-4-n-butylfuran, and the like.
The catalysts of this invention are organo-metallic complexes or salts of the metals of Groups IVB, VB, VIB, VIIB or VIII of the Periodic classlflcation of elements.
These complexes have the general formùla:
~RXM (L)y]æ
wherein R is an organic li~and selected from the group conslsting of a kyl, aryl, alkene, diene, triene or alkyne radicals containing from 1 to 8 carbon atoms;
L is a l~gand selected from the grou~
consisting o~ carbon monoxide and a halogen;
M is a transition metal or their mixtures selected from the grou~s IVB, VB, VIB, VIIB and ~III of the Pe-iodic classificatior of elements, and wherein x is O to 2, y is 0 to 6 and x + y is 1 to 6, and wherein z is 1 to ~.
~13~
Specl~ic examples o~ sultable catalysts lnclude OsC13, o~3tCo)l2, ~CpMo(C0)3]2 (Cp ~ cyclopentadienyl radlcal), CpV(C0~4, CpTiC12, CpMn(C0)3, (Cp)2Pe, M ( 6 (CO)2]2, (C4H6)Fe(CO)3, Co2(CO)8~ ~U3(C)12' Rh6(C0)16 and W(C0)6.
Whlle these complexes and salts are effectlve catalystæ ln thelr own rlght, it may also be advantageous to utlllze certaln promoters rOr these catalysts as defined by the general rormula:
A R m Xn whereln A can be mercury, thalllum, indlum, or a Group IV A element such as slllcon, germanlum, tln or lead;
R can be a hydrlde, alkyl, aryl or an amlne group;
X can be an anlon of a mineral acid or a carboxyllc acld, and whereln m ~s 0-4, n ls 0-4 and m ~ n ls 1 to 4.
Specirlc examples of these types o~ promoters lnclude such compounds as Hg(C2~302)2, SnC12, (C2H~)2SnC12~
R-C-C-R
R-C C-R
o wherein each R ls indl~dually selected from the group consisting of hydrogen and an alkyl radlcal havlng from 1 to 6 carbon atoms, the total carbon atoms in the R
radicals being in the range of 0 to 6. Representative products include furan, 2-methylfuran, 3-methylfuran, 2,5-dlethyl~uran, 2-n-hexylfuran, 2-isopropyl-3-methylfuran, 3,4-n-dipropylfuran, 3-methyl-4-n-butylfuran, and the like.
The catalysts of this invention are organo-metallic complexes or salts of the metals of Groups IVB, VB, VIB, VIIB or VIII of the Periodic classlflcation of elements.
These complexes have the general formùla:
~RXM (L)y]æ
wherein R is an organic li~and selected from the group conslsting of a kyl, aryl, alkene, diene, triene or alkyne radicals containing from 1 to 8 carbon atoms;
L is a l~gand selected from the grou~
consisting o~ carbon monoxide and a halogen;
M is a transition metal or their mixtures selected from the grou~s IVB, VB, VIB, VIIB and ~III of the Pe-iodic classificatior of elements, and wherein x is O to 2, y is 0 to 6 and x + y is 1 to 6, and wherein z is 1 to ~.
~13~
Specl~ic examples o~ sultable catalysts lnclude OsC13, o~3tCo)l2, ~CpMo(C0)3]2 (Cp ~ cyclopentadienyl radlcal), CpV(C0~4, CpTiC12, CpMn(C0)3, (Cp)2Pe, M ( 6 (CO)2]2, (C4H6)Fe(CO)3, Co2(CO)8~ ~U3(C)12' Rh6(C0)16 and W(C0)6.
Whlle these complexes and salts are effectlve catalystæ ln thelr own rlght, it may also be advantageous to utlllze certaln promoters rOr these catalysts as defined by the general rormula:
A R m Xn whereln A can be mercury, thalllum, indlum, or a Group IV A element such as slllcon, germanlum, tln or lead;
R can be a hydrlde, alkyl, aryl or an amlne group;
X can be an anlon of a mineral acid or a carboxyllc acld, and whereln m ~s 0-4, n ls 0-4 and m ~ n ls 1 to 4.
Specirlc examples of these types o~ promoters lnclude such compounds as Hg(C2~302)2, SnC12, (C2H~)2SnC12~
4 3 3 ~C~3)2, GeI2~ (n-C4Hg)3GeI, (~ -C5H5)Ge(CH ) (C2H5)3 PbCl, (CH3)3 SlH, or SiH3I.
2~ When promoters are employed for the catalysts of this invention, they may be added to the reaction mixture as separate species or they may be reacted with the catalyst to give a separa~e chemical compound which can be isolated and purified prior to its use as a catalytic agent. Representa-tive examples of compounds ~ormed by reactions occurring between the catalyst and the promoter include: ClHgFe(Cp)2, ~Ig[Co(C0)4]2, C12Sn~Fe(CO)2Cp]2, I2Ge[Co(CO)~ 2, [(C2~;5)3Pb~2.-e(CO)4, H3SiCo(C0)4, Cl(CH3)2Sn[Mn(C0)5], and [Cp(C0)3Mo-Sn(C~3)2-M~(C0)5].
~ (5063) The promoter compounds o~ the catalyst system are ad~antageously employed in molar ratios of from 0.25 to 2.0 moles of promoter per ~ole of the transition metal catalyst~
However preferred molar ratios Or promoter compound to the transltion metal catalyst are about 0.~:1 to 2:1. The catalysts o~ thls lnventlon (with or wlthout promoters) may be dissolved in the reaction medium as homogeneous catalysts, slurried ln the reactlon medlum as lnsoluble, unsupported heterogeneous catalysts, or ln some cases where advantageous, they may be supported on carrlers such as sllica, alumlna, or polymeric materials and slurrled ln the reactlon medlum.
It ls preferred, however that the catalyst system be a homogeneous system where the catalyst ls soluble in the ! reaction sol~ent.The ~oncentratlon of the catalyst ln the 15 sol~ent medlum may range rrom 10 6 to 10.0 moles/liter.
Preferably a catalyst concentration of from about 10 5 to 1.0 moles/liter is employed.
The reactlon medium suitable for the process of this invention is an essentially inert, non-coordinating or weakly coordinating organic solvent having a boiling point signiflcantly higher than the boiling points of the feed or the products obtained. Solvents with boiling points of from 130~ to 22~C are especially preferred. Also desirable are those solvents having an absence of abstractable hydro~ens which could lead to oxidation of the solvent or the binding of the active sites of the metal or metals in the catalyst, thereby deactivating the catalyst. Examples o~ suitabie solvents include paraffinic hydrocarbons, aromatic hydrocarbons, chlorinated hydrocarbons, and nitrile aromatics such as heptanes, decanes, and the l~ke; toluene and the xylenes;
chlorobenzene, chlorofor~, carbon tetrachioride, etc; and ber.zonitrile; with chlorobenzene being the most Dre~erred.
~ t5063) Subst~tuted rurans such as alkyl-furans or 2,3-benzofuran may also serve as suit~ble solvents in some cases.
The oxidation reaction of the present in~ention is very sensitive to reaction condltlons and lt ls an essential ~eature of the invention that the reaction be carried out under conditlons whlch maxlmlze selectivlty. The reactlon may be carried out at temperatures in the range of from about 20 to 200C, and pre~erably at temperatures in the range of ~rom about 50 to 130C. Temperatures above thls 1~ range bring about the formatlon o~ additional oxidation products such as crotonaldehyde and increase the formatlon of undeslrable polymer.
The reaction pressure may range from 1 to 20 atmospheres, and pre~erably ~rom 1 to 10 atmospheres. The partial pressure o~ oxygen ls of particular importance to the selectivity of the reaction, and oxygen pressures of from 0.~ to ~ atmospheres and expecially oxygen pressures of from l to 3 atmospheres are advantageously employed.
Another critical reactlon variable affectin~
selectivlty of the reaction is the ratio of diolefin to oxygen. While the molar ratio of diolefin to oxygen may vary from 0.001 to 100.0, a ratio of from 0.33 to 5.0 is preferred.
In those instances where the reaction is carried out in a sealed reaction vessel, the reaction times may range from 0.5 to 10 hours and a reaction time of from 1,0 to 4 hours is preferable. Continuous operation in which the reaction mixture is maintained at constant temperature and pressure is also contemplated to be within the scope of the present invention. Under such conditions, the diolefin and 3 air or oxygen are continuously fed to the reactor while volatile products and the unreacted feed are continuousl~
removed. ~he vo atile products can be collected and the unreacted feed recycled to the reactor.
~S1;3~L1 ~ ~
(~063) The reactor vessel may be constructed ~rom stain-less steel, or in certain instances the reaction vessel may be lined wlth glass, quartz or a stable resinous material in order to minimize side reactions between reaction intermediates and the walls of the reaction vessel.
Specific Examples Examples 1-12 The oxidation of butadiene to furan in the presence of a variety Or promoted and unpromoted transition metal catalyst complexes was conducted in a series of experiments according to the following procedure:
An amount Or catalyst requlred to give a concentra-tion of 1 x 10 4 moles of catalyst in the reaction solvent was weighed into a stainless steel reaction tube (180 mm long x 9.~ mm diameter) equipped with a stainless steel ball valve and septum cap. The tube was evacuated and charged with a mixture of butadiene and oxygen in a 1:1 molar ratio at an initial oxygen pressure of 2.2 a~tmospheres. Four milliliters of chlorobenzene solvent was introduced into the tube wlth a metering pump. The tube and its contents were heated to a temperature of 110~ in a heating block for a period of two hours. At ~he end of this time period, the tube was qu~ckly cooled to room temperature and the reactlon mixture analyzed by gas chromatography.
4`~
The pexcent conVersion of the hutadiene and the percent selectivity to uran based on t~e percent of butadiene converted that were obtained in Examples 1 to 12 are summarized in Table I below.
TABLE I
% Total ~ Selectivity Exam~le Catalyst Converstion to Furan 1 (Cp)2Fe 2.9 99.0 2 (Cp)2Ee/SnC12 10.2 81.1 3 Mo(CO)6 1.4 97.7 4 Mo(CO)6/Hg(c2H3O2)216.7 65.4 CpV(CO)4 9.4 82.2 6 CpTi2C12 13.3 77.5 7 [CpMo(CO)3]2 17.6 68.2 8 Os3(CO)12* 18.2 92.0 9 S3(C)12/Sncl2 14.2 71.6 OsC13 20.5 57.4 11 Ru3(CO)12 0.1 100.0 12 3(CO)l2/(n-c4H9)3GeI 13-2 99 0 ~Cp = cyclopentadiene) *Reaction conducted in a resin coated stainless steel reactor.
2~ When promoters are employed for the catalysts of this invention, they may be added to the reaction mixture as separate species or they may be reacted with the catalyst to give a separa~e chemical compound which can be isolated and purified prior to its use as a catalytic agent. Representa-tive examples of compounds ~ormed by reactions occurring between the catalyst and the promoter include: ClHgFe(Cp)2, ~Ig[Co(C0)4]2, C12Sn~Fe(CO)2Cp]2, I2Ge[Co(CO)~ 2, [(C2~;5)3Pb~2.-e(CO)4, H3SiCo(C0)4, Cl(CH3)2Sn[Mn(C0)5], and [Cp(C0)3Mo-Sn(C~3)2-M~(C0)5].
~ (5063) The promoter compounds o~ the catalyst system are ad~antageously employed in molar ratios of from 0.25 to 2.0 moles of promoter per ~ole of the transition metal catalyst~
However preferred molar ratios Or promoter compound to the transltion metal catalyst are about 0.~:1 to 2:1. The catalysts o~ thls lnventlon (with or wlthout promoters) may be dissolved in the reaction medium as homogeneous catalysts, slurried ln the reactlon medlum as lnsoluble, unsupported heterogeneous catalysts, or ln some cases where advantageous, they may be supported on carrlers such as sllica, alumlna, or polymeric materials and slurrled ln the reactlon medlum.
It ls preferred, however that the catalyst system be a homogeneous system where the catalyst ls soluble in the ! reaction sol~ent.The ~oncentratlon of the catalyst ln the 15 sol~ent medlum may range rrom 10 6 to 10.0 moles/liter.
Preferably a catalyst concentration of from about 10 5 to 1.0 moles/liter is employed.
The reactlon medium suitable for the process of this invention is an essentially inert, non-coordinating or weakly coordinating organic solvent having a boiling point signiflcantly higher than the boiling points of the feed or the products obtained. Solvents with boiling points of from 130~ to 22~C are especially preferred. Also desirable are those solvents having an absence of abstractable hydro~ens which could lead to oxidation of the solvent or the binding of the active sites of the metal or metals in the catalyst, thereby deactivating the catalyst. Examples o~ suitabie solvents include paraffinic hydrocarbons, aromatic hydrocarbons, chlorinated hydrocarbons, and nitrile aromatics such as heptanes, decanes, and the l~ke; toluene and the xylenes;
chlorobenzene, chlorofor~, carbon tetrachioride, etc; and ber.zonitrile; with chlorobenzene being the most Dre~erred.
~ t5063) Subst~tuted rurans such as alkyl-furans or 2,3-benzofuran may also serve as suit~ble solvents in some cases.
The oxidation reaction of the present in~ention is very sensitive to reaction condltlons and lt ls an essential ~eature of the invention that the reaction be carried out under conditlons whlch maxlmlze selectivlty. The reactlon may be carried out at temperatures in the range of from about 20 to 200C, and pre~erably at temperatures in the range of ~rom about 50 to 130C. Temperatures above thls 1~ range bring about the formatlon o~ additional oxidation products such as crotonaldehyde and increase the formatlon of undeslrable polymer.
The reaction pressure may range from 1 to 20 atmospheres, and pre~erably ~rom 1 to 10 atmospheres. The partial pressure o~ oxygen ls of particular importance to the selectivity of the reaction, and oxygen pressures of from 0.~ to ~ atmospheres and expecially oxygen pressures of from l to 3 atmospheres are advantageously employed.
Another critical reactlon variable affectin~
selectivlty of the reaction is the ratio of diolefin to oxygen. While the molar ratio of diolefin to oxygen may vary from 0.001 to 100.0, a ratio of from 0.33 to 5.0 is preferred.
In those instances where the reaction is carried out in a sealed reaction vessel, the reaction times may range from 0.5 to 10 hours and a reaction time of from 1,0 to 4 hours is preferable. Continuous operation in which the reaction mixture is maintained at constant temperature and pressure is also contemplated to be within the scope of the present invention. Under such conditions, the diolefin and 3 air or oxygen are continuously fed to the reactor while volatile products and the unreacted feed are continuousl~
removed. ~he vo atile products can be collected and the unreacted feed recycled to the reactor.
~S1;3~L1 ~ ~
(~063) The reactor vessel may be constructed ~rom stain-less steel, or in certain instances the reaction vessel may be lined wlth glass, quartz or a stable resinous material in order to minimize side reactions between reaction intermediates and the walls of the reaction vessel.
Specific Examples Examples 1-12 The oxidation of butadiene to furan in the presence of a variety Or promoted and unpromoted transition metal catalyst complexes was conducted in a series of experiments according to the following procedure:
An amount Or catalyst requlred to give a concentra-tion of 1 x 10 4 moles of catalyst in the reaction solvent was weighed into a stainless steel reaction tube (180 mm long x 9.~ mm diameter) equipped with a stainless steel ball valve and septum cap. The tube was evacuated and charged with a mixture of butadiene and oxygen in a 1:1 molar ratio at an initial oxygen pressure of 2.2 a~tmospheres. Four milliliters of chlorobenzene solvent was introduced into the tube wlth a metering pump. The tube and its contents were heated to a temperature of 110~ in a heating block for a period of two hours. At ~he end of this time period, the tube was qu~ckly cooled to room temperature and the reactlon mixture analyzed by gas chromatography.
4`~
The pexcent conVersion of the hutadiene and the percent selectivity to uran based on t~e percent of butadiene converted that were obtained in Examples 1 to 12 are summarized in Table I below.
TABLE I
% Total ~ Selectivity Exam~le Catalyst Converstion to Furan 1 (Cp)2Fe 2.9 99.0 2 (Cp)2Ee/SnC12 10.2 81.1 3 Mo(CO)6 1.4 97.7 4 Mo(CO)6/Hg(c2H3O2)216.7 65.4 CpV(CO)4 9.4 82.2 6 CpTi2C12 13.3 77.5 7 [CpMo(CO)3]2 17.6 68.2 8 Os3(CO)12* 18.2 92.0 9 S3(C)12/Sncl2 14.2 71.6 OsC13 20.5 57.4 11 Ru3(CO)12 0.1 100.0 12 3(CO)l2/(n-c4H9)3GeI 13-2 99 0 ~Cp = cyclopentadiene) *Reaction conducted in a resin coated stainless steel reactor.
Claims (31)
1. A process for converting acyclic conjugated diolefinic hydrocarbons containing from 4 to 10 carbon atoms to furan and alkyl-substituted furans comprising reacting said conjugated diolefins with molecular oxygen in the liquid phase in an inert organic solvent in the presence of a catalyst having the composition:
[RxM (L)y]z wherein R is an organic ligand selected from the group consisting of alkyl, aryl, alkene, diene, triene, or alkyne radicals containing from 1 to 8 carbon atoms;
L is a ligand selected from the group consisting of carbon monoxide and a halogen;
M is a transition metal or mixtures thereof, selected from Groups IVB, VB, VIB, VIIB and VIII of the Periodic classification of elements;
and wherein x is 0 to 2, y is 0 to 6 and x + y is 1 to 6, and wherein z is 1 to 6.
[RxM (L)y]z wherein R is an organic ligand selected from the group consisting of alkyl, aryl, alkene, diene, triene, or alkyne radicals containing from 1 to 8 carbon atoms;
L is a ligand selected from the group consisting of carbon monoxide and a halogen;
M is a transition metal or mixtures thereof, selected from Groups IVB, VB, VIB, VIIB and VIII of the Periodic classification of elements;
and wherein x is 0 to 2, y is 0 to 6 and x + y is 1 to 6, and wherein z is 1 to 6.
2. The process in claim 1 wherein the catalyst is promoted with a compound having the formula:
A Rm Xn wherein A is an element selected from the group consisting of mercury, thallium, indium, silicon, germanium, tin and lead;
R is a hydride, an alkyl, aryl or an amine radical; and X is an anion of a mineral acid or a carboxylic acid;
and wherein m and n each are numbers from 0 to 4, and m + n is 1 to 4.
A Rm Xn wherein A is an element selected from the group consisting of mercury, thallium, indium, silicon, germanium, tin and lead;
R is a hydride, an alkyl, aryl or an amine radical; and X is an anion of a mineral acid or a carboxylic acid;
and wherein m and n each are numbers from 0 to 4, and m + n is 1 to 4.
3. The process in claim 2 wherein the promoter is employed in a molar ratio of from 0.25 to 2 0 moles per mole of the transition metal catalyst.
4. The process in claim 3 wherein the reaction is carried out within the temperature range of 20° to 200°C.
5. The process in claim 4 wherein the molar ratio of diolefin to oxygen is within the range of 0.001 to 100Ø
6. The process in claim 5 wherein the reaction is carried out in an inert organic solvent having a boiling point in the range of from 130 to 225°C.
7. The process in claim 6 wherein the solvent is selected from the group consisting of paraffinic hydrocarbons, aromatic hydrocarbons, chlorinated hydrocarbons, nitrile aromatics, and alkyl or aryl-substituted furans.
8. The process in claim 7 wherein the solvent is chlorobenzene.
9. The process in claim 6 wherein the catalyst is soluble in the reaction solvent.
10. The process in claim 6 wherein the catalyst is slurried in the reaction solvent.
11. The process in claim 5 wherein the diolefin is butadiene.
12. The process of claim 1 wherein said acyclic conjugated diolefinic hydrocarbon is at least one of butadiene, pentadiene, iosprene, hexadiene and decadiene.
13. The process of claim 1 wherein said catalyst is selected from the group consisting of OsCl3, Os3(Co)12, [CpMo(CO)3]2 (Cp=cyclopentadienyl radical), CpV(CO)4, CpTiCl2, CpMn(CO)3, (Cp)2Fe, Mo(CO)6, [CpFe(CO)2]2 (C4H6)Fe(CO)3, Co2(CO)8, Ru3(CO)12, Rh6(CO)16 and W(CO)6.
14. The process of claim 2 wherein said catalyst contains a promoter selected from the group consisting of Hg(C2H3O2)2, SnCl2, (C2H5)2SnCl2, SnCl4, (CH3)3SnN(CH3)2, GeI2, (n-C4H9)3GeI, (.alpha.-C5H5)Ge(CH3)3, (C2H5)3PbCl, (CH3)3SiH, or SiH3I.
15. The process of claim 2 wherein said catalyst is selected from the group consisting of ClHgFe(Cp)2, Hg[Co(CO)4]2, C12Sn[Fe(CO)2Cp]2, I2Ge[Co(CO)4]2, 1(C2H5)3Pb]2 Fe(CO)4, H3SiCo(CO)4, Cl(CH3)2Sn[Mn(CO)5], and [Cp(CO)3Mo-Sn (CH3)2-Mn(CO)5].
16. The process of claim 1 wherein x is a positive number and y is zero.
17. The process of claim 16 wherein x is 2 and M is Fe.
18. The process of claim 1 wherein y is a positive number and x is zero.
19. The process of claim 18 wherein M is Os.
20. The process of claim 1 wherein x and y are both positive numbers.
21. The process of claim 20 wherein x is 2, y is 2 and M is Ti.
22. The process of claim 1 wherein M is at least one element selected from the group consisting of Group IVB, Group VB, Group VIB, Group VIIB, Os, Fe, Ru, Co, Rh and Ir.
23. The process of claim 22 wherein M is selected from Fe, Os, Mo, Ti, V and Ru.
24. The process of claim 23 wherein M is selected from Fe and Os.
25. The process of claim 1 wherein R is cyclopentadienyl.
26. The process of claim 1 wherein L is CO.
27. m e process of claim 1 wherein L is Cl.
28. The process of claim 2 wherein A is selected from the group consisting of Ge and Sn.
29. The process of claim 2 wherein A is Sn and M is Fe.
30. The process of claim 2 wherein A is Ge and M is Ru.
31. The process of claim 1 wherein said process is conducted in the absence of substantial amounts of water.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US86631378A | 1978-01-03 | 1978-01-03 | |
| US866,313 | 1978-01-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1113479A true CA1113479A (en) | 1981-12-01 |
Family
ID=25347341
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA318,274A Expired CA1113479A (en) | 1978-01-03 | 1978-12-20 | Process for the manufacture of furan compounds |
Country Status (10)
| Country | Link |
|---|---|
| JP (1) | JPS54100365A (en) |
| BG (1) | BG30177A3 (en) |
| BR (1) | BR7808621A (en) |
| CA (1) | CA1113479A (en) |
| DD (1) | DD141022A5 (en) |
| ES (1) | ES476490A1 (en) |
| NO (1) | NO790010L (en) |
| PT (1) | PT69011A (en) |
| RO (1) | RO76125A (en) |
| YU (1) | YU313678A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5108318B2 (en) * | 2007-02-01 | 2012-12-26 | 昭和シェル石油株式会社 | New organomolybdenum compounds |
| JP5108319B2 (en) * | 2007-02-01 | 2012-12-26 | 昭和シェル石油株式会社 | Friction modifier comprising organomolybdenum compound and lubricating composition containing the same |
| JP5395935B2 (en) * | 2012-08-31 | 2014-01-22 | 昭和シェル石油株式会社 | Friction modifier comprising organomolybdenum compound and lubricating composition containing the same |
-
1978
- 1978-12-20 CA CA318,274A patent/CA1113479A/en not_active Expired
- 1978-12-28 JP JP16444878A patent/JPS54100365A/en active Pending
- 1978-12-29 BR BR7808621A patent/BR7808621A/en unknown
- 1978-12-29 RO RO7896126A patent/RO76125A/en unknown
- 1978-12-29 YU YU313678A patent/YU313678A/en unknown
- 1978-12-29 ES ES476490A patent/ES476490A1/en not_active Expired
- 1978-12-29 PT PT6901178A patent/PT69011A/en unknown
-
1979
- 1979-01-02 BG BG7941937A patent/BG30177A3/en unknown
- 1979-01-02 NO NO790010A patent/NO790010L/en unknown
- 1979-01-03 DD DD21032079A patent/DD141022A5/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| PT69011A (en) | 1979-01-01 |
| NO790010L (en) | 1979-07-04 |
| RO76125A (en) | 1982-07-06 |
| YU313678A (en) | 1983-02-28 |
| DD141022A5 (en) | 1980-04-09 |
| BG30177A3 (en) | 1981-04-15 |
| JPS54100365A (en) | 1979-08-08 |
| BR7808621A (en) | 1979-08-07 |
| ES476490A1 (en) | 1979-07-16 |
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